CN1147499A - Prepn of cyclohexanol and cyclohexanone - Google Patents
Prepn of cyclohexanol and cyclohexanone Download PDFInfo
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- CN1147499A CN1147499A CN 95112470 CN95112470A CN1147499A CN 1147499 A CN1147499 A CN 1147499A CN 95112470 CN95112470 CN 95112470 CN 95112470 A CN95112470 A CN 95112470A CN 1147499 A CN1147499 A CN 1147499A
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- pimelinketone
- product
- heavy constituent
- hexalin
- oxidation
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Abstract
The prepn process of cyclohexanol and cyclohexanone by converting cyclohexane includes oxidation of cyclohexane with oxygenic gas into oxide mixture containing cyclohexyl hydrogen peroxide, cyclohexanol and cyclohexanone, decomposition of the said peroxide into cyclohexanol and cyclohexanone, and rectification to obtain cyclohexanol and cyclohexanone product. The present invention features that during oxidation, is added into cylohexane the cyclohexane-recombining by-product, X oil, which contains cyclohexane with cyclohexene group and other cyclohexane condensate.
Description
The present invention relates to the continuous preparation method of hexalin, pimelinketone, according to this method, production technique may further comprise the steps:
A. hexanaphthene is under cobalt metal catalyst condition, perhaps under the non-metal catalyst condition, in 130～200 ℃, 0.7～2.0MPa pressure and oxygen-containing gas (air) exist down, oxidized continuously, generation contains 0.5～5% (weight) cyclohexyl hydroperoxide, the oxidation mixture of 0.4～4% (weight) hexalin and pimelinketone.
B. with the cyclohexyl hydroperoxide in the oxidation mixture, under metal catalyst conditions such as cobalt, chromium, homogeneous decomposition is perhaps at NaOH, Na
2CO
3There is heterogeneous decomposition down in alkaline aqueous solutions such as the aqueous solution, generate hexalin and pimelinketone.
C. decompose later mixture, reclaim most of hexanaphthene that not have conversion through rectifying tower top, the hexanaphthene Returning oxidation reactor carries out oxidation again, then bottom product again rectifying obtain hexalin, pimelinketone and heavy constituent by-product X oil.X oil is to contain C
6Above organism, boiling point is than hexalin height, so be the heavy constituent by product.Through chemical analysis, the condenses of pimelinketone accounts for more than 60% in these heavy constituent, mainly contain dimerization pimelinketone compounds such as cyclohexenyl hexamethylene ketone, cyclohexylidene basic ring hexanone, also contain more than 100 kind of compound of trimerization pimelinketone, butyl cyclohexyl ether, hexalin, pimelinketone, cyclohexyl ring hexanone, valeric acid cyclohexyl, caproic acid cyclohexyl, cyclohexanediol, Succinic Acid cyclohexyl, pentanedioic acid cyclohexyl, hexanodioic acid cyclohexyl or the like in addition.But particularly importantly: mainly be to contain cyclohexenyl hexamethylene ketone, cyclohexylidene basic ring hexanone, hexalin basic ring hexanone or the like dimerization pimelinketone compound in this heavy constituent by product.The structural formula of dimerization pimelinketone is:
The method that above-mentioned cyclohexane oxidation and cyclohexyl hydroperoxide decompose at CA88105772.X, has been done detailed description among CA94110939.9 and the US5233092.The shortcoming of above-mentioned this currently known methods is: the selectivity that hexanaphthene finally changes into hexalin and pimelinketone is low, and reaction result forms a large amount of side reactions.For example: heavy constituent by product (X oil) quantum of output just accounts for 5～15% of hexalin, pimelinketone output.X oil is generally done waste oil and is incinerated, and this has just had a strong impact on the total recovery that hexanaphthene is produced hexalin and pimelinketone, and device raw material consumption is risen, and cost rises.
The objective of the invention is: a kind of method is provided, and the selectivity and the yield that make cyclohexane oxidation produce hexalin and pimelinketone are improved, and cyclohexane oxidation is carried out under the condition of milder.
Method provided by the invention is: the method that original cyclohexane oxidation is prepared hexalin and pimelinketone is improved, specifically, exactly in cyclohexane oxidation carries out, in the raw material hexanaphthene, add continuously account for hexanaphthene weight 0.05～2% contain the cyclohexane oxidation heavy constituent by product that cyclohexenyl hexamethylene ketone and ring have been pitched the basic ring hexanone.Method provided by the invention can reach purpose of the present invention fully.
Have found that, the adding of heavy constituent by product X oil, can suppress the pimelinketone condensation reaction in cyclohexane oxidation and the cyclohexyl hydroperoxide decomposition course, because heavy constituent by product X oil itself mainly is to be generated by the condensation reaction of pimelinketone, heavy constituent by product X oil is under acid and alkaline condition, can also depolymerize to pimelinketone, thereby the adding of heavy constituent by product X oil, can improve cyclohexane oxidation and cyclohexyl hydroperoxide and decompose selectivity and the yield that generates hexalin, pimelinketone, and can cause and promote the carrying out of cyclohexane oxidation.The adding of heavy constituent by product X oil can relatively reduce the temperature of reaction and the reaction pressure of cyclohexane oxidation, perhaps can obviously reduce the oxygen level in the cyclohexane oxidation tail gas, improves the stability and the security of cyclohexane oxidation.
In the heavy constituent by product X oil, generally contain metal catalyst, for example: cobalt and chromium etc.Also may contain alkalimetal ion, for example: sodium etc.Heavy constituent by product X oil in adding the raw material hexanaphthene before, preferably can adopt the method for distillatory method or washing to remove these metal ions.Because these metal ions to cyclohexane oxidation prepare hexalin with high yield, pimelinketone may be deleterious.When metal ion content is not high in the heavy constituent by product X oil certainly, also can return cyclohexane oxidation adding system with pump without handling directly.Heavy constituent by product X oil is to add the cyclohexane oxidation system together in company with the raw material hexanaphthene.The cyclohexane oxidation system generally is made up of placed in-line oxidation reactor.After heavy constituent by product X oil adds oxidation system, heavy constituent by product X oil at the bottom of alcohol rectifying tower or the alcohol ketone rectifying tower increases to some extent, but the quantity that increases is many not as the quantity that the front operation adds, and can be re-circulated to oxidation reactor, reach the quantum of output and the balance of returning the add-on of oxidation reactor of heavy constituent by product X oil at last.Prepare in the technology of hexalin, pimelinketone at some cyclohexane oxidation, for example: in the hexanaphthene non-catalyst oxidation technology, heavy constituent by product X oil mainly produces at the cyclohexyl hydroperoxide catabolic phase, and it is few at cyclohexane oxidation stage growing amount, at this moment the heavy constituent by product also can only add decomposing system, and needn't add oxidation system.
Below in conjunction with embodiment the present invention is further described in detail:
Embodiment 1:
In a volume is 1 liter stainless steel reactor, add 500 gram hexanaphthene and 2 grammes per square metre component by products, one X oil, under the condition of 170 ℃ and 1.2MPa, bubbling air is half an hour approximately, air feeding amount amounts to about 35 liters, the oxidation mixture that obtains is the adding 6%NaOH aqueous solution 100 grams under 90 ℃, make the cyclohexyl peroxide in the cyclohexane oxidation mixture decompose generation hexalin, pimelinketone, the organic acid that is generated with the oxidation side reaction in the while.Get organic phase rectifying at last, obtain the unreacted hexanaphthene of 475 grams, 25 gram hexalin and pimelinketone, 3 grammes per square metre component by product X oil.
Comparison example 1:
In volume is 1 liter stainless steel reactor, add 500 gram hexanaphthenes, do not add heavy constituent by product X oil.Equally under the condition of 170 ℃ and 1.2MPa, bubbling air is half an hour approximately, air feeding amount amounts to about 35 liters, mixture among oxidation mixture that obtains and the embodiment 1 is handled simultaneously, last rectifying obtains the unreacted hexanaphthene of 476 grams, 23 gram hexalin and pimelinketone, 2 grammes per square metre component by product X oil.
Example 2:
Be respectively 10m at four volumes
3Oxidation reactor, per hour add 30 continuously, 000kg hexanaphthene and 120kg heavy constituent by product X oil, the concentration that contains the catalyst cobalt metal ion in the retaining ring hexane is 0.2ppm, the concentration of the HEDP ester that adds also is 0.2ppm, under 156 ℃ and 1.0MPa, with airborne molecular oxygen oxidizing ethyle alkyl partly.The oxidation mixture that obtains is by decomposition, neutralization, saponification, rectifying, arrive unreacted 28 in the alkane rectification recovered overhead, 500kg/ hour hexanaphthene gets 1400kg/ hour pimelinketone in the ketone rectifying tower top, obtains 170kg/ hour heavy constituent by product X oil at the bottom of pure rectifying tower.
Comparison example 2:
Technical process and other controlling index and example 2 are identical, just heavy constituent by product X oil does not circulate, be that X oil is not squeezed into oxidation reactor, the result arrives unreacted 28500kg/ hour hexanaphthene in the alkane recovered overhead, and have to 1300kg/ hour pimelinketone at the ketone cat head, at the bottom of pure tower, obtain 110kg/ hour heavy constituent by product X oil.
Example 3:
At placed in-line five oxidation reactors, add 165 continuously, 000kg/ hour hexanaphthene, 165 ℃ of control reaction temperature, pressure 1.2MPa is not with metal catalyst, with airborne molecular oxygen oxidizing ethyle alkyl partly.The oxidation mixture that obtains carries out heterogeneous low-temperature decomposition in the presence of the NaOH aqueous solution and Cobaltous diacetate catalyzer, when adding the NaOH aqueous solution continuously, add 700kg/ hour heavy constituent by product X oil continuously to splitter.Be recovered to 159 at the alkane tower at last, 225kg/ hour hexanaphthene obtains 5775kg/ hour pimelinketone and hexalin mixture at the alcohol ketone tower, obtains 873kg/ hour heavy constituent by product X oil at the bottom of alcohol/ketone tower.
Comparison example 3:
Technical process and other control indication are identical with example 3, and just heavy constituent by product X oil is not recycled to splitter, promptly do not decompose to cyclohexyl peroxide and add X oil.Being recovered to unreacted hexanaphthene at the alkane tower at last is 159, and 255kg/ hour hexanaphthene is had to 5500kg/ hour hexalin and pimelinketone at alcohol/ketone tower, obtains 350kg/ hour heavy constituent by product X oil at the bottom of alcohol/ketone tower.
Claims (10)
1, a kind of hexanaphthene is converted into the technology of hexalin and pimelinketone, may further comprise the steps:
A. under 130～200 ℃ of temperature and 0.7～2.0MPa pressure, use the oxygen-containing gas oxidizing ethyle alkyl, make it generation and contain 0.5～5% (weight) cyclohexyl hydroperoxide, the oxidation mixture of 0.4～4% (weight) hexalin and pimelinketone.
B. with the cyclohexyl hydrogen peroxide decomposition in the oxidation mixture, generate hexalin and pimelinketone.
C. reclaim the hexanaphthene Returning oxidation reactor through rectifying, and then rectifying obtains pimelinketone, hexalin and cyclohexane oxidation heavy constituent by product---X oil.The invention is characterized in: in cyclohexane oxidation or decomposition reaction are carried out, in this system, add cyclohexane oxidation heavy constituent by-product---the X oil that contains cyclohexenyl hexamethylene ketone that accounts for hexanaphthene weight 0.05～2% continuously.
According to the method for claim 1, it is characterized in that 2, cyclohexane oxidation heavy constituent by product mainly is to contain C
6Above oxidized byproduct, its boiling point is than hexalin height, the component complexity, generally be X oil again, by analysis, the condenses of pimelinketone accounts for more than 60% in these heavy constituent, mainly contain dimerization pimelinketone such as cyclohexenyl hexamethylene ketone, cyclohexylidene basic ring hexanone, in addition, also contain more than 100 kind of compound of trimerization pimelinketone, butyl cyclohexyl ether, hexalin, pimelinketone, cyclohexyl ring hexanone, valeric acid cyclohexyl, caproic acid cyclohexyl, cyclohexanediol, Succinic Acid cyclohexyl, pentanedioic acid cyclohexyl, hexanodioic acid cyclohexyl or the like.But particularly importantly mainly contain dimerization pimelinketone such as cyclohexenyl hexamethylene ketone, cyclohexylidene basic ring hexanone in this heavy constituent by product.The structural formula of dimerization pimelinketone as:
3, according to arbitrary method of claim 1-2, it is characterized in that: when the heavy constituent by product is cyclohexane oxidation process production pimelinketone, heavy constituent by product at the bottom of the tower of hexalin rectifying tower, or cyclohexane oxidation process is when producing pimelinketone hexalin mixture (KA oil), heavy constituent by product at the bottom of the tower of keto-alcohol rectifying tower.
4, according to arbitrary method of claim 1-3, it is characterized in that: the add-on of heavy constituent by product is 0.1～1% (weight) of hexanaphthene add-on.
5, according to arbitrary method of claim 1-4, it is characterized in that: the add-on of heavy constituent by product is 0.3～0.6% (weight) of hexanaphthene add-on.
6. according to arbitrary method of claim 1-5, it is characterized in that: the temperature during cyclohexane oxidation is 140～190 ℃.
7, according to arbitrary method of claim 1-6, it is characterized in that: the pressure during oxidizing reaction is 0.75～2.0MPa.
8, according to arbitrary method of claim 1-7, it is characterized in that: cyclohexane oxidation can carry out under the condition of metal catalyst metal catalyst being arranged or do not having.
9, according to arbitrary method of claim 1-8, it is characterized in that: the decomposition of cyclohexyl hydroperoxide can be decomposed in homogeneous catalysis, perhaps carries out under the condition that the heterogeneous catalysis in the presence of alkaline aqueous solution is decomposed.
10, according to arbitrary method of claim 1-9, it is characterized in that: the heavy constituent by product can wash with water before adding the cyclohexane oxidation system or the method for vacuum distilling is handled, to remove wherein contained metal ion, as Co
+ 2, Cr
+ 3, Na
+, Fe
+ 2Deng, also can directly add in the cyclohexane oxidation system without processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95112470 CN1147499A (en) | 1995-10-10 | 1995-10-10 | Prepn of cyclohexanol and cyclohexanone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95112470 CN1147499A (en) | 1995-10-10 | 1995-10-10 | Prepn of cyclohexanol and cyclohexanone |
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| CN1147499A true CN1147499A (en) | 1997-04-16 |
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| CN 95112470 Pending CN1147499A (en) | 1995-10-10 | 1995-10-10 | Prepn of cyclohexanol and cyclohexanone |
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Cited By (10)
| 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 |
| 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 |
| CN102452968A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing methyl cyclohexyl hydrogen peroxide with methylcyclohexane subjected to aerobic oxidation |
| WO2013143212A1 (en) * | 2012-03-28 | 2013-10-03 | Xiao Zaosheng | Process for preparing cyclohexanol and cyclohexanone by cyclohexane oxidation, and device for same |
| CN105316024A (en) * | 2015-08-01 | 2016-02-10 | 梁毅 | X oil recycling method |
| CN107778133A (en) * | 2016-08-25 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of method for preparing cyclohexanol and cyclohexanone |
| CN108129286A (en) * | 2018-01-23 | 2018-06-08 | 山东亚科环保科技有限公司 | A kind of method that catalytic oxidation of cyclohexane prepares cyclohexanol and cyclohexanone |
| CN109232206A (en) * | 2018-10-19 | 2019-01-18 | 平顶山市神马万里化工股份有限公司 | A method of cyclohexanone is prepared using cyclohexanol distillation residual liquid |
| CN111153831A (en) * | 2020-02-19 | 2020-05-15 | 湘潭大学 | Preparation method of cyclohexanone oxime |
| CN113277929A (en) * | 2021-05-24 | 2021-08-20 | 聊城鲁西聚酰胺新材料科技有限公司 | Cyclohexanol byproduct waste oil treatment and recovery system and treatment process |
-
1995
- 1995-10-10 CN CN 95112470 patent/CN1147499A/en active Pending
Cited By (14)
| 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 |
| 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 |
| CN102452968A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing methyl cyclohexyl hydrogen peroxide with methylcyclohexane subjected to aerobic oxidation |
| WO2013143212A1 (en) * | 2012-03-28 | 2013-10-03 | Xiao Zaosheng | Process for preparing cyclohexanol and cyclohexanone by cyclohexane oxidation, and device for same |
| US9162956B2 (en) | 2012-03-28 | 2015-10-20 | Zaosheng Xiao | Process and device for preparing cyclohexanol and cyclohexanone by cyclohexane oxidation |
| CN105316024A (en) * | 2015-08-01 | 2016-02-10 | 梁毅 | X oil recycling method |
| CN107778133A (en) * | 2016-08-25 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of method for preparing cyclohexanol and cyclohexanone |
| CN108129286A (en) * | 2018-01-23 | 2018-06-08 | 山东亚科环保科技有限公司 | A kind of method that catalytic oxidation of cyclohexane prepares cyclohexanol and cyclohexanone |
| CN109232206A (en) * | 2018-10-19 | 2019-01-18 | 平顶山市神马万里化工股份有限公司 | A method of cyclohexanone is prepared using cyclohexanol distillation residual liquid |
| CN109232206B (en) * | 2018-10-19 | 2021-08-06 | 平顶山市神马万里化工股份有限公司 | Method for preparing cyclohexanone by using cyclohexanol distillation residual liquid |
| CN111153831A (en) * | 2020-02-19 | 2020-05-15 | 湘潭大学 | Preparation method of cyclohexanone oxime |
| CN111153831B (en) * | 2020-02-19 | 2022-11-01 | 湘潭大学 | Preparation method of cyclohexanone oxime |
| CN113277929A (en) * | 2021-05-24 | 2021-08-20 | 聊城鲁西聚酰胺新材料科技有限公司 | Cyclohexanol byproduct waste oil treatment and recovery system and treatment process |
| CN113277929B (en) * | 2021-05-24 | 2023-02-21 | 聊城鲁西聚酰胺新材料科技有限公司 | Cyclohexanol byproduct waste oil treatment and recovery system and treatment process |
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