CN116139788B - Device, system and method for continuously producing cyclohexanone oxime - Google Patents
Device, system and method for continuously producing cyclohexanone oxime Download PDFInfo
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- CN116139788B CN116139788B CN202310249127.6A CN202310249127A CN116139788B CN 116139788 B CN116139788 B CN 116139788B CN 202310249127 A CN202310249127 A CN 202310249127A CN 116139788 B CN116139788 B CN 116139788B
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- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 91
- 239000000945 filler Substances 0.000 claims abstract description 66
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 52
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000006146 oximation reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 73
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 58
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 28
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 28
- 238000001704 evaporation Methods 0.000 claims description 17
- 230000008020 evaporation Effects 0.000 claims description 17
- 238000005191 phase separation Methods 0.000 claims description 17
- 239000002351 wastewater Substances 0.000 claims description 17
- 230000009471 action Effects 0.000 claims description 13
- 238000012856 packing Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 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 5
- 238000007670 refining Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 238000010924 continuous production Methods 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000006184 cosolvent Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000035484 reaction time Effects 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 abstract description 2
- LPRSRULGRPUBTD-UHFFFAOYSA-N butan-2-one;hydrate Chemical compound O.CCC(C)=O LPRSRULGRPUBTD-UHFFFAOYSA-N 0.000 abstract description 2
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 21
- 239000012071 phase Substances 0.000 description 16
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 7
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000011224 oxide ceramic Substances 0.000 description 3
- 229910052574 oxide ceramic Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003621 irrigation water Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NJNQUTDUIPVROZ-UHFFFAOYSA-N nitrocyclohexane Chemical compound [O-][N+](=O)C1CCCCC1 NJNQUTDUIPVROZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
-
- 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
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及化工技术领域，尤其为一种连续化生产环己酮肟的装置、系统及方法，包括反应釜，所述反应釜由液体分布器、旋转填料、旋转轴、夹套、底部液体出口、外置换热器A、外置循环泵A、外置换热器B和外置循环泵B构成，所述液体分布器的上方分别连通设置有液体进料口一、液体进料口二和液体进料口三，所述液体分布器的底端伸入旋转填料的空腔内，旋转填料固定在旋转轴上；本发明能够在不使用助溶剂的情况下，可以显著缩短环己酮肟化反应时间，使反应转化率提升，且反应时间短，环己酮肟的选择性可达99％以上，而且设置了余氨回收流程，使所有原料几乎完全转化为丁酮肟和水，原料利用率高，物耗降低，同时也让催化剂使用寿命得到了增加。
The invention relates to the field of chemical technology, and in particular to a device, system and method for continuously producing cyclohexanone oxime, comprising a reactor, wherein the reactor is composed of a liquid distributor, a rotating filler, a rotating shaft, a jacket, a bottom liquid outlet, an external heat exchanger A, an external circulating pump A, an external heat exchanger B and an external circulating pump B, wherein a liquid feed port 1, a liquid feed port 2 and a liquid feed port 3 are respectively connected and arranged on the top of the liquid distributor, and the bottom end of the liquid distributor extends into a cavity of the rotating filler, and the rotating filler is fixed on the rotating shaft; the invention can significantly shorten the cyclohexanone oximation reaction time without using a co-solvent, thereby improving the reaction conversion rate, and the reaction time is short, the selectivity of cyclohexanone oxime can reach more than 99%, and a residual ammonia recovery process is provided, so that all raw materials are almost completely converted into butanone oxime and water, the raw material utilization rate is high, the material consumption is reduced, and the service life of the catalyst is also increased.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a device, a system and a method for continuously producing cyclohexanone oxime.
Background
Caprolactam is an important chemical raw material and can be used for producing nylon 6 engineering plastics, fibers, films and the like. Cyclohexanone oxime rearrangement is currently the dominant process for producing caprolactam, and the purity of cyclohexanone oxime has a significant impact on the efficiency of the rearrangement process. How to produce high-purity cyclohexanone oxime with high efficiency and low consumption is one of key links for restricting the energy conservation and consumption reduction of the whole process of caprolactam production. The raw material for producing cyclohexanone oxime is usually cyclohexanone, and the traditional production process is that cyclohexanone reacts with hydroxylamine salt to directly produce cyclohexanone oxime. The method has the advantages of large discharge amount of three wastes, heavy environmental pollution, low-value ammonium sulfate byproduct, insufficient atomic economy and tendency of being replaced by a novel method. The cyclohexanone, ammonia water and hydrogen peroxide are directly synthesized into cyclohexanone oxime through the following reaction (shown in figure 3) under the catalysis of a titanium-silicon molecular sieve (TS-1), and the method has the advantages of high raw material utilization rate, high reaction selectivity, environmental friendliness and the like, and is expected to become a main flow process for producing the cyclohexanone oxime in the future.
In theory, the selectivity of the cyclohexanone oxime obtained by the process can be close to 100%, but when the operation condition is not ideal, side reactions are very easy to occur, mainly hydrogen peroxide and ammonia directly react to generate nitrogen and nitrogen oxides, cyclohexanone is condensed to generate a dimer, and the cyclohexanone oxime is deeply oxidized into nitrocyclohexane by the hydrogen peroxide and the like.
As cyclohexanone is not mutually dissolved with ammonia water and hydrogen peroxide, an oil-water two-phase is formed in the reaction process, the reaction is limited by mass transfer resistance, and the reaction rate is reduced. Meanwhile, the reaction liquid has long residence time in the reactor and poor mixing uniformity, so that a great deal of side reaction occurs, and the selectivity of cyclohexanone oxime in the product is low. Therefore, in the current ammoximation process, cosolvent such as tertiary butanol and the like is commonly added so as to make oil-water two-phase miscible, reduce mass transfer resistance and mixing difficulty, so that the reaction efficiency can be obviously improved, but the energy consumption of the subsequent separation cosolvent is increased, and the production cost of cyclohexanone oxime is increased.
The titanium-silicon molecular sieve is a catalyst commonly used in the process, and the excellent catalytic performance of the titanium-silicon molecular sieve is derived from the ultrahigh specific surface area caused by a porous structure, but in actual production, due to the lipophilicity of TS-1, the generated cyclohexanone oxime is difficult to diffuse out of a catalyst pore canal, and the efficiency of catalytic reaction is affected. Meanwhile, the selectivity of the current process is low, the reaction time is long, high-boiling macromolecular byproducts are easily coated on the surface of the catalyst, carbon deposition is easily caused, and the service life of the catalyst is shortened.
Disclosure of Invention
The invention aims to provide a device, a system and a method for continuously producing cyclohexanone oxime, which can obviously shorten the cyclohexanone oxime reaction time under the condition of not using a cosolvent, and the selectivity of the cyclohexanone oxime can reach more than 99 percent.
The device for continuously producing cyclohexanone oxime comprises a reaction kettle, wherein the reaction kettle consists of a liquid distributor, rotary filler, a rotating shaft, a jacket, a bottom liquid outlet, an external heat exchanger A, an external circulating pump A, an external heat exchanger B and an external circulating pump B, a liquid feeding port I, a liquid feeding port II and a liquid feeding port III are respectively communicated with the upper part of the liquid distributor, the bottom end of the liquid distributor stretches into a cavity of the rotary filler, the rotary filler is fixed on the rotating shaft, a bottom baffle plate is fixed on the surface of the rotating shaft and below the rotary filler, a sealing part is fixed at the bottom of the reaction kettle, a motor is fixed below the reaction kettle, an output shaft of the motor is fixedly connected with the sealing part, and external circulating pipelines are fixed on the left side and the right side of the outside of the reaction kettle.
Preferably, the rotary filler is any one of stainless steel embossed net filler, stainless steel wire net woven filler, aluminum oxide ceramic corrugated regular filler, plastic wire net filler, integral silicon carbide filler or foam metal filler, and the selected rotary filler is coated with a titanium-silicon molecular sieve film or other catalyst films.
Preferably, a semi-closed shell is fixed outside the rotary filler, a series of turbulence assemblies are fixed on the outer side of the semi-closed shell, and the bottom baffle is connected with the rotary shaft through a speed change gear set.
The utility model provides a system for serialization production cyclohexanone oxime, includes hydrogen peroxide entry, cyclohexanone entry, aqueous ammonia entry, hot steam entry, waste water export, reation kettle, phase separation jar, aqueous phase circulating pump, evaporation jar and cyclohexanone oxime export, hydrogen peroxide entry, cyclohexanone entry and aqueous ammonia entry respectively with liquid feed inlet one, liquid feed inlet two and liquid feed inlet three are connected, bottom liquid export is connected with the liquid entry of phase separation jar, the heavy phase export of phase separation jar bottom is connected with cyclohexanone oxime export, upper portion light phase export and aqueous phase circulating pump interconnect in the phase separation jar, the liquid entry interconnect of aqueous phase circulating pump and evaporation jar, hot steam entry is connected with the bottom gas entry of evaporation jar, the liquid export and the waste water exit linkage of evaporation jar bottom, the liquid export and the pipe connection of aqueous ammonia entry at phase separation jar top.
Preferably, a filler or sieve plate structure is arranged in the evaporation tank.
A process for the continuous production of cyclohexanone oxime, which process comprises the steps of:
firstly, pre-mixing fresh feeding hydrogen peroxide liquid, cyclohexanone liquid and ammonia water in a liquid distributor, then spraying the pre-mixed liquid onto a rotary filler at a high speed, carrying out oximation reaction under the action of a catalyst loaded on the rotary filler, enabling reaction liquid sheared by the filler to flow to the wall surface of a reaction kettle under the combined action of a semi-closed shell and a bottom baffle, enabling the baffle to rotate and a spoiler of the filler shell to enable the liquid to lift upwards and flow through the filler again for continuous reaction, and controlling the liquid level in the reaction kettle above the filler;
Part of reaction liquid in the reaction kettle flows into the liquid distributor through the external circulating pump and the external heat exchanger, and is sprayed onto the rotary filler together with fresh fed materials through the liquid distributor, the external heat exchanger and the reaction kettle jacket remove reaction heat together, the materials after full reaction in the reaction kettle are extracted from the bottom of the reaction kettle and enter the phase separation tank, crude cyclohexanone oxime products are extracted from heavy phases and are sent to the cyclohexanone oxime refining section, and ammonia-containing wastewater is extracted from light phases;
And thirdly, the ammonia-containing wastewater is in countercurrent contact with hot steam in an evaporation tank, ammonia gas is fully stripped by the steam and is dissolved in the fresh-fed concentrated ammonia water, and the wastewater after the residual ammonia is evaporated is sent to a wastewater treatment unit.
Preferably, in the first step, the ratio of the amounts of ammonia water, hydrogen peroxide and cyclohexanone entering the liquid distributor is 1.1:1:1 to 1.5:1:1.
Preferably, in the first step, the pressure in the reaction kettle is 1-10 atm, the liquid temperature is controlled to be 45-150 ℃, the residence time in the reaction kettle is 30-200 min, and the rotating speed of the rotary filler is 600-2500 rpm.
Compared with the prior art, the invention has the following beneficial effects:
1. The reaction raw materials are sheared at a high speed in the rotary filler, oil-water two phases are fully emulsified and uniformly mixed, and fully contact with the catalyst, so that mass transfer resistance is reduced, ammoximation reaction is rapidly carried out, cyclohexanone oxime generated in a catalyst pore channel can be rapidly separated from the pore channel under the action of a high-speed centrifugal force field due to the fact that the catalyst is loaded on the rotary filler, internal diffusion coefficient is greatly enhanced, and simultaneously external diffusion resistance is reduced and catalytic reaction efficiency is greatly enhanced through stirring of the rotary filler and automatic and passive annular flow of liquid in the kettle; due to the shorter residence time and more uniform mixing effect of the invention, the hydrogen peroxide always participates in the ammoximation reaction, the decomposition amount is reduced, when the invention is adopted to produce the cyclohexanone oxime under the combined action of the three factors, the cyclohexanone is almost completely converted into the cyclohexanone oxime, the conversion rate of the hydrogen peroxide and the ammonia water can reach more than 99.5 percent, and under the condition of not using a cosolvent, the reaction time is similar to the advanced level of the process of using the cosolvent, so that the reaction conversion rate is improved, and the reaction time is short.
2. The cyclohexanone, the hydrogen peroxide and the ammonia water can be uniformly mixed in the reaction kettle, the catalytic reaction efficiency is high, the ammonia water is controlled to be slightly excessive, the conditions ensure that the cyclohexanone and the hydrogen peroxide completely participate in the ammoximation reaction, the occurrence of side reactions such as direct oxidation of the cyclohexanone by the hydrogen peroxide, intermolecular crosslinking of the cyclohexanone, direct oxidation of the ammonia water by the hydrogen peroxide into nitrogen oxides and the like is reduced, under the combined action of the factors, the selectivity of the cyclohexanone oxime produced by the method can reach more than 99%, the concentration of the cyclohexanone oxime in a crude product of the cyclohexanone oxime reaches more than 99.5%, and the selectivity of the cyclohexanone oxime is improved.
3. Under the condition of ensuring that the reaction efficiency is not reduced or even improved, the invention omits the use of a cosolvent, saves a great amount of energy consumption in a cosolvent separation link, has high purity of the obtained crude product, low energy consumption in subsequent refining, and sets a residual ammonia recovery flow, so that all raw materials are almost completely converted into butanone oxime and water, the utilization rate of the raw materials is high, the material consumption is reduced, and the content of byproducts in a water phase is extremely low due to the high selectivity of the main product, and the impurity content in waste water after the residual ammonia recovery is low, thus the crude product can be directly used as industrial water or irrigation water, and the energy consumption and the material consumption are reduced.
4. The invention adopts the design of coating the catalyst by the fixed filler, strengthens the diffusion in the pore canal of the catalyst under the action of a high-speed centrifugal force plant provided by the rotary filler, reduces the accumulation and blockage of reactants, reduces the production of macromolecular byproducts with high selectivity, reduces the carbon accumulation on the surface of the catalyst, and can prolong the service life of the catalyst by 1 time compared with the current mainstream powder catalyst process, solve the problem of catalyst loss and prolong the service life of the catalyst.
5. The invention can achieve extremely high selectivity, the decomposition amount of hydrogen peroxide is extremely small, and the reaction of directly oxidizing ammonia water into nitrogen oxides by hydrogen peroxide is difficult to occur, so that the contents of oxygen and nitrogen oxides in the system are small; in conclusion, the invention optimizes the intrinsic safety of the cyclohexanone oxime production process, and the intrinsic safety of the production process is optimized.
Drawings
FIG. 1 is a cross-sectional view of a reaction vessel according to the present invention;
FIG. 2 is a flow chart of a system in accordance with the present invention;
FIG. 3 is a schematic diagram of the reaction of cyclohexanone with ammonia and hydrogen peroxide under the catalysis of a titanium silicalite TS-1.
In the figure, 1, a hydrogen peroxide inlet, 2, a cyclohexanone inlet, 3, an ammonia water inlet, 4, a hot steam inlet, 5, a waste water outlet, 6, a reaction kettle, 6-1, a first liquid feed inlet, 6-2, a second liquid feed inlet, 6-3, a third liquid feed inlet, 6-4, a liquid distributor, 6-5, a rotary filler, 6-6, a rotary shaft, 6-7-bottom baffle, 6-8, a sealing component, 6-9, a jacket, 6-10, a bottom liquid outlet, 6-11, a motor, 6-12, an external heat exchanger A, 6-13, an external circulating pump A, 6-14, an external heat exchanger B, 6-15, an external circulating pump B, 7, a phase separation tank, 8, a water phase circulating pump, 9, an evaporation tank, 10 and a cyclohexanone oxime outlet.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to 1-2, a device for continuously producing cyclohexanone oxime comprises a reaction kettle 6, wherein the reaction kettle 6 comprises a liquid distributor 6-4, a rotary filler 6-5, a rotary shaft 6-6, a jacket 6-9, a bottom liquid outlet 6-10, an external heat exchanger A6-12, an external circulating pump A6-13, an external heat exchanger B6-14 and an external circulating pump B6-15, a liquid feed inlet 6-1, a liquid feed inlet two 6-2 and a liquid feed inlet three 6-3 are respectively communicated above the liquid distributor 6-4, the bottom end of the liquid distributor 6-4 extends into a cavity of the rotary filler 6-5, the rotary filler 6-5 is fixed on the rotary shaft 6-6, a bottom baffle 6-7 is fixed below the rotary filler 6-5 on the surface of the rotary shaft 6-6, the bottom of the reaction kettle 6 is fixed with a sealing part 6-8, the bottom end of a rotating shaft 6-6 is fixed with the sealing part 6-8, a motor 6-11 is fixed below the reaction kettle 6, an output shaft of the motor 6-11 is fixedly connected with the sealing part 6-8, the left side and the right side of the outside of the reaction kettle 6 are both fixed with an outer circulation pipeline, the outer circulation pipeline passes through the kettle bottom and is connected with a liquid distributor 6-4 after passing through an external circulation pump and an external heat exchanger, the rotating filler 6-5 is any one of stainless steel embossing net filler, stainless steel wire net woven filler, aluminum oxide ceramic corrugated regular filler, plastic wire net filler, integral silicon carbide filler or foam metal filler, preferably stainless steel wire net filler and aluminum oxide ceramic corrugated regular filler, the selected rotating packing 6-5 is coated with a titanium silicalite film or other catalyst film.
The outer part of the rotary filler 6-5 is fixed with a semi-closed shell, and the outer side of the semi-closed shell is fixed with a series of turbulence assemblies, so that better stirring effect is achieved, and the bottom baffle is connected with the rotary shaft through a speed change gear set, so that the speed regulation effect is achieved.
A system for continuously producing cyclohexanone oxime comprises a hydrogen peroxide inlet 1, a cyclohexanone inlet 2, an ammonia water inlet 3, a hot steam inlet 4, a wastewater outlet 5, a reaction kettle 6, a phase separation tank 7, a water phase circulating pump 8, an evaporation tank 9 and a cyclohexanone oxime outlet 10, wherein the hydrogen peroxide inlet 1, the cyclohexanone inlet 2 and the ammonia water inlet 3 are respectively connected with a first liquid feed port 6-1, a second liquid feed port 6-2 and a third liquid feed port 6-3, a bottom liquid outlet 6-10 is connected with the liquid inlet of the phase separation tank 7, a heavy phase outlet at the bottom of the phase separation tank 7 is connected with the cyclohexanone oxime outlet 10, a light phase outlet at the middle upper part of the phase separation tank 7 is connected with the water phase circulating pump 8, the water phase circulating pump 8 is connected with the liquid inlet of the evaporation tank 9, the hot steam inlet 4 is connected with the bottom gas inlet of the evaporation tank 9, the liquid outlet at the bottom of the evaporation tank 9 is connected with the wastewater outlet, the liquid outlet at the top of the phase separation tank 7 is connected with a pipeline of the ammonia water inlet 3, and a filler or sieve plate structure is arranged in the evaporation tank 9.
A process for the continuous production of cyclohexanone oxime, which process comprises the steps of:
Firstly, pre-mixing fresh feeding hydrogen peroxide liquid, cyclohexanone liquid and ammonia water in a liquid distributor 6-4, then spraying the mixture onto a rotary filler 6-5 at a high speed, carrying out oximation reaction under the action of a catalyst loaded on the rotary filler 6-5, enabling the reaction liquid sheared by the filler to flow to the wall surface of a reaction kettle 6 under the combined action of a semi-closed shell and a bottom baffle 6-7, enabling the liquid to be lifted upwards by a baffle rotating and a spoiler of the filler shell to flow through the filler again for continuous reaction, controlling the liquid level in the reaction kettle to be above the filler, controlling the mass ratio of ammonia water, hydrogen peroxide and cyclohexanone entering the liquid distributor to be 1.1:1:1-1.5:1, and optimally to be 1.2:1:1, wherein the pressure in the reaction kettle is 1-10 atm, the liquid temperature is controlled to be 45-150 ℃, preferably normal pressure to be 92-99 ℃, the residence time in the reaction kettle is preferably 65-85 min, and the rotating speed of the rotary filler is 600-2500rpm, preferably 1000-1500rpm;
Part of reaction liquid in the reaction kettle flows into a liquid distributor through an external circulating pump and an external heat exchanger, is sprayed onto a rotary filler 6-5 together with fresh fed materials through a liquid distributor 6-4, the external heat exchanger and a reaction kettle jacket remove reaction heat together, the materials after full reaction in the reaction kettle 6 are extracted from the bottom of the reaction kettle 6 and enter a phase separation tank, a crude cyclohexanone oxime product is extracted from a heavy phase, the crude cyclohexanone oxime product is sent to a cyclohexanone oxime refining section, and ammonia-containing wastewater is extracted from a light phase;
and thirdly, the ammonia-containing wastewater is in countercurrent contact with hot steam in an evaporation tank 9, ammonia gas is fully stripped by the steam and is dissolved into fresh-fed concentrated ammonia water, and the wastewater after the residual ammonia is evaporated is sent to a wastewater treatment unit.
Example 1
The system, the device and the method of the invention are adopted for preparing the cyclohexanone oxime by continuous reaction, and TS-1 catalyst is adopted. The molar flow rate of the ammonia water and the hydrogen peroxide entering the liquid distributor is 1, the ratio (r) of the molar flow rate of the ammonia water and the hydrogen peroxide entering the liquid distributor is 1.2:1.01, the pressure in the reaction kettle is 1atm, the liquid temperature (T) is controlled at 95 ℃, the retention time (T) of the materials in the reaction kettle is 70 minutes, and the rotating speed (N) of the rotary filler is 1000rpm. The operation was stabilized for 4 hours, and the concentration of each outlet substance was measured, and the cyclohexanone oxime selectivity in the product was calculated to be (a) 99.6%, cyclohexanone conversion (b) 100%, ammonia conversion (c) 98.1%, and hydrogen peroxide conversion (d) 99.2%.
Examples 2 to 10
The procedure is the same as in example 1, except that the operating parameters are modified, and for simplicity, the parameters and units thereof appearing in example 1 are indicated by the letters indicated.
Examples 1 to 4 are within the technological parameters claimed by the invention, and the results of the examples can be used for obtaining that the conversion rate of raw materials and the selectivity of products can be obviously improved.
Wherein, some of the process parameters of examples 5-10 are outside the process parameters claimed in the present invention, and are comparative examples. From the comparative examples, it can be reversed that the effect achieved by the process of the present invention is indeed obtained by the relative process and equipment improvements made by the present invention.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises an element.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A system for continuously producing cyclohexanone oxime comprises a hydrogen peroxide inlet (1), a cyclohexanone inlet (2), an ammonia water inlet (3), a hot steam inlet (4), a waste water outlet (5), a reaction kettle (6), a phase separation tank (7), a water phase circulating pump (8), an evaporation tank (9) and a cyclohexanone oxime outlet (10), and is characterized in that the reaction kettle (6) consists of a liquid distributor (6-4), rotary fillers (6-5), a rotating shaft (6-6), a jacket (6-9), a bottom liquid outlet (6-10), an external heat exchanger A (6-12), an external circulating pump A (6-13), an external heat exchanger B (6-14) and an external circulating pump B (6-15), a first liquid feed port (6-1), a second liquid feed port (6-2) and a third liquid feed port (6-3) are respectively communicated above the liquid distributor (6-4), the bottom end of the liquid distributor (6-4) stretches into a cavity of the rotary fillers (6-5), the rotary fillers (6-5) are fixed on the rotating shaft (6-6), the surface of the rotating shaft (6-6) and the lower part of the rotating packing (6-5) are fixedly provided with a bottom baffle (6-7), the bottom of the reaction kettle (6) is fixedly provided with a sealing part (6-8), the bottom end of the rotating shaft (6-6) is fixedly provided with a sealing part (6-8), the lower part of the reaction kettle (6) is fixedly provided with a motor (6-11), the output shaft of the motor (6-11) is fixedly connected with the sealing part (6-8), the left side and the right side of the outer part of the reaction kettle (6) are respectively fixedly provided with an external circulation pipeline, the hydrogen peroxide inlet (1), the cyclohexanone inlet (2) and the ammonia water inlet (3) are respectively connected with a first liquid feed port (6-1), a second liquid feed port (6-2) and a third liquid feed port (6-3), a bottom liquid outlet (6-10) is connected with a liquid inlet of a phase separation tank (7), a heavy phase outlet at the bottom of the phase separation tank (7) is connected with a cyclohexanone oxime outlet (10), an upper water phase outlet of the water phase tank (7) is connected with a light phase circulation pump (8) and a vapor inlet of the vapor pump (9) is connected with the vapor inlet (9) of the vapor inlet, the liquid outlet at the bottom of the evaporation tank (9) is connected with the wastewater outlet, and the liquid outlet at the top of the phase-splitting tank (7) is connected with the pipeline of the ammonia water inlet (3).
2. A system for the continuous production of cyclohexanone oxime according to claim 1, characterized in that the evaporation tank (9) is provided with a packing or sieve plate structure.
3. A system for continuously producing cyclohexanone oxime according to claim 1, wherein the rotary packing (6-5) is composed of any one of stainless steel gauze packing, alumina ceramic corrugated structured packing, plastic wire gauze packing, monolithic silicon carbide packing or foam metal packing, and the rotary packing (6-5) is coated with a titanium-silicon molecular sieve film or other catalyst film.
4. A system for continuously producing cyclohexanone oxime according to claim 1, wherein the outer part of the rotary packing (6-5) is fixed with a semi-closed shell, the outer side of the semi-closed shell is fixed with a series of turbulence components, and the bottom baffle is connected with the rotary shaft through a speed change gear set.
5. A method for continuously producing cyclohexanone oxime, using a system for continuously producing cyclohexanone oxime as claimed in claim 1, characterized in that the production method comprises the steps of:
Firstly, pre-mixing fresh feeding hydrogen peroxide liquid, cyclohexanone liquid and ammonia water in a liquid distributor (6-4), then spraying the mixture onto a rotary filler (6-5) at a high speed, carrying out oximation reaction under the action of a catalyst loaded on the rotary filler (6-5), enabling reaction feed liquid sheared by the filler to flow to the wall surface of a reaction kettle (6) under the combined action of a semi-closed shell and a bottom baffle (6-7), enabling the liquid to be lifted upwards by the baffle rotating and a spoiler of the filler shell, enabling the liquid to flow through the filler again for continuous reaction, and controlling the liquid level in the reaction kettle above the filler, wherein the ratio of the amounts of ammonia water, hydrogen peroxide and cyclohexanone entering the liquid distributor is 1.1:1 to 1.5:1:1;
Part of reaction liquid in the reaction kettle flows into a liquid distributor through an external circulating pump and an external heat exchanger, is sprayed onto a rotary filler (6-5) together with fresh fed materials through the liquid distributor (6-4), the external heat exchanger and a reaction kettle jacket remove reaction heat together, the materials after the reaction kettle (6) fully react are extracted from the bottom of the reaction kettle (6) and enter a phase separation tank (7), a cyclohexanone oxime crude product is extracted from a heavy phase, the crude product is sent to a cyclohexanone oxime refining section, and ammonia-containing wastewater is extracted from a light phase;
And thirdly, the ammonia-containing wastewater is in countercurrent contact with hot steam in an evaporation tank (9), ammonia gas is fully stripped by the steam and is dissolved in the fresh-fed concentrated ammonia water, and the wastewater after the residual ammonia is evaporated is sent to a wastewater treatment unit.
6. The method for continuously producing cyclohexanone oxime according to claim 5, wherein in the first step, the pressure in the reaction vessel is 1-10 atm, the liquid temperature is controlled to be 45-150 ℃, the residence time in the reaction vessel is 30-200 min, and the rotating speed of the rotary filler is 600-2500 rpm.
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| CN1939897A (en) * | 2006-09-27 | 2007-04-04 | 湘潭大学 | Separating production of ketoxime by three-phase amino-oximate reaction |
| CN104262196A (en) * | 2014-09-02 | 2015-01-07 | 河北美邦工程科技有限公司 | Ammoximation reaction and separation coupling process and device |
| CN105080446A (en) * | 2014-04-18 | 2015-11-25 | 北京化工大学 | Multi-stage material feeding supergravity liquid-liquid reactor apparatus and applications thereof |
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| JP4595804B2 (en) * | 2004-12-22 | 2010-12-08 | 住友化学株式会社 | Method for producing cyclohexanone oxime |
| SG123723A1 (en) * | 2004-12-22 | 2006-07-26 | Sumitomo Chemical Co | Process for producing cyclohexanone oxime |
| WO2020078884A1 (en) * | 2018-10-17 | 2020-04-23 | Cap Iii B.V. | An improved process and plant for the production of oximes |
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| CN1939897A (en) * | 2006-09-27 | 2007-04-04 | 湘潭大学 | Separating production of ketoxime by three-phase amino-oximate reaction |
| CN105080446A (en) * | 2014-04-18 | 2015-11-25 | 北京化工大学 | Multi-stage material feeding supergravity liquid-liquid reactor apparatus and applications thereof |
| CN104262196A (en) * | 2014-09-02 | 2015-01-07 | 河北美邦工程科技有限公司 | Ammoximation reaction and separation coupling process and device |
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