CN103664587A - Method for preparing cyclohexyl acetate and method for preparing cyclohexanol ethanol - Google Patents
Method for preparing cyclohexyl acetate and method for preparing cyclohexanol ethanol Download PDFInfo
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- CN103664587A CN103664587A CN201210560214.5A CN201210560214A CN103664587A CN 103664587 A CN103664587 A CN 103664587A CN 201210560214 A CN201210560214 A CN 201210560214A CN 103664587 A CN103664587 A CN 103664587A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention relates to a method for preparing cyclohexyl acetate. According to the method, addition esterification reaction on acetic acid and cyclohexene is performed by pre-esterification and reaction rectification; and the method has very high cyclohexene conversion rate and cyclohexyl acetate selectivity. The invention relates to a method for preparing cyclohexanol and ethanol, which comprises the following steps: carrying out addition esterification reaction on acetic acid and cyclohexene by using pre-esterification and reaction rectification to prepare the cyclohexyl acetate; and hydrogenating the cyclohexyl acetate to coproduce the cyclohexanol and ethanol.
Description
Technical field
The present invention relates to a kind of a kind of method and method of preparing hexalin and ethanol of preparing hexalin acetate.
Background technology
Hexalin acetate is a kind of liquid with banana or apple aroma, with the fruit flavour type essence of its preparation, is widely used in the industries such as food, beverage and makeup.In addition, hexalin acetate has good solubility energy to resin, is also often used as the environment-friendly type solvent of high-grade paint, paint.
At present, the synthetic method of industrial hexalin acetate is acetic acid and hexalin esterification.Esterification reaction need to could carry out smoothly under the effect of an acidic catalyst.Song Guijia, Wu Xionggang (chemical propellant and macromolecular material, 2009, V0l.7 (2): P31-33), the progress of synthesis situation of having summarized acetic acid and hexalin esterification Synthesis of Cyclohexyl Acetate, related catalyzer comprises the sulfonic acid catalyzes systems such as thionamic acid, tosic acid, SO
4 2-/ TiO
2, S
2o
8 2-/ ZnO
2-Fe
2o
3-SiO
2, S
2o
8 2-/ Fe
2o
3-MoO
3deng solid super acid catalyst system, inorganic salt catalyst system, phospho-wolframic acid and the Over Supported Heteropolyacid Catalyst systems such as ferrous sulfate, sodium pyrosulfate, sal enixum, iron trichloride, copper sulfate.
CN102060697 has proposed a kind of synthesis technique of hexalin acetate, first by cupric oxide and the synthetic copper p-toluenesulfonate of tosic acid reaction, take copper p-toluenesulfonate as catalyzer, with cyclohexane give band aqua, by acetic acid and hexalin reaction Synthesis of Cyclohexyl Acetate again.There is catalyzer and product separation difficulty, need to use the problems such as band aqua, hexalin price height in alcoholic acid esterification Synthesis of Cyclohexyl Acetate, is therefore difficult to scale operation.
JPA254634/1989 discloses the preparation method of a kind of hexalin and hexalin acetate, and employing strong-acid ion exchange resin is catalyzer, by the method for aqueous acetic acid and tetrahydrobenzene reaction synthesizing cyclohexanol and hexalin acetate.The best result that this patent example is mentioned is, cyclohexene conversion rate 62.7%, hexalin yield 18.4%, hexalin acetate yield 43.7%.
CN1023115C, JP flat-313447 discloses a kind of preparation method of hexalin, and adopting ZSM5 or supersiliceous zeolite is under catalyzer and water exist, by acetic acid and tetrahydrobenzene reaction Synthesis of Cyclohexyl Acetate, at 120 ℃ of reaction 4h, the output of hexalin and hexalin acetate only has respectively 12.5% and 65%.
EP0461580A2, USP5254721 disclose a kind of employing heteropoly acid containing tungsten catalyzer and have been reacted by acetic acid and tetrahydrobenzene, hexalin acetate processed.This patent proposes crystal water content in heteropolyacid molecule and is preferably 0～3.The best result that patent provides is, at 370 ℃ of roasting 3h, obtain completely not containing 12 silicotungstic acid catalysts of crystal water, in 200mL autoclave pressure, add 61.5g acetic acid, 13.5g tetrahydrobenzene, 5g catalyzer, at 0.5MPA, under 130 ℃ of conditions, react 0.5h, cyclohexene conversion rate 95.2%, hexalin acetate selectivity 99.2%.As can be seen here, under the condition of very high sour alkene ratio, tetrahydrobenzene can not transform completely.Owing to can not realizing the conversion completely of tetrahydrobenzene.
From existing disclosed document, existing document discloses the various solid acid catalysts of acetic acid and tetrahydrobenzene addition esterification, addition esterification generally adopts tank reactor, reaction raw materials is pure tetrahydrobenzene, even if adopt very high sour alkene ratio, be also difficult to realize the conversion completely of tetrahydrobenzene.
Reactive distillation has been widely used in the processes such as alfin etherificate, alcoholic acid esterification, transesterify, ester hydrolysis, aldolization, but up to now, has no the report for acetic acid and tetrahydrobenzene addition esterification process by reactive distillation.
Hexalin and ethanol are all important chemical feedstocks and solvents.Hexalin is mainly for the production of nylon 6, nylon 66 etc., and ethanol is the raw material of the multiple Chemicals such as synthesizing ester, is also widely used as the fuel dope of gasoline.
The method of industrial synthesizing alcohol is mainly ethene direct hydration method, but in the abundant country of some agricultural byproducts, fermentation method is still the main method of producing ethanol.Because China is populous and cultivated area is not enough, and fermentation legal system ethanol exists the problem of " striving grain with mouth ", so fermentation method does not meet the national conditions of China.In addition, the pollution of fermentation method is also more serious.China's oil relative inadequacy of resources, and ethene price is subject to the influence of fluctuations of international oil price very large, therefore at China's application ethylene hydration method, can face certain raw materials cost pressure.In addition, the reaction conditions of ethene direct hydration method is harsher, need under High Temperature High Pressure, carry out.In sum, developing new ethanol synthesis route is the inevitable requirement of technology and Economic development.
CN102149661A discloses a kind of platinum/tin catalyst that uses and by the direct selectivity of acetic acid, has been prepared the method for ethanol, comprise: the incoming flow containing acetic acid and hydrogen contacts with applicable hydrogenation catalyst in rising temperature, described hydrogenation catalyst be included in platinum in applicable support of the catalyst and tin group and and optional load on the 3rd metal on described carrier, wherein said the 3rd metal choosing is the following group forming freely: palladium, rhodium, ruthenium, rhenium.Iridium, chromium, copper, molybdenum, tungsten, vanadium and zinc.
CN1022228831A discloses a kind of catalyzer of acetic acid gas phase hydrogenation ethanol production, this catalyzer is comprised of main active ingredient, auxiliary agent and carrier three parts, carrier is any one in gac, graphite or multiple-wall carbon nanotube, it is characterized in that, described main active ingredient is catalyst weight 0.1～30.0%, the weight of auxiliary agent is 0.1～10.0% of catalyst weight, and surplus is carrier.Main active ingredient is any one or two kinds of metal W or Mo.Auxiliary agent is one or more of Pd, Re, Pt, Rh or Ru.
Industrial, the production method of hexalin mainly contains air oxidation of cyclohexane method, phenol hydrogenation method and cyclohexene hydration method, and wherein the application of cyclohexane oxidation process is the most general.
Cyclohexane oxidation process is current topmost cyclohexanol production technique.This technology utilization oxygenant (being generally air) is cyclohexyl hydroperoxide by cyclohexane oxidation, and decomposing cyclohexyl hydrogen peroxide obtains the mixture (being commonly called as KA oil) of hexalin and pimelinketone.The advantage of this technique is that oxidizing process condition relaxes, slagging scorification is less, cycle of operation is long.Shortcoming is that operational path is long, energy consumption is high, pollution is large, and the cyclohexane conversion of this technique only has 3～5%; Particularly, in the decomposition course of cyclohexyl hydroperoxide, the selectivity of hexalin is poor, and yield is low; In addition, this technique also produces a large amount of unmanageable waste lyes, is still so far global the difficult problem of environmental protection.
Phenol hydrogenation method is to produce the comparatively clean technological line of hexalin, and has that technical process is short, product purity advantages of higher.Phenol hydrogenation is produced hexalin and is mainly adopted gas phase hydrogenation method.The method adopts 3～5 reactors in series conventionally.Under the effect of Supported Pd-Catalyst, under 140～170 ℃ and 0.1MPa, the yield of pimelinketone and hexalin can reach 90%～95%.Yet, this technique phenol (vaporization heat 69kJmol that need to vaporize
-1) and methyl alcohol (vaporization heat 35.2kJmol
-1), energy consumption is higher, and catalyzer in use easily carbon deposit cause active decline, short, the expensive and use noble metal catalyst of phenol, is restricted the industrial application of the method in addition.
The eighties in 20th century, Japan Asahi Kasei Corporation has developed the technique by partial hydrogenation of benzene cyclohexene, cyclohexene hydration hexalin processed, and having realized industrialization in nineteen ninety, relevant Chinese patent application has CN1079727A, CN1414933A and CN101796001A.Cyclohexene hydration method is relatively new cyclohexanol production method, and the reaction preference of the method is high, and process does not almost have three waste discharge, but exist reaction conversion ratio very low, to the more high deficiency of tetrahydrobenzene purity requirement.As adopt high silica ZSM-5 catalyzer, and in two series connection slurry reactors, stopping 2h, cyclohexene conversion rate only has 12.5%.
CN86105765A proposes a kind of carboxylicesters Hydrogenation that passes through for the method for alcohol, the method is under the existence of solid copper containing catalyst that has reduction activation, under high temperature, normal pressure or high pressure by carboxylicesters hydrogenation, outside this catalyzer copper removal, also contain magnesium, at least one in lanthanide series metal or actinide metals.Catalyzer represented with following general formula before reduction activation: Cu
am
1m
2 ba
co
x, M
1magnesium, at least one in lanthanide series metal or actinide metals, M
2be selected from Ca, Mo, Rh, Pt, Cr, Zn, Al, Ti, V, Ru, Re, Pd, Ag and Au; A is a kind of basic metal; A is 0.1～4; B is 0～1.0; C is 0～0.5; X is for can meet the numeral of other element to the total valence mumber requirement of oxygen.Basic metal in this catalyzer is a kind of selection component, and its form by an alkali metal salt is introduced catalyzer.The acyclic monobasic that the applicable carboxylicesters of the method and catalyzer is C1-C24 or binary, saturated or unsaturated, straight or branched carboxylicesters, do not relate to the production of the cycloalkanol as hexalin.
CN1075048C proposes a kind of method and catalyzer of direct hydrogenation of carboxylic esters, comprise and make one or more esters contact and react under following catalyzer exists with hydrogen, this catalyzer contains a kind of copper compound, a kind of zn cpds and at least one and is selected from the compound of aluminium, zirconium, magnesium, a kind of rare earth element or its mixture as its component, by these catalyst components are made to this catalyzer 200 to being less than roasting in the temperature range of 400 ℃, the method is under liquid phase, at 170～250 ℃ and 20.7～138 bar tables, depresses and carries out.The applicable carboxylicesters of the method and catalyzer is the transesterify by the natural oil C6～C22 dimethyl ester, C6～C66 natural glycerin three esters that make or the C6～C44 compound making do transesterify for natural glycerin three esters.
US4939307 proposes the technique of a kind of ester through hydrogenation alcohol processed.By general formula, be R
1-CO-OR
2or R
4o-CO-R
3-CO-OR
2(R wherein
1for H or C
1-C
20alkyl, R
2and R
4for C
1～C
20alkyl, R
3for-(CH
2) n-group, n=1～10) ester and H
2with CO gas mixture, at 30～150 ℃, under 5～100 bar pressures, carry out hydrogenation reaction and generate alcohol, its catalyzer is composed of the following components: (a) VIII family metal ion compound in a kind of periodictable; (b) alkoxide of a kind of basic metal or alkaline-earth metal; (c) a kind of alcohol.
US4113662 and USP4149021 disclose a kind of ester through hydrogenation catalyzer, this catalyzer is comprised of element, oxide compound, oxyhydroxide or the carbonate of cobalt, zinc, copper, the most applicable carboxylicesters of this catalyzer is polyglycolide, the preparation of not mentioned cycloalkanol in document.
US4611085 discloses a kind of C
1～C
20the method of carboxylicesters gas phase hydrogenation alcohol processed, it is characterized in that catalyzer is comprised of a kind of VIII family element, a kind of auxiliary agent and charcoal carrier, wherein said VIII family element comprises Ru, Ni, Rh, auxiliary agent comprises IA (except Li), IIA family (except Be and Mg), group of the lanthanides and actinide elements, and the BET specific surface area of charcoal carrier is greater than 100m
2/ g.Hydrogenation reaction is at 100～400 ℃, gas space velocity 100～120000h
-1under condition, carry out.Basic metal in this catalyzer is to introduce with the form of an alkali metal salt, as alkali-metal nitrate, carbonate or acetate.The method is applicable to the carboxylicesters that can vaporize under reaction conditions, and the alcohol derivative moiety carbon number in carboxylicesters is preferably less than 5 and the carbon that is connected with oxygen primary carbon preferably.
GB2250287A(Eduard Karek Poles, Dirk Ryk Evert Polman, JohannedJoesphus Vreeswijk.Unichema Chemie BV) disclose a kind of method of fatty acid ester Hydrogenation alcohol, the feature of the method is that hydrogenation adopts copper containing catalyst and in ester raw material, adds a certain amount of water to maintain the activity of catalyzer.
US5334779 discloses a kind of catalyst composition and the application in carboxylicesters hydrogenation thereof, and this catalyzer is comprised of cupric oxide, zinc oxide and the 3rd component (oxide compound of aluminium, magnesium, zirconium or its mixture).The carboxylicesters that this catalyzer and method are used is cyclohexane diacid dimethyl ester, the lower alkyl ester of C10～C20 carboxylic acid, two lower alkyl esters of two lower alkyl esters of hexanodioic acid and toxilic acid.
From open source literature, in prior art, there is not any information disclosure about ethyl cyclohexyl ester through hydrogenation energy coproduction hexalin and ethanol.
Summary of the invention
The invention provides a kind of method of preparing hexalin acetate, the pre-esterification of the method utilization and reactive distillation carry out the addition esterification of acetic acid and tetrahydrobenzene, can, with partial hydrogenation of benzene product as raw material, there is very high cyclohexene conversion rate and hexalin acetate selectivity.The present invention also provides a kind of method of preparing hexalin and ethanol, and the method first utilizes pre-esterification and reactive distillation to carry out the addition esterification of acetic acid and tetrahydrobenzene, prepares expeditiously hexalin acetate; And then come coproduction hexalin and ethanol by ethyl cyclohexyl ester through hydrogenation, hydrogenation process is used hydrogenation catalyst provided by the invention, can under higher space velocity, almost quantitatively hexalin acetate be converted into hexalin and ethanol, and does not almost have side reaction to occur.
In the present invention, " addition esterification " refers to that carboxylic acid generates the reaction of ester to olefinic double bonds addition.
A method of preparing hexalin acetate, comprising:
(1) by acetic acid and tetrahydrobenzene raw material input pre-esterification reactor device, under the existence of solid acid catalyst, react; Described tetrahydrobenzene raw material is tetrahydrobenzene or is the mixture of tetrahydrobenzene and hexanaphthene and/or benzene composition;
(2) by the discharging input reactive distillation column of step (1), contact with solid acid catalyst, the separation of reaction product is carried out in reaction simultaneously, at the bottom of tower, obtains hexalin acetate.
The described tetrahydrobenzene raw material mixture that to be tetrahydrobenzene form with hexanaphthene and/or benzene, tetrahydrobenzene content is preferably 20m%～80m%, more preferably 20m%～60m%.Industrial tetrahydrobenzene generally adopts the selective hydrogenation of benzene to produce, its product logistics is the mixture of tetrahydrobenzene, hexanaphthene and benzene, wherein the content of tetrahydrobenzene is generally 20m%～60m%, if carry out a step extracting and separating, can obtain the logistics that tetrahydrobenzene content is generally 40m%～80m%, the present invention preferably adopts these logistics as tetrahydrobenzene raw material, does like this and can avoid or simplify investment and the very high sepn process of process cost.
Described tetrahydrobenzene raw material is tetrahydrobenzene and the mixture that hexanaphthene and/or benzene form, and from reactive distillation tower top, obtains the mixture that acetic acid and hexanaphthene and/or benzene form.
Described pre-esterification reactor device can be tank reactor, fixed-bed reactor, fluidized-bed reactor or ebullated bed reactor.Described fixed-bed reactor are preferably tubular fixed-bed reactor, more preferably shell shell and tube reactor.The operating method of pre-esterification reactor system can be carried out by intermittent mode, also can carry out in a continuous manner, preferably carries out in a continuous manner.Because tubular fixed-bed reactor has, manufacturing expense is low, simple operation and other advantages, is therefore the preferred reactor of the present invention.Fixed-bed reactor can adopt thermal insulation or isothermal mode to operate.Adiabatic reactor can adopt cartridge reactor, and catalyzer is fixed in reactor, and reactor outer wall is incubated adiabatic.Because addition esterification is thermopositive reaction, therefore need to control reactant concn to control reactor bed temperature rise, or be circulated to reactor inlet with diluting reaction substrate concentration after adopting partial reaction product cooling.Isothermal reactor can adopt shell shell and tube reactor, and catalyzer is fixed in tubulation, at shell side by water coolant to remove the liberated heat of reaction.
Pre-esterification reactor need to be controlled at a certain temperature and carry out, and too low thermotonus speed is low, although and too high temperature speed of reaction is accelerated greatly, also easily there is side reaction, and unfavorable to the equilibrium conversion of esterification.Selected temperature of reaction is relevant with catalyzer, is generally 50～200 ℃, is preferably 60～120 ℃.
The pressure of pre-esterification reactor is relevant with temperature of reaction.Because addition esterification is carried out in liquid phase, so reaction pressure should guarantee that reaction is in liquid phase state.In general, reaction pressure is normal pressure～10MPa, is preferably normal pressure～1MPa.
The sour alkene mol ratio of pre-esterification reactor is 0.2～20:1, is preferably 1.2～4:1.
The liquid feeding air speed of pre-esterification reactor is 0.5～20h
-1, optimal conditions is 1～5h
-1.
The discharging of step (1) contains unreacted acetic acid, tetrahydrobenzene and esterification products hexalin acetate, if adopt the mixture of tetrahydrobenzene and hexanaphthene and/or benzene as raw material, the discharging of step (1) also contains hexanaphthene and/or benzene.
Under these conditions, the cyclohexene conversion of pre-esterification reactor generally can reach more than 80%, and the selectivity of esterification can reach more than 99%.
In step (2), described reactive distillation column is identical with common rectifying tower in form, generally tower body, overhead condenser, return tank, reflux pump, tower reactor and reboiler etc., consists of.The type of tower can be tray column, can be also packing tower, can also be both combinations.Adoptable tray column type comprises valve tray column, sieve-tray tower, bubble-plate column etc.The filler that packing tower uses can adopt random packing, as Pall ring, θ ring, Berl saddles, ladder ring packing etc.; Also can adopt structured packing, as corrugated plate packing, ripple silk net filler etc.
According to method provided by the present invention, in reactive distillation column, be furnished with solid acid catalyst.Know with those skilled in the art know that, catalyst arrangement mode in reactive distillation column should meet following 2 requirements: (1) wants to provide enough passages passing through for vapour-liquid two-phase, or there is a larger bed voidage (general requirement is more than at least 50%), with assurance vapour-liquid two-phase, can convection current pass through, and do not cause liquid flooding; (2) will have good mass-transfer performance, reactant will be delivered in catalyzer and react from fluid-phase, and simultaneous reactions product will transmit out from catalyzer.In existing document, disclose the decoration form of multiple catalysts in reactive distillation column, these decoration forms all can be the present invention and adopt.The decoration form of existing catalyzer in reaction tower can be divided into following three kinds: (1) is directly arranged in tower by catalyzer in the mode of fractional distillation filling-material, major way is by by a certain size and shape granules of catalyst and fractional distillation filling-material mechanically mixing or catalyzer is clipped between structured packing and forms whole filler with structured packing, or catalyzer is directly made to fractional distillation filling-material shape; (2) catalyzer packed in the permeable small vessels of gas-liquid and be arranged on the column plate of reaction tower, or by catalyst arrangement in the downtake of reaction tower; (3) catalyzer is directly packed in reaction tower in fixed bed mode, liquid phase directly flows through beds, and be that gas phase is set up special-purpose passage, adopt in this way at the position that catalyzer is housed, by beds and rectifying tower tray, be arranged alternately, liquid on tower tray enters next beds through downtake and redistributor, carries out addition reaction in bed, and the liquid of beds bottom enters next tower tray by liquid header.
Described reactive distillation column must have enough theoretical plate numbers and reaction stage number could meet reaction and separation processes requirement.The theoretical plate number 10～150 of described reactive distillation column, wherein between 10～120 blocks of plates, select 5～30 blocks of plates to arrange catalyzer, the theoretical plate number that more preferred scheme is reaction tower is 30～100, wherein between 10～80 blocks of plates, selects 8～20 blocks of plates to arrange catalyzer.
In the present invention, need to guarantee that reactant has enough residence time, to realize the conversion completely of tetrahydrobenzene.With respect to the total fill able volume of catalyzer, liquid feeding air speed is 0.1～20h
-1, be preferably 0.2～
2h
-1。
In the present invention, the working pressure of reactive distillation column can operate under negative pressure, normal pressure and pressurized conditions.The working pressure of reactive distillation column is-0.0099MPa to 5MPa to be preferably normal pressure to 1MPa.
The service temperature of reactive distillation column is relevant with the pressure of reactive distillation column, can, by regulating the working pressure of reaction tower to regulate the temperature distribution of reaction tower, make the temperature of catalyst filling zone within the scope of the active temperature of catalyzer.The temperature of catalyst filling zone is between 40～200 ℃, preferably between 60～150 ℃.
The reflux ratio of reactive distillation column should meet requirement separated and reaction simultaneously, generally, increases reflux ratio and is conducive to improve separating power and reaction conversion ratio, but can increase process energy consumption simultaneously.
In the present invention, if use pure tetrahydrobenzene and acetic acid as reaction raw materials, can realize total reflux in theory.While having a small amount of light constituent impurity in reaction raw materials, a small amount of overhead stream need to be drawn to reactive distillation column.In the present invention, reflux ratio is 0.1～100:1, is preferably 0.5～10:1.
The solid acid catalyst of the solid acid catalyst of step (1) and step (2) can be identical or different, is selected from respectively one or more in strong acid ion exchange resin catalyzer, heteropolyacid catalyst and molecular sieve catalyst.
Optional one or more in strong acid ion exchange resin catalyzer, heteropolyacid catalyst and molecular sieve catalyst of described solid acid catalyst.
Described strong acid ion exchange resin catalyzer had both comprised common macropore sulfonic acid type polystyrene-divinylbenzene resin, also comprised the sulfonic resin after halogen atom modification.This resinoid is easy to buy from market, and the method that also can record by classical documents is produced.The preparation method of macropore sulfonic acid type polystyrene-divinylbenzene resin normally splashes into the mixture of vinylbenzene and Vinylstyrene and in the aqueous phase system that contains dispersion agent, initiator, pore-creating agent, carries out suspension copolymerization under the condition of high-speed stirring, resulting polymer globules (Archon) is separated from system, with solvent, pump pore-creating agent wherein, take again ethylene dichloride as solvent, the vitriol oil be sulphonating agent, carry out sulfonation reaction, finally by operations such as filtration, washings, finally make product.In the skeleton of common strong acid ion exchange resin, introduce halogen atom, as fluorine, chlorine, bromine etc., can further improve heat resistance and the strength of acid of resin.This halogen-containing strongly-acid fire resistant resin at least can obtain by following two kinds of approach, a kind of approach is to introduce halogen atom on the phenyl ring of sulfonated styrol resin skeleton, chlorine atom for example, because the strong electron attraction of halogens not only can make phenyl ring stable, but also can improve the acidity of sulfonic acid group on phenyl ring, can make like this strength of acid function (Hammett function) H0≤-8 of resin catalyst, and can be at more than 150 ℃ life-time service, this resinoid can conveniently buy from the market, such as the Amberlyst45 resin that abroad ROHM & HASS company produces, the D008 resin that Ji Zhong chemical plant, domestic Hebei produces etc., another kind of approach all replaces the hydrogen on resin matrix with fluorine, strong electrophilic due to fluorine, make it have superpower acidity and the thermostability of superelevation, strength of acid function (Hammett function) H0 can be less than-12, and heat resisting temperature reaches more than 250 ℃, the exemplary of this class fire resistant and highly acidic resin is the Nafion resin that DuPont company produces.
Described heteropolyacid catalyst can be both heteropolyacid and/or heteropolyacid acid salt, can be also the catalyzer of carried heteropoly acid and/or heteropolyacid acid salt.The strength of acid function H0 of heteropolyacid and acid salt thereof can be less than-13.15, and can be up to more than 300 ℃ life-time service.Described heteropolyacid and acid salt thereof comprise heteropolyacid and the acid salt thereof of Kegin structure, Dawson, Anderson structure, Silverton structure.The heteropolyacid of preferred keggin structure, as 12 phospho-wolframic acid (H
3pW
12o
40xH
2o), 12 silicotungstic acid (H
4siW
12o
40xH
2o), 12 phosphomolybdate (H
3pMo
12o
40xH
2o), 12 molybdovanaphosphoric acid (H
3pMo
12-yv
yo
40xH
2o) etc.The described preferred acid Tricesium dodecatungstophosphate of heteropolyacid acid salt salt (Cs
2.5h
0.5p
12wO
40), its strength of acid function H0 is less than-13.15, and specific surface area can reach 100m
2more than/g.In the catalyzer of described carried heteropoly acid and/or heteropolyacid acid salt, carrier is SiO
2and/or gac.
In the present invention, described solid acid catalyst can also be molecular sieve catalyst.Described molecular sieve can be one or more in H β, HY and HSZM-5, preferably uses H β, the HY of fluorine and/or phosphorus modification and one or more in HSZM-5.These molecular sieves after fluorine, phosphorus modification, the acidity of the molecular sieve that can further improve and catalytic performance.
In preferred situation, the theoretical plate number of described reactive distillation column is 30～100, selects 8～20 blocks of plates to arrange solid acid catalyst between 10～80 blocks of plates; Described solid acid catalyst is macropore strong acid Hydrogen ion exchange resin or acid phospho-wolframic acid cesium salt; With respect to the total fill able volume of catalyzer, liquid feeding air speed is 0.2～2h
-1; The working pressure of reactive distillation column is that normal pressure is to 1MPa; The temperature of catalyst filling zone is between 120～180 ℃; Reflux ratio is 0.5～10:1.
The feature of aforesaid method is: the mode that adopts pre-esterification and reactive distillation esterification to combine, first by pre-esterification, realize the conversion of most of tetrahydrobenzene, and then in reactive distillation column, arrange that a small amount of catalyzer further realizes the conversion completely of tetrahydrobenzene.Adopt reaction to combine with rectifying separation, can with the product logistics of partial hydrogenation of benzene or a step extracting and separating containing tetrahydrobenzene logistics as esterification feed, and realize the conversion completely of tetrahydrobenzene, thereby avoid or simplify and invest and the very high separation of extractive distillation process of process cost.
The present invention also provides a kind of method of preparing hexalin and ethanol, comprising:
(1) by acetic acid and tetrahydrobenzene raw material input pre-esterification reactor device, under the existence of solid acid catalyst, react; Described tetrahydrobenzene raw material is tetrahydrobenzene or is the mixture of tetrahydrobenzene and hexanaphthene and/or benzene composition;
(2) by the discharging input reactive distillation column of step (1), contact with solid acid catalyst, the separation of reaction product is carried out in reaction simultaneously, at the bottom of tower, obtains hexalin acetate;
(3) under the existence of hydrogenation catalyst, the hexalin acetate that step (2) is obtained and hydrogen contact reacts; Described hydrogenation catalyst comprises: (a) cupric oxide, (b) zinc oxide, (c) be selected from the oxide compound of one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals, (d) one or more in alkali metal hydroxide and alkaline earth metal hydroxides; In described catalyzer, in mass fraction, component (a) is 5～60 parts, and component (b) is 10～50 parts, and component (c) is 5～30 parts, and component (d) is 0.2～2 part.
Step (1) and (2) are identical with the aforementioned method of preparing hexalin acetate, do not repeat them here.
The reactor that step (3) adopts is one or more, and type of reactor can be selected from one or more in tank reactor, tubular fixed-bed reactor, ebullated bed reactor and fluidized-bed reactor.
Step (3) both can adopt mode intermittently to implement, and also can adopt continuous mode to implement.Intermittent type hydrogenation reaction generally adopts reactor to make reactor, hexalin acetate and hydrogenation catalyst are dropped in reactor, pass into hydrogen reacts under certain temperature and pressure, after reaction finishes, reaction product is adopted and drawn off from still, isolate product, then drop into next batch material and react.Continous way hydrogenation reaction can adopt shell-and-tube shell and tube reactor, and hydrogenation catalyst is fixed in tubulation, at shell side by water coolant to remove the liberated heat of reaction.
In step (3), hydrogenation reaction temperature is 150～400 ℃, is preferably 200～300 ℃; Reaction pressure is normal pressure～20MPa, is preferably 4～10MPa; Hydrogen ester mol ratio is 1～1000:1, is preferably 5～100:1; The liquid feeding air speed of hexalin acetate is 0.1～20h
-1, be preferably 0.2～2h
-1.
For realizing object of the present invention, the present invention first provides a kind of carboxylicesters hydrogenation catalyst, comprise: (a) cupric oxide, (b) zinc oxide, (c) be selected from the oxide compound of one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals, (d) one or more in alkali metal hydroxide and alkaline earth metal hydroxides; In described catalyzer, in mass fraction, component (a) is 5～60 parts, and component (b) is 10～50 parts, and component (c) is 5～60 parts, and component (d) is 0.2～2 part.
In preferred situation, in described catalyzer, in mass fraction, component (a) is 10～50 parts, and component (b) is 15～45 parts, and component (c) is 15～55 parts, and component (d) is 0.2～2 part.
In preferred situation, in described catalyzer, in mass fraction, component (a) is 30～45 parts, and component (b) is 20～35 parts, and component (c) is 20～50 parts, and component (d) is 0.5～1.5 part.
From being easy to get property, cost and the result of use of raw material, consider, component (d) is preferably one or more in potassium hydroxide, sodium hydroxide and hydrated barta.
Be to be understood that, catalyzer is generally concluded the business and stores with the form of precursor (or being called precursor), although catalyst precursor can not direct catalytic reaction, yet traditionally catalyst precursor is just being called to " catalyzer ".Catalyst precursor just has catalytic activity after reduction, and this is completed by the operator of full scale plant conventionally, and those skilled in the art know this reduction process, and the present invention does not repeat them here.Catalyst precursor can be made the shape of various needs according to user's demand, as the bead through overmolding, can be also the state before moulding, as powder.
The present invention also provides a kind of preparation method of carboxylicesters hydrogenation catalyst, comprising:
(1) by coprecipitation method, prepare complex metal oxides; Described complex metal oxides comprises (a) cupric oxide, and (b) zinc oxide (c) is selected from the oxide compound of one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals; In described complex metal oxides, in mass fraction, component (a) is 5～60 parts, and component (b) is 10～50 parts, and component (c) is 5～60 parts;
(2) alkali metal hydroxide that complex metal oxides step (1) being obtained is 0.5～5% with massfraction and/or alkaline earth metal hydroxides aqueous solution dipping, more after filtration, dry, roasting, obtain product.
In preferred situation, in step (2), dipping temperature is 30 ℃～80 ℃, and dipping time is 1～48h; Drying temperature is 100 ℃～200 ℃, and be 3～48h time of drying; Maturing temperature is 250 ℃～400 ℃, and roasting time is 3～48h.
Coprecipitation method refers to homogeneous phase two or more metallic cations that exist in solution reacts with precipitation agent, metallic cation in solution is precipitated, obtain the precipitation of various uniform component, the precipitation mixture or the sosoloid presoma that generate, after filtration, washing, roasting (making precipitation mixture or the thermolysis of sosoloid presoma), obtain the method for complex metal oxides.Described coprecipitation method can take different modes to realize, both the solution that contains metallic cation can be joined in precipitant solution, also precipitant solution can be joined in the solution that contains metallic cation, the solution that contains metallic cation and precipitant solution can also be joined in solvent simultaneously.The solvent that coprecipitation method is used both can make water, also can use the mixed solvent of second alcohol and water.
In more detail, the coprecipitation method in step (1) comprises:
(I) preparation mixes soluble metal salt brine solution, and described metal comprises (a) copper, (b) zinc and (c) be selected from one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals;
(II), at 15 ℃～80 ℃, adds the precipitation agent aqueous solution to the aqueous solution of step (I), to pH be 6～9, generate the mixed precipitation of metallic element described in step (I), it is metal oxide that described precipitation agent makes the precipitation energy pyrolysis generating;
The precipitation system that (III) obtains step (II), between 30 ℃～80 ℃, keep after 1～48h, filter and wash, until the metallic cation in filtrate is less than 100ug/g, at 100 ℃～200 ℃, dry 3～48h, 250 ℃～400 ℃ roasting 3～48h, obtain composite metal oxide powder.
In step (I), the implication of described " solubility " refers to that the solubleness of every kind of metal-salt in water can meet the composition requirement of the complex metal oxides of preparation.
In step (I), suitable soluble metallic salt can be selected from: the nitrate of described metal, vitriol, hydrochloride, acetate or their hydrate.
In step (II), preferably under agitation, to the aqueous solution of step (I), add the precipitation agent aqueous solution, this will be conducive to improve the homogeneity of catalyzer.
In step (II), described precipitation agent is preferably one or more in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, volatile salt, ammonia, urea, sodium oxalate, potassium oxalate and ammonium oxalate.
Embodiment
Embodiment 1～4 is for illustrating the method for preparing hexalin acetate.
The test that embodiment 1～4 carries out is all carried out at hexalin acetate model test device.This mode device is comprised of fixed bed pre-esterification reactor device and reactive distillation esterification column.Pre-esterification reactor device is the 316L stainless steel tube of φ 48 * 4 * 1200mm, and reaction tubes outside, with hot water jacket, can pass into hot water to control temperature of reaction in chuck.Reactive distillation esterification column is that diameter (internal diameter) is that 50mm, height are the titanium steel of 3m (TA2) tower.The bottom of tower connects the tower reactor that volume is 5L, disposes the electrically heated rod of 10KW in still, and this heating rod is controlled tower reactor heating amount by intelligent controller by silicon controlled rectifier (SCR).Tower top is connected with the return tank that condenser that heat interchanging area is 0.5m2 and volume are 2L.Raw material acetic acid and tetrahydrobenzene are respectively charged in 30L storage tank, and are driven in pre-esterification reactor device and are reacted by volume pump, and pre-esterification products enters reactive distillation column and further reacts.By regulating the heating power of tower reactor to regulate the heat that adds of reaction tower.By the reflux ratio of trim the top of column ratio regulators adjusting tower.From overhead extraction light constituent.From extraction ethyl cyclohexyl ester products at the bottom of tower.
Embodiment 1
By 500mL macropore strong acid Hydrogen ion exchange resin, (laboratory is synthetic by classical literature method, the styrene solution that contains 15% Vinylstyrene is carried out to suspension copolymerization and make Archon, then make through concentrated acid sulfonation, and recording its exchange capacity is 5.2mmolH
+/ g butt) pack the middle part of pre-reactor into, a certain amount of quartz sand is filled at two ends.Separately by high temperature resistant sulfonic acid ion exchange resin, (trade mark is Amberlyst45, by Rhom & Hass company, produced) with multistage high speed disintegrator, be ground into the powder that granularity is less than 200 orders (0.074mm), add perforating agent, lubricant, oxidation inhibitor and tackiness agent to mix on high-speed mixer, again on Banbury mixer in 180 ℃ of banburying 10min, material is plastified completely, injecting afterwards mould, to make diameter be 5mm, high 5mm, wall thickness is 1mm Raschig ring type resin catalyst filler.Respectively pack up and down the middle part of this filler 1950mL loading pattern reaction tower (high 1m is equivalent to 8 blocks of theoretical trays) into the glass spring filler 1950mL that diameter is 3mm, long 6mm (loading height is 1m, is equivalent to 10 blocks of theoretical trays).Tetrahydrobenzene and acetic acid are squeezed in pre-reactor and reacted by volume pump respectively, and pre-reaction product further reacts entering reaction tower.By regulating pre-reactor chuck hot water temperature to regulate pre-reaction temperature.Regulate tower reactor heating amount and trim the top of column amount to react continuously, the reaction conditions of steady operation conditions and reaction result are in Table 1.
Embodiment 2
The configuration of reaction tower and catalyzer is identical with embodiment 1.Just with tetrahydrobenzene, hexanaphthene and benzol mixture replacement tetrahydrobenzene, test, and pre-reactor pressure is 2.0MPa, reaction tower operates under condition of normal pressure.Regulate tower reactor heating amount and trim the top of column amount to react continuously, the reaction conditions of steady operation conditions and reaction result see the following form 2.
Embodiment 3
By the ball-type H of 500mL φ 3～4
0.5cs
2.5pW
12o
40/ SiO
2catalyzer packs the middle part of pre-reactor into, and a certain amount of quartz sand is filled at two ends.Another by the ball-type H of φ 3～4
0.5cs
2.5pW
12o
40/ S iO
2catalyzer is (by H
0.5cs
2.5pW
12o
40powder and granularity are less than 200 object silochrom powder, after fully mixing in mixer, in coater, take silicon sol as bonder roller forming, then drying, roasting form) sandwich in titanium wire network ripple plate, making diameter is the cylinder shape structured packing of 50mm, high 50mm.Respectively packing up and down the middle part of this packing type catalyzer L loading pattern reaction tower (high 1m is equivalent to 12 blocks of theoretical trays) into diameter is that 4mm, height are the 1950mL glass spring filler of 4mm (loading height is 1m, is equivalent to 15 blocks of theoretical trays).Tetrahydrobenzene and acetic acid are squeezed in pre-reactor and reacted by volume pump respectively, and pre-reaction product further reacts entering reaction tower.By regulating pre-reactor chuck hot water temperature to regulate pre-reaction temperature.Regulate tower reactor heating amount and trim the top of column amount to react continuously, the reaction conditions of steady operation conditions and reaction result are in Table 3.
Embodiment 4
The configuration of reaction tower and catalyzer is identical with example 3.Just with tetrahydrobenzene, hexanaphthene and benzol mixture, replace tetrahydrobenzene to test, pre-reaction pressure 2.0MPa reaction tower operates under 0.2MPa condition.Regulate tower reactor heating amount and trim the top of column amount to react continuously, the reaction conditions of steady operation conditions and reaction result are in Table 4.
The preparation of embodiment 5～10(catalyzer)
The catalyzer of embodiment 5～10 is prepared by follow procedure: by table 1 formula, take a certain amount of soluble metallic salt, be placed in 2000mL there-necked flask, be dissolved in water preparation into about 1000mL solution, on flask, load onto agitator, pH meter and thermometer, and flask is placed in to the adjustable water bath with thermostatic control of temperature, open and stir, regulating thermostatic bath temperature, certain density precipitant solution is splashed in flask gradually, control the rate of addition of the precipitation agent aqueous solution, the temperature rising of solution is controlled in 1 ℃.With pH value of solution, raising, there is precipitation in solution, and raises and increase gradually with pH, stops dripping the precipitation agent aqueous solution when pH value of solution arrives prescribed value.Then continuing to keep the aging certain hour of certain temperature under the condition stirring.Stop stirring, naturally cool to room temperature, will be deposited in centrifuging on supercentrifuge, and with deionized water wash 5 times, gained is deposited in baking oven and is dried, transfer in muffle furnace and carry out roasting, obtain mixed metal oxide.This metal oxide is at room temperature flooded with certain density alkaline solution, through vacuum filtration, remove steeping fluid, mixture is dried in baking oven, transfer to roasting in muffle furnace, finally obtain mixed metal oxide.Adopt ICP method to analyze the composition of gained sample.Concrete preparation condition and the results are shown in Table 5.
Embodiment 11～19(autoclave evaluate catalysts)
Embodiment 11～19 for carrying out the hexalin acetate hydropyrolysis experiment of example 5～10 obtained catalyzer in autoclave, testing sequence is as follows: get a certain amount of that catalyst fines is placed in 500mL autoclave, add 250g hexalin acetate, reactor is sealed, with nitrogen replacement three times, pass into hydrogen to certain pressure, heat up gradually, in the time of about 80 ℃, still internal pressure starts to decline, show that still inner catalyst starts reduction, and start to carry out ester through hydrogenation reaction, hydrogen make-up makes reactor maintain certain pressure in time, finally be warmed up to fixed temperature, and at this temperature, maintain after stress reaction certain hour, stopped reaction, cool to after room temperature, draw off reaction product and catalyzer.Use gas chromatographic analysis product composition, and by following formula, calculate the selectivity of ethyl cyclohexyl ester conversion rate and hexalin according to analytical results.
Ethyl cyclohexyl ester conversion rate=[1-unreacted hexalin acetate mole number/(unreacted hexalin acetate mole number+hexanaphthene mole number+hexalin mole number+ethyl hexamethylene ether mole number] * 100%
Hexalin selectivity=[hexalin mole number/(hexalin mole number+hexanaphthene mole number+ethyl cyclohexyl ether mole number)] * 100%
Experimental result is in Table 6.
Table 1
According to the transformation efficiency 99.76% of testing data ring hexene, hexalin acetate selectivity 99.03%.
Table 2
According to the transformation efficiency 98.38% of testing data ring hexene, hexalin acetate selectivity 99.11%.
Table 3
According to the transformation efficiency 99.9% of testing data ring hexene, hexalin acetate selectivity 99.35%.
Table 4
According to the transformation efficiency 99.02% of testing data ring hexene, hexalin acetate selectivity 99.19%.
Table 5 catalyzer is prepared result and is gathered
Table 6 autoclave evaluating catalyst result gathers
Claims (13)
1. a method of preparing hexalin acetate, comprising:
(1) by acetic acid and tetrahydrobenzene raw material input pre-esterification reactor device, under the existence of solid acid catalyst, react; Described tetrahydrobenzene raw material is tetrahydrobenzene or is the mixture of tetrahydrobenzene and hexanaphthene and/or benzene composition;
(2) by the discharging input reactive distillation column of step (1), contact with solid acid catalyst, the separation of reaction product is carried out in reaction simultaneously, at the bottom of tower, obtains hexalin acetate.
2. in accordance with the method for claim 1, it is characterized in that, the described tetrahydrobenzene raw material mixture that to be tetrahydrobenzene form with hexanaphthene and/or benzene, tetrahydrobenzene content is 20m%～80m%.
3. in accordance with the method for claim 2, it is characterized in that, tetrahydrobenzene content is 20m%～60m%.
4. in accordance with the method for claim 1, it is characterized in that, described pre-esterification reactor device is tank reactor, tubular fixed-bed reactor, fluidized-bed reactor or ebullated bed reactor.
5. in accordance with the method for claim 1, it is characterized in that, pre-esterification reactor temperature is 50～200 ℃, and reaction pressure is normal pressure～10Mpa, and the sour alkene mol ratio of pre-esterification reactor is 0.2～20:1, and liquid feeding air speed is 0.5～20h
-1.
6. in accordance with the method for claim 1, it is characterized in that, the theoretical plate number of described reactive distillation column is 10～150, selects 5～30 blocks of plates to arrange solid acid catalyst in theoretical plate number between 10～120 blocks of plates; With respect to the total fill able volume of catalyzer, liquid feeding air speed is 0.1～20h
-1; The working pressure of reactive distillation column is-0.0099MPa to 5MPa; The temperature of beds filling area is between 40～200 ℃; Reflux ratio is 0.1～100:1.
7. in accordance with the method for claim 1, it is characterized in that, the solid acid catalyst of the solid acid catalyst of step (1) and step (2) is selected from respectively one or more in strong acid ion exchange resin catalyzer, heteropolyacid catalyst and molecular sieve catalyst.
8. in accordance with the method for claim 7, it is characterized in that, described strong acid ion exchange resin catalyzer is macropore sulfonic acid type polystyrene-divinylbenzene resin or the sulfonic resin after halogen atom modification.
9. in accordance with the method for claim 7, it is characterized in that, described heteropolyacid catalyst is the heteropolyacid of keggin structure and/or the heteropolyacid acid salt of keggin structure, or the catalyzer of the heteropolyacid of load keggin structure and/or the heteropolyacid acid salt of keggin structure.
10. in accordance with the method for claim 9, it is characterized in that, described heteropolyacid acid salt is acid phospho-wolframic acid cesium salt.
11. in accordance with the method for claim 7, it is characterized in that, described molecular sieve catalyst is one or more in H β, HY and HZSM-5.
12. 1 kinds of methods of preparing hexalin and ethanol, comprising:
(1) by acetic acid and tetrahydrobenzene raw material input pre-esterification reactor device, under the existence of solid acid catalyst, react; Described tetrahydrobenzene raw material is tetrahydrobenzene or is the mixture of tetrahydrobenzene and hexanaphthene and/or benzene composition;
(2) by the discharging input reactive distillation column of step (1), contact with solid acid catalyst, the separation of reaction product is carried out in reaction simultaneously, at the bottom of tower, obtains hexalin acetate;
(3) under the existence of hydrogenation catalyst, the hexalin acetate that step (2) is obtained and hydrogen contact reacts; Described hydrogenation catalyst comprises: (a) cupric oxide, (b) zinc oxide, (c) be selected from the oxide compound of one or more metals in following group, aluminium, gallium, tin, titanium, zirconium, chromium, molybdenum, tungsten, manganese, rhenium, lanthanide series metal and actinide metals, (d) one or more in alkali metal hydroxide and alkaline earth metal hydroxides; In described catalyzer, in mass fraction, component (a) is 5～60 parts, and component (b) is 10～50 parts, and component (c) is 5～30 parts, and component (d) is 0.2～2 part.
13. in accordance with the method for claim 12, it is characterized in that, and in step (3), 150～400 ℃ of temperature, reaction pressure 1～20MPa, hydrogen ester mol ratio 1～1000:1; Hexalin acetate liquid feeding air speed is 0.1～20h
-1.
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