CN103880598B - A kind of method of coproduction hexalin and ethanol and device - Google Patents

A kind of method of coproduction hexalin and ethanol and device Download PDF

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CN103880598B
CN103880598B CN201210559981.4A CN201210559981A CN103880598B CN 103880598 B CN103880598 B CN 103880598B CN 201210559981 A CN201210559981 A CN 201210559981A CN 103880598 B CN103880598 B CN 103880598B
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reactor
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CN103880598A (en
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宗保宁
马东强
温朗友
孙斌
杨克勇
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Priority to US14/429,189 priority patent/US9561991B2/en
Priority to PCT/CN2013/001100 priority patent/WO2014044020A1/en
Priority to KR1020157010078A priority patent/KR102008352B1/en
Priority to TW102133691A priority patent/TWI612031B/en
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    • C07—ORGANIC CHEMISTRY
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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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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
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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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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
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    • C07C67/00—Preparation of carboxylic acid esters
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    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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    • 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
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    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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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, ethyl cyclohexyl ester through hydrogenation.Present invention also offers the device realizing the method.Feature of the present invention is: (1) esterification 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, not only can significantly improve reaction efficiency, separation of extractive distillation process can also be simplified.

Description

A kind of method of coproduction hexalin and ethanol and device
Technical field
The present invention relates to method and the device of a kind 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 preparing cyclohexene from benzene added with hydrogen 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.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, 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, prepares hexalin and ethanol by benzene selective hydrogenation, tetrahydrobenzene addition esterification, ethyl cyclohexyl ester through hydrogenation.Present invention also offers the device that can realize aforesaid method.
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; Reaction product is separated, obtains hexanaphthene/tetrahydrobenzene logistics and benzene logistics;
(2) hexanaphthene/tetrahydrobenzene logistics that step (1) obtains is contacted with acetic acid, addition esterification occurs under the effect of the first catalyzer; Reaction product is separated, obtains hexalin acetate logistics;
(3) the hexalin acetate logistics that step (2) obtains is contacted with hydrogen, ester through hydrogenation reaction occurs under the effect of the second catalyzer; 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 existing to utilize prepared from benzene and hydrogen all to can be the present invention for the method for tetrahydrobenzene and benzene hydrogenating catalyst used.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.
In step (1), the mixture that reaction product is mainly made up of hexanaphthene, tetrahydrobenzene and unreacted benzene, needs benzene wherein to separate before carrying out next step.The separation method of existing hexanaphthene, tetrahydrobenzene and benzene is all applicable to 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.Such as, benzene hydrogenation product stream can be sent into extractive distillation column from middle part, N,N-dimethylacetamide is introduced from tower top, and tower top obtains hexanaphthene/tetrahydrobenzene logistics; Obtain the solution of benzene and N,N-dimethylacetamide at the bottom of tower, this solution is sent into rectifying tower and is separated further, can obtain benzene logistics, obtain N,N-dimethylacetamide by the bottom of rectifying tower by tower top.
In preferred situation, the benzene logistics separated from step (1) reaction product is as a part for step (1) reaction feed.
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), the first 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 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), adopt the reactor of one or more parallel connection, type of reactor is 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) is primarily of hexanaphthene, tetrahydrobenzene, acetic acid and hexalin acetate composition, and 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.A kind of optional separate mode carries out rectifying separation to esterification products logistics, obtains hexanaphthene/tetrahydrobenzene logistics, acetic acid stream and hexalin acetate logistics.Can carry out Hydrogenation for hexanaphthene to hexanaphthene/tetrahydrobenzene logistics, acetic acid stream can be used as a part for step (2) reaction feed, the raw material that hexalin acetate logistics is reacted as step (3).The present invention also can carry out separation of extractive distillation to hexanaphthene/tetrahydrobenzene logistics further, obtains hexanaphthene logistics and tetrahydrobenzene logistics, and tetrahydrobenzene logistics can be used as a part for step (2) reaction feed, and hexanaphthene logistics goes out device as byproduct.The present invention can also remove the heavy constituent in above-mentioned hexalin acetate logistics by rectifying separation, using the raw material removing the hexalin acetate logistics after heavy constituent and react as step (3), isolated heavy constituent logistics is as byproduct discharger.
Specifically, esterification products separating unit can arrange a decylization hexane/tetrahydrobenzene tower and a desacetoxy tower.First addition esterification products enters decylization hexane/tetrahydrobenzene tower and is separated, this tower can adopt atmospheric operation, by controlling tower reactor heating amount, reflux ratio, tower top and tower reactor produced quantity, from overhead extraction hexanaphthene/tetrahydrobenzene logistics, enter desacetoxy tower be separated from the decylization hexane/logistics of tetrahydrobenzene tower tower reactor extraction, this tower also can adopt atmospheric operation, by controlling tower reactor heating amount, reflux ratio, tower top and tower reactor produced quantity, from overhead extraction acetic acid stream, from the logistics of tower reactor extraction hexalin acetate.Described esterification products separating unit can arrange an extractive distillation column again, enters separation of extractive distillation tower, be separated into hexanaphthene logistics and tetrahydrobenzene logistics further from the hexanaphthene/tetrahydrobenzene logistics of decylization hexane/tetrahydrobenzene column overhead extraction.Esterification products separating unit can also arrange a de-heavy oil column again, enters de-heavy oil column, remove the heavy constituent in logistics further from the hexalin acetate logistics of desacetoxy tower tower reactor extraction, thus obtains the hexalin acetate logistics removing heavy constituent.
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 hexalin acetate logistics, obtain hexanaphthene/acetic acid stream from reactive distillation column overhead.
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 preferably 30 ~ 100, between 1/3 to 2/3 position of theoretical plate number, 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 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 is 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 is 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 preferably 0.5 ~ 10:1.
According to method provided by the invention, the raw material that the hexalin acetate logistics obtained at the bottom of reactive distillation column is reacted as step (3).For hexanaphthene/acetic acid stream that reactive distillation tower top obtains, rectifying separation can be adopted to be isolated into hexanaphthene logistics and acetic acid stream, acetic acid stream can be used as a part for step (2) reaction feed, and hexanaphthene logistics goes out device as byproduct.Specifically, hexanaphthene/acetic acid stream can carry out rectifying separation at a decylization hexane tower, and this tower can adopt atmospheric operation, by controlling tower reactor heating amount, reflux ratio, tower top and tower reactor produced quantity, from the logistics of overhead extraction hexanaphthene, from tower reactor extraction acetic acid stream.
Three, ethyl cyclohexyl ester through hydrogenation
According to method provided by the present invention, be separated by addition esterification products the hexalin acetate logistics obtained and be admitted to ester through hydrogenation reactor and carry out hydrogenation reaction.In step (3), can arrange the reactor of one or more parallel connection, type of reactor is selected from one or more in tank reactor, fixed-bed reactor, ebullated bed reactor and fluidized-bed reactor.In step (3), the tubular fixed-bed reactor of one or more parallel connection is preferably set.In step (3), more preferably arrange the shell shell and tube reactor of one or more parallel connection, ester through hydrogenation catalyzer is fixed in tubulation, removes reaction liberated heat at shell side by heat-eliminating medium.
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.
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 chromium.
Ester through hydrogenation reaction member both 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 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 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.
Ester through hydrogenation reaction product is mainly containing ethanol and hexalin, also a certain amount of ethyl acetate and pimelinketone may be contained, also a certain amount of unreacted hexalin acetate may be contained simultaneously, and a small amount of high boiling material (two polyketone), these mixtures can adopt the method for rectifying and/or extracting rectifying to be separated, and preferably adopt rectifying separation.Rectifying separation 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.The present invention preferably adopts continuous rectification to be separated ester through hydrogenation product.Continuous rectification needs to utilize a series of rectifying tower to be separated various component.Can design various separation process according to the sequencing of the separation of each component, the flow scheme that preferred sequence of the present invention is separated, namely ester through hydrogenation product separation unit sets gradually for de-ethanol tower, decylization hexanol tower, hexalin acetate recovery tower.Ester through hydrogenation product is introduced into the separation of de-ethanol tower and obtains ethanol, and 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 carrying device.The present invention also only can arrange a rectifying tower, is only gone out by separation of ethanol, obtains the hexalin containing a small amount of impurity.
In step (3), after reaction product is separated, the hexalin acetate logistics obtained can be used as a part for step (3) reaction feed.
The invention provides the device of a kind of coproduction hexalin and ethanol, comprise the benzene hydrogenation unit, benzene hydrogenation product separation unit, addition esterification unit, addition esterification products separating unit, ester through hydrogenation reaction member and the ester through hydrogenation product separation unit that are connected successively; Described benzene hydrogenation product separation unit at least arranges an extractive distillation column and a rectifying tower.
Those skilled in the art, according to method provided by the invention, easily can determine the pipeline mode of connection between each unit.
Described benzene hydrogenation unit is provided with the reactor of one or more parallel connection, and type of reactor is selected from fixed-bed reactor and/or tank reactor.
Described addition esterification unit arranges 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 addition esterification unit at least arranges a reactive distillation column.
Before described reactive distillation column, be also arranged in series a pre-esterification reactor device, described pre-esterification reactor device is tank reactor, fixed-bed reactor, fluidized-bed reactor or ebullated bed reactor.
Described addition esterification products separating unit at least arranges a rectifying tower.
Described ester through hydrogenation reaction member arranges 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 ester through hydrogenation reaction member arranges the shell shell and tube reactor of one or more parallel connection.
Described ester through hydrogenation product separation unit at least arranges a rectifying tower.
Present invention also offers the device of another kind of coproduction hexalin and ethanol, comprise the benzene hydrogenation unit, benzene hydrogenation product separation unit, addition esterification unit, ester through hydrogenation reaction member and the ester through hydrogenation product separation unit that are connected successively; Described benzene hydrogenation product separation unit at least arranges an extractive distillation column and a rectifying tower; Described addition esterification unit arranges the reactive distillation column of one or more parallel connection.
Those skilled in the art, according to method provided by the invention, easily can determine the pipeline mode of connection between each unit.
Described benzene hydrogenation unit is provided with the reactor of one or more parallel connection, and type of reactor is selected from fixed-bed reactor and/or tank reactor.
Before described reactive distillation column, be also arranged in series a pre-esterification reactor device; Described pre-esterification reactor device is tank reactor, fixed-bed reactor, fluidized-bed reactor or ebullated bed reactor.
Described ester through hydrogenation reaction member arranges 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 ester through hydrogenation reaction member arranges the shell shell and tube reactor of one or more parallel connection.
Described ester through hydrogenation product separation unit at least arranges a rectifying tower.
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 ester through 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 benzene hydrogenation product separation unit 2 through pipeline 11, through being separated, obtain tetrahydrobenzene/hexanaphthene logistics and benzene logistics, benzene stream passes via line 21 loops back benzene hydrogenation device 1, tetrahydrobenzene/hexanaphthene stream passes via line 22 enters addition esterifier 3, mix with the acetic acid entered through pipeline 31, under the effect of solid acid catalyst, carry out addition esterification, addition esterification products stream passes via line 32 enters addition esterification products separating unit 4, through being separated, obtain hexanaphthene logistics 41, tetrahydrobenzene logistics 42, acetic acid stream 43 and hexalin acetate logistics 44, hexanaphthene logistics 41 goes out device as byproduct, acetic acid stream 43 and tetrahydrobenzene logistics 42 loop back addition esterifier 3, hexalin acetate logistics 44 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 product stream 51 enters ester through hydrogenation product separation unit 6, through being separated, obtain hexalin logistics 62, ethanol stream 63, hexalin acetate logistics 61 and high boiling material logistics 64, hexalin logistics 62 and ethanol stream 63 go out device as product, high boiling material logistics 64 goes out device as byproduct, hexalin acetate logistics 61 loops back ester through hydrogenation reactor 5.
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 hydrogenating catalyst, carry out hydrogenation reaction, benzene hydrogenation product stream enters benzene hydrogenation product separation unit 2 through pipeline 11, through being separated, obtain tetrahydrobenzene/hexanaphthene logistics and benzene logistics, benzene stream passes via line 21 loops back benzene hydrogenation device 1, tetrahydrobenzene/hexanaphthene stream passes via line 22 enters reactive distillation column 3, mix with the acetic acid entered through pipeline 31, under the effect of solid acid catalyst, carry out addition esterification, carry out the separation of addition esterification products simultaneously, acetic acid/hexanaphthene logistics is obtained from reactive distillation column 3 tower top, hexalin acetate logistics is obtained at the bottom of reactive distillation column 3 tower, acetic acid/hexanaphthene stream passes via line 32 enters addition esterification products separating unit 4, through being separated, obtain hexanaphthene logistics 42 and acetic acid stream 41, hexanaphthene logistics 42 goes out device as byproduct, acetic acid stream 41 loops back addition esterifier 3, hexalin acetate logistics 33 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 product stream enters ester through hydrogenation product separation unit 6, through being separated, obtain hexalin logistics 62, ethanol stream 63, hexalin acetate logistics 61 and high boiling material logistics 64, hexalin logistics and ethanol stream go out device as product, high boiling material logistics goes out device as byproduct, hexalin acetate logistics loops back ester through hydrogenation reactor 5.
Further illustrate the present invention by the following examples, but not thereby limiting the invention.
Embodiment 1
The present embodiment is for illustration of 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 53.3m%, tetrahydrobenzene 35.4m%, hexanaphthene 11.3m%.Take N,N-dimethylacetamide as extraction agent, extracting and separating is carried out to aforesaid liquid product, obtain hexanaphthene and tetrahydrobenzene mixture.
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.Acetic acid and tetrahydrobenzene raw material (are obtained by embodiment 1 method, consist of: tetrahydrobenzene 75m%, hexanaphthene 25m%) 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 rings hexene and acetic acidreaction, cyclohexene conversion rate is greater than 90%, and ester products selectivity is greater than 99%, and run 600 hours, catalyst activity and selectivity is stablized constant.
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 2%).Reaction conditions and the results are shown in Table 2.From table 2, cyclohexene conversion rate 90%, ester products selectivity is greater than 99%, and run 480 hours, catalyst activity and selectivity is stablized constant.
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.
Embodiment 5 ~ 6 prepares the method for hexalin acetate for illustration of reactive distillation.
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).Tower top is connected with the condenser that heat interchanging area is 0.5m2, and 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 is respectively charged in 30L storage tank with tetrahydrobenzene raw material (identical with embodiment 2), 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.
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.
Embodiment 7 ~ 8 is for illustration of the method for hydrotreating of hexalin acetate.
Embodiment 7
Adopt purity be 99.6% hexalin acetate be hydrogenating materials.
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 6.Table 6 result shows, adopt copper zinc-aluminium ester through hydrogenation catalyzer, hexalin acetate hydrogenation reaction transformation efficiency reaches as high as more than 99%, and hexalin selectivity is greater than 99%, and run 1000 hours, transformation efficiency and selectivity all do not decline.
Embodiment 8
Adopt purity be 99.6% hexalin acetate be hydrogenating materials.
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 7.Table 7 result shows, adopt copper zinc-aluminium ester through hydrogenation catalyzer, hexalin acetate hydrogenation reaction transformation efficiency can reach more than 98%, and hexalin selectivity is greater than 99%, and run 500 hours, transformation efficiency and selectivity all do not decline.
Embodiment 9
Collect the reaction product 4000g of example 7 ~ 8, 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.
Table 1 strong-acid ion exchange resin catalysis acetic acid and hexanaphthene/tetrahydrobenzene esterification testing data
Table 2H beta-molecular sieve catalyst acetic acid and tetrahydrobenzene esterification testing data
Table 3 addition esterification products rectifying separation testing data
The reactive distillation testing data of table 4 is high temperature resistant sulfonic acid ion exchange resin catalyzer
According to the transformation efficiency 99.9% of testing data ring hexene, hexalin acetate selectivity 99.2%.
Table 5H 0.5cs 2.5pW 12o 40/ SiO 2the reactive distillation testing data of catalyzer
According to the transformation efficiency 98.66% of testing data ring hexene, hexalin acetate selectivity 99.3%.
The hexalin acetate hydropyrolysis experiment data of table 6 copper zinc-aluminium ester through hydrogenation catalyzer
The hexalin acetate hydropyrolysis experiment data of table 7 copper chromium ester through hydrogenation catalyzer
The rectifying separation testing data of table 8 hexalin acetate hydrogenation products

Claims (31)

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; Reaction product is separated, obtains hexanaphthene/tetrahydrobenzene logistics and benzene logistics;
(2) hexanaphthene/tetrahydrobenzene logistics that step (1) obtains is contacted with acetic acid, addition esterification occurs under the effect of solid acid catalyst; 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 hexalin acetate logistics, obtain hexanaphthene/acetic acid stream from reactive distillation column overhead;
(3) the hexalin acetate logistics that step (2) obtains is contacted with hydrogen, ester through hydrogenation reaction occurs under the effect of ester through hydrogenation catalyzer; 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 (1), adopt extracting rectifying and separating benzene hydrogenation reaction product, extraction agent is METHYLPYRROLIDONE, N,N-dimethylacetamide, adiponitrile, dimethyl malonate, Succinic acid dimethylester, ethylene glycol or tetramethylene sulfone.
5. 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.
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, in step (2), sour alkene mol ratio is 1.2 ~ 3:1.
14. in accordance with the method for claim 1, it is characterized in that, described reactive distillation column is tray column, packing tower or both combinations.
15. 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.
16. in accordance with the method for claim 15, it is characterized in that, the theoretical plate number of described reactive distillation column is 30 ~ 100.
17. in accordance with the method for claim 15, it is characterized in that, relative to the total fill able volume of catalyzer, liquid feeding air speed is 0.5 ~ 5h -1.
18. in accordance with the method for claim 15, it is characterized in that, the working pressure of reactive distillation column is that normal pressure is to 1MPa.
19. in accordance with the method for claim 15, it is characterized in that, the temperature of catalyst filling zone is between 60 ~ 120 DEG C.
20. in accordance with the method for claim 15, it is characterized in that, the reflux ratio of reactive distillation column is 0.5 ~ 10:1.
21. 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, ruthenium catalyst and precious metal series catalysts.
22. in accordance with the method for claim 21, it is characterized in that, described ester through hydrogenation catalyzer is Cu-series catalyst, hydrogenation reaction temperature 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.
23. in accordance with the method for claim 22, it is characterized in that, hydrogenation reaction temperature is 200 ~ 300 DEG C, and reaction pressure is 4 ~ 10MPa, and hydrogen ester mol ratio is 5 ~ 100:1, and liquid feeding air speed is 0.2 ~ 2h -1.
24. in accordance with the method for claim 21, it is characterized in that, described Cu-series catalyst is the Cu-series catalyst containing zinc and/or chromium.
25. in accordance with the method for claim 1, it is characterized in that, in step (3), after reaction product is separated, also obtains hexalin acetate logistics, it can be used as a part for step (3) reaction feed.
26. in accordance with the method for claim 1, it is characterized in that, the benzene logistics separated from step (1) reaction product is as a part for step (1) reaction feed.
27. devices implementing the claims method described in 1, comprise the benzene hydrogenation unit, benzene hydrogenation product separation unit, addition esterification unit, ester through hydrogenation reaction member and the ester through hydrogenation product separation unit that are connected successively; Described benzene hydrogenation product separation unit at least arranges an extractive distillation column and a rectifying tower; Described addition esterification unit arranges the reactive distillation column of one or more parallel connection.
28., according to device according to claim 27, is characterized in that, before described reactive distillation column, are also arranged in series a pre-esterification reactor device; Described pre-esterification reactor device is tank reactor, fixed-bed reactor, fluidized-bed reactor or ebullated bed reactor.
29. according to device according to claim 27, it is characterized in that, described ester through hydrogenation reaction member arranges 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.
30., according to device according to claim 29, is characterized in that, described ester through hydrogenation reaction member arranges the shell shell and tube reactor of one or more parallel connection.
31., according to device according to claim 27, is characterized in that, described ester through hydrogenation product separation unit at least arranges a rectifying tower.
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CN108003017B (en) * 2016-10-28 2021-07-09 中国石油化工股份有限公司 Method for separating cyclohexyl acetate, method for producing cyclohexanol, and cyclohexanol production apparatus
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