CN113072461B - Preparation method of butanone oxime - Google Patents
Preparation method of butanone oxime Download PDFInfo
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- CN113072461B CN113072461B CN202110374908.9A CN202110374908A CN113072461B CN 113072461 B CN113072461 B CN 113072461B CN 202110374908 A CN202110374908 A CN 202110374908A CN 113072461 B CN113072461 B CN 113072461B
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- 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
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of butanone oxime. In the presence of solvent water, ammonia, butanone and hydrogen peroxide are used as raw materials, and heteropoly acid or heteropoly acid salt is used as a catalyst to catalyze and synthesize butanone oxime. The invention solves the problems of expensive catalyst, large raw material loss and quick decomposition of reaction raw materials in the prior art, and simultaneously adopts inorganic solvent as reaction solvent, thereby being more beneficial to the separation of products after the amidoxime reaction and greatly saving the process production time.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of butanone oxime.
Background
Butanone oxime is also called methyl ethyl ketoxime, is colorless oily transparent liquid, has stronger complexing effect with metal ions, and is volatile in air. The butanone oxime is used as a chemical oxygen scavenger and has the advantages of low toxicity, high efficiency, high speed and the like. The high-purity butanone oxime can be used for synthesizing organosilicon cross-linking agents, silicon curing agents and isocyanate sealing agents, and can also play a role in preventing skinning in the storage and transportation processes of oil-based paint, alkyd paint, epoxy ester paint and the like.
Chinese patent CN1651405A discloses a method for synthesizing butanone oxime, and proposes a new method for directly synthesizing butanone oxime by ammoxidation of butanone in an oxidation system composed of titanium-silicon molecular sieve and hydrogen peroxide solution. In a catalytic oxidation system consisting of a titanium-silicon molecular sieve and a 30% hydrogen peroxide solution, butanone and a 25% ammonia water solution are reacted in a proper solvent at normal pressure to directly synthesize butanone oxime.
Chinese patent CN 104610094A discloses a method for preparing butanone oxime, which mainly comprises the following five procedures: raw material process, reaction process, membrane filtration process, oxime-water separation process and refining process. The raw material process mainly comprises the steps of storing raw materials and conveying the raw materials meeting the requirements of the production process to a reaction process, wherein the raw materials mainly comprise butanone, liquid ammonia and hydrogen peroxide, the purity of the butanone is more than or equal to 99.5wt%, the purity of the liquid ammonia is more than or equal to 99.5wt%, and the purity of the hydrogen peroxide is more than or equal to 27.5wt%. The reaction mechanism of synthesizing butanone by ammoxidation and oximation of titanium-silicon molecular sieve is to use the catalytic oxidation system composed of titanium-silicon molecular sieve and hydrogen peroxide to perform ammoxidation of butanone to synthesize butanone oxime.
It can be known from the above patents that the prior domestic method for producing butanone oxime mainly comprises that butanone is subjected to an amidoximation reaction in the presence of a catalyst titanium silicalite molecular sieve, and then a solvent is recovered by distillation; then extracting butanone oxime from the reaction liquid by using an extracting agent in an extraction kettle or a tower, and separating the butanone oxime from the reaction liquid; and rectifying the extract phase to collect the butanone oxime and the extractant.
The production method has the following disadvantages:
(1) The production flow is long, the butanone oxime synthesized in the production process is distilled firstly, the solvent is recovered, then the extraction is carried out, and then the extractant and the butanone oxime are rectified and separated in a rectifying tower;
(2) The titanium-silicon molecular sieve is expensive and has quick inactivation;
(3) The production temperature is relatively high, and the raw materials are decomposed quickly.
Disclosure of Invention
The invention aims to provide a preparation method of butanone oxime, which uses inorganic solvent water as a reaction solvent; the heteropolyacid or heteropolyacid salt is used as a catalyst to replace an expensive titanium silicalite molecular sieve, so that the production cost is reduced; the reaction temperature is reduced, and the utilization rate of the hydrogen peroxide is increased.
The preparation method of the butanone oxime comprises the step of catalytically synthesizing the butanone oxime by taking ammonia, butanone and hydrogen peroxide as raw materials and heteropoly acid or heteropoly acid salt as a catalyst in the presence of solvent water.
The heteropoly acid is phosphotungstic acid.
The heteropoly acid salt is phosphotungstate.
The ammonia is ammonia water or ammonia gas.
The mass ratio of ammonia, butanone, hydrogen peroxide and solvent is 85-90:48-52:125-130:190-210.
The mass of the catalyst is 5-15% of the mass of butanone.
The synthesis temperature is 10-40 ℃, and the synthesis time is 60-300 minutes.
The preparation method of the butanone oxime comprises the following steps:
(1) Synthesis of butanone oxime: in the presence of solvent water, ammonia, butanone and hydrogen peroxide are used as raw materials, and heteropoly acid or heteropoly acid salt is used as a catalyst to perform catalytic synthesis to obtain butanone oxime solution;
(2) Ammonia distillation of reaction liquid: distilling the butanone oxime solution to remove unreacted ammonia, standing, performing phase separation to obtain a butanone oxime oil phase and a butanone oxime water phase, and extracting and recovering a butanone oxime extraction phase from the water phase;
(3) And (3) butanone oxime rectification: and (3) mixing the butanone oxime extraction phase obtained in the step (2) with the butanone oxime oil phase, and then rectifying and purifying to obtain a butanone oxime product.
The distillation temperature in the step (2) is 85-95 ℃, and the distillation time is 60-90 minutes.
The extraction in the step (2) is carried out by adding toluene.
The rectification temperature in the step (3) is 60-130 ℃, and the rectification time is 2-6 hours.
The rectification vacuum degree in the step (3) is-0.085-0.095 MPa.
The preparation method of the butanone oxime comprises the following specific steps:
(1) Synthesizing butanone oxime: adding a catalyst and butanone into solvent water, heating while stirring, then dropwise adding ammonia water at a constant speed or introducing ammonia gas, dropwise adding hydrogen peroxide at a constant speed for reaction, and filtering the catalyst after the reaction is finished to obtain a butanone oxime solution;
(2) Ammonia distillation of reaction liquid: cooling the butanone oxime solution synthesized in the step (1), transferring the butanone oxime solution into an ammonia evaporation reactor, heating the solution to full reflux, and recovering unreacted ammonia; carrying out phase separation after standing to obtain a butanone oxime oil phase and a butanone oxime water phase, and extracting the water phase by toluene to recover a butanone oxime extract phase (namely a toluene extract phase);
(3) And (3) rectification of the butanone oxime product: and (3) adding the butanone oxime oil phase obtained by phase separation in the step (2) into a rectifying tower to be mixed with the toluene extraction phase, heating, distilling out the toluene serving as an extractant under negative pressure, and rectifying to obtain a qualified butanone oxime product.
In the invention, inorganic solvent is used as reaction solvent, and unreacted ammonia is removed by distilling the synthetic and filtered butanone oxime solution; then phase separation is carried out, and the upper layer product butanone oxime oil phase and the water phase are subjected to phase separation; and (3) performing extraction separation on the butanone oxime aqueous phase for multiple times by using an extractant, combining the upper extractant oil phase, distilling to remove the extractant, and rectifying together with the butanone oxime oil phase to obtain the qualified butanone oxime product.
The chemical reaction equation of the invention is as follows:
the catalytic mechanism of the catalyst of the invention is as follows:
the invention has the following beneficial effects:
(1) The invention solves the problems of expensive catalyst, large raw material loss and fast decomposition of reaction raw materials in the prior art, and simultaneously adopts inorganic solvent as reaction solvent, which is more beneficial to the product separation after the amine oximation reaction and greatly saves the process production time.
(2) According to the invention, the solvent water, unreacted ammonia and butanone can be recycled, so that the raw materials consumed by synthesizing the butanone oxime mainly comprise hydrogen peroxide, butanone and ammonia, the three raw materials are rich in sources and low in cost, no side reaction is generated, and the synthesis process is green and environment-friendly.
(3) The invention does not use expensive titanium-silicon molecular sieve as catalyst, uses cheap and easily obtained heteropoly acid or heteropoly acid salt as catalyst, produces butanone oxime by the processes of amine oximation, ammonia distillation, split-phase extraction and rectification, has low reaction temperature, reduces steam consumption, and saves raw material cost and energy consumption cost.
(4) According to the method, water is used as a reaction solvent, an organic solvent is not adopted, and ammonia distillation and phase separation are directly carried out without distilling the organic solvent after the reaction is finished, so that the operation time is greatly saved in the separation of the amidoxime product, and the operation sustainability of the whole production process is improved.
(5) Compared with the existing method for synthesizing butanone oxime by catalyzing with a titanium-silicon molecular sieve, the method disclosed by the invention has the advantages that the reaction temperature is reduced, the high-temperature decomposition of the reaction raw material hydrogen peroxide is prevented, and the hydrogen peroxide can be fully utilized.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention is further described below with reference to examples.
The reagents and starting materials used in the examples are commercially available.
Example 1
(1) Synthesis of butanone oxime: putting 200ml of water into a 500ml glass reaction bottle, adding 5g of phosphotungstic acid catalyst, adding 50g of butanone under stirring, heating in a water bath, controlling the temperature at 30 ℃, adding 88g of ammonia water and 128g of hydrogen peroxide at a constant speed, and finishing the addition within 3 hours; keeping the temperature of the reaction system at 28-33 ℃ for reaction for 1.5 hours, filtering out catalyst phosphotungstic acid after the reaction is finished, and reserving the reaction solution for later use.
(2) Distilling ammonia from the reaction liquid in a reaction bottle, controlling the temperature in the reaction bottle to be 85 ℃, performing ammonia distillation operation, recovering unreacted ammonia, absorbing the recovered ammonia with clear water, measuring the content of the ammonia, and then using the ammonia for the reaction in the step (1); after ammonia distillation is finished, cooling the liquid in the reaction bottle to room temperature, and pouring the liquid into a separating funnel for separating liquid to obtain a butanone oxime oil phase and a butanone oxime water phase; extracting the lower water phase with 50ml toluene, repeating the extraction for 2 times, combining the upper toluene extract phase, and entering the next process;
(3) Mixing the toluene extraction phase and the butanone oxime oil phase, adding the mixture into a tower kettle of a rectifying tower, starting a vacuum pump, controlling the distillation temperature in the kettle to be 118-125 ℃ under stirring, distilling and recovering toluene, and recycling the toluene to extraction; distilling until no toluene flows out, controlling the vacuum degree to be-0.09 MPa to carry out negative pressure distillation, collecting 56.5g of butanone oxime by distillation, detecting the content by liquid chromatography to be 99.1 percent, and obtaining the yield to be 91.4 percent.
Example 2
(1) Synthesizing butanone oxime: putting 200ml of water into a 500ml glass reaction bottle, adding 6.5g of ammonium phosphotungstate catalyst, adding 50g of butanone under stirring, heating in a water bath, controlling the temperature to be 29 ℃, adding 88g of ammonia water and 128g of hydrogen peroxide at constant speed, and finishing the adding within 2.5 hours; keeping the temperature of the reaction system at 28-33 ℃ for reaction for 1.5 hours, filtering out the catalyst ammonium phosphotungstate after the reaction is finished, and reserving the reaction solution for later use.
(2) Distilling ammonia from the reaction liquid in a reaction bottle, controlling the temperature in the reaction bottle to be 90 ℃, performing ammonia distillation operation, recovering unreacted ammonia, absorbing the recovered ammonia with clear water, and measuring the ammonia content to be used for the reaction in the step (1); after ammonia distillation is finished, cooling the liquid in the reaction bottle to room temperature, pouring the liquid into a separating funnel for separating liquid to obtain a butanone oxime oil phase and a butanone oxime water phase, extracting the lower water phase by using 50ml of toluene for 3 times, combining the upper toluene extract phase, and then entering the next procedure;
(3) Mixing the toluene extraction phase and the butanone oxime oil phase, adding the mixture into a rectifying tower kettle, starting a vacuum pump, controlling the distillation temperature in the kettle to be 115-121 ℃ under stirring, distilling and recovering toluene, and recycling the toluene to extraction; distilling until no toluene flows out, controlling the vacuum degree to be-0.095 MPa to carry out negative pressure distillation, distilling and collecting 57.1g of butanone oxime, detecting the content by liquid chromatography to be 99.0 percent, and obtaining the yield to be 92.4 percent.
Example 3
(1) Synthesis of butanone oxime: putting 200ml of water into a 500ml glass reaction bottle, adding 7g of sodium phosphotungstate catalyst, adding 50g of butanone under stirring, heating in a water bath, controlling the temperature to be 32 ℃, adding 88g of ammonia water and 128g of hydrogen peroxide at a constant speed, and finishing the addition within 3.5 hours; keeping the temperature of the reaction system at 28-33 ℃ for reaction for 1.5 hours, filtering out the catalyst sodium phosphotungstate after the reaction is finished, and reserving the reaction solution for later use.
(2) Distilling ammonia from the reaction liquid in a reaction bottle, controlling the temperature in the reaction bottle to be 95 ℃, performing ammonia distillation operation, recovering unreacted ammonia, absorbing the recovered ammonia with clear water, and measuring the ammonia content to be used for the reaction in the step (1); after ammonia distillation is finished, cooling the liquid in the reaction bottle to room temperature, pouring the liquid into a separating funnel for separating liquid to obtain a butanone oxime oil phase and a butanone oxime water phase, extracting the lower water phase with 50ml of toluene for 2 times, combining the upper toluene extract phase, and entering the next procedure;
(3) Mixing the toluene extraction phase and the butanone oxime oil phase, adding the mixture into a tower kettle of a rectifying tower, starting a vacuum pump, controlling the distillation temperature in the kettle to be 110-120 ℃ under stirring, distilling and recovering toluene, and recycling the toluene to extraction; distilling until no toluene flows out, controlling the vacuum degree to be-0.09 MPa to carry out negative pressure distillation, collecting 55.5g of butanone oxime by distillation, detecting the content by liquid chromatography to be 99.3 percent, and obtaining the yield to be 89.8 percent.
Comparative example 1
0.58g of titanium silicalite TS-1 (A), 20ml of deionized water and 5.7ml of 30% hydrogen peroxide solution are sequentially added into a three-port jacket glass reaction bottle with a condensing reflux pipe, when the temperature is raised to 75 ℃, 3ml of butanone is added, 10ml of 25% ammonia water is added in a continuous feeding mode, the dropwise adding time exceeds 60 minutes, and the reaction is continued for 3 hours after the addition. After the reaction, the reaction solution was cooled, the catalyst was centrifuged, and the reaction solution was analyzed by gas chromatography. The concentration of hydrogen peroxide is measured by iodometry. The conversion rate of butanone after the reaction was 85%, and the selectivity of butanone oxime was 97.5%.
Claims (8)
1. A preparation method of butanone oxime is characterized in that ammonia, butanone and hydrogen peroxide are used as raw materials, and heteropoly acid is used as a catalyst to catalyze and synthesize the butanone oxime in the presence of solvent water;
the heteropoly acid is phosphotungstic acid;
synthesizing butanone oxime: adding a catalyst and butanone into solvent water, heating while stirring, then dropwise adding ammonia water or introducing ammonia gas at a constant speed, dropwise adding hydrogen peroxide at a constant speed for reaction, and filtering the catalyst after the reaction is finished to obtain the butanone oxime solution.
2. The butanone oxime preparation method according to claim 1, wherein the ammonia is ammonia water or ammonia gas, and the mass ratio of ammonia, butanone, hydrogen peroxide and solvent is 85-90:48-52:125-130:190-210 percent, and the mass of the catalyst is 5-15 percent of the mass of the butanone.
3. The process for producing butanone oxime as claimed in claim 1, wherein the synthesis temperature is 10-40 ℃ and the synthesis time is 60-300 minutes.
4. The process for producing butanone oxime according to any one of claims 1-3, characterized by comprising the steps of:
(1) Synthesizing butanone oxime: in the presence of solvent water, ammonia, butanone and hydrogen peroxide are used as raw materials, and heteropoly acid is used as a catalyst to perform catalytic synthesis to obtain butanone oxime solution;
(2) Ammonia distillation of reaction liquid: distilling the butanone oxime solution to remove unreacted ammonia, standing, performing phase separation to obtain a butanone oxime oil phase and a butanone oxime water phase, and extracting and recovering a butanone oxime extraction phase from the water phase;
(3) And (3) butanone oxime rectification: and (3) mixing the butanone oxime extraction phase obtained in the step (2) with the butanone oxime oil phase, and then rectifying and purifying to obtain the butanone oxime product.
5. A process for producing butanone oxime as claimed in claim 4, wherein the distillation temperature in step (2) is 85-95 ℃ and the distillation time is 60-90 minutes.
6. A process for producing butanone oxime as claimed in claim 4, wherein the extraction in step (2) is performed by adding toluene.
7. A butanone oxime production method as claimed in claim 4 wherein the rectification temperature in step (3) is 60-130 ℃ and the rectification time is 2-6 hours.
8. A butanone oxime production method as claimed in claim 4 wherein the rectification vacuum in step (3) is-0.085 to-0.095 MPa.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651405A (en) * | 2004-11-04 | 2005-08-10 | 大连理工大学 | Method of synthesizing butanone oxime |
| CN107311128A (en) * | 2017-07-05 | 2017-11-03 | 郑州大学 | A kind of method for preparing hydroxylamine hydrochloride |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651405A (en) * | 2004-11-04 | 2005-08-10 | 大连理工大学 | Method of synthesizing butanone oxime |
| CN107311128A (en) * | 2017-07-05 | 2017-11-03 | 郑州大学 | A kind of method for preparing hydroxylamine hydrochloride |
Non-Patent Citations (1)
| Title |
|---|
| "Aqueous biphasic catalysis with polyoxometalates:Oximation of ketones and aldehydes with aqueous ammonia and hydrogen peroxide";Sloboda-Rozner,Dorit,et.;《Green Chemistry》;20060626;第8卷(第8期);第679-681页 * |
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