CN104177231A - Method for extracting cyclohexanol from waste liquor obtained by cyclohexanone preparation by cyclohexane oxidation - Google Patents
Method for extracting cyclohexanol from waste liquor obtained by cyclohexanone preparation by cyclohexane oxidation Download PDFInfo
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- CN104177231A CN104177231A CN201410420015.3A CN201410420015A CN104177231A CN 104177231 A CN104177231 A CN 104177231A CN 201410420015 A CN201410420015 A CN 201410420015A CN 104177231 A CN104177231 A CN 104177231A
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- 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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- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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- 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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Abstract
The invention discloses a method for extracting cyclohexanol from waste liquor obtained by cyclohexanone preparation by cyclohexane oxidation. The method comprises the steps of normal-pressure crude distillation and reduced-pressure extraction and rectification. The extractant in the reduced-pressure extraction and rectification is a double-component extractant composed of triglycol and polyethyleneglycol (PEG-300), and the weight ratio of the triglycol to the PEG-300 to the cyclohexanone waste liquor is 1:(0.8-1.2):(1.4-3.1). By adopting the cyclohexanol extraction method, the cyclohexanol yield is higher than 92%, and the purity of the prepared cyclohexanol finished product is higher than 99.3%.
Description
Technical field
The recovery method that the present invention relates to organic solvent in a kind of hazardous substance waste treatment industry field, more particularly, relates to a kind of method of extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid.
Background technology
Hexalin is mainly for the production of hexanodioic acid, hexanolactam, soluble cotton paint, nylon 66, 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, 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 of soap and synthesis of detergent agent emulsion etc., almost can find the purposes of this product in all chemical industries.
The main synthetic method of domestic hexalin has:
A, laboratory are prepared through hydroboration-oxidizing reaction by tetrahydrobenzene, and chemical reaction signal formula is as follows:
B, phenol hydrogenation or cyclohexane oxidation preparation
C, taking hexanaphthene as raw material, at 170～200 DEG C of pressure 1.47～1.96MPa and temperature, directly use atmospheric oxidation, after concentrated, then with molybdenum, vanadium, cobalt/cobalt oxide be catalyzer, make it to decompose, can obtain hexalin and pimelinketone, then fractionation is refined.
D, pimelinketone is reduced to hexalin.
E, taking hexanaphthene as raw material, under 150～170 DEG C and 0.9～1.2MPa pressure, with acid reaction, then hydrolysis, can generate rough hexalin, after separation, distillation is refining.F, industrial while 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 be by phenol shortening hexalin.
Consider many reasons such as domestic raw material sources, Technological Economy, most domestic adopts cyclohexane oxidation process.Cyclohexane oxidation more complicated, first it generate cyclohexyl hydroperoxide, is then decomposed into hexalin and pimelinketone.Most of pimelinketone is to be generated by hexalin oxidation, and pimelinketone can generate again various oxidized byproducts, and alcohol alcohol/ketone mixtures, through rectifying, is just isolated hexalin and pimelinketone.Isolate in the raffinate of pimelinketone and contain the components such as pimelinketone, hexalin, epoxy cyclohexane, hexanaphthene, water, will environment be produced to very large pollution if do not process direct discharge, 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 of isolating pimelinketone is boiled off after light constituent, adds sodium Metal 99.5, react with hexalin and generate hexamethylene sodium alkoxide, then with pimelinketone layering, after layering, in hexamethylene sodium alkoxide, add water, layering, then separate;
B, the raffinate of isolating pimelinketone is boiled off after light constituent, add SULPHURYL CHLORIDE to kettle base solution, it easily and hexalin be reacted into ester, recycle the poorly soluble different or different cyclohexanone that first steams of boiling-point difference, remaining ester alkali catalyzed hydrolysis, gets back to encircle steaming purifying after alcohol.
Above two kinds of methods owing to operating more complicated, high, the deficiency in economic performance reason that consumes energy, current less employing.
Because the boiling point of hexalin under normal pressure is 161.5 DEG C, the boiling point of pimelinketone is 155.6 DEG C, and boiling-point difference is less, and condensation reaction easily occurs pimelinketone in the time approaching boiling point; There is decomposition and aggregation in hexalin, the long meeting of pimelinketone heated time simultaneously, therefore, separate the raffinate taking hexalin as the pimelinketone of the blending ingredients main, cyclohexanone content is lower, adopt conventional distillating liquid separation method to be difficult to prove effective, even distill under employing high vacuum condition, because hexalin is that master, pimelinketone relative volatility are still lower, obtain high purity cyclohexanol technical difficulty larger, must adopt special rectificating method.Extracting rectifying process is to realize by the difference of Intermolecular Forces between extraction agent and separated key ingredient, because extraction agent is different from the avidity between separated key ingredient, thereby extraction agent can increase separated key ingredient relative volatility, the system that makes general rectifying be difficult to separate can be separated by extracting rectifying process.Extracting rectifying is very potential operating process aspect the separating of nearly boiling point system and azeotrope, domestic University Of Xiangtan once carried out using the research of glycol ether as extraction agent separating ring hexanol-cyclohexanone mixture, also set up separation mathematical model, form related art scheme, but for various reasons, do not realize industrialization; Chemical engineering institute of South China Science & Engineering University has been studied with LiCl, MgCl
2for the extracting and separating effect to this system containing the composite extractant of salt of main ingredient, proposed 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, make it both there is good selectivity, there is again higher solvability, the two is often difficult to ideally take into account, and this point has also directly limited the application of extracting rectifying in more areas.
Summary of the invention
The object of the invention is to overcome the defect of prior art, a kind of method of extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid is provided, reach the object that improves hexalin yield, raising hexalin finished product purity, shortening operational cycle, reduces 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 the two component extraction agents of triglycol, 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 that hexalin content progressively improves and purity higher than 99%, when gas phase temperature is steady rising trend on 115 DEG C of bases simultaneously, switch receiving tank, adjusting reflux ratio is 1.1-1.3, a gas phase temperature 115-118 DEG C cut is put into hexalin receiving tank, make the finished product hexalin.
Described reflux ratio is 1.26.
Described decompression extracting rectifying step, also comprises and regulates 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 is moved 15 minutes under total reflux condition.In the time that 104 DEG C of top gaseous phase temperature arrival, vacuum tightness reach 0.07-0.08MPa, start to intercept pimelinketone, slowly regulating reflux ratio is 1.1-1.3, intercepting 104-106 DEG C of cut of top gaseous phase temperature is pimelinketone, analyzes cyclohexanone content.
Described decompression extracting rectifying step, also comprise and intercept intermediate blend step: when detect that cyclohexanone content declines and purity lower than 99%, when gas phase temperature is in rising trend on 106 DEG C of bases simultaneously, switch receiving tank, adjusting reflux ratio is 1.1-1.3, intercepts 106-115 DEG C of cut of top gaseous phase temperature as intermediate blend.
Adopt the method for described extraction hexalin, hexalin yield is greater than 92%, and the hexalin finished product purity making is greater than 99.3%.
beneficial effect:
The present invention uses two component extraction agents, adopts normal pressure simple distillation and decompression extraction and distillation technology, has formed the novel process of extracting hexalin from the waste liquid of pimelinketone, has following beneficial effect:
1, select the solvent of two kinds of different structures, different physicochemical property, different boiling as extraction agent, bring into play collaborative to the selectivity of triglycol, two kinds of extraction agents of polyoxyethylene glycol (PEG-300) and solvability, significantly improve pimelinketone in pimelinketone waste liquid, hexalin relative volatility, promotion pimelinketone separates with hexalin, under selected operational condition, pimelinketone separates completely with hexalin, the yield of hexalin can reach more than 92%, and the hexalin purity making reaches more than 99.3%.
2, selected simple distillation, two technological process optimal processing parameters of extracting rectifying 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, the disposable still kettle that adds of extraction agent, easy and simple to handle, process is easy to control, and has suitable handiness, economy and practicality, adds under vacuum condition and operates, and pimelinketone and hexalin loss reduce.
4, this technique is simple, and the operational cycle shortens nearly 3 hours, and two component extraction agents can recycle, and reduce production costs, and realize cyclohexane oxidation product maximum revenue, rationally process the three wastes and realize comprehensive utilization of resources.
Embodiment
Embodiment 1
A method of extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid, comprises the following steps:
Normal pressure simple distillation:
(1) by vacuum suction still kettle for pimelinketone waste liquid, open steam valve, 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 steams from distillation tower gradually with a small amount of moisture azeotropic, and intercepting gas phase temperature is the phlegma of 40-100 DEG C.Pause time in rising trend after for some time at 100 DEG C when observing gas phase temperature, steam off valve stops heating.The phlegma that by the gas phase temperature of intercepting is 40-100 DEG C is put into sedimentation still from receiving tank, and in sedimentation still, after 24-48 hour natural subsidence, lightweight oil reservoir separates obvious with water layer, and water is discharged and obtained lightweight oil.
Decompression extracting rectifying:
(1) extraction agent adds step
Using triglycol, polyoxyethylene glycol (PEG-300) as two component extraction agents, triglycol, polyoxyethylene glycol (PEG-300) are squeezed into still kettle with pump, the add-on of two component extraction agents 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) regulate still internal pressure step
Steam regulation pressure is 0.5-0.7MPa, observes temperature in the kettle and tower top temperature changing conditions;
(3) open vacuum jet pump step
In the time observing 100 DEG C of gas phase temperature arrival and be rapid ascendant trend, steam off valve, opens vacuum jet pump;
(4) open steam valve step
Slowly open vacuum valve, in the time that 0.07MPa is above, open steam valve until vacustat;
(5) intercept pimelinketone step
Still kettle system is moved 15 minutes under total reflux condition.In the time that 104 DEG C of top gaseous phase temperature arrival, vacuum tightness reach 0.07-0.08MPa, start to intercept pimelinketone, slowly regulating reflux ratio is 1.1-1.3, intercepting 104-106 DEG C of cut of top gaseous phase temperature is pimelinketone, analyzes cyclohexanone content;
(6) intercept intermediate blend step
When detect that cyclohexanone content declines and purity lower than 99%, when gas phase temperature is in rising trend on 106 DEG C of bases simultaneously, switch receiving tank, adjustings reflux ratio is 1.1-1.3,106-115 DEG C of cut of intercepting top gaseous phase temperature is as intermediate blend;
(7) intercept the finished product hexalin step
Analyze hexalin content in intermediate blend, when detect that hexalin content progressively improves and purity higher than 99%, when gas phase temperature is steady rising trend on 115 DEG C of bases simultaneously, switch receiving tank, adjusting reflux ratio is 1.1-1.3, a gas phase temperature 115-118 DEG C cut is put into hexalin receiving tank, make the finished product hexalin.
Through experiment, hexalin yield is greater than 92%, and the hexalin finished product purity making is greater than 99.3%.
In decompression extracting rectifying, processing parameter is selected:
(1) two component extraction agents is selected
The impact that difference extraction agents bring for quality product and operation needs comprehensive consideration, and one-component extraction agent and two component extraction agents differ larger in the effect of power consumption, increase relative volatility etc.Because extraction agent generally adopts high boiling substance, the overwhelming majority rests on tower reactor, and the chance contacting with feed liquid is very limited, poor to system separating effect.And along with component distillates, tower reactor composition changes, and must choose suitable extraction agent than obtaining higher economy and feasibility, the selection of two component solvents is extremely important for extracting rectifying process, and it is the key that difficult separate substance successfully separates.
In the time selecting, many factors be to consider, source, expense, corrodibility, vapour pressure, thermostability, vaporization heat, reactivity, the infinite dilution activity coefficient of separated component in solvent etc. comprised.Two component mixed solvents can solve selectivity and the conflicting problem of solvability that single solvent exists, and the mixed extraction agent of two components exists best group proportional, over-all properties is better than single solvent, if the mixed extraction agent of two components is selected proper, have under the same conditions higher selectivity than single solvent, the selectivity of the mixed extraction agent of two components is not only closely related with main extraction agent but also have direct relation with another component.
In order to improve the selectivity of extraction agent and to avoid forming two liquid phases of not exclusively dissolving each other in rectifying tower in extracting rectifying process, adopt mixed extractant to improve extracting and separating effect.Mixed extractant all makes hexalin obtain increase in various degree to the relative volatility of pimelinketone.
Through testing: be that extraction agent operates according to embodiment 1 above-mentioned steps by triglycol, two kinds of components of polyoxyethylene glycol (PEG-300), use separately glycol ether to operate according to the same step of embodiment 1 as extraction agent, while using two component extraction agents than independent use glycol ether, hexalin yield improves more than 6.8%, and the purity that makes product improves more than 0.3%.
(2) determining of the consumption of extraction agent
The consumption of extraction agent has a significant impact for separating effect and the economy of extracting rectifying.Ideal situation should be to add a small amount of extraction agent just can increase considerably the relative volatility between component.Extraction agent add-on is conducive to greatly the carrying out of sepn process, but the corresponding increase of required thermal load and operating time, excessive Solvent quantity may be given the batch extracting rectified disadvantageous effect of bringing.
When the concentration of extraction agent is higher, the relative volatility between stock blend is larger, separates required stage number also less.But additive amount is large, recovery cost increases.
Improving adds the amount of the extraction agent in tower to be conducive to the separation of mixture, this is that when because of extraction agent, in tower, concentration increases, the relative volatility of separated key ingredient increases, so under reflux ratio and the certain condition of number of theoretical plate, can steam more qualified product.Can make output improve a lot when extraction agent add-on hour increases its value, now the degree that changes is very little the operating time; But in the time that extraction dosage arrives certain value greatly, product volume has approached all light component in stock liquid, substantially again without the space of improving, also make the thermal load of tower reactor strengthen and there is a large amount of extraction agents in tower, offset owing to adding extraction agent to improve the effect that relative volatility reduces required number of theoretical plate, it is large that the amplitude that the operating time increases becomes.
According to the operation steps of embodiment 1, in the constant situation of other condition, adopt different extraction agent add-ons, the hexalin purity of hexalin yield and preparation is as following table:
Table 1: the impact of extraction agent add-on on 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) determining of reflux ratio
Increase reflux ratio and be conducive to improve quality, but the operating time obviously increase, should combine from the pimelinketone rate of recovery and operating times two aspect and select suitable reflux ratio; When raw material and extraction agent add fashionablely by a certain percentage, also has corresponding optimum reflux ratio.When operation, increase inadequately reflux ratio, just reduced extractant concentration, make on the contrary separating effect variation.
The purity of the reflux ratio in mixture stage that intercepts cyclohexanone, cyclohexanone and hexalin in decompression extracting rectifying mid-early stage on final product and yield impact are not quite, but output, purity and the yield impact of the control of reflux ratio while intercepting the finished product hexalin on final product is very large, 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 reflux ratio is that the hexalin purity of 1.26 o'clock hexalin yields and preparation is best.
Claims (9)
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 the two component extraction agents of triglycol, polyoxyethylene glycol PEG-300.
2. a kind of method of 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 1:0.8-1.2:1.4-3.1.
3. a kind of method of extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid as claimed in claim 2, 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.
4. a kind of method of extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid as claimed in claim 1, it is characterized in that: described decompression extracting rectifying step, comprise and intercept the finished product hexalin step: when detect that hexalin content progressively improves and purity higher than 99%, when gas phase temperature is steady rising trend on 115 DEG C of bases simultaneously, switch receiving tank, adjusting reflux ratio is 1.1-1.3, a gas phase temperature 115-118 DEG C cut is put into hexalin receiving tank, make the finished product hexalin.
5. a kind of method of extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid as claimed in claim 4, is characterized in that: described reflux ratio is 1.26.
6. a kind of method of extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid as claimed in claim 1, is characterized in that: described decompression extracting rectifying step, and also comprise and regulate still internal pressure step, steam regulation pressure is 0.5-0.7MPa.
7. a kind of method of extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid as claimed in claim 1, is characterized in that: described decompression extracting rectifying step, also comprises and intercept pimelinketone step: still kettle system is moved 15 minutes under total reflux condition; In the time that 104 DEG C of top gaseous phase temperature arrival, vacuum tightness reach 0.07-0.08MPa, start to intercept pimelinketone, slowly regulating reflux ratio is 1.1-1.3, intercepting 104-106 DEG C of cut of top gaseous phase temperature is pimelinketone, analyzes cyclohexanone content.
8. a kind of method of extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid as claimed in claim 1, it is characterized in that: described decompression extracting rectifying step, also comprise and intercept intermediate blend step: when detect that cyclohexanone content declines and purity lower than 99%, when gas phase temperature is in rising trend on 106 DEG C of bases simultaneously, switch receiving tank, adjusting reflux ratio is 1.1-1.3, intercepts 106-115 DEG C of cut of top gaseous phase temperature as intermediate blend.
9. a kind of method of extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid as claimed in claim 1, is characterized in that: adopt the method for described extraction hexalin, hexalin yield is greater than 92%, and the hexalin finished product purity making is greater than 99.3%.
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| 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 |
| CN201410420015.3A CN104177231B (en) | 2014-08-25 | 2014-08-25 | A kind of method extracting hexalin from cyclohexane oxidation preparing cyclohexanone waste liquid |
| 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 |
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| 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 |
| CN201510471917.4A Division 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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| CN201510471910.2A Expired - Fee Related CN105061138B (en) | 2014-08-25 | 2014-08-25 | Extractive distillation process for extracting cyclohexanol from cyclohexanone liquid waste |
| 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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| CN104909984A (en) * | 2015-06-10 | 2015-09-16 | 中国天辰工程有限公司 | Method for recycling cyclohexanol from cyclohexanone device waste liquid |
| CN105669346A (en) * | 2016-03-03 | 2016-06-15 | 中国天辰工程有限公司 | Method for comprehensively recycling cyclohexanone device waste oil |
| CN111662160A (en) * | 2019-03-06 | 2020-09-15 | 中国石油化工股份有限公司 | Method for improving productivity of cyclohexanol dehydrogenation device |
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| 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 |
| JPH0931001A (en) * | 1995-07-17 | 1997-02-04 | Mitsubishi Chem Corp | Production of cyclohexanol |
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2014
- 2014-08-25 CN CN201410420015.3A patent/CN104177231B/en not_active Expired - Fee Related
- 2014-08-25 CN CN201510471909.XA patent/CN105152865B/en not_active Expired - Fee Related
- 2014-08-25 CN CN201510471910.2A patent/CN105061138B/en not_active Expired - Fee Related
- 2014-08-25 CN CN201510471917.4A patent/CN105130754B/en active Active
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| US4569726A (en) * | 1984-07-19 | 1986-02-11 | Lloyd Berg | Process for the separation of ethyl acetate from ethanol and water by extractive distillation |
| US5840160A (en) * | 1996-12-06 | 1998-11-24 | Berg; Lloyd | Separation of 3-carene from limonene by extractive distillation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104909984A (en) * | 2015-06-10 | 2015-09-16 | 中国天辰工程有限公司 | Method for recycling cyclohexanol from cyclohexanone device waste liquid |
| CN105669346A (en) * | 2016-03-03 | 2016-06-15 | 中国天辰工程有限公司 | Method for comprehensively recycling cyclohexanone device waste oil |
| CN111662160A (en) * | 2019-03-06 | 2020-09-15 | 中国石油化工股份有限公司 | Method for improving productivity of cyclohexanol dehydrogenation device |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104177231B (en) | 2015-12-02 |
| CN105061138A (en) | 2015-11-18 |
| CN105130754A (en) | 2015-12-09 |
| CN105152865A (en) | 2015-12-16 |
| CN105061138B (en) | 2017-01-11 |
| CN105152865B (en) | 2017-04-05 |
| CN105130754B (en) | 2017-02-01 |
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