TW201113361A - Method of converting feeds from renewable sources in co-processing with a petroleum feed using a catalyst based on molybdenum - Google Patents

Abstract

The invention relates to a method of hydrotreatment in co-processing of petroleum feeds, in a mixture with at least one feed obtained from renewable sources, for producing fuel bases (kerosene and/or gas oil) having a sulphur content below 10 ppm, said method comprising a first hydrotreatment stage in which said feed passes through at least one first fixed-bed catalytic zone comprising at least one supported or bulk catalyst comprising an active phase constituted by a sulphide of a group VIB element, the group VIB element being molybdenum, said catalyst being in the form of sulphide, said catalyst also comprising at least one doping element selected from phosphorus, fluorine and boron and a second hydrotreatment stage into which the effluent leaving the first hydrotreatment stage is sent directly, and in which said effluent passes through at least one second fixed-bed catalytic zone comprising at least one hydrotreatment catalyst.

Description

201113361 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a hydrotreating process for a feed combined with a stone domain, the feed being obtained from an oil of renewable origin and especially of vegetable or animal origin. A feed mixture is formed which is intended to produce a gasoline fuel matrix. The present invention relates to a process which can meet, for example, the environmental specifications required for atmospheric gasoline, which is obtained by directly distilling a mixture of crude oil and a feed obtained from a renewable source to produce good quality. Gasoline and/or kerosene fuels, ie complying with the 2009 specification, have a sulfur content of less than 10 ppm and a modified cetane number in the case of gasoline fuel. The s conversion of the feed from the renewable source takes advantage of the complex reactions promoted by the nitridation catalyst system. These reactions include, inter alia: - hydrogenation of unsaturated moieties, - deoxygenation - hydrogenation deoxidation according to two reaction pathways (HDO eliminates oxygen - depurination / decarbonylation by depleting hydrogen and forming water (DCO) Eliminating oxygen by forming carbon monoxide and carbon dioxide (c〇 and C〇2). The present invention relates to treating a mixture of feeds of such renewable sources with petroleum derived petroleum fractions, such as gasoline of various sources in a refining process The chemical structure of the triglyceride and/or fatty acid type contained in the feed obtained from the renewable source can be completely converted into a paraffin-type hydrocarbon under the hydroprocessing operating conditions and using the catalyst used in the present invention. The treatment of such feeds with a mixture of petroleum-derived gasoline fractions typically processed in refining has the following advantages: 150153.doc 201113361 Limits the polymerization associated with preheating of renewable feedstock in a furnace system, "renewable The desired temperature of the mixture and the petroleum feed mixture is obtained by adjusting the temperature of the thermally stable petroleum feed prior to mixing. In fact, it is known to those skilled in the art. Increase the temperature of only vegetable oil (> 1 8 square 〇C) is eligible for thermal oxidation degradation or favor the formation of extremely heavy plastic or polymer by a hot vegetable oil (A. Rosssignol-Castera 'La thermo-oxydation des.

Huiles v0g6tales" Institut des corps gras ITERG 2006). The presence of unsaturation of fatty acids and trace metals (such as cu, Fe, Zn, A1) can diminish this phenomenon. These reactions mainly produce a triglyceride or a previously oxidized triglyceride polymer by forming an epoxy bridge or by double bond polymerization (free radical mechanism) (j丄pERRIN et al. "Etude analytique profonde d^" Uiles chauffees -Techniques analytiques et essais preliminaires j Revue fran9aise des corps gras, 1992, Vol. 32, No. 4, pp. 151-158). The process management of these compounds is cumbersome because of their tendency to clog the reactor or Undesirable degradation products are produced. In the process, thermal degradation of vegetable oil in the preheating equipment can be avoided by mixing the feed obtained from the renewable source with the petroleum source stream and heating the feed in the presence of hydrogen. Risk of diluting to reduce the levels of sulfur, nitrogen and aromatics in the feed to be completely treated in the hydrotreating stage of the process of the invention. In fact, feeds from renewable sources are generally free of aromatics. a compound having a sulfur and nitrogen content lower than that of a petroleum source and especially a feed of gasoline processed in a refinery process. This allows a significant relaxation of the Requires the operation 150153.doc 201113361 conditions and reduces the consumption of hydrogen in this stage. Limits the exothermic effect associated with the hydrotreating of these plant and / or animal source feeds. Therefore 'and oil source parts and especially gasoline The mixing treatment allows for better management of the exothermic effect and thus protects the catalyst from the formation of its hot spots which tends to promote coke formation and thus degrade performance stability and shorten cycle times. Furthermore, it is advantageous to heat the mixture using a thermal gradient. The temperature required for the inlet to the second hydrotreating stage where the hydrodesulfurization reaction takes place. The surface is formed by the hydrogenation of triglycerides and/or fatty acid structures to form a paraffin-type hydrocarbon (characterized by excellent hexadecane). And improve the quality of all gasoline produced and especially the cetane number. Increase the solubility of hydrogen in the mixture to be treated during the deoxygenation phase. In fact, the solubility of hydrogen in the feed from petroleum sources Higher than the solubility in feeds obtained from renewable sources only. Therefore, by feeding and customizing from renewable sources The petroleum feed mixing can increase the solubility of hydrogen in the mixture to be hydrotreated and thus limit the use of high pressure for increasing the amount of hydrogen in the solution required for the hydrogenation and deoxygenation reactions. Controlling the amount of hydrogen dissolved in the liquid phase promotes the hydrodeoxygenation reaction and limits the formation of coke on the catalyst and the polymerization of oxygenates. [Prior Art] Patent Application EP 1,693,432 A1 (Petrobras) explains the permissible A method of performing hydroconversion by applying a mixture of 1% by volume to 75% by volume of vegetable oil and 99% by volume to 25% by volume of a hydrocarbon in a single hydrotreating reactor. The method 150153.doc 201113361 is in the range of 4 MPa to 10 MPa. The operation is carried out at a temperature between 320 ° C and 4001 in the presence of a hydrotreating catalyst comprising a sulfide of a viB transition metal promoted by a Group VIII metal. The benefit of this method is to increase the cetane number and reduce the density produced by mixing with vegetable oil, relative to the properties obtained by direct treatment of the petroleum matrix. Furthermore, mixing the hydrocarbon feed with the vegetable oil relative to the effluent obtained by treating only the vegetable oil makes it possible to improve the low temperature properties of the obtained effluent. Patent FR2904324 (all) describes NiMo, Ni W, CoMo, Pt,

A similar application of a Pd-type catalyst on a process for catalytically hydrotreating gasoline-type petroleum-derived feeds, where 3 〇 wt. 〇 /. The maximum amount is included in animal oil or fat. However, such applications have several drawbacks. The first drawback is the use of a single stage to synergistically treat vegetable oils and petroleum matrices. In fact, this is a limiting operation for the above-described hydrogenation treatment catalyst, which must simultaneously achieve a deoxygenation reaction and a hydrodesulfurization reaction. Carbon monoxide and carbon dioxide, which are by-products formed by the decarboxylation/decarbonylation reaction promoted by such catalysts under the pressure and temperature conditions (by forming carbon monoxide and carbon dioxide to eliminate oxygen from the feed of renewable sources) The effect on the activity and stability of the catalysts used in these patents. In fact, those skilled in the art are familiar with the inactivation and inhibition effects of such molecules on hydrotreating catalysts, respectively (2003/0221994). Furthermore, the application described in these documents (EP i, 693, 432 phantom and FR 2904324) will result in the refiner operating with a large amount of catalyst and at a higher temperature to meet current specifications. This will result in excessive consumption of the facility and accelerated catalyst aging for the maintenance of 150153.doc 201113361. Considering the cost of loading and unloading operations, the cost of the catalyst raw materials and their recycling, it is important for the refiner to maximize the cycle time of the unit and thus the working life of the hydrotreating catalyst to meet the specifications. fuel. In addition, patent application WO 08/084145 proposes the use of synergistic treatment of oils derived from plant or animal sources and petroleum substrates obtained from distillation or conversion units in a hydrotreating process comprising two extension units with intermediate stripping. The resulting mixture is directed to produce a gasoline fuel matrix that meets specifications, particularly in terms of sulfur content, density, and low temperature stability properties. More specifically, the first unit is dedicated to the hydrodeoxygenation of mixed plant or animal source oils while pretreating the hydrocarbon feed, while the second unit acts to promote hydrodesulfurization more rigorously. . The intermediate stripping allows removal of carbon monoxide, carbon dioxide and water produced from the hydrotreated triglyceride prior to the final desulfurization stage, the triglycerides forming the source of the oil on the first catalyst bed. However, the installation of intermediate stripping is expensive,... = additional capital expenditures and more complex management of these gases. In addition, the main disadvantage of this application is still related to the presence of carbon monoxide and carbon dioxide. (4) (4) The special materials required for co-processing applications in the case of glycerol tris(4) and CO and co2 produced. In terms of investment, the investment is extremely high. The synergistic treatment of petroleum feeds and the use of feedstock from renewable sources has enormous industrial demand, but at the same time limits capital expenditures, operating costs associated with catalyst deactivation and deterioration of the unit due to septic. In order to overcome these disadvantages, the inventors have therefore sought to find a method which can reduce the oxidation and carbon monoxide during the co-processing operation of the feed from the renewable source and the feed from the petroleum source. At the same time produce good quality gasoline and / or kerosene parts. The process of the invention comprises mixing a feed obtained from a renewable source with a portion of the petroleum typically treated in refining. Since the conditions required to effect the structural conversion of the triglyceride and/or fatty acid contained in the feed obtained from the renewable source are generally milder than those required to achieve the deep desulfurization of the petroleum source portion and the preferred gasoline fraction, The total feed is sent to the hydrogenation reaction and the deoxygenation reaction of the unsaturated portion of the fatty acid chain in which the triglyceride (constituting the feed obtained from the renewable source) is mainly carried out in the first hydrotreating reaction zone. Hydrodeoxygenation (HD〇) reaction. The liquid and gaseous effluent leaving the first reaction zone are then fed to a second catalytic zone which is intended for the hydrotreating of the effluent, ie for the hydrodesulfurization of aromatic compounds Hydrogenation, denitrification and hydrogenation, such that the effluent meets the required environmental specifications, i.e., less than 1 〇 ppm by weight of sulfur. Preferably, the second catalytic zone is substantially intended for use in the hydrodesulfurization of any sulfur containing compounds present. Therefore, the presence of carbon monoxide (C〇) and carbon dioxide (C〇2) generated during the deoxygenation reaction in the first catalytic zone poisons the conventional hydrotreating catalyst used in deep hydrodesulfurization. We have found that by using a specific catalyst in the first catalytic zone, the reductive process of the hydrodeoxygenation pathway (HDO) can be greatly promoted, thereby significantly reducing the production of c〇 and c〇2, and thus avoiding occurrence in the second catalytic zone. Significant inhibition of the hydrotreating reaction. The use of a particular nitriding and hydrodeoxygenation catalyst favoring the HDO pathway in the first hydrotreating stage and subsequent use of a conventional hydrodesulfurization catalyst in the second hydrotreating stage is due to the absence of the first stage The formula 150I53.doc 201113361 into CO and C〇2 and relative to the application based on conventional hydrotreating catalysts makes it possible to: - avoid loss of activity in the HDS in the second stage. - Avoid corrosion phenomena' so that existing refinery units can be used more easily. In fact, the presence of CO and C〇2 will mean the use of more expensive corrosion resistant materials and may significantly alter existing units in refining and therefore require an increase in total investment. - Improved fuel matrix yield due to the excellent selectivity of the hydrodeoxygenation pathway (HD(R)) such that the formation of the same number of carbon atoms as the fatty acid chains present in the feed to the renewable source can be formed. - reducing the size of the section used to purify the recycle gas. In fact, in the presence of CO and c〇2 formed in the first reaction zone, it will be necessary to increase the size of the section washed with amine to purify the recycle gas in order to remove H:2S and C〇2, and On the one hand, a methanation or water gas transfer section is provided for removing C 不能 which cannot be treated by washing with an amine strip. SUMMARY OF THE INVENTION More specifically, the present invention relates to a hydrotreating process for co-processing a mixture of a petroleum feed with at least one feed obtained from a source of T regeneration for producing a fuel matrix having a sulfur content of less than 10 ppm (kerosene and/or gasoline), the process comprising the following stages: a) a first hydrotreating stage wherein the feed passes through at least one first fixed bed catalytic zone comprising at least one supported or bulk catalyst, the catalyst comprising An active phase composed of a sulfide of a Group VIB element, the VIB group is a molybdenum, the catalyst also comprises at least one selected from the group consisting of phosphorus, fluorine and boron, 150153.doc •10-201113361 doping element, b) second addition The hydrogen treatment stage 'where the effluent leaving the first hydrotreating stage is sent directly thereto, and wherein the effluent passes through at least one second fixed bed catalytic zone comprising at least one hydrotreating catalyst. Preferably, the effluent from the first hydrotreating stage is sent without an intermediate separation stage and, optimally, without the interstage stripping stage. [Embodiment] According to the present invention, the hydrotreating process treats a mixture of a petroleum feed and at least one feed obtained from a renewable source for producing a fuel base. The petroleum feed treated by the hydrotreating process of the present invention is advantageously a feed of the intermediate distillate type. In the meaning of the present specification, the term intermediate steamed crane means a boiling point of from about 13 (rc to about 41 (rc, usually about 14 to about π °c and, for example, about 15 (rc to about 37 (rc) The hydrocarbon portion containing at least 〇〇ι wt·% of sulfur. The steamed material feed between the towels may also contain gasoline or diesel oil' or may be named after one of these names. From direct distillation or autocatalytic cracking (LCO) Or the gasoline obtained from the other-transformation method (coking of the residue, visbreaking, twisting conversion, etc.) constitutes a typical feed of the method of the present invention. Μ ' 'Petroleum into the self-contained group 1 from direct Steaming Μ > fly oil, gasoline obtained from the conversion process, such as their self-coking, fixed bed hydroconversion (for example, they are from the HYV 胤 8 process developed by the applicant for processing heavy parts) In the case of fluidized bed hydrotreating, heavy oil = two processes (such as those from H_〇IL8 process), or oil (for example, using propylene, butyl or pentylene) to asphalt oil, such Oil system from 150I53.doc 201113361 for vacuum distillation of direct distillation or for the conversion of heavy The residue obtained by the system (:!, such as hunger 8 and η Vision 8) is subjected to deasphalting. #: The feeds may also be advantageously formed by mixing the parts, which may also advantageously contain The distillation curve is about loot: light k^ to 370 ° C or kerosene fraction 4 may also advantageously contain ϋ aromatic extract and sarcophagus in the manufacture of lubricating oil. It is obtained from a renewable source in the present invention. The feed (iv) is selected from the group consisting of plant 2 animal derived oils and fats, or a mixture of such feeds. The feeds contain triglycerides and/or free fatty acids and/or esters. The vegetable oil may advantageously be wholly or partially The ground is not refined or refined and can be obtained from the following plants: rapeseed, sunflower, soybean, palm stalk, palm palm, olive, coconut, jatropha, this list is not comprehensive. 7 from 7 (four) or fish oil Suitably, the oils are also obtained from genetically modified organisms. The animal fats are advantageously selected from the group consisting of lard fat or fat, which consists of residues obtained from the food industry or from the catering industry. The feeds essentially comprise glycerol. The chemical structure of the acid ester type, Those skilled in the art are also familiar with such structures by the names fatty acid triesters and free fatty acids. Thus, fatty acid triesters are composed of three esterified fat k bonds with glycerol. These are in the form of triesters or in the form of free fatty acids. Each chain in the fatty acid chain has a number of unsaturated moieties (also known as the number of carbon-carbon double bonds in each chain), which typically consists between 0 and 3, but is especially obtained for the self-sloating class. It can be higher in terms of oil, and the oil obtained from the algae usually has 5 to 6 many unsaturated moieties per chain. Therefore, the feed used in the present invention is obtained from a renewable source 150153.doc 201113361 The subunit has many unsaturations, and each molecule of triglyceride does not necessarily contain an unsaturated moiety between 〇 and 18. In such feeds, the degree of unsaturation expressed as the number of unsaturations in each hydrocarbon fatty chain advantageously comprises between 0 and 6 unsaturation. The feed obtained from the renewable source has an iodine value of from 〇〇6, usually from 5 to 200 and an oxygen content of from 5% to 2 〇0/〇 and preferably from 8% and 3%. The feed obtained from the renewable source may have a nitrogen content between 1 and 500 ppm by weight and typically between 5 and 40 ppm by weight. Mixtures of conventional petroleum feeds with feeds from renewable sources may advantageously consist of 1 wt.% to 99 wt.% petroleum base and 99 wt% to 1 Wt.% of vegetable or animal source oil and 60%.% to 99 wt.% of conventional petroleum feed and 1 wt.% to 4% by weight of vegetable or animal source oil and excellent 70 wt.% to 99 wt.% of conventional petroleum feed and 1 wt·% to 3 〇 % by weight of vegetable or animal derived oil. The gasoline base produced in accordance with the present invention has excellent qualities: • It has a low sulfur content, i.e., less than 1 〇 ppm by weight, and the diaromatic compound + content is less than 11 Wt.0/. . - it has an excellent sixteen burning value higher than 51, preferably higher than 55. - It has good properties of low temperature stability. - The resulting density is low, usually between 825 kg/m3 and 845 kg/m3. According to the invention, the hydrotreating process uses a mixture of a petroleum feed and at least one feed obtained from a renewable source in a first hydrotreating stage, wherein the feed passes through at least one first comprising at least one specific catalyst a fixed bed catalytic zone to effect hydrogenation of the unsaturated portion of the fatty acid chain of the triglyceride (constituting the feed obtained from the renewable source) and deoxygenation 150153.doc -13 - 201113361 and preferably hydrodeoxygenation (HD0) reaction, followed by direct delivery of the effluent from the first hydrotreating stage to the second hydrotreating stage, and preferably without an intermediate separation stage and excellent without an intermediate stripping stage, and wherein the effluent passes through ' At least one second fixed bed catalytic zone comprising at least one hydrotreating catalyst is preferably subjected to hydrodesulfurization. During hydrotreating (HDT), the total feed consisting of a mixture of a petroleum feed and a feed of at least one renewable source is subjected to the following reactions: - Triglycerides constituting the feed obtained from a renewable source And hydrogenation of the unsaturated portion of the fatty acid unsaturated bond of the ester. - an oxygen scavenging reaction which can be divided into: - a decarbonylation reaction which represents all reactions in which oxygen and carbon are removed from the carboxyl group to form carbon monoxide (CO). a decarboxylation reaction which represents all reactions in which a carboxyl group is removed from a carboxylic acid group to form carbon dioxide (co2). - Hydrodeoxygenation (HDO) reaction, which corresponds to the reaction in the presence of hydrogen to form water. - Hydrodesulfurization (HDS) reaction, which represents the reaction of removing sulfur from the petroleum feed to produce h2s. A denitrification (HDN) reaction is indicated, which represents the reaction of removing nitrogen from the petroleum feed to produce NH3. - Hydrogenation of an aromatic compound which represents the conversion of an aromatic compound in a petroleum feed to a cycloalkane and a cycloalkane aromatic compound. Each stage may comprise one or more reactors and one or more catalytic zones (or beds). Therefore, the processing conditions in each unit and/or zone can be adjusted to vary from 150153.doc • 14· 201113361. Therefore, the dehydrogenation reaction and the hydrogenation counter unit and/or The reaction occurring in the zone is carried out by hydrotreating the hydrotreating of the mixture of the feed and the hydrocarbon, and the hydrodesulfurization reaction at a temperature and pressure. Stage 1) - the feed of the hydrotreating source of the total feed and the petroleum feed mix advantageously will preferably be adjusted by the addition of the previously added stone & feed. The temperature condition of the stream at the inlet of the first catalytic zone of the first-hydrotreating stage (d) of the process of the invention. The temperature of the first-hydrogenation stage a) - the catalytic zone stream (which is comprised of a mixture of feed and petroleum feed obtained from a renewable source) is advantageously between 15 Torr and 260. (: between and preferably between 18 〇t: and 220 ° C and excellently between 180. (: and 21 〇 between it. The temperature conditions of the incoming stream can be obtained from renewable sources The hydrogenation of the unsaturated portion of the triglyceride contained in the feed while controlling the exothermic effect of the reactions. Thus, the temperature change between the incoming stream and the effluent exiting the first catalytic zone is advantageously The restriction is such that the temperature of the effluent leaving the first catalytic zone is advantageously between 2801 and 3701, preferably between 280 ° C and 330 ° C and optimally above 3 ° C. Thus, the principle This allows an overall reduction in the extent of the average temperature of the reaction zone to be achieved at a low temperature in the first hydrotreating stage and thus achieves an overall reduction in the average temperature of the reaction zone, thereby promoting the hydrodeoxygenation reaction and thus the yield of the gasoline matrix. In the case where the first hydrotreating stage a) uses more than one catalytic zone and preferably at least 150153.doc -15-201113361 two catalytic zones, after the first catalytic zone of the first hydrotreating stage a) In each catalytic zone, 'preferably due to the following The temperature of the stream entering the catalytic zone after entering and leaving the first catalytic zone is within the bounds of the first catalytic zone: - a feed from a renewable source or from a petroleum feed and at least one renewable source The feed mixture constitutes a total feed comprising a stream, or a hydroprocessed stage a) or b) hydrotreated effluent stream having a recycle ratio between 1 ·· 1 〇 and 8:1 The temperature of the stream is between 20 ° C and 100. (Between: this makes it possible to manage the exothermic effect in each catalytic zone and thus the temperature increase. The feed containing at least the petroleum feed can be preheated by any means known to the art, after which it is Feeding to the first hydrotreating stage. Without being limited by the scope of the invention, mention may be made of the use of heat exchangers and/or preheating furnaces. The sources available from renewable sources may be obtained at various points in the refining process. The feed is mixed with the petroleum feed. The first possibility involves passing the petroleum feed through the feed/effluent exchanger in the presence of hydrogen and then preheating through the preheater and then injecting it from the renewable source. The second method comprises preheating the petroleum feed by passing the petroleum feed through a feed/effluent exchanger, and then mixing the petroleum feed with the feed obtained from the renewable source in the presence of hydrogen, The effluent is from the first zone. The feed obtained from the feed and from the renewable source may be as follows: The mixing is completed by passing through the preheating furnace. 150153.doc 201113361 Finally 'the presence of hydrogen in the presence of hydrogen before heating Access from renewable sources Mixed with the petroleum feed, in this case, 兮, q人 & 隹 this rf Φ A, the temperature of the 6 hai mixture is first passed through the feed-effluent exchanger and squid _& It is also possible to add the feed through the preheating furnace. The feeds may also be mixed before or after the introduction of hydrogen. Preferably, before the feed-effluent exchanger, before the preheating furnace or The feed obtained from the renewable source in the presence of hydrogen prior to entering the reactor is combined with the petroleum feed. Excellently, in the presence of hydrogen after increasing the temperature of the petroleum feed by at least one heating stage The feed obtained from the regeneration source is mixed with the petroleum feed. In the case where the second hydrotreatment stage b) uses more than one catalytic zone and preferably at least two catalytic zones, it may advantageously be in the second gassing treatment stage. The petroleum feed is injected into each of the catalytic zones of b). Mixtures of conventional petroleum feeds with feeds from renewable sources may advantageously consist of .1 wt.% to 99 wt_. /. The petroleum matrix is 99 wt·. /. Up to 1 wt· /〇 of the feed from the regeneration source and preferably 6 〇wt·% to 99 wt.% of the conventional petroleum feed and 1 wt.% to 4 〇wt% of the renewable source of feed and pole Jiachuan wt.% to 99 Wt.% of conventional petroleum feed and 丨wt% to 3〇 renewable source feed. According to a first preferred embodiment, the mixture of the conventional petroleum feed and the renewable source feed is from 60 wt% to 99 wt% of a conventional petroleum feed and from i wt.% to 40 wt.% of a renewable source. The exothermic effect of managing the hydrodeoxygenation reaction in the case of feed and an excellent 7 〇 to % to 99 wt% of conventional petroleum feed with a feedstock of 1 wt% to 3 〇wt% of renewable source No need for 150153.doc • 17· 201113361 to recycle the effluent from the hydrotreated liquid produced by the process of the invention. In fact, the effluent from the first hydrotreating stage a) is due to the hydrogen evolution of the unsaturated portion of the total feed and the heat released by the exothermic effect of the deoxygenation reaction of the feed portion obtained from the renewable source ( It constitutes the feed of the second hydrotreating 13b and b) advantageously to the temperature required to enter the second hydrotreating stage b) (ie between 280. (: and 370 ° C, preferably between 28 (between TC and 330 C and more preferably higher than 300 〇c), thereby allowing in particular a hydrodesulfurization reaction without any recycling of the hydrotreated liquid effluent. Moreover, this avoids Exceeding the temperature that causes the risk of coke formation in the first deoxygenation stage, i.e., a temperature above 35 ° C. According to the second preferred embodiment, the mixture of the conventional petroleum feed and the renewable source feed is 40 wt·% to 99 wt·% of the renewable source feed with 1 wt.% to 60 wt.% of the petroleum matrix, advantageously comprising between 1:10 and 8:1 The recycle ratio recycles the hydrotreated liquid effluent produced by the process of the invention so that The hydrogenation reaction of the unsaturated moiety and the exothermic effect of the deoxygenation reaction of the feed obtained from the renewable source. The application is also intended to maintain the amount of hydrogen dissolved in the liquid phase to promote the hydrodeoxygenation reaction. Forming a polymerization phenomenon of coke and oxygenates. The amount of recycle used is such that the heat released during the hydrogenation and deoxygenation reactions means at the outlet of the first hydrotreating stage a), which is not More than the temperature required to enter the second hydrotreating stage b), i.e. between 280 ° C and 370 ° C, preferably between 28 Torr. (A temperature between 3 and 330 ° C and more preferably higher than 300 ° C, thereby allowing in particular a hydrodesulfurization reaction. 150153.doc • 18· 201113361 in the second preferred embodiment h in the first hydrotreating In the case where more than one catalytic zone is used and preferably at least two catalytic zones are present, the feed from the renewable source or the feed from the petroleum is at least at a temperature between 2 〇. - The total (4) constituents of the mixture of feedstocks of renewable sources may also be advantageously implemented in the respective catalytic zones after the first - catalytic zone of the first hydrotreating stage a) in order to manage the different catalytic zones The exothermic effect and thus the increase in temperature. Therefore, the temperature of the stream of each catalytic zone after the first catalytic zone in the first stage of the hydrotreating stage is advantageously 'I between 150 C and 26 G ° C: And preferably between ??? and 22 generations and between 18 〇t and 21 〇t. Advantageously - in the first hydrotreating stage a) the m material can be pretreated or pre-refined by Properly treated to remove contaminants from natural feedstocks from renewable sources such as alkali metals and bases Earth metal and transition metals as well as nitrogen. Suitable treatments may be, for example, those well known to those skilled in the art, and/or chemical treatments, and preferably a capture bed, which is advantageously located in the same inverse state or different from the hydrotreating stage of the process of the invention. The response of the person is beneficial. Catalysts for use in the capture bed are well known to those skilled in the art. According to the invention, the pre-pretreated total feed, as appropriate, is subjected to a first hydrotreating stage a)' wherein the feed passes through at least one first solid bed catalytic zone comprising at least one supported or bulk catalyst The catalyst comprises an active phase composed of a sulfide of a Group VIB element, the vib group element is turned over, and the catalyst also comprises at least one doping element selected from the group consisting of phosphorus, fluorine and boron. Therefore, the catalyst is in the form of a sulfide. According to the present invention, the catalyst may also advantageously contain at least one selected from the group consisting of 150153.doc -19-201113361 fluorine and substituted auxins, and preferably scales, to achieve a high degree of conversion, while maintaining hydrogenation. Selectivity of the oxygen (HD0) reaction pathway. It is known to those skilled in the art that these elements have an indirect effect on the catalytic activity: to better disperse the sulfide active phase and increase the acidity of the money, thereby facilitating the addition of chlorine. Catalysis Today 86 (2003) 173) The carrier in the case where the catalyst is in bulk form and/or in the case where the catalyst is in a supported form may also advantageously contain at least one #hetero-element. In the case where the catalyst is in the bulk form, it may be advantageous to deposit the replacement element on the active phase and deposit it on the support in the case where the pure agent is in the form of a carrier. The catalyst used in the 'hydrotreating stage a' according to the invention may be subjected to a load, i.e., it comprises an amorphous mineral carrier selected from the group consisting of: Oxidation of Oxidation, Dioxo-Oxidation, Magnesium Oxide , a mixture of clay and at least two of the specialty minerals. The support may also advantageously contain other compounds, e.g., an oxide selected from the group consisting of boron oxide, zirconium oxide, titanium oxide, phosphoric anhydride. Preferably, it is not a day-to-day mineral support alumina support (η, δ or γ). In the case where the catalyst is in a supported form, the content of the group element is advantageously between the 15% and 35 cores of the Group VIB elemental oxide relative to the total weight of the catalyst, preferably with good mediation; Wt.〇/. Between 35 wt % and excellent between 20 wt·% and 32 wt.%. According to the present invention, in the case where the catalyst g is in a supported form, the catalyst also contains at least one doping element selected from the group consisting of phosphorus, ruthenium fluoride, ruthenium and boron, and 150153.doc - 20, 201113361 Preferably, the doping element is phosphorus to achieve a high degree of conversion while maintaining the selectivity of the hydrodeoxygenation reaction pathway. In the case where the catalyst is in the form of a load, it may be advantageous to introduce the doping element into the matrix or to deposit it on the carrier. Preferably, the doping element is deposited on the support. It is also advantageous to deposit ruthenium on the support alone or together with phosphorus and/or boron and/or fluorine. In the case where the catalyst is in a supported form, the content of the doping element (the doped halogen is preferably phosphorus) is advantageously strictly greater than 0.5% and less than 8 wt. Q/ with respect to the total weight of the catalyst. The oxide ία is preferably greater than ι% and less than 8 〇 and is preferably greater than 3% and less than 8 wt%. In the case of using a supported catalyst, the hydrogenation function can be introduced onto the catalyst by any method known to those skilled in the art (e.g., /, mixing, dry impregnation, etc.). According to the invention, the catalyst may additionally be a bulk catalyst and in this case the catalyst does not contain a support. In the case where the catalyst is in the form of a bulk, the content of the Group VIB element is advantageously between 92 wt% and 丨〇〇% of the Group VIB elemental oxide, preferably greater than 92%, relative to the total weight of the catalyst. Strictly below $wt. /〇, preferably between 92 wt.% and 99 wt.% and very preferably between 92 wt.0/0 and 97 wt.%. According to the present invention, in the case where the catalyst is in the form of a body, the catalyst contains at least one doping element selected from the group consisting of phosphorus, fluorine and boron, and preferably the doping element is phosphorus to achieve a high conversion while maintaining the addition. The selectivity of the hydrogen deoxygenation pathway. In the case where the catalyst is in the form of a body, the doping element is advantageously deposited on the active phase. In the case where the catalyst is in the form of a body, the content of the doping element (preferably phosphorus is preferably phosphorus) is advantageously strictly 150153.doc • 21 · 201113361 is greater than 0.5% and less than 8 with respect to the total weight of the catalyst. Wt% of the oxide P205 and preferably greater than 1% and less than 8% and preferably greater than 3% and less than 8 wt.% ^ in the case where the catalyst is in the form of a body - it is by those skilled in the art Any synthetic method known (for example, direct vulcanization of an oxide precursor and thermal decomposition of a metal sulfide salt) is obtained. In the case where the first hydrotreating stage a) comprises at least two catalytic zones, the 4 catalytic zones may use the same or different catalysts, and preferably the catalysts are the same. The use of the catalyst in the first hydrotreating stage a) makes it possible to obtain very high selectivity for the hydrodeoxygenation (HDO) reaction and to limit the decarboxylation/decarbonylation (DCO) reaction and thus to limit the formation of carbon oxides. The problem that caused it. Within the scope of the invention, the selectivity to hydrodeoxygenation (HDO) can thus be obtained in the first hydrotreating stage a), which is advantageously greater than or equal to 9% and preferably greater than or equal to 95% and preferably Greater than or equal to 96%, preferably greater than or equal to 97% and even more preferably greater than 99%. In the first hydrotreating stage a), the selectivity to decarboxylation/decarbonylation of the feed from the renewable source is advantageously limited to at most ,%, and is preferably limited to at most 5% and more preferably at most 4% and even better is limited to at most 1%. The selectivity of hydrodeoxygenation (HDO) is calculated as follows: RDC0 is used to represent the theoretical yield of C〇+C〇2 of the feed obtained from a given renewable source, which is based entirely on the decarboxylation (dc〇) pathway. Converted and expressed in terms of % by weight relative to the feed, and using R to indicate that the yield of CO + c 〇 2 obtained experimentally during the hydrotreating of the feed obtained from the pure renewable source is S_ is defined as the selectivity of HDO by the following simple formula 150153.doc -22- 201113361.

Shydro- 1 00*(Rdco-R)/Rdc〇 In addition, co-processing of feeds and petroleum feeds obtained from renewable sources allows for gasification reactions and HDO in the unsaturated portion of fatty acid hydrocarbon chains of triglycerides Better control of the exothermic effect during the reaction. This makes it possible to limit the use of recirculation. Furthermore, it is advantageous to use a thermal gradient to bring the effluent from the first hydrotreating stage, which constitutes the feed to the second hydrotreating stage, into the second hydrotreating stage and in particular to allow for the initial hydrodesulfurization reaction. The temperature. Thus, the temperature of the effluent of the first hydrotreating stage a) constituting the feed of the second hydrotreating stage b) is advantageously between 28 (rc and 34 〇t: and preferably between 280 C and 320) A temperature between ° C and preferably higher than 3 Torr, in particular allowing a hydrodesulfurization reaction. The first hydrotreating stage a) is advantageously operated under the following conditions: between 120 ° C and 450. (: between, preferably between 12 (rc and 35〇〇c, preferably between 150C and 320C and even better between 丨(9) and its temperature; between i MPa and 10 MPa Between, preferably between i Μρ^6 Qing 3; the space velocity between Gl h·1 and 1G h.1 and preferably between Q2 h, 5; and between 5〇 Between Nm3 hydrogen/m3 feed and 3000 Nm hydrogen/m3 feed, preferably between 7 Torr 3 hydrogen~3 feed tray 2_W hydrogen feed and preferably between i5Q _3 hydrogenation 3 feed and 1500 Hydrogen/feed ratio between Nm3 hydrogen/m3 feed. The method of the present invention provides a choice of carrying out operations in the first reactor to introduce hydrogen in a countercurrent form of the cargo c^ 匕L仏 formula to limit the generation of the permanent seat king The inhibition of the catalytic system in the first stage of the hydrogenation of the deuterated flute milk by water and the formation of water and the dilution of hydrogen by propane. 150153.doc , 23· 201113361 Eventually, due to its fixed bed process Therefore, the gas generated toward the bottom of the reactor has a concentration gradient. Introducing hydrogen in a countercurrent form allows the catalyst to have better activity by increasing the h2/hc ratio. The hydrotreating stage a) is advantageously primarily a hydrogenation site for the unsaturated portion of the fatty acid chain of the triglyceride and a hydrodeoxygenation site for the feed of the renewable source. The second hydrotreating stage b) is primarily aromatic Hydrogenation of the compound to desulfurization 'hydrogenation of denitrification and hydrogenation of ruthenium and mainly carried out the stone" by gas addition desulfurization reaction. The first hydrotreating stage b) (referred to as the hydrodesulfurization stage) operates under more severe conditions than the first hydrotreating stage a), referred to as the hydrodeoxygenation zone. Stage 2) Hydrotreating of the effluent from the first hydrotreating stage followed by direct development of the hydrodeoxygenated effluent obtained from hydrotreating stage a) to the second hydrotreating stage, and preferably without intermediate The separation stage and preferably no intermediate stripping stage. The effluent of the first hydrotreating stage a) constituting the feed of the second hydroprocessing stage b) is advantageously at 28 Torr due to the temperature gradient in the hydrotreating stage a). (: between 37 and TC, preferably between 28 〇. (: and 33 (and preferably between 300 C and leaving the first phase and then directly injecting at least one and preferably at least two) Catalytic zone of at least one hydrotreating catalyst. Thus, it is advantageous to use a thermal gradient to heat the effluent of the first hydrotreating stage a) to the second hydrotreating stage... and in particular to allow the initial hydrodesulfurization reaction The temperature required. 150153.doc • 24· 201113361 The hydrotreating catalyst used in the second hydrotreating stage b) of the process of the invention advantageously comprises a hydrogenation-dehydrogenation function and a support. Preferably, the support is selected from the group consisting of a group of alumina, cerium oxide, aluminosilicate, oxidized town, clay, and mixtures of at least two of the minerals. The carrier may also advantageously contain other compounds and, for example, selected from the group consisting of Telluride. Boron oxide, cerium oxide, titanium dioxide, phosphoric anhydride. Preferably, the support is composed of alumina and excellent η, δ or γ alumina. Used in the second hydrotreating stage b) of the process of the invention Catalyst of hydrogen

The chemistry function advantageously comprises at least one Group VIII metal and/or at least one Group VIB metal. Preferably, the catalyst advantageously comprises at least one metal of the vm group selected from the group consisting of nickel and cobalt and at least one metal of the group VIB selected from the group consisting of molybdenum and tungsten. Preferably, the group viii element is nickel and the group VIB element is molybdenum and the catalyst is between 5 wt./. The content of nickel oxide between 1〇 wt·% and preferably between 1 and $ is between! a molybdenum trioxide content between wt% and 3〇wt% and preferably between 5 wt.% and 25 wt% and is on an alumina amorphous mineral support, the percentage being relative to the total weight of the catalyst Expressed by wt.%. The catalyst used in the second hydrotreating stage b) of the indigenous process may also advantageously have at least one element selected from the group consisting of scales and deleted elements. The halogen can advantageously be introduced into the matrix or preferably deposited on the support. Advantageously, it may also be deposited on the support alone or together with phosphorus and/or butterfly and/or fluorine. The weight content of the monobasic oxide is generally advantageously less than 2% and preferably less than 1% and is generally advantageously at least 0.0 (Π%. In the second hydrotreating stage b of the process of the invention) The metal of the oximation agent 150153.doc •25- 201113361 is advantageously a metal sulfide or metal phase. In the case where the second hydrotreating stage # is combined with the two catalytic zones of V, the catalytic zones may be made of the same or different reminders (4). The hydrotreating stage b) advantageously operates under the following conditions: between 25 and 450 C and preferably between 7 and 4. . The temperature between the two; 〇, 5 MPa to 30 MPa (compared with (4) 丨 hall performance 25 Mpa) total pressure; 0.1 ^ to 2Gh., (better between) space velocity per hour; The hydrogen volume of the liquid feed (measured under normal temperature and normal dust conditions) represents the hydrogen/feed ratio (usually 5 〇N丨/丨 to 2〇〇〇ni/i). In order to produce a gasoline fuel having improved properties, the hydrocarbon effluent is subsequently treated according to the following optional stages: subsequently subjecting the hydrotreated effluent produced by the process of the invention to a stage and preferably a gas/liquid In the separation stage, water and at least one liquid hydrocarbon substrate are then separated as appropriate, and the stages are optional and can be carried out in any order relative to each other. Preferably, the hydrotreated effluent produced by the process of the invention is first subjected to a gas/liquid separation stage. The purpose of this stage is to separate the gas from the liquid, and in particular to recover a hydrogen-rich gas, which may also contain gases such as HjS, traces of CO and C〇2 and propane, and at least one liquid effluent' and such The gas may also be advantageously purified by methods known to those skilled in the art. Preferably 'subsequently performing at least some and preferably all of the formed water and at least one liquid separated from the substrate from the liquid effluent produced by said optional gas/liquid separation, the water system is produced during the hydrodeoxygenation reaction, The hydrogenation 150153.doc -26 - 201113361 deoxygenation reaction separates the hydrocarbon effluent during the first hydrotreating stage a) of the process of the invention. Removing water means raw water. Hydrogenation used in an optional stage which is more complete or less complete may be beneficial to the removal of water produced by the removal of hydrodeoxygenation (HDO) from water and liquids by those skilled in the art. The change in water resistance of the isomerization catalyst according to the process of the present invention. Removal of water by any method and technique of a combination of desiccant, flash, or at least two, such as drying, steaming, solvent extraction, distillation, and decantation or a combination of zeros in conventional petroleum feeds and renewable sources. The mixture is from 4 〇 wt·% to 99 wt. 〇 /. In the case where the feedstock of the renewable source and the petroleum matrix of % to 4% are formed, at least a portion of the hydrotreated liquid effluent (which has been subjected to the stage of removing water as appropriate) can be advantageously recycled to The hydrotreating stage a) the top of each catalytic zone after the first catalytic zone and/or the top of each catalytic zone of the second hydrotreating stage b). Preferably, the impurities have been reduced (from the gaseous state during the separation phase) Purification of at least a portion of the hydrogen-rich effluent of the optional separation stage for the purpose of concentration of the reaction present in the product, advantageously advantageously with at least a portion of the hydrotreated liquid effluent from the separation stage In the form of a mixture (in the case where it is expected to recycle the hydrotreated liquid effluent) or separately injected into the top of each of the catalytic zones of hydrotreating stages a) and b). The separation stage can be obtained by those skilled in the art. Any method known to be advantageously implemented, such as one or more high pressure and/or low pressure separators, and/or a combination of high pressure and/or low pressure distillation and/or stripping stages. 150153.doc -27- 2011133 61 Stage 3). Hydroisomerization of hydrotreated effluent The hydrotreated liquid effluent produced by the process of the invention consists essentially of normal paraffin, which can be incorporated into the gasoline pool _. Improving the low temperature properties of the hydrotreated liquid effluent requires a hydroisomerization stage to convert the normal paraffin to a branched paraffin having better low temperature properties. Subsequently, in a selective hydroisomerization catalyst In the presence of, at least a portion, and preferably all of the hydrotreated liquid effluent, optionally subjected to the above described separation stage, is subjected to an optional hydroisomerization stage. Advantageously, the hydrogenation is carried out in a separate separator. Isomerization stage. The hydroisomerization catalyst used is advantageously of a dual function type, i.e., it has a hydrogenation/dehydrogenation function and a hydroisomerization function. The shai hydroisomerization catalyst advantageously comprises at least one a Group 111 metal and/or at least one Group VIB metal (having a hydrodehydrogenation function) and at least one molecular sieve or amorphous mineral support (having a hydroisomerization function). The hydroisomerization catalyst is advantageously packaged. At least one Group VIII noble metal preferably selected from the group consisting of palladium-initiating (having a reduced form of activity) or at least one Group VIB metal preferably selected from molybdenum or tungsten and at least one Group VIII base metal preferably selected from the group consisting of nickel and cobalt ( Preferably, the wind isomerization catalyst comprises at least one Group VIB metal preferably selected from the group consisting of turned or tungsten and at least one selected from the group consisting of nickel and cobalt. a combination of a family of base metals, preferably in the form of their sulfides. Excellently, the group element is molybdenum and the Group VIII base metal is nickel. In the case where the hydroisomerization catalyst comprises at least one Group VIII noble metal, The total content of the precious metal in the hydroisomerization catalyst is advantageously between 0.01 wt.% and 5 wt.%, preferably between 0.1 wt% and %, relative to the finished product. Between 4 wt. % and excellent between 0 · 2 wt _ % and 2 wt· %. Preferably, the hydroisomerization catalyst comprises platinum or, more preferably, the hydroisomerization catalyst comprises. In the case where the hydroisomerization catalyst comprises a combination of at least one Group VIB metal and at least one Group VIII base metal, the amount of Group VIB metal in the hydroisomerization catalyst is advantageous relative to the finished catalyst in terms of oxide equivalents. Between 5 wt.% and 40 wt.%, preferably between 1% and 35 wt.%, and preferably between 丨5 wt·% and 3 〇 wt.%, and The content of the Group VIII metal in the catalyst is advantageously between 0-5 wt.% and 1 wt.%, preferably between 丨~% and 8 wt.%, and is excellent in terms of oxide equivalent. Between 5 wt. ° / 〇 and 6 wt · %. The catalytic m metal chlorination/dehydrogenation function can advantageously be effected by any method known to those skilled in the art (e.g., co-mixing, dry impregnation, exchange impregnation). a crystalline mineral carrier (having a hydroisomerization function), according to a preferred embodiment, the hydroisomerization catalyst comprises at least one amorphous mineral carrier selected cerium oxide-oxidation, the non-self-cerium dioxide-alumina and aluminum The phthalate and preferably the preferred hydroisomerization catalyst comprises a nickel- and tungsten-rhenium-alumina-based amorphous mineral support. According to another preferred embodiment, the addition of the active phase and the dioxin addition of the isomerization catalyst comprises at least one at least one recording.

150153.doc —10 10-2011-201113361 r Atlas of Zeolite Structure Types j WM Meier, DH 〇ls〇I^Ch Βμγ1〇—γ, 仏 multi-book, 20 (H, defined by the classification of Elsevier, this application Reference is also made to the publication, wherein the zeolite is classified according to its pore size or channel opening. 1 〇MR dimension 4 stone molecular sieve has pores or channels, the opening of which is by a ring having 1 oxygen atom (1〇 Defined by the MR opening. The channel in the zeolite molecular sieve having a 10 MR opening is advantageously a non-interconnected one-dimensional channel that leads directly to the outside of the zeolite. The 1st prison is present in the hydroisomerization catalyst. The zeolitic molecular sieve advantageously comprises ruthenium and at least one element selected from the group consisting of aluminum, iron, gallium, phosphorus and boron, preferably aluminum. The Si/Al ratio of the above zeolites is advantageously during synthesis Obtained by those obtained after post-synthesis dealuminization as is well known to those skilled in the art, such as (non-exhaustive) hydrothermal treatment (whether or not subsequently eroded with acid) or alternatively mineral or organic acid The solution is directly subjected to acid Preferably, it is substantially completely in acid form, i.e., the atomic ratio of the monovalent compensating cation (e.g., sodium) to the element T inserted into the crystal lattice of the solid is advantageously less than 〇1, preferably less than 0.05 and is preferably less than 0.01. Thus, the zeolite comprised in the composition of the selective aerated isomerization catalyst is advantageously calcined and exchanged with at least one ammonium salt solution by at least one treatment to obtain an ammonium form of the zeolite which is produced after calcination The acid form of the zeolite. The 1 〇 MR_dimensional zeolite molecular sieve is advantageously selected from the group consisting of structural TON (for example NU-10), FER (for example ferrierite), EUO (selected from EU- Zeolite molecular sieves of 1 and ZSM-50) (used alone or in the form of mixed & material type), or bergamot molecules ZSM-48, ΖΒΜ-30, ΙΖΜ-150153.doc -30· 201113361 1, COK-7 , EU-2 and EU-11 (used alone or in a mixture). Preferably, the 10 MR-dimensional zeolite molecules are screened from zeolite molecular sieves ZSM-48, ZBM-30, IZM-1 and COK-7, Used alone or in a mixture. Even more preferably, the 10 MR-dimensional zeolite The sub-screens are selected from zeolite molecular sieves ZSM-48 and ZBM-30, either alone or in a mixture. Excellently, the 10 MR-dimensional zeolite molecular sieve system ZBM-30 and even more preferably 'the 10 MR-dimensional zeolite molecular sieve Is a ZBM-30 synthesized by using an organic structuring agent, tri-ethyltetramine. Preferably, the hydroisomerization catalyst comprises a metal active phase composed of a hydroisomerization function based on ZBM-30, and Preferably, the hydroisomerization catalyst comprises a metal active phase derived from platinum and based on the hydroisomerization function of ZBM-3 0 synthesized using an organic structuring agent, trimethylethylamine. Fossil ZBM-30 is described in the patent EP-A-46 504, and the singularity of the singularity is described in the patent application EP 1 702 888 A1 or FR 2 882 744 A1. Zeolite IZM-1 is described in patent application FR-A-2 9 11 866. Structural TON zeolite is described in the book "Atlas of Zeolite Structure Types", W. M. Meier, D. H. Olson and Ch. Baerlocher, 5th revised edition, 2001, Elsevier. The structural type TON zeolite is described in the above-mentioned book "Atlas of Zeolite Structure Types" and the zeolite NU-10 is described in the patents EP-65400 and EP-77624. The structured FER zeolite is described in the above-mentioned book "Atlas of Zeolite Structure Types". Compared with the finished catalyst, the content of 10 MR-dimensional zeolite molecular sieve is favorable 150153.doc -31 · 201113361 The ground accounts for 5 wt. /. Between 95 wt.%, preferably between 1〇wt% and 9〇wt%) 1515 between 1010 and 85 wt% and excellent between 2〇% and 80wt· %between. Preferably. The hydroisomerization catalyst also comprises a binder composed of a porous mineral matrix which can advantageously be used during the formation phase of the hydroisomerization catalyst. It is preferred to use a binder composed of a matrix containing oxidized oxide (in all forms known to those skilled in the art) to form, and, optimally, to form using a matrix containing gamma oxide. The obtained hydroisomerization catalyst is advantageously formed into particles of various shapes and sizes. Although it is usually used in the form of a cylindrical extrudate or a multi-lobed extrudate of a straight or twisted shape (for example, a bilobal shape, a trilobal shape, a multilobal shape), it may be pulverized as a powder or a sheet. , rings, spheres, and wheels are made and used. Techniques other than extrusion, such as tableting or particle coating, can be advantageously employed. In the case where the nitrogen-added isomerization catalyst contains at least a noble metal, it must be advantageous to reduce the precious metal contained in the hydroisomerization catalyst. A preferred method of effecting metal reduction is to treat the treatment under hydrogen at a temperature between 15 Torr and 65 Torr and a total pressure between i bar and 2 S0 bar. For example, the reduction phase consists of a plateau that lasts for two hours at 15 (rc) and then rises to 45 at the rate of It/min (the temperature of rc and then at 45 〇. (: the plateau lasts for two hours; Throughout the reduction stage, the hydrogen flow rate is 1000 standard m3 hydrogen/m3 catalyst and the total pressure is maintained constant at i & it is advantageously contemplated to use any of the off-site reduction methods. 150153.doc -32- 201113361 In the stage of the reaction, the feed is advantageously contacted with the hydroisomerization catalyst in the presence of hydrogen under operating temperatures and pressures which advantageously allow for the non-converted feed to beomerized toomerization. This means hydrogenation. The structuring system is carried out in the case of 〇C. The conversion rate of the trowel to 15 〇c portion is less than 2 〇wt.%, preferably less than 1 〇wt·% and preferably less than 5% by weight. Therefore, the method of the present invention The optional hydroisomerization stage is advantageously operated under the following conditions: between 15 〇 (: and 5 〇〇. (: between, preferably between 15 〇. 〇 and 450 ° C and excellent intermediaries At 2〇〇. (: with 45〇. (: the temperature between; between 1 MPa and 1〇MPa, and excellent The pressure between 2 and 9 servings; advantageously between (M hi and 10 p, preferably between 〇 2 ^ and h-1 and excellent between 〇.5 h-丨 and 5 h·, hourly space velocity; the helium/hydrocarbon volume ratio is advantageously between 7〇Nm3/m3 feed and 1〇〇〇Ny/m3 feed, between 100 standard m3 hydrogen/m3 The hydrogen flow between the feed and the 1 〇〇〇 standard ^ hydrogen feed and preferably between 15 G standard m ^ / m 3 feed and i 嶋 standard ^ hydrogen / m3 feed. Preferably, optional The hydroisomerization stage operates in a countercurrent manner. Subsequently, at least one (four) and preferably all of the hydroisomerization effluent is also subjected to - or multiple separations. The purpose of this stage is to separate the gas from the liquid, and In particular, the hydrogen-rich gas is recovered, which may also contain light fractions, such as Cl-C4 depots and at least one gasoline score and naphtha column, which meet the specifications. Although the object of the present invention is not to utilize the naphtha fraction, This is advantageously sent to the steam cracking or catalytic reforming unit. EXAMPLES The following examples illustrate the invention without limiting its scope. 150153.doc -33- 201113361 Comparative Example i: A method of hydrotreating petroleum gasoline using a NiM〇p/oxidized gasification treatment catalyst (not according to the invention) in one stage. Therefore, it is not a synergistic treatment of a mixture of petroleum feed and feed from a renewable source. The hydrotreating process, which only processes the petroleum feed. The petroleum feed treated in the comparative m is from direct steamed atmospheric gasoline (obtained from Middle East crude). Its main characteristics are as follows:

0.8522 g/cm3 13000 ppm by weight 120 ppm by weight 29.5 wt.% 12 wt.% 56 + 1 °C -15 °C density - sulfur-nitrogen-total aromatic compound-diaromatic compound + - motor method Burning Value - TLF (*) (*) Temperature Limit of Filtration The hydrotreating of the feed was carried out in a downflow fixed bed isothermal unit containing 100 ml of closely packed NiMoP/alumina type catalyst. The catalyst contained 21.0 wt.% Mo〇3, 5〇 wt% p2〇5 and 4·3 wt·% NiO supported on r alumina. The catalyst was subjected to in situ vulcanization in a unit by adding 2 wt% of dimethyldisulfide to petroleum gasoline under a certain pressure. Subsequently, on a 50 ml NiW/ceria-alumina catalyst (characterized by a NiO content of 3.5 wt.% and a W〇3 content of 27 wt%) (located downstream of the catalytic zone containing the NiM〇p hydrotreating catalyst) Hydroisomerization is carried out on the effluent leaving the hydrotreating stage. Table 1 below shows the operating conditions used in the hydrotreating and the characteristics of the produced gasoline 150153.doc -34- 201113361 fraction. Table 1 Characteristics of gasoline produced by hydrotreating petroleum gasoline on a NiMoP/alumina catalyst Operating conditions Total pressure (MPa rel) H2/HC reactor inlet (Nl/1) LHSV (h·1) Temperature (°C) 5 700 1.6 350 Characteristics of fuel matrix (15 (TC + fraction) Sulfur (ppm by weight) 8 Nitrogen (ppm by weight) 5 Total aromatic compound (wt.%) 25.0 Diaromatic compound + (wt· %) 6.0 Motor method hexadecimal value 58 TLF (°〇+1 Comparative Example 2: Using a conventional NiMo/alumina type catalyst (not according to the invention) in two twisting treatment stages (without intermediate stripping) A two-stage hydrotreating process was carried out on a mixture of petroleum feed and vegetable oil. The petroleum feed was the same as that of normal steam from direct steam (obtained from Middle East crude) and its characteristics are shown in Table 1 of Example 1. The feed from the regenerative source is DND grade (degummed, neutralized and dried) rapeseed vegetable oil, the main characteristics of which are as follows: density at -15 ° C 0.920 g / cm 3 - sulfur 5 wtppm Example 2 hydrotreating treatment Mixed with 70 wt·% of the above petroleum feed and 30 wt·% DND rapeseed oil Therefore, the sulfur content of the total feed is 150100.doc -35· 201113361. The nitrogen content is 9100 ppm by weight, and the nitrogen content is 84 wt. PPm. The total aromatic content is 2〇7 wt%. The content of one aromatic compound + is 8.4 wt.0 /. The synergistic treatment of the mixture is carried out in a downflow fixed bed isothermal unit containing 100 ml of closely packed NiM〇p/alumina catalyst. NiMW catalyst and The ones described in Example 1 have the same composition, namely 21.0 wt·% Μο〇3, 5.0 wt% ρ2〇5 and 4 3 %% Ni〇 on yttrium alumina. The same catalyst is used in the hydrogen treatment stage to effect the HDO (deoxygenation) reaction and the HDS (hydrodesulfurization) reaction and thus the same catalyst is also used in both catalytic zones. The two hydrotreating stages are carried out without intermediate stripping In order to improve the low temperature properties of the gasoline fraction and especially the temperature limit of the filter by hydroisomerization, 5 〇ml NiW/Calcium Oxide Oxidation Type Catalyst (characterized by a Ni 〇 content of 3.5 wt .% and w〇3 content is 27 wt·%) Downstream of the catalytic zone containing the NiMoP hydrotreating catalyst. After in situ vulcanization of the catalyst at a pressure of 350 in a unit by adding 2 wt.% dimethyl disulfide to petroleum gasoline. Hydrotreating was then carried out under the following conditions summarized in Table 2. Table 2 Operating conditions of each catalytic zone Total feed rate (cm3/h) 160 Total pressure (MPa rel) 5 Zone 1 (HDO) " - H2/HC inlet (Nl/1) 700 LHSV catalyst NiMoP (IT1) 3.2 150153.doc -36- 201113361 Temperature (°c) 300 Zone 2 (HDS) H2/HC inlet (N 1/1) 700 LHSV catalyst NiMoP (h-1) 3.2 Temperature (°C) 350 Zone 3 (hydrogenation) Structure) H2/HC inlet (N1/1) 700 LHSV catalyst NiW (h-1) 3.2 Temperature (°C) 340 Table 3 below shows the yields obtained in each catalytic zone (in relation to fresh start feed) The wt·% represents) and the main characteristics of the fuel fraction produced at the exit of each zone. Table 3 Petroleum gasoline/vegetable oil mixture (70 wt.% petroleum gasoline + 30 wt.% DND rapeseed oil) in the hydrotreating zone on the NiMoP catalytic system and subsequent hydroisomerization stage on the NiW catalyst Yield obtained in the hydrotreating zone Zone 1 NiMoP (HDO) 2 zone NiMoP (HDS) Zone 3 NiW (hydroisomerization) Deoxidation (%) 100 - - HDO selectivity (wt.%) 70 - - Yield (wt·%/fresh feed) h2s 0.9 0.9 C1+C2 0.2 0.2 C3 1.5 1.5 C4 0.1 0.1 CO +co2 1.4 1.4 h2o 2.6 2.6 Naphtha (150°c-) - 7.0 Kerosene + Gasoline ( 150°C+) 94.7 87.7 H2 consumption 1.4 1.4 150153.doc -37- 201113361 Characteristics of fuel matrix (150°C+saturated) Sulfur (ppm by weight) Nitrogen (ppm by weight) 1250 40 240 10 200 10 Total aromatics (wt .%) 19.3 . 18.0 18.0 Diaromatic compound + (wt.%) 7.5 6.5 6.5 Motor method 16 Hyun • Value 59 60 60 TLF (°〇+1 +1 -1 In hydrotreating stage 1, basically Deoxygenation is complete for the purpose of de-oxidizing rapeseed oil, but the selectivity of the HDO pathway (to eliminate oxygen in water to achieve hydrogenation deoxygenation) is 70%. Calculate the selectivity of hydrodeoxygenation (HDO): Use Rdco to represent the theoretical yield of C〇+CO2 of the feed obtained from a given renewable source, which is converted entirely according to the decarboxylation (DCO) pathway, and Expressed in terms of % by weight relative to the feed, and R is used to indicate the yield of C0+C02 obtained experimentally during the hydrotreating of the feed obtained from the pure renewable source, then SHD0 is used by The simple formula is defined as the selectivity of HDO. S hydro- 1 00* (Rdco_R)/Rdco can be seen, as compared to the results set forth in Example 1 obtained by treating only the petroleum feed and under the same hydroprocessing conditions, The HDS performance is significantly degraded because the sulfur content of the obtained intermediate distillate fraction is 200 ppm. In order to meet the required specification of the maximum gasoline score of 10 ppm by weight, the operating temperature needs to be increased by 20 ° C. Such an increase in operating temperature may adversely affect the catalyst deactivation rate due to coking, and the cycle time of the catalyst will be greatly shortened under industrial conditions. Example 3 The present invention: in both hydrotreating stages a) and b ) (without intermediate stripping 150153.doc • 38 - 201113361 stage) use - system coffee 2 / oxidation Ming + NiM. / Oxidation - A method of hydrotreating a mixture of petroleum feed and vegetable oil. The oil feed and oil (iv) oil feed are strictly the same as those in (4) (4) 2 . The treated mixture was also exactly the same as described in Example 2 and was 70 wt. Petroleum gasoline and 3 〇 wt % DND rapeseed oil. The association of the mixture is carried out in a downflow fixed bed isothermal unit: subjecting the total feed to a first hydrotreating stage a), in which the feed passes through a catalyst containing 50 mi of MoP/oxidized catalyst (IV) Promote the HDO reaction of vegetable oils. The effluent of the first hydrotreating stage a) is sent directly to the second hydrotreating stage b)' containing 50 ml of NiMoP/alumina catalyst without an intermediate stripping stage to promote the hds reaction of the feed. Subsequent dewatering of all hydrotreated effluent to the water separation stage followed by hydroisomerization of the hydrocarbon liquid effluent on 50 ml of NiW/ceria-alumina catalyst is intended to be improved The temperature limit of the low temperature properties of the gasoline fraction and especially the filterability. The M〇p/alumina catalyst used in the catalytic zone of the first hydrotreating stage a) is characterized by a Mo03 content of 25.3 wt_% iP2〇5 content of 6.1 wt.% and supported on 7 alumina. The NiMoP/alumina catalyst used in the catalytic zone of the first hydrotreating stage b) has the same composition as described in Example 1, which is 21.0 wt·% Mo〇3, 5.0 wt. supported on r alumina. % P205 and 4.3 wt.% NiO.

Hydrogen isomerization of paraffin waxes converted from vegetable oil at the end of the first and second stages of the NiW/cerium oxide-alumina catalyst (essentially used in hydrotreating a) 150153.doc •39- 201113361 and b) It is characterized by a NiO content of 3.5 wt.% and a W03 content of 27 wt.%. These catalysts are prepared by subjecting the oxide precursor to dry impregnation in an aqueous solution. The method of preparing such catalysts does not limit the scope of the invention. The catalyst was subjected to in situ vulcanization at 350 ° C under a certain pressure at 350 ° C by adding 2 wt. ° / dimethyl disulfide to petroleum gasoline, and then summarized in Table 4 below. The hydrotreating is carried out. The operating conditions are the same as those used in their example 2. The only change is the catalyst nature of the first hydrotreating stage a) which is essentially used in the deoxygenation stage and in particular hydrodeoxygenation. Table 4 Operating conditions of each catalytic zone Total feed rate (ml/h) 160 Total pressure (MPa rel) 5 Zone 1 (HDO) H2/HC inlet (Nl/1) 700 LHSV Catalyst ΜοΡΟι·1) 3.2 Temperature (° C) 300 Zone 2 (HDS) H2/HC inlet (Nl/1) 700 LHSV Catalyst NiMoP(h-1) 3.2 Temperature (°C) 350 Zone 3 (hydroisomerization) H2/HC inlet (Nl/1 700 LHSV Catalyst NiW(h_1) 3.2 Temperature (°C) 340 Table 5 below shows the yields obtained in each catalytic zone (expressed in wt.% relative to the fresh start 150153.doc -40- 201113361 feed) And the main characteristics of the fuel fraction produced at the exit of each district. Table 5 Petroleum gasoline/vegetable oil mixture (70 wt.% petroleum gasoline + 30 wt.% DND rapeseed oil) in various stages of hydrotreating on the MoP+NiMoP catalytic system and subsequent hydroisomerization on the NiW catalyst Yield obtained in the chemical conversion zone Hydrotreating zone Catalyst Zone 1 (HDO) MoP 2 zone (HDS) NiMoP 3 zone (hydroisomerization) NiW Deoxidation (%) 100 - - HDO selectivity (wt. %) 99.8 - - (wt.%) yield (wt.%/fresh feed) h2s 0.9 0.9 C1+C2 0.2 0.2 C3 1.5 1.5 C4 0.1 0.1 C0+C02 0.01 0.01 H20 3.7 3.7 Naphtha (150°〇 ) - 6.0 Kerosene + Gasoline (150 ° C + ) 95.2 89.2 H2 Consumption 1.6 1.6 Fuel Matrix Characteristics (150 ° C + Fraction) . Sulfur (ppm by Weight) 1500 5 4 Nitrogen (ppm by Weight) 50 3 3 Total Aromatic Compound (wt .%) 19.5 17.5 17.5 diaromatic compound + (wt.%) 8.0 6.0 6.0 motor method cetane index 58 63 62 TLF (°〇+1 +1 -5 relative to example 2 (not according to the invention) As a result, the following knot was observed 150153.doc -41 - 201113361: - A better yield of the gasoline matrix obtained by promoting the hydrodeoxygenation pathway (HD0) (by weight) to improve the yield of the gasoline matrix. - The resulting gasoline matrix has a better quality. - A significant improvement in the performance of hydrodesulfurization (HDS), which makes it possible for the second hydroprocessing stage b) HDS 3 5 〇. (At the temperature, a gasoline base having a sulfur maximum of 10 ppm by weight is produced. The result may be the first addition of the catalyst of the present invention used in the first-hydrotreating stage & The conventional NiMo catalyst used in the hydrogen treatment stage is achieved with particularly high selectivity, and the catalyst of the present invention is extremely advantageous in accordance with the hydrodeoxygenation pathway (HD〇) (which is accompanied by water formation) rather than the decarboxylation pathway (which is accompanied by The formation of C0 and C〇2) to deoxygenate vegetable oil. The extremely small amounts of C0 and C〇2 formed demonstrate this excellent selectivity for hydrodeoxygenation (hd〇). BRIEF DESCRIPTION OF THE DRAWINGS The drawings illustrate preferred embodiments of the method of the present invention. The feed (1) from the renewable source is mixed with the hydrogen (2) and the preheated feed (3) from the petroleum source, and the heating member is not shown in the figure. The mixture is fed to a first ratification treatment stage a) comprising two catalytic zones (丨〇) and (11), wherein the unsaturated moiety is generated according to a so-called hydrodeoxygenation route of the feed from a renewable source The hydrogenation reaction and the deoxygenation reaction 'restrict the formation of CO and C〇2. The effluent leaving the second catalytic zone (U) of the first hydrotreating stage a) is then injected into a second hydrotreating stage comprising a catalytic zone (12) in which a conventional hydrotreating reaction takes place and in particular hydrogenation Sulfur reaction. The effluent leaving the second catalytic zone 150153.doc • 42- 201113361 (12) is then fed via line (5) to the zone for gas/liquid separation and water separation (13) 'where the gaseous stream (6) And water (8) is separated from the hydrocarbon liquid effluent (7). The feed from the renewable source is injected into the second catalytic zone (11) in stages via line (14). The hydrocarbon effluent (7) is sent to the final catalytic zone (14) for hydroisomerization. After separation of the gases, the effluent produced is a fuel base (kerosene and/or gasoline) having a sulfur content of less than 10 ppm. [Main component symbol description] 1 Feed from renewable source 2 Hydrogen 3 Preheating feed from petroleum source 5 Pipe 6 Gaseous stream 7 Hydrocarbon liquid effluent 8 Water 9 Effluent 10 Catalytic zone 11 First catalytic zone 12 The second catalytic zone 13 $ & Ί gastric / 3⁄4 body separation and moisture 14 for the final reminder of hydroisomerization / 150153.doc -43.

Claims (1)

201113361 VII. Patent Application Range: l A hydrotreating process for co-processing a mixture of a petroleum feed with at least one feed obtained from a renewable source for producing a fuel matrix having a sulfur content of less than 10 ppm, The method comprises the following stages: a) a first hydrotreating stage, wherein the feed passes through at least one first fixed bed catalytic zone comprising at least one supported or bulk catalyst comprising a Group VIB element a sulfide-forming active phase, the Group VIB element is molybdenum, the catalyst also comprises at least one doping element selected from the group consisting of phosphorus, fluorine and boron, b) a second hydrotreating stage from which the first hydrotreating stage is derived The peach extract is sent directly thereto, and wherein the effluent passes through at least one second fixed bed catalytic zone comprising at least one hydrotreating catalyst. 2. The method of claim 1, wherein the temperature of the stream entering the first catalysis II of the first gassing treatment stage is between 18 Gt and 22 generations, the stream being obtained from the self-renewable source And the mixture of the petroleum feed is composed. 3. The method of claim 1 or 2, wherein the supported catalyst used in the first hydrotreating stage is capable of "man," : alumina, - strip a, - cerium oxide, cerium oxide - alumina, oxidation, clay, and mixtures of at least two of the minerals. 4' or 2: method 'where the supported catalyst comprises relative The content of the Group VIB element of the Chu group element oxide between 15 wt% and 35 wt% of the total weight of L 4 . 150153.doc 201113361 5. The method of claim 2 or 2, wherein the first hydrogenation The treatment stage is operated under the following conditions: between uot and 45 (temperature between rc; total pressure between i MPa and 10 MPa2; hourly space velocity between 〇ι ^ and (7)^; Usually between 50 > ^1/1 and 3〇〇〇N1/l hydrogen/feed ratio, expressed as the volume of hydrogen per volume of liquid feed, the hydrogen volume is at normal temperature and pressure 6. The method of claim 1 or 2, wherein the first hydrotreating stage is linked to a fatty acid of a triglyceride The deuteration of the unsaturated portion of the chain and the stage of hydrodeoxygenation of the feed. 7. The method of claim 1 or 2, wherein the first hydrotreating stage is hydrogeno-deoxygenated (HDO) The selectivity is greater than 970/〇. 8. The method of claim 1 or 2, wherein the effluent leaving the first hydrotreating stage a) is sent directly to the second hydrotreating stage b) without intermediate steam The method of the first or second embodiment, wherein the temperature of the effluent leaving the first hydrotreating stage &) is greater than 3 〇〇. 10. The method of claim 1 or 2, The hydrotreating catalyst used in the second hydrotreating stage 包含) comprises nickel as a vm group element and molybdenum as a group VIB element, and the catalyst comprises between 〇.5 ..% and 10 Wt.%. The amount of nickel oxide between and between 3 wt.% and 30 wt.% is on the oxidized amorphous mineral support, and the percentages are based on the total weight of the catalyst. Wt.%. U. The method of claim 1 or 2, wherein the second hydroprocessing stage b) is operated under the following conditions: 25〇<^ and 45〇. The temperature between 〇; 〇5 Mpa 150153.doc 201113361 to 25 MPa (preferably between 1 MPa and 25 MPa) total pressure; Ο.1 h1 to 20 h·1 The hourly space velocity; and the hydrogen/feed ratio, usually 5〇Ν1/1 to 2000 NI/1, which is expressed as the hydrogen volume per volume of liquid feed. The hydrogen volume is at normal temperature and pressure. 12. 13. 14. 15. The method of claim 1 or 2 wherein the hydrotreating effluent is subjected to a stage of separation of water and at least one liquid hydrocarbon substrate. The process of claim 1 or 2 wherein all of the hydrotreated liquid effluent is subsequently subjected to a hydroisomerization stage in the presence of a selective hydroisomerization catalyst. The method of claim 1 or 2, wherein the hydroisomerization stage operates under the following conditions: a temperature between 15 (TC and 5001; a pressure between i Mpa and 10 MPa; between oj The hourly space velocity between 丨 and (7)ρ; and the hydrogen flow rate between the hydrogen/hydrocarbon volume ratio between 7〇Nm3/m3 feed and 1000 Nm3/m3 feed. Self-contained from the group, and the source Oil and fatty oil triester and/or method of claim 1 or 2 wherein the petroleum feed is selected from direct distillation gasoline, the gasoline obtained from the conversion process, etc., the feed from the renewable source is selected from the group consisting of plants or animals. A mixture of such feeds containing sweet or free fatty acids and/or esters. 150153.doc