CN109809973A - A method of preparing 2- ethyl hexanal - Google Patents
A method of preparing 2- ethyl hexanal Download PDFInfo
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Abstract
The present invention relates to a kind of methods for preparing 2- ethyl hexanal.The reaction solution comprising 2- ethyl -2- hexenoic aldehyde is obtained as raw material through condensation dehydration using n-butanal, first contacted with one section of catalyst comprising Pd, Pt, Cu, Ni, aldehyde polymer can be made to be converted to 2- ethyl hexanal etc., then contacted with two sections of catalyst comprising Pd, Co, Ag, so that remaining a small amount of 2- ethyl -2- hexenoic aldehyde is converted into 2- ethyl hexanal, while further decomposing aldehyde polymer；Kettle base solution comprising 2- ethyl hexanal, 2- ethyl -2- hexenoic aldehyde, 2-Ethylhexyl Alcohol and aldehyde polymer after rectifying, it is recycled back in first stage reactor, 2- ethyl -2- hexenoic aldehyde conversion ratio is improved, while high-boiling components such as aldehyde polymer etc. are partially converted into 2- ethyl hexanal, promotes 2- ethyl hexanal yield.The present invention can highly selective, continuous production 2- ethyl hexanal in high yield, superior product quality, low energy consumption for the three wastes.
Description
Technical field
The present invention relates to the preparation method of 2- ethyl hexanal, specifically a kind of two-stage hydrogenation, two sections of circulations prepare 2-
The method of ethyl hexanal.
Background technique
2- ethyl hexanal, also known as different octanal (2-EH), is the synthesis material of fragrance and isooctyl acid (also known as 2 ethyl hexanoic acid).
Isooctyl acid is a kind of important Organic chemical products, can be widely used for coating, plastics, process hides, medicine, timber, chemical fibre, pesticide etc.
Field, but it is mostly used in the metal salt of production isooctyl acid.Since ethylhexanoate salt urges dry effect with more more obvious than naphthenate
Fruit and be widely used in coating industry, to meet the needs of people are to high-grade light-coloured coating.Isooctyl acid is mainly used as in terms of medicine
The salt-forming reagent of solvent method syncillin sodium salt.In addition, isooctyl acid glyceride is excellent plasticizer, with the hair of industrial or agricultural
Exhibition, the demand of isooctyl acid increase year by year, have the potentiality that grow a lot.
Industrial production 2- ethyl hexanal, through condensation dehydration and liquid separation, obtains 2- ethyl-mainly using n-butanal as raw material
2- hexenoic aldehyde (also known as isooctene aldehyde) condensation liquid, 2- ethyl -2- hexenoic aldehyde add the method for hydrogen to synthesize to obtain 2- through liquid phase selective
Ethyl hexanal.The difficult point of the technique is to realize the high conversion of raw material, while occurring with needing hydrogenation selectivity double in carbon carbon
On key, rather than occur on carbonyl, meanwhile, material contains double bond and aldehyde functions, and the side reactions such as polymerization easily occur, cause
The three wastes are high, yield reduces.Therefore, technical process and corresponding catalyst are crucial.
Pd/SiO has been used in patent DEA1941634 and US3903171A2Catalyst is original with 2- ethyl -2- hexenoic aldehyde
Material makees solvent with hydrogenation products circulation, and the shortcomings that technique is that pressure is high (1-25MPa), and feedstock air speed is small, conversion ratio and
Selectivity is lower, and the yield of purpose product is low.
Pd-Ni/Al is used in patent US4018831A2O3Catalyst, 2- ethyl -2- hexenoic aldehyde at 90~180 DEG C, 0.7~
2- ethyl hexanal, air speed 0.5~3 is made in catalytic hydrogenation under 3.5MPa pressure, and hydrogen-oil ratio 2:1~3:1 (mol/mol) passes through control
Hydrogen manufacturing throughput and reaction condition make liquid phase upstream by catalyst bed, improve the selectivity of purpose product, reduce pair
The generation of product 2-Ethylhexyl Alcohol, 2- ethyl -2- hexenoic aldehyde conversion ratio 74% in embodiment, 2- ethyl hexanal selectivity
97.5%, target product yield is integrally relatively low.
Jilin Chemical research institute Lee just grade (document 2- ethyl hexenal liquid-phase hydrogenatin 2- ethyl hexanal, Jilin Chemical science and technology, 1991,1
(4): 2- ethyl -2- hexenoic aldehyde selective hydrogenation 35~38) is developed, using Pd/ γ-Al2O3Catalyst, palladium content 0.37%,
It using thick 2- ethyl hexanal round-robin method, is tested with 5L catalyst, reacts 85~95 DEG C of hot(test)-spot temperature, pressure 2.45MPa,
Charge ratio 3.4:1~3.8:1,0.15~0.30h of hydrogen-oil ratio 2.6:1~5.2:1,2- ethyl -2- hexenoic aldehyde liquid air speed-1, 2-
Ethyl hexanal yield up to 97~98%, 2- ethyl hexanal production capacity be 0.2g 2- ethyl hexanal/gcath, although whole
Yield is higher, but catalyst treatment amount is lower, and catalyst is at high cost.
Patent US4273945A has studied the liquid-phase hydrogenatin under palladium catalyst catalysis of olefines unsaturated aldehyde and prepares saturated fat
Fat race aldehyde, catalyst active component group become 2~90% palladium and 10~98% rare-earth oxide or salt, Al2O3Content
Greater than 90%.Wherein, as 1~3.5Mpa of reaction pressure, 80~150 DEG C of temperature, 2- ethyl hexenal conversion ratio is greater than 95%,
2- ethyl hexanal is selectively greater than 94%.The reaction conversion ratio of the patent report and selectivity not high, later separation and product
Cost will increase.
Patent CN1569789A uses the two sections of bubble type insulation fix bed reactors fed from lower part to add hydrogen, reduces and follows
Circular rector avoids channel, and reduction finishes carbon amounts, is conducive to improve selectivity；Hydrogenation catalyst palladium content is 0.2~0.4%
(wt), carrier is γ-Al2O3.Using the two sections of bubble type insulation fix bed reactors fed from lower part, first reactor
Condition are as follows: inlet temperature is 50~80 DEG C, and hot(test)-spot temperature is 80~110 DEG C, and reaction pressure is 1.50~2.50Mpa, and air speed is
0.4~1.2h-1, recycle ratio is 7~20, and hydrogen is than 3~20.Second reactor condition are as follows: inlet temperature is 50~70 DEG C, hot spot
Temperature is 60-80 DEG C, and reaction pressure is 1.50~2.50Mpa.After two-stage hydrogenation, feed stock conversion reaches 99.9%, 2- ethyl
Hexanal selectively reaches 99.5% or more.The patent carries out in such a way that material lower part is fed, and bubbling style reactor is opposite to stop
It stays the time longer, and blisters and be easy to happen coalescence, cause reaction result unstable, equipment and process control condition are more severe
It carves.
Patent US5756856A is with Pd (0.5wt.%)/γ-Al2O3For catalyst, returned what two tandem reactors were formed
Circulation hydrogenation is carried out in road, reaction temperature is at 80~130 DEG C.Pressure is in 0.5~2Mpa.With traditional hydrogenation process phase
Than two-stage hydrogenation technique makes yield improve 30% or more.2- ethyl hexenal conversion ratio is selected greater than 99.9%, 2- ethyl hexanal
Property be greater than 99%.But the technique is that the circulation that raising conversion ratio needs is bigger, and energy consumption is relatively high, while not referring to aldehydes
The case where heavy constituents such as polymerization.
N-butanal obtains 2- ethyl -2- hexenoic aldehyde through condensation dehydration, while can generate such as butyraldehyde tripolymerAnd 2- ethyl -2- hexenoic aldehyde dimer (2- ethyl -2- hexenoic aldehyde dimer)Equal polymer.
2- ethyl -2- hexenoic aldehyde inevitably generates 2- ethyl hexanal dimer (2- ethyl hexanal in hydrogenation process
Dimer)2- ethyl hexanal and 2- ethyl -2- hexene aldehyde polymer (2- ethyl hexanal and 2-
Ethyl -2- hexene aldehyde polymer)Equal impurity.
The appearance of above-mentioned impurity reduces the yield of 2- ethyl hexanal indirectly, increases the difficulty of separation, influences heavy constituent
Waste liquid amount is big, for this problem, needs to improve method of hydrotreating, selects suitable process program and catalyst, simultaneously
Effectively inhibit the high-boiling components such as generation or the decomposing copolymer of the high-boiling components such as polymer, improve the yield of 2- ethyl hexanal, reduces weight
Component waste liquid amount.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for preparing 2- ethyl hexanal, to solve current 2- ethyl hexanal production
The heavy constituent three wastes are high in the process, whole process yield is low, and catalyst treatment ability is low, the aspect such as reaction and subsequent separation process energy consumption height
The problem of.By two-stage hydrogenation, two sections of circulations, guarantees the high conversion ratio of 2- ethyl -2- hexenoic aldehyde, improve catalyst treatment energy
Power；Simultaneously by the circulation of heavy constituent, aldehyde polymer impurity is made to be converted into 2- ethyl hexanal, reduces 2- ethyl hexanal depth and add
Hydrogen is converted into 2-Ethylhexyl Alcohol, further promotes product yield, reduces the three wastes.
To achieve the goals above, present invention employs following technical solutions:
A method of 2- ethyl hexanal is prepared, is included the following steps:
1) in first stage reactor, 2- ethyl -2- hexenoic aldehyde raw material carries out one section and adds under one section of catalyst with hydrogen
Hydrogen reacts to obtain one section of hydride；
2) a part of one section of hydride obtained by step 1) enters in second stage reactor, under two sections of catalysts, and
Hydrogen carries out secondary hydrogenation and reacts to obtain two sections of hydrides (hydride of the ethyl hexanal containing 2-)；One section of hydride obtained by step 1)
Remainder be recycled to first stage reactor carry out circulation plus hydrogen；
3) two sections of hydrides in step 2) are separated through rectifying, obtain 2- ethyl hexanal product, heavy constituent and light component,
A part of middle heavy constituent is recycled to first stage reactor and carries out circulation plus hydrogen, and the remainder of heavy constituent is as discharging of waste liquid.
One section of catalyst of the present invention is the supported catalyst comprising Pd, Pt, Cu and Ni, in terms of catalyst gross mass,
Pd content is 0.05-0.5%, preferably 0.08-0.3%, such as 0.08%, 0.12%, 0.16%, 0.20% or 0.25%；Pt
Content is 0.01-0.1%, preferably 0.02-0.1%, such as 0.02%, 0.04%, 0.06%, 0.08% or 0.1%；Cu content
For 0.01-0.1%, preferably 0.02-0.1%, such as 0.02%, 0.04%, 0.06%, 0.08% or 0.1%；Ni content is
0.01-0.1%, preferably 0.02-0.1%, such as 0.02%, 0.04%, 0.06%, 0.08% or 0.1%；Carrier 99.2-
99.92%, preferably 99.45%-99.86%.
Two sections of catalyst of the present invention are the supported catalyst comprising Pd, Co and Ag, and in terms of catalyst gross mass, Pd contains
It measures as 0.5-1%, preferably 0.6-0.8%, such as 0.5%, 0.6%, 0.7%, 0.8% or 1%；Co content is 0.02-
0.2%, preferably 0.06-0.16%, such as 0.02%, 0.06%, 0.1%, 0.16% or 0.2%；Ag content is 0.02-
0.2%, preferably 0.06-0.16%, such as 0.02%, 0.06%, 0.1%, 0.16% or 0.2%；Carrier 98.6-99.46%,
It is preferred that 98.88-99.28%.
In step 1) of the present invention, one section of catalyst polymerize aldehydes outside with good double bond selective hydrogenation
Object (i.e. Aldol Condensation Products) has apparent discomposing effect.
One section of catalyst has high suction-operated, catalyst to oxygen while the absorption to carbon-carbon double bond adds hydrogen
Activated centre forms a kind of six annulus intermediate states in conjunction with carbonyl in above structure and the oxygen in hydroxyl, rear that the fracture of C-C key occurs
Parsing forms two molecule aldehyde.Specifically, butyraldehyde tripolymer is decomposed into 2- ethyl hexanal and 2- ethyl -3- hydroxyl hexanal, and 2-
Ethyl -3- hydroxyl hexanal easily occurs dehydration and generates 2- ethyl -2- hexenoic aldehyde；2- ethyl hexanal dimer is decomposed into two molecules
2- ethyl hexanal；2- ethyl -2- hexenoic aldehyde dimer is decomposed into two molecule 2- ethyl -2- hexenoic aldehydes；2- ethyl hexanal and 2- second
Base -2- hexene aldehyde polymer is decomposed into a molecule 2- ethyl hexanal and a molecule 2- ethyl -2- hexenoic aldehyde.
In step 2) of the present invention, 2- ethyl -2- hexene aldehyde concentration and one-stage hydrogenation raw material in the raw material of secondary hydrogenation
It compares, significantly reduces, and 2- ethyl hexanal concentration is significantly raised, secondary hydrogenation process 2- ethyl hexanal deep hydrogenation and polymerization
Reaction speed of the side reaction speed compared with one section faster, thus need to be adjusted catalyst formulation and reaction temperature, guarantee
While 2- ethyl -2- hexenoic aldehyde conversion ratio, side reaction is reduced, improves whole yield.Reaction temperature is reduced, can effectively reduce master
Side reaction speed improves selectivity；The content of active metal Pd in the catalyst is improved, is conducive to guaranteeing in low-temperature operation
Feed stock conversion adjusts catalyst formulation, and Co, Ag metallic element is added, is conducive to improve the selectivity to carbon-carbon double bond.
2- ethyl -2- hexenoic aldehyde raw material of the present invention can be obtained through condensation dehydration comprising 2- ethyl-for n-butanal
The reaction solution of 2- hexenoic aldehyde.It is well known in the art by the process that n-butanal prepares 2- ethyl -2- hexenoic aldehyde, in the present invention, institute
The composition for stating the reaction solution comprising 2- ethyl -2- hexenoic aldehyde includes: the 2- second of the n-butanal of 0.5-1.5wt%, 95-97wt%
Aldehyde polymer (including butyraldehyde tripolymer 1-2.5wt%, 2- ethyl -2- hexenoic aldehyde two of base -2- hexenoic aldehyde, 2.5-3.5wt%
Aggressiveness 1-1.5wt%).
In step 1) of the present invention, the temperature of one-stage hydrogenation reaction is 80-120 DEG C, such as 90 DEG C, 100 DEG C or 110
℃；Pressure (absolute pressure) is 1-5MPa, such as 1.5,3.0 or 4.5MPa.
In step (1) of the present invention, the molar ratio of hydrogen and 2- ethyl -2- hexenoic aldehyde is 5-25:1, for example, 10:1 or
20:1。
In step 2) of the present invention, the temperature of secondary hydrogenation reaction is 50-90 DEG C, such as 60 DEG C, 70 DEG C or 80 DEG C；
Pressure (absolute pressure) is 1-5MPa, such as 1.5,3.0 or 4.5MPa.
The hydrogen of secondary hydrogenation reaction of the present invention is one-stage hydrogenation reactor outlet hydrogen.
The mass ratio of one section of catalyst of the present invention and two sections of catalyst is 1-10:1, such as 3:1,6:1 or 9:1.
In the method for the invention, total liquid hourly space velocity (LHSV) is 0.1-1h-1, such as 0.2,0.5,0.8h-1.Total liquid space-time
Speed meaning be unit quality catalyst (by one section of catalyst and two sections of catalyst qualities and in terms of) per hour handle 2- ethyl -2-
The quality of 2- ethyl -2- hexenoic aldehyde in hexenoic aldehyde raw material.
In step 3) of the present invention, the condition of rectifying separation is separating pressure (absolute pressure) 10-30kPa, tower reactor temperature
100-150 DEG C of degree, separates number of plates 10-30, such as 20 by 90-122 DEG C of tower top temperature.
In step 2) of the present invention, the recycle ratio of one section of hydride (remainder of one section of hydride with it is described
The ratio of a part of one section of hydride) it is 10-40:1, such as 20:1 or 30:1.
Recycle ratio (the ratio of the remainder of a part and heavy constituent of heavy constituent of heavy constituent in step 3) of the present invention
Example) it is 60-100:1, such as 70:1,80:1 or 90:1.
The preparation method of one section of catalyst of the present invention, comprising the following steps: proportionally,
A1 the mixed aqueous solution of the compound containing Pd, Pt, Cu and Ni and alkaline precipitating agent) are instilled into nano-oxide simultaneously
Aqueous dispersions in reacted, control reaction process in temperature of reaction system be 80-90 DEG C, pH 5.0-8.0, be added dropwise 2-
3h uses alkaline precipitating agent regulation system pH to 7.5-9.0 after completion of dropwise addition, be warming up to 85-95 DEG C and carry out then aging, 1-2h
After be down to room temperature and obtain slurry；
B1) slurry is filtered, is washed, is broken in 100-120 DEG C of dry 12-24h in 800-1200 DEG C of roasting 5-10h
Broken, tabletting forming carries out catalyst reduction using hydrogen, and 120-150 DEG C of temperature, pressure (absolute pressure) 1-5MPa, when reduction
Between 24-48h, dry and remove reductive water, obtain one section of catalyst.
Step a1 of the present invention) in, the solid content of the mixed aqueous solution of the compound containing Pd, Pt, Cu and Ni is 0.2-
2wt%, such as 0.5wt%, 1.0wt% or 1.5wt%.
The preparation method of two sections of catalyst of the present invention, comprising the following steps: proportionally,
A2 the mixed aqueous solution of the compound containing Pd, Co and Ag and alkaline precipitating agent) are instilled into nano-oxide simultaneously
It is reacted in aqueous dispersions, controlling temperature of reaction system in reaction process is 80-90 DEG C, and reaction system pH is 5.0-8.0, drop
Add 2-3h, alkaline precipitating agent regulation system pH to 7.5-9.0 is used after completion of dropwise addition, is warming up to 85-95 DEG C of progress aging, 1-2h
After be down to room temperature and obtain slurry；
B2) slurry is filtered, is washed, in 100-120 DEG C of dry 12-24h, in 800-1200 DEG C of roasting 5-10h, broken
Broken, tabletting forming carries out catalyst reduction using hydrogen, and 120-150 DEG C of temperature, pressure (absolute pressure) 1-5MPa, when reduction
Between 24-48h, dry and remove reductive water, obtain two sections of catalyst.
Step a2 of the present invention) in, the solid content of the mixed aqueous solution of the compound containing Pd, Co and Ag is 0.2-
2wt%, such as 0.5wt%, 1.0wt% or 1.5wt%.
The partial size 20-50nm of nano-oxide of the present invention；The nano-oxide dosage, consolidating in dispersion liquid
Content is 0.5-2wt%, such as 1wt% or 1.5wt%.The nano-oxide be selected from nano aluminium oxide, nano-titanium oxide and
One of nano zircite is a variety of.
The compound of Pd, Pt, Cu, Ni, Co, Ag of the present invention are selected from nitrate, chloride and the acetic acid of the metal
One of salt is a variety of, preferably palladium nitrate, platinum nitrate, copper nitrate, nickel nitrate, cobalt nitrate, silver nitrate.
Alkaline precipitating agent of the present invention is sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, sodium hydroxide, hydrogen-oxygen
Change one of potassium, ammonium carbonate, ammonium hydrogen carbonate and ammonium hydroxide or a variety of.
In the present invention, one-stage hydrogenation catalyst polymerize aldehydes while to 2- ethyl -2- hexenoic aldehyde selective hydrogenation
Object is decomposed；Secondary hydrogenation catalyst guarantees that remaining 2- ethyl -2- hexenoic aldehyde adds hydrogen in the hydrogenation liquid of one-stage hydrogenation outlet,
While guaranteeing 2- ethyl -2- hexenoic aldehyde conversion ratio, while continuing to decompose aldehyde polymer raising 2- ethyl hexanal yield.
Compared with prior art, the invention has the following advantages that
(1) one section of catalyst element containing Pd, Pt, Cu, Ni, can generate synergy, add carrying out double bond with high selectivity
While hydrogen, moreover it is possible to decompose aldehyde polymer, inhibit the polymerization of aldehyde compound, effectively reduce polymer production amount, improve
2- ethyl hexanal yield.
(2) two sections of catalyst contain Pd, Co, Ag, and the conversion that 2- ethyl -2- hexenoic aldehyde is effectively ensured at low temperature is complete, together
When reduce the selectivity of 2- ethyl hexanal deep hydrogenation and polymerization, improve 2- ethyl hexanal selectivity.
(3) 2- ethyl hexanal is produced with 2- ethyl -2- hexenoic aldehyde two-stage hydrogenation, one-stage hydrogenation is exported by first stage reactor
The part of liquid recycles, and reduces the concentration of charging 2- ethyl -2- hexenoic aldehyde, is conducive to control bed temperature, avoids thermal discharge big
Caused by temperature runaway etc. is dangerous or unusual service condition；It is recycled by the part of 2- ethyl hexanal rectifying column kettle liquid, makes polymer therein
Decomposition or hydrogenolysis improve 2- ethyl hexanal yield.2- ethyl hexanal is produced using this method, production procedure is simple, realizes production
The high yield of product, economic benefit are very considerable.
Specific embodiment
The following examples will be further described technique provided by the present invention, but the present invention is not limited to listed
Embodiment out should also include other any well known changes in interest field of the presently claimed invention.
Wherein, in following embodiment gas-chromatography carry out composition analysis condition are as follows: Agilent HP-5 chromatographic column, area are returned
One change method, 140 DEG C of injector temperature, 250 DEG C of detector temperature, hydrogen flowing quantity 40ml/min, air mass flow 400ml/min.
If not otherwise specified, reagent used below is that analysis is pure, and related content is mass percentage below.
Embodiment 1
One section of catalyst preparation:
65.6L deionized water is added into reaction kettle, the nano aluminium oxide 998.6g of partial size 20-50nm is then added, matches
Nano-oxide dispersion liquid is made, dispersion liquid temperature is 75 DEG C；
1.73g Pd (NO is weighed respectively3)2、0.33gPt(NO3)2、0.59gCu(NO3)2、0.62gNi(NO3)2, it is added
323.95g water, by obtained mixed-salt aqueous solution and alkaline precipitating agent sodium carbonate be added in nano-oxide dispersion liquid simultaneously into
Row reaction, 80 DEG C of reaction temperature, time for adding 2h, controlling reaction system pH in reaction process is 6, and alkalinity is added after being added dropwise
Precipitating reagent adjusts pH to 8, and then aging, 90 DEG C of aging temperature, ageing time 1.5h obtains slurry；
Slurry is filtered, is washed, 100 DEG C of dry 18h, obtains filter cake；Then at 1000 DEG C, 8h is roasted, is crushed, pressure
Piece forming, restores 30h at 135 DEG C, 2.5MPa, obtains one section of catalyst 1000g after drying and removing reductive water.
Two sections of catalyst preparations:
13.1L deionized water is added into reaction kettle, the nano aluminium oxide 198.92g of partial size 20-50nm is then added, matches
Nano-oxide dispersion liquid is made, dispersion liquid temperature is 75 DEG C；
Weigh 1.67g PdCl2、0.16g CoCl2·6H2O and 0.06g AgNO3, it is added in 119.35g water, will obtains
Mixed-salt aqueous solution instill in nano-oxide dispersion liquid and reacted simultaneously with alkaline precipitating agent sodium carbonate, reaction temperature 80
DEG C, time for adding 2h, control reaction process in reaction system pH be 6.0, after being added dropwise be added alkaline precipitating agent adjust pH to
8.0, then aging, 90 DEG C of aging temperature, ageing time 1.5h obtains slurry；
Slurry is filtered, is washed, 100 DEG C of dry 18h, then in 1000 DEG C of roasting 8h, is crushed, tabletting forming, makes
With hydrogen reducing, 135 DEG C of temperature, absolute pressure 2.5MPa, recovery time 30h, two sections of catalysis are obtained after drying and removing reductive water
Agent 200g.
Above-mentioned one or two sections of catalyst are No. 1 catalyst combination.
Embodiment 2
One section of catalyst preparation:
98.8L deionized water is added into reaction kettle, the nano-titanium oxide 997.6g of partial size 20-50nm is then added, matches
Nano-oxide dispersion liquid is made, dispersion liquid temperature is 75 DEG C；
2.60g Pd (NO is weighed respectively3)2、0.65gPt(NO3)2、1.18gCu(NO3)2、1.25gNi(NO3)2, it is added
372.8g water, by obtained mixed-salt aqueous solution and alkaline precipitating agent saleratus be added in nano-oxide dispersion liquid simultaneously into
Row reaction, 85 DEG C of reaction temperature, time for adding 2.5h, controlling reaction system pH in reaction process is 5, and alkali is added after being added dropwise
Property precipitating reagent adjust pH to 7.5, then aging 85 DEG C of aging temperature, ageing time 1h, obtains slurry；
Slurry is filtered, is washed, 100 DEG C of dry 12h, obtains filter cake；Then at 800 DEG C, 10h is roasted, is crushed, pressure
Piece forming, the reductase 12 4h at 120 DEG C, 5MPa obtain one section of catalyst 1000g after drying and removing reductive water.
Two sections of catalyst preparations:
98.3L deionized water is added into reaction kettle, the nano-titanium oxide 992.8g of partial size 20-50nm is then added, matches
Nano-oxide dispersion liquid, solid content 1% is made, dispersion liquid temperature is 75 DEG C；
Weigh 10g PdCl2、2.42g CoCl2·6H2O and 0.94g AgNO3, it is added in 1214.22g water, by what is obtained
Mixed-salt aqueous solution instills in nano-oxide dispersion liquid simultaneously with alkaline precipitating agent saleratus to be reacted, reaction temperature 85
DEG C, time for adding 2.5h, control reaction process in reaction system pH be 5, after being added dropwise be added alkaline precipitating agent adjust pH to
7.5, then aging, aging temperature 85, ageing time 1h obtains slurry.
Slurry is filtered, is washed, 100 DEG C of dry 12h, in 800 DEG C of roasting 10h, is crushed, tabletting forming, uses hydrogen
Gas reduction, 120 DEG C of temperature, absolute pressure 5MPa, the recovery time for 24 hours, obtains two sections of catalyst after drying and removing reductive water
1000g。
Above-mentioned one or two sections of catalyst are No. 2 catalyst combinations.
Embodiment 3
One section of catalyst preparation:
198.3L deionized water is added into reaction kettle, the nano zircite 996.6g of partial size 20-50nm is then added, matches
Nano-oxide dispersion liquid is made, dispersion liquid temperature is 75 DEG C；
3.46g Pd (NO is weighed respectively3)2、0.98gPt(NO3)2、1.77gCu(NO3)2、1.87gNi(NO3)2, it is added
Obtained mixed-salt aqueous solution and alkaline precipitating agent ammonium hydrogen carbonate are added in nano-oxide dispersion liquid 1608.80g water simultaneously
It is reacted, 85 DEG C of reaction temperature, time for adding 2.5h, controlling reaction system pH in reaction process is 7, is added after being added dropwise
Alkaline precipitating agent adjusts pH to 8.5, and then aging, 90 DEG C of aging temperature, ageing time 2h obtains slurry；
Slurry is filtered, is washed, 100 DEG C of dryings for 24 hours, obtain filter cake；Then at 1200 DEG C, 5h is roasted, is crushed, pressure
Piece forming, restores 48h at 150 DEG C, 1MPa, obtains one section of catalyst 1000g after drying and removing reductive water.
Two sections of catalyst preparations:
19.7L deionized water is added into reaction kettle, the nano zircite 99.1g of partial size 20-50nm is then added, prepares
At nano-oxide dispersion liquid, dispersion liquid temperature is 75 DEG C；
Weigh 1.17g PdCl2、0.4g CoCl2·6H2O and 0.16g AgNO3, it is added in 307.3g water, by what is obtained
Mixed-salt aqueous solution instills in nano-oxide dispersion liquid simultaneously with alkaline precipitating agent ammonium hydrogen carbonate to be reacted, reaction temperature 85
DEG C, time for adding 2.5h, control reaction process in reaction system pH be 7, after being added dropwise be added alkaline precipitating agent adjust pH to
8.5, then aging, 90 DEG C of aging temperature, ageing time 2h obtains slurry；
Slurry is filtered, is washed, 100 DEG C of dryings for 24 hours, in 1200 DEG C of roasting 5h, be crushed, tabletting forming, use hydrogen
Gas reduction, 150 DEG C of temperature, absolute pressure 1MPa, recovery time 48h, drying obtains two sections of catalyst 100g after removing reductive water.
Above-mentioned one or two sections of catalyst are No. 3 catalyst combinations.
Embodiment 4
One section of catalyst preparation:
65.4L deionized water is added into reaction kettle, the nano aluminium oxide 995.6g of partial size 20-50nm is then added, matches
Nano-oxide dispersion liquid is made, dispersion liquid temperature is 80 DEG C；
4.33g Pd (NO is weighed respectively3)2、1.31gPt(NO3)2、2.36gCu(NO3)2、2.49gNi(NO3)2, it is added
Obtained mixed-salt aqueous solution and alkaline precipitating agent potassium hydroxide are added in nano-oxide dispersion liquid 5234.80g water simultaneously
It is reacted, 90 DEG C of reaction temperature, time for adding 3h, controlling reaction system pH in reaction process is 7.5, is added after being added dropwise
Alkaline precipitating agent adjusts pH to 8.5, and then aging, 95 DEG C of aging temperature, ageing time 2h obtains slurry；
Slurry is filtered, is washed, 100 DEG C of dry 16h, obtains filter cake；Then at 900 DEG C, 8h is roasted, is crushed, pressure
Piece forming, restores 35h at 130 DEG C, 4MPa, obtains one section of catalyst 1000g after drying and removing reductive water.
Two sections of catalyst preparations:
21.6L deionized water is added into reaction kettle, the nano aluminium oxide 329.6g of partial size 20-50nm is then added, matches
Nano-oxide dispersion liquid is made, dispersion liquid temperature is 80 DEG C；
Weigh 4.44g PdCl2、2.15g CoCl2·6H2O and 0.84g AgNO3, it is added in 424.11g water, will obtains
Mixed-salt aqueous solution instill in nano-oxide dispersion liquid and reacted simultaneously with alkaline precipitating agent potassium hydroxide, reaction temperature
90 DEG C, time for adding 3h, controlling reaction system pH in reaction process is 7.5, and alkaline precipitating agent is added after being added dropwise and adjusts pH
To 8.5, then aging, 95 DEG C of aging temperature, ageing time 2h obtains slurry；
Slurry is filtered, is washed, 100 DEG C of dry 16h, in 900 DEG C of roasting 8h, is crushed, tabletting forming, uses hydrogen
Reduction, 130 DEG C of temperature, absolute pressure 4MPa, recovery time 35h, drying obtains two sections of catalyst 333.3g after removing reductive water.
Above-mentioned one or two sections of catalyst are No. 4 catalyst combinations.
Embodiment 5
One section of catalyst preparation:
48.7L deionized water is added into reaction kettle, the nano aluminium oxide 994.5g of partial size 20-50nm is then added, matches
Nano-oxide dispersion liquid is made, dispersion liquid temperature is 70 DEG C；
5.41g Pd (NO is weighed respectively3)2、1.64gPt(NO3)2、2.95gCu(NO3)2、3.11gNi(NO3)2, it is added
Obtained mixed-salt aqueous solution is added in nano-oxide dispersion liquid simultaneously with alkaline precipitating agent ammonium hydroxide and carries out by 642.55g water
Reaction, 90 DEG C of reaction temperature, time for adding 3h, controlling reaction system pH in reaction process is 8, and it is heavy that alkalinity is added after being added dropwise
Shallow lake agent adjusts pH to 9, and then aging, 95 DEG C of aging temperature, ageing time 1h obtains slurry；
Slurry is filtered, is washed, 100 DEG C of dry 20h, obtains filter cake；Then at 1100 DEG C, 6h is roasted, is crushed, pressure
Piece forming, restores 40h at 140 DEG C, 2MPa, obtains one section of catalyst 1000g after drying and removing reductive water.
Two sections of catalyst preparations:
6L deionized water is added into reaction kettle, the nano aluminium oxide 123.25g of partial size 20-50nm is then added, prepares
At nano-oxide dispersion liquid, dispersion liquid temperature is 70 DEG C；
Weigh 2.08g PdCl2、1.01g CoCl2·6H2O and 0.39g AgNO3, it is added in 148.35g water, will obtains
Mixed-salt aqueous solution instill in nano-oxide dispersion liquid and reacted simultaneously with alkaline precipitating agent ammonium hydroxide, reaction temperature 90
DEG C, time for adding 3h, controlling reaction system pH in reaction process is 8, alkaline precipitating agent is added after being added dropwise and adjusts pH to 9,
Then aging, 95 DEG C of aging temperature, ageing time 1h obtains slurry；
Slurry is filtered, is washed, 100 DEG C of dry 20h, in 1100 DEG C of roasting 6h, is crushed, tabletting forming, uses hydrogen
Gas reduction, 140 DEG C of temperature, absolute pressure 2MPa, recovery time 40h, drying obtains two sections of catalyst 125g after removing reductive water.
Above-mentioned one or two sections of catalyst are No. 5 catalyst combinations.
Comparative example 1
One section of catalyst preparation:
48.9L deionized water is added into reaction kettle, the nano aluminium oxide 997.5g of partial size 20-50nm is then added, matches
Nano-oxide dispersion liquid is made, dispersion liquid temperature is 70 DEG C；
Weigh 5.41g Pd (NO3)2, 265.22g water is added, obtained solution and alkaline precipitating agent ammonium hydroxide are added simultaneously
It is reacted in nano-oxide dispersion liquid, 90 DEG C of reaction temperature, time for adding 3h, controlling reaction system pH in reaction process is
8, alkaline precipitating agent is added after being added dropwise and adjusts pH to 9, then aging, 95 DEG C of aging temperature, ageing time 1h is starched
Material；
Slurry is filtered, is washed, 100 DEG C of dry 20h, obtains filter cake；Then at 1100 DEG C, 6h is roasted, is crushed, pressure
Piece forming, restores 40h at 140 DEG C, 2MPa, obtains catalyst 1000g after drying and removing reductive water.
Two sections of catalyst preparations:
6.1L deionized water is added into reaction kettle, the nano aluminium oxide 123.75g of partial size 20-50nm is then added, matches
Nano-oxide dispersion liquid is made, dispersion liquid temperature is 70 DEG C；
Weigh 2.08g Pd (Cl)2, it is added in 102.06g water, obtained solution and alkaline precipitating agent ammonium hydroxide is dripped simultaneously
Enter and reacted in nano-oxide dispersion liquid, 90 DEG C of reaction temperature, time for adding 3h, controls reaction system pH in reaction process
It is 8, alkaline precipitating agent is added after being added dropwise and adjusts pH to 9, then aging, 95 DEG C of aging temperature, ageing time 1h is starched
Material；
Slurry is filtered, is washed, 100 DEG C of dry 20h, in 1100 DEG C of roasting 6h, is crushed, tabletting forming, uses hydrogen
Gas reduction, 140 DEG C of temperature, absolute pressure 2MPa, recovery time 40h, drying obtains two sections of catalyst 125g after removing reductive water.
Above-mentioned one or two sections of catalyst are No. 6 catalyst combinations.
The each component content of 1-6 catalyst combination is as shown in table 1 below
The each component content of 1 1-6 catalyst combination of table
The 1-5 hydrogenation catalyst combination being prepared in embodiment 1-5 is respectively adopted in following example 6-10.Comparative example
2 using No. 6 hydrogenation catalysts combination being prepared in comparative example 1.
Embodiment 6
1) one-stage hydrogenation
2- ethyl -2- hexenoic aldehyde crude product (2- ethyl -2- hexenoic aldehyde, the 1.8wt% of n-butanal, 96.0wt% containing 1wt%
Butyraldehyde tripolymer and 1.2wt% 2- ethyl -2- hexenoic aldehyde dimer), feed rate 625g/h, with one-stage hydrogenation reaction solution
Exit portion circular response liquid and rectifying part heavy constituent circulation fluid are mixed into first stage reactor, one-stage hydrogenation reaction
100 DEG C of temperature, pressure 3MPa, hydrogen flow rate 1065L/h, one-stage hydrogenation reactor outlet material 13394.05g/h is obtained, is recycled
To first stage reactor entrance material flow 12746.71g/h, surplus material enters second-stage hydrogenation reactor.
2) secondary hydrogenation
Hydrogen after one-stage hydrogenation flows into second-stage hydrogenation reactor, the temperature 70 C of secondary hydrogenation reaction, reaction pressure
3MPa, reactor outlet material flow velocity 638.77g/h.
3) rectifying separates
Reactor outlet material enters distillation system, rectifying theoretical cam curve 20, rectifying pressure 10kPa, tower in step 2)
100 DEG C of kettle temperature degree, tower reactor recombinates shunt volume 15.46g/h, and the heavy constituent extraction flow as waste liquid is 0.191g/h, remaining is followed
Ring is to one-stage hydrogenation reactor inlet；90 DEG C of temperature of 2- ethyl hexanal overhead extraction, obtain 2- ethyl hexanal product, flow
619.4g/h.Each substance carries out analyzing its composition using gas-chromatography.
Embodiment 7
1) one-stage hydrogenation
2- ethyl -2- hexenoic aldehyde crude product (the 2- ethyl -2- hexenoic aldehyde of n-butanal, 95.7wt% containing 1.5wt%,
The butyraldehyde tripolymer of 1.3wt% and the 2- ethyl -2- hexenoic aldehyde dimer of 1.5wt%), feed rate 418g/h adds with one section
Hydrogen reaction solution exit portion circular response liquid and rectifying part heavy constituent circulation fluid are mixed into first stage reactor, and one section
90 DEG C of hydrogenation reaction temperature, pressure 1.5MPa, hydrogen flow rate 1420L/h obtain one-stage hydrogenation reactor outlet material
13196.8g/h, is recycled to first stage reactor entrance material flow 12771.09g/h, and surplus material enters secondary hydrogenation reaction
Device.
2) secondary hydrogenation
Hydrogen after one-stage hydrogenation flows into second-stage hydrogenation reactor, the temperature 60 C of secondary hydrogenation reaction, reaction pressure
1.5MPa, reactor outlet material flow velocity 426.49g/h.
3) rectifying separates
Reactor outlet material enters distillation system, rectifying theoretical cam curve 10, rectifying pressure 20kPa, tower in step 2)
140 DEG C of kettle temperature degree, tower reactor recombinates shunt volume 7.77g/h, and the heavy constituent extraction flow as waste liquid is 0.109g/h, remaining circulation
To one-stage hydrogenation reactor inlet；110 DEG C of temperature of 2- ethyl hexanal overhead extraction, obtain 2- ethyl hexanal product, flow
411.1g/h.Each substance carries out analyzing its composition using gas-chromatography.
Embodiment 8
1) one-stage hydrogenation
2- ethyl -2- hexenoic aldehyde crude product (the 2- ethyl -2- hexenoic aldehyde of n-butanal, 95.9wt% containing 0.8wt%,
The butyraldehyde tripolymer of 2.0wt% and the 2- ethyl -2- hexenoic aldehyde dimer of 1.3wt%), feed rate 917.6g/h, with one section
Hydrogenation reaction solution exit portion circular response liquid and rectifying part heavy constituent circulation fluid are mixed into first stage reactor, and one
110 DEG C of temperature of hydrogenation reaction of section, pressure 4.5MPa, hydrogen flow rate 2343L/h obtain one-stage hydrogenation reactor outlet material
24249.1g/h, is recycled to first stage reactor entrance material flow 23316.44g/h, and surplus material enters secondary hydrogenation reaction
Device.
2) secondary hydrogenation
Hydrogen inflow second-stage hydrogenation reactor after one-stage hydrogenation, 80 DEG C of temperature of secondary hydrogenation reaction, reaction pressure
4.5MPa, reactor outlet material flow velocity 934.05g/h.
3) rectifying separates
Reactor outlet material enters distillation system, rectifying theoretical cam curve 30, rectifying pressure 30kPa, tower in step 2)
150 DEG C of kettle temperature degree, tower reactor recombinates shunt volume 11.99g/h, and the heavy constituent extraction flow as waste liquid is 0.132g/h, remaining is followed
Ring is to one-stage hydrogenation reactor inlet；122 DEG C of temperature of 2- ethyl hexanal overhead extraction, obtain 2- ethyl hexanal product, flow
912.9g/h.Each substance carries out analyzing its composition using gas-chromatography.
Embodiment 9
1) one-stage hydrogenation
2- ethyl -2- hexenoic aldehyde crude product (the 2- ethyl -2- hexenoic aldehyde of n-butanal, 95.9wt% containing 1.4wt%,
The butyraldehyde tripolymer of 1.2wt% and the 2- ethyl -2- hexenoic aldehyde dimer of 1.5wt%), feed rate 139g/h adds with one section
Hydrogen reaction solution exit portion circular response liquid and rectifying part heavy constituent circulation fluid are mixed into first stage reactor, and one section
80 DEG C of hydrogenation reaction temperature, pressure 1MPa, hydrogen flow rate 120L/h obtain one-stage hydrogenation reactor outlet material 1552.82g/
H, is recycled to first stage reactor entrance material flow 1411.65g/h, and surplus material enters second-stage hydrogenation reactor.
2) secondary hydrogenation
Hydrogen after one-stage hydrogenation flows into second-stage hydrogenation reactor, the temperature 50 C of secondary hydrogenation reaction, reaction pressure
1MPa, reactor outlet material flow velocity 141.33g/h.
3) rectifying separates
Reactor outlet material enters distillation system, rectifying theoretical cam curve 15, rectifying pressure 20kPa, tower in step 2)
140 DEG C of kettle temperature degree, tower reactor recombinates shunt volume 0.94g/h, and the heavy constituent extraction flow as waste liquid is 0.015g/h, remaining circulation
To one-stage hydrogenation reactor inlet；110 DEG C of temperature of 2- ethyl hexanal overhead extraction, obtain 2- ethyl hexanal product, flow
137.4g/h.Each substance carries out analyzing its composition using gas-chromatography.
Embodiment 10
1) one-stage hydrogenation
2- ethyl -2- hexenoic aldehyde crude product (the 2- ethyl -2- hexenoic aldehyde of n-butanal, 96.0wt% containing 0.5wt%,
The butyraldehyde tripolymer of 2.5wt% and the 2- ethyl -2- hexenoic aldehyde dimer of 1.0wt%), feed rate 1171.9g/h, with one section
Hydrogenation reaction solution exit portion circular response liquid and rectifying part heavy constituent circulation fluid are mixed into first stage reactor, and one
120 DEG C of temperature of hydrogenation reaction of section, pressure 5MPa, hydrogen flow rate 4991L/h obtain one-stage hydrogenation reactor outlet material
49011.3g/h, is recycled to first stage reactor entrance material flow 47815.9g/h, and surplus material enters second-stage hydrogenation reactor.
2) secondary hydrogenation
Hydrogen inflow second-stage hydrogenation reactor after one-stage hydrogenation, 90 DEG C of temperature of secondary hydrogenation reaction, reaction pressure
5MPa, reactor outlet material flow velocity 1197.02g/h.
3) rectifying separates
Reactor outlet material enters distillation system, rectifying theoretical cam curve 25, rectifying pressure 20kPa, tower in step 2)
140 DEG C of kettle temperature degree, tower reactor recombinates shunt volume 24.69g/h, and the heavy constituent extraction flow as waste liquid is 0.244g/h, remaining is followed
Ring is to one-stage hydrogenation reactor inlet；110 DEG C of temperature of 2- ethyl hexanal overhead extraction, obtain 2- ethyl hexanal product, flow
1167.5g/h.Each substance carries out analyzing its composition using gas-chromatography.
Comparative example 2
1) one-stage hydrogenation
2- ethyl -2- hexenoic aldehyde crude product (the 2- ethyl -2- hexenoic aldehyde of n-butanal, 96.0wt% containing 0.5wt%,
The butyraldehyde tripolymer of 2.5wt% and the 2- ethyl -2- hexenoic aldehyde dimer of 1.0wt%), feed rate 1171.9g/h, with one section
Hydrogenation reaction solution exit portion circular response liquid is mixed into first stage reactor, and 120 DEG C of one-stage hydrogenation reaction temperature, pressure
5MPa, hydrogen flow rate 4991L/h obtain one-stage hydrogenation reactor outlet material 51386.87g/h, are recycled to first stage reactor and enter
Mouth material flow 50133.53g/h, surplus material enter second-stage hydrogenation reactor.
2) secondary hydrogenation
Hydrogen inflow second-stage hydrogenation reactor after one-stage hydrogenation, 90 DEG C of temperature of secondary hydrogenation reaction, reaction pressure
5MPa, reactor outlet material flow velocity 1258.52g/h.
3) rectifying separates
Reactor outlet material enters distillation system, rectifying theoretical cam curve 25, rectifying pressure 20kPa, tower in step 2)
140 DEG C of kettle temperature degree, tower reactor recombinates shunt volume 274.82g/h, no circulation；110 DEG C of temperature of 2- ethyl hexanal overhead extraction, obtain 2-
Ethyl hexanal product, flow 976.36g/h.Each substance carries out analyzing its composition using gas-chromatography.
Embodiment 6-10 and the second-stage hydrogenation reactor of comparative example 2 outlet composition and mass content are as shown in table 2 below
2 second-stage hydrogenation reactor of table outlet composition
As shown in Table 2, the butyraldehyde tripolymer in embodiment 6-10 in hydrogenation reaction solution, 2- ethyl -2- hexenoic aldehyde dimer,
2- ethyl hexanal dimer and 2- ethyl hexanal and 2- ethyl -2- hexenoic aldehyde polymer content are much smaller than comparative example 2, illustrate to implement
Catalyst and technique in example 6-10 have significant decomposition to above-mentioned aldehyde polymer, improve the receipts of 2- ethyl hexanal
Rate；Excessive hydrogenation by-product 2-Ethylhexyl Alcohol content is much smaller than comparative example 2 in embodiment 6-10 simultaneously, illustrates in embodiment 6-10
Catalyst and technique have positive effect in terms of reducing 2-Ethylhexyl Alcohol by-product.Due to above-mentioned beneficial to effect in embodiment 6-10
Fruit, 2- ethyl hexanal content in reaction solution significantly improve, therefore waste liquid amount is substantially reduced after rectifying separation, and product yield is substantially
It improves.
Claims (10)
1. a kind of method for preparing 2- ethyl hexanal, includes the following steps:
1) in first stage reactor, 2- ethyl -2- hexenoic aldehyde raw material is under one section of catalyst and hydrogen progress one-stage hydrogenation is anti-
It should obtain one section of hydride；
2) a part of one section of hydride obtained by step 1) enters in second stage reactor, under two sections of catalysts and hydrogen
Secondary hydrogenation is carried out to react to obtain two sections of hydrides (hydride of the ethyl hexanal containing 2-)；Step 1) one section of hydride of gained remains
The remaining first stage reactor that is partly recycled to carries out circulation plus hydrogen；
3) two sections of hydrides in step 2) are separated through rectifying, 2- ethyl hexanal product, heavy constituent and light component are obtained, wherein weighing
A part of component is recycled to first stage reactor and carries out circulation plus hydrogen, and the remainder of heavy constituent is as discharging of waste liquid.
2. the method according to claim 1, wherein one section of catalyst is negative comprising Pd, Pt, Cu and Ni
Carried catalyst, in terms of catalyst gross mass, Pd content is 0.05-0.5%, preferably 0.08-0.3%；Pt content is 0.01-
0.1%, preferably 0.02-0.1%；Cu content is 0.01-0.1%, preferably 0.02-0.1%；Ni content is 0.01-0.1%, excellent
Select 0.02-0.1%；Carrier 99.2-99.92%, preferably 99.45%-99.86%.
3. the method according to claim 1, wherein two sections of catalyst are the load comprising Pd, Co and Ag
Catalyst, in terms of catalyst gross mass, Pd content is 0.5-1%, preferably 0.6-0.8%；Co content is 0.02-0.2%, preferably
0.06-0.16%；Ag content is 0.02-0.2%, preferably 0.06-0.16%；Carrier 98.6-99.46%, preferably 98.88-
99.28%.
4. the method according to claim 1, wherein the 2- ethyl -2- hexenoic aldehyde raw material is n-butanal warp
Condensation dehydration obtains the reaction solution comprising 2- ethyl -2- hexenoic aldehyde, the composition of the reaction solution comprising 2- ethyl -2- hexenoic aldehyde
It include: the butyraldehyde tripolymer and 1- of the n-butanal of 0.5-1.5wt%, the 2- ethyl -2- hexenoic aldehyde of 95-97wt%, 1-2.5wt%
2- ethyl -2- hexenoic aldehyde the dimer of 1.5wt%.
5. the method according to claim 1, wherein in the step 1), the temperature of one-stage hydrogenation reaction is
80-120 DEG C, absolute pressure 1-5MPa；In the step 2), the temperature of secondary hydrogenation reaction is 50-90 DEG C, absolute pressure
For 1-5MPa.
6. the method according to claim 1, wherein the mass ratio of one section of catalyst and two sections of catalyst is
1-10:1。
7. the method according to claim 1, wherein the recycle ratio of one section of hydride is 10- in the step 2)
40:1。
8. the method according to claim 1, wherein the recycle ratio of heavy constituent is 60-100 in the step 3):
1。
9. the method according to claim 1, wherein total liquid hourly space velocity (LHSV) is 0.1-1h-1。
10. the method according to claim 1, wherein in the step (1), hydrogen and 2- ethyl -2- hexenoic aldehyde
Molar ratio be 5-25:1.
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| CN101759533A (en) * | 2008-11-18 | 2010-06-30 | 熊长宏 | New method for synthesizing 2-ethylhexanal |
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| CN107930647A (en) * | 2017-12-06 | 2018-04-20 | 万华化学集团股份有限公司 | A kind of preparation method of catalyst, its preparation method and 2 ethyl hexanals |
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| US5756856A (en) * | 1995-07-08 | 1998-05-26 | Huels Aktiengesellschaft | Process for the preparation of 2-ethylhexanal |
| CN1569789A (en) * | 2003-07-11 | 2005-01-26 | 中国石油化工股份有限公司齐鲁分公司 | Process for the preparation of 2-ethylhexanal |
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