Preparation method of organic-solvent-free diacetylmonoxime with 100% butanone conversion rate

Abstract

The invention discloses an organic-solvent-free preparation method of diacetylmonoxime with 100% butanone conversion rate, and belongs to the technical field of organic synthesis.Under the condition that no organic solvent exists, the instantaneous molar ratio of raw materials is controlled through a peristaltic pump, hydrogen peroxide and ammonia gas are introduced into the bottom of a reaction kettle, and the butanone conversion rate and the diacetylmonoxime selectivity can both reach 100%.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate. Background Art

[0002] Butanone oxime is a colorless or light yellow oily transparent liquid with the characteristics of easy volatility, strong complexation, and the ability to react with hydrochloric acid and sulfuric acid to release butanone. High-purity butanone oxime can be used to synthesize silane crosslinkers, silicon curing agents, and isocyanate blocking agents; it can prevent skinning and stabilize viscosity during the storage of various alkyd resin paints, epoxy resins, and polyurethanes. Synthetic silane crosslinkers include methyl tributylidene oxime silane, vinyl tributylidene oxime silane, phenyl tributylidene oxime silane, etc.

[0003] There are two methods for synthesizing butanone oxime in industry. The first method uses hydroxylamine hydrochloride or hydroxylamine sulfate and butanone through non-catalytic oximation reaction, but this synthesis method has the disadvantages of strong raw material corrosion, inconvenient operation, low yield, low value of by-products, and high environmental pressure during the production process. The second method uses the ammoximation reaction of butanone in the presence of a catalyst, which is the mainstream method for producing butanone oxime in industry.

[0004] At present, a large amount of organic solvent tert-butanol needs to be added in the process of synthesizing butanone oxime by the ammoximation method, which greatly increases the energy consumption and separation cost of the subsequent process. Studies have found that a large excess of ammonia water can improve the selectivity of the product, but too much excess ammonia water can easily dissolve the Si in the catalyst skeleton, thereby causing the loss of Ti and leading to catalyst deactivation. The deactivated catalyst will lead to poor product selectivity and more by-products will appear in the product.

[0005] Chinese patent document 200410155431.1 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. The method is to directly synthesize butanone oxime with butanone and 25% ammonia solution under normal pressure in a catalytic oxidation system composed of titanium silicon molecular sieve and 30% hydrogen peroxide solution, in an appropriate solvent (water or tert-butyl alcohol or water / tert-butyl alcohol mixture), by continuous dripping of ammonia, one-time addition of hydrogen peroxide or continuous dripping, the molar ratio of ammonia: hydrogen peroxide: butanone is 2-4.6:1.0-2.1:1, the volume ratio of solvent and butanone is 3.3-8.5:1, the conversion rate of butanone as a reactant can reach 99%, and the selectivity of butanone oxime in the product reaches 98%. However, the method still has the disadvantages of being easy to generate a small amount of by-products, and the raw materials ammonia, hydrogen peroxide, and solvent are consumed greatly, and the solvent post-processing needs to consume more energy. Summary of the invention

[0006] The main purpose of the present invention is to provide a method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate. The preparation method comprises the following steps: in the absence of any organic solvent, the instantaneous molar ratio of raw materials and hydrogen peroxide and ammonia are respectively controlled by a peristaltic pump to pass into the bottom of a reaction kettle, and both the butanone conversion rate and butanone oxime selectivity can reach 100%. The catalyst TS-1 can be reused for 5 times after filtering and high-temperature drying, and the butanone conversion rate and butanone oxime selectivity remain unchanged.

[0007] To achieve the above object, the present invention provides a method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate, comprising the following steps:

[0008] (1) adding water and catalyst into a reaction kettle 1, heating, mixing and stirring uniformly;

[0009] (2) preheating the reactor 2, then pumping ammonia water into the reactor 2, and passing the resolved ammonia gas from the bottom of the reactor 1 into the reactor 1;

[0010] (3) pumping butanone and hydrogen peroxide into the reactor 1 in sequence, wherein the hydrogen peroxide is pumped into the reactor 1 from the bottom of the reactor 1;

[0011] (4) After the butanone and hydrogen peroxide are pumped out in sequence, the pumping of ammonia water is stopped, the heating of reactor 2 is stopped and the temperature is lowered. At this time, no ammonia gas is released into reactor 1, and reactor 1 continues to be kept warm for reaction. After the reaction is completed, the reaction is cooled and filtered, and the filtrate and the filter cake are separated. The filter cake is a catalyst. The filtrate is allowed to stand and then separated into layers, and the upper oil phase is collected to obtain the butanone oxime with a butanone conversion rate of 100% without organic solvent.

[0012] Preferably, the catalyst in step (1) is titanium silicon molecular sieve TS-1; and the heating and stirring temperature is 68-72°C.

[0013] Preferably, the preheating temperature in step (2) is 70-80° C.; and the concentration of the aqueous ammonia is 20-25 wt %.

[0014] Preferably, the molar ratio of butanone in step (3) to water in step (1) is 1:3-5.

[0015] Preferably, the concentration of hydrogen peroxide in step (3) is 25-27.5wt%, and the molar ratio of the pump speed of ammonia gas resolved by butanone, hydrogen peroxide and ammonia water in step (2) is 1:1.0-1.1:1.0-1.1.

[0016] Preferably, the temperature of the insulation reaction in step (4) is 68-72° C., and the insulation reaction time is 10-60 min.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] 1. The present invention uses inorganic solvent water instead of the commonly used organic solvent tert-butyl alcohol, which greatly reduces the energy consumption and separation cost of subsequent processes and is beneficial to environmental protection.

[0019] 2. The present invention controls the instantaneous molar ratio of raw materials and the hydrogen peroxide and ammonia gas to be introduced into the bottom of the reaction kettle through a peristaltic pump, and the butanone conversion rate and butanone oxime selectivity can both reach 100%.

[0020] 3. The catalyst of the present invention can be reused 5 times, and the butanone conversion rate and butanone oxime selectivity can still reach 100%. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical solution and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the embodiments. Of course, the specific embodiments described here are only used to explain the present invention and are not used to limit the present invention.

[0022] Although the steps in the present invention are arranged with numbers, they are not used to limit the order of the steps. Unless the order of the steps is clearly stated or the execution of a certain step requires other steps as a basis, the relative order of the steps can be adjusted. It is understood that the term "and / or" used in this article involves and covers any and all possible combinations of one or more of the associated listed items.

[0023] Unless otherwise specified, the chemical reagents and materials in the present invention are purchased from commercial sources or synthesized from raw materials purchased from commercial sources.

[0024] Example 1

[0025] A method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate comprises the following steps:

[0026] (1) Add 54 g of water and 4.1 g of titanium silicalite TS-1 into a 500 mL reactor 1 and stir and mix evenly at 69° C.;

[0027] (2) Preheat the 250 mL reactor 2 to 75° C., then pump 100 g of 25 wt % ammonia water into the reactor 2, control the molar ratio of ammonia gas to butanone pumped in to be 1:1 (the final residual ammonia water concentration in the reactor 2 at this temperature is 8.0%), and pass the resolved ammonia gas from the bottom of the reactor 1 into the reactor 1;

[0028] (3) 72 g of butanone and 123.64 g of 27.5 wt % hydrogen peroxide were sequentially pumped into the reactor 1, and the molar ratio of the two pumped in was controlled to be 1:1, wherein the hydrogen peroxide was pumped into the reactor 1 from the bottom of the reactor 1;

[0029] (4) After butanone and hydrogen peroxide are pumped out in sequence, the pumping of ammonia water is stopped, and the heating of reactor 2 is stopped and the temperature is lowered. At this time, no ammonia gas that has been resolved enters reactor 1. Reactor 1 is kept at 70°C for 30 minutes and then cooled and filtered. The filtrate and the filter cake are separated. The filter cake is catalyst TS-1. The filtrate is allowed to stand and then separated into layers. The upper oil phase is collected to obtain the butanone oxime. After testing, the conversion rate of butanone is 100%, and the selectivity of butanone oxime is 100%.

[0030] The recovered filter cake was dried at 100°C for 6 h and then reused 5 times, with both the butanone conversion and butanone oxime selectivity maintained at 100%.

[0031] Example 2

[0032] A method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate comprises the following steps:

[0033] (1) Add 54 g of water and 5.6 g of titanium silicalite TS-1 into a 500 mL reactor 1 and stir and mix at 69 ° C.

[0034] (2) Preheat the 250 mL reactor 2 to 75° C., then pump 105 g of 25 wt % ammonia water into the reactor 2, control the molar ratio of ammonia gas to butanone pumped in to be 1.05:1 (the final residual ammonia water concentration in the reactor 2 at this temperature is 8.0%), and pass the resolved ammonia gas from the bottom of the reactor 1 into the reactor 1;

[0035] (3) 72 g of butanone and 129.82 g of 27.5 wt % hydrogen peroxide were sequentially pumped into the reactor 1, and the molar ratio of the two pumped in was controlled to be 1:1.05, wherein the hydrogen peroxide was pumped into the reactor 1 from the bottom of the reactor 1;

[0036] (4) After the butanone and hydrogen peroxide are pumped out in sequence, the pumping of ammonia water is stopped, and the heating of reactor 2 is stopped and the temperature is lowered. At this time, no ammonia gas that has been resolved enters reactor 1. Reactor 1 is kept at 70°C for 30 minutes, and then the heating and stirring are stopped. The reactor is left to stand and cool for 50 minutes, and then filtered to separate the filtrate and the filter cake. The filter cake is catalyst TS-1. The filtrate is allowed to stand and then separated into layers. The upper oil phase is collected to obtain the butanone oxime. After testing, the conversion rate of butanone is 100%, and the selectivity of butanone oxime is 100%.

[0037] The recovered filter cake was dried at 110° C. for 8 h and then reused 5 times, with both the butanone conversion and butanone oxime selectivity maintained at 100%.

[0038] Example 3

[0039] A method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate comprises the following steps:

[0040] (1) Add 54 g of water and 7.2 g of titanium silicalite TS-1 into a 500 mL reactor 1 and stir to mix evenly at 70° C.;

[0041] (2) Preheat the 250 mL reactor 2 to 75° C., then pump 105 g of 25 wt % ammonia water into the reactor 2, control the molar ratio of ammonia gas to butanone pumped in to be 1.05:1 (the final residual ammonia water concentration in the reactor 2 at this temperature is 8.0%), and pass the resolved ammonia gas from the bottom of the reactor 1 into the reactor 1;

[0042] (3) 72 g of butanone and 136 g of 27.5 wt % hydrogen peroxide were sequentially pumped into the reactor 1, and the molar ratio of the two pumped in was controlled to be 1:1.1, wherein the hydrogen peroxide was pumped into the reactor 1 from the bottom of the reactor 1;

[0043] (4) After butanone and hydrogen peroxide are pumped out in sequence, the pumping of ammonia water is stopped, and the heating of reactor 2 is stopped and the temperature is lowered. At this time, no ammonia gas released enters reactor 1. Reactor 1 is kept at 70°C for 30 minutes, and then heating and stirring are stopped. It is allowed to stand for 50 minutes and then filtered to separate the filtrate and the filter cake. The filter cake is catalyst TS-1. The filtrate is allowed to stand for stratification, and the upper oil phase is collected to obtain the butanone oxime. After testing, the conversion rate of butanone is 100%, and the selectivity of butanone oxime is 100%.

[0044] The recovered filter cake was dried at 120° C. for 10 h and then reused 5 times, with both the butanone conversion and butanone oxime selectivity maintained at 100%.

[0045] Example 4

[0046] A method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate comprises the following steps:

[0047] (1) Add 72 g of water and 4.4 g of titanium silicalite TS-1 into a 500 mL reactor 1 and stir and mix evenly at 69° C.;

[0048] (2) Preheat the 250 mL reactor 2 to 75° C., then pump 100 g of 25 wt % ammonia water into the reactor 2, control the molar ratio of ammonia gas to butanone pumped in to be 1:1 (the final residual ammonia water concentration in the reactor 2 at this temperature is 8.0%), and pass the resolved ammonia gas from the bottom of the reactor 1 into the reactor 1;

[0049] (3) 72 g of butanone and 123.64 g of 27.5 wt % hydrogen peroxide were sequentially pumped into the reactor 1, and the molar ratio of the two pumped in was controlled to be 1:1, wherein the hydrogen peroxide was pumped into the reactor 1 from the bottom of the reactor 1;

[0050] (4) After butanone and hydrogen peroxide are pumped out in sequence, the pumping of ammonia water is stopped, and the heating of reactor 2 is stopped and the temperature is lowered. At this time, no ammonia gas released enters reactor 1. Reactor 1 is kept at 70°C for 30 minutes, and then heating and stirring are stopped. It is allowed to stand for 30 minutes and then filtered to separate the filtrate and the filter cake. The filter cake is catalyst TS-1. The filtrate is allowed to stand for stratification, and the upper oil phase is collected to obtain the butanone oxime. After testing, the conversion rate of butanone is 100%, and the selectivity of butanone oxime is 100%.

[0051] The recovered filter cake was dried at 130° C. for 12 h and then reused 5 times, with both the butanone conversion and butanone oxime selectivity maintained at 100%.

[0052] Example 5

[0053] A method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate comprises the following steps:

[0054] (1) Add 72 g of water and 6.0 g of titanium silicalite TS-1 into a 500 mL reactor 1 and stir to mix evenly at 69° C.;

[0055] (2) Preheat the 250 mL reactor 2 to 75° C., then pump 105 g of 25 wt % ammonia water into the reactor 2, control the molar ratio of ammonia gas to butanone pumped in to be 1.05:1 (the final residual ammonia water concentration in the reactor 2 at this temperature is 8.0%), and pass the resolved ammonia gas from the bottom of the reactor 1 into the reactor 1;

[0056] (3) 72 g of butanone and 129.82 g of 27.5 wt % hydrogen peroxide were sequentially pumped into the reactor 1, and the molar ratio of the two pumped in was controlled to be 1:1.05, wherein the hydrogen peroxide was pumped into the reactor 1 from the bottom of the reactor 1;

[0057] (4) After butanone and hydrogen peroxide are pumped out in sequence, the pumping of ammonia water is stopped, and the heating of reactor 2 is stopped and the temperature is lowered. At this time, no ammonia gas released enters reactor 1. Reactor 1 is kept at 70°C for 30 minutes, and then heating and stirring are stopped. It is allowed to stand for 30 minutes and then filtered to separate the filtrate and the filter cake. The filter cake is catalyst TS-1. The filtrate is allowed to stand for stratification, and the upper oil phase is collected to obtain the butanone oxime. After testing, the conversion rate of butanone is 100%, and the selectivity of butanone oxime is 100%.

[0058] The recovered filter cake was dried at 140°C for 10 h and then reused 5 times, with both the butanone conversion and butanone oxime selectivity maintained at 100%.

[0059] Example 6

[0060] A method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate comprises the following steps:

[0061] (1) Add 72 g of water and 7.7 g of titanium silicalite TS-1 into a 500 mL reactor 1 and stir to mix evenly at 71° C.;

[0062] (2) Preheat the 250 mL reactor 2 to 75° C., then pump 110 g of 25 wt % ammonia water into the reactor 2, control the molar ratio of ammonia gas to butanone pumped in to be 1.1:1 (the final residual ammonia water concentration in the reactor 2 at this temperature is 8.0%), and pass the resolved ammonia gas from the bottom of the reactor 1 into the reactor 1;

[0063] (3) 72 g of butanone and 136 g of 27.5 wt % hydrogen peroxide were sequentially pumped into the reactor 1, and the molar ratio of the two pumped in was controlled to be 1:1.1, wherein the hydrogen peroxide was pumped into the reactor 1 from the bottom of the reactor 1;

[0064] (4) After butanone and hydrogen peroxide are pumped out in sequence, the pumping of ammonia water is stopped, and the heating of reactor 2 is stopped and the temperature is lowered. At this time, no ammonia gas released enters reactor 1. Reactor 1 is kept at 70°C for 30 minutes, and then heating and stirring are stopped. It is allowed to stand for 30 minutes and then filtered to separate the filtrate and the filter cake. The filter cake is catalyst TS-1. The filtrate is allowed to stand for stratification, and the upper oil phase is collected to obtain the butanone oxime. After testing, the conversion rate of butanone is 100%, and the selectivity of butanone oxime is 100%.

[0065] The recovered filter cake was dried at 150°C for 7 h and then reused 5 times, with both the butanone conversion and butanone oxime selectivity maintained at 100%.

[0066] Example 7

[0067] A method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate comprises the following steps:

[0068] (1) Add 90 g of water and 4.6 g of titanium silicalite TS-1 into a 500 mL reactor 1 and stir and mix evenly at 70 °C;

[0069] (2) Preheat the 250 mL reactor 2 to 75° C., then pump 100 g of 25 wt % ammonia water into the reactor 2, control the molar ratio of ammonia gas to butanone pumped in to be 1:1 (the final residual ammonia water concentration in the reactor 2 at this temperature is 8.0%), and pass the resolved ammonia gas from the bottom of the reactor 1 into the reactor 1;

[0070] (3) 72 g of butanone and 123.64 g of 27.5 wt % hydrogen peroxide were sequentially pumped into the reactor 1, and the molar ratio of the two pumped in was controlled to be 1:1, wherein the hydrogen peroxide was pumped into the reactor 1 from the bottom of the reactor 1;

[0071] (4) After the butanone and hydrogen peroxide are pumped out in sequence, the pumping of ammonia water is stopped, the heating of reactor 2 is stopped and the temperature is lowered. At this time, no ammonia gas is released into reactor 1. Reactor 1 is kept at 70° C. for 30 min, and then the heating and stirring are stopped. Reactor 1 is allowed to stand for 30 min and then filtered to separate the filtrate and the filter cake. The filter cake is catalyst TS-1. The filtrate is allowed to stand for stratification, and the upper oil phase is collected to obtain the butanone oxime. After testing, the conversion rate of butanone is 100%, and the selectivity of butanone oxime is 100%.

[0072] The recovered filter cake was dried at 120° C. for 6 h and then reused 5 times, with both the butanone conversion and butanone oxime selectivity maintained at 100%.

[0073] Example 8

[0074] A method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate comprises the following steps:

[0075] (1) Add 90 g of water and 6.4 g of titanium silicalite TS-1 into a 500 mL reactor 1 and stir to mix evenly at 69 °C;

[0076] (2) Preheat the 250 mL reactor 2 to 75° C., then pump 110 g of 25 wt % ammonia water into the reactor 2, control the molar ratio of ammonia gas to butanone pumped in to be 1.05:1 (the final residual ammonia water concentration in the reactor 2 at this temperature is 8.0%), and pass the resolved ammonia gas from the bottom of the reactor 1 into the reactor 1;

[0077] (3) 72 g of butanone and 129.82 g of 27.5 wt % hydrogen peroxide were sequentially pumped into the reactor 1, and the molar ratio of the two pumped in was controlled to be 1:1.05, wherein the hydrogen peroxide was pumped into the reactor 1 from the bottom of the reactor 1;

[0078] (4) After butanone and hydrogen peroxide are pumped out in sequence, the pumping of ammonia water is stopped, and the heating of reactor 2 is stopped and the temperature is lowered. At this time, no ammonia gas released enters reactor 1. Reactor 1 is kept at 70°C for 30 minutes, and then heating and stirring are stopped. It is allowed to stand for 30 minutes and then filtered to separate the filtrate and the filter cake. The filter cake is catalyst TS-1. The filtrate is allowed to stand for stratification, and the upper oil phase is collected to obtain the butanone oxime. After testing, the conversion rate of butanone is 100%, and the selectivity of butanone oxime is 100%.

[0079] The recovered filter cake was dried at 100°C for 10 h and then reused 5 times, with both the butanone conversion and butanone oxime selectivity maintained at 100%.

[0080] Example 9

[0081] A method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate comprises the following steps:

[0082] (1) Add 90 g of water and 8.1 g of titanium silicalite TS-1 into a 500 mL reactor 1 and stir to mix evenly at 69 °C;

[0083] (2) Preheat the 250 mL reactor 2 to 75° C., then pump 110 g of 25 wt % ammonia water into the reactor 2, control the molar ratio of ammonia gas to butanone pumped in to be 1.05:1 (the final residual ammonia water concentration in the reactor 2 at this temperature is 8.0%), and pass the resolved ammonia gas from the bottom of the reactor 1 into the reactor 1;

[0084] (3) 72 g of butanone and 136 g of 27.5 wt % hydrogen peroxide were sequentially pumped into the reactor 1, with the molar ratio of the two being controlled to be 1:1.05, wherein the hydrogen peroxide was pumped into the reactor 1 from the bottom of the reactor 1;

[0085] (4) After the butanone and hydrogen peroxide are pumped out in sequence, the pumping of ammonia water is stopped, the heating of reactor 2 is stopped and the temperature is lowered. At this time, no ammonia gas is released into reactor 1. Reactor 1 is kept at 70° C. for 30 min, and then the heating and stirring are stopped. Reactor 1 is allowed to stand for 30 min and then filtered to separate the filtrate and the filter cake. The filter cake is catalyst TS-1. The filtrate is allowed to stand for stratification, and the upper oil phase is collected to obtain the butanone oxime. After testing, the conversion rate of butanone is 100%, and the selectivity of butanone oxime is 100%.

[0086] The recovered filter cake was dried at 130° C. for 8 h and then reused 5 times, with both the butanone conversion and butanone oxime selectivity maintained at 100%.

[0087] Comparative Example 1

[0088] A method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate is similar to Example 1, except that the raw materials are added at one time, and specifically comprises the following steps:

[0089] 54 g of water and 4.1 g of titanium silicalite TS-1 were added to a reactor and stirred at 69° C. to mix evenly. 72 g of butanone, 123.64 g of 27.5 wt% and 100 g of 25 wt% ammonia water were added in sequence. After keeping the reaction at 70° C. for 30 min, heating and stirring were stopped, the mixture was allowed to stand and cool, and then filtered. The filtrate and the filter cake were separated. The filter cake was catalyst TS-1. The filtrate was separated after standing and the upper oil phase was collected to obtain butanone oxime with a purity of 63%.

[0090] Comparative Example 2

[0091] A method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate is similar to Example 1, except that hydrogen peroxide and ammonia water are both introduced from the upper feeding port of the reactor, and specifically comprises the following steps: A method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate comprises the following steps:

[0092] (1) Add 54 g of water and 4.1 g of titanium silicalite TS-1 into a 500 mL reactor 1 and stir and mix evenly at 69° C.;

[0093] (2) Preheat the 250 mL reactor 2 to 75° C., then pump 100 g of 25 wt % ammonia water into the reactor 2, control the molar ratio of ammonia gas to butanone pumped in to be 1:1 (the final residual ammonia water concentration in the reactor 2 at this temperature is 8.0%), and pass the resolved ammonia gas into the reactor 1 from the feed port at the upper end of the reactor 1;

[0094] (3) 72 g of butanone and 123.64 g of 27.5 wt % hydrogen peroxide were sequentially pumped into the reactor 1, with the molar ratio of the two being controlled to be 1:1, wherein the hydrogen peroxide was pumped into the reactor 1 from the feed port at the upper end of the reactor 1;

[0095] (4) After the butanone and hydrogen peroxide are pumped out in sequence, the pumping of ammonia water is stopped, and the heating of reactor 2 is stopped and the temperature is lowered. At this time, no ammonia gas released enters reactor 1. Reactor 1 is kept at 70°C for 30 minutes, and then the heating and stirring are stopped. The reactor is left to stand for 30 minutes and then filtered to separate the filtrate and the filter cake. The filter cake is catalyst TS-1. The filtrate is left to stand and then separated into layers. The upper oil phase is collected to obtain the butanone oxime. After testing, the conversion rate of butanone is 0%, and the selectivity of butanone oxime is 0%.

[0096] The above are only preferred embodiments of the present invention, and do not limit the patent scope of the present invention. For those skilled in the art, the present invention may have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the patent protection scope of the present invention.

Claims

1. A method for preparing butanone oxime without organic solvent and with 100% butanone conversion rate, characterized in that: The steps include: (1) adding water and catalyst into a reaction kettle 1, heating, mixing and stirring uniformly; (2) preheating the reactor 2, then pumping ammonia water into the reactor 2, and passing the resolved ammonia gas from the bottom of the reactor 1 into the reactor 1; (3) pumping butanone and hydrogen peroxide into the reactor 1 in sequence, wherein the hydrogen peroxide is pumped into the reactor 1 from the bottom of the reactor 1; (4) After the butanone and hydrogen peroxide are pumped out in sequence, the pumping of ammonia water is stopped, the heating of reactor 2 is stopped and the temperature is lowered. At this time, no ammonia gas is released into reactor 1, and reactor 1 continues to be kept warm for reaction. After the reaction is completed, the reaction is cooled and filtered, and the filtrate and the filter cake are separated. The filter cake is a catalyst. The filtrate is allowed to stand and then separated into layers, and the upper oil phase is collected to obtain the butanone oxime with a butanone conversion rate of 100% without organic solvent.

2. The preparation method according to claim 1, characterized in that: The following steps are involved: The catalyst in step (1) is titanium silicon molecular sieve TS-1.

3. The preparation method according to claim 1, characterized in that: The heating and stirring temperature in step (1) is 68-72°C.

4. The preparation method according to claim 1, characterized in that: The preheating temperature in step (2) is 70-80°C.

5. The preparation method according to claim 1, characterized in that: The concentration of the aqueous ammonia in step (2) is 20-25 wt %.

6. The preparation method according to claim 1, characterized in that: The molar ratio of butanone in the step (3) to water in the step (1) is 1:3-5.

7. The preparation method according to claim 1, characterized in that: The concentration of hydrogen peroxide in step (3) is 25-27.5 wt %.

8. The preparation method according to claim 1, characterized in that: The molar ratio of the pump speed of the ammonia gas resolved by butanone, hydrogen peroxide in step (3) and the ammonia solution in step (2) is 1:1.0-1.1:1.0-1.

1.

9. The preparation method according to claim 1, characterized in that: The temperature of the heat preservation reaction in the step (4) is 68-72°C.

10. The preparation method according to claim 9, characterized in that: The insulation reaction time is 10-60 minutes.