(it-, r

\u(,f

i(1

-fJ
Liu

r.r-'(,.

,i
'

( i \

.,(.. 1l'\

STAGE

r-,rn? . ,),' 4 ' .

,nL \V

^(

: IDEA GENERATION
I

Look into technologies that

will

play asignificant role in clean and renewable energ

This also ensures that we are in line with the company vision : Green solutions
address the

to

world's rreed in renewable energy

Voice of Customers: Concern for the environment- reduce pollution by using clean fuels
and try to make use of agricultural and cooking waste.

However, it is known that alternative fuels like bioethanol and biodiesel have been using
feedstock which compete with the food market and are expensive. Hence, the cost

of

bioethanol and biodiesel are more costly than conventional petroleum.

Our company looked into ideas that can address pollution and sustainability issues by focusing on alternative fuels such as bioethanol and biodiesel that can tackle fuel
shortages and high carbon-dioxide emissions and make efficient use of industrial and

agricultural waste.

LIST OF IDEAS

I.

Biodiesel production from restaurant grease: Biodiesel is produced mainly from food
grade vegetable oils and the high cost of the feedstock makes production of a cost

effective fuel very challenging. Availability of large amounts of restaurant grease are a potential feedstock. However, they pose a technical challenge due to the high free fatty acid content which results in saponihcation during chemical transesterification thereby reducing the yield of biodiesel. This research project is aimed at developing novel and

efficient enzymes for the esterification of free fatty acids with methanol.

II.

Bioethanol production from crude glycerol: Glycerol is a by-product in the production of biodiesel from natural oils. This vastly growing biodiesel market produces large
quantities of crude glycerol which can be used as a sustainable resource in chemical industries. This research will focus on screening microbial strains that can convert crude

glycerol into ethanol. This would be more cost effective than producing ethanol from
corn derived sugars.

( i t tlrt,rr

luzurt

' {i lt
--'

--

1-'"'-'lj fr\. t"'lr'I

,.

III. O]:+ryt

bioethanol purification process: Bioethanol is one of the most promising

biofuels, because of its energy content similar to that of gasoline and it also generates lower pollutant emissions than gasoline. However, to use ethanol as an automotive fuel mixed with gasoline, the bioethanol must have less than 0.5 wt% water. To achieve this,

distillation is carried out. However, this process is expensive and makes the overall
production of ethanol not cost effective. This project will look into more efficient purifi cation processes.

IV.

Drop-In Biofuels to replace jet-fuel: This project focuses on extracting algal oils and
converting them to low molecular weight crude oil. This crude needs to be treated to a specifc quality so that they can be dropped in directly
as

jetldiesel fuel. Overall, this

research is targeted at achieving a continuous process of growing algae using industrial waste, extracting algal oils and converting them to low molecular weight crude, which is then treated to be used as drop-in fuels.

The project that

|

will

be chosen

will

be based on a selection criteria which is as follows;

! ' . '

The project should be aligned with the company's vision and objective : Green

solutions to address the world's need in renewable energy

In-house expertise in the area of innovative renewable energy technologies Sponsor and funding for the project Business and economics : Target market includes energy companies, automobile

industry

The aforementioned selection criteria

will

be used to choose one of the four projects and this

will

also be weighed against the pros and cons of each project. This

will also include the economics,

environmental issues and the feasibility of each project.

I will c0nrplete

thi,s

purt

-. (- I r') ( -) lrir( ry' /"r-J.a'r.

t)

4iodiesel production from.

resturanl grese

Pros

Stage 1: Scoping

o o

Quick paper study based on available knowledge Develop Preliminary Business Case

. . o
lf

lntegrated Product Definition including product requirements and value to customer Market, Financial, and Competitive Assessment

PIglmllgly Technical Assessment

Is this husiness case meanl to he done ey|.t.l'or the selecled proiecl?

so how cletqil shoultl

I write tlts
,tck t !

to'?'? An,st,rg4gesions.

C Cra:(i<

('w

(Urt"

ir

'

\--u^-:',. ,,,r),o, ,^ (\/f lt "1

(r1/nt

,--k
a,f/', i'tt )- l'

f''

'' ')

{
tc

,---li

'

't -J-

/tl/'-'l
<1 c'

Stage 2a

Upon the clearance of Gate 2, the team has concluded that Ethanol Purification will be the focus of the R&D project. The technique selected a priori is a novel Liquid-Liquid Extraction method. As part of stage 2a, we will evaluate the feasibility of the Liquid-liquid Extraction method in greater detail in comparison with other alternative technologies in the same domain. ln order to specifi clearly the goal of Ethanol Purification, we have defined it to be the purification of ethanol from a feedstock of lo wt% to a product of 90 wt% ethanol.

Understanding the Ethanol purification - Alternatives

lterature on fractional distillation of ethanol is well established and documented. For example, the Process Flow Diagram of an established ethanol distillation setup to produce high purity ethanol from beer feed is documented below:

the boiling points of ethanol and water are within 25oc of each other, simple distillation cannot be used' Hence currelntly, the conventional method for purifuing ethanol is through fractional distillation, limited by the azeotrope at 95'6 vol%. Aserious disadvantage of this issue is the high energy costs as well as fixed costs incurred to run a complicated fractional distiltation setup on an industrial
As

scale. The

d*'t*

rrlrr

condnsl

Ftrfl!r

l.r

Pr**fkld
irflFPtry/

Fltltl
Fussl @ndncr
C'rV

rDstMnc

lEr

Ell

c.mb

trhtngGr

Fnhltri

I I

+ The process has been optimized to minimize energy consumption and is able to produce ethanol at 95 vol% purity but this has come at the expense of additional equipment. Furthermore, the need to pressurize the system at 4 bars add to high the operational
costs. Hence, in order for such conventional systems to be economically feasible, the scale of such plants have to be large and the minimum size production capacity for such a plant has to be more than 40 million

gallons per year.

Our team is also aware of the development of other alternative methods of ethanol purification which include:

o
A group

Pervaporation

Vfn (Mf mbrane Technology and Research) inc. is in the process of developing a method of purifyine\*has11.o 90 wt% through the use of zeolite mixed-matrix membranes. They intend to develop special ethanol permeable membranes capable of increasing ethanol from a I0 wt% concentration to 40 wt% concentration and then further purify it to 90 wt% through the use of fractional
condensation (dephlegmation).
As much of their technology s

z'

'\

till not revealed to the public, we are unable to make definitive

conclusions about the performance and costs of this new technology. Serious doubts exist with regard to the production costs of these unique zeolite mixed-matrix membranes, costs of dephlegmation units and the energy required to operate thenl-as well as perfnance of pervaporation itself. The company has admitted that "Commercially successful applications (of pervaporotion in the field of removal ond recovery of organic solvents from wterl are hard to find".

Preliminary Technical Evaluation of

LLE

Concept

Liquid-Liquid , woter nhonol J, ' Extractor g

i

Solvent,
Etha nol,

Water

Ethanol (90 wt%)

+

Water

Firstly, the ethanol in solution is extracted by a suitable solvent using Liquid-Liquid Extraction. This process allows us to increase the concentration of ethanol in solution when using a solvent that can

extract ethanol preferably over water. The resulting three-species mixture of solvent, water and ethanol will then pass through to the next stage - Flash Distillation.
The second part of the technique involves the flash distillation of this mixture. The organic solvent is removed from this solution and recycled back to perform extraction, leaving us with an ethanol solution of higher purity than the original ethanol feed.

lterature Review on Liquid-Liquid Extraction

The key to the feasibility of the Liquid-Liquid Extraction method lies in the discovery of a solvent that simultaneously has a high affinity for ethanol and a high selectivity for ethanol over water. Numerous research groups in academia have been publishing results on the suitability of different organic solvents.
For example, Offeman et al. attempted to use alcohols as well as carboxylic acids as solvents and as an example, a part of his results are presented here: The x-axis of the graph indicates affinity for ethanol while the y-axis indicates selectivity.

An ideal solvent would reside in Quadrant 4 having both high selectivity as well as affinity.
d

rv \o ( 2a v 3A A t 4t f EI 5<
6*
0.0

.:; bronclpd

. .t -o.
t7 VV
V-

Failing which, the second most ideal quadrant

would be 3, as selectivity takes precedence over ethanol affinity.

We observe that there were no solvents that were found in Quadrant 4,

A major breakthrough came in2OILwhere phosphonium-based ionic liquids were tested for use in ethanol purification and the results were promising and indicated that the customized ionic solvents can be used for ethanol purification through

KDE

liquid-liquid extraction.
Research into solvent

Our group will pursue further research into the development of a customized ionic solvent that fulfils

the following criteria:

o o o o o

High selectivity for ethanol over water and high affinity for ethanol ( c > 30 and Kp > L.0)

Minimize toxicity and attempt to keep chemical structure as simple as possible

Method for manufacturing solvent as simple as possible

Experimental Techniques to be used include: Liquid Liquid Extracton on a laboratory scale followed by gas chromatography to determine solve nt cha racteristics

lnvestigation on efficient methods to produce chosen solvent economically

Research Outcome

Our group managed to achieve a breakthrough with the development of a phosphonium-ion based ionic solvent, henceforth known as ChemicalX. Laboratory tests indicated the following properties: . Kor = 2.5 : Using the Mac-Cabe and Thiele Method, only 2-3 stages of >90% of the ethanol from the initial feed.

LLE

is required

to recover

a (selectivity)

40 : Water co-extracted

is 40

times less than the ethanol extracted

:.,) )

.
C and is easily blended

Chemical X has a high boiling point

of

with readily available

chemicals found on the market.

Simulation performed on HYSYS regarding the flash distillation of the ionic solvent with ethanol gave positive results. Energy consumption was half that of the conventional fractional distillation case.
The Process Flow Diagram developed after Stage 2a is as follows:

Ethanol (10 wt%), Water, Flowrate F

Solvent,
Ethanol,

Water

Ethanol (90 wt%)

+

Water

Equipment Required:
For a provisional scale up process, we would require a 2 stage liquid-liquid extractor, a flash distillation column together with simple laboratory apparatus such as a gas chromatograph and piping

infrastructure.

l\rrr..-trirr

fuhit ______t Tr,..1rVr t\,{tf

(l

Business Plan
D

ot

t'i

/zBia*thonol

' ,

Market size

A review on the Bioethonol Market will be given in this section; its generol trends and potterns will be onolysed to give on all-round outlook for the future of bioethonol, and how these will determine the relotive success of our novel purification process.

ln 201L, world ethanol production rose to attain a level of approximately 26 billion gallons. The U.S, and Brazil are the world's largest producers of ethanol, together they account for more than 80% of ethanol produced worldwide.

Market Snapshot: Global Ethanol Production 2010

.l

., d\' gu:l.rz

Chlnai 542

fhe allobal Renewsble

Suets llian*e {GRFf

frec$ts elhrl

I :t

i::1::::::;::-

tl

l;

producton fo hit 8.7 blllfor litraq n 20ll

,'/

Source: NREL (National Renelvable Energy Laboratory) Data Book,

20'1

Currently, the global fuel ethanol market is experiencing tremendous growth due to the increasing use of ethanol in the end-use market. lts usage is being encouraged due to the ban on gasolne in most countries. lt is replacing other vehicular fuels and also being used as an additive along with petroleum products. lncredible hike in crude oil prices, and increased greenhouse gas emissions are encouraging governments to promote consumption of ethanol. ln addition, ethanol also finds numerous industrial applications as Pharmaceutical raw materials and as Chemical Feedstocks. There are two main types of ethanol - fermentation and synthetic. The major

outlets for industrial ethanol are as a solvent and in chemical synthesis. Some 60% of US industrial demand goes to solvent applications in pharmaceuticals, toiletries and cosmetics, detergents and
household cleaners, coatings and inks and processing solvents,

Ethanol is also used as a chemical intermediate for the manufacture of ethyl acetate, ethyl acrylate, acetic acid, glycol ethers and ethylamines, as well as other products. lt is also used as an additive to food and beverages. However, a much larger and growing outlet for ethanol is as a fuel, oxygenate additive to gasoline and a gasoline extender. Globally, fuel ethanol accounts for73% of production, with beverage ethanol atLT% and industrial ethanol at LO%.
Corn and sugarcane are common feedstocks for fermentation ethanol, along with grain, and sugar beet,

while synthetic ethanol's primary feedstock is ethylene, Fuel grade or bio-ethanol is produced from fermentation ethanol sources. Synthetic ethanol cannot be used for fuel ethanol purposes.
The major outlet of fuel ethanol in Europe is in ethyl tertiary butyl ether (ETBE), and also blending, whereby ethanol is used as a fuel oxygenate additive to gasoline and a gasoline extender.

Another use is direct blending, in which ethanol is directly blended into gasoline. Both uses are set to grow following the introduction of the European Union's Renewable Energy Directive (RED) which stipulates that renewable energy should have a minimum 10% share in transport bV 2O20.
ln the US, 92% of fermentation ethanol is used in fuel applications,with 4% going into food and

beverages, and 4o/o as industrial solvents and chemicals. ln Asia, most ethanol produced and traded is fermentation ethanol. The feedstock varies from sugarcane in lndia, Thailand and Pakistan to corn and tapioca in China. The biggest downstream application in Asia is industrial chemicals - for production of acetic acid and ethyl acetate and also as a solvent in pharmaceuticals and personal care products. The other use is for beverage industries. Hydrous or industrial ethanol is also known as 'B-grade' ethanol, which refers to a second-tier specification grade of Brazilian cane-based hydrous ethanol traded in northeast Asia.
Fuel blending use is increasing in countries like Thailand, China and lndia. Thailand is the leader in terms

of conversion on a large scale to LO% ethanol blended gasoline. Fuel blending applications are the most important sector driving the ethanol production in Asia. Exports from Asia to Europe and the US have also spurred the fuel demand in these regions.l

worth noting that in the ethanol market, automotive fuel market is the fastest growing segment of and it is estimated that ethanol will completely replace gasoline by 2030. Ethanol is produced from petroleum derivatives by the process of fermentation. Carbohydrate rich raw materials, such as Feedstock rich on sugar, Starches and Cellulosic Materials, are all suitable for production of ethanol.
It
is

Brazil is the world's largest producer of sugarcane ethanol. According to Unica (Brazil's national union of sugarcane producers), 20.5 billion litres (5.4 billion gallons) of fuelwere produced in the country in the 2OLL-20I2 harvest.

http;//www.icis.com/energv/ethanol/price-reporting-methodol ogvl

:
lrr 20lfl" approxlrrrately

'-'-

.'--

'-

Iodi*dpro(Arctkm

/00 milli+n

b{lels nl

.-

biofrls were prrrthrcd.' Over 45% of th was

'.-:9.*9
Cocef,teog Solff Wk
Scllsr Pvlgtd

Y Anot2fllo (ilesPdod)

Solt hwafttEtnt

.20f0

lydcrds

corn-bssed thanol n the U.S. rtd >25%

r)rr:ed Was sgarcane-based elhanol ln Brazll

c(fiffilpor,r lhdd Fflr

Portr

-ocrEcd

q*t)

S&rPv

ln the year ending 2010, bioethanol production was set to ncrease at a rate of L7% AGR. The global fuel ethanol market has experienced significant growth over the perod from 2007 to 20L2, and ths market

to continue its growth momentum, reaching approximately US598.5 billion by 2OL7 with a CAGR of I4.2% over the next five years. lndeed, with the future of the bioethanol production market looking bright, there exists great opportunities for market proliferation and utitisation of our novel purification process.
is largely expected

Pricing Trends n the Fuel thqnal Market

ln this section, on onalysis of the pricing trends in the Fuel Ethanol Market will be conducted to ascertain the economic feosibility of our innovation from o refinels perspective. lt witt atso determine the company's business and manufacturing directions in terms of choosng the torgeted types and grades of ethonot to be produced from the novel method, ond who our potential clients may be.

With rsing rlemand for fuel ethonol ond the unsuitability of synthetc ethanot for use in fuels, our propasecl system s prsised to tGke odvantage of the increasing bioethanol productictn thot is set to occur

in the short to medium term.

Flgura 1. lr*d of Monthly Grude Ol[, Gaeollne, and Ethanol Prleee

C.rnn

M qnth|v Etho \oleuen ue

qgt of E! ha wllrod lt cti on

The price of ethanol hos more than doubled in the last decade, qs seen

in

FIGULE

!. Coupled wth strong

globol demond for ethanol, revenue strem-s for bioethanol refiners have olso been increasing. Yet, this hss not had a positive effect on praducer profit margins as the cost of ethanol production has also increosed by about the sqme proportions, s seen from FIGUBES xl qnd !!!. Hence, it is imperotive for producers ond refiners, be it smoll locol ones or huge mega conglomerqtes, to find solutions to increose their proft morgins whilst smultsneously retoining or even increasing their producton output. Currently, the energy yield of bioethanol -thot is to soy,the amount of energy we cdn get out of refned bioethanol to the amount of energy input nto its production - is about 2.3:1.. With our innovation, refineries ond producers of bioethanol may be ble to attain much higher energy yields ronging fram 3 to 4, depending on the scale of the refinery. Furthermore, our novel system also has reduced maintenance requirements due to its simple and easy-to-implement design, providing clients with venues to profit from potentidl economies. Hence, with lower energy consumption ond mantenance costs, refineries my be ble to reduce their "natural gas" and "other voriable" companents

in the producton
can achieve

ct.f biaethunol, sigrtificantly lowering production costs. Having in ptuce a systerrt that gotd econornics and produclion capabilities will allaw <:omponies in this ntarket lo mctinoin

Our clientele will consist of companies with very rigid and strict demands in terms of product quality and production safety. The following paragraphs detail how our innovation can meet our clients' demands, while concurrently bettering existing purification methods:

Quonti ty ond Quatity

ctf

Deliverert Product

Bioethanol producers usuully look to refine ond produce ethanol of differing grodes, to meet industriul ond domestc use. The innovation we ore promotng is suitoble for att types of producers s t s sca!ble ta meet a wide ranqe af production specilications. The Productian capacity, Rate of Production onr)

Quolity af the fnal product can all be tuned manly through the simple monpulotictn of the Liquid-Liquid
Extraction proceclure and the subsequent refinng process.

,K

Cost-competitiveness of our syster

Current methods oJ turifying ethanol are energy-intensive and may involve lorge columns ancl heeruy equipment ta strip ethunol from solution. Our system will allaw bioethanol producers to increuse ttte enery yield of ther final product, from o current value of 2.i to a rane from ctnywhere between 3 to 4, providing praducers the rneans to attain higher profit rnargins relative ta those ottuined currently. The use and subsequent retycling of the Extraction Salvent olsa aids in cuttng medium to lang-terrr cosfs and provides additional safety n the production process.

t-y' /'i

rase

of tnstatlton snd Mointenence

The simple circutry af aur system will make nstallalian and maintenance hassle-free. Furthermare, aur system is desgned to occc;unt for surges in nturket demond; whence t s bult with o 30% additianut

capacity to that requested far by customers. I'his is to allow production to be adjusted to meet shif ts in rnarket demond as and when necessory. Start-up and shutdown pracedures ore alsr relatively simple ta implement.

,\Sustorna bility antt

'['he

Eca-f riendtiness of

our System

increased energy yield of bioethanol ond the recycling ot' the Extraction Solvent wil! serve to pt aur innovation ahead af conventonal purfcation methods in the Green Technolagies rend. Not only witt t uid companes usng aur process economically, t wll also help them in their quest for ochieving better Corporote Social Responsibility and the attinment of their Enviranmental Torgets, such as lower
carban footprnt etc.

c. Intellectual
Fietd of

Propcrty Rights ilpRs)

tnvention

'

l){,1

rk t

Fn'Ililt\< "

r,t lr"tt '$uc ltrnr,tti tr,trrlr {,r \rril\ tlftt'lk

The present innovatiot relotes generally to processes

particular, to pracesses
feedstocks.

for producing and/ or purfying ethanol und, in for producing and/ or purifyinq ethanol from row solution of fermenterl organic

4ackground

of the lnvention

Ethonolfor industrial use is conventiono!ly produced from petrochenticul feed stocks, such as o1, nutural gas, or coal, from t'eed stock intermediates, such as syngas, or from starchy mttteriols or cellulose naterials, such s corn ar sugrcdne. Conventional rnethods for producn ethonol from petrochernical feedstocks, os well as from cellulose mterials, include the acid-catalysed hydration of ethylene, methanol homologation, direct lcohol synthesis, und f ischer-'l'ropsch synthess. lnstctblity n petrocherncol feed stock prices contributes to fluctuotions in the cast of conventir:nally produced ethonol, moking the ne.ed t'or alternative sources af ethanol productictn all the gredter. In light ot' increosing globol demand for alternative fuels, the global bioethanal murket is set far a period of steady growth. Starchy ntuterals, as well as cellulose moterial, ore canverted tr ethunol by fermentutian und it s this source of ethanol that is typicolly used far cansumer production of hanol for fuels. Distllation is generally employed to purify n aqueous crude ethanol srlutian. 'I'his distillation methad requires o large number of distilling columns ond it cansumes a large quantity af steam for distillatian. Nence, the conventonal process far the purifcation of ethanol using ct large number af distllng columns is very poor in energy efficiency. ln order to improve the problem with poor energy efficiency a process is praposed thot encampasses ot' first concentrat'ing the ethonal t'ram raw solution via means of liquidphase extrqetion usng o suitable solvent and thereafter by oppliccttion of flash rlistilation to obtain the purified ethanol. Fnergy consumption from this method will be reduced and ecctnomies moy be reped"

lPRs

in Existing lndustril Producton Methads

A search af US and European patents offices have shottn that nurnerous ethnol purficotion technicues

huve been potented, but none af these uses the prncple af Lquid-Liquid xtracton with an Orgnic Solvent or lanic Fluid to perform such an endevour. A brief description of severol af such patents will be dlscvssed below lo show that aur present invention has nat infringed upon ny exsting patents:
)..

Purifying ond/or recovery of ethanol from o crude ethnol product abtined from the hydragenation of acetic acid. Seporation and purification processes of crude ethnol mixture are emplayed ta allow recovery of ethanol and remave impurit[es. In sdclition, the pracess involves returning acetoldehyde separated fram the crude ethanol product to the reoctor. The invention relates to processes for recovering ethanol produced by a hydrogenaton process comprising hydrogenating ocetc ocid in the presence of o ccttalyst. ln prtrticulor, the present inventan reltes to recavering and/or purifying ethanol front u crude ethanol product preferobly produced by the hydrogenotion pracess. The process includes d step of separatng dcetaldehyde from the crude reoction mxture and returning seporoted rcetaldehyde to the reaction process, preferably to the acetic acid feed, to the voporizer, or to the hydrogenation resctor. The returned acetoldehyde may be reacted under hydrogenation conditans to make odditional ethanol. ln one embodiment, the acetldehyde is separuted frorn a stream comprising ethyl acetdte derived from the crude ethonol praduct. This moy llow a major portion of the ethyl acette to be removed f rom the pracess withaut ltuilding up ethyl acetdte throughout the

separation process. Embodiments of the present inventian beneficially rnay be used in opplcotions for racovering ond/or purfying elhanol on an industriol st.qle.

2.

Eurqpean Potefi Nuqter, EP 0 _UZ^AJL gllppl, af Srant of ptenj 29 Jon t997) f he stoted invention trovides a trocess for the turification of te aqueous crude ethanot
sol

ution,
o

w hi

ch cont pri se s:

(i)

first extracton step wherein the aqueous crude ethnot solution s extracted with un extractant far rernoving the lipophilir; impurities contained in the aqueous crude ethano! solution by subjectng the uqueaus crude ethanol salution to extracton with the
extractont in a pressurzed state, which camprises carbon dioxide in a liquidized state or corbon dioxide gas in a supercritical stnte,

() (ii) (iv)

a concentration-distillaton step wherein a raffnate obtained in the frst extroction step is fed to a distilling column to thereby obtin a highly concentrdted aqueous ethanol

solution from the top af the rlistilline column o second extroction step wherein the sde stream is braught into contact with the extract in a pressurized stte, obtqned in the first extrscton step, t6 thereby extractthe
C3-C4 ulcohols cantained in the side stream intts the extract; ond

d water washing step wherein the extrnct n o pressurized stote, oltained in the second extraction "sle is brought into countercurrent contact with water in a pressurized state

to recover \he ethanol contained in the extract into an aqueous pose,

The extrqctqnt to be employed

far

this inventon rnoy nclude carban diaxide n the liqudzed

stdte or curhon dioxide goses in the supercritcal stdte. For the process according to this invention, it is preferred ta use the carban dirsxide sustained at pressure in the range of from 40

ta

150 kg/cm? nc!

ot tentperature n the range offrom 2A"C b

50"C,

Conclusions

Attr present nvention relates to u wdely-studied field, but it does not infringe on any existing ln fact, the present inventio- should rightly come under the relevant patent protections as the techniques used tread on new frontiers in the field of ethonol purification, making it more sustoinoble and prafitable ol'the same time. lt is recommended ot ths stage to proceed with further developrnerlt a the present invention as it clears all the critera from the perspectve of
patents.
/Ps.

Bibliography
AlgenolBiofuels. (2013). Retrieved fromhttp://www.algenolbiofuels.com/commercialization/ethanolmarket
Frost & Sullivan.

(2}ttl.

A Bio-bosed Future for the Chemicols and Moteriols Market. London: Frost &

Sullivan Publications Division.

Hofstrand, D. (February,2OI2l. Seasonalityof Corn EthanolProfitability.AgMRCRenewoble Energy&

Climote Chonge Newsletter.

JeWic, R. J. (2012). United States of America Potent No. US 8,304,586 82.

Lucintel. (20t2.. Growth Opportunities in the Globol Fuel Ethonol Market 2012-2017: Trends, Forecast ond Market Shore Anolysis. Medeiros, V. (2013). Ethonol: A Leap into the Future. Retrieved from Petrobras lnternational Website: http ://www. petrobras.com.sg/en/magazi ne/post/deta I he-11. htm

Muto, T. K. (1997). Europeon Pqtent Office Potent No.

EP

0 543 012 81.

O'Brien, D. (July, 2009). The Relationship of Ethanol, Gasoline and Oil Prices. AgMRC Renewoble Energy

Newsletter.
Renewable Fuels Association. (20131. Pocket Guide to Ethanol 2073. Washington, D.C.: Renewable Fuels Association. Retrieved lromhttp://www.ethanolrfa.org/pages/rfa-pocket-guide-to-ethanol Silicon Valley Bank Cleantech Practice. (2012). The Advonced Biuofuel and Biochemicol Overview. Santa
Clara, California: Silicon Valley Bank Financial Group.

Wisner,

R. (August, 2009). Corn, Ethanol and Crude Oil Price Relationships

- lmplications for the Biofuels

lndustry. AgMRC Renewable Energy Newsletter.

Stase 3 - Develoment
ln stage 3, the development of the liquid-liquid extraction process is first looked into, with focus on sizing the required equipment for the plant, by simulation of the process using an appropriate software. Next, the performance of the liquid-lquid extraction process is evaluated when subjected to several change in the process conditions. Then, using size information from simulation results, the techno-economic of the liquid-liquid extraction process is studied to determine the cost competitiveness of the process compared to conventional bio-ethanol pu rificaton processes.

t.

Equipment Sizing The following information is obtained by simulating the liquid-liquid extraction purification of bio-ethanol using a Extrocton Column Column type: Continuous Counterflow contactors, no mechanical agitation, Single Section Cascade Column material: 316 stainless steel Packing type: 25-mm Saddle rings, Random Packing Column height: 10m Column diameter:4m Feed rate: 103m3/hr
Feed Flosh Drum

velocity:8.Zm/hr

Drum type: Single stage, vertical drum

Drum Material: 316 stainless steel Drum height:8m Drum diameter: 2m Feed rate: tq.Sm3/hr

velocity:4.6m/hr Heating type: Electric immersion heater 200kW

Feed

c. Pumps
Pumps for

All pumps are centrifugal, stainless steel

:103m3/hr : t2m3/hr :15m3/hr

2.

Performance Evaluation During the actual manufacturing process, the plant is likely to be affected by change(s) in commercial condition. In this section, several scenarios are discussed and the performance of the bio-ethanol purification process are investigated.

d.

Chqnae

in ethanol concentration in the inputf-oJ

Changes in the operating condition of upstream processes may affect the

condition of the feed entering the extraction column. A higher ethanol concentration in the feed is favourable to the process. Less energy is used to achieve the desired output. Conversely, a lower ethanol concentration in the feed may require a reflux of the product back to the extractor or use more energy to achieve the target product purity, which is likely to affect the costeffectiveness a dversely.

b.

Hiaher product puritv Depending on consumer application, the client may demand a higher bioethanol purity. In this situation, the process parameters can be adjusted to achieve a higher ethanol purity in the product stream, up to . This would inevitably increase the costs of production. More studies are required to investigate the cost-effectiveness prior to actual implementation.

c,

Hiaher supplv

3.

lP Position

ffi ffir:l
ffi

fl'.--w'qtL'Ac -'
t,(E,un(sl

4. Techno-economics
the Bio-ethanol Purification facility is performed to evaluate the economic viability of the process. The equipment cost of the plant is estimated based on data provided by Peters, M.S. et al. and the total capital investment is determined using the Percentage of Delivered-Equipment Cost Method [A].
The techno-economic analysis of

a.

CopitalCost
The data published by Peters, M.S. et al. is dated January 2002. The estimated prices are correctedto2OL2 value based on the Chemical

Engineering Plant Cost lndex (CEPCI). The CEPCI for 2OO2 and2OL2 are 395.6 [C] and 585.6 [ respectively.

i.

Purchased Equipment Cost

t
Extraction column
Packings
Flash drum

Cost

s.
25,OOO $

100,000

Electric immersion heter for flash drum

'$ 33,000 s 8,000

,$'
L2,0O0

s 4,800

5;'2 s TotalCost of Equipment (2002) 388,000 Totol Cost of Purchases Equpment ,$.i. (odjusted to 2072) 57.41350

the purchased equipment estimated, the direct and indirect costs were calculated to determine the total capital investment required.
Based on the cost of

Direct Costs
'$'.1'

Purchosed Equipment Purchsed Equi pment Delivery

Pu

5,7,4y350

s 57,435

rch ased Equi pme

nt I nsta llati on
o

.26
$

),

945

nstru m entti on

nd

co

ntrols
Piping

206,766 ,r$,:-',.,
'R.0iS5-B

Electricol systems

s 63,L79

Buildings ond Services

Yord lmprovements

$-t"' tr0.3 83
$

57,435

Service Fscilities

402t0#5 s
2,L25,O95

Total Direct Costs

lndirect Costs
Engi n eeri ng

nd

su

pervisi on

s 189,536

r$.;iir,
Construction expenses
2:g$.4

,.

s Legal expenses 22,974 ,.siriiii,., Contractor's fee ,Sjg"p.H; s Contingency 252,7L4 Totol lndirecf Costs

'$,iffii
8.2-ttpf,rl

Fixed-co pito I i nv estm

nt

Working capital

442,824 Total captal nvestment

s 3,394983

Manufacturing Cost c-8even,en d. Return on lnvestm entL

b.

Reference

[A] Peters, M.S., Timmerhaus, K.D. and West, R.E. (2004). Plant Design and Economics for Chemical Engineers, Sth edition. New York, Ny: McGraw-Hill
IB] "Chemical Engineering Plant Cost lndex (CEPCI)." Chemicol Engineering Plqnt HighBeam Business, 01 Oct. 2012. Web. Retrieved, 22 Septemb er ZOL3, from
Cost tndex (CEpCt).

[C] Norwegian University of Science and Technology, NTNU - Trondheim. Retrieved, 22 September 2OI3, lrom http://www. nt. ntn u. nolusers//maene hi/ce oci 2011 pv. pdf

///)
l) I

/-

v--a

& i' ,/ti"'1""/'/(

-.

t/

,..
Gate 4: Decision to invest in scale-uo and oroduct

'.

testino

lt (/ /t' "'
!\ !

\if.,, r,,//, t,' rt{l

The decision to go ahead with scale-up is contingent on:

Sufficient thermodynamic equilibrium data

experiments & are of sufficient accuracy

& mass transfer data has been compiled from

Partition,ffiili?li;anor

. . . . . . o .
Scale:

in reed stream & sorvenr stream Mass transfer coefficients across feed/solvent interface A detailed design of unit operations & the plant equipment use by the unit operations has been

comPleted'

Packed corumn LLE Flash Drum A sensitivity analysis of the full-scale plant process has been performed & knowledge of what the

. .

/ /' / ,," '/ 2 Prototypes relevant? lt's just LLE, quite well-established. ,, ,,4, , Relevant tests using HPLC (what analytcal methods?j' othr analytical methods have ben devised for quality assurance of product stream, i.e. to test whether the product stream meets man ufacturing specifications. A detailed schedule of the manufacturing trial runs that will be carried out (e.9. what temperatures, pressures & feed flowrates & concentrations will be tested) Detailed design of pilot-scale equipment (based on full production-scale equipment designs) must be completed. A detailed plan of how data from the pilot-plant will be used to test whether the designed process is able to meet manufacturing specifications. HAZOP & safety analysis of full-scale plant must be completed t ',: (.,, l", . ..(- , HAZOP & safety analysis of pilot plant must be completed
I

specifications.

range of physical (e.9. temperature & pressure) & chemical (e.9. feed concentration of bioethanol) process conditions have to be within for the product to meet manufacturing

Staoe 4: Detailed desion of nilot-scale aouioment

l.-,.:t

o o

Full

.t""'""0 stream = 900,000 MTA =

Product stream = 100,000 MTA = 1 I ,905 kg/h Pilot scale:

107,143

kgrh

..1 t..
.

: i{t*t*#*t1i;:""uratey
ta.

represent mass rransrer & other processing conditions in the actual plant while minimizing amount of feedstock used for trial run.

Equipment Designtll: . LLE Column o No. of equilibrium stages in the LLE column taken from Stage3 calculations

o o

Height of each stage determined by mass transfer coefficient between feed & solvent
phases.

! ,*-.<

Column diameter determined from feed & solvent flowrate. Column diameter should be such that flow velocity low enough to allow transport of bioethanol from aqueous to
organic phase. . Suitable column diameter can be calculated from D'Arcy's equation:

'

P =41Lu2 29AP wheref=frictionfactor:

't

.','

\
)

o .

P is as specified in the full-scale manufacturing plant in Stage 3 D has to be solved for iteratively. The finaltotalcolumn height (L) & column diameter (D) should be such that L/D - 8

. .

o h=r.nr_1..74tn(+.#)

Flash Drum o The final separation of the bioethanol product from the solvent stream is performed using flash separation. A vertical flash sepa ation drum with dimensions L/D = 4 as specifed foi the full-scale plant design will be used. o Since the L/D is known, the key dimension to calculate is the vessel diameter, D. . D is dependent on the maximum vapour flowrate, Uu"p,r"ri

Uuop,^o,

= O'02

O.Ol99 m/s

.,(

\ I I
i ( o

For the feed (900 kg/h) & sotvent (900 kg/h) ftowrates specified, the volumetric flowrates qt the flash drum operating temperature & pressure results in 3.52e-6 m3/s liquid bottoms flowrat & o.OO428 upui flowrate. This results in a minimum drum cross-sectional area of 0.215 m2 which translates to a minimum column of 0.523 m. . rut For Lrl-'l LID 4, the rne pilot-scale -.r, orum height netgnl would woulo lnus thus be e 2.09 m. Pilor-scate drum The flash separation is fully heat integrated with the heat from the vapour feed used to preheat the feed stream to the flash drum to reduce the energy consumption of the etectrcal heaters within the flash drum.

rtl"

diameter

Staqe 4: Trial run. Product Validation. & product Testino

Trial Run & Samplinq

bioethanol product stream mass flowrate. Sampling was done at the following points in the process to ensure that the process meets manufacturing specifications: o Extract stream of LLE column: To determine extraction efficiency of the LLE process ' Raffinate stream of LLE column: : To determine how much bioethanol is lost in the waste stream Final Product stream: determine if the final bioethanol product stream meets the manufacturing ' specifications

As previously stated, the trial run involves operating the designed process at the pilot scale of 100 kg/h of

taken together with the bioethanol losses in the raffinate stream, to determine the total bioethanol product loss of the entire process. The following methods will be used to test: o Gas chromatography (GC) will be used to determine the ethanol content in the sampled streams stated above ln addition, a sensitivity analysis was performed in accordance with the full-scale plant design: . Feed bioethanol concentration was varied from Bo/o wt - 12o/o wt. Product stream purity requirements was varied from 90o/o wt - 9g% wt.

Flash drum bottoms stream: To determine how much bioethanol is lost in the waste stream, &

TrialRun Results
Performance Metrics for Meetinq Manufacturinq Soecifications
& waste minimization:

The pilot-scale plant was found to be able to meet the manufacturing specifications for the product stream

Extract stream was found to contain bioethanol concentration of 10% wt concentration.

. . .

Raffinate stream was found to contain bioethanol concentration of 0.75o/o wt concentration Final Product stream was found to contain bioethanol concentration of 90.03% wt concentration. Flash drum bottoms stream was found to contain bioethanol concentration of 2.7o/o wt concentration

Enerqv Yield Energy vield = (Energy Value of Ethanol as a fuel)/(Energy consumed by process) The energy yield of the entire pilot plant process after heat integration was found to be 3.64, indicating a highly energy efficient process. Energy cost per unit mass of product stream produced = ??? USD/kg

Product & Feed Cost

??? USD/kg production cost & ??? USD/kg sale price possible on

,. -

Total Mass Balance Results of bioethanol fed to process recovered in product f bioethanol lost in the raffinate stream. / f bioethanol lost in the flash bottoms stream.
-

stream.

,''

Resulls of Sensitivitv Analvsis

ln addition, the plant was also able to meet the product stream requirement range of 90% wt - 99% wt bioethanol based on customer specifications while being subjected to the sensitivity analysis feed concenlrations of 8% wl - 12o/o vtl.
The total energy requirements as determined during the sensitivity analysis are as follows:

Feed
Puritv 8% wt 10o/o t

Concentration\Product

90% wt

99% wt ??? kJlko ( USD/ko) ??? kJlko I USD/ko) ??? kJlko ( USD/kq)
/a,

??? kJlks ( USD/kq) ??? kJlko ( USD/kq) 12o/o t'tl ??? kJlkq ( USD/ko) Table 1' Fne rgy requirements rements resulfi resulting from sens sensitivity e analy sts

The total energy yield as determined during the sensitivity analysis are as follows:
Feed Puritv

Concentration\Product

90% wt 3.50
3.64 3.75

99o/o

wt

8% wt
10o/o

vtt

3.05 3.15
3.24

12o/o v'

Table 2: Energy yield resulting from sensitivity analysts

While the process was found to be energy efficient for all conditions tested, it is worth noting that increasing the required product purity significantly decreases the energy efficiency of the process due to the increased amount of energy expended at the flash drum to purify the product stream.

The total bioethanolwastage as determined during the sensitivity analysis are as follows:

Feed
Purity
8o/o

Concentration\product

90% wt ???
of feed of feed "/o ?'l'? Yo o feed
o/o

99% wt

tvt
wt

1Oo/" tt'tl
70
I

l'/'/

2?2
(t

o/^

nf feol

aDle 3: tsioetha

wastage resulting from sensitivity anatysis

???

-/o OI o/" of

d
feel

iled.

ted market. ct stream samples. uction process to meet cutomer requirements.

Gate 5 : PRODUCT TAUNCH AppROVAt

The result obtained from the pilot plant shows the

LLE

process of Bio ethanol is more efffective and

efficient than conventional distillation process.

Convention method for producing Bio Ethanol Distllation

Since water and Ethanol contain almost same temperature the process

of distillation

is

o o o o o

difficult
Design is too complicated High energy consumption Heavv investment and over head cost

Our Novel Process

The design for LLE and flash distillaton is simple compare to conventional distillation

Very less energy consumption More efficient method for Bio Ethanol Production ( Purity ??)

SWOT Analysis

Strength

. o o

Energy Efficient Low capex Less space occupied than conventional method

Weakness

Raw materials used for Novel Method

Opputunity Alternate for the existing conventional simple distillation Renewable energy market

o o

Threats

Proper solvent to increase the efficiency

Stage5:PRODUCTTAUNCH
Execute the launch plans

Demonstrate control of the Manufacturing and Sales & Marketing control plans. Review project, compare actualwith projected results ldentify process improvement opportunities. Develop the hand-off plan to transition the new process into ongoing business operations.

POST IAUNCH REVIEW

) ) )

)
)

Verify business opportunity is being achieved Manage product value chain for maximum return Use the control plans developed in Launch Use Lean Six Sigma tools for continuous improvement Gather customer feedback to identify opportunities for further development Reducing post development gap