CN104177231B - A kind of method extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid - Google Patents
A kind of method extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid Download PDFInfo
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- CN104177231B CN104177231B CN201410420015.3A CN201410420015A CN104177231B CN 104177231 B CN104177231 B CN 104177231B CN 201410420015 A CN201410420015 A CN 201410420015A CN 104177231 B CN104177231 B CN 104177231B
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- pimelinketone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
- C07C29/84—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by extractive distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
- C07C45/83—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation by extractive distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
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- C07C2601/14—The ring being saturated
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Abstract
The invention discloses a kind of method extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid, the method comprises normal pressure simple distillation, decompression extracting rectifying step, in described decompression extracting rectifying, extraction agent is triglycol, the two component extraction agent of polyoxyethylene glycol (PEG-300), the consumption triglycol of extraction agent: polyoxyethylene glycol PEG-300: pimelinketone waste liquid weight ratio is 1:0.8-1.2:1.4-3.1, adopt the method for this extraction hexalin, hexalin yield is greater than 92%, and obtained hexalin finished product purity is greater than 99.3%.
Description
Technical field
The present invention relates to the recovery method of organic solvent in a kind of hazardous substance waste treatment industry field, more particularly, relate to a kind of method extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid.
Background technology
Hexalin is mainly for the production of hexanodioic acid, hexanolactam, soluble cotton paint, nylon66 fiber, nylon 6, softening agent, sterilizing agent, Insecticides (tech) & Herbicides (tech), sterilant, fibre trimmer, refining of petroleum auxiliary agent, rubber accelerator, pharmaceuticals, makeup etc.; As the broad-spectrum high boiling solvent of one, be used as the solvent of paint, shellac, varnish, rubber, resin and dyestuff etc.; As Degreasing Agent, fur scouring agent, metal detergent and polishing material agent etc.; Also be used as the stablizer etc. of soap and synthesis of detergent agent emulsion, almost can find the purposes of this product in all chemical industries.
Domestic hexalin primary synthetic methods has:
A, laboratory react preparation by tetrahydrobenzene through hydroboration-oxidation, and chemical reaction signal formula is as follows:
Prepared by b, phenol hydrogenation or cyclohexane oxidation
C, be raw material with hexanaphthene, at pressure 1.47 ~ 1.96MPa and temperature 170 ~ 200 DEG C, directly using atmospheric oxidation, after concentrated, then is catalyzer with molybdenum, vanadium, cobalt/cobalt oxide, make it to decompose, can obtain hexalin and pimelinketone, then fractionation is refining.
D, pimelinketone is reduced to hexalin.
E, be raw material with hexanaphthene, with acid reaction under 150 ~ 170 DEG C and 0.9 ~ 1.2MPa pressure, be then hydrolyzed, can generate rough hexalin, after separation, distillation is refining.F, industrial when being prepared by tetrahydrobenzene, tetrahydrobenzene and 70% ~ 80% sulfuric acid reaction, or pimelinketone in alkaline medium by platinum, silica gel catalyst hydrogenation, or make catalyzer vapour phase hydrogenation in 140 ~ 150 DEG C by nickel, also can by phenol shortening hexalin.
Consider many reasons such as internal sources source, Technological Economy, most domestic adopts cyclohexane oxidation process.Cyclohexane oxidation more complicated, first it generate cyclohexyl hydroperoxide, is then decomposed into hexalin and pimelinketone.Major part pimelinketone is generated by cyclohexanol, and pimelinketone can generate various oxidized byproduct again, alcohol alcohol/ketone mixtures, through rectifying, just isolates hexalin and pimelinketone.Isolate containing components such as pimelinketone, hexalin, epoxy cyclohexane, hexanaphthene, water in the raffinate of pimelinketone, if do not process directly discharge environment will be produced to very large pollution, this is also that state's laws regulation institute is unallowed.Under prior art condition, from view of theory, the possible separation method of hexalin and pimelinketone has:
A, the raffinate isolating pimelinketone is boiled off light constituent after, add sodium Metal 99.5, react with hexalin and generate hexamethylene sodium alkoxide, then with pimelinketone layering, after layering, add water in hexamethylene sodium alkoxide, layering, then be separated;
B, the raffinate isolating pimelinketone is boiled off light constituent after, add SULPHURYL CHLORIDE to kettle base solution, it easily and hexalin be reacted into ester, recycle poorly soluble different or boiling-point difference is different first steams cyclohexanone, remaining ester alkali catalyzed hydrolysis, gets back to ring and steams purifying after alcohol.
Above two kinds of methods owing to operating more complicated, consume energy high, deficiency in economic performance reason, current less employing.
Boiling point due to hexalin under normal pressure is 161.5 DEG C, and the boiling point of pimelinketone is 155.6 DEG C, and boiling-point difference is less, and easily there is condensation reaction close to pimelinketone during boiling point; Can there is decomposition and aggregation in hexalin, pimelinketone heated time length simultaneously, therefore, be separated based on hexalin, the raffinate of the pimelinketone of blending ingredients that cyclohexanone content is lower, conventional distil-lation liquid separation method is adopted to be difficult to prove effective, even if distill under employing high vacuum condition, due to hexalin be main, pimelinketone relative volatility is still lower, obtain high purity cyclohexanol technical difficulty comparatively large, special rectificating method must be adopted.Extracting rectifying process is realized by the difference of Intermolecular Forces between extraction agent and separated key ingredient, because the avidity between extraction agent from separated key ingredient is different, thus extraction agent can increase separated key ingredient relative volatility, and the system making general rectifying be difficult to be separated can be separated by extracting rectifying process.Extracting rectifying is very potential operating process in being separated of nearly boiling point system and azeotrope, domestic University Of Xiangtan once carried out the research using glycol ether as extraction agent isolate cyclohexanol-cyclohexanone mixture, also separation mathematical model is established, define related art scheme, but for various reasons, do not realize industrialization; Chemical engineering institute of South China Science & Engineering University have studied with LiCl, MgCl
2for the composite extractant containing salt of main ingredient is to the extracting and separating effect of this system, propose comparatively believable operational path and energy-saving effect, but overall technology do not have important breakthrough.
Extracting rectifying generally uses single solvent as extraction agent traditionally, but the solvent with highly selective is often with not mutual solubility or lower solvability, therefore need to choose suitable solvent by balance, it is made both to have had good selectivity, there is again higher solvability, both is often difficult to ideally take into account, and this point also directly limit the application of extracting rectifying in more areas.
Summary of the invention
The object of the invention is to the defect overcoming prior art, a kind of method extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid is provided, reach the object improving hexalin yield, improve hexalin finished product purity, shorten the operational cycle, reduce energy consumption.
For achieving the above object, the present invention is by the following technical solutions:
From cyclohexane oxidation preparing cyclohexanone waste liquid, extract a method for hexalin, comprise normal pressure simple distillation step and decompression extracting rectifying step, in described decompression extracting rectifying, extraction agent is triglycol, the two component extraction agent of polyoxyethylene glycol PEG-300.
Below the further improvement to technique scheme:
The consumption of described extraction agent is: triglycol: polyoxyethylene glycol PEG-300: pimelinketone waste liquid weight ratio is 1:0.8-1.2:1.4-3.1.
The consumption of described extraction agent is: triglycol: polyoxyethylene glycol PEG-300: pimelinketone waste liquid weight ratio is 1:1.0:2.0.
Described decompression extracting rectifying step, comprise and intercept the finished product hexalin step: when detect hexalin content progressively improve and purity higher than 99%, when gas phase temperature is steady slowly ascendant trend on 115 DEG C of bases simultaneously, switch receiving tank, adjustment reflux ratio is 1.1-1.3, a gas phase temperature 115-118 DEG C cut is put into hexalin receiving tank, obtained the finished product hexalin.
Described reflux ratio is 1.26.
Described decompression extracting rectifying step, also comprise and regulate still internal pressure step, steam regulation pressure is 0.5-0.7MPa.
Described decompression extracting rectifying step, also comprises and intercepts pimelinketone step: still kettle system runs 15 minutes under total reflux conditions.When top gaseous phase temperature arrive 104 DEG C, vacuum tightness reach 0.07-0.08MPa time, start to intercept pimelinketone, slowly regulate reflux ratio to be 1.1-1.3, intercepting top gaseous phase temperature 104-106 DEG C of cut is pimelinketone, analyzes cyclohexanone content.
Described decompression extracting rectifying step, also comprise and intercept intermediate blend step: when detect cyclohexanone content decline and purity lower than 99%, gas phase temperature is in rising trend on 106 DEG C of bases simultaneously time, switch receiving tank, adjustment reflux ratio is 1.1-1.3, intercepts top gaseous phase temperature 106-115 DEG C of cut as intermediate blend.
Adopt the method for described extraction hexalin, hexalin yield is greater than 92%, and obtained hexalin finished product purity is greater than 99.3%.
beneficial effect:
The present invention uses two component extraction agent, adopts normal pressure simple distillation and decompression extraction and distillation technology, defines the novel process extracting hexalin from the waste liquid of pimelinketone, have following beneficial effect:
1, select the solvent of two kinds of different structures, different physicochemical property, different boiling as extraction agent, the selectivity of triglycol, polyoxyethylene glycol (PEG-300) two kinds of extraction agents and solvability are worked in coordination with and brings into play, significantly improve pimelinketone waste liquid cyclohexanone, hexalin relative volatility, promotion pimelinketone is separated with hexalin, under selected operational condition, pimelinketone separates completely with hexalin, the yield of hexalin can reach more than 92%, and obtained hexalin purity reaches more than 99.3%.
2, selected simple distillation, extracting rectifying two technological process optimal processing parameters and the rational optimum extraction condition of two component extraction agents, reduce energy consumption, and energy consumption declines 3%.
3, adopt batch extracting rectified technique, extraction agent is disposable adds still kettle, easy and simple to handle, and process is easy to control, and have suitable handiness, economy and practicality, operate under adding vacuum condition, pimelinketone and hexalin loss reduce.
4, this technique is simple, and the operational cycle shortens nearly 3 hours, and two component extraction agent can recycle, and reduces production cost, realizes cyclohexane oxidation product maximum revenue, and rationally the process three wastes realize comprehensive utilization of resources.
Embodiment
Embodiment 1
From cyclohexane oxidation preparing cyclohexanone waste liquid, extract a method for hexalin, comprise the following steps:
Normal pressure simple distillation:
(1) by pimelinketone waste liquid vacuum suction still kettle, steam valve is opened, material in heating kettle;
(2) steam regulation pressure is 0.2-0.7MPa, observes temperature in the kettle and tower top temperature changing conditions;
(3) the lightweight oil component in waste liquid and a small amount of moisture azeotropic steam from distillation tower gradually, intercept the phlegma that gas phase temperature is 40-100 DEG C.When observing gas phase temperature and being in rising trend after 100 DEG C are paused for some time, steam off valve stops heating.Be that the phlegma of 40-100 DEG C puts into sedimentation still from receiving tank by the gas phase temperature of intercepting, in sedimentation still after 24-48 hour natural subsidence, light oil bed is separated with water layer obviously, is discharged by water and obtains lightweight oil.
Decompression extracting rectifying:
(1) extraction agent adds step
Using triglycol, polyoxyethylene glycol (PEG-300) as two component extraction agent, with pump, triglycol, polyoxyethylene glycol (PEG-300) are squeezed into still kettle, the add-on of two component extraction agent is by triglycol: polyoxyethylene glycol (PEG-300): pimelinketone waste liquid weight ratio is that 1:0.8-1.2:1.4-3.1 adds, open steam valve, material in heating kettle;
(2) still internal pressure step is regulated
Steam regulation pressure is 0.5-0.7MPa, observes temperature in the kettle and tower top temperature changing conditions;
(3) vacuum jet pump step is opened
When observing gas phase temperature and arrive 100 DEG C and in rapid ascendant trend, steam off valve, opens vacuum jet pump;
(4) steam valve step is opened
Slow unlatching vacuum valve, when vacustat is at more than 0.07MPa, opens steam valve;
(5) pimelinketone step is intercepted
Still kettle system runs 15 minutes under total reflux conditions.When top gaseous phase temperature arrive 104 DEG C, vacuum tightness reach 0.07-0.08MPa time, start to intercept pimelinketone, slowly regulate reflux ratio to be 1.1-1.3, intercepting top gaseous phase temperature 104-106 DEG C of cut is pimelinketone, analyzes cyclohexanone content;
(6) intermediate blend step is intercepted
When detect cyclohexanone content decline and purity lower than 99%, gas phase temperature is in rising trend on 106 DEG C of bases simultaneously time, switch receiving tank, adjustments reflux ratio is 1.1-1.3, and intercepting top gaseous phase temperature 106-115 DEG C of cut is as intermediate blend;
(7) the finished product hexalin step is intercepted
Analyze hexalin content in intermediate blend, when detect hexalin content progressively improve and purity higher than 99%, when gas phase temperature is steady slowly ascendant trend on 115 DEG C of bases simultaneously, switch receiving tank, adjustment reflux ratio is 1.1-1.3, a gas phase temperature 115-118 DEG C cut is put into hexalin receiving tank, obtained the finished product hexalin.
Through experiment, hexalin yield is greater than 92%, and obtained hexalin finished product purity is greater than 99.3%.
In decompression extracting rectifying, processing parameter is selected:
(1) two component extraction agent is selected
Different extraction agent needs to consider for the impact that quality product and operation are brought comprehensively, and one-component extraction agent differs larger with two component extraction agent in the effect of the relative volatility etc. that consumes energy, increases.Because extraction agent generally adopts high boiling substance, the overwhelming majority rests on tower reactor, and the chance contacted with feed liquid is very limited, poor to system separating effect.And distillate along with component, the change of tower reactor composition, must choose suitable extraction agent than obtaining higher economy and feasibility, and the selection of two component solvent is for extremely important extracting rectifying process, and it is the key that difficult separate substance is successfully separated.
Many factors to be considered when selecting, comprising source, expense, corrodibility, vapour pressure, thermostability, vaporization heat, reactivity, separated component infinite dilution activity coefficient etc. in a solvent.Two component mixed solvent can solve selectivity and the conflicting problem of solvability of single solvent existence, and two component mixes extraction agent there is best proportion of composing, over-all properties is better than single solvent, select proper if two component mixes extraction agent, have higher selectivity under the same conditions than single solvent, it is not only closely related with main extraction agent but also have direct relation with another component that two component mixes the selectivity of extraction agent.
In order to improve the selectivity of extraction agent and avoid forming two liquid phases of not exclusively dissolving each other in extracting rectifying process in rectifying tower, mixed extractant is adopted to improve extracting and separating effect.The increase that mixed extractant all makes the relative volatility of hexalin to pimelinketone obtain in various degree.
Through test: be that extraction agent operates according to embodiment 1 above-mentioned steps by triglycol, polyoxyethylene glycol (PEG-300) two kinds of components, be used alone glycol ether to operate according to the same step of embodiment 1 as extraction agent, when using two component extraction agent ratio to be used alone glycol ether, hexalin yield improves more than 6.8%, and the purity of obtained product improves more than 0.3%.
(2) determination of the consumption of extraction agent
The consumption of extraction agent has a significant impact for the separating effect of extracting rectifying and economy.Ideal situation should be add a small amount of extraction agent just can increase considerably relative volatility between component.Extraction agent add-on is conducive to greatly the carrying out of sepn process, but required thermal load and operating time corresponding increase, excessive Solvent quantity may bring disadvantageous effect to batch extracting rectified.
When the concentration of extraction agent is higher, the relative volatility between stock blend is comparatively large, and the stage number needed for separation is also less.But additive amount is large, recovery cost increases.
The amount improving the extraction agent added in tower is conducive to the separation of mixture, this is because extraction agent in tower concentration increase time separated key ingredient relative volatility increase, so under reflux ratio and the certain condition of number of theoretical plate, more qualified product can be steamed.Increasing its value when extraction agent add-on is less can make output improve a lot, and now the degree of operating time change is very little; But when extracting dosage and arriving greatly certain value, product volume is close to Light ends whole in stock liquid, substantially again without the space of improving, and have a large amount of extraction agents in tower and also make the thermal load of tower reactor strengthen, counteract the effect required number of theoretical plate being reduced owing to adding extraction agent raising relative volatility, the amplitude that the operating time increases becomes large.
According to the operation steps of embodiment 1, when other condition is constant, adopt different extraction agent add-ons, the hexalin purity of hexalin yield and preparation is as following table:
Table 1: extraction agent add-on is on the impact of preparation result
As seen from the above table, triglycol: polyoxyethylene glycol (PEG-300): when pimelinketone waste liquid weight ratio is 1:0.8-1.2:1.4-3.1, hexalin yield reaches 92.1%-92.8%, the hexalin purity of preparation reaches 99.3%-99.7%.
Triglycol: polyoxyethylene glycol (PEG-300): hexalin yield 94.8% when pimelinketone waste liquid weight ratio is 1:1.0:2.0, the hexalin purity 99.7% of preparation, this add-on is optimum value.
(3) determination of reflux ratio
Increase reflux ratio to be conducive to improving quality, but the operating time obviously increases, should combine from the pimelinketone rate of recovery and operating time two aspect and select suitable reflux ratio; When raw material and extraction agent add fashionable by a certain percentage, also has corresponding optimum reflux ratio.Increase reflux ratio inadequately during operation, just reduce extractant concentration, make separating effect be deteriorated on the contrary.
The reflux ratio intercepting the mixture stage of cyclohexanone, cyclohexanone and hexalin in decompression extracting rectifying mid-early stage affects not quite on the purity of final product and yield, but control of reflux ratio when intercepting the finished product hexalin is very large on the impact of the output of final product, purity and yield, through test of many times, the hexalin purity of hexalin yield and preparation when reflux ratio is 1.1-1.3 is all better, and the hexalin purity of hexalin yield and preparation when reflux ratio is 1.26 is best.
Claims (2)
1. one kind is extracted the method for hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid, comprise normal pressure simple distillation step and decompression extracting rectifying step, it is characterized in that: in described decompression extracting rectifying, extraction agent is triglycol, the two component extraction agent of polyoxyethylene glycol PEG-300;
The consumption of described extraction agent is: triglycol: polyoxyethylene glycol PEG-300: pimelinketone waste liquid weight ratio is 1:0.8-1.2:1.4-3.1.
2. a kind of method extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid as claimed in claim 1, is characterized in that: the consumption of described extraction agent is: triglycol: polyoxyethylene glycol PEG-300: pimelinketone waste liquid weight ratio is 1:1.0:2.0.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510471917.4A CN105130754B (en) | 2014-08-25 | 2014-08-25 | Method for extracting cyclohexanol from cyclohexanone waste liquid by using composite extractant |
| CN201510471910.2A CN105061138B (en) | 2014-08-25 | 2014-08-25 | Extractive distillation process for extracting cyclohexanol from cyclohexanone liquid waste |
| CN201410420015.3A CN104177231B (en) | 2014-08-25 | 2014-08-25 | A kind of method extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid |
| CN201510471909.XA CN105152865B (en) | 2014-08-25 | 2014-08-25 | It is a kind of that the method that high purity cyclohexanol is extracted in cyclohexanone waste liquid is produced from hexamethylene |
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| CN201410420015.3A CN104177231B (en) | 2014-08-25 | 2014-08-25 | A kind of method extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid |
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| CN201510471917.4A Division CN105130754B (en) | 2014-08-25 | 2014-08-25 | Method for extracting cyclohexanol from cyclohexanone waste liquid by using composite extractant |
| CN201510471909.XA Division CN105152865B (en) | 2014-08-25 | 2014-08-25 | It is a kind of that the method that high purity cyclohexanol is extracted in cyclohexanone waste liquid is produced from hexamethylene |
| CN201510471910.2A Division CN105061138B (en) | 2014-08-25 | 2014-08-25 | Extractive distillation process for extracting cyclohexanol from cyclohexanone liquid waste |
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| CN104177231A CN104177231A (en) | 2014-12-03 |
| CN104177231B true CN104177231B (en) | 2015-12-02 |
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| CN201510471909.XA Expired - Fee Related CN105152865B (en) | 2014-08-25 | 2014-08-25 | It is a kind of that the method that high purity cyclohexanol is extracted in cyclohexanone waste liquid is produced from hexamethylene |
| CN201510471910.2A Expired - Fee Related CN105061138B (en) | 2014-08-25 | 2014-08-25 | Extractive distillation process for extracting cyclohexanol from cyclohexanone liquid waste |
| CN201410420015.3A Expired - Fee Related CN104177231B (en) | 2014-08-25 | 2014-08-25 | A kind of method extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid |
| CN201510471917.4A Active CN105130754B (en) | 2014-08-25 | 2014-08-25 | Method for extracting cyclohexanol from cyclohexanone waste liquid by using composite extractant |
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| CN201510471909.XA Expired - Fee Related CN105152865B (en) | 2014-08-25 | 2014-08-25 | It is a kind of that the method that high purity cyclohexanol is extracted in cyclohexanone waste liquid is produced from hexamethylene |
| CN201510471910.2A Expired - Fee Related CN105061138B (en) | 2014-08-25 | 2014-08-25 | Extractive distillation process for extracting cyclohexanol from cyclohexanone liquid waste |
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| CN104909984B (en) * | 2015-06-10 | 2016-08-17 | 中国天辰工程有限公司 | A kind of method reclaiming Hexalin from pimelinketone device waste liquid |
| CN105669346B (en) * | 2016-03-03 | 2018-11-27 | 中国天辰工程有限公司 | A kind of method of pimelinketone device waste oil recycling comprehensive utilization |
| CN111662160B (en) * | 2019-03-06 | 2024-04-12 | 中国石油化工股份有限公司 | Method for improving productivity of cyclohexanol dehydrogenation device |
| CN114920624A (en) * | 2022-05-27 | 2022-08-19 | 辽宁石油化工大学 | Separation and purification method and system for cyclohexanol and butyl cyclohexyl ether |
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| GB774687A (en) * | 1953-02-20 | 1957-05-15 | Bayer Ag | Process for the production of -e-hydroxycaproic acid esters |
| US3987100A (en) * | 1974-04-11 | 1976-10-19 | E. I. Du Pont De Nemours And Company | Cyclohexane oxidation in the presence of binary catalysts |
| US4187152A (en) * | 1978-12-29 | 1980-02-05 | Allied Chemical Corporation | Extractive distillation for separating ketones and/or alcohols from phenol and/or cresol |
| US4569726A (en) * | 1984-07-19 | 1986-02-11 | Lloyd Berg | Process for the separation of ethyl acetate from ethanol and water by extractive distillation |
| JPH0931001A (en) * | 1995-07-17 | 1997-02-04 | Mitsubishi Chem Corp | Production of cyclohexanol |
| US5840160A (en) * | 1996-12-06 | 1998-11-24 | Berg; Lloyd | Separation of 3-carene from limonene by extractive distillation |
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| CN105152865A (en) | 2015-12-16 |
| CN105061138B (en) | 2017-01-11 |
| CN105061138A (en) | 2015-11-18 |
| CN105130754A (en) | 2015-12-09 |
| CN104177231A (en) | 2014-12-03 |
| CN105152865B (en) | 2017-04-05 |
| CN105130754B (en) | 2017-02-01 |
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