CN117865811A - Method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride - Google Patents
Method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride Download PDFInfo
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- CN117865811A CN117865811A CN202410268768.0A CN202410268768A CN117865811A CN 117865811 A CN117865811 A CN 117865811A CN 202410268768 A CN202410268768 A CN 202410268768A CN 117865811 A CN117865811 A CN 117865811A
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- nitrobenzotrifluoride
- benzotrifluoride
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- nitrifying
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- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 230000001546 nitrifying effect Effects 0.000 title claims abstract description 68
- NDZJSUCUYPZXPR-UHFFFAOYSA-N 1-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=CC=C1C(F)(F)F NDZJSUCUYPZXPR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 304
- 239000003054 catalyst Substances 0.000 claims abstract description 106
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 73
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 46
- 239000002808 molecular sieve Substances 0.000 claims description 36
- 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 36
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 26
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000011049 filling Methods 0.000 claims description 18
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 229920001661 Chitosan Polymers 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 9
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- NIESTGKUHZUQLW-UHFFFAOYSA-N C1(=CC=CC=C1)C(F)(F)F.[N+](=O)(O)[O-] Chemical compound C1(=CC=CC=C1)C(F)(F)F.[N+](=O)(O)[O-] NIESTGKUHZUQLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- XKYLCLMYQDFGKO-UHFFFAOYSA-N 1-nitro-4-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(C(F)(F)F)C=C1 XKYLCLMYQDFGKO-UHFFFAOYSA-N 0.000 abstract description 17
- WHNAMGUAXHGCHH-UHFFFAOYSA-N 1-nitro-3-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=CC(C(F)(F)F)=C1 WHNAMGUAXHGCHH-UHFFFAOYSA-N 0.000 abstract description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000003429 antifungal agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- ZOCSXAVNDGMNBV-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile Chemical compound NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 description 1
- 239000005899 Fipronil Substances 0.000 description 1
- 239000005857 Trifloxystrobin Substances 0.000 description 1
- 239000005858 Triflumizole Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229940013764 fipronil Drugs 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ONCZDRURRATYFI-TVJDWZFNSA-N trifloxystrobin Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1CO\N=C(/C)C1=CC=CC(C(F)(F)F)=C1 ONCZDRURRATYFI-TVJDWZFNSA-N 0.000 description 1
- HSMVPDGQOIQYSR-KGENOOAVSA-N triflumizole Chemical compound C1=CN=CN1C(/COCCC)=N/C1=CC=C(Cl)C=C1C(F)(F)F HSMVPDGQOIQYSR-KGENOOAVSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride, which belongs to the technical field of nitrobenzotrifluoride and comprises the following steps of: loading a catalyst and reacting; the reaction is carried out, benzotrifluoride liquid and nitrifying reagent are respectively preheated and then enter a tubular reactor at the same time, the preheating temperature is controlled to be 40-140 ℃, the feeding rate of benzotrifluoride is controlled to be 11-42mL/min, the feeding rate of nitrifying reagent is controlled to be 47-88mL/min, the benzotrifluoride liquid and nitrifying reagent are directly introduced into a micro-reaction device after coming out of the tubular reactor, and the temperatures in the tubular reactor and the micro-reaction device are controlled to be 40-140 ℃ and the pressure is controlled to be 0.1-1MPa. The nitrobenzotrifluoride prepared by the invention has stable quality, high purity and safe and reliable production, and the contents of the o-nitrobenzotrifluoride, m-nitrobenzotrifluoride and p-nitrobenzotrifluoride in the product can be controlled by adjusting the reaction parameters.
Description
Technical Field
The invention relates to the technical field of nitrobenzotrifluoride, in particular to a method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride.
Background
The nitrobenzotrifluoride includes ortho-nitrobenzotrifluoride, meta-nitrobenzotrifluoride, and para-nitrobenzotrifluoride. The nitrobenzotrifluoride is taken as an important intermediate product and is widely used for synthesizing medical and pesticide intermediates and the like, and downstream products thereof comprise antifungal medicines of triflumizole, trifloxystrobin, fipronil and the like. At present, the market demands of the o-nitrobenzotrifluoride, m-nitrobenzotrifluoride and p-nitrobenzotrifluoride are stabilized at 1.5 ten thousand tons/year, the main synthetic route is that the anti-fungal drug is prepared by nitration reaction of benzotrifluoride, nitric acid and fuming sulfuric acid, and then the anti-fungal drug can be synthesized.
The traditional production method of nitrobenzotrifluoride adopts a batch kettle production method, and the reaction raw materials are added into a reaction kettle to react under proper conditions, but the method has the following disadvantages: firstly, intermittent kettle equipment is not closed, so that the defects of serious pollution and high risk coefficient exist, and secondly, the intermittent kettle production method has low reaction efficiency, and the reaction process is violently exothermic, reactants and products are concentrated in the reaction kettle, the temperature is not easy to control, and the purity and the yield of the final product are low; thirdly, the intermittent kettle type production method is unstable operation and periodic production process, the control index of production process parameters changes along with the reaction progress, and the product quality is not easy to keep stable.
The continuous production is steady-state operation, the process parameter control index is stable, and the operator is sensitive to the variation of the process parameter deviation control index in the production, so that the deviation correction is facilitated in time, the stable product quality is ensured, the continuous production is also facilitated to the automatic control of the production, and the production safety and the product quality can be effectively improved. Therefore, more and more nitrobenzotrifluoride manufacturers change from batch kettle production to continuous production.
The micro-reaction device is used for producing the nitrobenzotrifluoride, mass transfer and heat transfer can be realized in production, the reaction pressure and the reaction temperature can be well reduced, but the reaction speed is low, and as the nitro is a meta-position locating group, in the produced product, m-nitrobenzotrifluoride accounts for about 85wt%, o-nitrobenzotrifluoride accounts for about 10%, p-nitrobenzotrifluoride accounts for about 5%, the yields of the o-nitrobenzotrifluoride and the p-nitrobenzotrifluoride are low, and the contents of the o-nitrobenzotrifluoride, m-nitrobenzotrifluoride and p-nitrobenzotrifluoride in the product are difficult to control by adjusting the reaction parameters.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride, the prepared nitrobenzotrifluoride has stable quality, high purity and safe and reliable production, and the contents of the o-nitrobenzotrifluoride, m-nitrobenzotrifluoride and p-nitrobenzotrifluoride in the product can be controlled by adjusting reaction parameters.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride comprises the following steps: loading a catalyst and reacting;
the catalyst A and the catalyst B are uniformly mixed according to the mass ratio of 10-12:1 to obtain a mixed catalyst, and the mixed catalyst is filled in the middle part of the tubular reactor with the filling amount of 30-31g;
the diameter of the tubular reactor is 20mm, and the length of the tubular reactor is 0.5m;
the preparation method of the catalyst A comprises the steps of adding potassium permanganate, zinc nitrate, ferric nitrate, cerium nitrate and deionized water into a reaction kettle, controlling the temperature of the reaction kettle to be 20-40 ℃, stirring at 50-100rpm, stirring for 30-60min, adding SAPO-11 molecular sieve, increasing the temperature of the reaction kettle to 70-90 ℃, continuously stirring for 6-7h, centrifuging, controlling the rotating speed during centrifuging to be 6000-7000rpm, controlling the time to be 7-10min, cleaning a precipitate by using deionized water for 2-3 times after centrifuging, putting into nitrogen atmosphere, and calcining for 1.5-2h at 400-500 ℃ to obtain the catalyst A;
in the preparation of the catalyst A, the mass volume ratio of potassium permanganate, zinc nitrate, ferric nitrate, cerium nitrate, deionized water and SAPO-11 molecular sieve is 1.5-1.6g:4-4.5g:2-2.2g:0.6-0.65g:950-1000mL:10-12g;
the particle size of the SAPO-11 molecular sieve is 800nm, and the molar ratio of Si to P to Al is 0.5 to 1;
adding a P123 template agent, cetyltrimethylammonium chloride, absolute ethyl alcohol and deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 20-35 ℃, stirring at 50-100rpm, stirring for 30-60min, adding glacial acetic acid and chitosan, stirring for 30-40min, adding tetraethoxysilane, continuing stirring for 22-25h, adding a ZSM-5 molecular sieve, increasing the temperature of the reaction kettle to 70-80 ℃, continuing stirring for 10-12h, centrifuging, controlling the rotating speed at 6000-7000rpm for 10-12min, cleaning the precipitate by using deionized water for 2-3 times after centrifuging, placing into a nitrogen atmosphere, calcining at 500-550 ℃ for 5-6h, then adding a hydrochloric acid aqueous solution of palladium chloride into the reaction kettle, controlling the temperature of the reaction kettle to 15-30 ℃, stirring at 100-200rpm, stirring for 1-2h, continuing stirring for 2-3h, controlling the rotating speed at 6000-rpm for 10-12min, drying the precipitate at 5-60 MPa after centrifuging, and drying the precipitate at 5-60 MPa for 5.07 MPa;
in the preparation of the catalyst B, the mass volume ratio of the P123 template agent, the cetyl trimethyl ammonium chloride, the absolute ethyl alcohol, the deionized water, the glacial acetic acid, the chitosan, the ethyl orthosilicate, the ZSM-5 molecular sieve, the hydrochloric acid aqueous solution of palladium chloride and the hydrazine hydrate is 7-8g:2-2.2g:24-26mL:11-12mL:1.5-2mL:1-1.2g:30-32mL:10-12g:230-250mL:12-14g;
the mass concentration of the palladium chloride in the hydrochloric acid aqueous solution of the palladium chloride is 3-3.5%, and the mass concentration of the hydrochloric acid is 2-3%;
the particle size of the ZSM-5 molecular sieve is 500nm, and the molar ratio of Si to Al is 100:1;
the method comprises the steps of respectively preheating benzotrifluoride liquid and a nitrifying reagent, then simultaneously entering a tubular reactor, controlling the preheating temperature to be 40-140 ℃, controlling the feeding rate of benzotrifluoride to be 11-42mL/min, controlling the feeding rate of the nitrifying reagent to be 47-88mL/min, enabling the nitrifying reagent to be concentrated sulfuric acid and fuming nitric acid, enabling the volume ratio of the concentrated sulfuric acid to the fuming nitric acid to be 2-8:1, directly entering a 1 st reaction plate of a micro-reaction device after exiting from the tubular reactor, controlling the temperature in the tubular reactor and the micro-reaction device to be 40-140 ℃ and the pressure to be 0.1-1MPa, and then sequentially flowing out after passing through the 1 st-12 reaction plates of the micro-reaction device, so as to obtain benzotrifluoride nitrate, wherein the reaction time in the micro-reaction device is 48-98s;
the mass concentration of the concentrated sulfuric acid is 98%;
the micro-reaction device consists of 12 reaction plates, the reaction plates are connected in series, the reaction channels of the reaction plates are heart-shaped reaction channels, and the reaction channels of each reaction plate are formed by connecting 53 heart-shaped structures in series.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method for preparing the nitrobenzotrifluoride by continuously nitrifying benzotrifluoride can realize continuous production and is safe and reliable in production;
(2) According to the method for preparing the nitrobenzotrifluoride by continuously nitrifying the benzotrifluoride, the prepared nitrobenzotrifluoride has stable quality and high purity, the content of the o-nitrobenzotrifluoride, m-nitrobenzotrifluoride and p-nitrobenzotrifluoride in the product can be controlled by adjusting the reaction parameters, the total conversion rate of the prepared o-nitrobenzotrifluoride, m-nitrobenzotrifluoride and p-nitrobenzotrifluoride can reach 98.5-99.5%, and the mass ratio range of the o-nitrobenzotrifluoride, m-nitrobenzotrifluoride and p-nitrobenzotrifluoride in the product can be controlled to 25-67:3-60:11-72 by adjusting the reaction parameters.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
A method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride specifically comprises the following steps:
1. and (2) supporting a catalyst: uniformly mixing a catalyst A and a catalyst B according to a mass ratio of 10:1 to obtain a mixed catalyst, and filling the mixed catalyst into the middle part of a tubular reactor with a filling amount of 31g;
the diameter of the tubular reactor is 20mm, and the length of the tubular reactor is 0.5m;
the preparation method of the catalyst A comprises the following steps: adding 1.5g of potassium permanganate, 4g of zinc nitrate, 2g of ferric nitrate, 0.6g of cerium nitrate and 950mL of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to be 20 ℃, stirring at 50rpm, stirring for 30min, adding 10g of SAPO-11 molecular sieve, increasing the temperature of the reaction kettle to 70 ℃, continuing stirring for 6h, centrifuging, controlling the rotating speed during centrifuging to be 6000rpm, controlling the time to be 7min, cleaning a precipitate by using deionized water for 2 times after centrifuging, putting into a nitrogen atmosphere, and calcining for 1.5h at 400 ℃ to obtain a catalyst A;
the particle size of the SAPO-11 molecular sieve is 800nm, and the molar ratio of Si to P to Al is 0.5 to 1;
the preparation method of the catalyst B comprises the following steps: adding 7g of P123 template agent, 2g of hexadecyl trimethyl ammonium chloride, 24mL of absolute ethyl alcohol and 11mL of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 20 ℃, stirring at 50rpm, stirring for 30min, adding 1.5mL of glacial acetic acid and 1g of chitosan, stirring for 30min, adding 30mL of tetraethoxysilane, continuing stirring for 22h, adding 10g of ZSM-5 molecular sieve, increasing the temperature of the reaction kettle to 70 ℃, continuing stirring for 10h, centrifuging, controlling the rotating speed at 6000rpm for 10min, washing the precipitate with deionized water for 2 times after centrifuging, placing into nitrogen atmosphere, calcining at 500 ℃ for 5h, adding hydrochloric acid aqueous solution of 230mL of palladium chloride into the reaction kettle, controlling the temperature of the reaction kettle to 15 ℃, stirring at 100rpm, stirring for 1h, adding 12g of hydrazine hydrate, continuing stirring for 2h, centrifuging, controlling the rotating speed at 6000rpm for 10min, vacuum drying the precipitate after centrifuging, controlling the temperature at 60 MPa for 5h, and vacuum drying the catalyst after vacuum drying is finished;
the mass concentration of palladium chloride in the hydrochloric acid aqueous solution of palladium chloride is 3%, and the mass concentration of hydrochloric acid is 2%;
the particle size of the ZSM-5 molecular sieve is 500nm, and the molar ratio of Si to Al is 100:1;
the micro-reaction device consists of 12 reaction plates, wherein the reaction plates are connected in series, the 1 st reaction plate is used for heat exchange of benzotrifluoride, the 2 nd reaction plate is used for heat exchange of nitrifying reagent, benzotrifluoride after heat exchange is mixed with nitrifying reagent in the 3 rd reaction plate, and then flows out after sequentially flowing through the 4 th to 12 th reaction plates, so that a benzotrifluoride nitro product is obtained;
the reaction channels of the reaction plates in the micro-reaction device are heart-shaped reaction channels, and each reaction channel of each reaction plate is formed by connecting 53 heart-shaped structures in series;
2. the reaction: respectively preheating benzotrifluoride liquid and a nitrifying reagent, then simultaneously entering a tubular reactor, controlling the preheating temperature to 140 ℃, controlling the feeding rate of benzotrifluoride to 11mL/min, controlling the feeding rate of the nitrifying reagent to 47mL/min, wherein the nitrifying reagent is concentrated sulfuric acid and fuming nitric acid, the volume ratio of the concentrated sulfuric acid to the fuming nitric acid is 8:1, directly entering a 1 st reaction plate of a micro-reaction device after exiting the tubular reactor, controlling the temperature in the tubular reactor and the micro-reaction device to 140 ℃, controlling the pressure to 1MPa, sequentially passing through the 1 st to 12 th reaction plates of the micro-reaction device, and then flowing out to obtain nitrobenzotrifluoride, wherein the reaction time in the micro-reaction device is 98s;
the mass concentration of the concentrated sulfuric acid is 98%;
the micro-reaction device consists of 12 reaction plates, the reaction plates are connected in series, the reaction channels of the reaction plates are heart-shaped reaction channels, and the reaction channels of each reaction plate are formed by connecting 53 heart-shaped structures in series;
after 120s of continuous operation, the samples were tested, and the total conversion of o-nitrobenzotrifluoride, m-nitrobenzotrifluoride, p-nitrobenzotrifluoride was 99.5% (calculated on the basis of benzotrifluoride), wherein the mass ratio of o-nitrobenzotrifluoride, m-nitrobenzotrifluoride, p-nitrobenzotrifluoride was 25:3:72.
Example 2
A method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride specifically comprises the following steps:
1. and (2) supporting a catalyst: uniformly mixing a catalyst A and a catalyst B according to a mass ratio of 10:1 to obtain a mixed catalyst, and filling the mixed catalyst into the middle part of a tubular reactor with a filling amount of 30.5g;
the diameter of the tubular reactor is 20mm, and the length of the tubular reactor is 0.5m;
the preparation method of the catalyst A comprises the following steps: adding 1.5g of potassium permanganate, 4.2g of zinc nitrate, 2.1g of ferric nitrate, 0.61g of cerium nitrate and 970mL of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to be 25 ℃, stirring at 60rpm, stirring for 40min, adding 10.5g of SAPO-11 molecular sieve, increasing the temperature of the reaction kettle to 72 ℃, continuing stirring for 6.5h, centrifuging, controlling the rotating speed during centrifuging to 6200rpm, controlling the time to be 7.5min, cleaning the precipitate with deionized water for 2 times after centrifuging is finished, placing into a nitrogen atmosphere, and calcining for 1.6h at 410 ℃ to obtain a catalyst A;
the particle size of the SAPO-11 molecular sieve is 800nm, and the molar ratio of Si to P to Al is 0.5 to 1;
the preparation method of the catalyst B comprises the following steps: adding 7.2g of P123 template agent, 2g of hexadecyl trimethyl ammonium chloride, 24.5mL of absolute ethyl alcohol and 11.2mL of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 23 ℃, stirring at 60rpm, stirring for 35min, adding 1.6mL of glacial acetic acid and 1.2g of chitosan, stirring for 35min, adding 31mL of ethyl orthosilicate, continuing stirring for 22.5h, adding 10.5g of ZSM-5 molecular sieve, increasing the temperature of the reaction kettle to 75 ℃, continuing stirring for 10.5h, centrifuging, controlling the rotating speed at the centrifuging time to 6200rpm, controlling the time to 10.5min, cleaning the precipitate by using deionized water for 2 times, placing into a nitrogen atmosphere, calcining at 520 ℃ for 5.5h, then adding hydrochloric acid aqueous solution of 250mL of palladium chloride into the reaction kettle, controlling the temperature of the reaction kettle to 30 ℃, stirring at 200rpm, stirring for 2h, adding 14g of hydrazine hydrate, continuing stirring for 3h, controlling the rotating speed at the centrifuging time to 7000rpm, controlling the rotating speed at the centrifuging time to be 12min, drying the precipitate at the vacuum drying temperature of 70 MPa after the centrifuging is finished, and controlling the drying temperature of the vacuum catalyst to be at the vacuum drying time to be 6 MPa, and obtaining the vacuum catalyst after the vacuum drying time is finished;
the mass concentration of the palladium chloride in the hydrochloric acid aqueous solution of the palladium chloride is 3.5%, and the mass concentration of the hydrochloric acid is 3%;
the particle size of the ZSM-5 molecular sieve is 500nm, and the molar ratio of Si to Al is 100:1;
the micro-reaction device consists of 12 reaction plates, wherein the reaction plates are connected in series, the 1 st reaction plate is used for heat exchange of benzotrifluoride, the 2 nd reaction plate is used for heat exchange of nitrifying reagent, benzotrifluoride after heat exchange is mixed with nitrifying reagent in the 3 rd reaction plate, and then flows out after sequentially flowing through the 4 th to 12 th reaction plates, so that a benzotrifluoride nitro product is obtained;
the reaction channels of the reaction plates in the micro-reaction device are heart-shaped reaction channels, and each reaction channel of each reaction plate is formed by connecting 53 heart-shaped structures in series;
2. the reaction: the method comprises the steps of respectively preheating benzotrifluoride liquid and a nitrifying reagent, then simultaneously entering a tubular reactor, controlling the preheating temperature to be 120 ℃, controlling the feeding rate of benzotrifluoride to be 15mL/min, controlling the feeding rate of the nitrifying reagent to be 50mL/min, enabling the nitrifying reagent to be concentrated sulfuric acid and fuming nitric acid, enabling the volume ratio of the concentrated sulfuric acid to the fuming nitric acid to be 6:1, directly entering a 1 st reaction plate of a micro-reaction device after exiting the tubular reactor, controlling the temperature in the tubular reactor and the micro-reaction device to be 120 ℃, controlling the pressure to be 0.8MPa, sequentially passing through the 1 st-12 th reaction plates of the micro-reaction device, and then flowing out to obtain nitrobenzotrifluoride, wherein the reaction time in the micro-reaction device is 88s;
the mass concentration of the concentrated sulfuric acid is 98%;
the micro-reaction device consists of 12 reaction plates, the reaction plates are connected in series, the reaction channels of the reaction plates are heart-shaped reaction channels, and the reaction channels of each reaction plate are formed by connecting 53 heart-shaped structures in series;
after 120s of continuous operation, the samples were tested, and the total conversion of o-nitrobenzotrifluoride, m-nitrobenzotrifluoride, p-nitrobenzotrifluoride was 99.4% (calculated on the basis of benzotrifluoride), wherein the mass ratio of o-nitrobenzotrifluoride, m-nitrobenzotrifluoride, p-nitrobenzotrifluoride was 43:5:52.
Example 3
A method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride specifically comprises the following steps:
1. and (2) supporting a catalyst: uniformly mixing a catalyst A and a catalyst B according to a mass ratio of 11:1 to obtain a mixed catalyst, and filling the mixed catalyst into the middle part of a tubular reactor with a filling amount of 30.5g;
the diameter of the tubular reactor is 20mm, and the length of the tubular reactor is 0.5m;
the preparation method of the catalyst A comprises the following steps: adding 1.6g of potassium permanganate, 4.4g of zinc nitrate, 2.2g of ferric nitrate, 0.64g of cerium nitrate and 980mL of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to be 35 ℃, stirring at 80rpm for 50min, adding 11.5g of SAPO-11 molecular sieve, increasing the temperature of the reaction kettle to 85 ℃, continuing stirring for 6.8h, centrifuging, controlling the rotating speed during centrifuging to 6800rpm for 9min, cleaning a precipitate 3 times by using deionized water after centrifuging, placing into a nitrogen atmosphere, and calcining for 1.8h at 500 ℃ to obtain a catalyst A;
the particle size of the SAPO-11 molecular sieve is 800nm, and the molar ratio of Si to P to Al is 0.5 to 1;
the preparation method of the catalyst B comprises the following steps: adding 7.8g of P123 template agent, 2.1g of cetyltrimethylammonium chloride, 25mL of absolute ethyl alcohol and 11.5mL of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 30 ℃, stirring at 80rpm, stirring for 50min, adding 1.8mL of glacial acetic acid and 1g of chitosan, stirring for 35min, adding 31.5mL of tetraethoxysilane, continuing stirring for 24h, adding 11g of ZSM-5 molecular sieve, increasing the temperature of the reaction kettle to 78 ℃, continuing stirring for 11.5h, centrifuging, controlling the rotating speed at 6800rpm for 11.5min, cleaning the precipitate by using deionized water after centrifugation is finished for 2-3 times, placing into a nitrogen atmosphere, calcining at 540 ℃ for 5.5h, then adding hydrochloric acid aqueous solution of 240mL of palladium chloride into the reaction kettle, controlling the temperature of the reaction kettle to 20 ℃, stirring at 150rpm, stirring for 1.5h, adding 13g of hydrazine hydrate, continuing stirring for 2.5h, controlling the rotating speed at 6500rpm during centrifugation, controlling the centrifuging time at 11min, drying the precipitate at 0.07MPa after the end of centrifugation, and drying the precipitate under vacuum condition at the vacuum condition of vacuum condition, and drying the catalyst under vacuum condition of 0.07MPa, and obtaining the catalyst after the vacuum drying.
The mass concentration of the palladium chloride in the hydrochloric acid aqueous solution of the palladium chloride is 3.2%, and the mass concentration of the hydrochloric acid is 2.5%;
the particle size of the ZSM-5 molecular sieve is 500nm, and the molar ratio of Si to Al is 100:1;
the micro-reaction device consists of 12 reaction plates, wherein the reaction plates are connected in series, the 1 st reaction plate is used for heat exchange of benzotrifluoride, the 2 nd reaction plate is used for heat exchange of nitrifying reagent, benzotrifluoride after heat exchange is mixed with nitrifying reagent in the 3 rd reaction plate, and then flows out after sequentially flowing through the 4 th to 12 th reaction plates, so that a benzotrifluoride nitro product is obtained;
the reaction channels of the reaction plates in the micro-reaction device are heart-shaped reaction channels, and each reaction channel of each reaction plate is formed by connecting 53 heart-shaped structures in series;
2. the reaction: the method comprises the steps of respectively preheating benzotrifluoride liquid and a nitrifying reagent, then simultaneously entering a tubular reactor, controlling the preheating temperature to be 80 ℃, controlling the feeding rate of benzotrifluoride to be 30mL/min, controlling the feeding rate of the nitrifying reagent to be 88mL/min, enabling the nitrifying reagent to be concentrated sulfuric acid and fuming nitric acid, enabling the volume ratio of the concentrated sulfuric acid to the fuming nitric acid to be 5:1, directly entering a 1 st reaction plate of a micro-reaction device after exiting the tubular reactor, controlling the temperature in the tubular reactor and the micro-reaction device to be 80 ℃, controlling the pressure to be 0.4MPa, sequentially passing through the 1 st-12 th reaction plates of the micro-reaction device, and then flowing out to obtain nitrobenzotrifluoride, wherein the reaction time in the micro-reaction device is 48s;
the mass concentration of the concentrated sulfuric acid is 98%;
the micro-reaction device consists of 12 reaction plates, the reaction plates are connected in series, the reaction channels of the reaction plates are heart-shaped reaction channels, and the reaction channels of each reaction plate are formed by connecting 53 heart-shaped structures in series;
after 120s of continuous operation, the samples were tested, and the total conversion of o-nitrobenzotrifluoride, m-nitrobenzotrifluoride, p-nitrobenzotrifluoride was 99.1% (calculated on the basis of benzotrifluoride), wherein the mass ratio of o-nitrobenzotrifluoride, m-nitrobenzotrifluoride, p-nitrobenzotrifluoride was 67:8:23.
Example 4
A method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride specifically comprises the following steps:
1. and (2) supporting a catalyst: uniformly mixing a catalyst A and a catalyst B according to a mass ratio of 12:1 to obtain a mixed catalyst, and filling the mixed catalyst into the middle part of a tubular reactor with a filling amount of 30.5g;
the diameter of the tubular reactor is 20mm, and the length of the tubular reactor is 0.5m;
the preparation method of the catalyst A comprises the following steps: adding 1.6g of potassium permanganate, 4.5g of zinc nitrate, 2.2g of ferric nitrate, 0.65g of cerium nitrate and 1000mL of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to be 40 ℃, stirring at 100rpm, stirring for 60min, adding 12g of SAPO-11 molecular sieve, increasing the temperature of the reaction kettle to 90 ℃, continuing stirring for 7h, centrifuging, controlling the rotating speed during centrifuging to be 7000rpm, controlling the time to be 10min, cleaning the precipitate with deionized water for 3 times after centrifuging, putting into nitrogen atmosphere, and calcining for 2h at 500 ℃ to obtain a catalyst A;
the particle size of the SAPO-11 molecular sieve is 800nm, and the molar ratio of Si to P to Al is 0.5 to 1;
the preparation method of the catalyst B comprises the following steps: adding 8g of P123 template agent, 2.2g of hexadecyl trimethyl ammonium chloride, 26mL of absolute ethyl alcohol and 12mL of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 35 ℃, stirring at a speed of 100rpm, stirring for 60min, adding 2mL of glacial acetic acid and 1.1g of chitosan, stirring for 40min, adding 32mL of tetraethoxysilane, continuing stirring for 25h, adding 12g of ZSM-5 molecular sieve, increasing the temperature of the reaction kettle to 80 ℃, continuing stirring for 12h, centrifuging, controlling the rotating speed at the centrifuging time to 7000rpm, controlling the time to 12min, cleaning the precipitate by using deionized water for 3 times after centrifuging, placing the precipitate into nitrogen atmosphere, calcining at 550 ℃ for 6h, adding 245mL of hydrochloric acid aqueous solution of palladium chloride into the reaction kettle, controlling the temperature of the reaction kettle to 25 ℃, stirring at a speed of 150rpm, stirring for 2h, adding 13.5g of hydrazine hydrate, continuing stirring for 2.5h, controlling the rotating speed at the centrifuging time to 6500rpm, vacuum drying the precipitate after centrifuging, controlling the temperature of 65 MPa, controlling the vacuum drying time to be 0.08MPa, and vacuum drying the catalyst to be obtained after the centrifuging is finished;
the mass concentration of the palladium chloride in the hydrochloric acid aqueous solution of the palladium chloride is 3.4%, and the mass concentration of the hydrochloric acid is 2%;
the particle size of the ZSM-5 molecular sieve is 500nm, and the molar ratio of Si to Al is 100:1;
the micro-reaction device consists of 12 reaction plates, wherein the reaction plates are connected in series, the 1 st reaction plate is used for heat exchange of benzotrifluoride, the 2 nd reaction plate is used for heat exchange of nitrifying reagent, benzotrifluoride after heat exchange is mixed with nitrifying reagent in the 3 rd reaction plate, and then flows out after sequentially flowing through the 4 th to 12 th reaction plates, so that a benzotrifluoride nitro product is obtained;
the reaction channels of the reaction plates in the micro-reaction device are heart-shaped reaction channels, and each reaction channel of each reaction plate is formed by connecting 53 heart-shaped structures in series;
2. the reaction: the method comprises the steps of respectively preheating benzotrifluoride liquid and a nitrifying reagent, then simultaneously entering a tubular reactor, controlling the preheating temperature to be 50 ℃, controlling the feeding rate of benzotrifluoride to be 38mL/min, controlling the feeding rate of the nitrifying reagent to be 74mL/min, enabling the nitrifying reagent to be concentrated sulfuric acid and fuming nitric acid, enabling the volume ratio of the concentrated sulfuric acid to the fuming nitric acid to be 3:1, directly entering a 1 st reaction plate of a micro-reaction device after exiting the tubular reactor, controlling the temperature in the tubular reactor and the micro-reaction device to be 50 ℃, controlling the pressure to be 0.2MPa, sequentially passing through the 1 st-12 th reaction plates of the micro-reaction device, and then flowing out to obtain nitrobenzotrifluoride, wherein the reaction time in the micro-reaction device is 51s;
the mass concentration of the concentrated sulfuric acid is 98%;
the micro-reaction device consists of 12 reaction plates, the reaction plates are connected in series, the reaction channels of the reaction plates are heart-shaped reaction channels, and the reaction channels of each reaction plate are formed by connecting 53 heart-shaped structures in series;
after 120s of continuous operation, the samples were tested, and the total conversion of ortho-, meta-, and para-nitrobenzotrifluoride was 98.9% (calculated on the basis of benzotrifluoride), with the mass ratio of ortho-, meta-, and para-nitrobenzotrifluoride being 42:31:27.
Example 5
A method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride specifically comprises the following steps:
1. and (2) supporting a catalyst: uniformly mixing a catalyst A and a catalyst B according to a mass ratio of 12:1 to obtain a mixed catalyst, and filling the mixed catalyst into the middle part of a tubular reactor with a filling amount of 30g;
the diameter of the tubular reactor is 20mm, and the length of the tubular reactor is 0.5m;
the preparation method of the catalyst A comprises the following steps: adding 1.6g of potassium permanganate, 4.5g of zinc nitrate, 2.2g of ferric nitrate, 0.65g of cerium nitrate and 1000mL of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to be 40 ℃, stirring at 100rpm, stirring for 60min, adding 12g of SAPO-11 molecular sieve, increasing the temperature of the reaction kettle to 90 ℃, continuing stirring for 7h, centrifuging, controlling the rotating speed during centrifuging to be 7000rpm, controlling the time to be 10min, cleaning the precipitate with deionized water for 3 times after centrifuging, putting into nitrogen atmosphere, and calcining for 2h at 500 ℃ to obtain a catalyst A;
the particle size of the SAPO-11 molecular sieve is 800nm, and the molar ratio of Si to P to Al is 0.5 to 1;
the preparation method of the catalyst B comprises the following steps: adding 8g of P123 template agent, 2.2g of hexadecyl trimethyl ammonium chloride, 26mL of absolute ethyl alcohol and 12mL of deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 35 ℃, stirring at 100rpm, stirring for 60min, adding 1.9mL of glacial acetic acid and 1.2g of chitosan, stirring for 40min, adding 32mL of tetraethoxysilane, continuing stirring for 25h, adding 11g of ZSM-5 molecular sieve, increasing the temperature of the reaction kettle to 80 ℃, continuing stirring for 12h, centrifuging, controlling the rotating speed at 7000rpm for 12min, cleaning the precipitate with deionized water for 3 times after centrifuging, placing into nitrogen atmosphere, calcining at 550 ℃ for 6h, adding hydrochloric acid aqueous solution of 250mL of palladium chloride into the reaction kettle, controlling the temperature of the reaction kettle to 30 ℃, stirring at 200rpm, stirring for 2h, adding 14g of hydrazine hydrate, continuing stirring for 2.5h, controlling the rotating speed at 7000rpm for 12min, vacuum drying the precipitate after centrifuging, controlling the temperature at 70 MPa for 0.08MPa, and vacuum drying for 6h to obtain the catalyst;
the mass concentration of the palladium chloride in the hydrochloric acid aqueous solution of the palladium chloride is 3.5%, and the mass concentration of the hydrochloric acid is 3%;
the particle size of the ZSM-5 molecular sieve is 500nm, and the molar ratio of Si to Al is 100:1;
the micro-reaction device consists of 12 reaction plates, wherein the reaction plates are connected in series, the 1 st reaction plate is used for heat exchange of benzotrifluoride, the 2 nd reaction plate is used for heat exchange of nitrifying reagent, benzotrifluoride after heat exchange is mixed with nitrifying reagent in the 3 rd reaction plate, and then flows out after sequentially flowing through the 4 th to 12 th reaction plates, so that a benzotrifluoride nitro product is obtained;
the reaction channels of the reaction plates in the micro-reaction device are heart-shaped reaction channels, and each reaction channel of each reaction plate is formed by connecting 53 heart-shaped structures in series;
2. the reaction: the method comprises the steps of respectively preheating benzotrifluoride liquid and a nitrifying reagent, then simultaneously entering a tubular reactor, controlling the preheating temperature to be 40 ℃, controlling the feeding rate of benzotrifluoride to be 42mL/min, controlling the feeding rate of the nitrifying reagent to be 62mL/min, enabling the nitrifying reagent to be concentrated sulfuric acid and fuming nitric acid, enabling the volume ratio of the concentrated sulfuric acid to the fuming nitric acid to be 2:1, directly entering a 1 st reaction plate of a micro-reaction device after exiting the tubular reactor, controlling the temperature in the tubular reactor and the micro-reaction device to be 40 ℃, controlling the pressure to be 0.1MPa, sequentially passing through the 1 st-12 th reaction plates of the micro-reaction device, and then flowing out to obtain nitrobenzotrifluoride, wherein the reaction time in the micro-reaction device is 55s;
the mass concentration of the concentrated sulfuric acid is 98%;
the micro-reaction device consists of 12 reaction plates, the reaction plates are connected in series, the reaction channels of the reaction plates are heart-shaped reaction channels, and the reaction channels of each reaction plate are formed by connecting 53 heart-shaped structures in series;
after 120s of continuous operation, the samples were tested for a total conversion of 98.5% of ortho-, meta-, and para-nitrobenzotrifluoride (calculated on benzotrifluoride basis), with a mass ratio of 29:60:11.
Comparative example 1
A method for producing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride in the same manner as in example 1 except that the step 1 supported catalyst was omitted, i.e., the mixed catalyst was not packed in the tubular reactor;
after 120s of continuous operation, the samples were tested for a total conversion of 96.7% of ortho-, meta-, and para-nitrobenzotrifluoride (calculated on the basis of benzotrifluoride), with a mass ratio of 17:71:12.
Comparative example 2
A method for producing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride in the same manner as in example 2 except that the step 1 supported catalyst was omitted, i.e., the mixed catalyst was not packed in the tubular reactor;
after 120s of continuous operation, the samples were tested, and the total conversion of ortho-, meta-, and para-nitrobenzotrifluoride was 96.2% (calculated on benzotrifluoride basis), with the mass ratio of ortho-, meta-, and para-nitrobenzotrifluoride being 15:76:9.
Comparative example 3
A method for producing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride in the same manner as in example 3 except that the step 1 supported catalyst was omitted, i.e., the mixed catalyst was not packed in the tubular reactor;
after 120s of continuous operation, the samples were tested, and the total conversion of ortho-, meta-, and para-nitrobenzotrifluoride was 95.8% (calculated on benzotrifluoride basis), with the mass ratio of ortho-, meta-, and para-nitrobenzotrifluoride being 12:82:6.
Comparative example 4
A method for producing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride in the same manner as in example 4 except that the step 1 supported catalyst was omitted, i.e., the mixed catalyst was not packed in the tubular reactor;
after 120s of continuous operation, the samples were tested, and the total conversion of ortho-, meta-, and para-nitrobenzotrifluoride was 95.1% (calculated on the basis of benzotrifluoride), with the mass ratio of ortho-, meta-, and para-nitrobenzotrifluoride being 10:84:6.
Comparative example 5
A method for producing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride in the same manner as in example 5 except that the step 1 supported catalyst was omitted, i.e., the mixed catalyst was not packed in the tubular reactor;
after 120s of continuous operation, the samples were tested, and the total conversion of o-nitrobenzotrifluoride, m-nitrobenzotrifluoride, p-nitrobenzotrifluoride was 94.8% (calculated on the basis of benzotrifluoride), wherein the mass ratio of o-nitrobenzotrifluoride, m-nitrobenzotrifluoride, p-nitrobenzotrifluoride was 9:87:4.
Comparative example 6
The same method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride as in example 1 is adopted, except that the use of a slight reaction device is omitted, a tubular reactor is changed to be connected in series by two reaction tubes, the diameter of the tubular reactor is 20mm, the length of each reaction tube is 0.5m, and only the middle part of the first reaction tube is filled with catalyst, and the filling amount of the catalyst is unchanged;
after 120s of continuous operation, the samples were tested, and the total conversion of ortho-, meta-, and para-nitrobenzotrifluoride was 93.1% (calculated on benzotrifluoride basis), with the mass ratio of ortho-, meta-, and para-nitrobenzotrifluoride being 28:5:67.
Comparative example 7
The same method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride as in example 2 is adopted, except that the use of a slight reaction device is omitted, a tubular reactor is changed to be connected in series by two reaction tubes, the diameter of the tubular reactor is 20mm, the length of each reaction tube is 0.5m, and only the middle part of the first reaction tube is filled with catalyst, and the filling amount of the catalyst is unchanged;
after 120s of continuous operation, the samples were tested, and the total conversion of ortho-, meta-, and para-nitrobenzotrifluoride was 93.0% (calculated on benzotrifluoride basis), with the mass ratio of ortho-, meta-, and para-nitrobenzotrifluoride being 47:8:45.
Comparative example 8
The same method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride as in example 3 is adopted, except that the use of a slight reaction device is omitted, a tubular reactor is changed to be connected in series by two reaction tubes, the diameter of the tubular reactor is 20mm, the length of each reaction tube is 0.5m, and only the middle part of the first reaction tube is filled with catalyst, and the filling amount of the catalyst is unchanged;
after 120s of continuous operation, the samples were tested, and the total conversion of ortho-, meta-, and para-nitrobenzotrifluoride was 92.8% (calculated on benzotrifluoride basis), with the mass ratio of ortho-, meta-, and para-nitrobenzotrifluoride being 62:13:25.
Comparative example 9
The same method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride as in example 4 is adopted, except that the use of a slight reaction device is omitted, a tubular reactor is changed to be connected in series by two reaction tubes, the diameter of the tubular reactor is 20mm, the length of each reaction tube is 0.5m, and only the middle part of the first reaction tube is filled with catalyst, and the filling amount of the catalyst is unchanged;
after 120s of continuous operation, the samples were tested, and the total conversion of ortho-, meta-, and para-nitrobenzotrifluoride was 92.4% (calculated on benzotrifluoride basis), with the mass ratio of ortho-, meta-, and para-nitrobenzotrifluoride being 40:37:23.
Comparative example 10
The same method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride as in example 5 is adopted, except that the use of a slight reaction device is omitted, a tubular reactor is changed to be connected in series by two reaction tubes, the diameter of the tubular reactor is 20mm, the length of each reaction tube is 0.5m, and only the middle part of the first reaction tube is filled with catalyst, and the filling amount of the catalyst is unchanged;
after 120s of continuous operation, the samples were tested, and the total conversion of ortho-, meta-, and para-nitrobenzotrifluoride was 92.1% (calculated on the basis of benzotrifluoride), with the mass ratio of ortho-, meta-, and para-nitrobenzotrifluoride being 21:71:8.
Comparative example 11
The same method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride as in example 1 was adopted, except that the use of a slight reaction apparatus was omitted, and the diameter, length, type of catalyst packed, and amount of catalyst packed of the tubular reactor were unchanged;
after 120s of continuous operation, the samples were tested for a total conversion of 57.2% of ortho-, meta-, and para-nitrobenzotrifluoride (calculated on benzotrifluoride basis), with a mass ratio of 25:11:64.
Comparative example 12
The same method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride as in example 2 was adopted, except that the use of a slight reaction apparatus was omitted, and the diameter, length, type of catalyst packed, and amount of catalyst packed of the tubular reactor were unchanged;
after 120s of continuous operation, the samples were tested for a total conversion of 57.0% of ortho-, meta-, and para-nitrobenzotrifluoride (calculated on benzotrifluoride basis), with a mass ratio of 41:17:42.
Comparative example 13
The same method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride as in example 3 was adopted, except that the use of a slight reaction apparatus was omitted, and the diameter, length, type of catalyst packed, and amount of catalyst packed of the tubular reactor were unchanged;
after 120s of continuous operation, the samples were tested, and the total conversion of ortho-, meta-, and para-nitrobenzotrifluoride was 56.7% (calculated on the basis of benzotrifluoride), with the mass ratio of ortho-, meta-, and para-nitrobenzotrifluoride being 55:25:20.
Comparative example 14
The same method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride as in example 4 was employed, except that the use of a slight reaction apparatus was omitted, and the diameter, length, type of catalyst packed, and amount of catalyst packed of the tubular reactor were unchanged;
after 120s of continuous operation, the samples were tested for a total conversion of 56.6% of ortho-, meta-, and para-nitrobenzotrifluoride (calculated on benzotrifluoride basis), with a mass ratio of 31:52:17.
Comparative example 15
The same method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride as in example 5 is adopted, except that the use of a slight reaction device is omitted, and the diameter, the length, the type of the catalyst to be packed and the packing amount of the catalyst of the tubular reactor are unchanged;
after 120s of continuous operation, the samples were tested, and the total conversion of ortho-, meta-, and para-nitrobenzotrifluoride was 56.1% (calculated on the basis of benzotrifluoride), with the mass ratio of ortho-, meta-, and para-nitrobenzotrifluoride being 13:84:3.
It can be seen from the test results of examples 1 to 5 and comparative examples 1 to 15 that the mass ratio of the ortho-nitrobenzotrifluoride, the meta-nitrobenzotrifluoride and the para-nitrobenzotrifluoride can be adjusted by filling the catalyst into the tubular reaction and adjusting the feed rate, the reaction temperature and the reaction pressure of the raw materials in the reaction, and the total conversion rate can be improved; the tubular reactor is connected with the micro-reaction device in series, so that the reaction time can be shortened, and the total conversion rate can be improved;
the mixed catalyst consists of a catalyst A and a catalyst B, wherein the catalyst A is zinc oxide and iron oxide which are obtained by carrying out hydrothermal synthesis and calcination on potassium permanganate, zinc nitrate, iron nitrate and cerium nitrate, and can catalyze and improve the contact area with reaction raw materials; the catalyst B is a structure which takes ZSM-5 molecular sieve as a core and porous silicon dioxide as a shell and is formed by fully coating and calcining the ZSM-5 molecular sieve after mixing a mixed solution of tetraethoxysilane and chitosan with the ZSM-5 molecular sieve, and palladium chloride is adsorbed by the coated ZSM-5 molecular sieve and then reduced by hydrazine hydrate, so that the palladium catalyst is loaded in the pores of the silicon dioxide; during the reaction, zinc oxide, ferric oxide and palladium can catalyze, so that the substitution efficiency of ortho-position and meta-position is improved, and the influence of the feeding rate, the reaction temperature and the reaction pressure is great during the substitution, so that the mass ratio of ortho-nitrobenzotrifluoride, meta-nitrobenzotrifluoride and para-nitrobenzotrifluoride in the product can be adjusted through the feeding rate, the reaction temperature and the reaction pressure; the tubular reactor is connected with the micro-reaction device in series, so that mass transfer and heat transfer can be performed by utilizing the micro-scale flow channel of the micro-reaction device, the reaction conversion rate is improved, the mixed catalyst is filled in the tubular reactor in advance, and the problem that the micro-reaction device is blocked due to the fact that the mixed catalyst, benzotrifluoride and a nitrifying reagent are introduced into the micro-reaction device together can be avoided.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride, which is characterized by comprising the following steps: loading a catalyst and reacting;
the catalyst A and the catalyst B are uniformly mixed according to the mass ratio of 10-12:1 to obtain a mixed catalyst, and the mixed catalyst is filled in the middle part of the tubular reactor with the filling amount of 30-31g;
the preparation method of the catalyst A comprises the steps of adding potassium permanganate, zinc nitrate, ferric nitrate, cerium nitrate and deionized water into a reaction kettle, controlling the temperature of the reaction kettle to be 20-40 ℃, stirring, adding a SAPO-11 molecular sieve, increasing the temperature of the reaction kettle to 70-90 ℃, continuing stirring, centrifuging, cleaning a precipitate, and calcining at 400-500 ℃ in a nitrogen atmosphere to obtain the catalyst A;
adding a P123 template agent, cetyl trimethyl ammonium chloride, absolute ethyl alcohol and deionized water into a reaction kettle, controlling the temperature of the reaction kettle to 20-35 ℃, stirring, adding glacial acetic acid and chitosan, stirring, adding tetraethoxysilane, continuously stirring, adding a ZSM-5 molecular sieve, increasing the temperature of the reaction kettle to 70-80 ℃, continuously stirring, centrifuging, cleaning a precipitate, placing the precipitate into a nitrogen atmosphere, calcining at 500-550 ℃, then adding the precipitate and a hydrochloric acid aqueous solution of palladium chloride into the reaction kettle, controlling the temperature of the reaction kettle to 15-30 ℃, stirring, adding hydrazine hydrate, continuously stirring, centrifuging, and vacuum drying the precipitate to obtain a catalyst B;
the method comprises the steps of respectively preheating benzotrifluoride liquid and a nitrifying reagent, then simultaneously entering a tubular reactor, controlling the preheating temperature to be 40-140 ℃, controlling the feeding rate of benzotrifluoride to be 11-42mL/min, controlling the feeding rate of the nitrifying reagent to be 47-88mL/min, enabling the nitrifying reagent to be concentrated sulfuric acid and fuming nitric acid, enabling the volume ratio of the concentrated sulfuric acid to the fuming nitric acid to be 2-8:1, directly entering a 1 st reaction plate of a micro-reaction device after exiting from the tubular reactor, controlling the temperature in the tubular reactor and the micro-reaction device to be 40-140 ℃, controlling the pressure to be 0.1-1MPa, and then sequentially flowing out after passing through the 1 st-12 reaction plates of the micro-reaction device, so as to obtain benzotrifluoride nitrate, wherein the reaction time in the micro-reaction device is 48-98s.
2. The method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride according to claim 1, wherein in the preparation of the catalyst A, the mass-volume ratio of potassium permanganate, zinc nitrate, ferric nitrate, cerium nitrate, deionized water and SAPO-11 molecular sieve is 1.5-1.6g:4-4.5g:2-2.2g:0.6-0.65g:950-1000mL:10-12g;
the particle size of the SAPO-11 molecular sieve is 800nm, and the molar ratio of Si to P to Al is 0.5 to 1.
3. The method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride according to claim 1, wherein in the preparation of the catalyst B, the mass volume ratio of a P123 template agent, cetyltrimethylammonium chloride, absolute ethyl alcohol, deionized water, glacial acetic acid, chitosan, tetraethoxysilane, ZSM-5 molecular sieve, aqueous hydrochloric acid solution of palladium chloride and hydrazine hydrate is 7-8g:2-2.2g:24-26mL:11-12mL:1.5-2mL:1-1.2g:30-32mL:10-12g:230-250mL:12-14g;
the mass concentration of the palladium chloride in the hydrochloric acid aqueous solution of the palladium chloride is 3-3.5%, and the mass concentration of the hydrochloric acid is 2-3%;
the particle size of the ZSM-5 molecular sieve is 500nm, and the molar ratio of Si to Al is 100:1.
4. The method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride according to claim 1, wherein the mass concentration of the concentrated sulfuric acid is 98%.
5. The method for preparing nitrobenzotrifluoride by continuously nitrifying benzotrifluoride according to claim 1, wherein the diameter of the tubular reactor is 20mm and the length is 0.5m;
the micro-reaction device consists of 12 reaction plates, the reaction plates are connected in series, the reaction channels of the reaction plates are heart-shaped reaction channels, and the reaction channels of each reaction plate are formed by connecting 53 heart-shaped structures in series.
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