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
  • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
  • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
• • 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
  • C10G3/50—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
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
  • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or 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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
  • C10G47/04—Oxides
• • 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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
  • C10G47/06—Sulfides
• • 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
  • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
  • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
  • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
• • 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
• • 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
  • C10G2300/1003—Waste materials
• • 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
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
• • 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
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1048—Middle distillates
  • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
• • 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
  • C10G2400/20—C2-C4 olefins
• • 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
• • 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
  • Y02P30/40—Ethylene production

Definitions

• the invention described here is part of this framework. It consists in hydrotreating charges from renewable sources and in particular in hydrogenating vegetable oils so as to obtain linear paraffins containing 6 to 25 carbon atoms. These paraffins are then sent to a steam cracking plant (or according to the Anglo-Saxon steam-cracking determination) sized as for the treatment of petroleum fractions but also able to convert these paraffins into ethylene and propylene and resulting polymers with significantly higher yields.
• the objective of the invention is therefore the production, with very high yields, of ethylene and propylene from a paraffin section resulting from the hydrotreatment of charges from renewable sources.
• U.S. Patent 4,620,050 discloses a process for the production of high purity ethylene or a mixture of ethylene / carbon monoxide directly usable by decomposition in the gas phase of certain ethyl esters of aliphatic carboxylic acids at a temperature of between 150 and 300 ° C. in the presence of a zeolitic catalyst.
• US Patent Application 2007/0015947 discloses a process for producing C2-C5 olefins from feeds from a renewable source comprising a first charge pretreatment step for removing contaminants such as alkali metals and a second step of cracking the purified feed in a fluidized catalytic cracking (FCC) zone.
• FCC fluidized catalytic cracking
• a method of treating a feedstock from a renewable source comprising the following steps: a) two-stage hydrotreatment wherein said first mild prehydrogenation treatment stage operates at a temperature of between 50 and 50.degree. 300 ° C., at a hydrogen partial pressure of between 0.1 and 10 MPa, and at a catalyst hourly space velocity of between 0.1 h -1 and 10 h -1, wherein said prehydrogenation catalyst comprising at least one noble metal of group VIII chosen from palladium and platinum or comprising at least one non-noble metal of group VIII and / or at least one metal of group VIB, the non-noble metal of group VIII being chosen from nickel and the cobalt and the group VIB metal being selected from molybdenum and tungsten, said prehydrogenation catalyst being a metal phase catalyst and wherein said second stage of the process It is carried out at a temperature of between 200 and 450 ° C., at a pressure of between 1 MPa and 10 MPa, at a catalyst hourly space velocity
• the feedstocks are derived from renewable sources, such as vegetable or animal oils and fats, or mixtures of such fillers, containing triglycerides and / or fatty acids and / or esters.
• vegetable oils they can be raw or refined, wholly or in part, and derived from the following plants: rapeseed, sunflower, soybean, palm, palm kernel, olive, coconut, this list not being limiting.
• fats there may be mentioned all animal fats such as bacon or fats consisting of residues from the food industry or from the food service industries.
• the charges thus defined contain triglyceride and / or fatty acid structures and their esters, whose fatty chains contain a number of carbon atoms of between 6 and 25.
• the hydrocarbons produced during the conversion of the feedstock are characterized by: a) a number of carbon atoms equal to that of the chains of the starting fatty acids, if the mechanism is a mechanism for hydrogenation of the carboxylic group into an alkyl group . b) A hydrocarbon chain containing one carbon atom less than the chains of the starting fatty acids, if the mechanism involved is a decarboxylation / decarbonylation.
• the mechanism a) has the advantage of offering a very good paraffin yield of carbon number equivalent to that of the starting fatty acid, but on the other hand has the disadvantage of causing a very significant hydrogen consumption. up to 3.6% wt hydrogen.
• Mechanism b) has the disadvantage of a slightly lower weight yield related to the reduction of a carbon atom in the chain, which for example passes from Cl 8 to C 17 for a rapeseed oil, but on the other hand allows to limit H2 consumption to only 1.6% wt.
• One of the advantages of the invention is to optimize the consumption of hydrogen in the hydrogenation mechanism according to a) while minimizing the decarboxylation / decarbonylation mechanism according to b).
• An object of the present invention is the preparation of steam cracker feeds making it possible to obtain a very high yield of ethylene and propylene and resulting polymers, and this from feedstock from renewable sources.
• feedstocks from renewable sources consist of all vegetable oils and animal fats, mainly containing triglycerides and fatty acids or esters, with hydrocarbonaceous fatty chains having a number of carbon atoms of between 6 and 25 carbon atoms.
• These oils may be palm, palm kernel, coconut, castor oil, cotton, peanut, flax and crambe oils and all oils derived for example from sunflower or rapeseed by genetic modification or hybridization. .
• Fried oils, various animal oils such as fish oils, tallow, lard can be used.
• 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, alkali, alkaline earth and phosphorus, for example on ion exchange resins.
• Suitable treatments may for example be heat and / or chemical treatments well known to those skilled in the art.
• step a) of hydrotreating feedstock from renewable sources is carried out in two stages.
• Step a) consists, advantageously, in a first treatment step consisting of a gentle prehydrogenation of at least 50% of the double bonds contained in the hydrocarbon chain of the fatty acids of said filler, preferably at least 80% double bonds, very preferably at least 90% of the double bonds and even more preferably at least 99% of the double bonds, followed by a second treatment stage consisting of hydrogenation of at least 50% of the ester functions contained in the hydrocarbon chain of the fatty acids of said filler, preferably at least 80% of the double bonds, very preferably at least 90% of the ester functions and even more preferably at least 99% of the ester functions.
• step a) consists of a first treatment step consisting of a gentle prehydrogenation of at least 50% of the double bonds contained in the hydrocarbon chain of the fatty acids of said feedstock. followed by a second treatment step consisting of a hydrogenation of at least 50% of the ester functions contained in the hydrocarbon chain of the fatty acids of said feedstock.
• step a) consists of a first treatment step consisting of a gentle prehydrogenation of at least 90% of the double bonds contained in the hydrocarbon chain of the fatty acids of said charge, followed by a second treatment step consisting of a hydrogenation of at least 90% of the ester functions contained in the hydrocarbon chain of the fatty acids of said charge.
• step a) consists of a first treatment step consisting of a gentle prehydrogenation of at least 99% of the double bonds contained in the hydrocarbon chain of the fatty acids of said charge, followed by a second treatment step consisting of a hydrogenation of at least 99% of the ester functions contained in the hydrocarbon chain of fatty acids of said charge.
• the double bonds of the hydrocarbon chains can be determined by several analytical methods:
• the measurement of the iodine index consists in measuring the amount of diiodine (I 2 ) capable of being fixed on the unsaturations of the hydrocarbon chains. expressed in mg of I 2 fixed on 100 g of product.
• the iodine value is for example 90 on oleic acid, 181 for linoleic acid and 274 for linolenic acid.
• the iodine number is measured in the vegetable oil methyl esters (VOME), according to the standardized method EN 14111.
• Other standard methods can also be cited as ASTM D1959 and ASTM D5554.
• the bromine number is applicable for contents of less than 1000 mg / 100 g of product, according to the ASTM D2710 standard.
• the number of bromine concerns potentiometric assays for contents greater than 1 g / 100 g of product, according to the ASTM D1159 standard.
• ester functions is demonstrated according to an infra-red spectrometry method.
• the principle of the method is based on the presence of a specific infra-red band of the ester function.
• the hydrogenation of the ester functions therefore results in a disappearance of the specific band detected in infra-red.
• the first step of treating said charge consisting of a mild prehydrogenation is intended to saturate the double bonds contained in the hydrocarbon chain of the fatty acids of the charge, so as to avoid the secondary reactions of the double bonds, such as, for example, reactions of polymerization resulting in the formation of coke or gums.
• This first prehydrogenation step operates according to the invention at a temperature between 50 and 300 0 C, preferably between 50 and 200 0 C and more preferably between 100 and 200 0 C and 3 at a partial pressure of hydrogen between 0.1 and 10 MPa.
• the hourly space velocity on the catalyst is between 0.1 hr -1 and 10 hr -1 .
• the amount of hydrogen consumed during this mild prehydrogenation step is between 0.5 and 1% by weight of hydrogen relative to the feedstock.
• the catalyst used in the first charge treatment stage advantageously comprises at least one hydrodehydrogenating element and a support of the alumina and / or silica and / or silica-alumina type.
• said prehydrogenation catalyst comprises at least one noble metal from the group VTII preferably chosen from palladium and platinum, said prehydrogenation catalyst being a metal phase catalyst.
• said prehydrogenation catalyst comprises at least one non-noble metal of group VIII and / or a metal of group VTB, the non-noble metal of group VIII being chosen from nickel and cobalt and metal group VIB being selected from molybdenum and tungsten, said prehydrogenation catalyst being a metal catalyst.
• the noble or noble metal content of group VIII is advantageously between 0.5 and 20% by weight and preferably between 5 and 10% by weight relative to the total mass of the catalyst.
• the metal content of group VIB is between 0.5 and 20% by weight and preferably between 7 and 17% by weight relative to the total mass of the catalyst.
• the non-noble metal of group VIII is nickel and the metal of group VIB is molybdenum.
• nickel-molybdenum and cobalt-molybdenum are also used: nickel-molybdenum and cobalt-molybdenum.
• said prehydrogenation catalyst is a metal phase catalyst whose metal phase consists of nickel alone.
• the effluent from this first mild prehydrogenation step is then contacted in a second step of treating said feed with a heterogeneous catalyst, said second processing step operating at a temperature between 200 and 450 0 C and preferably between 220 and 350 ° C.
• the pressure is between 1 MPa and 10 MPa and preferably between 2 MPa and 6 MPa.
• the hourly space velocity on the catalyst 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-to-feed ratio is between 50 and 1000 Nm 3 of hydrogen per m 3 of feedstock and preferably between 100 and 500 Nm 3 of hydrogen per m 3 of filler.
• the hydrogen consumption during this second stage is typically between 2 and 3% by weight relative to the initial charge.
• Said second charge treatment step operating at operating conditions that are more severe than those of said first mild prehydrogenation stage advantageously allows the hydrogenation of at least 50% of the ester functions contained in the hydrocarbon chain of the fatty acids in the charge. preferably at least 80%, preferably at least 90% and even more preferably at least 99% of the ester functions.
• ester functions is demonstrated according to the infrared spectrometry method defined above.
• At least one fixed bed of catalyst comprising a hydrogenating function dispersed on a suitable support is used.
• the catalyst support used in the second charge treatment step is advantageously chosen from the group formed by alumina, silica, silica-aluminas, magnesia and clays, taken alone or as a mixture.
• Said support may advantageously also contain other compounds such as, for example, oxides chosen from the group formed by boron oxides, zirconia, titanium oxide and phosphoric anhydride, taken alone or as a mixture.
• an alumina support is used and even more preferably an alumina support ⁇ , ⁇ or ⁇ .
• the hydrogenating function is advantageously ensured by at least one metal of group VIII and / or group VI B.
• the catalyst used in the second charge treatment stage of the process according to the invention comprises at least one non-noble metal of group VIII and / or at least one metal of group VIB 5 the non-noble metal of the group VIII being selected from nickel and the cobalt and the group VIB metal being selected from molybdenum and tungsten, said catalyst being a sulphide phase catalyst.
• the non-noble metal of group VIII is nickel and the metal of group VIB is molybdenum.
• the total content of Group VIB and VIII metal oxides in the catalyst used in the second charge treatment step is advantageously between 5 and 40% by weight and preferably between 7 and 30% by weight relative to the weight. total 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, preferably between 10 and 2.
• a preferred catalyst used in the second charge treatment stage of the process according to the invention advantageously comprises a nickel oxide (NiO) content of between 0.5 and 10% by weight and preferably between 1 and 5% by weight. and a content of molybdenum oxide (MoO 3 ) of between 1 and 30% by weight and preferably of between 5 and 25% by weight on an amorphous mineral support, the percentages being expressed as% by weight relative to the total mass of the catalyst.
• NiO nickel oxide
• MoO 3 molybdenum oxide
• the catalyst used in the second charge treatment step of the process according to the invention may also advantageously contain at least one doping element chosen from phosphorus, silicon, fluorine and boron.
• This element may advantageously be introduced into the matrix or preferably be 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 doping element content by weight of oxide of said element is usually advantageously less than 20% and preferably less than 10%.
• a preferred metal phase catalyst used in the second charge treatment stage of the process according to the invention has a nickel content of between 20% and 70%.
• the support of the said The catalyst is advantageously chosen from the group formed by alumina, magnesium oxide and silica, and preferably the support is composed of alumina.
• sulfur-containing compound the dimétyl-disulfide (DMDS) 5 carbon disulfide (CS2)
• DMDS dimétyl-disulfide
• CS2 carbon disulfide
• organic polysulphides organic polysulphides
• mercaptans organic polysulphides
• sulfides disulfides
• oxygenated sulfur compounds oxygenated sulfur compounds
• dissolved elemental sulfur dissolved elemental sulfur and / or partially suspension.
• the catalyst used in the first treatment step consisting of a mild prehydrogenation is a metal phase catalyst and the catalyst used in the second treatment stage is a sulphide phase catalyst.
• the catalyst used in the first treatment step consisting of a mild prehydrogenation is advantageously a nickel catalyst on alumina metal phase and the catalyst used in the second treatment step is advantageously a nickel / molybdenum catalyst on alumina sulfide phase.
• step b) of the process according to the invention the hydrotreated effluent from step a) of the process according to the invention is subjected at least in part, and preferably entirely, to one or more separations.
• step b) of the process according to the invention is to separate the gases from the liquid, and in particular to recover the hydrogen-rich gases which may also contain gases such as carbon monoxide (CO), carbon dioxide (CO 2 ) and propane, and at least one hydrocarbon liquid effluent consisting of at least 50% by weight of linear n-paraffins, preferably at least 80 weight, very preferably at least 90% by weight and even more preferably at least 98% by weight of n linear paraffins and having a number of carbon atoms of between 6 and 25.
• gases such as carbon monoxide (CO), carbon dioxide (CO 2 ) and propane
• at least one hydrocarbon liquid effluent consisting of at least 50% by weight of linear n-paraffins, preferably at least 80 weight, very preferably at least 90% by weight and even more preferably at least 98% by weight of n linear paraffins and having a number of carbon atoms of between 6 and 25.
• paraffin contents normal paraffins and iso-paraffins
• chromatographic method Coupling with a mass spectrometer is used. This method also gives access to olefins, naphthenes and aromatics contents (PONA analysis).
• Step b) of separation of the process according to the invention can therefore be followed by a step of removing the water.
• the mixture of hydrogen gas (H 2 ) carbon monoxide (CO), carbon dioxide (CO 2 ) and separated propane can then, advantageously, itself undergo treatments known to those skilled in the art to eliminate the carbon monoxide (CO) and carbon dioxide (CO 2 ) and separate hydrogen from propane, the latter can advantageously be sent to a steam cracking furnace dedicated to the steam-cracking of liquefied gases.
• the separated hydrocarbon liquid effluent from step b) of the process according to the invention is then sent at least partly and preferably completely in a steam cracking oven, in accordance with step c) of the process according to the invention.
• the hydrocarbon liquid effluent resulting from the separation step b) of the process according to the invention and containing at least 50% by weight of linear n-paraffins, preferably at least 80% by weight, very preferably at least 90% by weight weight and even more preferably at least 98% by weight of n linear paraffins, is at least partly, and preferably entirely, sent to a steam-cracking furnace in which these n-paraffins are converted into ethylene and propylene with remarkable yields and significantly higher than those obtained in the case where the feedstock sent to the steam cracker is a conventional steam cracker feed, such as for example in the case where the charge consists of medium naphtha.
• Steam cracking is generally the method of choice for obtaining petrochemical feedstocks such as, for example, ethylene and propylene.
• the current steam cracker charges are derived entirely from petroleum gases and liquids ranging from emanated to diesel with varying yields of ethylene and propylene depending on the quality of the charges.
• the operating conditions generally used in step c) of steam-cracking of the process according to the invention are the following: the steam-cracker operates at temperatures of between 750 and 850 ° C. in the presence of injected water vapor, preferably in a weight ratio relative to the oil cut of between 0.5 and 1.5.
• the residence time under these conditions is generally between 0.2 s and 1.2 s.
• step c) of the process according to the invention the hydrocarbon liquid effluent resulting from the separation step b) of the process according to the invention, containing at least 50% by weight of n-paraffins.
• Linear is sent, at least in part and preferably entirely, into the steam cracking furnace mixed with an external petroleum cut such as for example a naphtha cut or a diesel cut.
• the ethylene and propylene yields will be lower than those obtained with only the hydrocarbon liquid effluent from the separation step b) of the process according to the invention, containing at least 50% by weight of linear n-paraffins.
• the methane produced in the steam-cracking unit, in stage c) of the process according to the invention, may advantageously be sent to a steam-reforming or steam-reforming unit to produce hydrogen by the following reaction:
• the hydrogen yield can be increased by carrying out the conversion of carbon monoxide (CO) or in the English terminology "shift conversion” according to the following reaction also well known:
• Vapor reforming and carbon monoxide (CO) conversion reactors can be easily integrated into the steam cracking plant.
• the product mixture, rich in hydrogen, can then be sent to the separator train of the steam cracker, which itself produces purified hydrogen used in the various hydrogenations and hydrotreatments of the vapo-reforming effluents.
• One of the advantages of the invention is the use as charge of the steam cracker of the hydrocarbon liquid effluent resulting from the separation step b) according to the invention and containing at least
• Step a) The treatment of a load from renewable sources in two integrated stages.
• a fixed bed of 40 g of nickel-based soft prehydrogenation catalyst on alumina containing 15% weight calculated in nickel and previously reduced is charged.
• 100 g / h of pre-refined rapeseed oil whose composition is detailed below.
• TPN normal conditions of temperature and pressure
• the prehydrogenated mixture from this first stage is sent directly and entirely into a second reactor operating isothermal and fixed bed charged with 89 g of a second stage catalyst for treating the feedstock, said hydrotreatment catalyst being based nickel and molybdenum and having a nickel oxide content equal to 4.3% by weight and a molybdenum oxide content equal to 21.5% by weight on an alumina support, the catalyst being previously sulphurized.
• 150: 1 TPN of H2 per liter of feed are introduced into this reactor maintained at 300 ° C. under a pressure of 4 MPa.
• paraffinic hydrocarbon liquid effluent thus obtained is analyzed by a gas chromatography method, coupled with a mass spectrometer: it consists of 98% by weight of n paraffins having a number of carbon atoms of 6 to 25 and of 2% isoparaffins ranging from C 17 to C 21. N paraffins are more than 95% in the range C 6 to C 22 .
• step a) of hydrotreating of the process according to the invention is separated to be sent to a steam cracking furnace sized to treat the liquefied gases, it is possible to obtain from 3.2 kg of propane, indicated in Table 3, the following productions:
• the process according to the invention thus makes it possible to obtain ethylene yields that are very much higher than those obtained from petroleum liquid fractions while obtaining improved yields of propylene.
• the ethylene and propylene products can then be sent to polymerization units known to those skilled in the art so that the end products (polyethylene, polypropylene, etc.) are entirely derived from renewable sources.

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