CN114805025A - Separation and purification method of cyclohexanol and butyl cyclohexyl ether - Google Patents
Separation and purification method of cyclohexanol and butyl cyclohexyl ether Download PDFInfo
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- cyclohexanol
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- butyl cyclohexyl
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- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000000926 separation method Methods 0.000 title claims abstract description 107
- GKRALBJDXHXFNB-UHFFFAOYSA-N butoxycyclohexane Chemical compound CCCCOC1CCCCC1 GKRALBJDXHXFNB-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000000746 purification Methods 0.000 title claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 239000002608 ionic liquid Substances 0.000 claims abstract description 17
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 10
- -1 alkyl imidazole Chemical compound 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims description 39
- 239000012071 phase Substances 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 238000012856 packing Methods 0.000 claims description 6
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 claims 1
- KZKQFFFEMJUSJN-UHFFFAOYSA-N [N].CN1CCOCC1 Chemical compound [N].CN1CCOCC1 KZKQFFFEMJUSJN-UHFFFAOYSA-N 0.000 claims 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 abstract description 44
- 230000008569 process Effects 0.000 abstract description 23
- 239000002131 composite material Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 3
- 239000002798 polar solvent Substances 0.000 abstract description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000000630 rising effect Effects 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 235000019437 butane-1,3-diol Nutrition 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000006276 transfer reaction Methods 0.000 description 4
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 4
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical class CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000001174 ascending effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- HPXRVTGHNJAIIH-PTQBSOBMSA-N cyclohexanol Chemical class O[13CH]1CCCCC1 HPXRVTGHNJAIIH-PTQBSOBMSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for separating and purifying cyclohexanol and butyl cyclohexyl ether, wherein the purity of the butyl cyclohexyl ether and the purity of the cyclohexanol separated by the method are both more than 99.5 wt%. The extracting agent in the method is a high-boiling-point composite extracting agent, and the alkyl imidazole ionic liquid belongs to a strong polar solvent, and can remarkably increase the relative volatility between cyclohexanol and butyl cyclohexyl ether; the heterocyclic compound containing N or S can play a role in adjusting the viscosity of a composite system, has good solubility and can ensure that an extracting agent and a cyclohexanol system are in a homogeneous phase state, so that the separation efficiency in the rectification process is ensured, the low rectification separation efficiency caused by poor intersolubility of ionic liquid and alcohol is avoided, and the problems of increased material consumption and energy consumption of system operation, shortened service life of a dehydrogenation catalyst and the like caused by continuous accumulation of a byproduct butyl cyclohexyl ether in a cyclohexanol circulating material in the cyclohexanone production process can be solved.
Description
Technical Field
The invention relates to the technical field of separation and purification, and particularly relates to a separation and purification method of cyclohexanol and butyl cyclohexyl ether.
Background
Cyclohexanone is an important chemical raw material for preparing nylon intermediates such as caprolactam, adipic acid and the like, and is widely applied to aspects such as organic solvents, synthetic rubber, industrial coatings and the like.
At present, the production processes of cyclohexanone at home and abroad mainly comprise three types: one is the phenol hydrogenation process; second, benzene hydro-oxidation method; and the third is cyclohexane liquid phase air oxidation process. Wherein, the cyclohexane liquid phase air oxidation method is a process which is widely applied in preparing cyclohexanone at present. The process is carried out in two steps, the first step is an oxidation reaction, and the second step is a decomposition reaction. In the oxidation reaction process, a catalyst is not used, cyclohexanone and cyclohexanol are used as initiators, and the cyclohexane is oxidized into cyclohexyl hydroperoxide, cyclohexanol, cyclohexanone, monocarboxylic acid below C6, dicarboxylic acid below C6 and other byproducts by air or oxygen. In the decomposition reaction process, cobalt acetate is used as a catalyst, cyclohexyl hydrogen peroxide is decomposed into cyclohexanol and cyclohexanone under the conditions of low temperature and alkalinity, and the decomposed reaction product is rectified and separated to finally obtain a high-purity cyclohexanone product and crude cyclohexanol. The crude cyclohexanol is used as a circulating material and is converted into cyclohexanone through dehydrogenation reaction, and the reaction product is converged with a main reaction product and then is refined and separated, so that a cyclohexanone product is mainly obtained.
In the process of preparing cyclohexanone by a cyclohexane liquid-phase air oxidation method, the conversion rate in the cyclohexane oxidation process is generally 3% -5%, the total selectivity of cyclohexanol and cyclohexanone is about 80%, wherein the ratio of cyclohexanone to cyclohexanol is about 1:1, and byproducts are generated simultaneously, wherein butyl cyclohexyl ether is one of the byproducts. The difference between the boiling point of the butyl cyclohexyl ether and the boiling point of the cyclohexanol is small, and the conventional separation process cannot realize effective separation of the butyl cyclohexyl ether and the cyclohexanol, which means that the butyl cyclohexyl ether and the cyclohexanol are always circulated in a system, and are accumulated in the system continuously, and the concentration of the butyl cyclohexyl ether and the cyclohexanol is increased continuously. In the prior production, when the concentration of butyl cyclohexyl ether in a cyclohexanol circulating material is more than 10%, the device needs to be shut down, and a system cyclohexanol material is thrown outwards, so that the production is influenced, the economic benefit of the device is reduced, and the service life of a cyclohexanol dehydrogenation catalyst is also reduced.
Based on this, patent 201911418141.4 discloses a separation process for separating cyclohexanol and butyl cyclohexyl ether by extractive distillation, which uses solvents such as octanol, 1, 3-butanediol, triethylene glycol dimethyl ether and the like as extracting agents, and has the main problems that the performance of alcohol solvents is unstable, high-temperature polymerization phenomenon exists, and the long-period operation requirement of industrial devices cannot be met; meanwhile, the polarity of the solvent molecules is weak, the influence on the relative volatility of the cyclohexanol and the butyl cyclohexyl ether is small, the separation effect of the cyclohexanol and the butyl cyclohexyl ether is poor, the separation energy consumption is large, the purity of the separated butyl cyclohexyl ether can only reach about 97%, the purity of the cyclohexanol can only reach 99.3%, and the application range and the occasion of products are limited. In addition, the boiling point of the solvent is low, and the problems of high separation difficulty, high regeneration energy consumption and the like in the solvent regeneration process exist.
Disclosure of Invention
The invention provides a method for separating and purifying cyclohexanol and butyl cyclohexyl ether, which aims to solve the problems of increased material consumption and energy consumption of an operation system and shortened service life of a dehydrogenation catalyst caused by continuous accumulation of butyl cyclohexyl ether in a cyclohexanone production process.
The invention provides a separation and purification method of cyclohexanol and butyl cyclohexyl ether, which comprises the following steps:
s01: feeding the liquid-phase crude cyclohexanol and the liquid-phase extracting agent into a first separation section of a separation and purification tower, heating the liquid-phase crude cyclohexanol and the liquid-phase extracting agent into a gas phase through a common stripping section of the separation and purification tower, and returning the gas phase to the first separation section and a second separation section of the separation and purification tower; wherein the first separation section is parallel to the second separation section and is located above the common stripping section.
The device used by the method for separating and purifying the cyclohexanol and the butyl cyclohexyl ether can be a double rectifying tower, and can also adopt a separating and purifying tower with an upper partition plate. For convenience of description, the separation and purification column is specifically described in the present invention. In the invention, the top end in the separation and purification tower is provided with a partition board which is vertically arranged and extends along the axis of the tower body of the separation and purification tower. Thereby, the upper interior portion of the separation and purification column is isolated into a first separation section and a second separation section of the separation and purification column, and the first separation section is parallel to the second separation section. The common stripping section is arranged below the first separation section and the second separation section, namely, the separation and purification tower is divided into three spaces by the partition plate. In the invention, the height of the packing of the first separation section is equivalent to 20 to 50 theoretical plates, the height of the packing of the second separation section is equivalent to 10 to 30 theoretical plates, and the height of the packing of the common stripping section is equivalent to 20 to 40 theoretical plates. The separation and purification tower adopts negative pressure operation, and the operation pressure is 5-25 kPa.
Feeding the crude cyclohexanol of the liquid phase and the extractant of the liquid phase generated in the cyclohexanone production device into a first separation section of the separation and purification tower, wherein the feeding position of the extractant is higher than that of the crude cyclohexanol. The crude cyclohexanol comprises cyclohexanone, cyclohexanol, and butyl cyclohexyl ether. Heating the liquid-phase crude cyclohexanol and the liquid-phase extracting agent into gas phase through a common stripping section of the separation and purification tower, and then returning the gas phase rising from the common stripping section to the first separation section and the second separation section.
In the invention, the extracting agent is a high-boiling point composite extracting agent which comprises ionic liquid and a heterocyclic compound solvent containing N or S. The ionic liquid comprises alkyl imidazole ionic liquid, and specifically, the alkyl imidazole ionic liquid comprises chlorinated 1-butyl-3-methylimidazolium salt (chemical formula: [ BMIm ] Cl) or 1-butyl-3-methylimidazolium fluoborate (chemical formula: [ BMIm ] BF 4); the heterocyclic compound solvent containing N or S includes N-methylpyrrolidone or N-methylmorpholine. The alkyl imidazole ionic liquid belongs to a strong polar solvent, has strong intermolecular acting force with cyclohexanol molecules, has small intermolecular acting force with butyl cyclohexyl ether with small molecular polarity, and can remarkably increase the relative volatility between cyclohexanol and butyl cyclohexyl ether; the heterocyclic compound containing N or S can play a role in adjusting the viscosity of a composite system, has good solubility, and can ensure that an extracting agent and a cyclohexanol system are in a homogeneous phase state, so that the separation efficiency of a rectification process is ensured, and the problem of low rectification separation efficiency caused by poor intersolubility of ionic liquid and alcohol is avoided.
Furthermore, the ionic liquid accounts for 40-90 wt%, and the heterocyclic compound solvent containing N or S accounts for 10-60 wt%. More preferably, the ionic liquid accounts for 60 to 80 wt%, and the heterocyclic compound solvent containing N or S accounts for 20 to 40 wt%.
S02: and butyl cyclohexyl ether is obtained at the top of the first separation section, part of the butyl cyclohexyl ether is extracted, and the other part of the butyl cyclohexyl ether is refluxed to the top of the first separation section.
And after the gas phase rising from the common stripping section returns to the first separation section, the gas phase is in countercurrent contact with the crude cyclohexanol to generate mass and heat transfer reaction, so that the cyclohexanol and the butyl cyclohexyl ether are effectively separated. Thus, the top of the first separation section is provided with high-purity gas-phase butylcyclohexyl ether, and the purity of the butylcyclohexyl ether is more than 99 wt%. And condensing the gas-phase butyl cyclohexyl ether obtained from the tower top of the first separation section by using a condenser, collecting a part of obtained liquid-phase butyl cyclohexyl ether as a product, and refluxing the other part of the obtained liquid-phase butyl cyclohexyl ether to the tower top of the first separation section as reflux liquid.
In the invention, in order to effectively separate cyclohexanol and butyl cyclohexyl ether, the tower top temperature of the first separation section is 100-140 ℃, the reflux ratio is 5-20, and the operation pressure is 5-25 kPa.
S03: cyclohexanol is obtained at the top of the second separation section, part of the cyclohexanol is extracted, and the other part of the cyclohexanol reflows to the top of the second separation section.
And after the gas phase rising from the common stripping section returns to the second separation section, the gas phase is in countercurrent contact with the crude cyclohexanol to generate mass and heat transfer reaction, so that the cyclohexanol and the butyl cyclohexyl ether are effectively separated. Thus, high-purity cyclohexanol is obtained at the tower top of the second separation section, and the purity of the cyclohexanol is more than 99 wt%. And condensing the gas-phase cyclohexanol obtained from the tower top of the second separation section by using a condenser, wherein part of the obtained liquid-phase cyclohexanol is extracted as a product, and the other part of the obtained liquid-phase cyclohexanol is refluxed to the tower top of the second separation section as reflux.
In the invention, in order to effectively separate the cyclohexanol and the butyl cyclohexyl ether, the tower top temperature of the second separation section is 100-140 ℃, and the reflux ratio is 3-10.
S04: and the regenerated extracting agent is obtained at the bottom of the common stripping section and enters the first separation section after being condensed.
Liquid phase liquids such as liquid phase butyl cyclohexyl ether from the reflux of the first separation section, liquid phase cyclohexanol from the reflux of the second separation section, liquid phase crude cyclohexanol generated in a cyclohexanone production device, liquid phase extracting agent and the like are in countercurrent contact with ascending gas phase crude cyclohexanol and extracting agent at the bottom of the common stripping section, and mass and heat transfer processes occur. Because the boiling points of all the components of the composite extracting agent are higher than the boiling points of the cyclohexanol and the butyl cyclohexyl ether, the extraction regeneration process is simple in the process of countercurrent contact, and can be realized by only needing a few theoretical plates. Meanwhile, the crude cyclohexanol and the liquid-phase extractant are heated to become gas phase and then enter the first separation section and the second separation section again. Thus, the bottom of the common stripping section obtains the regenerated extracting agent with the purity of more than 99.9wt percent. The regenerated extractant is condensed and then enters the first separation section for recycling.
In the invention, in order to effectively separate cyclohexanol and butyl cyclohexyl ether, the bottom temperature of the public stripping section is 200-280 ℃.
The technical scheme provided by the embodiment of the invention can have the following beneficial effects:
the invention provides a method for separating and purifying cyclohexanol and butyl cyclohexyl ether, the purity of the butyl cyclohexyl ether and cyclohexanol separated by the method can respectively reach more than 99.5 wt% and 99.9 wt%, and the product purity is greatly superior to that of CN 113117361A. The extracting agent in the method provided by the invention is a high-boiling-point composite extracting agent, the alkylimidazole ionic liquid belongs to a strong polar solvent, and has strong intermolecular acting force with cyclohexanol molecules and small intermolecular acting force with butyl cyclohexyl ether with small molecular polarity, so that the relative volatility between cyclohexanol and butyl cyclohexyl ether can be remarkably increased; the heterocyclic compound containing N or S can play a role in adjusting the viscosity of a composite system, has good solubility and can ensure that an extracting agent and a cyclohexanol system are in a homogeneous phase state, so that the separation efficiency in the rectification process is ensured, the low rectification separation efficiency caused by poor intersolubility of ionic liquid and alcohol is avoided, and the problems of increased material consumption and energy consumption of system operation, shortened service life of a dehydrogenation catalyst and the like caused by continuous accumulation of a byproduct butyl cyclohexyl ether in a cyclohexanol circulating material in the cyclohexanone production process can be solved.
The cyclohexanol and the butyl cyclohexyl ether are combined with the molecular property and the solubility of cyclohexanol series, the defect of a single solvent is overcome through compounding of different solvents, the separation effect is greatly improved, the high-efficiency separation of the cyclohexanol and the butyl cyclohexyl ether can be realized, and the high-purity cyclohexanol and the butyl cyclohexyl ether are obtained.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious to those skilled in the art that other drawings can be obtained according to the drawings without any inventive exercise.
FIG. 1 is a process flow diagram for the separation and purification of cyclohexanol and butylcyclohexyl ether provided by the embodiments of the present invention.
Detailed Description
The method for separating and purifying cyclohexanol and butyl cyclohexyl ether provided by the invention comprises the following steps:
s01: crude cyclohexanol in liquid phase produced in a cyclohexanone production plant was fed into the first separation section of a separation and purification column at a feed flow rate of 1000kg/h together with an extractant in liquid phase, and the feed position of the extractant was higher than the feed position of the crude cyclohexanol. The composition of the crude cyclohexanol comprised cyclohexanol in an amount of 0.3 wt% cyclohexanone, in an amount of 90.1 wt% cyclohexanol and in an amount of 9.6 wt% butyl cyclohexyl ether. Heating the liquid-phase crude cyclohexanol and the liquid-phase extracting agent into gas phase through a common stripping section of the separation and purification tower, and then returning the gas phase rising from the common stripping section to the first separation section and the second separation section.
S02: and after the gas phase rising from the common stripping section returns to the first separation section, the gas phase is in countercurrent contact with the crude cyclohexanol to generate mass and heat transfer reaction, so that the cyclohexanol and the butyl cyclohexyl ether are effectively separated. Thus, the top of the first separation section is high-purity gas-phase butylcyclohexyl ether, and the purity of the butylcyclohexyl ether is more than 99.5 wt%. And condensing the gas-phase butyl cyclohexyl ether obtained from the tower top of the first separation section by using a condenser, collecting a part of obtained liquid-phase butyl cyclohexyl ether as a product, and refluxing the other part of the obtained liquid-phase butyl cyclohexyl ether to the tower top of the first separation section as reflux liquid.
S03: and after the gas phase rising from the common stripping section returns to the second separation section, the gas phase is in countercurrent contact with the crude cyclohexanol to generate mass and heat transfer reaction, so that the cyclohexanol and the butyl cyclohexyl ether are effectively separated. Thus, high-purity cyclohexanol is obtained at the tower top of the second separation section, and the purity of the cyclohexanol is more than 99.9 wt%. And condensing the gas-phase cyclohexanol obtained from the tower top of the second separation section by using a condenser, wherein part of the obtained liquid-phase cyclohexanol is extracted as a product, and the other part of the obtained liquid-phase cyclohexanol is refluxed to the tower top of the second separation section as reflux.
S04: liquid phase liquids such as liquid phase butyl cyclohexyl ether from the reflux of the first separation section, liquid phase cyclohexanol from the reflux of the second separation section, liquid phase crude cyclohexanol generated in a cyclohexanone production device, liquid phase extracting agent and the like are in countercurrent contact with ascending gas phase crude cyclohexanol and extracting agent at the bottom of the common stripping section, and mass and heat transfer processes occur. Because the boiling points of all the components of the composite extracting agent are higher than the boiling points of the cyclohexanol and the butyl cyclohexyl ether, the extraction regeneration process is simple in the process of countercurrent contact, and can be realized by only needing a few theoretical plates. Meanwhile, the crude cyclohexanol and the liquid-phase extractant are heated to become gas phase and then enter the first separation section and the second separation section again.
In order to facilitate comparison of the purity of cyclohexanol, the purity of butyl cyclohexyl ether and the purity of regenerated extractant after separation under different process conditions, the following is specified in the form of a table, wherein the feed flow of crude cyclohexanol is 1000kg/h, and the composition of crude cyclohexanol is 90.1 wt% cyclohexanol, 0.3 wt% cyclohexanone and 9.6 wt% butyl cyclohexyl ether. Please refer to table 1 for specific numerical values.
In addition, in order to show that the method for separating and purifying cyclohexanol and butyl cyclohexyl ether provided by the invention has outstanding effects compared with the existing method, the invention also takes an extracting agent formed by combining octanol, 1,3 butanediol and triglyme as an example for comparison, and forms a comparative example, wherein the mass ratio of octanol, 1,3 butanediol and triglyme is 1:2: 1. In the process for separating cyclohexanol and butyl cyclohexyl ether of this comparative example, the process conditions were the same as in example 4 except that the selection of the extractant was different, and the purity of the obtained butyl cyclohexyl ether and the purity of cyclohexanol were as shown in table 1.
Table 1: cyclohexanol purity, butyl cyclohexyl ether purity and regenerated extractant purity after separation under different process conditions
As can be seen from Table 1, under the same feeding flow rate, when the extractant is only a single component, the purity of the butyl cyclohexyl ether is only 85.8 wt%, the purity of the cyclohexanol is 97.99 wt%, and the purity of the regenerated extractant is 99.93 wt%; when the extractant is a composite extractant, the purity of the butyl cyclohexyl ether can reach 99.6 wt%, the purity of the cyclohexanol is 99.91 wt%, and the purity of the regenerated extractant is 99.93 wt%. Therefore, the composite extracting agent can remarkably improve the separating capacity of the butyl cyclohexyl ether and the cyclohexanol.
Under the condition of the same type of the fed extracting agent, the purity of the butyl cyclohexyl ether and the purity of the cyclohexanol are gradually improved along with the improvement of the feeding flow. In addition, for the composite extractant, under the condition that the type and the flow rate of the fed extractant are the same, the purity of the butyl cyclohexyl ether and the cyclohexanol is the maximum when the compounding ratio is 7:3 and the [ BMIm ] Cl + N-methyl pyrrolidone is adopted.
It can be seen from example 4 and the comparative example that, under the same process conditions, when the existing extracting agent is selected from octanol, 1,3 butanediol and triglyme, the purity of the cyclohexanol product obtained by separation is only 97.3%, and the purity of butyl cyclohexyl ether is only 96.6%, while when the extracting agent of the present invention is selected from [ BMIm ] Cl + N-methylpyrrolidone, the purity of the cyclohexanol product obtained by separation is 99.91%, and the purity of butyl cyclohexyl ether is 99.6%, which is obviously higher than that of the extracting agent composed of octanol and the like.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure herein. This invention is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It is to be understood that relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. The invention is not limited to the precise arrangements described above and shown in the drawings, and various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (10)
1. A method for separating and purifying cyclohexanol and butyl cyclohexyl ether is characterized by comprising the following steps:
feeding the liquid-phase crude cyclohexanol and the liquid-phase extracting agent into a first separation section of a separation and purification tower, heating the liquid-phase crude cyclohexanol and the liquid-phase extracting agent into a gas phase through a common stripping section of the separation and purification tower, and returning the gas phase to the first separation section and a second separation section of the separation and purification tower; wherein the first separation section is parallel to the second separation section and above the common stripping section;
butyl cyclohexyl ether is obtained at the top of the first separation section, part of the butyl cyclohexyl ether is extracted, and the other part of the butyl cyclohexyl ether refluxes to the top of the first separation section;
cyclohexanol is obtained at the top of the second separation section, part of the cyclohexanol is extracted, and the other part of the cyclohexanol reflows to the top of the second separation section;
and the regenerated extracting agent is obtained at the bottom of the common stripping section and enters the first separation section after being condensed.
2. The method for separating and purifying cyclohexanol and butylcyclohexyl ether as claimed in claim 1, wherein the extractant comprises ionic liquid, N-or S-containing heterocyclic compound solvent.
3. The method for separating and purifying cyclohexanol and butylcyclohexyl ether according to claim 2, wherein the ratio of the ionic liquid is 40 to 90 wt%, and the ratio of the N-or S-containing heterocyclic compound solvent is 10 to 60 wt%.
4. The method for separating and purifying cyclohexanol and butylcyclohexyl ether according to claim 2, wherein the ionic liquid comprises an alkyl imidazole ionic liquid.
5. The method for separating and purifying cyclohexanol and butylcyclohexyl ether according to claim 4, wherein the alkyl imidazole ionic liquid comprises 1-butyl-3-methylimidazolium chloride or 1-butyl-3-methylimidazolium fluoroborate.
6. The method for separating and purifying cyclohexanol and butylcyclohexyl ether according to claim 2, wherein the N-or S-containing heterocyclic compound solvent includes nitrogen methyl pyrrolidone, nitrogen methyl morpholine.
7. The separation and purification method of cyclohexanol and butylcyclohexyl ether according to claim 1, wherein the packing height of the first separation section is 20 to 50 theoretical plates, the packing height of the second separation section is 10 to 30 theoretical plates, and the packing height of the common stripping section is 20 to 40 theoretical plates.
8. The method for separating and purifying cyclohexanol and butylcyclohexyl ether as claimed in claim 1, wherein the overhead temperature of the first separation section is 100-140 ℃ and the reflux ratio is 5-20.
9. The method for separating and purifying cyclohexanol and butylcyclohexyl ether as claimed in claim 1, wherein the overhead temperature of the second separation section is 100-140 ℃ and the reflux ratio is 3-10.
10. The method for separating and purifying cyclohexanol and butylcyclohexyl ether as claimed in claim 1, wherein the bottom temperature of the common stripping section is 200-280 ℃.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524006A (en) * | 2001-03-20 | 2004-08-25 | �����ɷ� | Ionic liquids as selective additives for separation of close-boiling or azeotropic mixtures |
| CN101265152A (en) * | 2007-03-16 | 2008-09-17 | 中国石油大学(北京) | Application of ionic liquid used as solvent in benzene and cyclohexane extraction, rectification and separation |
| CN102399134A (en) * | 2011-11-29 | 2012-04-04 | 开滦能源化工股份有限公司 | Method for preparing cyclohexanol by cyclohexene hydration |
| CN105435809A (en) * | 2014-08-27 | 2016-03-30 | 中国石油化工股份有限公司 | A hydrogenation catalyst, a preparing method thereof, applications of the hydrogenation catalyst and a hydrogenation reaction method |
| CN105503501A (en) * | 2016-01-17 | 2016-04-20 | 济南大学 | Butanol-cyclohexane azeotropic mixture extractive distillation method |
| CN113004113A (en) * | 2021-03-01 | 2021-06-22 | 广东工业大学 | Method for separating cyclohexane and KA oil by taking ionic liquid as extracting agent |
| CN113214049A (en) * | 2021-05-08 | 2021-08-06 | 青岛科技大学 | Method for separating isopropanol and isopropyl ether by liquid-liquid extraction-flash evaporation |
| CN114315522A (en) * | 2021-12-31 | 2022-04-12 | 昌德新材科技股份有限公司 | Method for purifying cyclohexanol and method for producing cyclohexanone |
-
2022
- 2022-05-27 CN CN202210591702.6A patent/CN114805025A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524006A (en) * | 2001-03-20 | 2004-08-25 | �����ɷ� | Ionic liquids as selective additives for separation of close-boiling or azeotropic mixtures |
| CN101265152A (en) * | 2007-03-16 | 2008-09-17 | 中国石油大学(北京) | Application of ionic liquid used as solvent in benzene and cyclohexane extraction, rectification and separation |
| CN102399134A (en) * | 2011-11-29 | 2012-04-04 | 开滦能源化工股份有限公司 | Method for preparing cyclohexanol by cyclohexene hydration |
| CN105435809A (en) * | 2014-08-27 | 2016-03-30 | 中国石油化工股份有限公司 | A hydrogenation catalyst, a preparing method thereof, applications of the hydrogenation catalyst and a hydrogenation reaction method |
| CN105503501A (en) * | 2016-01-17 | 2016-04-20 | 济南大学 | Butanol-cyclohexane azeotropic mixture extractive distillation method |
| CN113004113A (en) * | 2021-03-01 | 2021-06-22 | 广东工业大学 | Method for separating cyclohexane and KA oil by taking ionic liquid as extracting agent |
| CN113214049A (en) * | 2021-05-08 | 2021-08-06 | 青岛科技大学 | Method for separating isopropanol and isopropyl ether by liquid-liquid extraction-flash evaporation |
| CN114315522A (en) * | 2021-12-31 | 2022-04-12 | 昌德新材科技股份有限公司 | Method for purifying cyclohexanol and method for producing cyclohexanone |
Non-Patent Citations (3)
| Title |
|---|
| 刘诗尧: "萃取精馏分离丁基环己基醚/环己醇二元难分离物系", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, pages 1 * |
| 唐悦等: "离子液体在萃取分离中的应用现状与发展趋势", 《矿冶》, vol. 30, no. 6, pages 54 - 62 * |
| 尹伟超: "共沸物系的离子液体萃取精馏", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, pages 1 * |
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