Journal June08 WWW - Petrotechsociety

PETROTECH
Journal of the
Society
Journal of the Petrotech Society
Volume V No. 2
June 2008
Editorial
Dear Patrons,
Yet another issue of the Journal of Petrotech Society is in your hands. With this issue, an attempt has been made to bring in a varied mix of relevant articles on all aspects of hydrocarbon chain. We sincerely thank our expert contributors who have taken pains to focus relevant ideas on the latest technology development both in upstream and down stream areas. As you may be aware, we are mid way through the preparatory year of the forthcoming mega event viz PETROTECH 2009, the 8th International Oil & Gas Conference and Exhibition being held under the aegis of Ministry of Petroleum and Natural Gas. Indian Oil Corporation, the lead company organizing this event on behalf of our Society, has constituted seven nodal committees under the leadership of all functional directors to continuously review the progress and make midcourse corrections wherever necessary. The Conference has a very important theme Energy Independence with Global Cooperation: Challenges and Solutions and call for papers related to the theme has already been sent by technical committee. A countdown calendar released by Chairman during the 2nd Steering Committee held on 12th march 2008 is in place for monitoring progress/milestones for the Conference. Major milestones achieved so far are : Vigyan Bhawan has been booked as Conference venue and Hall No 14 &18 at Pragati Maidan has been booked for Exhibition. M/s Reed Exhibition Ltd, UK has been selected as the Professional Exhibition Organizer for the above Exhibition. The Parallel Track Event is being Organized by IndianOil alongwith BPCL and FICCI. Honble Minister of Petroleum & Natural Gas has kindly consented to be Patron-in-Chief for PETROTECH-2009. Honble Minister of State for Petroleum & Natural Gas and Secretary, MoP&NG have also agreed to be Patron and Conference Chairman respectively. Honble Minister of Petroleum & Natural Gas has sent request letter to Honble Prime Minister of India for inaugurating the Conference. During the 1st Core Group Meeting held on 17th January 2008, Honble Minister for Petroleum and Natural Gas & Patron-in-Chief, PETROTECH-2009 had formally released the rst Information Brochure and launched website of PETROTECH-2009. For promotion & Marketing of the above event, PETROTECH 2009 Posters were displayed in International Aviation Conference held on 21st-22nd February 2008 at Jodhpur; 5th Asia Gas Partnership Summit 2008, held on 14th-15th April 2008 at New Delhi & Made in India Exhibition held in November 2007 at Cairo. A stall was set up during ISFL-2008, held from 9th -12th March 2008 at New Delhi. The stalls would also be set up at 19th World Petroleum Congress being held from 29th June-3rd July 2008 at Madrid, Spain.
While the preparations of the above event are in full swing, the Society has been equally active on other fronts particularly in organizing several programmes for the benet of industry and academia. As informed earlier, the Society had organized 2nd R&D Conclave alongwith Indian Oil Corporation, R&D Centre at Goa from 9th-11th January 2008. Similar preparations are through for 3rd Summer School Programme Petroleum Rening and Petrochemicals which is being organized with Indian Oil Corporation Ltd from 23rd-28th June 2008 at IIPM, Gurgaon and also 4th seminar on Modern Practices in Petroleum Exploration alongwith ONGC being organized on 22nd-27th September 2008 at Dehradun. For the rst time, Society joined hands with National Institute of Personnel Management to organize a Pre Conference-Panel Discussion Linking Management, Industry and Education: Challenges during NatCon08 under the leadership of Dr A K Balyan, National President, NIPM & Director (HR), ONGC, It was a live debate between academia and industry experts on 7th February 2008 at Vadodara and telecast by NDTV Prot on 27th February 2008. Similarly, Petrotech Society also associated itself with Directorate General of Hydrocarbon during International Conference on Gas Hydrates held from 6-8 February 2008 at Radisson MBD Hotel, Noida. A programme on Hydrocarbon Industry Growth - Prospects & Challenges in North East on April 24-25th 2008 was also organized for the rst time in north-east at Guwahati alongwith IndianOil Guwahati Renery. As many as 58 participants from academia and industry from north-east region participated. Again for the rst time, an industry education tour to Alberta is being organized by the Society alongwith its MoU partner, University of Alberta for experts of different member organizations. As part of Industry Awareness Programme, the Society has embarked on organizing industry expert visits to different Universities for imparting basic hands-on type knowledge to senior under/post graduate students. Several universities and institutions have responded very favourably to the programme. Draft Vision/Mission statement has been debated with senior experts and their views are being incorporated before nalizing the same. Two new Corporate Members viz Lubrizon India Pvt Ltd & British Gas India Pvt Ltd have joined Petrotech during the month of February & March 2008 respectively in addition to 27 Corporate members and 11 Institutional Members. Student Chapters are active at UPES, Dehradun, ISM Dhanbad and MIT Pune and the initiative is continuing with other Universities. The Society is planning to hold rstever seminar on Technology Advancement in South India alogwith Chennai Petroleum Corporation Ltd during later half of the year. The Secretariat is trying to keep updated its esteemed members through regular monthly activity highlight reports and it is hoped that all members are receiving this regularly. With this issue, a focal write up on various universities imparting Petroleum Engineering Courses in India and abroad, is proposed to be started, starting with exposure on University of Alberta, our MoU Partner.
J L Raina
Secretary General & CEO
Message
By the time the next Petrotech Journal would be in your hand we would be about the nish Petrotech 2009 which is to be held January 11-15 in New Delhi. Countdown has already begun and everybody is looking forward for the Petrotech 2009 which we hope will be class apart from any other oil and gas conference and exhibition. Energy Independence with global Cooperation: Challenges and Solutions probably the most suitable theme for the conference, will generate interesting debate and address some of the most critical concerns of modern day problem Energy Security. The Petrotech Journal is carrying forward the good work of sharing knowledge and providing technological update to hydrocarbon industry professionals. With crude prices in the range of $140 a barrel, we can only speculate what would be the future of crude prices, But thats for sure sole dependency on fossil fuel can be decisive for any country like India which imports three quarter of the energy needs. Future lies in conservation and optimum use of energy sources that too on a global scale. I again wish all the best for all the stakeholders who are putting their best efforts to make Petrotech 2009 show a grand success.
(Naresh Kumar)
MD Jindal Drilling and Industries Ltd. President, Petrotech Society
JOURNAL OF THE PETROTECH SOCIETY Advisory Board

Dr Hari Narain
Former Director, NGRI
CONTENTS
J A N UA RY 2008
N B Prasad
Former Chairman, ONGC
Dr Avinash Chandra
Former DGH
Dr S Varadarajan
Former DG, CSIR
Dr A K Bharnagar
Former Director (R&D), IOC
Dr T S R Prasad Rao
Former Director, IIP
Diamonds are Forever, Oil is Not...

by R S Sharma
Dr M O Garg
Director, IIP
Polyolefin Materials and Catalysts: An Introduction

G S Kapur, D K Tuli, R K Malhotra, Anand Kumar
10
Dr S Ramanathan
Former Member Personnel ONGC
Revival of Non-Flowing wells and production enhancement through implementation of Hydrofracturing Technology in Geleki field of Assam Asset
Shri J G Chaturvedi
17
P K Mukhopadhyay
Former Director (R&D) IOC
Sustainable Development Key issues and steps for oil industries Dr D M Kale
ED (R&D) ONGC A B Chakraborty, Shantanu Dasgupta
23
Surface Exploration Techniques for Hydrocarbons: An Overview

R R Singh
26
Editorial Board
J L Raina
Editor Secretary General & CEO, PETROTECH Society
Energy Beyond Oil - Underground Coal Gasification

R K Sharma
34
Ethanol from Lignocellulosic Biomass: Prospects and Challenges

M P Singh, D K Tuli, R K Malhotra and Anand Kumar
39
Bacterial biosurfactant in enhancing solubility of petroleum hydrocarbons G Sarpal

Secretary B K Konwar and N K Bordoloi
45
Suman Gupta
Manager
Flow Measurement Applications in the Oil & Gas Industry Different Technologies for Different Applications
Dieter Huller
53
PETROTECH Activities
The views expressed by the authors are their own, and do not neccessarily represent that of the Petrotech Society.
60
Printed and published by

Petrotech Society at Core 8, Scope Complex, 3rd Floor, New Delhi - 110 003 India
JOURNAL OF THE PETROTECH SOCIETY
Diamonds are Forever, Oil is not

R S Sharma
CMD, ONGC
Mr R S Sharma,
is the Chairman & Managing Director of Indias agship Navratna Public Sector Undertaking, Oil and Natural Gas Corporation. He is a Fellow Member of the Institute of Cost & Works Accountants of India and an Associate Member of the Indian Institute of Bankers. Mr Sharma is also the Chairman of Mangalore Reneries and Petrochemicals Ltd., ONGC Videsh Ltd., and other group companies of ONGC.
argue that peak lies within the very near future, if not already reached. However, few others feel that the peak is still some decades away and would be a bumpy plateau. But it is quite clear that the peak in world production will happen soon and after it oil production will start its terminal decline. For our economy to grow, a plateau would be disastrous, let alone a decline in oil production. Quoting ofcials from The International Energy Agency (IEA), The Wall Street Journal online on May 22, 2008, mentioned that the IEA which earlier had been predicting that supplies of crude and other liquid fuels will arc gently upwards and keep pace with rising demand crossing 116 million barrels a day by 2030 from the current level of 85 million barrels per day, has been forced to rethink. The agency now feels that companies could struggle to surpass 100 million barrels a day over the next two decades. The Energy Information Administration (EIA) of the U.S. Energy Department also has started casting a gloomier picture; that it will be tough to push global fuel supplies over 100 million barrels a day by 2030. The decision to rigorously survey supply, instead of just demand as was done in the past by these and many other agencies is a grim reminder of the fact that supply is not on the same track as demand. These fears are also echoed in the available production data. Our past optimism stemmed from the reserves and production capacity of the Middle East and the Russians despite slumps in production from other major producers viz: the USA, North Sea, Mexico, Venezuela etc. Former Soviet Union countries (FSU) had recorded a massive growth of 34% in the last 5 years (ending 2007; Source : BP Statistical Review of World Energy 2008) while OPEC production grew by 18% over the same period. These two
contributed signicantly to increase in the global oil production which has recorded a growth of 10% during this period. However, while OPEC did grow during 2002 to 2004, its growth in later years has been stunted and in fact registered a negative growth in 2007. OPECs average annual production growth declined from 8% in 2004 to 3% in 2005 and nally to (-)1% in 2007. Similarly, though oil production in FSU countries are still growing, its average annual production growth had dipped from 9% in 2004 to 4% in 2005 and remained almost static till 2007. Global oil production, following a trend similar to OPEC, grew with an average annual growth of 4% in 2004, but there after started its downward slide to nally register a negative growth of (-)0.2% in 2007. To add to the woes, Cambridge Energy Research Associates (CERA) in a recent report (Sept2007) titled Finding the Critical Numbers: What Are the Real Decline Rates for Global Oil Production, has drawn a conclusion that the depletion rate of the world's 811 largest elds is around 4.5% a year. At that rate, oil companies have to make huge investments just to keep overall production steady. But if the projections of various other agencies, which say the depletion rate could be higher still, the situation may well be hardly redeemable. IEA researchers have warned that even if there is enough oil under the ground, which are probable, supply barriers may not be surmountable due to lack of sufficient investments in surface facilities and equipment.
s the writing on the wall? Ageing elds, tight supplies, rising demand, soaring oil prices. Oil which ruled the 20th century seems like its shortage will rule the next few decades of the 21st century.
Oil, unquestionably has driven the globe predominantly since middle of the last century. It is critical for almost every important function of modern life. No other existing energy source can match its versatility and convenience. The demand for oil is not waning, not even at the current prices which has breached USD138 (June 6th 2008) from a mere USD10, barely a decade earlier. It is expected to grow exponentially fuelled by rising demand from developing nations, led by China.
Will the supply sustain the rising demand?

Evidences point to the contrary; that our tank may not be able to last long at the current rate of extraction or at the rate at which it is predicted to be extracted in future. Though, the debate is on; whether we have reached the peak or not? Many
6 J U N E 2008
Bad habits are like a comfortable bed, easy to get into, but hard to get out of

In fact in an article published in The Scientic American in April 2008, the last decade has been described as The Lost Decade. First, it points out, when the oil price collapsed from $25 to $12 per barrel at the end of the 1990s, E&P companies slashed their technical and scientic staffs. These cuts were so extreme that when the companies nally began, belatedly, to hire again in 2005 (when oil was >$40/ bbl), an entire generation of knowledge-workers had been lost, leaving the industry technically crippled. Today, there are few new scientists or engineers entering the industry and even fewer top-notch, experienced petroleum professionals to hire, leading to poaching and attrition. Secondly, the booming markets of the early to mid 2000 led to massive industry failure to invest for sustainable protability in the long haul. The record jump in the crude prices in the recent past has once again left many fretting on a diminished incentive for the producers to sink more billions to ramp up output. Today, the oil industry is spending lot of money and using all available technologies to nd new oil in unfavorable areas (like the Arctic and deep seas). But resources are few, especially deepwater drilling rigs. The loss of investment in technical people and infrastructure due to oil industry having taken a holiday- missing-in-action, over the last 10 years is going to cost dearly. And therefore pessimism is sweeping, so much so that many feel that it may not take long for the taps to run dry. Perhaps, Brazil may delay this eventuality. The state owned Brazilian oil company, Petrobras, recently made three huge oil discoveries in its ultra deepwaters which prompted the Brazilian President to even comment that God is Brazilian. The Tupi and the Jupiter elds each are estimated to have 5-8 billion barrels of oil equivalent while the Carioca eld is estimated to be even bigger, though earlier claims of it having 33 billion barrels have later been denied by the company. However, sceptics are quick to point out that these sub-salt layers nds located in ultra deepwaters would pose considerable technological and investment challenges.
1.30
Oil production in India grew by 6% in the last ve years up to 2006-07; even though the preceding five years had witnessed a decline, a trend identical to ONGC.
1.10
1.00 Total 0.90

C O P C he vr on
0.80
0.70
ONGC oil pro0.60 duction had declined from 0.50 31.64 MMt in 2002 2003 2004 2005 2006 1995-96 to Data Source : PFC Energy 25.06 MMt in 2000-01. And also our contribution to national oil year 2007 remained below that of production reduced from 90% to 77%, ONGC, viz: Exxon Mobil-XOM (106%), thanks largely to the handing over in Chevron-CVX (21%), BP (113%), Total 1994-95 of our medium sized elds like (79%), ConocoPhillips-COP(117%). To Ravva, Panna-Mukta-Tapti and PY3 to dispel any sceptism that this may be JVs with ONGCs interest reduced to an aberration, 7 years data taken from the year 2001 to 2007 and smoothened 40% in these elds. by taking 3 years moving average, However, in the next 5 years, i.e. shows that while the International Oil 2001-02 to 2006-07, ONGC registered Companies had more or less a roller a growth of 5.4% at a CAGR of 1.1%. coaster ride, ONGC has grown conMore remarkably, ONGC groups oil sistently. production grew by 28% (including overseas production through ONGC ONGCs RRR with 1P reserves at 149% Videsh Ltd.) with a CAGR of 5.0% and 161% in FY 2008 and FY 2007 during the same period. In comparison respectively, is still more impressive. during the same period, some of the This is primarily on account of reserve international oil majors, like Chev- up-gradation to proved category from ron (-2%), Royal Dutch Shell (-2%) probable and possible category, which registered negative CAGR, while BP the company is constantly endeavour(5.1%), ExxonMobil (2%), PetroChina ing to achieve. (2%), Sinopec (2%), Total (1%) all ranged on or below ONGCs growth The reversal in the oil production of trajectory path. The oil production of ONGC has been made possible by the other Indian NOC, Oil India Ltd. the three corporate strategies which registered but a modest fall during the O N G C i m p l e m e n t e d f ro m 2 0 0 1 . Though it would take time for reaping same period. the benefits from the first strategy, ONGCs Reserve Replacement Ratio that of doubling the reserves by 2030, (RRR) (i.e. ratio of reserve being re- the second strategy of enhancing plenished to being extracted) at 132% recovery factor from 28% to 40% in FY 2008 is more impressive than and the third of acquiring overseas most of its illustrious global counter- equity have already started paying parts. Organic RRR of some of the rich dividends. major E&P companies for calendar
J U N E 2 008 7
Only the person who is going somewhere needs to watch his step
BP
XO Sh M el l
1.20
O N
What do we have in our part of the world?
Internal RRR
3 years Moving Average
G C

predicted that a large pool still lay undiscovered.
31.63
ONGC Oil Production (MMt) 25.06 25.95

While we are hovering around the practical limits of Recovery Factor using present technology, new-age technology may yet be on the horizon that could enhance the global Recovery Factor even further. This would add substantially to the currently estimated resource base. However we can not play Ostrich and assume that oil is going to last for ever. All our resources and technology are bounded by the finiteness of the reserves and our extraction capability. Therefore, we must try to manage oil judiciously. Demand-side management is vital for economies that shield consumers from market driven oil prices through subsidies. We would also need to discover and exploit the bridge fuel, i.e. gas, in all its manifestations viz.: natural gas, CBM, UCG, Gas hydrates etc. Fuel diversification, use of bio-fuel, use of waste products for energy, fuel efcient vehicles, energy saving building and devices, wide use of Mass Rapid Transport system etc. would not only conserve energy but in turn add extra units of energy for consumption for longer period. But, above all, for a sustainable future, we need to develop alternate source(s) of energy. A smoother transition to new energy era will depend on our ability to develop abundant, economical and sustainable alternative source(s) of energy. Earnest effort to discover alternate sources must start now itself, lest it becomes too late. Lord Oxburgh, the former CEO of Shell in September 2007 had reminded us about the danger, we are just about to enter hot water. And the danger is that we sit there blissfully like the frog in the pan of water gently heating on the stove until it wakes up to nd itself dead. While oil will certainly be with us for some time yet, it is opportune to commit resources to development of alternatives now lest Lord Oxburghs prediction comes true.
1995-96 1997-98 1999-00 2001-02 2003-04 2005-06 2007-08
The growth of OVL (ONGC Videsh Limited), the wholly owned subsidiary and the foreign arm of ONGC has been phenomenal. From a single equity till 2001, it has now truly turned global acquiring 38 projects spanning 18 countries. In fact it has become the second highest hydrocarbon producer in India after its parent, ONGC. The other initiative, the Improved Oil Recovery (IOR) / Enhanced Oil Recovery (EOR) scheme implemented in 2000-01 to enhance recovery, has been the major contributor in augmenting production and arresting production decline from mature elds. These IOR/ EOR schemes enabled arrest of overall production decline of around 21% (CAGR : -4.5%) that set in between 1995-96 and 2000-01 and if continued with the same rate, would have resulted in production of only 18.09 MMt in 2007-08. Instead we produced 25.95 MMt in 2007-08 (over 43% more). The recovery factor (RF) of the 15 major elds accounting for 80% of ONGC oil production and where these schemes were implemented, went up from 27.5% in 2000-01 to 30.5% in 2005-06. Though, it is difcult to draw comparison as reservoir characteristics and the drive mechanism differ across the reservoirs, however, the average range of global RF has been statistically estimated between 27% and 35% by several agencies/ literature.
8 J U N E 2008
In fact we have acquired a high degree of competence in arresting decline of mature fields through IOR/EOR schemes and the In-Situ-combustion (ISC) project, one of the high point of ONGCs successes in IOR/EOR schemes. ONGC expertise has specically been sought by PDVSA, the Venezuelan state oil company for conceptual mining of their 80 API heavy crude. IOR/EOR schemes have already been implemented by ONGC in Sudan and are currently being sought by Oman as well. ONGC has also developed an ingenious and cost effective Microbial EOR (MEOR) technology in collaboration with The Energy and Resources Institute (TERI). After successfully pilot testing in few sick wells, ONGC is now planning to roll out MEOR technique on eld scale. These technologies and the nds like those in Brazil have given us hope that ever evolving technology and the men behind them can squeeze out additional barrels of oil from existing reserves and even unearth a few more prospects that are as yet undiscovered. Notwithstanding the dire predictions of the Peak Oil school of thought, we can draw comfort from CERA that has consistently maintained that the remaining global oil resource base is three times (3.7 trillion barrels) as large as estimated by the Peak Oil proponents (1.2 trillion barrels). Even United States Geological Survey (USGS) in its last estimate in 2000
Live as it you were to die to-day. Learn as if you have to live forever M Gandhi
Polyolen Materials and Catalysts: An Introduction

G S Kapur, D K Tuli, R K Malhotra, Anand Kumar
Indian Oil Corporation Limited, Research and Development Centre, Sector-13, Faridabad, Haryana, India (kapurgs@iocl.co.in)
Dr G S Kapur, is
presently working as Senior Research ManagerPetrochemicals and Polymers at the IndianOil R&D. He did his M.Tech. and Ph.D. from Indian Institute of Technology, Delhi in the area of synthesis and characterization of polymers. After that, he carried out postdoctoral work
at Institute of Macromolecular Science, Prague and at the University of Leipzig, Germany. He is a recipient of prestigious international fellowships like Alexander Von-Humboldt, Germany and UNESCO. He has 4 patents and more than 60 research papers to his credit, published in International peer reviewed Journals and presented more than 35 papers in various National/international conferences.
Dr R K Malhotra, did his

Mechanical Engineering from IT, BHU and Ph.D. from IIT, Delhi. He has 30 years of experience in the application and testing of Fuels and lubricants, engine / vehicle testing, vehicular emissions and alternative fuels. He has published more than 50 research papers on fuels, alternate fuels, lubricants and emissions and has 4 international patents to his credit. He has been member of several national committees for formulation of fuel quality and emission norms in India and is closely associated with the Expert Committee on Auto Fuel Policy headed by Dr.R. A. Mashelkar. Dr. Malhotra is Secretary in the ISAS India Board and Chairman of ISAS India Northern Section. Presently he is Executive Director (R&D) of IndianOil Corporation Ltd.
Introduction
Petrochemicals and Polymers (Polyolefins)
Petrochemical industry has become the largest part of global chemical industry by virtue of its importance in the dayto-day modern living. Petrochemicals are chemicals, obtained by rening or processing petroleum and are used in many manufacturing elds. The industry is built in a small number of basic commodity chemicals, also known as basic building blocks such as ethylene, propylene, butadiene, benzene, toluene and xylene. Ethylene, propylene and
butadiene are commonly refereed to as olens, while benzene, toluene, xylene are known as aromatics. Together, they form the basis of all petrochemical production. Manufacturing involves a whole range of chemical reactions to convert base chemicals into either intermediate petrochemicals, such as vinyl chloride and styrene monomer (used in the production of polyvinyl chloride and polystyrene respectively), or directly into downstream end products, such as polyethylene and polypropylene. Polymers/plastics are the most important component of the petrochemical industry. Today, it is not possible to
Figure 1: A generic manufacturing process sequence for various petrochemical products is depicted below:
Figure 2: Low Density PE (LDPE) 0.915-0.030 g/cc
Figure 3: High Density PE (HDPE) 0.940-0.965 g/cc
Figure 4: Linear Low Density PE (LLDPE)
10 J U N E 2008
Our lives begin to end the day we become silent about things that matter

Figure 5
Polyolens are very attractive materials in terms of cost-performance. Modern day Polyolens cost much less to produce & process, than other plastics and materials they tend to replace. Besides, there has been a continuous improvement in strength & durability, which enables to use less of them in various applications. For example, weight of a super market bag was reduced from 23 grams in 1982 to merely 6 grams in 1990. Besides, these are highly versatile material and come in many varieties. Some are tough & rigid materials for car parts, outdoor furniture applications, whereas, others are used as soft & exible bers for babies' diapers. Some have high heat resistance (microwave food containers), while others melt easily (heat-sealable food packaging). Some are as clear as glass, whereas, others are completely opaque. The base monomers, ethylene and propylene are gases at room temperature and getting the monomers to link together is achieved through polymerization in the presence of a catalyst system. All the above varied properties coming from same set of raw materials is a result of advances in catalyst and reactor technology leading to tailor made polyolen materials. Without these powerful, sophisticated and remarkable catalysts systems, production of polyolens and hence the polyolen success story would simple be not possible. Basic structure of polyolens can be represented as follows, which also place these materials into different categories. Polyethylene, for example, can be placed in three broad categories like; low density polyethylene (LDPE), High-density polyethylene (HDPE), linear low density polyethylene (LLDPE) Propylene being slightly more complex, could attach itself to the growing polymer chain in one of the three different ways, resulting in different alignment of the backbone (grey) and pendant methyl groups (red), as shown in gure 5: Main PP products consist of the following types, dominated by homopolymers:
J U N E 2 008 11 11
imagine life without polymers, the wonder materials found in such a large variety of products that they have shaped the modern world. Polyolens, which is the generic term used to describe a family of polymers derived from a particular group of base materials known as olens, are the worlds fastest growing polymer family. Polyolens, such as
polyethylene (PE) and polypropylene (PP), are commodity plastics found in applications varying from house hold items such as grocery bags, containers, carpets, toys and appliances, to high-tech products such as engineering plastics, industrial pipes, automotive parts, medical appliances, and even prosthetic implants.
Table 1: Polyethylene/Polypropylene-Market Coverage
Polymer Types
Grade Film grade Pipe grade Large BM grade Small BM grade Raffia grade Injection Molding Films
Market Coverage Blown films with paper like quality, suitable for counter bags, carrier bags & wrapping films Pipes PE-80/100 class, drinking water & gas pipes, waste pipes & sewer pipes-their fittings etc Universal container grade, vol. appx 1-500 lit; heating oil storage tanks, transport containers disinfectant bottles up to 2 lit, tubes for cosmetics, containers from few ml upto 10 lit Stretched films & tapes for production of high strength knitted & woven sacks /bags/ nets etc For transport & stacking crates, particularly bottle crates Garment bags, grocery sacks, liners, blends, trash bags, cast like film diapers etc Large industrial parts used indoors, large industrial / agricultural tanks, shipping drums, toys etc. House wares, crates, master batches, pails, food containers etc Injection moulding (Battery cases, crates, furniture, house ware, luggage, sports/toys), Blow moulding, Sheets, Tape/ Raffia, FIBC, TQPP/BOPP films (food packaging, bottle labels etc), Extrusion coatings etc.
HDPE
LLDPE
Roto Moulding Injection Moulding
Homopolymer
PP
Thin walled Injection moulding, Low heat seal & high Random Copolymer transparency films, Blow moulding, Packaging parts, Automotive parts etc. Automotive parts (bumper, exterior trims, instrument Impact Copolymer- panels, interior trims), Appliances, House wares, Rigid packaging, Thermoforming etc.
An honest man never fears to eyes of strangers

Figure 6: Breakup-World Major Thermoplastics Demand Estimate -2007(183 Million MT)
made up of LDPE, LLDPE, HDPE, PP & PVC, was estimated at 148 Million MT during 2007. Demand for Global Thermoplastics is dominated by Polyolens (PP & PE). They represent over 60 % of all the commodity resins consumed on an annual basis. PE is the largest category including LDPE, LLDPE & HDPE. PP represents the single largest category at 24 %. Global Per capita consumption for PE is about 10 Kg while PP is about 6 Kg. In 2007, the global capacity of polyethylene was 78 Million tones and consumption crossed 68 Million tones. Whereas, global capacity of PP was 49 Million tones and demand was 44 million tones.
Figure 7: Per Capita consumption (Kg) of Plastics in 2005- 06
Indian Polymer Industry

The total consumption of polymers for plastics application in India in 2007 was of the order of 6.5-7.0 million tons. Polyolens consumption in 2007 was around 4 million tons and thus continues to account for more than 60% of total polymer consumption. With 4.2 Kgs per capita consumption of polymers annually the scope of growth is tremendous when compared to global average of 25 Kgs, with the developed nations having it as high as 100 Kgs on a per annum basis. Aggregated consumption of PE, PP and PVC in India crossed 5 Million tones in 2007-08, registering an impressive growth of 15%. Domestic Suppliers
Homopolymers (HPP) - 78% market

share Impact Co-polymers (ICP) 16% market share Random Co-polymers (RCP) 6% market share
Table 2: Polymer Consumption Estimate of India in 2007
Global Scenario
Today, Polymer industry is worth more than 180 Billion US$. Global polymer consumption (including Thermoplastics, Thermosetting and others) in 2007 has estimated to reach almost 235-240 Million tons from 225 Million tons in 2006. Out of which, 183 Million MT is the market for thermoplastic polymers. Demand for commodity Polymers;
Table 3
Polymer Polyolefins Total LDPE/EVA LLDPE HDPE PP PVC Others (PS/EPS, ABS, SAN, PET, Acrylates, PU and other thermosets) Total
12 J U N E 2008
(KT) 325 750 1100 1775
(KT) 3950
Company 1480 1440 6790 Reliance Industries Ltd Haldia Petrochemicals Ltd Gas Authority of India Ltd Total
There are three domestic suppliers of polyethylene and polypropylene, with total production capacity of around 3.9 Million tones of PE and PP. Reliance Industries Ltd. including Vadodara Manufacturing Plant (erstwhile IPCL) Haldia Petrochemi cals Ltd. Products (in KTA) Gas Authority of In LLDPE/ dia Ltd PP LDPE HDPE 205 1665 850 Most of the suppliers men300 560 tioned in table 3 are en310 hancing their capacities to 1965 1720 205 meet the growing demand To forget your troubles remember GOD

Table 4
Polyolefin Catalysts Family

Under Implementation Naphtha Cracker (ABB Lummus) 857 KTA of Ethylene / 600 KTA of propylene MEG - 320 KTA (Scientific Design) Swing LLDPE/ HDPE - 350 KTA (Nova-SCLAIRTECH)-Solution HDPE - 300 KTA (Basell-Hostalen) Slurry PP - 600 KTA (Basell-Spheripol) Bulk/Gas Planned Liquid Cracker (PDRP-Phase-II) HDPE /LLDPE, LDPE (PDRP-Phase-II) PP 680 KTA (PDRP-Phase-I) (Basell-Spheripol PX (PDRP-Phase-I) MEG (PDRP-Phase-II) Styrene 600 KTA (PDRP-Phase-I) (ABB Lummus) There are four major families of catalysts used for olen polymerization: Ziegler-Natta, Phillips (Chrome) Metallocene and Late-transition metal catalysts. The main characteristics, with some representative examples, of these catalyst systems are given in table 5. The rst two categories; Ziegler-Natta and Chrome are so called Conventional Polyolefin catalysts, whereas, Metallocene and Late-transition metal based catalysts are termed as Non-conventional or single site catalysts (SSCs). This is so because these catalysts produce polymers with much more uniform properties than the ones made with Phillips or heterogeneous Ziegler-Natta catalysts.
Today, more than 90% of the commercial catalysts are Conventional Catalysts (Ziegler-Natta based systems and Chrome), whereas, more than 90% of the research efforts are focused on the development of single site catalysts (SSCs).
Implemented MTBE 38 KTA (CD Tech) 1-Butene 15 KTA (IFP/Sulzer) LAB - 120 KTA (UOP) PX - 360 KTA (UOP) PTA - 553 KTA (Invista)
of polymers. With the new 900 KTA capacity expected to come on stream by Reliance, the companys total capacity will increase to 2.7 Million tones. This expansion will take Reliance from current 7th largest producer of PP to 3rd largest producer globally. In addition to the existing suppliers, Indian Oil Corporation is also setting up plants for production of HDPE, LLDPE and PP, with a total capacity of 1.25 Million tons per annum. A summary of the Petrochemicals and Polymers plants of IOCL, already implemented and/or under implementations, using
Figure 8
world class technologies are shown in table 4.
Catalysts for polyolens

At the heart of all polyolen manufacturing processes is the catalyst system used to initiate polymer chain growth.
Technology Drivers for Polyolefin Catalysts

There are various technology drivers for Polyolen catalysts, both at resin level and at end-use level, as depicted in gure 8.
Conventional PO Catalyst Catalysts for Polyethylene There are two main types of the conventional catalysts systems for polyethylene used widely in the industry: Ziegler* Chrome on silica (Philips Catalysts)
The term Ziegler and Ziegler-Natta catalysts will be used interchangeably in this article. Karl Ziegler successfully prepared linear polyethylene in 1953, whereas, Giulio Natta prepared polypropylene in 1954. Karl Ziegler and Giulio Natta shared the Noble prize in chemistry in 1963. However, the federal courts decided that Robert L. Banks and J. Paul Hogan of Phillips Petroleum Company were in fact the rst to discover these catalysts and, the composition-ofmatter patent on PP was awarded to Phillips in 1983
Phillips and Ziegler-Natta catalysts, discovered in the 1950s, were the rst catalysts systems to be used for olen Once your experience God. There is no need to look for anyone better
J U N E 2 008 13 13

Table 5
Co-Catalysts State Heterogeneous Homogeneous Heterogeneous Homogeneous Heterogeneous Typical Examples TiCl3, TiCl4/MgCl2 VCl4, VOCl3 CrO3/SiO2 Cp2ZrCl2 Cp2ZrCl2/MgCl2
Chrome on Silica (Philips Catalysts) Phillips catalysts are always heterogeneous. Phillips catalysts are based on Cr (IV) supported on Si02. Most of the existing chromium-based catalyst polymerization technology employs oxochromium systems; organochromes like silylchromate derived catalyst are also extensively used for commercial PE manufacturing. These catalysts systems are different from Ziegler-Natta catalysts in the following respects: No co-catalyst is required MWD is regulated by the characteristics of the support; The catalyst needs to be treated at high temperatures to be active; long induction times are very common and Hydrogen, the usual chain transfer agent for Ziegler-Natta, Metallocene, and late transition metal catalysts, is not effective for Phillips catalysts. As Phillips catalysts also have lower reactivity ratios toward a-olen incorporation, they are not used to produce LLDPE and polypropylene. However, they are excellent catalysts for HDPE and dominate the market for this resin. HDPEs made with Phillips catalysts have a very broad IMWD, often with PDls of 10 or higher. Salient Features of Chrome Catalysts are: Work-horse catalyst for Slurry Processes for producing HDPE (Cant be used for making LLDPE and polypropylene) Key resin attributes : Broad MWD, Long chain branching Process technology: Slurry and Gas-Phase End use demand drivers (AAGR ~ 5 %) - Blow molding applications (major growth Area) - Pipe and Conduits - Blown lms - Thermoforming
Both homogeneous a n d h e t e ro g e n e o u s Ziegler-Natta catalysts must be activated by Metallocene a cocatalyst(s). Most Ni, Pd, Co, Fe with commonly used CoLate-transition Homogeneous diimine, and other c a t a l y s t s a re ; a l k y l metal absed ligands aluminum compounds such as trimethyl aluminum (TMA) and triethyl polymerization. They created a revolution in the polyolen industry; they are, aluminium (TEAL), Diethyl aluminium to this day, the dominant catalysts for chloride, Di-ethyl aluminium ethoxide etc. polyolen production. Ziegler Ziegler-Natta catalysts can be homogeneous i.e. soluble in the reaction medium, or heterogeneous. The most common type of heterogeneous Ziegler-Natta catalyst today is TiCl4 supported on MgCl2, while one of the rst types was crystalline TiCI3. Homogeneous Ziegler-Natta catalysts are generally (but not exclusively) vanadium-based. Contrary to their heterogeneous counterparts, soluble vanadium-based Ziegler-Natta catalysts have only one site type and synthesize polyole ns with uniform properties. They make polymers with uniform microstructures: narrow MWD and CCD, and polydispersity indices (PDI) close to 2.0.
Figure 9
Type Ziegler / Ziegler-Natta Philips (Chrome)
Salient features of the Ziegler Catalysts can be described as follows: Products: LLDPE & HDPE Processes: Gas-phase and Solution End use demand drivers: LLDPE (AAGR ~ 7.8%) - Film (Major growth area) - Wire & cable - Injection moulding HDPE (AAGR ~ 5%) - Film - Injection moulding - Rotational moulding Bimodal HDPE (AAGR ~ 7.2% ) - Film - Pipe (Major growth area)
Global PE Catalysts Market Chrome-on-Silica Catalysts continue

to be the major catalyst for HDPE
Ziegler catalysts find extensive

use in LLDPE production, and in injection molded (and other grades requiring narrow MWD) HDPE
14 J U N E 2008
Happiness is when what you think, what you say, and what you do are all in harmony

In summary, the global PE Catalysts Market (2006) can be depicted as in gure 9: Catalysts for Polypropylene (PP) The history of the development of ZieglerNatta catalysts for polypropylene is truly fascinating. Since G. Nattas discovery in 1954 for preparing highly Isotactic-PP, with TiCl4, and later with TiCl3 along with AlR3/AlR2Cl as co-catalysts, the development of more stereo specic, efcient and sophisticated catalyst has been relentless, even today. The original catalysts had relatively lower activity and poor stereo-selectivity, requiring the removal of both atactic polypropylene and catalyst residues (deashing; from the isotactic polypropylene product). Whereas, Polypropylene made with latest generation catalysts, has an insignicant amount of catalyst residues because of their very high activity and practically no atactic content. For this reason, modern processes do not require postreactor purication. Some catalysts, such as the ones used in the Spheripol process of Basell (now LyondellBasell) are capable of producing large spherical polypropylene particles with controlled morphology, and may not even require pelletization. The phenomenal development in PP catalyst systems, resulting in different Generations of the catalyst systems, is mainly driven by; the discovery of MgCl2 as an ideal support for TiCI4, and the development of appropriate Lewis bases, called internal donors (Di) and external donors (De)electron donors. The donors are used to control stereoregularity by selectively poisoning or modify aspecic sites responsible for the formation of atactic polypropylene. Aromatic esters (Ethyl benzoate) can be used as internal donors, whereas, aromatic esters, alkoxysilanes and hindered amines can be used as external donors. Non-Conventional Catalysts Metallocene catalysts Metallocene catalysts are single-site catalysts. They produce polyole ns with unimodal and narrow Chemical Every life has its dark and cheerful hours Happiness comes from choosing which to remember J U N E 2 008 15 15
Figure 10
composition distribution (CCD) and narrow MWD with PDls close to 2.0. Under some conditions, usually when supported, they may make polymer with broader distributions. Metallocenes had a very large impact in the polyole n industry when they were discovered in the 1980s because, for the rst time, polyethylene and polypropylene could be produced under conventional industrial conditions with uniform and well controlled microstructures. Structurally, Metallocene catalysts are called sandwich compounds because they are composed of a transition metal atom sandwiched between two rings and the rings may be connected through different bridges to vary the angle between the two rings.
complexes are called constrained geometry catalysts (CGC) or half-sandwich catalysts. Their most important property is a very high reactivity ratio toward aolen incorporation, allowing the easy copolymerization of ethylene with long a-olens (1-hexene, 1-octene).
Metallocenes can be used directly in solution processes but need to be supported (SiO2) to be used in slurry and gas-phase processes. Structures of some of the commercial Metallocene catalyst are shown in gure 10.
Metallocene Catalysts are still used primarily in-house by the catalyst technology developers to produce differentiated products.
Another important type of Metallocene catalyst i.e. monocyclopentadienyl

Figure 11
The global Metallocene market demand, sector wise is shown in gure 11.

Global demand for m-polyolens in 2006 was of the order of 2,700 KT, and Metallocene based Polyolens are expected to grow at an AAGR ~ 12.5%
Catalyst Attributes While developing a catalyst system suitable for production of a particular grade of polyolen depends upon many factors. In summary, following catalyst attributes determine the suitability of a catalyst system, apart from cost considerations: Activity: unit polymer/unit catalyst obtained in the polymerisatio Fouling tendency: propensity for polymer formation on reactor walls Fines: propensity for catalyst or polymer nes to form, related to line choking problems Bulk density: bulk density of the polymer in the reactor and transfer lines Catalyst quality: lot-to-lot consistency and catalyst performance Product breadth: ability of catalyst to make wide range of density, MI (polymer with varied molecular weights) Melt Index (MI) oor: related to the ability of catalyst to make high MW product H2 response: Reflects ability of catalyst to respond to Hydrogen to control molecular weight of the polymers H2 response differential: ability of catalyst to make polymers with high and medium molecular eight Comonomer incorporation: ability of catalyst to incorporate comonomer (i-hexene, 1-octene) in different concentration Catalyst life: kinetic lifetime of the catalyst, especially in presence of Hydrogen Application/product focuses and process technology used, determine the desired balance/combination of catalyst attributes.
demand growth for PE at 17% and PP at 16% during the year 2007-08. Technology advances continue to reshape the competitive landscape globally despite Polyolens being introduced over 60 years ago. Catalyst technology has tremendous inuence over the type and quality of Polyolen resins being produced today. Conventional ZieglerNatta catalyst are robust, cheap and versatile systems that are still going strong, more than 55 years after their discovery, thanks to the development of advanced Donor chemistry. Even today, more than 90% of the commercial catalysts are Conventional Catalysts (Ziegler-Natta based systems and Chrome), whereas, more than 90% of the research efforts are focused on the development of single site catalysts (SSCs). Metallocene Catalysts are still used primarily in-house by the catalyst technology developers to produce differentiated products. General References/Source of Information: Chemical Market Resources (CMR) Inc., USA www.dow.com www.mitsuichem.com www.plastmart.com Reliance Industries Limited, Annual Report, 2007-08, and www.ril.com www.gailonline.com www.haldiapetrochemicals.com Proceedings, Workshop on Advances in Polyolefins 2007), CA, USA, Sept, 2007 The opinion/data expressed in the article are ascribed to authors only and not to the organization they belong to. Illustrations shown in this article are for representation purposes only only.
The drawback of Metallocene catalysts is that they are unable to polymerize polar molecules, such as acrylics or vinyl chloride. Introduction of a polar monomer into reaction system kill the catalyst activity to almost zero. Co-Catalysts for Metallocenes Bulky non-coordinating anions such as methylaluminoxane (MAO) can activate and stabilize metallocene catalysts, resulting in a highly active, stable catalyst. MAO is an oligomeric compound with degree of oligomerization varying approximately from 6 to 20. In general, a large excess of MAO is needed to achieve high activity, and ratios of 1000 aluminum atoms (or hundreds, in case of supported catalysts) to transition metal atoms are common for solution polymerization. Other co-catalysts used with Metallocene catalysts are tris(pentauorophenyl) borane (TPFB), which has the advantage of being required in nearly stoichiometric amounts. Late-transition Metal Catalysts The above limitation of Metallocene catalyst forced polymer scientist to search for new types of single site catalysts, using metals from all over the periodic table. This led to the discovery of late transition metal compounds (Group 6 and higher). These catalysts being much less sensitive to polar compounds can be used, to copolymerize olens with polar monomers such as acrylates and methylacrylates. By varying the polymerization temperature and monomer pressure, it is possible to make polymers with densities varying from those of HDPE to LLDPE, VLDPE, ULDPE etc. A typical late-transition metal catalyst is shown below:
Summary
Out of 183 million tonnes of thermoplastic consumption globally, polyethylene (HDPE, LDPE and LLDPE) constitute around 38%, followed by polypropylene (PP) at 24%. Combined global demand for PE and PP was estimated at 113 million tones during 2007, with China and India contributing signicantly to the global demand. Aggregated consumption of Polyolens in India was around 4 million tones, witnessing domestic The more you try to guess, the less you are at rest
16 J U N E 2008
Revival of Non-Flowing wells and production enhancement through implementation of Hydrofracturing Technology in Geleki eld of Assam Asset
Shri J G Chaturvedi
Executive Director, Assam Asset, ONGC, Nazira, Assam
eleki eld in Assam Asset of ONGC was discovered in 1968 and put on commercial production in 1974. The reservoir is sandstone and multi-layered, with composition of sand and silt. The Tipam Sands are the main oil bearing sands. Among the various Tipam Sands, TS-4B and TS-5A are very tight and hydraulic fracturing provides a viable alternative for production from these sands. Despite the intention for hydrofracturing since 1980s, success could be attained only in 2006 after meeting all the constraints like high breakdown pressures, surface/sub surface completion restrictions, procurement of sintered bauxite etc. All the constraints were overcome by meticulous planning, coordination of Assam Asset with other Well Stimulation Services (WSS) units of ONGC and re-completion of wells with higher grade tubings, 10,000 psi differential pressure permanent packer etc.
able to carry sintered bauxite, which is heavier than conventional proppant, into the fracture created deep inside the reservoir and to break in time, so as to allow better owback and also minimize damage to formation. The equipments required like 2250 HP frac pumpers, blender, sand dumper, tree-saver etc were mobilized from all over ONGC in addition to chemicals and sintered bauxite. The renowned WSS Base of ONGC at Ahmedabad alongwith IOGPT (Institute Of Oil and Gas Production Technology) of ONGC at Navi Mumbai with assistance of WSS Karaikal/Rajahmundry and operational support of WSS, Sivasagar carried out the hydro-fracturing. The pre-HF well preparation and post-HF well completion/activation was done as per requirements by meticulous planning and execution by Workover and Geleki Sub Surface Team of Assam Asset. The start of hydro-fracturing was with Phase-I in which 6 wells namely GLK# 23, #44, #76, #77, #233 & #272 were fractured in March 2006. Though teething problems were encountered dur-
ing this Phase, satisfactory fracturing was completed. In view of technology breakthrough achieved, three (3) more Phases i.e. Phase-II, Phase-III and Phase-IV were also taken up in the Geleki Field. 12 (twelve) more wells were covered under these three (3) Phases, thus completing a total of 18 (eighteen) wells till Jan08. An MDT was constituted in the Asset with representatives of different sections like surface, subsurface, workover, WSS, Civil, logistics, chemistry and WSS, Ahmedabad. The regular interaction and close coordination with detailed planning led to successful implementation of HF Jobs in the Geleki Field. It was also worked out with WSS, Ahmedabad that HF jobs are implemented in Phases and the wells are prepared accordingly. This will help in smooth coordination and better execution. Keeping in view of the above fact, the next three Phases were implemented during April07, Oct07 and Jan08 respectively. Phase wise implementa-
The frac job design was carried out on 3-D Frac Simulator FRACPRO and validated after analyzing the minifrac job in each well. The frac uid formulation was done after ensuring that it is
J G Chaturvedi,
Executive Director, Assam Asset, ONGC has an experience of more than 30 years in ONGC and has worked in various positions. These positions include Basin manager, Chief HR and now as Asset Manager. During his tenure in ONGC he has worked on number of projects leading to major gains of ONGC. He was involved in mapping of Geleki eld where fracturing has been carried out during last two (2) years.
Figure 1: Number of wells covered for HF in Geleki eld.
Nobody can become perfect by merely ceasing to act Bhagwad Gita
J U N E 2 008 17 17

Hydraulic fracturing is widely used to stimulate oil and gas production from a reservoir. This technique improves well productivity by removing near well bore damage and by increasing conductivity in low as well as high permeable formations. A hydraulic fracture is a superimposed structure that remains undisturbed outside the fracture, however, thus effective permeability of reservoir remains unchanged by this process. The increase of productivity results from an increase of the well bore radius, because after hydro fracturing there will be a large contact surface between the well and reservoir. Hydraulic fracturing uids are used to initiate and propagate fracture, as well as transport proppant into fracture to create a conductive path to enhance production. Proppant are sand grains or other granular substances that are injected into the formation to hold or prop open formation fractures that have been created by hydraulic fracturing. Proppants wedged within the fracture serve to increase the conductivity which promotes liberation of hydrocarbon from the reservoir rock and thereby enhanced production. The fracturing uids injected through the fractures and into the wellbore. Refer Fig-2. The Design of Frac Unit operation layout is referred in Fig-3.
tion approach helped in organizing the resources in an organized way and WSS, Ahmedabad team took up the challenge in batches. Following gure has given the details of the wells taken up for fracturing during different Phases: Refer Fig-1.
and Kopilis of Eocene age. The main oil bearing formations in Geleki eld are Tipam sandstone of Miocene age. Tipam sands in Geleki field are interpreted as fresh water sands deposited under complex braided river system. Braided river system is characterized by multiple channels owing with relatively high energy and changing their position rapidly leaving behind thick pile of coarser clastics. At the terminal part of depositional cycle, energy is depleted and thin layers of ner sediments such as silts and clays are deposited. So Tipams sands are heterogenous and tight in nature
Geleki eld
Geleki eld, the second largest oil eld of ONGC in Assam, located towards the southern fringe of Upper Assam valley, was discovered in 1968. It covers an area of about 25 sq km. Trial production from this eld began in August 1970 and regular production started from August 1974. Commercial oil production has been established in Tipam of Miocene age, Barails of Oligocene age
Hydraulic Fracturing Methodology Adopted

Selection of Candidate Wells
HF wells were selected based on sub surface position with respect to nearby water injectors, production history of well and block, oil saturation, logs, reservoir characteristics, CBL-VDL and completion of well. As the technology was tried for the rst time, the non-owing wells were identied for fracturing in the eld.
Hydraulic Fracturing
Pre-HF Work Over of Wells

These wells were required to be completed for Hydrofracturing and this required lowering of P-110 new tubing in the well. Following job was involved: The Old completion strings were pulled out and Well bore was cleared and if required, the desired interval
18 J U N E 2008
It is not the mountain ahead that wears you out. Its the grain of sand in your shoe

any excess proppant. The higher grade tubings pulled out through workover rig and activation carried out for checking / improving productivity. Wells were completed with GLV through Gas lift design.
Well Production
As most of the wells had water / gel of about 150-200 m3 it required knocking out of same through compressor application. Post activation of wells required consistent application of compressor and gas through intensive efforts. In some of the wells the rate of inux was found to be poor and it required hole clearing / acid / stimulation job carried out through CTU. This helped in activation of wells and thus leading to the production from wells.
Chemicals used in Hydrofracturing job execution

was opened up by zone transfer or cement squeeze. The Casing hermiticity was tested at around 250 ksc and injectivity improvement, if required, was carried out in the interval of hydro-fracturing. Solvent jobs were taken up in identied wells against the perforations for removing organic deposition. All the wells were completed with permanent packer of 10,000 psi differential pressure, new 2 7/8, 8.7 PPF tubing together with seal-bore assembly so that the old casings are not exposed to fracturing pressures. The wells were tested at 4000 psi with respect to casing and tubing integrity. carried out by hooking up all equipments, installation of tree saver, pressurized annulus and applied pressure through tubing to achieve formation break down. 2% KCI formulation was used for carrying out the mini-frac job. An analysis of mini-frac data was taken up with design improvement which was followed by main HF job. The estimated and designed quantity of sintered bauxite was placed as on line job monitoring was carried out. The wells were owed back with bean. A typical frac chart can be seen below in Fig- 4 . The fracture uid formulation was nalized on the basis of the laboratory studies carried out on the chemicals proposed for use, at the known formation depths and temperatures. The eld is having high fracture gradient and generally wells have high skin around well bore. The uid had to carry the sintered bauxite into the fracture and break for ow back. The frac uid formulation also plays a crucial role in the success of the frac job. The candidate wells in Geleki eld are deep (about 2800 meters), which could contribute to high pressure during fracturing. Another typical parameter in these wells is low formation temperature (70-75C), which makes breaking of fracturing uid during post-frac owback very crucial. Following chemicals/ liquid were used for the fracturing job: 1. Treated Water 2. Gelling agent (GD-II/III Guar polymer)
Post-HF Work Over of Wells Hydro-fracturing job design & Execution The job execution strategy was
prepared after detailed deliberations and a tentative job design was prepared for the wells with the aid of latest 3-D Frac Simulator FRACPRO based on the known parameters. Further, the hole probing / acid / xylene job was carried out by CTU prior to HF so as to ensure clear formation and no obstruction is available. The mini frac Job was Most of the wells require installation of Articial Lift and the wells required to be worked over for the same. Prior to installation of A/Lift the well bore was cleaned upto bottom by CTU to lift out
Good judgment comes from experience. Experience comes from bad judgment
J U N E 2 008 19 19

Fig-5: Photograph of Gel quality prepared for HF Job.
4. 5. 6. 7.
Frac Tanks WSS, Sivasagar. Treating iron WSS, Ahmedabad. Tree Saver - WSS, Ahmedabad. Data acquisition system - WSS, Ahmedabad.
Improvement in Injectivity for HF job

Based on the experience of Phase-I it emerged that wells require pre-HF acid treatment for enhancing the injectivity and after detailed analysis the acid receipe was formulated. The composition included solvent, pad/ Spacer, acid preush, mud acid and pad/ Spacer. Following chemicals were used for the solvent & acid job for injectivity enhancement. Xylene with diesel & naphthalene. Pad/spacer: Water and ammonium chloride. Acid preush: Water with HCL, Acetic Acid, EDTA & surfactant. Mud Acid: Water with HCL, Acetic Acid, EDTA, surfactant, ACI and ABF. Pad/spacer: Water with ammonium chloride. The above formulation greatly helped in improving the injectivity and following results were obtained: These jobs helped in better HF job execution and smooth proppant placement in the wells. The combination of proppants and Chemicals is shown in Fig- 5. Solvent:
3. 4. 5. 6. 7. 8. 9.
Sintered Bauxite (20/40 mesh)Proppant Potassium Chloride (KCl)- To prevent formation clay swelling Soda Ash- for raising pH Borax / Boric Acid- As crosslinker Non- Emulsier- To prevent emulsion formation in the reservoir Breaker (APS)- For breaking the gel after proppant placement Formaldehyde- As Bactericide
Equipments used in Hydrofracturing job execution

The Hydrofracturing job required mobilization of set up from karaikal/ Rajahmundry and Ahmedabad and mobilization of same safely to Assam Asset. Following units were brought to Assam Asset. 1. Frac Pumpers (2250 HP) 2 nos from Karaikal/Rajahmundry & 1 (one) from Ahmedabad. (refer Fig.5.4) 2. Sand dumpers 2 nos. from Karaikal/ Rajahmundry.(refer Fig.5.2) 3. Blender - Karaikal/ Rajahmundry. (refer Fig.5.3)
Fig. 5.2 Sand Dumper during the execution of HF Job
The Gel formulated was tested at the well site with chemical operation and continuous monitoring was carried out at the site. Refer Fig-5.
Fig. 5.1 ED visit during HF Job.
Analysis of Hydrofracturing Pressure

Till January2008 a total of 18 wells have been fractured in Geleki eld with sandwise breakup as following:
Fig.-5.3 Blender during the execution of HF Job Fig. 5.4 Pumper during the execution of HF Job
TS-3A TS-4B Sl. No. 1 2 3
- 2 Wells (G#128 & G# 317 - 7 wells (G#77, G#272, Well No G#130 G#20 G#178 Pre Job Injectivity 80 lpm at 3000 psi 150 lpm at 2000 psi 180 lpm at 1000psi Post Job Injectivity 130 lpm at 3000 psi 400 lpm at 2000 psi 300 lpm at 1000 psi.
20 J U N E 2008
If you have your sight, you are blessed. If you have insight, you are a thousand times blessed

Fig-6. (Fracturing Pressure Graph)
mum job size through design and data analysis with continuous improvement. (refer Fig-7)
Production from HF Wells

Out of 18 (eighteen) numbers of wells fractured. 16 (sixteen) wells were non owing prior to Hydrofracturing and only one (1) well was owing i.e. G#128. One water injection well i.e. G#317 was also fractured resulting in enhancement of water injection through this well. Most of the non-owing wells have now been brought in the owing category as shown below thus enhancing the production from these wells which were closed for more than a decade. A cumulative production of more than 27000 Tons has been taken from these wells thus generating a revenue of about 55 Crores of rupees till Feb2008 (refer Fig-8) The success of fracturing has opened up a new dimension of production in Geleki eld and has become a favoured option for better recovery from the tight sands of Geleki. It has been an actual eld based learning experience for Assam Asset with different section and working as a team approach. Current status of Hydro-fractured Geleki wells:
TS-5A
G#76, G#178, G#20, G#60 & G#55) - 9 wells (G#233, G#23, G#22, G#70, G#104, G#127, G#63 & G#130 Total 18 wells
The wide variation of pressure occurred due to location of wells in different blocks and different geological characteristics. The analysis of Frac Pressures is shown in Fig.6.
Job size in different sands

An analysis of pressures shows that in TS-3A sand break down pressures vary from 6300 to 8000 psi. TS-4B sand has witnessed a maximum breakdown pressure of 9450 psi & minimum being 7300 psi. Further, deeper sand i.e. TS-5A saw the minimum pressure as 5600 psi while maximum breakdown pressure was 9500 psi. The maximum job size in the well was 40 tons and four (4) wells were fractured with 40 tons of sintered bauxite. These wells were G#128, G#60 G#70 & G#23. The minimum size of the job was 10 tons in wells no G#272 which was terminated due to operational problems. The remaining 13 wells witnessed a job size of 20 to 30 tons as shown below. The Phase wise implementation approach helped in planning for the opti-
Figure 7: HF Jobs size in different phases.
Costing of Hydrofracturing
A detailed cost analysis of Hydrofracturing jobs has been carried out by the Asset team which includes pre & post HF workover, HF job execution alongwith chemical cost, site preparation and activation cost. It has been calculated that a total expenditures of Rs. 28 crores has been made inclusive of all the above cost components and average cost works out to be following:
Field implementation and results

The hydro-fracturing jobs in Geleki
eld were planned and executed for six non owing wells (G#23, G#76, G#44, G#77, G#233 & G#272) of TS4B and TS-5A sands in Phase-I. The jobs were executed in March 2006. With the success of Phase I, further HF was done in four wells It is not the weathercock that changes; it is the wind
J U N E 2 008 21 21

Current status of Hydro-fractured Geleki wells:
Sl. No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Phase
No of Wells
Well No G # 77 G # 272 G # 233 G # 76 G # 23 G # 44 G # 22 G # 70 G # 178 G # 128 G # 130 G # 20 G # 104 G # 63 G # 60 G # 55 G # 127 G # 317
Sand TS-4B TS-4B TS-5A1 TS-4B TS-5A1 TS-5A1 TS-5A1 TS-5A TS-4B TS-3A TS-4B+5A TS-4B TS-5A TS-5A TS-4B TS-4B TS-5A TS-3A
Phase-I ( March'06 April'06)
Phase-II ( April'07May'07) Phase - III
Phase - IV ( Jan'08)
Date of Non-flowing Mar'98 Mar'02 Mar'02 Apr'04 Mar'97 Mar'02 Dec'06 Jun'87 Feb'99 Flowing before HF Oct'05 Mar'98 No Yield Jul'98 Jan'04 Dec'94 Water injection
Pre HF Well Status NF NF NF NF NF NF NF NF NF F NF NF NF NF NF NF NF WI
Oil Rate (M3/ day) 10 Poor influx 13 12 6 1 Water Only Water Only 4 7 4 6
Gas Rate (M3/ day) 450 Nil 2850 19950 1430 Negligible Nil Nil 3570 1320 20000 Negligible
Cost summary of HF Jobs (in Lakhs): Phase I to Phase - IV
Cost component Hydraulic Fracturing (A) Civil work (B) Workover (C ) Well Completion (D) Activation (E) Manpower (F) Total cost
Phase-I 187.00 9.30 235.00 242.52 36.40 20.00 730.22
Phase-II 112.00 10.00 416.00 180.00 40.00 20.00 778.00
Phase-III 56.02 9.37 165.92 90.00 12.00 20.00 353.31
Phase-IV 256.82 19.40 303.28 270.00 60.00 20.00 929.50
Total 611.84 48.07 1120.20 782.52 148.40 80.00 2791.03
3.
4.
(G#22, G#70, G#128 and G#178) under phase-II, in April 2007. Out of these four wells two wells (G#128 & G#178) are presently owing and two other wells (G#22 & G#70) have produced water. After technological break through of hydro-fracturing, this campaign was taken up in a structured manner and third Phase of HF was executed in October 2007 in two non owing wells (G#20 & G#130). The fourth Phase was completed in January 2008 in six (6) wells. Out of six (6) wells one (1) water injector has also been hydro-fractured for the rst time in Assam.
A new lease of life has been given

to the non owing wells as a result of a meticulous planning and careful execution of mini-fracturing followed by main-fracturing job.
5.
Conclusions
1. Six (6) nos. of Hydraulic fracturing jobs in Phase-1, on R&D basis, have technically proved successful which led to implementation of a total of four (4) Phases of Hydrofracturing in Geleki covering 18 (eighteen) wells. Dedicated team effort, focused attention and coordination at the highest level enabled Assam
6.
2.
Asset with WSS Team to achieve this technological breakthrough despite several challenges. The success of hydro-fracturing in Geleki eld has again proven the abilities of the in-house WSS, Ahmedabad, ONGC alongwith other Sections. The reliability of Surface and Sub Surface well completion hardware used (especially the X-mass tree saver of 15000 psi rating) in high pressure situations has been validated. Post-job production and economic analysis are in favour of hydraulic fracturing jobs. This technique can be applied on a routine basis to enhance production in Assam Asset. Total oil production from these non owing wells till Feb08 has generated a revenue of more than Rs. 50 crores with a cumulative expenditure of about Rs. 28 crores including all the cost components.
22 J U N E 2008
Sustainable Development Key issues and steps for oil industries

A B Chakraborty, Shantanu Dasgupta
A. B. Chakraborty,
Group General Manager, is currently heading the Carbon Management Group in ONGC. He is responsible for the development of ONGCs CDM Projects, Climate Change & Sustainable development activities. Being the project proponent of ONGC CDM Projects, four projects have been registered by UNFCCC so far & many more projects are under development. Since joining ONGC in June 1975, he has worked in different areas; Quality control, Workshops, Maintenance, Operations, Drilling, HSE, CDM, Climate Change & Sustainable development. He has considerable experience in the area of Carbon Management, HSE, and development of procedures, guidelines & regulations besides addressing
HSE organizational issues. He has also initiated M2M program with US EPA in ONGC. He has presented 7 papers in the SPEs HSE international conferences & few on Carbon Management, as well. His core specialization includes Environment, Safety, Occupational health, CDM & Sustainable development. He has done M.Tech (Production Engg) from IIT Delhi, MAM (Jamnalal Bajaj) Mumbai, MSc (Environmental Science) from Kakatiya University Warangal besides, PG Diplomas in Environmental Management & Environmental Economics from Hyderabad University and Safety Management from British Safety Council, London. He is Fellow of the institute of Engineers India, Chartered Engineer, Member SPE & life member of the National institute of Personal Mgt.
Economic growth so far is closely associated with increased usage of energy. In its World Energy Outlook 2006 report, the International Energy Agency pointed out that the economies and population of developing countries were growing faster than those of the wealthier nations, shifting the centre of gravity of global energy demand. It estimated that more than 70 % of the increase in global primary energy demand between now and 2030 would come from the developing countries2. India needs to increase its primary energy supply 3 to 4 fold over 2003-04 level to sustain a continuous 8-10% growth for next 25 years, which is absolutely crucial to eradicate poverty. Energy, till date, is mostly sourced by fossil fuel. As per an estimate, the fossil fuel dependence scenario will remain unchanged at least for another 300 years unless a viable alternative source is established. Fossil fuel burning generates CO2, the most signicant Green House Gas accounting for more than 60% of the total atmospheric concentration of GHG. Increased usage of energy will thus increase the per capita GHG emission. Increased eco-
his article is a treatise of the sustainable development and the ways to develop a sustainable development business model in an oil industry. With global warming threatening the basic survival of the living beings, the greatest challenge today is to synergise the economic development with environmental sustainability and social development. This calls for the concept of sustainable development.
sustainable development in the oil industry is synonymous to Carbon management. Carbon management has two aspects, Accounting and Management. This article has dealt various steps involved in accounting and management with reference to an oil industry. The article concludes that sustainable development in an oil industry can be developed as a viable business model.
Shantanu Dasgupta, Superintending Chemist, ONGC is working with the Carbon Management Group. Shantanu has 19 years professional experience in ONGC in different areas: drilling, production and processing, R&D on processing, training institute, and carbon management. A gold medalist from Ranchi University and a KS Krishnan DAE research scholar, Shantanu has also done his PG Diploma on Ecology& Environment and Masters in Business Administration. He has published several papers in national and international journals.
Introduced in the UN charter way back in 1987, sustainable development is a concept of an all encompassing development for the present without jeopardizing the future. To actually project sustainable development into actionable programme, measurement of the resource utilization is the most important step. In an energy intensive industry as oil industry, energy is the main resource. Thus sustainable development in fact connotes measurement of energy usage, which in turn implies measurement of CO2( GHG) emission. Thus
Scenario-An introduction
World has witnessed rapid economic growth after industrial revolution in 1740. Post World War II, the economic growth has been unprecedented. As per the Earth Policy Institutes report on Eco Economic Indicators 2005, World output of goods and services increased from $7 trillion in 1950 to $56 trillion in 2004, while annual income per person grew from $2,835 to $8,753 during this time1. It is estimated that the growth will continue which seems inevitable considering the increasing population.
Education is not only for earning a living but also for learning to live
J U N E 2 008 23 23

nomic growth has therefore affected the ecological balance adversely and has caused unprecedented climate change and global warming, as per IPCC reports3. Herein lays the importance of Sustainable Development, a holistic development of economy, society and environment. The article is a treatise on the concept of sustainable development with special reference to oil industries. word Carbon of CO2 which is one of the most common Green House Gases. Sustainable development in oil industry is therefore closely linked to the Carbon management. and competitive pressure, all combine to present an even more difcult and challenging situation. Managing the risk involves extensive exploration and discovery of organizational potential, business processes and options for greenhouse gas abatement. Timing of investment, technological investment and place of investment are of distinct competitive advantage. What is Companys goal towards GHG emissions is important i.e. Whether the Companys long term objective is to become Carbon Positive or Carbon neutral or remain as it is. Carbon Strategy for the Carbon Management is to address tomorrows actions today. Assessment of Risks and Opportunity: Climate change poses regulatory, physical and other risks to business all over the world. A smart corporate strategy on GHG management can help to convert these risks into commercial opportunities and/or better corporate risk management.There is a need to enhance understanding of the risks and opportunities that climate change presents and to develop an effective risk management strategy. For example, a Company is looking at business expansion in terms of Greeneld projects or Brown eld acquisitions. The expansions may be in the existing facilities within the country or new / acquired projects in other countries which include developed (featuring in annex 1 of Kyoto Protocol) as well as developing countries6. Accordingly, the likely commitments in terms of GHG reductions have to be factored in while arriving at the business investment decisions. Foot printing, to develop a corporate target. This foot printing will conform to the corporate strategy on Sustainable development. It may like to improve in curtailing wastage in ofce usages but may think otherwise about the business trips. In any case, the company will have to decide how it wants to improve upon its energy consumption. This will help develop the carbon foot printing. It is absolutely essential, since a future action plan will emerge from this foot printing. It requires a proper cost benet analysis of every operation. This foot printing should form the basis of the future sustainability reporting. This will form the annual target, as well.
Carbon Management in oil industry

Carbon Management pertains to Accounting & Management of Green House Gases--commonly called GHG Accounting & Management6. Thus the entire process has two facets:
Concept of Sustainable Development

Sustainable development is a pattern of resource use that aims to meet human needs while preserving the environment so that these needs can be met not only in the present, but in the indenite future. The term was used by the Brundtland Commission in 1987 which coined what has become the most often-quoted denition of sustainable development as development that "meets the needs of the present without compromising the ability of future generations to meet their own needs4 However, Sustainable Development does not focus on environment alone. The UN 2005 World Summit Outcome document refers to the "interdependent and mutually reinforcing pillars" of sustainable development as economic development, social development, and environmental protection 5.
Accounting and Management

The Accounting is done based on specic standards, using Carbon foot print assessment tools or GHG inventories. Various processes involved in GHG accounting are as follows: Carbon Mapping, where the total fuel consumption related to all the operations of the organisation will be mapped in terms of emission. The operations typically for oil industry include operations survey, drilling, workover, production, transportation, processing R&D( up and midstream),rening, processing, distribution and marketing( for downstream), as well as usage of energy in ofce and travels etc. This carbon mapping is the basic inventory of any oil company and will be reected as Carbon Disclosure in the Balance Sheet. Benchmarking, where the inventory will be benchmarked against the industry best practices. There may be areas where a company is the best and thus form the industry benchmark, there may be areas, where a company will need to improve its activities in terms of energy consumption.
Sustainable developmentIn context of Oil industry

To project the concept of sustainable development into actual actionable parameters in an industry, exact measurement of the resource usage and its management are of paramount importance. Resource includes both physical and intellectual resources. The Oil industry is one of the most energy intensive industries where all its operation in up, mid and downstream use energy to a substantial degree. Thus energy becomes the most important physical resource. The rst step of sustainable development therefore amounts to measuring of energy usage or Carbon footprinting. Carbon footprinting derives its term from the
24 J U N E 2008
Various steps involved in management are as follows

Developing Corporate Strategy: It is about developing and implementing a management tool to assess and address the risks and opportunities that climate change poses to the business. Climate change is one of the more difcult and challenging issues for business today. The scientic complexity, Government policy, international debate
Meditation is the way to a healthy heart

Implementation of the target set in the footprinting. Action plan has to be developed in this regard. It is extremely critical because a proper cost benet analysis is a must to consider the best option. A company may mull over setting up alternative energy sources to offset the energy consumption. Another may mull over developing green buildings or invest in social forestry, the choices are many and hence caution is required. The nal aim is to limit the GHG emission to a corporate decided strategy. Once this has been achieved, the programme has to be communicated to everyone. Sustainability reporting indicating the initial target and the achievement. The target must be in terms of limiting GHG emission which includes offsets if considered. This will be a publicly available document. Exploiting opportunities: Climate change and its mitigation has opened up a number of opportunities6 to an oil company. The proper assessment , coupled with carbon footprinting and implementation will open up many potential opportunities to explore. This can be divided into two aspects: Quantifying benets: For example, if an upstream oil company in a developing nation decides to adopt a zero leakage norm and implements the strict monitoring and maintenance practice by detecting and arresting any leakage, the company will be able to improve its operational efciency and its natural gas production. At the same time, the company may derive benets by developing a potential CDM project. Similarly, any energy efciency initiative after benchmarking the operations will ensure less usage of energy and help develop potential CDM. Such a project developed by an oil industry in an Annex 1 nations( Kyoto Protocol) will help them achieve the cap. Monetising: In the above example, monetising involves trading of the emission reductions achieved by implementing the emission reduction project and also the additional natural gas saved. In some cases, the monetisation may be notional.Similar project developed in an Annex 1 country will reduce its dependence on the external source and hence saves money. However, all the money received/ receivable from the project is reportable as additional revenue. ment with environmental and social development. Sustainable development will be successful only when the we all are committed to it and proper communication channels are established so that people down below are adequately informed about the imperatives and their reservations, if any, are properly addressed. A word of caution, though. No business model is a talisman or a change agent unless it is properly practiced. Sustainable Development is no exception. A model is as good as the sincerity and commitment of the organization. In short, Think Ahead, Think Fast and Act Forward, the basic tenets of any leader should be the mantra.
References
1. Eco Economy indicators 2005Earth Policy institute resources on economic growth World energy outlook 2006- International Energy Agency 4th Assessment Report IPCC United Nations. 1987."Report of the World Commission on Environment and Development 2005 World Summit Outcome document Carbon Management The Emerging Paradigm for the oil industry,Ashok B. Chakraborty, SPE(110239)
2. 3. 4.
Conclusions
It is evident from the above that Sustainable Development in oil industry meets all criteria of good business practices and can be developed as a viable and sustainable business model which synergizes economic develop5. 6.
IOC, Oil India acquire stake in Reliances East Timor block

New Delhi June 7
India Oil Corporation Ltd (IOC), along with Oil India Ltd (OIL), has reached an understanding with Reliance Industries Ltd (RIL) to acquire stake in the latters offshore oil block in East Timor. Sources told Business Line that an agreement was inked between the State-owned companies and RIL this week. Both IOC and OIL will acquire an equity stake of 12.5 per cent each in the project. RIL will hold a majority stake in the block and will be the operator of the area spread over 2,384 sq km. Sources said that IOC and OIL have made a nancial commitment of $27 million. The entries are now going to approach the East Timor Government for approval. Though the consortium of IOC and OIL has been working together in acquiring hydrocarbon assets abroad, this is the rst time that the two have joined hands with RIL. Under phase-I, in three years of the exploration activity the companies are going to undertake three-dimensional seismic surveys and drill one exploratory well. Both IOC and OIL had taken their respective Boards approval to acquire equity in RILs asset as farm-in partners in 2007-08 scal. The approval of the respective Boards was taken after the technical teams of IOC and OIL expressed satisfaction on the data made available by RIL. In May 2006, RIL had won a block in East Timor area K offshore blocks tendered. RIL has now signed an agreement to explore for oil and gas in East Timor and will explore the offshore area in contract area K that has proven reserves in the Australian North West Shelf and is adjacent to the Timor Sea.
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Stop analyzing life. Just live it. Analysis is what makes it complicated
Surface Exploration Techniques for Hydrocarbons: An Overview

R.R. Singh
Geochemistry Group, KDM Institute of Petroleum Exploration, Kaulagarh Road, Dehradun-248195, Uttrakhand, India ram_raj_singh@rediffmail.com
ndia is a growing economy facing the critical challenge of meeting a rapidly increasing demand for energy. Import of petroleum products constitute the single largest item in the country's total annual import bill. More than 40 per cent of the export earnings are funneled back into importing petroleum products for domestic consumption. There is a tremendous growth in exploration and production (E&P) activities in hydrocarbon sector in India. The advancement in technology is crucial in every sphere of energy sector including petroleum sector. The surface geochemical exploration technology is a reconnaissance exploration tool applied to soils or seabed sediments in order to detect and determine the nature of any hydrocarbons that may have seeped to the surface from underlying reservoirs within the lithied strata of sedimentary basins. Surface geochemical exploration for petroleum is the search for chemically identiable surface or near-surface occurrences of hydrocarbons, or hydrocarbon-induced changes, as a clue for sub-surface oil and gas accumulations.
tions favorable for the development of specialized bacterial populations that feed on the hydrocarbons. This leads to signicant increases in the microbial cell numbers and cell activity of these specialized microbes. The state of art development in the eld of surface geochemical exploration involves the use of a sorbent based passive sampler for detecting and quantifying organic compounds in the C2 (ethane) to C20 (phytane) range. Today geochemical surface prospecting is a mature technology which on integration with geophysical and geological inputs provides additional exploratory leads for prioritization of prospects and reducing exploration risk. For reconnaissance surveys, hydrocarbon seeps and microseeps provide direct evidences for presence of an active petroleum system and identify and prioritize the prospects. The geochemical surface exploration have been carried out in Western and Eastern offshore basins, Cambay, Krishna-Godavary, Cauvery and most of the frontier onshore basins of India.
increasing demand for energy. With over a billion people, a fth of the world population, India ranks sixth in the world in terms of energy demand. Its economy is projected to grow 7%-8% over the next two decades, and in its wake will be a substantial increase in demand for oil to fuel land, sea, and air transportation. While India has signicant reserves of coal, it is relatively poor in oil and gas resources. Its oil reserves amount to 5.9 billion barrels, (0.5% of global reserves) with total proven, probable, and possible reserves of close to 11 billion barrels. The majority of India's oil reserves are located in elds offshore Bombay and onshore in Assam and Cambay. Due to stagnating domestic crude production, India imports approximately 70% of its oil, much of it from the Middle East. Its dependence is growing rapidly. The World Energy Outlook, published by the International Energy Agency (IEA), projects that India's dependence on oil imports will grow to 91.6% by the year 2020. The past few months have seen global oil prices entering the "super-spike" phase. International oil prices have vaulted to over $135 a barrel. Energy experts predict that prices could surge all the way above $200 as consumption peaks in near future. With the prospect of a further steep hike in fuel prices looming large, the vulnerability of the economy to the vagaries of the global oil market comes into focus yet again. Studies have indicated that a sustained 5 per cent rise in the oil price over a year would slash India's GDP growth rate by 0.25 per cent and raise the ination rate by 0.6 per cent. Indias energy vulnerability can be gauged from the fact that the country imports about 70 per cent of the total oil consumed. Oil imports constitute the single largest item in the country's total annual import bill. About 40 per cent of the export earnings are
Surface indications of oil and gas seepage have been noted for thousands of years and such seeps have led to the discovery of many important petroleum producing areas in the past. Over the past sixty years, numerous geochemical methods have been developed and the application of these methods to oil and gas exploration has resulted in varied success. Surface geochemical survey is applied as a reconnaissance tool provide direct evidences hydrocarbon generation and thus they document the presence of a sub-surface active petroleum system. Geomicrobial survey is the technique based on specic utilization of seeped hydrocarbons by specialized groups of bacteria. The basis for microbial detection of hydrocarbons is the principle that light hydrocarbons from oil and gas reservoirs escape to the earths surface and creates condi26 J U N E 2008
Introduction
Energy is the most vital input for economic and social development of any society. It is also a fair index for benchmarking nations progress. The economy is highly dependent upon the availability of energy. The sustainable, environmentally-friendly and socially responsible management of energy resources forms an integral component of any economic activity. "Energy Security" as a transition to total "Energy Independence" is an important area. As we know, India has 17% of the world's population, and we have just 0.8% of the world's known oil and natural gas resources. India is a growing economy facing the critical challenge of meeting a rapidly
Success is a measure decided by others. Satisfaction is a measure decided by you

funneled back into importing oil for domestic consumption. These are challenging times. Energy consumption is growing at a rapid pace worldwide and each nation is faced with the widening gap in supply and demand. Fossil fuels like oil, natural gas and coal will remain the predominant means of energy, meeting the worlds growing energy needs in near future. To meet the increasing demand of energy and feed stock for petrochemicals, new options are seriously considered all over the world. In India also the non conventional sources of energy are receiving special attention. To maintain our economic growth rate of 8-10%, India needs all the energy it can get. Our focus is to develop our economy through efcient utilization of available energy resources while preserving the ecology and be instrumental in giving social and economic equity to the one billion population of India. This grim situation requires immediate acquisition and application of all available state-of-art techniques and technologies in the eld of petroleum exploration. Surface Geochemical Exploration (SGE) is one of the techniques which establish the presence and distribution of hydrocarbons in a basin. AAPG Memoir 66 contained papers on hydrocarbon migration and its near surface expression. It included an introduction to the main mechanisms, models, interpretation methods and analytical techniques as well as selected case histories (Piggot and Abrams 1996, Abrams, M.A, 1996a; Abrams, M.A, 1996b; Machel, H.G., 1996; Matthews, M.D., 1996; Potter, R.W et al., 1996; Thrasher, J.A. et al., 1996). It was a landmark publication which presented a clear overview of the scientic background of geochemical prospecting and its application which was viewed skeptically by many organic geochemists and petroleum geologists. or play is oil-prone or gas-prone. If the objective is to evaluate individual exploration leads and prospects, the results of geochemical surveys can lead to better risk assessment by identifying those associated with strong hydrocarbon anomalies, thereby high-grading prospects on the basis of their probable hydrocarbon charge (Price, 1986). In petroleum exploration, surface geochemistry is applied to soils or seabed sediments in order to detect and determine the nature of any hydrocarbons that may have leaked to the surface from sources at depth within the lithied strata of sedimentary basins. Naturally, many of the rst discoveries of oil and gas reservoirs were made following attention to obvious occurrences of seeps (macro-seeps) onshore. These crude visible methods of seep detection were followed by developments of analytical instruments to detect invisible amounts of seeping hydrocarbons (micro-seeps) in both onshore and offshore sediments (Brooks, et al., 1986; Jones and Drozd, 1983, Klusman, 1993; Link, 1952). The potential benets of a successful geochemical exploration program include the following: Directly detect hydrocarbons and/ or hydrocarbon-induced changes in soils, near surface sediments, and/ or on the sea oor. Document the presence of a working petroleum system in the area of interest. Permit high-grading of basins, plays, or prospects prior to acquiring leases or before conducting detailed seismic surveys. Permit post seismic high-grading of leads and prospects; generate geochemical leads for further geological or geophysical evaluation. Use geochemical data to inll between seismic lines and constrain mapping of AVO/amplitude anomalies between lines. Evaluate areas where seismic surveys are impractical or are ineffective due to geological or environmental factors. Have little or no negative environmental impact (most surface geochemical methods).
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Surface geochemical principles All petroleum basins exhibit some

type of near-surface hydrocarbon leakage Petroleum accumulations are dynamic and their seals are imperfect Hydrocarbon seepage can be active or passive and is visible (microseepage) or only detectable analytically (microseepage) Hydrocarbons move vertically through thousands of meters of strata without observable faults or fractures in a relatively short time (weeks to years) Migration is mainly vertical but can also occur over great distances laterally Relationships between surface anomalies and subsurface accumulations range from simple to very complex.
Surface geochemical exploration for hydrocarbons

Surface indications of oil and gas seepage have been noted for thousands of years, and such seeps have led to the discovery of many important petroleum producing areas. Over the past sixty years, numerous geochemical and non-seismic geophysical surface exploration methods have been developed. The application of these geochemical prospecting methods to oil and gas exploration has resulted in varied success and occasional controversy. Surface geochemical methods have been used since the 1930s, (Laubmeyer, 1933) but the past decade has seen a renewed interest in geochemical exploration. Many of these developments are summarized in American Association of Petroleum Geology Memoir No. 66 (AAPG Memoir-66, Hydrocarbon Migration and Its Near-Surface Expression ed. Schumacher and Abrams, 1996).
Objectives and Benefits

The principal objective of a geochemical exploration survey is to establish the presence and distribution of hydrocarbons in the area and, more importantly, to determine the probable hydrocarbon charge to specic exploration leads and prospects. For reconnaissance surveys, seeps and microseeps provide direct evidence that thermogenic hydrocarbons have been generated; that is, they document the presence of a working petroleum system and identify the portions of the basin that are most prospective. Additionally, the composition of these seeps can indicate whether a basin
There are no unanswered prayers. At times, the answer is NO

Fig. 1: Surface Geochemistry as a Reconnaissance Exploration Tool
one extreme to identication of minute traces of hydrocarbons (microseepage) or hydrocarbon-induced changes at the other. It should however be emphasized that the results from a surface geochemical study should not be used alone in determining the petroleum potential and the possible commercial exploitability of a region. Results should always be considered alongside those from other techniques such as seismic. Under these conditions there can be little doubt that they make a contribution to more successful basin evaluation and subsequent selection of drilling sites. The use of surface geochemistry data, integrated with other geological information, will then give a more thorough recommendation for exploration in a basin.
Evaluating leads, prospects and development projects

If the objective is to evaluate individual exploration leads and prospects, the results of geochemical surveys can identify those leads associated with strong hydrocarbon anomalies and thereby enable high-grading prospects on the basis of their association with hydrocarbon indicators. Regional geochemical surveys can help determine which leases should be renewed and which ones do not warrant additional expense. Detailed seepage surveys can also generate geochemical leads for evaluation with geologic and seismic dataleads that might otherwise go unnoticed. For development projects, detailed microseepage surveys can help evaluate inll or step out drilling locations, delineate productive limits of undeveloped fields, and identify bypassed pay or undrained reservoir compartments. Hydrocarbon microseepage surveys have the potential to add value to 2-D and 3-D seismic data by identifying those features or reservoir compartments that are hydrocarbon charged. Detailed geochemical surveys of prospects generated by other means can be very useful. Often the integration of the geochemical data will improve the interpretation of the data used to generate the prospect. An ultra high
Surface geochemistry as a reconnaissance exploration tool

The objective of a reconnaissance survey is to find seeps and microseeps that provide direct evidence that thermogenic hydrocarbons have been generated, i.e., they document the presence of a working petroleum system. Additionally, the composition of these seeps can indicate whether a basin or play is oil prone or gas prone. Hydrocarbons from surface and seaoor seeps can be correlated with known oils and gases to identify the specic petroleum system(s) present. Seepage data allow the explorationist to screen large areas quickly and economically, determining where additional and more costly exploration is warranted. For example, results of preseismic geochemical surveys can guide the location and extent of subsequent seismic acquisition by ensuring that areas with signicant hydrocarbon anomalies are covered by seismic data. (Abrams, M.A., 1992, Piggot and Abrams 1996, Schiemer et al. 1995, Thrasher et al. 1996). The signicance of Surface Geochemistry as a Reconnaissance Exploration Tool in petroleum
28 J U N E 2008
exploration is explained in Fig. 1.
Innovative surface geochemical exploration for conventional and unconventional hydrocarbon reservoirs
Organic and inorganic surface geochemical methods are integrated to explore for hydrocarbon reservoirs. Where possible, these geochemical data are combined with geological and geophysical data to further reduce risk in hydrocarbon exploration. The organic variables are a direct indicator of hydrocarbon presence and type, and inorganic variables such as calcium, magnesium, strontium, barium, lithium, lead, zinc and chloride can be indicative of uid leakage from underlying hydrothermal dolomite. Surface geochemical exploration for petroleum is the search for chemically identifiable surface or near-surface occurrences of hydrocarbons, or hydrocarbon-induced changes, as clues to the location of oil and gas accumulations. It extends through a range of observations from clearly visible oil and gas seepage (microseepage) at
Peace is not absence of activity, but absence of uncertainty and confusion

Fig. 2: Surface geochemistry as a detailed exploration tool
tification and characterization of near-surface migrated hydrocarbons are well documented (Abrams and Segall, 2001).
density geochemical survey is often warranted based on the relatively minor additional costs verses the enhanced data. Geochemistry can be used to "check" prospects. Depending on the size, as few as four high density lines using 40 to 60 samples can condently evaluate a prospect. Failure to nd a geochemical signature does not mean the prospect will not be successful it just means the odds have gotten very long. If on the other hand the limited evaluation shows promise the survey can be expanded to help guide drill site selection and future development. The surface geochemistry as a detailed exploration tool is detailed in Fig. 2.
Standardized, comprehensive shallow sea bed sampling programs are specially designed for detection, identication and characterization of adsorbed hydrocarbons on the sediments. The sediment samples are normally coll e c t e d t h ro u g h grab sampling or gravity coring. T h e s h i p b o a rd sampling procedures are conducted immediately upon retrieval of core. The sub-sampling is done to collect sub-samples from several depth intervals to provide multiple geochemical measurements throughout the full length of the core.
Microbiologists Mogilewskii (1938, 1940) in the U.S.S.R. and Taggart (1941) and Blau (1942) in the United States described the use of hydrocarbonoxidizing bacteria (HCO), when measured in surface soil samples, as an indicator for oil and gas elds in the deeper subsurface. In the 1950s and early1960s many relevant publications (Updegraff et al., 1954; Maddox, 1956; Subbota, 1947a, b; Bokova et al., 1947) documented the applicability of this technique with case histories. Davis (1967) and Sealy (1974 a, b) published reviews of early work carried out in this eld. Several microbiological methods for detecting the distribution and activity of HCO were developed, such as enumeration of cell content in soil samples, measuring gas-consumption rates, and radioautography. Beghtel et al. (1987) described a new Microbial Oil Survey Technique (MOST) which uses the higher butanol resistance of butane-oxidizing bacteria to detect hydrocarbon microseepage. The activities of hydrocarbon-oxidizing bacteria cause the development of near-surface oxidation-reduction zones and the alteration of soils and sediments above the reservoirs. These changes form the basis for other surface exploration techniques, such as soil carbonate methods, magnetic and electrical methods, and radioactivity and satellitebased methods (Richers et al., 1982; Jones and Drozd, 1983; Schumacher, 1996; Saunders et al., 1999). In addition to onshore exploration, microbial prospecting has also been used successfully offshore (Hitzman et al., 1994; Baum et al., 1997; Wagner et al., 1998a). Today Geomicrobial prospecting along with the surface geochemical prospecting for hydrocarbon exploration is a mature technology and microbial surveys have been carried out in most of the frontier onshore basins of India.
Geomicrobial prospecting for hydrocarbon exploration

Geomicrobial survey for hydrocarbon exploration is a surface prospecting technique based on specic utilization of seeped gases from sub surface petroleum deposits by specialized groups of bacteria i.e. Propane and butane oxidizers. The basis for microbial detection of hydrocarbons is the principle that light hydrocarbons from oil and gas reservoirs escape to the earths surface, and this increased hydrocarbon supply above the elds creates conditions favorable for the development of highly specialized bacterial populations that feed on the hydrocarbons. This leads to signicant increases in the microbial cell numbers and cell activity of these specialized microbes. The technique on integration with geophysical and geological inputs provides additional exploratory leads for prioritization of prospects and reducing the risks.
Offshore surface geochemical exploration

All petroliferous basins exhibit some type of near-surface occurrence of hydrocarbons in very-minute concentrations. When these are in subtle chemically detectable concentrations, they are called micro seeps. Offshore sampling programme are specially designed to detect, identify and characterize the micro seeps greatly enhance conventional exploration programme. The best practices in detection, iden-
Case studies
Geochemical surveys have been carried out in Western and Eastern offshore, Cambay, Cauvery and most of the frontier onshore basins of India. Two case studies, one from
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The one who truly understands himself is able to stand by himself

Fig. 3: Adsorbed hydrocarbon concentration (C1, C2, C3, iC4 and nC4 from soil samples at 30m depth in the study area. (Concentration in ppm by weight)
The north northeastern and southwestern parts of study area appear to be interesting (warm due to presence of hydrocarbons). However, extension of anomalies further, to the southwest part of the study area, indicate the block to be prospective for focusing future exploration activities and possible leads. Adsorbed hydrocarbon concentration (C1, C2, C3, iC4 and nC4) from soil samples at 30m depth in the study area is shown in Fig. 3. C2+ (sum of ethane through butane) concentration contour map in the study area is shown in Fig. 4.
Surface Geochemical Exploration of NELP-IV Block from Gujarat Saurastra Deep Water Offshore Basin
Surface Geochemical Exploration in Gujarat - Saurastra Deep Water Offshore Basin was carried out with following objectives: To detect the hydrocarbon microseeps. To genetically classify the seeped/ adsorbed gases. To delineate the adsorbed gas anomalies in the studied area. To prioritize the prospective areas for hydrocarbon exploration based on above studies in block.
MandapetaEndamuru Area of Krishna-Godavary Basin and other from NELP-IV Block in Gujarat - Saurastra Deep Water Offshore Basin, are described below:
Surface Geochemical Exploration in MandapetaEndamuru Area of Krishna-Godavary Basin

Surface Geochemical Exploration in MandapetaEndamuru Area of KrishnaGodavary Basin was carried out with following objectives: To detect the hydrocarbon microseeps. To delineate the adsorbed gas anomalies in the studied area. To establish the genesis of seeped/ adsorbed gases. To prioritize the prospective areas for hydrocarbon exploration based on above studies in KG Basin. The studies conclude that:
ary alteration effects during their upward migration and subsequent adsorption onto soil particles. The seeped hydrocarbons are co-genetic in nature Halos resulted due to strong anomalies are discernible in the northwestern and southwestern parts of the study area. The other one seen in the northeastern part does not seem to be promising
Fig. 4: C2+ (sum of ethane through butane) concentration contour map in Mandapeta Endamuru Area of Krishna-Godavary Basin
Adsorbed gas (C1 C4) analysis

results show presence of light hydrocarbons in decreasing order, C1>C2>C3>C4, indicating thermogenic nature of hydrocarbons. The gases studied are of catagenic origin, petroliferous in nature and have migrated from sub surface petroleum sources. Further, these gases are not inuenced by second30 J U N E 2008
Things not understood are best admired

Fig. 5: C2+ (sum of ethane through butane) concentration contour map in the study area
separation and mass selective detection (TD/GC/MS). This yields chemical data from methane (C1) to phytane (C20). Data processing and modeling is carried out by Hierarchical Cluster Analysis, Principal Component Analysis, Canonical Variate Analysis, Discriminant Analysis and other methods. Contour maps of geochemical probability are drawn. Survey results are then integrated with other geological and geophysical data to prioritize area for future exploration.
Conclusion
Energy is the most vital input for economic and social development of any society. India imports approximately 70% of its oil, mainly from the Middle East ant its dependence on imported oil is growing rapidly. The World Energy Outlook, published by the International Energy Agency (IEA), projects that India's dependence on oil imports will grow to 91.6% by the year 2020. Studies have indicated that a sustained 5 per cent rise in the oil price over a year would slash India's GDP growth rate by 0.25 per cent and raise the ination rate by 0.6 per cent. This grim situation requires immediate acquisition and application of all state-of-art techniques and technologies in the eld of petroleum exploration. Surface
Conclusions of the study All the samples show the presence of light hydrocarbons (C1 C4). The microseeps contain hydrocarbons in order, C1>C2>C3>C4, indicating thermogenic nature of hydrocarbons. The microseep gases are of late catagenetic origin, petroliferous in nature and have not been inuenced by secondary alterations during their upward migration and subsequent adsorption onto soil particles. Based on Point anomalies distribution, the southern part of the study area is better than northern part. However, no prominent geochemical anomaly is observed in the block. C2+ (sum of ethane through butane) concentration contour map in the study area is shown in Fig. 5.
This technology involves the use of a patented sorbent based passive sampler (Fig. 6). This hydrophobic adsorbent of 5-6 mm diameter allows easy insertion in pre-drilled small diameter (~1cm) holes of 30 to 60cm depth. For soil gas sampling an insertion rod pushes the adsorbent into bottom of the hole. This adsorbent contains sorbent material selected for their afnity to a large range of volatile and semi-volatile organic compounds. The sampler is then retrieved from the hole for further analysis. Sampling plan typically follows a grid pattern with regular or variable spacing of samplers. Locations of samplers are marked on a map and location co-ordinates are secured with GPS receiver. The target time for exposure in the ground is 17 days. This time is found optimum for most regions and climatic conditions. All soil gas samples are thermally desorbed and analyzed by gas chromatographic
Fig. 6: Module (a synthetic, patented sorbent) used for sampling of hydrocarbon vapors emanating from deeply buried source
The state-of-art in surface geochemical exploration:

Amplified geochemical imaging
The state of art development in the eld of SGE is offered by many companies. One of them, Amplied Geochemical Imaging, is currently under application in ONGC. This is an advanced surface geochemical prospecting tool capable of directly detecting and quantifying many organic compounds in the C2 (ethane) to C20 (phytane) range. When the results are integrated with other geological/ geophysical data, it l reduces exploration risk.
Time is most valuable. Consider every breath to be your last breath
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Geochemical Exploration (SGE) is one of the available technologies which establishes the presence and distribution of hydrocarbons in the area. For reconnaissance surveys, hydrocarbon seeps and microseeps provide direct evidence that thermogenic hydrocarbons have been generated; thus they establish the presence of an active petroleum system and identify and prioritize the prospects. Geomicrobial survey for hydrocarbon exploration is a surface prospecting technique based on specic utilization of seeped gases from sub surface petroleum deposits by specialized groups of specializes bacteria i.e. Propane and butane oxidizers. The technique on integration with geophysical and geological inputs provides additional exploratory leads for prioritization of prospects leading to risk reduction in exploration. The state of art development in the eld of SGE involves the use of a sorbent based passive sampler selected for their afnity to a large range of volatile organic compounds and directly detecting and quantifying organic compounds in the C2 (ethane) to C20 (phytane) range. Today Surface Geochemical Exploration (SGE) for hydrocarbon exploration is a mature technology and geochemical surveys have been carried out in Western and Eastern offshore, Cambay, Cauvery and most of the frontier onshore basins of India. M.A. Abrams, eds., AAPG Memoir 66, p. 114. Abrams, M.A, 1996b, Interpretation of methane carbon isotopes extracted from surcial marine sediments for detection of subsurface hydrocarbons, AAPG Memoir 66, p. 309318. Baum, M., K. H. Bleschert, M. Wagner, and M. Schmitt, 1997, Application of surface prospecting methods in the Dutch North Sea: Petroleum Geoscience, v. 3, p. 171181. Beghtel, F. W., D. O. Hitzman, and K. R. Sundberg, 1987, Microbial oil survey technique (MOST): Evaluation of new wildcat wells in Kansas: The Association of Petroleum Geochemical Explorationist Bulletin, v. 3, no. 1, p. 114. Blau, L. W., 1942, Process for locating valuable subterranean deposits: U. S. Patent 2,269,889. Bokova, E. N., V. A. Kusnetsova, and S. I. Kusnetsov, 1947, The oxidation of gaseous hydrocarbons through bacteria as a basis of microbial indication of reservoirs: Doklady, Akademia Nauk, S.S.S.R., 56, p. 755757. Brooks, J.M., M.C. Kennicutt, and B.D. Carey, 1986, Offshore surface geochemical exploration: Oil & Gas Journal, October 20, p. 6672. Davis, J. B., 1967, Petroleum Microbiology: Elsevier Publishing Company, p. 197245. Duchscherer, W., Jr., 1984, Geochemical Hydrocarbon Prospecting, with Case Histories: Tulsa, PennWell Publishing Co., 196 p. Hitzman, D. C., J. D. Tucker, and P. D. Heppard, 1994, Offshore Trinidad survey identifies hydrocarbon microseepage: 26th Annual Offshore Technology Conference, OTC 7378, Houston, Texas. Jones, V.T., and R.J. Drozd, 1983, Predictions of oil or gas potential by near-surface geochemistry: AAPG Bulletin, vol. 67, p. 932952. Klusman, R.W., 1993, Soil gas and related methods for natural resource exploration: New York, John Wiley & Sons, 483 pp. Link, W.K., 1952, Significance of oil and gas seeps in world oil exploration: AAPG Bulletin, vol. 36, p. 15051541. Lopez, J.P., D.C. Hitzman, and J.D. Tucker, 1994, Combined microbial, seismic surveys predict oil and gas occurrences in Bolivia: Oil & Gas Journal, October 24, p. 6870. Laubmeyer, G., 1933, A new geophysical prospecting method, especially for deposits of hydrocarbons, Petroleum, Vol. 29, No. 18, pp. 1-4 Macgregor, D.S., 1993, Relationships between seepage, tectonics, and subsurface petroleum reserves: Marine and Petroleum Geology, vol. 10, p. 606619. Machel, H.G., 1996, Magnetic contrasts as a result of hydrocarbon seepage and migration, in D. Schumacher and M.A. Abrams, eds., AAPG Memoir 66, p. 99109. Maddox, J., 1956, Geomicrobiological prospecting: U. S. Patent 2,875,135. Matthews, M.D., 1996, Migration a view from the top, in D. Schumacher and M. A. Abrams, eds., AAPG Memoir-66, p. 139155. Mogilewskii, G. A., 1938, Microbiological investigations in connecting with gas surveying: Razvedka Nedr, v. 8, p. 5968. Mogilewskii, G. A., 1940, The bacterial method of prospecting for oil and natural gases: Razvedka Nedr, v. 12, p. 3243. Piggott, N. and M.A. Abrams, 1996, Near-surface coring in the Beaufort and Chukchi Seas, northern Alaska, in D. Schumacher and M.A. Abrams, eds., AAPG Memoir 66, p. 385399. Potter, R.W. P.A. Harrington, A.H. Silliman, and J.H. Viellenave, 1996, Signicance of geochemical anomalies in hydrocarbon exploration: one companys experience, in D. Schumacher and M. A. Abrams, eds., AAPG Memoir 66, p. 431439. Price, L. C., 1986, A critical overview and proposed working model of surface geochemical exploration, in M. J. Davidson, ed., Unconventional Methods in Exploration for Petroleum and
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The biggest limitation is the thought, I Cant

Natural Gas IV: Dallas, Texas, Southern Methodist Univ. Press, p. 81129. Richers, D.M., and L.E. Maxwell, 1991, Application and theory of soil gas geochemistry in petroleum exploration, in R.K. Merrill, ed., Source and Migration Processes and Techniques: AAPG Treatise of Petroleum Geology, Handbook of Petroleum Geology, p. 141158 Richers, D. M., R. J. Reed, K. C. Horstman, G. D. Michels, R. N. Baker, L. Lundell, and R. W. Marrs, 1982, Landsat and soilgas geochemical study of Patrick Draw oil eld, Sweetwater Country, Wyoming: AAPG Bulletin, v. 66, p. 903922. Saunders, D. F., K. R. Buraon, and C. K. Thompson, 1999, Model for hydrocarbon microseepage and related near-surface alterations: AAPG Bulletin, v. 83, no. 1, p. 107185. Saunders, D.F., K.R. Burson, J.J. Brown, and C.K. Thompson, 1993, Combined geological and surface geochemical methods discovered Agaritta and Brady Creek elds, AAPG Bull., Vol. 77, p. 12191240. Schiemer, E.J., G. Stober, and E. Faber, 1995, Surface geochemical exploration for hydrocarbons in offshore areasprinciples, methods and results, in Petroleum Geochemistry in Exploration of the Norwegian Shelf: London, Graham and Trotman, p. 223238. Schumacher, D., 1996, Hydrocarbon-induced alteration of soils and sediments, in D. Schumacher and M. A. Abrams, eds., Hydrocarbon migration and its nearsurface expression: AAPG Memoir 66, p. 7189. Sealy, J. R., 1974a, A Geomicrobial method of prospecting for oil: Oil & Gas J., v. 8, p. 14246. Sealy, J. R., 1974b, A Geomicrobial method of prospecting for oil: Oil & Gas J., v. 15, p. 98. Stahl, W., E. Faber, B.D. Carey, and D.L. Kirksey, 1981, Nearsurface evidence of migration of natural gas from deep reservoirs and source rocks: AAPG Bulletin, vol. 65, p.15431550. Subbota, M. I., 1947a, A complex study of the causes of seasonal variation of data in soil-gas surveys: Neftjanoe Khozjostwo, v. 25, p. 1317. Subbota, M. I., 1947b, Field problems in oil prospecting by the bacterial survey method: Razvedka Nedr, v. 13, p. 2024. Taggart, M. S., 1941, Oil prospecting method: U. S. Patent 2,234,637. Tedesco, S.A., 1995, Surface Geochemistry in Petroleum Exploration: New York, Chapman and Hall, Inc., 206 p. Thrasher, J.A., D. Strait, and R.A. Lugo, 1996, Surface geochemistry as an exploration tool in the South Caribbean, in D. Schumacher and M.A. Abrams, eds., AAPG Memoir 66, p. 373384. Updegraff, D.M. and H.H.Chase, 1954, Microbiological prospecting method: U. S. Patent 2,861,921. Wagner, M., M. Wagner, H. J. Rasch, J. Piske, and M. Baum, 1998a, MPOGMicrobial prospection for oil and gas: Field examples and their geologic background: Conference Cracow, Poland, AO-05, p. 118 121.
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GAIL inks gas co-op pact with Tidco

Infrastructure Bueau, Chennai, June 6
Gas transmission and marketing major GAIL (India) Ltd has entered into a gas cooperation agreement with Tamil Nadu Industrial Development Corporation (Tidco)-to evaluate medium and long term demand of gas potential of the state. As per the agreement, a working committee will be set up soon to conduct a preliminary technoeconomic feasibility study on this, said UD Choubey, chairman and managing director, GAIL (India) Ltd. Addressing a press conference along with Tidco CMD S Ramasundaram here on Friday, the GAlL chief said the working committee, comprising members of both the companies, will evaluate the short-medium-long term demand of gas in industrial, commercial, transport, residential sectors of the state, gas pipelines and other networks required for gas marketing, sources for ensuring continued supply at competitive prices, optical bre cable network in potential gas pipelines. We expect to come out with a comprehensive study in the next six months and accordingly go ahead with this project, Choubey said. While Tidco will provide all the necessary data/information, including studies pertaining to gas demand in the state, extend its cooperation on best effort basis to developers of gas pipeline infrastructure, associated facilities and optic bre cable networks and other back-up supports. Based on this, GAIL will determine the exact natural gas supply options to the state, he said. According to him, the company has identied gas sources in places such as Nagapattinam, Karaikkal, Puduchery,
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Kuttalam, Bhuvanagiri among other areas to put up gas pipline and the same will be extended to Chennai. According to Ramasundaram, the corporation has entered into a nonexclusive basis agreement with GAIL. We have options to source from Cauvery basin or from neighbouring KG basin sources or can even import and supply to the requirement. Our objective is to go for optimal gas utilisation of the available gas resources, he added. The move will immensely benet the state in a big way in bringing in new industries apart from cutting down the cost of manufacturing / production of the industries.
Divine love releases the human soul from its various accounts of karma
Energy Beyond Oil - Underground Coal Gasication

R K Sharma
Institute of Reservoir Studies, Chandkheda, Ahmedabad, India
Sri R K Sharma,
G e n e r a l M a n a g e r, Head UCG, ONGC, IRS, Ahmedabad Took his M.Tech. in Applied Geophysics in rst class rst from erstwhile University of Roorkee, Roorkee in 1976. Joined ONGC as Petroleum Reservoir Engineer in 1977. Has received extensive training in Petroleum Reservoir Engineering subjects like Reservoir Simulation and Petroleum Data Management. Involved for over one and half decade in the eld of Development of Oil and Gas elds and Reservoir Management. Handled a state- of- art Petroleum
Data Management project in Western and Eastern sectors of ONGC operational areas. Involved in implementing a knowledge management project in the entire Eastern sector of ONGC. Involved in the UCG Project since the year 2005 with base at Institute of Reservoir Studies, ONGC, IRS, Ahmedabad. Has been on a number of task forces both technical and related to organizational matters. Has participated in a number of National and International conferences on the subjects related to Hydro carbon and Coal Gasication. 25 internal publications and 15 publications in National and International journals.
the following main reactions may be considered: C+CO22CO H = +159.7 kJ mol-1 C+H2OCO+H2 H = +118.9 kJmol-1 C+O2CO2 H = -405.9 kJ Mol-1 CO+H20CO2+H2 H = -40.9 kJ mol-1 C+2H2CH4 H = -87.4 kJ mol-1
(1)
(2)
(3)
(4)
(5)
oncept of converting coal into gas has existed for many years. Underground Coal Gasication (UCG) involves in-situ conversion of coal into combustible gas without physically mining it. In the simplest terms, the process involves drilling a pair of wells (Injector and Producer) into a coal seam, establishing a link between these two wells and injecting gasifying agents like oxygen or air and steam through the Injector. After ignition and gasication of coal, the product gas known as Syngas is brought to the surface through the Producer and used as fuel or chemical feedstock. Though the principle appears simple, practical conversion of coal into gas in-situ and ensuring a consistent and environmentally safe exploitation of coals especially deeper seams, is a challenging task. Overcoming these difculties provides a good opportunity for todays highly developed drilling and engineering technologies. A number of disciplines like geology, mining, chemistry, chemical engineering, mechanical engineering, production, drilling etc. need to be applied for the exploitation of coal in this manner.
Coal gasication is a two step process: Pyrolysis and Char gasication. The rst step of Pyrolysis involves evolution of low molecular weight compounds. These compounds are mainly tars and non-condensable gases. The pyrolysis occurs at 300-500o C. Normally, pyrolysis residue or char represents 55-70% of original coal. During char gasication
Reactions (1) and (2) are endothermic and can be considered the most important for gasication process. Oxidation reaction (3) provides energy needed for the promotion of reactions (1) and (2). The shift reaction (4) occurs mainly at high steam concentrations, while reaction (5) is more important at high pressures. As gasication proceeds, char loses mass. The burnout rate is used to determine the gasication reactivity. Reaction rate is studied when char is reacting with CO2 or H2O at
34 J U N E 2008
The lie you tell today will force you to lie again tomorrow

trial was that it established that deeper coals could be gasied through deviation and horizontal in-seam coal drilling for linking wells. Another innovation was insertion of exible casing into the deviated and horizontal section of the well. Technical risks included inaccurate azimuth, insertion of exible casing, low permeability of coal at deeper depths, corrosion and high temperature. Economic risks included high cost of deep boreholes, uncertainty about consistent heating value of produced gas, efciency of gasication and percentage of unburned coal. temperatures between 800 and 1200o C. Typically Syngas consists of CO, H2 and CH4 in addition to non-combustible gases like N2, CO2. The caloric value of gas ranges from 800-1000 Kcal/m3 when air is used as an injectant. The calorific value can be enhanced by replacing air injection with oxygen. oil crisis, USA again embarked on the development of UCG in 1972, involving in the process a number of institutes. More than 30 trials were conducted till early 1990s. This led to considerable technological development. French attempted to gasify the coals at deeper depths which were conventionally un-mineable and their objective was to bring to surface, the medium caloric value gas through injection of oxygen and steam and convert the gas into high caloric value methane at the surface. Two main tests carried out in Bruay-en-Artois (1978-1981) and Haute Deule (1982-85) provided some valuable insights into adequate well ttings to withstand pressure variations, possibility to link by hydrofracturing, easy ignition of coal with an electric heater, possibility to prevent spontaneous combustion with the injection of low oxygen content. In a related development, in Loire eld, electrolinking was tried. The results were successful and the same was conrmed by open casting the coal seam and back checking the results. Attempts were made to link wells by Reverse Combustion in a Belgo-German trial at Thulin. The attempt was unsuccessful because of high overburden lithostatic pressure. Reverse combustion attempts were stopped. However, a collaborative project in 1985 attempted connecting existing wells at Thulin through lateral drilling. The two wells were linked through lateral drilling and side tracking. A small gasier circuit was established and about 340 tons of coal were gasied at a depth of 860 meters for about six months. The gasier pressure was maintained at about 20-30 bar. The greatest benet of this The results of this experiment encouraged further research and this resulted in the formation of European Working Group on Underground Coal Gasication for formulating a proposal for further research. The Group submitted a proposal for a large scale experiment involving the Belgian team of Thulin experiment, Spain and UK. The aim of this project was to test the technology on coals which are thinner and deeper and typical of Europe. Initially, it was proposed to test the technology at about 500m and later at 1000m and beyond. Deviation and in seam drilling was used to establish link between injector and producer and different methods for Gasier control and development were to be tested. The project was proposed in Al Tremidal in the province of Tereul, NE Spain. The site was chosen on the grounds of geological suitability. Extensive borehole data was also available for this site. The trial was successful and it proved the viability of directional drilling and benets of CRIP (Controlled Retractable and Injection Point). About 90 m of channel was created and estimates concluded requirements of about 300 tons of coal for conversion into power of 8MW. The quality of gas was very high in this case. The programme also included a post burn activity material analysis, environmental impact monitoring, cavity sampling etc. The pilot duration was short but lessons were learnt on the detailed engineering, drilling and plant design.
Historical Perspective
Sir William Siemens, in the year 1868, was perhaps the rst to suggest underground gasication of waste coal in the mine. The rst experimental work can be traced to 1912 when William Ramsey began work on UCG in Durham but was not able to complete it till the onset of rst world war. All the efforts in Underground Gasication in Western Europe were discontinued till the end of Second World War. On the other hand, intensive work on coal gasication began in the then USSR in 1930s in coal seams at shallower depths. This led to industrial scale UCG in several parts of USSR particularly in Russia and Uzbekistan. One project in Uzbekistan is still operational. These trials established the basic technology of underground gasication. Shortage of energy between 1944 -1959 induced a renewed interest in in-situ coal gasication in Western European coal mining countries. The first attempts were directed at thin seams at shallower depths. Borehole method was tested in Britain in Newman Spinney and Bayton (1949-50) and a few years later attempt was made for a commercial pilot in P5 trial in Newman Spinney (1958-59). During 1960s, low cost fuel was available in plenty and therefore, there was lull on progress of UCG in Europe. However, after the rst
Developments in the millennium

UK has large coal reserves and including that of offshore, is probably the largJ U N E 2 008 35 35
Violence at home can lead to blood in the streets

est in Western Europe. It is estimated that only 1-2% has been mined since Industrial Revolution. Most of the coal in UK is bituminous and exists right from the outcrop to a depth of 2000m. Exploitation of this resource at deeper depths is not possible through conventional mining. As per an estimate, 17 billion tones of un-mineable coal are suitable for UCG. Department of Trade and Industry (DTI), U.K., identied UCG as a potential source of future energy. The DTI Report (2004) highlights that coal will continue to play a prominent part in future as a source of energy. UCG could provide a combination of high generating efciency and potentially satisfactory method for clean coal technology. The report also mentions that evidence to date suggests that UCG compares well with, for example Integrated Gasification Combined Cycle (IGCC) and supercritical thermal plant. The report concludes that if planning and environmental issues can be dealt with, UCG, in conjunction with carbon capture and storage, increases diversity of supply and hence contribute to security within the context of a low carbon economy. UK and China have collaborated for UCG. The principal partners in this project are Wardell Armstrong, Craneeld University, Alstom Power, University of Nottingham, China University of Mining and Technology and many other organizations. China has adopted two approaches for the exploitation of coal. One is Undersurface Gasication (UG) method and the other is Long Tunnel, large section, two stage method. Undersurface Gasication is an extension of underground mining in which gasier replaces working faces and are controlled from underground independently for optimal performance. The access is made all the time from underground. In the other method, a long tunnel is constructed using mining methods and connections to the surface are made using production and injection wells drilled. The system is monitored and operated from the surface. The two stage method involves injecting air rst so that a high temperature is attained. Then the steam is injected resulting in the process of gasication. The method has been shown to produce gas with heating values of 12-14 MJ/m3 and a
36 J U N E 2008
hydrogen content of 50%. The method has been found to be difcult to control. China as per the latest reports has embarked on a programme of testing UCG at deeper depths. Chinchila IGCC Project, Australia, has been under development since 1999. This is the largest UCG trial so far and resulted in the gasication of 35,000 tons of coal and claimed 95% recovery of targeted coal resource. Consistency and high quality of syngas has also been claimed and availability of gas has been ensured for 28 months at a time. The project has reported no contamination of aquifer and has had a special shutdown programme. Several companies are preparing for operating industrial UCG sites in the state of Queensland (Australia) and with two centers of UCG research located in Brisbane (at The University of Queensland and CSIRO Division of Exploration and Mining). During the last decade, the Queensland capital became one of the world's leading centers in UCG development. The large coal reserves of Queensland are suitable to UCG and there is evidence of low gas production costs. UCG-IGCC produces lower green house gas emissions. In terms of technical operation and cost, Chinchila UCG test is perhaps the most successful ever conducted in the western world. The company has now embarked on a UCG project called Kingaroy UCG Project spread over about 15 sq. km with 12 m thick coal seams at depths below 160m. Eskom Holdings Ltd. has commissioned 6-MW underground coal gasification pilot plant based on Ergo Exergys technology at Majuba coaleld in Mumalanga, South Africa. The rst aring of gas from UCG pilot plant occurred in January 2007 as a result of systematic work for four years. There are now plans to set up a 2100MW power plant using Syngas as fuel. Besides power generation (IGCC), synthesis of liquid fuels, synthetic natural gas, ammonia and Dimethyl Ether is also possible using Syngas. It is estimated that Powder River Basin has 307 Billion tons of coal amenable to UCG where the seams are >500 ft deep and > 30 ft thick. UCG project of Gas Tech in Wyoming's Powder River
Basin (PRB) has coal leases covering 125 Sections containing 13 billion tons of coal at depths from 500 feet to 2,400 feet. Each section could support 200 MWe UCG power plant for about 68 years. Well spacing of 200 ft is proposed here and the resource recovered could be 65% of coal- in place. Raw syngas production was expected to cost US$ 1.62 /MMBtu including 15% ROI on UCG investment. These leases are spread across the basin, giving GasTech the perfect "natural laboratory" for demonstrating and commercializing UCG, where any combination of coal depth, seam thickness, hydrostatic head, surface infrastructure, etc., can be selected. GasTech reported last fall that it had essentially completed its analysis of the entire PRB and its 80,000-acre leasehold is in the choicest spots, where the coal is thick and around 1,000 feet deep. GasTech is in advanced discussions with potential partners. Laurus Energys UCG project in Canada is developing a base load UCG-IGCC power plant in Alberta with further expansion in syngas production to supply fuel for Alberta oil sands projects. Laurus energy is shortly completing site selection and pre-feasibility stage of project development. BP and Ergo Exergy Technologies Inc. signed a technical alliance agreement to work cooperatively on UCG technology.
Environmental Issues
UCG process, as a method for exploitation of coal/lignite is an environmental improvement over the combination of conventional mining and surface combustion of coal. As the process is carried out underground, there are lower particulate emissions, lower water requirement, no waste (like ash) generation, no venting of green house gases as in mining etc. In short, the detrimental impacts of UCG process are perceived to be fairly low as the main product of the process is gas and by products are either left in the ground or they can be removed by conventional processes. Therefore, the environmental impacts of mining and ash disposal are avoided.
Being co-operative does not mean becoming a slave

it is possible to reduce risk of UCG to acceptable levels through assessment tools for Site selection and screening, operations and facilities planning based on site specic risk indexing and setting operation guidelines based on site parameters. We should also identify operating ranges that limit production of contaminants and prevent migration of contaminants out of cavity during and post UCG. One should also include evaluation of mitigation and remediation options and economics appropriate to UCG sites.
Strides made in India

ONGC embarked on Underground Coal Gasication in 1980s. The core team at that time recommended that UCG is the only technology available for exploitation of coal at deeper depth in India. One well (UCG-1) was drilled to a depth of 1005 m to acquire data. All exploratory studies such as complete set of logs, VSP, dipmeter, geohydrology, production, testing etc. were carried out in this well. The coal samples were also collected from UCG-3 and detailed studies were carried out. The contracts with Indian and foreign agencies, could not be nalized due to various reasons and the project was shelved. Horizontal drilling, in-situ combustion etc. were some of the developments which could be extended to UCG technology. Coupled with the fact that oil and gas prices were rapidly increasing, ONGC embarked again on UCG by signing an Agreement of Collaboration with Skochinsky Institute of Miming-National Mining Research Centre, Moscow in November 2004. The institute was established in 1927 and has a long experience in the eld of UCG. The rst phase of work involved identication of a suitable site for the UCG project. MOUs were signed with a number of major coal companies in India for their involvement in the Project. Initially eleven sites belonging to the partnering coal companies were taken up for evaluation of suitability to UCG. Various types of data like Geological, geo-hydrological, geo-mechanical data including properties of coal and overburden etc. was generated and used for selecting a suitable site for UCG. Out of these sites, one site in south of
J U N E 2 008 37 37
However, there are environmental issues that arise and can be summarized as surface and subsurface impacts. Along with Syngas, pollutants like phenols, tars, aromatic hydrocarbons are co-produced, which could contaminate ground or surface waters. Gaseous pollutants may include hydrogen sulphide, ammonia, oxides of nitrogen etc. Some of these gases could be converted into valuable products. As the coal/lignite is consumed, a void is created in the subsurface. This could lead to strata relaxation and some subsidence of the overburden. The environmental impacts of UCG can be minimized by choosing an appropriate site suitable to UCG. For example, for preventing contamination of ground/ surface waters those sites are avoided where major good quality aquifers exist. Tectonically stable sites are favorable. Sites, where more than a specic overburden ratio exists, are considered to be suitable. Infact, a complete suite of data consisting of geological, hydro geological, geo-mechanical data of coal seams and the overburden etc. is evaluated for arriving at the suitability of a site to UCG. More than 30 UCG trials have been conducted in USA and only two trials showed environmental problems of aquifer contamination. The main objective of these two trials was to evaluate different permeability enhancement techniques that could be used to link
the injection wells with the production wells. In one case explosive fracturing was used and in another case reverse combustion technique was tried. Water influx occurred in the latter and therefore, gasication pressure had to be increased resulting in gas loss and collapse of burn zone. It is perhaps noteworthy to mention here that the recent protocols developed for site evaluation, would have classed this site as having high environmental risk. The possibility of carbon capture and storage (CCS) during the process of UCG has been highlighted by Lawrence Livermore National Laboratory (LLNL), USA. Close proximity of CO2 storage found near coal seams chosen for UCG, make an attractive carbon management package. The Laboratory's current CO2 capture program combines ASPEN analysis of surface processes with advanced membranes and novel engineering concepts for downhole separation. The CO2 storage program focuses on advanced simulation, monitoring and verication technology and risk assessment and quantication. A number of companies worldwide are seeking assistance from LLNL, USA for environmental issues of UCG as the laboratory has developed a large suite of tools for environmental assessment. LLNL has developed expertise in carbon management and CO2 sequestration. However, CO2 storage in the cavity is not commercially ready yet. It was pointed out that
In the long run the most difcult thing is to search for an easy way out

Gujarat was selected as suitable for the process. The site has been chosen because of minimum possible impact on the environment apart from that the fact that site has sufcient coal / lignite reserves. Premier agencies of India viz. National Environmental Engineering Research Institute, Indian School of Mines and Central Institute of Mining of Fuel Research have been involved for environmental monitoring issues. UCG pilot to be carried out at the site shall involve drilling of a few wells, some of which shall have to be drilled horizontally at shallow depths. The task is quite challenging. Syngas processing is different from the conventional natural gas since the hot gas comes to surface and needs to be processed accordingly. Seismic survey for mapping of lignites was carried out for the rst time on trial basis and the results were quite encouraging. The survey has now been carried out in entire area. Additional sites needed to be evaluated for UCG and for this process, knowledge gained from previous screening was applied more thoroughly and it is quite likely that additional sites shall become available for UCG. Per capita consumption of energy in India is one of the lowest in the world. India consumed 520 Kg of oil equivalent (kgoe) per person of primary energy in 2003 as compared to the world average of 1688 kgoe. Per capita electricity consumption in India is 435 KWH and world average is 2429 KWH. Presently electricity shortage varies from state to state, from 0 to 25.4% with an all India average of 11.7%. Similarly the present energy shortage varies from 0 - 20.1% with an all India average of 7.3%. The total oil reserves of India are stagnating in the range of 739 MMt. India is importing 72.2% of its consumption, and our import dependence is growing rapidly. Coal shall remain Indias primary energy source till 2031-2032. Coal accounts for over 50% of Indias commercial energy consumption and 78 % of domestic coal production is dedicated to power generation. With current growth rate of 5% in domestic production, current extractable coal reserves will be exhausted in about 40 years. Extractable coal reserves can be increased by underground coal gasication which permits using coal deposits at greater depths which are not easily extractable by conventional methods. Only 5% of world coal resources are economically extractable as reserves and most resources are simply too deep. UCG has the potential to convert coal resources to coal reserves. India faces formidable challenges in meeting its energy needs and providing adequate energy of desired quantity in various forms, in a sustainable manner and at reasonable cost. GDP of India is growing at 8 to 10% and is likely to maintain the rate in future as well. To deliver a sustained growth of about 8% upto 2031, India would need to grow its primary energy supply by 3-4 times and electricity supply by 5-7 times of todays consumption. Power generation capacity would have to increase from 1,31,424 MW to 7, 78,095 MW by 2031-2032 and the annual coal requirement would increase to 2040 MT. Assured supply of such energy at all times considering the shocks and distribution is essential to providing energy security. Meeting such energy needs would require that India pursues all available fuel options and forms of energy, both conventional and non conventional as well as new emerging technologies and energy sources. It is here that UCG can play an important role in view of the fact that out of 255.15 BT of coal, only 93 BT are mineable and out of 38.76 BT lignite, only 2.0 BT are mineable. The potential for UCG in India is thus immense. a fresh beginning and has reached pilot stage for UCG.
References
1. Best Practices in UCG Draft Report by Elizabeth Burton, Julio Friedmann and Ravi Upadhye, Lawrence Livermore National Laboratory, 2006. Germany, 23-24Sept 1998. Rugby, UK, Institution of Chemical Engineers, pp 1-15 (1998). Covell, J.R. and Thomas M.H., 1996 Combined air sparging and bioremediation of an Underground Coal Gasication site. EG &G report DEAC21-95MC31346. Creedy D and Tilly H (2002) Underground Coal Gasication. World Coal:11(1);40-42(Jan.2002) Creedy, D.P. and K.Garner, 2004. Clean energy from Underground Coal Gasication in China, DTI Cleaner Coal Technology Transfer Programme, Draft Report of the Expert Committee on Integrated Energy Policy, Planning Commission, GOI, New Delhi, Dec2005. DTI Report (September 2004) Review of the Feasibility of Underground Coal Gasication in the UK. Green MB (1999) Underground Coal Gasification-a joint European trial in Spain. Report no. COAL R 169. Harwell, UK, ETSU Energy Technology Support Unit, 50 pp(Aug. 1999). Sapru, R. K., Sharma, R.K., Kuznetsov, A. A. and Kapralov, A.V., Petrotech, (2007), New Delhi, India. Schilling, H., Bonn, B. and Krauss, U., Coal Gasification: Existing Process and New Developments. Graham and Trotman, London, 1981. Summerfield I (2000) Environmental studies. In: New opportunities for deep cola resources in the UK.CD-ROM. Manseld, N o t t i n g h a m s h i re , U K , C o a l Authority,11pp (January 2000) Vamuka D (1999) Underground Coal Gasification. Energy Exploration and Exploitation: 17(6);515-581.
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Conclusions
Worldwide, UCG is being pursued with renewed vigour and a number of countries have embarked on Syngas production. India is an energy deficient country with a rapidly growing economy. The growth can be sustained by exploiting other forms of energy in view of limited oil and gas reserves. India has large un-mineable coal and lignite and thus has potential for UCG in a big way. ONGC in cooperation with Indian coal companies has made
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38 J U N E 2008
This is a mad world, but it is good sense to be madly in love with GOD
Ethanol from Lignocellulosic Biomass: Prospects and Challenges

M P Singh, D K Tuli, R K Malhotra and Anand Kumar
Indian Oil Corporation Ltd., Research & Development Center, Sector-13, Faridabad 121 007, India
Sugars (like molasses, cane sugar,
Dr D K Tuli, hold
P h . D . i n Sy n t h e t i c Chemistry with over two decades of rich and varied experience in research and development in the hydrocarbon industry with a special interest in synthetics and biotics. Dr. Tuli has to his credit, 12 U.S.patents, two European patents and over 20 Indian patents. He has published over 50 research papers in professional journals.He has guided students from various Indian Univer-
sities for their Ph.D. thesis. Dr. Tuli was also a SERC post-doctoral fellow at the University of Liverpool, Robort Robinson Laboratories, England during 1979-81 and 1987-89 and carried out advance research in the areas of new synthetic and analytical methods. Since July 2003, Dr. Tuli is the Chief Executive Ofcer of IndianOil Technologies Limited, a subsidiary of Indian Oil Corporation. He is responsible for marketing of technologies & technical services of IOC(R&D).
beet, sweet sorghum and fruits) Starches (like corn, wheat, rice, potatoes, cassava, sweet potatoes etc.) and Lignocelluloses (like rice straw, bagasse, other agricultural residues, wood, and energy crops). The most common sugar used for bioethanol production is sucrose, which is composed of glucose and fructose. Fermentation of sucrose is performed using commercial yeast Saccharomyces cerevisiae. After the enzymatic hydrolysis (invertase enzyme present in the yeast)
he crude oil prices are surging unabated. The global crude oil reserves are nite and hence, the only prudent energy policy could be one of diversity and exibility. Therefore, in the recent years, a new round of enthusiasm on alternate energy sources has been initiated to ameliorate the economic dependency of various countries on crude oil as well as the resulting effect on global climate and environment.
Advantages of lignocellulose for ethanol production:

To a larger extent, locally/domestically and provide security of supply. Generate low net greenhouse gas emission, reducing environmental
impacts, particularly climate change.
Also provide employment in rural areas. Greater avoidance of conicts with land use for food and feed production.
A much greater displacement of fossil energy per litre of fuel, due to

nearly completely biomass-powered system.
Much lower net well-to-wheels greenhouse gas emissions than with

grain-to-ethanol processes powered primarily by fossil energy.
The alternate energy sources will play a growing role and biofuels, mainly ethanol, are expected to grow fairly rapidly, reaching about 2% of total liquid supplies by 2030. The major drivers for ethanol fuel has been the: Cause of energy security
Slower potential for global warming and
Converting waste to energy

There are three main types of feedstocks used for ethanol production:
step of sucrose glucose or fructose is fermented into ethanol and CO2 by zymase enzyme also present in the yeast. Sucrose comes mainly from sugarcane and sugar beet. It may be sweet
Anand Kumar,
is a Chemical Engineer and after a brief stint of teaching, joined India Oil in 1974. He has undergone specialized training in Petroleum Refining Engineering from IIP and Renery Planning and Economics from Oxford Petroleum School, besides having attended management development pro-
grammes at MDI and IIM-A and business school in Europe and USA. He has a rich experience of 30 years, in various areas of oil rening viz Process Engineering, Projects, Supply Chain Management and Human Potential Management and has served at all major reneries of Indian Oil including Port Harcourt Renery of NNPC, Nigeria, where he left behind a distinct mark in commissioning and operating the renery and setting up related
system training and improving of Renery protability. An Environmentalist to the core, he developed one of the countrys best ECO-PARK at Barauni, which became an important bird spot and he is also credited with the rst experimentation of biodegradation of menacing oily sludge process. Currently he is Director (R&D), IndianOil Corporation Ltd. He is an active member of many forums, associations and professional bodies.
Things not understood are best admired
J U N E 2 008 39 39

sorghum also. Worldwide bioethanol fuel (>60%) comes from sugarcane juice. Being advantaged for sugarcane production Brazil exhibits the lowest production costs of bio-ethanol fuel. Starch from corn, wheat, rice, potatoes, cassava, sweet potatoes etc is converted to ethanol by a hydrolysis of starch (-glucose polymer) with glucoamylose enzyme into glucose units and then fermentation process.
Figure-1: Cellulose Structure
CH2OH H CH2OH H CH2OH H CH2OH H CH2OH H CH2OH H OH H O O H H H OH OH H H H H OH O O OH H H H H OH O O OH H H H H OH O O OH H H H H OH
CH2OH O H H H HO OH OH H H OH
O O
OH H
OH
glucose
Food verses Fuel

On the earth there is limited arable land and grain reserves have been limiting. There is typically a 30 day supply of wheat in storage at any given time. When supply is 33 days, it is considered a glut and prices drop; at 27 days the prices skyrocket (Gressel, 2008). The aggressive diversion of grains (mainly sugarcane, maize, wheat, rice and oil seeds etc.,) for biofuel has had a domino effect, leading to doubling of food prices. Hence, a dramatic increase in ethanol production using the current grain based technology may not be practical because crop production for ethanol will compete for the limited agricultural land needed for food and feed production. Thus to overcome the bioethical issue of burning grain for fuel to run automobiles at cost of undernourished people, a potential source for ethanol production is to utilize lignocellulosic materials such
as crop residues, grasses, sawdust, wood chips, solid animal waste and industrial wastes.
Energy crops: The energy crops

group includes herbaceous energy crops, woody energy crops, industrial crops, agricultural crops and aquatic crops. Agricultural residues and waste: Agricultural waste mainly includes crop waste remained after harvesting and processing of crop and animal waste. Forestry waste and residues: In this group mill wood waste, logging residues, trees and shrub residues are the major wastes. Industrial and municipal waste: Municipal solid waste (MSW), sewage sludge and industry wastes.
Lignocellulosic Biomass
Ameliorating the food verses fuel conflict
Lignocellulosic biomass typically refers to organic material such as wood chips, corn stalks, switch grass, straw, animal waste and food-processing byproducts etc., is the most abundant renewable biological resource on earth. It contributes to around 12% of todays world primary energy supply, while in many countries its contribution ranges from 40% to 50% (Demirbas, 2006). Biomass comes in many different types, which may be grouped into four main categories:
Indias Biomass Potential

In India, agricultural, urban and industrial residue is present in huge amount and increasing day by day, which could be utilized for ethanol production and improve upon disposal problem of wastes and to make clean environment (Pachauri and Sridharan, 1998; Ravindranath et al., 2005). Straw, a low-density residue, is the dominant residue. Rice husk, a byproduct of rice milling, accounts for 20% of paddy. Unlike the cereals, crops such as red gram, cotton, rapeseed, mustard, mulberry and plantation crops produce woody (ligneous) residues. Industrial wheat bran usually accounts for 1419% of the grain and comprises the outer coverings, the aleurone layer and the remnants of the starchy endosperm and has the potential to serve as low cost feedstock to increase the production of fuel ethanol (Palmarola-Adrados et al., 2005). The dominant residues are those of rice, wheat, sugarcane and
Table-1: Composition of common agricultural residues and wastes
Agricultural residue Hardwood stem Softwood stem Nut shells Corn cobs Grasses Wheat straw Rice straw Leaves Sorted refuse Cotton seed hairs Coastal Bermuda grass Switch grass Solid cattle manure Swine waste Primary wastewater solids Paper Newspaper Waste papers from chemical pulps
Cellulose (%) 4050 4550 2530 45 2540 3340 40 1520 60 8090 25 3050 1.64.7 6.0 815 8599 4055 6070
Hemicellulose (%) 2440 2535 2530 35 3550 2025 18 8085 20 520 35.7 1040 1.43.3 28 NA 0 2540 1020
Lignin (%) 1825 2535 3040 15 1030 1520 5.5 0 20 0 6.4 520 2.75.7 2429 015 1830 510
Kaur et al.
Source: Boopathy (1998), Cheung and Anderson (1997), Dewes and Hunsche (1998), (1998), McKendry (2002) and Reshamwala et al. (1995).
40 J U N E 2008
Laughter is a tranquilizer with no side effect Arnold Glasow

Figure-2: Structure of hemicellulose
H H H OH OH H OH O H OH OH H H H H H H HO OH H OH HO OH H H OH CH2OH CH2OH O H HO H O H OH H OH CH2OH O H OH H
Ethanol from lignocellulosic biomass

Composition of lignocellulosic biomass
Lignocellulosic biomass is composed of cellulose, hemicellulose and lignin and a remaining smaller part (extractives, acids, salts and minerals).. The carbohydrate polymers (cellulose and hemicelluloses) are tightly bound to the lignin, by hydrogen and covalent bonds. Typically, biomass contains 40% to 60% cellulose, 20% to 40% hemicellulose, and 10% to 25% lignin. The contents of cellulose, hemicellulose and lignin in common agricultural residues and wastes are presented in Table-1. Cellulose is a very large polymer molecule composed of many hundreds or thousands of glucose molecules (polysaccharide). The molecular linkages in cellulose form linear chains that are rigid, highly stable, and resistant to chemical attack. Hemicellulose consists of short, highly branched, chains of sugars. It contains ve-carbon sugars (usually Dxylose and L-arabinose) and six carbon sugars (D-galactose, D-glucose and D-mannose) and uronic acid. Hemicellulose is amorphous and relatively easy to hydrolyze to its constituent sugars. When hydrolyzed, the hemicellulose from hardwoods releases products high in xylose (a ve-carbon sugar). The hemicellulose contained in softwoods, by contrast, yields more six-carbon sugars. There is more experience for fermenting six-carbon sugars than the ve-carbon sugars, but both are valuable fermentation feedstocks, especially with recent advances in fermenting ve-carbon sugars. Lignin is a large, cross-linked, macromolecule having molecular masses in excess of 10,000u. It is relatively hydrophobic and aromatic in nature. Different types of lignin have been described depending on the means of isolation. Lignin is a polymer constructed of non-carbohydrate, alcohol units that are not fermented, but must be separated from the cellulose and hemicellulose by chemical and other means. Lignocellulose materials vary in their proportions of cellulose, hemicellulose, and lignin.
Xylose
O O OH
Arabinofuranose
O O R O
Mannofuranose
Galactose
O OH O OH O OCH3 HO O OH
O O
OH
OH
O R COCH3
COOH
Figure-3: Lignin monomeric structure
3 4 5 C
1 C
6 R1= H R2= H H R1= H R2= OCH3 G R1= OCH3 R2= OCH3 S
R2 OH
R1
cotton accounting for 66% of the total residue production. Sugarcane and cotton residue production is 110 and 50 Mt, respectively. Crop residues, which are used as fodder, may not be available as feedstock for energy. The total
potential of non-fodder crop residues available for energy is estimated to be 450 MMT for 2010. Only the woody (ligneous) crop residues, rice husk and bagasse are considered for energy production (Ravindranath et al., 2005).
Figure- 4: A schematic view lignocellulosic biomass and pretreatment (Hsu et. al., 1980)
Greater the self-discipline, less is theimpose discipline Jawaharlal Nehru
J U N E 2 008 41 41

Table-2: Characteristics of selected pretreatment processes
Pre-treatment process Steam Explosion
Main Principle Partial hydrolysis and solubilization of hemicellulose, redistribution of lignin on fiber surfaces
Advantages Provision for Chemical recycling, Less waste generation Low energy inputs. Effective for hardwood.
Limitations Production of large number of inhibitors. Lignin and carbohydrate matrix is not completely broken down, generation of degradation products. High cost involved and produced low-value lignin Not very effective for biomass with high lignin content No/less scope for Chemical recycling, High cost involved Production of large number of inhibitors pH neutralization is necessary. No/less scope for Chemical recycling Waste generation High cost involved Fermentable sugars produced is less Moderate cost involved No/less scope for Chemical recycling, High cost involved Enzyme loading & recoveries of solvent and hemicellulose remain issue
Ammonia fiber explosion (AFEX)
Cleavage of lignin and partial Improves saccharification of depolymerisation of cellulose and various herbaceous crops, hemicellulose grasses and other wastes. Less inhibitors Less waste generation Partial hydrolysis and solubilization of hemicellulose, redistribution of lignin on fiber surfaces Fermentable sugars produced very high
Dilute acid
Wet Oxidation
Removal and partial degradation of lignin, solubilisation and oxidation of some hemicelluloses Removal of lignin and some hemicelluloses
Scope for Chemical recycling Less Inhibitors Fermentable sugars produced very high Less inhibitors Less Waste generated Produce lignin of high quality.
Organosolvents
The combination of hemicellulose and lignin provides a protective sheath around the cellulose, which must be modied or removed before efcient hydrolysis of cellulose can occur, and the crystalline structure of cellulose makes it highly insoluble and resistant to attack. Lignin is the most refractory component of biomass and poses difculties in pre-treatment of biomass conversion processes.
are important for comparison with conventional and established sugar or starch based processes: Efcient depolymerisation of cellulose and hemicellulose Efcient fermentation of hexose and pentose sugars Process integration for reduced energy demand Cost efcient use of lignin. All the conversion schemes involve following basic steps: Feedstock harvest, trans port and storage. Pretreatment of lignocellulosic biomass. Enzymatic hydrolysis of cellulose in the lignocellulosic materials to fermentable reducing sugars.
Fermentation of sugars into ethanol.
Downstream processing of ethanol.
Pre-treatment
Most of the conversion schemes rely on combination of chemical and enzymatic treatments. The basic purpose of pretreatment is to reduce recalcitrance by depolymerizing and solubilizing the hemicellulose, which can be further hydrolysed or fermented. Table 2 summarizes the advantages and limitations of selected pre-treatment processes. The most commonly used methods are steam explosion and dilute acid pre-hydrolysis, which are followed by enzymatic hydrolysis. After pre-treatment, solid suspension is subjected to hydrolysis to release glucose sugars from crystalline cellulose. The reaction is catalysed by dilute acid, concentrated acid, or enzymes (cellulase). Hydrolysis with-
Conversion Technologies: Status

Several schemes for conversion of lignocellulosic biomass to sugars and then ethanol have been demonstrated in laboratory and pilot scale (HahnHagerdal et al 2006). But regardless of which one is chosen, following issues
Table-3: Comparison of process conditions and performances of three cellulose hydrolysis processes
Consumable Dilute acid Concentrated acid Enzymatic

42 J U N E 2008
< 1% H2SO4 70-30% H2SO4 Cellulase
Temperature (oC) 215 40 70
Time 3 min 2-6 h 1.5 days
Glucose Available yield 50-70% Yes 90% Yes 75% - 95% Now - 2010
Carve your name on hearts and not on marble

out proceeding pre-treatment yields typically <20%, whereas yields after pre-treatment often exceed 90%. The typical process conditions and performance of these hydrolysis approaches are summarized in Table -3. The dilute acid process has a low sugar yield (5070% of the theoretical maximum). The enzymatic hydrolysis has currently high yields (7585%) and improvements are still projected (8595%). Acid hydrolysis is only applied in the two-stage acid processes, following acid pre-treatment. Both dilute and concentrated versions occur. The dilute acid process is the oldest technology for converting cellulose biomass to ethanol. If the reaction would continue, the sugars produced would convert into other chemicals typically furfural. The sugar degradation not only reduces the sugar yield, but the furfural and other by-products can also inhibit the fermentation process. Therefore, the rst stage is conducted under mild process conditions (e.g., 0.7% sulphuric acid, 190 oC) to recover the 5- carbon sugars, while in the second stage only the remaining solids with the more resistant cellulose undergo harsher conditions (215 oC, but a milder 0.4% acid) to recover the 6-carbon sugars. Both stages have a 3-min residence time. The enzymatic hydrolysis is accomplished by cellulase enzyme. The cellulase enzyme is a complex mix of enzymes that work together synergistically to attack typical parts of the cellulose bre and. Effective cellulose hydrolysis requires several different kinds of cellulases working synergically. The enzymatic hydrolysis has several advantages: Very mild process conditions give potentially high yields, Maintenance costs are low compared to acid or alkaline hydrolysis (no corrosion problem). The process is compatible with many pre-treatment options, Enzymes can be recovered and recycled, so that the enzyme concentration can be higher against lower enzyme cost, although the enzyme quality decreases. In the past few years, new cellulases and hemicellulases from both bacteria and fungal sources have been isolated. Signicant progress has been made in the cost of cellulases, particularly the non-complexed cellulases. Cellulases from the aerobic fungus Trichoderma and Aspergillus are the most commonly used cellulases in the lab and pilotscale bioethanol production. A greater than 10-fold cost reduction for T. reesei cellulases was recently reported (Greer, 2005; Moreira, 2005). Cost reduction was achieved by combination of enzyme engineering and fermentation process developmen. ferment pentoses, but are inhibited already at low sugar and ethanol concentrations. In addition, the ethanolic fermentation occurs with considerable by-product formation, which reduces the ethanol yield (Desai, et al 2004). Natural xylose-fermenting yeast, notably Pichia stipitis CBS 6054, ferment xylose to ethanol with reasonable yield and productivity; however, these yeast strains are inhibited by compounds generated during pretreatment and hydrolysis of the lignocellulose material (Hahn-Hagerdal, 1994). Filamentous fungi tolerate inhibitors but are too slow for a competitive industrial process. Therefore, efforts have predominantly been made to obtain recombinant strains of bacteria and yeast able to meet the requirements of industrial lignocellulose fermentation. Some of the commonly used genetically engineered microbes for lignocellulosic ethanol fermentation are Escherichia coli Klebsiella oxytoca, Pichia stipitis and Zymomonas mobilis.
Fermentation
The sugars from the pretreatment and enzymatic hydrolysis steps are fermented by bacteria, yeast or lamentous fungi, enzymatic hydrolysis and fermentation can be performed in combination, the process known as simultaneous saccharication and fermentation (SSF). The fermentation of xylose released from pre-hydrolysis process can be carried out in separate vessel or in SSF reactor using genetically modified strain from the bacterium Zymomanas mobilis that can convert both glucose and xylose. The latter method is named simultaneous saccharication and co-fermentation (SSCF). Compared to the sequential saccharification and fermentation process, SSCF exhibits several advantages like low requirement of enzymes, shorter process time and cost reduction due to economy in fermentation reactor. Contrary to sucrose and starch-based ethanol production, lignocellulosebased production is a mixed-sugar fermentation in the presence of inhibiting compounds low molecular weight organic acids, furan derivatives, phenolics and inorganic compounds released and formed during pretreatment and/or hydrolysis of the raw material. Lignocellulosic raw materials, in particular hardwood and agricultural raw materials contain 5 >20% of the pentose sugars xylose and arabinose, which are not fermented to ethanol by the most commonly used industrial fermentation microorganism, the yeast Saccharomyces cerevisiae. Anaerobic bacteria
Downstream processing of ethanol

After the fermentation of pretreated biomass the downstream process involves recovery of ethanol from the fermentation broth. The most common method employed for the recovery of ethanol from fermentation liquid is distillation process, rectication and dehydration. Since, distillation process is energy consuming thereby, increase the cost of downstream processing. Beside this process solid sorption (e. g., commercially available divinyl benzene cross-linked polystyrene in bead form, molecular sieve with hydrophobic properties) and pervaporation are used to recover the ethanol from fermentation broth.
Challenges
Although, in the last three decades signicant R&D advancements have been made in the area of lignocellulosic ethanol production but no commercial plant exists. A key challenge to commercializing production of fuels and chemicals from cellulosic biomass is to reduce processing costs enough to achieve attractive goals for investors. Economic analyses point out that the greatest fraction of projected cost almost 40%
J U N E 2 008 43 43
When I become dear to GOD, I have touched the goal of fortune

is associated with pre-treatment, hydrolysis and enzyme. Pre-treatment is alone responsible for 8% of this cost. Therefore, drastic improvement in following areas are needed to realize the goal of commercialization: Developing fast growing biomass with minimized external inputs such as water, fertilizers and pesticides which can be easily processed. Pretreatment is among the most costly steps and has a major inuence on the cost of both prior (e.g., size reduction) and subsequent (e.g., enzymatic hydrolysis and fermentation) operations. Better pretreatment can reduce use of expensive enzymes. Thus, more attention must be given to gaining insight into interactions among these operations and applying that insight to advance biomass conversion technologies that reduce costs. In addition, although several pretreatments are promising, their relative attributes differ, but comparisons have been difcult due to differences in research methodology and substrate use. Improving the understanding of differences among pretreatment technologies and the effect of each pretreatment on other operations can facilitate selection, reduce commercialization risk and suggest opportunities for step change improvements. Cellulases are relatively costly enzymes, and a signicant reduction in cost will be important for their commercial use in lignocellulosic ethanol. Cellulase-based strategies that will make the processing more economical include: increasing commercial enzyme volumetric productivity, producing enzymes using elevated temperature and at a certain pH, and higher tolerance to end-product inhibition. Overcoming the recalcitrance of cellulosic biomass to utilize all sugars present in the feedstock (i.e. converting cellulosic biomass into reactive intermediates). Product diversification to value recovery from non-carbohydrate feedstock fractions (i.e. converting reactive intermediates into useful products. All the known xylose-fermenting organisms possess some drawbacks, among them low ethanol-production rate and low yield are the most important parameters. aged farms. Biol Agric Hortic;16: 25168. Greer, D., 2005. Spinning straw into fuel. Biocycle, 46: 61-65 Gressel J., 2008, Transgenics are imperative for biofuel crops, Plant Science 174,246-263 Hahn-Hagerdal, B. et al. 1994. An interlaboratory comparison of the performance of ethanol-producing microorganisms in a xylose-rich acid hydrolysate. Appl. Microbiol. Biotechnol., 41: 6272 Hahn-Hagerdal B., Galbe, M., Gorwa-Grauslund, M.F., Liden, G. and Zacchi, G. 2006. Bio-ethanol the fuel of tomorrowfrom the residues of today. Trends in Biotechnol., 24(2): 549-556. Kaur P.P., Arneja J.S. and Singh J. 1998. Enzymatic hydrolysis of rice straw by crude cellulose from Trichoderma reesei. Bioresour Technol; 66: 2679. McKendry P. 2002. Energy production from biomass (part I): overview of biomass. Biores. Technol., 83: 3746. Moreira N. 2005. Growing expectations: new technology could turn fuel into a bump crop. Sci News Online 2005; 168(14): 20924. Pachauri RK and Sridharan PV. 1998. Solid wastes. In looking back to think ahead. New Delhi: Tata Energy Research Institute; pp. 245265. Hsu, T.A., Ladisch, M.R., Tsao, G.T. 1980. Alcohol from cellulose. Chemical Technology 10 (5), 315319. Ravindranath N.H., Somashekar H.I., Nagaraja M.S., Sudha P., Sangeetha G and Bhattacharya S.C. 2005. Assessment of sustainable non-plantation biomass resources potential for energy in India. Biomass Bioenergy, 29: 17890. Reshamwala S, Shawky BT, Dale BE. 1995. Ethanol production from enzymatic hydrolysis of AFEX-treated coastal Bermuda grass and switch grass. Appl Biochem Biotechnol., 51/52:4355.
6. 7.
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Concluding remarks
Lignocellulosic ethanol represents a sustainable solution to offset the increasing cost and dwindling supply of crude oil. In the last three decades signicant R&D efforts have been made for biological processing for ethanol production to reap the benets this abundantly available renewable resource. In order to overcome the challenges of commercialization sincere efforts in the improvement of various process steps like pre-treatment, cellulase enzyme improvement and cost reduction, process integration and co processing of lignin for value added products are needed. With these concerted efforts, full potential of lignocellulosic ethanol may be realized in 10 to 15 years.
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References
1. Bhoopathy, R. 1998. Biological treatment of swinewaste using anaerobic bafed reactors. Bioresour Technol., 64:16. Cheung S.W. and Anderson B.C. 1997. Laboratory investigation of ethanol production from municipal primary wastewater. Bioresour Technol; 59: 8196. Demirbas, M. F. 2006. Current technologies for biomass conversion into chemicals and fuel. Energy Source, Part A, 28: 1181-1188. Desai S.G., Guerinot M. L. and Lynd L. R. 2004. Cloning of the L-lactate dehydrogenase gene and elimination of lactic acid production via gene knockout in Thermoanaerobacterium saccharolyticum JW/SL-YS485. Appl. Microbiol. Biotechnol. 65, 600605. Dewes T. and Hunsche E. 1998. Composition and microbial degradability in the soil of farmyard manure from ecologically man-
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44 J U N E 2008
Everything is perfect, with much room for improvement Zen Master
Bacterial biosurfactant in enhancing solubility of petroleum hydrocarbons

B K Konwar and N K Bordoloi
ONGC Centre for Petroleum Biotechnology, Department of Molecular Biology and Biotechnology, Tezpur University, Tezpur-784028, Assam, India
B K Konwar, obtained DIC in Microbiology from Imperial College, London and Ph D in Biotechnology from University of London in 1992. He started the career as a Lecturer in Assam Agricultural University, Jorhat from 1984. He became Asstt. Professor in 1986 and Associate Professor in 1994. In 1995, he joined Tocklai Experimental Station, TRA, Jorhat as a Sr. Scientist (Biotech) and Head, Dept of Botany. In 2002, he joined as Professor & Head, Dept of Mol Biology & Biotechnology, Tezpur
University (Central), Assam. He was also the Head, ONGC-Centre for Petroleum Biotechnology since 2002 to 2008. In 2008, Prof. Konwar became the Dean, School of Science & Technology of the University. He carried out 11 research projects funded by agencies like DBT, Tea Board, ICAR, CSIR, ONGC and NMPB. He published more than 90 research papers in national/international journals and conference/seminar proceedings and wrote extensively in news papers and magazines on popular science and other topics. He published a historical book in Assamese.
io-surfactant exerts inuence on inter-faces in both aqueous solutions and hydrocarbon mixtures. It can make hydrocarbon complexes more mobile with the potential use in enhanced oil recovery, pumping of crude oil as well as in bioremediation of crude oil contaminant. In the culture medium supplemented with the poly-cyclic aromatic hydrocarbons like phenanthrene, pyrene and ourene, there was a gradual decrease in their concentration with corresponding increase in biomass and protein. The medium having the combined application of ourene and phenanthrene caused better biosurfactant production by Pseudomonas aeruginosa strains MTCC7815 and MTCC7814. Bio-surfactants produced by the strains MTCC7815 and MTCC7812 exhibited more solubilization of pyrene; MTCC8165 caused three times higher solubilization of phenanthrene, whereas the biosurfactant of MTCC7812 and MTCC8163 caused more solubilization of ourene. Bio-surfactants secreted by the strains MTCC7815 and MTCC8163 were lipopeptide in nature, whereas, those secreted by MTCC7812, MTCC8165 and MTCC7814 were complex mixtures of
lipopeptides and glycoproteins. Further study is necessary to understand the microbial ecology and their application in bioremediation, pumping of crude oil and enhanced oil recovery through enhanced mobility caused by the biosurfactant induced reduction of surface tension (). Key words: Crude oil, mobility, bacteria, biosurfactant Polycyclic aromatic hydrocarbon, a major component of petroleum requires solubilization in aqueous phase through the addition of surfactants. Surfactant amendment may enhance the oil mobility and increase its availability, improving the biodegradation rates (Alexander, 1994; Laha and Luthy, 1992; Kim et al., 2000). Microbial biosurfactants can also exert some influence on interfaces in both aqueous solutions and hydrocarbon mixtures. These properties cause micro-emulsions in which micelle formation occurs where hydrocarbons can solubilize in water, or water in hydrocarbon (Banat, 1995; Das and Mukherjee, 2005 and Bordoloi and Konwar, 2008). The
structures of various biosurfactants are elaborately reviewed (Cooper et al., 1986). Generally biosurfactants are classified into five major groups viz glycolipids, phospholipids and fatty acids, lipopeptides (lipoprotein); polymeric biosurfactant and particulate biosurfactant. Biosurfactant production is generally associated with utilization of hydrocarbon by microbial community. At low concentrations, surfactants are soluble in water, and with the increasing concentration, they form micelles in solution. The concentration at which micelles begin to form is called the critical micelle concentration (CMC). Above the CMC, biosurfactants can solubilize petroleum hydrocarbons in soil-water systems, but some biosurfactants may increase the water solubility of hydrocarbon molecules below the CMC (Deshphande, 1999 and Bordoloi and Konwar, 2008). Therefore, biosurfactants may be useful in degradation of soil contaminating hydrocarbons. The aim of the present work was to evaluate biosurfactants and their effective concentration to enhance the biodegradation of petroleum hydrocarbons in a contaminated soil.
Materials and Methods

Biosurfactant producing Microorganisms
Biosurfactant producing five bacterial strains belonging to the species P. aeruginosa MTCC7815, MTCC7812, MTCC7814, MTCC8165 and MTCC8163 were isolated from petroleum contaminated soil samples collected from different oil elds of Assam and Assam-Arkan Basin and identied in collaboration with the IMTECH, Chandigarh. The bacterial strains were sub-cultured on nutrient agar or LB agar plates before use as inoculums.
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Table 1. Bacterial growth and yield of biosurfactant in pyrene and pyrene + phenanthrene containing media in 96 h of culture (Mean +S.D of 3 experiments)
Carbon source Bacterial isolates Pyrene + + + + + + + + + + Phenanthrene + + + + +
P. aeruginosa (MTCC7815) P. aeruginosa (MTCC7812) P. aeruginosa (MTCC7814) P. aeruginosa (MTCC8163) P. aeruginosa (MTCC8165)
After 48 h of growth Yield of Dry biomass biosurfactant (g.l-1) (g.l-1) 0.800.01 0.200.01 1.000.1 0.250.01 0.600.02 0.150.01 0.700.01 0.170.01 0.900.02 0.200.01 1.100.1 0.180.01 0.500.01 0.100.01 0.720.02 0.200.01 0.600.01 0.180.01 1.200.1 0.240.01
Media and microbial growth in the presence of PAHs

The mineral salt medium (MSM) was used for the culture of the bacterial strains. Polycyclic aromatic hydrocarbons (PAHs) dissolved in N, N-dimethylformamide (5% v/v) was taken in a sterile 250ml Erlenmeyer ask, shaken in an orbital shaking incubator at 200 rpm and 37oC before addition to the MSM to give a nal concentration of 200 mg.l-1 as described by Boonchan et al. (2000). Phenanthrene was used as the second or co-carbon source at a nal concentration of 100 mg.l-1. Replicated batch cultures were grown in 100 ml of mineral salt medium supplemented with either pyrene/ oueren/oueren or phenanthrene as the carbon source. All culture flaks were maintained in a rotary shaker incubator at 32oC, pH 7.0 and 200 rpm. Un-inoculated asks and those without PAHs were used as controls.
PAHs were purchased from MerckSchuchardt, Germany; acetone and HPLC grade hexane from Merck limited, Mumbai, India. Crude oil was collected from ONGC, Assam, India.
PAHs biodegradation
PAHs degradation by bacteria was determined by quantization the amount remained in the culture broth at different time intervals. The residual PAHs in the flasks were extracted with a mixture of chloroform and methanol (v/v 20:10) as described by Zhang et al. (2004). An aliquot of 1ml extracted sample was then filtered through a 0.4m pore sized filter and 20l of the filtrate was analyzed for PAHs content by high performance liquid chromatography (HPLC) on a Waters reverse-phase C18 Nova pak column (3.9 mm X 150 mm) by using isocratic elution with acetonitrile-water (Pickard et al., 1999). Flow rate was adjusted to 1.0ml/min and elution was monitored at 273, 250 and 253 nm. The decrease in the amount of pyrene, ourene and phenanthrene was estimated by measuring the peak area of UV absorbance at the said wave lengths, respectively and by comparing with the peak area
Determination of bacterial growth in the presence of PAHs

Bacterial growth by utilizing pyrene, flourene and phenanthrene were assessed by the bacterial protein concentration and the residual PAHs remained in the culture medium after 48 and 96h of culture following the method of Vila et al. (2001). Bacterial dry biomass was determined after extracting the residual PAH from the culture broth and pelleting of cells as done by Makkar and Cameotra (1998). The protein concentration was measured using the ask contents of duplicate cultures by a modication of the Lowry method (Daniels et al., 1994).
Table 2. Bacterial biomass and yield of biosurfactant in uorene and uorene + phenanthrene supplemented media in 96 h of culture (Mean +S.D of 3 experiments)
Carbon source Bacterial isolates Fluorene + + + + + + + + + + Phenantherne + + + + +
P. aeruginosa (MTCC7815) P. aeruginosa (MTCC7812) P. aeruginosa (MTCC7814) P. aeruginosa (MTCC8163) P. aeruginosa (MTCC8165)
46 J U N E 2008
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of the control asks. The concentration of pyren, ourene and phenanthrene was expressed as the mean and the standard deviation based on the results obtained with triplicate asks. and 1ml biosurfactant solution (0.5mg/ ml) were added. Tubes were capped and incubated in vertical position overnight at 32oC with shaking (200 rpm) in dark. Samples were ltered through 1.2m pore sized lters (Whatman), 2ml was removed in to a clean test tube to which 2.0ml hexane was added prior to extraction by vortexing for 2 min. The emulsion was centrifuged at 10,000 rpm for 10 min to separate the aqueous and hexane phases. PAHs and crude oil in the hexane extracts were measured spectrophotometrically at A 273, A 250, A253 and A254 nm and also using the calibration curve of PAHs and crude oil in hexane, the concentrations were determined. Control experiments were also run in parallel where no biosurfactant was added to PAHs and crude oil before extraction with hexane. by the bacterial isolates was conrmed by its removal from the medium with a corresponding increase in the bacterial protein. The concentration of phenanthrene decreased dramatically in the culture medium over the next 12 days. The bacterial strains MTCC7815, followed by MTCC7812 and MTCC7814 exhibited the maximum utilization of phenanthrene with reduction to 70, 85 and 87g, respectively from initial application of 180 g. In the case of pyrene supplemented medium, no significant growth was observed in the initial 24h period of culture. The strains MTCC7814, followed by MTCC8165 exhibited better utilization of pyrene with reduction to 89 and 93 g, respectively from the initial application of 180 g in 12 days of culture. In fluorene-supplemented medium, the strains MTCC7814, followed by MTCC7815 and MTCC8163 exhibited higher utilization in 12 days of culture with reduction of concentration to 89, 90 and 92 g, respectively from the initial application of 180 g .
Uptake of pyrene, flourene, phenanthren and crude oil by bacteria

Pyrene, fourene, phenanthrene and crude oil uptake by bacterial isolates was measured by spectrophotometric rate assay as described by Stringfellows and Aitken (1995). Briey 1X107 bacterial cells (nal volume of 3ml in 20mM phosphate buffer containing 150mM NaCl, pH 7.0) were placed in a 3.5 ml quartz cuvette in a Backman DU-530 Life Science UV/Vis Spectrophotometer (USA) and 60g of pyrene, ourene, phenanthrene and crude oil (in 10l of acetone) were injected in to the cuvette. A decrease concentration at A273, A250, A253 and A254 was measured from 0 sec to 60 min post addition of PAHs and crude oil. PAHs and crude oil uptake was also measured in the presence of suspension of killed cells. From a standard curve of representative PAHs and crude oil, the decrease concentration in PAHs and crude oil was calculated and results were expressed as g of PAHs and crude oil uptake by 1X107 bacterial cells. To study the bacterial uptake of solubilized PAHs and crude oil as mediated by biosurfactant, stock solutions of PAHs and crude oil (in acetone) were incubated overnight with biosurfactants (0.5mg/ml) from the respective bacterial isolates at 32oC. Aliquots of 60g of biosurfactant-solubilized PAHs and crude oil were injected in to the separate cuvettes containing 1X10 7 bacterial cells (nal volume of 3ml). PAHs and crude oil uptake measurement was done in the same manner as describe above.
Isolation of biosurfactant and determination of its surface-active properties

The crude biosurfactant from each of the bacterial strains was isolated following the method of Makkar and Cameotra (1998). Surface tension of the culture broth was determined using a Du-Nouy Tensiometer (Kruss 9KT Tensiometer, Kruss, Germany) at room temperature (25oC) using the ring correction mode of the instrument.
Biosurfactant production during microbial growth on PAHs

Observation on surface-active properties supported that all the isolates used in this study produced biosurfactants in pyrene or uorene-supplemented medium with or without the addition of phenanthrene. Results obtained are presented in Table 1 and 2. The yield of biosurfactant in the culture supernatant increased dramatically after 96h of culture. The bacterial isolates exhibited better biosurfactant yield of 0.23 0.5 g.l-1 in the medium supplemented with pyrene and phenanthrene as compared to the medium without phenanthrene (0.18 0.30 g.l -1). Concomitantly, the bacterial biomass of 0.7-1.2 g.l-1 increased to 0.7-1.4 g.l-1 after 96 h of culture. In the case of medium having the combined addition of ourene and phenanthrene caused better biosurfactant yield of 0.45 and 0.38 g.l-1 in the case the strains MTCC7815 and MTCC7814, respectively in the growth period of 96h. In uorene containing medium,
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Results
Growth of microbes using PAHs
All bacterial isolates used in the investigation were able to utilize PAHs as the sole source of carbon and energy. This was evident as there was a decrease in the concentration of phenanthrene, pyrene and fluorene in the medium supplemented with PAHs with a concomitant increase in the bacterial dry biomass and protein content with respect to time. The bacterial isolates were separately cultured in mineral salt medium supplemented with phenanthrene, pyrene and uorene for 12 days. Increase in protein concentration as the index for bacterial growth and utilization of the hydrocarbon component was estimated at an interval of 2 days. Data thus obtained are presented in Fig. 1, 2 and 3. The utilization of phenanthrene as the sole source of carbon and energy
PAHs and crude oil solubilization assay

PAHs and crude oil solubilization assay was carried out as described by Barkay et al. (1999). Aliquots of 60g of PAHs and crude oil (6mg/ml stock in hexane) were distributed in to glass test tubes and kept open inside a chemical fume hood to remove the solvent. Then 3ml assay buffer (20mM Tris-HCL, pH 7.0)
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Table 3. Reduction of crude oil, phenanthrene, pyrene, and uorene from the culture medium as acted upon by the bacterial isolates following the addition of biosurfactant (Mean +SD of 3 experiments)
Carbon sources
Bacterial strains of P. aeruginosa MTCC7815 MTCC7812
Uptake (g) in min Biosurfactant + + + + + + + + + + + + + + + + + + + + 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 15 6.80.2 36.90.1 1.60.04 8.80.03 4.50.1 42.80.1 3.90.1 34.11.0 4.40.4 10.70.7 7.90.2 17.10.02 9.10.1 21.40.3 16.50.4 14.30.4 21.10.13 15.70.4 7.30.1 42.60.5 16.00.15 18.30.5 5.80.3 5.50.4 9.20.2 14.10.4 1.00.01 8.80.1 7.90.7 20.40.2 2.40.2 5.10.8 0.50.05 11.40.8 130.2 21.90.3 4.30.2 18.70.1 4.10.0 16.30.1 30 10.000.30 40.210.06 2.540.21 11.370.31 7.870.47 44.790.84 5.210.07 35.280.22 8.730.05 18.640.28 10.580.16 18.320.07 9.690.15 42.000.65 23.500.49 25.140.05 22.340.09 28.120.21 11.300.23 33.010.11 15.020.13 27.800.13 8.070.03 20.910.22 20.320.09 21.450.21 3.400.14 11.830.27 14.350.14 20.980.19 4.910.46 9.120.22 6.910.17 24.270.32 14.140.07 48.260.26 10.600.21 20.360.0.19 6.190.26 16.060.07 45 10.240.02 40.310.02 4.400.18 11.450.06 9.050.10 45.920.10 8.380.58 35.280.02 9.000.14 19.600.37 12.300.10 19.470.52 11.230.05 43.120.10 23.710.08 25.220.06 22.390.11 28.120.18 10.950.23 33.260.18 15.840.30 35.120.09 8.260.08 26.420.35 20.800.13 21.450.13 3.600.16 15.330.08 14.870.09 21.350.12 5.940.10 10.170.52 15.870.05 24.360.10 14.520.08 49.040.06 11.300.11 13.800.23 6.700.18 16.690.30 60 10.650.14 40.310.02 4.490.07 11.530.77 10.20.08 45.920.71 10.240.08 35.280.26 9.140.11 20.310.52 12.570.16 20.550.13 11.720.10 43.870.79 23.710.06 25.050.17 22.440.13 28.370.54 10.950.14 33.840.20 15.680.17 41.700.32 8.370.04 26.970.09 21.770.14 21.540.05 4.150.04 15.670.17 15.640.17 21.710.09 8.270.16 11.230.13 16.170.10 24.450.79 14.750.06 49.560.17 11.650.33 24.490.54 6.700.14 17.010.20
Crude oil
MTCC7814 MTCC8163 MTCC8165 MTCC7815 MTCC7812
Phenanthrene
Pyrene
Fluorene
MTCC7814 MTCC8163 MTCC8165
devoid of phenanthrene the bacterial biomass increased from 0.6-1.2 g.l-1 in 48h of culture to a maximum of 1-1.5 g.l-1 in 96h.
Solubilization of PAHs and crude oil by biosurfactants

The effect of biosurfactants on the solubility of phenanthrene, pyrene, flourene (PAHs) and crude oil was determined by the test tube solubilization assay (Barkay et al., 1999) in the presence of biosurfactant at the
48 J U N E 2008
rate 500 g.ml-1. Data obtained are presented in Fig. 4. The solubility of PAHs and crude oil in the mineral salt medium was found to be higher due to the addition of biosurfactant as compared to the one without the addition of biosurfactant. The solubilization of PAHs in biosurfactant-supplemented medium occurred when the concentration of the biosurfactant exceeded the CMC value. However, biosurfactant from the strains MTCC7815 and MTCC7812 exhibited 41 and 26 g.ml-1, respectively more solubiliza-
tion of pyrene as compared to the control. In the case of crude oil, the biosurfactant from the strain MTCC8165 showed 20 g.ml -1 more solubilization as compared to the control. The biosurfactant of MTCC8165 displayed three times more solubilization of phenanthrene as compared to the biosurfactant of MTCC7812. On the other hand, the crude biosurfactants from MTCC7815, MTCC7814 and MTCC8163 displayed almost similar solubilization. The bio-
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Fig. 1. Utilization of phenanthrene by the bacterial strains (a) MTCC7815 (b) MTCC7812) (c) MTCC8163 (d) MTCC8165) and (e) MTCC7814 in phenanthrene containing medium at 30C and 200 rpm. [growth as an increase in cell protein in cultures ( ) and in controls( ); phenanthrene ( ) and controls ( )]
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respect to time. The utilization of phenanthrene as the sole source of carbon and energy by the bacterial isolates was conrmed by its removal from the medium, with a corresponding increase in the bacterial protein. The concentration of phenanthrene decreased dramatically in the culture medium over the next 12 days. The bacterial strains MTCC7815, followed by MTCC7812 and MTCC7814 exhibited the maximum utilization of phenanthrene reducing the content from that of the initial application of 180g (Fig. 1, 2 and 3). Non-actinomycetes bacteria such as P. aeruginosa, P. pudita and Flavobacterium species were reported to utilize pyrene, when supplemented with other forms of organic carbons (Trzesicka-Mlynarz et al., 1995). In the present investigation, the bacterial strains MTCC7814 and MTCC8165 exhibited better utilization of pyrene with increased biomass and protein production, and a concomitant reduction in pyrene content from the culture medium. The growth of the bacterial isolates at the expense of uorene as the sole source of carbon suggested higher utilization of uorene from the initial application. There were reports Pseudomonas species capable of degrading PAHs, but it failed to utilize them as the sole source of carbon and energy (Foght et al., 1988). Phylogenetic analysis revealed the existence of wide diversity among the biosurfactant-producing microbes suggesting biosurfactant production to be an important survival tool for the producing microbes and this has evolved to be an independent but a parallel process (Bodour et al., 2003). Biosurfactant producing bacteria are present in higher concentration in hydrocarbon-contaminated soils (Bodour and Maier, 2003,; Bordoloi and Konwar, 2008). In the present investigation, biosurfactant production by all ve bacterial strains increased significantly when the medium was supplemented with phenanthrene along with pyrene and uorene (Table 1 and 2). The yield of biosurfactant in the culture supernatant with acid precipitaJ U N E 2 008 49 49
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surfactant from MTCC7812, followed by MTCC8163 exhibited more solubilization of uorene with 24.4-24.5 g.ml-1.
Role of biosurfactants in culture media

Following the addition of biosurfactant of the respective bacterial isolates, the uptake of crude oil and its components like pyrene, uorene and phenanthrene by the cultured bacteria was assayed. Data obtained are presented in Table 3. The uptake of crude oil and its components increased signicantly in all bacterial cultures on addition of biosurfactant. The bacterial strain MTCC7814, followed by MTCC7815 and MTCC8163 showed the highest uptake of crude oil with 45.92, 40.31 and 36.28 g during the incubation period of 60min. In the case of biosurfactant-supplemented medium, MTCC7812 and MTCC8165 utilized 43.87 and 33.84 g of phenanthrene, respectively in 60min of culture. Similarly, MTCC7815 utilized 41.70 g pyrene from the medium while supplemented with the biosurfactant. The strain MTCC7814 exhibited the
highest uptake of ourene with 49.6 g in 60min culture. MTCC8163 and MTCC7812 exhibited comparatively higher uptake of ourene with 24.5 and 24.4 g, respectively. Uptake of crude oil and PAHs like pyrene, fluorene and phenanthrene was also measured in the presence of a suspension of heat killed bacterial cells. Heat killed bacterial cells were put in culture medium separately supplemented with biosurfactant isolated from the respective bacterial strain. Crude oil and PAHs uptake did not occur in the presence of the suspension of heat killed bacterial cells.
Discussion
Variation was observed in the utilization of phanathrene, pyrene, uorene (PAHs) and crude oil as the sole source of carbon and energy by ve strains of P. aeruginosa. There was a decrease in the content of PAHs in the media with a concomitant increase in the bacterial dry biomass and protein with
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Protein (ug/ml)
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Table 4. Reduction of crude oil, phenanthrene, pyrene, and uorene from the culture medium as acted upon by the heat killed bacterial isolates following the addition of biosurfactant
Carbon sources Crude oil Phenanthrene Pyrene Fluorene
Heat killed P.aeruginosa Strains MTCC7815 MTCC7812 MTCC8163 MTCC8165
Uptake (g) Biosurfactant + + + + 0 min 0 0 0 0 15 min 0 0 0 0 30 min 0 0 0 0 45 min 0 0 0 0 60 min 0 0 0 0
tion increased dramatically after 96h of culture. The bacterial isolates exhibited better biosurfactant yield in medium having combined application of pyrene and phenanthrene, as compared to phenanthrene alone. Concomitantly, the bacterial biomass increased. This result might be viewed in the context of increased rate of co-metabolism of pyrene in the presence of phenanthrene (McKenna, 1977 and Cerniglia, 1984). Stringfellow et al. (1995) observed that Pseudomonas saccharophila p-15 could degrade pyrene on being induced by either phenanthrene or salicylate. In media having the combined addition of ourene and phenanthrene caused better biosurfactant yield (0.45 and
protein (ug/ml)
pyrene (ug/ml)
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10 8
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10
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protein (ug/ml)
Pyrene(ug/ml)
the utilization of available hydrophobic substrates by the producing bacteria from their natural habitat, presumably by increasing the surface area of substrates and increasing their apparent solubility (Ron and Rosenberg, 2001). Therefore, use of biosurfactants has been reported as a mechanism to enhance the bioavailibility of hydrophobic pollutants and PAHs for microbial degradation (Thiem, 1994). Low molecular weight biosurfactants like lipopeptides having low critical micelle concentrations increased the apparent solubility of hydrocarbons by incorporating them in to the hydrophobic cavities of micelles (Miller and Zhang, Production of biosurfactant is related to 1997). On the other hand, alasan, a high molecular weight bioemulsier Fig. 2. Utilization of pyrene by the bacterial strains (a) MTCC7815 (b) MTCC7812) complex produced by Acinetobacter (c) MTCC8163 (d) MTCC8165 and (e) MTCC7814 in phenanthrene containing medium radioresistens KA 53 enhanced the at 30C and 200 rpm. [growth as an increase in cell protein in cultures ( ) and in controls ( ); aqueous solubility of PAHs by a phenanthrene ( ) and controls ( )] physical interaction most likely of a hydrophobic nature and increases the biodegradation rate of PAHs (Barkay et al., 1999).
250 16 14 12
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0.38 g.l-1) in the case of the strains MTCC7815 and MTCC7814, respectively during the growth period of 96h. In the same medium, the bacterial biomass increased from 0.6 1.2 g.l-1 at 48h of inoculation to a maximum of 1-1.5 g.l-1 at 96h of culture. Bouchez et al. (1995) reported that addition of uorene as a co-substrate could increase utilization of phenanthrene. Bouchez et al. (1995) also reported that phenanthrene might be a poor inducer of its own degradation, but uorene could enhance phenanthrene biodegradation, possibly by a positive analog effect on enzyme induction.
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In this investigation, biosurfactant of the bacterial strains belonging to P. aeruginosa MTCC7815 and MTCC7812 having the concentration of 0.5mg.ml-1 exhibited 41 and 26g.ml-1 solubilization of pyrene. Subsequently, the apparent solubility of pyrene was enhanced by factors 5-7 resulting in its higher uptake and metabolism as compared to non-solubilized pyrene. The difference in pyrene solubilization by the biosurfactants from different bacterial strains in this investigation might be related to the chemical nature as well as surface properties of the biosurfactants. The biosurfactants secreted by MTCC7815 and MTCC8163 were lipopeptide in nature, whereas those secreted by MTCC7812, MTCC8165 and MTCC7814 were complex mixtures of lipopeptides and glycoproteins.

Higher solubilization of pyrene by the biosurfactant of MTCC7815 and MTCC7812 reinforced the hypothesis that variation in biosurfactant isoforms between these two isolates might result in a large variation of the emulsification property and specicity of biosurfactants. It may be concluded that higher pyrene solubilization effect of biosurfactant from MTCC7815 dramatically enhanced the metabolism of pyrene that sustained the growth of this bacterial isolate in pyrene; otherwise it would not be able to grow on pyrene. Similar trend was observed in the case of uorene solubilization by the biosurfactant of MTCC7812 as compared to MTCC8163. Further studies to understand the microbial ecology leading to PAHs degradation is necessary.
Fig. 3. Utilization of uorene by the bacterial strains (a) MTCC7815 (b) MTCC7812) (c) MTCC8163 (d) MTCC8165 and (e) MTCC7814 in phenanthrene containing medium at 30C and 200 rpm. [growth as an increase in cell protein in cultures ( ) and in controls ( ); phenanthrene ( ) and controls ( )]
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We gratefully acknowledge the receipt a generous project grant from the Oil and Natural Gas Corporation, India. We would also like to thank the university authority to allow us to participate in the seminar organized by the Petrotech Society of India.
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References
Alexander, M. 1994. Biodegradation and Bioremediation. Academic Press, New York. Banat, I. M. 1995. Biosurfactants
production and possible uses in microbial enhanced oil recovery and oil pollution remediation: A review. Bioresour. Technol. 51: 1-12. Barkay, T., Navon-Venezia, S.,
Fig. 4. Solubilization of PAHs and crude oil by the bacterial biosurfactants (Mean +S.D)
45 40
PAHs and Crude oil solubilization (ug/ml)
Phenanthrene 35 30 25 20 15 10 5 0 control P.aeruginosa P. aeruginosa P. aeruginosa P.aeruginosa P.aeruginosa (MTCC7815) (MTCC7812) (MTCC7814) (MTCC 8163) (MTCC 8165) Pyrene Flourene Crude oil
Biosurfactants of bacterial isolates
Ron, E.Z. and Rosenberg, E. 1999. Enhancement of solubilization and biodegradation of polyaromatic hydrocarbons by the bioemulsier Alasan. Appl. Environ. Microbiol. 65: 2697-2702. Bodour, A.A., Drees, K.P. and Maier, R.M. 2003. Distribution of biosurfactant-producing bacteria in undisturbed and contaminated arid southwestern soils. Appl. Environ. Microbiol. 69: 3280-3287. Boonchan, S., Britz, M. and Stanley, G.A. 2000. Degradation and mineralization of high molecular weight polycyclic aromatic hydrocarbons by dened fungal-bacterial cocultures. Appl. Environ. Microbiol. 66, 1007-1019. Bouchez, M., Blanchet, D., Besnainou,B., and Vandecasteele, J.-P. 1995. Substrate availability in phenanthrene biodegradation: transfer mechanism and inuence on metabolism. Appl. Microbiol. Biotechnol. 43: 952 960. Cerniglia, C. E. 1984. Microbial metabolism of polycyclic aromatic
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Let hundreds like me perish, but let truth prevail Mahatma Gandhi
Protein (ug/ml)
Acknowledgment
180 160
Protein (ug/ml)
Protein (ug/ml)

hydrocarbons. Adv. Appl. Microbiol. 30: 31-71. Cerniglia, C. E. 1992. Biodegradation of polycyclic aromatic hydrocarbons. Biodegradation. 3:351-368. Cooper, D.G. 1986. Biosurfactants. Microbiol. Sci. 3: 145-149. Daniels, L., Handson, R.S. and Phillips, J.A. 1994. Chemicals analysis. Pp. 512. In: Gerhardt, A.P., Murray, R.G.E., Wood, W.A. and Krieg, N.R. (ed). Methods for general and molecular bacteriology. ASM Press, Washington, D.C. Daniel, W.W. 2000. In: Biostatistics: A foundation for analysis in the health sciences.7th ed. pp 166-167. John Wiley and Sons, Inc, New York, Foght, J.M. and Westlake, D.W.S. 1988. Degradation of polycyclic aromatic hydrocarbons and aromatic heterocyctles of Pseudomonas species. Can. J. Microbiol. 34: 1135-1141. Kanaly, R. A. and Harayama, S. 2000. Biodegradation of high-molecular weight polycyclic aromatic hydrocarbons by bacteria. J. Bacteriol. 182: 2059-2067. Kim, H. S., Lim, E. J., Lee, S. O., Lee, J. D. and Lee, T.H. 2000. Purication and characterization of biosurfactants from Nocardia sp. L-417. Biotechnol. Appl. Biochem. 31: 249253.
Makkar, R. S. and Cameotra, S.S.

1998. Production of biosurfactant at mesophilic and thermophilic conditions by a strain of Bacillus subtis. J. Ind. Microbiol. Biotechnol. 20: 48-52. McKenna, E. J. 1977. In Biodegradation of polynuclear Aromatic Hydrocarbon Pollutants by soil and water Microorganisms. 70th Annu. Mtg. Am. Inst. Chem. Eng., New York. Miller, R.M. and Zhang, Y. 1997. Measurment of biosurfactant-enhanced solubilization and biodegradation of hydrocarbons. In: Sheehan, D. (Ed.), Methods in Biotechnology, vol.2.Humana Press, Totowa, pp 59-66. Pickard, M. A., Roman, R., Tinoco, R. and Vazquez-Duhalt, R. 1999. Polycyclic aromatic hydrocarbon metabolism by white rot fungi and oxidation by Coriolopsis gallica UAMH 8260 laccase. Appl. Environ. Microbiol. 65: 3805-3809. Ron, E. Z. and Rosenberg, E. 2001. Natural roles of biosurfactants. Environ. Microbiol. 3: 229-236. Stringfellow, W. T. and Aitken, M. D. 1995. Competitive metabolism of naphthalene, methylnaphthalenes and fluorene by phenanthrenedegrading Pseudomonads. Appl. Environ. Microbiol. 61: 357-362.
Tiehm, A. 1994. Degradation of

polycyclic aromatic hydrocarbons in the presence of synthetic surfactants. Appl. Environ. Microbiol. 60: 258-263. Trzesicka-Mlynarz, D. and Ward, O. P. 1995. Degradation of polycyclic aromatic hydrocarbons (PAHs) by a mixed culture and its component pure cultures obtained from PAHcontaminated soil. Can. J. Microbiol. 41: 470476. Vila, J., Lopez, Z., Sabate, J., Minguillon, C., Solanas, A. M. and Grifoll, M. 2001. Identification of a novel metabolite in the degradation of pyrene by Mycobacterium sp. strain AP1: Actions of the isolate on two-and three-ring polycyclic aromatic hydrocarbons. Appl. Environ. Microbiol. 67: 5497-5505. White, K. L.1986. An overview of immunotoxicology and carcinogenic polycyclic aromatic hydrocarbons. Environ. Carcinogen Rev. C 4:163-202. Zhang, H., Kallimanis, A., Koukkou, A.I. and Drainas, C. 2004. Isolation and characterization of novel bacteria degrading polycyclic aromatic hydrocarbons from polluted Greek soils. Appl. Microbiol. Biotechnol. 65: 124-131.
Plans CNG corridor in TN Infrastructure Bureau

Chennai, Jun 6
As part of its efforts to bring some parts of Tamil Nadu under the Compressed Natural Gas (CNG) ambit, GAIL (India) Ltd has proposed to set up a CNG corridor, consisting of Nagapattinam, Karaikkal, Puducherry, Tiruvarur, Ramanathapuram among other areas of the state, said UD Choubey, CMD of GAIL. GAIL Gas, a 100% subsidiary of GAIL will work out a suitable strategy in this regard. He said the plan is in initial stage and the company will consider exploiting the gas sources in these places at maximum level to supply as a fuel for the increasing demand from host of sectors in the state, he said the Given the growing fuel cost and the expected increase over the years, it is ideal to go for natural gas, which is more cleaner, cheaper and environment-friendly. It not only help utilizing the gas optimally but will also help indutrialising the state in a big way, he said. cation process in order to qualify the Sevan drilling rig for operations offshore India. After technical qualication, the commercial bids were opened on Thursday, in which Sevan emerged as the lowest bidder, the ling said. The rig provided by the rm would be based on its proprietary Sevan 650 design. The rig will have a capacity to drill in water depths down to 10,000ft. The Norwegian company partners Jindal Drilling & Industries in India.
Sevan Marine bags contract from ONGC

New Delhi
Norwegian rm Sevan Marine ASA said it has bagged a contract from staterun Oil and Natural Gas Company for deepwater drilling rigs. In a lling to the Oslo stock exchange, Sevan said, Subject to the signing of a Letter of Intent between the parties shortly, the
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drilling contract will have a xed term of 3 years. The company expects to generate revenue of about 569 million dollars, including mobilization, over the contract period, the ling added. Last month Sevan Marine and ONGC carried out a detailed technical clari-
Flow Measurement Applications in the Oil&Gas Industry Different Technologies for Different Applications
Dieter Huller
Siemens AG, Germany
Dieter Huller, born 24.5.52 in Freiburg / Germany

1971 1974 1974 1978 1978 1984 Study of Physics, Bachelor of Physics 1974 Study of Chemical Engineering, Diploma of Engineering (Master degree) 1978 Researcher at the University of Karlsruhe, Institute of Mechanical and Chemical Engineering Doctor degree (Ph.D.) Thesis about optical measurement of particle size and shape analysis Siemens AG, Control and Process Automation, Technology introduction of Machine Vision Marketing and Business development for Automotive Diagnostic Systems Akquisition and Integration of Laser Analytics business Field Instrumentation and Analytics: Cross-group business support for the Oil & Gas Industries, Account Management for Oil & Gas Industries, Business Development for Process Analytics
owing uid. A loss of energy from the owing uid, primarily a loss of pressure, is the consequence in any case. Electrical and electronic technology have had a major impact on developments in the last 50 years. New technologies were employed, which used their own energy source instead of relying on energy contained in the process uid. These devices did not necessarily lead to a pressure loss in the medium that was being measured. Such measurement principles are magnetic-inductive, ultrasonic, and in certain cases the mass ow measurement, based on the Coriolis principle. The various measurement principles are classied into 10 groups in the British Standard BS 7405. The different technologies have been developed to cover a wide range of applications, as with other instruments or measurement principles, no ideal principle can be found. The selection of the best suited principle is a compromise between desired accuracy, unwanted side effects and cost.
July 1984 June 1984 Oct. 1994 July 2001 From July 2002
hile in the manufacturing industries discrete products need to be handled, owing product streams need to be controlled in the process industries. This is valid for every stage of production in the Oil&Gas and Hydrocarbon Processing Industry the products flow from the wellhead through several processing steps and nally to the end user. Every stage of the oil industry has ow measurement applications that have an impact on the overall plant performance. The internet search engine Google leads to approx. 0,7 Million hits for the expression Flow measurement (in inverted commas, as indicated here), and by the time this article reaches publication, it denitively will be several more. Flow is likely to be the most frequently measured parameter in industry. The large number of suppliers of instruments may also be surprising and underline the signicance of ow measurement: According to the Internet directory Global Spec The Engineering Search Engine 2) you can nd 965 (!) companies listed under the key word ow meters.
From the beginning of the last century standard practices and methods were developed. They are all still in commercial use today: Examples are Venturi tubes, turbine wheels and devices based on the principles of positive displacement or variable area. Any of these devices based on the principles above, function the transfer of energy from the
Fig 1 - Overview of the most frequently used principles of ow measurement
Only he who can see the invisible can do the impossible
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Fig 2 - Flow measurement based on the principle of differential pressure measurement. A change in the diameter of the tube results in an increased velocity of ow at the orice and leads to a differential pressure pp. The differential pressure represents a relationship to the ow.
correlation of the differential pressure is created by means of an orice plate. Primary differential pressure devices are suitable for single-phase media such as gas, vapor and liquids without solid components. On lines with small nominal diameters (DN 10 to DN 50) the measurements are inuenced by the wall roughness and diameter tolerances of the pipe. These inuences can be compensated for by using specially manufactured metering pipe sections made of precision engineered pipe. The ow coefcient C must be determined experimentally to permit exact measurements with metering pipes.
Benefits + Primary differential pressure devices are very robust and can be used in a wide range of nominal diameters + Suitable for wide ranges of temperature and pressure + No calibration required as the process is standardized + The electronics required in addition can be used over a long distance from the measuring location + The differential pressure method is well known and has a large installed base + The electronics is easy to re-parameterize if process data should change. Adaptation is done by recalculation and re-parameterization of the transmitter or, in the case of the version with annular chamber orifice plate, by using a new orifice disk An overview of the most commonly used principles of ow measurement is given in g 1 Various technologies for flow measurement are applied in the process industries. All of these are based on different physical principles. These are: differential pressure, ultrasonic sound propagation, magnetic eld induction, Coriolis force, Doppler effect, thermal conductivity, the hydrodynamic effects of gases, mechanical force balance and even others. The presence of all these different technologies in the marketplace demonstrates that there is no universal ow measurement principle or device available. Depending on the respective application and its conditions the most
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Limitations
Magnetic Flow Meters

- Causes a pressure drop - Low dynamic range (Turndown) - Non-linear relationship between pressure and flow - Standardized build-in conditions to be met An electromagnetic ow meter generally consists of a magnetically nonconducting metering tube with an internal electrically insulated surface. Electromagnetic coils connected in series are mounted on the tube, diametrically opposite each other. At least two electrodes are inserted through the pipe wall perpendicular to the magnetic eld and are in contact with the uid to be measured. The magnetic eld produced by the coils through which the current passes generates a pulsed electromagnetic eld perpendicular to the pipe axis. This magnetic eld penetrates the magnetically non-conducting metering tube and the uid owing through it, which must be electrically conductive, above a minimum level. According to Faradays law of induction, a voltage U is generated in an electrically conductive fluid, and is proportional to the velocity of the owing uid, the magnetic ux density, and the distance between the electrodes (internal diameter of pipe). The signal voltage U, which is proportional to the velocity of the owing uid, is detected by the electrodes which are in contact with the owing uid,passing through the electrically insulated pipe wall and converted into appropriate standard signal, such as 4 to 20 mA, by an associated transducer.
- Sensitive for variations in density and deposit of material
- Aging
suitable principle of operation needs to be carefully selected to ensure correct operation and return on investment.
The different principles of ow measurement

Differential pressure
Primary differential pressure devices are standardized mechanical ow sensors. This technology takes benet of Bernoullis law and the principle of continuity. Through a constriction of the pipe diameter by the device the ow creates a differential pressure across the device, that is converted by the use of a differential pressure transmitter into an electrical current signal which is proportional to the ow value. The
Coriolis Mass Flow Meter

The ow measuring principle is based on the Coriolis law of movement.
Love is the invitation of the wise one who loves what he knows, and knows what he loves

Fig 3 - Basic principle of a magnetic ow meter
through the existing pipe wall, without any interference or need to interrupt the ow in the pipe during installation. The ow meter automatically compensates for any change in uid sound velocity (or beam angle) in response to variations in the average transit time between transducers 1 and 2. By subtracting the computed xed times (within the transducers and pipe wall) from the measured average transit time, the meter can then infer the required transit time in the fluid. The sound waves traveling in the same direction as the ow arrive earlier than sound waves traveling against the direction of ow. This time difference is used to compute the line integrated ow velocity. Once the raw ow velocity is determined, the uid Reynolds number must be determined to properly correct for a fully developed ow prole. In all wetted type ultrasonic ow meters the meter constants are congured prior to leaving the factory. As this is not possible with clamp-on meters, the settings must be made by the customer at the time of installation. These settings include pipe diameter, wall thickness, liquid viscosity, etc. State-of-the-art Clamp-On meters that include temperature sensing such as the SITRANS F US clamp-on meter can be congured to dynamically infer changes in uid viscosity for the purpose of computing the compensation value to provide the most accurate ow prole. Two basic types of clamp-on transducers are in use. The lower cost universal transducer is the most common type in the industry and is suitable for most single liquid applications where the sound velocity of the uid does not vary much. This transducer type can be used on any sonically conductive pipe material (including steel) making it well suited to portable survey applications. The second transducer type is the patented high precision WideBeam transducer (ZeroMatic Path), which utilizes the pipe wall as a kind of loudspeaker to optimize the signal to noise ratio and provide a wider area of vibration. That makes this kind of transducer less sensitive to any change in uid properties. The WideBeam transducer is designed
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Benefits + Well proven in use, large installed basis + Accurate measurement, down to 0,2 % of the measured value + High linearity over the entire range + No pressure drop + Influence of particles (suspensions, sludge, slurries) can be calibrated out. The sensors are energized by an electro mechanical driver circuit which oscillates the pipe at its resonant frequency. Two pick-ups are placed symmetrically on both sides of the driver. When liquid or gas ows through the sensor, Coriolis force will act on the measuring pipe and cause a pipe deection which can be measured as a phase shift on the pick-ups. The phase shift is proportional to the mass ow rate. The temperature of the sensor is measured by a Pt1000, in a Wheatstone conguration (4-wire). The ow-proportional signal from the 2 pick-ups, the temperature measurement and the driver frequency are fed into the transmitter for calculations of mass, volume, fraction, temperature and density. The mass ow meter does not require any ow conditioning inlet straight sections. Care should be taken to ensure that any valves, gates, sight glasses etc. do not cavitate and are not set into vibration by the ow meter.
Limitations - Fluid must be conductive - Spool piece is part of the pipe - Lost of signal for deposits on electrodes
acoustic permeability, independent of conductivity, viscosity, temperature, density, and pressure. In Ultrasonic Flow Meters two ultrasonic transducers are placed at an angle in relation to the pipe axis. The transducers function as transmitters and receivers of the ultrasonic signals. Measurement is performed by determining the time the ultrasonic signal takes to travel with and against the ow. This measuring principle offers the advantage of being independent of variations in the actual sound velocity of the liquid, i.e. independent of the temperature. Ultrasonic flow measurement comprises of two different methods of operation. In the rst the ultrasonic sensors are directly in contact with the owing uid. These devices are commonly called wetted ow meters or intrusive to distinguish them from the so called clamp on sensors which are mounted on the outside of the pipe.
Ultrasonic Flow Meter Wetted Sensors

Ultrasonic ow meters in general are used to measure liquids with good
Ultrasonic Flow Meter Clamp-on Sensors

Ultrasonic clamp-on transducers transmit and receive acoustic signals
My obligation is to do the right thing. The rest is in Gods hands Martin Luther King, Jr

Fig 4 -Basic principle of a Coriolis ow meter: A mass M moving from the center to the edge of a rotating plate will take path B as shown above. A uid of mass M owing through an oscillating bended tube will tend to deect the tubes. A phase shift of the oscillation is observed and measured
for steel pipes, but can also be used with aluminum, titanium, and plastic pipes. It is the preferred transducer for the Hydrocarbon and Petrochemical Industries as well as gas applications. Note that unlike the universal type, this transducer selection is dependent only on the pipes wall thickness. When WideBeam transducers are installed in the Reect mode conguration shown in g.6, the acoustic signal travels in two different paths between transducers. One path travels through the pipe wall and uid, while the other path never enters the uid medium. This latter path provides the meter with a reference signal that is completely independent of the ow rate and can therefore be used as a measure of transducer mis-match. By continually analyzing this pipe-wall signal the meter can dynamically correct for ow errors caused by zero drift. For improved flow profile averaging, redundancy, or better cost per measurement, clamp-on meters can be supplied with 1, 2 or 4 measurement channels.
Benefits + Most accurate flow measurement today + Independent of temperature variations, entrained air, viscosity, density, conductivity, and pressure changes + Measures density and temperature as well + Multi-parameter Information: flow, density, and temperature
Limitations - Sensitive to vibrations - Limited to small and medium pipe diameters due to technology and product cost
Applications of Flow Meters in the Oil & Gas Industry

Fig 5 Intrusive Ultrasonic ow meter (wetted sensors): An ultrasonic wave is directed from transducer 1 to transducer 2 and vice versa. If there is a ow in direction of the arrow, the wave from 1 to 2 is faster than the wave from 2 to 1. The measured difference between the two signals expresses the ow velocity.
Most applications of ow measurement are in process measurement. The signals are used by the DCS system for plant control. Additional applications, not described in detail here, comprise safety and environmental measurement tasks. Flow measurement can provide much more benet in plants. Applying the appropriate principles, such applications range from exact dosing of chemicals by injection of scale inhibitors on an offshore platform, scal metering for custody transfer, providing interface detection of two dissimilar products being pumped sequentially through a pipeline, help to keep oating platforms in their horizontal position and trigger an alarm when a leak is detected in oil and gas transportation pipelines and locate its position somewhere out in the desert. Examples of ow measurement applications for the different principles are described below.
Benefits + No pressure drop + Not dependant on media conductivity + Economic for large dimensions + Fiscal Metering and custody transfer meters available + Multi channel option for higher accuracy
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Limitations - Installation requirements to be respected - Liquid needs to be free of gas bubbles - Deposits affect the measurement - Pipes need to be completely full
Its not that Im so smart, its just that I stay with problems longer Albert Einstein

Fig 6 - Ultrasonic clamp-on ow meter. Ultrasonic clamp-on sensors are mounted externally to the wall of the pipe in a reect conguration. Sensors act as transmitters and as receivers, to provide measurement in both directions. Sensors can operate in direct mode (mounted opposite of each other) or in reection mode (mounted on same side of the pipe).
Benefits + No wetted parts, no pressure drop + No limitation in pressure rating + Wide turn-down ratio + Easy installation without pipe intervention or shutdown of the process + Not affected by corrosive media + Multi-channel option for higher accuracy + Portable meters available
Limitations - Gas measurement in steel pipe requires 10bar min. - Does not work on concrete pipes - Coupling media between sensors and pipe needs certain maintenance - Pipes need to be completely full
measuring oil or gas ow, but nevertheless are used in many applications in the Oil&Gas industry. Typically, magnetic ow meters measure water ow. Water is used at many locations within oil and gas production. The crude which comes out of the ground is a composite of hydrocarbons in a liquid and gas phase of water and solids. An oil reservoir can be considered a wet sponge. As it gets dryer by exploitation, the more difcult it is to make the hydrocarbons accessible. Water is separated, processed and used for re-injection. Re-injection causes a pressure increase in the hydrocarbon reservoir and thus increases the production rate. Pressures used are in the range of 10.000 15.000PSI (700-1000bar). Even after processing, the water is never really clean. MAG Flow meters can deal with contaminants like sand and low quantities of oil. The meter tends to indicate a low value (as oil and sand have no electrical conductivity), but the meter still continues to measure the water phase. Siemens has applications in the Netherlands where the sand content in water is as high as 70 % and the ow meter still functions. A totally different application in the industry is the stabilization of offshore platforms. Based on the fact that oil and gas reserves are increasingly located in deeper waters, platforms for drilling in deep water are not xed on the seabed. They oat in the sea. In order to maintain platform stability, even in rough seas, complex electronic systems are employed. This stabilization is called ballasting and requires the use of large quantities water to weight the platform, as loads on the platform vary the water is moved around the so called ballasting tanks to keep the platform level and stable. The sensors used to measure the water ow for this application are typically Magentic Flow Meters. The photo below shows an application for stabilization of an offshore platform.
Differential pressure based Flow Meters

Differential pressure is worldwide the most frequently used technology for ow meters, as the method is proven and standardized. Applications are found in many places in the Oil&Gas and petrochemical industries for the measurement of water, steam and liquid or gas hydrocarbons. In the case of the use of differential pressure ow meters, the medium to be measured is extracted from the process to a measurement station. Here the pressure transmitter is situated. In
contrast, in any other of the methods described later, the sensors are directly mounted in or at the process stream, they generate an electrical signal which is transferred to the transmitter, in case that the transmitter itself is mounted in a remote location. An application for a gas pipeline in the Libyan Desert is shown below, including the measurement station (containing two differential pressure transmitters).
Magnetic Flow Meters

Magnetic ow meters, due to the principle of operation are not capable of
Fig 7 - Differential pressure method for ow measurement in a gas pipeline
Coriolis Mass Flow Meters

Mass Flow Meters based on the Coriolis Effect have clear benets as their principle of operation does not depend on physical effects like conductivity, density, viscosity, pressure or temperature. They Perfection is possible otherwise there would be no word for it Dadi Janki
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Fig 8 - MAG Flow Meters used for stabilization of an offshore platform
2). The exact quantities of the constituent chemicals need to be measured very accurately in the make up of the drilling mud this application is ideally suited to Coriolis owmeters.
Ultrasonic Flow Meter Wetted Sensors

The example below shows a crude oil transfer station at the South Arne eld in Denmark on ANSI 20 anges. The two systems shown in the picture work on the same line; one is operated by the exporting company, the other by the importer.
Ultrasonic Flow Meter Clamp-on Sensors

are well suited for exact measurement of low ow rates for a wide variety of different uids. In Oil&Gas applications, this is the case for chemical dosing. Chemicals are used as drilling mud (or drilling uid) and also as scale inhibitor which is used to production wells. Drilling uids have various functions to fulll, such as carrying the pieces of rock excavated by the drill bit, called cuttings, up to the surface, these cuttings are carried in suspension in the drilling mud , controlling formation pressures, cooling, lubricating and supporting the bit and drilling assembly. Water-based drilling mud may consist of bentonite clay (gel) with additives such as barium sulfate (barite), calcium carbonate (chalk) or hematite. Various thickeners are used to inuence the viscosity of the uid, e.g. Xanthan Gum, guar gum, glycol, carboxymethylcellulose, polyanionic cellulose (PAC), or starch. In turn, deocculants are used to reduce viscosity of clay-based muds; anionic polyelectrolytes (e.g. acrylates, polyphosphates, lignosulfonates (Lig) or tannic acid derivates such as Quebracho) are frequently used. Red mud was the name for a Quebracho-based mixture, named after the color of the red tannic acid salts. Many other chemicals are also used to maintain or create some of the properties needed Clamp-on ow meters are the perfect t for applications involving liquid hydrocarbons including crude oil, rened petroleum products and liqueed gas. The major benet over other technologies is the ability to get those meters installed without any interruption of the ow or major encroachments to the pipe. A proper installation, provided, clampon ow meters provide the same range of accuracy as the meters with wetted sensors. As ultrasonic ow meters measure the ultrasonic velocity of the uid being transported, this uid material property can be used for additional applications beyond just ow. Pipelines often are used in batch operation; they do not only transport one single product. They are transporting different refined products or crude sequentially. At the end of the pipe the different batches need to be separated by switching a valve to the respective storage vessels. This so called Batch tracking is performed by ultrasonic ow sensors, in addition to their ability to measure ow they are also capable of detecting changes to density. Typical applications are batch tracking of different rened products such as diesel, kerosene, super and regular fuels. But ow meters can do even more than just measure the ow. By combining the ow values with the measured density, the temperature as an additional param58 J U N E 2008
Fig 9 - Coriolis Mass Flow Meters for dosing of chemicals in an offshore operation process
Man does not live by bread alone. Many Prefer self-respect to food Mahatma Gandhi

Fig 10 - Ultrasonic Flow Meters in a crude oil transfer station
conditions. They permit the system to detect and integrate very small leaks and extractions. Even in the pilot phase of the project unanticipated benets of the program became obvious: After unloading the rst ship into the supervised pipe, 22 suspicious events were identied. Soon after, a rumor spread within the local community that Pemex was deploying a new weapon that would locate unauthorized extractions and catch thieves. This immediately caused thieves to stop tapping. After rumor spread, only one suspicious event was recorded (and turned out to be an actual known leak). The second and third ships had no losses during unloading. The cost return on investment was given within a month of activation; the deterrence value had been underestimated by far. The different examples given here only serve to demonstrate a small selection of the various applications of ow measurement in the Oil&Gas industry. The intention with the selection of these examples is not to give a complete picture of applications, but to show some typical applications and to discuss some experience with these applications.
eter and with the help of a ow table, the mass ow can be calculated. By calculating a mass ow balance along the pipe an additional and important measurement task is achieved: leak detection. Oil producers and transporters are under high pressure to reduce or eliminate the amount of petroleum products lost from pipelines either through theft or leaks, accidentally or otherwise. 15% of the total petroleum products transported by pipelines world wide are at risk of theft by illegal tapping of the pipelines At over $100USD per barrel (March 2008) and a world wide consumption of over 84,000,000 barrels per day, the losses from pipeline intrusions are staggering economically and environmentally. In Mexico alone, 5 Billion USD in product value is at risk.
PEMEX, the state-owned oil company of Mexico with 98 Billion USD annual revenue and 138,000 Employees, has insufcient rening capability. Therefore they need to export crude oil and import rened products. Pipelines are their primary delivery mechanism and greatly increase the points of vulnerability to illegal tapping of pipelines. Pemex incurs annual losses due to theft in excess of 2 billion USD, 51 % of stolen product is diesel. In early 2006, a pilot project was launched into the viability of noninvasive leak detection technology. Clamp-on Ultrasonic Flow Meters were installed on the extreme ends of an 8 km pipeline. Ultrasonic Flow Meters are used as they are extremely sensitive at and around zero ow and provide ow data during both ow and no ow
Bibliography
1) Global Spec The Engineering Search Engine http://sensorstransducers.globalspec.com/ Industrial-Directory/vortex_owmeter_guide http://en.wikipedia.org/wiki/Drilling_mud
2)
Fig 11 - Setup of the leak detection system and location of the leak detected
Success is to stand in the presence of God unashamed
J U N E 2 008 59 59

PETROTECH ACTIVITIES Mr J L Raina, Secretary General & CEO welcomed the delegates to the Conclave and assured PETROTECHs untiring efforts to encourage R&D as well as to be an agent in enhancing its effectiveness in the Hydrocarbon Sector. To catalyze Mr. Sarthak Behuria, Chairman IOCL delivering inaugural address this, PETROTECH during R&D conclave II has instituted 5 Research Scholarships per year for re- bring together partnerships between search in the Hydrocarbon Sector. technical institutes and the industry. Mr Anand Kumar, Director (R&D), IOCL gave an overview of the R&D efforts of IOCL and stressed the need for research for the common cause of the hydrocarbon sector. He indicated that research should be such, which is implementable and be benecial in chalking out new procedures/ processes besides reducing costs. Mr B M Bansal, Director (Business Development & Planning), IOCL; Mr K K Acharya, Managing Director, CPCL alongwith Mr M K Joshi, Director (Tech), EIL delivered the Keynote Addresses. They stressed upon the need to encourage research and Mr M B Lal, Chairman, Scientic Advisory Committee, Ministry of Petroleum & Natural Gas delivered the Inaugural Address. A Special Address was given by Swami Sukhabodhananda, Chairman of Prasanna Trust, who spoke on Nurturing Innovations in Oneself, Organization and Society. This two hours address to the participants was mind blowing, tantalizing and kept the participants glued attentively throughout the session. The Valedictory Address was delivered by Mr Subir Raha, Executive Vice Chairman, Hinduja Group India. While addressing the need for research & development in the industry, he wanted the ownership to be that of the top brass of each organizations. Meaningful R&D which can be commercialized was the need of hour.
R&D Conclave II of Petroleum Industry

9th - 11th January 2008, Hotel Cidade de Goa, Goa
R&D Conclave II of Petroleum Industry was organized by PETROTECH Society in collaboration with IOCL R&D and held at Hotel Cidade de Goa, Goa from 9th11th January 2008. The conclave was attended by 110 participants, who were drawn from various R&D Centres both in the public, private sector and Practicing Managers from the upstream/downstream of the oil industry. During the two and a half days conclave various topics were covered by 33 eminent Speakers / Chairpersons and 5 VVIPs, who addressed the delegates in the inaugural and valedictory sessions.
Mr. Subir Raha, Executive Vice Chairman Hinduja Group India, delivering valedictory address
NIPM pre conference panel discussions

7th - 9th February 2008, Baroda
NIPM had their 26th Annual National Conference-NatCon08 at Baroda from 7th-9th February 2008. Petrotech was requested by the organizers NIPM/ O N G C t o o rg a n i z e and sponsor the Pre Conference-Panel Discussions on the theme Linking Management, Education and Industry: Challenges held on 7th February 2008 at ONGC Baroda. The Pre Conference-Panel Discussions was presided over by Dr A K Balyan, National President NIPM and Keynote Address was delivered by Dr B S Sahay, Director, IMT, Ghaziabad and Mr S P Parashar, Director, IIM (Indore). Besides the above dignitaries 14 eminent panelists from the academia, industry and management had participated in the above
Dignitaries lighting the ceremonial lamp

60 J U N E 2008

Pre Conference-Panel Discussions. Over 300 delegates from various organizations/ institutes also attended this event. Pre Conference-Panel Discussions revolved around the needs of the academia and the oil industry and how both could be brought together to assist each other in their respective activities for the benet of the industry as a whole. The Pre Conference-Panel Discussions were a grand success and the event was anchored, covered and telecast by NDTV Prot.
A view of the audience at the pre-conference discussions
Seminar on Hydrocarbon Industry Growth Prospects & Challenges in North East

April 24-25th 2008, Guwahati Renery
of N E Reneries; Indane Maximization Unit In house design for maximization of LPG; Hydroprocessing Process; Catalyst & Reactors; Polyolen Recent Advances in Catalysts & Materials, Napthacracker to produce petrochemical feedstock, thermal cracking process delayed coking with reference to needle coke measures; auto fuel policy and Alternate Fuels; Bio-diesel; Hydrogen etc. Mr. Raina while extending a warm welcome to the Chief Guests and Participants also expressed his happiness for the assistance provided by IOCL Guwahati Renery. Mr. Bhanumurthy in his Keynote Address spoke on the crude oil scenario
During the inaugural session of the workshop PETROTECH Society and Indian Oil Corporation Ltd, Guwahati Refinery took an initiative to bring together the Academia and practicing managers by organizing a seminar on Hydrocarbon Industry Growth Prospects & Challenges in the North East held on 24-25 April 2008 at Indian Oil Guwahati Renery. The two days programme was designed to share the advances made in the eld of exploration/production, rening and petrochemicals and was attended by 58 participants. The topics covered were oil scenario international, national & in north east; Petroleum exploration National & International Scenario; Petroleum Exploration Synergy is Key; Overview
Group photograph of participant of dignitaries

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region like the UAE for free flow of trade. The Govt. of India has approve Rs 54 billion for the Brahmaputra Cracker and Polymer Ltd, which would herald an ear of economic growth for the region. Dr B K Das, MD Inductory with the participants of Assam and mantras of protability high distillate yield, reduction in fuel and loss and low MBN. The Inaugural Session was presided over by Mr Anand Kumar, Director (R&D), IOCL. In his speech Mr. Kumar said oil and gas scenario in the North East poses many challenges as well as provides several opportunities. He said that Tripura, Bangladesh and Myanmar with the available natural gas can form a special economic North East is endowed with rich deposits of coal and shale oil. The oil shale reserves which can yield a liquid similar to natural crude oil can sustain production of 140 million tones of crude oil for 100 yrs. Assam also has a reserve of 295 MMT of low ash high Sulphur Coal which has the possibility of being converted to liquid fuel. He also spoke on contribution of IOC R&D to the growth of oil industry of NE. The valedictory session was chaired by Dr B K Das, Managing Director, NRL and the two panelists were Dr R K Malhotra, ED (R&D), IOCL and Mr. A C Mishra, DGM(T), IOCL Guwahati Renery. Dr Das exhorted the participants to carry forward the knowledge gained for meeting the objectives of academia. He wished good luck to all the participants in their future endeavour.
A View of the Participant of the North East Workshop
2nd Steering Committee Meeting

T h e 2 nd S t e e r i n g C o m m i t t e e o f PETROTECH - 2009 was held on 12th March, 2008 at Hotel Le-Meridian. The meeting was chaired by Shri Sarthak Behuria, Chairman, Indian Oil Corporation Limited and Chairman, Steering Committee, PETROTECH-2009. Among others, the meeting was attended by Shri R S Sharma, Chairman, ONGC and Chairman, PETROTECH SOCIETY. Shri Behuria welcomed Shri R S Sharma and all other members of the Steering Committee. He also informed the members about the formal release of 1st Announcement Brochure and launch of PETROTECH-2009 website by Mr Murli Deora, Honble Minister of Petroleum & Natural Gas and Patron-in-Chief, PETROTECH-2009 during the 1st Core Group Meeting held on 17th January, 2008 and gave a brief overview about the development so far and the salient decisions of 1 st Core Group Meeting. Shri R S Sharma complimented Indian Oil for taking early initiatives in commencing the planning process of PETROTECH-2009 and expressed his happiness about the progress made by the Organising Committee, PETROTECH-2009.
62 J U N E 2008
The Chairman, Organising Committee gave a detail presentation about the activities so far undertaken by the Committee and plans for further activities for taking the event forward. Thereafter, all the Nodal Committees gave their presentations about the activities undertaken by them so far and their plan of activities for taking the event forward.
ONGC's fourth CDM project registered by UNFCCC

May 24, 2008
aring from the Hazira processing plant and qualies for a CDM project under the fuel substitution category. The expected annual accruable CER is 8793 for a sustained period of 10 years, equivalent to an annual earning of Rs 7.7 million (approx.) of green revenue (1 CER drawing 16 Euro these days on a conservative basis). Mr. A B Chakraborty, GGM, Head - Carbon Management Group formally handed over the registration certicate to CMD on May 23, 2008. CMD has conveyed his compliments on the registration of the fourth CDM project of ONGC. ONGC was the only PSU under MoPNG to have included two CDM Projects as parameter in the MoU with MoPNG for 2007-08. It was as much a belief and condence of the Board on ONGC's capability as a test of ONGC's conviction to sustainable development. Registration of the project has enabled ONGC to achieve the coveted target of 100% performance in this parameter (the GFR at Uran plant, ONGC's third registered CDM project was the other project). It has, at the same time, vindicated the condence and conviction. A view of the Hazira Plant The registration of this project has come shortly after ONGC's bagging the inaugural Earth Care Award. This is a day of rejoice for ONGC that has come through untiring efforts of CMG and constant guidance from Director(Onshore), Mr. A K Hazarika over two years. However, the success would not have been possible without the extremely proactive cooperation from the Hazira Plant. Sustainable Development is fast becoming a viable business model across the world. Developing CDM projects is just a part of the entire model, albeit a very alluring part. ONGC has realized its business potential like other global oil majors, as is evident from the recent letter from Mr. R S Sharma, CMD to all Key executives to consider CDM benets in any future project at the inception level and his desire to set up a separate web page on CDM. We are hopeful that with such unwavering commitment and guidance, ONGC's quest for sustainable development will reach its desired destination successfully.
Mr A B Chakraborty handing over UNFCCC registration to CMD ONGC's pursuit towards sustainable management is well documented and has earned ONGC many laurels. The latest initiative towards this is the registration of the fourth Clean Development Mechanism (CDM) project with the United Nations Framework Convention on Climate Change (UNFCCC) on May 16, 2008. The formal communication from the UNFCCC in this regard came late hours of May 19. The project, 'Flare Gas Recovery Project at Hazira Gas Processing Complex (HGPC), Hazira' involves reducing gas
ONGC bags international recognition for Combating Climate Change

ONGC's good work in Combating Climate Change has won it international recognition. An eminent jury, under the chairmanship of Justice P N Bhagwati, former Chief justice of India and Member of UN Human Rights Commission, adjudged ONGC the winner for 2008 Golden Peacock award for an impeccable record in the Climate change mitigation. Apart from this corporate recognition, ONGC's Institute of Drilling Technology secured the Golden Peacock award under ECO-Innovation category in Oil & Gas Sector, while Corporate Health Safety & Environment (HSE) section of ONGC bagged the award under the Environment Management category. The award for Combating Climate Change was handed over to ONGC by the Hon'ble Chief Minister of Himachal Pradesh Professor Prem Kumar Dhumal on 30th May 2008 during the Global Convention on Climate Change at Palampur, witnessed by many dignitaries, corporate leaders and opinion makers from 25 countries. ONGC's Director (Onshore) Mr. A K Hazarika, who is Director In-Charge of Environment Management, received along with ONGC's Head Carbon Management Group Dr. A B Chakraborty.
Speaking on the occasion Mr. Hazarika said, "ONGC has taken the ongoing Climate Change and Global Warming very seriously. Climate change entails risks, costs as well as opportunities. We feel that Sustainable development is the solution; and
ONGC Director A K Hazarika (2nd from right) and Dr. A B Chakraborty (extreme right) receiving the international Golden Peacock award 2008 for Combating Climate Change, from Hon'ble Chief Minister of Himachal Pradesh Professor Prem Kumar Dhumal sustainable developments solutions can be evolved into a business model of a company thereby creating value for the company and also contribute effectively to Climate change mitigation".
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About the University of Alberta

John Doyle
he University of Alberta is our provinces leading university. It was founded exactly a century ago, and now is a cornerstone institution for a region that is setting Canadian standards in economic growth, technological innovation, and workplace diversity. There is a very wide range of part-time professional, or short term post-degree training programs offered here, including courses for resident executives in the energy sector. More than 35,000 regularly enrolled students pursue studies in over 170 accredited graduate, and 200 undergraduate, elds of study here. The U of A also has a signicant international footprint, with over 1500 non-resident students in attendance, from over 105 countries.
The University of Alberta was ranked in 2007 as best overall in the annual rankings of Canadian universities by Macleans magazine. Professional training should provide to participating managers several opportunities to gain types of experience which would not easily be available to them in their
normal work, and yet which should nonetheless positively affect their outlooks and capacities when they return to work. If I were to describe what specically these types of experience were, I would cite at least three. First, most employees, even ones who are outstanding and who are recognized as likely leaders or as high yers in their departments, still often feel that their work duties dont usually enable them to gain a broad or full understanding of how the several functional units or departments within their company or ministry connect one to another. The oil and gas program which is our agship course, although it is only four weeks duration, still enables participating managers to gain a comprehensive and current picture of the larger petroleum sectorfrom exploration and development, to transportation, to downstream aspects. Secondly, this type of training is designed to
be interactive. That is, the participants come together with managers from several different regions of the world, and are encouraged within sessions to share related experience, debate perspectives on the problems which are presented to them, and take away valuable, long-term sectoral contacts from the time together. The end result, we believe, is an employee who is much more prepared to see him or herself as a manager. They understand better the leadership element which being a manager entails. They feel much more enduringly the need to think broadly on how their own department ts within the larger company, or even how the company ts strategically within the entire global petroleum framework.
64 J U N E 2008
PETROTECH
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PETROTECH

Journal of the Petrotech Society

JOURNAL OF THE PETROTECH SOCIETY Advisory Board

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1.00 Total 0.90

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1995-96 1997-98 1999-00 2001-02 2003-04 2005-06 2007-08

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Polyolen Materials and Catalysts: An Introduction

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Figure 3: High Density PE (HDPE) 0.940-0.965 g/cc

Figure 4: Linear Low Density PE (LLDPE)

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Roto Moulding Injection Moulding

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Figure 7: Per Capita consumption (Kg) of Plastics in 2005- 06

Indian Polymer Industry

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JOURNAL OF THE PETROTECH SOCIETY

Polyolefin Catalysts Family

world class technologies are shown in table 4.

Catalysts for polyolens

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Type Ziegler / Ziegler-Natta Philips (Chrome)

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JOURNAL OF THE PETROTECH SOCIETY

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Nobody can become perfect by merely ceasing to act Bhagwad Gita

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Hydraulic Fracturing Methodology Adopted

Pre-HF Work Over of Wells

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Chemicals used in Hydrofracturing job execution

JOURNAL OF THE PETROTECH SOCIETY

Improvement in Injectivity for HF job

Equipments used in Hydrofracturing job execution

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TS-3A TS-4B Sl. No. 1 2 3

JOURNAL OF THE PETROTECH SOCIETY

Production from HF Wells

Job size in different sands