CN110981749A - Process for producing cyclohexanone oxime - Google Patents
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- CN110981749A CN110981749A CN201911399146.7A CN201911399146A CN110981749A CN 110981749 A CN110981749 A CN 110981749A CN 201911399146 A CN201911399146 A CN 201911399146A CN 110981749 A CN110981749 A CN 110981749A
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- C07—ORGANIC CHEMISTRY
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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
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Abstract
The invention provides a preparation method of cyclohexanone oxime, wherein a fixed bed reactor is provided with a plurality of beds, a feed inlet is respectively arranged corresponding to each bed, and each bed is filled with a catalyst. Mixing hydrogen peroxide with part of organic solvent to obtain a first mixture; and dividing part of the first mixture into a plurality of parts of a second mixture, wherein the parts of the second mixture are one less than the number of the beds; then cyclohexanone and NH3Feeding the rest of the organic solvent and the rest of the first mixture from a feeding hole of the topmost bed layer; finally, feeding each part of the second mixture from each feed inlet of each bed layer except the topmost bed layer. The processes are coordinated, so that the utilization rate of hydrogen peroxide is greatly improved while the high conversion rate of cyclohexanone and the selectivity of cyclohexanone oxime are kept. And the catalyst of the invention can withstand calcination up to 1000 ℃ without damage.
Description
Technical Field
The invention relates to the field of production of cyclohexanone oxime, and particularly relates to a preparation method of cyclohexanone oxime.
Background
Cyclohexanone oxime is a key intermediate for synthesizing caprolactam, and is an important chemical raw material. In the process of preparing cyclohexanone oxime by cyclohexanone ammoximation, the titanium silicalite molecular sieve catalyst shows high selectivity, so that ammonia is not needed to neutralize sulfuric acid as in the prior method of oximation by hydroxylamine sulfate. In the actual preparation process, in order to ensure the maximum catalytic activity of the catalyst, technicians often control the particle size of the titanium silicalite catalyst to be a very small level (0.1 μm to 15 μm), however, the catalyst with a small particle size brings great difficulty to the separation of the catalyst and a product in the post-treatment process, and the production efficiency is low.
Aiming at the problem of low production efficiency caused by the catalyst with small particle size, technicians generally adopt a fixed bed reactor with higher selectivity, small catalyst loss and simple structure for reaction. However, the catalytic activity of the titanium silicalite molecular sieve is easily lost due to the adsorption and covering of the pore canal and the surface of the titanium silicalite molecular sieve by raw materials, products, by-products and impurities, the activity of the titanium silicalite molecular sieve is recovered by removing the organic matters through high-temperature roasting, the roasting temperature is at least over 500 ℃, and the traditional titanium silicalite molecular sieve cannot maintain the original structure after the high-temperature roasting, so the preparation cost of the cyclohexanone oxime is greatly increased.
Disclosure of Invention
Based on this, it is necessary to provide a method for producing a liquid-solid fixed bed cyclohexanone oxime capable of long-cycle operation. The method can greatly prolong the deactivation time of the catalyst and improve the utilization rate of hydrogen peroxide while keeping the high cyclohexanone conversion rate and cyclohexanone oxime selectivity.
The technical scheme of the invention is as follows.
The invention provides a preparation method of cyclohexanone oxime, which comprises the following steps:
providing raw materials and a fixed bed reactor; the raw material comprises cyclohexanone and NH3Organic solvent, hydrogen peroxide and catalyst; the fixed bed reactor is provided with a plurality of bed layers, a feed inlet is respectively arranged on the fixed bed reactor corresponding to each bed layer, each bed layer is filled with a catalyst, and the catalyst is a titanium-silicon molecular sieve loaded with oxide;
mixing the hydrogen peroxide with part of the organic solvent to obtain a first mixture; wherein, in the total organic solvent, the mass content of part of the organic solvent is more than or equal to zero and less than 100 percent;
dividing a portion of said first mixture into a plurality of portions of a second mixture, the portions of the second mixture being one less than the number of said beds;
mixing the above cyclohexanone and NH3Feeding the rest of the organic solvent and the rest of the first mixture from a feeding hole of the topmost bed layer; feeding each part of the second mixture from each feed port of the rest beds except the topmost bed respectively, and reacting to obtain the cyclohexanone-oxime.
The cyclohexanone and NH in the raw materials3The molar ratio of the organic solvent to the hydrogen peroxide contained in the hydrogen peroxide is 1 (2-5) to (4-12) to (0.8-1.2).
In the above preparation method, the weight of the second mixture is equal.
In the fixed bed reactor, the number of layers of the bed layer is 2-15.
In the catalyst, the mass ratio of the oxide to the titanium silicalite molecular sieve is (1-4): (9-6), the oxide is selected from at least one of alumina or silica, and the titanium silicalite molecular sieve is selected from at least one of titanium silicalite TS-1 and hollow titanium silicalite HTS.
NH as described above3Fed in the form of ammonia gas or in the form of aqueous ammonia.
The height of each layer of the fixed bed reactor is 0.2 m-5 m.
Further, the mass space velocity of the cyclohexanone in the topmost bed layer was 0.1h-1～1.2h-1(ii) a The mass space velocity of the cyclohexanone in each of the rest of the beds except the topmost bed is 0.01h-1～0.6h-1。
The reaction temperature of the reaction is 50-100 ℃.
The organic solvent is selected from organic alcohol with 2-10 carbon atoms.
Advantageous effects
The researchers of the invention find that the conventional fixed bed reactor is adopted for reaction, the main reason that the utilization rate of the hydrogen peroxide is too low is that the hydrogen peroxide can be subjected to decomposition reaction in an alkaline environment after being mixed with ammonia, cyclohexanone and an organic solvent, so that the utilization rate of the hydrogen peroxide and the conversion rate of the cyclohexanone are influenced, the higher the concentration of the hydrogen peroxide is, the faster the decomposition is, and the obvious bubbles generated by the decomposition of the hydrogen peroxide can be observed as long as the concentration of the hydrogen peroxide reaches more than 1%.
Based on this, the invention sets up a fixed bed reactor with a plurality of beds as follows: a feed inlet is respectively arranged corresponding to each bed layer, and each bed layer is filled with catalyst. Firstly, mixing hydrogen peroxide with part of organic solvent to obtain a first mixture; and dividing part of the first mixture into a plurality of parts of a second mixture, wherein the parts of the second mixture are one less than the number of the beds; then cyclohexanone and NH3Feeding the rest of the organic solvent and the rest of the first mixture from a feeding hole of the topmost bed layer; finally, feeding all parts of the second mixture from all feed inlets of all beds except the topmost bed so as to reduce the reaction with NH in the reaction system3The concentration of the contacted hydrogen peroxide effectively improves the utilization rate of the hydrogen peroxide and reduces the accident risk. Meanwhile, the catalyst is a titanium silicalite molecular sieve catalyst loaded with oxide, and the catalyst can be roasted at the temperature of 1000 ℃ without being damaged, thereby being beneficial to the recycling of the catalyst. The coordination of all the processes can greatly improve the utilization rate of hydrogen peroxide while keeping the high cyclohexanone conversion rate and cyclohexanone oxime selectivity.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
One embodiment of the present invention provides a method for producing cyclohexanone oxime, including the following steps S1 to S5.
S1, providing raw materials and a fixed bed reactor; the raw material comprises cyclohexanone and NH3Organic solvent, hydrogen peroxide and catalyst; the fixed bed reactor is provided with a plurality of bed layers, a feed inlet is respectively arranged on the fixed bed reactor corresponding to each bed layer, each bed layer is filled with a catalyst, and the catalyst is a titanium-silicon molecular sieve loaded with oxide.
It should be noted that, in the current method for producing cyclohexanone oxime, raw materials are generally fed from the top of a fixed bed reactor, and reaction raw materials containing cyclohexanone, ammonia, hydrogen peroxide and solvent pass through a catalyst bed layer in the fixed bed reactor, so that the process is simple and the catalyst loss is small. However, the utilization rate of the hydrogen peroxide in the method is very low, huge waste is brought, and meanwhile, potential safety hazards are brought to production, the main reason is that after the hydrogen peroxide is mixed with ammonia, cyclohexanone and an organic solvent, the hydrogen peroxide can be subjected to decomposition reaction in an alkaline environment, so that the utilization rate of the hydrogen peroxide and the conversion rate of the cyclohexanone are influenced, the higher the concentration of the hydrogen peroxide is, the faster the decomposition is, and the obvious bubbles generated by the decomposition of the hydrogen peroxide can be observed, wherein the concentration of the hydrogen peroxide reaches more than 1%.
In one embodiment, in the above raw materials, cyclohexanone and NH3The molar ratio of the organic solvent to the hydrogen peroxide contained in the hydrogen peroxide solution is 1 (2-5) to (4-12) to (0.8-1.2).
Under the action of catalyst, cyclohexanone reacts with NH3The hydrogen peroxide generates ammoximation reaction, the fixed bed reactor is provided with a plurality of bed layers, and each bed layer is filled with catalyst, which is beneficial to increasing the catalyst, cyclohexanone and NH3And the contact area of hydrogen peroxide, thereby achieving better catalytic effect.
In one embodiment, in the fixed bed reactor, the number of the bed layers is 2-15.
In a preferred embodiment, in the fixed bed reactor, the number of the bed layers is 2 to 10.
In one embodiment, each layer of the fixed bed reactor has a height of 0.2m to 5 m.
In one embodiment, the mass ratio of the oxide to the titanium silicalite molecular sieve in the catalyst is (1-4): 9-6. Further, the oxide is selected from at least one of alumina or silica. Further, the titanium silicalite molecular sieve is selected from at least one of titanium silicalite TS-1 and hollow titanium silicalite HTS.
The titanium silicalite molecular sieve catalyst preferably has a titanium silicalite molecular sieve with an MFI topological structure, such as titanium silicalite TS-1 and hollow titanium silicalite molecular sieve HTS, and has a unique MFI topological structure, a regular ordered three-dimensional pore channel structure, and a larger pore volume and a larger specific surface area, so that the titanium silicalite molecular sieve catalyst has high sensitivity resistance, catalytic activity and selectivity.
The catalyst of the invention is loaded with oxide, can be roasted up to 1000 ℃ without damage, and is beneficial to the recycling of the catalyst.
S2, mixing hydrogen peroxide with part of the organic solvent to obtain a first mixture; wherein, in the total organic solvent, the mass content of partial organic solvent is more than or equal to zero and less than 100 percent.
It can be understood that, in the step S2, when the mass content of the organic solvent in the used part is 0 in the total organic solvent, the step S2 is equivalent to the step of adding no organic solvent, and in this case, the step of mixing hydrogen peroxide and the organic solvent is not required, and hydrogen peroxide is directly used as the first mixture. Accordingly, in step S4, the remaining organic solvent is all the organic solvent in the raw material, i.e., the mass content of the organic solvent in step S4 in the total organic solvent is 100%.
It is understood that the hydrogen peroxide of the present invention can be a commercially available hydrogen peroxide, or a self-made hydrogen peroxide obtained by mixing hydrogen peroxide and water in any ratio.
Further, in step S2, the mass content of part of the organic solvent in the total organic solvent is greater than or equal to zero and less than 50%.
S3, dividing part of the first mixture into a plurality of parts of the second mixture, the parts of the second mixture being one less than the number of beds.
In one embodiment, the weight of each second mixture is equal.
It can be understood that when the mass content of the part of the organic solvent used in step S2 is 0 in the total organic solvent, the first mixture in step S3 is hydrogen peroxide, that is, it is equivalent to divide part of the hydrogen peroxide into a plurality of parts.
In one embodiment, the mass content of the part of the first mixture in the step S3 is greater than or equal to 60% and less than 100% in the total first mixture.
S4, cyclohexanone, NH3The remaining organic solvent and the remaining first mixture are fed from the feed inlet of the topmost bed.
In one embodiment, NH3Fed in the form of ammonia gas or in the form of aqueous ammonia.
In step S4, cyclohexanone and NH are added3The rest of the organic solvent and the rest of the first mixture are fed from the feeding port of the topmost bed layer, and the feeding can be mixed or can be independent from each other, and the feeding sequence is not specific.
S5, feeding the second mixtures from the feed inlets of the rest beds except the topmost bed respectively, and reacting to obtain the cyclohexanone oxime.
It should be noted that there is no specific sequence in step S5 for feeding each second mixture from each feed inlet of each bed except the topmost bed. And step S4 and step S5 have no specific sequence.
Further, in one of the examples, the mass space velocity of cyclohexanone in the topmost bed was 0.1h-1～1.2h-1(ii) a The mass space velocity of cyclohexanone in each bed layer except the topmost bed layer is 0.01h-1～0.6h-1。
Mixing hydrogen peroxide with part of organic solvent to obtain a first mixture; and dividing part of the first mixture into a plurality of parts of a second mixture, the parts of the second mixture being compared with the number of bedsThe amount is one less; then cyclohexanone and NH3Feeding the rest of the organic solvent and the rest of the first mixture from a feeding hole of the topmost bed layer; finally, feeding all parts of the second mixture from all feed inlets of all beds except the topmost bed so as to reduce the reaction with NH in the reaction system3The concentration of the contacted hydrogen peroxide effectively improves the utilization rate of the hydrogen peroxide and reduces the accident risk. The utilization rate of hydrogen peroxide can be greatly improved while the extremely high conversion rate of cyclohexanone and selectivity of cyclohexanone oxime are kept by the coordination of all the processes.
In one embodiment, the reaction temperature of the reaction is 50 ℃ to 100 ℃.
In one embodiment, the organic solvent is selected from organic alcohols with 2-10 carbon atoms.
In one embodiment, the organic solvent is tert-butanol.
While the present invention will be described with respect to particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover by the appended claims the scope of the invention, and that certain changes in the embodiments of the invention will be suggested to those skilled in the art and are intended to be covered by the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Here, the process for producing cyclohexanone oxime according to the present invention is exemplified, but the present invention is not limited to the following examples.
Example 1
The method comprises the following specific steps:
1) providing raw materials: cyclohexanone, ammonia gas, tertiary butanol, hydrogen peroxide and a catalyst, and a fixed bed reactor, wherein the catalyst contains 20% of alumina and 80% of HTS, the fixed bed reactor is provided with 10 beds, the height of each bed is 0.5 m, and a feeding hole is respectively arranged corresponding to each bed. The molar ratio of cyclohexanone to ammonia to hydrogen peroxide contained in the tert-butyl alcohol and hydrogen peroxide is 1:3:12: 1. And (5) standby.
2) Mixing hydrogen peroxide and half mass of tertiary butanol to obtain a first mixture, and dividing the first mixture accounting for 9/10 parts by weight of the total mass of the first mixture into 9 parts by weight of a second mixture for later use.
3) Mixing cyclohexanone, ammonia water and residual tert-butyl alcohol, feeding from the feeding hole of the topmost bed layer, and feeding the rest first mixture with 1/10 mass from the feeding hole of the topmost bed layer, wherein the mass space velocity of the cyclohexanone in the bed layer is 0.2h-1。
4) 9 parts of the second mixture were fed from the remaining 9 feed ports in a one-to-one correspondence.
5) Reacting at 70 ℃ to obtain cyclohexanone oxime.
Example 2
The method comprises the following specific steps:
1) providing raw materials: cyclohexanone, ammonia gas, tertiary butanol, hydrogen peroxide and a catalyst, and a fixed bed reactor, wherein the catalyst contains 30% of alumina and 70% of HTS, the fixed bed reactor is provided with 3 beds, the height of each bed is 2 meters, and a feeding hole is respectively arranged corresponding to each bed. The molar ratio of cyclohexanone to ammonia to hydrogen peroxide contained in the tert-butyl alcohol and hydrogen peroxide is 1:3:12: 1. And (5) standby.
2) Mixing hydrogen peroxide and 1/3 mass of tertiary butanol to obtain a first mixture; the first mixture, which accounted for 7/10 in the total mass of the first mixture, was divided into 2 parts by weight of the second mixture, which was then ready for use.
3) Mixing cyclohexanone, ammonia water and residual tert-butyl alcohol, feeding from the feeding hole of the topmost bed layer, and feeding the rest first mixture with 3/10 mass from the feeding hole of the topmost bed layer, wherein the mass space velocity of the cyclohexanone in the bed layer is 0.3h-1。
4) 2 parts of the second mixture were fed from the remaining 2 feed ports in a one-to-one correspondence.
5) Reacting at 80 ℃ to obtain cyclohexanone oxime.
Example 3
The method comprises the following specific steps:
1) providing raw materials: cyclohexanone, ammonia gas, tertiary butanol, hydrogen peroxide and a catalyst, and a fixed bed reactor, wherein the catalyst contains 20% of alumina and 80% of HTS, the fixed bed reactor is provided with 5 beds, the height of each bed is 1 m, and a feeding hole is respectively arranged corresponding to each bed. The molar ratio of cyclohexanone to ammonia to hydrogen peroxide contained in the tert-butyl alcohol and hydrogen peroxide is 1:3:12: 1. And (5) standby.
2) Mixing hydrogen peroxide and 1/6 mass of tertiary butanol to obtain a first mixture; dividing the first mixture into 4 equal parts by weight of a second mixture, wherein the second mixture accounts for 4/5, 3) mixing cyclohexanone, ammonia water and residual tert-butyl alcohol, and feeding the mixture from the feed inlet of the topmost bed, and then feeding the rest 1/5 mass of the first mixture from the feed inlet of the topmost bed, wherein the mass space velocity of cyclohexanone in the bed is 0.4h-1。
4) 4 parts of the second mixture were fed from the remaining 4 feed ports in a one-to-one correspondence.
5) Reacting at 85 ℃ to obtain cyclohexanone oxime.
Example 4
Example 4 is essentially the same as example 1, except that: in the step 1), 13 beds are arranged in a fixed bed reactor, and correspondingly, in the step 2), the first mixture accounting for 12/13 parts of the total mass of the first mixture is divided into 12 parts by weight of second mixture; accordingly, the remaining 1/13 mass portions of the first mixture were fed from the top-most bed feed inlet in step 3), and the remaining 12 portions of the second mixture were fed from the remaining 12 feed inlets in a one-to-one correspondence in step 4).
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that: in step 1), the catalyst is a catalyst containing 50% alumina and 50% HTS.
Comparative example 2
The method comprises the following specific steps:
1) providing raw materials: cyclohexanone, ammonia gas, tertiary butanol, hydrogen peroxide and a catalyst, and a fixed bed reactor, wherein the catalyst contains 20% of alumina and 80% of HTS, the fixed bed reactor is provided with 10 beds, the height of each bed is 0.5 m, and a feeding hole is arranged corresponding to the topmost bed; the molar ratio of cyclohexanone to ammonia to hydrogen peroxide contained in the tert-butyl alcohol and hydrogen peroxide is 1:3:12: 1. And (5) standby.
2) Cyclohexanone, ammonia water and residual tert-butyl alcoholFeeding the mixture from a feed inlet after mixing, and then feeding hydrogen peroxide from the feed inlet, wherein the mass airspeed is 0.2h based on the mass of cyclohexanone-1。
3) Reacting at 70 ℃ to obtain cyclohexanone oxime.
Note: the mass concentration of hydrogen peroxide used in each example and comparative example is 27.5%.
Example 5
The hydrogen peroxide utilization rate, cyclohexanone conversion rate and cyclohexanone oxime selectivity in examples 1 to 4 and comparative examples 1 to 2 were calculated according to the following formulas. The results are shown in Table 1.
(1) The yield of hydrogen peroxide is equal to the molar amount of hydrogen peroxide required for cyclohexanone oxime to be produced in the product/molar amount of hydrogen peroxide fed x 100%.
(2) Cyclohexanone conversion ═ molar amount of cyclohexanone in the feed-molar amount of cyclohexanone in the product)/molar amount of cyclohexanone in the feed x 100%.
(3) Cyclohexanone oxime selectivity is the molar amount of cyclohexanone oxime in the product/(molar amount of cyclohexanone fed-molar amount of cyclohexanone in the product) x 100%.
TABLE 1
The results in table 1 show that the utilization rate of hydrogen peroxide is greatly improved in examples 1 to 4 while the high cyclohexanone conversion rate and cyclohexanone oxime selectivity are maintained.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of cyclohexanone oxime is characterized by comprising the following steps:
providing raw materials and a fixed bed reactor; the raw material comprises cyclohexanone and NH3Organic solvent, hydrogen peroxide and catalyst; the fixed bed reactor is provided with a plurality of bed layers, a feed inlet is respectively arranged on the fixed bed reactor corresponding to each bed layer, the catalyst is filled in each bed layer, and the catalyst is a titanium-silicon molecular sieve loaded with oxide;
mixing the hydrogen peroxide with part of the organic solvent to obtain a first mixture; wherein, in the total organic solvent, the mass content of part of the organic solvent is more than or equal to zero and less than 100 percent;
dividing a portion of the first mixture into a plurality of portions of a second mixture, the portions of the second mixture being one less than the number of beds;
reacting said cyclohexanone and said NH3The rest of the organic solvent and the rest of the first mixture are fed from a feed inlet of the topmost bed layer; feeding all parts of the second mixture from all the feeding holes of all the rest beds except the topmost bed respectively, and reacting to obtain the cyclohexanone-oxime.
2. The production method according to claim 1, wherein in the raw material, the cyclohexanone, the NH3The molar ratio of the organic solvent to the hydrogen peroxide contained in the hydrogen peroxide is 1 (2-5) to (4-12) to (0.8-1.2).
3. The method of claim 1, wherein the second mixtures are equal in weight.
4. The method according to claim 1, wherein the number of layers of the bed layer in the fixed bed reactor is 2 to 15.
5. The preparation method of claim 1, wherein the mass ratio of the oxide to the titanium silicalite in the catalyst is (1-4): 9-6), the oxide is selected from at least one of alumina or silica, and the titanium silicalite is selected from at least one of titanium silicalite TS-1 and hollow titanium silicalite HTS.
6. The process according to any one of claims 1 to 5, wherein the NH is3Fed in the form of ammonia gas or in the form of aqueous ammonia.
7. The production method according to any one of claims 1 to 5, wherein each layer of the fixed-bed reactor has a height of 0.2m to 5 m.
8. Process according to any of claims 1 to 5, wherein the mass space velocity of cyclohexanone in the topmost bed is 0.1h-1～1.2h-1(ii) a The mass space velocity of the cyclohexanone in each bed layer except the topmost bed layer is 0.01h-1～0.6h-1。
9. The production method according to any one of claims 1 to 5, wherein the reaction temperature of the reaction is 50 ℃ to 100 ℃.
10. The method according to any one of claims 1 to 5, wherein the organic solvent is selected from organic alcohols having 2 to 10 carbon atoms.
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