CN110240538B - Method for preparing high-carbon branched-chain secondary alcohol - Google Patents
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Abstract
The invention relates to a method for preparing high-carbon branched secondary alcohol. The branched olefine aldehyde is prepared by self-condensation of straight-chain or branched aliphatic aldehyde without tertiary carbon, the branched olefine aldehyde and aliphatic ketone without tertiary carbon are subjected to gas-liquid heterogeneous condensation reaction under the catalysis of organic base to prepare branched dienone, and the obtained branched dienone is hydrogenated to prepare unsaturated or saturated branched secondary alcohol. The method has wide raw material source and low cost; the product has definite structure, and is particularly suitable for manufacturing narrow molecular weight distribution secondary alcohol polyoxyethylene ether and derivatives thereof; the alcoholic hydroxyl group of the product is secondary alcohol, contains a branched chain structure but has no tertiary carbon structure, and has excellent low-temperature performance and good biodegradability.
Description
Technical Field
The invention relates to a method for preparing high-carbon branched secondary alcohol.
Background
The high-carbon secondary alcohol can be used for preparing the surfactant, and compared with the surfactant corresponding to the linear chain primary alcohol, the surfactant prepared from the secondary alcohol has certain advantages in low-temperature performance and emulsifying performance, and has good biodegradability. The branched primary alcohol prepared by carbonylation of propylene and butylene oligomers has better low-temperature performance than linear secondary alcohol due to rich branched structure, but has lower biodegradability than linear secondary alcohol due to tertiary carbon structure. Guerbet alcohols prepared by condensation of two molecules of linear alcohols or hydrogenation of two molecules of linear aldehydes have branched chains to improve low temperature performance, but do not contain tertiary carbon structures to maintain good biodegradability, but the most used amount of surfactant is C12-C16 alcohol, if Guerbet alcohol is used, C6-C8 linear alcohol is needed for preparation, the proportion of C6-C8 linear alcohol in natural fatty alcohol is very low, and C5-C7 linear olefin is needed if C6-C8 linear alcohol is synthesized by using carbonyl, and resources are very scarce, so that the cost of C12-C16 Guerbet alcohol is high (surfactant chemistry and technology).
The high-carbon secondary alcohol is generally prepared by oxidizing straight-chain alkane or paraffin, and because aromatic hydrocarbon has certain influence on the activity of the oxidation reaction, fuming sulfuric acid or sulfur trioxide is needed to remove the aromatic hydrocarbon, so that on one hand, the raw material cost is increased, a large amount of three wastes are generated, and the requirement on equipment material is higher. Because the activation energy of the continuous oxidation of the alcoholic hydroxyl group is similar to the energy required for the hydroxylation of the alkane, the method has the advantages that the activation energy is similar to that of the continuous oxidation of the alcoholic hydroxyl groupIn order to avoid over-oxidation, boric acid is generally used as a catalyst, the conversion per pass needs to be controlled to be 15-30%, a large amount of alkane needs to be separated and recycled, and the energy consumption is high; even so, the selectivity of secondary alcohol is only 65-84%, which brings great difficulty to product purification, needs alkali liquor saponification, layering, water washing and distillation, generates a large amount of three wastes, and the product tends to have yellow color (JP62-79267, US3442959, research on preparation of secondary alcohol by oxidation of normal alkane). In addition, there are also reports of methods for the preparation of higher secondary alcohols by reduction of linear alkyl ketones (2-decadione, 7-tridecone, 2-hexadecone), but the hydrogen source is lithium aluminum hydride, sodium borohydride, (EtO)2The hydride such as MeSiH, etc. has large consumption and high cost, and the key point is that the source of the high-carbon straight chain ketone is very limited and is not suitable for large-scale production.
In a word, the existing high-carbon secondary alcohol and the preparation method thereof are difficult to ensure low cost and high quality and simultaneously have excellent biodegradability, low temperature and emulsifying property of the product.
Disclosure of Invention
The invention aims to provide a method for preparing high-carbon branched secondary alcohol. The method has the advantages of wide raw material source, low cost, high product quality, few byproducts, no tertiary carbon in a molecular structure, excellent low-temperature performance and good degradability.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a process for the preparation of a high carbon linear secondary alcohol comprising the steps of:
1) self-condensation of straight-chain or tertiary carbon-free branched-chain aliphatic aldehydes to produce branched-chain alkenals; 2) condensing the branched olefine aldehyde prepared in the step 1) and aliphatic ketone without tertiary carbon under the catalytic action of organic base to prepare branched dienone; 3) and 2) hydrogenating the branched-chain dienone obtained in the step 2) to prepare branched-chain secondary alcohol.
By way of example, the reaction equation for an overall reaction can be expressed as follows:
step 1):
step 2):
step 3):
in the process of the present invention, the branched aliphatic aldehyde having a straight chain or a branched chain not containing a tertiary carbon has no branch at the beta-position.
In the method, the carbon number of the linear chain or the branched chain aliphatic aldehyde without tertiary carbon is 3-9, and the aliphatic aldehyde can be prepared from ethylene, propylene, normal/isobutene, butadiene, normal/isopentene, normal/isohexene, normal/isoheptene and normal/isooctene through carbonylation reaction; aliphatic aldehydes having a carbon number of 3 to 5 such as propionaldehyde, n-butyraldehyde, valeraldehyde, 3-methylbutyraldehyde and the like are preferable.
In the method, the branched olefine aldehyde is prepared by a known method, for example, self-condensation and reaction are completed under the catalysis of a basic catalyst (NaOH, KOH, trimethylamine, triethylamine and the like), then the basic catalyst is removed from a product by methods of neutralization, water washing and the like, and unreacted raw materials and by-products such as acetal, hemiacetal, acid, ester and the like are removed by rectification or distillation to obtain the branched olefine aldehyde (refer to the literature, 2-propylheptanol synthesis process research by condensation of valeraldehyde, zhang, doctor paper of Tianjin university).
In the method of the present invention, the aliphatic ketone containing no tertiary carbon has a carbon number of 3 to 7, such as acetone, methyl ethyl ketone, methyl isopropyl ketone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, heptanone, etc.; aliphatic ketones having a carbon number of 3 to 6 such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone are preferred.
In the method of the present invention, the boiling point of the branched alkenal in the step 2) or the bubble point thereof in the solvent used is higher than the boiling point of the aliphatic ketone. If 2-methylpenteneal (bp 134 ℃) is used, the corresponding ketone can be acetone (bp 56.5 ℃), methyl ethyl ketone (bp 73.4 ℃), methyl isobutyl ketone (bp 94 ℃), 3-pentanone (bp 100 ℃), 2-pentanone (bp 102 ℃), methyl isobutyl ketone (bp 117 ℃) but not heptanone (bp 149 ℃). The molar ratio of alkenal to aliphatic ketone is 0.01 to 100, preferably 0.1 to 10.
In the method of the invention, the condensation reaction in the step 2) has the operation pressure of 5-1000kPaA, and the operation temperature is lower than the boiling point of the branched olefine aldehyde and higher than the boiling point of the aliphatic ketone under the corresponding operation pressure, so that the reaction is carried out in two phases of gas (aliphatic ketone) -liquid (branched olefine aldehyde). For example, 2-methylpenteneal (bp 134 ℃) and methylisobutylketone (bp 94 ℃) need to be operated at normal pressure at temperatures higher than 94 ℃ and lower than 134 ℃.
In the method of the invention, the organic base catalyst in the step 2) is N- [3- (dimethylamino) propyl ] -perfluoroalkyl amide, wherein the carbon atom number of the perfluoroalkyl is 2-10, preferably 4-8. The advantages of using the catalyst are that: the boiling points of the catalysts are all more than 239 ℃, and the n-valeraldehyde condensate with the highest boiling point in the olefine aldehyde is 2-propylheptenal (the boiling point is 224 ℃), so that the catalysts are also in liquid phase under the operating conditions; the N- [3- (dimethylamino) propyl ] of the catalyst is a basic group with catalytic activity, and the basic group is combined with the perfluoroalkyl group through an amide group, so that the surface tension of the catalyst is reduced to between 16 and 24dyne/cm and is lower than that of the branched olefine aldehyde (the surface tension is more than 25dyne/cm) in the step 2), therefore, the catalyst is prone to migrate to the surface of the branched olefine aldehyde after being mixed with the branched olefine aldehyde, the aliphatic ketone in a gas phase can react only after being diffused into a liquid film of the branched olefine aldehyde, and the concentration of the catalyst in the liquid film is the highest, thereby being very beneficial to improving the catalytic efficiency of the catalyst and having high product selectivity. In addition, because the fluoroalkyl compound has the lipophobic property, and the density of the series of catalysts is more than 1.2g/ml and is far greater than that of the branched olefine aldehyde and the aliphatic ketone (about 0.8g/ml), the catalysts can be separated from reaction liquid by standing or centrifuging after the reaction is finished, and the recycling of the catalysts is convenient.
Under the conditions, the aliphatic ketone is in a gas phase in a reaction system, the branched olefine aldehyde is in a liquid phase in the reaction system, the organic base catalyst is uniformly dispersed in the branched olefine aldehyde in the liquid phase, and the beta position of the branched olefine aldehyde does not contain active hydrogen, so that the self-condensation of the olefine aldehyde is not easy to occur; meanwhile, because the catalyst is only in the liquid phase, the ketone in the gas phase is not easy to be catalyzed to undergo self-condensation; the reaction takes place under the catalysis of the organic base in the liquid phase only when the ketone in the gas phase diffuses into the liquid film of enal, and the reaction tends to take place more between the ketone and the enal, since the molar ratio of enal to ketone in the liquid film is greatly excessive. In the traditional aldehyde-ketone condensation reaction, in order to avoid the self-condensation of ketone, a method of slowly dripping ketone into aldehyde is generally adopted, the problem that the ketone is difficult to avoid and the condensation of the ketone is caused by high local concentration is caused, the reaction is usually intermittent, the efficiency is not high, and the method can overcome the difficulty.
N- [3- (dimethylamino) propyl group]The preparation method of the perfluoroalkyl amide comprises the following steps: n, N-dimethyl-1, 3-propanediamine ((CH)3)2NCH2CH2CH2NH2，
) Reacting with perfluoromethyl alkanoate at a molar ratio of 1.1:1 for 3-5 h at 120-150 ℃ by using sodium methoxide with a molar amount of 3-5% of that of the perfluoromethyl alkanoate as a catalyst, completely converting the perfluoromethyl alkanoate, washing with water to remove methanol, the catalyst and excessive N, N-dimethyl-1, 3-propane diamine, and obtaining an oil phase product, namely the target catalyst.
In the method of the invention, the condensation reaction in the step 2) adopts a ratio of the area of the bubble to the volume of the liquid phase of 20-1000000m2/m3Preferably the ratio of the area of the gas bubbles to the volume of the liquid phase is 1000-1000000m2/m3Such as falling film reactor, spray tower, plate tower, packed tower, jet loop reactor, spray loop reactor, more preferably the ratio of gas bubble area to liquid phase volume is 10000-1000000m2/m3Jet loop reactors and spray loop reactors. The use of a reactor of the type described above ensures that the volume per unit volume is sufficientThe large liquid film area ensures the contact of the ketone and the aldehyde and improves the reaction efficiency. The catalyst is used in an amount of 0.1 to 20 mol%, preferably 0.5 to 10 mol%, based on the branched enal. The liquid phase residence time is 5s-3h, preferably 1-10 min.
In the method of the present invention, the target product of the dienone in step 2) can be obtained by distilling the unreacted olefine aldehyde out of the reaction system from the mixture obtained after the catalyst is removed from the reaction solution in step 2) by a known rectification or distillation method.
In the method, the branched secondary alcohol is saturated or unsaturated alcohol, the existence of carbon-carbon double bonds in the unsaturated alcohol is more favorable for the biodegradability of the branched secondary alcohol, the surface tension is also influenced to a certain extent, and the biodegradability and the surface tension of the product can be adjusted by adjusting the number of the carbon-carbon double bonds.
In the method, when the target product in the step 3) is an unsaturated branched secondary alcohol, because the bond energy (615kJ/mol) of a carbon-carbon double bond is less than the bond energy (715kJ/mol) of a carbon-oxygen double bond, in order to avoid preferential hydrogenation of the carbon-carbon double bond over the carbon-oxygen double bond, a supported Pt catalyst containing one or more elements of Sn, Fe, Ru and Co is adopted as the catalyst, preferably supported Pt-Sn and/or Pt-Ru is adopted, the molar ratio of Pt to other metals is 0.1-1, preferably 0.2-0.5, and the metal loading is 2-6 wt%, preferably 3-5 wt%; the carrier is one or more of activated carbon, alumina, zeolite molecular sieve, silicon dioxide and titanium dioxide, and preferably alumina and/or titanium dioxide. The catalyst is prepared by a conventional equivalent-volume impregnation method, wherein the reduction temperature is 350-550 ℃, and preferably 400-450 ℃. Hydrogenation reaction in the presence of solvent-free or supercritical CO2The solvent is preferably supercritical CO without auxiliary agent or tertiary amine, tertiary phosphine or tertiary phosphite2As a solvent, triphenylphosphine or triphenylphosphine oxide is used as a cocatalyst; the reaction temperature is 40-150 ℃, the hydrogen pressure is 4-8MPaG, CO2Pressure 8-15MPaG, catalyst amount 5-20 wt% of substrate (ketene), assistant 0.5-5 wt% of substrate, and liquid phase residence time 1-10h, preferably 2-5 h. The conversion rate is more than or equal to 95 percent, the selectivity of the enol is more than or equal to 95 percent, and the byproduct is mainly saturated alcohol. CO after pressure relief after hydrogenation reaction2Escape of catalystFiltering and separating, separating unreacted ketene from the product mixture by rectification, and then rectifying to remove the cocatalyst (such as triphenylphosphine) to obtain the target product (the content of saturated secondary alcohol is less than or equal to 5%).
In the method, when the target product in the step 3) is a saturated branched secondary alcohol, the catalyst adopts copper-zinc-aluminum, copper-chromium, a skeleton nickel alloy, supported palladium, supported ruthenium, supported platinum and supported cobalt, and preferably one or more of copper-zinc-aluminum, copper-chromium and a skeleton nickel alloy; the copper-zinc-aluminum catalyst contains 5-55 wt% of copper oxide, 10-60 wt% of ZnO and the balance of aluminum oxide; the content of copper oxide in the copper-chromium catalyst is 5-75 wt%, and the balance is chromium oxide; the content of active components of the supported catalyst is 0.1-25 percent (if the supported amount of the noble metal is 0.1-5 percent, if the supported amount of the non-noble metal is 2-25 percent); the dosage of the catalyst is 0.5-20 wt% of the substrate branched-chain dienone; the reaction temperature is 60-250 ℃, preferably 80-160 ℃; the reaction pressure is 0.1-30MPaA, preferably 2-10 MPa; the liquid phase residence time is 0.2-20h, preferably 2-10 h. The conversion rate is more than or equal to 99 percent, the selectivity is more than or equal to 98 percent, and the by-product is mainly alkane generated by over-hydrogenation, and the target product is obtained after rectification and separation. The amount of hydrogen used is 3 to 100 times (molar ratio) that of the substrate branched dienone, preferably 3.5 to 10 times.
The invention has the positive effects that: the raw materials for preparing the branched secondary alcohol are conventional bulk chemicals, the sources are wide, and the cost is low; the product has a definite structure, is not a mixture, and is particularly suitable for manufacturing narrow molecular weight distribution secondary alcohol polyoxyethylene ether and derivatives thereof; the alcoholic hydroxyl group of the product is secondary alcohol and contains a branched structure, the low-temperature performance is excellent, but no tertiary carbon structure exists, and good biodegradability can be maintained.
Drawings
FIG. 1 is a process flow diagram for the preparation of high carbon branched secondary alcohols in accordance with an embodiment of the present invention.
Detailed Description
The method according to the invention will be further illustrated by the following examples, but the invention is not limited to the examples listed, but also encompasses any other known modification within the scope of the claims of the invention.
The gas chromatographic conditions were as follows: DB-5 capillary chromatographic column with the diameter of 30m multiplied by 0.3mm, an FID detector, a gasification chamber temperature of 280 ℃, a column box temperature of 50-300 ℃, a detector temperature of 280 ℃, an argon carrier gas flow of 20ml/min, a hydrogen flow of 30ml/min, an air flow of 300ml/min, a sample injection amount of 1 microliter, a split ratio of 10:1, a temperature rise program: keeping the temperature at 50 deg.C for 2min, heating from 50 deg.C to 300 deg.C at 15 deg.C/min, keeping the temperature at 300 deg.C for 5min, and cooling to 50 deg.C.
Gas chromatography: agilent 9790
The conversion and selectivity in the examples were calculated by gas chromatography analysis.
Nuclear magnetism: Varian-NMR 300, chemical shifts are indicated in ppm;
gas chromatography-mass spectrometry (EI-MS): finnigan MAT 95,70 eV;
an element analyzer: ThermoFisher Flash 2000 CHNS/O organic element analyzer.
As shown in FIG. 1, the preparation of high carbon branched secondary alcohols according to the present invention can be carried out by the following scheme: after the catalytic condensation of the aliphatic aldehyde in an aldehyde condensation reactor, removing the catalyst by water in a catalyst removal tower 1, removing unreacted aliphatic aldehyde by a crude product after the catalyst removal through an aliphatic aldehyde recovery tower for recycling, then removing heavy components in an olefine aldehyde refining tower to obtain a branched olefine aldehyde product, preheating the branched olefine aldehyde product and the catalyst to the reaction temperature, then reacting the branched olefine aldehyde product and the catalyst with gas phase aliphatic ketone preheated to the target temperature (above the boiling point), circulating a part of a liquid phase product to an inlet of the reactor, removing the catalyst and water by a centrifugal separator and a chromatographic apparatus, circulating the catalyst at the lower layer of the chromatographic apparatus to the inlet of the reactor, and pumping the water out of a system; and feeding the crude product without the catalyst into a diene ketone refining tower, continuously returning unreacted olefine aldehyde to the inlet of the reactor, feeding the diene ketone into a hydrogenation reactor for hydrogenation, and feeding the product into a product refining tower for removing the light component subjected to excessive hydrogenation and the heavy component as a byproduct to obtain a branched secondary alcohol product. The catalyst solution in the bottom of the catalyst removing tower 1 is recycled and reused by modes of distillation, rectification, extraction, crystallization and the like.
Example 1
Propionaldehyde is treated at 20 ℃ and normal pressure with 2mol/L NaOHTaking an aqueous solution as a catalyst (the molar ratio of NaOH to propionaldehyde is 0.13), reacting for 2 hours, wherein the conversion rate of propionaldehyde is 99 percent, the selectivity of 2-methyl pentenal is 98 percent, separating oil and water phases after the reaction is finished, washing an oil phase with water to be neutral, and then rectifying in a rectifying tower (the theoretical plate number of the rectifying tower is 20, the reflux ratio is 2, normal pressure operation is carried out, fractions of a tower top temperature of 134 and 136 ℃ are collected), and obtaining a target product, namely 2-methyl-2-pentenal
Distilled off from the top of the tower.
2-methyl-2-pentenal with 10 mol% equivalents of N- [3- (dimethylamino) propyl group]-perfluoroethylamide (synthetic method: (CH)3)2NCH2CH2CH2NH2Reacting with perfluoromethyl acetate at a molar ratio of 1.1:1 for 3h at 120 ℃ in the presence of sodium methoxide with a molar weight of 3% of that of the fluoromethyl acetate as a catalyst, completely converting the fluoromethyl acetate, washing with water to remove methanol, the catalyst and excessive N, N-dimethyl-1, 3-propanediamine to obtain an oil phase product, namely the target catalyst, mixing and preheating the oil phase product to 120 ℃, and introducing the mixture into a falling film reactor in a liquid phase manner (the gas-liquid surface area per unit volume of the liquid phase is 4000 m)2/m3) Heating methyl isopropyl ketone to 120 ℃ to a gasification state, introducing the methyl isopropyl ketone into a falling film reactor, maintaining the pressure of the reactor at 101KPaA, keeping the one-way residence time of a liquid phase for 1min, circulating 90 vol% of a liquid phase product at the outlet of the reactor back to the reactor for continuous reaction, pumping 10 vol% of the product, standing for layering, feeding an upper oil phase into a rectifying tower, and respectively extracting unreacted 2-methyl pentenal and a byproduct heavy component from the tower top and a tower bottom to obtain a product C11 dienone
(theoretical plate number of the rectifying tower is 20, reflux ratio is 2, operation pressure is 5KPaA, and fraction of tower top temperature of 135-. The conversion per pass of the 2-methyl-2-pentenal is 10 percent, and the selectivity of the target product is 99.9 percent.
And (3) qualitative analysis:
nuclear magnetism:1H NMR(500MHz，C6D6，TMS),δ(ppm):1.11(m,9H),2.00(m,2H),2.21(m,3H),3.16(m,1H),5.44(m,1H),6.33(d,J＝14Hz,1H),7.40(d,J＝14Hz,1H)
13C NMR(150MHz，C6D6，TMS),δ(ppm):12,15,19,23,34,39,130,134,147,203
mass spectrum 166,167
Elemental analysis (%): C, 79.46; h, 10.91; o,9.62
Reducing a Pt-Sn catalyst (Pt supporting amount of 1.43 wt%, Sn supporting amount of 3.57 wt%, New materials science and technology Co., Ltd. of Shanghai Xun) supported on gamma-alumina by an equal volume impregnation method at 450 ℃ with hydrogen, hydrogenating C11 dienone with a catalyst corresponding to 15 wt% of C11 dienone, adding triphenylphosphine oxide corresponding to 0.5 wt% of C11 dienone, and carrying out hydrogenation at 60 ℃ under hydrogen pressure of 7MPaG and CO2The hydrogenation is carried out under the pressure of 11MPaG, the conversion rate of C11 dienone reaches 96 percent after 5 hours of reaction, and the C11 dienol
99% selectivity (confirmed by chromatography).
Nuclear magnetism:1H NMR(500MHz，C6D6，TMS),δ(ppm):0.91(d,J＝9Hz,6H),1.06(t,J＝2Hz,3H),1.95(m,3H),2.21(m,3H),2.80(s,1H),3.89(t,J＝14Hz,1H),5.33(m,1H),5.80(m,1H),6.24(m,1H)
13C NMR(150MHz，C6D6，TMS),δ(ppm):15,19,23,34,78,133
mass spectrum 168,169
Elemental analysis (%): C, 78.51; h, 11.98; o,9.51
Example 2
N-butyraldehyde reacts for 0.5h at 100 ℃ and 0.5MPaG by taking 0.5 wt% of NaOH aqueous solution as a catalyst (the mass ratio of NaOH to butyraldehyde is 0.02), the conversion rate is 99%, the selectivity is 98%, oil and water phases are separated after the reaction is finished, the oil phase is washed by water to be neutral, and then the oil phase is rectified in a rectifying tower, and the target product, namely the 2-ethyl-2-hexenal
Distilling from the top of the column (theoretical plate number of the rectifying column is 20, reflux ratio is 2, normal pressure operation, collectingFraction with overhead temperature 174-176 deg.c).
2-Ethyl-2-hexenal with 20 mol% equivalents of N- [3- (dimethylamino) propyl]-perfluorobutylamide (synthetic method: (CH)3)2NCH2CH2CH2NH2Reacting with perfluoromethyl butyrate at a molar ratio of 1.1:1 for 3% in terms of molar weight of the perfluoromethyl butyrate as a catalyst at 125 ℃ for 3.5h, completely converting the perfluoromethyl butyrate, washing with water to remove methanol, the catalyst and excessive N, N-dimethyl-1, 3-propanediamine to obtain an oil phase product, namely a target catalyst, mixing and preheating to 120 ℃, and introducing into a jet loop reactor in a liquid phase form (the gas-liquid surface area of unit liquid phase volume is 10000 m)2/m3) Heating methyl isobutyl ketone to 120 ℃, introducing the methyl isobutyl ketone into the reactor, maintaining the steam pressure of the reactor at 50KPaA, circulating 95 vol% of liquid-phase products at the outlet of the reactor back to the reactor for continuous reaction, keeping the average residence time of the liquid phase for 10min, pumping 5 vol% of the products, standing and layering, feeding the upper oil phase into a rectifying tower, and respectively extracting unreacted 2-ethyl-2-hexenal and byproduct heavy components from the tower top and the tower bottom to obtain a product C14 dienone
(theoretical plate number of the rectifying tower is 20, reflux ratio is 2, operating pressure is 1KPaA, and fraction of the tower top temperature is 127-. The conversion per pass of 2-ethyl-2-hexenal is 5%, and the selectivity of the target product is 99.9%.
Nuclear magnetism:1H NMR(500MHz，C6D6，TMS),δ(ppm):0.91(m,9H),1.06(t,J＝6Hz,3H),1.44(m,2H),1.98(m,1H),2.18(m,2H),2.44(m,2H),2.90(m,2H),5.44(m,1H),6.33(d,J＝17Hz,1H),7.40(d,J＝17Hz,1H)
13C NMR(150MHz，C6D6，TMS),δ(ppm):11,14,23,30,53,128,133,141,163,197
mass spectrum 208,209,210
Elemental analysis (%): C, 80.71; h, 11.61; o,7.68
Will be impregnated in TiO by an equal volume impregnation method2Supported Pt-Ru catalyst (Pt loading 0.33 wt%, Ru)1.67 wt% of load, Shanghainekha New Material science and technology Co., Ltd.) was reduced with hydrogen at 500 ℃ to hydrogenate C14 dienone with a catalyst corresponding to 8 wt% of C14 dienone, the hydrogenation was carried out at 120 ℃ under a hydrogen pressure of 5MPaG, the conversion of C14 dienone reached 98% after 2 hours of reaction, and C14 dienol alcohol was added
The selectivity of (3) was 95%.
Nuclear magnetism:1H NMR(500MHz，C6D6，TMS),δ(ppm):0.91(m,9H),1.06(d,J＝11Hz,3H),1.44(m,4H),1.62(m,1H),2.18(m,2H),2.44(m,2H),2.80(s,1H),3.90(m,1H),5.33(m,1H),5.80(m,1H),6.24(m,1H),
13C NMR(150MHz，C6D6，TMS),δ(ppm):11,14,24,30,48,71,133,163
mass spectrum 210, 211,212
Elemental analysis (%): C, 79.94; h, 12.46; o,7.61
Example 3
N-valeraldehyde reacts for 0.5h at 110 ℃ and 0.5MPaG by using 1.5 wt% of NaOH aqueous solution as a catalyst (the volume ratio of the valeraldehyde to the NaOH aqueous solution is 1), the conversion rate is 99%, the selectivity is 95%, oil and water are separated after the reaction is finished, the oil phase is washed by water to be neutral, and then the oil phase is rectified in a rectifying tower, and the target product, namely the 2-propyl-2-heptenal
Distilling from the tower top (theoretical plate number of the rectifying tower is 20, reflux ratio is 5, operating pressure is 5KPaA, batch rectification, and collecting fraction at tower top temperature of 130 ℃ and 135 ℃).
2-propyl-2-heptenal with 5 mol% equivalent of p-N- [3- (dimethylamino) propyl group]-perfluorohexyl amide (synthetic method: (CH)3)2NCH2CH2CH2NH2Reacting with perfluoromethyl hexanoate at a molar ratio of 1.1:1 in the presence of 4% sodium methoxide as catalyst at 130 deg.C for 4 hr to completely convert the perfluoromethyl hexanoate, washing with water to remove methanol, catalyst and excessive N, N-dimethyl-13-propane diamine is the target catalyst), mixed and preheated to 100 ℃, and then introduced into a spray circulation flow reactor in a liquid phase form (the gas-liquid surface area of unit liquid phase volume is 1000000 m)2/m3) Heating 2-heptanone to 100 ℃, introducing into a falling film reactor, maintaining the steam pressure in the reactor at 10KPaA, circulating 95 vol% of liquid phase product at the outlet of the reactor back to the reactor for continuous reaction, drawing out 5s of liquid phase average residence time, drawing out 5 vol% of product, standing for layering, feeding the upper oil phase into a rectifying tower, respectively extracting unreacted 2-propyl-2-heptenal and byproduct heavy components from the tower top and the tower bottom to obtain a product C17 dienone
(theoretical plate number of the rectifying tower is 20, reflux ratio is 5, operating pressure is 1KPaA, batch rectification is carried out, and fractions with tower top temperature of 156 ℃ and 166 ℃ are collected). The conversion per pass of 2-propyl-2-heptenal is 5 percent, and the selectivity of the target product is 99.9 percent.
Nuclear magnetism:1H NMR(500MHz，C6D6，TMS),δ(ppm):0.91(t,J＝12Hz,9H),1.29-1.44(m,12H),2.18(m,2H),2.41(t,J＝12Hz,2H),2.94(t,J＝12Hz,2H),5.44(m,1H),6.33(d,J＝20Hz,1H),7.40(d,J＝21Hz,1H)
13C NMR(150MHz，C6D6，TMS),δ(ppm):14,23,30,40,53,128,135,141,163,200
mass spectrum 250,251,252
Elemental analysis (%): C, 81.54; h, 12.08; o,6.39
Reducing a Pt-Co catalyst (Pt supporting 1.33 wt%, Co supporting 2.67 wt%, New Material science and technology Co., Ltd. of Shanghai) supported on activated carbon by an isometric impregnation method at 350 ℃ with hydrogen, hydrogenating C17 dienone with a catalyst corresponding to 10 wt% of C17 dienone, adding triphenyl phosphite corresponding to 3 wt% of C17 dienone, and carrying out hydrogenation at 150 ℃ under hydrogen pressure of 6MPaG and CO2Hydrogenation is carried out under the pressure of 15MPaG, the conversion rate of C17 dienone reaches 97 percent after 4 hours of reaction, and C17 dienol
The selectivity of (2) is 99%.
Nuclear magnetism:1H NMR(500MHz，C6D6，TMS),δ(ppm):0.91(m,9H),1.29-1.48(m,14H),2.18(m,2H),2.41(m,2H),2.80(s,1H),3.90(m,1H),5.33(m,1H),5.80(m,1H),6.24(m,1H),
13C NMR(150MHz，C6D6，TMS),δ(ppm):15,22,29,30,38,73,133,136,164
mass spectrum 253,254
Elemental analysis (%): C, 80.88; h, 12.78; o,6.34
Example 4
Reacting n-heptanal at 120 ℃ and 0.5MPaG for 1h by using 2 wt% NaOH aqueous solution as a catalyst (the volume ratio of the heptanal to the NaOH solution is 1.5), wherein the conversion rate is 99% and the selectivity is 97%, separating oil and water phases after the reaction is finished, washing an oil phase with water to be neutral, and rectifying the oil phase in a rectifying tower to obtain a target product 2-pentyl-2-nonenal
Distilling from the tower top (theoretical plate number of the rectifying tower is 20, reflux ratio is 5, operating pressure is 1KPaA, batch rectification is carried out, and fraction with tower top temperature of 124 ℃ and 134 ℃ is collected).
2-pentyl-2-nonenal with 0.5 mol% equivalent of p-N- [3- (dimethylamino) propyl]-perfluorooctylamide (synthetic method: (CH)3)2NCH2CH2CH2NH2Reacting with perfluoro methyl caprylate at a molar ratio of 1.1:1 for 4% in the presence of sodium methoxide as catalyst at 135 deg.C for 4.5h to completely convert the perfluoro methyl caprylate, washing with water to remove methanol, catalyst and excessive N, N-dimethyl-1, 3-propanediamine, mixing, preheating to 90 deg.C, and introducing into packed tower reactor in liquid phase (the gas-liquid surface area per unit volume of liquid phase is 1000 m)2/m3) Heating methyl ethyl ketone to 90 ℃, introducing the methyl ethyl ketone into the reactor, maintaining the steam pressure in the reactor to be 101KPaA, circulating 80 vol% of liquid-phase product at the outlet of the reactor back to the reactor for continuous reaction, keeping the average residence time of the liquid phase for 1h, pumping 20 vol% of product, standing for layering, and collecting the upper oil phaseFeeding into a rectifying tower to respectively extract unreacted 2-amyl-2-nonenal and byproduct heavy components from the tower top and the tower bottom to obtain a product C18 dienone
(theoretical plate number of the rectifying tower is 20, reflux ratio is 5, operating pressure is 1KPaA, batch rectification is carried out, and fraction with tower top temperature of 167-. The conversion per pass of the 2-amyl-2-nonenal is 20 percent, and the selectivity of the target product is 99.9 percent.
Nuclear magnetism:1H NMR(500MHz，C6D6，TMS),δ(ppm):0.91(m,6H),1.29-1.31(m,14H),2.18(m,2H),2.27(m,3H),2.41(m,5H),5.44(m,1H),7.12(s,1H)
13C NMR(150MHz，C6D6，TMS),δ(ppm):10,14,23,30,40,53,128,136,139,166,196
mass spectrum 264,265,266
Elemental analysis (%). C, 81.75; h, 12.20; o,6.05
Will be impregnated on SiO by an equal volume impregnation method2The supported Pt-Fe catalyst (Pt supporting 3 wt%, Fe supporting 3 wt%, Shanghai Xun New Material science and technology Co., Ltd.) was reduced with hydrogen at 550 deg.C, C18 dienone was hydrogenated with a catalyst corresponding to 5 wt% of C18 dienone, triphenylphosphine corresponding to 5 wt% of C18 dienone was added, hydrogenation was carried out at 150 deg.C under a hydrogen pressure of 4MPaG, the conversion of C18 dienone reached 99% after 1 hour of reaction, and C18 dienol alcohol was added
The selectivity of (2) was 96%.
Nuclear magnetism:1H NMR(500MHz，C6D6，TMS),δ(ppm):0.91(m,6H),1.29(m,17H),1.82(s,3H),2.18(m,2H),2.41(m,2H),2.80(s,1H),4.08(m,1H),5.33(m,1H),5.96(m,1H)
13C NMR(150MHz，C6D6，TMS),δ(ppm):11,14,22,27,29,30,48,73,128,133,136,166
mass spectrum 266,267,268
Elemental analysis (%): C, 81.13; h, 12.86; o,6.00
Example 5
N-nonanal reacts for 1.5h at 130 ℃ and 0.5MPaG with 2.5 wt% of NaOH aqueous solution as a catalyst (the volume ratio of pentanal to NaOH solution is 2), the conversion rate is 99%, the selectivity is 98%, oil and water phases are separated after the reaction is finished, the oil phase is washed with water to be neutral, and then the oil phase is rectified in a rectifying tower, and the target product 2-heptyl-2-undecenal
Distilled from the tower top (theoretical plate number of the rectifying tower is 20, reflux ratio is 5, operating pressure is 1KPaA, batch rectification is carried out, and fraction with tower top temperature of 163-.
2-heptyl-2-undecenal with 0.1 mol% equivalent of N- [3- (dimethylamino) propyl ] aldehyde]-perfluorodecyl amide (synthetic method: (CH)3)2NCH2CH2CH2NH2Reacting with perfluoro methyl decanoate at a molar ratio of 1.1:1 and with sodium methoxide with a molar weight of 5% of that of the perfluoro methyl decanoate as a catalyst at 140 ℃ for 5h, completely converting the perfluoro methyl decanoate, washing with water to remove methanol, the catalyst and excessive N, N-dimethyl-1, 3-propane diamine to obtain an oil phase product, namely the target catalyst, mixing and preheating to 160 ℃, and introducing into a bubbling stirring kettle reactor in a liquid phase form (the gas-liquid surface area of unit liquid phase volume is 20 m)2/m3) Heating acetone to 160 ℃, introducing the acetone into the reactor, maintaining the steam pressure of the acetone in the reactor at 1000KPaA, keeping the average residence time of a liquid phase for 3h, extracting the product, standing and layering, feeding the upper oil phase into a rectifying tower, and respectively extracting unreacted 2-heptyl-2-undecenal and byproduct heavy components from the tower top and the tower kettle to obtain a product C21 dienone
(theoretical plate number of the rectifying tower is 20, reflux ratio is 5, operating pressure is 1KPaA, batch rectification is carried out, and fraction with tower top temperature of 196 ℃ and 206 ℃ is collected). The conversion per pass of the 2-heptyl-2-undecylenic aldehyde is 90 percent, and the selectivity of the target product is 99.9 percent.
Nuclear magnetism:1H NMR(500MHz，C6D6，TMS),δ(ppm):0.88(t,J＝16Hz,6H),1.29-1.31(m,22H),2.18(m,2H),2.21(s,3H),2.47(m,2H),5.44(m,1H),6.33(d,J＝25Hz,1H),7.40(d,J＝25Hz,1H)
13C NMR(150MHz，C6D6，TMS),δ(ppm):11,14,22,27,29,30,48,73,131,136,141,166,197
mass spectrum 306,307,308
Elemental analysis (%). C, 82.28; h, 12.50; o,5.22
The Pt-Ru-Sn catalyst (Pt loading 0.27 wt%, Ru loading 0.34 wt%, Sn loading 2.39 wt%) supported on a zeolite molecular sieve by an isometric impregnation method was reduced with hydrogen at 400 ℃ to hydrogenate C21 dienone with a catalyst equivalent to 20 wt% of C21 dienone at a temperature of 40 ℃ under a hydrogen pressure of 8MPaG, CO2Hydrogenation is carried out under the pressure of 8MPaG, the conversion rate of C21 dienone reaches 95 percent after 10 hours of reaction, and C14 dienol
The selectivity of (3) was 95%.
Nuclear magnetism:1H NMR(500MHz，C6D6，TMS),δ(ppm):0.88(t,J＝9Hz,6H),1.29(m,25H),2.18(m,2H),2.41(m,2H),2.80(s,1H),4.08(m,1H),5.33(m,1H),5.96(m,1H),6.24(m,1H)
13C NMR(150MHz，C6D6，TMS),δ(ppm):14,22,29,30,68,133,136,166
mass spectrum 308,309,310
Elemental analysis (%). C, 81.75; h, 13.07; o,5.19
Example 6
The C11 dienone prepared in example 1 was added
At 60 ℃, hydrogenation is carried out under the condition of hydrogen pressure of 30MPaG and the conversion rate can reach 100 percent after reaction for 0.2h by using 1 weight percent of palladium-carbon catalyst (metal load is 3 weight percent, Shanghai Xuan New Material science and technology Co., Ltd.) and the target product
The selectivity is 98%, and the by-products are mainly alkanes with excessive hydrogenation.
Nuclear magnetism:1H NMR(500MHz，C6D6，TMS),δ(ppm):0.88(m,12H),1.29-1.44(m,8H),1.65(m,1H),1.92(m,1H),3.20(m,1H),3.58(s,1H)
13C NMR(150MHz，C6D6，TMS),δ(ppm):14,18,21,31,32,33,40,78
mass spectrum 172,173
Elemental analysis (%): C, 76.68; h, 14.04; o,9.29
Example 7
The C14 dienone prepared in example 2 was added
At 250 ℃,5 wt% of nickel alumina catalyst (25 wt% of load, Shanghai Xueki New Material science and technology Co., Ltd.) is used for hydrogenation under the condition of hydrogen pressure of 0.1MPaG, the conversion rate can reach 100% after 20h of reaction, and the target product
The selectivity is 97%, and the by-products are mainly alkanes with excessive hydrogenation.
Nuclear magnetism:1H NMR(500MHz，C6D6，TMS),δ(ppm):0.90(t,J＝11Hz,12H),1.29-1.55(m,16H),3.21(m,1H),3.58(s,1H)
13C NMR(150MHz，C6D6，TMS),δ(ppm):12,14,23,25,29,31,32,33,47,69
mass spectrum 214,215,216
Elemental analysis (%): C, 78.43; h, 14.10; o,7.46
Example 8
The C17 dienone prepared in example 3 was added
At 160 deg.C, hydrogen pressure 2MPaG with 5 wt% Cu-Zn-Al catalyst (55 wt% copper oxide, 10 wt% ZnO, and the balance alumina; Shanghai Xueki New Material science and technology Co., Ltd.)Hydrogenation is carried out under the condition, the conversion rate can reach 100 percent after 10 hours of reaction, and the target product
The selectivity is 98%, and the by-products are mainly alkanes with excessive hydrogenation.
Nuclear magnetism:1H NMR(500MHz，C6D6，TMS),δ(ppm):0.90(m,9H),1.29-1.47(m,25H),3.21(m,1H),3.58(s,1H)
13C NMR(150MHz，C6D6，TMS),δ(ppm):14,20,23,25,29,30,32,38,39,48,72
mass spectrum 256,257,258
Elemental analysis (%): C, 79.61; h, 14.15; o,6.24
Example 9
The C18 dienone prepared in example 4 was added
At 80 ℃, 1.5 wt% of ruthenium-carbon catalyst (load is 5 wt%, Shanghai Xueki New Material science and technology Co., Ltd.) is used for hydrogenation under the condition of hydrogen pressure of 10MPaG, the conversion rate can reach 100% after 2h of reaction, and the target product
The selectivity is 99%, and the by-products are mainly alkanes with excessive hydrogenation.
Nuclear magnetism:1H NMR(500MHz，C6D6，TMS),δ(ppm):0.88(t.J＝16Hz,6H),0.96(d,J＝8Hz,3H),1.29-1.47(m,25H),1.47(m,1H),1.73(m,1H),3.38(m,1H),3.58(s,1H)
13C NMR(150MHz，C6D6，TMS),δ(ppm):14,16,20,22,27,29,32,39,71
mass spectrum 270,271,272
Elemental analysis (%): C, 79.93; h, 14.16; and O, 5.91.
Claims (16)
1. A method for preparing a high carbon branched secondary alcohol, comprising the steps of:
1) self-condensation of straight-chain or tertiary carbon-free branched-chain aliphatic aldehydes to produce branched-chain alkenals; 2) condensing the branched olefine aldehyde prepared in the step 1) and aliphatic ketone without tertiary carbon under the catalytic action of an organic base catalyst to prepare branched dienone; 3) hydrogenating the branched dienone obtained in the step 2) to prepare a branched secondary alcohol containing 0-2 carbon-carbon double bonds;
the organic base catalyst in the step 2) is N- [3- (dimethylamino) propyl ] -perfluoroalkyl amide, wherein the carbon atom number of the perfluoroalkyl is 2-10;
the mol ratio of the branched chain olefine aldehyde to the fatty ketone in the step 2) is 0.01-100;
the condensation reaction in the step 2) adopts the ratio of the area of the air bubble to the volume of the liquid phase of 20-1000000m2/m3The reactor of (1).
2. The process according to claim 1, wherein the branched aliphatic aldehyde, linear or branched, without tertiary carbon, is unbranched in the beta position; the carbon number of the straight chain or the branched chain aliphatic aldehyde without tertiary carbon is 3-9.
3. The method according to claim 2, wherein the linear or tertiary-carbon-free branched aliphatic aldehyde has a carbon number of 3 to 5.
4. The method according to claim 1 or 2, wherein the aliphatic ketone having no tertiary carbon has a carbon number of 3 to 7.
5. The method of claim 4, wherein said aliphatic ketone having no tertiary carbon has a carbon number of 3 to 6.
6. The process according to any one of claims 1 to 3, wherein the branched alkenal in step 2) has a boiling point or a bubble point in the solvent used which is higher than the boiling point of the aliphatic ketone.
7. A process according to any one of claims 1 to 3, wherein the number of carbon atoms of the perfluoroalkyl group in the N- [3- (dimethylamino) propyl ] -perfluoroalkylamide in step 2) is from 4 to 8; the dosage of the catalyst is 0.1-20 mol% of branched olefine aldehyde; the liquid phase retention time is 5s-3 h.
8. The method of claim 7, wherein the catalyst is present in an amount of 0.5 to 10 mol% based on the branched enal; the liquid phase retention time is 1-10 min.
9. The process of any one of claims 1 to 3, wherein the molar ratio of branched alkenal to aliphatic ketone in step 2) is between 0.1 and 10.
10. The process according to any one of claims 1 to 3, wherein the condensation reaction in step 2) is carried out at a pressure of from 5 to 1000kPaA and at a temperature lower than the boiling point of the branched alkenal and higher than the boiling point of the aliphatic ketone at the respective operating pressure.
11. The method as claimed in any one of claims 1 to 3, wherein the condensation reaction in step 2) is carried out using a ratio of gas bubble area to liquid phase volume of 1000-2/m3The reactor of (4); and 2) after the condensation reaction in the step 2) is finished, separating the catalyst from the reaction system by using water, concentrating and recycling, and distilling or rectifying and purifying the product to obtain the branched-chain dienone.
12. The method as set forth in claim 11, wherein the condensation reaction in step 2) is carried out by using a ratio of the area of the gas bubbles to the volume of the liquid phase of 10000-2/m3Jet loop reactors and spray loop reactors.
13. The method as claimed in any one of claims 1 to 3, wherein when the target product of step 3) is an unsaturated branched secondary alcohol, the hydrogenation catalyst is a supported Pt catalyst containing one or more elements selected from Sn, Fe, Ru and Co; the carrier is active carbon, alumina, zeolite molecular sieve, silicon dioxide or titanium dioxideOne or more of (a); hydrogenation in solvent-free or supercritical CO2As a solvent, without an auxiliary agent or tertiary amine, tertiary phosphine or tertiary phosphite; the reaction temperature is 40-150 ℃, the hydrogen pressure is 4-8MPaG, CO2The pressure is 8-15MPaG, the dosage of the catalyst is 5-20 wt% of the substrate, the dosage of the auxiliary agent is 0.5-5 wt% of the substrate, and the liquid phase retention time is 1-10 h.
14. The method as claimed in claim 13, wherein when the target product of the step 3) is unsaturated branched secondary alcohol, the hydrogenation catalyst adopts supported Pt-Sn and/or Pt-Ru, the mole ratio of Pt and other metal is 0.1-1, and the metal loading is 2-6 wt%; the carrier is one or more of alumina and titanium dioxide; hydrogenation using supercritical CO2As solvent, triphenylphosphine or triphenylphosphine oxide is used as cocatalyst.
15. The method as claimed in any one of claims 1 to 3, wherein when the target product of the step 3) is a saturated branched secondary alcohol, the catalyst is one or more of copper-zinc-aluminum, copper-chromium, a skeletal nickel alloy, supported palladium, supported ruthenium, supported platinum and supported cobalt; the reaction temperature is 60-250 ℃; the reaction pressure is 0.1-30 MPaA; the liquid phase retention time is 0.2-20h, and the catalyst dosage is 0.5-20 wt% of the substrate branched-chain dienone.
16. The method as claimed in any one of claims 1 to 3, wherein when the target product of step 3) is a saturated branched secondary alcohol, the catalyst is one or more of copper-zinc-aluminum, copper-chromium and skeletal nickel alloy; the reaction temperature is 80-160 ℃; the reaction pressure is 2-10 MPa; the liquid phase has a retention time of 2-10h, and the catalyst amount is 0.5-20 wt% of the substrate branched dienone.
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| WO2007065891A1 (en) * | 2005-12-05 | 2007-06-14 | Laboratorios Del Dr. Esteve, S.A. | Process for the homogeneous hydrogenation of ketones using ruthenium catalytic systems |
| JP2009207976A (en) * | 2008-03-03 | 2009-09-17 | Ne Chemcat Corp | Platinum-fixed carbon catalyst for catalytically hydrogenating aliphatic ketone and method for producing secondary aliphatic alcohol from aliphatic ketone by using the same |
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| WO2007065891A1 (en) * | 2005-12-05 | 2007-06-14 | Laboratorios Del Dr. Esteve, S.A. | Process for the homogeneous hydrogenation of ketones using ruthenium catalytic systems |
| JP2009207976A (en) * | 2008-03-03 | 2009-09-17 | Ne Chemcat Corp | Platinum-fixed carbon catalyst for catalytically hydrogenating aliphatic ketone and method for producing secondary aliphatic alcohol from aliphatic ketone by using the same |
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