CN118047667A - Method and device for preparing high-purity 4-oxo-isophorone - Google Patents
Method and device for preparing high-purity 4-oxo-isophorone Download PDFInfo
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- CN118047667A CN118047667A CN202311674098.4A CN202311674098A CN118047667A CN 118047667 A CN118047667 A CN 118047667A CN 202311674098 A CN202311674098 A CN 202311674098A CN 118047667 A CN118047667 A CN 118047667A
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- AYJXHIDNNLJQDT-UHFFFAOYSA-N 2,6,6-Trimethyl-2-cyclohexene-1,4-dione Chemical compound CC1=CC(=O)CC(C)(C)C1=O AYJXHIDNNLJQDT-UHFFFAOYSA-N 0.000 title claims abstract description 283
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000002425 crystallisation Methods 0.000 claims abstract description 74
- 230000008025 crystallization Effects 0.000 claims abstract description 74
- 238000010438 heat treatment Methods 0.000 claims abstract description 51
- 238000001816 cooling Methods 0.000 claims abstract description 50
- 238000002844 melting Methods 0.000 claims abstract description 40
- 230000008018 melting Effects 0.000 claims abstract description 40
- 239000000047 product Substances 0.000 claims abstract description 28
- 230000035900 sweating Effects 0.000 claims abstract description 25
- 239000012043 crude product Substances 0.000 claims abstract description 7
- 239000012452 mother liquor Substances 0.000 claims description 35
- 210000004243 sweat Anatomy 0.000 claims description 35
- 238000003860 storage Methods 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 9
- 235000021190 leftovers Nutrition 0.000 claims description 7
- 230000004580 weight loss Effects 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 16
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 230000003068 static effect Effects 0.000 description 49
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 32
- 239000007788 liquid Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 23
- 208000008454 Hyperhidrosis Diseases 0.000 description 22
- 239000000203 mixture Substances 0.000 description 18
- LKOKKQDYMZUSCG-UHFFFAOYSA-N 3,5,5-Trimethyl-3-cyclohexen-1-one Chemical compound CC1=CC(C)(C)CC(=O)C1 LKOKKQDYMZUSCG-UHFFFAOYSA-N 0.000 description 12
- 238000012856 packing Methods 0.000 description 12
- 238000009835 boiling Methods 0.000 description 10
- GKOBUKITZSFCJC-UHFFFAOYSA-N lanierone Chemical compound CC1=CC(C)(C)C=C(O)C1=O GKOBUKITZSFCJC-UHFFFAOYSA-N 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229930003427 Vitamin E Natural products 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229940046009 vitamin E Drugs 0.000 description 3
- 235000019165 vitamin E Nutrition 0.000 description 3
- 239000011709 vitamin E Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000011869 dried fruits Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method and a device for preparing high-purity oxo-isophorone, wherein the method comprises the following steps: (1) Removing light components from a crude product containing 4-oxo-isophorone by rectification, removing heavy components by rectification, and removing 2, 6-trimethyl-1, 4-cyclohexanedione to obtain a rectification product; (2) Removing 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadiene-1-ketone from the rectification product obtained in the step (1) through melting crystallization to obtain high-purity oxo isophorone; the melting crystallization comprises two stages of cooling crystallization and heating sweating. According to the method, the crude product of the 4-oxo-isophorone is purified in a rectification and melt crystallization coupling mode, so that the impurity content can be reduced efficiently, the product purity of the oxo-isophorone is improved, an organic solvent is not needed, and the method is more environment-friendly.
Description
Technical Field
The invention belongs to the technical field of chemical separation and purification, and particularly relates to a method and a device for preparing high-purity 4-oxo-isophorone by adopting a rectification and melt crystallization coupling mode.
Background
4-Oxo-isophorone, chemical name: 2, 6-trimethyl-2-cyclohexene-1, 4-dione, also known as theadione, is a natural compound found in a variety of plants. The tea-flavored ketone is a light yellow liquid or solid at normal temperature, has strong and lasting pure fragrance, is slightly sour and sweet costustoot and dried fruit fragrance, and has obvious flavoring effect on various cigarettes. Tea-flavored ketones are not only flavors or fragrances in food or cosmetic preparations, but also intermediates in the preparation of various carotenoids, vitamins and fragrances.
4-Oxo-isophorone, which is very low in natural products, is currently mainly derived from synthetic processes, obtained by catalytic oxidation of alpha-isophorone or beta-isophorone. Since the oxidation reaction activity of beta-isophorone is high and the selectivity of 4-oxo-isophorone is high, most researches at present use beta-isophorone as a raw material.
Certain by-products, such as 2, 6-trimethyl-1, 4-cyclohexanedione or 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one, are produced in the oxidation of beta-isophorone to 4-oxoisophorone. These byproducts can continue to participate in the reaction to produce byproducts in the next step of acylation aromatization, which affects the selectivity of the main reaction. It is therefore necessary to remove these by-products.
The prior art concerning the post-treatment of 4-oxoisophorone mainly comprises:
patent CN 108070875B mentions that 4-oxo-isophorone is isolated only by means of rectification. The defects are incomplete separation, the product purity is not high, and the product with the purity required by the downstream is difficult to obtain.
Patent application CN 110256219A discloses a purification process of 2, 6-trimethyl-2-cyclohexene-1, 4-dione, which comprises the steps of firstly distilling 4-oxo-isophorone with the content of less than 30% under reduced pressure to remove a catalyst, then rectifying to obtain a product with the content of 45% -70%, discharging the product, cooling to-5 to-10 ℃, centrifugally filtering the crystal, adding a low-boiling point solvent (acetone, petroleum ether and ethanol) to perform solution crystallization to obtain the 4-oxo-isophorone with the content of 99%. The disadvantages of this method are: the investment of the solution crystallization and filtration equipment for multiple times is large, a large amount of low-boiling solvents are adopted, resources are wasted, and recovery is difficult; and the reaction temperature is low and the energy consumption is high.
Patent US3960966 mentions separation and purification by distillation or crystallization with a solvent of n-hexane solution. The disadvantages are: the crystallization heating and cooling of the solution consumes more energy due to larger total material amount, the crystallization mother liquor needs to recover the solvent to consume more energy, and meanwhile, the recovery scheme of the product in the mother liquor needs to be considered.
Patent CN1150182C mentions that 2,3, 5-trimethyl-p-diphenol diester is a key intermediate for vitamin E synthesis, 4-oxo isophorone is a key precursor for 2,3, 5-trimethyl-p-diphenol diester synthesis, and the main impurities in technical grade 4-oxo isophorone are 2, 6-trimethyl-1, 4-cyclohexanedione (impurity 1) and 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one (impurity 2, lanierone). Impurities 1 and lanierone are secondary organisms generated in the vitamin E production process, lanierone can be removed only through rectification or alkaline environment reaction extraction, and 4-oxo-isophorone containing the impurities cannot be used for synthesizing pure vitamin E. The disadvantages of this method are: the removal cost of rectification is too great, the single-pass yield is low, and the method is not feasible in industry. Basic environment reactive extraction involves a series of problems such as acid-base regulation and the use of various solvents.
In summary, the existing method for purifying beta-isophorone generally has the defects of harsh operation conditions, low boiling point solvent, insufficient purity of the product and high residue of impurities (especially impurities 2 lanierone).
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the method for preparing the high-purity 4-oxo-isophorone can improve the product purity of the 4-oxo-isophorone, reduce the content of impurity 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadiene-1-ketone, and simultaneously does not need to adopt an organic solvent, so that the method is more environment-friendly.
A process for preparing high purity 4-oxoisophorone comprising the steps of:
(1) Removing light components from a crude product containing 4-oxo-isophorone by rectification, removing heavy components by rectification, and removing 2, 6-trimethyl-1, 4-cyclohexanedione to obtain a rectification product;
(2) Removing 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadiene-1-ketone from the rectification product obtained in the step (1) through melt crystallization to obtain high-purity oxo-isophorone;
the melting crystallization comprises two stages of cooling crystallization and heating sweating;
the final temperature of the cooling crystallization is 9-15 ℃, and the temperature of the heating sweating is 20-25 ℃.
According to the invention, the reaction liquid obtained in the production of 4-oxo-isophorone is taken as a raw material, the main impurity 2, 6-trimethyl-1, 4-cyclohexanedione is removed through rectification, and then the main impurity 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadiene-1-one is removed through a melt crystallization mode.
In the invention, the crude product containing 4-oxo-isophorone is obtained from a process for preparing oxo-isophorone by oxidizing beta-isophorone, and preferably, the crude product containing 4-oxo-isophorone comprises the following components in percentage by mass:
70 to 75 percent of 4-oxo isophorone, 20 to 25 percent of 2, 6-trimethyl-1, 4-cyclohexanedione, 1.4 to 2 percent of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one and 3.5 to 4 percent of light components. Wherein the light component comprises alpha-isophorone and contains about 1% of other light components with boiling points lower than that of the alpha-isophorone.
In the invention, the purpose of rectification and light component removal is mainly used for removing light components in the reaction liquid, and preferably, in the step (1), the conditions of rectification and light component removal are as follows: the temperature of the tower bottom is 118-122 ℃, the temperature of the tower top is 58-63 ℃, the number of tower plates is 75-85, and the tower height is 22-26 m.
In the invention, the main impurity 2, 6-trimethyl-1, 4-cyclohexanedione in the reaction liquid can be removed by rectification and weight removal, and preferably, in the step (1), the conditions of rectification and weight removal are as follows: the temperature of the tower bottom is 130-140 ℃, the temperature of the tower top is 110-125 ℃, the number of tower plates is 40-45, and the tower height is 12-16 m.
In the present invention, the main impurity 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one can be removed by melt crystallization, and the conditions affect the impurity content in the final product 4-oxoisophorone, preferably, in step (2), the conditions of cooling crystallization: the initial temperature of the cooling crystallization is 25-35 ℃, the temperature is rapidly cooled to 12-20 ℃, the cooling rate is 7-10 ℃/h, then the temperature is slowly cooled to 10-15 ℃, the cooling rate is 0.5-2.0 ℃/h, finally the temperature is kept for 30-60 min, as further preference, the initial temperature of the cooling crystallization is 25-35 ℃, the temperature is rapidly cooled to 16-18 ℃, the cooling rate is 7-10 ℃/h, then the temperature is slowly cooled to 10-12 ℃, the cooling rate is 0.5-1.2 ℃/h, and finally the temperature is kept for 50-60 min.
Preferably, in the step (2), the heating and sweating modes are as follows; the first stage is heated to 18-20 ℃, the heating rate is 5-8 ℃/h, the second stage is heated to 20-25 ℃, the heating rate is 1-7 ℃/h, and then the temperature is kept for 20-90 min; as a further preferred mode, the heating up and sweating is as follows; the first stage is heated to 18-19 ℃, the heating rate is 6-8 ℃/h, the second stage is heated to 20-25 ℃, the heating rate is 4-6 ℃/h, and then the temperature is kept for 20-40 min.
In the invention, the heavy phase component obtained by rectification and weight removal, the mother solution obtained by melt crystallization and the sweating liquid all contain a certain amount of 4-oxo-isophorone, and preferably, the heavy phase component obtained by rectification and weight removal is recovered and reused after heavy phase leftovers are further removed.
Preferably, the mother solution and the sweat obtained by melting and crystallizing are recovered and reused after heavy phase scraps are further removed. The total yield is more than 98 percent after recycling and reuse.
The invention also provides a device for preparing high-purity oxo-isophorone, which comprises: the device comprises an N1 raw material storage tank, a light component removing tower, a heavy component removing tower and a melting crystallization device which are connected in sequence;
the light component removing tower is provided with a light component removing tower feeding port, a light component removing tower light phase outlet and a heavy component removing tower heavy phase outlet, and the light component removing tower feeding port is positioned in the middle of the light component removing tower;
The heavy-removal tower is provided with a heavy-removal tower feed inlet, a heavy-removal tower light phase outlet and a heavy-removal tower heavy phase outlet, and the heavy-removal tower feed inlet is positioned in the middle of the heavy-removal tower;
The N1 raw material storage tank is communicated with the light component removing tower feed inlet, the heavy component removing tower heavy phase outlet is communicated with the heavy component removing tower feed inlet, and the light component removing tower light phase outlet is communicated with the melting crystallization device.
The device for preparing the high-purity oxo-isophorone further comprises a heavy phase leftover processing system connected with the heavy phase outlet of the heavy phase removal tower, and the heavy phase leftover processing system is connected with an N1 raw material storage tank.
The device for preparing the high-purity oxo-isophorone further comprises a crystallization mother liquor sweating treatment system connected with the melting crystallization device, and the crystallization mother liquor sweating treatment system is connected with an N1 raw material storage tank.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method can more effectively reduce the content of specific impurities, especially the content of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadiene-1-ketone by means of rectification and melt crystallization coupling, and the obtained oxo-isophorone has higher purity;
(2) The method can solve the problems of high cost and high energy consumption caused by simple rectification and can avoid the waste liquid treatment caused by solution crystallization;
(3) The total yield can be improved to more than 98% by further applying the heavy phase component obtained by rectification and weight removal, the mother solution obtained by melt crystallization and the sweating liquid.
Drawings
FIG. 1 is a schematic diagram of a high purity oxoisophorone production apparatus and process flow diagram of the present invention;
FIG. 2 shows the result of GC analysis of the melt obtained in example 4;
FIG. 3 shows the result of GC analysis of the melt obtained in example 10.
Detailed Description
The process of the present invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a high purity oxo-isophorone preparation apparatus and process flow diagram of the present invention, as shown in FIG. 1, the preparation apparatus mainly comprises an N1 raw material storage tank, a light component removal tower, a heavy component removal tower, a melting crystallization device and a crystallization mother liquor sweat treatment system which are connected in sequence. The light component removing tower is provided with a light component removing tower feeding port, a light component removing tower light phase outlet and a light component removing tower heavy phase outlet, wherein the light component removing tower feeding port is positioned in the middle of the light component removing tower; the heavy-removal tower is provided with a heavy-removal tower feed inlet, a heavy-removal tower light phase outlet and a heavy-removal tower heavy phase outlet, and the heavy-removal tower feed inlet is positioned in the middle of the heavy-removal tower.
The N1 raw material storage tank is connected with the feed inlet of the light component removal tower, and a preheater is arranged between the N1 raw material storage tank and the feed inlet of the light component removal tower; the light phase outlet of the light component removal tower is connected with an N2 storage tank, the N2 storage tank is used for collecting light components comprising alpha-isophorone, and the heavy phase outlet of the light component removal tower is communicated with the feed inlet of the heavy component removal tower; the heavy phase outlet of the heavy phase removing tower is communicated with a heavy phase leftover treatment system through an N4 buffer tank, the heavy phase leftover treatment system is used for treating heavy phase components containing 2, 6-trimethyl-1, 4-cyclohexanedione and 4-oxo-isophorone, separating impurities from the 4-oxo-isophorone, and returning the 4-oxo-isophorone to an N1 raw material storage tank through an N5 buffer tank for recycling; the light phase material at the light phase outlet of the de-duplication tower enters a melting crystallization device after passing through an N3 buffer tank, two processes of melting crystallization and heating sweating are carried out in the melting crystallization device, mother liquor obtained by the melting crystallization and sweating liquid obtained by the heating sweating enter a crystallization mother liquor sweating liquid treatment system for treatment, heavy phase leftovers are removed and then returned to an N1 raw material storage tank for recycling, and meanwhile, a high-purity oxo isophorone product is obtained and stored in an N8 product storage tank and is output as a product.
The invention is further described below in connection with specific embodiments.
Example 1 (rectification Process)
The reaction liquid obtained in the production of 4-oxo-isophorone is used as raw material liquid, and the composition is as follows: in mass percent, the composition contains 70.54 percent of 4-oxo isophorone, 24.12 percent of 2, 6-trimethyl-1, 4-cyclohexanedione and 1.50 percent of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one, and further contains 2.84 percent of alpha-isophorone and 1 percent of light components with boiling point lower than that of the alpha-isophorone.
BX-500 packing is adopted in the first rectifying tower, the packing height is 16m, the theoretical plate number is 80, and the position of a feed inlet in the tower is 15 th plate. The raw material liquid is fed from a feeding port in a tower of the first rectifying tower, reduced pressure distillation is adopted, the pressure of the tower is 5KPa, and the reflux ratio of the tower top is 15:1. Heating a tower kettle, wherein the temperature of the tower kettle is 120 ℃, materials in a 625kg/h N storage tank are continuously fed into the tower, 597kg/h of materials are continuously discharged from the tower kettle, 21kg/h of materials are continuously taken from the tower top into an N2 storage tank, the temperature of the tower top is 60 ℃, and the composition of the tower top is as follows: 6.0% of 4-oxo-isophorone, 0.9% of 2, 6-trimethyl-1, 4-cyclohexanedione, 0.9% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one, 84% of alpha-isophorone and 8.2% of light components with a boiling point lower than that of alpha-isophorone, 597kg/h of material is obtained in the tower kettle, the composition is as follows: 73.40% of 4-oxoisophorone, 25.10% of 2, 6-trimethyl-1, 4-cyclohexanedione, 1.50% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one.
The second rectifying tower adopts BX-500 packing, the packing height is 9m, the theoretical plate number is 45, and the position of a feed inlet is 15 th plate. The tower bottom liquid of the first rectifying tower is fed from a feed inlet of the second rectifying tower, reduced pressure distillation is adopted, the pressure of the tower is 5KPa, the reflux ratio of the tower top is 7.5:1, the tower bottom is heated, the temperature of the tower bottom is 135 ℃, 597kg/h of materials are continuously fed in the tower, and the tower bottom continuously discharges 210kg/h of materials to an N4 buffer tank, and the composition is as follows: 32.86% of 4-oxo isophorone, 67.02% of 2, 6-trimethyl-1, 4-cyclohexanedione and 0.12% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one, wherein the temperature of the top of the tower is 114 ℃, 373kg/h of materials are continuously discharged from the top of the tower to an N3 cache tank, and the compositions are as follows: 98.80% of 4-oxoisophorone, 0.17% of 2, 6-trimethyl-1, 4-cyclohexanedione, 1.03% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one.
And (3) carrying out melt crystallization on the liquid extracted from the top of the second rectifying tower.
Example 2 (rectification Process)
The reaction liquid obtained in the production of 4-oxo-isophorone is used as raw material liquid, and the composition is as follows: in mass percent, the composition contains 70.54 percent of 4-oxo isophorone, 24.12 percent of 2, 6-trimethyl-1, 4-cyclohexanedione and 1.50 percent of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one, and further contains 2.84 percent of alpha-isophorone and 1 percent of light components with boiling point lower than that of the alpha-isophorone.
BX-500 packing is adopted in the first rectifying tower, the packing height is 15m, the theoretical plate number is 75, and the position of a feed inlet in the tower is the 14 th plate. The raw material liquid is fed from a feeding port in a tower of the first rectifying tower, reduced pressure distillation is adopted, the pressure of the tower is 5KPa, and the reflux ratio of the tower top is 15:1. Heating a tower kettle, wherein the temperature of the tower kettle is about 120 ℃, 625kg/h N kg/h of materials in a storage tank are continuously fed into the tower, 598kg/h of materials are continuously discharged from the tower kettle, 21kg/h of materials are continuously taken from the tower top into an N2 storage tank, the temperature of the tower top is 60 ℃, and the composition of the tower top is as follows: 5.81% of 4-oxo-isophorone, 0.87% of 2, 6-trimethyl-1, 4-cyclohexanedione, 0.91% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one, 84.11% of alpha-isophorone and 8.30% of light components with a boiling point lower than that of alpha-isophorone, 598kg/h of material is obtained in the column bottom, the composition is: 73.45% of 4-oxoisophorone, 25.02% of 2, 6-trimethyl-1, 4-cyclohexanedione, 1.53% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one.
The second rectifying tower adopts BX-500 packing, the packing height is 9m, the theoretical plate number is 45, and the position of a feed inlet is 15 th plate. The tower bottom liquid of the first rectifying tower is fed from a feed inlet of the second rectifying tower, reduced pressure distillation is adopted, the pressure of the tower is 5KPa, the reflux ratio of the tower top is 7.5:1, the tower bottom is heated, the temperature of the tower bottom is 135 ℃, 598kg/h of materials are continuously fed in the tower, 205kg/h of materials are continuously discharged from the tower bottom to an N4 buffer tank, and the composition is as follows: 32.10% of 4-oxo isophorone, 67.73% of 2, 6-trimethyl-1, 4-cyclohexanedione and 0.17% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one, wherein the temperature of the top of the tower is 114 ℃, and 378kg/h of materials are continuously discharged from the top of the tower to an N3 cache tank, and the compositions are as follows: 98.65% of 4-oxoisophorone, 0.25% of 2, 6-trimethyl-1, 4-cyclohexanedione, 1.10% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one.
Example 3 (rectification Process)
The reaction liquid obtained in the production of 4-oxo-isophorone is used as raw material liquid, and the composition is as follows: in mass percent, the composition contains 70.54 percent of 4-oxo isophorone, 24.12 percent of 2, 6-trimethyl-1, 4-cyclohexanedione and 1.50 percent of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one, and further contains 2.84 percent of alpha-isophorone and 1 percent of light components with boiling point lower than that of the alpha-isophorone.
BX-500 packing is adopted in the first rectifying tower, the packing height is 16m, the theoretical plate number is 80, and the position of a feed inlet in the tower is 15 th plate. The raw material liquid is fed from a feeding port in a tower of the first rectifying tower, reduced pressure distillation is adopted, the pressure of the tower is 15KPa, and the reflux ratio of the tower top is 15:1. Heating a tower kettle, wherein the temperature of the tower kettle is about 120 ℃, 625kg/h N kg/h of materials in a storage tank are continuously fed into the tower, 598kg/h of materials are continuously discharged from the tower kettle, 21kg/h of materials are continuously taken from the tower top into an N2 storage tank, the temperature of the tower top is 60 ℃, and the composition of the tower top is as follows: 6.0% of 4-oxo-isophorone, 0.9% of 2, 6-trimethyl-1, 4-cyclohexanedione, 0.9% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one, 84% of alpha-isophorone and 8.2% of light components with a boiling point lower than that of alpha-isophorone, 598kg/h of material is obtained in the tower kettle, the composition is as follows: 73.35% of 4-oxoisophorone, 25.10% of 2, 6-trimethyl-1, 4-cyclohexanedione, 1.50% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one.
The second rectifying tower adopts BX-500 packing, the packing height is 8m, the theoretical plate number is 40, and the position of a feed inlet is 15 th plate. The tower bottom liquid of the first rectifying tower is fed from a feed inlet of the second rectifying tower, reduced pressure distillation is adopted, the pressure of the tower is 5KPa, the reflux ratio of the tower top is 5:1, the tower bottom is heated, the temperature of the tower bottom is 135 ℃, 598kg/h of materials are continuously fed in the tower, 202kg/h of materials are continuously discharged from the tower bottom to an N4 buffer tank, and the composition is as follows: 33.06% of 4-oxo isophorone, 66.68% of 2, 6-trimethyl-1, 4-cyclohexanedione and 0.26% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one, wherein the temperature of the top of the tower is 114 ℃, 386kg/h of materials are continuously discharged from the top of the tower to an N3 cache tank, and the compositions are as follows: 96.15% of 4-oxoisophorone, 1.79% of 2, 6-trimethyl-1, 4-cyclohexanedione, 2.06% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one.
As is clear from the results of examples 1 to 3, the removal effect of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one was poor when purification was carried out by the rectification method, and the content of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one was not reduced even after two rectification.
Example 4 (melt crystallization procedure)
1) 226.00Kg of crude 4-oxo-isophorone (wherein, according to mass percent, 98.80% of 4-oxo-isophorone, 0.17% of 2, 6-trimethyl-1, 4-cyclohexanedione, 1.03% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one) at about 28 ℃ is pumped into a static melt crystallizer, and is stabilized for 10min;
2) Rapidly cooling at a speed of 10 ℃/h, and preserving heat for 20min after the temperature is reduced to 18 ℃; then slowly cooling to 12 ℃ for 300min, wherein the cooling rate is 1.2 ℃/h, the end temperature of cooling crystallization is 12 ℃, finally opening a discharge port at the bottom of the static melting crystallizer after heat preservation is carried out for 60min, connecting the discharge port to a mother liquor receiving tank until mother liquor in the static melting crystallizer is discharged, and obtaining 15.33kg of mother liquor, wherein the mass percentage of 4-oxo-isophorone is 95.55%;
3) Switching the valve to a sweat receiving tank so that a discharge port at the bottom of the static melt crystallizer is connected to the sweat receiving tank; heating the static melting crystallizer at a heating rate of 6 ℃/h, and adjusting the heating rate to 4 ℃/h when the temperature reaches 18 ℃; stopping heating when the temperature reaches 22 ℃, keeping the temperature constant for 20min, sampling and analyzing from a discharge port at the bottom of the static melting crystallizer, and finishing sweating when the mass percent of 4-oxo-isophorone in the sweating liquid is 97.82%, wherein 18.24kg of sweat liquid is obtained altogether, and the mass percent of 4-oxo-isophorone in the sweating liquid is 94.82%;
4) The valve was switched to a 4-oxoisophorone finish pot so that the discharge port at the bottom of the static melt crystallizer was connected to the finish pot, the temperature was raised to 30 ℃ to melt 4-oxoisophorone completely, the resulting 4-oxoisophorone melt was released into the finish pot to obtain 192.03kg of product liquid, and the melt was sampled and analyzed, as a result, see fig. 2, which shows that the mass percent of 4-oxoisophorone was 99.59%, the mass percent of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one was 0.03%, and the mass percent of 2, 6-trimethyl-1, 4-cyclohexanedione was 0.35%, and the yield of single pass 4-oxoisophorone melt crystallization was 85.65% as calculated.
Example 5 (melt crystallization procedure)
1) 226.00Kg of crude 4-oxo-isophorone (wherein, according to mass percent, 98.80% of 4-oxo-isophorone, 0.17% of 2, 6-trimethyl-1, 4-cyclohexanedione, 1.03% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one) at about 28 ℃ is pumped into a static melt crystallizer, and is stabilized for 10min;
2) Rapidly cooling at a speed of 10 ℃/h, and preserving heat for 20min after the temperature is reduced to 18 ℃; then slowly cooling to 15 ℃, wherein the cooling rate is 1.2 ℃/h, the end temperature of cooling crystallization is 15 ℃, finally, after 60 minutes of heat preservation, opening a discharge port at the bottom of the static melting crystallizer, connecting the discharge port to a mother liquor receiving tank until mother liquor in the static melting crystallizer is discharged completely, and obtaining 16.12kg of mother liquor, wherein the mass percent of 4-oxo isophorone is 95.85%;
3) Switching the valve to a sweat receiving tank so that a discharge port at the bottom of the static melt crystallizer is connected to the sweat receiving tank; heating the static melting crystallizer at a heating rate of 6 ℃/h, and adjusting the heating rate to 4 ℃/h when the temperature reaches 18 ℃; stopping heating when the temperature reaches 22 ℃, keeping the temperature constant for 20min, and finishing sweating to obtain 18.01kg of sweat, wherein the mass percentage of the sweat containing 4-oxo-isophorone is 94.55%;
4) The valve was switched to a 4-oxoisophorone finish pot so that a discharge port at the bottom of a static melt crystallizer was connected to the finish pot, the temperature was raised to 30 ℃, 4-oxoisophorone was completely melted while the obtained 4-oxoisophorone melt was released into the finish pot to obtain 191.24kg of a product liquid, and the melt was sampled and analyzed, which showed that the mass percent of 4-oxoisophorone was 99.65%, the mass percent of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one was 0.03%, and the mass percent of 2, 6-trimethyl-1, 4-cyclohexanedione was 0.32%, and the yield of single pass 4-oxoisophorone melt crystallization was 85.35% as calculated.
Example 6 (melt crystallization procedure)
1) 226.00Kg of crude 4-oxo-isophorone (wherein, according to mass percent, 98.80% of 4-oxo-isophorone, 0.17% of 2, 6-trimethyl-1, 4-cyclohexanedione, 1.03% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one) at about 28 ℃ is pumped into a static melt crystallizer, and is stabilized for 10min;
2) Rapidly cooling at a speed of 10 ℃/h, and preserving heat for 20min after the temperature is reduced to 18 ℃; then slowly cooling to 12 ℃, wherein the cooling rate is 1.2 ℃/h, the end temperature of cooling crystallization is 12 ℃, finally, after 60 minutes of heat preservation, opening a discharge port at the bottom of the static melting crystallizer, connecting the discharge port to a mother liquor receiving tank until mother liquor in the static melting crystallizer is discharged completely, and obtaining 15.27kg of mother liquor, wherein the mass percentage of 4-oxo isophorone is 95.80%;
3) Switching the valve to a sweat receiving tank so that a discharge port at the bottom of the static melt crystallizer is connected to the sweat receiving tank; heating the static melting crystallizer at a heating rate of 6 ℃/h, stopping heating when the temperature reaches 25 ℃, keeping the temperature constant for 20min, and finishing sweating to obtain 19.57kg of sweat which contains 95.75% of 4-oxo-isophorone;
4) The valve was switched to a 4-oxoisophorone finish pot so that a discharge port at the bottom of a static melt crystallizer was connected to the finish pot, the temperature was raised to 30 ℃, 4-oxoisophorone was completely melted while the obtained 4-oxoisophorone melt was released into the finish pot to obtain 191.98kg of a product liquid, and the melt was sampled and analyzed, which showed that the mass percent of 4-oxoisophorone was 99.59%, the mass percent of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one was 0.04%, and the mass percent of 2, 6-trimethyl-1, 4-cyclohexanedione was 0.37%, and the yield of single pass 4-oxoisophorone melt crystallization was 85.63% as calculated.
Example 7 (melt crystallization procedure)
1) 226.00Kg of crude 4-oxo-isophorone (wherein, according to mass percent, 98.80% of 4-oxo-isophorone, 0.17% of 2, 6-trimethyl-1, 4-cyclohexanedione, 1.03% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one) at about 28 ℃ is pumped into a static melt crystallizer, and is stabilized for 10min;
2) Rapidly cooling at a speed of 10 ℃/h, and preserving heat for 20min after the temperature is reduced to 16 ℃; then slowly cooling to 10 ℃, wherein the cooling rate is 1.2 ℃/h, the end temperature of cooling crystallization is 10 ℃, finally, after 60 minutes of heat preservation, opening a discharge port at the bottom of the static melting crystallizer, connecting the discharge port to a mother liquor receiving tank until the mother liquor in the static melting crystallizer is discharged completely, and obtaining 14.75kg of mother liquor, wherein the mass percent of 4-oxo isophorone is 94.55%;
3) Switching the valve to a sweat receiving tank so that a discharge port at the bottom of the static melt crystallizer is connected to the sweat receiving tank; heating the static melting crystallizer at a heating rate of 6 ℃/h, and adjusting the heating rate to 4 ℃/h when the temperature reaches 18 ℃; stopping heating when the temperature reaches 20 ℃, keeping the temperature constant for 40min, and finishing sweating to obtain 17.25kg of sweat, wherein the mass percentage of the sweat containing 4-oxo-isophorone is 94.10%;
4) The valve was switched to a 4-oxoisophorone finish pot so that a discharge port at the bottom of a static melt crystallizer was connected to the finish pot, the temperature was raised to 30 ℃, 4-oxoisophorone was completely melted while the obtained 4-oxoisophorone melt was released into the finish pot to obtain 191.85kg of a product liquid, and the melt was sampled and analyzed, which showed that the mass percent of 4-oxoisophorone was 99.65%, the mass percent of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one was 0.03%, and the mass percent of 2, 6-trimethyl-1, 4-cyclohexanedione was 0.32%, and the yield of single pass 4-oxoisophorone melt crystallization was 85.62% as calculated.
Example 8 (melt crystallization procedure)
1) 226.00Kg of crude 4-oxo-isophorone (wherein, according to mass percent, 98.80% of 4-oxo-isophorone, 0.17% of 2, 6-trimethyl-1, 4-cyclohexanedione, 1.03% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one) at about 28 ℃ is pumped into a static melt crystallizer, and is stabilized for 10min;
2) Rapidly cooling at a speed of 10 ℃/h, and preserving heat for 20min after the temperature is reduced to 16 ℃; then slowly cooling to 12 ℃, wherein the cooling rate is 0.5 ℃/h, the end temperature of cooling crystallization is 12 ℃, finally, after 60 minutes of heat preservation, opening a discharge port at the bottom of the static melting crystallizer, connecting the discharge port to a mother liquor receiving tank until mother liquor in the static melting crystallizer is discharged completely, and obtaining 15.26kg of mother liquor, wherein the mass percent of 4-oxo isophorone is 95.65%;
3) Switching the valve to a sweat receiving tank so that a discharge port at the bottom of the static melt crystallizer is connected to the sweat receiving tank; heating the static melting crystallizer at a heating rate of 8 ℃/h, and adjusting the heating rate to 4 ℃/h when the temperature reaches 18 ℃; stopping heating when the temperature reaches 22 ℃, keeping the temperature constant for 20min, and finishing sweating to obtain 18.23kg of sweat, wherein the mass percent of the sweat containing 4-oxo-isophorone is 94.75%;
4) The valve was switched to a final tank of 4-oxoisophorone so that the discharge port at the bottom of the static melt crystallizer was connected to the final tank, the temperature was raised to 30 ℃, 4-oxoisophorone was completely melted while the resulting 4-oxoisophorone melt was released to the final tank, 191.97kg of the product liquid was obtained, and the melt was sampled and analyzed, showing that the mass percent of 4-oxoisophorone was 99.60%, the mass percent of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one was 0.04%, and the mass percent of 2, 6-trimethyl-1, 4-cyclohexanedione was 0.36%, and the yield of single pass 4-oxoisophorone melt crystallization was 85.63% as calculated.
Example 9 (melt crystallization procedure)
1) 226.70Kg of crude 4-oxo-isophorone (wherein, according to mass percent, 98.65% of 4-oxo-isophorone, 0.25% of 2, 6-trimethyl-1, 4-cyclohexanedione, 1.10% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one) at about 28 ℃ is pumped into a static melt crystallizer, and is stabilized for 10min;
2) Rapidly cooling at a speed of 10 ℃/h, and preserving heat for 20min after the temperature is reduced to 16 ℃; then slowly cooling to 12 ℃, wherein the cooling rate is 1.2 ℃/h, the end temperature of cooling crystallization is 12 ℃, finally, after 60 minutes of heat preservation, opening a discharge port at the bottom of the static melting crystallizer, connecting the discharge port to a mother liquor receiving tank until the mother liquor in the static melting crystallizer is discharged completely, and obtaining 15.68kg of mother liquor, wherein the mass percent of 4-oxo isophorone is 96.85%;
3) Switching the valve to a sweat receiving tank so that a discharge port at the bottom of the static melt crystallizer is connected to the sweat receiving tank; heating the static melting crystallizer at a heating rate of 7 ℃/h, and adjusting the heating rate to 4 ℃/h when the temperature reaches 18 ℃; stopping heating when the temperature reaches 22 ℃, keeping the temperature constant for 20min, and finishing sweating to obtain 18.89kg of sweat, wherein the mass percent of the sweat containing 4-oxo-isophorone is 94.85%;
4) The valve was switched to a 4-oxoisophorone finish pot so that a discharge port at the bottom of a static melt crystallizer was connected to the finish pot, the temperature was raised to 30 ℃, 4-oxoisophorone was completely melted while the obtained 4-oxoisophorone melt was released into the finish pot to obtain 191.57kg of a product liquid, and the melt was sampled and analyzed, showing that the mass percent of 4-oxoisophorone was 99.43%, the mass percent of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one was 0.18%, and the mass percent of 2, 6-trimethyl-1, 4-cyclohexanedione was 0.39%, and the yield of single pass 4-oxoisophorone melt crystallization was 85.17% as calculated.
Example 10 (melt crystallization procedure)
1) 226.70Kg of crude 4-oxo-isophorone (wherein, according to mass percent, 98.65% of 4-oxo-isophorone, 0.25% of 2, 6-trimethyl-1, 4-cyclohexanedione, 1.10% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one) at about 28 ℃ is pumped into a static melt crystallizer, and is stabilized for 10min;
2) Rapidly cooling at a speed of 10 ℃/h, and preserving heat for 20min after the temperature is reduced to 16 ℃; then slowly cooling to 12 ℃, wherein the cooling rate is 1.2 ℃/h, the end temperature of cooling crystallization is 12 ℃, finally, after 60 minutes of heat preservation, opening a discharge port at the bottom of the static melting crystallizer, connecting the discharge port to a mother liquor receiving tank until the mother liquor in the static melting crystallizer is discharged completely, and obtaining 15.68kg of mother liquor, wherein the mass percent of 4-oxo isophorone is 96.85%;
3) Switching the valve to a sweat receiving tank so that a discharge port at the bottom of the static melt crystallizer is connected to the sweat receiving tank; heating the static melting crystallizer at a heating rate of 7 ℃/h, and adjusting the heating rate to 4 ℃/h when the temperature reaches 18 ℃; stopping heating when the temperature reaches 22 ℃, keeping the temperature constant for 40min, and finishing sweating to obtain 19.03kg of sweat, wherein the mass percent of the sweat containing 4-oxo-isophorone is 95.16%;
4) The valve was switched to a 4-oxoisophorone finish pot so that a discharge port at the bottom of a static melt crystallizer was connected to the finish pot, the temperature was raised to 30 ℃, 4-oxoisophorone was completely melted while the resulting 4-oxoisophorone melt was released into the finish pot, 191.43kg of the product liquid was obtained, and the melt was sampled and analyzed, and as a result, see fig. 3, it was shown that the mass percent of 4-oxoisophorone was 99.51%, the mass percent of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one was 0.14%, and the mass percent of 2, 6-trimethyl-1, 4-cyclohexanedione was 0.36%, and the yield of single pass 4-oxoisophorone melt crystallization was 85.18% as calculated.
Example 11 (melt crystallization procedure)
1) 226.70Kg of crude 4-oxo-isophorone (wherein, according to mass percent, 96.35% of 4-oxo-isophorone, 0.79% of 2, 6-trimethyl-1, 4-cyclohexanedione, 2.86% of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one) at about 28 ℃ is pumped into a static melt crystallizer, and is stabilized for 10min;
2) Rapidly cooling at a speed of 10 ℃/h, and preserving heat for 20min after the temperature is reduced to 16 ℃; then slowly cooling to 12 ℃, wherein the cooling rate is 1.2 ℃/h, the end temperature of cooling crystallization is 12 ℃, finally, after 60 minutes of heat preservation, opening a discharge port at the bottom of the static melting crystallizer, connecting the discharge port to a mother liquor receiving tank until mother liquor in the static melting crystallizer is discharged completely, and obtaining 16.06kg of mother liquor, wherein the mass percent of 4-oxo isophorone is 97.15%;
3) Switching the valve to a sweat receiving tank so that a discharge port at the bottom of the static melt crystallizer is connected to the sweat receiving tank; heating the static melting crystallizer at a heating rate of 7 ℃/h, and adjusting the heating rate to 4 ℃/h when the temperature reaches 18 ℃; stopping heating when the temperature reaches 22 ℃, keeping the temperature constant for 20min, and finishing sweating to obtain 19.24kg of sweat, wherein the mass percent of the sweat containing 4-oxo-isophorone is 95.66%;
4) The valve was switched to a final tank of 4-oxoisophorone so that the discharge port at the bottom of the static melt crystallizer was connected to the final tank, the temperature was raised to 30 ℃, 4-oxoisophorone was completely melted while the resulting 4-oxoisophorone melt was released to the final tank, 190.84kg of the product liquid was obtained, and the melt was sampled and analyzed, showing that the mass percent of 4-oxoisophorone was 99.39%, the mass percent of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one was 0.20%, and the mass percent of 2, 6-trimethyl-1, 4-cyclohexanedione was 0.40%, and the yield of single pass 4-oxoisophorone melt crystallization was 86.84% as calculated.
Comparative example 1
The rectification process of comparative example 1 was the same as in example 1, except that recrystallization was employed. The specific process is as follows:
100g of the product obtained in the embodiment 1 after rectification is taken and put into a crystallization kettle, 50g of ethanol is added, the temperature is reduced for crystallization after dissolving, the temperature is reduced to-4 ℃, the product with the content of 99.11 percent is obtained by filtering and air-drying at low temperature, and the mother liquor is 60.5g, wherein the content of the oxo-isophorone product is 30.25 percent.
Claims (11)
1. A process for preparing high purity 4-oxoisophorone comprising the steps of:
(1) Removing light components from a crude product containing 4-oxo-isophorone by rectification, removing heavy components by rectification, and removing 2, 6-trimethyl-1, 4-cyclohexanedione to obtain a rectification product;
(2) Removing 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadiene-1-one from the rectification product obtained in the step (1) through melt crystallization to obtain high-purity 4-oxo isophorone;
the melting crystallization comprises two stages of cooling crystallization and heating sweating;
The temperature of the cooling crystallization is 9-15 ℃, and the temperature of the heating sweating is 20-25 ℃.
2. The process for preparing high-purity 4-oxoisophorone according to claim 1, wherein the crude product containing 4-oxoisophorone comprises, in mass percent:
70 to 75 percent of 4-oxo isophorone, 20 to 25 percent of 2, 6-trimethyl-1, 4-cyclohexanedione, 1.4 to 2 percent of 2-hydroxy-4, 6-trimethyl-2, 5-cyclohexadien-1-one and 3.5 to 4 percent of light components.
3. The process for preparing high purity 4-oxo-isophorone according to claim 1, wherein in step (1), the conditions for the distillation and the light removal are: the temperature of the tower bottom is 118-122 ℃, the temperature of the tower top is 58-63 ℃, the number of tower plates is 75-85, and the tower height is 22-26 m.
4. The process for preparing high purity 4-oxo-isophorone according to claim 1, wherein in step (1), conditions for distillation and weight loss are: the temperature of the tower bottom is 130-140 ℃, the temperature of the tower top is 110-125 ℃, the number of tower plates is 40-45, and the tower height is 12-16 m.
5. The process for preparing high-purity 4-oxoisophorone according to claim 1, wherein in step (2), the conditions for cooling crystallization are: the initial temperature of the cooling crystallization is 25-35 ℃, the temperature is rapidly reduced to 12-20 ℃ at a cooling rate of 7-10 ℃/h, then the temperature is slowly reduced to 10-15 ℃ at a cooling rate of 0.5-2.0 ℃/h, and finally the temperature is kept for 30-60 min.
6. The process for producing high-purity 4-oxoisophorone according to claim 1, wherein in step (2), the manner of heating to sweat is as follows; the first stage is heated to 18-20 ℃, the heating rate is 5-8 ℃/h, the second stage is heated to 21-25 ℃, the heating rate is 1-7 ℃/h, and then the temperature is kept for 30-90 min.
7. The method for preparing high-purity 4-oxo-isophorone according to claim 1, wherein the heavy phase component obtained by rectification and weight removal is recovered and reused after heavy phase leftovers are further removed.
8. The process for preparing high-purity 4-oxo-isophorone according to claim 1, wherein the mother liquor and the perspiration obtained by the melt crystallization are recovered after further removal of heavy phase scraps.
9. An apparatus for preparing high purity 4-oxo-isophorone comprising: the device comprises an N1 raw material storage tank, a light component removing tower, a heavy component removing tower and a melting crystallization device which are connected in sequence;
the light component removing tower is provided with a light component removing tower feeding port, a light component removing tower light phase outlet and a heavy component removing tower heavy phase outlet, and the light component removing tower feeding port is positioned in the middle of the light component removing tower;
The heavy-removal tower is provided with a heavy-removal tower feed inlet, a heavy-removal tower light phase outlet and a heavy-removal tower heavy phase outlet, and the heavy-removal tower feed inlet is positioned in the middle of the heavy-removal tower;
The N1 raw material storage tank is communicated with the light component removing tower feed inlet, the heavy component removing tower heavy phase outlet is communicated with the heavy component removing tower feed inlet, and the light component removing tower light phase outlet is communicated with the melting crystallization device.
10. The apparatus for preparing high purity 4-oxo-isophorone according to claim 9, further comprising a heavy phase heel treatment system connected to the heavy phase outlet of the de-weight column, wherein the heavy phase heel treatment system is connected to an N1 feedstock storage tank.
11. The apparatus for preparing high purity 4-oxo-isophorone according to claim 9, further comprising a crystallization mother liquor sweat treatment system connected to the melt crystallization apparatus, wherein the crystallization mother liquor sweat treatment system is connected to the N1 raw material storage tank.
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| CN202311674098.4A Pending CN118047667A (en) | 2023-12-07 | 2023-12-07 | Method and device for preparing high-purity 4-oxo-isophorone |
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