CN1519218A - Technique for catalytic decompoositing hydrogen dioxide cyclohexyl by using metalloporphyrin - Google Patents
Technique for catalytic decompoositing hydrogen dioxide cyclohexyl by using metalloporphyrin Download PDFInfo
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- CN1519218A CN1519218A CNA031180434A CN03118043A CN1519218A CN 1519218 A CN1519218 A CN 1519218A CN A031180434 A CNA031180434 A CN A031180434A CN 03118043 A CN03118043 A CN 03118043A CN 1519218 A CN1519218 A CN 1519218A
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- Prior art keywords
- pimelinketone
- metalloporphyrin
- cyclohexyl
- hexalin
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Abstract
A process for preparing cyclohexanol and cyclohexanone features that under the catalyst of monometalloporphyzin or mu-oxybimetallo porphyrin, the hydrogen cyclohexylperoxide is decomposed to generate said products. Its advantages are high selectivity (92% or more), less consumption of alkali and high utilization rate of oxygen in air.
Description
Technical field
The present invention relates to catalysis of metalloporphyrin decomposing cyclohexylhdroperoxide technology, particularly under monometallic porphyrin or μ-oxygen bimetallic porphyrin katalysis, the technology of cyclohexyl hydroperoxide catalytic decomposition.
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, wherein the system that is connected into by a plurality of bubble stirring reactors of oxidized portion.Fresh cyclohexane and Cyclic Rings hexane heat up through preliminary heat exchange, ℃ enter stills for air blowing by oxidation feed heater heats to 160～170 again, a plurality of stills for air blowing adopt the hexanaphthene series connection to add, the air continuous cascade reaction pattern that adds in parallel, reacted tail gas is through the tail gas absorption 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 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 80～96 ℃, 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, the pimelinketone yield is 82%, pimelinketone consumption hexanaphthene is 1041kg/t, wherein oxidation cyclohexyl hydroperoxide selectivity can reach 96% (molar percentage), and hexalin, pimelinketone selectivity that cyclohexyl hydroperoxide decomposes only are 84% (molar percentage).
Summary of the invention
The object of the present invention is to provide a kind of catalysis of metalloporphyrin decomposing cyclohexylhdroperoxide technology, under monometallic porphyrin or μ-oxygen bimetallic porphyrin katalysis, the technology of cyclohexyl hydroperoxide catalytic decomposition makes cyclohexyl hydroperoxide resolve into hexalin, pimelinketone.
The objective of the invention is to realize in the following manner:
The technology of cyclohexyl hydroperoxide catalytic decomposition, under the condition that monometallic porphyrin or μ-oxygen bimetallic porphyrin catalyzer synthetic catalyzer such as () chemical institute of Changsha, Hunan Hunan University Guo Can cities exist, catalyst concn is 1～10ppm, in 80 ℃～140 ℃ temperature and 0.4～1.0Mpa pressure range, in acidity or basicity is under 0.2～2.0 milligramequivalent condition, and the cyclohexyl hydroperoxide in the cyclohexane oxidation product decomposes generation hexalin and pimelinketone in the fully mixing reactor.
The technology of cyclohexyl hydroperoxide catalytic decomposition compares with the existing decomposition technique of using among the present invention, its remarkable advantage is that the selectivity of hexalin and pimelinketone improves, can reach more than 92%, reduced the consumption of alkali, reduce the discharging of waste lye, reduce environmental protection pressure, improved the utilization ratio of oxygen in the air simultaneously.
Embodiment:
Embodiment 1 is 0.4M at a container
3In the decomposition reactor, decomposition reactor per hour adds 0.8M continuously for band mechanical stirring fully mixing reactor
3Oxidation liquid, the content of cyclohexyl hydroperoxide is 5% in the oxidation liquid, add the two iron porphyrin catalyzer of 1ppm μ-oxygen in the oxidation liquid, making it fully dissolving and homogeneous phase distributes, in 120 ℃ of temperature and 0.6Mpa pressure range, in oxidation liquid, do not add under the acidic conditions of alkali, the cyclohexyl hydroperoxide in the cyclohexane oxidation product decomposes generation hexalin and pimelinketone in the fully mixing reactor, in 30 minutes reaction times, the selectivity of hexalin and pimelinketone is 92%.
Embodiment 2 is 0.4M at a container
3In the decomposition reactor, decomposition reactor per hour adds 0.8M continuously for band mechanical stirring fully mixing reactor
3Oxidation liquid, the content of cyclohexyl hydroperoxide is 5% in the oxidation liquid, add 1ppm monometallic iron porphyrin catalyzer in the oxidation liquid, making it fully dissolving and homogeneous phase distributes, in 120 ℃ of temperature and 0.6Mpa pressure range, be under the 1 milligramequivalent condition in basicity, the cyclohexyl hydroperoxide in the cyclohexane oxidation product decomposes generation hexalin and pimelinketone in the fully mixing reactor, in 30 minutes reaction times, the selectivity of hexalin and pimelinketone is 92.2%.
Claims (1)
1. catalysis of metalloporphyrin decomposing cyclohexylhdroperoxide technology, it is characterized in that: under monometallic porphyrin or μ oxygen bimetallic porphyrin catalyst action, catalyst concn is that 1ppm～10ppm, temperature are that 80 ℃～140 ℃, pressure are that 0.4Mpa～1.0Mpa, acidity or basicity are under 0.2～2.0 milligramequivalent condition, and the cyclohexyl hydroperoxide in the cyclohexane oxidation product decomposes in the fully mixing reactor and produces hexalin and pimelinketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031180434A CN1519218A (en) | 2003-01-24 | 2003-01-24 | Technique for catalytic decompoositing hydrogen dioxide cyclohexyl by using metalloporphyrin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031180434A CN1519218A (en) | 2003-01-24 | 2003-01-24 | Technique for catalytic decompoositing hydrogen dioxide cyclohexyl by using metalloporphyrin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1519218A true CN1519218A (en) | 2004-08-11 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031180434A Pending CN1519218A (en) | 2003-01-24 | 2003-01-24 | Technique for catalytic decompoositing hydrogen dioxide cyclohexyl by using metalloporphyrin |
Country Status (1)
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| CN (1) | CN1519218A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2003
- 2003-01-24 CN CNA031180434A patent/CN1519218A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| WD01 | Invention patent application deemed withdrawn after publication |