阅读说明：本技术 用于低聚烯烃的方法 (Process for oligomerizing olefins ) 是由 C-J·理查德森 L·吉尔曼诺德 S·克斯曼 于 2019-03-15 设计创作，主要内容包括：本发明涉及一种用于制备烃流体的方法,包含初始烃组合物的低聚步骤,该初始烃组合物包含相对于所述初始烃组合物总重量的至少2重量％的3-甲基丁-1-烯、至少5重量％的2-甲基丁-2-烯和至少5％重量的2-甲基丁-1-烯。(The invention relates to a process for the preparation of hydrocarbon fluids comprising an oligomerization step of an initial hydrocarbon composition comprising at least 2 wt% of 3-methylbut-1-ene, at least 5 wt% of 2-methylbut-2-ene and at least 5 wt% of 2-methylbut-1-ene, relative to the total weight of the initial hydrocarbon composition.)

1. A process for the preparation of hydrocarbon fluids comprising an oligomerization step of an initial hydrocarbon composition comprising at least 2 wt.% 3-methylbut-1-ene, at least 5 wt.% 2-methylbut-2-ene and at least 5 wt.% 2-methylbut-1-ene, relative to the total weight of the initial hydrocarbon composition.

2. The method of the preceding claim, wherein the initial hydrocarbon composition is derived from biomass.

3. The method of any one of the preceding claims, wherein the initial hydrocarbon composition is obtained by dehydration of an alcohol, preferably by dehydration of a fusel oil.

4. A process according to any one of the preceding claims, wherein the initial hydrocarbon composition comprises at least 20 wt%, preferably at least 30 wt%, more preferably at least 40 wt%, even more preferably at least 50 wt%, still even more preferably at least 60 wt% of branched olefins having 5 carbon atoms selected from 3-methylbut-1-ene, 2-methylbut-2-ene and 2-methylbut-1-ene, relative to the total weight of the initial composition.

5. A process according to any one of the preceding claims, wherein the initial hydrocarbon composition comprises at least 20 wt%, preferably at least 30 wt%, more preferably at least 40 wt%, further preferably at least 50 wt%, still further preferably at least 60 wt% of 2-methylbut-2-ene relative to the total weight of the composition.

6. A process according to any one of the preceding claims, wherein the initial hydrocarbon composition comprises 3-methylbut-1-ene in a weight proportion such that 3-methylbut-1-ene represents the olefin having 5 carbon atoms present in the initial hydrocarbon composition in the majority amount.

7. The process of any one of the preceding claims, wherein the oligomerization step is carried out in the presence of a catalyst selected from the group consisting of alumina and aluminosilicate.

8. The process of any one of the preceding claims, wherein the catalyst is an aluminosilicate and the SiO of the catalyst₂/Al₂O₃The molar ratio is from 10 to 80, preferably from 15 to 50.

9. The process of any one of the preceding claims, wherein the catalyst is a mesoporous aluminosilicate having a thickness of greater than or equal to 50m²BET specific surface area/g, preferably from 150 to 1200m²A/g, preferably from 250 to 550m²/g。

10. The process of any one of claims 1 to 7, wherein the catalyst is an amorphous SiAl catalyst (ASA) and has 5 to 95 wt% Silica (SiO)₂) Is 100 to 550m²A BET specific surface area in g and a accessible pore diameter in the range from 2 to 14 nm.

11. The process of any one of the preceding claims, carried out at a temperature of from 80 to 220 ℃, preferably from 90 to 210 ℃, more preferably from 100 to 200 ℃.

12. The process of any one of the preceding claims, carried out at a pressure of from 2 to 50 bar, preferably from 5 to 40 bar, more preferably from 10 to 30 bar.

13. The process according to any one of the preceding claims, further comprising at least one treatment step, preferably a hydrogenation step and/or a fractionation step.

14. The process of any one of the preceding claims, comprising the step of recovering an effluent comprising unreacted C5 olefins.

15. A hydrocarbon fluid obtainable according to the method of any one of claims 1 to 14.

16. Use of the hydrocarbon fluids according to the preceding claims as crude or hydrogenated and/or fractionated solvent fraction for formulating inks, paints, varnishes, cleaning products, lubricants for metal working, dielectric fluids, drilling fluids, cosmetics.

Technical Field

The present invention relates to a process for oligomerizing olefins with good yields and good selectivity for various uses, in particular as solvent fluids and jet fuels.

Background

Hydrocarbon fluids are widely used as solvents, for example, solvents for adhesives, cleaning fluids, explosives, solvents for decorative coatings and printing inks, light oils for uses such as metal extraction, metal working or stripping, industrial lubricants, and drilling fluids. Hydrocarbon fluids may also be used as diluent oils in adhesives and sealing systems (e.g. silicone mastics), as viscosity reducers in formulations containing plasticized polyvinyl chloride, as carriers in polymer formulations used as flocculants in, for example, water treatment, mining operations or paper industry, and also as thickeners for printing pastes. Hydrocarbon fluids are also widely used as solvents in other applications, such as chemical reactions.

The chemistry and composition of hydrocarbon fluids vary widely based on the intended use of the fluid. The main properties of hydrocarbon fluids are: distillation curves (generally determined according to ASTM D86 or ASTM D1160 methods, which use vacuum distillation techniques for heavier materials), flash point, density, aniline point (determined according to ASTM D611 methods), aromatics content, sulfur content, viscosity, color, and refractive index. These fluids can be classified as paraffins, isoparaffins, dearomatics, cycloparaffins, non-dearomatics and aromatics.

Document US5008466 discloses a process for the isomerization of olefins having terminal double bonds to obtain olefins having internal double bonds. This document does not disclose a process for the oligomerization of branched C5 olefins.

Disclosure of Invention

These objects are achieved by a novel process for oligomerizing olefins.

The invention relates to a process for the preparation of hydrocarbon fluids comprising an oligomerization step of an initial hydrocarbon composition comprising at least 2 wt% of 3-methylbut-1-ene, at least 5 wt% of 2-methylbut-2-ene and at least 5 wt% of 2-methylbut-1-ene, relative to the total weight of the initial hydrocarbon composition.

In one embodiment of the invention, the initial hydrocarbon composition is derived from biomass.

In one embodiment of the invention, the initial hydrocarbon composition is obtained by dehydration of an alcohol, preferably by dehydration of a fusel oil.

In one embodiment of the invention, the initial hydrocarbon composition comprises at least 20 wt%, preferably at least 30 wt%, more preferably at least 40 wt%, further preferably at least 50 wt%, still further preferably at least 60 wt% of branched olefins having 5 carbon atoms selected from 3-methylbut-1-ene, 2-methylbut-2-ene and 2-methylbut-1-ene, relative to the total weight of the initial composition.

In one embodiment of the invention, the initial hydrocarbon composition comprises at least 20 wt.%, preferably at least 30 wt.%, more preferably at least 40 wt.%, even more preferably at least 50 wt.%, still even more preferably at least 60 wt.% 2-methylbut-2-ene relative to the total weight of the composition.

In one embodiment of the invention, the initial hydrocarbon composition comprises 3-methylbut-1-ene in a weight proportion such that 3-methylbut-1-ene represents the olefin having 5 carbon atoms present in the initial hydrocarbon composition in a majority amount.

In one embodiment of the invention, the oligomerization step is carried out in the presence of a catalyst selected from the group consisting of alumina and aluminosilicate.

In one embodiment of the invention, the catalyst is an aluminosilicate and the SiO of the catalyst₂/Al₂O₃The molar ratio is from 10 to 80, preferably from 15 to 50.

In one embodiment of the invention, the catalyst is a mesoporous aluminosilicate having a thickness greater than or equal to 50m²BET specific surface area/g, preferably from 150 to 1200m²A/g, preferably from 250 to 550m²/g。

In another embodiment of the invention, the catalyst is an amorphous Si Al catalyst (ASA) and has a Silica (SiO) content of 5 to 95 wt. -%₂) Is 100 to 550m²A BET specific surface area in g and a accessible pore diameter in the range from 2 to 14 nm.

In one embodiment, the process of the invention is carried out at a temperature of from 80 to 220 ℃, preferably from 90 to 210 ℃, more preferably from 100 to 200 ℃.

In one embodiment, the process of the invention is carried out at a pressure of from 2 to 50 bar, preferably from 5 to 40 bar, more preferably from 10 to 30 bar.

In one embodiment, the process of the invention further comprises at least one treatment step, preferably a hydrogenation step and/or a fractionation step.

In one embodiment, the process of the present invention comprises the step of recovering an effluent comprising unreacted C5 olefins.

The invention also relates to a hydrocarbon fluid obtainable with the process of the invention.

Finally, the invention relates to the use of the hydrocarbon fluids of the invention as crude or hydrogenated and/or fractionated solvent fractions for formulating inks, paints, varnishes, cleaning products, lubricants for metal processing, dielectric fluids, drilling fluids, cosmetics.

By the process of the invention, hydrocarbon fluid mixtures can be obtained in good yield and with good selectivity.

The process of the invention may be carried out from a feedstock of biological origin.

The process of the present invention allows to obtain various hydrocarbon fractions using a single oligomerization step, optionally followed by a hydrogenation and/or fractionation step.

Detailed Description

The invention relates to a process for the preparation of hydrocarbon fluids comprising an oligomerization step of an initial hydrocarbon composition comprising at least 2 wt.% of 3-methylbut-1-ene, at least 5 wt.% of 2-methylbut-2-ene and at least 5 wt.% of 2-methylbut-1-ene, relative to the total weight of the hydrocarbon composition.

Initial Hydrocarbon composition (referred to as "initial composition")

The initial composition (subjected to oligomerization) contained three different branched olefins, each having 5 carbon atoms. In particular, the initial composition comprises at least 2% by weight of 3-methylbut-1-ene, at least 5% by weight of 2-methylbut-2-ene and at least 5% by weight of 2-methylbut-1-ene, relative to the total weight of the initial composition.

"branched olefin having 5 carbon atoms" means an olefin comprising a branched hydrocarbon chain having 5 carbon atoms. In the meaning of the present invention, the term "branched C5 olefin" designates a branched olefin having 5 carbon atoms.

In one embodiment, the initial composition comprises at least 20 wt.%, preferably at least 30 wt.%, more preferably at least 40 wt.%, even more preferably at least 50 wt.%, still even more preferably at least 60 wt.%, relative to the total weight of the initial composition, of a branched olefin having 5 carbon atoms, selected from 3-methylbut-1-ene, 2-methylbut-2-ene and 2-methylbut-1-ene.

In a particular embodiment, the initial composition comprises at least 20% by weight, preferably at least 30% by weight, more preferably at least 40% by weight, further preferably at least 50% by weight, still further preferably at least 60% by weight of 2-methylbut-2-ene relative to the total weight of the initial composition.

In one embodiment of the invention, the initial composition comprises between 50 and 90% by weight, preferably between 55 and 80% by weight, of 2-methylbut-2-ene relative to the total weight of the olefins having 5 carbon atoms.

In another embodiment of the invention, the initial hydrocarbon composition comprises 3-methylbut-1-ene in a weight proportion such that 3-methylbut-1-ene represents the olefin having 5 carbon atoms present in the initial hydrocarbon composition in a majority amount. Thus, preferably, the initial composition has a weight ratio of (3-methylbut-1-ene)/(each C5 olefin other than 3-methylbut-1-ene) greater than or equal to 1, preferably strictly greater than 1, more preferably greater than or equal to 1.2, still more preferably greater than or equal to 1.5.

In one embodiment of the invention, the initial composition comprises at least 50% by weight of 3-methylbut-1-ene relative to the total weight of olefins having 5 carbon atoms.

In one embodiment of the invention, the starting composition is derived from the conversion of biomass. Derived from the conversion of biomass, means a composition produced from a feedstock of biological origin, preferably selected from sugars and sugar precursors, such as cellulose, hemicellulose, lignocellulose and mixtures thereof, the latter possibly being produced by microorganisms (such as yeasts, algae and bacteria).

In particular, the initial composition may be obtained by dehydration of an alcohol (preferably derived from the conversion of biomass). Some yeasts produce high quality alcohols in large quantities, e.g. Esteban Espinosa Vidal, Marcos Antonio de MoraisJr, Jean Marie

And "biosynthesis of high alcohol flavor compounds by Saccharomyces cerevisiae", published by Gustavo M.de Billerbeck topic group in Yeast journal (journal Yeast)2015, volume 32, pages 47-56: the oxygen availability and the effect on the glucose-pulsed reaction in minimal growth media with leucine as the sole nitrogen source (biosynthesis of lipid and lipid to glucose pulse in minor with lipid) or Yuan J, Mishra P and ChingCB groups in Industrial microbiology and Biotechnology journal (journal J Ind. Microbiologics.) published in 2017, volume 44, page 107, publication of "Engineering of the biosynthetic pathway for overproduction of isoamyl alcohol in Saccharomyces cerevisiae" are shown.

In a preferred embodiment, the initial composition is obtained by dehydration of fusel oil. "fusel oil" refers to an alcohol mixture derived from the fermentation of a feedstock of biological origin followed by distillation of the effluent obtained after fermentation. Fusel oils are well known to those skilled in the art as byproducts of alcohol fermentation. The fusel alcohol is a mixture of alcohols (e.g., propanol, butanol, isobutanol, pentanol, methyl butanol, hexanol, fatty alcohols), terpenes, and furfural. They are formed as metabolic byproducts by alcohol fermentation. The main compounds contained in the so-called fusols are: propanol, butanol, pentanol, isoamyl alcohol and hexanol. Fusel oils may optionally comprise heavier linear alcohols, such as C7 and/or C8. These products are formed during fermentation when the temperature and pH are high. They are concentrated in the distillation tails at the end of the process. They then have an oily appearance and are therefore referred to as fusel oils. The fusel oil may also optionally comprise ethanol, depending on the separation effect after fermentation.

Fusel oils can be obtained by different processes well known to the skilled person, for example by direct sampling in a distillation column followed by cooling. The sample may optionally be purified, for example by extraction followed by decantation. Two phases can be obtained by liquid/liquid extraction by decantation after addition of water. The top phase contains essentially amyl and butanol, which are practically insoluble in water. It is called decanted or crude fusel oil. It may be chemically treated (typically with a salt saturated solution) and/or fractionated by distillation to remove moisture and separate residual ethanol. Then the "refined" fusel oil is obtained. Other purification methods for fusel oils use regenerated adsorbents to separate the different fractions. Among the many adsorbents tested, granular activated plant carbon is preferred because it can adsorb 8 times its weight of fusel oil. The alcohol may then be separated from the other components by a fractionation step.

In one embodiment, the initial composition is obtained by dehydration of a mixture comprising at least 12% by weight of alcohol having 5 carbon atoms, at least 1% by weight of ethanol, less than 5% by weight of esters and less than 5% by weight of water, relative to the total weight of the mixture. In one embodiment, 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, further preferably at least 50% by weight, still further preferably at least 60% by weight of alcohol having 5 carbon atoms, relative to the total weight of the mixture.

The alcohol having 5 carbon atoms contained in the mixture is preferably selected from the group consisting of C5 isoamyl iso-alcohol, preferably from the group consisting of 3-methylbutan-1-ol, 2-methylbutan-1-ol and mixtures thereof. C5 Isoalcohol refers to an alcohol having a branched hydrocarbon chain having 5 carbon atoms.

In the present invention, the alcohol is preferably a primary alcohol, in other words, one in which the-OH function is associated with-CH₂-a group-linked alcohol.

The dehydration may be carried out using a dehydration catalyst, for example selected from zeolites, alumina, silica-alumina and acid catalysts, preferably selected from zeolites, alumina and silica-alumina. In one embodiment of the invention, the dehydration catalyst is a silica-alumina selected from the group consisting of zeolites and aluminas. In another embodiment of the present invention, the dehydration catalyst is alumina. Preferably, the dehydration catalyst is selected from the group consisting of gamma alumina, H-beta zeolite, and H-gamma zeolite. Such dehydration catalysts are well known to the skilled artisan and are commercially available.

In one embodiment, the catalyst for dehydration is selected from zeolites and has a SiO of greater than or equal to 10₂/Al₂O₃The molar ratio is preferably not less than 20, more preferably not less than 30, still more preferably not less than 60, and most preferably not less than 80.

In another embodiment, the catalyst for dehydration is selected from alumina, preferably gamma alumina. As examples of catalysts of the alumina type, mention may be made of those sold by the company Sasol

A series of catalysts.

In an advantageous embodiment, the catalyst used for the dehydration is a zeolite of ferrierite type, for example in the form of a powder or extrudate. By way of example, mention may be made of the ammonium ferrierite powder formOr in the form of extrudates

CYL 1.6, both sold by Zeolyst.

Between the dehydration step and the oligomerization step, a separation step may be provided to remove the water-type compounds present and optionally the residual esters and alcohols, to obtain the initial composition required for the oligomerization according to the invention.

Catalyst for oligomerization

The catalyst used for the oligomerization may be selected from zeolites, alumina, silica-alumina and aluminosilicates. Such catalysts are well known to the skilled person and are commercially available.

In one embodiment of the invention, the catalyst for oligomerization according to the invention has a SiO of 10 to 80₂/Al₂O₃The molar ratio is preferably 15 to 50.

In one embodiment of the invention, the catalyst used for the oligomerization is selected from aluminosilicates. Thus, in one embodiment, the catalyst for oligomerization of the present invention is different from zeolite.

In one embodiment of the invention, the catalyst is selected from aluminosilicates having a pore size of 1 to 50nm, preferably 1 to 25nm, more preferably 2 to 20 nm.

In one embodiment, the aluminosilicate-type catalyst used in the present invention is a mesoporous aluminosilicate, which typically has a thickness of greater than or equal to 50m²BET specific surface area/g, preferably from 150 to 1200m²(iv) g, more preferably 250 to 550m²(ii) in terms of/g. An example of such a catalyst is an Al-MCM-41 type catalyst.

In another embodiment, the aluminosilicate-type catalyst used in the present invention is an amorphous Si Al catalyst (ASA), typically having a Silica (SiO) content of 5 to 95 wt. -%₂) Is 100 to 550m²BET specific surface area/g and pore diameter of 2 to 14 nm.

In the present invention, the specific surface area is measured by a BET method and the specific surface area is measured by an adsorbed gas, which are well known to the skilled person.

In the present invention, the pore size is determined by physical adsorption of nitrogen … …

Oligomerization

In one embodiment of the process of the present invention, the initial composition (oligomerization feed) is contacted with the catalyst at a temperature of from 80 to 220 ℃, preferably from 90 to 210 ℃, more preferably from 100 to 200 ℃.

In one embodiment of the present invention, the oligomerization step is carried out at a pressure of from 2 to 50 bar, preferably from 5 to 40 bar, more preferably from 10 to 30 bar.

In one embodiment of the invention, the oligomerization step is carried out at a temperature of from 90 to 220 ℃, preferably from 95 to 210 ℃, more preferably from 100 to 200 ℃, and at a pressure of from 2 to 50 bar, preferably from 5 to 40 bar, more preferably from 10 to 30 bar.

In one embodiment, the oligomerization process is carried out in the liquid phase.

Oligomerization allows the obtainment of C10 dimers, C15 trimers and other molecules, such as C6-C9 molecules and C11-C14 molecules.

A separation step may be provided after the oligomerization step to separate molecules having 5 or less carbon atoms used as feed from molecules having 6 or more carbon atoms produced. Thus, this separation step allows to obtain a first stream comprising molecules having 5 or less carbon atoms and a second stream comprising molecules having 6 or more carbon atoms. In this embodiment, a step may be provided for recovering an effluent comprising unreacted C5 olefins. Thus, a recycle loop may be provided such that all or part of the first stream, or the second stream, is returned upstream of the oligomerization reaction.

After the oligomerization step, the reaction product obtained can be subjected to different treatments. If a separation step is carried out after the oligomerization, the subsequent treatment is preferably carried out on a second stream comprising molecules having 6 or more carbon atoms.

In the subsequent work-up, hydrogenation and/or fractionation may be mentioned.

In one embodiment, the process of the invention comprises an oligomerization step, such as described above, followed by a hydrogenation step. The hydrogenation can be carried out using methods well known to the skilled person.

In one embodiment, the process of the invention comprises an oligomerization step, such as described above, followed by a fractionation step.

In one embodiment, the process of the invention comprises an oligomerization step such as described above followed by a hydrogenation step which is followed by a fractionation step.

Fractionation of hydrocarbon fluids is well known to the skilled person. In particular, it allows to obtain hydrocarbon fractions with different distillation ranges. The process of the invention allows to obtain a hydrocarbon fraction defined by its distillation range.

Hydrocarbon fluids

The invention also relates to a hydrocarbon fluid obtainable by the preparation process of the invention.

Finally, the invention also relates to the use of the hydrocarbon fluids of the invention as crude or hydrogenated and/or fractionated solvent fractions for formulating inks, paints, varnishes, cleaning products, lubricants for metal processing, dielectric fluids, drilling fluids, cosmetics.