CN100335473C - Method for preparing gamma-butyrolactone and cyclohexanone by couple process - Google Patents

Method for preparing gamma-butyrolactone and cyclohexanone by couple process Download PDF

Info

Publication number
CN100335473C
CN100335473C CNB2005100481905A CN200510048190A CN100335473C CN 100335473 C CN100335473 C CN 100335473C CN B2005100481905 A CNB2005100481905 A CN B2005100481905A CN 200510048190 A CN200510048190 A CN 200510048190A CN 100335473 C CN100335473 C CN 100335473C
Authority
CN
China
Prior art keywords
butyrolactone
pimelinketone
gamma
cis
hexalin
Prior art date
Application number
CNB2005100481905A
Other languages
Chinese (zh)
Other versions
CN1789255A (en
Inventor
朱玉雷
李永旺
郑洪岩
黄龙
王珏
相宏伟
Original Assignee
中国科学院山西煤炭化学研究所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国科学院山西煤炭化学研究所 filed Critical 中国科学院山西煤炭化学研究所
Priority to CNB2005100481905A priority Critical patent/CN100335473C/en
Publication of CN1789255A publication Critical patent/CN1789255A/en
Application granted granted Critical
Publication of CN100335473C publication Critical patent/CN100335473C/en

Links

Classifications

    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

The present invention relates to a method for preparing gamma-butyrolactone and cyclohexanone in a coupling mode. In the method, the mixture of cyclohexanol and maleic anhydride is treated with integral reaction by using hydrogenation catalysts at an optimal temperature under the conditions of gas phases and attach hydrogenation or no-attach hydrogenation. Compared with the prior art, in the integral process of hydrogenation and dehydrogenation, energy required by the reaction is little without hydrogenation or hydrogen recovery, and the present invention has the advantages of low production cost, high selectivity, yield, simple preparing process and easy operation.

Description

A kind of coupling technique prepares the method for gamma-butyrolactone and pimelinketone
Affiliated field
The invention belongs to a kind of method for preparing gamma-butyrolactone and pimelinketone, relating in particular to a kind of is the method for feedstock production gamma-butyrolactone and pimelinketone with cis-butenedioic anhydride and hexalin.
Background technology
Gamma-butyrolactone is a kind of important organic chemical industry's product; widespread use petrochemical complex, medicine, dyestuff, agricultural chemicals and fine chemistry industry aspect, in recent years especially in synthesis of pyrrolidine ketone, N-Methyl pyrrolidone, vinyl pyrrolidone, α-staple products such as ethanoyl butyrolactone application quantity bigger.Gamma-butyrolactone or high boiling solvent in addition, solvency power is strong, and electroconductibility and good stability use and Administrative Security makes things convenient for.
Mainly contain two kinds of raw material routes at present in the world and produce gamma-butyrolactones, promptly 1,4-butanediol dehydrogenation method and maleic anhydride hydrogenation method.Wherein the maleic anhydride hydrogenation method is because raw material cis-butenedioic anhydride source is sufficient, low price and being widely adopted.
Maleic anhydride hydrogenation legal system gamma-butyrolactone equation is as follows:
The maleic anhydride hydrogenation process is divided into two kinds of raw material routes of liquid and gas hydrogenation.In the cis-butenedioic anhydride liquid-phase hydrogenatin process, be solvent, mix with recycle hydrogen through preheating, at 6-12Mpa, under 160-280 ℃, by the reactor hydrogenation of catalyzer is housed with the gamma-butyrolactone; This liquid phase cracking process is favourable to strong exothermal reaction, but needs solvent, carry out in the mesohigh condition, and the process complexity, investment is high.
Cis-butenedioic anhydride gas phase hydrogenation process is fairly simple, and the cis-butenedioic anhydride of gasification and hydrogen mix, under normal pressure, 200-300 ℃, by the fixed bed hydrogenation catalyst hydrogenation.This gas phase process operational condition is gentle, less investment.
Chinese patent " cis-anhydride normal pressure gas phase synthetic gamma butyrolactone " (CN1058400A) disclosed catalyzer by Cu, ZnO, Al 2O 3Reach at least a the mixing in Ni, Ru, four kinds of elements of Ce, Zr.Catalyzer consists of Cu 25% (wt%), ZnO 30%, Al 2O 340%, Ni 4%, Ce+Zr1%, catalyst grain size 20-40 order is at internal diameter 16mm, react hydrogen and cis-butenedioic anhydride mol ratio 40,290 ℃ of temperature of reaction on the stainless steel fixed-bed reactor of long 75mm, cis-butenedioic anhydride transformation efficiency 99.6%, gamma-butyrolactone selectivity 84.5%.
U.S. Pat 5,122,495 introduce the Cu-Zn-Al catalyzer uses in the cis-butenedioic anhydride hydrogenation preparing gama-butalactone.Catalyzer consists of: CuO 55%, and ZnO 23%, Al 2O 318%, with the 400g catalyzer fixed-bed reactor of packing into, 250-280 ℃, under the hydrogen acid anhydride mol ratio 230-280 condition, cis-butenedioic anhydride transformation efficiency 100%, the gamma-butyrolactone selectivity is average 90%, and catalyzer uses 100-500hr continuously, promptly need under 400-450 ℃ of high temperature, to regenerate, thereby increased the difficulty of industrial application.
It is strong exothermal reaction that the cis-butenedioic anhydride ordinary-pressure gas-phase hydrogenation prepares gamma-butyrolactone, because focus is obvious, cause gamma-butyrolactone reaction decarburization to generate propyl alcohol, system's foreign gases such as propionic acid and carbon monoxide are cumulative, need continuous emptying just can keep the reaction hydrogen content, the hydrogen consumption is significantly increased.In a word, this hydrogenation process yield is low, and the hydrogen consumption is high, makes gamma-butyrolactone lose market price competition power.
Pimelinketone is a kind of colourless oil liquid, and water-soluble, pure, ether and common solvent have earth fragrance.Pimelinketone is the raw material of nylon intermediates such as preparation hexanolactam, hexanodioic acid as a kind of important chemical material.Pimelinketone also is a kind of good middle high boiling organic solvent, has fabulous solvability and low volatility.It can dissolve that poly-acetic acid second is rare, urethane, polymethylmethacrylate and ABS resin etc., also solubilized polystyrene, Synolac, acrylic resin, natural resin, natural rubber, synthetic rubber, chlorinated rubber etc.When pimelinketone is used as paint solvent, have good spraying and brushing function, can improve coating gloss.It can also be used as the silk-screen ink solvent, the sensitive materials coating is used thinner with the rumbling compound in solvent, the process hides shoe industry and leather grease-removing agent, covering with paint, is used for pesticide industry preparation aerosol bomb etc. in addition.Along with making rapid progress of science and technology, the applicating and exploitation of pimelinketone is just towards field development widely.
Mainly contain oxidation style and two kinds of technologies of dehydriding by the hexalin preparing cyclohexanone.Wherein the side reaction of dehydriding technological process is few, processing ease, and the yield height, and compare safety, therefore, larger pimelinketone industrial production generally adopts the dehydriding of hexalin.Industrial, the hexalin catalytic dehydrogenation is to pass through heating dehydrogenation tube furnace with pure hexalin gasification and with hydrogen, carries out continuous vapor catalytic dehydrogenation reaction.Reaction mixture is cooled off by condenser, and thick product is removed less water and tetrahydrobenzene from cat head after distillation is purified, carry out underpressure distillation again under the pressure of high-efficient spiral-screen column at about 4kPa, makes that cyclohexanone content reaches 98%-99% in the product.
Chinese patent CN1169417A and CN1381434A, report such as Japanese Patent JP2000288395 adopts the operational path of preparing cyclohexanone by cyclohexanol dehydrogenation.
The preparing cyclohexanone by cyclohexanol dehydrogenation equation is as follows:
It is the reversible thermo-negative reaction on thermodynamics that pimelinketone is produced in cyclohexanol dehydrogenation, because reaction is inhaled
Heat, being subjected in the actual production process to conduct heat influences, its high liquid air can not be given full play of, be subjected to the characteristics of thermodynamics equilibrium limit simultaneously, make the preparing cyclohexanone by cyclohexanol dehydrogenation transformation efficiency not high, the hydrogen emptying of reaction generation then causes waste in addition, if through a series of unit operations recovery then having increased production costs.The cyclohexanol dehydrogenation reaction also generates tetrahydrobenzene, phenol, cyclonene, hexanaphthene, benzene and cyclohexyl ring hexanone etc. because of side reaction except that the principal product pimelinketone.
Summary of the invention
The purpose of this invention is to provide a kind ofly need not sources of hydrogen, be the preparation of coupling gamma-butyrolactone of raw material and the method for pimelinketone with cyclohexanol dehydrogenation and maleic anhydride hydrogenation cheaply.
The object of the present invention is achieved like this: traditional technological line, and adopt cyclohexanol dehydrogenation to produce the direct emptying of pimelinketone by-product hydrogen, or reclaim through multiple unit operation, increase production cost.In addition, maleic anhydride hydrogenation is produced gamma-butyrolactone, and sources of hydrogen needs to buy from other places or build hydrogen producer, has increased cost, so two processes unite two into one, can make full use of sources of hydrogen, has reduced production cost, improves the market competitiveness, sees formula (3).
From top hydrogenation dehydrogenation coupled wave equation Shi Kede, hexalin and cis-butenedioic anhydride mol ratio are to get final product at 3: 1, consider system's gas leakage in the actual procedure, and rare gas element accumulative total needs emptying, factors such as hexalin can not transform fully generally take hexalin and cis-butenedioic anhydride mol ratio greater than 3.
Preparation method of the present invention is as follows:
The mixture of these two kinds of materials of cis-butenedioic anhydride and hexalin in gas phase, additional hydrogen is arranged or do not have under the additional hydrogen condition, in optimal temperature, carries out integrated reacting on the hydrogenation catalyst.
Because the used catalyzer of the present invention uses as hydrogenation (being hydrogenation) catalyzer industrial usually, although these catalyzer have dehydrogenation within the scope of the present invention, continues to be called " hydrogenation catalyst " in the method that the present invention narrated.
In the method for the present invention, the mixture of these two kinds of compounds of hexalin and cis-butenedioic anhydride is under gas phase condition, on the hydrogenation catalyst, the mol ratio of circulating hydrogen/hexalin and cis-butenedioic anhydride mixture is 1-60, is preferably 5-50, hexalin/cis-butenedioic anhydride mol ratio 3-10, be preferably 4-7, reaction pressure is a normal pressure, temperature of reaction 220-350 ℃, be preferably and carry out dehydrogenation hydrogenation integrated reacting under the 250-300 ℃ of condition, generate gamma-butyrolactone and pimelinketone.
As the heterogeneous catalyst in present method, not only can use the sedimentation type catalyzer, and the immersion type carried catalyst can be used also.Catalyzer prepares by the following method: at first with catalytic active component from their salts solution, especially from their nitrate and/or the solution of acetate, by adding basic metal and/or alkaline earth metal hydroxides solution and/or carbonate solution, for example as the oxyhydroxide of indissoluble, oxide hydrate, basic salt or carbonate deposition come out, and the throw out that obtains filters subsequently, washing and dry, and calcining.
Supported catalyst preparation: can adopt carrier direct impregnation active constituent, perhaps from relevant salts solution, be precipitated out then more favourable simultaneously with carrier active ingredient.Used carrier substance is generally aluminium and titanyl compound, and the oxide compound of zinc, zirconium dioxide, silicon-dioxide, diatomite, silica gel, shale soil if you would take off stone, silicate such as magnesium or aluminosilicate, zeolite such as ZSM-5 or ZSM-10 zeolite and gac.Preferred carrier is aluminum oxide, titanium dioxide, zinc oxide, zirconium dioxide, gac and silicon-dioxide.Certainly if need, the mixture of various carriers also can be used as the carrier of the catalyzer that uses in the present invention.
Particularly preferred catalyzer comprises a kind of metal in the copper metal at least.The precipitated catalyst that contains copper contains the 25-80%wt that accounts for total catalyst weight usually, preferably contains the copper of 45-70%wt, calculates with CuO.By the dipping of solid support material or the copper containing carrier catalyzer of coating preparation, the CuO weight content is 1-30%, and preferred content is 3-25%wt.
Catalyzer is handled at 100-300 ℃ usually by with hydrogen or hydrogenous gas, is reduced into corresponding metal and/or than the oxide compound of suboxide valency, and changes into the form of their real catalytic activity.Can select other suitable reductive agent for this reason, as: formaldehyde, hydrazine to replace hydrogen, have economic worth or hydrogen most certainly.Usually under certain reductive condition, be reacted to and do not consume hydrogen, or beds import and export hydrogen richness is constant, and the generation water yield does not become principle.
Method of the present invention is preferably carried out continuously.At this, can adopt tubular reactor, preferably dispose at this kind catalyst reactor with the fixed bed form.
Raw material hexalin and cis-butenedioic anhydride before they are passed through catalyzer, can be vaporized in vaporizer.Raw material is preferably in the carrier gas stream and is vaporized, can be for example adopted as carrier gas at this: rare gas, nitrogen or C 1-C 4Hydrocarbon, preferably methane and most preferably be hydrogen.
Carrier gas stream used during feed vaporization is preferably formed as the loop, that is to say, when breaking away from catalyst bed, in carrier gas stream, contain product, in a gas-liquid separator or after separated going out in the condenser, can be reused for the gasification of raw material, serve as carrier gas stream.
Gaseous phase crude product from reactor comes out after cooling and condensation, becomes the liquid crude product, gets final product sampling analysis, obtains its crude product and constitutes, and grasps the activity and the selectivity of catalyzed reaction.Crude product can be handled by traditional mode, by fractional distillation, removes by product, obtains qualified product.
The present invention compared with prior art has following advantage:
(1) is that two reactions of carrying out are respectively lumped together, avoided the hydrogen compressed of dehydrogenation gained in another reactor, to carry out hydrogenation again.
(2) dehydrogenation is thermo-negative reaction, and hydrogenation is thermopositive reaction, and the two coupling can be alleviated the heat effect in the reaction process.Coupling will be a process efficiently.
(3) hydrogenation dehydrogenation integrated process can be saved hydrogen producer.
(4) the present invention reacts required little energy, need not hydrogenation or reclaims hydrogen.
In the following embodiments, the transformation efficiency, the selectivity that provide are measured with vapor-phase chromatography.Because the integrated back of cyclohexanol dehydrogenation and maleic anhydride hydrogenation purpose product is pimelinketone and gamma-butyrolactone, so the selectivity of pimelinketone and gamma-butyrolactone is calculated by the following method:
Pimelinketone selectivity=100%* (mole number of pimelinketone in the product)/(mole number of the hexalin that has transformed)
Gamma-butyrolactone selectivity=100%* (mole number of gamma-butyrolactone in the product)/(mole number of the cis-butenedioic anhydride that has transformed)
Embodiment
Comparative Examples 1 preparing gamma-butyrolactone from cis-aldehyde by ordinary-pressure gas-phase hydrogenation
(1) catalyst preparation process: take by weighing needed cupric nitrate and zinc nitrate, being neutralized to the pH value with sodium carbonate solution is 7-8, throw out after filtration, washing, dry, 400 ℃ of calcinings, add 1% Graphite Powder 99 compression molding at last, obtain required catalyst sample.Each constituent mass percentage composition of this example catalyst system therefor is: CuO 60%, and ZnO 40%
(2) reactivity worth:
Catalyst activity evaluation and stability test are all carried out on fixed bed evaluating apparatus (being commonly called as small testing device).Wherein reactor is made by the stainless steel tube of internal diameter 12mm, long 500mm, and there is  4mm Thermal couple casing pipe at the center, and metal sleeve is arranged outward, is tied with electric stove wire on it.Temperature of reaction is measured by the  1mm armoured thermocouple that inserts center sleeve, and controls with temperature controller (passing through solid state relay).Each catalyzer (20-40 order) 5 grams of packing into, about 4.5 milliliters estimated.The about 50mm of catalyst bed layer height is positioned at the reaction tubes constant temperature zone.The activity rating procatalyst need be used hydrogen reducing, reducing gas air speed>500h -1The reduction process bed heats up gradually, ℃ approximately needs 30 hours by room temperature to 270.Reduction finishes, and can feed intake.
Normal pressure, hydrogen acid anhydride than 35, liquid air speed 0.06hr -1Condition under, when temperature of reaction was 260 ℃, the cis-butenedioic anhydride transformation efficiency was 97.6%, gamma-butyrolactone selectivity 85.5%.When temperature of reaction was 280 ℃, the cis-butenedioic anhydride transformation efficiency was 98.2%, gamma-butyrolactone selectivity 85.3%.In the reaction operation process, need continuous hydrogen make-up.
Comparative Examples 2 hexalin normal pressure preparing cyclohexanone by dehydrogenating
Catalyst loading is in the gas phase fixed-bed reactor, at normal pressure, hydrogen alcohol ratio 9, liquid air speed 0.3hr -1Condition under, when temperature of reaction was 260 ℃, the hexalin transformation efficiency was 52.8%, pimelinketone selectivity 85.9%.When temperature of reaction was 280 ℃, the hexalin transformation efficiency was 65.0%, pimelinketone selectivity 80.5%.In the normal reaction process, need constantly toward the outer emptying hydrogen of the recycle system.All the other are with Comparative Examples 1.
Embodiment 1
In the gas phase fixed-bed reactor (the catalyzer composition and activating and reducing and structure of reactor adorned with comparison example 1), Qi Hua hexalin, cis-butenedioic anhydride enter reactor after mixing by 6.3: 1 mol ratios and circulating hydrogen respectively.In normal pressure, the total air speed of liquid is 0.4hr -1, circulating hydrogen and mixing raw material mole ratio be that when temperature was 260 ℃, the hexalin transformation efficiency was 53.3%, cis-butenedioic anhydride transformation efficiency 99.0%, pimelinketone selectivity 92.6%, gamma-butyrolactone selectivity 89.5% under 7: 1 the condition; When temperature of reaction was 280 ℃, the hexalin transformation efficiency was 66.1%, cis-butenedioic anhydride transformation efficiency 99.5%, pimelinketone selectivity 91.3%, gamma-butyrolactone selectivity 87.8%; Run well after the reaction, need not extraneous hydrogen supply gas.
Embodiment 2
In the gas phase fixed-bed reactor (the catalyzer composition and activating and reducing and structure of reactor adorned with Comparative Examples 1), 270 ℃ of reaction pressure normal pressure, temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 6: 1 mol ratios respectively, the mole ratio of circulating hydrogen and mixing raw material is 15: 1, and the total air speed of liquid is about 0.4hr -1Condition, hexalin transformation efficiency 58.1%, cis-butenedioic anhydride transformation efficiency 99.3%, pimelinketone selectivity 92.0%, gamma-butyrolactone selectivity 88.2%.
Embodiment 3
In the gas phase fixed-bed reactor (the catalyzer composition and activating and reducing and structure of reactor adorned with comparison example 1), under the normal pressure, 290 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 4.5: 1 mol ratios respectively, circulating hydrogen and mixing raw material mole ratio are 10: 1, and the total air speed of liquid is about 0.5hr -1Condition, hexalin transformation efficiency 75.8%, cis-butenedioic anhydride transformation efficiency 98.8%, pimelinketone selectivity 89.0%, gamma-butyrolactone selectivity 86.8%.
Embodiment 4
In the gas phase fixed-bed reactor (the catalyzer composition and activating and reducing and structure of reactor adorned with comparison example 1), under the normal pressure, 270 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 6: 1 mol ratios respectively, circulating hydrogen and mixing raw material mole ratio are 49: 1, and the total air speed of liquid is about 0.4hr -1Condition, hexalin transformation efficiency 57.0%, cis-butenedioic anhydride transformation efficiency 99.5%, pimelinketone selectivity 92.2%, gamma-butyrolactone selectivity 88.8%.
Embodiment 5
(each constituent mass percentage composition of this example catalyst system therefor is: CuO 57%, and ZnO 43% in the gas phase fixed-bed reactor.Method for preparing catalyst, activating and reducing and structure of reactor are with comparison example 1), under the normal pressure, 270 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 6.1: 1 mol ratios respectively, circulating hydrogen and mixing raw material mole ratio are 50: 1, and the total air speed of liquid is about 0.4hr -1Condition, hexalin transformation efficiency 56.8%, cis-butenedioic anhydride transformation efficiency 99.0%, pimelinketone selectivity 91.2%, gamma-butyrolactone selectivity 87.8%.
Embodiment 6
(each constituent mass percentage composition of this example catalyst system therefor is: CuO 47%, and ZnO 53% in the gas phase fixed-bed reactor.Method for preparing catalyst, activating and reducing and structure of reactor are with comparison example 1), under the normal pressure, 270 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 5.8: 1 mol ratios respectively, circulating hydrogen and mixing raw material mole ratio are 10: 1, and the total air speed of liquid is about 0.4hr -1Condition, hexalin transformation efficiency 59.3%, cis-butenedioic anhydride transformation efficiency 99.6%, pimelinketone selectivity 92.0%, gamma-butyrolactone selectivity 86.9%.
Embodiment 7
The composition of this example catalyst system therefor; Copper is with the CuO restatement, and CuO 51%, and Cr is with Cr 2O 3Meter 49%, caking agent about 1%.The catalyzer method for making: copper nitrate solution and chromic acid solution neutralize, and regulate acid-basicity with ammoniacal liquor simultaneously, obtain that precipitation is washed, drying, and 350 ℃ of roastings add caking agent and carry out moulding.Catalyst activation reduction and structure of reactor are with comparison example 1.Under the normal pressure, 260 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 5.8: 1 mol ratios respectively, and circulating hydrogen and mixing raw material mole ratio are 5: 1, and the total air speed of liquid is about 0.4hr -1Condition, hexalin transformation efficiency 56.3%, cis-butenedioic anhydride transformation efficiency 99.2%, pimelinketone selectivity 94.0%, gamma-butyrolactone selectivity 90.0%.
Embodiment 8
This example catalyst system therefor, its composition (weight percent) CuO 49%, CaO 2%, Cr 2O 348%, caking agent 1%, its method for making is with embodiment 7.Catalyst activation reduction and structure of reactor are with comparison example 1.Under the normal pressure, 265 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 6: 1 mol ratios respectively, and circulating hydrogen and mixing raw material mole ratio are 7: 1, and the total air speed of liquid is about 0.4hr -1Condition, hexalin transformation efficiency 57.0%, cis-butenedioic anhydride transformation efficiency 99.3%, pimelinketone selectivity 94.2%, gamma-butyrolactone selectivity 90.5%.。
Embodiment 9
This example catalyst system therefor, its composition (weight percent) is CuO 20%, SiO 280%; The preparation method: with the copper carbonate solution impregnating carrier of dropping ammonia, the carrier of dipping is at 110 ℃, 450 ℃ of roastings.Catalyst activation reduction and structure of reactor are with comparison example 1.Under the normal pressure, 275 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 5.2: 1 mol ratios respectively, and circulating hydrogen and mixing raw material mole ratio are 7: 1, and the total air speed of liquid is about 0.3hr -1Condition, hexalin transformation efficiency 64.0%, cis-butenedioic anhydride transformation efficiency 99.6%, pimelinketone selectivity 92.2%, gamma-butyrolactone selectivity 87.5%.
Embodiment 10
This example catalyst system therefor, its composition (mass percent) is 22% for CuO, gac 78%; The preparation method: with the copper liquid impregnated carrier that drips sal volatile, the carrier of dipping is 110 ℃ of dryings, 400 ℃ of roastings (protecting in the oxide gas).Catalyst activation reduction and structure of reactor are with comparison example 1.Under the normal pressure, 287 ℃ of temperature of reaction, Qi Hua hexalin, cis-butenedioic anhydride were by 5: 1 mol ratios respectively, and circulating hydrogen and mixing raw material mole ratio are 20: 1, and the total air speed of liquid is about 0.5hr -1Condition, hexalin transformation efficiency 69.9%, cis-butenedioic anhydride transformation efficiency 99.8%, pimelinketone selectivity 89.8%, gamma-butyrolactone selectivity 87.0%.

Claims (11)

1, the method for a kind of preparation of coupling gamma-butyrolactone and pimelinketone, the mixture that it is characterized in that these two kinds of compounds of hexalin and cis-butenedioic anhydride is under gas phase condition, on the hydrogenation catalyst, the mol ratio of circulating hydrogen/hexalin and cis-butenedioic anhydride mixture is 5-60, hexalin/cis-butenedioic anhydride mol ratio 3-10, reaction pressure is a normal pressure, carries out dehydrogenation hydrogenation integrated reacting under the temperature of reaction 220-350 ℃ of condition, generates gamma-butyrolactone and pimelinketone.
2, the method for a kind of according to claim 1 preparation of coupling gamma-butyrolactone and pimelinketone, the mol ratio that it is characterized in that circulating hydrogen/hexalin and cis-butenedioic anhydride mixture is 5-50, and hexalin/cis-butenedioic anhydride mol ratio is 4-7, and temperature of reaction is 250-300 ℃.
3. the method for a kind of preparation of coupling gamma-butyrolactone according to claim 1 and 2 and pimelinketone is characterized in that described catalyzer is the copper containing carrier catalyzer of cupric precipitation hydrogenation catalyst or dipping that passes through solid support material or coating preparation.
4. the method for a kind of preparation of coupling gamma-butyrolactone according to claim 3 and pimelinketone is characterized in that the cupric oxide content of described cupric precipitation hydrogenation catalyst accounts for the 25-80%wt of total catalyst weight.
5. the method for a kind of preparation of coupling gamma-butyrolactone according to claim 4 and pimelinketone is characterized in that the cupric oxide content of described cupric precipitation hydrogenation catalyst accounts for the 45-70%wt of total catalyst weight.
6. the method for a kind of preparation of coupling gamma-butyrolactone according to claim 3 and pimelinketone is characterized in that the cupric oxide content of the copper containing carrier hydrogenation catalyst of described dipping preparation by solid support material accounts for the 1-30% of total catalyst weight.
7. the method for a kind of preparation of coupling gamma-butyrolactone according to claim 6 and pimelinketone is characterized in that the cupric oxide content of the copper containing carrier hydrogenation catalyst of described dipping preparation by solid support material accounts for the 3-25% of total catalyst weight.
8,, it is characterized in that described solid support material is oxide compound, the titanyl compound of aluminium, oxide compound, zirconium dioxide, silicon-dioxide, diatomite, silica gel, shale soil, magnesium silicate, aluminosilicate, ZSM-5 zeolite, ZSM-10 zeolite or the gac of zinc according to the method for claim 6 or 7 described a kind of preparation of coupling gamma-butyrolactone and pimelinketone.
9, the method for a kind of preparation of coupling gamma-butyrolactone according to claim 8 and pimelinketone is characterized in that described solid support material is aluminum oxide, titanium dioxide, zinc oxide, zirconium dioxide, gac or silicon-dioxide.
10, the method for a kind of preparation of coupling gamma-butyrolactone according to claim 1 and 2 and pimelinketone, the mixture that it is characterized in that these two kinds of compounds of described hexalin and cis-butenedioic anhydride is to be vaporized in the carrier gas stream at gas phase condition, and carrier gas is: rare gas, nitrogen, C1-C4 hydrocarbon or hydrogen.
11, the method for a kind of preparation of coupling gamma-butyrolactone according to claim 10 and pimelinketone is characterized in that described carrier gas is methane or hydrogen.
CNB2005100481905A 2005-12-14 2005-12-14 Method for preparing gamma-butyrolactone and cyclohexanone by couple process CN100335473C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2005100481905A CN100335473C (en) 2005-12-14 2005-12-14 Method for preparing gamma-butyrolactone and cyclohexanone by couple process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2005100481905A CN100335473C (en) 2005-12-14 2005-12-14 Method for preparing gamma-butyrolactone and cyclohexanone by couple process

Publications (2)

Publication Number Publication Date
CN1789255A CN1789255A (en) 2006-06-21
CN100335473C true CN100335473C (en) 2007-09-05

Family

ID=36787404

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2005100481905A CN100335473C (en) 2005-12-14 2005-12-14 Method for preparing gamma-butyrolactone and cyclohexanone by couple process

Country Status (1)

Country Link
CN (1) CN100335473C (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103030539B (en) * 2012-12-09 2015-03-04 南京化工职业技术学院 Method for simultaneous production of methyl ethyl ketone and cyclohexane

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021490A (en) * 1975-10-14 1977-05-03 Phillips Petroleum Company Process for production of phenol and cyclohexanone
CN1035819A (en) * 1988-03-07 1989-09-27 三井石油化学工业株式会社 The production method of phenol and/or pimelinketone
CN1053442C (en) * 1993-08-10 2000-06-14 阿克佐诺贝尔公司 Process for producing gamma-butyrolactone

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021490A (en) * 1975-10-14 1977-05-03 Phillips Petroleum Company Process for production of phenol and cyclohexanone
CN1035819A (en) * 1988-03-07 1989-09-27 三井石油化学工业株式会社 The production method of phenol and/or pimelinketone
CN1053442C (en) * 1993-08-10 2000-06-14 阿克佐诺贝尔公司 Process for producing gamma-butyrolactone

Also Published As

Publication number Publication date
CN1789255A (en) 2006-06-21

Similar Documents

Publication Publication Date Title
CA2899318C (en) Production of higher alcohols
CN1021636C (en) Improved aldehyde hydrogenation catalyst and process
RU2484895C2 (en) Method of regenerating catalyst used in dehydration of glycerol
EP2809643B1 (en) Ethyl acetate production
Li et al. Synthesis of methyl methacrylate by aldol condensation of methyl propionate with formaldehyde over acid–base bifunctional catalysts
CN105358521B (en) carbonylation method
US9862664B2 (en) Process for the production of alkenols and use thereof for the production of 1,3-butadiene
US10081588B2 (en) Production of butyl acetate from ethanol
CN102245549B (en) An improved process for hydrogenating alkyl ester(s) in the presence of carbon monoxide
RU2692477C2 (en) Method of producing dienes
CN103702963A (en) Improved process of dehydration reactions
KR20110058002A (en) Process for preparing of n-methyl pyrrolidone from 1,4-butanediol
KR101125853B1 (en) Process for preparing of n-methyl pyrrolidone
CN1021049C (en) Vapor-phase hydrogenation of maleic anhydride to tetrahydrofuran and gamma-butyrolactone
WO2004060843A1 (en) Process for producing alcohol and/or ketone
CN1047104C (en) Catalyzer for direct synthesis of aromatic hydrocarbon from methane and its application of in building-up reaction
CN100335473C (en) Method for preparing gamma-butyrolactone and cyclohexanone by couple process
CN1962574A (en) Process for producing cyclohexene
CN106582788A (en) Modified ZSM-5 molecular sieve, preparation method, and synthetic method for catalytically preparing 3-methyl-3-butene-1-alcohol
US4115462A (en) Gas phase aromatic hydrogenation using palladium lithium aluminum spinel catalyst
CN1109027C (en) Process for preparing gamma-butyrolactone
CN101032693A (en) Catalyst for producing pyridine alkali and its preparation method
CN1198811C (en) Method for the preparation of coupling gamma-butyrolactone and silvan
CN1704160A (en) Catalyst for hydrogen oxidation reaction in ethylbenzene dehydrogenation process
CN1789256A (en) Preparation of 2-methylfuran and cyclohexanone by couple method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
C14 Grant of patent or utility model
TR01 Transfer of patent right

Effective date of registration: 20081017

Address after: 3, building 1, Tsinghua Science and Technology Park, No. 609, Zhongguancun East Road, Beijing, Haidian District

Patentee after: Synefuels China Inc.

Address before: 165 mailbox, Taiyuan City, Shanxi Province

Patentee before: Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences

C41 Transfer of patent application or patent right or utility model
ASS Succession or assignment of patent right

Owner name: ZHONGKE OIL PROJECT CO., LTD.

Free format text: FORMER OWNER: SHANXI INST. OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES

Effective date: 20081017

C56 Change in the name or address of the patentee
CP02 Change in the address of a patent holder

Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park

Patentee after: Synefuels China Inc.

Address before: 100195, Haidian District Zhongguancun East Road, No. 1, building 3, Tsinghua Science and Technology Park, pioneering building, 609, Beijing

Patentee before: Synefuels China Inc.

Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park

Patentee after: Synefuels China Inc.

Address before: 100195, Haidian District Zhongguancun East Road, No. 1, building 3, Tsinghua Science and Technology Park, pioneering building, 609, Beijing

Patentee before: Synefuels China Inc.

CP01 Change in the name or title of a patent holder

Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park

Patentee after: SYNFUELS CHINA

Address before: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park

Patentee before: Synefuels China Inc.

Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park

Patentee after: SYNFUELS CHINA

Address before: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park

Patentee before: Synefuels China Inc.

C56 Change in the name or address of the patentee

Owner name: SYNEFUELS CHINA CO., LTD.

Free format text: FORMER NAME: SYNEFUELS CHINA INC.

CP03 Change of name, title or address
CP03 Change of name, title or address

Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone Park south two Street No. 1

Patentee after: SYNEFUELS CHINA Inc.

Address before: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park

Patentee before: SYNFUELS CHINA