CN102757305B - Method of oxidizing cyclohexane - Google Patents
Method of oxidizing cyclohexane Download PDFInfo
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- CN102757305B CN102757305B CN201110111313.0A CN201110111313A CN102757305B CN 102757305 B CN102757305 B CN 102757305B CN 201110111313 A CN201110111313 A CN 201110111313A CN 102757305 B CN102757305 B CN 102757305B
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- tubular reactor
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- 238000000034 method Methods 0.000 title claims abstract description 70
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000012528 membrane Substances 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 239000011344 liquid material Substances 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 239000011343 solid material Substances 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 150000002825 nitriles Chemical group 0.000 claims description 16
- 230000004888 barrier function Effects 0.000 claims description 14
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 4
- CFXQEHVMCRXUSD-UHFFFAOYSA-N 1,2,3-Trichloropropane Chemical compound ClCC(Cl)CCl CFXQEHVMCRXUSD-UHFFFAOYSA-N 0.000 claims description 4
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 230000000274 adsorptive effect Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- PFKLDGNDUZQYMM-UHFFFAOYSA-N 1,1,5-trichloropentane Chemical class ClCCCCC(Cl)Cl PFKLDGNDUZQYMM-UHFFFAOYSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- IGMIMBPUIOBFPU-UHFFFAOYSA-N 1,2,5-trichloropentane Chemical class ClCCCC(Cl)CCl IGMIMBPUIOBFPU-UHFFFAOYSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- PQBOTZNYFQWRHU-UHFFFAOYSA-N 1,2-dichlorobutane Chemical compound CCC(Cl)CCl PQBOTZNYFQWRHU-UHFFFAOYSA-N 0.000 claims description 2
- PPLBPDUKNRCHGG-UHFFFAOYSA-N 1,2-dichloropentane Chemical compound CCCC(Cl)CCl PPLBPDUKNRCHGG-UHFFFAOYSA-N 0.000 claims description 2
- QMLLRWZQACTYAX-UHFFFAOYSA-N 1,3-dichloropentane Chemical compound CCC(Cl)CCCl QMLLRWZQACTYAX-UHFFFAOYSA-N 0.000 claims description 2
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 claims description 2
- IJZUPZAYWWVHIO-UHFFFAOYSA-N 1,4-dichloropentane Chemical compound CC(Cl)CCCCl IJZUPZAYWWVHIO-UHFFFAOYSA-N 0.000 claims description 2
- MNXVHBFCELLVBA-UHFFFAOYSA-N 2,2-dichloropentane Chemical compound CCCC(C)(Cl)Cl MNXVHBFCELLVBA-UHFFFAOYSA-N 0.000 claims description 2
- ZEOVXNVKXIPWMS-UHFFFAOYSA-N 2,2-dichloropropane Chemical compound CC(C)(Cl)Cl ZEOVXNVKXIPWMS-UHFFFAOYSA-N 0.000 claims description 2
- RMISVOPUIFJTEO-UHFFFAOYSA-N 2,3-dichlorobutane Chemical compound CC(Cl)C(C)Cl RMISVOPUIFJTEO-UHFFFAOYSA-N 0.000 claims description 2
- HVFJQRZGBBKTPL-UHFFFAOYSA-N 2,3-dichloropentane Chemical compound CCC(Cl)C(C)Cl HVFJQRZGBBKTPL-UHFFFAOYSA-N 0.000 claims description 2
- DYGOBGYJRRKFEN-UHFFFAOYSA-N 2,4-dichloropentane Chemical compound CC(Cl)CC(C)Cl DYGOBGYJRRKFEN-UHFFFAOYSA-N 0.000 claims description 2
- MOUDFOLIRVUWKC-UHFFFAOYSA-N 3,3-dichloropentane Chemical compound CCC(Cl)(Cl)CC MOUDFOLIRVUWKC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 14
- 239000002808 molecular sieve Substances 0.000 abstract description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052719 titanium Inorganic materials 0.000 abstract description 8
- 239000010936 titanium Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 24
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 22
- 230000009466 transformation Effects 0.000 description 22
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 230000001020 rhythmical effect Effects 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 5
- 229960002163 hydrogen peroxide Drugs 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012857 repacking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001915 proofreading effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000010530 solution phase reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method of oxidizing cyclohexane, wherein the method is performed in a membrane tube reactor; the membrane tube reactor comprises a plurality of tubular reactors and membrane structures; the outlet end of each tubular reactor is hermetically connected with one membrane structure; and each membrane structure is arranged to allow a liquid material in each tubular reactor to pass through but not allow a solid material to pass through. The method comprises the following steps of: feeding the liquid feed material containing the cyclohexane, a hydrogen peroxide aqueous solution and an organic solvent into the tubular reactors from a feed port of the membrane tube reactor to be in contact with titanium silicalite molecular sieves in the tubular reactors under an oxidation reaction condition; and performing solid-liquid separation on a product obtained after the contact through the membrane structure which is hermetically connected with the outlet end of each tubular reactor to obtain the liquid material. By using the method, continuous reaction can also be realized by only using the titanium silicalite molecular sieve without a performed catalyst, the speed of oxidation reaction of the cyclohexane is increased, reaction and separation can be performed simultaneously by using the method, and the separation cost after oxidation of the cyclohexane is effectively reduced.
Description
Technical field
The present invention relates to a kind of method of cyclohexane oxidation.
Background technology
Pimelinketone, hexalin, as important industrial chemicals, are widely used in the every field such as fiber, synthetic rubber, industrial coating, medicine, agricultural chemicals, organic solvent.Along with developing rapidly of polymeric amide industry, as pimelinketone, the hexalin of preparing nylon 6 and nylon 66 intermediates, the annual demand in the whole world is all more than 2,000,000 tons.
For the demand, investigator is devoted to develop efficient, free of contamination pimelinketone (alcohol) production technique always both at home and abroad, investigator thinks taking hydrogen peroxide as oxygenant, the technique of taking HTS as catalyzer being prepared by cyclohexane oxidation to pimelinketone (alcohol) meets the requirement of Green Chemistry and atom economy idea of development, is a kind of green cyclohexane oxidation technique that has development prospect.
The influence factor of titanium molecular sieve catalysis oxidizing ethyle alkyl reaction is a lot, as the character of HTS itself, oxidants hydrogen peroxide H
2o
2character, the selection of solvent, reaction conditions (as temperature, proportioning raw materials, reaction pressure etc.) etc., investigator is in order to improve the selectivity of pimelinketone in cyclohexane oxidation process, mainly be devoted to exploitation titanium-silicon molecular sieve catalyst (as the hollow HTS HTS with MFI structure of Research Institute of Petro-Chemical Engineering's exploitation) more efficiently, and the reaction conditions of optimizing in this process is realized aforementioned target.
Although the research of existing more titanium molecular sieve catalysis oxidizing ethyle alkyl reaction at present, major part only rests on the research of laboratory stage, still cannot realize serialization industrial production.Trace it to its cause or be too harsh to the requirement of equipment, or be that energy consumption is high but productive rate is low, separation difficulty etc.
Therefore technique, how to develop a set of titanium molecular sieve catalysis oxidizing ethyle alkyl reaction that is applicable to industrial continuous production will be in the future about HTS/H
2o
2the emphasis striving direction of the research of cyclohexane oxidation in system.
And the most important thing of developing the technique of the titanium molecular sieve catalysis oxidizing ethyle alkyl reaction that is applicable to industrial continuous production is also the equipment that this reaction is carried out continuously that is applicable to of development of new.
Summary of the invention
The object of the invention is a kind of method for cyclohexane oxidation that is applicable to industrial application is provided.
HTS/H
2o
2there is solid-liquid two-phase in the cyclohexane oxidation in system, generally speaking, what rhythmic reaction all adopted is that HTS is as catalyzer, therefore,, in rhythmic reaction system, the mixture of reaction mass, reaction product and catalyzer is slurry state, after completing, reaction by filtering, solid-liquid two is separated, and can reaction mass and reaction product be separated by separation means such as distillations, for rhythmic reaction, can only solid-liquid be separated by manual operation, although there is not the problem of above-mentioned solid-liquid separation difficulty in successive reaction, but will realize at present successive reaction generally can react in fixed bed, and it is well-known, in fixed bed, catalyzer must be carried out to moulding just can react, just there is a very large problem in this, preformed catalyst not only needs to waste time and energy HTS is carried out to moulding, and because there is a large amount of sizing agents in catalyzer after moulding, the speed of its catalysis has greatly slowed down, therefore in industry, to obtain the time that high transformation efficiency need to be longer, no matter be that rhythmic reaction or successive reaction all exist above-mentioned all defects based on prior art, whether the present inventor attempts imagination and can propose a kind of without adopting the preformed catalyst also can continuous the carrying out of realization response, and in reaction, can realize the technique of more effective solid-liquid separation.Manufacture the present invention based on this imagination.
To achieve these goals, the invention provides a kind of method of cyclohexane oxidation, the method is carried out in a kind of film pipe reactor (as shown in Figure 1), described film pipe reactor comprises tubular reactor and membrane structure, the exit end of described tubular reactor and described membrane structure are tightly connected, described membrane structure be set to allow liquid material in described tubular reactor by and do not allow solid materials to pass through, the method is included under oxidation reaction condition, to contain hexanaphthene, the liquid feeding of aqueous hydrogen peroxide solution and organic solvent is sent into tubular reactor from the opening for feed of film pipe reactor, contact with the HTS in tubular reactor, product after contact carries out solid-liquid separation by the membrane structure being tightly connected with the exit end of described tubular reactor, obtain liquid material.
Adopt method of the present invention to carry out HTS/H
2o
2the oxidizing reaction of the hexanaphthene in system, do not need preformed catalyst and only need use HTS just can realize continuous reaction, this has accelerated the speed of this oxidizing reaction undoubtedly greatly, and adopt method of the present invention limit coronite to separate, greatly reduce the separation costs after cyclohexane oxidation, as can be seen here, method of the present invention is highly suitable for HTS/H
2o
2the suitability for industrialized production of the cyclohexane oxidation in system.
Brief description of the drawings
The schematic diagram of the equipment that Fig. 1 adopts for a kind of concrete embodiment according to the present invention.
Embodiment
Further describe method provided by the invention below in conjunction with accompanying drawing.
The invention provides a kind of method of cyclohexane oxidation, the method is carried out in a kind of film pipe reactor (as shown in Figure 1), described film pipe reactor comprises tubular reactor 1 and membrane structure 2, the exit end of described tubular reactor 1 and described membrane structure 2 are tightly connected, described membrane structure 2 be set to allow liquid material in described tubular reactor 1 by and do not allow solid materials to pass through, the method is included under oxidation reaction condition, to contain hexanaphthene, the liquid feeding of aqueous hydrogen peroxide solution and organic solvent is sent into tubular reactor 1 from the opening for feed of film pipe reactor, contact with the HTS in tubular reactor 1, product after contact carries out solid-liquid separation by the membrane structure 2 being tightly connected with the exit end of described tubular reactor 1, obtain liquid material.
Method of the present invention can successive reaction also can rhythmic reaction, and normally under the condition of successive reaction, carry out in industrial application process, therefore, under preferable case, method of the present invention adopts successive reaction.
The method according to this invention, as long as being tightly connected, the exit end of described film pipe reactor and described membrane structure 2 can realize object of the present invention, but under preferable case, described equipment comprises two described membrane structures 2, the two ends of tubular reactor 1 are tightly connected with a described membrane structure 2 respectively, this tubular reactor 1 can be horizontal reactor thus, also can be vertical reactor, and while being vertical reactor, can adopt stream mode or downward stream mode charging on reaction mass, stream mode charging in preferred feed.
According to the present invention, the present invention to the various parameters of described membrane structure without particular requirement, as long as ensure that exit end and the described membrane structure 2 of described tubular reactor 1 is tightly connected, described membrane structure 2 be set to allow liquid material in described tubular reactor 1 by and do not allow solid materials to pass through.Generally speaking, the membrane structure with above-mentioned functions can be filtering membrane or film pipe, described filtering membrane or film pipe all can be manufactured according to prior art, as long as the parameter requirement according to the invention of the membrane structure arranging, and described in there is the membrane structure of above-mentioned functions important parameter aperture also can select according to the size of concrete adopted catalyst Ti-si molecular sieves particle, generally speaking the aperture of described membrane structure 2 is 5-500nm, is preferably 10-100nm.In the time that described membrane structure is film pipe, this film pipe can, for being positioned at the inside of the exit end of tubular reactor 1 completely, also can make one end of film pipe and tubular reactor 1 be tightly connected, and the other end stretches out the outside of tubular reactor 1.
The present invention, can carry out with reference to prior art without particular requirement the described method being tightly connected, and does not repeat them here.
According to equipment of the present invention, in order to make equipment of the present invention be more applicable for industrial applications, described tubular reactor 1 is divided at least two sections, between adjacent two sections, separate by barrier film 3, this barrier film 3 be set to allow liquid material in described tubular reactor 1 by and do not allow solid materials to pass through.
According to the present invention, the present invention to the material of described barrier film 3 without particular requirement, as long as can meet aforementioned requirement of the present invention, and the present inventor thinks, based on foregoing description of the present invention, the needs that those skilled in the art can practical situation are selected barrier film, as being set to have identical aperture by barrier film, also can be according to concrete need of production, barrier film is set to different apertures.
According to the present invention, under preferable case, described tubular reactor 1 can be divided into 2-50 section, and the length of every section can be set to 0.2-5m.Between adjacent two sections, can be directly contact, also can, according to plant location needs, install and production operation for ease of equipment, between adjacent two sections, also can have interval, those skilled in the art all can know this, not repeat them here.
According to the present invention, for ensureing that membrane structure 2 and barrier film 3 are not stopped up by titanium-silicon molecular sieve catalyst, under preferable case, described film pipe reactor also comprises recoiling device (not shown), and described recoiling device is for providing gas stream or liquid stream that described membrane structure 2 and barrier film 3 are carried out to back flushing.The present invention to described recoiling device without particular requirement, as long as thereby can realize for providing and described membrane structure 2 and barrier film 3 are carried out to the gas stream of back flushing or liquid stream realize described membrane structure 2 and barrier film 3 are carried out to back flushing.
According to the present invention, the flow of described gas stream or liquid stream can be selected according to factors such as liquid hourly space velocity, catalyst particle size and catalyst concns, and the flow of gas stream or liquid stream can regulate manually or automatically according to practical situation, those skilled in the art all can know this, not repeat them here.
According to the present invention, described gas stream can be the various gas that does not participate in oxidizing reaction, for example, can be rare gas element, and described liquid stream is preferably hexanaphthene, described organic solvent or described liquid material.
The method according to this invention, in order to be more applicable for the serialization operation of a whole set of cyclohexane oxidation technique, described film pipe reactor can also comprise the separating unit 4 for reaction mass is separated with reaction product.This separating unit 4 can be the various devices that can realize the separation of liquid liquid, under preferable case, this separating unit 4 can comprise opening for feed, product discharge port and reaction mass discharge port, and under preferable case, the opening for feed of described separating unit is communicated with the discharge port of described tubular reactor, described reaction mass discharge port is communicated with the opening for feed of described tubular reactor, as shown in Figure 1.More have under selection condition, described separating unit is rectifying tower.While adopting this film pipe reactor, method of the present invention can also will be carried out rectifying to liquid material by described separating unit, obtain reaction mass and reaction product after separating, and the reaction mass after this separation is sent into tubular reactor 1 and recycled from the opening for feed of film pipe reactor.
According to the present invention, the condition of described oxidizing reaction can be conventional employing HTS/H
2o
2the oxidizing condition of system catalytic oxidation of cyclohexane, the mass ratio that generally comprises hexanaphthene, hydrogen peroxide, water and organic solvent is 1: 0.003-1: 0.001-5: 0.5-30, is preferably 1: 0.03-0.8: 0.1-3: 3-15; The temperature of contact is 30-150 DEG C, is preferably 50-120 DEG C; The pressure of contact is 0.01-2MPa, is preferably 0.1-0.5MPa, and liquid hourly space velocity is 0.5-10h
-1, be preferably 0.5-5h
-1; The weight ratio of liquid material and HTS is 1: 0.01-0.3, is preferably 1: 0.03-0.12.
In the present invention, described liquid hourly space velocity is the definition of the conventional liquid hourly space velocity using in this area, be a kind of representation of air speed, its meaning is the volume of unit reaction volume (for the reaction that adopts solid catalyst, being per volume of catalyst) treatment solution phase reaction thing per hour.
In the present invention, described pressure refers to the gauge pressure in reaction system.
According to the present invention, organic solvent can be conventional organic solvent, as being one or more in alcohol, ketone, acid, nitrile and halohydrocarbon.Described alcohol can be the alcohols materials such as methyl alcohol, ethanol, and described ketone can be the organic ketone materials such as acetone, butanone, and described acid can be the organic acid substances such as acetic acid.And the present inventor finds unexpectedly in research process, while adopting nitrile and/or halohydrocarbon as solvent, not only can increase substantially the transformation efficiency of hexanaphthene and the yield of hexalin, and adopt the reaction system separation of these two kinds of solvents to be more prone to, therefore the preferred described solvent of the present invention is aforesaid nitrile and/or halohydrocarbon.
The present inventor finds unexpectedly in research process, by mixed with halohydrocarbon described nitrile during for organic solvent, can make transformation efficiency and the hexalin yield of hexanaphthene obtain further raising, particularly preferably in situation, described organic solvent is the mixture of nitrile and halohydrocarbon, and the mass ratio that is preferably nitrile and halohydrocarbon is 0.1-10: 1.In the situation that organic solvent is above-mentioned mixed solvent, the temperature of described contact is preferably 50-120 DEG C, and more preferably 60-110 DEG C time, hexalin yield obviously improves.Although while adopting two kinds of solvents, the transformation efficiency of hexanaphthene, the yield of target product has further raising, but the reaction system of two kinds of solvents, can make troubles to follow-up mask work, therefore, generally speaking, can select whether to need to adopt two kinds of solvents to react according to the objectives in concrete industrial production, as mainly pursued aborning the words of the transformation efficiency of hexanaphthene and the yield of target product, can be chosen under the reaction system of aforementioned two kinds of solvents and react, otherwise, if integrated artistic requires comparatively strict words to sepn process, can be chosen under preferred a kind of solvent system and react, those skilled in the art all can know this, this is no longer going to repeat them.
All can realize object of the present invention although adopt above-mentioned nitrile and/or halogenated hydrocarbon solvent, under preferable case, described nitrile is mononitriles and/or the dinitrile of C1-C10, be preferably mononitriles and/or the dinitrile of C2-C8, further preferably, described nitrile is one or more in acetonitrile, propionitrile, valeronitrile, adiponitrile, is preferably acetonitrile and/or adiponitrile, described halohydrocarbon is the alkane of the C1-C10 that replaced by one and/or multiple identical or different halogen atom and/or the naphthenic hydrocarbon that is replaced C6-C10 by one and/or multiple identical or different halogen atom, the more preferably dichloro-alkane of C1-C6 and/or three chloroparaffins, more preferably methylene dichloride, trichloromethane, 1, 1-ethylene dichloride, 1, 2-ethylene dichloride, 1, 1, 1-trichloroethane, 1, 1, 2-trichloroethane, 1, 2-propylene dichloride, 2, 2-propylene dichloride, 1, 3-propylene dichloride, 1, 2, 3-trichloropropane, 1, 2-dichlorobutane, 2, 3-dichlorobutane, 1, 4-dichlorobutane, 1, 2-dichloropentane, 2, 2-dichloropentane, 1, 3-dichloropentane, 2, 3-dichloropentane, 3, 3-dichloropentane, 1, 4-dichloropentane, 2, 4-dichloropentane, 1, 2, 5-tri-chloropentanes, 1, 1, 5-tri-chloropentanes and 1, one or more in 2-dichloro hexanaphthene.
The present inventor studies discovery, and in the time that described solvent is nitrile, when the temperature of described contact is preferably 60-120 DEG C, the transformation efficiency of hexanaphthene and hexalin yield can further improve; Or in the time that described solvent is halohydrocarbon, when the temperature of described contact is 50-90 DEG C, the transformation efficiency of hexanaphthene and hexalin yield can further improve.
According to the present invention, HTS in described titanium-silicon molecular sieve catalyst can be conventional HTS, can for modification can be also non-modification, be preferably at least one in the HTS (as Ti-β) of HTS (as TS-2), BETA structure of HTS (as TS-1), the MEL structure of MFI structure; More preferably having structural formula is xTiO
2siO
2, wherein, x is 0.0001-0.04, is preferably 0.01-0.03, more preferably the HTS of 0.015-0.025.
In the present invention, described HTS can be commercially available, also can prepare, prepare the method for described HTS for conventionally known to one of skill in the art, for example, can be with reference to [Cyclohexane Oxidation Catalyzed by Titanium Silicalite (TS-1) With HydrogenPeroxide Journal of Natural Gas Chemistry 2001,10 (4): 295-307] the method preparation described in, also can make with reference to the method for disclosed Kaolinite Preparation of Catalyst in CN101279959A.
More preferably, the HTS in described titanium-silicon molecular sieve catalyst is MFI structure, and HTS crystal grain is hollow structure, and the radical length of the cavity part of this hollow structure is 5-300nm, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity that records under the condition of 1 hour is for being no less than 70 milligrams/gram, between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm, there is hysteresis loop, the HTS with said structure and character is commonly referred to as hollow HTS, the commercial HTS that is called, its correlation parameter and preparation method thereof can be referring to CN1301599A.
The following examples will be further described the present invention, but not thereby limiting the invention.
In comparative example and embodiment, reagent used is commercially available chemically pure reagent.
In embodiment, hollow HTS HTS used is that (Hunan Jian Chang company manufactures for the Industrial products of HTS described in CN1301599A, it is the HTS of MFI structure through X-ray diffraction analysis, between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, have hysteresis loop, crystal grain is that the radical length of hollow crystal grain and cavity part is 15-180nm; This sieve sample is at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recording under the adsorption time condition of 1 hour is 78 milligrams/gram), titanium oxide content is 2.5 % by weight.
In embodiment, traditional HTS (TS-1) used is by document [CyclohexaneOxidation Catalyzed by Titanium Silicalite (T S-1) With Hydrogen PeroxideJournal of Natural Gas Chemistry 2001,10 (4): 295-307] the 296th page of (TS-1) sieve sample that the capable described method of 9-24 is prepared in, the content of titanium oxide is 2.5 % by weight.
In the present invention, adopt gas-chromatography to carry out the analysis of each composition in system, undertaken quantitatively, all can carrying out with reference to prior art by proofreading and correct normalization method, calculate on this basis the transformation efficiency of reactant, the evaluation index such as yield and selectivity of product.
In the present invention, the transformation efficiency calculation formula of hexanaphthene is as follows:
The calculation formula of compositional selecting is as follows:
The calculation formula of component yield is as follows:
V
hexalin=S
hexalin× X
hexanaphthene
Wherein, X is transformation efficiency; S is selectivity; Y is yield; M is the quality of component; N is the amount of substance of component; Wherein m
0and n
0represent respectively quality and the molar weight before reaction.
In the embodiment of the present invention, all adopt the film pipe reactor shown in Fig. 1, wherein the total height of tubular reactor is 2m, the diameter of tubular reactor is 1.2cm, membrane structure (is produced the repacking of ceramic membrane with Nanjing Tian Ya membrane separation technique company limited, aperture is 100nm) be tightly connected with tubular reactor, and adopt three barrier films (to produce the repacking of ceramic membrane with Nanjing Tian Ya membrane separation technique company limited, aperture is 100nm), tubular reactor is evenly divided into 4 sections, and film pipe reactor of the present invention also comprises the separator (separator is rectifying tower) for separating of reaction mass and reaction product, the content of the HTS in film pipe reactor in every section of tubular reactor is identical.(providing temperature of reaction by being wound around heating zone on the tubular reactor at film pipe reactor).
Embodiment 1
According to hexanaphthene and hydrogen peroxide (concentration is 27.5 % by weight) and solvent 1, the ratio that the mass ratio of 2-propylene dichloride (96.8 DEG C of boiling points) is 1: 1.72: 15 is from the opening for feed continuously feeding of film pipe reactor, the weight ratio of HTS and liquid material is 0.04: 1, liquid hourly space velocity 1h
-1temperature in film pipe reactor is 60 DEG C, pressure is 0.2MPa, then the separating unit of sending into film pipe reactor from discharge port mixture is out carried out to separating of reaction product and reaction mass, reaction mass is continued to be fed in tubular reactor and reacted, sampling analysis after system stable operation 4h, records transformation efficiency, keto-alcohol selectivity and the hexalin yield of hexanaphthene in table 1.
Embodiment 2
Identical with the method for embodiment 1, different is that solvent is Isosorbide-5-Nitrae-dichloropentane, and the mass ratio of Isosorbide-5-Nitrae-dichloropentane and hexanaphthene is 5: 1, and the temperature in film pipe reactor is 80 DEG C, and transformation efficiency, keto-alcohol selectivity and the hexalin yield of hexanaphthene are in table 1.
Embodiment 3
Identical with the method for embodiment 1, different is that solvent is adiponitrile, and the mass ratio of adiponitrile and hexanaphthene is 10: 1, and the temperature in film pipe reactor is 110 DEG C, and transformation efficiency, keto-alcohol selectivity and the hexalin yield of hexanaphthene are in table 1.
Embodiment 4
Identical with the method for embodiment 3, different is that solvent is acetonitrile, and the temperature in film pipe reactor is 70 DEG C, and transformation efficiency, keto-alcohol selectivity and the hexalin yield of hexanaphthene are in table 1.
Embodiment 5
Identical with the method for embodiment 1, different, solvent is trichloromethane, and temperature of reaction is 50 DEG C.
Embodiment 6
Identical with the method for embodiment 1, different, solvent is 1,1,5-trichloropropane, and temperature of reaction is 90 DEG C.
Embodiment 7
Identical with the method for embodiment 1, different, solvent 1,2-propylene dichloride is replaced by the mixed solvent of 1,2-propylene dichloride and propionitrile, and the mass ratio of the two is 1: 1, and transformation efficiency, keto-alcohol selectivity and the hexalin yield of hexanaphthene are in table 1.
Embodiment 8
Identical with the method for embodiment 3, different is that solvent adiponitrile is replaced by the mixed solvent of 1,2-propylene dichloride and adiponitrile, heating medium is hexanaphthene, and the mass ratio of 1,2-propylene dichloride and adiponitrile is 1: 9, transformation efficiency, keto-alcohol selectivity and the hexalin yield of hexanaphthene are in table 1.
Embodiment 9
Identical with the method for embodiment 4, different is, and solvent acetonitrile is replaced by acetonitrile and 1,3-propylene dichloride, and the mass ratio of acetonitrile and 1,3-propylene dichloride is 1: 9, and transformation efficiency, keto-alcohol selectivity and the hexalin yield of hexanaphthene are in table 1.
Embodiment 10
Identical with the method for embodiment 1, different is solvent 1, and 2-propylene dichloride is replaced by n-propyl chloride, and transformation efficiency, keto-alcohol selectivity and the hexalin yield of hexanaphthene are in table 1.
Embodiment 11
Identical with the method for embodiment 1, different is that solvent is acetone, and transformation efficiency, keto-alcohol selectivity and the hexalin yield of hexanaphthene are in table 1.
Embodiment 12
Identical with the method for embodiment 1, different is that solvent is acetic acid, and transformation efficiency, keto-alcohol selectivity and the hexalin yield of hexanaphthene are in table 1.
Embodiment 13
Identical with the method for embodiment 1, different is that catalyzer is the catalyzer that contains conventional HTS (TS-1), and transformation efficiency, keto-alcohol selectivity and the hexalin yield of hexanaphthene are in table 1.
Table 1
| Embodiment | Cyclohexane conversion/% | Keto-alcohol selectivity/% | Hexalin yield/% |
| 1 | 74％ | 100％ | 59％ |
| 2 | 73％ | 100％ | 60％ |
| 3 | 73％ | 100％ | 61％ |
| 4 | 74％ | 100％ | 62％ |
| 5 | 73％ | 100％ | 60％ |
| 6 | 73％ | 100％ | 61％ |
| 7 | 78％ | 100％ | 69％ |
| 8 | 77％ | 100％ | 67％ |
| 9 | 78％ | 100％ | 66％ |
| 10 | 64％ | 100％ | 47％ |
| 11 | 47％ | 90％ | 17％ |
| 12 | 34％ | 85％ | 17％ |
| 13 | 24％ | 90％ | 14％ |
As can be seen from Table 2, adopt method of the present invention, the transformation efficiency of hexanaphthene and the yield of hexalin are all higher, and the present invention because react in film pipe reactor, effectively realize the beneficial effect that limit coronite separates, overcome rhythmic reaction solid-liquid separation difficulty, successive reaction is sluggish problem under the condition of preformed catalyst.
Claims (12)
1. the method for a cyclohexane oxidation, it is characterized in that, the method is carried out in a kind of film pipe reactor, described film pipe reactor comprises tubular reactor (1) and membrane structure (2), the exit end of described tubular reactor (1) and described membrane structure (2) are tightly connected, described membrane structure (2) be set to allow liquid material in described tubular reactor (1) by and do not allow solid materials to pass through, the method is included under oxidation reaction condition, to contain hexanaphthene, the liquid feeding of aqueous hydrogen peroxide solution and organic solvent is sent into tubular reactor (1) from the opening for feed of film pipe reactor, contact with the HTS in tubular reactor (1), product after contact carries out solid-liquid separation by the membrane structure (2) being tightly connected with the exit end of described tubular reactor (1), obtain liquid material, wherein, described organic solvent is nitrile and halohydrocarbon, the mass ratio of nitrile and halohydrocarbon is 0.1-10:1, described film pipe reactor also comprises recoiling device, described recoiling device is used for providing gas stream or liquid stream that described membrane structure (2) and barrier film (3) are carried out to back flushing, described gas stream is rare gas element, and described liquid stream is hexanaphthene, described organic solvent or described liquid material, the temperature of contact is 50-120 DEG C, described nitrile is mononitriles and/or the dinitrile of C1-C10, described halohydrocarbon is the alkane of C1-C10 and/or the naphthenic hydrocarbon of C6-C10 being replaced by and/or multiple identical or different halogen atom, described HTS is MFI structure, and HTS crystal grain is hollow structure, and the radical length of the cavity part of this hollow structure is 5-300nm, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recording under the condition of 1 hour is at least 70 milligrams/grams, between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm, has hysteresis loop.
2. method according to claim 1, wherein, described film pipe reactor comprises two described membrane structures (2), the two ends of tubular reactor (1) are tightly connected with a described membrane structure (2) respectively.
3. method according to claim 1, wherein, the aperture of described membrane structure (2) is 5-500nm.
4. method according to claim 1, wherein, described membrane structure (2) is filtering membrane or film pipe.
5. according to the method described in any one in claim 1-4, wherein, described tubular reactor (1) is divided at least two sections, between adjacent two sections, separate by barrier film (3), this barrier film (3) be set to allow liquid material in described tubular reactor (1) by and do not allow solid materials to pass through.
6. method according to claim 5, wherein, described tubular reactor (1) is divided into 2-50 section, and the length of every section is 0.2-5m.
7. method according to claim 1, wherein, the method also comprises carries out rectifying by described liquid material, obtains reaction mass and reaction product after separating, and the reaction mass after this separation is sent into tubular reactor (1) and recycled from the opening for feed of film pipe reactor.
8. method according to claim 1, wherein, the condition of described oxidizing reaction comprises that the mass ratio of hexanaphthene, hydrogen peroxide, water and organic solvent is 1:0.003-1:0.001-5:0.5-30, the pressure of contact is that 0.01-2MPa, liquid hourly space velocity are 0.5-10h
-1, the weight ratio of liquid material and HTS is 1:0.01-0.3.
9. method according to claim 1, wherein, the temperature of described contact is 60-110 DEG C.
10. method according to claim 1, wherein, the mononitriles that described nitrile is C2-C8 and/or dinitrile.
11. methods according to claim 10, wherein, described nitrile is one or more in acetonitrile, propionitrile, valeronitrile, adiponitrile; Described halohydrocarbon is dichloro-alkane and/or three chloroparaffins of C1-C6.
12. methods according to claim 11, wherein, described nitrile is acetonitrile and/or adiponitrile, described halohydrocarbon is methylene dichloride, trichloromethane, 1, 1-ethylene dichloride, 1, 2-ethylene dichloride, 1, 1, 1-trichloroethane, 1, 1, 2-trichloroethane, 1, 2-propylene dichloride, 2, 2-propylene dichloride, 1, 3-propylene dichloride, 1, 2, 3-trichloropropane, 1, 2-dichlorobutane, 2, 3-dichlorobutane, 1, 4-dichlorobutane, 1, 2-dichloropentane, 2, 2-dichloropentane, 1, 3-dichloropentane, 2, 3-dichloropentane, 3, 3-dichloropentane, 1, 4-dichloropentane, 2, 4-dichloropentane, 1, 2, 5-tri-chloropentanes, 1, 1, 5-tri-chloropentanes and 1, one or more in 2-dichloro hexanaphthene.
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| PCT/CN2012/074289 WO2012146146A1 (en) | 2011-04-29 | 2012-04-18 | Apparatus and method for oxidization of cyclohexane |
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