CN112174850A - Cyclohexanone oxime preparation system and preparation method - Google Patents
Cyclohexanone oxime preparation system and preparation method Download PDFInfo
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- CN112174850A CN112174850A CN201910963090.7A CN201910963090A CN112174850A CN 112174850 A CN112174850 A CN 112174850A CN 201910963090 A CN201910963090 A CN 201910963090A CN 112174850 A CN112174850 A CN 112174850A
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- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 187
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- 239000007788 liquid Substances 0.000 claims abstract description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 34
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000007599 discharging Methods 0.000 claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004140 cleaning Methods 0.000 claims abstract description 22
- 239000012528 membrane Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 13
- 238000011084 recovery Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 112
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 11
- 230000003247 decreasing effect Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000006146 oximation reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000013024 troubleshooting Methods 0.000 description 1
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- 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
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
-
- 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
- C07C249/14—Separation; Purification; Stabilisation; Use of additives
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a cyclohexanone oxime preparation system, which comprises a primary mixer, a secondary mixer and a reaction kettle which are sequentially connected through a pipeline, wherein a discharge hole at the bottom of the reaction kettle is sequentially connected with a circulating pump, a membrane group and a heat exchanger through pipelines, and the heat exchanger is connected with a feed inlet of the primary mixer through a pipeline; the reaction kettle is also provided with a stirrer. The preparation method comprises the following steps of cleaning the catalyst when the feeding of the cyclohexanone, the gas ammonia and the hydrogen peroxide raw materials is stopped in the reaction kettle: the liquid level of the reaction kettle is adjusted to 70-90% through multiple times of adjustment of the feeding speed and the discharging speed, then the liquid level is reduced to 30% and then the liquid level is increased to 70-90%; meanwhile, closing the cooling circulating water of the heat exchanger, opening the steam of the reaction kettle, and controlling the temperature to be 60-75 ℃; and after the cleaning is finished, starting the system to enable the second mixed liquid to be added into the reaction kettle to continuously react with the catalyst. The invention can realize the recovery of the catalyst and the cleaning of the catalyst during the temporary fault, increase the activity of the catalyst and improve the generation rate of the cyclohexanone oxime.
Description
Technical Field
The invention relates to cyclohexanone oxime, and in particular relates to a preparation system and a preparation method of cyclohexanone oxime.
Background
Cyclohexanone oxime is an important intermediate for preparing caprolactam, and ammoximation reaction is an important step for preparing cyclohexanone oxime. The activity of the catalyst is an important factor influencing the ammoximation reaction, and how to maintain the activity of the catalyst is an important guarantee for ensuring high conversion rate and high selectivity of ammoximation reaction raw materials.
When the trouble-shooting occurs, the feeding of the reaction kettle needs to be stopped temporarily, and the catalyst in the reaction kettle needs to be cleaned after the feeding is stopped. Temporarily stopping the reaction kettle, and closing the feeding of the raw materials of hydrogen peroxide, ammonia gas and cyclohexanone; the original catalyst cleaning operation is finished by adding tert-butyl alcohol and desalted water into the reaction kettle in sequence, a small amount of cyclohexanone oxime is left in the reaction kettle after the operation method is finished, the residual cyclohexanone oxime is separated into solid due to the high solidification point to block catalyst pore channels so as to inactivate part of catalyst, the catalyst after the original operation cleaning treatment is recovered to carry out feeding reaction again, the conversion rate and the selectivity of reaction raw materials are low, the chromaticity of reaction products is high due to more impurities, the feeding load of the reaction kettle is not improved, and the quality and the yield of cyclohexanone oxime products are seriously influenced. According to the original catalyst cleaning operation method, a reaction product cyclohexanone oxime is difficult to completely remove in the cleaning process of tert-butyl alcohol and desalted water, the cyclohexanone oxime is easy to precipitate into a solid state in the cleaning process due to the high freezing point of the cyclohexanone oxime, and the precipitated cyclohexanone oxime changes into a solid to block catalyst pore channels, so that the catalyst is easy to deactivate, the reaction conversion rate and selectivity of raw materials are reduced, and the quality and yield of the product cyclohexanone oxime are influenced.
Disclosure of Invention
Technical problem to be solved
In order to solve the above problems in the prior art, the present invention provides a cyclohexanone oxime production system, which can realize the recovery of a catalyst and the cleaning of the catalyst in case of temporary failure, increase the activity of the catalyst, and improve the production rate of cyclohexanone oxime.
Correspondingly, the invention also provides a preparation method of the cyclohexanone oxime, which can improve the recovery rate of the catalyst.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
the invention provides a cyclohexanone oxime preparation system, which comprises a primary mixer, a secondary mixer and a reaction kettle which are sequentially connected through a pipeline, wherein a discharge hole at the bottom of the reaction kettle is sequentially connected with a circulating pump, a membrane group and a heat exchanger through pipelines, and the heat exchanger is connected with a feed inlet of the primary mixer through a pipeline; the reaction kettle is also provided with a stirrer.
Further, the cyclohexanone oxime preparation system also comprises a gas ammonia feeding channel, a cyclohexanone feeding channel, a tert-butyl alcohol feeding channel and a water vapor feeding channel; the gas ammonia feeding channel, the cyclohexanone feeding channel and the tert-butyl alcohol feeding channel are arranged on a pipeline connected with the heat exchanger and the primary mixer side by side and communicated with the pipeline, and valves are arranged at the joints of the gas ammonia feeding channel, the cyclohexanone feeding channel and the tert-butyl alcohol feeding channel and the pipeline; the hydrogen peroxide feeding port is arranged on a pipeline connected with the primary mixer and the secondary mixer, is communicated with the pipeline, and is provided with a valve at the joint with the pipeline; the gas outlet of the steam feed channel is arranged on the outer wall of the reaction kettle, so that the steam can heat the reaction kettle on the outer wall of the jacket of the reaction kettle.
The invention provides a cyclohexanone oxime preparation method, which comprises the following steps:
s1 first mixing: mixing tertiary butanol, ammonia gas and cyclohexanone in a first-stage mixer to obtain a first mixed solution;
s2 second mixing: mixing the obtained first mixed solution and hydrogen peroxide in a secondary mixer to obtain a second mixed solution;
reaction in an S3 reaction kettle: adding the obtained second mixed solution into a reaction kettle, mixing the second mixed solution with a catalyst added into the reaction kettle, and reacting to generate cyclohexanone oxime to obtain a tert-butyl alcohol mixed solution containing cyclohexanone oxime and the catalyst;
s4 separation and purification: conveying the obtained tert-butyl alcohol mixed liquor to a membrane for separation through the bottom of the reaction kettle by the pressure increase of a circulating pump to obtain a mixture containing a catalyst and cyclohexanone oxime;
recovery of the S5 catalyst: and (3) conveying the mixture containing the catalyst to a heat exchanger, cooling, and then entering a reaction kettle through a first-stage mixer.
Further, step S3 includes the following steps, when the feeding of the reaction kettle is stopped, the catalyst is cleaned:
s31 first adjustment: the tertiary butanol feed rate of the reaction kettle was adjusted to 10m3H, adjusting the discharging speed of the reaction kettle to be 40-50 m3After the reaction is carried out for one hour, the liquid level is reduced to 30 percent, and then the tert-butyl alcohol is added for 40 to 50m3H ofFeeding the mixture into the reaction kettle at a speed until the liquid level of the reaction kettle reaches 70-90%; meanwhile, closing cooling circulating water of the heat exchanger, opening steam of the reaction kettle, and ensuring that the temperature of the reaction kettle is controlled at 60-75 ℃;
s32 second adjustment: after completion of step S31, the feed rate of t-butanol was decreased to 10m3The discharging speed of the reaction kettle is increased to 40-50 m3The liquid level of the reaction kettle is reduced to 30 percent;
s33 adjustment for the third time: after the step S32 is completed, the discharging speed of the reaction kettle is reduced to 0-10 m3H, increasing the feeding speed of the reaction kettle to 40-50 m3H, until the liquid level of the reaction kettle rises to 70-90%;
s34 repeating the steps from S32 to S33 for 2-3 times, so that the liquid level of the final reaction kettle is reduced to 30%, and the discharging speed of the reaction kettle is reduced to 0-10 m3/h；
And after S35 cleaning, starting the cyclohexanone oxime preparation system, and adding the second mixed solution into the reaction kettle to continuously react with the catalyst.
Further, in the process of steps S31-S34, when the liquid level of the reaction kettle drops, the mixed liquid in the reaction kettle flows out from the discharge port of the reaction kettle to the membrane group for separation to obtain the mixture of cyclohexanone oxime and catalyst; and cooling the mixture containing the catalyst by a heat exchanger, and then feeding the mixture into the reaction kettle through a first-stage mixer.
Wherein the mixture containing the catalyst comprises but is not limited to the catalyst, tertiary butanol, gaseous ammonia, water and a small amount of cyclohexanone oxime.
The technical principle of the invention is as follows:
because the freezing point of the cyclohexanone oxime is higher, the cyclohexanone oxime is in a solid state at normal temperature, the cyclohexanone oxime is slightly soluble in water but is easily soluble in tert-butyl alcohol, the cyclohexanone oxime is not separated out in the cleaning process, desalted water is not used in the cleaning process, the concentration of the tert-butyl alcohol in the reaction kettle is ensured, and the cyclohexanone oxime is prevented from being separated out to form a solid to block a catalyst pore channel. Maintaining a certain temperature in the cleaning process of the reaction kettle, wherein the higher the temperature of the reaction kettle is, the more favorable the cyclohexanone oxime is dissolved in the tertiary butanol, and ensuring that the cyclohexanone oxime is completely dissolved in the tertiary butanol solvent. Meanwhile, a certain temperature of the reaction kettle is kept, partial ammonia in the reaction kettle is evaporated to reduce the alkalinity of the reaction kettle, and the catalyst is prevented from being dissolved and lost in an alkaline environment for a long time. The reation kettle stops temporarily and can remain some organic impurity in its reation kettle of feeding, and its impurity circulates in the reation kettle for a long time, and its organic impurity is adsorbed by the catalyst easily, and when reation kettle resumes the feeding start-up, adsorbed organic impurity can lead to the reaction product impurity to be on the high side, and its reaction product colourity can rise by a wide margin. Through adding tertiary butanol to the reation kettle and washing, can wash the filtering part to organic impurity in the reation kettle to avoid a large amount of organic impurity to be adsorbed by the catalyst, thereby reduce the organic impurity residual quantity in the reation kettle.
(III) advantageous effects
The invention has the beneficial effects that:
1. according to the invention, the catalyst is effectively recovered and reused through the cyclohexanone-oxime recyclable preparation system.
2. The catalyst in the preparation method of the cyclohexanone oxime is cleaned in a high-temperature and tert-butyl alcohol manner and a temperature-raising manner, the traditional desalted water cleaning is replaced, the tert-butyl alcohol concentration in the reaction kettle is ensured, and the cyclohexanone oxime is prevented from being separated out into solid to block catalyst pore channels. Maintaining a certain temperature in the cleaning process of the reaction kettle, wherein the higher the temperature of the reaction kettle is, the more favorable the cyclohexanone oxime is dissolved in the tertiary butanol, and ensuring that the cyclohexanone oxime is completely dissolved in the tertiary butanol solvent. Meanwhile, a certain temperature of the reaction kettle is kept, partial ammonia in the reaction kettle is evaporated to reduce the alkalinity of the reaction kettle, and the catalyst is prevented from being dissolved and lost in an alkaline environment for a long time. Through adding tertiary butanol to the reation kettle and washing, can wash the filtering part to organic impurity in the reation kettle to avoid a large amount of organic impurity to be adsorbed by the catalyst, thereby reduce the organic impurity residual quantity in the reation kettle.
Drawings
FIG. 1 is a schematic view of a cyclohexanone oxime production system according to the present invention.
Reference numerals
1-a reaction kettle; 2-a circulating pump; 3-a heat exchanger; 4-a secondary mixer; 5-a first-stage mixer, 6-a hydrogen peroxide feeding port and 7-a stirrer; 8-membrane group, 9-ammonia gas feed inlet, 10-cyclohexanone feed inlet, 11-tert-butanol feed inlet and 12-steam feed inlet.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the present invention by way of specific embodiments thereof.
In the present invention, the liquid level in the reaction vessel 1 is understood to be the ratio of the liquid in the reaction vessel 1 to the volume of the reaction vessel 1.
As shown in fig. 1: the cyclohexanone oxime preparation system comprises a first-stage mixer 5, a second-stage mixer 4 and a reaction kettle 1 which are sequentially connected through pipelines, wherein a discharge port at the bottom of the reaction kettle 1 is sequentially connected with a circulating pump 2, a membrane group 8 and a heat exchanger 3 through pipelines, and the heat exchanger 3 is connected with a feed inlet of the first-stage mixer 5 through a pipeline; the reaction kettle 1 is also provided with a stirrer 7.
Further, the cyclohexanone oxime production system also comprises a gas ammonia feed channel 9, a cyclohexanone feed channel 10, a tert-butyl alcohol feed channel 11 and a water vapor feed channel 12; the gas ammonia feeding channel 9, the cyclohexanone feeding channel 10 and the tertiary butanol feeding channel 11 are arranged on a pipeline connected with the heat exchanger 3 and the primary mixer 5 side by side and communicated with the pipeline, and valves are arranged at the joints of the gas ammonia feeding channel, the cyclohexanone feeding channel and the tertiary butanol feeding channel; the hydrogen peroxide feeding port 6 is arranged on a pipeline connected with the primary mixer 5 and the secondary mixer 4, is communicated with the pipeline, and is provided with a valve at the joint with the pipeline; the steam feed channel is communicated with the inner cavity of the reaction kettle 1.
The oximation reaction is a strong exothermic reaction, the filtration systems of the membrane groups are combined, the reaction temperature is controlled in an external circulation heat taking mode, the stable control of the reaction temperature is realized by automatically adjusting the cooling water amount of an external circulation cooler, when the reaction kettle stops running, the tertiary butanol is enabled to enter the reaction kettle to clean the catalyst, and organic byproducts which can affect the catalyst are taken away by the tertiary butanol.
The method for preparing cyclohexanone oxime by using the cyclohexanone oxime preparation system comprises the following steps:
s1 first mixing: mixing tertiary butanol, ammonia gas and cyclohexanone through a first-stage mixer 5 to obtain a first mixed solution;
s2 second mixing: mixing the obtained first mixed solution and hydrogen peroxide in a secondary mixer 4 to obtain a second mixed solution;
reaction in S3 Reation kettle 1: adding the obtained second mixed solution into the reaction kettle 1, mixing the second mixed solution with the catalyst added into the reaction kettle 1, and reacting to generate cyclohexanone oxime to obtain tert-butyl alcohol mixed solution containing cyclohexanone oxime and the catalyst;
s4 separation and purification: the obtained tert-butyl alcohol mixed solution is sent to a membrane group 8 through the bottom of a reaction kettle 1 by the pressure increase of a circulating pump 2 to be separated to obtain a mixture containing a catalyst and cyclohexanone-oxime;
recovery of the S5 catalyst: the mixture containing the catalyst is sent to a heat exchanger 3, the heat is removed, and the mixture enters the reaction kettle 1 through a first-stage mixer 5 after being cooled.
The mixture containing the catalyst comprises the catalyst, tertiary butanol, gaseous ammonia, water and a small amount of cyclohexanone oxime.
Further, step S3 includes the following steps, when the feeding of reaction kettle 1 is stopped, the catalyst needs to be cleaned, the feeding is stopped while the feeding is stopped including gas ammonia, cyclohexanone and hydrogen peroxide, and the alcohol washing of the catalyst in the reaction kettle is performed by adjusting the feeding speed of 11-tert-butyl alcohol, including the following steps performed in sequence:
s31 first adjustment: the tert-butanol feed rate of reaction vessel 1 was adjusted to 10m3H, simultaneously adjusting the discharging speed of the reaction kettle 1 to be 40-50 m3After the reaction is carried out for one hour, the liquid level is reduced to 30 percent, and then the tert-butyl alcohol is added for 40 to 50m3The feed speed of the reaction kettle 1 is increased to 70-90% until the liquid level of the reaction kettle 1 is increased; meanwhile, closing the heat exchanger 3 to cool circulating water, and opening steam of the reaction kettle 1 to ensure that the temperature of the reaction kettle 1 is controlled at 60-75 ℃;
s32 second adjustment: after completion of step S31, the feed rate of t-butanol was decreased to 10m3The discharging speed of the reaction kettle 1 is increased to 40-50 m3The liquid level of the reaction kettle 1 is reduced to 30 percent;
s33 adjustment for the third time: after the step S32 is completed, the discharging speed of the reaction kettle 1 is reduced to 0-10 m3H, increasing the feeding speed of the reaction kettle 1 to 40-50 m3H, until the liquid level of the reaction kettle 1 rises to 70-90%;
s34 repeating steps S32 to S33 timesThe number of the reaction kettle is 2-3, so that the liquid level of the reaction kettle 1 is reduced to 30%, and the discharging speed of the reaction kettle 1 is reduced to 0-10 m3/h；
And after S35 cleaning, starting the cyclohexanone oxime preparation system, and adding the second mixed solution into the reaction kettle 1 to continuously react with the catalyst.
In the process of steps S31-S34, when the liquid level of the reaction kettle 1 drops, the reaction kettle 1 is discharged to the membrane group 8 for separation to obtain cyclohexanone oxime and a mixture containing a catalyst, and the mixture containing the catalyst is cooled by the heat exchanger 3 and then enters the reaction kettle 1 through the first-stage mixer 5.
Wherein, the membrane group 8 is a membrane filter consisting of a filtering membrane group 8, and is provided with a fault processing system, when a fault occurs, the quick opening valve at the permeation side is quickly closed, the connection with the liquid flowing out of the reaction kettle 1 is cut off, and the standby membrane group 8 is put into use; the membrane group 8 is provided with an automatic back washing system, and the washing medium is filtered clear liquid.
Specific examples are provided below:
when the reaction kettle 1 stops feeding, the cleaning of the catalyst in the reaction kettle comprises the following steps:
example 1
S31 first adjustment: the tert-butanol feed rate of reaction vessel 1 was adjusted to 10m3H, simultaneously adjusting the discharging speed of the reaction kettle 1 to be 40m3H, until the liquid level is reduced to 30%, and adding tert-butyl alcohol to 40m3The feed speed of the reaction kettle 1 is increased until the liquid level of the reaction kettle 1 reaches 70%; meanwhile, closing the heat exchanger 3 to cool circulating water, and opening steam of the reaction kettle 1 to ensure that the temperature of the reaction kettle 1 is controlled at 60 ℃;
s32 second adjustment: after completion of step S31, the feed rate of t-butanol was decreased to 10m3H, raising the discharging speed of the reaction kettle 1 to 40m3The liquid level of the reaction kettle 1 is reduced to 30 percent;
s33 adjustment for the third time: after the step S32 is completed, the discharging speed of the reaction kettle 1 is reduced to 0m3H, increasing the feeding speed of the reaction kettle 1 to 40m3H, until the liquid level of the reaction kettle 1 rises to 70 percent;
s34 number of times of repeating steps S32 to S332, the liquid level of the final reaction kettle 1 is reduced to 30 percent, and the discharging speed of the reaction kettle 1 is reduced to 0m3/h；
And after S35 cleaning, starting the cyclohexanone oxime preparation system, and adding the second mixed solution into the reaction kettle 1 to continuously react with the catalyst.
In the process of steps S31-S34, when the liquid level of the reaction kettle 1 drops, the reaction kettle 1 is discharged to the membrane group 8 for separation to obtain cyclohexanone oxime and a mixture containing a catalyst, and the mixture containing the catalyst is cooled by the heat exchanger 3 and then enters the reaction kettle 1 through the first-stage mixer 5.
The yield of the catalyst in the embodiment reaches 95% after cleaning, and the activity of the catalyst is recovered to 98%.
Example 2
S31 first adjustment: the tert-butanol feed rate of reaction vessel 1 was adjusted to 10m3H, simultaneously adjusting the discharging speed of the reaction kettle 1 to be 50m3H, until the liquid level is reduced to 30%, adjusting the tert-butyl alcohol to 50m3The feed speed of the reaction kettle 1 is increased until the liquid level of the reaction kettle 1 reaches 90%; meanwhile, closing the heat exchanger 3 to cool circulating water, and opening steam of the reaction kettle 1 to ensure that the temperature of the reaction kettle 1 is controlled at 75 ℃;
s32 second adjustment: after completion of step S31, the feed rate of t-butanol was decreased to 10m3H, raising the discharging speed of the reaction kettle 1 to 50m3The liquid level of the reaction kettle 1 is reduced to 30 percent;
s33 adjustment for the third time: after the step S32 is completed, the discharging speed of the reaction kettle 1 is reduced to 10m3H, increasing the feeding speed of the reaction kettle 1 to 50m3H, until the liquid level of the reaction kettle 1 rises to 90 percent;
s34 repeating the steps S32 to S33 for 3 times, so that the liquid level of the reaction kettle 1 is reduced to 30% finally, and the discharging speed of the reaction kettle 1 is reduced to 0-10 m3/h；
And after S35 cleaning, starting the cyclohexanone oxime preparation system, and adding the second mixed solution into the reaction kettle 1 to continuously react with the catalyst.
In the process of steps S31-S34, when the liquid level of the reaction kettle 1 drops, the reaction kettle 1 is discharged to the membrane group 8 for separation to obtain cyclohexanone oxime and a mixture containing a catalyst, and the mixture containing the catalyst is cooled by the heat exchanger 3 and then enters the reaction kettle 1 through the first-stage mixer 5.
The yield of the catalyst in the embodiment reaches 92% after being cleaned, and the activity of the catalyst is recovered to 99%.
Example 3
S31 first adjustment: the tert-butanol feed rate of reaction vessel 1 was adjusted to 10m3H, simultaneously adjusting the discharging speed of the reaction kettle 1 to be 50m3H, until the liquid level is reduced to 30%, and adjusting the tert-butyl alcohol to be 45m3The feed speed of the reaction kettle 1 is increased until the liquid level of the reaction kettle 1 reaches 72 percent; meanwhile, closing the heat exchanger 3 to cool circulating water, and opening steam of the reaction kettle 1 to ensure that the temperature of the reaction kettle 1 is controlled at 70 ℃;
s32 second adjustment: after completion of step S31, the feed rate of t-butanol was decreased to 10m3H, raising the discharging speed of the reaction kettle 1 to 50m3The liquid level of the reaction kettle 1 is reduced to 30 percent;
s33 adjustment for the third time: after the step S32 is completed, the discharging speed of the reaction kettle 1 is reduced to 0-10 m3H, increasing the feeding speed of the reaction kettle 1 to 46m3H, until the liquid level of the reaction kettle 1 rises to 75 percent;
s34 repeating the steps S32 to S33 for 3 times, so that the liquid level of the reaction kettle 1 is reduced to 30% finally, and the discharging speed of the reaction kettle 1 is reduced to 5m3/h；
And after S35 cleaning, starting the cyclohexanone oxime preparation system, and adding the second mixed solution into the reaction kettle 1 to continuously react with the catalyst.
In the process of steps S31-S34, when the liquid level of the reaction kettle 1 drops, the reaction kettle 1 is discharged to the membrane group 8 for separation to obtain cyclohexanone oxime and a mixture containing a catalyst, and the mixture containing the catalyst is cooled by the heat exchanger 3 and then enters the reaction kettle 1 through the first-stage mixer 5.
The yield of the catalyst in the embodiment reaches 96% after being cleaned, and the activity of the catalyst is recovered to 97%.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (5)
1. The cyclohexanone oxime preparation system is characterized by comprising a first-stage mixer (5), a second-stage mixer (4) and a reaction kettle (1) which are sequentially connected through a pipeline, wherein a discharge port at the bottom of the reaction kettle (1) is sequentially connected with a membrane group (8) and a heat exchanger (3) through pipelines, and the heat exchanger (3) is connected with a feed port of the first-stage mixer (5) through a pipeline; and a stirrer (7) is also arranged on the reaction kettle (1).
2. The cyclohexanone oxime production system according to claim 1, further comprising a gas ammonia feed passage (9), a cyclohexanone feed passage (10), a t-butanol feed passage (11), and a water vapor feed passage (12); the gas ammonia feeding channel (9), the cyclohexanone feeding channel (10) and the tert-butyl alcohol feeding channel (11) are arranged on a pipeline connected with the heat exchanger (3) and the primary mixer (5) side by side and communicated with the pipeline, and valves are arranged at the joints of the gas ammonia feeding channel, the cyclohexanone feeding channel and the tert-butyl alcohol feeding channel; the hydrogen peroxide feeding port (6) is arranged on a pipeline connected with the first-stage mixer (5) and the second-stage mixer (4) and communicated with the pipeline, and a valve is arranged at the joint of the hydrogen peroxide feeding port and the pipeline; and the gas outlet of the steam feeding channel is arranged on the outer wall of the reaction kettle (1).
3. A cyclohexanone oxime preparation method is characterized by comprising the following steps:
s1 first mixing: mixing tertiary butanol, ammonia gas and cyclohexanone through a first-stage mixer (5) to obtain a first mixed solution;
s2 second mixing: mixing the obtained first mixed solution and hydrogen peroxide in a secondary mixer (4) to obtain a second mixed solution;
reaction in S3 reaction kettle (1): adding the obtained second mixed solution into a reaction kettle (1), mixing the second mixed solution with a catalyst added into the reaction kettle (1), and reacting to generate cyclohexanone oxime to obtain a tertiary butanol mixed solution containing cyclohexanone oxime and the catalyst;
s4 separation and purification: the obtained tert-butyl alcohol mixed solution is sent to a membrane group (8) through the bottom of a reaction kettle (1) by the pressure increase of a circulating pump (2) for separation to obtain a mixture containing a catalyst and cyclohexanone oxime;
recovery of the S5 catalyst: the mixture containing the catalyst is sent to a heat exchanger (3), and enters a reaction kettle (1) through a first-stage mixer (5) after being cooled.
4. The process for producing cyclohexanone oxime as claimed in claim 3, characterized in that: step S3 further includes the following steps, when the reaction vessel (1) stops feeding, the catalyst is cleaned:
s31 first adjustment: the tert-butanol feed rate of the reaction vessel (1) was adjusted to 10m3H, simultaneously adjusting the discharging speed of the reaction kettle (1) to be 40-50 m3After the reaction is carried out for one hour, the liquid level is reduced to 30 percent, and then the tert-butyl alcohol is added for 40 to 50m3The feed speed of the reaction kettle is increased to the reaction kettle (1) until the liquid level of the reaction kettle (1) reaches 70-90%; meanwhile, the cooling circulating water of the heat exchanger (3) is closed, the steam of the reaction kettle (1) is opened, and the temperature of the reaction kettle (1) is controlled to be 60-75 ℃;
s32 second adjustment: after completion of step S31, the feed rate of t-butanol was decreased to 10m3The discharging speed of the reaction kettle (1) is increased to 40-50 m3H, reducing the liquid level of the reaction kettle (1) to 30%;
s33 adjustment for the third time: after the step S32 is completed, the discharging speed of the reaction kettle (1) is reduced to 0-10 m3H, increasing the feeding speed of the reaction kettle (1) to 40-50 m3H, until the liquid level of the reaction kettle (1) rises to 70-90%;
s34 repeating the steps from S32 to S33 for 2-3 times, so that the liquid level of the reaction kettle (1) is reduced to 30% finally, and the discharging speed of the reaction kettle (1) is reduced to 0-10 m3/h；
And (3) after the cleaning of S35 is finished, starting the cyclohexanone oxime preparation system, and adding the second mixed solution into the reaction kettle (1) to continuously react with the catalyst.
5. The process for producing cyclohexanone oxime as claimed in claim 3, characterized in that: in the process of steps S31-S34, when the liquid level of the reaction kettle (1) is lowered, the reaction kettle (1) is discharged to a membrane group (8) for separation to obtain cyclohexanone oxime and a mixture containing a catalyst, and the mixture containing the catalyst is cooled by a heat exchanger (3) and then enters the reaction kettle (1) through a first-stage mixer (5).
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Application publication date: 20210105 Assignee: China Chemical Tianchen Green Energy New Material Technology Research and Development (Zibo) Co.,Ltd. Assignor: FUJIAN TIANCHEN YAOLONG NEW MATERIAL Ltd. Contract record no.: X2024980003415 Denomination of invention: A method for preparing cyclohexanone oxime Granted publication date: 20221122 License type: Common License Record date: 20240403 |