CN114478188A - Preparation method of long carbon chain isomeric alcohol - Google Patents
Preparation method of long carbon chain isomeric alcohol Download PDFInfo
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- CN114478188A CN114478188A CN202210155067.7A CN202210155067A CN114478188A CN 114478188 A CN114478188 A CN 114478188A CN 202210155067 A CN202210155067 A CN 202210155067A CN 114478188 A CN114478188 A CN 114478188A
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 18
- 150000001298 alcohols Chemical class 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 150000001721 carbon Chemical group 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000012074 organic phase Substances 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 9
- 150000002191 fatty alcohols Chemical class 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 3
- 238000007037 hydroformylation reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- -1 aliphatic alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000006546 Horner-Wadsworth-Emmons reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002192 fatty aldehydes Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Abstract
The invention relates to the technical field of organic synthesis, and in particular relates to a preparation method of long carbon chain isomeric alcohol, which comprises the following steps: the compound shown in the formula (1) is obtained by two-stage fixed bed catalytic hydrogenation reaction, and the carbon atom number of the isomeric alcohol is an even number; wherein, the structure of formula (1) is as follows:
the isomeric alcohols have the following structure:
Description
Technical Field
The invention relates to the technical field of organic synthesis, and particularly relates to a preparation method of long carbon chain isomeric alcohol.
Background
The isomeric fatty alcohol has different physical properties compared with normal fatty alcohol, belongs to saturated alcohol and has the characteristics of higher primary aliphatic alcohol. Because of the branched chain, the product is in a net structure, so that the isomeric alcohol and the derivative thereof have good oxidation stability, low freezing point and low irritation, and have good compatibility with various oiliness agents and inactive substances. The isomeric fatty alcohol is widely used in cosmetics, fiber oil, printing ink assistant, textile printing and dyeing assistant and high-grade lubricating oil additive. The sulfonate of isomeric alcohol or polyoxyethylene ether prepared from isomeric alcohol and ethylene oxide has strong wetting power, low foaming property and good washing power and diffusibility as a surfactant, and is widely applied to the fields of textile industry, daily chemical industry and industrial cleaning. The isomeric alcohol is an important higher aliphatic alcohol due to its special structure and unique performance.
The process route of the higher fatty alcohol mainly comprises two process routes of natural oil hydrogenation and high-carbon olefin carbonyl synthesis. The natural oil and fat are hydrogenated to obtain straight chain normal fatty alcohol with even number of carbon atoms, such as n-decyl alcohol, lauryl alcohol (C12 alcohol), myristyl alcohol (C14 alcohol), cetyl alcohol (C16 alcohol), and stearyl alcohol (C18 alcohol). The oxo route can give branched isomeric aliphatic alcohols such as isomeric C10-14, but requires high pressure oxo process starting from long chain olefins and is a capital and hazardous process. The current mainstream process of oxo synthesis is a low-pressure rhodium method, which is suitable for short-carbon olefins below C6, while the deactivation problem of the rhodium catalyst can not be solved all the time due to the high temperature of the product and the catalyst during the separation of the olefins above C6, so that the low-pressure rhodium method can not be applied to the industry of the long-carbon olefins. On the other hand, the structures of fatty alcohols condensed from hydroformylation products of short-carbon alkenes are all Guerbet alcohols, and isomeric alcohols of other structures are rarely reported.
Disclosure of Invention
In view of the problems in the prior art, the first aspect of the present invention provides a method for preparing long carbon chain isomeric alcohol, comprising: the compound shown in the formula (1) is obtained by two-stage fixed bed catalytic hydrogenation reaction, and the isomeric alcoholThe number of carbon atoms of (a) is an even number; wherein, the structure of formula (1) is as follows:
the isomeric alcohols have the following structure:
n is any integer from 1 to 4, and m is any integer from 1 to 5.
As the isomeric alcohols in the present application, there may be mentioned C10 isomeric alcohols, C12 isomeric alcohols, C14 isomeric alcohols and the like.
In one embodiment, in the first stage fixed bed catalytic hydrogenation reaction, the catalyst is a nickel-based catalyst.
As the nickel-based catalyst in the present application, Ni/Al can be exemplified2O3Ni/diatomite, Ni/SiO2And the like.
Preferably, the nickel-based catalyst has a nickel content of 15 to 25 wt%, more preferably 20 wt%.
In one embodiment, in the second stage fixed bed catalytic hydrogenation reaction, the catalyst is a copper-based catalyst.
As the copper-based catalyst in the present application, Cu/SiO can be exemplified2、Cu/Al2O3、Cu-Zn/Al2O3、Cu-Cr/Al2O3And so on.
Preferably, the copper-based catalyst has a copper content of 15 to 25 wt.%, preferably 20 wt.%.
The catalyst content can be routinely selected by those skilled in the art during the two-stage fixed bed catalytic hydrogenation reaction.
In one embodiment, the two-stage fixed bed catalytic hydrogenation reaction comprises: controlling the hydrogen-oil ratio to be (50-500): 1, the reaction pressure is 0.5-5MPa, and the organic phase solution containing the compound shown in the formula (1) is added for 0.1-3h-1The space velocity of (2) is added into a fixed bed, and the reaction is carried out under the action of a catalyst.
Preferably, the reaction temperature is 80-120 ℃ in the first-stage fluidized bed catalytic hydrogenation reaction process.
Preferably, the reaction temperature is 180-280 ℃ in the second-stage fluidized bed catalytic hydrogenation reaction process.
In the application, the first section of the curing bed realizes olefin reduction through catalytic hydrogenation, and the second section of the curing bed realizes ester reduction through catalytic hydrogenation.
In the catalytic hydrogenation process of the two-stage fluidized bed in the application, the solvent is an aromatic hydrocarbon solvent or an alcohol solvent.
In one embodiment, a method of preparing a compound of formula (1) comprises: the compound shown in the formula (3) and triethyl phosphonoacetate react to obtain the compound; wherein, the structure of formula (3) is as follows:
n is any integer of 1-4.
The compounds of formula (3) are not particularly limited in their origin and are either commercially available or may be prepared by methods well known to those skilled in the art, for example, hydroformylation and condensation of short carbon chain C3, C4, C5 α -olefins.
Preferably, the reaction temperature during the preparation of the compound represented by formula (1) is-30 to 50 ℃.
In one embodiment, a method of preparing a compound of formula (1) comprises: adding triethyl phosphonoacetate and a solvent into a reaction vessel, keeping the temperature between minus 5 ℃ and minus 10 ℃, adding an alkaline substance in batches, adding a compound with a structure shown in the formula (3) for reaction, heating to room temperature after complete reaction, adding an organic phase and a water phase, standing for layering, and washing with saturated salt water and water.
Preferably, the molar ratio of the structural compound shown in the formula (3) to triethyl phosphonoacetate is 1: (0.9-1.5).
Preferably, the molar ratio of the structural compound represented by the formula (3) to the basic substance is 1: (1-2).
In one embodiment, the basic substance is an inorganic base and/or an organic base, and preferably, the basic substance is one or more selected from potassium tert-butoxide, sodium methoxide and sodium hydroxide.
The solvent described herein is not particularly limited and may be routinely selected by those skilled in the art. In a preferred embodiment, the solvent is selected from one or more of tetrahydrofuran, alkanes, toluene, xylene. The amount of such solvent is routinely selected by those skilled in the art.
In a preferred embodiment, the process for preparing the compound represented by the formula (1) comprises: adding triethyl phosphonoacetate and a solvent into a reaction vessel, keeping the temperature at-5 ℃, adding an alkaline substance in batches within 10-20min, stirring for 10-20min, adding a toluene solution of a compound with the structure shown in the formula (3) for reaction for 6g, heating to room temperature, adding toluene and water, standing for layering, and washing with saturated saline and water.
In the preparation method of the compound represented by the above formula (1), those skilled in the art can make routine selections in portions not disclosed in the present application.
The concentration of the toluene solution of the compound having the structure represented by the formula (3) in the present application is 55 to 80g/100 mL.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the long carbon chain isomeric alcohol is easy to operate, and the product yield is high and is higher than 80 wt%.
(2) The isomeric alcohol prepared in the application is different from the traditional straight-chain natural fatty alcohol and branched-chain Guerbet alcohol, and the unique structure of the isomeric alcohol can have special application in the industries of daily chemicals, coatings and the like.
(3) The method starts from an intermediate unsaturated fatty aldehyde prepared by catalyzing C3-C5 alpha-olefin through hydroformylation and condensation process by a low-pressure rhodium method as a raw material, prepares long-carbon-chain unsaturated acid ester through Wittig-Horner reaction, and obtains isomeric alcohol through two-stage fixed bed catalytic hydrogenation reaction.
(4) The method obtains the isomeric alcohol with the yield higher than 81 wt% by two-section fixed bed catalytic reaction and simultaneously controlling the catalyst of each section of catalytic reaction.
(5) By controlling the content of nickel and copper in the catalyst, the reaction is easy to control, and the batch stability is good.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
Examples
Example 1
A preparation method of isomeric decal alcohol relates to the following reaction:
into a 1000mL three-necked flask were added 268g of triethyl phosphonoacetate and 600mL of anhydrous THF, followed by replacement of N2Cooling to-5 ℃, adding 149g of potassium tert-butoxide in batches, stirring for 15min, then beginning to dropwise add the compound 1(167g) in toluene (300mL), after dropwise adding for 2h, keeping the temperature and reacting for 6 h. After the reaction is finished, raising the temperature to room temperature, adding 300mL of toluene, stirring uniformly, adding 500mL of water, standing for layering, washing an organic phase with saturated saline solution and water to obtain an organic phase containing the compound 2, wherein the organic phase can be directly used for the next hydrogenation reaction.
60ml of cloverleaf nickel catalyst (nickel content is 20 wt%) is filled in a tubular fixed bed reactor with the size of phi 21mm multiplied by 500mm, and after full activation, a feeding pump is used for accurately feeding materials. Controlling the hydrogen-oil ratio to be 300:1 by a flowmeter, controlling the pressure of a fixed bed to be 1.0MPa, and controlling the organic phase solution in the previous step at 90 ℃ for 1h-1The volume space velocity of the catalyst is introduced into a fixed bed, the reaction releases heat, the temperature of the bed layer is controlled not to exceed 120 ℃, and effluent liquid from the fixed bed is collected and enters the next fixed bed hydrogenation device.
60ml of a strip-shaped copper catalyst (copper content: 20 wt%) was packed in a tubular fixed bed reactor having a size of phi 21mm x 500mm, and after sufficient activation, the material was precisely fed using a feed pump. Controlling the hydrogen-oil ratio to be 300:1 and the fixed bed pressure to be 2.0MPa by a flowmeter, and hydrogenating the previous step at 250 DEG CThe organic phase solution is added for 2 hours-1The volume space velocity of (2) is introduced into a fixed bed, reaction liquid flowing out of the fixed bed is collected, after the solvent of the reaction liquid is removed, the reaction liquid is rectified to obtain 175g of isomeric dodecyl alcohol product, and the yield is 84 wt%.
Example 2
A preparation method of isomeric dodecanol relates to the following reaction:
into a 1000mL three-necked flask were added 268g of triethyl phosphonoacetate and 600mL of anhydrous THF, followed by replacement of N2Cooling to-5 ℃, adding 71g of sodium methoxide in batches, adding the sodium methoxide in 15min, stirring for 15min, then beginning to dropwise add compound 3(203g) anhydrous toluene solution (300mL), after dropwise adding for 2h, keeping the temperature and reacting for 6 h. After the reaction is finished, raising the temperature to room temperature, adding 300mL of toluene, stirring uniformly, adding 500mL of water, standing for layering, washing an organic phase with saturated saline solution and water to obtain an organic phase containing a compound 4, and directly using the organic phase for the next hydrogenation reaction.
60ml of cloverleaf nickel catalyst (nickel content is 20 wt%) is filled in a tubular fixed bed reactor with the size of phi 21mm multiplied by 500mm, and after full activation, a feeding pump is used for accurately feeding materials. Controlling the hydrogen-oil ratio to be 300:1 by a flowmeter, controlling the pressure of a fixed bed to be 1.5MPa, and controlling the organic phase solution in the previous step at 90 ℃ for 1h-1The volume space velocity of the catalyst is introduced into a fixed bed, the temperature of the bed layer is controlled not to exceed 120 ℃, and effluent liquid from the fixed bed is collected and enters a next fixed bed hydrogenation device.
60ml of a strip-shaped copper catalyst (copper content: 20 wt%) was packed in a tubular fixed bed reactor having a size of phi 21mm x 500mm, and after sufficient activation, the material was precisely fed using a feed pump. Controlling the hydrogen-oil ratio to be 300:1 and the fixed bed pressure to be 2.0MPa by a flowmeter, and carrying out hydrogenation on the organic phase solution obtained in the previous step at 250 ℃ for 2h-1Introducing the reaction solution into a fixed bed at a volume space velocity, collecting the reaction solution flowing out of the fixed bed, removing the solvent from the reaction solution, and rectifying to obtain an isomeric dodecanol product198g, yield 81 wt%.
Example 3
A preparation method of isomeric tetradecanol relates to the following reaction:
into a 1000mL three-necked flask were added 268g of triethyl phosphonoacetate and 600mL of anhydrous THF, followed by replacement of N2And (3) cooling to-10 ℃, adding 53g of sodium hydroxide in batches, stirring for 15min, then beginning to dropwise add a compound 5(240g) toluene solution (300mL), keeping the temperature and reacting for 6h after dropwise adding for 2 h. After the reaction is finished, raising the temperature to room temperature, adding 300mL of toluene, stirring uniformly, adding 500mL of water, standing for layering, washing an organic phase with saturated saline solution and water to obtain an organic phase containing the compound 6, wherein the organic phase can be directly used for the next hydrogenation reaction.
60ml of cloverleaf nickel catalyst (nickel content is 20 wt%) is filled in a tubular fixed bed reactor with the size of phi 21mm multiplied by 500mm, and after full activation, a feeding pump is used for accurately feeding materials. Controlling the hydrogen-oil ratio to be 300:1 and the fixed bed pressure to be 2.0MPa by a flowmeter, and controlling the organic phase solution in the previous step at 90 ℃ for 2h-1The volume space velocity of the catalyst is introduced into a fixed bed, the temperature of the bed layer is controlled not to exceed 120 ℃, and effluent liquid from the fixed bed is collected and enters a next fixed bed hydrogenation device.
60ml of a strip-shaped copper catalyst (copper content: 20 wt%) was packed in a tubular fixed bed reactor having a size of phi 21mm x 500mm, and after sufficient activation, the material was precisely fed using a feed pump. Controlling the hydrogen-oil ratio to be 300:1 and the fixed bed pressure to be 2.0MPa by a flowmeter, and carrying out hydrogenation on the organic phase solution obtained in the previous step at 250 ℃ for 2h-1The volume space velocity of (2) is introduced into a fixed bed, reaction liquid flowing out of the fixed bed is collected, after the solvent of the reaction liquid is removed, the reaction liquid is rectified to obtain 231g of an isomeric tetradecanol product, and the yield is 82 wt%.
Claims (10)
1. A method for preparing long carbon chain isomeric alcohol is characterized by comprising the following steps: the compound shown in the formula (1) is obtained by two-stage fixed bed catalytic hydrogenation reaction, and the carbon atom number of the isomeric alcohol is an even number; wherein, the structure of formula (1) is as follows:
the isomeric alcohols have the following structure:
2. The method for preparing long carbon chain isomeric alcohol according to claim 1, wherein the catalyst in the first stage fixed bed catalytic hydrogenation reaction is a nickel-based catalyst.
3. The method for preparing long carbon chain isomeric alcohols according to claim 2, wherein the nickel-based catalyst comprises nickel in an amount of 15 to 25 wt%.
4. The method for preparing long carbon chain isomeric alcohol according to claim 2, wherein the catalyst in the second stage fixed bed catalytic hydrogenation reaction is copper-based.
5. The method for preparing long carbon chain isomeric alcohol according to claim 4, wherein the copper-based catalyst contains copper in an amount of 15-25 wt%.
6. The method for preparing long-carbon chain isomeric alcohol according to any of claims 1 to 5, wherein the two-stage fixed bed catalytic hydrogenation reaction comprises: controlling the hydrogen-oil ratio to be (50-500): 1, the reaction pressure is 0.5-5MPa, and the organic phase solution containing the compound shown in the formula (1) is added for 0.1-3h-1The space velocity of (2) is added into a fixed bed, and the reaction is carried out under the action of a catalyst.
7. The method for preparing long-carbon chain isomeric alcohol according to claim 6, wherein the reaction temperature is 80-120 ℃ during the first stage of the catalytic hydrogenation reaction in the fluidized bed.
8. The method for preparing long chain isomeric alcohols according to claim 7, wherein the reaction temperature during the second stage of catalytic hydrogenation in the fluidized bed is 180-280 ℃.
9. The method for producing a long-carbon chain isomeric alcohol according to claim 6, wherein the method for producing the compound represented by the formula (1) comprises: the compound shown in the formula (3) and triethyl phosphonoacetate react to obtain the compound; wherein, the structure of formula (3) is as follows:
n is any integer of 1-4.
10. The method for preparing a long carbon chain isomeric alcohol as recited in claim 9, wherein the reaction temperature is-30 to 50 ℃ during the preparation of the compound represented by formula (1).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101239888A (en) * | 2008-03-10 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Method for preparing isobutyl alcohol by methylacrolein hydrogenation |
| CN102850181A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Preparation method of higher alcohol |
| CN111875475A (en) * | 2020-07-21 | 2020-11-03 | 万华化学集团股份有限公司 | High-carbon isomeric fatty alcohol and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101239888A (en) * | 2008-03-10 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Method for preparing isobutyl alcohol by methylacrolein hydrogenation |
| CN102850181A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Preparation method of higher alcohol |
| CN111875475A (en) * | 2020-07-21 | 2020-11-03 | 万华化学集团股份有限公司 | High-carbon isomeric fatty alcohol and preparation method and application thereof |
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