Classifications

• • 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
• • 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
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
  • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
  • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
  • B01J8/0476—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more otherwise shaped beds
  • B01J8/0488—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more otherwise shaped beds the beds being placed in separate reactors
• • 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
• • 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
  • C10G3/42—Catalytic treatment
  • C10G3/44—Catalytic treatment characterised by the catalyst used
  • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
• • 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
  • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
  • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
• • 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/60—Controlling or regulating the processes
• • 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
  • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
  • C10G49/002—Apparatus for fixed bed hydrotreatment processes
• • 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
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
  • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
  • C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
  • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
  • C11C3/126—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on other metals or derivates
• • 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00002—Chemical plants
  • B01J2219/00004—Scale aspects
  • B01J2219/00006—Large-scale industrial plants
• • 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
  • C10G2300/10—Feedstock materials
  • C10G2300/1022—Fischer-Tropsch products
• • 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
  • C10G2300/1074—Vacuum distillates
• • 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
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/80—Additives
  • C10G2300/805—Water
• • 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
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel
• • 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

• the invention relates to a process for the hydrotreatment of a diesel fuel charge, a hydrotreatment unit for carrying out said process, and a corresponding hydrorefining unit.
• the desired bases are therefore light bases, with low sulfur content, high cetane number, and distilling completely before 360 ° C.
• the objectives are to further reduce the sulfur content to a value of less than 10 mg / kg by 2009 and to increase the minimum value of the cetane engine.
• One solution for improving the cetane number is to add a procetane additive. It is most often of alkyl nitrates which intervene in the elementary stages of oxidation before the self-ignition of the mixture. They reduce the ignition time and increase the cetane number by 3 to 5 points depending on the amount added.
• Another solution is to add to the mixture a substitute fuel, such as a biofuel, because the vegetable oil esters generally have a good cetane number.
• a substitute fuel such as a biofuel
• the European Directive 2003/30 / EC aims in particular to promote the use of biofuels.
• the European community has adopted a 5.75% biofuel fuel (fuel burn) target for fuel in 2010. That is, the amount of biofuel present in the mixture must provide 5.75% of the mixture's PCI.
• EMC rapeseed oil methyl ester
• the mixtures obtained from vegetable oil methyl esters have the advantage of a cetane conforming to the standard, but they pose problems of cold resistance and oxidation stability. In addition, these mixtures are too heavy and have a density much higher than the specification of the standard, which causes formulation difficulties at high incorporation rates.
• the patent application EP 1 693 432 describes a process for hydrotreating a mixture of a charge of petroleum origin and a charge of biological origin.
• the treatment of such a mixture of petroleum and biological feedstock at the top of the reactor causes a drop in the hydrogen partial pressure and therefore a decrease in the catalytic activity in hydrotreatment of the petroleum charge.
• parallel reactions during hydropowering of triglycerides lead to the production of gases such as carbon dioxide CO2, methane CH 4 , and carbon monoxide CO which is considered a reversible inhibitor of desulphurizing activity. catalyst.
• the applicant has proposed in its French patent application 06.06892, a process for the hydrotreatment of a mixture of a charge of petroleum origin of diesel type and a load of biological origin of the vegetable oils and / or animal fats type. without liquid effluent recycle device at the reactor head.
• This mixture is introduced at the reactor head, in the manner of a usual charge.
• the process described in this application in one of its variants, comprises a unit for separating and treating carbon monoxide present in the recycle gases.
• the invention proposes a process for the catalytic hydrotreatment of a fuel of petroleum origin of diesel type and of a feed of biological origin based on vegetable oils and / or animal fats in a unit of hydrotreating, characterized in that said hydrotreatment unit comprises at least one hydrotreating reactor operating against the current.
• the subject of the invention is also a hydrotreating unit for implementing said method, and a corresponding hydrorefining unit.
• charge of biological origin is intended to mean any renewable charge commonly defined by the term biomass.
• HDO triglyceride oxygenation
• the gases formed due to the HDO reactions of the triglycerides are removed by the countercurrent flow of gas, thus avoiding the CO 2 and CO 2 inhibition effect. dilution effect of hydrogen by the gases formed.
• the hydrorefining reactions of the petroleum fraction thus take place under favorable conditions where the partial pressure of hydrogen is higher. This also makes it possible to obtain very low levels of sulfur, since the heavier and most refractory sulfur molecules, which are generally the most difficult and the longest to be desulphurized, are found at the bottom of the reactor at a partial pressure. higher hydrogen, and are more easily desulfurized.
• there is no H 2 S and other elements harmful to the reaction which facilitates all the more, the desulfurization of these molecules refractory.
• the process according to the invention also minimizes the residence time in the CO reactor formed in the HDO reaction, which limits methanation reactions of CO to produce CH4. Hydrogen consumption is therefore reduced, and the overall exothermicity of the reaction is lower.
• Another advantage of the invention is that since the processing of the biologically based feeds based on vegetable and / or animal oils is highly exothermic, it requires a means of controlling the reaction temperature such as the use of a volume. important dilution. As a result, up to now, these vegetable and / or animal oils have been processed in dedicated units with high liquid effluent recycling. It is thus possible to limit or even eliminate the recycling of liquid effluent by using the process according to the invention compared with known processes for refining a feedstock of biological origin alone, since the feedstock of biological origin is either injected with the charge of petroleum origin, or downstream of the injection thereof, so that it is always diluted.
• the hydrotreatment unit comprises a single countercurrent reactor in which the charges of petroleum and biological origin are injected.
• the two charges are injected at the top of the reactor.
• the charge of petroleum origin is injected at the head of the reactor, whereas the charge of biological origin is, as for it, injected downstream of it.
• the feedstock of biological origin is injected, in part, at the reactor head, such as the feedstock of petroleum origin, and partly downstream of it.
• CoMo for the hydroprocessing zone of the oil cut and preferably NiMo for the second zone treating the triglycerides.
• This variant has the advantage of allowing the use of an existing hydrotreatment unit in which an entry for the charge of biological origin will have been added.
• the hydroprocessing unit comprises two separate reactors, a first reactor operating in cocurrent and a second reactor operating in countercurrent and receiving the liquid effluent leaving the first reactor, the petroleum feed being injected. in the first cocurrent reactor, and the feedstock of biological origin being injected into the first cocurrent reactor and / or into the second countercurrent reactor mixed with the liquid effluent exiting the first reactor.
• the feedstock of petroleum origin is injected at the top of the first cocurrent reactor and the charge of biological origin is injected at the head of the second reactor in countercurrent, mixed with the liquid effluent leaving the first reactor.
• the feedstock of biological origin is also possible for the feedstock of biological origin to be injected, in part, into the first co-current reactor downstream of the feed of petroleum origin, and partly, at the head of the second countercurrent reactor. mixing with the liquid effluent leaving the first reactor.
• This variant has the advantage of allowing the treatment of the feedstock of biological origin at a temperature lower than the treatment temperature of the feedstock of petroleum origin.
• the hydrotreatment of the feedstock of biological origin can be done at a lower temperature, so that it is not necessary to heat the feed much to treat it.
• a large part of the hydrotreating treatment of the petroleum feed has already taken place in the first reactor, the second reactor then allows the hydrofinishing of the treatment of the petroleum feedstock and does not require such high temperatures. This hydrofinishing makes it possible to obtain sulfur content much lower compared to the levels usually obtained in hydrorefining.
• This lower temperature in the second countercurrent reactor also makes it possible to limit any problems related to the thermal stability of the feedstock of biological origin, in particular when the liquid effluent leaving the first reactor is cooled prior to its mixing. with the charge of biological origin.
• the countercurrent configuration makes it possible to obtain a further hydrogenation of the aromatic compounds due to a greater hydrogen partial pressure at the bottom of the reactor and a lower operating temperature.
• This allows a substantial improvement in the cetane of the final product, which is all the more important when the introduced petroleum feed comprises cuts of high aromatic content, such as those from FCC units or coking.
• the diesel-type feedstock is chosen from diesel fuel cuts derived from the distillation of a crude oil and / or a synthetic crude resulting from the treatment of oil shale or heavy crude oils and extra-heavy or of the effluent from the Fischer Tropsch process, the diesel fuel cuts resulting from different conversion processes, in particular, those resulting from catalytic and / or thermal cracking (FCC, coking, visbreaking).
• FCC catalytic and / or thermal cracking
• the charge of biological origin based on vegetable oils and / or animal fats is introduced up to a level of 30% by weight. More particularly, the level of biological filler based on vegetable oils and / or animal fats is preferably less than or equal to 15% by weight.
• the introduction of such a load rate of biological origin only slightly affects the cold properties of the final product.
• the cloud point of the final effluent generally only has a difference of 1 ° C with respect to the effluent obtained without injection of biomass. This result, which differs from what the mixtures laws would have predicted, is very interesting because it demonstrates the synergy, during the process according to the invention, between the two types of charges.
• the vegetable or animal oils contained in the feed of biological origin used according to the invention are mainly composed of triglycerides of fatty acids (> 90% by weight), whose chain lengths depend on the nature of the oil used. They may also contain fatty acids. For the purposes of the invention, vegetable oils and animal fats may also contain fatty acid esters.
• vegetable oils and animal fats can be used raw. But they are preferentially refined in order to avoid fouling of the processing unit. In this case, we speak of degummed oils, that is to say after removal of a large part of the phospholipids.
• Vegetable oils can in particular be palm oil, soybean oil, rapeseed oil, sunflower oil, linseed oil, oil of rice bran, corn oil, olive oil, castor oil, sesame oil, pine oil, peanut oil, palm kernel oil, lemon coconut oil, babasu oil, seaweed oil or a mixture of two or more of these oils. These oils will produce essentially C 12 to C 18 paraffins.
• Palm oil is particularly preferred because it is one of the oils with the carbon chains closest to the average length of the carbon chains of a diesel engine, with nearly 50% of C 16. Palm oil is one of the most saturated, its hydrotreatment requires a lesser amount of hydrogen compared to other oils. In addition, the thermal stability of the palm oil limits the clogging of the heat exchangers located upstream of the reactor in a conventional hydrorefining unit. Palm oil also has the advantage of having its profile centered on that of the diesel fuel, which limits the disruption of the latter, to be economical, and to be little used for human food.
• animal fats one can for example use fish fat, animal oil.
• a particularly advantageous way of using the invention is therefore to preferentially use palm oil or any other vegetable or animal oil that can produce, by hydrotreatment, a maximum of linear C15 to C18 paraffins so as to induce a significant increase in the cetane number of the charges produced while decreasing the density, and to better efficientlyze bases with low cetane number and high density, such as the LCO ("Light Cycle OiI") which is characterized by a density It has a high cetane number and a very low cetane number, and gas oils derived from acidic crude oils which have excellent cold properties but have the characteristics of having a high density and a low cetane number.
• the process according to the invention makes it possible to promote the hydrogenation of the aromatic compounds and to substantially improve the cetane of the final product.
• the catalytic injection zone of the charge of biological origin comprises a first layer of metal trap catalyst.
• metal trap catalysts are known in themselves, and are generally composed of macroporous alumina. The purpose of using such a metal trap, commercially known is to rid the vegetable oils and / or animal fats of any impurities they contain (Na, K, Cl ).
• the charge treatment temperature in the countercurrent reactor is from 250 to 420 ° C., preferably from 280 to 400 ° C.
• the different charges are treated at a pressure of 25 to 150 bar, preferably 30 to 70 bar.
• the WH of the feedstock in the countercurrent reactor is from 0.3 to 10, preferably from 0.6 to 5.
• the charge of biological origin is treated on at least one catalytic bed in the hydrotreatment unit, the catalytic bed containing at least one catalyst based on metal oxides chosen from the oxides of the metals of the group VI-B (Mo, W) and VIII-B (Co, Ni, Ru, Rh) and / or noble metals such as Pt and Pd, supported on a support selected from alumina, silica, silica alumina, zeolite , ferrierite, phosphated alumina, phosphated alumina silica, mordenite, mazite.
• the catalyst used will be NiMo, CoMo, NiW, PtPd, or a mixture of two or more thereof.
• the catalyst used may also be based on metals in the mass state such as the catalyst commercially known as Nebula.
• the charge of biological origin introduced into the hydrotreatment unit is treated on at least one catalytic bed containing at least partly a catalyst with an isomerizing function, based on metal oxides or noble metals such as Pt, Pd, on an acidic support such as amorphous silica, zeolite, ferrierite, phosphated alumina, phosphated silica alumina.
• the catalytic beds containing metal oxides on an acidic support have the advantage of promoting the isomerization reactions, which can make it possible to improve, that is to say to reduce very clearly, the cloud point of the final product.
• This catalyst may be composed of metal oxides on an acidic support such as amorphous silica, zeolite, ferrierite, phosphated alumina, phosphated silica alumina.
• the countercurrent configuration makes that I ⁇ 2S and other impurities such as CO and CO2 are almost absent in the lower part of the reactor, and that the partial pressure of hydrogen is very high, which means that allows the installation of a catalytic bed based on noble metal oxides, thus leading to better hydrodesulfurization and isomerization activity.
• the first catalytic zone intended for treating the petroleum feed contains one or more catalyst beds containing catalysts which have a good performance.
• the second catalytic zone intended for treatment of the charge of biological origin contains one or more catalyst beds containing catalysts having a good performance for the deoxygenation of the triglycerides of the charge (for example based on NiMo) and / or or catalysts promoting isomerization reactions.
• a catalyst with an isomerizing function to improve the cold properties of the product.
• water is injected into the hydroprocessing unit in the biological charge treatment zone.
• the presence of water in the reactor, and more specifically in the biological load treatment zone makes it possible to shift the equilibrium of the "CO shift" reaction towards the conversion of CO to CO2, which can be much more easily eliminated.
• the conversion of the CO produced by the dichlorodeoxygenation reaction to CO2 and H2 is facilitated by limiting the methanation reaction which produces the methane CH 4 , which results in a decrease in the exothermicity and the consumption of Fh.
• the water, in vapor form is removed by the counter-current circulating gas flow.
• CO treatment can be implemented when the CO content of the recycle gases reaches a predetermined value.
• the separation and treatment of carbon monoxide can be achieved by introducing into the recycle gas treatment system, a device for separating and treating carbon monoxide.
• CO conversion equipment referred to as "CO shift” by specialists
• CO shift by specialists
• a PSA treatment unit abbreviation for Pressure Swing Adsorption
• This technology is known in itself.
• the adsorbents are selected according to the nature of the impurities to be removed from hydrogen-carrying streams, which in our case are carbon monoxide CO and optionally methane CH4, ethane C2H6 and propane C3H8.
• the gases thus separated are used in a steam reformer, such as a methane steam reformer (“SMR": steam methane reformer).
• SMR methane steam reformer
• the CO and the other products of deoxygenation of the charge of biological origin are thus valued as synthesis gas for the production of a hydrogenated gas of biological origin.
• the CO is therefore valued and therefore, in order to avoid its inhibitory effect, it is not necessary to reduce its concentration in favor of the CO2 concentration which can be more easily eliminated.
• a treatment is also carried out in which the carbon dioxide (CO2) and the hydrogen sulphide (H2S) present in said recycle gas are separated and treated before reinjection thereof into the hydrotreatment unit.
• This treatment is for example carried out by passing the recycle gas into an amine absorber.
• This additional treatment thus makes it possible to eliminate from the circuit the gases to be treated, ie CO2 and I ⁇ 2S.
• Another particularly advantageous way of using the invention is to compensate for the exothermicity which necessarily results from the addition of these oils.
• the exothermicity of the hydroprocessing of the feed is controlled by means of thermal regulation systems.
• a conventional hydrotreatment unit this is a example of the improvement of the liquid / gas distribution, gaseous and / or liquid quench (that is to say the supply of cold gases or liquids in the reactor), distribution of the volume of catalyst on several catalytic beds , preheating management of the charge at the reactor inlet, in particular by action on the furnace and / or the heat exchangers located upstream of the reactor, on bypass lines, etc. to lower the temperature at the reactor inlet.
• a liquid liquid quench
• This liquid may for example consist of a part of the hydrorefined charge exiting the hydroforming unit. It is introduced at the level of the biological load treatment zone, in particular when the hydrotreating unit comprises a single reactor. When the hydroprocessing unit comprises two reactors, this liquid may consist of a part of the effluent of the first reactor. It is introduced, likewise, at the level of the treatment area of the load of biological origin.
• a thermal regulation system consists of recovering heat from the effluent leaving the first reactor in order to lower its temperature before injection into the second reactor. This allows to achieve a significant energy gain.
• the invention also relates to a dtrydroraffinage unit comprising at least one catalytic hydrotreatment unit for carrying out said method.
• the hydrotreatment unit comprises at least one fixed bed hydrotreatment reactor operating countercurrently.
• the hydrorefining unit comprises a system for treating recycle gases from the hydrotreating unit before being reinjected into said unit, this treatment system comprising a device for separating and treating carbon monoxide so as to removing the carbon monoxide present in said recycle gas.
• the hydrotreatment unit comprises a single reactor operating against the current. The charges of petroleum and biological origin are then injected into this reactor.
• the hydrotreatment unit comprises two distinct reactors, a first reactor operating in cocurrent and a second reactor operating in countercurrent, receiving the liquid effluent leaving the first reactor, the charge of petroleum origin being injected into the first reactor co-current.
• the charge of biological origin is then injected into the first cocurrent reactor and / or into the second countercurrent reactor mixed with the liquid effluent leaving the first reactor.
• FIG. 1 is a simplified diagram of a hydrorefining unit comprising a hydrotreating unit according to a first embodiment of the invention, comprising a single countercurrent reactor.
• FIG. 2 is a simplified diagram of a hydrorefining unit comprising a hydrotreatment unit according to a second embodiment of the invention, comprising a first cocurrent reactor and a second countercurrent reactor.
• a catalytic hydrotreating unit is formed of a single reactor (1), as shown in FIG. 1.
• This counter-current reactor (1) is provided with a first inlet (2) for the introduction of a petroleum feedstock (Cp) of diesel type and a second inlet (3) for the introduction of a feedstock of biological origin (Cb) based on vegetable and / or animal oils.
• Cp petroleum feedstock
• Cb biological origin
• these inputs are located at the reactor head.
• it could be expected that the two charges are combined before entering the reactor and enter through the usual inlet of the reactor.
• the reactor (1) comprises an inlet (4) for the introduction of hydrogen H 2 in countercurrent.
• a line (5) brings the charge of petroleum origin (Cp) to the first inlet (2) of the reactor, while a line (6) brings the charge of biological origin (Cb) to the second inlet (3) of the reactor.
• the liquid effluent leaving the reactor (1) is discharged by means of a line (14).
• a heat exchanger (7) is placed downstream of the reactor (1) on the line (14) to heat the charge Cp circulating in the line (5), upstream of the reactor (1).
• the gas leaving the reactor (1) is sent to a separator (9) which makes it possible to separate from the effluent a gas rich in hydrogen and also containing CO and CO 2 .
• This gas is fed into a unit (10) for the treatment and separation of CO2, for example an amine absorber, then in a unit (1 1) for separation and treatment of CO, of the PSA type.
• the CO separated in this unit (1 1), as well as other separated gases such as CH 4 , C 2 H 6, C 3 H 8 can be advantageously sent to a unit SMR (12) for the production of hydrogen H 2 .
• This hydrogen can then optionally be returned to the line (13) bringing the recycle gas into the reactor (1) against the current.
• a catalytic hydrolysis unit according to the invention is formed of two reactors (20), (21).
• FIG. 2 represents a hydrorefining unit equipped with such a catalytic hydrotreatment unit.
• the first reactor (20) operates in co-current, while the second reactor (21) operates against the current.
• the charge of petroleum origin Cp is brought to the top of this first reactor (20) by means of a line (22), but the liquid effluent leaving this first reactor, instead of being directed towards a separation section , is sent to the top of the second reactor (21) by means of a line (23).
• a line (25) recovers the liquid effluent at the outlet of the second reactor (21) and conducts it to a separation section.
• a heat exchanger (26) is placed downstream of the first reactor (20) on the line (23) in order to heat the charge Cp circulating in the line (22), upstream of the first reactor (20).
• the diihydrorefining unit comprises, in addition, a second heat exchanger (27) placed downstream of the second reactor (21) on the line (25), and also heating the charge Cp circulating in the line (22) upstream of the first reactor (20), this second exchanger (27) being for example placed upstream of the first exchanger ( 26).
• a line (28) connected to the line (22) provides the charge Cp to be treated in the first cocurrent reactor, a gas rich in H2.
• the liquid effluent is recovered which is cooled and then separated in a separation section not shown here.
• the gas leaving the second reactor (21) is sent to a separator (30) which separates from the effluent a gas rich in hydrogen and also containing CO and CO2.
• This gas is fed into a unit (31) for treating and separating CO2, for example an amine absorber, and then in a unit (32) for separating and treating CO, of the PSA type.
• the CO separated in this unit (32), as well as the other separated gases such as CH4, C2H6 and C3H8, can be advantageously sent to a SMR unit (33) for the production of H2 hydrogen.
• This hydrogen can then optionally be returned to the line (28) bringing the recycle gas into the first reactor (20) co-currently and into the line (34) bringing the recycle gas into the second reactor (21) against - current.
• This unit thus makes it possible to carry out the hydrorefining of the petroleum fractions in the first reactor (20) and to carry out a finishing of the ltrydroraffinage of the petroleum fractions in the second reactor (21), as well as the deoxygenation of the triglycerides of the charge of biological origin against a current.
• this hydrorefining unit can be used for the hydrotreatment of a petroleum-based filler with or without the addition of a filler of biological origin.
• the diesel-based feedstock studied is composed of 30% LCO ("Light Cycle OII") and 70% diesel fuel cuts from straight-run (SR) according to the English name). a crude oil.
• LCO Light Cycle OII
• SR straight-run
• Tables 1 and 2 The characteristics of this diesel fuel as well as those of palm oil incorporated at about 15% by weight are shown in Tables 1 and 2 respectively.
• Myristic acid 14 0 1, 1
• Palmitoleic acid 16 1 0.2
• Oleic acid 18 1 37.7
• Linolenic acid 18 3 0.2
• Arachidic acid 20 0 0.4
• Gondoic acid 20 1 0, 1
• Example 1 which serves as a reference, the treatment is carried out on a unit comprising a hydrotreating reactor operating in co-current, in which the catalyst volume is 54.6 m 3 .
• the simultaneous feeding of palm oil and the feedstock Diesel is at the top of the reactor.
• the hydrogen partial pressure is 63 bars, and the average treatment temperature is 362 ° C. This temperature makes it possible to ensure a sulfur content of 10 ppm from the feedstock treated here.
• Example 2 the treatment is carried out on a unit comprising a hydrotreating reactor operating against the current.
• the diesel feed and the palm oil feed are incorporated at the top of the reactor.
• the overall volume of catalyst in the unit is 54.6 m 3 (identical to that of Example 1).
• the average reaction temperature is 350 ° C., which makes it possible to ensure a sulfur content of 10 ppm from the feedstock treated here.
• the treatment is also done on a unit comprising a treatment reactor operating against the current.
• the diesel fuel feed and the palm oil feed are incorporated at the reactor head.
• the overall catalyst volume of 33.3 m 3 .
• the average reaction temperature in the first reactor is 362 ° C. (identical to that of Example 1), which allows the unit (together of the two reactors in series) to ensure a sulfur content of 10 ppm. from the load processed here.
• the reactors contain a commercial hydrodesulfurization catalyst known to those skilled in the art, consisting of porous alumina on which nickel and molybdenum oxides are deposited.
• This catalyst is in the form of extrudates 1 to 2 mm in diameter of trilobal shape.
• the loading density is 950 kg / m 3 of catalyst loaded into the unit.
• the hydrogen partial pressure at the inlet of the reactor is 63 bars.
• the hydrogen blanket used for the exposed examples is 350 Nl / l (i.e., the amount of Normal-liters of hydrogen per liter of feedstock).
• a stripping section of the liquid effluent is present at the outlet of the reactor to eliminate gases such as H2S, NH3, CO, CO2 when these compounds are present in the effluent.
• Table 3 summarizes the operating conditions of the unit used. Table 3: Operational conditions for obtaining a diesel with 10 ppm of sulfur
• the cycle time is lengthened. In this case, one can expect to have an extended cycle time of at least 1 year.
• Table 4 groups together the results of a detailed analysis of the effluent obtained for Examples 1, 2 and 3.
• the incorporation of palm oil in charge of a hydrodesulfurization unit comprising a reactor operating against the current has the consequence of adding normal paraffins in the final product, and the characteristics of the products obtained are favorably affected.
• the cloud point of effluents is -2 ° C, then One would have expected, with the incorporation of 15% of palm oil to the diesel fuel load, to a greater impact on the cloud point.

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