CN103910603B - A kind of method of coproduction hexalin and ethanol - Google Patents
A kind of method of coproduction hexalin and ethanol Download PDFInfo
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- 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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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
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- 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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- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
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Abstract
The invention provides a kind of method of coproduction hexalin and ethanol, the method take benzene as starting raw material, comes coproduction hexalin and ethanol by benzene selective hydrogenation, tetrahydrobenzene addition esterification, acetic acid and ethyl cyclohexyl ester through hydrogenation.Feature of the present invention is: (1) esterification, acid and ester through hydrogenation reaction all have very high selectivity, and atom utilization is very high; (2) process environment is friendly; (3) co-producing ethanol while production hexalin; (4) adopt reactive distillation to carry out addition esterification, can reaction efficiency be significantly improved.
Description
Technical field
The present invention relates to a kind of method of coproduction hexalin and ethanol.
Background technology
Hexalin and ethanol are important industrial chemicals and solvent.Hexalin is mainly for the production of products such as nylon 6, nylon66 fiber; And the raw material of the multiple Chemicals such as synthesizing ester is not only by ethanol, be 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%.
The traditional method of producing tetrahydrobenzene is dehydration of cyclohexanol method and cyclohexane halide dehydrohalogenation method.Partial hydrogenation of benzene and oxidative dehydrogenation of cyclonexane are other two kinds of methods preparing tetrahydrobenzene.Partial hydrogenation of benzene is prepared tetrahydrobenzene and is mainly contained vapor phase process, liquid phase method and homogeneous phase complexing hydrogenation method.Liquid phase method can adopt gas (hydrogen), liquid (benzene), liquid (polar solvent), solid (catalyzer) four phase reaction system, as adopted the method passing into benzene and hydrogen in the slurry comprising catalyzer and water.As adopted four phase reaction systems, the consumption of water at least will meet and can form water-oil phase, usually adds metal-salt in water, and good metal-salt is zinc sulfate or rose vitriol.The reaction conditions of liquid phase method is generally: temperature of reaction 25 ~ 250 DEG C; Hydrogen partial pressure 0.1 ~ 20MPa, catalyst levels is 0.001 ~ 0.2 times of water weight.Partial hydrogenation of benzene catalyzer generally with one or more in the metals such as Pt, Pd, Ru, Rh and Ni for main catalyst component; In order to improve hydrogenation activity and selectivity further, one or more in the metals such as K, Zr, Hf, Co, Cu, Ag, Fe, Mo, Cr, Mn, Au, la and Zn usually also can be introduced in the catalyst as adjuvant component.Partial hydrogenation of benzene catalyzer can be loading type or unsupported catalyst, and the method for load can adopt ion exchange method, spraying process, impregnation method, evaporation drying method etc., and the carrier of employing can be natural clay, sepiolite, ZrO
2, SiO
2, TiO
2, Al
2o
3, La
2o
3, gac, insoluble vitriol, insoluble phosphoric acid salt or molecular sieve etc.For ruthenium catalyst, loaded catalyst is by by ruthenium salt separately or be jointly immersed on carrier with other metal-salts, then drying, also original preparation; Unsupported catalyst by ruthenium salt separately or with other metal-salt coprecipitations, then drying, also original preparation, also can be prepared by the mixture of direct-reduction ruthenium compound or ruthenium compound and other metallic compounds.The method and apparatus of ruthenium catalyst and benzene hydrogenation is described later in detail in CN102264471A.
Hexalin acetate is a kind of liquid with banana or apple aroma, is widely used in the industries such as food, beverage and makeup with the fruit flavour type essence of its preparation.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.Recently, the present inventor also finds, its hydrogenation can be produced hexalin co-production ethanol, can predict, and hexalin acetate will become a kind of important organic synthesis intermediate.
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.
JPA254634/1989 discloses the preparation method of a kind of hexalin and hexalin acetate, and employing strong-acid ion exchange resin is catalyzer, by aqueous acetic acid and tetrahydrobenzene Reactive Synthesis hexalin and hexalin acetate.The best result mentioned in document example is, cyclohexene conversion rate 62.7%, hexalin yield 18.4%, hexalin acetate yield 43.7%.
CN1023115C, JP equal the preparation method that-313447 disclose a kind of hexalin, adopt ZSM5 or supersiliceous zeolite to be catalyzer, in the presence of water, by acetic acid and tetrahydrobenzene Reactive Synthesis hexalin and hexalin acetate.In the document, 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 method being prepared hexalin acetate by acetic acid and tetrahydrobenzene.The method adopts heteropoly acid containing tungsten catalyzer, and in heteropolyacid molecule, crystal water content is preferably 0 ~ 3.The best result provided in document 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, reacts 0.5h under 0.5MPa, the condition of 130 DEG C, cyclohexene conversion rate is 95.2%, and the selectivity of hexalin acetate is 99.2%.As can be seen here, under the condition of very high sour alkene ratio, tetrahydrobenzene can not transform completely.
From existing disclosed document, existing document has disclosed 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 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.
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 preparation of the cycloalkanol as hexalin in document.
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 carry out C6 ~ C22 dimethyl ester that transesterify obtains, C6-C66 natural glycerin three ester by 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 mixing, 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, its 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, and its carboxylicesters be suitable for is the fatty acid methyl ester of C12 ~ C18.
From open source literature, without any the information disclosure about ethyl cyclohexyl ester through hydrogenation energy coproduction hexalin and ethanol in prior art, more do not prepared the information disclosure of hexalin and ethanol by benzene selective hydrogenation, tetrahydrobenzene addition esterification, acetic acid/ethyl cyclohexyl ester through hydrogenation.
Summary of the invention
The invention provides a kind of method of coproduction hexalin and ethanol, the method take benzene as starting raw material, comes coproduction hexalin and ethanol by benzene selective hydrogenation, tetrahydrobenzene addition esterification, acetic acid and ethyl cyclohexyl ester through hydrogenation.
In the present invention, for logistics, represent the mixture of A and B with " A/B "; For catalyzer, " A/B " representative " active ingredient/carrier ".
A method for coproduction hexalin and ethanol, comprising:
(1) under the condition of preparing cyclohexene from benzene added with hydrogen, benzene and hydrogen generation hydrogenation reaction, obtain containing tetrahydrobenzene logistics;
(2) what step (1) obtained contacts with acetic acid containing tetrahydrobenzene logistics, and addition esterification occurs under the effect of catalyzer; Reaction product is separated, obtains acetic acid/hexalin acetate logistics;
(3) hydrogenation is carried out to acetic acid/hexalin acetate logistics that step (2) obtains; Reaction product is separated, obtains hexalin and ethanol.
Above-mentioned three steps are below described respectively.
One, preparing cyclohexene from benzene added with hydrogen
To the method for preparing cyclohexene from benzene added with hydrogen and catalyzer, there is no particular limitation in the present invention, and it is used that existing preparing cyclohexene from benzene added with hydrogen technique and benzene hydrogenating catalyst all can be the present invention.The present invention preferably adopts liquid phase method technique.Benzene hydrogenating catalyst preferably adopts ruthenium catalyst, more preferably adopts the ruthenium catalyst containing cobalt and/or zinc.Ruthenium catalyst containing cobalt and/or zinc can be prepared by the method for co-precipitation or dipping identical carrier.
The product stream that benzene hydrogenation obtains is the mixture of hexanaphthene, tetrahydrobenzene and benzene.In step (1), described is the logistics that benzene hydrogenation product stream or benzene hydrogenation product stream isolate hexanaphthene and/or benzene containing tetrahydrobenzene logistics; Be preferably benzene hydrogenation product stream.
The separation method of existing hexanaphthene, tetrahydrobenzene and benzene all can be used for the present invention, as extracting rectifying or azeotropic distillation.The present invention preferably adopts extracting rectifying and separating benzene hydrogenation reaction product, and extraction agent can adopt METHYLPYRROLIDONE, N,N-dimethylacetamide, adiponitrile, dimethyl malonate, Succinic acid dimethylester, ethylene glycol or tetramethylene sulfone.
Two, tetrahydrobenzene addition esterification
In the present invention, " addition esterification " refers to that carboxylic acid generates the reaction of ester to olefinic double bonds addition.
In step (2), described catalyzer is acid catalyst, both can be liquid acid catalyst, also can be solid acid catalyst.Described liquid acid catalyst can be both mineral acid, as sulfuric acid, phosphoric acid etc.; Also can be organic acid, as toluene sulfonic acide, amidosulfonic acid etc.The present invention preferably adopts solid acid catalyst.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 structure with Keggin, 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
4siW
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
2.5h
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.Described heteropolyacid catalyst can be selected from one or more in above-mentioned preferred heteropolyacid and heteropolyacid acid salt.In the catalyzer of described carried heteropoly acid and/or heteropolyacid acid salt, carrier is generally SiO
2and/or gac.
Described addition esterification 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.
Below illustrate two kinds of embodiments of step (2).
The first embodiment:
Catalyzer adopts solid acid catalyst.In step (2), can adopt the reactor of one or more parallel connection, type of reactor can be selected from one or more in tank reactor, fixed-bed reactor, ebullated bed reactor and fluidized-bed reactor.The tubular fixed-bed reactor of the one or more parallel connection of preferred employing.More preferably the shell shell and tube reactor of one or more parallel connection is adopted.The operating method of reactor both can be the mode of interval, also can be continuous print mode, preferably adopted operate continuously mode.Fixed-bed reactor can adopt adiabatic or isothermal mode to operate.Adiabatic reactor can adopt cartridge reactor, catalyzer is fixing in the reactor, 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.
Temperature of reaction is generally 50 ~ 200 DEG C, and optimizing temperature of reaction is 60 ~ 120 DEG C.
The pressure of described addition esterification 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, and optimizing pressure is normal pressure ~ 1MPa.
The sour alkene mol ratio of described addition esterification is generally 0.2 ~ 20:1, and optimal conditions is 1.2 ~ 3:1.
In described addition esterification, liquid feeding air speed is generally 0.5 ~ 20h
-1, optimal conditions is 0.5 ~ 5h
-1.
Under these conditions, the cyclohexene conversion of addition esterification generally can reach more than 80%, and the selectivity of esterification can reach more than 99%.
The reaction product of step (2) contains a certain amount of unreacted tetrahydrobenzene, acetic acid and hexalin acetate, also may contain hexanaphthene and/or benzene, and it forms and which kind of adopts relevant as the reaction raw materials of step (2) containing tetrahydrobenzene logistics.The separation of this product can be carried out in the addition esterification products separating unit being provided with rectifying separation part and/or separation of extractive distillation part, concrete separation scheme also with employing which kind of containing tetrahydrobenzene logistics relevant as the reaction raw materials of step (2).Rule is, adopts rectifying reaction product to be separated into acetic acid/hexalin acetate logistics and C6 hydrocarbon stream (containing tetrahydrobenzene, also may contain hexanaphthene and/or benzene), the raw material that acetic acid/hexalin acetate logistics is reacted as step (3); If C6 hydrocarbon stream is mixture, Hydrogenation can be carried out for hexanaphthene to it, extracting rectifying also can be adopted to be separated it.These are separated in the logistics obtained, and tetrahydrobenzene/benzene logistics or benzene logistics can be used as a part for step (1) reaction feed, and tetrahydrobenzene logistics can be used as a part for step (2) reaction feed, and hexanaphthene logistics goes out device as byproduct.
The second embodiment:
Catalyzer adopts solid acid catalyst.In step (2), adopt the reactive distillation column of one or more parallel connection, while carrying out addition esterification, carry out the separation of reaction product, at the bottom of reactive distillation column tower, obtain acetic acid/hexalin acetate logistics.
Adopt different from tetrahydrobenzene logistics, obtain different logistics from reactive distillation tower top.
The first situation, in step (1), described is isolate the logistics that hexanaphthene obtains in benzene hydrogenation product stream containing tetrahydrobenzene logistics; In step (2), obtain benzene logistics from reactive distillation column overhead, the benzene logistics obtained can be used as a part for step (1) reaction feed.
The second situation, in step (1), described is isolate the logistics that benzene obtains in benzene hydrogenation product stream containing tetrahydrobenzene logistics; In step (2), obtain hexanaphthene logistics from reactive distillation column overhead, obtain hexanaphthene logistics and go out device as byproduct.
The third situation, in step (1), described is benzene hydrogenation product stream containing tetrahydrobenzene logistics; In step (2), hexanaphthene/benzene logistics is obtained from reactive distillation column overhead, this logistics can produce hexanaphthene by hydrogenation, also hexanaphthene logistics and benzene logistics can be obtained through separation of extractive distillation, the benzene logistics obtained can be used as a part for step (1) reaction feed, obtains hexanaphthene logistics and goes out device as byproduct.
The theoretical plate number of described reactive distillation column is 10 ~ 150, between 1/3 to 2/3 position of theoretical plate number, arrange solid acid catalyst; 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.
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 of described reactive distillation column is 10 ~ 150, 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.Described reflux ratio is 0.1 ~ 100:1, is preferably 0.5 ~ 10:1.
According to method provided by the invention, the raw material that the acetic acid obtained at the bottom of reactive distillation column/hexalin acetate logistics is reacted as step (3).The logistics that reactive distillation tower top obtains may be hexanaphthene and/or benzene, also may be a small amount of light impurity brought into by raw material, and its composition is relevant with the reaction raw materials that step (2) adopts; If overhead stream is the mixture of C6 hydrocarbon, Hydrogenation can be carried out for hexanaphthene to it, extracting rectifying also can be adopted to be separated it.What these directly obtained from reactive distillation tower top is separated the logistics obtained with to it further, benzene logistics can be used as a part for step (1) reaction feed, tetrahydrobenzene logistics can be used as a part for step (2) reaction feed, and hexanaphthene logistics goes out device as byproduct.
Three, acetic acid/ethyl cyclohexyl ester through hydrogenation
According to method provided by the invention, hydrogenation is carried out to acetic acid/hexalin acetate logistics that step (2) obtains; Reaction product is separated, obtains hexalin and ethanol.
A kind of hydrogenation mode is that the acetic acid that step (2) obtains/hexalin acetate logistics is introduced into the first reaction zone, contacts under the effect of the first catalyzer with hydrogen, and hydrogenation of carboxylic acids reaction occurs; And then enter second reaction zone, contact with hydrogen under the effect of the second catalyzer, ester through hydrogenation reaction occurs.Described two reaction zones both can be different reactor, also can be the different piece of same reactor.
According to above-mentioned hydrogenation mode, should be understood that, described first catalyzer is mainly used in catalysis acetic acid hydrogenation and generates ethanol, and described second catalyzer is mainly used in catalysis ethyl cyclohexyl ester through hydrogenation and generates hexalin and ethanol.
According to above-mentioned hydrogenation mode, the hydrogenation of acetic acid/hexalin acetate logistics can carry out in the hydrogenation reaction unit of two series connection, each hydrogenation reaction unit can arrange the reactor of one or more parallel connection, and type of reactor is selected from one or more in tank reactor, fixed-bed reactor, ebullated bed reactor and fluidized-bed reactor.Described reactor is preferably tubular fixed-bed reactor; Be more preferably shell shell and tube reactor, hydrogenation catalyst is fixed in tubulation, removes reaction liberated heat at shell side by heat-eliminating medium.
Described first catalyzer is hydrogenation of carboxylic acids catalyzer.Described hydrogenation of carboxylic acids catalyzer can be made up of main active ingredient, auxiliary agent and carrier; Wherein, main active ingredient can be selected from one or more in platinum, palladium, ruthenium, tungsten, molybdenum, cobalt, auxiliary agent can be selected from one or more in tin, chromium, aluminium, zinc, calcium, magnesium, nickel, titanium, zirconium, rhenium, lanthanum, thorium, gold, one or more in the optional autoxidation silicon of carrier, aluminum oxide, titanium oxide, zirconium white, gac, graphite, carbon nanotube, Calucium Silicate powder, zeolite, pure aluminium silicate.Usually, with the total mass of catalyzer for benchmark, main active ingredient accounts for 0.1% ~ 30, and auxiliary agent accounts for 0.1% ~ 25%, and all the other are carrier.
The reaction conditions of the first reaction zone: temperature of reaction is 100 ~ 400 DEG C, reaction pressure is 0.1 ~ 30MPa, and hydracid mol ratio is 1 ~ 500:1, and liquid feeding air speed is 0.1 ~ 5h
-1; Optimum condition is: temperature of reaction is 180 ~ 300 DEG C, and reaction pressure is 2 ~ 10MPa, and hydracid mol ratio is 5 ~ 50:1, and liquid feeding air speed is 0.2 ~ 2h
-1.
The second described catalyzer is ester through hydrogenation catalyzer.Although existing disclosed document is 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., there are no the report of any carboxylicesters hydrogenation reaction derived about cycloalkanol, but the present inventor finds, the hydrogenation of hexalin acetate can adopt existing ester through hydrogenation catalyzer.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.The composition that ruthenium catalyst is general: Ru/Al
2o
3or Ru-Sn/Al
2o
3.The composition that precious metal series catalysts is general: Pt/Al
2o
3, Pd-Pt/Al
2o
3or Pd/C.
Described 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 chromium.
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 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.
The present invention can adopt continuous rectification to be separated hydrogenation products.Continuous rectification needs to utilize a series of rectifying tower to be separated various component.Can according to the various separation process of sequence design of each component boiling point, the flow scheme that the present invention is preferably separated in order, is namely separated by boiling point order from low to high.
Separately it should be noted that each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
The present invention produces the new technology path that hexalin provides a high-level efficiency, low cost.Feature of the present invention is: (1) esterification and hydrogenation reaction all have very high selectivity, and therefore atom utilization is very high; (2) process environment is friendly; (3) 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; (4) adopt reactive distillation to carry out addition esterification, not only can significantly improve reaction efficiency, separation of extractive distillation process can also be simplified, greatly reduce investment and operation cost.
Accompanying drawing explanation
Fig. 1 is the block diagram of the first embodiment of the present invention.
Fig. 2 is the block diagram of the second embodiment of the present invention.
Embodiment
Below in conjunction with the preferred two kinds of technical process of Brief Description Of Drawings the present invention.
In the first technical process, addition esterifier adopts tank reactor, tubular fixed-bed reactor, ebullated bed reactor or fluidized-bed reactor.As shown in Figure 1: benzene and hydrogen enter benzene hydrogenation device 1, under the effect of benzene hydrogenating catalyst, carry out hydrogenation reaction, benzene hydrogenation product stream enters addition esterifier 2 through pipeline 11, mix with the acetic acid entered through pipeline 21, under the effect of solid acid catalyst, carry out addition esterification, addition esterification products stream passes via line 22 enters addition esterification products separating unit 3, hexanaphthene logistics 31 is obtained through separation, tetrahydrobenzene logistics 32, benzene logistics 33, acetic acid/hexalin acetate logistics 34, benzene logistics loops back benzene hydrogenation device 1, tetrahydrobenzene logistics loops back addition esterifier 2, hexanaphthene thing is as byproduct bleeder, acetic acid/hexalin acetate logistics enters hydrogenation of carboxylic acids reactor 4, under the effect of hydrogenation of carboxylic acids catalyzer, contact with hydrogen and carry out hydrogenation of carboxylic acids reaction, hydrogenation of carboxylic acids product stream enters ester through hydrogenation reactor 5, under the effect of ester through hydrogenation catalyzer, contact with hydrogen and carry out ester through hydrogenation reaction, ester through hydrogenation reaction product stream enters hydrogenation products separating unit 6, hexalin logistics 61 is obtained through separation, ethanol stream 62.
In the second technical process, addition esterifier adopts reactive distillation column.As shown in Figure 2: benzene and hydrogen enter benzene hydrogenation device 1, under the effect of benzene selective hydrogenation catalyst, carry out hydrogenation reaction, benzene hydrogenation product stream enters reactive distillation column 2 through pipeline 11, mixes with the acetic acid entered through pipeline 21, under the effect of solid acid catalyst, carry out addition esterification, carry out the separation of esterification products simultaneously, obtain hexanaphthene/benzene logistics from reactive distillation column 2 tower top, at the bottom of reactive distillation column 2 tower, obtain acetic acid/hexalin acetate logistics, hexanaphthene/benzene stream passes via line 22 enters addition esterification products separating unit 3, hexanaphthene logistics and benzene logistics is obtained through separation, benzene logistics loops back benzene hydrogenation device 1, hexanaphthene logistics goes out device as byproduct, acetic acid/hexalin acetate logistics enters hydrogenation of carboxylic acids reactor 4, under the effect of hydrogenation of carboxylic acids catalyzer, contact with hydrogen and carry out hydrogenation of carboxylic acids reaction, hydrogenation of carboxylic acids product stream enters ester through hydrogenation reactor 5, under the effect of ester through hydrogenation catalyzer, contact with hydrogen and carry out ester through hydrogenation reaction, ester through hydrogenation reaction product stream enters hydrogenation products separating unit 6, hexalin logistics 61 is obtained through separation, ethanol stream 62.
Further illustrate the present invention by the following examples, but not thereby limiting the invention.
Embodiment 1
The present embodiment illustrates the method for benzene selective hydrogenation to prepare cyclohexene.
Benzene and hydrogen 1:3 injection are in molar ratio filled with the hydrogenator of ruthenium beaded catalyst, benzene hydrogenation is carried out under the condition of temperature of reaction 135 DEG C, pressure 4.5MPa, residence time 15min, after reaction product isolates hydrogen, collect product liquid, run 1000h continuously.After off-test, carry out gas chromatographic analysis to the product liquid collected, it consists of: benzene 53.3%, tetrahydrobenzene 35.4%, hexanaphthene 11.3%.
Embodiment 2
By 100mL 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 φ 32 × 4 × 1000mm with the middle part in the stainless steel tube reactor of chuck, a certain amount of quartz sand is filled at two ends.By acetic acid and tetrahydrobenzene raw material (benzene 53.3%, tetrahydrobenzene 35.4%, hexanaphthene 11.3%) to be squeezed in reactor by volume pump respectively by certain flow and react, in reaction tubes external jacket, pass into hot water to control temperature of reaction, control reactor pressure by reactor outlet back pressure valve.Reactor outlet product is sampled by on-line period valve and carries out on-line chromatograph analysis, is made up of calculates cyclohexene conversion rate and hexalin acetate selectivity product.Reaction conditions and the results are shown in Table 1.
As shown in Table 1, adopt strong acid ion exchange resin catalyst tetrahydrobenzene raw material and acetic acidreaction, cyclohexene conversion rate is greater than 80%, and ester products selectivity is greater than 99%, and run 600 hours, catalyst activity and selectivity is stablized constant.
Table 1 strong-acid ion exchange resin catalysis acetic acid and hexanaphthene/tetrahydrobenzene/phenyl ester testing data
Embodiment 3
Testing apparatus, method and raw material are with embodiment 2, the H beta-molecular sieve catalyzer of difference to be catalyzer be P Modification (by silica alumina ratio be the H beta-molecular sieve of 50 through the phosphoric acid modification of 85%, then mediate extruded moulding with aluminum oxide, through 120 DEG C of oven dry, 500 DEG C of roastings obtain, and phosphorus content is 2m%).Reaction conditions and the results are shown in Table 2.From table 2, tetrahydrobenzene and acetic acidreaction transformation efficiency are greater than 80%, and ester products selectivity is greater than 99%, and run 480 hours, catalyst activity and selectivity is stablized constant.
Table 2H beta-molecular sieve catalyst acetic acid and hexanaphthene/tetrahydrobenzene/phenyl ester testing data
Embodiment 4
Collect the addition esterification products of embodiment 2 and 3, carry out rectifying separation test.Rectifying adopts high 2m diameter to be the glass tower rectifier unit of 40mm, king-post is equipped with the stainless steel Dixon ring highly efficient distilling filler of Ф 3mm, and tower reactor is the L glass flask of volume 5, and charge amount is 4L, by electric mantle, tower reactor is heated, regulate 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 3.
Table 3 addition esterification products rectifying separation test-results
Embodiment 5 ~ 6 is for illustration of the method adopting reactive distillation to prepare hexalin acetate.
The test carried out in embodiment 5 ~ 6 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.Acetic acid and tetrahydrobenzene raw material 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 5
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 raw material 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 4.
The reactive distillation testing data of table 4 is high temperature resistant sulfonic acid ion exchange resin catalyzer
According to the transformation efficiency 99% of testing data ring hexene, hexalin acetate selectivity 99.2%.
Embodiment 6
By the ball-type H of φ 3 ~ 4
0.5cs
2.5pW
12o
40/ SiO
2catalyzer is (by H
0.5cs
2.5pW
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 raw material 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 5.
Table 5H
0.5cs
2.5pW
12o
40/ SiO
2the reactive distillation testing data of catalyzer
According to the transformation efficiency 98.3% of testing data ring hexene, hexalin acetate selectivity 99.5%.
Embodiment 7
The present embodiment illustrates the method for hydrotreating of acetic acid and ethyl cyclohexyl ester mixture.
Hydrogenating materials is the mixture (acetic acid 39.5%, hexalin acetate 60.5%) of acetic acid and hexalin acetate.
Reactive system is made up of the fixed-bed reactor of two series connection.Two reactors are the titanium matter steel pipe with chuck, are of a size of φ 20 × 2.5 × 800mm.Front reactor is acetic acid hydrogenation reactor, and the silicon dioxide carried platinum palladium tin acetic acid hydrogenation catalyzer of in-built 40g (synthesize, and consists of Pt (10m%)-Pd (5m%)-Sn (5m%)/SiO by laboratory
2, by 20 ~ 40 object macroporous silicon dioxide carrier (BET specific surface area 400m
2/ g, pore volume 0.35mL/g) flood the mixing solutions of Platinic chloride, Palladous chloride and tin protochloride, then through 120 DEG C of dryings, 500 DEG C of roastings obtain).Post-reactor is ester through hydrogenation reactor, and in-built 40g copper zinc-aluminium ester through hydrogenation catalyzer (synthesize, and consists of CuO40%, ZnO29.6%, Al by laboratory
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).Catalyzer loads the middle part of reactor, and a certain amount of quartz sand is filled at two ends, as heating raw materials gasification zone or filler.Thermal oil can be passed in reactor jacket and control temperature of reaction.After installing catalyzer in reactor, ligation system, and after completion system tightness test, pass into hydrogen (1000mL/min) 300 DEG C, under 6MPa condition after reductase 12 4h, be down to the temperature and pressure of hydrogenation reaction.The mixture of acetic acid and hexalin acetate is squeezed in reactor by volume pump, hydrogen enters reactive system through mass flow controller and carries out hydrogenation reaction, controlling temperature of reaction by passing into thermal oil in reaction tubes external jacket, controlling reactor pressure by reactor outlet back pressure valve.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 6.
Table 6 acetic acid/hexalin acetate hydropyrolysis experiment data
Embodiment 8
The present embodiment illustrates the method for hydrotreating of acetic acid and ethyl cyclohexyl ester mixture.
Hydrogenating materials is the mixture (acetic acid 39.5%, hexalin acetate 60.5%) of acetic acid and hexalin acetate.
Reactive system is made up of single fixed-bed reactor, and reactor is the titanium matter steel pipe with chuck, is of a size of φ 20 × 2.5 × 800mm.Catalyzer divides two-layer loading reactor.Upper strata loads the silicon dioxide carried platinum palladium tin acetic acid hydrogenation catalyzer of 20g, and (laboratory is synthesized, and consists of Pt (10%)-Pd (5%)-Sn (5%)/SiO
2, by 20 ~ 40 object macroporous silicon dioxide carrier (BET specific surface area 400m
2/ g, pore volume 0.35mL/g) flood the mixing of Platinic chloride, Palladous chloride and tin protochloride easily, then through 120 DEG C of dryings, 500 DEG C of roastings obtain); Lower floor loads 20g copper zinc-aluminium ester through hydrogenation catalyzer, and (laboratory is synthesized, and consists of CuO40%, 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).Catalyzer loads the flat-temperature zone, middle part of reactor, and separated by glasscloth between two-layer catalyzer, a certain amount of quartz sand is filled at reactor two ends, as heating raw materials gasification zone or filler.Thermal oil can be passed in reactor jacket and control temperature of reaction.After loading catalyzer in reactor, ligation system, and after completion system tightness test, pass into hydrogen (500mL/min) 300 DEG C, under 6MPa condition after reductase 12 4h, be down to the temperature and pressure of hydrogenation reaction.The mixture of acetic acid and hexalin acetate is squeezed in reactor by volume pump, hydrogen enters reactive system through mass flow controller and carries out hydrogenation reaction, controlling temperature of reaction by passing into thermal oil in reaction tubes external jacket, controlling reactor pressure by reactor outlet back pressure valve.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 7.
Table 7 acetic acid/hexalin acetate hydropyrolysis experiment data
Embodiment 10
Collect the hydrogenation reaction product 4000g of example 8 ~ 9, 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 8.
The rectifying separation testing data of table 8 hydrogenation products
Claims (19)
1. a method for coproduction hexalin and ethanol, comprising:
(1) under the condition of preparing cyclohexene from benzene added with hydrogen, benzene and hydrogen generation hydrogenation reaction, obtain containing tetrahydrobenzene logistics; Described is the logistics that benzene hydrogenation product stream or benzene hydrogenation product stream isolate hexanaphthene or benzene containing tetrahydrobenzene logistics;
(2) what step (1) obtained contacts with acetic acid containing tetrahydrobenzene logistics, and addition esterification occurs under the effect of catalyzer; In this step, adopt the reactive distillation column of one or more parallel connection, while carrying out addition esterification, carry out the separation of reaction product, at the bottom of reactive distillation column tower, obtain acetic acid/hexalin acetate logistics;
Described is, when isolating logistics that hexanaphthene obtains in benzene hydrogenation product stream, obtain benzene logistics from reactive distillation column overhead containing tetrahydrobenzene logistics;
Described is, when isolating logistics that benzene obtains in benzene hydrogenation product stream, obtain hexanaphthene logistics from reactive distillation column overhead containing tetrahydrobenzene logistics;
When described is benzene hydrogenation product stream containing tetrahydrobenzene logistics, obtain hexanaphthene/benzene logistics from reactive distillation column overhead;
(3) hydrogenation is carried out to acetic acid/hexalin acetate logistics that step (2) obtains; Reaction product is separated, obtains hexalin and ethanol.
2. in accordance with the method for claim 1, it is characterized in that, in step (1), the benzene hydrogenating catalyst of use is ruthenium catalyst.
3. in accordance with the method for claim 2, it is characterized in that, in step (1), the benzene hydrogenating catalyst of use is the ruthenium catalyst containing cobalt and/or zinc.
4. in accordance with the method for claim 1, it is characterized in that, in step (2), described catalyzer is solid acid catalyst.
5. in accordance with the method for claim 4, 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.
6. in accordance with the method for claim 5, 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.
7. in accordance with the method for claim 5, it is characterized in that, described heteropolyacid catalyst is heteropolyacid and/or heteropolyacid acid salt, or the catalyzer of carried heteropoly acid and/or heteropolyacid acid salt.
8. 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.
9. in accordance with the method for claim 7, it is characterized in that, in the catalyzer of described carried heteropoly acid and/or heteropolyacid acid salt, carrier is SiO
2and/or gac.
10. in accordance with the method for claim 5, it is characterized in that, described heteropolyacid catalyst is selected from one or more in 12 phospho-wolframic acids, 12 silicotungstic acids, 12 phosphomolybdate, 12 molybdovanaphosphoric acids and acid phospho-wolframic acid cesium salt.
11. in accordance with the method for claim 5, it is characterized in that, described molecular sieve is one or more in H β, HY and HZSM-5.
12. in accordance with the method for claim 11, it is characterized in that, described molecular sieve is by one or more in H β, HY and HZSM-5 of fluorine or P Modification.
13. 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, between 1/3 to 2/3 position of theoretical plate number, arrange solid acid catalyst; 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.
14. in accordance with the method for claim 1, it is characterized in that, in step (3), acetic acid/hexalin acetate logistics is introduced into the first reaction zone, contacts under the effect of the first catalyzer with hydrogen, and hydrogenation of carboxylic acids reaction occurs; And then enter second reaction zone, contact with hydrogen under the effect of the second catalyzer, ester through hydrogenation reaction occurs.
15. in accordance with the method for claim 14, it is characterized in that, in step (3), the first described catalyzer is hydrogenation of carboxylic acids catalyzer.
16. in accordance with the method for claim 14, it is characterized in that, in step (3), the reaction conditions of the first reaction zone: temperature of reaction is 100 ~ 400 DEG C, reaction pressure is 0.1 ~ 30MPa, and hydracid mol ratio is 1 ~ 500:1, and liquid feeding air speed is 0.1 ~ 5h
-1.
17. in accordance with the method for claim 14, it is characterized in that, in step (3), the second described catalyzer is ester through hydrogenation catalyzer.
18. in accordance with the method for claim 17, it is characterized in that, described ester through hydrogenation catalyzer is selected from one or more in Cu-series catalyst, ruthenium catalyst and precious metal series catalysts.
19. in accordance with the method for claim 18, it is characterized in that, in step (3), described ester through hydrogenation catalyzer is Cu-series catalyst, the reaction conditions of second reaction zone: temperature of reaction is 150 ~ 400 DEG C, 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.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310001152.9A CN103910603B (en) | 2013-01-05 | 2013-01-05 | A kind of method of coproduction hexalin and ethanol |
| US14/429,189 US9561991B2 (en) | 2012-09-18 | 2013-09-17 | Process and apparatus for co-producing cyclohexanol and alkanol |
| PCT/CN2013/001100 WO2014044020A1 (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 |
| KR1020157010078A KR102008352B1 (en) | 2012-09-18 | 2013-09-17 | Method and device for coproducing cyclohexanol and alkanol |
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| CN105582956B (en) * | 2014-10-21 | 2018-07-31 | 中国石油化工股份有限公司 | The method of hydrogenation catalyst and its preparation method and application and hydrogenation reaction |
| CN107698425A (en) * | 2017-09-12 | 2018-02-16 | 沈阳化工大学 | A kind of synthetic method of absolute ethyl alcohol and anhydrous liquid alcohol |
| CN107573216A (en) * | 2017-09-12 | 2018-01-12 | 沈阳化工大学 | A kind of synthetic method of absolute ethyl alcohol |
| 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 |
| 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 |
| CN110105208A (en) * | 2019-06-11 | 2019-08-09 | 中触媒新材料股份有限公司 | A method of preparing cyclohexyl acetate |
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| CN102149661A (en) * | 2008-07-31 | 2011-08-10 | 国际人造丝公司 | Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst |
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| CN102149661A (en) * | 2008-07-31 | 2011-08-10 | 国际人造丝公司 | Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst |
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