PROCESS FOR HYDROTREATING RENEWABLE MATERIALS WITH AN OPTIMIZED GAS RECYCLE

专利摘要:
The invention relates to a method for hydrotreating a feedstock from renewable sources in which the flow of the total feed F is divided into a number of different partial feed streams F1 to Fn equal to the number of catalytic zones n, with n an integer between 1 and 10, the mass flow rate of hydrogen sent to the first catalytic zone representing more than 80% by weight of the total mass flow rate of hydrogen used in the hydrotreatment process, to produce at the outlet of the reactor at least one effluent containing paraffinic hydrocarbons, said effluent from step a) is subjected to at least one separation step, at least a portion of said liquid fraction containing the paraffinic hydrocarbons is recycled to the first catalytic zone and the following catalytic zones of so that the local recycling rate on each of the beds, that is to say the mass ratio between the flow of said recycled liquid fraction and the flow part iel load introduced into the catalytic zone Fn is less than or equal to 2 and the local dilution rate on each of the beds that is to say the mass ratio between the amount of liquid and gaseous flows introduced into the catalytic zone n and the partial charge flow introduced into the catalytic zone Fn is less than 4.
公开号:FR3039160A1
申请号:FR1557053
申请日:2015-07-24
公开日:2017-01-27
发明作者:Thierry Chapus；Frederic Bazer-Bachi；Elodie Tellier；Yves Scharff；Stephane Fedou；Octavio Carvalho；Sebastien Boucher
申请人:IFP Energies Nouvelles IFPEN；
IPC主号:

专利说明:

On souhaite traiter 100 g/h de cette charge dans un réacteur d'hydrotraitement constitué de 2 lits catalytiques.
Chaque zone catalytique est constituée d'un lit de catalyseur. Le catalyseur utilisé est identique dans les deux zones catalytiques de l'étape d'hydrotraitement et comprend 4% poids de NiO, 21% poids de M0O3 et 5% poids de P2O5 supporté sur une alumine gamma. Ledit catalyseur présente un rapport atomique Ni/Mo égal à 0.4.
Les catalyseurs supportés sont préparés par imprégnation à sec des précurseurs oxydes en solution puis sulfurés in-situ préalablement au test, à une température de 350°C, à l'aide d'une charge gazole de distillation directe additivée de 2% en poids de soufre ex-diméthyldisulfure (DMDS). Après sulfuration in-situ dans l'unité sous pression, la charge issue d'une source renouvelable constituée par l'huile de palme décrite dans le tableau 1a, est envoyée dans chacune des deux zones catalytiques.
La méthode de préparation des catalyseurs ne limite pas la portée de l'invention.
La charge huile de palme totale (F = 100 g/h) est divisée en deux flux, un flux Fl de 40 g/h injecté dans la zone ZI, et un deuxième flux de 60 g/h injecté dans la zone Z2.
La quantité de recycle liquide utilisé est injectée avec la charge intégralement sur la zone ZI, avec un débit RL1=90 g/h.
Le gaz injecté avec la charge est intégralement composé d’hydrogène. Cet hydrogène est injecté intégralement avec les deux flux de charge alimentant les zones ZI et Z2, avec un débit tel qu’en entrée de chacune des zones catalytiques, on a un même ratio RG1/F1 = RG2/F2 = 700 Nm^/m^
Ainsi, le débit massique d’hydrogène envoyé vers la première zone catalytique ZI représente 35%poids du débit massique total d’hydrogène utilisé dans le procédé d’hydrotraitement.
La pression opératoire totale est de 50 bar rel (5 MPa rel).
Le tableau 1b indique les débits de chacun des deux flux de charge, ainsi que les taux de recycle liquide et les taux de dilution pour chacune des 2 zones catalytiques.
Tableau 1b
Conditions opératoires de la section hydrotraitement Et caractéristiques de l’effluent produit
On obtient une élimination complète de l’oxygéne lors de cette étape d’hydrotraitement. On obtient un produit liquide essentiellement composé d’hydrocarbures avec un rendement de 81.0 % poids. EXEMPLE 2 (CONFORME A L'INVENTION)
La même charge que dans l’exemple 1 est traitée dans un réacteur d’hydrotraitement constitué de deux zones catalytiques comportant chacune le même catalyseur que dans l’exemple 1. Dans l’exemple 2 conforme, le débit massique d’hydrogène envoyé vers la première zone catalytique ZI représente 80%poids du débit massique total d’hydrogène utilisé dans le procédé d’hydrotraitement.
Le même protocole d’activation du catalyseur par sulfuration est appliqué, et la pression opératoire totale est de 50 bar rel (5 MPa rel).
Le tableau 2 indique les débits de chacun des deux flux de charge, ainsi que les taux de recycle liquide et les taux de dilution pour chacune des 2 zones catalytiques
La même quantité de produit liquide est recyclée (R=90 g/h), mais contrairement à l’exemple 1 ce recycle est pour partie envoyé dans la zone catalytique ZI (RL1=72 g/h) et pour partie envoyé dans la zone catalytique Z2 (RL2=18 g/h). La nature et le débit gazeux recyclé au réacteur d’hydrotraitement est identique globalement à celui de l’exemple 1 (100% hydrogène, RG1= 5,46 g/h, correspondant à un ratio volume H2/volume charge en entrée réacteur de 700 Nm3/m3). Ce débit gazeux est en revanche distribué différemment, puisque le débit massique d’hydrogène envoyé vers la première zone catalytique ZI représente 80%poids du débit massique total d’hydrogène.
Tableau 2
Conditions opératoires de la section hydrotraitement Rendement et caractéristiques de l’effluent produit
EXEMPLE 3 (CONFORME A L'INVENTION)
La même charge que dans l’exemple 1 est traitée dans un réacteur d’hydrotraitement constitué de deux zones catalytiques comportant chacune le même catalyseur que dans l’exemple 1. Dans l’exemple 3 conforme, le débit massique d’hydrogène envoyé vers la première zone catalytique Z1 représente 100%poids du débit massique total d’hydrogène utilisé dans le procédé d’hydrotraitement.
Le même protocole d’activation du catalyseur par sulfuration est appliqué, et la pression opératoire totale est de 50 bar rel (5 MPa rel).
Le tableau 3 indique les débits de chacun des deux flux de charge, ainsi que les taux de recycle liquide et les taux de dilution pour chacune des 2 zones catalytiques
La même quantité de produit liquide est recyclée (R=90 g/h), mais contrairement à l’exemple 1 ce recycle est pour partie envoyé dans la zone catalytique Z1 (RL1=60 g/h) et pour partie envoyé dans la zone catalytique Z2 (RL2=30 g/h).
La nature et le débit gazeux recyclé au réacteur d’hydrotraitement est identique globalement à celui de l’exemple 1 (100% hydrogène, RG1=6,83 g/h, correspondant à un ratio volume H2/volume charge en entrée réacteur de 700 Nm3/m3). Ce débit gazeux est en revanche distribué différemment, puisqu’il est intégralement envoyé dans la zone catalytique ZI.
Tableau 3
Conditions opératoires de la section hydrotraitement Rendement et caractéristiques de l’effluent produit
Les exemples 1 à 3 démontrent que la mise en œuvre de la présente invention permet de gérer un taux de recycle faible dans toutes les zones catalytiques grâce à l’application d’un fort débit d’hydrogène à l’entrée du premier lit contrairement à l’exemple 1 non conforme dans lequel l’hydrogène est distribué sur les lits catalytiques de manière uniforme et ou l’exothermie n’est pas maitrisée, les delta de température entre la sortie et l’entrée des lits catalytiques étant trop élevés.
Par ailleurs, la bonne gestion de l’exothermie dans les exemples 2 et 3 conformes à l’invention fait que l’on opère a une température moyenne de lit abaissée par rapport à l’exemple 1 non conforme, ce qui permet une désactivation du catalyseur plus faible et donc une durée de vie du catalyseur plus longue.
TECHNICAL FIELD The invention relates to a process for the production of paraffinic hydrocarbons that can be used as fuels from renewable materials such as oils and fats of vegetable or animal origin.
The current international context is marked first and foremost by the rapid growth in need of fuels, in particular diesel and kerosene bases, and then by the importance of the problems linked to global warming and the emission of greenhouse gases. The result is a desire to reduce energy dependence on fossil-based raw materials and on reducing CO2 emissions. In this context, the search for new charges from renewable sources is an issue of increasing importance. Among these fillers, mention may be made, for example, of vegetable oils (food or not) or derived from algae and animal fats.
These fillers are mainly composed of triglycerides and free fatty acids, these molecules comprising hydrocarbon chains of fatty acids with a number of carbon atoms of between 4 and 24, and a number of unsaturations generally between 0 and 3. , with higher values for algae oils for example. Renewable fillers contain impurities such as nitrogen compounds and metals in the form of phospholipids containing elements such as phosphorus, calcium, magnesium, iron, potassium and sodium.
The very high molecular weight (> 600 g / mol) of the triglycerides and the high viscosity of the feeds in question make their direct or mixed use in the fuel bases pose difficulties for modern engines. However, the hydrocarbon chains which constitute the triglycerides are essentially linear and their length (number of carbon atoms) is compatible with the hydrocarbons present in the fuel bases.
It is therefore necessary to transform these charges to obtain fuel bases (including diesel and kerosene) of good quality responding in particular specifications directly or after mixing with other cuts from crude oil. The diesel must meet the EN590 specification and the kerosene must meet the requirements outlined in the "International Air Transport Equipment Association (IATA) Guidance Material for Aviation Turbine Fuel Specifications" as ASTM D1655.
One possible approach is the catalytic conversion of triglycerides into deoxygenated paraffinic fuel in the presence of hydrogen (hydrotreatment).
During the hydrotreatment, the reactions undergone by the feed containing the triglycerides are as follows: the hydrogenation reaction of the unsaturations of the hydrocarbon chains of the fatty acids of the triglycerides and esters, the deoxygenation reactions according to two reaction routes: hydrodeoxygenation (HDO) leading to the formation of water by hydrogen consumption and the formation of carbon number (Cn) hydrocarbons equal to that of the initial fatty acid chains, O decarboxylation / decarbonylation leading to formation oxides of carbon (carbon monoxide and carbon dioxide: CO and CO2) and the formation of less carbon-containing hydrocarbons (Cn-1) compared to the initial fatty acid chains, • hydrodenitrogenation reactions ( HDN), which denotes the reactions for removing nitrogen from the feed with the production of NH3. The hydrogenation of the unsaturations of the hydrocarbon chains (carbon-carbon double bonds) is strongly exothermic and the increase in temperature caused by the release of heat can lead to temperature levels where the share of the decarboxylation reactions becomes significant. The hydrodeoxygenation reactions, and the decarboxylation reactions, are also exothermic reactions. The hydrodeoxygenation is generally favored at a lower temperature compared to the decarboxylation / decarbonylation which induces a loss in yield. Hydrodenitrogenation reactions are more difficult and require higher temperatures than hydrogenation and hydrodeoxygenation.
Therefore, strict control of the temperature in the hydrotreatment section is necessary, too high a temperature has the disadvantage of promoting undesirable side reactions such as polymerization, cracking, coke deposition and deactivation of the catalyst.
Prior art
Thus, EP 1 741 768 A1 which discloses a method of hydrotreating a feedstock comprising a fresh vegetable oil feed which contains more than 5% by weight of free fatty acids, which creates undesirable reactions. In order to alleviate this problem, there is provided a process for producing diesel fuel in which a feedstock is hydrotreated and then isomerized, said feedstock comprising a feedstock containing more than 5% by weight of free fatty acids and at least one diluent, the hydrotreatment step being carried out at a temperature of from 200 to 400 ° C and the ratio of coolant dipping agent being in the range of 5 to 30% by weight. The diluting agent may be a hydrocarbon compound of biological origin or not and is preferably a recycled product resulting from the process. EP 1 741 768 A1 also discloses that the content of the fresh feed (vegetable oil) in the total feed entering the hydrotreating step is less than 20% by weight.
Thus, it is emphasized that the very large dilution of the fresh feedstock before its hydrotreatment makes it possible to reduce the production of products resulting from side reactions and to improve the life of the catalyst to allow stable operating conditions for about 9 months. .
However, the method proposed in EP 1 741 768 A1 has the following disadvantages: - The amount of recycle to provide the necessary amount of diluent is very high. The use of a high liquid flow leads to a high pressure drop and requires a considerable transformation of the existing units in order to adapt the necessary dimensions of the reactor. Hydrogen consumption is reduced by promoting deoxygenation by decarboxylation reactions (formation of CO and CO2) by appropriate selection of the hydrotreatment catalyst. However, the deoxygenation of triglycerides by decarboxylation leads to a significant loss of paraffin yield, a loss of catalyst activity due to the inhibitory effect of CO and increased corrosion due to the presence of CO2.
The document US2009 / 0318737 describes a process for producing (diesel) fuels derived from renewable raw materials such as oils and fats of plant and animal origin. The method comprises treating a first portion of a renewable raw material by hydrogenation and deoxygenation in a first reaction zone and a second portion of a renewable raw material by hydrogenation and deoxygenation in a second reaction zone. A portion of the liquid hydrocarbon product obtained is recycled to the first reaction zone to increase the hydrogen solubility of the reaction mixture by using a ratio recycled to the first part of renewable raw materials between 2 and 8 by volume (mass ratio between 1.7 and 6.9). The document US2009 / 0318737 thus describes a local recycling rate on the first bed of between 2 and 8 by volume (mass ratio between 1.7 and 6.9). Maximizing the amount of hydrogen in the liquid phase reduces the rate of catalyst deactivation, thereby reducing pressure, promoting decarboxylation / decarbonylation reactions, and reducing hydrodeoxygenation reactions, and therefore to reduce hydrogen consumption. No information is given on the amount of nitrogen in raw materials and paraffinic effluents.
Document US2009 / 0082606 describes a process for producing diesel fuel from feedstocks derived from renewable sources such as vegetable oils. The process comprises treating said feedstock in a reaction zone by hydrogenation and deoxygenation in the presence of hydrogen to produce paraffins between 8 and 24 carbon atoms. A portion of the liquid reaction product is recycled to the reaction zone at a ratio recycled to volume load of between 2 and 8 (mass ratio between 1.7 and 6.9). It is the liquid part of the reaction product after separation of the gaseous compounds which is recycled in the reaction zone. The document US2009 / 0082606 thus describes a liquid recycle rate of between 2 and 8 by volume or between 1.7 and 6.9 (by mass).
Application EP 2,226,375 A1 describes a process for the continuous hydrogenation of a feedstock from renewable sources containing triglycerides in a fixed bed reactor system having a plurality of catalytic beds comprising a hydrogenation catalyst and arranged in series in which the feedstock, the hydrogen-containing gas and a diluent are injected into the catalyst beds under hydrogenation conditions. The charge is introduced by a stepped injection so that the different catalytic beds receive more and more charge in the direction of flow. The diluent is only added to the feed streams and hydrogen-containing gas entering the first catalyst bed, the diluent being composed of the hydrogenation product formed in each catalyst bed in addition to the diluent added which is a fraction of the hydrogenated product obtained by the process according to the invention and which is recovered at the outlet of the reactor after separation. This limitation of the amount of recycled product in the reactor makes it possible to limit the total flow rate in the reactor and then the hydraulic load downstream of the reactor. Thus, the first catalytic bed is fed with a mixture consisting of a partial flow of charge F1, a partial flow of hydrogen-containing gas Ht and recycled added liquid diluent. The second catalytic bed is fed with a mixture consisting of a partial flow of feed F 2, a partial flow of gas containing hydrogen FI 2 and the hydrogenated product from bed 1, the gas containing hydrogen reacted and diluent added at the inlet of the bed 1. The ratio by weight of diluent on the filler is essentially the same at the inlet of all the catalytic beds and is less than or equal to 4. The EP 2 application 226 375 A1 thus describes a dilution ratio for each bed which only takes into account the liquid flows and does not take into account the gas flows.
It is known that the use of a high liquid recycle rate allows better management of the exotherm and in particular a maintenance of the temperature difference between the outlet and inlet temperature of each catalytic zone in an acceptable range for the industrial exploitation of the process.
However, the Applicant has shown that a hydrotreatment process of charges from renewable sources using a stepped injection of charge in the different catalytic zones allowed a good management of the exothermie without imposing a significant liquid recycle in the different catalytic zones, thanks to the mass flow rate of hydrogen sent to the first catalytic zone which represents more than 80% by weight of the total mass flow rate of hydrogen used in the hydrotreatment process. SUMMARY OF THE INVENTION The objective of the present invention is then to propose a process for hydrotreating renewable charges allowing improved management of the exotherm while limiting the amount of recycled liquid.
Thus, the present invention relates to a process for hydrotreating a feedstock from renewable sources to produce paraffinic hydrocarbons in the presence of hydrogen in a fixed bed reactor having a plurality of catalytic zones arranged in series and each comprising at least one catalytic converter. hydrotreatment in which: a) the flow of the total charge F is divided into a number of different partial flows of charge F1 to Fn equal to the number of catalytic zones n, with n being an integer between 1 and 10 in the reactor, the first partial flow of charge F1 being injected into the first catalytic zone ZI, the second partial feed flow F2 being injected into the second catalytic zone Z2 and so on, if n is greater than 2, the hydrotreatment process operating at a temperature between 180 and 400 ° C, at a pressure between 0.1 MPa and IMPa, at a space velocity of between 0.1 hr-1 and 10 hr-1, and with a rati o between the flow rate of hydrogen and the feed rate of between 150 and 1500 Nm 2 / m 2, the mass flow rate of hydrogen sent to the first catalytic zone representing more than 80% by weight of the total mass flow rate of hydrogen used in the hydrotreatment process, to produce at the output of the reactor at least one effluent containing paraffinic hydrocarbons, b) said effluent from step a) is subjected to at least one separation step for separating at least one gaseous fraction and at least one liquid fraction containing the paraffinic hydrocarbons, c) at least a portion of said liquid fraction containing the paraffinic hydrocarbons is recycled to the first catalytic zone and the following catalytic zones so that - the local recycling rate on each of the beds that is to say the mass ratio between the flow of said recycled liquid fraction and the partial feed flow introduced into the catalytic zone Fn is infer ur or equal to 2, preferably 1.7, more preferably 1.5 .- the local dilution ratio on each of the beds, that is to say the mass ratio between the quantity of liquid and gas flows dilaunts introduced. in the catalytic zone n and the partial feed flow introduced into the catalytic zone Fn is less than 4, preferably less than 3.8, preferably less than 3.5, very preferably less than 3, more preferably preferred less than 2.5 and even more preferably less than 2.
An interest of the present invention is to provide a process which, despite the implementation of a low liquid recycle rate and in particular less than 2 on each of the catalytic zones, allows optimized management of the exotherm within the different zones. catalytic, especially through the combination of said low recycle rate on each of the catalytic zones and a high flow of hydrogen at the entrance of the first bed.
Another advantage of the present invention lies in the use of a weak liquid recycle which facilitates the revamping of existing units. The term "revamping" in the English terminology or debottlenecking means the revision of the design of equipment already in operation which are not necessarily units of hydrotreatment of vegetable oils, but may be for example units fossil fuel hydrotreating process, to increase production, technical, economic and environmental performance as well as reliability.
Another advantage of the present invention lies in reducing the amount of liquid recycle required which limits the pressure drop and allows the use of smaller sized reactors, the injection of concentrated hydrogen at the reactor head allowing to maintain a good distribution on the catalytic bed.
Another advantage of the invention, in the preferred case where the hydrogen-rich gas recycle is injected at 100% at the reactor head, is not to have gas injection into the cooling zones (quench) between the beds. , which greatly simplifies the design of these areas as well as the control around these areas.
Another advantage of the present invention consists in favoring the hydrodeoxygenation route by elimination of oxygen and the formation of water, rather than the elimination of oxygen by decarboxylation reactions by controlling the temperatures adapted to the hydrodeoxygenation at the inlet of each catalytic zone. The advantages provided by this solution are an increase in the yield of paraffinic hydrocarbons, and the reduction of the amount of CO / CO2 formed, which makes it possible to limit the inhibitory effect of CO on the activity of the hydrotreatment catalyst and thus allows allows a reduction of the amount of catalyst used. Favoring the hydrodeoxygenation route also reduces the corrosion due to the presence of CO2 in the reactor and reduces the need for amine necessary to separate the CO2.
Description of the invention
The process according to the present invention consists in converting into paraffinic hydrocarbons, and more precisely into middle distillates (kerosenes and / or gasolines), a wide range of charges of renewable origin, mainly composed of triglycerides and fatty acids. These fillers are generally characterized by a high molar mass (greater than 800 g / mol most often), and the fatty acid chains that compose them have a number of carbon atoms generally between 4 and 30, or even reaching higher values and a number of chain unsaturations generally between 0 and 3, with higher values that can be reached on certain specific charges.
The feedstocks from renewable sources according to the invention are advantageously chosen from vegetable oils, algal or algal oils, fish oils, used edible oils, and fats of vegetable or animal origin, or mixtures of such fillers, containing triglycerides and / or free fatty acids and / or esters.
Among the fillers that can be converted by the process according to the present invention, mention may be made of this list, which is not exhaustive: vegetable oils such as rapeseed, jatropha, soya, palm, sunflower, d olive, copra, camelina, fish oils or heterotrophic or autotrophic algal oils, or animal fats such as beef tallow, or residues from the paper industry (such as tall oil). "), or mixtures of these various charges.
All these fillers contain high oxygen contents, as well as, at very variable contents depending on the origin of the charges, sulfur compounds, but also nitrogen compounds, and metals such as phosphorus, calcium, magnesium and potassium. or sodium. The metal content can be up to 2500 ppm. The nitrogen and sulfur contents are generally between about 1 ppm and about 100 ppm by weight and preferably below 100 ppm, depending on their nature. They can reach up to 1% weight on particular loads.
The treated feed may be crude, or may also have undergone a refining or pre-refining treatment, the purpose of which is to lower the metal content. This pretreatment step may have been carried out beforehand, or in a pre-treatment section placed upstream of the hydrotreatment reactor. This optional pretreatment step may consist of a heat treatment, associated with a passage over solids such as aluminas or silica-aluminas, or a treatment with water vapor, or an acid treatment as per phosphoric acid, or an ion exchange resin treatment, or a combination of several of these pretreatment steps. In general, the pretreatment may include any method (degumming, dephosphatation ...) known to those skilled in the art of refining the oil for food purposes.
Hydrotreatment
The process according to the invention relates to a process for hydrotreating a feedstock from renewable sources to produce paraffinic hydrocarbons in the presence of hydrogen in a fixed bed reactor having a plurality of catalytic zones arranged in series and each comprising at least one catalyst hydrotreating.
According to the invention, said filler is mixed with a gas rich in hydrogen, which may also contain other inert hydrocarbon compounds, that is to say which do not react as such on the hydrotreatment catalysts, unlike the constituents of load. The hydrogen may advantageously come from a hydrogen booster and / or the recycling of the hydrogen-rich gas from the separation stage b) downstream from the hydrotreatment stage and / or the recycling of the high-enriched gas. hydrogen from a subsequent step of the hydrotreatment process according to the invention and preferably from a separation step downstream of the subsequent hydroisomerization step. In practice, the additional hydrogen can come from steam reforming or catalytic reforming, and its hydrogen purity is most often between 75 and 99.9% by volume, the other gases present being generally ethane, propane and butane. The hydrogen-rich gas resulting from the separation step b) downstream from the hydrotreating step or from the separation step downstream from the optional hydroisomerization step preferably undergoes one or more treatments beforehand. intermediate purification before being recycled in the hydrotreatment process and / or in the optional hydroisomerization step.
For an easier understanding of the present invention, the following definitions are introduced. They refer to FIG. 2. The hydrotreatment reactor of the process according to the invention may contain a variable number n of catalytic zones.
By catalytic zone is meant a catalytic bed. Each catalytic zone may comprise one or more catalyst layers, which may be identical or different, optionally supplemented with inert layers. The catalytic zones may contain identical or different catalysts.
According to the invention, the reactor comprises a number n of catalytic zones, n being an integer between 1 and 10, preferably between 1 and 6, preferably between 2 and 5, very preferably between 2 and 4, and even more preferably between 2 and 3.
In a very preferred embodiment, the reactor comprises two catalytic zones.
All flows are expressed in mass flow.
F: total flow of the renewable feedstock treated in the process F1: partial flow of the feed introduced into the first catalytic zone ZI F2: partial flow of the feed introduced into the second catalytic zone Z2 F3: partial flow of the feed introduced into the third catalytic zone Z3 and so on ...
Fn: partial flow of the feed introduced into the last catalytic zone Zn RL1: liquid recycle stream, recycled in the first catalytic zone Z1 RL2: liquid recycle stream, recycled in the second catalytic zone Z2 and so on ... RLn : liquid recycle stream, recycled in the last catalytic zone Zn RG1: recycled gas stream in the first catalytic zone Z1, the gas stream comprising predominantly hydrogen. RG2: recycled gas stream in the second catalytic zone Z2, the gas stream comprising predominantly hydrogen. and so on ... RGn: recycled gas stream in the last catalytic zone Zn, the gas stream mainly comprising hydrogen.
When an addition of gas containing hydrogen is carried out at any catalytic zone, the mass flow rate of this booster is added to the mass flow rate of the recycled gas stream of said zone and thus accounted for in RG1, ... RGn.
Throughout the remainder of the text, the term "local recycling rate" on each of the catalytic zones (TRn), the mass ratio between the sum of the liquid recycle streams supplying the catalytic zones Z1 to Zn-1 and the introduced liquid recycle stream. in the catalytic zone Zn on the partial flow of the feed introduced into the catalytic zone Zn (Fn).
Indeed, the total amount of liquid recycle passing through the catalytic zone Zn comprises the liquid recycle introduced into the catalytic zones Z1 to Zn-1 (RL1 + RL2 + ... RLn-1) and which feeds and passes through the catalytic zones Z1 to Zn-1 then the catalytic zone Zn and the liquid recycle introduced into the catalytic zone Zn (RLn).
Thus, the local recycling rate is expressed on each of the beds by the following formula: ## EQU1 ##
With regard to the catalytic zone 1, the local recycling rate on the catalytic zone 1 is the mass ratio between the flow of the liquid recycle sent into the first catalytic zone ZI (RL1) and the partial flow of the feedstock introduced into the first catalytic zone 1 (F1): TR1 = RL1 / F1
Throughout the rest of the text, by dilution rate of the charge on each of the catalytic zones (TDn) is meant the mass ratio between the quantity of dilute liquid and gaseous flows arriving in the catalytic zone n and the partial flow of charge. introduced into the catalytic zone Fn.
For the calculation of the dilution ratio, the dilution of the load by both liquid and gaseous flows is taken into account. The quantity of the liquid and gaseous diluent flows through the catalytic zone n comprises the liquid recycle introduced into the catalytic zone n-1 (RLn-1) which passes through the n-bed, the gas recycle consisting of the gas containing non-hydrogen reacted in the catalytic zone n-1 (RGn-1), the liquid and gaseous recycle introduced into the catalytic zone n (RLn + RGn), and the hydrotreated product from the catalytic zone n-1. It is considered that the conversion of the charge in each catalytic bed is 100%, the amount of hydrotreated product from the catalytic zone n-1 is therefore equal to the amount of feed introduced into the catalytic zone n-1 (Fn-1 ).
Thus, the dilution ratio on each of the catalytic zones is defined according to the invention by the following formula: ## STR1 ## ... -i- RLn-1 -i- RLn) + (RG1 + ... -i- RGn-1 + RGn) / Fn
In particular, with regard to the catalytic zone 1, the dilution rate of the feedstock on the catalytic zone 1 is the mass ratio between the flow of the liquid and gaseous diluent recycle, sent into the first catalytic zone ZI (RL1 + RG1). and the partial flow of the feed introduced into the first catalytic zone 1 (F1): TD1 = (RL1 -i-RG1) / F1.
According to step a) of the process according to the invention, the flow of the total charge F is divided into a number of different partial flows F1 to Fn equal to the number of catalytic zones n in the reactor, the first partial flow of charge F1 being injected into the first catalytic zone, the second partial feed stream F2 being injected into the second catalytic zone and so on, if n is greater than 2, said hydrotreatment process operating at a temperature of between 180 and 400 ° C. , at a pressure of between 0.1 MPa and 15 MPa at a space velocity of between 0.1 hr and 10 h and with a ratio between the hydrogen flow rate and the feed rate is between 150 and 1500 Nm ^ / m ^, the mass flow rate of hydrogen sent to the first catalytic zone representing more than 80% by weight of the total mass flow rate of hydrogen used in the hydrotreatment process, to produce at the outlet of the reactor at least one efflu ent containing paraffinic hydrocarbons,
Except during the start-up phase of the process, at least a portion of said liquid fraction containing paraffinic hydrocarbons from the separation step b) is recycled to the first catalytic zone ZI and the following catalytic zones Zn. Said liquid fraction containing paraffinic hydrocarbons thus plays the role of liquid diluent for the charge.
Since the hydrotreatment section of the process is designed to completely convert the treated feedstock, the liquid recycle produced is a stream of paraffinic hydrocarbons whose oxygen content is very low and preferably below the analytical detection limit, and is essentially composed of paraffins. Consequently, this liquid recycle is inert with respect to the hydrotreatment reactions that take place in the different catalytic zones, and thus fully plays its role of liquid diluent of the feed, which makes it possible to limit the rise in temperature. in the first catalytic zone as well as in the following catalytic zones, due to the exothermicity of the reactions occurring therein.
During the start-up phase, a wide range of hydrocarbons can be injected as a liquid diluent, such as a light gas oil fraction until enough hydrotreated product is available for recycling to the first catalytic zone. ZI and the following catalytic zones Zn.
According to the invention, said hydrotreatment process operates at a temperature of between 180 and 400 ° C., preferably at a temperature of between 200 and 350 ° C., at a pressure of between 0.1 MPa and 15 MPa, preferably between between 0.5 and 10 MPa, and preferably between 1 MPa and lOMPa, at a space velocity between 0.1 h "'and 10 h and with a ratio between the total hydrogen flow rate and Total charge rate is between 150 and 1500 Nm ^ / m ^.
As indicated above, hydrogen is used in excess. In the process according to the invention, the total amount of hydrogen used in said process is such that the ratio between the total hydrogen flow rate and the total charge rate is between 150 and 1500 Nm 2 / m 2, preferably between 400 and 1200 Nm 2 / m 2, preferably between 600 and 900 Nm 3 / m 2.
Preferably, the hourly space velocity defined as being the ratio between the total volume flow rate of treated filler and the total volume of catalyst in the hydrotreating section is between 0.1 and 5 hours and preferably between 0.1 and 3 hours. h '.
The hydrotreatment process according to the invention can advantageously operate counter-current or upflow co-current or downward co-current and preferably cocurrent downward.
An essential criterion of the invention lies in the fact that the mass flow rate of hydrogen sent to the first catalytic zone represents more than 80% by weight of the total mass flow rate of hydrogen used in the hydrotreatment process, preferably more than 90% and preferably, the total mass flow rate of hydrogen used in the hydrotreatment process is sent to the first catalytic zone ZI. The use of a high gas flow rate at the inlet of the first catalytic zone ZI makes it possible to use a low liquid recycle flow rate in all the catalytic zones, and in particular in the zone 1 (the following ones). benefiting from the dilution resulting from the treated load in the upper beds). In fact, the use of a high gas flow rate at the inlet of the first catalytic zone ZI constitutes a volume of reactive gas which heats up by absorbing a part of the exotherm of the reaction. A very high liquid recycle flow rate is no longer needed to manage the exotherm. This makes it possible to use hydrotreatment reactors of dimensions comparable to those of petroleum fraction hydrotreating reactors such as gas oils (and thus to limit costs), to limit the pressure losses and to avoid clogging phenomena. of the reactor. The use of a large amount of hydrogen at the first catalytic zone also facilitates the transfer of hydrogen from the gas phase to the liquid phase and therefore to the catalyst. Indeed, in the process according to the invention and in particular in the first catalytic zone, the overall efficiency of the hydrodeoxygenation reaction is potentially limited by the intensity of this transfer. Indeed, the catalyst is not always used optimally in the early phases of the hydrodeoxygenation reaction because of the difficulty in supplying the catalyst with hydrogen. The transfer of the gas to the liquid remains important, but not always sufficient to match the demand for hydrogen to convert the charge. The increase of the hydrogen flow rate in the first catalytic zone goes in the direction of an increase of the gas-liquid transfer, and therefore of a better supply of hydrogen to the catalyst. This is therefore used optimally, the overall efficiency of the reactor being less limited by the intensity of the gas-liquid transfer. At iso-conversion of the charge, the amount of catalyst to be placed in the reactor, and in particular in the first catalytic zone, is optimized.
In the case where more than 80% by weight of the total mass flow rate of hydrogen used in the hydrotreatment process is sent to the first catalytic zone, one or more hydrogen streams may advantageously be injected between the catalytic zones following the first zone. .
Furthermore, it has been discovered that it is advantageous to inject the charge into the different catalytic zones (mass flow F1 injected in the zone Z1, F2 in the zone Z2, etc.) by making the proportions increasing charges are injected into the successive catalytic zones. This results in the following relationship: F (n-1) / F less than or equal to Fn / F, for the general case where n is the number of catalytic zones involved.
Thus, preferably, the different partial flows of charge are injected into the successive catalytic zones in increasing proportions such that F1 / F is less than or equal to F2 / F, itself less than or equal to F3 / F and thus The advantage provided by such a distribution of the charge in the different successive catalytic zones is that the different zones follow a rising profile, which makes it possible to adjust the temperature difference between the outlet and inlet temperature of each catalytic zone so that it is comparable for each catalytic zone.
The partial feed streams injected at the inlet of the catalytic zones situated downstream of the first catalytic zone Z1 may advantageously be strictly identical to the feed flow injected at the ZI zone inlet, but also be a load of renewable origin but of a different nature.
Thus, the total charge is distributed in different flows Fl, F2,..., Fn feeding the various successive catalytic zones. An addition of hydrogen-rich gas may optionally be injected upstream of the first catalytic zone ZI as well as between the catalytic zones Zn and Zn + 1 according to the first. The flow of charge F1, which may optionally be supplemented with a supplement of gas containing hydrogen, is mixed with a stream of liquid and gaseous recycle streams (RL1 and RG1) preferably before said flow of charge F1 is sent into the first zone. catalytic ZI, or directly in the first catalytic zone ZI. Similarly, the flow of charge (F2) optionally supplemented with an additional gas containing hydrogen is mixed with a stream of liquid recycle RL2 and optionally gaseous RG2 in the case where 100% of the mass flow rate of hydrogen used in the hydrotreating process is not sent to the first catalytic zone ZI and so on until the n-th catalytic zone.
Similarly, the partial feed streams injected into the catalytic zones downstream of the first zone F2 to Fn, possibly supplemented with a supplement of gas containing hydrogen, and mixed with the corresponding liquid recycle streams RL2 to RLn. and optionally to the gaseous recycle streams RG2 to RGn, are mixed with the compounds from the preceding catalytic zones, preferably in zones of mixtures, between said catalytic zones. Said partial feed streams can also optionally be directly sent to the mixing zones between the catalytic zones before mixing.
The flows entering the second catalytic zone are therefore: the charge injected at the zone inlet Z2 (F2), such that the mass ratio F2 / F is greater than or equal to the mass ratio F1 / F, the liquid recycle injected at the inlet zone Z2 (RL2), composed almost exclusively of paraffinic hydrocarbons, - the gaseous recycle injected at the entry of zone Z2 (RG2), composed mainly of hydrogen, including a possible addition of gas containing hydrogen also accounted for in RG2, - the flows from the catalytic liquid and gaseous zone coming from catalytic zone 1: (RL1 + RG1 + F1 in mass flow): - RL1 being the liquid recycle injected at zone inlet Z1, composed almost exclusively of paraffinic hydrocarbons and having passed through zone Z1, - RG1 being the gaseous recycle injected at zone Z1 input, composed mainly of unreacted hydrogen in zone Z1, F1 corresponding to the hydrotreated effluent formed by the conv ersion of the charge in zone ZI, considering that the operating conditions applied make it possible to obtain 100% conversion of the charge in each catalytic zone. The liquid hydrocarbons present in this effluent are free of oxygen and almost exclusively paraffinic hydrocarbons.
Before introduction into the hydrotreatment process, the temperature of the partial feed streams F1, F2,..., Fn is advantageously less than 150 ° C. It must be sufficient to allow a sufficient lowering of viscosity and thus an adequate transfer of the storage tanks to the reaction section of the hydrotreatment. It is neither useful nor desirable to raise the temperature of the feed to higher values in the absence of hydrogen, so as to avoid any degradation of the loads as a result of polymerization and hence coking for example and to control the inlet temperature of the catalytic zones following the first.
Similarly, the temperature of the gaseous recycle RG1 to RGn injected, optionally mixed with additional hydrogen at the inlet of the catalytic zones ZI to Zn predominantly composed of hydrogen, which is mixed with the partial flows of charge, is the lowest possible compatible with the operation of the process, since it is advantageous for the process to mix the feedstock with hydrogen at low temperature, so as to lower the temperature by quenching effect applied to the hydrocarbon products leaving the process. different catalytic zones.
The temperature of the total flow (liquid-gaseous) injected at the inlet of the catalytic zone ZI (charge + recycle liquid -i-recycle gas -i- optionally H2 make-up) must be carefully adjusted.
However, since the hydrodeoxygenation and / or decarboxylation reactions occurring in the catalytic zones are exothermic, the temperature increases as the charge is transformed in the different catalytic zones.
Preferably, the inlet temperature of the first catalytic zone ZI is greater than 180 ° C., preferably greater than 200 ° C., and the temperature at the outlet of said first zone is preferably less than 350 ° C., preferably less than 320 ° C, and preferably less than 300 ° C.
The temperature at the inlet of each of the catalytic zones according to the first must also be controlled so that the temperature of the mixture at the outlet of a preceding catalytic zone is not too high so as to avoid secondary reactions such as polymerization, cracking and deactivation of the catalyst.
The temperatures at the inlet of the catalytic zones following the first may advantageously be greater than that at the inlet of the preceding zone, generally less than 300 ° C. and preferably less than 280 ° C.
The temperature at the outlet of at least one catalytic zone following the first is preferably greater than 260 ° C, preferably greater than 280 ° C. The temperatures at the outlet of each of the following catalytic zones are preferably less than 400 ° C, and more preferably less than 380 ° C, and more preferably less than 350 ° C. Generally, a temperature difference between the outlet and inlet temperature of each catalytic zone of between 1 and 80 ° C, preferably between 20 and 78 ° C, preferably between 25 and 75 ° C is maintained.
The partial flows of charge F2 to Fn, supplemented with liquid recycles RL2 to RLn and gas recycles RG2 to RGn, injected into the catalytic zones located downstream of the first catalytic zone ZI, in which they mix with the hydrotreated effluent from of zone n-1, allow a lowering of the temperature of the hydrotreated product formed and therefore a control of the inlet temperature of the next catalytic zone. The same families of reactions occur in the Zn zone and the Zn-1 zone, with a slightly faster kinetics in the Zn-1 zone due to a higher average temperature.
According to a preferred variant, the partial flow control valves for charge, liquid recycle and gas containing hydrogen can be controlled by the temperature values at the inlet of the first catalytic zone and the outlet temperature difference. and entering each catalytic zone so as to adjust the partial flows of charge and hydrogen as well as the flow of the liquid recycle during operation. Similarly, temperature control can be achieved by varying the temperature of the feed and / or injected hydrogen and / or liquid and gaseous recycle. In this way the desired temperature at the inlet of the catalytic zones and / or the temperature delta in the catalytic zones is maintained and preferably the rising temperature profile in the catalytic zones is adjusted.
According to the invention, at least a portion of said liquid fraction containing the paraffinic hydrocarbons is recycled to the first catalytic zone and the following catalytic zones so that the local recycling rate on each of the beds, that is to say the mass ratio between the flow of said recycled liquid fraction and the partial flow of feed introduced into the catalytic zone Fn is less than or equal to 2, preferably less than or equal to 1.7, preferably less than or equal to 1.5 .
It is known that the use of a high liquid recycle rate allows better management of the exotherm and in particular a maintenance of the temperature difference between the outlet and inlet temperature of each catalytic zone in an acceptable range for the industrial exploitation of the process. Surprisingly, despite the implementation of a low liquid recycle rate, the present invention allows optimized management of the exotherm in the different catalytic zones by combining said low recycle rate and a high flow rate of hydrogen at the entrance to the first bed.
In addition, the use of a weak liquid recycle facilitates the revamping of existing units. The term "revamping" in the English terminology means the revision of the design of equipment already in operation to increase production, technical, economic and environmental performance as well as reliability.
Preferably, the local dilution ratio on each of the beds, that is to say the mass ratio between the quantity of the liquid and gaseous flows introduced into the catalytic zone n and the partial feed flow introduced into the catalytic zone Fn, is less than at 4, preferably less than 3.8, more preferably less than 3.5, most preferably less than 3, more preferably less than 2.5, and even more preferably less than 2.
According to the invention, each catalytic zone comprises at least one hydrotreatment catalyst.
The type of hydrotreatment catalysts used in the process according to the invention is well known in the prior art and may be an association of the catalysts described below. A single catalyst or several identical or different catalysts can advantageously be used in the catalytic zones. Inert solid may also be added at the top and / or bottom of the catalyst bed to ensure good hydrodynamics in the catalyst bed.
The hydrotreatment catalyst is advantageously a hydrotreatment catalyst comprising a hydro-dehydrogenating function comprising at least one metal of the VIN group, preferably chosen from nickel and cobalt, taken alone or as a mixture, preferably in combination with at least one metal. group VIB preferably selected from molybdenum and tungsten, taken alone or in mixture and a support selected from the group consisting of alumina, silica, silica-aluminas, magnesia, clays and mixtures of minus two of these minerals. This support may also advantageously contain other compounds and for example oxides selected from the group formed by boron oxide, zirconia, titanium oxide, phosphoric anhydride. The preferred support is an alumina support.
Preferably, a NiMo type catalyst is used on an alumina support.
The content of metal oxides of groups VIII and preferably of nickel oxide is advantageously between 0.5 and 10% by weight of nickel oxide (NiO) and preferably between 1 and 5% by weight of oxide of nickel. nickel and the content of metal oxides of groups VIB and preferably of molybdenum trioxide is advantageously between 1 and 30% by weight of molybdenum oxide (M0O3), preferably from 5 to 25% by weight, the percentages being expressed in% by weight relative to the total mass of the catalyst.
Said catalyst may also advantageously contain a doping element chosen from phosphorus and boron, taken alone or as a mixture with a content by weight of oxide of said doping element advantageously less than 20% and preferably less than 10% and advantageously of at least 0.001% relative to the total mass of the catalyst. As active catalysts in sulphide form, and the treated feeds generally having limited sulfur contents (less than 100 ppm by weight generally, and most often less than 50 ppm by weight), it is generally appropriate to add to set of charge streams, a sulfur compound known to those skilled in the art. This device makes it possible to retain in their sulphide form the hydrotreatment catalysts used in the present process, and thus to maintain a sufficient catalytic activity throughout the cycle.
The catalyst volume and the formulation of the catalyst (s) used in the catalytic zones of the process according to the invention are adapted so that the conversion of the charge, that is to say the rate of elimination of oxygen is almost complete and preferably complete exit from the first zone ZI and preferably in the following catalytic zones.
It would not be departing from the scope of the present invention by using in the hydrotreating step of the process according to the invention, simultaneously or successively, a single catalyst or several different catalysts in the catalytic zones.
The process according to the invention uses fixed bed reactors with trickle flow known to those skilled in the art. The reactants (filler and hydrogen) are introduced into the reactor in a downward flow co-current from the top to the bottom of the reactor. Such reactors are for example described in US Pat. No. 7,070,745.
Between each catalytic zone, it is possible to inject supplemental additional hydrogen and / or recycle hydrogen-rich gas from step b) of separation, in order to take advantage of a quenching effect (quenching). according to the Anglo-Saxon term) and to achieve the desired temperatures at the inlet of the next catalytic zone. Thus, quenching boxes can advantageously be installed between each catalytic zone, in order to ensure a better homogeneity of temperature deltas over the entire section of the reactor, and for all the catalytic zones.
In the same way, distributors are possibly preferably installed under the quenching devices between each catalytic zone, in order to guarantee a homogeneous supply of liquid and gas feed over the entire section of the reactor, and for all the catalytic zones.
However, according to a preferred variant in which 100% of the hydrogen-rich gas recycle is injected at the top of the reactor, only liquid is injected into the inter-catalyst bed zones, which considerably simplifies the design of these zones.
An advantage of the method according to the invention consists in its great flexibility, according to the origin of the load. Charges differing significantly from each other, in particular by their different degrees of unsaturation of the hydrocarbon chains, can be converted totally as well with regard to the removal of oxygen (which leads to a maximum efficiency of dilution of the charge in the next zone) with regard to the elimination of nitrogen (which allows a much better operation of the possible stage of downstream hydroisomerisation).
Optionally, the charges from renewable sources can also be treated in the process according to the invention in admixture with petroleum fractions such as gas oils, kerosenes or even petrol from petroleum refining processes. Preferably, the petroleum fractions are petroleum fillers of the middle distillate type chosen from the group consisting of gas oils and / or kerosines of direct atmospheric distillation and gas oils and / or kerosens resulting from conversion processes, or any of their mixture.
Preferably, the petroleum fractions are chosen from the group formed by atmospheric straight-run gas oils, gas oils resulting from conversion processes such as, for example, those originating from the coker, and a fixed bed hydroconversion (such as those derived from the processes). HYVAHL® for the treatment of heavy materials developed by the applicant), a catalytic cracking unit (LCO cut from the FCC) or ebullated bed hydrotreating processes (such as those derived from the H-OIL® processes). ), or solvent deasphalted oils (for example propane, butane, or pentane) coming from the deasphalting of residue under direct distillation vacuum, or residues resulting from heavy-weight conversion processes such as, for example, HYVAHL® and H-OIL®. The fillers can also advantageously be formed by mixing these various fractions. They may also advantageously contain light gas oil or kerosene cuts with a distillation profile of about 100 ° C to about 370 ° C. They may also advantageously contain aromatic extracts and paraffins obtained in the context of the manufacture of lubricating oils.
In this case, the amount of liquid recycle sent to the first catalytic zone of the hydrotreating section can be greatly reduced or even eliminated, since these petroleum feed streams lead, during their treatment with hydrogen, to heat releases. more limited than when treating renewable loads with significant amounts of oxygen. Separation
According to the invention, the effluent containing paraffinic hydrocarbons from step a) is subjected to at least one separation step b) for separating at least one gaseous fraction and at least one liquid fraction containing the paraffinic hydrocarbons.
Said separation step advantageously also makes it possible to separate at least one liquid fraction containing water.
Said gaseous fraction separated at the end of step b) and comprising hydrogen is recycled in step a). Said gaseous fraction also advantageously comprises CO, CO2, H 2 S, light gases, and possibly water.
According to one variant, the separation can be carried out in at least two stages and preferably in a high-pressure high-temperature separator (HTHP) making it possible to separate a gaseous fraction comprising hydrogen, CO, CO2, H2S, gases light and a large part of the water formed during the hydrodeoxygenation reactions and a liquid fraction containing the paraffinic hydrocarbons, the gaseous fraction then being sent to a high-temperature low-temperature separator so as to separate a gaseous fraction comprising hydrogen, CO, CO2, H2S, light gases and much of the water formed during the hydrodeoxygenation reactions and a liquid fraction containing the paraffinic hydrocarbons.
The high pressure high temperature separator (HTHP) preferably operates without significant reduction of pressure with respect to the pressure in the hydrotreating reactor, ie at a pressure such that the pressure of the separation is not less than the pressure in the hydrotreating step minus 1 MPa, and at a temperature between 145 ° C and 360 ° C and preferably between 150 and 300 ° C. Said high pressure high temperature separation (HTHP) makes it possible to separate a gaseous fraction comprising hydrogen, CO, CO2, HaS, light gases and a large part of the water formed during the hydrodeoxygenation reactions and a liquid fraction containing the paraffinic hydrocarbons.
In the case where the separation step b) is carried out in at least two stages, a step of separating the water is advantageously carried out downstream of said step b), so as to separate a gaseous fraction comprising hydrogen, CO, CO2, H2S, light gases, a liquid fraction comprising water and a liquid fraction including paraffinic hydrocarbons. Said step of separating the water is advantageously carried out according to the methods known to those skilled in the art and preferably in a low temperature high pressure separator. The separation of the water in a high-pressure low-temperature separator may optionally be followed by a separation step in a low-pressure low-temperature separator.
Said gaseous fraction comprising hydrogen can then advantageously be recycled in step a).
According to another variant, the separation step b) is carried out in two stages, the first separation being carried out in a high-pressure low-temperature separator (LTHP), preferably without significant reduction of pressure with respect to the pressure in the reactor. hydrotreatment, that is to say at a pressure such that the pressure of the separation is not less than the pressure in the hydrotreating step minus 1 MPa, said first step operating at a temperature between 25 ° C. and 200 ° C., preferably between 50 and 150 ° C. and at a pressure of between 0.1 and 15 MPa and preferably between 2 and 10 MPa, the second separation being carried out in a low-temperature low-pressure separator (LTLP) at a temperature of between 25 ° C and 200 ° C and preferably between 50 and 150 ° C and at a pressure between 0.1 and 8 MPa and preferably between 0.5 and 5MPa. The first separation step (LTHP) makes it possible to separate a gaseous fraction comprising hydrogen, CO, CO2, H2S, and light gases freed from water, a liquid fraction comprising water and a liquid fraction. containing paraffinic hydrocarbons.
Said gaseous fraction comprising hydrogen can then advantageously be recycled in step a).
The purpose of this step is to separate the water from the liquid hydrocarbon effluent. The elimination of water is understood to mean the elimination of the water produced by the hydrodeoxygenation (HDO) reactions and / or injected into the reaction section. The more or less complete elimination of water is advantageously a function of the water tolerance of the hydroisomerization catalyst used in the next optional step of the process according to the invention. The elimination of water can be carried out by any of the methods and techniques known to those skilled in the art, such as, for example, by drying, passing through a desiccant, flash, extraction by solvent, distillation and decantation or by combination of at least two of these methods.
The hydrogen-containing gas which has been separated during the separation step b) according to the invention and / or the optional hydroisomerisation step, is advantageously, if necessary, at least partially separated to reduce its content. in light (C1 to C4). Likewise, it advantageously undergoes one or more intermediate purification treatments, preferably at least one wash with at least one amine intended to evacuate the CO 2, preferably followed by methanation and / or pressure swing adsorption separation. (English Pressure Swing Adsorption or (PSA)), before being recycled.
It is advantageous to introduce the recycle hydrogen, preferably purified, either with the feedstock entering into the process according to the invention and / or into the optional hydroisomerization step, or in the form of quenching hydrogen between the feed beds. hydrodeoxygenation catalysts according to the invention and / or hydroisomerization.
Optionally, a final purification step of the various pollutants can be carried out by methods known to those skilled in the art such as for example by stripping with steam or nitrogen or by coalescence and / or capture mass or vacuum drying.
According to the invention, at least a portion of said liquid fraction containing the paraffinic hydrocarbons is recycled to the first catalytic zone and to the following catalytic zones with the recycle and dilution rates as described above, mixed with the flows corresponding partial charges.
The portion of the liquid effluent that is not recycled to be added to the partial stream of injected feed F1 to Fn as liquid recycle can advantageously be sent either directly to the fuel pool to be incorporated into the diesel fuel pool, or directly in an optional step hydroisomerization (HIS), in order to produce kerosene and / or gas oil bases with improved cold properties.
Hvdroisomérisation
According to a preferred embodiment, at least part of the liquid fraction containing the paraffinic hydrocarbons obtained at the end of the separation step b) is hydroisomerized in the presence of a hydroisomerization catalyst.
Thus, the optional hydroisomerization step of the process according to the invention advantageously operates at a temperature of between 150 ° C. and 500 ° C., preferably between 150 ° C. and 450 ° C., and very preferably between 200 ° C. C and 450 ° C, more preferably between 250 ° C and 400 ° C at a pressure between 1 MPa and 10 MPa, preferably between 2 MPa and 9 MPa and very preferably between 3 MPa and 7 MPa, at a space velocity hourly advantageously between 0.1 h-1 and 10 h-1, preferably between 0.2 and 7 h-1 and very preferably between 0.5 and 5 h-1, at a flow rate of Hydrogen such that the hydrogen / hydrocarbon volume ratio is advantageously between 70 and 1000 Nm 2 / m 2 of filler, preferably between 100 and 1000 Nm 3 of hydrogen per m 2 of filler and very preferably between 150 and 1000. Nm 2 of hydrogen per m 2 of charge.
Said hydroisomerization step may operate counter-current or co-current and preferably co-current.
The hydroisomerization catalysts used are advantageously of the bifunctional type, that is to say that they have a hydro / dehydrogenating function and a hydroisomerizing function and advantageously comprises at least one metal of the VIN group chosen from active platinum and palladium. in their reduced form and nickel and cobalt preferably used in their sulfurized form and / or at least one Group VIB metal selected from molybdenum or tungsten as a hydrodehydrogenating function and at least one molecular sieve or an amorphous mineral support as a hydroisomerizing function.
In the case where the hydroisomerization catalyst comprises at least one noble metal of the VIN group, the total noble metal content of the hydroisomerization catalyst is advantageously between 0.01 and 5% by weight relative to the finished catalyst, so preferred between 0.02 and 4% by weight and very preferably between 0.005 and 2% by weight.
In the case where the hydroisomerisation catalyst comprises at least one group VIB metal in combination with at least one group VIII non-noble metal, the group VIB metal content of the hydroisomerization catalyst is advantageously comprised, in oxide equivalent, between 5 and 40% by weight relative to the finished catalyst, preferably between 10 and 35% by weight and very preferably between 15 and 30% by weight and the metal content of group VIII of said catalyst is advantageously included, oxide equivalent, between 0.5 and 10% by weight relative to the finished catalyst, preferably between 1 and 8% by weight and very preferably between 1.5 and 6% by weight. Preferably, the hydroisomerization catalyst comprises NiW.
According to a preferred embodiment, said hydroisomerization catalyst comprises at least one amorphous mineral support as a hydroisomerizing function, said amorphous mineral support being chosen from fluorine and / or chlorine doped aluminas, silica-aluminas and siliceous aluminas. and preferably the silica-aluminas. Most preferably, the catalyst comprises NiW on silica-alumina.
According to another preferred embodiment, said hydroisomerization catalyst comprises at least one molecular sieve, preferably at least one zeolitic molecular sieve and more preferably at least one one-dimensional 10 MR zeolite molecular sieve as a hydroisomerizing function.
The zeolite molecular sieves are defined in the "Atlas of Zeolite Structure Types" classification, W.M. Meier, DH Oison and Ch.Berlocher, 5th revised edition, 2001, and in which reference is also made to the present application and are selected from molecular sieves. zeolites of structural type TON, such as NU-10, FER, such as ferrierite, EDO, chosen from EU-1 and ZSM-50, taken alone or as a mixture, or zeolitic molecular sieves ZSM-48, ZBM -30, IZM-1, COK-7, EU-2 and EU-11, taken alone or in admixture.
Preferably, said hydroisomerization catalyst also comprises a binder consisting of a porous mineral matrix. Said binder may advantageously be used during the shaping step of said hydroisomerization catalyst.
Fractionation The hydroisomerized effluent is then advantageously subjected at least in part, and preferably in all, to one or more separations.
The step or step of separation of the effluent from the hydroisomerization step is (are) advantageously carried out in the same manner as the step b) of separation of the hydrotreated effluent, with the same modes of production. The at least one separation step enables at least one gaseous fraction to be separated, at least one liquid fraction comprising water and at least one fraction comprising the hydrocarbons.
The fraction comprising the hydrocarbons can then advantageously undergo a fractionation step which advantageously comprises a flash separation for separating the gases from the liquid and / or a stripping column or an atmospheric distillation. Preferably the fractionation step comprises atmospheric distillation. The purpose of this step is to separate the gases from the liquid, and in particular to recover the hydrogen-rich gases that may also contain light such as the C1-C4 cut, a gasoline cut (150 ° C), and at least one cutting distillatesmoyens (150 ° C +) containing kerosene and / or diesel.
The valorization of the petrol (or naphtha) cut is not the object of the present invention, but this cut can advantageously be sent to a steam cracking unit for the production of olefins and associated hydrogen or steam reforming for the hydrogen production, or catalytic reforming for the production of gasoline. The hydrogen thus produced can be injected in step a) of hydrotreatment and / or optional hydroisomerization.
The middle distillate cutter, which represents the desired fuel bases, may comprise a cut containing gas oil and kerosene, or the two cuts may be recovered separately. These products are based on renewable sources and do not contain sulfur compounds.
At least a portion of the middle distillate cup (s) may be recycled to the hydrotreating step as a recycle.
Alternatively, at least a portion of the 150 ° C + fraction may be recycled to the hydroisomerization step. Thus, this fraction is resubmitted to isomerization which improves the cold properties.
According to another variant, at least part of the fraction 300 ° C + can be recycled in the hydroisomerization step. Thus, this fraction is resubmitted to isomerization which makes it possible to value this cut in lighter products and to improve cold properties.
According to another variant, at least part of the 150 ° C. + fraction can be recycled in the hydrotreating step.
Description of figures
FIG. 1 represents a general diagram of a process according to the invention comprising n catalytic zones.
The raw load, also called the fresh feed F, is injected into the line (1) shown in FIG. 1. The feedstock is distributed in different streams F1, F2,..., Fn feeding the various successive catalytic zones. The gaseous recycle (GR) is mixed with a hydrogen-rich gas (2). The flow (RG) (line 13) is subdivided into different streams RG1, RG2 ..RGn. The stream (17) of liquid recycle sub-divides into several streams RL1 to RLn. The feed flow F1 is mixed with a liquid and gaseous recycle stream (RL1 and RG1) via the lines (15), (16) and (17) before said feed stream F1 is sent into the first catalytic zone ZI . Thus, likewise, the feed stream (F2) is mixed with a liquid RL2 and optionally gaseous RG2 recycle stream in the case where 100% of the mass flow rate of hydrogen used in the hydrotreatment process is not sent to the first catalytic zone ZI and so on until the n-th catalytic zone. The hydrotreated effluent is withdrawn via line (11) and sent to a first separator (8) for separating a gaseous flow (20) and a paraffinic liquid flow (19), the gas flow being sent to a second separator (9). ) so as to separate a gas stream (RG) which is recycled via the pipe (13) and a liquid stream which is sent to a final separation stage (12). The separator (12) separates the water (18) and a second paraffinic liquid stream (21) and a gas stream (22), a part (R) of which is recycled via the line (16) before being subdivided divided and sent into the different catalytic zones of the reactor. The other part of the liquid flow (21) and collected and mixed in the pipe (10) to the liquid stream (19) from the separation (8) to be sent to the hydrosiomerization step (not shown in FIG. 1 ), or recycled.
FIG. 2 represents the flows entering and leaving the hydrotreatment reactor. The fresh load F is divided into different streams Fl, F2 and F3 and sent into zones ZI, Z2 and Z3, respectively. The flow of charge F1 enters the catalytic bed ZI mixed with a gaseous recycle RG1, an additional hydrogen and a liquid recycle RL1. And so on for each zone Z2 and Z3.
EXAMPLES EXAMPLE 1 (NOT CONFORMING TO THE INVENTION) Example 1 is not in accordance with the invention in that the mass flow rate of hydrogen sent to the first catalytic zone ZI represents 35% by weight of the total mass flow rate of hydrogen used. in the hydrotreatment process.
The feedstock to be treated is palm oil, the main characteristics of which are shown in Table 1a. This charge has previously undergone treatment with phosphoric acid and bleaching earth treatment according to the protocols known to those skilled in the art.
Table 1a
Characteristics of the processed filler (palm oil)
It is desired to treat 100 g / h of this feed in a hydrotreating reactor consisting of 2 catalytic beds.
Each catalytic zone consists of a catalyst bed. The catalyst used is identical in the two catalytic zones of the hydrotreating step and comprises 4% by weight of NiO, 21% by weight of MoO 3 and 5% by weight of P2O5 supported on a gamma alumina. Said catalyst has a Ni / Mo atomic ratio equal to 0.4.
The supported catalysts are prepared by dry impregnation of the precursor oxides in solution and then sulphuretted in situ prior to the test, at a temperature of 350 ° C., with the aid of a straight-run diesel fuel feed additive supplemented with 2% by weight of sulfur dimethyl disulphide (DMDS). After in situ sulphurization in the pressurized unit, the feedstock from a renewable source constituted by the palm oil described in Table 1a is sent into each of the two catalytic zones.
The catalyst preparation method does not limit the scope of the invention.
The total palm oil charge (F = 100 g / h) is divided into two streams, a flow Fl of 40 g / h injected into the zone ZI, and a second stream of 60 g / h injected into the zone Z2.
The amount of liquid recycle used is injected with the charge in the zone ZI, with a flow rate RL1 = 90 g / h.
The gas injected with the charge is integrally composed of hydrogen. This hydrogen is injected integrally with the two feed streams feeding zones ZI and Z2, with a flow rate such that, at the inlet of each of the catalytic zones, the same ratio RG1 / F1 = RG2 / F2 = 700 Nm.sup.-1 / m ^
Thus, the mass flow rate of hydrogen sent to the first catalytic zone ZI represents 35% by weight of the total mass flow rate of hydrogen used in the hydrotreatment process.
The total operating pressure is 50 bar rel (5 MPa rel).
Table 1b shows the flow rates for each of the two feed streams, as well as the liquid recycle rates and the dilution ratios for each of the two catalyst zones.
Table 1b
Operating conditions of the hydrotreating section And characteristics of the effluent produced
Complete elimination of the oxygen is obtained during this hydrotreating step. A liquid product essentially composed of hydrocarbons is obtained with a yield of 81.0% by weight. EXAMPLE 2 (COMPLIES WITH THE INVENTION)
The same feedstock as in Example 1 is treated in a hydrotreatment reactor consisting of two catalytic zones each comprising the same catalyst as in Example 1. In Example 2 compliant, the mass flow rate of hydrogen sent to the first catalytic zone ZI represents 80% by weight of the total mass flow rate of hydrogen used in the hydrotreatment process.
The same catalyst activation protocol by sulfurization is applied, and the total operating pressure is 50 bar rel (5 MPa rel).
Table 2 shows the flow rates for each of the two load streams, as well as the liquid recycle rates and the dilution ratios for each of the two catalytic zones.
The same amount of liquid product is recycled (R = 90 g / h), but unlike in Example 1, this recycle is partly sent into the catalytic zone ZI (RL1 = 72 g / h) and partly sent into the zone. catalytic Z2 (RL2 = 18 g / h). The nature and the gas flow rate recycled to the hydrotreatment reactor is identical overall to that of Example 1 (100% hydrogen, RG1 = 5.46 g / h, corresponding to a volume ratio H2 / volume reactor inlet load of 700 Nm3 / m3). This gas flow is however distributed differently, since the mass flow rate of hydrogen sent to the first catalytic zone ZI represents 80% by weight of the total mass flow rate of hydrogen.
Table 2
Operating conditions of the hydrotreating section Efficiency and characteristics of the effluent produced
EXAMPLE 3 (COMPLIES WITH THE INVENTION)
The same charge as in Example 1 is treated in a hydrotreatment reactor consisting of two catalytic zones each comprising the same catalyst as in Example 1. In Example 3, the mass flow rate of hydrogen sent to the first catalytic zone Z1 represents 100% by weight of the total mass flow rate of hydrogen used in the hydrotreatment process.
The same catalyst activation protocol by sulfurization is applied, and the total operating pressure is 50 bar rel (5 MPa rel).
Table 3 shows the flow rates for each of the two load streams, as well as the liquid recycle rates and the dilution ratios for each of the two catalytic zones.
The same amount of liquid product is recycled (R = 90 g / h), but unlike in Example 1, this recycle is partly sent into the catalytic zone Z1 (RL1 = 60 g / h) and partly sent into the zone. catalytic Z2 (RL2 = 30 g / h).
The nature and the gas flow rate recycled to the hydrotreatment reactor is identical overall to that of Example 1 (100% hydrogen, RG1 = 6.83 g / h, corresponding to a volume ratio H2 / volume reactor inlet load of 700 Nm3 / m3). This gas flow is however distributed differently, since it is integrally sent into the catalytic zone ZI.
Table 3
Operating conditions of the hydrotreating section Efficiency and characteristics of the effluent produced
Examples 1 to 3 demonstrate that the implementation of the present invention makes it possible to manage a low recycle rate in all the catalytic zones by virtue of the application of a high flow of hydrogen at the inlet of the first bed, contrary to non-compliant Example 1 in which the hydrogen is distributed on the catalyst beds uniformly and or the exotherm is not mastered, the temperature delta between the outlet and the inlet of the catalyst beds being too high.
Moreover, the good management of the exotherm in Examples 2 and 3 in accordance with the invention makes it possible to operate at a lowered average bed temperature with respect to non-compliant Example 1, which allows for a deactivation of the lower catalyst and therefore a longer catalyst life.

权利要求:
Claims (14)
[1" id="c-fr-0001]
A process for hydrotreating a feedstock from renewable sources to produce paraffinic hydrocarbons in the presence of hydrogen in a fixed bed reactor having a plurality of catalytic zones arranged in series and each comprising at least one hydrotreating catalyst in which: a) the flow of the total charge F is divided into a number of different partial flows of charge F1 to Fn equal to the number of catalytic zones n, with n integer between 1 and 10 in the reactor, the first partial flow of charge F1 being injected into the first catalytic zone ZI, the second partial feed stream F2 being injected into the second catalytic zone Z2 and so on, if n is greater than 2, the hydrotreatment process operating at a temperature of between 180 and 400 C. at a pressure of between 0.1 MPa and 15 MPa, at a space velocity of between 0.1 hr and 10 h and with a ratio of total hydrogen flow rate and the total charge rate is between 150 and 1500 Nm ^ / m 2, the mass flow rate of hydrogen to the first catalytic zone being greater than 80% by weight of the total mass flow rate of hydrogen used in the process. hydrotreatment, to produce at the output of the reactor at least one effluent containing paraffinic hydrocarbons, b) said effluent from step a) is subjected to at least one separation step for separating at least one gaseous fraction and at least one fraction liquid containing the paraffinic hydrocarbons, c) at least a portion of said liquid fraction containing the paraffinic hydrocarbons is recycled to the first catalytic zone and the following catalytic zones so that - the local recycling rate on each of the beds is the mass ratio between the flow of said recycled liquid fraction and the partial feed flow introduced into the catalytic zone Fn is less than or equal to al to 2, the local dilution ratio on each of the beds, that is to say the mass ratio between the quantity of the diluent liquid and gaseous flows introduced into the catalytic zone n and the partial flow of feed introduced into the catalytic zone. Fn is less than 4.
[2" id="c-fr-0002]
2. Method according to the preceding claim wherein the charges from renewable sources according to the invention are chosen from vegetable oils, algae or algal oils, fish oils, used cooking oils, and the original greases. plant or animal, or mixtures of such fillers, containing triglycerides and / or free fatty acids and / or esters.
[3" id="c-fr-0003]
3. Method according to one of claims 1 or 2 wherein the mass flow rate of hydrogen sent to the first catalytic zone representing more than 90% by weight of the total mass flow rate of hydrogen used in the hydrotreatment process.
[4" id="c-fr-0004]
4. The method of claim 3 wherein the total mass flow rate of hydrogen used in the hydrotreatment process is sent into the first catalytic zone ZI.
[5" id="c-fr-0005]
5. Method according to one of claims 1 to 4 wherein the local recycle rate on each of the beds that is to say the mass ratio between the flow of said recycled liquid fraction and the partial flow of charge introduced into the catalytic zone Fn is less than or equal to 1.7.
[6" id="c-fr-0006]
6. The method of claim 3 wherein the local recycle rate on each of the beds that is to say the mass ratio between the flow of said recycled liquid fraction and the partial flow of feed introduced into the catalytic zone Fn is lower. or equal to 1.5.
[7" id="c-fr-0007]
7. Method according to one of claims 1 to 6 wherein the hydrotreatment catalyst comprises a hydro-dehydrogenating function comprising at least one metal of the VIN group selected from nickel and cobalt, taken alone or as a mixture, optionally in combination with at least one Group VIB metal chosen from molybdenum and tungsten, taken alone or as a mixture and a support selected from the group formed by alumina, silica, silica-aluminas, magnesia, clays and mixtures at least two of these minerals.
[8" id="c-fr-0008]
8. Method according to one of claims 1 to 7 wherein the step b) of separation is carried out in at least two stages in a high pressure high temperature separator for separating a gaseous fraction comprising hydrogen, CO, the CO2, I'H2S, the light gases and the water formed during the hydrodeoxygenation reactions and a liquid fraction containing the paraffinic hydrocarbons, the gaseous fraction then being sent to the high-pressure low-temperature separator so as to separate a gaseous fraction comprising hydrogen, CO, CO2, H2S, light gases and water formed during the hydrodeoxygenation reactions and a liquid fraction containing the paraffinic hydrocarbons.
[9" id="c-fr-0009]
9. Process according to one of claims 1 to 7 wherein the separation step b) is carried out in two stages, the first separation being carried out in a high-pressure low-temperature separator followed by a separation step of at least part of the water formed.
[10" id="c-fr-0010]
10. Method according to one of claims 1 to 9 wherein said gaseous fraction separated at the end of step b) and comprising hydrogen is recycled in step a).
[11" id="c-fr-0011]
11. Method according to one of claims 1 to 10 wherein at least a portion of the liquid fraction containing the paraffinic hydrocarbons obtained at the end of the separation step b) is hydroisomerized in the presence of a hydroisomerization catalyst. .
[12" id="c-fr-0012]
12. The process as claimed in claim 11, wherein said hydroisomerization step operates at a temperature of between 150 ° C. and 500 ° C., at a pressure of between 1 MPa and 10 MPa, at an hourly space velocity advantageously between 0.degree. 1 h-1 and 10 h-1 at a hydrogen flow rate such that the volume ratio hydrogen / hydrocarbons is advantageously between 70 and 1000 Nm ^ / m ^ load.
[13" id="c-fr-0013]
13. Method according to one of claims 11 or 12 wherein the hydroisomerisation catalyst comprises at least one metal of group VIII selected from platinum and palladium active in their reduced form and nickel and cobalt used in their sulfurized form and / or at least one Group VIB metal selected from molybdenum or tungsten and at least one molecular sieve or an amorphous mineral support.
[14" id="c-fr-0014]
14. Method according to one of claims 11 to 13 wherein the effluent of the hydroisomerisation step is subjected to at least one separation step and at least one fractionation step to obtain a gaseous cut, a cut gasoline, and at least one middle distillate cutter containing kerosene and / or diesel.

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同族专利:

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公开号 | 公开日

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CA2937087A1|2017-01-24|

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DK3121248T3|2018-05-22|

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MY174325A|2020-04-07|

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FR3039160B1|2017-07-28|

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CN106635119B|2020-12-29|

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HUE037011T2|2018-08-28|

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CN106635119A|2017-05-10|

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EP3121248A1|2017-01-25|

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US20170022424A1|2017-01-26|

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JP2017039910A|2017-02-23|

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ES2667645T3|2018-05-14|

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EP3121248B1|2018-02-07|

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NO3121248T3|2018-07-07|

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PL3121248T3|2018-08-31|

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BR102016016875A2|2017-01-31|

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PT3121248T|2018-05-15|

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JP6872323B2|2021-05-19|

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US10190059B2|2019-01-29|

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法律状态:
2016-07-19| PLFP| Fee payment|Year of fee payment: 2 |

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2017-01-27| PLSC| Publication of the preliminary search report|Effective date: 20170127 |

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2017-07-31| PLFP| Fee payment|Year of fee payment: 3 |

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2018-07-25| PLFP| Fee payment|Year of fee payment: 4 |

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2019-07-25| PLFP| Fee payment|Year of fee payment: 5 |

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2020-07-28| PLFP| Fee payment|Year of fee payment: 6 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1557053A|FR3039160B1|2015-07-24|2015-07-24|PROCESS FOR HYDROTREATING RENEWABLE MATERIALS WITH AN OPTIMIZED GAS RECYCLE|FR1557053A| FR3039160B1|2015-07-24|2015-07-24|PROCESS FOR HYDROTREATING RENEWABLE MATERIALS WITH AN OPTIMIZED GAS RECYCLE|

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EP16305930.6A| EP3121248B1|2015-07-24|2016-07-20|Method for hydrotreating renewable materials with improved gas recycling|

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DK16305930.6T| DK3121248T3|2015-07-24|2016-07-20|PROCEDURE FOR HYDROGEN TREATMENT OF RENEWABLE MATERIALS WITH OPTIMIZED GAS RECYCLING|

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NO16305930A| NO3121248T3|2015-07-24|2016-07-20|

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ES16305930.6T| ES2667645T3|2015-07-24|2016-07-20|Hydrotreatment procedure for renewable materials with optimized gas recycling|

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HUE16305930A| HUE037011T2|2015-07-24|2016-07-20|Method for hydrotreating renewable materials with improved gas recycling|

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PL16305930T| PL3121248T3|2015-07-24|2016-07-20|Method for hydrotreating renewable materials with improved gas recycling|

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PT163059306T| PT3121248T|2015-07-24|2016-07-20|Method for hydrotreating renewable materials with improved gas recycling|

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BR102016016875A| BR102016016875A2|2015-07-24|2016-07-21|hydrotreating process of renewable materials with improved gas recycling|

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MYPI2016702649A| MY174325A|2015-07-24|2016-07-21|Process for the hydrotreatment of renewable materials, with an optimized gas recycle|

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CN201610876422.4A| CN106635119B|2015-07-24|2016-07-22|Method for hydroprocessing renewable materials with optimized gas recycle|

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CA2937087A| CA2937087A1|2015-07-24|2016-07-22|Hydrotreatment process of renewable materials with an optimized recycled gas|

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JP2016143954A| JP6872323B2|2015-07-24|2016-07-22|Hydrogenation of renewable materials with maximal gas recirculation|

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US15/217,071| US10190059B2|2015-07-24|2016-07-22|Process for the hydrotreatment of renewable materials, with an optimized gas recycle|