Hydroprocessing of diesel and vegetable oil blends

T.M. Sankaranarayanan, M. Banu, A.K. Tiwari and S. Sivasanker

National Centre for Catalysis Research, Indian Institute of Technology - Madras, Chennai-600036

NCCR3rd Annual day 01st Aug 2009

1

INTRODUCTION

The use of fossil fuels at the present rate is not sustainable due to:
1) Rapid depletion of resources 2) Carbon emission – global warming due to greenhouse gases (GHG)

USE RENEWABLE and CARBON NEUTRAL BIO-MASS BASED FUELS

Global fossil fuel consumption ~ 7 Gt/y Biomass produced annually ~ 200 Gt/y
2

NCCR3rd Annual day 01st Aug 2009

OIL USE – SECTOR WISE (million tons, oil equivalent)
1985
Transport Petrochem. 1180 140

1995
1600 192 1216

2000
1870 250 1265

2010
2320 300 1430

Heating and 1340 Industrial Other 140
Total Share of Transport 2800 42

192
3200 50

215
3600 52

250
4300 54

• Share of transportation sector is increasing

• Replacing diesel & petrol with biofuels is important for sustainable growth 3
NCCR3rd Annual day 01st Aug 2009

Paris) "The use of vegetable oils for engine fuels may seem insignificant today. But such oils may become in the course of time as important as the petroleum and coal tar products of the present time" .Rudolf Diesel (1858 – 1913) His first engine ran on peanut oil (1900. 4 NCCR3rd Annual day 01st Aug 2009 . 1912.Rudolf Diesel.

5 NCCR3rd Annual day 01st Aug 2009 . but are blended (5 . vegetable oils possess 1) Higher viscosity (difficulty in feed injection) 2) Lower cetane number (poor engine performance) 3) Lower heating value (lower energy output) 4) High cloud and pour points (limited use in winter) 5) Lower stability due to unsaturation (tank deposits) 6) Larger carbon deposition in engine (engine damage) 7) Contain many impurities .phospholipids Hence. biodiesel) by transesterification with methanol They (FAME) are generally not used as neat fuels.20%) with diesel and used.Disadvantages of neat vegetable oils as diesel fuel Compared to diesel. vegetable oils are converted into FAME (Fatty Acid Mono Esters.

transesterification is not possible with conventional base catalysts if free fatty acids are present in the oil (non-edible oils) – these oils require expensive fatty acid separation or use of less effective (or expensive) acid catalysts 6 NCCR3rd Annual day 01st Aug 2009 .) 4) Lower heating value of the fuel (power output. tank capacity) 5) Compatibility problems of some components in the engine (cost) Also. water requirement for washing etc.Diesel-FAME blends also have many drawbacks These are: 1) Expensive transesterification process (cost of fuel increases) 2) Need for conversion of by-product glycerol into value added chemicals 3) Environmental effects of transesterification (waste disposal.

there are no commercial processes for economic reasons Cracking: Cracking of neat vegetable oils produces poor quality products and catalyst stability is poor. Presently. they can be cracked / hydrocracked into diesel range hydrocarbons Many reports of cracking and hydrocracking of vegetable oils into hydrocarbons are available in the literature.Other options for converting vegetable oils into diesel range fuels Diesel fuel is a mixture of hydrocarbons (majority paraffins) mostly in the carbon number range of 15 – 22. Vegetable oils are triglycerides of mostly C16 and C18 fatty acids Hence. yield is also low Hydrocracking: Hydrocracking of neat vegetable oils requires high pressures 7 (>150bars) for complete conversion and is an expensive process .

Another option is to blend the vegetable oil with the diesel and hydroprocess at low severity conditions 8 .

temp.: 350C or less] 9 NCCR3rd Annual day 01st Aug 2009 .We now present our preliminary studies on the hydroprocessing of blends of a straight run diesel oil fraction and a commercial Sunflower oil over a zeolite containing Ni-Mo-alumina catalyst The objective of this study is to investigate the cracking and hydrogenation of triglyceride molecules blended with diesel into hydrocarbons (C17 and C18 paraffins) under the moderate process conditions typically used in the hydrodesulfurization (HDS) of Straight Run diesel [pressure: 60 bars or less.

Feeds used: Diesel: A straight run diesel fraction supplied by Chennai Petroleum Corporation Ltd. oleic acid and oil The properties of the feeds are presented in the following slides 10 NCCR3rd Annual day 01st Aug 2009 . (CPCL) Vegetable oil: A commercial sunflower oil Blends: 1) 80:20 and 2) 60:40 by wt.EXPERIMENTAL 1. diesel: sunflower oil. 3) 90:10 diesel: Oleic acid and 4) 80:10:20 diesel.

5 17600 (140) Distillation characteristics ASTM. C Aniline point.Properties of the straight run diesel fraction Property Source Density at 15C. ppm 58. cSt Pour point.5 41. C Value PG mix 0. D2887 IBP 90% 233C 371C IBP 90% 101C 399C 92.. g/cc Viscosity at 40C. C Flash point.8% 380C 95% 418C 11 . Dist. wt% Aromatics. wt% Sulfur (N).03 0 74 121 Non-aromatics.8610 5. D86 GC Sim.

Gas chromatograms of the feeds used Straight run diesel 40 n-paraffins C14 C16 30 Diesel fraction 50 20 C15 40 C17 10 30 C12 C11 C18 0 5 10 15 20 25 30 35 40 45 20 C20 C24 10 Standard n-paraffins 0 5 10 15 20 C28 C 32 C 36 C 40 12 25 30 NCCR3rd Annual day 01st Aug 2009 35 40 45 .

538% steric.(0. 22.20% vegetable oil blend 60 10% FFA (oleic acid) with diesel 50 30 C18 fatty acid 40 Vegetable oil 20 30 20 10 10 Diesel oil 0 5 10 15 20 25 30 35 40 45 50 55 Diesel oil 0 10 20 30 40 50 The fatty acid composition of the sunflower oil was established by esterification with methanol and GC analysis of the esters.53% 2) C18 acids .6. Composition of the vegetable oil used (wt %): 1) C16 acids .54% linoleic)13 .38% oleic and 70.

Sasol) and zeolite beta (Zeolyst International). drying /calcining The characteristics of the catalyst are presented in the following slide 14 NCCR3rd Annual day 01st Aug 2009 .2. drying /calcining 3) Impregnation of NiO (from Ni(NO3)2). beta (30) and alumina (55). The composition (wt% on dry basis) of the catalyst was NiO (3). MoO3 (12). The catalyst was prepared by the following sequence of operations: 1) Preparation of extrudates of alumina (from Plural SB. drying /calcining 2) Impregnation of MoO3 (from ammonium heptamolybdate). Catalyst: A Ni-Mo-alumina-zeolite beta was used as the catalyst.

15 NCCR3rd Annual day 01st Aug 2009 .098 Total 0.278 - 12%MoO3.154 Sample Al2O3 BEA Support (30% BEA -55% Al2O3) 580 282 0. 40 - - - * From TPD of NH3.49 0.042 - 0.60 Acidity (mmol/g)* Weak 0. 3% NiO/Support 213 0.236 - 0. respectively. weak and strong refer to amount of NH3 desorbed below 200C and above 200C.55 0.Physicochemical characteristics of the catalyst BET Surface area (m2/g) 212 Total pore volume (cm3/g) 0.056 Strong 0.

Analysis of the gaseous products were done in a GC (Mayura) 16 using molecular sieve and Hysep columns. The process parameter ranges used were: Temperature.350C. Product analysis was done in a GC (Perkin-Elmer) using a short metal capillary column used for simulated distillation analysis. 1 – 4 h-1 and H2/oil ratio.3. WHSV. 500v/v. . Pressure. Catalytic experiments: The hydroprocessing of the blends was carried out at different process conditions in a high pressure fixed bed reactor using 30 g of catalyst. 30 – 60 bars. The catalyst was presulfided with a DMDS/diesel feed (2.5 wt % S) at 330C prior to carrying out the catalytic studies. 320 .

O H2C O C C17 C17 paraffin O HC O C C17 C18 paraffin [C18 acids] O H2C O C C17 CO2 Propane The likely products are: 1) C17 n-paraffin. 2) C18 n-paraffin. 3) C18 fatty acids. 5) propane and 6) CO2.RESULTS AND DISCUSSIONS i. Products expected from the vegetable oil Different products are expected from hydrocracking of a typical triglyceride molecule depending on which bonds are cracked. 17 NCCR3rd Annual day 01st Aug 2009 . 4) C18 alcohol.

 The triglyceride molecule itself may crack into di.5%) .and monoglycerides  The fatty acids formed are expected to undergo hydrogenation into the alcohols and paraffins  Negligible olefinic products are expected at the experimental conditions (high pressures of H2)  Cracking/isomerization may occur at the olefinc bonds producing light hydrocarbons and isomerized products  Products from C16 fatty acids will also be present (about 6.C16 and C15 hydrocarbons 18 NCCR3rd Annual day 01st Aug 2009 .

experiments were done with the straight run diesel alone. 60 bars pressure and WHSV (h-1) 2.ii.51 396. Experiments with straight run diesel Before carrying out studies with the diesel-vegetable oil blends.81 6. A small boiling point reduction as a result of cracking / isomerization / hydrogenation of the heavier ends took place (typical data are shown below) Temp oC WHSV P H2 Mass (h-1) (Bar) (v/v) balance IBP  Temp. The diesel feed underwent mild hydrocracking depending on the operating conditions About 4% cracking of the feed into lighter components (<IBP) was noticed at 340C.35 2. oC 90 % 95 % FBP 340 2 60 500 97 1.77 456.10 Feed Diesel IBP 90% 95% FBP 132.27 Gas chomatograms of some typical products of the reaction with the different 19 feeds are presented in the next slide .86 414.0 7.

WHSV (h-1). 500 v/v 25 20 15 10 5 0 5 10 15 20 25 30 35 40 45 50 55 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 80 C17 C18 60 40% oil blend 320C. 4 30 bars. WHSV (h-1). H2/oil. Gas chromatograms of some typical products 80 40 60 C17 & C18 35 Diesel 320C. WHSV (h-1). H2/oil.iii. H2/oil. 1 60 bars. 1 60 bars. 500 v/v Light fraction 40 20 C18 acid triglycerides Mono? Di? 20 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 . 500 v/v 30 40 Light fraction 20 20% oil blend 320C.

only a trace amount of free fatty acid is seen in the 21 chromatogram at WHSV (h-1) = 2 and 320C. the oil is completely converted into hydrocarbons even at 320C at WHSV (h-1) = 1 and 60 bar pressure In the case of the 40% blend. . At 60 bars pressure. Effect of temperature 20% blend Conversion Diesel yield 40% blend Diesel yield Conversion Pressure = 60 bar WHSV = 1 h-1 Pressure = 60 bar WHSV = 2 h-1 In the case of the 20% blend. conversion of the oil is complete at WHSV (h-1) 1 and not at WHSV (h-1) 2.iv.

The effect is more noticed in the case of 40% blend. Some free fatty acids are seen in the chromatograms of 40% blend at 22 higher flow rates (WHSV 2 & 4 h-1) . 60 bars. H2/oil. 500 v/v Conversion Yield As expected. 60 bars. conversion of vegetable oil decreases with feed rate. 500 v/v 20% oil blend 320C. Effect of feed rate (WHSV) Yield Conversion 40% oil blend 320C. H2/oil.v.

H2/oil = 500v/v Yield Conversion 20% blend 40% blend Conversion Yield 10% oleic acid blend Higher pressures increase conversion and diesel yield 10% oleic acid blend is fully converted even at 30 bars pressure 23 NCCR3rd Annual day 01st Aug 2009 . Effect of pressure Yield Conversion Temp. WHSV (h-1) = 2.vi. = 320oC.

678 Conv.vii. (C) 320 320 320 320 320 WHSV (h-1) 1 1 2 2 2 Press. The cracking of the glyceride molecules into C17 paraffin is more rapid than cracking of the acid Hydrogenation of the acid is more affected by SV than cracking 24 .643 0. Conversion of free fatty acids The following two blends of diesel with oil and free fatty acid (oleic acid) were prepared: 1) Diesel (70%) + Oil (20%) + oleic acid (10%) 2) Diesel (90%) + oleic acid (10%) The results of the studies are shown below in the table Feed (Diesel +) 10%FFA + 20% oil 10%FFA Temp. (%) 98. 320C and WHSV (h-1) = 1.0 95.3 96.8 100 100 100 100 Yield (%) 97.2 97.637 0.4 97. 30 bar pressure.0 It is found that the fatty acids are entirely converted into hydrocarbons even at moderate conditions.503 0.691 0. (bar) 60 60 60 45 30 nC17/nC18 0.

Pressure = 60 bar and WHSV = 1 h-1 10%FFA with 20% blend 60 80 10% FFA with Diesel 60 40 40 20 20 0 10 20 30 40 50 0 10 20 30 40 50 25 NCCR3rd Annual day 01st Aug 2009 .Chromatograms (see below) of both the blends reveal that the free fatty acids are entirely converted over the catalyst. Temp.= 320oC .

Ratio of C17 and C18 hydrocarbons 40% Blend Temp.= 320oC Pressure = 60 bar H2/Oil = 500 v/v 20% Blend 40% Blend 10% Oleic Acid Blend Pressure = 60 bar WHSV = 2 H2/oil = 500v/v 26 NCCR3rd Annual day 01st Aug 2009 .viii.

= 320 WHSV = 2 H2/Oil = 500 v/v Increase in temperature / feed rate increases C17formation Increase in pressure decreases C17 formation. the effect is not significant in the case of the FFA blend 27 NCCR3rd Annual day 01st Aug 2009 .Ratio of C17 and C18 hydrocarbons 20% Blend 40% Blend 10%Oleic acid blend Temp.

Based on the hydrocracking of the oil and FFA blends and the products obtained in the reaction. the following conclusions are reached: O H2C O C C17 C17 paraffin is formed from two sources: glycerides and C18 acid C17 paraffin is formed from C18 acid by decarbonylation and from glycerides by the cracking of the –C(=O)---C17 bonds C18 paraffin is formed from C18 acid by hydrogenation O HC O C C17 O H2C O C C17 28 NCCR3rd Annual day 01st Aug 2009 .

also increases cracking of –C(=O)---CH2 bond compared to -C---O.Temperature increases cracking of the –C(=O)---CH2 bond in the glycerides Higher pressures increase hydrogenation of the C18 acid and cracking (hydrogenolysis) of the -C---O.bond (ether linkage) in the glycerides Increasing the feed rate decreases hydrogenation relative to cracking of the acid.bond Other observations: Only traces of di.and monoglycerides were detected (?) Glycerol and the alcohol could not be identified (?) Light hydrocarbons could also be formed by cracking of hydrocarbons and others Based on the above conclusions and observations. the following 29 scheme for the cracking of triglycerides is proposed .

Conversion pathways for the oil The studies and the products obtained suggest the following pathway for the conversion of the oil Triglyceride Diglyceride Monoglyceride Glycerol CO2 + C17 paraffin + C18 acid Propane C18 alcohol C18 paraffin Further studies to understand the mechanism of the individual steps in the reaction are in progress 30 .ix.

WHSV=1 340C.60 bar P.3381) 22. WHSV=1 350C.89 (0.4314) 40% blend (0.704%)* Diesel (1.1964 ) 91.52 (0.66 (0.60 bar P. wt%) 20 % blend (1. WHSV=1 HDS % (S in product.408%)* Conditions 320C. %) 64.97 (0.60 bar P.60 bar P. % HDS increases with temperature and decreases with feed rate for the blends 31 NCCR3rd Annual day 01st Aug 2009 .12 (0.4975 ) 72. WHSV=1 320C.60 bar P. Hydrodesulfurization (HDS) activity Composition (S. % S-removed from the feeds is nearly the same for both diesel and for diesel + oil blends (at least for 20% blend) As expected.48 (0.3868) 86.60 bar P.96 (0.x.76%) * Calculated assuming zero S in the vegetable oil Regarding the desulfurizability of the feeds. It is found that at similar conditions. WHSV=2 320C. WHSV=4 330C.05 (0.60 bar P.60 bar P. WHSV=1 320C. WHSV=1 330C.5423) 17.1249) 51.5780) 75.

3. Conclusions 1.xi. The catalyst is expected to possess a long life – the catalyst has not deactivated for more than 200 hours of operation 4. An advantage of the process is that it can also be used in the case of non-edible vegetable oils containing free fatty acids. 5. It is possible to transform diesel-vegetable oil (20%) blends at relatively moderate operating HDS conditions into a pure hydrocarbon fuel 2. Zeolite beta is a suitable acidic hydrocracking component for the reaction. The processing of vegetable oil and diesel blend can be carried out during the HDS of the diesel provided a suitable catalyst is used 32 NCCR3rd Annual day 01st Aug 2009 .

33 NCCR3rd Annual day 01st Aug 2009 .