CN113105358A - Method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water - Google Patents
Method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water Download PDFInfo
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- CN113105358A CN113105358A CN202110407849.0A CN202110407849A CN113105358A CN 113105358 A CN113105358 A CN 113105358A CN 202110407849 A CN202110407849 A CN 202110407849A CN 113105358 A CN113105358 A CN 113105358A
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- cyclohexanone
- ozone water
- water
- oxidizing
- organic solvent
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 80
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 title claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003112 inhibitor Substances 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000003182 D-alloisoleucine group Chemical group [H]N([H])[C@@]([H])(C(=O)[*])[C@](C([H])([H])[H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006146 oximation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of cyclohexanone oxime preparation, and discloses a method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water, wherein ozone water is used as an oxidant, and under the conditions that the temperature is 0-200 ℃ and the pressure is 0.1-5 MPa, the molar ratio of cyclohexanone to ozone water to ammonia water to a solvent is 1: 0.3-20: 1-10: carrying out mixing reaction in a proportion of 1-200, and controlling the reaction time of the mixing reaction to be 30-120 minutes; wherein, the ozone water is also called as super-oxygen water, which is formed by dissolving ozone in water by utilizing gas-liquid mixing equipment, and the ozone water has super-strong oxidizing capability and is used as a high-efficiency oxidant; in conclusion, in the method provided by the invention, ozone water is used as an oxidant, a catalyst is not needed, any initiator and inhibitor are not needed to be added in the reaction process, the conversion rate of cyclohexanone and the selectivity of cyclohexanone oxime are high after the reaction, the process is simple and easy to control, and compared with the existing method, the production cost is greatly reduced.
Description
Technical Field
The invention belongs to the technical field of cyclohexanone oxime preparation, and particularly relates to a method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water.
Background
Cyclohexanone oxime is an organic compound having the formula C6H11NO, the molecular weight is 113.6g/mol, the melting point is 88-92 ℃, the boiling point is 206-210 ℃, and the pure product is a white prismatic crystal at normal temperature; insoluble in water and soluble in ethanol, ether and methanolAlcohol and other organic solvents are used for organic synthesis and are key intermediates of monomer caprolactam for synthesizing nylon-6.
At present, cyclohexanone oxime is generally prepared from cyclohexanone, hydrogen peroxide and gaseous ammonia through an oximation reaction, and the specific steps are as follows: taking tert-butyl alcohol as a solvent, taking hydrogen peroxide as an oxidant, and directly reacting cyclohexanone, hydrogen peroxide and ammonia gas in a molar ratio of 1: 1.05: 1.2, heating to 80 ℃, and reacting for about 70 minutes to generate cyclohexanone oxime.
In the preparation method, the conversion rate of the cyclohexanone is about 97 percent; in addition, the process uses a titanium silicalite molecular sieve as a catalyst, firstly hydroxylamine is generated from ammonia and hydrogen peroxide, and then the hydroxylamine reacts with cyclohexanone to generate cyclohexanone oxime. From this, it is understood that the performance, concentration and the like of the catalyst directly affect the reaction rate, the quality of cyclohexanone oxime and the like, and the stability and life of the condition directly determine the production load; in addition, the catalyst is expensive, so that the preparation cost is high.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing cyclohexanone oxime with lower cost and simpler process, and the method specifically uses ozone water as an oxidant and realizes oxidation of cyclohexanone by ozone water without a catalyst to prepare cyclohexanone oxime.
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water comprises the following specific steps: using ozone water as an oxidant, and under the conditions that the temperature is 0-200 ℃ and the pressure is 0.1-5 MPa, mixing the cyclohexanone, the ozone water, the ammonia water and the solvent according to a molar ratio of 1: 0.3-20: 1-10: 1-200, and controlling the reaction time of the mixing reaction to be 30-120 minutes. Wherein, the ozone water is also called super oxygen water, which is formed by dissolving ozone in water by utilizing gas-liquid mixing equipment, and the ozone water has super strong oxidizing power and can be used as an efficient oxidant.
Specifically, the concentration of the ozone water is 1-100 mg/L. And the concentration of the ozone water is more preferably 15 to 100 mg/L.
Specifically, the mass fraction of the ammonia water is 10-50%. And the mass fraction of ammonia water is more preferably 25 to 35 percent.
Preferably, the mixing reaction temperature is 20-80 ℃, and the mixing reaction pressure is 0.1-2.5 MPa.
Preferably, the solvent is one or a mixture of water, an alcohol organic solvent, a ketone organic solvent, an ether organic solvent, a nitrile organic solvent and an acid organic solvent.
Further, the alcohol organic solvent is at least one of methanol, ethanol and tert-butyl alcohol, the ketone organic solvent is acetone, the ether organic solvent is diethyl ether, the nitrile organic solvent is acetonitrile, and the acid organic solvent is acetic acid.
Further, the solvent is water or tert-butyl alcohol or a mixture of the two.
Preferably, the cyclohexanone, the ozone water, the ammonia water and the solvent are mixed according to a molar ratio of 1: 0.3-10: 1.2-5: mixing at a ratio of 10-100.
Compared with the prior art, the invention has the following beneficial effects:
in the method provided by the invention, ozone water is used as an oxidant, a catalyst is not needed, any initiator and inhibitor are not needed to be added in the reaction process, the conversion rate of cyclohexanone and the selectivity of cyclohexanone oxime are high after the reaction, the process is simple and easy to control, the production cost is reduced compared with the existing method, and the industrial production and application are facilitated.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples:
the reagents used were all commercially available analytical grade reagents.
The ozone water is provided by an ozone water making machine, and the concentration of the ozone water is adjustable.
Cyclohexanone conversion (%) ═ M0-M1)/M0×100％；
Cyclohexanone oxime selectivity (%) ═ M2/(M0-M1)×100％；
The following steps: mOIs the number of moles of cyclohexanone added; m1Is the number of moles of cyclohexanone remaining; m2To generate the moles of cyclohexanone oxime.
Example 1
Under the conditions that the temperature is 20 ℃ and the pressure is 0.1MPa, and ozone water with the concentration of 15mg/L is used as an oxidant, cyclohexanone, ozone water, ammonia water and diethyl ether are mixed according to the molar ratio of 1: 0.3: 1.2: 10, wherein the mass fraction of ammonia water is 10 percent, the reaction time is controlled to be 30 minutes, and then the reaction product is separated and weighed.
After weighing, calculating according to the formula to obtain: the cyclohexanone conversion was 20% and the cyclohexanone oxime selectivity was 32%.
Example 2
Under the conditions of 40 ℃ and 0.3MPa of pressure, taking ozone water with the concentration of 30mg/L as an oxidant, and mixing cyclohexanone, ozone water, ammonia water and acetone in a molar ratio of 1: 0.5: 1.5: 15, wherein the mass fraction of ammonia water is 25 percent, the reaction time is controlled to be 90 minutes, and then the reaction product is separated and weighed.
After weighing, calculating according to the formula to obtain: the cyclohexanone conversion was 51% and the cyclohexanone oxime selectivity was 78%.
Example 3
Under the conditions that the temperature is 80 ℃ and the pressure is 1.2MPa, and ozone water with the concentration of 55mg/L is used as an oxidant, cyclohexanone, ozone water, ammonia water and tertiary butanol are mixed according to the molar ratio of 1: 1: 2: 20, wherein the mass fraction of ammonia water is 35 percent, the reaction time is controlled to be 120 minutes, and then the reaction product is separated and weighed.
After weighing, calculating according to the formula to obtain: the cyclohexanone conversion was 73% and the cyclohexanone oxime selectivity was 93%.
Example 4
Under the conditions that the temperature is 110 ℃ and the pressure is 2MPa, and ozone water with the concentration of 35mg/L is used as an oxidant, cyclohexanone, ozone water, ammonia water and acetic acid are mixed according to the molar ratio of 1: 1.5: 2.5: 30 percent of ammonia water, wherein the mass fraction of ammonia water is 40 percent, the reaction time is controlled to be 60 minutes, and then the reaction product is separated and weighed.
After weighing, calculating according to the formula to obtain: the cyclohexanone conversion was 68% and the cyclohexanone oxime selectivity was 81%.
Example 5
Under the conditions that the temperature is 60 ℃ and the pressure is 1.2MPa, and ozone water with the concentration of 60mg/L is used as an oxidant, cyclohexanone, ozone water, ammonia water and ethanol are mixed according to the molar ratio of 1: 1.5: 5: 50 percent of ammonia water, wherein the mass fraction of ammonia water is 50 percent, the reaction time is controlled to be 80 minutes, and then the reaction product is separated and weighed.
After weighing, calculating according to the formula to obtain: the cyclohexanone conversion was 85% and the cyclohexanone oxime selectivity was 92%.
In conclusion, although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made herein without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims (10)
1. A method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water is characterized by comprising the following steps:
using ozone water as an oxidant, and under the conditions that the temperature is 0-200 ℃ and the pressure is 0.1-5 MPa, mixing the cyclohexanone, the ozone water, the ammonia water and the solvent according to a molar ratio of 1: 0.3-20: 1-10: 1-200, and controlling the reaction time of the mixing reaction to be 30-120 minutes.
2. The method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water according to claim 1, wherein: the concentration of the ozone water is 1-100 mg/L.
3. The method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water as claimed in claim 2, wherein: the concentration of the ozone water is 15-100 mg/L.
4. The method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water according to claim 1, wherein: the mass fraction of the ammonia water is 10-50%.
5. The method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water as claimed in claim 4, wherein: the mass fraction of the ammonia water is 25-35%.
6. The method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water according to claim 1, wherein: the reaction temperature of the mixing reaction is 20-80 ℃, and the reaction pressure of the mixing reaction is 0.1-2.5 MPa.
7. The method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water according to claim 1, wherein: the solvent is one or a mixture of water, an alcohol organic solvent, a ketone organic solvent, an ether organic solvent, a nitrile organic solvent and an acid organic solvent.
8. The method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water as claimed in claim 7, wherein: the alcohol organic solvent is at least one of methanol, ethanol and tert-butyl alcohol, the ketone organic solvent is acetone, the ether organic solvent is diethyl ether, the nitrile organic solvent is acetonitrile, and the acid organic solvent is acetic acid.
9. The method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water as claimed in claim 8, wherein: the solvent is water or tert-butyl alcohol or a mixture of the two.
10. The method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water according to claim 1, wherein: the cyclohexanone, the ozone water, the ammonia water and the solvent are mixed according to a molar ratio of 1: 0.3-10: 1.2-5: mixing at a ratio of 10-100.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110407849.0A CN113105358A (en) | 2021-04-15 | 2021-04-15 | Method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110407849.0A CN113105358A (en) | 2021-04-15 | 2021-04-15 | Method for preparing cyclohexanone oxime by oxidizing cyclohexanone with ozone water |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1683323A (en) * | 2005-03-17 | 2005-10-19 | 华东师范大学 | Process for producing cyclohexanone-oxime |
| US20060205939A1 (en) * | 2005-02-28 | 2006-09-14 | Sumitomo Chemical Company, Limited | Process for producing cyclohexanone oxime |
| CN103172535A (en) * | 2013-03-15 | 2013-06-26 | 华东师范大学 | Liquid-phase fixed bed preparation method of cyclohexanone oxime |
-
2021
- 2021-04-15 CN CN202110407849.0A patent/CN113105358A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060205939A1 (en) * | 2005-02-28 | 2006-09-14 | Sumitomo Chemical Company, Limited | Process for producing cyclohexanone oxime |
| CN1683323A (en) * | 2005-03-17 | 2005-10-19 | 华东师范大学 | Process for producing cyclohexanone-oxime |
| CN103172535A (en) * | 2013-03-15 | 2013-06-26 | 华东师范大学 | Liquid-phase fixed bed preparation method of cyclohexanone oxime |
Non-Patent Citations (3)
| Title |
|---|
| HOMA CHOOPAN TAYEFE 等: "Co/Zn-Grafted Mesoporous Silica Nanoparticles Catalyzed Cyclohexanimine Oxidation under UV Irradiation: High Performance Ozonation Process", 《SILICON》 * |
| 周少东 等: "催化合成肟的绿色新工艺", 《浙江大学学报（工学版）》 * |
| 朱凌皓: "环己酮肟的生产方法", 《化工设计》 * |
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Address after: Room 01, 1st floor, building 23, high tech torch Park, 666 Shenma Avenue, Pingdingshan City, Henan Province Applicant after: Henan Zihuan Mining Technology Co.,Ltd. Address before: Room 01, 1st floor, building 23, high tech torch Park, 666 Shenma Avenue, Pingdingshan City, Henan Province Applicant before: Henan Zihuan Testing Technology Co.,Ltd. |
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Application publication date: 20210713 |