INDIAN OIL CORPORATION LIMITED

Study Of Kinetics of Hydro-Processing of Vegetable oil

[Type the document subtitle]

2012

IOCL R&D FARIDABAD SEC-13A, HARYANA, INDIA

KINETICS OF HYDRO-PROCESSING OF VEGETABLE-OIL

Project Completed By:Atul-Goel B.Tech Summer Training Report July-2012

Deepak Pandey B.Tech Summer Training Report July-2012

ACKNOWLEDGEMENT

Apart from the efforts of myself, the success of any project depends largely on the encouragement and guidelines of many others. I take this opportunity to express my gratitude to the people who have been instrumental in the successful completion of this project. I would like to show my greatest appreciation to Mr.B.Ravi Kumar, SRO (AE&TD). I can't say thank you enough for his tremendous support and help. Without his encouragement and guidance this project would not have materialized. I wish to express my sincere gratitude to Mr. Sarvesh Kumar, SRM (AE&TD), for his initial support and guidance. I would also like to thank Mr. Alok Sharma, CRM (AE&TD), for allowing me to work in this department and helping me to gain profound knowledge about various key elements. I also record my sincere thanks to the entire staff of Refining Technology-II Department and Library for their cooperation and guidance in successful out coming of this report. At last I would like to express my thanks to the IOCL R&D Training and Placement Department for allowing me to undergo my training at their organization.

SUMMARY The project assigned was to study the kinetics of hydro-processing of vegetable oil. The mixture of mustard oil with diesel was made to run at different operating condition of temperature, pressure and composition. The kinetic model for the reaction was proposed. It was observed that the hydrogenation of vegetable oil proceeded through two different reaction that are decarboxylation and hydro deoxygenation. The two side reaction of reverse water gas reaction and methanation reaction were also observed. The rate equation for different model like power law and Langmuir hinshelwood mechanism were calculated. The decarboxylation and hydro-deoxygenation reaction were observed first order with respect to vegetable oil. Methanation reaction was found to behave first order with respect to carbon mono-oxide. The mechanism and the rate determining step in the reaction were also proposed at the end of the report.

ABBREVIATION

FIGURES

CONTENTS

I. II. III. IV. V. VI. VII. VIII.

Company Profile Introduction Extraction Of Jatropha Oil Experimental Method And Set-Up Experimental Investigation Of Rate of Hydrogenation Reactions Quality of Product Obtained Mathematic Model Of Trickle-Bed Conclusion Reference Appendix A Appendix B Appendix C

1.

COMPANY PROFILE

1. COMPANY OVERVIEW Indian Oils world class R&D centre, established in 1972, has state-of-the-art facilities & has delivered pioneering results in lubricants technology, refining process, pipeline transportation, bio-fuels & fuel-efficient appliances. Over the past three decades, Indian Oil R&D Centre has developed over thousands of formulations of lubricating oils and greases responding to the needs of Indian industry and consuming sectors like Defence, Railways, Public Utilities and Transportation. The Centre has also developed and introduced many new lubricant products to the Indian market like multigrade railroad oils. Focused research in the areas of lubricants and grease formulations, fuels, refining processes, biotechnology, additives, pipeline transportations, engine evaluation, tribological and emission studies, and applied metallurgy has won several awards. The R&D Centres activities in refining technology are targeted in the areas of fluid catalytic cracking (FCC), hydroprocessing, catalysis, residue upgradation, distillation simulation and modelling, lube processing, crude evaluation, process optimization, material failure analysis and remaining life assessment and technical services to operating units. In FCC, apart from process optimization and catalyst evaluation the accent is on the development of novel technologies aimed at value addition to various refinery streams. IndianOil's R&D Centre is fully equipped to provide technical support to commercial hydrocracker units in the evaluation of feed stocks and catalysts, optimization of operating parameters, evaluation of licensors' process technologies, development of novel processes and simulation models. Material failure analysis and remaining life assessment of refinery equipment and installations is a highly specialized service being provided by the R&D Centre to the refineries of IndianOil as well as other companies. With a vision of evolving into a leader as technology provider through excellence in management of knowledge, technology and innovation, IndianOil has launched IndianOil Technology Ltd. The new subsidiary markets the intellectual properties developed by IndianOil R&D Centre. In todays dynamic business environment, innovation through a sustained process of Research & Development (R&D) is the only cutting edge tool for organisation to thrive. With emphasis on development & speedy commercialisation of globally competitive products, process & technologies, the focus has now shifted from R&D to RD&D (Research, Development & Deployment).

Figure 1. INDMAX, a hallmark technology developed by the Centre for maximisation of LPG and light distillates from refinery residue, has been selected by IndianOil for setting up a 4 million metric tonnes per annum (MMTPA) INDMAX unit as a part of the 15 MMTPA integrated refinery-cum-petrochemicals complex at Paradip, as well as at Bongaigaon Refinery & Petrochemicals Ltd. (BRPL). The Centre has also licensed its Diesel Hydrotreating technology to these two refineries. These successes have catapulted IndianOil R&D into the elite league of multinational technology licensors. Standing in the company of six worldwide technology holders for Marine Oils, with the second global OEM (original equipment manufacturer) approval by Wartsila, Switzerland, IndianOil's SERVO Marine Oils are now technically qualified to cater to the lubrication requirements of more than 90% of the world's marine engine population. In the powergeneration segment, the newly developed SERVO Marine K-Series was approved by Yanmar Co. Ltd. of Japan for use in their engines operating on distillate fuels.

The R&D Centre continues to provide significant support to the IndianOil Group refineries in product quality improvement, evaluation of catalysts and additives, health assessment of catalysts, material failure analysis, troubleshooting and in improving overall efficiency of operations. In-house developed FCC models are not only being used in IndianOil refineries for process optimisation but a similar model has also been sold to a multinational company. IndianOil has formed a joint venture company, Indo Cat Pvt. Ltd., with Intercat, USA, for manufacturing 15,000 tonnes per annum of FCC (fluidised catalytic cracking) catalysts & additives in India, for catering to rising global demand. As a step towards ensuring energy security for the nation, IndianOil has launched several initiatives to exploit alternative sources of energy such as Hydrogen and Bio-fuels. Subsequent to commissioning India's first experimental H-CNG (Hydrogen-Compressed Natural Gas) dispensing unit at the R&D Centre campus at Faridabad, demonstration projects are underway on use of H-CNG blends in heavy and light vehicles. IndianOil is also setting up India's first commercial H-CNG dispensing station at one of its retail outlets in Delhi in the year 2008 for fuelling experimental vehicles running on H-CNG blends as well as on pure Hydrogen. IndianOil R&D is also working on production, storage, transportation, distribution & commercialization of Hydrogen as an alternative fuel. Bio-fuels, besides spearheading commercialisation of Ethanol-Blended Petrol in the country, Indian Oil has been in the forefront of technology development for Bio-diesel production from various edible and non-edible oils and its application in vehicles. Pioneering studies by Indian Oils R&D Centre established that Bio-diesel produced from Jatropha seeds were at par with that produced from vegetable oils. In the past few years, the R&D Centre has studied the entire value chain of Bio-diesel, starting from Jatropha plantation to field trials on
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passenger cars, light commercial vehicles and railway locos in collaboration with several vehicle manufacturers, railways and state transport undertakings.

Figure 2. Indian Oil along with its subsidiary Indian Oil Technologies Ltd. has been engaged in successful marketing of in house developed technologies, technical services & training not only in India but abroad too. Indian Oil has, till date, invested close to Rs. 1,000 crore in setting up world-class facilities at its R&D Centre for building world-class capabilities in analytical services, engines, test rigs and pilot plants for all major refinery processes, catalyst characterisation & development, etc. It plans to invest about Rs. 500 crore during the period 2007-12 to maintain its leadership in downstream R&D activities in the hydrocarbon sector. While continuing with cutting edge R&D in the core areas of lubricants formulations, refinery process technologies and pipeline transportation, the thrust would now be on commercialising the developed technologies and initiating research in new frontier areas such as petrochemicals, residue gasification, coal-toliquid, gas-to-liquid, alternative fuels, synthetic lubricants, nano-technology, etc. Through these R&D initiatives, IndianOil will continuously enhance value for all its stakeholders

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2.

INTRODUCTION

This chapter discusses the basic principles involved in processing of crude oil and hydroprocessing of vegetable oil.

CRUDE OIL Crude oil, The Black-Diamond for the world formed due to decaying activity of the microorganism on the buried dead plants and animals. The life couldnt be imagined without it. Crude oil, complex mixture of paraffins, olefins, aromatics, long chained carbon atom varying from C1-C100. Around 700 refineries across the globe are working 247 to meet the demand of its product. The figure 2-1 shows the regional share of world refining, with Americas making big bite.

FIGURE 2-0-1 REGIONAL SHARES OF WORLD REFINING

The extraction and refining of crude oil to finished product is a complex process. The extracted crude oil is being purchased on the basis of API gravity and its sulphur content. Then it is made to pass through a de-Salter removing the metals and mud from the crude. Then the crude oil is distillated in an atmospheric distillation column, where the product cuts are collected on the basis of their boiling point. The light ends separated are hydro-treated to remove the sulphur content in it and to bring them below the desired limit.

FIGURE 2-0-2 SCHEMATIC REFINIG OF CRUDE OIL

The heavy end left below need to be converted to light end products for this any one of the two techniques mentioned are used FCC: Fluid catalyzed cracking Hydro-Cracking
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The fig.2-3 shows the product obtained per barrel of crude oil

Figure 2-0-3 products per gallon of crude oil

FIGURE 2-4 CRUDE OIL REFINING PRODUCTS

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BIO DIESEL

Diesel being a fossil fuel, rising demand of it has always raised an unanswered question of what if, if not diesel? The answer to this if had been bio-diesel. But because of the higher viscosity of the biodiesel produced and the modification in the engine it required it has lost its ground Ref [1]. The production of bio-diesel is carried out by treating vegetable oil with methanol, namely trans-etherification reaction is order to produce the bio-diesel and glycerol.

The glycerol and ester produced are separated. Glycerol is recovered and sold to pharmaceutical industries, ester being used as bio-diesel. The major advantage of using biodiesel over the conventional fuel is that they produce comparatively less harmful products like CO, CO2 and H2O in comparison to SOx and NOx.

FIGURE 0-5: FLOW SHEET FOR BIO-DIESEL PRODUCTION

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The pre-requisite for using bio-diesel is to make major changes in the engine and these changes could not be attained in a day. This limitation of bio-diesel has lead to strict norm by the government to not to dope the diesel with vegetable oil by not more than 5% (w/w) Ref[2]. VEGETABLE OIL HYDRO-PROCESSING After bio-diesel loosing it ground the hydro-processing of vegetable oil has started gaining momentum. Many industries have already started commercializing this technology. The vegetable oil is made to react with hydrogen at the refining hydro processing temperature and pressure that is 360C and 55bar pressure the product obtained are C0, C02 and nC-18 paraffin.

FIGURE 0-6 HYDRO-PROCESSING REACTION OF VEGETABLE OIL REF [3] .

The vegetable is doped with either the diesel which is about to be de-sulpharised or mixed with heavy fraction of crude oil and send for hydro-treating. During the hydro-processing process many reaction take place simultaneously 1. 2. 3. The reactions of our concerned are those which directly produce n-paraffin the major component of the diesel. The consumption of hydrogen in a particular reaction plays an important role in deciding the price of the bio-diesel. The reaction which consumes least amount of hydrogen is R3. The aim of this project is to propose the kinetic model for the above reaction. And study the effects of various operating condition on the yield of each of the reaction, the project also discuss the quality of the diesel produced.

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Extraction of jatropha oil

Jatropha oil can be extracted from the seeds by three ways. They are: Mechanically Chemically Enzymatically Here is a chart that describes the process of oil extraction from the seeds, Jatropha oil extraction chart

Below are some of the methods that are usually followed to extracts the oils from jatropha seeds. Oil Presses Oil presses method is used to extract the oil using simple mechanical devices. It is also done manually. The most commonly used oil presses method is the Bielenberg ram press method. Bielenberg ram press method is a simple traditional method that uses simple devices to extract the oils. With the help of this method 3 liters of oil can be obtained with 12 kg of seeds.

Oil Expellers Oil expellers method is also use for jatropha oil extraction. The most commonly used method is the Sayari oil expeller method. This method is also called as Sundhara oil expeller. Komet
15

oil expellers are also used. These sayari oil expellers was developed in Nepal and is a diesel operated one. Now it is developed in Tanzania and Zimbabwe mainly for the production jatropha oil. Heavy oil expellers are made of heavy cast iron and the light ones are made up of iron sheets. Electricity driven models are also available. Komet oil expeller is a single oil expeller machine that is used not only to extract the jatropha oil as well for the preparation of the oil cakes. Traditional Methods Traditional methods are used in the rural and developing areas for extracting the oils. Traditional methods are simple and the oil is extracted by hand using simple equipment. Hot oil extraction The process of extracting the oil at high pressure is called as hot oil extraction method. Since jatropha oil can regulate the operating temperature it is extracted using the hot oil extraction method. Then the cold oil extraction method it is easy to extract the oil from the hot oil extraction since the oil flows more easily due to higher viscosity. And the press cake that remains after extracting the oil also have less oil content which might be 3 to 7 % approximately. These two reasons make the oil press method very interesting. During the oil extraction method many stuffing of the seeds are converted into gum like substances and some non organic substances. These are unwanted products and so they have to be refined. Modern Concepts Modern methods are followed to extract more oils from the jatropha seeds. In these modern concepts chemical methods like aqueous enzymatic treatment is used. The maximum yield by following this modern method is said to be about 74/5. The main idea in researching the modern concepts is to extract a greater percentage of oil from the jatropha seeds.

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4. EXPERIMENTAL SET UP AND METHODS

The chapter describe about the experimental set up on which the major part of the project was carried out, various techniques that were used in analysis of the product are also discussed in brief.

EXPER IMENTAL SET UP The experiment was carried out at laboratory scale reactor. The reactor was typical Trickle bed reactor, throughout the project reactor is assumed to be ideal fixed bed plug flow reactor. The schematic diagram of the micro-reactor unit

Gas REACTOR

GC

GAS

FEED HPS

PDT

Fig: 2.1 Schematic Dig of experimental set-up, HPS-high pressure separator, LPS-low pressure separator, GC-gas chromatography, PDT-product.

The reactor was charged with activated Ni-Mo catalyst, the reactor had ID-12mm and length of 1.5-m. The reactor was charged with 20cc of catalyst, the glass beads were placed above and below the catalyst. Three electrically heated coils surrounded the catalyst, the Pt-based
17

LPS

PRODUCT

GAS

thermostat were arranged to measure both the skin temperature and the temperature inside the bed. PRODUCT ANALYSIS TECHNIQUES Gas Chromatography: The common technique to analyze the compounds which can vaporize without decomposition. Gas chromatography consists of two phase, the mobile phase (or "moving phase") is a carrier gas, usually an inert gas such as helium or an un-reactive gas such as nitrogen. The stationary phase is a microscopic layer of liquid or polymer on an inert solid support, inside a piece of glass or metal tubing called a column. The gaseous compounds being analyzed interact with the walls of the column, which is coated with different stationary phases. This causes each compound to elute at a different time, known as the retention time of the compound. The temperature inside the column is generally controlled by the heaters. Based on the retention time of each component its composition in sample is calculated.

CATALYSIS The first introduction of the word catalysis was by Berzelius in 1836, while Ostwald presented the first correct definition of a catalyst in 1895. He described a catalyst as a substance that changes the rate of a chemical reaction without itself appearing in the products. The reaction of hydro-processing is a typical heterogeneous solid catalyzed reaction carried in trickle bed reactor. A catalyst accelerates a chemical reaction. It does so by forming bonds with the reacting molecules (i.e. adsorption), such that they can react to a particular product, which detaches itself from the catalyst (i.e. desorption), and leaves the catalyst unaltered so that it is ready to interact with the next set of molecules. In fact, we can describe the catalytic reaction as a cyclic event in which the catalyst participates and is recovered in its original form at the end of the cycle. A catalyst cannot alter the chemical equilibrium of a given reaction; it only creates a favourable reaction pathway. This is done by decreasing the activation barrier (Ea,cat) compared to the gas phase reaction (Ea, gas) and thus increasing the reaction rate. Consequently, the reaction can take place at lower temperatures and pressures, which decreases costs and amounts of energy for e.g. a chemical plant. Furthermore, if for a certain reaction different paths are possible that lead to various products, the catalyst can selectively
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decrease the activation energy of one of the possible reaction paths, thereby altering the selectivity of the reaction. In general a successful catalyst increases the yield of the desired product while decreasing that of other products, which has advantages for both economic and environmental reasons.

Figure 0-1: Potential energy diagram for a heterogeneous catalytic reaction (solid line), i.e. reaction of A and B to form AB, compared with the non-catalytic gas-phase reaction (dashed line). The presence of a catalyst lowers the activation energy (Eact) considerably.

NI-MO CATALYST The catalyst used in our project to carry hydro-treating reaction is a Ni-Mo catalyst.

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4. EXPERIMENTAL INVESTIGATION OF RATE OF HYDROGENATION REACTIONS The chapter summarizes the path followed during the hydro-processing of vegetable oil.

The proposed mechanism in literature estimates the production of CO2,CO and H2O directly from vegetable oil. But it became difficult to account for the moles of carbon monooxide. As there is no fixed mechanism in the literature regarding the conversion of vegetable oil to carbon mono-oxide. And the same could be commented as there was no trending graph for production of CO2 from vegetable oil. As depicted in the graph shown below. Fig 4.1 Moles CO,CO2 and H2O V/S Moles Of VO Following A Direct Production Path
0.7 0.6 0.5 Moles of product 0.4 0.3 0.2 0.1 0 0 0.001725429 0 0.071347203 0.036518311 0.017129189 0.01169457 0.05 0.019292465 0.2 0.315 CO2 v/s VO CO v/s VO H2O v/s VO 0.63

0.185

0.165795511

0.1 0.15 Moles of VO initially

with the number of hit and trial

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# Proposed Mechanism

#Moles of CO2

V/S moles of VO

CO2 V/s VO
0.2 0.18 Moles of CO2 produced 0.16 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0.001725429 0 0 0.05 0.1 Moles of VO initial 0.15 0.2 0.086836597 0.052430896 CO2 V/s Vo Linear (CO2 V/s Vo) 0.187266364

#Moles of H2O V/S moles of VO

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H2O via HDO

0.08 0.07 Moles of H2O via HDO 0.06 0.05 0.04 0.03 0.02 0.01 0 0 0.05 0.1 Moles of VO initial 0.15 0.2 0.031094816 H2O via HDO 0.028932256 0.070389577

# Moles of propane V/S Vo

0.07 0.06 0.05 0.04 0.03 0.02 0.01 0 0 0.05 0.1 Moels of VO initially 0.15 0.2 0.01607096 0.011731596 0.005182469 0.004822043 decarboxylation 0.029492131 HDO 0.061695992

#Moles of HC V/S moles of VO

Moles of propane via

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0.2 0.18 0.16 0.14 0.185087976

Moles of HC via

0.12 0.1 0.088476392 0.08 0.06 0.048212881 0.04 0.02 0 0 0.05 0.1 Moles of VO initially 0.15 0.2 0.035194789 0.015547408 0.014466128

HC via decarboxy lation

HC via HDO

#Moles of CO2 V/S moles of CO reverse water gas shift reaction

moles of CO2 v/s CO

0.18 0.16 0.14 Moles of CO formed 0.12 0.1 0.08 0.071347203 0.06 0.04 0.02 0 0 0.05 0.1 0.15 Total moles of CO2 formed 0.2 0.036518311 moles of CO2 v/s CO 0.165795511

#Moles of CH4 V/S moles of CO methanation reaction

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0.1 0.09 0.08 Moles of CH4 formed 0.07 0.06 0.05

CH4 V/S CO
0.09005001

CH4 V/S CO 0.038969092

0.04 0.03 0.02 0.01 0 0 0.02 0.04 0.020147667

0.06 0.08 of CO 0.1 0.12 Total moles formed

0.14

0.16

0.18

#Assuming 50%error in water estimation via HDO

H2O V/S VO
0.7 0.6 Mole of water via HDO 0.5 0.4 0.3 0.2 0.1 0 0 0.02 0.04 0.06 0.08 0.1 0.12 Moles of VO initially 0.14 0.16 0.18 0.1823 0.309 H2O V/S VO 0.632

#Moles of propane V/S Vo 50% error in water estimation via HDO

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Moles of propane v/s moles of vo with 50% error in water estimation

0.12 Moles of propane formmed 0.1 0.08 0.06 0.0515 0.04 0.0303833330.029492131 0.02 0 0 0.05 0.1 Moles of VO initially 0.15 0.2 0.01607096 0.061695992 decarboxylation HDO 50% error 0.105333333

#Moles of HC V/S moles of VO 50% error in water estimation via HDO

0.35 0.3 0.25 Moles of HC 0.2 0.15 0.1 0.05 0.01607096 0 0 0.05 0.1 Moles of VO initially 0.15 0.2 0.029492131 0.1545 decarboxylation HDO 50%error 0.09115 0.061695992

Moles of HC v/s moles of VO

0.316

#Kinetic order for de-carboxylation Rxn assuming first order kinetics (k=0.803479 sec-1 ) W/Fao (Kg/moles) Cao(moles/volume) Conversion Rate constant

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10.19157 5.822268 2.837434

0.05 0.1 0.2

0.344818 0.361497 0.368544

0.829787 0.77054 0.81011

#Kinetic order for HDO Rxn assuming first order kinetics(k=1.848858 sec-1 ) W/Fao (Kg/moles) Cao(moles/volume) Conversion Rate constant

10.19157 5.822268 2.837434

0.05 0.1 0.2

0.65083 0.6385 0.626227

2.064837 1.747589 1.734147

#Kinetic order for methanation Rxn assuming first order kinetics(k=1.437302 ) W/Fao (Kg/moles) Cao(moles/volume) Conversion Rate constant

10.19157 5.822268 2.837434

0.0391767 0.0874532 0.1980774

0.551714 0.546189 0.543139

1.574486 1.356989 1.38043

# Conversion data for reverse water gas shift reaction. Moles of CO2 Conversion

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0.048213 0.088476

0.757439 0.806398

0.185088

0.895766

#Conversion v/s moles of CO2

Conversion v/s moles of CO2

2.5 2.261116655 2 1.641951811 1.5 1.416501587 conversion v/s moles of CO2 1 0.806398201 0.757438887 0.5 0.895765974 ln(1-Xa) v/s moles of CO2

conversion

0 0 0.05 0.1 Moles of CO2 0.15 0.2

#Summary of rate constant Reaction Order Rate constant Rate determining step

Decarboxylation HDO

1st wrt VO 1st wrt VO

0.803479 1.848858

Methanation Reverse water gas shift reaction

1st wrt CO Kp

1.437302 0.063

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#PONA Composition Aromatics Olefins Saturates Naphthalene

100%PRDHDS 5%MOSLX+95%PRDHDS 10%MOSLX+90%PRDHDS 20%MOSLX+80%PRDHDS

17.9 15.1 15.4 15.9

0 0 0 0

82.1 84.9 84.6 84.1

12.8 13.5 13.3 13.2

#PONA
90 8082.1 70 60 Mg/lit??? 50 Aromatics 40 30 20 17.9 12.8 10 0 0 0.05 0.1 Moles of VO initially 0.15 0.2 Saturates Napthalenes 84.9 84.6 84.1

15.1 13.5

15.4 13.3

15.9 13.2

# Conclusion from PONA analysis

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 The aromatics increases, with increase in the moles of vegetable oil doped Where as there is decrease in moles of saturates and naphthalene with increase in vegetable oil doped.

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3.

MATHEMATIC MODEL FOR TRICKLE BED

This chapter summarizes the mathematical model for trickle bed as follows:

Figure a. Sketch showing the resistances involved in the G/L reaction on a catalyst surface. Graphically we show the resistances as in Fig. a. We can then write the following general rate equations:

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