FI129166B - Method for the production of hydrocarbon components - Google Patents

Abstract

The invention relates to a process for producing hydrocarbon components comprising isoparaffins from a feedstock of biological origin, comprising linear unsaturated fatty acids, for the preparation of components for diesel fuel, the process comprising step a), wherein at least a part of the feedstock's linear unsaturated fatty acids are converted to corresponding fatty acids, and step b), wherein said branched fatty acids are hydrodeoxygenated and residual linear fatty acids to obtain the corresponding isoparaffins and n-paraffins. The invention also relates to a device for carrying out the method according to the invention.

Description

METHOD OF MANUFACTURE HYDROCARBON COMPONENTS

FIELD OF THE INVENTION The present invention relates to the field of renewable fuels and biofuels and relates to the production of hydrocarbons from biological feedstocks for the production of biodiesel and its components. In particular, the invention relates to a process for the production of isoparaffins from a raw material feed of biological origin.

BACKGROUND OF THE INVENTION The production of hydrocarbon components from biological feedstocks for biofuel components and biofuels is of growing interest because of the desire to replace non-renewable fossil feedstocks with renewable feedstocks. Many methods are known in the art for producing fuels from biological raw materials.

Traditional biodiesel production methods include the hydrotreatment of triglycerides and free fatty acids to n-paraffins. However, the cold flow properties of the biodiesel thus produced, such as the cloud point and solidification point, are poor compared to diesel fuel oil, although the cetane value is higher. Attempts have been made to solve these problems by a number of methods which have been proposed for the production of biofuel components with high cetane number and good flow properties.

Intermediate distillates have been produced from vegetable oils by hydrogenation of vegetable oil fatty acids and triglycerides to n-paraffins, followed by isomerization to obtain branched paraffins. Branched paraffins are known to enhance the cold flow and physical properties of biofuels.

N 25 One problem with these processes is the use of noble metal catalysts N in the isomerization step. They are very expensive and very sensitive to catalyst toxins. This is very important when using biological feedstocks, 3 as they often contain heteroatoms, oxygen, sulfur, nitrogen and / or phosphorus, z which are catalyst poisons and inhibitors of precious metal catalysts.

+30 EP 1795576 A1 describes a process for the preparation of hydrocarbons in which fatty acids or fatty acid esters are used as feed.

O Branched hydrocarbons for the production of lubricants have been produced by an N process comprising the following steps: isomerization, ketonization and deoxygenation with hydrogen (HDO).

BRIEF DESCRIPTION OF THE INVENTION It is an object of the present invention to provide a novel solution for the production of biofuel components comprising branched hydrocarbons by treating a feed of biological origin for the production of high quality biodiesel and biodiesel components. The objects of the invention are achieved by a method which is characterized by what is stated in the independent claims. Preferred embodiments of the invention are set out in the dependent claims. One advantage of the invention is that it provides an efficient and economical solution for the production of biodiesel and / or biodiesel components. In addition, the process according to the invention gives products with excellent low-temperature properties. Since the process of the invention can avoid the hydrogen isomerization step after the hydrogen deoxygenation (HDO) step of the conventional process, there is no need to use expensive isomerization catalyst (s) comprising noble metals. Another advantage of the invention is that it makes it possible to use a feed which contains impurities which are detrimental to conventional catalysis processes.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will now be described in more detail by means of preferred embodiments and with reference to the accompanying drawings, in which Figure 1 is a schematic flow diagram of a process according to the invention for producing hydrocarbons comprising isoparaffins from a feed of biological origin. Figure 2 is a schematic representation of a first embodiment of a system used to carry out the method according to the invention for the production of hydrocarbons containing isoparaffins from an N feed of biological origin. = Figure 3 is a schematic representation of a second embodiment of a system used to carry out the process according to the invention for the production of hydrocarbons comprising isoparaffins E 30 from a feed of biological origin. =

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DETAILED DESCRIPTION OF THE INVENTION It has surprisingly been found that high quality biodiesel and biodiesel components can be produced by the process of the invention wherein the feed of biological origin comprises unsaturated fatty acids which are converted to branched saturated paraffins, i.e. isoparaffins.

In this specification and claims, the term "biofuel" refers to a renewable fuel, i.e. a fuel made directly from a renewable feed by catalytic hydrogen treatment. The feed can be purified before being used in the process, but is not intentionally processed to form its derivatives.

In this specification and claims, the term "biodiesel" refers to a renewable diesel fuel, i.e. diesel, which is made directly from a renewable feed by catalytic hydrogen treatment. The feed can be purified prior to use in the process, but is not intentionally processed to form its derivatives. The meaning of the term “biodiesel” should not be confused with ethyl esters of fatty acids from vegetable oils, which are generally classified as biodiesel.

The present invention relates to a process for the production of hydrocarbon components comprising isoparaffins from a feed of biological origin, which process comprises the steps of a) converting at least part of the linear unsaturated fatty acids contained in the feed into corresponding branched fatty acids, and b) said branched fatty acids; linear - unsaturated fatty acids are deoxygenated with hydrogen to provide the corresponding - isoparaffins and n-paraffins.

According to the invention, step a) is performed before step b).

b Referring to Figure 1, in an embodiment of the invention, a feed of unsaturated fatty acids of biological origin | T 30 is sent to conversion step A. In conversion step A, the input | reacting E in the presence of a conversion catalyst and under suitable reaction conditions to form a first leaving II comprising branched fatty acids. D Said first effluent II is fed to a hydrogenation deoxygenation step B and wherein the effluent is reacted in the presence of a hydrotreating catalyst under N 35 and under suitable reaction conditions to form a second effluent III comprising isoparaffins.

In order to carry out the process, there is further provided a system for producing hydrocarbon components comprising isoparaffins from a feed of biological origin, the system being adapted to convert at least a portion of the unsaturated fatty acids in the feed to branched fatty acids and then linear paraffins for the production of biodiesel fuel components.

According to one embodiment of the system used to carry out the process of the present invention, said system comprises: one or more conversion units which receive a hydrocarbon feed of biological origin and subject said feed to conversion reactions to produce a first effluent comprising branched fatty acids; to receive said first effluent and subject the first effluent to hydrotreatment in the presence of a hydrogen-containing gas to produce a second effluent comprising isoparaffins, and one or more hydrogen (or hydrogen-containing) gas sources to supply said gas to the unit, the feed being adapted to be fed to the conversion unit, the first outlet being adapted to be fed from the conversion unit to the hydrotreating unit and the second outlet being adapted to be recovered from the hydrotreating unit volume.

The conversion unit and the hydrotreating unit according to the invention can each be implemented separately with a catalyst bed comprising one or more catalyst layers, preferably 1 to 3 catalyst layers. If two or more catalyst layers are used in the catalyst bed e and two or more P conversion catalysts / hydrotreating catalysts are used, the ratio (s) of the two (or more) catalysts in the individual catalyst layers may be the same or different. E The conversion unit (s) and the hydrotreating unit (s) can be fitted - in the same pressure vessel or in separate pressure vessels.

s Hydrogen (or hydrogen-containing) gas can be fed into the system = suitably downstream or upstream of the inlet and / or outlet stream.

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The conversion unit (s) or hydrotreating unit (s) may be carried out together in a fixed bed reactor, preferably a trickle-bed reactor (TBR), comprising two or more catalyst beds. One or more inert layers may optionally be arranged between the conversion unit and the hydrotreating unit and / or any two catalyst beds. The inert layer is preferably arranged between the conversion unit and the hydrotreating unit. The inert layer may be introduced into separate catalyst beds and / or heating or cooling of the effluent between the catalyst beds may be allowed. Optionally, an inert layer can be arranged before the first conversion unit. Preferably, said inert layer is a distribution layer. The purpose of said application layer is to achieve a uniform application of liquid on the catalyst beds. A preheating unit may optionally be arranged in front of the conversion unit and / or between the conversion unit and the hydrotreating unit.

Figure 2 is a schematic representation of a preferred system used to implement the method of the invention. The system comprises a conversion catalyst bed 1, a hydrotreating catalyst bed 2 arranged in series in a reactor vessel 3 with an inlet 4 for feeding the feed 400, an outlet 5 for recovering the product stream 500 and a pipe 6 for feeding hydrogen or hydrogen-containing gas 600.

Referring to Figure 2, the feed 400 of biological origin is fed to the reaction vessel 3 through the inlet 4. Hydrogen (or hydrogen-containing) gas 600 may enter reactor 3 through line 6 or line 6 '. The feed 40 then comes into contact with the conversion catalyst bed 1, where it is subjected to a conversion reaction which converts at least some of the unsaturated fatty acids therein into corresponding branched fatty acids to obtain a effluent 100 comprising said branched fatty acids. The effluent N 100 then flows downwards and comes into contact with the hydrotreating bed 2, where N undergoes hydrotreating reactions in the presence of 600, whereby at least some of said branched fatty acids are converted to isoparaffins to provide effluent 200 comprising the desired product. The stream E of the desired product is recovered from the reactor 3 via the outlet 5 as the product 500. it is needed, for example, by connecting N 35 - one part to the upper end of the hydrotreating catalyst bed 2 and the other part to the middle part of the catalyst bed 2 or to any two catalysts of the catalyst bed 2.

between the lytic layer. A separation unit, such as a distillation unit, may be included in the outlet 5 to remove unwanted components from the product effluent 200 to provide a product stream 500 to be recovered from the reactor 3. In addition, a purification unit such as a filtration unit may be included in the inlet 4 to remove unwanted constituents from input 400.

The reactor can be operated under any suitable conditions depending on the feed and the desired product. The temperature of the conversion catalyst bed and the hydrotreating bed may be the same or different. One or more suitable conversion catalysts may be included in the conversion catalyst bed 1, and one or more suitable hydrogen treatment units may be included in the hydrotreating catalyst bed 2.

An alternative embodiment of the system used to implement the method according to the invention is schematically illustrated in Figure 3. In Figure 3, the same reference numerals are used as for the corresponding components in Figure 2. The system also comprises an outlet 7 and an inlet 7 'arranged in the reactor 3 and connected via a circulating pipe 70, and an outlet 8 and an inlet 8 arranged in the reactor 3 and connected via a circulating pipe 80.

A portion of the effluent 100 or the entire effluent comprising unreacted unsaturated fatty acids can be removed from the reactor 3 via outlet 7 prior to export to the hydrotreating bed and recycled via line 70 through inlet 7 'to reactor 3 for re-contact with conversion catalyst bed 1. Although Figure 7 shows inlet 7 'connected to inlet 4, recycled material may alternatively be fed separately to reactor 3. Part of the unreacted fatty acid effluent 200 may be taken from reactor 3 through outlet 8 and recycled via line 80 through inlet 8' to reactor 3 after conversion catalyst bed 1 re-contact with the hydrotreating catalyst bed 2. Although Fig. 3 shows the inlet 8 'connected to the reactor 3 S between the conversion catalyst bed 1 and the hydrotreating catalyst bed 2, where the recyclable effluent 200 is combined with the effluent 100, it is to be understood that the recyclable material 200 may alternatively be fed separately to the hydrotreating catalyst bed. E Figure 3 further shows an inert upper layer 9 arranged just before the conversion catalyst bed 1 and an inert layer 10 placed between the conversion catalyst bed 1 and the hydrotreating catalyst bed 2. The first distribution layer = and / or the first preheating unit may be included in the unreacted N 35 upper layer 9. The application layer is intended to spread the feed 400 evenly on the conversion catalyst bed 1 and the preheating unit is intended to adjust the feed and a second preheating unit may be included in the unreacted bed 10. Figure 3 also shows an inlet 11 connected to the reactor 3 between the conversion catalyst bed 1 and the hydrotreating catalyst bed 2 for feeding hydrogen sulphide or hydrogen sulphide releasing source 100 and mixing it with the outlet 100. adapted to join directly to the hydrotreating catalyst bed 2 at one or more suitable points. The gaps between the catalyst bed in Fig. 2 and Fig. 3 do not necessarily mean empty spaces between the catalyst layers and / or unreacted layers used, but are shown only for the sake of clarity of the drawings. The present invention also relates to the use of one or more conversion catalysts or one or more hydrotreating catalysts for the conversion of at least a portion of the unsaturated fatty acids in a feed of biological origin to the corresponding branched fatty acids and for the removal of oxygen from said branched fatty acids. Feed The feed according to the present invention comprises unsaturated and / or polyunsaturated free fatty acids having 4 to 28 carbon atoms and one or more double bonds in the carbon chain, and / or their triglycerides, esters or salts, preferably free fatty acids. The structure of several fatty acids (FA) in oils and fats is shown in Table 1.

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Table 1: (% by weight) (% by weight) (% by weight) sunflower oil 83% of - | 68% - Unless otherwise stated, the term 'fatty acid' in this context and hereinafter means carboxylic acids with a long, unbranched, - aliphatic hydrocarbon chain, either saturated or unsaturated.

The chain of more naturally occurring fatty acids has an even number of carbon atoms, a suitable number being 4 to 28. Unsaturated fatty acids have one or more double bonds between the carbon atoms of the hydrocarbon backbone.

Fatty acids with more than one double bond are often referred to as polyunsaturated fatty acids.

However, as used herein, the term "unsaturated fatty acids" is understood to refer to both monounsaturated and polyunsaturated fatty acids.

The two carbon atoms bonded adjacent to either side of the double bond may be in the cis or trans configuration.

Differences in configurations may be relevant for several different types of N 15 reactions of unsaturated fatty acids.

The fatty acids according to the invention may be in the form of free N fatty acids or their triglycerides, esters or salts, preferably as free fatty acids. = Fatty acids are widely distributed in vegetable oils and other oils or fats of biological origin.

Two examples of unsaturated fatty acids are oleic acid (OA) and linoleic acid (LA). In this context and hereinafter, the term "linoleic acid" and the like is defined as referring to a carboxylic acid having an 18 carbon chain and two cis-2 double bonds.

In this context and hereinafter, the term “oleic acid” is understood to refer to a monounsaturated omega-9 fatty acid present in a variety of animal and vegetable fats. The structures of OA and LA are shown below. 0 o KNN N Ån LAN = 0 Ål

OA LA The feed according to the invention preferably comprises at least 5% by weight (% by weight) of unsaturated and / or polyunsaturated fatty acids, more preferably more than 50% by weight (% by weight), most preferably 50-90% by weight (% by weight). The number of carbons of said fatty acid is preferably 12 to 28, preferably 16 to 24. According to one embodiment of the invention, the feed comprises linoleic acid and / or oleic acid. Oils and fats comprising linoleic and / or oleic acids are particularly suitable for the production of diesel components, since the chain length suitable for diesel components is in the range of Cs-Coo.

The feed according to the invention may consist of vegetable, animal and fish oils and fats and mixtures thereof. Examples of suitable oils and fats containing saturated and / or polyunsaturated fatty acids and / or their derivatives are almond oil, babassu oil, ben oil, butter, rapeseed oil, castor oil, chicken oil, rapeseed oil, corn oil, corn oil, corn oil, corn oil, corn oil, corn oil , fish oils, viinirypäleensiemenöljy, hempseed oil, honge- tree oil, jatropansiemenöljy oil, jojoba oil, lard, linseed oil, mustard oil, olive oil, palm oil, palm kernel oil, peanut oil, pecanpähkinäöljy, pistaa- - sipähkinäöljy, poppelinsiemenöljy, pumpkin, rapeseed oil, thawed animal fats, rice bran oil, sea buckthorn oil , sesame oil, sunflower oil, soybean oil, pine oil, tallow, chinese oil, turkey oil, walnut oil and wheat germ oil, but not limited thereto.

An example of a readily available, inedible vegetable oil comprising li-S 25 -nolenic acid is tall oil. Crude pine oil (CTO) is a by-product of the Kraft process for the production of wood pulp, when pulp-P is inherited mainly from conifers. In general, CTO contains unsaponifiables (5-30 =%), castor acids (20-50%), fatty acids (mainly palmitic acid, oleic acid and linoleic acid) (20-70%), fatty alcohols, some steroids and - 30 - other alkyl hydrocarbon derivatives. Tall oil fatty acid (TOFA), which mostly contains oleic acid, is obtained from crude pine oil by fractional distillation. According to a preferred embodiment of the invention, the feed comprises N crude pine oil, tall oil and / or TOFA.

According to the invention, the feed may contain sulfur, nitrogen, aromatic impurities and other impurities.

Prior to step a) according to the invention, the feed may be subjected to one or more pretreatment steps, for example a purification step, to remove contaminants, such as metals, from the feed.

The pretreatment step (s) may be performed by suitable known methods.

These methods include, but are not limited to, thermal and / or chemical treatments known to those skilled in the art, such as washing, filtration, distillation, purification, and resin removal.

If necessary, the free fatty acids can be prepared from the corresponding triglycerides, esters and / or metals present in the feed before the conversion step by standard methods known to a person skilled in the art.

These methods include, but are not limited to, vapor cleavage of triglycerides, base hydrolysis, and enzymatic hydrolysis. —Conversion step In the conversion step according to the process of the invention, step a), the feed, which may be preprocessed, is subjected to conditions suitable for converting at least part of the linear unsaturated fatty acids comprised in the feed into the corresponding branched fatty acids. —According to the invention, an effluent comprising branched fatty acids is produced from the feed of biological origin in step a), which branched fatty acids may be saturated or unsaturated depending on the nature of the parent fatty acid and / or the reaction conditions.

Preferably at least 30%, more preferably 30-50%, most preferably 50-80% of said fatty acids are converted to the corresponding branched fatty acids.

Said effluent may further comprise unreacted linear unsaturated fatty acids and / or other unreacted compounds present in the feed.

S In the conversion step of the process, the unsaturated fatty acids undergo a chemical conversion, referred to herein as the E 30 isomerization, which yields branched fatty acids having = the corresponding amount of carbon.

Although not intended to be limited to any particular theory, it is likely that the isomerization proceeds with the formation of a carbocation cation catalyzed by Bronsted acid (i) over a double bond of an unsaturated fatty acid and thereafter by a hydrocarbon backbone system of said fatty acid (ii) to give isomerized (branched) fatty acids, for example as follows

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HOP N NN ji

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HOA N N OR | i

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NV Carbocation formation can also lead to catalytic cracking to produce shorter alkanes, alkenes and / or fatty acids. However, careful selection of the acid catalyst and reaction conditions makes it possible to favor the isomerization mechanism over the cracking mechanism. Catalysis with Bronsted acid can also lead to double bond migration (DBM) and / or cis-trans isomerization of an unsaturated fatty acid double bond prior to carbocation formation. As a result, mixtures of regioisomers of the corresponding branched fatty acids are formed. The branches in the middle of the hydrocarbon body lower the equilibration point more than the branches near the ends of the chain. Polyunsaturated fatty acids may undergo a carbocation-mediated isomerization reaction at one or more double bond sites, resulting in multiple branches. Limits the number of branches - the number of double bonds in the fatty acids contained in the feed. The increasing number of branches lowers the cloud point, but the cetane index also decreases. The N conversion step can be carried out using a conversion catalyst N with Bronsted acid functionality. The conversion catalyst according to the invention can be amorphous aluminosilicate or zeolite, aluminosilicate phosphate N (SAPO) and / or aluminum phosphate (AIPO). Preferably, said catalyst is a one-dimensional zeolite molecular sieve. = The term “zeolite” as used herein and hereinafter refers to crystalline microporous aluminosilicate minerals having a well-defined pore-N system. The pores can be fitted into well-defined uniform openings, allowing adsorption of molecules smaller than the pore diameter while preventing larger molecules. The choice of zeolite catalyst can affect the distribution of branch locations in the fatty acid hydrocarbon backbone. The long hydrocarbon chain of the double-bonded unsaturated fatty acid diffuses into the zeolite to interact with the Bronsted acid functionality embedded within the zeolite backbone while the carboxylic acid functionality is excluded.

The physical and chemical interactions between the reacting molecule and the zeolite determine the ability of the hydrocarbon chain to reach the zeolite backbone. Thus, the optimal loading, channel size and shape (i.e., pore size) and location of the Bronsted acid functionality of the zeolite will depend on the nature of the diffusion molecule in the feed, i.e., the unsaturated fatty acids, and the desired outcome of the product, and vice versa. The amount of aluminum in the body determines the Bronsted acid strength of the zeolite. Examples of suitable zeolites include, but are not limited to, pentasil and modernites. Preferably, the conversion catalyst is selected from ZSM-5, ZSM-22, ZSM-23, SAPO-11, SAPO-41 and mixtures thereof.

According to step a) of the process according to the invention, the feed is contacted with one or more Bronsted acid catalysts. The temperature range may be, for example, 100-500 ° C, preferably 200-400 ° C and most preferably 250-290 ° C. The temperature of the conversion step depends on the desired product specification and / or the nature of the catalyst and / or the nature of the feed. The operating pressure can vary between 0 and 150 bar, more preferably between 10 and 90 bar. When using a fixed bed reactor, the WHSV (weight Hourly space velocity), defined as the feed weight per hour per weight of catalyst loaded into the reactor, is 0.1 to 100 h ", preferably 0.1 to 20 h", most preferably 0.3 to 10 h ". : According to the present invention, the effluent from step a) is fed to step b) according to the invention. Step a) and step b) are preferably carried out in the same pressure vessel. If desired, said removal from step a) e may be subjected to one or more purification steps to remove any undesired impurities before proceeding to step = 30 to b). In addition, the temperature of said outlet can be adjusted to the desired level before E is fed to step b). Furthermore, according to the present invention, part or all of said effluent can be recycled to step a) or to the feed to increase the conversion and / or selectivity of step a) before proceeding to step b).

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Hydrotreating step In the hydrotreating step of the process according to the invention, step b, the branched fatty acids obtained in the first step are deoxygenated with hydrogen (HDO) to obtain the corresponding branched paraffins.

In addition, the linear saturated and unsaturated fatty acids comprised in step b) of step a) of the process according to the invention can advantageously be deoxygenated with hydrogen and, if necessary, hydrogenated to the corresponding saturated n-paraffins. Furthermore, according to the invention, in step b) the effluent of step a) is subjected to a hydrotreating to obtain a product effluent comprising isoparaffins.

In this context and hereinafter, the terms "isoparaffin", "branched paraffin" and "* branched saturated hydrocarbons" are used for branched alkanes, all of which have the same meaning.

In this context and hereinafter, the term "hydrotreating" is used for a catalytic process which suitably includes HDO (deoxygenation with hydrogen), HDS (hydrogen desulfurization), HDN (nitrogen removal with hydrogen), HDH (halogenation with hydrogen) reactions. . Hydrogen treatment can also lead to the decarboxylation and / or decarbonylation of carbonyl-containing organic compounds and the hydrogenation of the carbon-carbon double bond of unsaturated organic compounds, the ring opening of cyclic and polycyclic organic compounds and, in some circumstances, the hydrogenation of organic compounds.

HDO is known to remove oxygen from organic molecules that contain oxygen, such as fatty acids, aldehydes, ketones, alcohols, and esters, such as water. HDS is known to remove sulfur from sulfur-containing organic molecules such as dihydrogen sulfide (H2S). HDN is known to remove nitrogen from nitrogen-containing compounds such as ammonia LÖ (NH3). HDH is known to remove halogens from compounds containing = halogens, such as the corresponding hydrogen halide acids. According to the invention, the hydrotreating step can be carried out using a hydrotreating catalyst E. In step b) of the process according to the invention, the effluent of step a) is contacted with a hydrotreating catalyst. Examples of suitable hydrotreating catalysts include, but are not limited to, those containing metals N 35 - from Group 6, Group 8, Group 9, and / or Group 10 of the IUPAC Periodic Table. Preferably, the hydrotreating catalyst is a supported monometallic catalyst or a multi-metal composite catalyst containing

Ni, Co, W, Mo or any combination thereof, or a catalyst mixture thereof, the support being preferably activated carbon, aluminum, aluminosilicate or silica. Thus, the metal portion of the catalyst may be NiMo, CoMo, NiW, NiCoMo or any mixture thereof. Most preferably, the hydrotreating catalyst is a NiMo catalyst supported on aluminum.

The operating conditions of the hydrotreating step depend on the desired definition of the product, the nature of the effluent from step a) and the nature of the hydrotreating catalyst. The temperature range may be, for example, 100 to 500 ° C, preferably 250 to 450 ° C, and more preferably 300 to 410 ° C. The operating pressure can vary between 10 and 150 bar, more preferably between 20 and 100 bar. Preferably, the pressure in step b) is the same as in step a). When a fixed bed reactor is used, the WHSV (weight Hourly space velocity), defined as the feed weight per hour per weight of catalyst loaded into the reactor, is 0.2-100 h ", preferably 0.5-3 h". According to the invention, the working conditions in step a) and step b) may be the same or different.

The amount of hydrogen gas required in the hydrotreating step is determined by the amount and nature of the effluent in step a). One skilled in the art can determine the appropriate amount of hydrogen with conventional skills.

It may be necessary to feed additional sulfur to the hydrotreating step to maintain the catalytic activity of the hydrotreating catalyst, depending on the nature of the feed.

- If desired, additional sulfur can be fed to the hydrotreating stage. Said hydrogen may be hydrogen sulphide (H2S) and / or any sulfur-containing compound which produces hydrogen sulphide in the process. Suitably sulfur-containing compounds include, but are not limited to, organosulfur compounds such as dimethyl disulfide. Additionally or alternatively, natural sulfur-containing compounds present in crude pine oil may be used as additional sources of sulfur in accordance with the invention.

The product extract obtained by the process of the invention comprises N isoparaffins. Said extractant may further comprise n-paraffins and / or other hydrocarbons. If desired, part or all of the product removal from step b) can be? recycling to step b) to increase the conversion and / or selectivity of step b) and / or to control the operating conditions.

E After step b), the product extract can be subjected to traditional separation and / or purification steps familiar to a person skilled in the art.

It will be apparent to those skilled in the art that as technology advances, the inventive idea can be implemented in various ways. The invention and its embodiments are not limited to the examples described above, but may vary within the scope of the claims.

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Claims (8)

Claims A process for the production of hydrocarbon components comprising isoparaffins from a feed of biological origin comprising linear - unsaturated fatty acids for the production of diesel fuels, characterized in that the feed comprises crude pine oil and the process comprises the steps of a) converting at least a portion of the feed —In the presence of a conversion catalyst, which is selected from amorphous aluminosilicates, zeolites, aluminosilicate phosphates (SAPO), aluminum phosphates (AIPO), and mixtures thereof for hydrogenation, to provide the corresponding isoparaffins and n-paraffins in the presence of a supported NiW hydrotreating catalyst. A method according to claim 1, characterized in that in step a) a effluent comprising branched fatty acids is produced and said effluent is then subjected to a hydrotreating step in b). Process according to one of Claims 1 or 2, characterized in that the hydrocarbon feed is selected from vegetable oils and fats, animal fats, fish oils and mixtures thereof. Process according to one of Claims 1 to 3, characterized in that the feed comprises at least 5% by weight of unsaturated N fatty acids. Process according to one of Claims 1 to 4, characterized in that the conversion catalyst is chosen from ZSM-5, ZSM-22, ZSM-23, SAPO-11, SAPO-41 and mixtures thereof. Process according to one of Claims 1 to 5, characterized in that the support for the hydrotreating catalyst is chosen from activated carbon, aluminum, silicate, aluminosilicates and mixtures thereof. Method according to one of Claims 1 to 6, characterized in that in step a) the temperature is 100 to 500 ° C, the operating pressure is between 0 and 150 bar and the WHSV (Hourly weight Hourly space velocity) is 0.1 to 100 h ™. Method according to one of Claims 1 to 7, characterized in that in step b) the temperature is 100 to 500 ° C, the operating pressure is between 10 and 150 bar and the WHSV (Hourly weight Hourly space velocity) is 0.2 to 10 h '! . OF O OF LÖ <Q + I = ~ <tr LO O O OF