CN1226255C - Process for preparing cyclohexanol and cyclohexanone - Google Patents
Process for preparing cyclohexanol and cyclohexanone Download PDFInfo
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- CN1226255C CN1226255C CN 02113940 CN02113940A CN1226255C CN 1226255 C CN1226255 C CN 1226255C CN 02113940 CN02113940 CN 02113940 CN 02113940 A CN02113940 A CN 02113940A CN 1226255 C CN1226255 C CN 1226255C
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- cyclohexane
- hexanaphthene
- pimelinketone
- cyclohexanone
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Abstract
The present invention discloses a technology for preparing cyclohexanol and cyclohexanone, which is characterized in that the technology comprises the following steps: (A) under the action of a metalloporphyrin catalyst, cyclohexane is oxidized in a liquid phase by using oxygen-containing air at the temperature of 140 to 150 DEG C and in the pressure range of 0.8 to 1.0Mpa, the conversion rate is kept at most 10%, the reaction comprises a plurality of reaction stages which are carried out in a laminar-flow reactor, and the oxygen concentration in the liquid phase is kept in a certain limit; (B) an oxidation product is treated with alkali wash, the temperature is controlled between 80 to 90 DEG C, and organic acid and a catalyst in the product are removed; (C) after separation, 95% o cyclohexane is circulated again to an oxidative system by using an organic phase through a cyclohexane distilling system, the product is put in a cyclohexanone and cyclohexanol rectifying system to obtain effective products (cyclohexanone and cyclohexanol). By using the technology of the present invention, the conversion rate and the yield of cyclohexane can be increased, cyclohexane and alkali which are consumed by cyclohexanone can be reduced, and the energy consumption can be reduced. Because the technological route is shortened and the technological condition is simplified, the construction investment can be reduced, and the goal of environmental protection can be achieved.
Description
Technical field
The present invention relates to a kind of technology for preparing hexalin and pimelinketone by hexanaphthene.
Background technology
It is one of at present main in the world operational path that important production process of chemical product such as hexalin and pimelinketone are produced in industrial hexanaphthene liquid phase air oxidation.Many large-size chemicals company all presses for raising output always, reduces unit consumption and cost.Now the hexanaphthene liquid-phase air oxidation is produced the pimelinketone process unit and is made up of cyclohexane oxidation, decomposition, alkane distillation, recovery of heat, salkali waste separation, saponification, refining, dehydrogenation several sections, and wherein oxidized portion is the system that is connected into by five bubble stirring reactors.Fresh cyclohexane heats up through the preliminary heat exchange of heat recovery system, ℃ enter stills for air blowing by oxidation feed heater heats to 165 again, five stills for air blowing adopt the hexanaphthene series connection to add, the air continuous cascade reaction pattern that adds in parallel, the reacted tail gas aspiration that truncates after the heat recovery system heat exchange is received system, useful component in the tail gas all is absorbed, non-condensable gas tail gas is sent to flare system, reacted thick oxidation liquid (is mainly hexanaphthene, superoxide) is sent to decomposing system, do at low temperature and Cobaltous diacetate that peroxide breakdown becomes hexalin under the alkaline condition of catalyzer, pimelinketone, temperature of reaction maintains 85～96 ℃, product after the decomposition is after separation system is separated inorganic phase (waste lye), organic phase enters the alkane Distallation systm and concentrates, thick alcohol ketone liquid after concentrating is sent to the pimelinketone low-voltage device, in the saponification system of pimelinketone low-voltage device thick alcohol ketone liquid under the highly basic condition saponification to remove ester and aldehyde wherein, then with the hybrid extraction of hexanaphthene and add water washing and remove inorganic salts, deliver to refining step after drying, isolate pimelinketone and send as product in three vacuum refining towers, hexalin is delivered to the dehydrogenation operation and cyclohexanol dehydrogenation is converted into pimelinketone is returned refining step again and separate.
According to relevant document as can be known, the principal reaction approach of hexanaphthene non-catalyst oxidation is shown below:
Pimelinketone is also having very big consumption aspect printing, medicine and plastics recovery, the solvent in addition mainly as the raw material of preparation hexanolactam.It is 3.5% that the optimal conversion that important production process of chemical product reached such as hexalin and pimelinketone are produced in present industrial hexanaphthene liquid phase air oxidation, and the hexanaphthene yield is 82%, and pimelinketone consumption hexanaphthene is 1041kg/t.
Summary of the invention
The object of the present invention is to provide a kind ofly to prepare the technology of hexalin and pimelinketone by hexanaphthene, make conversion of cyclohexane reach 10%, the hexanaphthene yield reaches 90%, and pimelinketone consumption hexanaphthene reaches 952kg/t.
The objective of the invention is to realize in the following manner:
Adding 2ppm～8ppm patent No. in 140 ℃～150 ℃, the hexanaphthene of pressure 0.8～1.1Mpa is 00113225.3 described cobalt dual-metal porphyrin catalyst, makes it fully dissolving and homogeneous phase and distributes; Oxidation reactor is a laminar flow formula reactor, and oxygen level is that 10%～21% air rationally distributes at reactor bottom, is furnished with the steam heating facility in the reactor; Under catalysis of metalloporphyrin agent effect, contain the oxygen air between 140 ℃～150 ℃, react in reactor with hexanaphthene under 0.8～1.1Mpa pressure, controlling reaction time is 20 minutes～40 minutes, making cyclohexane conversion is about 10%; The hexanaphthene that oxidized tail gas is taken out of reclaims by the heat recovery system condensation, and retrieval system.
Contain organic acid and ester type organic in the oxidation products, in a plurality of reactors, organism and alkali thorough mixing, acid in the organism and alkali reaction generate organic acid sodium salt, and the ester type organic is decomposed into organic acid and pure type organic, temperature of reactor is controlled at 60～90 ℃, pressure-controlling, is separated the inorganics in the organism by the alkali separation system at 0.3Mpa.
After, in the hexanaphthene water distilling apparatus of routine, reclaim hexanaphthene, in hexalin, pimelinketone rectifier unit, make with extra care out pimelinketone and hexalin, in the cyclohexanol dehydrogenation device, hexalin is converted into pimelinketone.
The present invention's advantage and positively effect compared with prior art is: the present invention compares with the existing hexanaphthene liquid-phase air oxidation technology of using, its remarkable advantage is cyclohexane conversion and yield height, can reach 10% and 90% respectively, reduce pimelinketone consumption hexanaphthene greatly.Because cyclohexane oxidation generation pimelinketone/hexalin step in oxidation system finishes in this invention, its oxidation products only needs also to have reduced the consumption of alkali through alkali cleaning.Concrete data are: cyclohexane conversion (%) brings up to 10% by 3.8%, and hexanaphthene yield (%) brings up to 90% by 82%, and pimelinketone consumption hexanaphthene is reduced to 952kg/t by 1041kg/t, and pimelinketone consumption alkali is reduced to 50kg/t by 132kg/t.The present invention has improved conversion of cyclohexane, and under identical pimelinketone output, the amount of round-robin hexanaphthene can reduce more than 50%, has reduced the production load of hexanaphthene Distallation systm, has reduced the consumption of the energy, and the production power cost of pimelinketone is significantly reduced.Because it is short that this invents the existing hexanaphthene liquid-phase air oxidation operational path of using of the operational path of producing pimelinketone, and the by product minimizing, the particularly minimizing of salkali waste amount can reduce construction investment and protection environment
Embodiment:
Embodiment 1 adds the 4ppm number of patent application in 145 ℃, the hexanaphthene of 0.8Mpa pressure be 00113225.3 cobalt dual-metal porphyrin catalyst, makes it uniform distribution; Oxidation reactor is a laminar flow formula reactor, and oxygen level is that 16% air rationally distributes at reactor bottom, is furnished with the steam heating facility in the reactor; Under this catalyst action, contain oxygen 16% air and under 145 ℃, 0.8Mpa pressure, in reactor, react with hexanaphthene, controlling reaction time is 30 minutes, making cyclohexane conversion is about 8%; The hexanaphthene that oxidized tail gas is taken out of reclaims by the heat recovery system condensation, and retrieval system.Contain organic acid and ester type organic in the oxidation products, in a plurality of reactors, organism and alkali thorough mixing, acid in the organism and alkali reaction generate organic acid sodium salt, and the ester type organic is decomposed into organic acid and pure type organic, temperature of reactor is controlled at 85 ℃, pressure-controlling, is separated the inorganics in the organism by the alkali separation system at 0.3Mpa.
Claims (1)
1 one kinds of technologies that prepare hexalin and pimelinketone.It is characterized in that may further comprise the steps: (A) the patent No. be under the condition that exists of 00113225.3 described cobalt dual-metal porphyrin catalyst and 140 ℃～150 ℃ of temperature, pressure 0.8～1.1Mpa scope in make hexanaphthene in liquid phase, carry out oxidation with containing the oxygen air, its transformation efficiency keeps being no more than 10%, reaction divides a plurality of stages to carry out in laminar flow formula reactor, and oxygen concentration keeps within limits in the liquid phase; (B) oxidation products is through alkali cleaning, and temperature is controlled at 60 ℃～90 ℃, removes organic acid and catalyzer in the product; (C) through after separating, organic phase makes 95% hexanaphthene be circulated to oxidation system again by the hexanaphthene Distallation systm, and product enters pimelinketone and hexalin distillation system, obtains effective product pimelinketone and hexalin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02113940 CN1226255C (en) | 2002-01-28 | 2002-01-28 | Process for preparing cyclohexanol and cyclohexanone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02113940 CN1226255C (en) | 2002-01-28 | 2002-01-28 | Process for preparing cyclohexanol and cyclohexanone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1435401A CN1435401A (en) | 2003-08-13 |
| CN1226255C true CN1226255C (en) | 2005-11-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02113940 Expired - Lifetime CN1226255C (en) | 2002-01-28 | 2002-01-28 | Process for preparing cyclohexanol and cyclohexanone |
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| CN (1) | CN1226255C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941120A (en) * | 2012-11-08 | 2013-02-27 | 衢州市科扬化工有限公司 | Catalytic system for preparing cyclohexanol and cyclohexanone by liquid-phase catalytic oxidation of cyclohexane and use method of catalytic system |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305829C (en) * | 2004-11-12 | 2007-03-21 | 中国科学院兰州化学物理研究所 | Selective oxidation process of cyclohexane to prepare cyclohexanone |
| CN1317247C (en) * | 2004-12-09 | 2007-05-23 | 中国石化集团巴陵石油化工有限责任公司 | Method of obtaining high purity cyclohexanol from cyclohexane oxidation product |
| CN100460374C (en) * | 2006-01-06 | 2009-02-11 | 中国石油天然气股份有限公司 | Method for prolonging alkali wash period of alcohol ketone device |
| CN101085714B (en) * | 2006-06-06 | 2011-12-07 | 中国石油化工集团公司 | Method for preparing cyclohexanone and cyclohexanol by oxidizing cyclohexane |
| CN114230458A (en) * | 2020-09-09 | 2022-03-25 | 长沙资材科技有限公司 | Method for separating alcohol ketonic acid complex oxidation product generated by air catalytic oxidation of cyclohexane |
-
2002
- 2002-01-28 CN CN 02113940 patent/CN1226255C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941120A (en) * | 2012-11-08 | 2013-02-27 | 衢州市科扬化工有限公司 | Catalytic system for preparing cyclohexanol and cyclohexanone by liquid-phase catalytic oxidation of cyclohexane and use method of catalytic system |
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| Publication number | Publication date |
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| CN1435401A (en) | 2003-08-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| ASS | Succession or assignment of patent right |
Owner name: CHINA PETROLEUM & CHEMICAL CORPORATION Free format text: FORMER OWNER: BALIN BRANCH CORP. SINOPEC Effective date: 20050107 |
|
| C10 | Entry into substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20050107 Address after: 414003 No. 1 Dongting Road, Hunan, Yueyang Applicant after: Sinopec Corp. Address before: 414003 No. 1 Dongting Road, Hunan, Yueyang Applicant before: Baling Branch, China Petro-Chemical Co., Ltd. |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20051109 |