CN114230482A - Method for producing cyclohexanone oxime by cyclohexanone ammoximation - Google Patents
Method for producing cyclohexanone oxime by cyclohexanone ammoximation Download PDFInfo
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 112
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 31
- 239000002808 molecular sieve Substances 0.000 claims description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052719 titanium Inorganic materials 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 5
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000006146 oximation reaction Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QZVPRDULYXKQML-UHFFFAOYSA-N azane;cyclohexanone Chemical compound N.O=C1CCCCC1 QZVPRDULYXKQML-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- HYYHQASRTSDPOD-UHFFFAOYSA-N hydroxylamine;phosphoric acid Chemical compound ON.OP(O)(O)=O HYYHQASRTSDPOD-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing cyclohexanone oxime by cyclohexanone ammoximation. The method comprises the following steps: (1) ammonia, cyclohexanone, solvent water and hydrogen peroxide enter a first reactor, and contact with a first catalyst in the first reactor to carry out a first reaction to obtain a first reaction product; (2) and the first reaction product and hydrogen peroxide enter a second reactor, and a second reaction is carried out in the presence of a second catalyst in the second reactor to prepare cyclohexanone oxime. The method can obviously improve the conversion rate of cyclohexanone and the selectivity of the target product cyclohexanone oxime after long-period operation, and can also improve the effective utilization rate of hydrogen peroxide.
Description
Technical Field
The invention relates to a method for producing cyclohexanone oxime by cyclohexanone ammoximation, belonging to the field of chemical industry.
Background
Cyclohexanone oxime is an important intermediate product for producing caprolactam, and the quality of the cyclohexanone oxime plays a decisive role in the quality of a caprolactam finished product. The processes for preparing cyclohexanone oxime in the world mainly comprise a phosphoric acid hydroxylamine method (HPO) and a cyclohexanone ammoximation method (HAO).
The main production flow of the cyclohexanone ammoximation method is as follows: the method comprises the steps of adopting a slurry bed reactor, reacting hydrogen peroxide (hydrogen peroxide), ammonia and cyclohexanone in the presence of a titanium silicalite molecular sieve catalyst and a tert-butyl alcohol solvent to produce cyclohexanone oxime, filtering the molecular sieve catalyst through a built-in membrane filtration system to obtain a reaction clear solution, and performing a series of rectification extraction processes to obtain the cyclohexanone oxime with high purity. The cyclohexanone oxime produced by cyclohexanone ammoximation is a liquid phase reaction, and a titanium silicalite molecular sieve catalyst is in a strong alkaline environment for a long time, so that the dissolution of framework silicon on the catalyst cannot be avoided, the ineffective loss of the catalyst is caused, the service life of the catalyst is shortened, and the stable operation of an ammoximation reaction system is influenced; in addition, the liquid-solid phase reaction has the defect of large mass transfer resistance, and the problem of catalyst diffusion is seriously influenced. By adopting a one-stage cyclohexanone ammoximation method, a part of unreacted cyclohexanone is taken as impurities to be accumulated in a system to cause the deterioration of the reaction condition, and a part of unreacted cyclohexanone is brought into a rearrangement procedure along with pure cyclohexanone oxime to cause adverse effect on Beckmann rearrangement reaction, thereby finally causing the quality of the finished caprolactam to be deteriorated. In a one-stage oximation reaction system, the utilization rate of ammonia and hydrogen peroxide is not high, the reaction conversion rate is often improved by increasing the feeding amount of hydrogen peroxide and ammonia gas, and the reaction risk and the consumption of raw materials are increased.
Disclosure of Invention
Aiming at the problems of the prior liquid-solid phase oximation reaction of cyclohexanone ammonia, the invention provides a method for producing cyclohexanone oxime by ammoximation of cyclohexanone. The method can obviously improve the conversion rate of cyclohexanone and the selectivity of the target product cyclohexanone oxime after long-period operation, can also improve the effective utilization rate of hydrogen peroxide, and can reduce the feeding amount of hydrogen peroxide.
The invention provides a method for producing cyclohexanone oxime by cyclohexanone ammoximation, which comprises the following steps:
(1) ammonia, cyclohexanone, solvent water and hydrogen peroxide enter a first reactor, and contact with a first catalyst in the first reactor to carry out a first reaction to obtain a first reaction product;
(2) and the first reaction product and hydrogen peroxide enter a second reactor, and a second reaction is carried out in the presence of a second catalyst in the second reactor to prepare cyclohexanone oxime.
Further, the mass concentration of the hydrogen peroxide is 20-40%.
Further, the ammonia is ammonia gas, liquid ammonia or ammonia water.
Further, the first reactor is a fixed bed reactor. Wherein the feeding comprises: ammonia, cyclohexanone, solvent water and hydrogen peroxide. The first reactor adopts the operation mode of feeding from bottom to top and discharging from top.
Further, the first catalyst in the first reactor is a titanium silicalite catalyst, and the titanium silicalite is selected from at least one of Ti-MOR and Ti-MWW. The titanium silicalite molecular sieve has an Si/Ti atomic ratio of 10 to 150, preferably 55 to 150. The titanium silicalite molecular sieve catalyst is preferably prepared by adopting the following method: the titanium silicalite molecular sieve and adhesive silica sol are kneaded, molded, dried and roasted to prepare the titanium silicalite molecular sieve catalyst, and the molding can adopt a conventional molding method, such as extrusion molding or rolling ball molding. In the kneading and molding process, at least one of silicon carbide, carbon fiber, graphite and the like can be added as an additive, and the addition amount of the additive accounts for less than 10 percent of the total mass of the catalyst, preferably 1 to 8 percent. The drying conditions were as follows: the drying temperature is 80-120 ℃, the drying time is 2-4h, and the roasting conditions are as follows: the roasting temperature is 500-600 ℃, and the roasting time is 4-8 h. The first catalyst (titanium silicalite molecular sieve catalyst) takes the weight of the catalyst as a reference, the content of the titanium silicalite molecular sieve is 60-85%, and the content of the binder calculated by silicon oxide is 15-40%.
Further, the operating conditions of the first reaction are as follows: the reaction temperature is 20-65 ℃, the reaction pressure is normal pressure, and the reaction pressure is cyclohexanone: NH (NH)3：H2O2: the molar ratio of the solvent water is 1: (1.0-3.5): (0.5-2.2): (10-50), preferably, cyclohexanone: NH (NH)3：H2O2: the molar ratio of the solvent water is 1: (1.0-2.5): (0.5-1.8): (10-50), the hourly space velocity of cyclohexanone liquid is 0.5-5h-1。
Further, the second reactor in the step (2) adopts a slurry bed reactor.
Furthermore, the first reaction product, the hydrogen peroxide solution which is pre-fed into the second reactor, and the catalyst (including fresh catalyst and catalyst recycled by the second reactor) can be mixed in the mixing tank and then fed into the second reactor.
Further, the operating conditions of the second reaction in step (2) are as follows: the reaction pressure is 0.25-0.40MPa, the reaction temperature is 70-90 ℃, and the average residence time of the materials is 60-70 min.
Further, in the total feed of step (2), the molar ratio of cyclohexanone: h2O21: (1.0 to 2.5), preferably, cyclohexanone: h2O21: (1.0-2.0). Wherein, the hydrogen peroxide is the hydrogen peroxide introduced by the feeding of the first reactor and the hydrogen peroxide introduced in the step (2), and the hydrogen peroxide introduced in the step (2) at least accounts for more than 10 percent of the total introduced mass of the hydrogen peroxide, preferably more than 20 percent.
Further, in the step (2), the mass ratio of the cyclohexanone to the second catalyst is 1: 0.03 to 0.15.
Further, the second catalyst in the step (2) is a titanium silicalite catalyst. The particle size of the second catalyst is 200nm-1 μm. The titanium-silicon molecular sieve is selected from at least one of Ti-MOR and Ti-MWW. The Si/Ti atomic ratio of the titanium-silicon molecular sieve is 10-150.
Further, the reaction product of the second reaction in step (2) is filtered, and the reaction clear solution obtained by removing the catalyst is separated (for example, rectification extraction) to obtain cyclohexanone oxime. Preferably, the second reactor is not provided with a filtering system, but is provided with a membrane tube filtering system outside the second reactor for removing the catalyst in the reaction products. The process of separating the reaction product obtained in the step (2) to obtain cyclohexanone oxime can be carried out by a conventional method, and the process is not particularly required in the present invention.
Compared with the prior art, the method has the following beneficial effects:
1. the method of the invention arranges the first reactor before the second reactor, and can obviously improve the conversion rate of cyclohexanone and the selectivity of the target product cyclohexanone oxime after long-period operation through comprehensive regulation and control, improve the effective utilization rate of hydrogen peroxide and reduce the feeding amount of hydrogen peroxide. But also the running period of the device can be obviously prolonged.
2. The method can reduce the severity of the second reactor, the reaction temperature is more stable, the main reaction is facilitated to be carried out, the side reaction is inhibited, and the operation period of the device can be obviously prolonged, the unit consumption of the second catalyst is reduced and the overall operation benefit of the device is increased under the condition that the conversion rate of cyclohexanone and the selectivity of the target product cyclohexanone-oxime are kept high because the first reaction product is introduced into the second reactor.
3. The invention adopts a liquid-solid phase reaction system and takes pure water as a solvent, thereby saving the separation cost of subsequent reaction products.
Detailed Description
The process of the present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
In the present invention, the cyclohexanone conversion (%) × (mass of starting material cyclohexanone-mass of cyclohexanone in reaction product)/mass of starting material cyclohexanone) × 100%.
In the present invention, cyclohexanone oxime selectivity (%) is 100% of cyclohexanone oxime (mass of cyclohexanone oxime in the reaction product/(mass of raw material cyclohexanone-mass of cyclohexanone in the reaction product)).
Example 1
Preparation of titanium silicalite catalyst a used in the first reactor:
77g of Ti-MWW titanium silicalite molecular sieve (the Si/Ti atomic ratio is 130), 67g of adhesive silica sol (the mass concentration is 30 percent), 3g of carbon fiber and a proper amount of water are kneaded, extruded into strips, formed, dried at 100 ℃ for 3h, and calcined at 550 ℃ for 5h to prepare the titanium silicalite molecular sieve catalyst A.
Preparation of titanium silicalite catalyst B for the first reactor:
82g of Ti-MWW titanium silicalite molecular sieve (the Si/Ti atomic ratio is 100), 50g of adhesive silica sol (the mass concentration is 30 percent), 3g of carbon fiber and a proper amount of water are kneaded, extruded into strips, formed, dried at 100 ℃ for 3h, and calcined at 550 ℃ for 5h to prepare the titanium silicalite molecular sieve catalyst B.
Preparation of titanium silicalite catalyst C for the first reactor:
80g of Ti-MOR titanium silicalite molecular sieve (the Si/Ti atomic ratio is 90), 60g of adhesive silica sol (the mass concentration is 30 percent), 3g of carbon fiber and a proper amount of water are kneaded, extruded into strips, formed, dried at 100 ℃ for 3h and roasted at 550 ℃ for 5h to prepare the titanium silicalite molecular sieve catalyst C.
Example 2
The method for preparing cyclohexanone oxime by ammoximation of cyclohexanone is as follows:
(1) ammonia gas, cyclohexanone, solvent water and hydrogen peroxide (the mass concentration is 30%) enter a first reactor (a fixed bed reactor), and contact with a titanium silicalite molecular sieve catalyst A in the first reactor to carry out a first reaction, so as to obtain a first reaction product; wherein, cyclohexanone: NH (NH)3：H2O2: the molar ratio of the solvent water is 1: 1.2: 1.0: 25, the first reaction conditions were as follows: inverse directionThe reaction temperature is 60 ℃, the reaction pressure is normal pressure, and the hourly space velocity of cyclohexanone liquid is 1.1h-1；
(2) The first reaction product, hydrogen peroxide (with the mass concentration of 30 percent) and a Ti-MWW molecular sieve catalyst (with the Si/Ti atomic ratio of 100 and the average particle size of 0.5 mu m) enter a mixing tank to be uniformly mixed, and the obtained mixed material enters a second reactor (a slurry bed reactor) to carry out a second reaction, wherein the reaction conditions are as follows: the reaction pressure is 0.22MPa, the reaction temperature is 85 ℃, and the retention time of the material reaction is 65min, so as to prepare the cyclohexanone oxime. Wherein, in the total feed of the step (2), the molar number of the cyclohexanone introduced in the feed of the first reactor is used as a reference, the molar number of the cyclohexanone: h2O21: 1.6. the mass ratio of the cyclohexanone to the Ti-MWW molecular sieve catalyst is 1: 0.08. the reaction results obtained with different reaction times are shown in Table 1.
Example 3
Compared with example 2, only in that the first catalyst is titanium silicalite catalyst B instead of titanium silicalite catalyst a, in step (1), cyclohexanone: NH (NH)3：H2O2: the molar ratio of the solvent water is 1: 1.2: 1.2: 30. the reaction results obtained with different reaction times are shown in Table 1.
Example 4
Compared with the example 2, only in that the first catalyst adopts a titanium silicalite catalyst C to replace the titanium silicalite catalyst A, and the reaction temperature in the step (1) is 55 ℃; the reaction conditions in the step (2) are as follows: the reaction pressure is 0.25MPa, the reaction temperature is 80 ℃, and the retention time of the material reaction is 65min, so as to prepare the cyclohexanone oxime. The reaction results obtained with different reaction times are shown in Table 1.
Comparative example 1
Compared with the example 2, the first reactor without the step (1) is as follows: ammonia gas, cyclohexanone, solvent water, hydrogen peroxide and a Ti-MWW molecular sieve catalyst (same as example 2, the Si/Ti atomic ratio is 100, the average particle size is 0.5 μm) enter a mixing tank to be uniformly mixed, and then the obtained mixed material enters a second reactor (slurry bed reactor) to react, wherein the reaction conditions are as follows: the reaction pressure is 0.22MPa, and the reaction temperature isThe temperature is 85 ℃, the retention time of the material reaction is 65min, and the cyclohexanone oxime is prepared. Wherein, cyclohexanone: NH (NH)3：H2O2: the molar ratio of the solvent water is 1: 1.2: 1.6: 25. the mass ratio of the cyclohexanone to the Ti-MWW molecular sieve catalyst is 1: 0.08. the reaction results obtained with different reaction times are shown in Table 1.
Comparative example 2
Compared with example 2, only in that there is no first reactor of step (1), and the feed amounts of the respective raw materials are adjusted as follows: ammonia gas, cyclohexanone, solvent water, hydrogen peroxide and a Ti-MWW molecular sieve catalyst (same as example 2, the Si/Ti atomic ratio is 100, the average particle size is 0.5 μm) enter a mixing tank to be uniformly mixed, and then the obtained mixed material enters a second reactor (slurry bed reactor) to react, wherein the reaction conditions are as follows: the reaction pressure is 0.22MPa, the reaction temperature is 85 ℃, and the retention time of the material reaction is 65min, so as to prepare the cyclohexanone oxime. Wherein, cyclohexanone: NH (NH)3：H2O2: the molar ratio of the solvent water is 1: 1.8: 1.8: 25. the mass ratio of the cyclohexanone to the Ti-MWW molecular sieve catalyst is 1: 0.08. the reaction results obtained with different reaction times are shown in Table 1.
Comparative example 3
Compared with example 2, only in that all the feeds were fed to the first reactor of step (1), specifically as follows:
(1) ammonia gas, cyclohexanone, solvent water and hydrogen peroxide (the mass concentration is 30%) enter a first reactor (a fixed bed reactor), and contact with a titanium silicalite molecular sieve catalyst A in the first reactor to carry out a first reaction, so as to obtain a first reaction product; wherein, cyclohexanone: NH (NH)3：H2O2: the molar ratio of the solvent water is 1: 1.2: 1.6: 25, the first reaction conditions were as follows: the reaction temperature is 60 ℃, the reaction pressure is normal pressure, and the hourly space velocity of cyclohexanone liquid is 1.1h-1；
(2) The first reaction product and the Ti-MWW molecular sieve catalyst (same as example 2, the Si/Ti atomic ratio is 100, the average particle size is 0.5 μm) enter a mixing tank to be uniformly mixed, and the obtained mixed material enters a second reactor (slurry bed reactor) to carry out a second reaction, wherein the reaction conditions are as follows: the reaction pressure is 0.22MPa, the reaction temperature is 85 ℃, and the retention time of the material reaction is 65min, so as to prepare the cyclohexanone oxime. The mass ratio of the cyclohexanone to the Ti-MWW molecular sieve catalyst is 1: 0.08. the reaction results obtained with different reaction times are shown in Table 1.
TABLE 1
Claims (10)
1. A method for producing cyclohexanone oxime by cyclohexanone ammoximation, which comprises the following steps:
(1) ammonia, cyclohexanone, solvent water and hydrogen peroxide enter a first reactor, and contact with a first catalyst in the first reactor to carry out a first reaction to obtain a first reaction product;
(2) and the first reaction product and hydrogen peroxide enter a second reactor, and a second reaction is carried out in the presence of a second catalyst in the second reactor to prepare cyclohexanone oxime.
2. The method according to claim 1, wherein the mass concentration of the hydrogen peroxide is 20-40%; and/or the ammonia is ammonia gas, liquid ammonia or ammonia water.
3. The process of claim 1, wherein the first reactor is a fixed bed reactor; the second reactor is a slurry bed reactor; preferably, no filtration system is provided in the second reactor, and a membrane tube filtration system is provided outside the reactor.
4. The process of claim 1 or 3, wherein the first catalyst in the first reactor is a titanium silicalite catalyst, the titanium silicalite being at least one selected from the group consisting of Ti-MOR and Ti-MWW; the Si/Ti atomic ratio of the titanium-silicon molecular sieve is 10-150, preferably 55-150;
preferably, the content of the titanium silicalite molecular sieve in the first catalyst is 60-85% and the content of the binder in terms of silica is 15-40% based on the weight of the catalyst.
5. The process according to claim 1 or 4, characterized in that the operating conditions of the first reaction are as follows: the reaction temperature is 20-65 ℃, the reaction pressure is normal pressure, and the reaction pressure is cyclohexanone: NH (NH)3：H2O2: the molar ratio of the solvent water is 1: (1.0-3.5): (0.5-2.2): (10-50), preferably, cyclohexanone: NH (NH)3：H2O2: the molar ratio of tert-butanol is 1: (1.0-2.5): (0.5-1.8): (10-50), the hourly space velocity of cyclohexanone liquid is 0.5-5h-1。
6. The process according to claim 1 or 5, wherein in the step (2), the operating conditions of the second reaction are as follows: the reaction pressure is 0.25-0.40MPa, the reaction temperature is 70-90 ℃, and the average residence time of the materials is 60-70 min.
7. The process according to claim 1, 5 or 6, characterized in that in the total feed to step (2), the molar ratio of cyclohexanone: h2O21: (1.0 to 2.5), preferably, cyclohexanone: h2O21: (1.0-2.0); wherein the hydrogen peroxide is the hydrogen peroxide introduced by the feeding of the first reactor and the hydrogen peroxide introduced in the step (2).
8. The process according to claim 1 or 7, wherein in step (2), the mass ratio of the mass of cyclohexanone to the mass of second catalyst, based on the mass of cyclohexanone introduced as feed to the first reactor, is 1: 0.03 to 0.15.
9. The process of claim 1 or 3, wherein the second catalyst of step (2) is a titanium silicalite catalyst; the particle size of the second catalyst is 200nm-1 μm.
10. The process of claim 9, wherein the titanium silicalite molecular sieves are selected from at least one of Ti-MOR, Ti-MWW; the Si/Ti atomic ratio of the titanium-silicon molecular sieve is 10-150.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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