AU2006264899A1 - Process for the manufacture of diesel range hydrocarbons - Google Patents

Description

WO 2007/003708 PCT/FI2006/050300 1 5 PROCESS FOR THE MANUFACTURE OF DIESEL RANGE HYDRO CARBONS Field of the invention 10 The invention relates to an improved process for the manufacture of diesel range hydrocarbons from bio oils and fats with reduced hydrogen consumption. Particu larly the invention relates to an improved process for the manufacture of diesel range hydrocarbons with high selectivity and which process yields a product with 15 improved cold flow properties concurrently without decreasing diesel yield during isomerisation. Background of the invention 20 Environmental interests and an increasing demand for diesel fuel, especially in Europe, encourage fuel producers to employ more intensively renewable sources available. In the manufacture of diesel fuel based on biological raw materials the main interest has concentrated on vegetable oils and animal fats comprising triglycerides of fatty acids. Long, straight and mostly saturated hydrocarbon 25 chains of fatty acids correspond chemically to the hydrocarbons present in diesel fuels. However, neat vegetable oils display inferior properties, particularly ex treme viscosity and poor stability and therefore their use in transportation fuels is limited. 30 Conventional approaches for converting vegetable oils or other fatty acid deriva tives into liquid fuels comprise processes such as transesterification, catalytic hy drotreatment, hydrocracking, catalytic cracking without hydrogen and thermal cracking. Typically triglycerides, forming the main component in vegetable oils, are converted into the corresponding esters by the transesterification reaction with 35 an alcohol in the presence of catalysts. The obtained product is a fatty acid alkyl ester, most commonly fatty acid methyl ester (FAME). Poor low-temperature WO 2007/003708 PCT/FI2006/050300 2 5 properties of FAME however limit its wider use in regions with colder climatic conditions. Poor cold flow properties are a result of the straight chain nature of the FAME molecule and thus double bonds are needed in order to create even bear able cold flow properties. Carbon-carbon double bonds and ester groups however decrease the stability of fatty acid esters, which is a major disadvantage of trans 10 esterification technology. Further, Schmidt, K., Gerpen J.V.: SAE paper 961086 teaches that the presence of oxygen in esters results in undesired and higher emis sions of NOx in comparison to conventional diesel fuels. Undesired oxygen may be removed from fatty acids or esters by deoxygenation 15 reactions. The deoxygenation of bio oils and fats, which mean oils and fats based on biological material, to hydrocarbons suitable as diesel fuel products, may be carried out in the presence of a catalyst under controlled hydroprocessing condi tions, known as hydrotreating or hydrocracking processes. 20 During hydrodeoxygenation oxogroups are reacted with hydrogen and removed through formation of water. The hydrodeoxygenation reaction requires relatively high amounts of hydrogen. Due to the highly exothermic reactions the control of reaction heat is extremely important. Unnecessary high reaction temperature, in sufficient control of reaction temperature or unnecessary low hydrogen availabil 25 ity in the feed stream cause increased formation of unwanted side reaction prod ucts and coking of catalyst. Unwanted side reactions, such as cracking, polymeri sation, ketonisation, cyclisation and aromatisation decrease the yield and the prop erties of diesel fraction. Unsaturated feeds and free fatty acids in triglyceridic bio oils may also promote the formation of heavy molecular weight compounds. 30 Patents US 4,992,605 and US 5,705,722 describe processes for the production of diesel fuel additives by conversion of bio oils into saturated hydrocarbons under hydroprocessing conditions with NiMo and CoMo catalysts. The hydrotreatment operates at high temperatures of 350-450 0 C and produces n-paraffins and other 35 hydrocarbons. The product has high cetane number but poor cold properties, WO 2007/003708 PCT/FI2006/050300 3 5 which limit the amount of product that can be blended in conventional diesel fuel in summer time and prevent its use during winter time. The formation of heavy compounds with a boiling point above 343 0 C was observed, especially when a fatty acid fraction was used as a feed. A lower limit of 350 0 C for reaction tem perature was concluded as a requirement for trouble-free operation. 10 A two-step process is disclosed in FI 100248 for producing middle distillates from vegetable oils by hydrogenating fatty acids or triglycerides of vegetable oil origin using commercial sulphur removal catalysts, such as NiMo and CoMo, to give n paraffims, followed by isomerizing said n-paraffins using metal containing 15 molecule sieves or zeolites to obtain branched-chain paraffins. The hydrotreating was carried out at rather high reaction temperatures of 330-450 0 C, preferably 390 0 C. Hydrogenating fatty acids at those high temperatures leads to shortened catalyst life resulting from coking and formation of side products. 20 EP 1 396 531 describes a process containing at least two steps, the first one being a hydrodeoxygenation step and the second one being a hydroisomerisation step utilizing counter-current flow principle, and biological raw material containing fatty acids and/or fatty acid esters serving as the feedstock. The process comprises an optional stripping step. 25 Cracking is significant side reaction in isomerisation of n-paraffins. Cracking in creases with higher isomerisation conversion (more severe reaction conditions) and decrease the yield of diesel. The severity of isomerisation conditions (isomer isation conversion) controls also the amount of methyl branches formed and their 30 distance from each other and therefore cold properties of bio diesel fraction pro duced. FR 2,607,803 describes a process for hydrocracking of vegetable oils or their fatty acid derivatives under elevated pressure to give hydrocarbons and to some extent 35 acid. The catalyst contains metal dispersed on a support. A high reaction tempera- WO 2007/003708 PCT/FI2006/050300 4 5 ture of 370 'C did not result in complete conversion and high selectivity of n paraffins. The product formed contained also some intermediate fatty acid com pounds. Water formation during hydrotreatment mainly results from deoxygenation of 10 triglyceride oxygen by the means of hydrogen (hydrodeoxygenation). Deoxygena tion using hydrodeoxygenation conditions is to some extent accompanied by de carboxylation reaction path, described below as reaction A, and decarbonylation reaction path (reaction BI and B2). Deoxygenation of fatty acid derivatives by decarboxylation and/or decarbonylation reactions forms carbon oxides (CO 2 and 15 CO) and aliphatic hydrocarbon chains with one carbon atom less than in the origi nal fatty acid molecule. Thereafter water-gas-shift reaction may balance the con centrations of CO and CO 2 (reaction E). Methanation reaction uses hydrogen and forms H 2 0 and methane if it is active during hydrotreatment conditions (reaction D). Hydrogenation of fatty acids gives aliphatic hydrocarbons and water (reaction 20 C). Reaction schemes A - E are described below. Decarboxylation: C 17

H

35 COOH -> C 17

H

36 + CO 2 (A) Decarbonylation: C 17

H

35 COOH + H 2 -> C 17

H

36 + CO + H20 (BI)

C

17

H

35 COOH -> C 17

H

34 + CO + H20 (B2) 25 Hydrogenation: C 17

H

35 COOH + 3H 2 -> C 1 8

H

38 + 2 H 2 0 (C) Methanation: CO + 3H 2 -> CH 4 + H 2 0 (D) Water-Gas-shift: CO + H 2 0 -> H 2 + CO 2 (E) The feasibility of decarboxylation varies greatly with the type of carboxylic acid 30 or derivative thereof used as the starting material. Alpha-hydroxy, alpha-carbonyl and dicarboxylic acids are activated forms and they are more easily deoxygenated by decarb-reactions, which mean here decarboxylation and/or decarbonylation. Linear aliphatic acids are not activated this way and generally they are difficult to deoxygenate through the decarb-reaction path and they need much more severe 35 reaction conditions.

WO 2007/003708 PCT/FI2006/050300 5 5 Decarboxylation of carboxylic acids to hydrocarbons by contacting carboxylic acids with heterogeneous catalysts was suggested by Maier, W. F. et al: Chemische Berichte (1982), 115(2), 808-12. Maier et al tested Ni/A1 2 0 3 and Pd/SiO 2 catalysts for decarboxylation of several carboxylic acids. During the reac tion the vapors of the reactant were passed through a catalytic bed together with 10 hydrogen. Hexane represented the main product of the decarboxylation of the tested compound heptanoic acid. Patent US 4,554,397 discloses a process for the manufacture of linear olefins from saturated fatty acids or esters, suggesting a catalytic system consisting of nickel 15 and at least one metal selected from the group consisting of lead, tin and germa nium. With other catalysts, such as Pd/C, low catalytic activity and cracking to saturated hydrocarbons, or formation of ketones when Raney-Ni was used, were observed. 20 Decarboxylation, accompanied with hydrogenation of oxo-compound, is de scribed in Laurent, E., Delmon, B.: Applied Catalysis, A: General (1994), 109(1), 77-96 and 97-115, wherein hydrodeoxygenation of biomass derived pyrolysis oils over sulphided CoMo/y-A1203 and NiMo/y-A1203 catalysts was studied. Di ethyldecanedioate was used among others as a model compound and it was ob 25 served that the rates of formation of the decarboxylation product, nonane and the hydrogenation product, decane were comparable under hydrotreating conditions (260-300 'C, 7 MPa, in hydrogen). The presence of hydrogen sulphide (H2S) in feed promoted the decarboxylation selectivity compared with zero sulphur in feed. Different sulphur levels studied however had no effect on the decarboxylation 30 selectivity of diethyldecanedioate. Biological raw materials often contain several impurities, such as metal com pounds, organic nitrogen, sulphur and phosphorus compounds, which are known catalyst inhibitors and poisons inevitably reducing the service life of catalysts and 35 necessitating more frequent catalyst regeneration or change. Metals in bio oils/fats WO 2007/003708 PCT/FI2006/050300 6 5 inevitable build up on catalyst surface and change the activity of catalyst. Metals can promote some side reactions and blocking of active sites of catalysts typically decreases the activity. Fatty acid composition, size and saturation degree of the fatty acid may vary con 10 siderably in feedstock of different origin. Melting point of bio oil or fat is mainly consequence of saturation degree. Fats are more saturated than liquid oils and in this respect need less hydrogen for hydrogenation of double bonds. Double bonds in fatty acid chains contribute also to different kinds of side reactions, such as oligomerisation/polymerization, cyclisation/aromatisation and cracking reactions, 15 which deactivate catalyst, increase hydrogen consumption and reduce diesel yield. Hydrolysis of triglycerides produces also diglycerides and monoglycerides, which are partially hydrolyzed products. Diglycerides and monoglycerides are surface active compounds, which can form emulsions and make liquid/liquid separations 20 of water and oil more difficult. Bio oils and fats can also contain other glyceride like surface-active impurities like phospholipids, suck as lecithin, which have phosphorus in their structures. Phospholipids are gum like materials, which can be harmful for catalysts. Natural oils and fats also contain non-glyceride components. These are among others waxes, sterols, tocopherols and carotenoids, some metals 25 and organic sulphur compounds as well as organic nitrogen compounds. These compounds can be harmful for catalysts or pose other problems in processing. Plant oils/fats and animal oils/fat may contain free fatty acids, which are formed during processing of oils and fats through hydrolysis of triglycerides. Free fatty 30 acids are a class of problematic components in bio oils and fats, their typical con tent being between 0 and 30% by weight. Free fatty acids are corrosive in their nature, they can attack the materials of the process unit or catalyst and they can promote side reactions like formation of metal carboxylates in the presence of metal impurities. Due to the free fatty acids contained in bio oils and fats, the 35 formation of heavy molecular weight compounds is significantly increased when WO 2007/003708 PCT/FI2006/050300 7 5 compared to triglyceridic bio-feedstock having only low amounts of free fatty acids, typically below 1% by weight. Deoxygenation of plant oils/fats and animal oils/fats with hydrogen requires rather much hydrogen and at the same time releases significant amount of heat. Heat is 10 produced from the deoxygenation reactions and from double bond hydrogenation. Different feedstocks produce significantly different amounts of reaction heat. The variation in reaction heat produced is mainly dependent of double bond hydro genation. The average amount of double bonds per triglyceride molecule can vary from about 1.5 to over 5 depending on the source of bio oil or fat. 15 Object of the invention An object of the invention is an improved process for the manufacture of diesel range hydrocarbons from bio oils and fats with reduced hydrogen consumption. 20 A further object of the invention is an improved process for the manufacture of diesel range hydrocarbons from bio oils and fats with high selectivity and which process yields a product with improved cold flow properties concurrently without decreasing diesel yield during isomerisation. 25 A further object of the invention is an improved process for the manufacture of high quality diesel range hydrocarbons from bio oils and fats with decreased hy drogen consumption and high diesel yield. 30 Characteristic features of the process according to the invention are provided in the claims. 35 WO 2007/003708 PCT/FI2006/050300 8 5 Definitions Here hydroprocessing is understood as catalytic processing of organic material by all means of molecular hydrogen. 10 Here hydrotreatment is understood as a catalytic process, which removes oxygen from organic oxygen compounds as water (hydrodeoxygenation, HDO), sulphur from organic sulphur compounds as dihydrogen sulphide (H 2 S) (hydrodesulphuri sation, HDS), nitrogen from organic nitrogen compounds as ammonia (NH 3 ) (hy drodenitrogenation, HDN) and halogens, such as chloride from organic chloride 15 compounds as hydrochloric acid (HC1) (hydrodechlorination, HDC1), typically under the influence of a sulphided NiMo or sulphided CoMo catalysts. Here deoxygenation is understood to mean removal of oxygen from organic molecules, such as fatty acid derivatives, alcohols, ketones, aldehydes or ethers by 20 any means previously described. Here hydrodeoxygenation (HIDO) of triglycerides or other fatty acid derivatives or fatty acids is understood to mean the removal of carboxyl oxygen as water by the means of molecular hydrogen under the influence of a catalyst. 25 Here decarboxylation and/or decarbonylation of triglycerides or other fatty acid derivatives or fatty acids is understood to mean removal of carboxyl oxygen as

CO

2 (decarboxylation) or as CO (decarbonylation) with or without the influence of molecular hydrogen. Decarboxylation and/or decarbonylation reactions are 30 referred to as decarb-reactions. Here hydrocracking is understood as catalytic decomposition of organic hydro carbon materials using molecular hydrogen at high pressures.

WO 2007/003708 PCT/FI2006/050300 9 5 Here hydrogenation means saturation of carbon-carbon double bonds by the means of molecular hydrogen under the influence of a catalyst. Here n-paraffins mean normal alkanes or linear alkanes that do not contain side chains. 10 Here isoparaffins means alkanes having one or more C1 - C 9 , typically C1 - C 2 alkyl side chains, typically mono-, di-, tri- or tetramethylalkanes. The feed ( total feed) to the hydrotreatment step is to be understood comprising 15 fresh feed and optionally at least one dilution agent. Summary of the invention The present invention relates to an improved process comprising a hydrotreatment 20 step and an isomerisation step, for the manufacture of diesel range hydrocarbons from renewable sources like bio oils and fats, such as plant oils/fats and animal and fish oils/fats, particularly C 12

-C

16 fatty acids and/or derivatives thereof in the presence of sulphur. The invention relates to hydrotreating of the feed comprising triglycerides, fatty acids and derivatives of fatty acids and particularly C 12

-C

16 25 fatty acids and/or derivatives thereof or combinations of thereof, into n-paraffinms with reduced hydrogen consumption during hydrotreating, in the presence of sul phur, followed by converting the n-paraffins into diesel range branched alkanes using isomerisation with high diesel yield. The hydrocarbon oil product formed via this method is a high quality diesel component. In the hydrotreating step the 30 feed is contacted with a sulphided hydrotreatment catalyst in the presence of sul phur, followed by the isomerisation step with an isomerisation catalyst. Detailed description of the invention 35 It was surprisingly found that hydrogen consumption in the hydrotreatment step, deoxygenation of fatty acids and/or fatty acid derivatives, and cracking during WO 2007/003708 PCT/FI2006/050300 10 5 isomerisation of n-paraffins can be significantly reduced by adding one or more sulphur compounds to the feed to achieve sulphur content of 50-20000 w-ppm, preferably 1000-8000 w-ppm, most preferably 2000-5000 w-ppm in the feed, cal culated as elemental sulphur, particularly when bio oils and fats comprising C 12 C 16 fatty acids and/or derivatives thereof are used as the fresh feed for the hy 10 drotreatment step. Feedstock The bio oil and/or fat used as the fresh feed in the process of the present invention 15 originates from renewable sources, such as fats and oils from plants and/or ani mals and/or fish and compounds derived from them. The basic structural unit of a typical plant or vegetable or animal oil/fat useful as the feedstock is a triglyceride, which is a triester of glycerol with three fatty acid molecules, having the structure presented in the following formula I: 20 O Formula 1. Structure of triglyceride In formula I R 1 , R 2 and R 3 are alkyl chains. Fatty acids found in natural triglyc 25 erides are almost solely fatty acids of even carbon number. Therefore R 1 , R 2 , and

R

3 typically are C 5 - C 23 alkyl groups, mainly Cu-C 1 9 alkyl groups and most typi cally C 1 5 or C 17 alkyl groups. R 1 , R 2 , and R 3 may contain carbon-carbon double bonds. These alkyl chains can be saturated, unsaturated or polyunsaturated. Suit able bio oils are plant and vegetable oils and fats, animal fats, fish oils, and mix 30 tures thereof containing fatty acids and/or fatty acid esters. Examples of said ma terials are wood-based and other plant-based and vegetable-based fats and oils WO 2007/003708 PCT/FI2006/050300 11 5 such as rapeseed oil, colza oil, canola oil, tall oil, sunflower oil, soybean oil, hempseed oil, olive oil, linseed oil, mustard oil, palm oil, peanut oil, castor oil, coconut oil, as well as fats contained in plants bred by means of gene manipula tion, animal-based fats such as lard, tallow, train oil, and fats contained in milk, as well as recycled fats of the food industry and mixtures of the above. 10 Typically a bio oil or fat, suitable as feedstock, comprises C 12 - C 24 fatty acids, derivatives thereof such as anhydrides or esters of fatty acids as well as triglyc erides of fatty acids or combinations of thereof The fatty acids or fatty acid de rivatives, such as esters may be produced via hydrolysis of bio oils or by their 15 fractionalization or esterification reactions of triglycerides. In the process according to the invention the fresh feed contains at least 20 %, preferably at least 30 % and most preferably at least 40 % by weight of triglyc eride C 1 2

-C

1 6 fatty acids or C 12

-C

16 fatty acid esters or C 12

-C

1 6 fatty acids or com 20 binations of thereof Examples of this kind of feed are palm oils and animal fats containing lower carbon numbers fatty acids, which are typically more saturated than C 18 fatty acids and their decarboxylation tendency is lower than that of higher carbon number fatty acids during hydrodeoxygenation. The fresh feed may also comprise feedstock of biological origin and a hydrocarbon or hydrocarbons. 25

C

12

-C

1 6 fatty acids can be bound to glycerol as triglycerides or other esters. Ani mal fats and palm oil triglycerides contain significant amounts of C 16 fatty acids, typically 15-45 wt-% and especially palmitic acid. Other vegetable triglycerides contain only 1-13 wt-% C 16 fatty acids, for example rapeseed oil only 1-5 wt-%. 30 In order to avoid catalyst deactivation and undesired side reactions the feed shall comply with the following requirements: The amount of alkaline and alkaline earth metals, calculated as elemental alkaline and alkaline earth metals, in the feed is below 10, preferably below 5 and most preferably below 1 w-ppm. The amount 35 of other metals, calculated as elemental metals, in the feed is below 10, preferably WO 2007/003708 PCT/FI2006/050300 12 5 below 5 and most preferably below 1 w-ppm. The amount of phosphorus, calcu lated as elemental phosphorus is below 30, preferably below 15 and most prefera bly below 5 w-ppm. In many cases the feedstock, such as crude plant oil or animal fat, is not suitable 10 as such for processing because of high impurity content and thus the feedstock is preferably purified using suitable one or more conventional purification proce dures, before introducing it to the hydrotreating step of the process. Examples of some conventional procedures are provided in the following. 15 Degumming of plant oils/fats and animal oils/fats means removal of phosphorus compounds, such as phospholipids. Solvent extracted vegetable oils contain often significant amounts of gums, typically 0.5-3% by weight, which are mostly phos phatides (phospholipids) and therefore a degumming stage is needed for crude plant oils and animal fats in order to remove phospholipids and metals present in 20 crude oils and fats. Iron and also other metals may be present in the form of metal-phosphatide complexes. Even a trace amount of iron is capable of catalys ing oxidation of the oil or fat. Degumming is performed by washing the feed at 90-105 'C, 300-500 kPa(a), with 25 H 3

PO

4 , NaOH and soft water and separating the formed gums. A major amount of metal components, which are harmful for the hydrotreatment catalyst, are also removed from the feedstock during the degumming stage. The moisture content of the degummed oil is reduced in dryer at 90-105 'C, 5-50 kPa(a). 30 The amount of free fatty acids present in vegetable oils is typically 1-5 wt % and in animal fat 10-25 wt-%. High amounts of free fatty acids in a feedstock may be reduced using a deacidification stage, which may be performed for example by steam stripping. A feedstock, which is optionally degummed, is typically first degassed under 5-10 kPa(a)a pressure at a temperature of approx. 90 'C. Thereaf 35 ter the obtained oil is heated to approx. 250-280 'C, 5-10 kPa(a) and directed to a WO 2007/003708 PCT/FI2006/050300 13 5 stripping column, where life steam strips at 230-260 'C the free fatty acids and deodorizes the oil under vacuum. The fatty acid fraction is withdrawn from the column overhead. A feedstock, which is optionally degummed or refined in another conventional 10 way, may be bleached. In bleaching the degummed or refined feedstock is heated and mixed with natural or acid-activated bleaching clay. Bleaching removes vari ous impurity traces left from other pretreatment steps like degumming, such as chlorophyll, carotenoids, phosphoipids, metals, soaps and oxidation products. Bleaching is typically carried out under vacuum to minimize possible oxidation. 15 Bleaching is used to reduce the color pigments in order to produce an oil of ac ceptable color and to reduce the oxidation tendency of oil. In the following the process according to the invention comprising a hydrotreating step and an isomerisation step is described in more detail. 20 Hydrotreating step The feed to the hydrotreating unit comprises fresh feed and optionally at least one diluting agent. The diluting agent can be a hydrocarbon of biological origin and/or 25 non biological origin. In the case the feed comprises additionally at least one di luting agent it is preferable that the feed contains less than 20 wt-% of fresh feed. The diluting agent can also be recycled product from the process (product recycle) and then the diluting agent / fresh feed-ratio is 5-30:1, preferably 10-30:1 and 30 most preferably 12-25:1. The total feed comprising fresh feed containing at least 20 %, preferably at least 30 % and most preferably at least 40 % by weight of triglyceride C 12

-C

16 fatty acids or C 12

-C

1 6 fatty acid esters or C 12

-C

1 6 fatty acids or combinations of thereof, 35 is hydrotreated in the presence of hydrogen with a catalyst at hydrotreating condi- WO 2007/003708 PCT/FI2006/050300 14 5 tions in the presence of 50-20000 w-ppm, preferably 1000-8000 w-ppm, most preferably 2000-5000 w-ppm of sulphur in the total feed, calculated as elemental sulphur. In the hydrotreating step of the process fatty acids, triglycerides and fatty acid 10 derivatives are deoxygenated, denitrogenated, desulphurisated and dechlorinated. In the hydrotreating step, known hydrogenation catalysts containing metals from Group VIII and/or VIB of the Periodic System may be used. Preferably, the hy drogenation catalysts are supported Pd, Pt, Ni, NiMo or a CoMo catalysts, the 15 support being alumina and/or silica, as described for instance in FI 100248. Typi cally, NiMo/A1 2 0 3 and CoMo/A1 2 0 3 catalysts are used. In the hydrotreating step, the pressure range can be varied between 2 and 15 MPa, preferably between 3 and 10 MPa and most preferably between 4 and 8 MPa, and 20 the temperature between 200 and 400 oC, preferably between 250 and 350 0 C and most preferably 280-345oC. It was found that the deoxygenation of starting materials originating from renew able sources can be controlled between two partially alternative reaction routes: 25 hydrodeoxygenation and decarboxylation and/or decarbonylation (decarb reactions). The selectivity of decarb-reactions and the deoxygenation through de carb-reactions can be promoted during hydrotreating over the hydroteatment cata lyst, by using sulphur content of 50 - 20000 w-ppm in the total feed. The specific sulphur content in the feed is able to double the extent of n-paraffins formed by 30 removal of COx. Complete deoxygenation of triglycerides by decarb-reactions can theoretically lower the consumption of hydrogen about 60% (max) compared with pure deoxygenation by hydrogen as can be seen in Table 3. At least one organic or inorganic sulphur compound may be fed along with hy 35 drogen or with the feed to achieve the desired sulphur content. The inorganic sul- WO 2007/003708 PCT/FI2006/050300 15 5 phur compound can be for example H 2 S or elemental sulphur or the sulphur com pound may be an easily decomposable organic sulphur compound such as di methyl disulphide, carbon disulphide and butyl thiol or a mixture of easily de composable organic sulphur compounds. It is also possible to use refinery gas or liquid streams containing decomposable sulphur compounds. 10 It was surprisingly observed from the examples that with added sulphur com pounds in the feed, resulting in sulphur contents of 100 - 10000 w-ppm in the feed the decarboxylation of short chain fatty acids and derivatives, such as C 16 fatty acids increases significantly more than that of C 1 8 fatty acids. 15 When C 16 containing fatty acids and derivatives thereof are hydrodeoxygenated, n-C 15 and n-C 16 paraffins are formed, with melting points of 9.9 0 C and 18.2 0 C respectively. The conversion of other vegetable oils like rapeseed oil and soybean oil produces almost totally n-C 1 7 and n-C 1 8 paraffims with significantly higher 20 melting points of 22.0 and 28.2 0 C. Hydrodeoxygenation of triglycerides facilitates controlled decomposition of the triglyceride molecule contrary to uncontrolled cracking. Double bonds are also hydrogenated during the controlled hydrotreatment. Light hydrocarbons and gases 25 formed, mainly propane, water, CO2, CO, H 2 S and NH3, are removed from hy drotreated product. In the case the fresh feed comprises more than 5 wt-% free fatty acids, it is prefer able to use diluting agent or product recycle in the process as described in Figure 30 1, wherein an improved reactor configuration is presented, particularly for the control of the increase of temperature over catalyst bed and side reaction forma tion. In Figure 1 a hydrotreatment process configuration is provided, comprising one or more catalyst beds in series, hydrotreated product recycle introduction on the top of the first catalyst bed and fresh feed, quench liquid and hydrogen intro 35 duction on top of each catalyst beds. This results in improved control of the reac- WO 2007/003708 PCT/FI2006/050300 16 5 tion temperature in the catalyst beds and hence diminishes undesired side reac tions. In Figure 1 the hydrotreatment reactor 100 comprises two catalyst beds 10 and 20. Fresh feed 11 is introduced as streams 12 and 13 on the catalyst beds 10 and 20, 10 respectively, and hydrogen as stream 22 and 23 on the catalyst beds 10 and 20, respectively. The fresh feed stream 12 is first mixed with the hydrotreated product recycle stream 41 and quench liquid stream 43 and the resulting mixture 31, di luted in the fresh feed concentration, is then introduced on the catalyst bed 10. In order to obtain a required sulphur concentration in the feed stream 31, required 15 amount of sulphur make up is added to the fresh feed stream 11 via stream 15. As mixture 31 passes through the catalyst bed 10 with the hydrogen stream 22, fatty acids and fatty acid derivatives of the fresh feed stream 12 are converted to the corresponding reaction products. A two-phase stream 32 is withdrawn from the bottom of the catalyst bed 10 and is mixed with the fresh feed stream 13, quench 20 liquid stream 44 and the hydrogen stream 23. The formed vapor-liquid mixture 33, diluted in the fresh feed concentration, is then introduced on the catalyst bed 20 at reduced temperature due to cooling effect of the hydrogen, quench liquid and fresh feed, passed through the catalyst bed 20 and finally withdrawn from the catalyst bed as a product stream 34. The stream 34 is separated in to a vapor 25 stream 35 and liquid stream 36 in the high temperature separator 101. Vapor stream 35 is rich in hydrogen and is directed to further treatment. Part of the liquid stream 36 is returned to the reactor 100 as recycle stream 40, which is further di vided to dilution stream 41 and total quench liquid stream 42. The quench liquid stream 42 is cooled in the heat exchanger 102 to provide adequate cooling effect 30 on the top of the catalyst beds 10 and 20. Hydrotreated product stream 51 is di rected from the hydrotreatment step to further processing. The catalyst beds 10 and 20 may be located in the same pressure vessel or in sepa rate pressure vessels. In the embodiment where the catalyst beds are in the same 35 pressure vessels the hydrogen streams 22 and 23 may alternatively be introduced WO 2007/003708 PCT/FI2006/050300 17 5 on the catalyst bed 10 and then be passed through the catalyst beds 10 and 20. In the embodiment where the catalyst beds are in separate pressure vessels, the cata lyst beds may operate in parallel mode with separate dilution streams, hydrogen streams and quench liquid streams. The number of catalyst beds may be one or two or more than two. 10 The sulphur make up to the hydrotreatment step may be introduced with the fresh feed stream 11. Alternatively, required amount of sulphur may be fed with the hydrogen streams 22 and 23 as gaseous sulphur component such as hydrogen sul phide. 15 Hydrogen is fed to the hydrotreating reactor in excess of the theoretical hydrogen consumption. During the hydrotreating step, triglyceride oils, fatty acids and de rivatives thereof are almost theoretically converted to n-paraffins without or al most without side reactions. Additionally, propane is formed from the glycerol 20 part of the triglycerides, water and CO and/or CO 2 from carboxylic oxygen, H 2 S from organic sulphur compounds and NH3 from organic nitrogen compounds. Using the above described procedures in the hydrotreating step, the temperature needed for reactions to start up is achieved in the beginning of each catalyst bed, 25 the temperature increase in the catalyst beds is limited, harmful and partially con verted product intermediates can be avoided and the catalyst life is extended con siderably. The temperature at the end of the catalyst bed is controlled by net heat of reactions and to the extent of diluting agent used. Diluting agent may be any hydrocarbon available, bio-origin or non bio-origin. It can also be product recycle. 30 If diluting agent is used, fresh feed content from total feed is less than 20 wt-%. If the product recycle is used, product recycle/fresh feed ratio is 5-30:1, preferably 10-30:1, most preferably 12-25:1. After the hydrotreatment step, the product is subjected to an isomerisation step. 35 WO 2007/003708 PCT/FI2006/050300 18 5 Isomerisation of n-paraffins formed during hydrotreatment In order to improve the cold properties of the products, isomerisation of n paraffims are needed. During the isomerisation branched isoparaffims are formed. Isoparaffims may typically have mono-, di-, tri- or tetramethyl branches. 10 The product obtained from the hydrotreatment step is isomerised with a catalyst under isomerisation conditions. The feed into the isomerisation reactor is a mix ture of pure n-paraffins and the composition of the feed can be predicted from the fatty acid distribution of each individual bio oil used as feed to the hydrotreat 15 ment. The isomerisation step may comprise an optional purification step, wherein the reaction product from the hydrotreatment step may be purified using a suitable method such as stripping with water vapour or a suitable gas such as light hydro 20 carbon, nitrogen or hydrogen. Preferably acid gases and water impurities are re moved as completely as possible before the hydrocarbons are contacted with the isomerization catalyst. In the isomerisation step, the pressure varies in the range of 2-15 MPa, preferably 25 in the range of 3-10 MPa and the temperature varies between 200 and 500 oC, preferably between 280 and 400 oC. In the isomerisation step, isomerisation catalysts known in the art may be used. Suitable isomerisation catalysts contain a molecular sieve and/or a metal selected 30 from Group VIII of the Periodic Table and/or a carrier. Preferably, the isomerisa tion catalyst contains SAPO-11 or SAPO-41 or ZSM-22 or ZSM-23 or ferrierite and Pt, Pd or Ni and A1 2 0 3 or SiO 2 .Typical isomerisation catalysts are, for exam ple, Pt/SAPO-11/A1 2 0 3 , Pt/ZSM-22/A1 2 0 3 , Pt/ZSM-23/A 2 0 3 and Pt/SAPO 11/SiO 2 . Most of these catalysts require the presence of hydrogen to reduce the 35 catalyst deactivation.

WO 2007/003708 PCT/FI2006/050300 19 5 The isomerised diesel product consists mainly of branched hydrocarbons and also linear hydrocarbons and it has a boiling range of 180 - 350 0 C. Additionally some gasoline and gas may be obtained. Advantages of the invention 10 The process according to the invention provides a way to reduce the formation of higher molecular weight compounds during the hydrotreatment of the fresh feed, which may contain fatty acids and derivatives thereof. The process according to the invention provides selective manufacture of diesel range hydrocarbons from 15 bio oils and fats with high diesel yield and without significant side-reactions. Branched hydrocarbons can be manufactured from plant and vegetable oils and fats as well as animal and fish oils and fats using promoted assistance of decarb reactions during hydrodeoxygenation and therefore the consumption of hydrogen is decreased by 20-60 %, typically 20-40 %. 20 During the deoxygenation of the feed through decarboxylation and/or decarbon ylation, oxygen is removed in the form of CO and CO 2 . The decarb-reactions de crease hydrogen consumption, theoretically in complete deoxygenation about 60 70 % compared to complete hydrodeoxygenation route, but depends on the 25 triglyceride source. C 12

-C

16 fatty acids and their derivatives have typically lower amount of double bonds and their decarboxylation tendency is lower than higher carbon number fatty acids and their derivatives during hydrodeoxygenation. How ever, it was surprisingly found that when 50-20 000 w-ppm of sulphur, calculated as elemental sulphur, was present in the feed comprising fresh feed containing at 30 least 20 % by weight of C 12

-C

16 fatty acids and/or their derivatives, the decar boxylation of C 16 fatty acids and derivatives thereof increases significantly more than that of C 18 fatty acids and its derivatives. This results in still lower consump tion of hydrogen. Added sulphur compounds in hydrodeoxygenation feed facili tate the control of catalyst stability and reduce hydrogen consumption. Feedstock WO 2007/003708 PCT/FI2006/050300 20 5 like palm oil or animal fat, containing more saturated fatty acid derivatives, pro duces less heat. It was also found that feeds having a high content of C 1 2

-C

1 6 fatty acids and/or their derivatives decreases hydrogen consumption in the isomerisation step and 10 also improve cold properties of diesel fuel. The yield of diesel range hydrocarbons is especially increased during isomerisation of n-paraffins due to the lower crack ing of n-paraffins formed from the fatty acid derivative feed to hydrotreatment. The C 11

-C

1 6 n-paraffins formed during hydrotreatment need lower conversion and lower reaction temperature during isomerisation in order to maintain same cold 15 properties of diesel and thus significantly lower the extent of cracking and coke formation compared to heavier n-paraffims. Alternatively improved cold proper ties can be achieved at the same reaction temperature without yield loss. The sta bility of the catalysts during hydrotreating and isomerisation is increased. 20 The invention is illustrated in the following with examples presenting some pref erable embodiments of the invention. However, it is evident to a man skilled in the art that the scope of the invention is not meant to be limited to these examples. Examples 25 Example 1. Effect of sulphur content of total feed Palm oil containing 0.3 area-% of free fatty acids was used as the fresh feed, along with product recycle 5:1 in the presence of hydrogen. The content of 30 triglyceride C 12

-C

1 6 fatty acids in the fresh feed was 58.3 wt-%. The total feed contained alkaline and alkaline earth metals, calculated as elemental alkaline and alkaline earth metals in a amount of below 10 w-ppm. The amount of other met als, calculated as elemental metals, in the feed was below 10 w-ppm. The amount of phosphorus, calculated as elemental phosphorus was below 30 w-ppm. 35 WO 2007/003708 PCT/FI2006/050300 21 5 During the test runs various amounts of dimethyl disulfide in the total feed were used. The reaction temperature was 305 'C, reactor pressure was 5 MPa and space velocity was 0.5 g/g for fresh feed. Higher content of sulphur in feed significantly increased the total deoxygenation reactions through CO and CO 2 (decarb reactions, production of one carbon less n-paraffins than original fatty acid) in 10 stead of deoxygenation by hydrogen (HIDO, production of same carbon number n paraffins than original fatty acid). However the decarb-reactions of C16-fatty ac ids increased significantly more than decarb-reactions of higher C18 or C20 fatty acids. High content of sulphur in the feed decreased the double bond hydrogena tion activity of catalyst and also decreased decarb-reactions as can be seen from 15 table 1, wherein the effect of sulphur content of total feed calculated as elemental sulphur, on decarb-% of different carbon number fatty acids observed in product oil (decarb-% calculated from fresh feed) is presented. Table 2 discloses relative increase of decarb-reactions compared to the feed with 100 w-ppm of sulphur and table 3 presents theoretical decrease of hydrogen consumption due to decarb 20 reactions. Table 1. Effect of sulphur content of total feed calculated as elemental sulphur Sulphur Sulphur Sulphur Sulphur Sulphur Sulphur 100 570 w- 1000 w- 3000 w- 5000 w- 10000 w-ppm ppm ppm ppm ppm w-ppm C15/(C15+C16) 29.1% 45.6 % 52.6 % 55.1 % 56.2 % 47.5 % C17/(C17+C18) 30.2 % 37.5 % 40.1% 42.5 % 43.3 % 39.7 % C19/(C19+C20) 36.6 % 43.4 % 46.0 % 48.1% 49.2 % 46.5 % Total decarb-% 32.0 % 42.2 % 46.2 % 48.6 % 49.5 % 44.6 % 25 WO 2007/003708 PCT/FI2006/050300 22 5 Table 2. Relative increase of decarb-reactions Sulphur Sulphur Sulphur Sulphur Sulphur 570 ppm vs 1 000 ppm vs 3 000 ppm vs 5 000 ppm vs 10 000 ppm 100 ppm 100 ppm 100 ppm 100 ppm vs 100 ppm C16 56.8 % 80.9 % 89.5 % 93.2 % 63.3 % C18 24.1% 32.7% 40.7% 43.2% 31.4% C20 18.7% 25.7% 31.5 % 34.4% 27.1% Total 31.9 % 44.6 % 52.0 % 55.0 % 39.5 % Table 3. Theoretical hydrogen consumption with and without decarb-reactions 10 Rapeseed Palm stearin Palm oil Animal fat oil Hydrogen consumption (H 2 molecules per triglyceride), 100% deoxygenation by hy drodeoxygenation Water 6 6 6 6 Subst. Hy drogen 6 6 6 6 Double bonds 4 1.16 1.8 2 Ttotal 16 13.16 13.8 14 Hydrogen consumption (H 2 molecules per triglyceride), 100% deoxygenation by de carb-reactions Water 0 0 0 0 Subst. Hy drogen 3 3 3 3 Double bonds 4 1.16 1.8 2 Total 7 4.16 4.8 5 H2 reduction (max) 56% 68% 65% 64% WO 2007/003708 PCT/FI2006/050300 23 5 Example 2. Effect of C16 fatty acids on cracking during isomerisation and diesel yield at same pour point level with palm oil feed Palm oil containing 44.8 wt-% of triglyceride C 1 2

-C

16 fatty acids was used in the fresh feed. Dimethyl disulphide was added to palm oil to obtain sulphur content of 10 about 600 w-ppm in the feed, calculated as elemental sulphur. The feed purity was same as in example 1, but the amount of free fatty acids was 0.2 area-%. No dilut ing agent was used. The feed was hydrotreated at 305 'C in the presence of hy drogen, reactor pressure was 5 MPa and space velocity was 2 g/g for fresh feed. The products contained mainly n-paraffins. The n-paraffin feeds were isomerised 15 at 317 'C, 4 MPa and WHSV was 3 1/h in presence of hydrogen. The catalyst (A) contained Pt, SAPO-11 and an alumina support. The amount of hydrocarbons >C10 was 97 wt-% in the product. The cloud point of the liquid product was -22 'C. Results of analysis of the product are provided in table 4. 20 A comparative test was carried out with rapeseed oil feed. Rapeseed oil contained of 4.5 wt-%. of triglyceride C 1 2

-C

16 fatty acids. Rapeseed oil was hydrotreated and isomerised at the same reaction conditions as described above. The amount of hydrocarbons >C10 was 96 wt-% in the product. The cloud point of the liquid product was -15 'C. Results of analysis of the product are provided in table 4. 25 Example 3. Effect of C16 fatty acids on pour point of isomerised diesel oil at same diesel yield with palm oil feed The hydrotreated palm oil obtained in Example 2 was isomerised at 312 'C, 4 30 MPa and WHSV was 3 1/h in the presence of hydrogen with catalyst A. This yielded a liquid product with a cloud point of -14 'C. The amount of hydrocar bons >C10 was now 98 wt-% in the product. A small amount of lighter hydrocar bons can be concluded from the flash point and in the distillation curve of the products as can be seen from table 4, which presents analysis results of hy- WO 2007/003708 PCT/FI2006/050300 24 5 drotreated and isomerised products from rapeseed oil and palm oil, and HRO=hydrotreated rapeseed oil, HPO=hydrotreated palm oil. Table 4. Analysis results of hydrotreated and isomerised products from rapeseed oil and palm oil. Feed Method Unit HRO HPO HPO Isomerisation T 0 C 317 317 312 EN ISO Density 15 0 C 12185 kg/m' 782.7 779.2 779.3 ASTM Cloud point D5773 0 C -15 -22 -14 ASTM Pour point D5949 0 C -24 -33 -24 CFPP EN 116 0 C -15 -22 -15 Flash point EN 22719 0 C 52 53 65 Distillation TA 0 C 117 123 185 EN ISO 3405 5 vol-% 0 C 274 264 268 10 vol-% 0 C 282 270 274 30 vol-% 0 C 290 279 280 50 vol-% 0 C 292 283 283 70 vol-% 0 C 294 287 287 90 vol-% 0 C 299 294 294 95 vol-% 0 C 306 298 299 TL oC 327 311 308 10 Example 4. Effect of C16 fatty acids on cracking during isomerisation and diesel yield at same pour point level with animal fat feed 15 Animal fat containing 30 wt-% of triglyceride C12-C16 fatty acids was used as fresh feed. The feed contained alkaline and alkaline earth metals, calculated as WO 2007/003708 PCT/FI2006/050300 25 5 elemental alkaline and alkaline earth metals in the amount of below 10 w-ppm. The amount of other metals, calculated as elemental metals, in the feed was below 10 w-ppm. The amount of phosphorus, calculated as elemental phosphorus was below 30 w-ppm. Dimethyl disulphide was added to animal fat to obtain sulphur content of about 100 w-ppm in the feed. Fresh feed contained free fatty acids 0.6 10 area-%. The feed was hydrotreated at 300 'C in the presence of hydrogen, reactor pressure was 5 MPa and space velocity was 2 g/g for fresh feed without any dilut ing agent. The products contained mainly n-paraffins. The n-paraffin feeds were isomerised at 316 'C, 4 MPa and WHSV was 1.5 1/h in the presence of hydrogen. The catalyst (B) contained Pt, SAPO-11 and an alumina support. The amount of 15 hydrocarbons >C10 was 95 wt-% in the product. The cloud point of the liquid product was -20 'C. As a comparative example, rapeseed oil was hydrotreated and isomerisated at the same reaction conditions as described above. Rapeseed oil contained 4.5 wt-% of 20 triglyceride C12-C16 fatty acids. In the isomerised product, the amount of hydro carbons >C10 was 95 wt-%. The cloud point of the liquid product was -14 'C. Example 5. Effect of C16 fatty acids on pour point of isomerised diesel oil at same diesel yield with animal fat feed 25 The hydrotreated animal fat obtained in Example 4 was isomerised at 312 'C, 4 MPa and WHSV was 1.5 1/h in the presence of hydrogen with catalyst B. This yielded a liquid product with a cloud point of -13 'C. The amount of hydrocar bons >C10 was now 98 wt-%. 30

Claims (20)

1. Process for the manufacture of diesel range hydrocarbons wherein a feed is hydrotreated in a hydrotreating step and isomerised in an isomerisation step, characterized in that the feed comprises fresh feed containing at least 20 % by 10 weight of triglyceride C 1 2 -C 16 fatty acids or C 1 2 -C 1 6 fatty acid esters or C 1 2 -C 1 6 fatty acids or combinations of thereof and the total feed contains 50 - 20000 w ppm sulphur calculated as elemental sulphur.

2. Process according to claim 1, characterized in that the fresh feed contains at 15 least 30 % by weight and preferably at least 40 % by weight of triglyceride C 1 2 C 1 6 fatty acids or other fatty acid esters or combinations of thereof.

3. Process according to claim 1 or 2, characterized in that the fresh feed contains more than 5 % by weight of free fatty acids. 20

4. Process according to any one of claims 1 - 3, characterised in that the feed contains less than 10 w-ppm alkaline and alkaline earth metals, calculated as ele mental alkaline and alkaline earth metals, less than 10 w-ppm other metals, calcu lated as elemental metals and less than 30 w-ppm phosphorus, calculated as ele 25 mental phosphorus.

5. Process according to any one of claims 1 - 4, characterized in that the feed comprises less than 20 wt-% of fresh feed and additionally at least one diluting agent. 30

6. Process according to claim 5, characterized in that the diluting agent is dilut ing agent is selected from hydrocarbons and recycled products of the process or mixtures thereof and the diluting agent / fresh feed-ratio is 5-30:1, preferably 10 30:1 and most preferably 12-25:1. 35 WO 2007/003708 PCT/FI2006/050300 27 5

7. Process according to any one of claims 1 - 6, characterized in that the feed contains 1000-8000 w-ppm and preferably 2000-5000 w-ppm of sulphur calcu lated as elemental sulphur.

8. Process according to any one of claims 1 - 7, characterized in that at least one 10 inorganic or organic sulphur compound or a refinery gas and/or liquid stream con taining sulphur compounds is added to the feed.

9. Process according to any one of claims 1 - 8, characterized in that the fresh feed is of biological origin selected from plant oils/fats, animal fats/oils, fish 15 fats/oils, fats contained in plants bred by means of gene manipulation, recycled fats of the food industry and mixtures thereof.

10. Process according to any one of claims 1 - 9, characterized in that the fresh feed is selected from rapeseed oil, colza oil, canola oil, tall oil, sunflower oil, soy 20 bean oil, hempseed oil, olive oil, linseed oil, mustard oil, palm oil, peanut oil, cas tor oil, coconut oil, lard, tallow, train oil or fats contained in milk or mixtures thereof.

11. Process according to any one of claims 1 - 10, characterized in that the fresh 25 feed comprises feed of biological origin and a hydrocarbon/hydrocarbons.

12. Process according to any of the claims 1 - 11, characterized in that in the hydrotreatment step a catalyst bed system is used comprising one or more catalyst beds. 30

13. Process according to any of the above claims 1-12, characterized in that in the hydrotreating step, the pressure varies in the range of 2-15 MPa, preferably in the range of 3-10 MPa, the temperature varying between 200 and 400 oC, prefera bly between 250 and 350 oC, and most preferably between 280 and 345 oC. 35 WO 2007/003708 PCT/FI2006/050300 28 5

14. Process according to any of the above claims 1-13, characterized in that in the isomerisation step, the pressure varies in the range of 2-15 MPa, preferably in the range of 3-10 MPa, the temperature varying between 200 and 500 oC, prefera bly between 280 and 400 oC. 10 15. Process according to any of the above claims 1-14, characterized in that the hydrotreatment is carried out in the presence of a hydrogenation catalyst, said hy drogenation catalyst containing a metal from the Group VIII and/or VIB of the Periodic System.

15

16. Process according to claim 15, characterized in that the hydrotreating catalyst is a supported Pd, Pt, Ni, NiMo or a CoMo catalyst, the support being alumina and/or silica.

17. Process according to any of the above claims 1-16, characterized in that an 20 isomerisation catalyst containing molecular sieve is used in the isomerisation step.

18. Process according to claim 17, characterized in that isomerisation catalyst comprises a metal from the Element Group VIII. 25

19. Process according to claim 17 or 18, characterized in that the isomerisation catalyst contains A1 2 0 3 or SiO 2 .

20. Process according to any one of claims 17 -19, characterized in that the isom erisation catalyst contains SAPO-11 or SAPO-41 or ZSM-22 or ZSM-23 or ferrier 30 ite and Pt or Pd or Ni and A1 2 0 3 or SiO 2 .