Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J29/166—Y-type faujasite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/084—Y-type faujasite
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/42—Catalytic treatment
  • C10G3/44—Catalytic treatment characterised by the catalyst used
  • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
  • C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/42—Catalytic treatment
  • C10G3/44—Catalytic treatment characterised by the catalyst used
  • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
  • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/42—Addition of matrix or binder particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/883—Molybdenum and nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
  • B01J29/7261—MRE-type, e.g. ZSM-48
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J29/7861—MRE-type, e.g. ZSM-48
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/20—Sulfiding
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1011—Biomass
  • C10G2300/1014—Biomass of vegetal origin
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1011—Biomass
  • C10G2300/1018—Biomass of animal origin
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4006—Temperature
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4012—Pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/06—Gasoil
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/08—Jet fuel
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• fillers include for example vegetable oils, animal fats, raw or having undergone prior treatment, as well as mixtures of such fillers.
• These fillers contain chemical structures of the triglyceride or ester or fatty acid type, the structure and the hydrocarbon chain length of the latter being compatible with the hydrocarbons present in gas oils and kerosene.
• patents include US Pat. No. 4,992,605, US Pat. No. 5,705,722, EP 1, 681, 337 and EP 1, 741, 768.
• transition metal sulphide solids allows the production of paraffins from ester-type molecules in two reaction routes: The hydrodeoxygenation 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,
• the liquid effluent resulting from these hydrotreatment processes consists essentially of n-paraffins which can be incorporated into the diesel fuel and kerosene pool.
• a hydroisomerization step is necessary to convert n-paraffins into branched paraffins having better cold properties.
• patent application EP 1 741 768 describes a process comprising a hydrotreatment followed by a hydroisomerization step in order to improve the cold properties of the linear paraffins obtained.
• the catalysts used in the hydroisomerization step are bifunctional catalysts consist of a metal active phase comprising a Group VIII metal selected from palladium, platinum and nickel dispersed on a type of acid material selected molecular sieve among SAPO-11, SAPO-41, ZSM-22, ferrierite or ZSM-23, said process operating at a temperature between 200 and 500 ° C, and at a pressure of between 2 and 15 MPa. Nevertheless, the use of this type of solid leads to a loss of yield in middle distillate.
• a catalyst for the hydroisomerization of paraffinic hydrocarbon feedstocks and in particular the hydrotreatment of feeds from a renewable source comprising an active phase containing at least one hydro-dehydrogenating element chosen from Group VIB and Group VIII elements and a support comprising at least one zeolite having at least one series of channels of which the aperture is defined by an 8-atom oxygen ring, said zeolite being modified by a particular modification process to obtain a higher activity, ie a higher conversion level, while allowing to obtain an improved yield of middle distillates (jet fuels and gas oils), the step hydroisomerization being implemented in a process for treating feedstock from a renewable source comprising upstream of said hydroisomerization step, a hydrotreating step.
• An object of the invention is therefore to provide a process for the treatment of feedstocks from a renewable source implementing, in a hydroisomerisation step, downstream of a hydrotreating step, a hydroisomerisation catalyst comprising a carrier based on of modified zeolite making it possible to obtain high yields of gasolines and kerosene bases.
• Another object of the invention is to provide a process for the treatment of feedstocks from a renewable source which, in a hydroisomerisation step, downstream of a hydrotreatment stage, uses a catalyst comprising a modified zeolite as support. to minimize the production of light fraction 150 ° C-.
• the invention relates to a process for treating charges from a renewable source comprising the following steps:
• step b) separating from the effluent from step a) hydrogen, gases and at least one hydrocarbon base,
• step b) hydroisomerization of at least a portion of said hydrocarbon base resulting from step b) in the presence of a fixed bed hydroisomerization catalyst, said catalyst comprising at least one hydro-dehydrogenating metal chosen from the group formed by the Group VIB and Group VIII metals of the Periodic Table, alone or in admixture, and a support comprising at least one zeolite having at least one series of channels, the opening of which is defined by a modified ring of 8 oxygen atoms by a ') at least one step of introducing at least one alkaline cation belonging to groups IA or IIA of the periodic table, b') a step of treating said zeolite in the presence of at least one molecular compound containing at least one at least one silicon atom, c ') at least one step of partial exchange of said alkaline cations with NH 4 + cations and d) at least one heat treatment step, said hydroisomerization step being carried out at a temperature between 150 and 500
• step d) separation, from the effluent from step c) of hydrogen, gases and at least one gas oil base and a kerosene base.
• the present invention is particularly dedicated to the preparation of gas oil and kerosene fuel bases corresponding to the new environmental standards, from charges from renewable sources.
• the feedstocks derived from renewable sources used in the present invention are advantageously chosen from oils and fats of vegetable or animal origin, or mixtures of such fillers, containing triglycerides and / or free fatty acids and / or esters.
• Vegetable oils can advantageously be crude or refined, wholly or in part, and derived from the following plants: rapeseed, sunflower, soybean, palm, palm kernel, olive, coconut, jatropha, this list not being limiting.
• Algae or fish oils are also relevant.
• Animal fats are advantageously selected from fat or fat composed of residues from the food industry or from the food service industries.
• fillers essentially contain triglyceride-type chemical structures which are also known to those skilled in the art as tri-ester of fatty acids as well as free fatty acids.
• a fatty acid ester tri is thus composed of three chains of fatty acids.
• These fatty acid chains in the form of tri-ester or in the form of free fatty acid have a number of unsaturations per chain, also called number of carbon-carbon double bonds per chain, generally between 0 and 3 but which can be higher especially for oils derived from algae, which generally have a number of chain unsaturations of 5 to 6.
• the molecules present in the feeds from renewable sources used in the present invention therefore have a number of unsaturations, expressed per molecule of triglyceride, advantageously between 0 and 18.
• the level of unsaturation expressed as the number of unsaturations by hydrocarbon fatty chain, is advantageously between 0 and 6.
• Charges from renewable sources generally also include different impurities including heteroatoms such as nitrogen.
• Nitrogen levels in vegetable oils are generally between about 1 ppm and about 100 ppm by weight, depending on their nature. They can reach up to 1% weight on particular loads.
• the feedstock may undergo before step a) of the process according to the invention a pre-treatment or pre-refining step so as to eliminate, by appropriate treatment, contaminants such as metals, such as alkaline compounds for example on ion exchange resins, alkaline earths and phosphorus.
• Suitable treatments may for example be heat and / or chemical treatments well known to those skilled in the art.
• step a) of the process according to the invention the charge, possibly pretreated, is brought into contact with a fixed-bed catalyst comprising a hydro-dehydrogenating function comprising at least one metal of group VIII and / or of the group VI B, taken alone or as a mixture and a support chosen from the group formed by alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals, said step of hydrotreater operating at a temperature between 200 and 450 ° C, preferably between 220 and 350 ° C, preferably between 220 and 320 ° C, and even more preferred between 220 and 310 ° C.
• a fixed-bed catalyst comprising a hydro-dehydrogenating function comprising at least one metal of group VIII and / or of the group VI B, taken alone or as a mixture and a support chosen from the group formed by alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of
• the pressure is between 1 MPa and 10 MPa, preferably between 1 MPa and 6 MPa and even more preferably between 1 MPa and 4 MPa.
• the hourly space velocity is between 0.1 hr-1 and 10 hr-1.
• the filler is contacted with the catalyst in the presence of hydrogen.
• the total quantity of hydrogen mixed with the feedstock is such that the hydrogen / feedstock ratio is between 70 and 1000 Nm3 of hydrogen / m.sup.3 of feedstock and preferably between 150 and 750 Nm.sup.3 of hydrogen / m.sup.3 of feedstock.
• the support of the catalyst used may also advantageously contain other compounds and for example oxides chosen from the group formed by boron oxide, zirconia, titanium oxide, phosphoric anhydride.
• the preferred support is an alumina support and very preferably alumina ⁇ , ⁇ or ⁇ .
• Said catalyst is advantageously a catalyst comprising metals of the group VIII preferably chosen from nickel and cobalt, taken alone or as a mixture, preferably in combination with at least one metal of group VI B preferably chosen from molybdenum and tungsten , taken alone or in a mixture.
• the nickel oxide is advantageously between 0.5 and 10% by weight of nickel oxide (NiO) and preferably between 1 and 5% by weight of nickel oxide and the content of metal oxides of groups VIB. and preferably molybdenum trioxide is advantageously between 1 and 30% by weight of molybdenum oxide (MoO 3 ), preferably from 5 to 25% by weight, the percentages being expressed as% by weight relative to the total mass catalyst.
• NiO nickel oxide
• MoO 3 molybdenum oxide
• the total content of metal oxides of groups VIB and VIII in the catalyst used in step a) is advantageously between 5 and 40% by weight and preferably between 6 and 30% by weight relative to the total mass. catalyst.
• the weight ratio expressed as metal oxide between metal (or metals) of group VIB on metal (or metals) of group VIII is advantageously between 20 and 1 and preferably between 10 and 2.
• Said catalyst used in step a) of the process according to the invention must advantageously be characterized by a high hydrogenating power so as to orient as much as possible the selectivity of the reaction towards a hydrogenation preserving the number of carbon atoms of the fatty chains. that is to say the hydrodeoxygenation route, this in order to maximize the yield of hydrocarbons entering the field of distillation of kerosenes and / or gas oils. This is why, preferably, one operates at a relatively low temperature. Maximizing the hydrogenating function also makes it possible to limit the polymerization and / or condensation reactions leading to the formation of coke which would degrade the stability of the catalytic performances.
• a Ni or NiMo type catalyst is used.
• Said catalyst used in step a) of hydrotreating of the process according to the invention may also advantageously contain a doping element chosen from phosphorus and boron, taken alone or as a mixture.
• Said doping element may be introduced into the matrix or preferably deposited on the support. It is also possible to deposit silicon on the support, alone or with phosphorus and / or boron and / or fluorine.
• the oxide weight content of said doping element is advantageously less than 20% and preferably less than 10% and is advantageously at least 0.001%.
• the metals of the catalysts used in step a) of hydrotreatment of the process according to the invention are sulphide metals or metal phases and preferably sulphurized metals.
• step a) of the process according to the invention can be carried out industrially in one or more reactors with one or more catalytic beds and preferably downflow of liquid.
• step b) of the process according to the invention the hydrotreated effluent from the atep a) is subjected at least in part, and preferably entirely, to one or more separations.
• the purpose of this step is to separate the gases from the liquid, and in particular to recover the hydrogen-rich gases which may also contain gases such as CO and CO 2 and at least one liquid hydrocarbon base with a sulfur content of less than 10 ppm by weight. .
• the separation is carried out according to all methods of separation known to man of career.
• the separation step may advantageously be carried out by any method known to those skilled in the art such as, for example, the combination of one or more high and / or low pressure separators, and / or distillation and / or distillation stages. high and / or low pressure stripping.
• the water that may be formed during step a) of hydrotreatment of the process according to the invention may also be advantageously separated at least in part from the liquid hydrocarbon base.
• the separation step b) may therefore advantageously be followed by an optional step of removing at least a portion of the water and preferably all of the water.
• the purpose of the optional water removal step is to remove at least a portion of the water produced during the hydrotreatment reactions.
• the elimination of water is the elimination of the water produced by the hydrodeoxygenation (HDO) reactions.
• the more or less complete elimination of the water may be a function of the water tolerance of the hydroisomerization catalyst used in the subsequent step c) of the process according to the invention.
• the elimination of water may be carried out by all methods and techniques known to those skilled in the art, for example by drying, passage on a desiccant, flash, decantation ....
• step c) of the process according to the invention at least part, and preferably all, of the liquid hydrocarbon base obtained at the end of step b) of the process according to the invention is hydroisomerized in the presence of a fixed bed hydroisomerization catalyst, said catalyst comprising at least one hydrodehydrogenating metal selected from the group consisting of the metals of the group.
• VI B and group VIII of the Periodic Table taken alone or as a mixture and a support comprising at least one zeolite having at least one series of channels, the openings of which are defined by an 8-atom ring, said zeolite being modified according to a particular method.
• the catalyst used in the hydroisomerization step c) of the process according to the invention comprises at least one hydro-dehydrogenating metal selected from the group formed by the metals of group VI II and the metals of the group VIB, alone or in combination.
• the group VIII elements are chosen from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum, taken alone or as a mixture.
• the elements of group VIII are chosen from the noble metals of group VIII, the elements of group VIII are advantageously chosen from platinum and palladium, taken alone or as a mixture.
• the elements of group VIII are selected from non-noble metals of group VIII, the elements of group VIII are advantageously chosen from iron, cobalt and nickel, taken alone or as a mixture.
• the group VIB elements of the catalyst according to the present invention are selected from tungsten and molybdenum.
• the catalyst comprises at least one Group VIB metal in combination with at least one Group VIII non-noble metal
• the Group VIB metal content is advantageously comprised, in oxide equivalent, of between 5 and 40% by weight per relative to the total mass of said catalyst, preferably between 10 and 35% by weight and very preferably between 15 and 30% by weight
• the non-noble metal content of group VIII is advantageously comprised, in oxide equivalent, between 0 , 5 and 10% by weight relative to the total mass of said catalyst, preferably between 1 and 8% by weight and very preferably between 1, 5 and 6% by weight.
• said catalyst may also advantageously comprise at least one doping element selected from the group consisting of silicon, boron and phosphorus, taken alone or as a mixture, the content of doping element being preferably between 0 and 20% by weight of oxide of the doping element, preferably between 0.1 and 15% by weight, very preferably preferred between 0.1 and 10% by weight very preferably between 0.5 and 6% by weight relative to the total mass of the catalyst.
• doping element selected from the group consisting of silicon, boron and phosphorus, taken alone or as a mixture, the content of doping element being preferably between 0 and 20% by weight of oxide of the doping element, preferably between 0.1 and 15% by weight, very preferably preferred between 0.1 and 10% by weight very preferably between 0.5 and 6% by weight relative to the total mass of the catalyst.
• the hydrogenating function comprises a group VIII element and a group VIB element
• the following metal combinations are preferred: nickel-molybdenum, cobalt-molybdenum, nickel-tungsten, cobalt-tungsten, and very preferably: nickel-molybdenum, cobalt-molybdenum, nickel-tungsten. It is also possible to use combinations of three metals such as for example nickel-cobalt-molybdenum.
• the catalyst is then preferably used in a sulfurized form.
• the catalyst When the hydro-dehydrogenating element is a noble metal of group VIII, the catalyst preferably contains a noble metal content of between 0.01 and 10% by weight, even more preferably from 0.02 to 5% by weight relative to to the total mass of said catalyst.
• the noble metal is preferably used in its reduced and non-sulphurized form.
• the metal content in its oxide form is advantageously between 0.5 and 25% by weight relative to the finished catalyst.
• the catalyst also contains, in addition to the reduced nickel, a group IB metal and preferably copper, or a group IVB metal and preferably tin in proportions such that the mass ratio of the group metal IB or IVB and nickel on the catalyst is advantageously between 0.03 and 1.
• Said hydroisomerization catalyst used in stage c) of the process according to the invention comprises a support comprising at least one modified zeolite and advantageously a porous oxide matrix of oxide type, said support comprising and preferably consisting of, preferably:
• 0.1 to 99.8% by weight preferably 0.1 to 80% by weight, even more preferably 0.1 to 70% by weight, and very preferably 0.1 to 50% by weight, weight of zeolite modified according to the invention relative to the total mass of the catalyst, 0.2 to 99.9% by weight, preferably 20 to 99.9% by weight, preferably 30 to 99.9% by weight and very preferably from 50 to 99.9% by weight, based on the total weight of the catalyst, of at least one oxide-type porous mineral matrix.
• the zeolite contained in the catalyst support used in step c) of the process according to the invention comprises at least one series of channels whose opening is defined by an 8-atom oxygen ring. (8 R) before being modified.
• Said zeolite is chosen from zeolites defined in the "Atlas of Zeolite Structure Types" classification, Ch. Baeriocher, LB Me Cusker, DH Oison, 6th Edition, Elsevier, 2007, Elsevier "exhibiting at least one series of channels whose opening of pores is defined by a ring containing 8 oxygen atoms.
• the zeolite initially used, before being modified may advantageously contain, in addition to at least one series of channels whose opening is defined by an 8-atom oxygen ring (8MR). at least one series of channels whose pore opening is defined by a ring containing 10 oxygen atoms (10 MR) and / or at least one series of channels whose pore opening is defined by a ring containing 12 oxygen atoms (12 MR).
• 8MR 8-atom oxygen ring
• the zeolite may advantageously contain at least one other element T, different from silicon and aluminum, integrating in tetrahedral form into the framework of the zeolite.
• said element T is chosen from iron, germanium, boron and titanium and represents a portion by weight of between 2 and 30% of all the constituent atoms of the zeolitic framework other than the oxygen atoms.
• the zeolite then has an atomic ratio (Si + T) / Al of between 2 and 200, preferably of between 3 and 100 and very preferably of between 4 and 80, T being defined as above.
• the zeolite contained in the support of the catalyst used in stage c) of the process according to the invention is chosen from zeolites Y, ZSM-48, ZBM-30, IZM-1 and COK-7, taken alone or in mixture.
• the zeolite is chosen from zeolites Y, ZSM-48, ZBM-30, IZM-1 and COK-7, taken alone or as a mixture.
• said zeolite is chosen from zeolites Y, ZSM-48 and ZBM-30, the ZBM 30 being preferably synthesized with the organic structuring agent triethylenetetramine, taken alone or as a mixture.
• Zeolite ZBM-30 is described in patent EP-A-46 504, and zeolite COK-7 is described in patent applications EP 1 702 888 A1 or FR 2 882 744 A1.
• Zeolite IZM-1 is described in FR-A-2 91 1 866 and zeolite ZSM 48 is described in Schlenker, JL Rohrbaugh, WJ ,, Chu, P., Valyocsik, EW and Kokotailo, GT Title: The framewrok topolgy of ZSM-48: a high silica zeolite Reference: Zeolites, 5, 355-358 (1985) Material * ZSM-48 ".
• the zeolite initially used is a FAU zeolite having a three-dimensional network of channels whose opening is defined by a ring with 12 oxygen atoms (12 MR) and even more preferably, the initial zeolite is the zeolite Y.
• said zeolite may advantageously be dealuminated in all the ways known to those skilled in the art, so that the atomic ratio of silicon to aluminum of the zeolite is between 2.5 and 200, preferably between 3 and 200. and 100 and even more preferably between 4 and 80.
• the atomic ratio of silicon to aluminum Si / Al framework of the zeolite is measured by NMR of silicon and aluminum according to a method known to those skilled in the art.
• the structural type zeolite FAU having undergone one or more dealumination steps which has a three-dimensional network of channels whose opening is defined by a ring of 12 oxygen atoms (12 MR) is suitable for the implementation of the catalyst used in the process according to the invention.
• the zeolite initially used is a dealuminated FAU zeolite and very preferably, the initial zeolite is the dealuminated Y zeolite;
• the zeolite contained in the catalyst support used in stage c) of the process according to the invention initially having, before being modified, at least one series of channels whose opening is defined by an 8-atom oxygen ring (8MR) is modified by a ') a step of introducing at least one alkaline cation belonging to groups IA or MA of the periodic table, b') a treatment step of said zeolite in the presence of at least one molecular compound containing at least one silicon atom, c ') at least partial exchange of the alkaline cations by NH 4 + cations and d) at least one heat treatment step.
• 8MR 8-atom oxygen ring
• Said initial zeolite is thus modified according to a modification process comprising at least one step a ') of introduction of at least one alkaline cation belonging to groups IA and IIA of the periodic table of the elements, the (s) said (s) cation (s) being preferably chosen from Na + , Li + , K + , Rb + , Cs + , Ba 2+ and Ca 2+ cations and very preferably, said cation being the Na + cation.
• This step can be carried out by any method known to those skilled in the art and preferably this step is performed by the so-called ion exchange method.
• the zeolite contained in the catalyst support used in step c) of the process according to the invention is in cationic form.
• the process for modifying said zeolite then comprises a treatment step b ') in the presence of at least one molecular compound containing at least one silicon atom.
• This step is called the step of selectivation of said zeolite.
• the term "selectivation" is used to mean the neutralization of the acidity of each of the crystals of the cationic zeolite.
• the neutralization of the acidity can be done by any method known to those skilled in the art. Conventional methods generally employ molecular compounds containing atoms that can interact with the zeolite crystal sites.
• the molecular compounds used in the context of the invention are organic or inorganic molecular compounds containing one or more silicon atom (s).
• the cationic zeolite prepared according to step a' is subjected to a treatment step in the presence of at least one molecular compound containing at least one silicon atom.
• Said step b ') allows the deposition of a layer of said molecular compound containing at least one silicon atom on the surface of the crystals of the zeolite which will be transformed after step c') into an amorphous silica layer on the surface of each of the crystals of the zeolite.
• the molecular compound containing at least one silicon atom is chosen from compounds of formula Si-FU and Si 2 -R 6 in which R is chosen from hydrogen, an alkyl group, an aryl group, an acyl group and an alkoxy group ( O-R '), a hydroxyl (-OH) group. or a halogen, and preferably an alkoxy (OR 1 ) group.
• R is chosen from hydrogen, an alkyl group, an aryl group, an acyl group and an alkoxy group ( O-R '), a hydroxyl (-OH) group. or a halogen, and preferably an alkoxy (OR 1 ) group.
• the group R may advantageously be either identical or different.
• the molecular compound is chosen from compounds of formula Si 2 H 6 or Si (C 2 H 5 ) 3 (CH 3 ).
• the molecular compound containing at least one silicon atom used in step b) of the process according to the invention may advantageously be a compound of silane,
• Said molecular compound used for the implementation of step b ') according to the invention preferably comprises at most two silicon atoms per molecule.
• said molecular compound has a composition of general formula Si- (OR ') 4 where R' is an alkyl, aryl or acyl group, preferably an alkyl group and very preferably an ethyl group.
• the molecular compound containing at least one silicon atom is the tetraethylorthosilicate (TEOS) molecular compound of formula Si (OCH 2 CH 3 ) 4 .
• Said step b ') of the modification process which consists in treating the cationic zeolite exchanged according to step a') in the presence of at least one molecular compound containing at least less than one silicon atom, is advantageously produced by deposition of said compound on the inner and outer surfaces of the zeolite.
• a gas phase deposit known as CVD (“Chemical Vapor Deposition") or a liquid phase deposit called CLD (“Chemical Liquid Deposition”) may be carried out by any method known to those skilled in the art.
• said step b ') is carried out by depositing said molecular compound containing at least one silicon atom in the liquid phase.
• step b ') of the modification process is carried out by gas phase deposition (CVD), it is advantageously carried out in a fixed bed reactor.
• the zeolite Prior to the gas phase deposition (CVD) reaction in said fixed bed reactor, the zeolite is preferably activated. Activation of the zeolite in the fixed bed reactor is carried out under oxygen, in air or under an inert gas, or in a mixture of air and inert gas or oxygen and inert gas.
• the activation temperature of the zeolite is advantageously between 100 and 600 ° C, and very advantageously between 300 and 550 ° C.
• the molecular compound containing at least one silicon atom to be deposited on the outer surface of each of the crystals of the zeolite is sent to the vapor phase reactor, said molecular compound being diluted in a carrier gas which may be either hydrogen ( H 2 ), either air, Argon (Ar), helium (He), or even nitrogen (N 2 j, preferably the carrier gas is an inert gas selected from Ar , He, and N 2.
• a carrier gas which may be either hydrogen ( H 2 ), either air, Argon (Ar), helium (He), or even nitrogen (N 2 j, preferably the carrier gas is an inert gas selected from Ar , He, and N 2.
• Said molecular compound containing at least one silicon atom is deposited on the outer surface of said zeolite in the vapor phase, in order to obtain an amorphous silica layer of optimum quality on the external surface of the zeolite.
• the temperature of the zeolite bed during the deposition is preferably between 10 and 300 ° C., and very preferably between 50 and 200 ° C.
• the partial pressure, in the gas phase, of the molecular compound to be deposited on the surface is preferably between 0.001 and 0.5 bar, and very preferably between 0.01 and 0.2 bar
• the duration of the deposit is preferably between 10 minutes and 10 hours and very preferably between 30 minutes and 5 hours and even more preferably between 1 and 3 hours.
• step b ') of the modification process is carried out by liquid phase deposition (CLD), it is advantageously carried out with stirring.
• a CLD phase deposition can be done either in aqueous medium or in an organic solvent.
• one or more surfactants may or may not be added to the impregnating solution.
• the CLD repository is well known those skilled in the art (Chon et al., Studies in Surface Science and Catalysis, 105, 2059-2065, 1997).
• said molecular compound containing at least one silicon atom is deposited on the outer surface of said zeolite in an anhydrous organic solvent.
• the organic solvent is advantageously chosen from saturated or unsaturated molecules containing from 5 to 10 carbon atoms, and preferably from 6 to 8 carbon atoms.
• the temperature of the organic solvent solution is preferably between 10 and 100 ° C, and very preferably between 30 and 90 ° C.
• the amount of silica added to the anhydrous solvent solution is advantageously between 0.0001 and 5% by weight, preferably between 0.0001 and 2% by weight, and even more preferably between 0.0005 and 1% by weight relative to to the amount of zeolite.
• the duration of the deposit is preferably between 5 minutes and 10 hours, preferably between 30 minutes and 5 hours and even more preferably between 1 and 3 hours.
• the process for modifying the zeolite then comprises a step c ') corresponding to at least one partial exchange, alkaline cations belonging to groups IA and IIA of the periodic table introduced during step a') and preferably Na cations. + by NH + cations.
• the exchange is 80 to 99%, preferably 85 to 98% and more preferably 90 to 98%.
• the amount of alkaline cations remaining and preferably, the amount of Na + cations remaining in the modified zeolite, relative to the amount of NH 4 + cations initially present in the zeolite, is advantageously between 1 and 20%, preferably between 1 and 5%. and 20% preferably, between 2 and 15% and more preferably between 2 and 10%.
• ion exchange (s) are carried out with a solution containing at least one ammonium salt selected from the salts of chlorate, sulfate, nitrate, phosphate, or ammonium acetate, to eliminate at least in part, the alkaline cations and preferably the Na + cations present in the zeolite.
• the ammonium salt is ammonium nitrate NH 4 NO 3 .
• the cation content of remaining alkali and preferably Na + cations in the modified zeolite at the end of step c ') is preferably such that the molar ratio alkali metal cation / aluminum and preferably the ratio molar Na / Al is between 0.2: 1 and 0.01: 1, preferably between 0.2: 1 and 0.015: 1, more preferably between 0.15: 1 and 0.02: 1 and even more preferably between 0.1: 1 and 0.02: 1.
• the desired Na / Al ratio is obtained by adjusting the NH 4 + concentration of the cation exchange solution, the cation exchange temperature, and the cation exchange number.
• concentration of the NH 4 + solution in the solution advantageously varies between 0.01 and 12 mol / l, and preferably between 1 and 10 mol / l.
• the temperature of the exchange step is advantageously between 20 and 100 ° C, preferably between 60 and 95 ° C, preferably between 60 and 90 ° C, more preferably between 60 and 85 ° C and even more preferred between 60 and 80 ° C.
• the cation exchange number advantageously varies between 1 and 10 and preferably between 1 and 4.
• Maintaining a controlled content of alkaline cations and preferably Na + cations in place of protons makes it possible to neutralize the most acidic Bnansted and Lewis sites of the zeolite. which decreases the secondary cracking of the middle distillery molecules in essence during the hydrocracking reactions. This effect makes it possible to obtain a gain in selectivity in middle distillates If the quantity of alkaline cations and preferably of Na + cations remaining in the structure of the modified zeolite is too great, the number of acidic Bransted sites decreases too much, which causes a loss of activity of the catalyst.
• the process for modifying the zeolite then comprises at least one step d) of heat treatment.
• This heat treatment allows both the decomposition of the molecular compound containing at least one silicon atom deposited on the zeolite at the end of step b ') and the transformation of the NH 4 + cations, partially exchanged at the end of step c '), in protons.
• the heat treatment according to the invention is carried out at a temperature preferably between 200 and 700 ° C, more preferably between 300 and 500 ° C.
• Said heat treatment step is advantageously carried out under air, under oxygen, under hydrogen, under nitrogen or under argon or under a mixture of nitrogen and argon.
• the duration of this treatment is advantageously between 1 and 5 hours.
• an amorphous silica layer is deposited on the surface of each of the crystals of the zeolite and the protons of the zeolite are partially regenerated.
• the support of the hydroisomerization catalyst used in stage c) of the process according to the invention advantageously contains a porous mineral matrix, preferably amorphous, which is advantageously constituted by at least one refractory oxide.
• Said matrix is advantageously chosen from the group formed by alumina, silica, clays, titanium oxide, boron oxide and zirconia.
• the matrix may consist of a mixture of at least two of the oxides mentioned above, and preferably silica-alumina. It is also possible to choose aluminates. It is preferred to use matrices containing alumina, in all these forms known to those skilled in the art, for example gamma-alumina.
• mixtures of alumina and silica mixtures of alumina and silica-alumina.
• the modified zeolite may be, without limitation, for example in the form of powder, ground powder, suspension, suspension having undergone a deagglomeration treatment.
• the modified zeolite may advantageously be slurried acidulated or not at a concentration adjusted to the final zeolite content referred to the support. This suspension commonly called a slip is then advantageously mixed with the precursors of the matrix.
• the modified zeoiite can advantageously be introduced during the shaping of the support with the elements that constitute the matrix.
• the modified zeolite according to the invention is added to a wet alumina gel during the step of forming the support.
• One of the preferred methods of forming the carrier in the present invention is to knead at least one modified zeolite with a wet alumina gel for a few tens of minutes and then pass the resulting paste through a die to form extrudates with a diameter of between 0.4 and 4 mm. .
• the modified zeoiite can be introduced during the synthesis of the matrix.
• the modified zeolite is added during the synthesis of the silicoaluminum matrix; the zeolite can be added to a mixture of an acidic alumina compound with a fully soluble silica compound.
• the support can be shaped by any technique known to those skilled in the art. The shaping can be carried out for example by extrusion, pelletizing, by the method of coagulation in drop (oil-drop), by rotating plate granulation or by any other method well known to those skilled in the art.
• At least one calcination may be performed after any of the steps of the preparation.
• the calcination treatment is usually carried out in air at a temperature of at least 150 ° C, preferably at least 300 ° C, more preferably at about 350 to 1000 ° C.
• Group VIII elements and / or Group VIB elements optionally at least one doping element chosen from boron, silicon and phosphorus and optionally the elements of groups IVB, and IB in the case of a catalyst based on reduced nickel, may be introduced, in whole or in part, at any stage of the preparation, during the synthesis of the matrix, preferably during the shaping of the support, or very preferably after the shaping of the support by any method known to those skilled in the art. They can be introduced after forming the support and after or before the drying and calcining of the support. According to a preferred embodiment of the present invention, all or part of the elements of the groups VIII and / or the elements of the group VIB, optionally at least one doping element chosen from boron, silicon and.
• phosphorus and optionally the elements of groups IVB, and IB in the case of a reduced nickel-based catalyst can be introduced during the shaping of the support, for example, during the kneading step of the zeolite modified with a wet alumina gel.
• all or part of the elements of groups VIII, optionally at least one doping element chosen from boron, silicon and phosphorus and optionally the elements of groups IVB, and IB in the case of a reduced nickel-based catalyst can be introduced by one or more impregnation operations of the shaped and calcined support, by a solution containing the precursors of these elements.
• the support is impregnated with an aqueous solution.
• the impregnation of the support is preferably carried out by the "dry" impregnation method well known to those skilled in the art.
• the following doping elements boron and / or silicon and / or phosphorus can be introduced into the catalyst at any level of the preparation and according to any technique known to those skilled in the art.
• the metals of group VIII are preferably introduced by one or more impregnation operations of the shaped and calcined support, and after those of group VIB or at the same time as the latter, in the case where said catalyst contains at least one Group VIII metal in combination with at least one Group VIB metal.
• oxides and hydroxides, molybdic and tungstic acids and their salts in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, ammonium tungstate, phosphomolybdic acid, phosphotungstic acid and their salts, silicomolybdic acid, siiicotungstic acid and their salts.
• oxides and hydroxides, molybdic and tungstic acids and their salts in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, ammonium tungstate, phosphomolybdic acid, phosphotungstic acid and their salts, silicomolybdic acid, siiicotungstic acid and their salts.
• Oxides and ammonium salts such as ammonium molybdate, ammonium heptamolybdate and ammonium tungstate are preferably used.
• non-noble group VIII elements that can be used are well known to those skilled in the art.
• non-noble metals use will be made of nitrates, sulphates, hydroxides, phosphates, halides, for example chlorides, bromides and fluorides, carboxylates, for example acetates and carbonates.
• the noble element sources of group VIII which can advantageously be used are well known to those skilled in the art.
• halides are used, for example chlorides, nitrates, acids such as hexachloroplatinic acid, hydroxides, oxychlorides such as ammoniacal oxychloride ruthenium. It is also advantageous to use cationic complexes such as ammonium salts when it is desired to deposit the metal on the Y-type zeolite by cation exchange.
• the noble metals of group VIII of the catalyst of the present invention may advantageously be present in whole or in part in metallic and / or oxide form.
• the element (s) promoter (s) chosen (s) in the group formed by silicon, boron and phosphorus can advantageously be introduced by one or more impregnation operations with excess solution on the calcined precursor.
• the boron source may advantageously be boric acid, preferably orthoboric acid H3B03, biborate or ammonium pentaborate, boron oxide, boric esters.
• Boron may for example be introduced in the form of a mixture of boric acid, hydrogen peroxide and a basic organic compound containing nitrogen such as ammonia, primary and secondary amines, cyclic amines, compounds of the family of pyridine and quinolines and compounds of the pyrrole family. Boron may be introduced for example by a boric acid solution in a water / alcohol mixture.
• the preferred phosphorus source is orthophosphoric acid H 3 PO 4, but its salts and esters such as ammonium phosphates are also suitable.
• the phosphorus may for example be introduced in the form of a mixture of phosphoric acid and a basic organic compound containing nitrogen such as ammonia, primary and secondary amines, cyclic amines, compounds of the family of phosphorus. pyridine and quinolines and compounds of the pyrrole family.
• ethyl orthosilicate Si (OEt) 4 siloxanes, polysiloxanes, silicones, silicone emulsions, halide silicates, such as ammonium fluorosilicate (NH4) 2SiF6 or fluorosilicate. sodium Na2SiF6.
• Silicomolybdic acid and its salts, silicotungstic acid and its salts can also be advantageously employed.
• Silicon may advantageously be added for example by impregnation of ethyl silicate in solution in a water / alcohol mixture. Silicon can be added, for example, by impregnating a silicon-type silicon compound or silicic acid suspended in water.
• The. Group IB element sources that can be used are well known to those skilled in the art.
• copper sources Cu (N0 3 ) 2 copper nitrate can be used.
• the sources of Group IVB elements that can be used are well known to those skilled in the art.
• tin chloride SnCl 2 can be used .
• the catalysts used in the process according to the invention advantageously have the form of spheres or extrudates. It is however advantageous that the catalyst is in the form of extrudates with a diameter of between 0.5 and 5 mm and more particularly between 0.7 and 2.5 mm.
• the shapes are cylindrical (which can be hollow or not), cylindrical twisted, multilobed (2, 3, 4 or 5 lobes for example), rings.
• the cylindrical shape is preferably used, but any other shape may be used.
• the catalysts according to the invention may optionally be manufactured and used in the form of crushed powder, tablets, rings, balls, wheels. According to the invention, the metals of group VIB and / or group VIII of said catalyst are present in sulphide form, the sulphurization treatment being described below.
• the noble metal contained in said hydroisomerization catalyst should advantageously be reduced.
• One of the preferred method for reducing the metal is treatment under hydrogen at a temperature between 150 ° C and 650 ° C and a total pressure between 1 and 250 bar
• a reduction consists of a stage at 150 ° C for two hours and a rise in temperature up to 450 ° C at the speed 1 ° C / min and then a two-hour stage at 450 ° C.
• the hydrogen flow rate is 1000 normal m 3 hydrogen / m 3 catalyst and the total pressure is kept constant at 1 bar. Any ex-situ reduction method can advantageously be considered.
• step c) of hydroisomerization of the process according to the invention at least a portion of the hydrocarbon base resulting from step b) is brought into contact, in the presence of hydrogen with said hydroisomerization catalyst, with temperatures and pressures. operatives advantageously to achieve a hydroisomerization of the non-converting load.
• the hydroisomerization is carried out with a conversion of the fraction 150 ° C + fraction 150 ° C less than 20% by weight, preferably less than 10% by weight and very preferably less than 5% by weight .
• step c) of hydroisomerization of the process according to the invention operates at a temperature of between 150 and 500 ° C., preferably between 150 ° C. and 450 ° C., and very preferably between 200 and 450 ° C, at a pressure of between 1 MPa and 10 MPa, preferably between 2 MPa and 10 MPa and very preferably between 1 MPa and 9 MPa, at an hourly space velocity 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 "
• the hydrogen / hydrocarbon volume ratio is advantageously between 70 and 1000 Nm 3 / m 3 of filler, between 100 and 1000 normal m 3 of hydrogen per m 3 of filler and, preferably, between 150 and 1000 normal m 3 of hydrogen per m 3 of charge.
• the optional hydroisomerization step operates cocurrently.
• the amount of alkali cation belonging to groups IA or MA of the periodic table and preferably the amount of alkaline cation Na + , remaining in the modified zeolite after the modifying treatment described above is measured by atomic adsorption according to a known method of the invention. skilled person.
• the acidity of Lewis and Bransted zeolites is measured by Pyridine adsorption followed by infra-red spectroscopy (FTIR).
• FTIR infra-red spectroscopy
• the diesel base obtained is of excellent quality:
• the total aromatic content is less than 5% by weight, and polyaromatics content of below 2% weight.
• ⁇ the cetane number is excellent, higher than 55.
• the density is less than 840 kg / m 3 , and most often less than 820 kg / m 3 .
• Its kinematic viscosity at 40 ° C is 2 to 8 mm 2 / s.
• the kerosene obtained has the following characteristics: ⁇ density between 775 and 840 kg / m 3
• 100 g of dealuminated HY zeolites with a Si / Al ratio of 11.5 and measured by NMR of silicon and aluminum are exchanged with a solution of NaN0 3 to obtain the cationic NaY form of the Y zeolite.
• the exchange is carried out in a flask containing 1 L of NaNO 3 solution at 80 ° C for 2 hours, then the suspension is filtered and the zeolite is dried at 120 ° C overnight.
• the NaY zeolite obtained is poured into a three-necked flask containing 1 L of anhydrous toluene and equipped with a refrigerant.
• the amount of TEOS tetraethylorthosilicate molecular compound corresponding to 1% by weight of silica is introduced slowly into the zeolite suspension using a syringe pump. After stirring for 1 hour, the suspension is filtered and the zeolite dried at 120 ° C overnight. The modified zeolite is then exchanged 3 times with a 1 N solution of NH 4 NO 3 to obtain the partially exchanged NH form, the exchange being carried out at a temperature of 80 ° C.
• the decomposition of TEOS and the transformation of NH 4 + cations into protons is carried out under N 2 saturated with H 2 O at 350 ° C.
• Unmodified HY zeolite which is not in accordance with the invention is called a dealuminated HY zeolite exchanged with an NH 4 NO 3 solution to obtain the cationic form of the zeolite Y but not modified according to the modification method described according to the invention.
• the catalyst supports according to the invention containing the modified or unmodified zeolites are manufactured using 19.5 g of zeolite mixed with 80.5 g of a matrix composed of ultrafine tabular boehmite or alumina gel marketed under the name SB3 by Condisputeda Chemie Gmbh. This powder mixture is then mixed with an aqueous solution containing nitric acid at 66% by weight (7% by weight of acid per gram of dry gel) and then kneaded for 15 minutes. The kneaded paste is then extruded through a die 1, 2 mm in diameter. The extrudates are then calcined at 500 ° C. for 2 hours in air.
• the carrier extrudates thus prepared are dry impregnated with a solution of a mixture of ammonium heptamolybdate and nickel nitrate and calcined in air at 550 ° C. in situ in the reactor.
• the weight contents of catalyst oxides obtained are shown in Table 2.
• hydrotreated hydrocarbon effluent obtained at the end of step b / is hydroisomerized with hydrogen lost in a hydroisomerisation reactor under the operating conditions below:
• VVH load volume / catalyst volume / hour
• the reaction temperature is set so as to reach a gross conversion (denoted by CB) equal to 70% by weight.
• the charge thus prepared is injected into the hydroisomerisation test unit which comprises a fixed-bed reactor with up-flow of the charge ("up-flow") into which 100 ml of catalyst is introduced.
• the catalyst is sulphurized with a straight-run diesel / DMDS and aniline mixture up to 320 ° C. It should be noted that any in situ or ex situ sulphurization method is suitable. Once the sulphurization is complete, the charge can be transformed.
• the operating conditions of the test unit are indicated above.
• the yield of jet fuel (kerosene, 150-250 ° C. cut, below Yt Kero) is equal to the weight percentage of compounds having a boiling point of between 150 and 250 ° C. in the effluents.
• the diesel yield (250 ° C + cut) is equal to the weight percentage of compounds having a boiling point greater than 250 ° C in the effluents.
• the " temperature of 300 ° C. is adjusted so as to have a conversion of the fraction 150 ° C + fraction 150 ° C " less than 5% by weight during hydroisomerization in the case where the hydroisomerization catalyst used in step c) of the process according to the invention contains the zeolite modified according to the invention.
• Table 3 we have reported the temperature yields of kerosene and diesel for the catalysts described in the examples above. Table 3: Catalytic Activities of Catalysts in Hydroisomerization.
• the process employing a catalyst containing an unmodified zeolite results in the production of a light cut at 150 ° C at a yield of 13% and thus the production of middle distillates at a lower yield per hour. report to the of a work of a catalyst containing a zeolite modified according to the invention.
• the method according to the invention thus demonstrates that the catalyst containing a zeolite modified according to the invention and used in said process according to the invention is more active than the non-compliant catalysts to obtain a conversion level of the fraction 150 ° C + less than 5% by weight, while making it possible to obtain higher average distillate yields, and thus a better selectivity for middle distillates, with respect to a hydroisomerization process using a non-compliant catalyst containing an unmodified or modified zeolite in a manner not in accordance with the invention.

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