CN103664529B - The method of coproduction hexalin and ethanol - Google Patents
The method of coproduction hexalin and ethanol Download PDFInfo
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- CN103664529B CN103664529B CN201210559915.7A CN201210559915A CN103664529B CN 103664529 B CN103664529 B CN 103664529B CN 201210559915 A CN201210559915 A CN 201210559915A CN 103664529 B CN103664529 B CN 103664529B
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- 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
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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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 present invention relates to the method for coproduction hexalin and ethanol, the method first utilizes reactive distillation to carry out the addition esterification of acetic acid and tetrahydrobenzene, prepares hexalin acetate; And then come coproduction hexalin and ethanol by ethyl cyclohexyl ester through hydrogenation.Adopt method of the present invention can high-level efficiency, prepare hexalin co-production ethanol at low cost.
Description
Technical field
The present invention relates to the method for coproduction hexalin and ethanol.
Background technology
Hexalin and ethanol are all important chemical feedstocks and solvent.Hexalin is mainly for the production of nylon 6, nylon66 fiber 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 mainly ethene direct hydration method of industrial synthesizing alcohol, but in the country that some agricultural byproducts enrich, fermentation method is still the main method of producing ethanol.Because China is populous and cultivated area not enough, and the legal system ethanol that ferments also exists the problem of " striving grain with mouth ", and therefore 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 very large by the influence of fluctuations of international oil price, therefore can face certain raw materials cost pressure at China's application ethylene hydration method.In addition, the reaction conditions of ethene direct hydration method is harsher, needs to carry out at high temperature under high pressure.In sum, the inevitable requirement that new ethanol synthesis route is technology and Economic development is developed.
CN1022228831A discloses a kind of catalyzer of acetic acid gas phase hydrogenation ethanol production, this catalyzer by main active ingredient, auxiliary agent and carrier three part form; Carrier is any one in gac, graphite or multiple-wall carbon nanotube, and main active ingredient is any one or two kinds of metal W or Mo, and auxiliary agent is one or more of Pd, Re, Pt, Rh or Ru; The content of main active ingredient is 0.1 ~ 30.0% of catalyst weight, and the content of auxiliary agent is 0.1 ~ 10.0% of catalyst weight, and surplus is carrier.
CN102149661A discloses a kind of platinum/tin catalyst that uses and prepares the method for ethanol by the direct selectivity of acetic acid, comprise: contact with hydrogenation catalyst at relatively high temperatures with the incoming flow of hydrogen containing acetic acid, described hydrogenation catalyst be included in platinum in applicable support of the catalyst and tin group and and optional load the 3rd metal on the carrier, the 3rd wherein said metal is selected from the group that following metal is formed: palladium, rhodium, ruthenium, rhenium.Iridium, chromium, copper, molybdenum, tungsten, vanadium and zinc.
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.Cyclohexane oxidation is cyclohexyl hydroperoxide by this technology utilization oxygenant (being generally air), 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 oxidation process conditions 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 lye, is still global the difficult problem of environmental protection so far.
Phenol hydrogenation method produces the technological line that comparatively cleans of hexalin, and have 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 usually.Under the effect of Supported Pd-Catalyst, under 140 ~ 170 DEG C and 0.1MPa, the yield of pimelinketone and hexalin can reach 90% ~ 95%.But this technique needs vaporization phenol (vaporization heat 69kJmol
-1) and methyl alcohol (vaporization heat 35.2kJmol
-1), energy consumption is higher, and catalyzer in use easily carbon deposit cause activity decrease, short, the expensive and use noble metal catalyst of phenol, makes the industrial application of the method be restricted in addition.
The eighties in 20th century, Asahi Kasei Corporation of Japan develops by the technique of partial hydrogenation of benzene cyclohexene, cyclohexene hydration hexalin, and achieving 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 adopted high silica ZSM-5 catalyzer, in two series connection slurry reactors, stop 2h, cyclohexene conversion rate only has 12.5%.
CN86105765A proposes a kind of by the method for carboxylicesters Hydrogenation for alcohol, the method is under the existence of solid copper containing catalyst having reduction activation, by carboxylicesters hydrogenation under high temperature, normal pressure or high pressure, this catalyzer apart from copper also containing 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 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 introduces catalyzer.The method and catalyzer the carboxylicesters that is suitable for be acyclic unitary or binary, saturated or unsaturated, the straight or branched carboxylicesters of C1 ~ C24, do not relate to the production of the cycloalkanol resemble hexalin.
CN1075048C proposes a kind of method and catalyzer of direct hydrogenation of carboxylic esters, comprise and make one or more esters and hydrogen contact under following catalyzer exists and react, this catalyzer contains a kind of copper compound, a kind of zn cpds and at least one and is selected from aluminium, zirconium, magnesium, a kind of compound of rare earth element or its mixture as its component, by the roasting in 200 to the temperature range being less than 400 DEG C of these catalyst components is obtained this catalyzer, the method is under liquid phase, carries out at 170 ~ 250 DEG C and the pressure of 20.7 ~ 138 bar tables.The method and catalyzer the carboxylicesters that is suitable for be the C6 ~ C22 dimethyl ester, C6 ~ C66 natural glycerin three ester that are obtained by the transesterify of natural oil or make the obtained C6 ~ C44 compound of transesterify for natural glycerin three ester.
US4939307 proposes a kind of technique of ester through hydrogenation alcohol.Be R by general formula
1-CO-OR
2or R
4o-CO-R
3-CO-OR
2(wherein R
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 DEG C, carry out hydrogenation reaction under 5 ~ 100 bar pressures and generate alcohol, its catalyzer is composed of the following components: group VIII metal ionic compound in (a) a kind of periodictable; The alkoxide of (b) a kind of basic metal or alkaline-earth metal; (c) a kind of alcohol.
US4113662 and USP4149021 discloses a kind of ester through hydrogenation catalyzer, this catalyzer is made up of the element of cobalt, zinc, copper, oxide compound, oxyhydroxide or carbonate, 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, it is characterized in that catalyzer is made up of a kind of VIII element, a kind of auxiliary agent and high-area carbon, wherein said VIII element comprises Ru, Ni, Rh, auxiliary agent comprises IA (except Li), IIA race (except Be and Mg), group of the lanthanides and actinide elements, and the BET specific surface area of high-area carbon is greater than 100m
2/ g.Hydrogenation reaction at 100 ~ 400 DEG C, gas space velocity 100 ~ 120000h
-1carry out under condition.Basic metal in this catalyzer is introduced in alkali metal salt, as alkali-metal nitrate, carbonate or acetate.The carboxylicesters that the method can be vaporized under being applicable to reaction conditions, the alcohol derivative moiety carbon number in carboxylicesters is preferably less than 5 and the carbon preferably primary carbon be connected with oxygen.
GB2250287A discloses a kind of method of fatty acid ester Hydrogenation alcohol, and 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.Its carboxylicesters be suitable for is the fatty acid methyl ester of C12 ~ C18.
US5334779 discloses a kind of catalyst composition and the application in carboxylicesters hydrogenation thereof, and this catalyzer is made up of cupric oxide, zinc oxide and three components (oxide compound of aluminium, magnesium, zirconium or its mixture).The carboxylicesters that this catalyzer and method use is cyclohexane diacid dimethyl ester, two lower alkyl esters of the lower alkyl ester of C10 ~ C20 carboxylic acid, two lower alkyl esters of hexanodioic acid and toxilic acid.
At present, the synthetic method of industrial hexalin acetate is acetic acid and hexalin esterification.Esterification reaction needs 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), review the progress of synthesis situation of acetic acid and hexalin lactate synthesis hexalin acetate, involved catalyzer comprises the sulfonic acid catalyzes such as thionamic acid, tosic acid system, 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 proposes a kind of synthesis technique of hexalin acetate, first by cupric oxide and tosic acid Reactive Synthesis copper p-toluenesulfonate, be catalyzer with copper p-toluenesulfonate again, use cyclohexane give water entrainer, by acetic acid and hexalin Reactive Synthesis hexalin acetate.There is catalyzer and product separation difficulty, need to use the problems such as water entrainer, hexalin price are high 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 Reactive Synthesis hexalin and hexalin acetate.The best result that this patent embodiment is mentioned is, cyclohexene conversion rate 62.7%, hexalin yield 18.4%, hexalin acetate yield 43.7%.
CN1023115C, JP equals the preparation method that-313447 disclose a kind of hexalin, adopts ZSM5 or supersiliceous zeolite to be under catalyzer and water exist, by acetic acid and tetrahydrobenzene Reactive Synthesis hexalin acetate, at 120 DEG C of reaction 4h, the output of hexalin and hexalin acetate only has 12.5% and 65% respectively.
EP0461580A2, USP5254721 disclose a kind of heteropoly acid containing tungsten catalyzer that adopts and are 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 12 silicotungstic acid catalysts not containing crystal water completely that 370 DEG C of roasting 3h obtain, in 200mL autoclave pressure, add 61.5g acetic acid, 13.5g tetrahydrobenzene, 5g catalyzer, at 0.5MPA, 0.5h is reacted, cyclohexene conversion rate 95.2%, hexalin acetate selectivity 99.2% under 130 DEG C of conditions.As can be seen here, under the condition of very high sour alkene ratio, tetrahydrobenzene can not transform completely.Due to the conversion completely of tetrahydrobenzene can not be realized, if using the product stream of benzene selective hydrogenation (mixture of tetrahydrobenzene and benzene and hexanaphthene) as raw material, to inevitably there is the separation problem of tetrahydrobenzene and benzene and hexanaphthene, because the boiling point of benzene, tetrahydrobenzene, hexanaphthene is very close, need to adopt the method for extracting rectifying to be separated, the investment be therefore separated and process cost are very high.
From published document, existing document has disclosed the various solid acid catalysts of acetic acid and tetrahydrobenzene addition esterification, and addition esterification generally adopts tank reactor, and reaction raw materials is pure tetrahydrobenzene, even if adopt very high sour alkene ratio, be also difficult to the conversion completely realizing 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 report reactive distillation being used for acetic acid and tetrahydrobenzene addition esterification process.
Up to now, without any about first by tetrahydrobenzene and acetic acid addition esterification and then the information disclosure being come coproduction hexalin and ethanol by hydrogenation in prior art, also without any the 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 coproduction hexalin and ethanol, the method first utilizes reactive distillation to carry out the addition esterification of acetic acid and tetrahydrobenzene, prepares hexalin acetate; And then come coproduction hexalin and ethanol by ethyl cyclohexyl ester through hydrogenation.
In the present invention, " addition esterification " refers to that carboxylic acid generates the reaction of ester to olefinic double bonds addition.
A method for coproduction hexalin and ethanol, comprising:
(1) by acetic acid and tetrahydrobenzene raw material input reactive distillation column, contact with solid acid catalyst, reaction, carries out the separation of reaction product simultaneously, at the bottom of tower, obtains hexalin acetate; The mixture that described tetrahydrobenzene raw material is tetrahydrobenzene or forms with hexanaphthene and/or benzene for tetrahydrobenzene;
(2) hexalin acetate that step (1) obtains enters hydrogenator, and under the existence of ester through hydrogenation catalyzer, carry out hydrogenation reaction, the material after hydrogenation reaction enters hydrogenation products separation system and is separated, and obtains hexalin and ethanol.
Described tetrahydrobenzene raw material is the mixture that tetrahydrobenzene forms with hexanaphthene and/or benzene, and tetrahydrobenzene content is preferably 20m% ~ 80m%, is more preferably 20m% ~ 60m%.Industrial tetrahydrobenzene generally adopts the selective hydrogenation of benzene to produce, its product stream 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, the logistics that tetrahydrobenzene content is generally 40m% ~ 80m% can be obtained, 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 the mixture that tetrahydrobenzene forms with hexanaphthene and/or benzene, obtains from reactive distillation tower top the mixture that acetic acid and hexanaphthene and/or benzene forms.
Described reactive distillation column is identical with common rectifying tower in form, is generally made up of tower body, overhead condenser, return tank, reflux pump, tower reactor and reboiler etc.The type of tower can be tray column, also can be 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 structured packing can be adopted, 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 passed through for vehicle repair major, or have larger bed voidage (general requirement is more than at least 50%), to ensure that vehicle repair major to flowing through, and can not cause liquid flooding; (2) will have good mass-transfer performance, reactant will be delivered in catalyzer from fluid-phase and react, and simultaneous reactions product will transmit out from catalyzer.Disclose the decoration form of multiple catalysts in reactive distillation column in existing document, these decoration forms all can be the present invention and adopted.The decoration form of existing catalyzer in reaction tower can be divided into following three kinds: catalyzer is directly arranged in tower in the mode of fractional distillation filling-material by (1), catalyzer by by a certain size and shape granules of catalyst and fractional distillation filling-material mechanically mixing or be clipped in by catalyzer between structured packing and form overall filler with structured packing, or is directly made fractional distillation filling-material shape by major way; (2) catalyzer to be loaded in the permeable small vessels of gas-liquid and to be arranged on the column plate of reaction tower, or by catalyst arrangement in the downtake of reaction tower; (3) catalyzer is directly loaded in reaction tower in fixed bed mode, liquid phase directly flows through beds, and be that gas phase sets up special passage, adopt in this way at the position that catalyzer is housed, be arranged alternately by beds and rectifying tower tray, liquid on tower tray enters next beds through downtake and redistributor, in bed, carry out addition reaction, 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, is preferably 30 ~ 100, between 1/3 to 2/3 position of theoretical plate number, arranges solid acid catalyst.
In the present invention, need to ensure that reactant has enough residence time, to realize the conversion completely of tetrahydrobenzene.Relative to the total fill able volume of catalyzer, liquid feeding air speed is 0.2 ~ 20h
-1, be preferably 0.5 ~ 5h
-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 be-0.0099MPa to 5MPa, be preferably normal pressure to 1MPa.
The service temperature of reactive distillation column is relevant with the pressure of reactive distillation column, by the temperature distribution regulating the working pressure of reaction tower to regulate reaction tower, makes the temperature of catalyst filling zone in the active temperature range of catalyzer.The temperature of catalyst filling zone between 50 ~ 200 DEG C, preferably between 60 ~ 120 DEG C.
The reflux ratio of reactive distillation column should meet the requirement being separated and reacting simultaneously, generally, increases reflux ratio and is conducive to improving 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, total reflux can be realized in theory.When there being a small amount of light constituent impurity in reaction raw materials, need a small amount of overhead stream to draw reactive distillation column.In the present invention, reflux ratio is 0.1 ~ 100:1, is preferably 0.5 ~ 10:1.
Described solid acid catalyst one or more in strong acid ion exchange resin catalyzer, heteropolyacid catalyst and molecular sieve catalyst optional.
Described strong acid ion exchange resin catalyzer had both comprised common macropore sulfonic acid polystyrene-divinylbenzene resin, also comprised through the modified sulfonic resin of halogen atom.This resinoid is easy to buy from market, and the method also can recorded by classical documents is produced.The mixture of vinylbenzene and Vinylstyrene normally instills in the aqueous phase system containing dispersion agent, initiator, pore-creating agent and carries out suspension copolymerization by the preparation method of macropore sulfonic acid polystyrene-divinylbenzene resin under the condition of high-speed stirring, obtained polymer globules (Archon) is separated from system, pore-creating agent is wherein pumped with solvent, be solvent again with ethylene dichloride, the vitriol oil is sulphonating agent, carry out sulfonation reaction, finally by operations such as filtration, washings, finally obtained 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 be obtained by following two kinds of approach, a kind of approach introduces halogen atom on the phenyl ring of sulfonated styrol resin skeleton, such as chlorine atom, strong electron attraction due to halogens not only can make phenyl ring stablize, but also the acidity of sulfonic acid group on phenyl ring can be improved, strength of acid function (Hammett function) H0≤-8 of resin catalyst can be made like this, and can more than 150 DEG C life-time service, this resinoid can conveniently buy from the market, the Amberlyst45 resin that such as external ROHM & HASS company produces, the D008 resin etc. that Ji Zhong chemical plant, domestic Hebei produces, hydrogen on resin matrix all replaces with fluorine by another kind of approach, electron-withdrawing by force 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 DEG C, the exemplary of this kind of fire resistant and highly acidic resin is the Nafion resin that DuPont company produces.
Described heteropolyacid catalyst both can be heteropolyacid and/or heteropolyacid acid salt, also can be 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 up to more than 300 DEG C life-time service.Described heteropolyacid and acid salt thereof comprise Kegin structure, Dawson, Anderson structure, the heteropolyacid of Silverton structure and acid salt thereof.The heteropolyacid of preferred keggin structure and acid salt thereof, as 12 phospho-wolframic acid (H
3pW
12o
40xH
2o), 12 silicotungstic acid (H
4s iW
12o
40xH
2o), 12 phosphomolybdate (H
3pMo
12o
40xH
2o), 12 molybdovanaphosphoric acid (H
3pMo
12-yv
yo
40xH
2o) etc.Described heteropolyacid acid salt preferred acid Tricesium dodecatungstophosphate salt (Cs
25h
0.5p
12wO
40), its strength of acid function H0 is less than-13.15, and specific surface area can reach 100m
2/ more 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 HZSM-5, preferably by one or more in H β, HY and HZSM-5 of fluorine or P Modification.These molecular sieves after fluorine, P Modification, the acidity of the molecular sieve that can improve further and catalytic performance.
In preferred situation, the theoretical plate number 30 ~ 100 of described reactive distillation column, arranges solid acid catalyst between 1/3 to 2/3 position of theoretical plate number; Described solid acid catalyst is high temperature resistant sulfonic acid ion exchange resin or acid phospho-wolframic acid cesium salt; Relative to the total fill able volume of catalyzer, liquid feeding air speed is 0.5 ~ 5h
-1; The working pressure of reactive distillation column is that-0.0099MPa is to 5MPa; The temperature of catalyst filling zone is between 120 ~ 180 DEG C; Reflux ratio is 0.5 ~ 10:1.
According to method provided by the present invention, the hexalin acetate obtained at the bottom of reactive distillation column tower is admitted to ester through hydrogenation reactor and carries out hydrogenation reaction.Described ester through hydrogenation reactor is one or more, and type of reactor is selected from one or more in tank reactor, fixed-bed reactor, ebullated bed reactor and fluidized-bed reactor.Described fixed-bed reactor are preferably tubular fixed-bed reactor, are more preferably shell shell and tube reactor.
Although from existing disclosed document mainly about the hydrogenation of carboxylate methyl ester or carboxylic acid, ethyl ester, employing fatty acid methyl ester hydrogenation as usual produces higher alcohols, maleic acid methyl ester hydrogenation produces 1,4-butyleneglycol, 1,6-dimethyl adipate hydrogenation produces 1,6-hexylene glycol etc., in have no the report of the hydrogenation reaction of any carboxylicesters hexalin acetate derived about cycloalkanol, but the present inventor finds, the hydrogenation of hexalin acetate can adopt existing ester compound hydrogenation catalyst.The hydrogenation of ester generally adopts Cu-series catalyst, ruthenium catalyst and precious metal series catalysts, the most conventional with Cu-series catalyst.Copper system ester through hydrogenation catalyzer take copper as Primary Catalysts, then one or more components of adding chromium, aluminium, zinc, calcium, magnesium, nickel, titanium, zirconium, tungsten, molybdenum, ruthenium, platinum, palladium, rhenium, lanthanum, thorium, gold etc. are as promotor or binder component.Copper system ester through hydrogenation catalyzer can conveniently be buied from market, and coprecipitation method also can be adopted to produce.The soluble salt solutions of each metal is put into and still by common preparation method, at certain temperature and stir speed (S.S.), add alkaline solution (sodium hydroxide, sodium carbonate, ammoniacal liquor, urea etc.) and carry out neutralization to PH8 ~ 12 growth precipitation, precipitate and form through aging, filtration, washing, drying, roasting, the operation such as shaping, finally reduce in hydrogen atmosphere and namely can be made into final ester through hydrogenation catalyzer.Ruthenium catalyst generally has: Ru/Al
2o
3or Ru-Sn/Al
2o
3; Precious metal series catalysts generally has: Pt/Al
2o
3, Pd-Pt/Al
2o
3or Pd/C(catalyzer is expressed as: active ingredient/carrier).
In the present invention, ester through hydrogenation catalyzer can be selected from one or more in Cu-series catalyst, ruthenium catalyst and precious metal series catalysts, is preferably Cu-series catalyst, is more preferably the Cu-series catalyst containing zinc and/or the Cu-series catalyst containing chromium.
Ester through hydrogenation reaction can operate in an intermittent fashion, also can carry out in a continuous manner.Intermittent reaction generally adopts reactor to make reactor, hexalin acetate and hydrogenation catalyst are dropped in reactor, passes into hydrogen and react under certain temperature and pressure, after reaction terminates, reaction product is adopted and draw off from still, isolate product, then drop into next batch material and react.Continuous hydrogenation reaction can adopt shell-and-tube shell and tube reactor, hydrogenation catalyst is fixed in tubulation, at shell side by water coolant to remove the liberated heat of reaction.
Hexalin acetate hydrogenation reaction temperature is relevant with the hydrogenation catalyst of selection, and for copper series hydrocatalyst, general hydrogenation reaction temperature is 150 ~ 400 DEG C, and optimizing temperature of reaction is 200 ~ 300 DEG C.Reaction pressure is normal pressure ~ 20MPa, and optimization pressure is 4 ~ 10MPa.
The control of the hydrogen ester mol ratio of hexalin acetate hydrogenation reaction is also very important.High hydrogen ester is than the hydrogenation being conducive to ester, but too high hydrogen ester is than the energy consumption that will increase hydrogen compression cycle.General hydrogen ester ratio is 1 ~ 1000:1, and optimal conditions is 5 ~ 100:1.
In hydrogenation reaction, the size of the Feed space velocities of ester is relevant with selecting the activity of catalyzer.High activated catalyst can adopt higher air speed.For selected catalyzer, reaction conversion ratio reduces with the increase of reaction velocity.In order to meet certain transformation efficiency, air speed must be limited within the specific limits.The liquid feeding air speed of general ester is 0.1 ~ 20h
-1, optimal conditions is 0.2 ~ 2h
-1.If employing intermittent reaction, then the reaction times is 0.5 ~ 20h, is preferably 1 ~ 5h.
According to method provided by the present invention, hexalin acetate hydrogenation products enters hydrogenation products separation system and is separated.Hydrogenation products enters in knockout drum and carries out gas-liquid separation, and gas phase is hydrogen mainly, uses through compressor compression Posterior circle.Liquid product is mainly containing ethanol and hexalin, also a certain amount of ethyl acetate and pimelinketone may be contained, also may contain a certain amount of unreacted hexalin acetate simultaneously, and the thing (two polyketone) that heavily boils on a small quantity, these mixtures adopt the method for rectifying and/or extracting and separating to be separated.The present invention preferably uses rectifying separation ester through hydrogenation product.Rectifying can adopt intermittent ann, also can adopt continuous print flow scheme.Batch fractionating, drop in rectifying tower reactor by ester through hydrogenation product, steam ethanol, ethyl acetate, hexalin, pimelinketone, hexalin acetate from tower top successively, tower reactor remains a small amount of high boiling material.Batch fractionating utilizes a separable various ingredients of tower, but frequent blocked operation, unstable product quality, and processing power is low, is commonly used in laboratory or small-scale products production.The present invention preferably adopts continuous rectification to be separated esterification products further.Continuous rectification needs to utilize a series of tower to be separated various component.Various separation process can be designed according to the sequencing of the separation of each component, the flow scheme that preferred sequence of the present invention is separated, namely hydrogenation products separation system sets gradually the knockout drum for separating of hydrogen, for separating of the rectifying tower of ethanol, for separating of the rectifying tower of hexalin, for separating of the rectifying tower of hexalin acetate, namely first addition esterification hydrogenation products is introduced into knockout drum and isolates hydrogen, then enter the separation of de-ethanol tower successively and obtain ethanol, then enter the separation of decylization hexanol tower and obtain hexalin, finally enter hexalin acetate recovery tower and reclaim unreacted hexalin acetate, tower reactor remains a small amount of high boiling material transmitting system.According to above-mentioned separation method, the material after hydrogenation reaction enters after hydrogenation products separation system is separated, isolated hexalin acetate capable of circulation time hydrogenator.
Present invention also offers the method for another kind of coproduction hexalin and ethanol, comprising:
(1) by acetic acid and tetrahydrobenzene raw material input pre-esterification reactor device, react under the existence of solid acid catalyst; The mixture that described tetrahydrobenzene raw material is tetrahydrobenzene or forms with hexanaphthene and/or benzene for tetrahydrobenzene;
(2) by the discharging of step (1) input reactive distillation column, contact with solid acid catalyst, reaction, carries out the separation of reaction product simultaneously, at the bottom of tower, obtains hexalin acetate;
(3) hexalin acetate that step (2) obtains enters hydrogenator, and under the existence of ester through hydrogenation catalyzer, carry out hydrogenation reaction, the material after hydrogenation reaction enters hydrogenation products separation system and is separated, and obtains hexalin and ethanol.
Described tetrahydrobenzene raw material is identical with first method provided by the invention.
Described tetrahydrobenzene raw material is the mixture that tetrahydrobenzene forms with hexanaphthene and/or benzene, obtains from reactive distillation tower top the mixture that acetic acid and hexanaphthene and/or benzene forms.
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, are 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 carry 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 fixing in the reactor, and it is adiabatic that reactor outer wall carries out insulation.Because addition esterification is thermopositive reaction, therefore need to control reactant concn to control reactor bed temperature rise, or adopt partial reaction product cooling Posterior circle to reactor inlet with diluting reaction substrate concentration.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 needs to control to carry out at a certain temperature, 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 DEG C, is preferably 60 ~ 120 DEG C.
The pressure of pre-esterification reactor is relevant with temperature of reaction.Because addition esterification is carried out in the liquid phase, therefore reaction pressure should ensure 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, then the discharging of step (1) is also containing 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 first method provided by the invention, understand the form of reactive distillation column and the mode of layout catalyzer in detail, do not repeat them here.
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, between 10 ~ 120 blocks of plates, wherein select 5 ~ 30 blocks of plates to arrange solid acid catalyst, more preferred scheme is the theoretical plate number of reaction tower is 30 ~ 100, between 10 ~ 80 blocks of plates, wherein select 8 ~ 20 blocks of plates to arrange solid acid catalyst.
In the present invention, need to ensure that reactant has enough residence time, to realize the conversion completely of tetrahydrobenzene.Relative 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 be-0.0099MPa to 5MPa, be preferably normal pressure to 1MPa.
The service temperature of reactive distillation column is relevant with the pressure of reactive distillation column, by the temperature distribution regulating the working pressure of reaction tower to regulate reaction tower, makes the temperature of catalyst filling zone in the active temperature range of catalyzer.The temperature of catalyst filling zone generally between 40 ~ 200 DEG C, preferably between 60 ~ 150 DEG C.
In the present invention, when tetrahydrobenzene raw material is tetrahydrobenzene, if use pure tetrahydrobenzene and acetic acid as reaction raw materials, total reflux can be realized in theory.When there being a small amount of light constituent impurity in reaction raw materials, need a small amount of overhead stream to draw reactive distillation column.In preferred situation, after derivated stream removing foreign matter, loop back reactive distillation column.
In the present invention, reflux ratio is 0.1 ~ 100:1, is preferably 0.5 ~ 10:1.In preferred situation, be separated the logistics of overhead extraction, the isolated logistics being rich in acetic acid loops back reactive distillation column.
The solid acid catalyst of step (1) and the solid acid catalyst of step (2) can be identical or different, are selected from one or more in strong acid ion exchange resin catalyzer, heteropolyacid catalyst and molecular sieve catalyst respectively.
In first method provided by the invention, describe strong acid ion exchange resin catalyzer, heteropolyacid catalyst and molecular sieve catalyst in detail, do not repeated them here.
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 form ion exchange resin or acid phospho-wolframic acid cesium salt; Relative 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-0.0099MPa is to 5MPa; The temperature of catalyst filling zone is between 120 ~ 180 DEG C; Reflux ratio is 0.5 ~ 10:1.
The feature of aforesaid method is: adopt pre-esterification and the reactive distillation esterification mode of combining to realize the esterification of tetrahydrobenzene and acetic acid, first realized the conversion of most of tetrahydrobenzene by pre-esterification, in reactive distillation column, then arrange that a small amount of catalyzer realizes the conversion completely of tetrahydrobenzene further.
The present invention produces the new technology path that hexalin provides a high-level efficiency, low cost.Feature of the present invention is: (1) adopts reaction to combine with rectifying separation, can with the product stream of partial hydrogenation of benzene or a step extracting and separating containing tetrahydrobenzene logistics as esterification feed, and realize the conversion completely of tetrahydrobenzene, thus avoid or simplify investment and the very high separation of extractive distillation process of process cost; (2) process flow is simple, less investment, energy consumption are low; (3) esterification and hydrogenation reaction all have very high selectivity, and therefore atom utilization is very high; (4) process environment is friendly; (5) co-producing ethanol while production hexalin, namely changes into the acetic acid of cheapness the ethanol that price is high and market capacity is huge by indirectly mode, greatly increases the economy of process.
By the following examples the present invention is further described, but not thereby limiting the invention.
Embodiment
Embodiment 1 ~ 4 is for illustration of the method adopting reactive distillation to prepare hexalin acetate.
The test carried out in embodiment 1 ~ 4 is all carry out at the reactive distillation model test device of following specification: the main body of mode device is diameter (internal diameter) is 50mm, height is the stainless head tower of 3m, it is the tower reactor of 5L that the bottom of tower connects volume, be configured with the electrically heated rod of 10KW in still, this heating rod controls tower reactor heating amount by intelligent controller by silicon controlled rectifier (SCR).It is 0.5m that tower top is connected with heat interchanging area
2condenser, overhead vapours becomes through this condenser condenses that to enter a volume after liquid be the return tank of 2L.Liquid in return tank is partly refluxed to reaction tower through reflux pump, and part extraction is as light constituent.The operating parameters of tower is shown by intelligent type automatic control instruments and controls.Tower quantity of reflux is controlled by return valve, and overhead extraction amount is controlled by the fluid level controller of return tank.Tower reactor produced quantity regulates tower reactor blow-off valve to control by tower bottoms level controller.Raw acetic acid and tetrahydrobenzene are respectively charged in 30L storage tank, and by volume pump squeeze into be preheating to certain temperature in corresponding preheater after enter reaction tower, input speed is controlled by volume pump, electronic scales accurate measurement.
Embodiment 1
By high temperature resistant sulfonic acid ion exchange resin, (trade mark is Amberlyst45, produced by Rhom & Hass company) be ground into multistage high speed disintegrator 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 DEG C of banburying 10min, material is plastified completely, diameter made by injection mould is afterwards 5mm, high 5mm, wall thickness is 1mm Raschig ring type resin catalyst filler.The middle part (high 1m is equivalent to 8 blocks of theoretical trays) of this filler 1950mL loading pattern reaction tower is respectively loaded the glass spring filler 1950mL (loading height is 1m, is equivalent to 10 blocks of theoretical trays) that diameter is 3mm, long 6mm up and down.Enter reaction tower after tetrahydrobenzene and acetic acid are squeezed into preheater preheats by volume pump respectively, regulate tower reactor heating amount and trim the top of column amount to react continuously, the reaction conditions under stable operation and reaction result are in table 1.
Embodiment 2
Reaction tower is identical with embodiment 1 with the configuration of catalyzer.Just replace tetrahydrobenzene to test with tetrahydrobenzene, hexanaphthene and benzol mixture, and reaction tower operate under 0.3MPa condition.Regulate tower reactor heating amount and trim the top of column amount to react continuously, the reaction conditions under stable operation and reaction result are in table 2.
Embodiment 3
By the ball-type H of φ 3 ~ 4
0.5cs
25pW
12o
40/ SiO
2catalyzer is (by H
0.5cs
25pW
12o
40powder and granularity are less than 200 object silochrom powder, after fully mixing in mixer, be bonder roller forming with silicon sol in coater, then drying, roasting form) sandwich in titanium wire network ripple plate, make the cylinder shape structured packing that diameter is 50mm, high 50mm.The middle part (high 1m is equivalent to 12 blocks of theoretical trays) of this packing type catalyzer L loading pattern reaction tower respectively being loaded up and down diameter is 4mm, the high 1950mL glass spring filler (loading height is 1m, is equivalent to 15 blocks of theoretical trays) for 4mm.Enter reaction tower after tetrahydrobenzene and benzene are squeezed into preheater preheats by volume pump respectively, regulate tower reactor heating amount and trim the top of column amount to react continuously, the reaction conditions under stable operation and reaction result are in table 3.
Embodiment 4
Reaction tower is identical with example 3 with the configuration of catalyzer.Just replace tetrahydrobenzene to test with tetrahydrobenzene, hexanaphthene and benzol mixture, 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 under stable operation and reaction result are in table 4.
Embodiment 5 ~ 8 is for illustration of the method adopting pre-esterification and reactive distillation to prepare hexalin acetate.
The test that embodiment 5 ~ 8 is carried out all is carried out at hexalin acetate model test device.This mode device is made up 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 is outside with hot water jacket, can pass into hot water to control temperature of reaction in chuck.Reactive distillation esterification column is diameter (internal diameter) is 50mm, high titanium steel (TA2) tower for 3m.It is the tower reactor of 5L that the bottom of tower connects volume, is configured with the electrically heated rod of 10KW in still, and this heating rod controls tower reactor heating amount by intelligent controller by silicon controlled rectifier (SCR).It is 0.5m that tower top is connected with heat interchanging area
2condenser and volume be the return tank of 2L.Raw material acetic acid and tetrahydrobenzene are respectively charged in 30L storage tank, and are driven in pre-esterification reactor device by volume pump and react, and pre-esterification product enters reactive distillation column and reacts further.By regulate tower reactor heating power regulate reaction tower add heat.By the reflux ratio of trim the top of column than setter adjusting tower.From overhead extraction light constituent.Extraction ethyl cyclohexyl ester products at the bottom of tower.
Embodiment 5
By 500mL macropore strong acid form ion exchange resin, (styrene solution containing 15% Vinylstyrene, by the synthesis of classical literature method, is carried out suspension copolymerization and is made Archon by laboratory, then obtains through concentrated acid sulfonation, and recording its exchange capacity is 5.2mmolH
+/ g butt) load the middle part of pre-reactor, a certain amount of quartz sand is filled at two ends.It is another that by high temperature resistant sulfonic acid ion exchange resin, (trade mark is Amberlyst45, produced by Rhom & Hass company) be ground into multistage high speed disintegrator 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 DEG C of banburying 10min, material is plastified completely, diameter made by injection mould is afterwards 5mm, high 5mm, wall thickness is 1mm Raschig ring type resin catalyst filler.The middle part (high 1m is equivalent to 8 blocks of theoretical trays) of this filler 1950mL loading pattern reaction tower is respectively loaded the glass spring filler 1950mL (loading height is 1m, is equivalent to 10 blocks of theoretical trays) that diameter is 3mm, long 6mm up and down.Tetrahydrobenzene and acetic acid are squeezed in pre-reactor by volume pump respectively and react, pre-reaction product reacts further entering reaction tower.Pre-reaction temperature is regulated by regulating pre-reactor chuck hot water 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 5.
Embodiment 6
Reaction tower is identical with embodiment 5 with the configuration of catalyzer.Just replace tetrahydrobenzene to test with tetrahydrobenzene, hexanaphthene and benzol mixture, and pre-reactor pressure is 2.0MPa, reaction tower operates in atmospheric conditions.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 6.
Embodiment 7
By the ball-type H of 500mL φ 3 ~ 4
0.5cs
2.5pW
12o
40/ SiO
2catalyzer loads the middle part of pre-reactor, and a certain amount of quartz sand is filled at two ends.Another by the ball-type H of φ 3 ~ 4
0.5cs
25pW
12o
40/ S iO
2catalyzer is (by H
0.5cs
25pW
12o
40powder and granularity are less than 200 object silochrom powder, after fully mixing in mixer, be bonder roller forming with silicon sol in coater, then drying, roasting form) sandwich in titanium wire network ripple plate, make the cylinder shape structured packing that diameter is 50mm, high 50mm.The middle part (high 1m is equivalent to 12 blocks of theoretical trays) of this packing type catalyzer L loading pattern reaction tower respectively being loaded up and down diameter is 4mm, the high 1950mL glass spring filler (loading height is 1m, is equivalent to 15 blocks of theoretical trays) for 4mm.Tetrahydrobenzene and acetic acid are squeezed in pre-reactor by volume pump respectively and react, pre-reaction product reacts further entering reaction tower.Pre-reaction temperature is regulated by regulating pre-reactor chuck hot water 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 7.
Embodiment 8
Reaction tower is identical with example 7 with the configuration of catalyzer.Just replace tetrahydrobenzene to test with tetrahydrobenzene, hexanaphthene and benzol mixture, 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 8.
Embodiment 9 ~ 10 is for illustration of the method for hydrotreating of hexalin acetate.
Embodiment 9
Hydrogenating materials to be purity be 99.6% hexalin acetate.
By 40g copper zinc-aluminium ester through hydrogenation catalyzer, (laboratory is synthesized, and consists of CuO40.5%, ZnO29.6%, Al
2o
330.4%.By the nitrate solution of copper, zinc, chromium, add sodium hydroxide solution and be neutralized to PH=9.0, through centrifugation, washing, dry, compression molding, roasting obtains) load φ 20 × 2.5 × 800mm with the middle part in the stainless steel tube reactor of chuck, a certain amount of quartz sand is filled at two ends.Pass into hydrogen (500mL/min) 280 DEG C, under 6MPa condition after reductase 12 4h, be down to the temperature and pressure of hydrogenation reaction.Squeeze in reactor by hexalin acetate by volume pump, hydrogen enters reactive system through mass flow controller and carries out hydrogenation reaction, controlling temperature of reaction, controlling reactor pressure by reactor outlet back pressure valve by passing into thermal oil in reaction tubes external jacket.Reaction product carries out on-line chromatograph analysis by the straight line sampling valve sampling at reactor rear portion.Reaction conditions and the results are shown in Table 9.Table 9 result shows, and adopt CuZnAl catalyst, hexalin acetate hydrogenation reaction transformation efficiency can reach more than 99.0%, and hexalin selectivity is greater than 99.9%, and run 1000 hours, transformation efficiency and selectivity all do not decline.
Embodiment 10
Hydrogenating materials to be purity be 99.6% hexalin acetate.
By (commercially available for 40g copper chromium ester through hydrogenation catalyzer, Xin Jida Chemical Co., Ltd. of Taiyuan City produces, the trade mark is C1-XH-1, CuO content is 55%, diameter 5mm tablet, be broken into 10 ~ 20 order particles) load φ 20 × 2.5 × 800mm with the middle part in the stainless steel tube reactor of chuck, a certain amount of quartz sand is filled at two ends.Pass into hydrogen (500mL/min) 280 DEG C, under 6MPa condition after reductase 12 4h, be down to and react to obtain temperature and pressure.Squeeze in reactor by hexalin acetate by volume pump, hydrogen enters reactive system through mass flow controller and carries out hydrogenation reaction, controlling temperature of reaction, controlling reactor pressure by reactor outlet back pressure valve by passing into thermal oil in reaction tubes external jacket.Reaction product carries out on-line chromatograph analysis by the straight line sampling valve sampling at reactor rear portion.Reaction conditions and the results are shown in Table 10.Table 10 result shows, and adopt CuZnAl catalyst, hexalin acetate hydrogenation reaction transformation efficiency can reach more than 98.0%, and hexalin selectivity is greater than 99.9%, runs 500 hours, and transformation efficiency and selection all do not decline.
Embodiment 11
Collect the reaction product 4000g of example 9 ~ 10, carry out rectifying separation test.Rectifying adopts high 2m glass tower, and king-post is equipped with the stainless steel Dixon ring highly efficient distilling filler of Ф 3mm, and tower reactor is 5L glass flask, is heated by electric mantle, regulates tower reactor heating amount by voltate regulator.The backflow of tower adopts reflux ratio setter to control.Rectifying separation the results are shown in Table 11.
Table 1
According to the transformation efficiency 99% of testing data ring hexene, hexalin acetate selectivity 99.72%.
Table 2
According to the transformation efficiency 98.8% of testing data ring hexene, hexalin acetate selectivity 98.0%.
Table 3
According to the transformation efficiency 98.7% of testing data ring hexene, hexalin acetate selectivity 99.43%.
Table 4
According to the transformation efficiency 99.35% of testing data ring hexene, hexalin acetate selectivity 99.6%.
Table 5
According to the transformation efficiency 99.76% of testing data ring hexene, hexalin acetate selectivity 99.03%.
Table 6
According to the transformation efficiency 98.38% of testing data ring hexene, hexalin acetate selectivity 99.11%.
Table 7
According to the transformation efficiency 99.9% of testing data ring hexene, hexalin acetate selectivity 99.35%.
Table 8
According to the transformation efficiency 99.02% of testing data ring hexene, hexalin acetate selectivity 99.19%.
Table 9 CuZnAl catalyst cyclohexyl hydrogenation data
Table 10 Cu-Cr catalyst cyclohexyl hydropyrolysis experiment data
Table 11 hexalin acetate hydrogenation products rectifying separation result
Claims (22)
1. a method for coproduction hexalin and ethanol, comprising:
(1) by acetic acid and tetrahydrobenzene raw material input reactive distillation column, contact with solid acid catalyst, reaction, carries out the separation of reaction product simultaneously, at the bottom of tower, obtains hexalin acetate; The mixture that acetic acid and hexanaphthene and/or benzene forms is obtained from reactive distillation tower top; Described tetrahydrobenzene raw material is the mixture that tetrahydrobenzene forms with hexanaphthene and/or benzene, and tetrahydrobenzene content is 20m% ~ 80m%;
(2) hexalin acetate that step (1) obtains enters hydrogenator, and under the existence of ester through hydrogenation catalyzer, carry out hydrogenation reaction, the material after hydrogenation reaction enters hydrogenation products separation system and is separated, and obtains hexalin and ethanol.
2. in accordance with the method for claim 1, it is characterized in that, tetrahydrobenzene content is 20m% ~ 60m%.
3. in accordance with the method for claim 1, it is characterized in that, described solid acid catalyst is selected from one or more in strong acid ion exchange resin catalyzer, heteropolyacid catalyst and molecular sieve catalyst.
4. in accordance with the method for claim 3, it is characterized in that, described strong acid ion exchange resin is macropore sulfonic acid polystyrene-divinylbenzene resin or through the modified sulfonic resin of halogen atom.
5. in accordance with the method for claim 3, 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.
6. in accordance with the method for claim 3, it is characterized in that, described molecular sieve is one or more in H β, HY and HZSM-5.
7. in accordance with the method for claim 1, it is characterized in that the theoretical plate number 10 ~ 150 of described reactive distillation column arranges solid acid catalyst between 1/3 to 2/3 position of theoretical plate number; Relative to the total fill able volume of catalyzer, liquid feeding air speed is 0.2 ~ 20h
-1; The working pressure of reactive distillation column is that-0.0099MPa is to 5MPa; The temperature of catalyst filling zone is between 50 ~ 200 DEG C; Reflux ratio is 0.1 ~ 100:1.
8. in accordance with the method for claim 1, it is characterized in that, described ester through hydrogenation reactor is one or more, and type of reactor is selected from one or more in tank reactor, fixed-bed reactor, ebullated bed reactor and fluidized-bed reactor.
9. in accordance with the method for claim 1, it is characterized in that, described ester through hydrogenation catalyzer is selected from one or more in Cu-series catalyst and precious metal series catalysts.
10. in accordance with the method for claim 9, it is characterized in that, described Cu-series catalyst is the Cu-series catalyst containing zinc and/or the Cu-series catalyst containing chromium.
11. in accordance with the method for claim 1, it is characterized in that, ester through hydrogenation temperature of reaction is 150 ~ 400 DEG C, and reaction pressure is normal pressure ~ 20MPa, and hydrogen ester mol ratio is 1 ~ 1000:1, and liquid feeding air speed is 0.1 ~ 20h
-1.
The method of 12. 1 kinds of coproduction hexalin and ethanol, comprising:
(1) by acetic acid and tetrahydrobenzene raw material input pre-esterification reactor device, react under the existence of solid acid catalyst; Described tetrahydrobenzene raw material is the mixture that tetrahydrobenzene forms with hexanaphthene and/or benzene, and tetrahydrobenzene content is 20m% ~ 80m%; Described pre-esterification reactor device is tank reactor, fixed-bed reactor, fluidized-bed reactor or ebullated bed reactor;
(2) by the discharging of step (1) input reactive distillation column, contact with solid acid catalyst, reaction, carries out the separation of reaction product simultaneously, at the bottom of tower, obtains hexalin acetate; The mixture that acetic acid and hexanaphthene and/or benzene forms is obtained from reactive distillation tower top;
(3) hexalin acetate that step (2) obtains enters hydrogenator, and under the existence of ester through hydrogenation catalyzer, carry out hydrogenation reaction, the material after hydrogenation reaction enters hydrogenation products separation system and is separated, and obtains hexalin and ethanol.
13. in accordance with the method for claim 12, it is characterized in that, tetrahydrobenzene content is 20m% ~ 60m%.
14. in accordance with the method for claim 12, 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; Relative 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 that-0.0099MPa is to 5MPa; The temperature of beds filling area is between 40 ~ 200 DEG C; Reflux ratio is 0.1 ~ 100:1.
15. in accordance with the method for claim 12, it is characterized in that, the solid acid catalyst of step (1) and the solid acid catalyst of step (2) are selected from one or more in strong acid ion exchange resin catalyzer, heteropolyacid catalyst and molecular sieve catalyst respectively.
16. in accordance with the method for claim 15, it is characterized in that, described strong acid ion exchange resin catalyzer is macropore sulfonic acid polystyrene-divinylbenzene resin or through the modified sulfonic resin of halogen atom.
17. in accordance with the method for claim 15, 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.
18. in accordance with the method for claim 15, it is characterized in that, described molecular sieve catalyst is one or more in H β, HY and HZSM-5.
19. in accordance with the method for claim 12, it is characterized in that, described ester through hydrogenation reactor is one or more, and type of reactor is selected from one or more in tank reactor, fixed-bed reactor, ebullated bed reactor and fluidized-bed reactor.
20. in accordance with the method for claim 12, it is characterized in that, described ester through hydrogenation catalyzer is selected from one or more in Cu-series catalyst and precious metal series catalysts.
21. in accordance with the method for claim 20, it is characterized in that, described Cu-series catalyst is the Cu-series catalyst containing zinc and/or the Cu-series catalyst containing chromium.
22. in accordance with the method for claim 12, it is characterized in that, ester through hydrogenation temperature of reaction is 150 ~ 400 DEG C, and reaction pressure is normal pressure ~ 20MPa, and hydrogen ester mol ratio is 1 ~ 1000:1, and liquid feeding air speed is 0.1 ~ 20h
-1.
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| PCT/CN2013/001100 WO2014044020A1 (en) | 2012-09-18 | 2013-09-17 | Method and device for coproducing cyclohexanol and alkanol |
| KR1020157010078A KR102008352B1 (en) | 2012-09-18 | 2013-09-17 | Method and device for coproducing cyclohexanol and alkanol |
| TW102133691A TWI612031B (en) | 2012-09-18 | 2013-09-17 | Method and device for co-production of cyclohexanol and alkanol |
| US14/429,189 US9561991B2 (en) | 2012-09-18 | 2013-09-17 | Process and apparatus for co-producing cyclohexanol and alkanol |
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| CN109534942A (en) * | 2017-09-21 | 2019-03-29 | 中国石油化工股份有限公司 | The method and apparatus of acetic acid are removed from hexamethylene raw material |
| CN109534954B (en) * | 2017-09-21 | 2022-02-08 | 中国石油化工股份有限公司 | Method and device for coproducing cyclohexanol and ethanol |
| CN109534947A (en) * | 2017-09-21 | 2019-03-29 | 中国石油化工股份有限公司 | The method and apparatus of acetic acid are removed from hexamethylene raw material |
| CN109534986A (en) * | 2017-09-21 | 2019-03-29 | 中国石油化工股份有限公司 | The method and apparatus of separating acetic acid from hexamethylene raw material |
| CN114100644A (en) * | 2021-10-29 | 2022-03-01 | 中国科学院金属研究所 | Solid acid catalytic separation integrated filler and preparation method and application thereof |
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