LECTURE NOTE Petrochemicals

LINEAR ALKYL BENZENE (LAB)

(Unit I)
Dr A K Gupta Head, Chemical & Biotechnology Division Indian Institute of Petroleum Dehradun - 248001

LINEAR ALKYL BENZENE (LAB) (Detergent Alkylate)

LINEAR ALKYL BENZENE

Linear alkyl benzene (LAB) is the primary raw material used to produced LAB sulfonate (LAS), a surfactant detergent intermediate. LAB global demand is about 2.7 million tonnes per year. Its growth is mainly expected in the less developed countries.

Traditional processes for LAB production include an alkylation unit with liquid catalysts, which depending on the process, may include the following: 1. Alkylation of benzene with olefins C10-C14 in presence of HF. 2. Alkylation of benzene with chloroparaffins C10C14 in presence of AlCl3. 3. Alkylation of benzene with olefins C10-C14 in presence of AlCl3.

Now-a-days most of LAB is produced from linear internal olefins and majority of commercial applications worldwide are based on HF catalyst.

RAW MATERIAL FOR LAB

Benzene Petroleum or natural gas based paraffins/olefins.
Paraffins from kerosene Olefins from wax cracking Olefins from ethylene.

Chemical Reactions (Linear Alkyl Benzenes)

(1)
R-CH=CH-R' + Olefin R-CH-CH2-R'

Alkyl Benzene

R-CH=CH2-R'

R-CH-CH2-R'

(2)

+ R-CH=CH-R' R-CH-CH2-R' Dialkyl Benzene

(3) Reaction with Diolefins:

R-CH=CH-CH=CH-R' + Diolefin R-CH=CH2-CH=CH2-R'

Contd
Diphenyl alkane

(4) Heavier components are formed by reactions (1), (2),and (3). (5) Olefin Reaction with HF:

combination of

H H R-CH=CH-R' + HF R - C - C - R' H F

Alkyl Fluorides

 Polyalkyl benzenes, indanes and tetralines are typical compounds produced by benzene side reactions.
Branched alkylbenzene and oligomers, which are precursors of tars, coke are usually produced by olefin side reactions.

CATALYSTSStrong Catalysts : AlBr3, AlCl3, HF.BF3 Product distribution same at room temperature or higher (35-37C). Weak Catalysts: HF, H2SO4, AlCl3.H2SO4, AlCl3 at low temperature. Product distribution depends upon: Chain length Location of double bond Ratio of reactants. Type of solvent (ratio also). Temperature. Homogenity of reaction medium.

Akylation of Benzene with 1-Dodecene

Product Distribution

Catalyst
SiO2-Al2O3 H-Montmorillonitea Amberlyst H-Y RE-Y H-BETA HMb HF
aWHSV

2 pH/6 pH ratio 6 pH 14.2 19.1 15.1 16.3 21.5 4.80 -25.3

2.4 1.4 2.3 1.8 0.8 8.2 70.7c 0.70

2 pH 33.4 26.0 34.5 29.5 17.6 39.1 63.7 16.7

3 pH 21.9 19.1 20.2 20.2 19.1 26.4 35.4 16.4

4 pH 14.8 16.7 14.3 17.1 19.8 18.9 0.90 17.5

5 pH 15.6 19.1 15.9 16.9 22.0 10.8 Trace 24.1

set to 0.5 to obtain 100% conversion. bincomplete conversion. c2 pH/4pH ratio, 6 pH not detected.

DETERGENT ALKYLATE
Produced by reaction of -olefins or internal olefins with benzene using AlCl3, HF or Conc. H2SO4 as catalyst. The reaction is conventional Friedel-Crafts Alkylation, highly exothermic reaction usually carried out in liquid-phase. Olefin concentration is kept low to minimize side reactions and control temperature. High Bz/Olefin ratios preferred to obtain high selectivity to mono alkylation.

Process for Detergent Alkylate Production

Name of Process/Comp any (Ref.)
UOP process (3,4)

Feed stock

Catalyst

Remarks

Benzene; olefins produced by dehydogenation of nparaffins. Benzene n-alkylchloride having 9 to 16 carbon atoms per molecule. Benzene; olefins from dehydrogenation of paraffins.

HF

Liquid phase; reaction is carried out in two stage reaction system. Reaction first carried out at 248 K for 9-10 minutes and then 303 to 379 K for at least 4 minutes. Reaction temperature ~312 K stirred tank reactors equipped with cooling coils; HF to olefin ratio is about 18:1 benzene to olefin ratio is 6:1. Temperature used are relatively higher around 363 K.

Lummus Company (5)

Friedel crafts catalysts. Anhydrous HF

Monsanto Co.

Atlantic Rickfield Co. (7)

Benzene; Olefin mixture

AlCl3 in slurry.

Commercial process for the production of LAB

Alkylation with chloroparaffins
Catalyst Temperature(C) Feed ratio Lab linearity (%) Tetralins (%) AlCl3 65-70 8/1 <90 3-4

Olefin/AlCl3 UOP/HF alkylation

AlCl3 60-75 8/1 98 <1.0 HF 40-60 8/1 92-94 <0.3

LATEST LAB DEVELOPMENT

PACOL Catalyst and operation conditions ALKYLATION Solid Catalysts, Zeolites, clays, resins.
REACTION IN HETEROGENEOUS FIXEDBED REACTORS => UOPs DETAL Process

ALKYLATION WITH SOLID CATALYSTS

Several solid catalysts, zeolites, clays, heteropolyacids, sulfated ziroconia, immobilised ionic liquids were tested.
=> not commercially exploited so far.

Benzene alkylation with C10-C13 olefins

Catalyst
Zeolite Y Beta ERB-1 L CaY ReY LaY Pillard clay Al-PILC AlCe-PILC AlGaCeMg-PILC

T(C)

Olefins conversion(%)
99 99.5 98.7 92.8 99.8 99.8 99.8 93.1 100 100

Lab linearity Life (%) (h)

91.7 78.5 88.45 72.92 41.8 91.61 94.89 98.5 93.8 94.2 140 120 <40 <20 >160 120 160 16 140 120

155 155 155 155 155 155 155 155 155 155

 An important breakthrough was achieved by UOP in 1992 New catalyst jointly with CESPA
Fluorinated silica-alumina

The process is known as DETAL process.

The catalyst SiO2/Al2O3 ratio is 65/35 to 85/15, impregnated with HF. The finished catalyst contains 1-6%.
Table : LAB by Delta process n-Alkyl benzene (wt.%) 95 Tetraline (wt%) <0.5

 DETAL process was tested in Petresas demonstration unit in Spain in 1992. Three LAB plants use this technology.

Table : Operating Requirements per ton of Lab (ARC) Process

Raw materials: n-Paraffins Benzene Chlorine vapour By Products Heavy alkylate HCl gas Chemicals: Aluminium powder Flake caustic Liquid caustic Utilities Steam Cooling Water Electric power Fuel (absorbed) 763 kg. 359 kg. 368 kg. 81 kg. 365 kg. 1.1 kg. 5 kg. 366 kg.

570 kg. 105 kg. 159 Kwh 1.58 mKcal

Operating Requirements per ton of Lab (EUTECO IMPIANTI S.P.A. Lab process)
Raw materials: n-Paraffins Benzene Chlorine vapour By Products Hydrochloric acid Heavy alkylates Utilities Steam Power Cooling water Fuel oil Bromine Colour hazen Biodegradability OECD Acidity (as ppm H2SO4) 750 kg. 360 kg. 380 kg.

360 kg. 70 kg.

1000 kg. 60 kWh 200 m3 1.7 MM Max. 0.03 Max. 10 % 97 Max. 10

The linear alkyl benzenes product has the following typical properties

Table : Yields in HF Alkylation for the production of detergent alkylate (UOPDetergent alkylate process)
A. Alkylbenzene starting with n-paraffins CHARGE STOCK
Linear paraffins, 98.5 wt% purity Benzene, 99.9 wt% purity
Total MATERIAL PRODUCED Hydrogen, 96 mol % purity Light ends HF regenerator bottoms Detergent alkylate Heavy alkylate Total Produced:

Weight per 100 weights of linear detergent alkylate

82.9 34.4
117.3

1.1 3.8 2.8 100.0 9.6 117.3

Contd

A. Alkylbenzene from Propylene tetamer CHARGE STOCK

Propylene tetramer Benzene

Weight per 100 weights of linear detergent alkylate 92.42 46.45

Total Charge 138.87 PRODUCT Light alkylate Dodecylbenzene Heavy alkylate Tar

20.29 100.00 14.67 3.91

Total Products: 138.87

Contd

PRODUCT QUALITY: The linear alkylbenzene product has the following typical properties.
Bromine number Saybolt Colour Doctor Test Linear alkylbenzene, wt% Unsulfonatable, % Biodegradability of the linear alkybenzene Sulfonate (ASTM D2667), % TYPICAL ALKYLATION CONDITIONS ARE: Temperature Pressure Catalyst Yield 0.01 30+ Sweet 94 1 97 40-70C Liquid phase HF 95%

Comparison of the conventional HF alkylation with the alkylation using solid polymer catalyst.
Conventional HF IIP Process alkylation LAB scale data
Conversion of olefins Selectivity to monoalkylation Catalyst Corrosion Handling problem Continuous regeneration Benzene to olefin ratio Catalyst to feed ratio >99% ~ 90% Liquid Yes Yes Required 5:1-10:1 10:1-20:1 >99% 95% Solid No No Not required 5:1 0.1:1-0.15:1

GROWTH OF LAB IN INDIA

Company-wise LAB plants with capacities, 2001-02

tons Company
IPCL (1978-79) RIL (1987-88) TPPL (1987-88) Nirma Ltd. (1998) Total

Plant Location
Baroda Patalganga Chennai Savil, Baroda

Capacity
43,500 100,000 93,000 75,000 311,500

Source: Department of Chemicals & Petrochemicals, Ministry of Chemicals & Fertilizers, Govt. of India, New Delhi.

Highest capacity of LAB plant was of RIL. After acquiring 26 percent of Governments stake of IPCL in May 2002, LAB capacity of RIL has risen to 1,43,500 tons, increasing its market share from 32 percent to 46 percent.

Trends in consumption of LAB during the period 1979-80 to 2000-01

Year
1979-80 1984-85 1989-90 1990-91 1994-95 1999-00 2000-01

Production
13500 28000 125570 180919 213560 325799 359012

tons Consumption

33000 64800 125570 156919 182270 300377 318439

Source: Department of Chemicals & Petrochemicals, Ministry of Chemicals & Fertilizers, Govt. of India, New Delhi and Monthly statistics of Foreign Trade in India, Part I & II, Mar 1980 to March 2001 (Directorate General of commercial intelligence & statistics, Calcutta).

Consumption of LAB was 318439 tons in 2000-01 as compared to its production of 356038 tons. With the rapid growth in demand for synthetic detergents, its is expected that the demand for LAB, which is the main raw material for synthetic detergents, will also grow commensurately.

Projected demand and supply gap of LAB during the period, 2001-02 to 2005-06
Year Demand projections Installed capacity Production, if plants operate @90% of the capacity 280 280 280 388 388

000 tons
Surplus (+) Deficit (-) -66 -95 -127 -54 -92

2001-02 2002-03 2003-04 2004-05 2005-06

346 375 407 442 480

311.5 311.5 311.5 431.5 431.5

Source : The Economics Department, Petrochemicals Data Service, Vadodra

Trends in exports and imports of LAB, 1990-91 to 2000-01

Year
1990-91 1991-92 1994-95 1995-96 1996-97 1999-00 2000-01

tons

Exports
0 7767 31420 19512 6290 25547 40591

Imports
0 1204 137 3413 98 125 19

Source: monthly statistics of Foreign Trade in India, Part I & II, Mar 1991 to Mar; 2001 (Directorate General of Commercial Intelligence & Statistics, Calcutta).

Indias Exports of LAB by countries, 1999-2000 and 2000-01

Country
German F Rep New Zeeland Philippines Portugal Saudi Arab Thailand Turkey UAE USA Yemen Republic Bangladesh Belgium Israel Japan Nepal Sri Lanka Uruguay Vietnam Total

1999-00
2000 18 525 2050 8750 5818 2100 3205 30 1050 25547

2000-01
4148 1030 12637 8597 5228 1840 3593 321 120 19 116 45 668 14 2215

40591 Source: monthly statistics of Foreign Trade in India, Part I , Mar 2000 to Mar; 2001 (Directorate General of Commercial Intelligence & Statistics, Calcutta).

Inidias Imports of LAB by countries, 1999-00 and 2000-01

Country
Chinese Taipei German F Rep Korea RP UK USA Total

1999-00
107.00 3.62 14.00

2000-01
0.55 5.53 12.48 0.204 18.8

124.62

Source: monthly statistics of Foreign Trade in India, Part II, Mar 2000 to Mar; 2001 (Directorate General of Commercial Intelligence & Statistics, Calcutta).