CN112745208A - Cyclohexanone recovery and separation process and system - Google Patents
Cyclohexanone recovery and separation process and system Download PDFInfo
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- CN112745208A CN112745208A CN201911047310.8A CN201911047310A CN112745208A CN 112745208 A CN112745208 A CN 112745208A CN 201911047310 A CN201911047310 A CN 201911047310A CN 112745208 A CN112745208 A CN 112745208A
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 410
- 238000011084 recovery Methods 0.000 title claims abstract description 79
- 238000000926 separation method Methods 0.000 title claims abstract description 20
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 91
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000007791 liquid phase Substances 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000012856 packing Methods 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 13
- 239000000945 filler Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- -1 cyclohexanol ester Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
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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
-
- 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
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a cyclohexanone recycling and separating process and a cyclohexanone recycling and separating system. The process comprises the following steps: feeding the cyclohexanone and cyclohexanol mixture from the front-end hydrolysis unit into a light component removal tower as a light component removal tower feed; the light components at the top of the light component removal tower sequentially enter a primary cyclohexanone recovery tower and a secondary cyclohexanone recovery tower to recover cyclohexanone; heavy components at the bottom of the light component removal tower enter a cyclohexanone tower, cyclohexanone products are produced at the top of the cyclohexanone tower, and the heavy components enter a cyclohexanol tower at the bottom of the cyclohexanone tower; producing high-concentration cyclohexanol at the tower top of the cyclohexanol tower, and discharging heavy component impurities at the tower bottom of the cyclohexanol tower; extracting a liquid phase from the middle section of the cyclohexanol tower and feeding the liquid phase as a liquid phase of a first-stage cyclohexanone recovery tower; and mixing the tower bottom material of the secondary cyclohexanone recovery tower with the tower bottom material of the lightness-removing tower, and then feeding the mixture into the cyclohexanone tower. The process of the invention effectively reduces the material consumption in the cyclohexanone separation process and improves the yield of cyclohexanone while ensuring the impurity removal efficiency.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a cyclohexanone separation and refining process.
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. In industrial production, cyclohexanone is mainly produced by dehydrogenation of cyclohexanol over a catalyst. The dehydrogenation reaction of cyclohexanol includes several parallel competing reactions, wherein the dehydrogenation of cyclohexanol to produce cyclohexanone is the main reaction, the side reaction mainly comprises dehydration of cyclohexanol to produce cyclohexene, aromatization of cyclohexanol to produce phenol, and condensation of cyclohexanone to produce cyclohexenyl cyclohexanone, etc., and the reaction products are collectively called as crude alcohol-ketone mixture. At present, the crude alcohol-ketone mixture after cyclohexanol dehydrogenation in the traditional process is generally refined by adopting a distillation flow of firstly removing light components and then removing heavy components. The main equipment in the process comprises a light component removing tower, a cyclohexanone tower and a cyclohexanol tower. The high-purity qualified product cyclohexanone (> 99.98%) and cyclohexanol (> 90%) meeting the dehydrogenation reaction requirement are obtained through separation and refining.
At present, the production processes of cyclohexanone at home and abroad mainly comprise three types: one is the phenol catalytic hydrogenation process; secondly, the yield of the cyclohexanol catalytic dehydrogenation method in the current industry is generally between 55 and 65 percent. And the method is a cyclohexane liquid-phase air oxidation method, which is a main process for producing cyclohexanone and cyclohexanol in the world at present.
The foreign research on the cyclohexanone production process mainly focuses on the optimization and upgrading of the catalyst, and aims to improve the conversion rate of the cyclohexane to the cyclohexanone and the cyclohexanol through catalytic oxidation and reduce the cyclohexane circulation amount of a system; while there is essentially no report on the process for the separation of cyclohexanone and cyclohexanol.
The process adopted by the domestic cyclohexanone production device is mainly a non-catalytic oxidation method (such as the holy petrochemical industry), and the method is characterized in that the reaction for preparing the cyclohexanone by oxidizing cyclohexane is carried out in two steps: the first step is an oxidation reaction, wherein a catalyst is not used in the reaction, cyclohexanone and cyclohexanol are used as initiators, and the cyclohexane is oxidized into cyclohexyl hydroperoxide, cyclohexanone, cyclohexanol, C6 lower mono-carboxylic acid, di-carboxylic acid and cyclohexanol ester thereof by using air or oxygen; the second step is decomposition reaction, cobalt acetate (or other cobalt salts) is used as a catalyst, cyclohexyl hydrogen peroxide is decomposed into cyclohexanol and cyclohexanone under low temperature and alkaline conditions, the decomposed reaction liquid is rectified and separated to obtain cyclohexanone and crude cyclohexanol, the crude cyclohexanol is dehydrogenated to obtain cyclohexanone, the cyclohexane conversion rate is generally 3% -5%, and the total selectivity of cyclohexanol and cyclohexanone is about 80%. In the process of converting benzene into cyclohexanone in the production process, the conversion rate and the selectivity are low, a large amount of byproducts are generated in the reaction process, and a series of separation and refining processes are required to obtain a high-purity cyclohexanone product.
CN201710254368.4 discloses a rectification device and a rectification method for cyclohexanone, which comprise a light component first tower, a cyclohexanone first tower, a light component second tower and a cyclohexanone second tower; and a tower kettle of the first cyclohexanone tower is provided with a waste heat reboiler. The method comprises the steps that a cyclohexanone/cyclohexanol mixed compound enters a light component first tower, a tower top extracted material of the light component first tower enters a waste heat reboiler, heat exchange is carried out on a tower bottom material of the cyclohexanone first tower, the extracted material is combined with condensate of uncondensed gas and then respectively enters a light component first tower reflux port and a light component second tower feed port, light oil is extracted from the tower top of the light component second tower, a tower bottom extracted material of the light component second tower enters a feed port of the cyclohexanone second tower, solvent-grade cyclohexanone is extracted from the tower top of the cyclohexanone second tower, tower bottom extracted materials of the light component first tower and the cyclohexanone second tower enter a tower first cyclohexanone feed port, and a tower top of the cyclohexanone first tower is used for extracting chemical fiber-grade cyclohexanone. The process flow of the invention is to synthesize the low temperature of a plurality of cyclohexanone separating devices into the high-efficiency utilization of heat energy, and the energy consumption is low.
The research of the prior cyclohexanone production process mainly focuses on the research of the cyclohexane oxidation catalyst, and aims to improve the selectivity of the cyclohexane oxidation catalyst, while the research of patents and documents on the refining process of the cyclohexanone crude product is less. In the refining process of cyclohexanone, the light components in products (such as cyclohexanone, cyclohexanol, butanone, butanol, pentanone, pentanol and other mixtures) from cyclohexane oxidation are more, and the high-purity cyclohexanone product needs to be subjected to the light component removal treatment firstly to obtain the high-purity cyclohexanone product. In the prior art, a cyclohexanone lightness-removing tower adopts a two-stage series process for separation and recovery, and the concentration of cyclohexanone in tower bottom materials of a two-stage cyclohexanone recovery tower is about 30 percent. The process flow has the problems of large cyclohexanone loss and high energy consumption, and how to reduce the cyclohexanone loss rate in the process of removing light cyclohexanone is not reported in relevant researches.
Disclosure of Invention
Aiming at the problems of large cyclohexanone loss and high material consumption in the existing cyclohexanone separation and refining process, the invention aims to provide a novel separation process and a novel separation system, which can effectively reduce the material consumption in the cyclohexanone separation process and improve the cyclohexanone yield while ensuring the impurity removal efficiency.
The invention provides a cyclohexanone recycling and separating process, which comprises the following steps:
feeding a cyclohexanone and cyclohexanol mixture from a front-end hydrolysis unit into a light component removal tower, and separating the mixture by the light component removal tower to obtain a raw material which is divided into two parts, namely a light component at the top of the light component removal tower and a heavy component at the bottom of the light component removal tower;
the light components at the top of the light component removal tower sequentially enter a primary cyclohexanone recovery tower and a secondary cyclohexanone recovery tower to recover cyclohexanone;
heavy component substances at the bottom of the light component removal tower are used as raw materials to enter a cyclohexanone tower, qualified cyclohexanone products are produced at the top of the cyclohexanone tower, and substances at the bottom of the cyclohexanone tower are used as raw materials to enter the cyclohexanol tower;
producing high-concentration cyclohexanol at the tower top of the cyclohexanol tower, producing heavy component impurities at the tower bottom of the cyclohexanol tower and discharging the heavy component impurities out of the device; extracting a liquid phase from the middle section of the cyclohexanol tower, and feeding the liquid phase as a liquid phase of a first-stage cyclohexanone recovery tower;
and mixing the tower bottom material of the secondary cyclohexanone recovery tower with the tower bottom material of the lightness-removing tower, and then feeding the mixture into the cyclohexanone tower.
Further, in the present invention, the light component removal column may be a float valve column or a packed column, and is preferably a packed column. The packing may be random packing or regular packing, preferably regular packing. The type of the filler can be one of 150Y, 250Y, 350Y, 550Y and the like, and is preferably 350Y type structured filler. The theoretical plate number is 50-60 layers. The pressure at the top of the light component removal tower is controlled to be 10-50 kPa, preferably 20-40 kPa, the temperature at the top of the light component removal tower is controlled to be 80-110 ℃, preferably 90-110 ℃; the reflux ratio at the top of the tower is controlled to be 2-8, preferably 2-7. The gas phase at the top of the tower is used as the gas phase feed of the cyclohexanone recovery tower. The temperature of the tower bottom is controlled to be 120-150 ℃, and preferably 120-140 ℃; the material at the bottom of the tower is the feeding material of the cyclohexanone tower.
Furthermore, the cyclohexanone tower can adopt a float valve tower and a packed tower, and is preferably a packed tower. The packing may be random packing or regular packing, preferably regular packing. The type of the filler can be one of 150Y, 250Y, 350Y, 550Y and the like, and is preferably 350Y type structured filler. The theoretical plate number is 80-90 layers. The pressure of the top pressure of the cyclohexanone tower is controlled to be 1-20 kPa, preferably 2-15 kPa, the temperature of the top of the cyclohexanone tower is controlled to be 50-70 ℃, preferably 50-65 ℃, and the reflux ratio of the top of the cyclohexanone tower is controlled to be 2-8, preferably 2-7. The material at the top of the tower is a high-purity cyclohexanone product. The temperature of the tower bottom is controlled to be 85-110 ℃, preferably 90-105 ℃, and the material at the tower bottom is used as the feeding material of the cyclohexanol tower.
Furthermore, the cyclohexanol tower can adopt a float valve tower and a packed tower, and is preferably a packed tower. The packing may be random packing or regular packing, preferably regular packing. The type of the filler can be one of 150Y, 250Y, 350Y, 550Y and the like, and is preferably 350Y type structured filler. The theoretical plate number is 80-90 layers. The pressure at the top of the cyclohexanol tower is controlled to be 1-20 kPa, preferably 2-15 kPa, the temperature at the top of the cyclohexanol tower is controlled to be 80-110 ℃, preferably 85-105 ℃, and the reflux ratio at the top of the cyclohexanol tower is controlled to be 1-8, preferably 1-7. The material at the top of the tower is high-concentration cyclohexanol and is used as a reaction raw material for subsequent cyclohexanol dehydrogenation. The temperature of the tower bottom is controlled to be 130-165 ℃, and preferably 140-165 ℃. And the material at the bottom of the tower is heavy component impurity and is sent out of the device. Arranging middle-section extraction between 1-80 layers of theoretical tower plates of the cyclohexanol tower, preferably between 40-75 layers; and cooling the extracted liquid phase to be used as liquid phase feed of a primary cyclohexanone recovery tower, and controlling the temperature to be 40-80 ℃ after cooling, preferably 40-70 ℃.
Further, the first-stage cyclohexanone recovery tower can adopt a float valve tower and a packed tower, and preferably adopts a packed tower. The packing may be random packing or regular packing, preferably regular packing. The type of the filler can be one of 150Y, 250Y, 350Y, 550Y and the like, and is preferably 350Y type structured filler. The theoretical plate number is 50-60 layers. The top pressure of the primary cyclohexanone recovery tower is controlled to be 1-20 kPa, preferably 2-15 kPa, and the top temperature is controlled to be 50-80 ℃, preferably 50-75 ℃. The cyclohexanol is extracted from the middle section and used as overhead liquid phase reflux. The temperature of the tower bottom is controlled to be 90-110 ℃, and preferably 90-100 ℃. The liquid phase at the bottom of the tower enters a subsequent secondary cyclohexanone recovery tower.
Further, the secondary cyclohexanone recovery tower can adopt a float valve tower and a packed tower, and is preferably a packed tower. The packing may be random packing or regular packing, preferably regular packing. The type of the filler can be one of 150Y, 250Y, 350Y, 550Y and the like, and is preferably 350Y type structured filler. The theoretical plate number is 40-50 layers. The top pressure of the secondary cyclohexanone recovery tower is controlled to be 1-60 kPa, preferably 20-50 kPa, and the top temperature is controlled to be 60-90 ℃, preferably 65-85 ℃. The cyclohexanol is extracted from the middle section and used as overhead liquid phase reflux. The temperature of the tower bottom is controlled to be 90-130 ℃, and preferably 100-120 ℃.
In the invention, the mass ratio of the liquid phase flow rate extracted from the middle section of the cyclohexanol tower to the gas phase feed rate of the primary cyclohexanone recovery tower is 2-10, and preferably 3-8.
In the process of the present invention, the cooling process is well known to those skilled in the art, and conventional coolers are used.
The invention also provides a cyclohexanone separating and recovering system. The system comprises:
the light component removal tower is used for treating the crude cyclohexanone mixture from the front-end hydrolysis unit, removing light component substances in the crude cyclohexanone mixture, and obtaining a tower top light component and a tower bottom heavy component in the light component removal tower; comprising a feed line for feeding a crude cyclohexanone mixture to the lightness-removing column, an overhead take-off for removing overhead lights, and a bottom take-off for removing bottom heavies;
the primary cyclohexanone recovery tower is used for treating cyclohexanone light component impurities (butanone, pentanone and the like) from the top of the lightness-removing tower and recovering cyclohexanone; the device comprises a feeding pipeline for feeding light components of a lightness-removing tower to the primary cyclohexanone recovery tower, a tower top removing device for removing gas-phase components at the tower top, a tower bottom removing device for removing tower bottom components and a feeding pipeline for feeding a middle liquid phase of cyclohexanol to the primary cyclohexanone recovery tower;
the secondary cyclohexanone recovery tower is used for separating the bottom component of the primary cyclohexanone tower into a light component and a heavy component; the device comprises a removing device for removing light components at the top of the tower, and a tower bottom removing device for removing heavy components at the bottom of the tower;
the cyclohexanone tower is used for processing the cyclohexanone and cyclohexanol mixture from the bottom of the light component removal tower and obtaining qualified cyclohexanone products at the tower top; the device comprises a feeding pipeline, a tower top removing device and a removing device, wherein the feeding pipeline is used for feeding heavy components at the bottom of a light component removal tower and components at the bottom of a secondary cyclohexanone recovery tower into a cyclohexanone tower;
the cyclohexanol tower is used for processing a cyclohexanol mixture from the bottom of the cyclohexanone tower to obtain a high-purity cyclohexanol product, and the cyclohexanol product is used as a reaction raw material for subsequent cyclohexanol dehydrogenation; the device comprises a feeding pipeline for feeding heavy components at the bottom of a cyclohexanone tower into the cyclohexanol tower, a tower top removing device for removing high-purity cyclohexanol, a tower bottom removing device for removing tower bottom components, and a removing device for extracting middle-section liquid-phase components.
Further, the first-stage cyclohexanone recovery tower also comprises:
-an overhead condensing unit for condensing the gaseous phase removed overhead;
-a gas-liquid separator for separating the feed cooled by the overhead condensing unit into a gas and a liquid; the device comprises a removing pipeline for feeding a part of liquid to the top part of the primary cyclohexanone recovery tower and a removing device for removing a part of liquid out of a gas-liquid separator.
In the present invention, the removal means in each column is typically a pipeline, which is typically provided with valves and flow meters.
Compared with the prior art, the process and the system have the following advantages:
(1) the side-stream extracted liquid of the cyclohexanol tower is added to be used as a supplement absorbent of the cyclohexanone tower, so that the recovery efficiency of cyclohexanone in light-component materials is improved, the economic benefit is increased, and the material consumption of a system is reduced;
(2) by introducing the supplementary absorbent, the operation requirement of the cyclohexanone recovery tower is reduced, the tower top reflux is reduced, the tower bottom heat load is reduced, and the system energy consumption is reduced.
(3) Compared with the original process flow, the whole process system has the advantages of lower reconstruction construction requirement, less investment, high benefit and strong feasibility of implementation.
Drawings
FIG. 1 is a flow diagram of a cyclohexanone separation process and system of the present invention.
FIG. 2 is a flow chart of a conventional cyclohexanone separation and purification process.
Wherein: the device comprises an A-lightness-removing tower, a B-primary cyclohexanone recovery tower, a C-cyclohexanone tower, a D-cyclohexanol tower, an E-secondary cyclohexanone recovery tower, an E1-primary cyclohexanone recovery tower top cooler and an F1-primary cyclohexanone recovery tower top liquid separation tank.
Detailed Description
The process and system of the present invention are described in detail below with reference to the accompanying drawings and examples to further illustrate the practice and utility of the invention.
As shown in fig. 1, the present invention further provides a cyclohexanone recycling system, which comprises a lightness-removing column a, a primary cyclohexanone recycling column B, a cyclohexanone column C, a cyclohexanol column D, a secondary cyclohexanone recycling column E, a primary cyclohexanone recycling column cooler E1, and a knockout drum F1; a liquid phase outlet at the bottom of the lightness-removing tower A is connected with a feeding hole of a cyclohexanone tower C through a pipeline 3/12, a gas phase outlet at the top of the lightness-removing tower A is connected with a gas phase inlet of a first-stage cyclohexanone recovery tower, a gas phase outlet at the top of the cyclohexanone recovery tower B is connected with an inlet of a separating tank F1 through a cooler E1, a liquid phase outlet of the separating tank F1 is divided into two paths, one path is connected with a pipeline of a discharging device, and the other path is connected with a feeding hole at the top of the first-stage cyclohexanone recovery tower B after being converged; and a liquid phase outlet of the tower B of the cyclohexanone recovery tower is connected with a feed inlet of the secondary cyclohexanone recovery tower through a pipeline. And a liquid phase outlet at the bottom of the cyclohexanone tower C is connected with a feed inlet of the cyclohexanol tower D through a pipeline, and the top of the cyclohexanol tower D is connected with a follow-up device through a pipeline. And (3) discharging a liquid phase at the bottom of the cyclohexanol tower.
The cyclohexanone recovery process flow of the invention is as follows: the crude cyclohexanone/cyclohexanol material 1 to be treated enters a light component removal tower A, the light component removal separation process is realized in the light component removal tower A, and a light component removal material flow 2 and a light component removal material flow 3 are obtained after separation. The light component material flow 2 enters a gas phase inlet of a first-stage cyclohexanone recovery tower B; mixing a middle-section extracted material flow 17 from the cyclohexanol tower D with the first-stage cyclohexanone recovery tower top gas-phase condensate 7 (material flow 9), feeding the mixture into a first feeding hole (tower top reflux liquid-phase feeding hole) of the first-stage cyclohexanone recovery tower, and discharging the first-stage cyclohexanone recovery tower top gas-phase condensate 8; the liquid phase 5 at the bottom of the first-stage cyclohexanone recovery tower enters a second-stage cyclohexanone recovery tower E to recover cyclohexanone again, the gas phase 10 at the top of the second-stage cyclohexanone recovery tower is discharged from the device, the liquid phase 11 at the bottom of the second-stage cyclohexanone recovery tower is a material containing cyclohexanone and is mixed with the liquid phase 3 at the bottom of the lightness-removing tower A (material flow 12) and then enters a cyclohexanone tower C, and the liquid phase 13 at the top of the cyclohexanone tower is a qualified cyclohexanone product discharge; a cyclohexanone bottom liquid phase 14 serving as a raw material enters a cyclohexanol tower D, a cyclohexanol tower top liquid phase 15 serving as a cyclohexanol dehydrogenation raw material enters a subsequent device, and a cyclohexanol tower bottom liquid phase 16 serving as a heavy component impurity outlet device; and (4) taking 17 from the middle section of the cyclohexanol tower as a circulating absorbent to enter a primary cyclohexanone recovery tower.
Comparative example 1
The process is carried out according to the prior art, the flow chart is shown in figure 2, and the specific process parameters and raw material compositions are shown in the following table.
TABLE 1 raw material composition
TABLE 2 operating parameters of the column process
Example 1
The process flow shown in fig. 1 is adopted. The composition of the treated raw materials is the same as that of comparative example 1, and the process parameters of the light component removal tower, the cyclohexanone tower and the cyclohexanol tower are unchanged. Adding the extracted liquid (the extracted position is a 66 th layer theoretical plate) from the middle section of the cyclohexanol tower into a first-stage cyclohexanone recovery tower, and properly adjusting the operating parameters of the first-stage cyclohexanone recovery tower and a second-stage cyclohexanone recovery tower.
Table 3 example 1 column process parameters
Example 2
The composition of the treated raw materials is the same as that of comparative example 1, and the process parameters of the light component removal tower, the cyclohexanone tower and the cyclohexanol tower are unchanged. Adding a liquid phase (a sampling position is a theoretical plate at the 45 th layer) at the top of the cyclohexanol tower into a first-stage cyclohexanone recovery tower, and properly adjusting the operating parameters of the first-stage cyclohexanone recovery tower and a second-stage cyclohexanone recovery tower.
Table 4 example 2 operating parameters of each column process
Example 3
The composition of the treated raw materials is the same as that of comparative example 1, and the process parameters of the light component removal tower, the cyclohexanone tower and the cyclohexanol tower are unchanged. Adding liquid phase (75 th layer of theoretical plate) extracted from the middle section of the cyclohexanol tower into the first-stage cyclohexanone recovery tower, and properly adjusting the operating parameters of the first-stage cyclohexanone recovery tower and the second-stage cyclohexanone recovery tower.
Table 5 example 3 operating parameters of each column process
TABLE 6 run results
From the above example and comparative example data, it can be seen that: compared with the traditional process, the process parameters of the primary cyclohexanone recovery tower and the secondary cyclohexanone recovery tower are more moderate, the amount of the byproducts and the concentration of the cyclohexanone are greatly reduced, the product loss in the process of separating and refining the cyclohexanone is greatly reduced, the product yield of the cyclohexanone is improved, and the economic benefit is very obvious.
Claims (16)
1. A cyclohexanone recovery and separation process, which comprises the following steps:
feeding a cyclohexanone and cyclohexanol mixture from a front-end hydrolysis unit into a light component removal tower, and separating the mixture by the light component removal tower to obtain a raw material which is divided into two parts, namely a light component on the top of the tower and a heavy component on the bottom of the light component removal tower;
the light components on the top of the tower sequentially enter a first-stage cyclohexanone recovery tower and a second-stage cyclohexanone recovery tower to recover cyclohexanone;
heavy component substances at the bottom of the light component removal tower are used as raw materials to enter a cyclohexanone tower, qualified cyclohexanone products are produced at the top of the cyclohexanone tower, and substances at the bottom of the cyclohexanone tower are used as raw materials to enter the cyclohexanol tower;
producing high-concentration cyclohexanol at the tower top of the cyclohexanol tower, producing heavy component impurities at the tower bottom of the cyclohexanol tower and discharging the heavy component impurities out of the device; liquid phase is extracted from the middle section of the cyclohexanol tower and enters a primary cyclohexanone recovery tower as liquid phase feed of the primary cyclohexanone recovery tower;
and mixing the tower bottom material of the secondary cyclohexanone recovery tower with the tower bottom material of the lightness-removing tower, and then feeding the mixture into the cyclohexanone tower.
2. The process as claimed in claim 1, wherein the light component removal tower is a packed tower, the packing is structured packing, and the number of theoretical plates of the light component removal tower is 50-60 layers.
3. The process according to claim 1 or 2, wherein the overhead pressure of the lightness-removing column is controlled to be 10 to 50kPa, preferably 20 to 40kPa, and the overhead temperature is controlled to be 80 to 110 ℃, preferably 90 to 110 ℃; the reflux ratio of the tower top is controlled to be 2-8, preferably 2-7; the temperature of the tower bottom is controlled to be 120-150 ℃, and preferably 120-140 ℃.
4. The process according to claim 1, wherein the cyclohexanone tower is a packed tower, and the packing is structured packing; the theoretical plate number of the cyclohexanone tower is 80-90 layers.
5. The process according to claim 1 or 4, wherein the top pressure of the cyclohexanone tower is controlled to be 1-20 kPa, preferably 2-15 kPa, the temperature at the top of the cyclohexanone tower is controlled to be 50-70 ℃, preferably 50-65 ℃, and the reflux ratio at the top of the cyclohexanone tower is controlled to be 2-8, preferably 2-7; the temperature of the tower bottom is controlled to be 85-110 ℃, and preferably 90-105 ℃.
6. The process according to claim 1, wherein the cyclohexanol column is a packed column, and the packing is structured packing; the theoretical plate number of the packed tower is 80-90 layers.
7. The process according to claim 1 or 6, wherein the pressure at the top of the cyclohexanol tower is controlled to be 1-20 kPa, preferably 2-15 kPa, the temperature at the top of the cyclohexanol tower is controlled to be 80-110 ℃, preferably 85-105 ℃, and the reflux ratio at the top of the cyclohexanol tower is controlled to be 1-8, preferably 1-7; the temperature of the tower bottom is controlled to be 130-165 ℃, and preferably 140-165 ℃.
8. The process according to claim 6, wherein the extraction is carried out in a middle section between 1 and 80 theoretical plates, preferably 40 to 75 theoretical plates of the cyclohexanol column.
9. The process according to claim 8, wherein the temperature of the liquid phase extracted from the middle section after cooling is controlled to be 40 to 80 ℃, preferably 40 to 70 ℃.
10. The process as claimed in claim 1, wherein the primary cyclohexanone recovery tower adopts a packed tower, the packing is structured packing, and the number of theoretical plates is 50-60 layers.
11. The process according to claim 10, wherein the top pressure of the primary cyclohexanone recovery tower is controlled to be 1-20 kPa, preferably 2-15 kPa, and the top temperature is controlled to be 50-80 ℃, preferably 50-75 ℃; the temperature of the tower bottom is controlled to be 90-110 ℃, and preferably 90-100 ℃.
12. The process according to claim 1, wherein the secondary cyclohexanone recovery tower adopts a packed tower, and the packing is structured packing; the theoretical plate number is 40-50 layers.
13. The process according to claim 1 or 12, wherein the top pressure of the secondary cyclohexanone recovery tower is controlled to be 1-60 kPa, preferably 20-50 kPa, and the top temperature is controlled to be 60-90 ℃, preferably 65-85 ℃; the temperature of the tower bottom is controlled to be 90-130 ℃, and preferably 100-120 ℃.
14. The process according to claim 13, wherein the mass ratio of the liquid phase flow rate extracted from the middle section of the cyclohexanol tower to the gas phase feed rate in the primary cyclohexanone recovery tower is 2-10, preferably 3-8.
15. A cyclohexanone separation recovery system, the system comprising:
the light component removal tower is used for treating the crude cyclohexanone mixture from the front-end hydrolysis unit, removing light component substances in the crude cyclohexanone mixture, and obtaining a tower top light component and a tower bottom heavy component in the light component removal tower; comprising a feed line for feeding a crude cyclohexanone mixture to the lightness-removing column, an overhead take-off for removing overhead lights, and a bottom take-off for removing bottom heavies;
the primary cyclohexanone recovery tower is used for treating cyclohexanone light component impurities from the top of the light component removal tower and recovering cyclohexanone; the device comprises a feeding pipeline for feeding light components of a lightness-removing tower to the primary cyclohexanone recovery tower, a tower top removing device for removing gas-phase components at the tower top, a tower bottom removing device for removing tower bottom components and a feeding pipeline for feeding a middle liquid phase of cyclohexanol to the primary cyclohexanone recovery tower;
the secondary cyclohexanone recovery tower is used for separating the bottom component of the primary cyclohexanone tower into a light component and a heavy component; the device comprises a removing device for removing light components at the top of the tower, and a tower bottom removing device for removing heavy components at the bottom of the tower;
the cyclohexanone tower is used for processing the cyclohexanone and cyclohexanol mixture from the bottom of the light component removal tower and obtaining qualified cyclohexanone products at the tower top; the device comprises a feeding pipeline, a tower top removing device and a removing device, wherein the feeding pipeline is used for feeding heavy components at the bottom of a light component removal tower and components at the bottom of a secondary cyclohexanone recovery tower into a cyclohexanone tower;
the cyclohexanol tower is used for processing a cyclohexanol mixture from the bottom of the cyclohexanone tower to obtain a high-purity cyclohexanol product, and the cyclohexanol product is used as a reaction raw material for subsequent cyclohexanol dehydrogenation; the device comprises a feeding pipeline for feeding heavy components at the bottom of a cyclohexanone tower into the cyclohexanol tower, a tower top removing device for removing high-purity cyclohexanol, a tower bottom removing device for removing tower bottom components, and a removing device for extracting middle-section liquid-phase components.
16. The cyclohexanone separation and recovery system according to claim 15, wherein the primary cyclohexanone recovery tower further comprises:
the tower top condensing device is used for condensing the gas phase removed from the tower top;
a gas-liquid separator for separating the feed cooled by the overhead condensing unit into a gas and a liquid; the device comprises a removing pipeline for feeding a part of liquid to the top part of the primary cyclohexanone recovery tower and a removing device for removing a part of liquid out of a gas-liquid separator.
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| CN113461500A (en) * | 2021-08-19 | 2021-10-01 | 中国天辰工程有限公司 | Device for refining cyclohexanone by cyclohexanol dehydrogenation |
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Effective date of registration: 20231031 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |