EP3765584A1 - Procede d'oligomerisation d'olefines - Google Patents
Procede d'oligomerisation d'olefinesInfo
- Publication number
- EP3765584A1 EP3765584A1 EP19711891.2A EP19711891A EP3765584A1 EP 3765584 A1 EP3765584 A1 EP 3765584A1 EP 19711891 A EP19711891 A EP 19711891A EP 3765584 A1 EP3765584 A1 EP 3765584A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- methyl
- ene
- catalyst
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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- 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
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/08—Alkenes with four carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/12—Silica and alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
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- 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
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- 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
- C10G2300/1088—Olefins
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- 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
- C10G2400/10—Lubricating oil
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- 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
- C10G2400/18—Solvents
Definitions
- the present invention relates to a process for oligomerization of olefins having good yields and good selectivity, for various applications including solvent fluids and jet fuels.
- Hydrocarbon fluids are widely used as solvents, for example in adhesives, cleaning liquids, explosives, solvents for decorative coatings and printing inks, light oils for applications such as metal mining, work metals or demolding, industrial lubricants and drilling fluids.
- Hydrocarbon fluids can also be used as diluting oils in adhesives and sealants such as silicone sealants, such as viscosity-lowering agents in plasticized polyvinylchloride formulations, as vehicles in polymeric flocculant formulations. for example in water treatment, mining operations or papermaking and also as thickeners in printing pastes.
- Hydrocarbon fluids can also be used as solvents in a wide range of other applications, for example in chemical reactions.
- hydrocarbon fluids vary considerably depending on the use for which the fluid is intended.
- the important properties of hydrocarbon fluids are as follows: distillation curve (generally determined according to ASTM D86 or ASTM D1160 by the vacuum distillation technique used for heavier materials), flash point, density, aniline point (determined according to ASTM D611), aromatic content, sulfur content, viscosity, color and refractive index.
- distillation curve generally determined according to ASTM D86 or ASTM D1160 by the vacuum distillation technique used for heavier materials
- flash point density
- aniline point determined according to ASTM D611
- aromatic content sulfur content
- viscosity color and refractive index
- the fluids can be classified as paraffinic, isoparaffinic, deflavored, naphthenic, non-dearomatised and aromatic.
- US5008466 discloses a process for the isomerization of alkenes having a terminal double bond to obtain alkenes having an internal double bond. This document does not disclose a process for oligomerization of C5 branched olefins.
- the invention relates to a method for preparing a hydrocarbon fluid comprising an oligomerization step of an initial hydrocarbon composition comprising, relative to the total weight of the initial hydrocarbon composition, at least 2% by weight of 3-methyl-butyl 1-butene, at least 5% by weight of 2-methyl-but-2-ene and at least 5% by weight of 2-methyl-but-1-ene.
- the initial hydrocarbon composition is derived from biomass.
- the initial hydrocarbon composition is obtained by dehydration of alcohol (s), preferably by dehydration of fusel oil.
- the initial hydrocarbon composition comprises at least 20% by weight, preferably at least 30% by weight, preferably at least 40% by weight, more preferably at least 50% by weight, and even more preferably at least 60% by weight of branched olefins having 5 carbon atoms chosen from 3-methyl-but-1-ene, 2-methyl-but-2-ene and 2-methyl-but-1- ene, based on the total weight of the initial composition.
- the initial hydrocarbon composition comprises at least 20% by weight, preferably at least 30% by weight, preferably at least 40% by weight, more preferably at least 50% by weight, and even more preferably at least 60% by weight, of 2-methyl-but-2-ene, relative to the total weight of the composition.
- the initial hydrocarbon composition comprises 3-methyl-but-1-ene in a mass proportion such that 3-methyl-but-1-ene represents the olefin having 5 carbon atoms. majority of the initial hydrocarbon composition.
- the oligomerization step is carried out in the presence of a catalyst chosen from alumina and aluminosilicates.
- the catalyst is an aluminosilicate and the molar ratio S102 / Al2O3 of the catalyst ranges from 10 to 80, preferably from 15 to 50.
- the catalyst is a mesoporous aluminosilicate having a BET specific surface area greater than or equal to 50 m 2 / g, preferably ranging from 150 to 1200 m 2 / g, preferably ranging from 250 to 550. m 2 / g.
- the catalyst is an amorphous Si Al catalyst (ASA) and has from 5 to 95% by weight of silica (SiO 2), a BET specific surface area ranging from 100 to 550 m 2 / g. and an accessible pore size ranging from 2 to 14 nm.
- ASA amorphous Si Al catalyst
- the process of the invention is carried out at a temperature ranging from 80 to 220 ° C, preferably from 90 to 210 ° C, preferably from 100 to 200 ° C.
- the process of the invention is carried out at a pressure ranging from 2 to 50 bar, preferably from 5 to 40 bar, preferably from 10 to 30 bar.
- the method of the invention further comprises at least one treatment step, preferably a hydrogenation step and / or a fractionation step.
- the process of the invention comprises a step of recycling an effluent comprising the unreacted C5 olefins.
- the invention also relates to a hydrocarbon fluid obtainable by the process according to the invention.
- the invention relates to the use of the hydrocarbon fluid according to the invention, as a crude or hydrogenated and / or fractionated solvent fraction for the formulation of inks, paints, varnishes, cleaning products, lubricants for the work. metals, dielectric fluids, drilling fluids, cosmetics.
- the process according to the invention makes it possible to obtain a mixture of hydrocarbon fluids with good yields and a good selectivity.
- the process according to the invention can be carried out starting from raw material of biological origin.
- the process according to the invention makes it possible to obtain various hydrocarbon cuts, using a single oligomerization step optionally followed by a hydrogenation and / or fractionation step.
- the invention relates to a method for preparing a hydrocarbon fluid comprising an oligomerization step of an initial hydrocarbon composition comprising, relative to the total weight of the hydrocarbon composition, at least 2% by weight of 3-methyl-but- 1-ene, at least 5% by weight of 2-methyl-but-2-ene and at least 5% by weight of 2-methyl-but-1-ene.
- the initial composition (which undergoes oligomerization) comprises three different branched olefins each having 5 carbon atoms.
- the initial composition comprises, relative to the total weight of the initial composition, at least 2% by weight of 3-methyl-but-1-ene, at least 5% by weight of 2-methyl-but-2- and at least 5% by weight of 2-methyl-but-1-ene.
- branched olefin having 5 carbon atoms is meant an olefin having a branched hydrocarbon chain containing 5 carbon atoms.
- the expression "branched olefin in C5" denotes a branched olefin having 5 carbon atoms.
- the initial composition comprises, relative to the total weight of the initial composition, at least 20% by weight, preferably at least 30% by weight, preferably at least 40% by weight, more preferably at least 50% by weight. % by weight, still more preferably at least 60% by weight, of branched olefins having 5 carbon atoms selected from 3-methyl-but-1-ene, 2-methyl-but-2-ene and 2- methyl-but-l-ene.
- the initial composition comprises, relative to the total weight of the initial composition, at least 20% by weight, preferably at least 30% by weight, preferably at least 40% by weight, more preferably at least 50% by weight, still more preferably at least 60% by weight, of 2-methyl-but-2-ene.
- the initial composition comprises between 50% and 90% by weight of 2-methyl-but-2-ene, relative to the total weight of olefins comprising 5 carbon atoms, preferably between 55 and 80% by weight.
- the initial hydrocarbon composition comprises 3-methyl-but-1-ene in a mass proportion such that 3-methyl-but-1-ene represents the olefin having 5 carbon atoms. major carbon of the initial hydrocarbon composition.
- the initial composition has a weight ratio (3-methyl-but-1-ene) / (each olefin C 5 other than 3-methyl-but-1-ene) greater than or equal to 1, preferably strictly greater than 1, preferably greater than or equal to 1.2, more preferably greater than or equal to 1.5.
- the initial composition comprises at least 50% by weight of 3-methyl-but-1-ene, relative to the total weight of olefins having 5 carbon atoms.
- the initial composition is derived from the conversion of the biomass.
- a composition produced from raw materials of biological origin preferably chosen from sugars and sugar precursors such as cellulose, hemicellulose, lignocellulose and mixtures thereof, these can be produced from microorganisms such as yeasts, algae and bacteria.
- the initial composition can be obtained by dehydration of alcohol (s), preferably alcohol (s) resulting (s) from the conversion of biomass.
- alcohol preferably alcohol (s) resulting (s) from the conversion of biomass.
- Some yeasts can produce the Preferred alcohols in majority quantity as shown by the works of Esteban Espinosa Vidal's teams, Marcos Antonio de Morais Jr, Jean Marie Institut and Gustavo M. de Billerbeck published in Yeast 2015; 32: 47-56.
- the initial composition is obtained by dehydration of fusel oil.
- fusel oil is meant a mixture of alcohols resulting from the fermentation of the raw material of biological origin followed by the distillation of the effluent obtained after fermentation.
- Fusel oil is well known to those skilled in the art as a by-product of alcoholic fermentation.
- Fusel alcohols are a mixture of alcohols such as propanol, butanol, isobutanol, pentanol, methylbutanols, hexanol, fatty alcohols, terpenes and furfural. They are formed by alcoholic fermentation as byproducts of metabolism.
- fusel alcohols The main compounds present in so-called fusel alcohols are: propanol, butanols, amyl alcohol, isoamyl alcohols, and hexanol.
- the fusel oil may optionally comprise heavier linear alcohols, for example C7 and / or C8. These products are formed during fermentation when the temperature and pH are high. They are concentrated in the bottoms at the end of the process. They present themselves under an oily appearance hence their name oil of fusel.
- the fusel oil may optionally also include ethanol depending on the quality of the separation after the fermentation.
- Fusel oil can be obtained by various methods well known to those skilled in the art, for example by direct sampling in the distillation column followed by cooling.
- the sample taken can optionally be purified for example by extraction followed by decantation.
- a liquid / liquid extraction by addition of water followed by decantation makes it possible to obtain two phases.
- the upper phase contains mainly amyl and butyl alcohols, poorly soluble in water. It is called decanted or crude fusel oil. It can be chemically treated (usually with a saturated salt solution) and / or fractionated by distillation to remove the water present and separate residual ethanol.
- a "refined" fusel oil is then obtained.
- Other methods of purifying the fusel oil use adsorbents, subsequently regenerated to separate the different fractions.
- the initial composition is obtained by dehydration of a mixture comprising at least 12% by weight of alcohols containing 5 carbon atoms, at least 1% by weight of ethanol, less than 5% by weight of d ester (s) and less than 5% by weight of water, based on the total weight of the mixture.
- the initial composition is obtained by dehydration of a mixture comprising at least 20% by weight, preferably at least 30% by weight, more preferably at least 40% by weight, preferably at least 50% by weight. by weight, more preferably at least 60% by weight of alcohols having 5 carbon atoms, relative to the total weight of the mixture.
- the one or more alcohols comprising 5 carbon atoms present in the mixture are chosen from C 5 isoamyl isoamines, preferentially from 3-methyl-butan-1-ol, 2-methyl-butan-1-ol. and their mixtures.
- C5 iso-alcohols is meant an alcohol having a branched hydrocarbon chain containing 5 carbon atoms.
- the alcohols are preferably primary alcohols, that is, alcohols in which the -OH functional group is attached to a -CH 2 - group.
- Said dehydration may be carried out using a dehydration catalyst, for example selected from zeolites, aluminas, silica-aluminas and acid catalysts, preferably from zeolites, aluminas and silica-aluminas.
- the dehydration catalyst is a silica-alumina selected from zeolites and aluminas.
- the dehydration catalyst is an alumina.
- the dehydration catalyst is chosen from y-aluminas, H-b zeolites and H-y zeolites. These dehydration catalysts as such are well known to those skilled in the art and are commercially available.
- the catalyst for dehydration is chosen from zeolites and has a molar ratio S102 / Al2O3 greater than or equal to 10, preferably greater than or equal to 20, preferably greater than or equal to 30, preferably greater than or equal to at 50, more preferably greater than or equal to 80.
- the catalyst for dehydration is chosen from aluminas, preferably gamma (alumina) aluminas.
- alumina catalyst there may be mentioned the catalysts of the range PurAI ® marketed by Sasol.
- the catalyst for dehydration is a zeolite of ferrierite type, for example in the form of powder or extrudates.
- examples include the CP914 ® form of zeolite powder or ammonium ferrierite CP914 CYL ® 1.6, as extrudates, both marketed by Zeolyst. It is possible to provide between the dehydration step and the oligomerization step, a separation step to remove the water-like compounds and optionally esters and residual alcohols present to obtain the desired initial composition for the oligomerization according to the invention. invention.
- the catalyst for the oligomerization may be chosen from zeolites, aluminas, silica-aluminas and aluminosilicates. These catalysts as such are well known to those skilled in the art and commercially available.
- the catalyst for the oligomerization according to the invention has a molar ratio S102 / Al2O3 ranging from 10 to 80, preferably ranging from 15 to 50.
- the catalyst for the oligomerization is chosen from aluminosilicates.
- the catalyst for the oligomerization according to the invention is according to a particular embodiment, different from a zeolite.
- the catalyst is chosen from aluminosilicates having a pore size ranging from 1 to 50 nm, preferably from 1 to 25 nm, and preferably from 2 to 20 nm.
- the aluminosilicate type catalyst used in the invention is a mesoporous aluminosilicate typically having a BET specific surface area greater than or equal to 50 m 2 / g, preferably ranging from 150 to 1200 m 2 / g, preferably ranging from from 250 to 550 m 2 / g.
- An example of such a catalyst is an AI-MCM-41 type catalyst.
- the aluminosilicate type catalyst used in the invention is an amorphous Si Al catalyst (ASA) typically having from 5 to 95% by weight of silica (SiO 2), a BET specific surface area ranging from 100 to 550 m 2 / g and a pore size ranging from 2 to 14 nm.
- ASA amorphous Si Al catalyst
- the specific surface area is measured according to the BET method, measurement of the specific surface area by adsorption of a gas, a method well known to those skilled in the art.
- the pore size is measured by nitrogen physisorption.
- the initial composition (charge of the oligomerization) is brought into contact with the catalyst at a temperature ranging from 80 to 220 ° C., preferably from 90 to 210 ° C., preferentially from 100 to 200 ° C.
- the oligomerization step is carried out at a pressure ranging from 2 to 50 bar, preferably from 5 to 40 bar, preferably from 10 to 30 bar.
- the oligomerization step is carried out at a temperature ranging from 90 to 220 ° C., preferably from 95 to 210 ° C., preferably from 100 to 200 ° C. and at a temperature of from 100 to 200 ° C. pressure ranging from 2 to 50 bar, preferably from 5 to 40 bar, preferably from 10 to 30 bar.
- the oligomerization process is carried out in the liquid phase.
- Oligomerization then makes it possible to obtain C10 dimers, C15 trimers, as well as other molecules, such as C6-C9 molecules and C11-C14 molecules.
- a separation step at the end of the oligomerization step so as to separate the molecules having 5 carbon atoms or less, used as a charge, produced molecules having 6 or more carbon atoms.
- This separation step then makes it possible to obtain a first stream comprising molecules having 5 carbon atoms or less, and a second stream comprising molecules having 6 or more carbon atoms.
- the reaction product obtained can undergo different treatments.
- the subsequent treatments are preferably carried out on the second stream comprising molecules having 6 or more carbon atoms.
- the process according to the invention comprises an oligomerization step as described above, followed by a hydrogenation step.
- the hydrogenation can be carried out according to any method well known to those skilled in the art.
- the method according to the invention comprises an oligomerization step as described above followed by a fractionation step.
- the method according to the invention comprises an oligomerization step as described above followed by a hydrogenation step, itself followed by a fractionation step.
- Fractionation of a hydrocarbon fluid is well known to those skilled in the art. It allows in particular to obtain hydrocarbon cuts varying by their distillation range. So, the method according to the invention makes it possible to obtain a hydrocarbon fraction, defined by its distillation range.
- the invention also relates to hydrocarbon fluids obtainable by the preparation process according to the invention.
- the invention also proposes the use of the hydrocarbon fluid according to the invention as a crude or hydrogenated and / or fractionated solvent cut for the formulation of inks, paints, varnishes, cleaning products, lubricants for the work. metals, dielectric fluids, drilling fluids, cosmetics.
- a catalyst for the dehydration of fusel oil is prepared from Y-Al 2 O 3 extrudates having a diameter of 1.2 mm, a surface area of 200 m 2 / g, a centered pore size distribution around 124 ⁇ and a pore volume of 0.588 mL / g.
- the extrudates are crushed and then sieved at 35-45 mesh (0.500-0.354 ⁇ m).
- a stainless steel tubular reactor having an internal diameter of 10 mm, is charged with 20 ml of the catalyst Y-Al 2 O 3 thus obtained.
- the empty spaces on either side of the catalyst are filled with powdered silicon carbide (SiC) 0.5 mm in diameter.
- the temperature profile is monitored using a thermocouple placed inside the reactor.
- the temperature of the reactor is increased at a rate of 60 ° C./h up to 550 ° C. under a flow of 45 NL / h of nitrogen and 10 NL / h of air.
- the temperature is maintained at 550 ° C and the nitrogen flow reduced to 30 NL / h.
- the nitrogen flow is further reduced to 10 NL / h.
- the nitrogen flow is stopped and the air flow is increased to 20 NL / h.
- the reactor temperature is lowered to 400 ° C and the reactor is purged with nitrogen.
- ol 0.1% by weight of ethyl pentanoate, 0.3% by weight of ethyl hexanoate, higher ethyl esters and pyrazine derivatives is filtered to remove the fine particles.
- the flow of nitrogen into the reactor is replaced by a stream of filtered fusel oil charge.
- the feedstock is passed through a preheater onto the catalyst bed at an initial internal reactor temperature of 400 ° C and an overall hourly volume (WH) velocity of 4 h 1 .
- the temperature is increased to 425 ° C.
- the catalytic tests are carried out in descending current, at a pressure of 2 barg (bar gauge, gauge pressure) in a temperature range from 300 to 450 ° C and with a space hourly space weight (WHSV) ranging from 2 to 7 h 1 .
- Product analysis is performed using an in-line gas chromatograph.
- a catalyst for the dehydration of fusel oil is prepared from a zeolite of the ferrierite-type (Zeolyst CP914 ® powder) calcined under a flow of 50 NL / h of nitrogen at 550 ° C for 6 hours (1 ° C per minute). The catalyst is then milled and sieved at 35-45 mesh (0.500-0.354 ⁇ m).
- a stainless steel tubular reactor having an internal diameter of 10 mm, is charged with 10 ml (5.53 g) of the ferrierite catalyst thus obtained.
- the empty spaces on either side of the catalyst are filled with powdered silicon carbide (SiC) 0.5 mm in diameter.
- the temperature profile is monitored using a thermocouple placed inside the reactor.
- the temperature of the reactor is increased at a rate of 60 ° C./h up to 550 ° C. under a flow of 10 NL / h of nitrogen. After 1 hour, the reactor temperature is lowered to 260 ° C and the reactor is purged with nitrogen.
- a batch of distilled biosourced fusel oil (125-135 ° C fraction) is prepared, containing, based on the total weight of the filler, less than 0.1% by weight of ethanol, less than 0.1% by weight. weight of propan-1-ol, less than 0.1% by weight of butan-1-ol, about 1.0% by weight of isobutanol, 83.5% by weight of 3-methyl-butan-1-ol 13.8% by weight of 2-methyl-butan-1-ol, less than 0.1% by weight of ethyl pentanoate, higher ethyl esters and pyrazine derivatives.
- the charge of distilled fusel oil is sent through a preheater to the catalyst bed at an internal reactor initial temperature of 260 ° C, an overall hourly volume velocity (WH) of 8 h 1 and a pressure of 2 barg.
- the temperature is gradually increased to 375 ° C.
- Product analysis is performed using an in-line gas chromatograph.
- a catalyst for the dehydration of fusel oil is prepared from a zeolite of the ferrierite-type (Zeolyst CP914 ® CYL-1.6) in the form of extrudates crushed and sieved to 35-45 mesh (0,500- 0,354 pm).
- a stainless steel tubular reactor having an internal diameter of 10 mm is charged with 10 ml of the ferrierite catalyst thus obtained.
- the empty spaces on either side of the catalyst are filled with powdered silicon carbide (SiC) 0.5 mm in diameter.
- the temperature profile is monitored using a thermocouple placed inside the reactor.
- the temperature of the reactor is increased at a rate of 60 ° C./h up to 550 ° C. under a flow of 10 NL / h of nitrogen. After 1 hour, the reactor temperature is lowered to 270 ° C and the reactor is purged with nitrogen.
- a batch of distilled biosourced fusel oil (125-135 ° C fraction) is prepared, containing, based on the total weight of the filler, less than 0.1% by weight of ethanol, less than 0.1% by weight. weight of propan-1-ol, less than 0.1% by weight of butan-1-ol, about 1.0% by weight of isobutanol, 83.5% by weight of 3-methyl-butan-1-ol 13.8% by weight of 2-methyl-butan-1-ol, less than 0.1% by weight of ethyl pentanoate, higher ethyl esters and pyrazine derivatives.
- the charge of distilled fusel oil is sent through a preheater to the catalyst bed at an internal reactor initial temperature of 270 ° C, an overall hourly volume velocity (WH) of 8 h 1 and a pressure of 2 barg.
- the temperature is gradually increased to 350 ° C.
- Product analysis is performed using an in-line gas chromatograph.
- Dehydration of fusel oil results in the mixture of isomers of isoamylenes as follows: 3-methyl-1-butene (3MB1), 2-methyl-but-2-ene (2MB2) and 2-methyl-but- 1-ene (2MB1).
- the ratio of the isoamylenes depends in particular on the dehydration catalyst used, the residence time and the temperature used during the dehydration reaction.
- the amorphous silica-alumina (ASA) catalyst has a BET specific surface area as measured by the ASTM D 4365-95 method (Reapproved 2008) ranging from 100 to 550 m 2 / g and a pore size ranging from 2 to 14 nm.
- the pressure is maintained at 25 bar in the system thanks to a Kammer valve controlled by a pressure sensor. Samples are taken after cooling to 0 ° C at the indicated times, diluted and analyzed by GC-MS.
- Table 2 Results of oligomerization
- Detection is performed using the following standards: C15 assay vs 1-pentadecene standard (counted at 97%, GC); CIO assay vs 1-decene standard (counted at 98%, GC); estimated C6-C9 compounds vs 1-decene standard; estimated C11-C14 compounds vs pentadecene standard; Compounds> C15 not dosed.
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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PCT/EP2019/056532 WO2019175377A1 (fr) | 2018-03-16 | 2019-03-15 | Procede d'oligomerisation d'olefines |
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EP (1) | EP3765584A1 (fr) |
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DE3812683A1 (de) * | 1988-04-16 | 1989-11-02 | Erdoelchemie Gmbh | Verfahren zur isomerisierung von alkenen mit endstaendiger doppelbindung zu alkenen mit innenstaendiger doppelbindung |
WO2007104385A1 (fr) * | 2006-03-10 | 2007-09-20 | Exxonmobil Chemical Patents Inc. | Diminution de la teneur en bases de lewis azotées pendant l'oligomérisation sur tamis moléculaire |
FI120627B (fi) * | 2007-08-24 | 2009-12-31 | Neste Oil Oyj | Menetelmä olefiinien oligomeroimiseksi |
FR2940801B1 (fr) * | 2009-01-06 | 2012-08-17 | Arkema France | Procede de fabrication d'un methacrylate de methyle derive de la biomasse |
EP2404980A1 (fr) * | 2010-07-08 | 2012-01-11 | Total Raffinage Marketing | Augmentation de la masse moléculaire moyenne de produits de départ d'hydrocarbure |
EA034710B1 (ru) * | 2015-01-29 | 2020-03-10 | Ламмус Текнолоджи Инк. | Производство олефинов c5 из потока углеводородов c5 установки парового крекинга |
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