CN104177218B - A kind of method reclaiming main ingredient from cyclohexanone by-product X oil - Google Patents
A kind of method reclaiming main ingredient from cyclohexanone by-product X oil Download PDFInfo
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Abstract
The invention belongs to technical field of organic chemistry, relate to a kind of from cyclohexanone by-product---reclaim the method for main ingredient X oil.It is characterized in that carrying out a series of process means such as pre-treatment, hydrogenation, hydrolysis and normal-rectification under vacuum to X oil successively, improve the decomposition of pimelinketone oligopolymer, the transformation efficiency of two polyketone is made to reach more than 95%, improve the total recovery that X oil main ingredient reclaims simultaneously, reach more than 60%, improve the utility value of X oil.
Description
Technical field
The invention belongs to technical field of organic chemistry, relate to the method reclaiming main ingredient a kind of by product from cyclohexane oxidation preparing cyclohexanone-X oil.
Background technology
Cyclohexane oxidation preparing cyclohexanone mainly contains following step: the first oxidized obtained cyclohexyl hydroperoxide of hexanaphthene; Cyclohexyl hydroperoxide is decomposed into pimelinketone and hexalin again; Alcohol alcohol/ketone mixtures is refined, and after removing light constituent, rectifying goes out pimelinketone, and remaining hexalin and heavy constituent carry out rectifying again, overhead extraction hexalin, and bottom product is X oil.X oil component is comparatively complicated, and not by comparatively good utilisation, be generally used as fuel and burn, this is large losses useful component not only, also can cause environmental pollution.
Test by analysis, wherein main containing condensess such as pimelinketone, hexalin, 1,2-cyclohexanediol, dicyclo hexyl ether and two polyketone (2-cyclohexylcyclohxanone, 2-(1-cyclohexenyl) pimelinketone), three polyketone in X oil.If can recycle its main ingredient, can economic benefit be produced, also can reduce environmental pollution.
CN1324905A relates to a kind of method being prepared paint by X oil residue, it is characterized in that X oil residue heating and filtering, and filtrate is mixed according to a certain ratio with resin, and a certain proportion of plumbic acetate is added in this mixture, modification at 250 DEG C ~ 400 DEG C after mixing, then aromatic hydrocarbons, C is added in modifier
5or solvent oil, reduce modifier viscosity, then add naphthenic siccative, just obtain paint base, finally in paint base, add pigment, obtain various colored paint.This technique mainly stays a kind for the treatment of method of residue for institute after X oil refining, belong to the oily secondary treatment of X.
CN1131654A relates to a kind of by product---the method for useful matter in X oil in recycling cyclohexane oxidation preparing cyclohexanone, hexalin technique, it is characterized in that by X oil under vacuo rectifying go out two polyketone and three polyketone, then using its softening agent as plastics and the crosslinked toughner of unsaturated polyester, the resource in X oil is made to obtain effective recycling.
Summary of the invention
The object of the present invention is to provide a kind of method reclaiming main ingredient from cyclohexanone by-product-X oil.
The present invention is achieved in that from cyclohexanone by-product---reclaims main ingredient X oil, comprises pre-treatment, hydrogenation, hydrolysis and normal-rectification under vacuum four part, it is characterized in that:
A. pre-treatment: X oil is heated to 80 DEG C ~ 100 DEG C, filtered while hot, removing solid mechanical impurity, obtains X oil filtrate;
B. hydrogenation: add X oil filtrate and hydrogenation catalyst in reactor, controlling temperature of reaction is 80 DEG C ~ 120 DEG C, and reaction pressure is 2MPa ~ 4MPa, and the reaction times is 1 ~ 3 hour, after reaction terminates, filtering recovering catalyst, filtrate is as next step reaction raw materials;
C. be hydrolyzed: in reactor, add above-mentioned process gained filtrate, under water and hydrolyst existence condition, be hydrolyzed reaction, controlling temperature of reaction is 160 DEG C ~ 240 DEG C, and the reaction times is 1 ~ 6 hour, and after reaction terminates, stratification, collects organic phase;
D. normal-rectification under vacuum: hydrolysis gained organic phase adopts continuously or the mode of batch fractionating, rectifying first in atmospheric conditions, and control of reflux ratio, at 1 ~ 6:1, is collected 80 DEG C ~ 83 DEG C cuts, obtained the tetrahydrobenzene that purity reaches more than 99%; Then rectifying at reduced pressure conditions, control vacuum tightness is-0.08MPa ~-0.09MPa, reflux ratio 1 ~ 10:1, collects 90 DEG C ~ 110 DEG C cuts, obtains pimelinketone, cyclohexanol mixture.
Usually, described activity of hydrocatalyst component is Pd, Ni or Pt.
Described catalyst carrier for hydrgenating is gac, aluminum oxide or molecular sieve.
Described carrier is granular, column or powdery.。
Described hydrogenation catalyst add-on is 0.1% ~ 2%(wt of X oil total amount after pre-treatment).
Described hydrolyst be sulfuric acid, carbonic acid, silicotungstic acid, phospho-wolframic acid, to toluene sulphur or solid acid, preferably sulfuric acid or tosic acid.
Described hydrolyst add-on is 2% ~ 10%(wt of X oil total amount after hydrotreatment).
The add-on of described water is 10% ~ 40% of X oil total amount after hydrotreatment.
The reflux ratio of often described-rectification under vacuum all controls at 4 ~ 8:1.
With existing Technical comparing, advantage of the present invention is: 1) by hydrotreatment, and the derivative of the unsaturated cyclohexyl in X oil contained by two polyketone can be converted into the derivative of saturated cyclohexyl, be conducive to two polyketone and be hydrolyzed more thorough, yield is higher; 2) by hydrolysis treatment X oil, 1,2-cyclohexanediol, dicyclo hexyl ether and two polyketone etc. all can better decompose, and obtain the chemical that the added values such as tetrahydrobenzene, pimelinketone and hexalin are higher, improve economic benefit; 3) after process, the residue that stays can continue to use as oil fuel, can not cause environmental pollution.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1
Get X oil 500g, wherein two polyketone content 50.1%, 1,2-cyclohexanediol content 12.3%, dicyclo hexyl ether content 9.18%, filtered while hot after 80 DEG C are heated to it, removing solid mechanical impurity, obtain X oil filtrate 496g; Join in reactor by gained filtrate and 2g palladium-carbon catalyst, temperature of reaction 100 DEG C, reaction pressure 3MPa, 3 hours reaction times, reaction terminates rear filtration, collects filtrate 491g; Gained filtrate and 20g sulfuric acid (98%), 80g water are joined in reactor, temperature of reaction 220 DEG C, 5 hours reaction times, after reaction terminates, stratification, collect organic phase 477g, carry out often-rectification under vacuum to organic phase, under condition of normal pressure, control reflux ratio is 4:1, collect 80 DEG C ~ 83 DEG C cuts, obtain the tetrahydrobenzene 98g that purity is 99.1%.Under reduced pressure, control vacuum tightness is-0.08MPa, reflux ratio 6:1, collects 90 DEG C ~ 110 DEG C cuts, analyzing and testing, containing pimelinketone 175g, hexalin 31g; Wherein the transformation efficiency of two polyketone is 96.5%, and main ingredient total recovery is 60.8%.
Embodiment 2
Get X oil 500g, wherein two polyketone content 37.6%, 1,2-cyclohexanediol content 17.6%, dicyclo hexyl ether content 12.3%, filtered while hot after 90 DEG C are heated to it, removing solid mechanical impurity, obtain X oil filtrate 491g; By gained filtrate and 1.5gPt/Al
2o
3catalyzer joins in reactor, temperature of reaction 110 DEG C, reaction pressure 2.5MPa, 2 hours reaction times, after reaction terminates, filters, collects filtrate 487g; Join in reactor by gained filtrate and 12.5g tosic acid, 100g water, temperature of reaction 240 DEG C, 4 hours reaction times, after reaction terminates, stratification, collects organic phase 476g; Carry out often-rectification under vacuum to organic phase, under condition of normal pressure, control of reflux ratio, at 5:1, collects 80 DEG C ~ 83 DEG C cuts, obtains the tetrahydrobenzene 138g that purity is 99.4%.Under reduced pressure, control vacuum tightness is-0.09MPa, reflux ratio 5:1, collects 90 DEG C ~ 110 DEG C cuts, analyzing and testing, containing pimelinketone 144g, hexalin 28g; Wherein the transformation efficiency of two polyketone is 97.2%, and main ingredient total recovery is 62%.
Embodiment 3
Get X oil 500g, wherein two polyketone content 45.6%, 1,2-cyclohexanediol content 14.3%, dicyclo hexyl ether content 10.4%, filtered while hot after 100 DEG C are heated to it, removing solid mechanical impurity, obtain X oil filtrate 493g; Gained filtrate and 2.5g skeletal nickel catalyst are joined in reactor, temperature of reaction 120 DEG C, reaction pressure 2MPa, 2 hours reaction times, after reaction terminates, filter, collect filtrate 488g; Join in reactor by gained filtrate and 30g solid acid, 50g water, temperature of reaction 230 DEG C, 6 hours reaction times, after reaction terminates, stratification, collects organic phase 473g; Carry out often-rectification under vacuum to organic phase, under condition of normal pressure, control of reflux ratio, at 6:1, collects 80 DEG C ~ 83 DEG C cuts, obtains the tetrahydrobenzene 106g that purity is 99.3%.Under reduced pressure, control vacuum tightness is-0.09MPa, reflux ratio 6:1, collects 90 DEG C ~ 110 DEG C cuts, analyzing and testing, containing pimelinketone 162g, hexalin 33g; Wherein the transformation efficiency of two polyketone is 95.8%, and main ingredient total recovery is 60.2%.
Claims (10)
1. from cyclohexanone by-product-X oil, reclaim a method for main ingredient, comprise pre-treatment, hydrogenation, hydrolysis and normal-rectification under vacuum four part, it is characterized in that:
A. pre-treatment: X oil is heated to 80 DEG C ~ 100 DEG C, filtered while hot, removing solid mechanical impurity, obtains X oil filtrate;
B. hydrogenation: add X oil filtrate and hydrogenation catalyst in reactor, controlling temperature of reaction is 80 DEG C ~ 120 DEG C, and reaction pressure is 2MPa ~ 4MPa, and the reaction times is 1 ~ 3 hour, after reaction terminates, filtering recovering catalyst, filtrate is as next step reaction raw materials;
C. be hydrolyzed: in reactor, add above-mentioned process gained filtrate, under water and hydrolyst existence condition, be hydrolyzed reaction, controlling temperature of reaction is 160 DEG C ~ 240 DEG C, and the reaction times is 1 ~ 6 hour, and after reaction terminates, stratification, collects organic phase;
D. normal-rectification under vacuum: hydrolysis gained organic phase adopts continuously or the mode of batch fractionating, rectifying first in atmospheric conditions, and control of reflux ratio, at 4 ~ 6:1, is collected 80 DEG C ~ 83 DEG C cuts, obtained the tetrahydrobenzene that purity reaches more than 99%; Then rectifying at reduced pressure conditions, control vacuum tightness is-0.08MPa ~-0.09MPa, reflux ratio 4 ~ 6:1, collects 90 DEG C ~ 110 DEG C cuts, obtains pimelinketone, cyclohexanol mixture.
2. method according to claim 1, is characterized in that the active ingredient of described hydrogenation catalyst is Pd, Ni or Pt.
3. method according to claim 1, is characterized in that the carrier of described hydrogenation catalyst is gac, aluminum oxide or molecular sieve.
4. the method according to claim 1 or 3, is characterized in that the carrier of described hydrogenation catalyst is granular, column or powdery.
5. method according to claim 1, is characterized in that described hydrogenation catalyst add-on is 0.1% ~ 2%(wt of X oil total amount after pre-treatment).
6. method according to claim 1, is characterized in that described hydrolyst is sulfuric acid, carbonic acid, silicotungstic acid, phospho-wolframic acid, tosic acid.
7. method according to claim 6, is characterized in that described hydrolyst is sulfuric acid or tosic acid.
8. the method according to claim 1,6 or 7, is characterized in that described hydrolyst add-on is 2% ~ 10%(wt of X oil total amount after hydrotreatment).
9. method according to claim 1, is characterized in that the add-on of water is 10% ~ 40% of X oil total amount after hydrotreatment.
10. method according to claim 1, is characterized in that the reflux ratio in atmospheric distillation and rectification under vacuum process all controls at 4 ~ 6:1.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105016969B (en) * | 2015-07-20 | 2020-11-03 | 沅江华龙催化科技有限公司 | Method for separating cyclohexanol and cyclohexanone from KA oil |
| 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 |
| CN108863746A (en) * | 2017-05-11 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of production method of methyl cyclohexanone |
| CN108299139B (en) * | 2018-01-30 | 2020-10-20 | 岳阳昌德环境科技有限公司 | Preparation method of cyclohexene |
| CN109160876B (en) * | 2018-11-06 | 2022-04-15 | 湖南东为化工新材料有限公司 | Preparation method of electronic grade cyclohexanone |
| CN113943217B (en) * | 2021-08-31 | 2023-08-29 | 唐山旭阳化工有限公司 | Recovery method of dimeric ketone in cyclohexane oxidation byproduct X oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324905A (en) * | 2000-05-22 | 2001-12-05 | 巴陵石化鹰山石油化工厂 | Paint preparing process with x oil residue |
| CN1600761A (en) * | 2003-09-28 | 2005-03-30 | 中国石油化工股份有限公司 | Method for preparing relevant alcohol and ketone by adding hydrogen into hydroperoxide of hydrocarbon |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324905A (en) * | 2000-05-22 | 2001-12-05 | 巴陵石化鹰山石油化工厂 | Paint preparing process with x oil residue |
| CN1600761A (en) * | 2003-09-28 | 2005-03-30 | 中国石油化工股份有限公司 | Method for preparing relevant alcohol and ketone by adding hydrogen into hydroperoxide of hydrocarbon |
Non-Patent Citations (2)
| Title |
|---|
| 环己烷氧化副产物X油的综合利用;吕亮等;《精细石油化工》;20000930(第5期);第1-2页 * |
| 环己烷氧化副产物的综合利用;穆志刚;《山西焦煤科技》;20040731(第7期);第10-12页 * |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |
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