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

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
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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

Rudolf Diesel (1858 1913) His first engine ran on peanut oil (1900, 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, 1912.
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NCCR3rd Annual day 01st Aug 2009

Disadvantages of neat vegetable oils as diesel fuel

Compared to diesel, 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, vegetable oils are converted into FAME (Fatty Acid Mono Esters; biodiesel) by transesterification with methanol They (FAME) are generally not used as neat fuels, but are blended (5 - 20%) with diesel and used.
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NCCR3rd Annual day 01st Aug 2009

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; water requirement for washing etc.) 4) Lower heating value of the fuel (power output; tank capacity) 5) Compatibility problems of some components in the engine (cost) Also, 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
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NCCR3rd Annual day 01st Aug 2009

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, 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. Presently, there are no commercial processes for economic reasons Cracking: Cracking of neat vegetable oils produces poor quality products and catalyst stability is poor; 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

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, temp.: 350C or less]
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EXPERIMENTAL

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

Properties of the straight run diesel fraction

Property
Source Density at 15C, g/cc Viscosity at 40C, cSt Pour point, C Aniline point, C Flash point, C

Value
PG mix 0.8610 5.03 0 74 121

Non-aromatics, wt%
Aromatics, wt% Sulfur (N), ppm

58.5
41.5 17600 (140)

Distillation characteristics
ASTM, D86 GC Sim. Dist., D2887

IBP 90%

233C 371C

IBP 90%

101C 399C

92.8%

380C

95%

418C

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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

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.
Composition of the vegetable oil used (wt %): 1) C16 acids - 6.53% 2) C18 acids - (0.538% steric, 22.38% oleic and 70.54% linoleic)13

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

BET Surface area (m2/g) 212 Total pore volume (cm3/g) 0.60 Acidity (mmol/g)* Weak 0.056 Strong 0.098 Total 0.154

Sample

Al2O3

BEA
Support (30% BEA -55% Al2O3)

580
282

0.55
0.49

0.236
-

0.042
-

0.278
-

12%MoO3, 3% NiO/Support

213

0. 40

* From TPD of NH3; weak and strong refer to amount of NH3 desorbed below 200C and above 200C, respectively.

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

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.
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, 4) C18 alcohol, 5) propane and 6) CO2.

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 The triglyceride molecule itself may crack into di- 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 6.5%) - C16 and C15 hydrocarbons
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ii. Experiments with straight run diesel

Before carrying out studies with the diesel-vegetable oil blends, experiments were done with the straight run diesel alone.
The diesel feed underwent mild hydrocracking depending on the operating conditions

About 4% cracking of the feed into lighter components (<IBP) was noticed at 340C, 60 bars pressure and WHSV (h-1) 2.
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, oC 90 % 95 % FBP

340

60

500

97

1.0

7.81

6.35

2.10

Feed Diesel

IBP 90% 95% FBP 132.51 396.86 414.77 456.27

Gas chomatograms of some typical products of the reaction with the different 19 feeds are presented in the next slide

iii. Gas chromatograms of some typical products

80
40

60

C17 & C18

35

Diesel 320C, WHSV (h-1), 1 60 bars; H2/oil, 500 v/v

30

40 Light

fraction
20

20% oil blend 320C, WHSV (h-1), 1 60 bars; H2/oil, 500 v/v

25

20

15

10

5 0 5 10 15 20 25 30 35 40 45 50 55

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 320C, WHSV (h-1), 4 30 bars; H2/oil, 500 v/v
Light fraction

40

20

C18 acid

triglycerides Mono? Di?

20

10

12

14

16

18

20

22

24

26

28

30

32

34

36

38

40

42

44

46

48

50

52

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

v. Effect of feed rate (WHSV)

Yield Conversion 40% oil blend 320C, 60 bars; H2/oil, 500 v/v 20% oil blend 320C, 60 bars; H2/oil, 500 v/v Conversion

Yield

As expected, conversion of vegetable oil decreases with feed rate. 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)

vi. Effect of pressure

Yield Conversion

Temp. = 320oC; WHSV (h-1) = 2; 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
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vii. 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. (C)
320 320 320 320 320

WHSV (h-1)
1 1 2 2 2

Press. (bar)
60 60 60 45 30

nC17/nC18
0.691 0.503 0.637 0.643 0.678

Conv. (%)
98.8 100 100 100 100

Yield (%)
97.2 97.4 97.3 96.0 95.0

It is found that the fatty acids are entirely converted into hydrocarbons even at moderate conditions, 30 bar pressure, 320C and WHSV (h-1) = 1.
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
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Chromatograms (see below) of both the blends reveal that the free fatty acids are entirely converted over the catalyst.
Temp.= 320oC ,Pressure = 60 bar and WHSV = 1 h-1

10%FFA with 20% blend

60
80

10% FFA with Diesel

60

40

40

20
20

10

20

30

40

50

10

20

30

40

50

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viii. 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

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NCCR3rd Annual day 01st Aug 2009

Ratio of C17 and C18 hydrocarbons

20% Blend 40% Blend 10%Oleic acid blend

Temp.= 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

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

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NCCR3rd Annual day 01st Aug 2009

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; also increases cracking of C(=O)---CH2 bond compared to -C---O- 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

ix. 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

x. Hydrodesulfurization (HDS) activity

Composition (S, wt%) 20 % blend (1.408%)* Conditions 320C,60 bar P, WHSV=1 330C,60 bar P, WHSV=1 340C,60 bar P, WHSV=1 350C,60 bar P, WHSV=1 320C,60 bar P, WHSV=1 320C,60 bar P, WHSV=2 320C,60 bar P, WHSV=4 330C,60 bar P, WHSV=1 HDS % (S in product, %) 64.66 (0.4975 ) 72.52 (0.3868) 86.05 (0.1964 ) 91.12 (0.1249) 51.97 (0.3381) 22.96 (0.5423) 17.89 (0.5780) 75.48 (0.4314)

40% blend (0.704%)*

Diesel (1.76%)

* Calculated assuming zero S in the vegetable oil

Regarding the desulfurizability of the feeds, It is found that at similar conditions, % S-removed from the feeds is nearly the same for both diesel and for diesel + oil blends (at least for 20% blend) As expected, % HDS increases with temperature and decreases with feed rate for the blends

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xi. Conclusions 1. 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. 3. 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. The processing of vegetable oil and diesel blend can be carried out during the HDS of the diesel provided a suitable catalyst is used
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NCCR3rd Annual day 01st Aug 2009