CN1059675C - Method for recovering n-pentanol and cyclohexene oxide from light oil, by-products of cyclohexanol and cyclohexanone preparation by cyclohexane oxidation - Google Patents
Method for recovering n-pentanol and cyclohexene oxide from light oil, by-products of cyclohexanol and cyclohexanone preparation by cyclohexane oxidation Download PDFInfo
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- CN1059675C CN1059675C CN94113151A CN94113151A CN1059675C CN 1059675 C CN1059675 C CN 1059675C CN 94113151 A CN94113151 A CN 94113151A CN 94113151 A CN94113151 A CN 94113151A CN 1059675 C CN1059675 C CN 1059675C
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- Prior art keywords
- cyclohexene oxide
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- water
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- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 239000006227 byproduct Substances 0.000 title claims abstract description 7
- 230000003647 oxidation Effects 0.000 title claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 7
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 238000004587 chromatography analysis Methods 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 7
- 238000007670 refining Methods 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract 1
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011112 process operation Methods 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for recovering n-pentanol and cyclohexene oxide from a cyclohexane oxidation by-product, namely light oil, which is characterized in that water and cyclohexene oxide in the light oil form a binary azeotrope, crude cyclohexene oxide is evaporated at 88-90.5 ℃, and then an organic entrainer is added for refining to obtain cyclohexene oxide, wherein the purity can reach 95%, and the recovery rate is more than or equal to 70%; evaporating n-pentanol at 135-137 deg.c to obtain n-pentanol product with purity not lower than 95% and recovery rate not lower than 70%.
Description
The present invention relates to a kind of by product from cyclohexane oxidation system hexalin, pimelinketone---reclaim the method for Pentyl alcohol and cyclohexene oxide the lightweight oil.
The light component waste liquid of by-product in cyclohexane oxidation system hexalin, the pimelinketone technology, this waste liquid that is called lightweight oil contains 20～50% Pentyl alcohol, 20～30% cyclohexene oxide, other impurity 20～30%, the lightweight oil smell is bigger in respect of the 10KT left and right sides by-product lightweight oil factory every year of family expenses cyclohexane oxidation preparing cyclohexanone surplus in the of domestic ten, certain toxicity is arranged, before Application and Development, not only wasted a considerable number of industrial chemicals, also cause environmental pollution.
It is reported domestic at present not about from above-mentioned lightweight oil, reclaiming the report of Pentyl alcohol and cyclohexene oxide, JK-74,11848 have introduced a kind of method that reclaims cyclohexene oxide, after it is characterized in that at first carrying out single flash, again with the blending fraction NH of contained cyclohexene oxide and valeral, butanols, hexanal, cyclopentanone
2OH handles, and then in 44～86 ℃ of distillations of 100mmHg post, gets the organic mixture of cyclohexene oxide and butanols, carries out rectifying for the third time again, recyclable like this 81% the cyclohexene oxide that obtains.JK-75,9528 introduce another kind of method handles with 0.2～0.5% alkaline solution earlier, valeral, this class low-boiling-point substance of cyclopentanone are changed into high boiling material, and 65～77 ℃ of distillations under the 100mmHg column condition again get a mixture, wherein cyclohexene oxide content is 36.2%, with this mixture and 10%NaOH aqueous solution, refluxed 1 hour at 98～100 ℃, wash oil reservoir with water, 95～102 ℃ of distillations under 295～305mmHg pressure condition again, recovery purity are 94.7% cyclohexene oxide.
The objective of the invention is to reclaim effectively Pentyl alcohol and cyclohexene oxide, select cheap entrainer to reduce cost recovery, and can alleviate environmental pollution, make it not produce secondary pollution.
The present invention is achieved in that and earlier lightweight oil is steamed in advance, collect 128～135 ℃ of cuts as raw material, weight with the contained cyclohexene oxide of this raw material is benchmark for 54 parts, add 46 parts in water, air distillation, cyclohexene oxide and water form binary azeotrope and distill out the cyclohexene oxide crude product 90 ± 0.5 ℃ of scopes, distill out the Pentyl alcohol product 135～137.8 ℃ of scopes, thick cyclohexene oxide adds organic entrainer rectifying, thick cyclohexene oxide chromatography determination, with the organic impurity content beyond the cyclohexene oxide in the thick cyclohexene oxide is benchmark for 50 parts, adds 25 parts of methyl alcohol or ethanol; Also can add 12.5 parts of methyl alcohol and 12.5 parts of water or 12.5 parts of ethanol and 12.5 parts of water, form azeotrope with cyclohexene oxide, go out smart cyclohexene oxide product in 130～132 ℃ of scope rectifying of temperature, its reflux ratio is 1～4: 1.
Details are as follows for concrete technology:
Earlier lightweight oil is steamed in advance, collect 128～135 ℃ of scope components for reclaiming the raw material of Pentyl alcohol and cyclohexene oxide, its still liquid is that thick pimelinketone deals with in addition, the component of 128～135 ℃ of scopes will collecting then is a raw material, weight with the contained cyclohexene oxide of this raw material is benchmark for 54 parts, add 46 parts in water, air distillation, its reflux ratio is 1～4: 1, cyclohexene oxide and water form binary azeotrope, distill out the cyclohexene oxide crude product 90 ± 0.5 ℃ of scopes, distill out the Pentyl alcohol product 135～137.8 ℃ of scopes, 90.5～135 ℃ of scope components return distillation, at last with the content of thick cyclohexene oxide with the chromatography determination organic impurity, with the organic impurity content beyond the cyclohexene oxide is benchmark for 50 parts, add methyl alcohol or ethanol and form azeotrope for 25 parts, also can take to add 12.5 parts of methyl alcohol and 12.5 parts of water or add 12.5 parts of ethanol and 12.5 parts of water formation azeotropes, its reflux ratio is 1～4: 1, rectifying goes out smart cyclohexene oxide product 130～132 ℃ of scope rectifying.
Positively effect of the present invention is to recycle bigger Pentyl alcohol of value and cyclohexene oxide effectively, and technology simply adopts conventional equipment, less investment, do not produce secondary environmental pollution, the product purity that reclaims reaches more than 95%, and the rate of recovery is up to more than 70%.
Embodiment (1): drop into 0.5 kilogram of raw material, chromatographic determination, Pentyl alcohol content is 46.20%, cyclohexene oxide content is 40.12%, adds water and carry out azeotropic distillation for 46 parts, reflux ratio 1: 1 in 54 parts of cyclohexene oxides of weight ratio, it is 95.40% Pentyl alcohol 184.5g that the described process operation of by specification gets purity, the rate of recovery 76.20%, content is 88.17% cyclohexene oxide 203.8g, the rate of recovery 89.58%.
Embodiment (2): by the thick cyclohexene oxide of embodiment (1) gained, content with organic impurity in the thick cyclohexene oxide of chromatography determination, with 50 parts of impurity, add 25 parts of methyl alcohol, the described process operation rectifying of by specification, reflux ratio 2: 1, refining purity are 95.05% cyclohexene oxide 158.4g, yield 75.05%.
Embodiment (3): by the cyclohexene oxide crude product of embodiment (1) gained, add 25 parts of ethanol, with the identical process operation rectifying of embodiment (2), reflux ratio 3: 1, refining purity are 96.10% cyclohexene oxide 152.9g, yield 73.25%.
Embodiment (4): press the identical method of embodiment (3), the thick cyclohexene oxide 203.81g that obtains with embodiment (1), adding 12.5 parts of methyl alcohol and 12.5 parts of water or 12.5 parts of ethanol and 12.5 parts of water makes with extra care, reflux ratio 4: 1, obtain purity and be 99.5% smart cyclohexene oxide 138.5g, yield 68.70%.
Claims (3)
1, a kind of from cyclohexane oxidation system hexalin, the by product of pimelinketone---reclaim the method for Pentyl alcohol and cyclohexene oxide in the lightweight oil, it is characterized in that earlier lightweight oil being steamed in advance, collect 128～135 ℃ of cuts as raw material, weight with the contained cyclohexene oxide of this raw material is benchmark for 54 parts, add 46 parts in water, air distillation, cyclohexene oxide and water form binary azeotrope, distill out the cyclohexene oxide crude product 90 ± 0.5 ℃ of scopes, distill out the Pentyl alcohol product 135～137.8 ℃ of scopes, thick cyclohexene oxide adds organic entrainer and the crystal heats up in a steamer, and its reflux ratio is 1～4: 1.
2, method according to claim 1, it is characterized in that thick cyclohexene oxide chromatography determination, with the organic impurity content beyond the cyclohexene oxide is benchmark for 50 parts, adds methyl alcohol or ethanol and forms azeotrope for 25 parts, steams the cyclohexene oxide product when 130～132 ℃ of temperature.
3, method according to claim 1, it is characterized in that thick cyclohexene oxide chromatography determination, with 50 parts of the organic impurity contents beyond the cyclohexene oxide is that benchmark adds 12.5 parts of methyl alcohol and 12.5 parts of water or adds 12.5 parts of ethanol and 12.5 parts of water, form azeotrope, when 130～132 ℃ of temperature, steam the cyclohexene oxide product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94113151A CN1059675C (en) | 1994-11-25 | 1994-11-25 | Method for recovering n-pentanol and cyclohexene oxide from light oil, by-products of cyclohexanol and cyclohexanone preparation by cyclohexane oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94113151A CN1059675C (en) | 1994-11-25 | 1994-11-25 | Method for recovering n-pentanol and cyclohexene oxide from light oil, by-products of cyclohexanol and cyclohexanone preparation by cyclohexane oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1106784A CN1106784A (en) | 1995-08-16 |
| CN1059675C true CN1059675C (en) | 2000-12-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94113151A Expired - Fee Related CN1059675C (en) | 1994-11-25 | 1994-11-25 | Method for recovering n-pentanol and cyclohexene oxide from light oil, by-products of cyclohexanol and cyclohexanone preparation by cyclohexane oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1059675C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060758C (en) * | 1996-07-15 | 2001-01-17 | 巴陵石油化工公司鹰山石油化工厂 | Method for recovering useful substances from saponified waste alkali liquor |
| CN1060169C (en) * | 1996-10-22 | 2001-01-03 | 岳阳昌德化工实业有限公司 | Method for recovering epoxy cyclohexane from the by-product clean oil of the oxydation of cyclohexane |
| TWI458700B (en) * | 2011-11-29 | 2014-11-01 | China Petrochemical Dev Corp Taipei Taiwan | Method for separating epoxycyclohexane with n-pentanol |
| CN104098438B (en) * | 2013-04-08 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of method of Separation and Recovery Pentyl alcohol from pimelinketone by-product lightweight oil |
| CN105016993B (en) * | 2015-05-26 | 2017-03-08 | 岳阳昌德化工实业有限公司 | A kind of process for purification of n-hexyl aldehyde |
| CN108624354B (en) * | 2017-03-17 | 2021-10-12 | 中国石油化工股份有限公司 | Method for treating organic by-products in cyclohexanone production process |
| CN113816928B (en) * | 2021-10-29 | 2023-04-21 | 昌德新材科技股份有限公司 | Clean production method for recovering and purifying cyclohexene oxide from oxidized light oil |
| CN116082276B (en) * | 2022-12-23 | 2024-01-23 | 中山大学 | Rectification method for refining ultra-dry cyclohexene oxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4911848A (en) * | 1972-05-16 | 1974-02-01 | ||
| JPS5095248A (en) * | 1973-12-25 | 1975-07-29 |
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1994
- 1994-11-25 CN CN94113151A patent/CN1059675C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4911848A (en) * | 1972-05-16 | 1974-02-01 | ||
| JPS5095248A (en) * | 1973-12-25 | 1975-07-29 |
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| Publication number | Publication date |
|---|---|
| CN1106784A (en) | 1995-08-16 |
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