CN114621095A - Clean nitrochlorobenzene production process - Google Patents
Clean nitrochlorobenzene production process Download PDFInfo
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- CN114621095A CN114621095A CN202210203420.4A CN202210203420A CN114621095A CN 114621095 A CN114621095 A CN 114621095A CN 202210203420 A CN202210203420 A CN 202210203420A CN 114621095 A CN114621095 A CN 114621095A
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- nitrochlorobenzene
- acid catalyst
- solid acid
- drying
- clean
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- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 70
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000011973 solid acid Substances 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 39
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000010457 zeolite Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 31
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000006396 nitration reaction Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 230000000802 nitrating effect Effects 0.000 claims abstract description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 238000007873 sieving Methods 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 239000007791 liquid phase Substances 0.000 claims description 16
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 claims description 14
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000005416 organic matter Substances 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 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 4
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 claims description 3
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- CELCMWUXMBTJRP-UHFFFAOYSA-N chlorobenzene;hydrochloride Chemical compound Cl.ClC1=CC=CC=C1 CELCMWUXMBTJRP-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002250 absorbent Substances 0.000 abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 6
- 238000004062 sedimentation Methods 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 239000000575 pesticide Substances 0.000 abstract description 4
- 230000002745 absorbent Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000004964 aerogel Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 2
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000004965 Silica aerogel Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000006198 methoxylation reaction Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of pesticide synthesis, and particularly discloses a process for clean production of nitrochlorobenzene, which comprises the steps of reacting chlorobenzene, a nitrating agent, a water absorbent and a modified solid acid catalyst in carbon tetrachloride to generate a nitrochlorobenzene mixture, obtaining the nitrochlorobenzene through filtering sedimentation, acid-base neutralization, washing drying and crystallization rectification, preparing zirconium oxychloride into an aqueous solution, cleaning artificial zeolite powder, adding the artificial zeolite powder into the aqueous solution, uniformly mixing, dropwise adding ammonia water, uniformly stirring, standing, aging and drying, heating, grinding and sieving the obtained product to obtain a powder material, adding the powder material into silica sol, uniformly mixing, adjusting the pH value to form gel, and freeze-drying the gel to form the modified solid acid catalyst; the chlorobenzene nitration reaction does not adopt heavy-pollution and strong-corrosion reaction substances such as sulfuric acid and nitric acid and the like, so that the chlorobenzene nitration reaction is more friendly to reaction equipment and environment, and the yield and the reaction speed are not inferior to those of a mixed acid reaction.
Description
Technical Field
The invention relates to the technical field of pesticide synthesis, in particular to a clean nitrochlorobenzene production process.
Background
Nitrochlorobenzene is an intermediate of many fine chemical products such as medicines, pesticides, dyes and the like. The nitrochlorobenzene is produced by using chlorobenzene as an original family, using mixed acid of nitric acid and sulfuric acid as a nitrating agent for nitration, and obtaining p-nitrochlorobenzene and o-nitrochlorobenzene by alkali washing and water washing of a crude product obtained by nitration and then separating and purifying by a rectifying tower.
The o-nitrochlorobenzene, the p-nitrochlorobenzene and the derivative products thereof, i.e. the p-nitroanisole, are important intermediates of dyes, medicines, pesticides and spices, and the main production route is as follows: the chlorobenzene is subjected to nitration reaction at a certain temperature and under a certain pressure to generate a nitrochlorobenzene mixture which comprises three isomers, wherein the nitrochlorobenzene accounts for 65 percent, the o-nitrochlorobenzene accounts for 32 percent and the m-nitrochlorobenzene accounts for 1 percent, and the nitrochlorobenzene mixture is separated and purified by adopting a method of rectification and crystalline phase combination to obtain the o-nitrochlorobenzene and the p-nitrochlorobenzene. Further, the p-nitrochlorobenzene and the methanol solution of sodium hydroxide are subjected to methoxylation reaction to generate p-nitroanisole.
In the process of separating the nitrochlorobenzene mixture, the intermediate nitrochlorobenzene composed of nitrochlorobenzene obtained from nitration reaction is only 1 percent, cannot be separated independently, and can only circulate in an operation system along with nitrochlorobenzene co-dissolved oil, and the m-nitrochlorobenzene is gradually enriched along with the increase of the circulation times, so that in order to ensure that the content of the m-nitrochlorobenzene in the p-nitrochlorobenzene product does not exceed the standard, when the concentration of the m-nitrochlorobenzene in the mixed nitrochlorobenzene reaches 12 to 13 percent, a part of the nitrochlorobenzene is required to be discharged. In the industry, m-nitrochlorobenzene in the mixture is generally concentrated to 20-45% and then is discarded, and the m-nitrochlorobenzene is called as m-nitrochlorobenzene oil.
In the prior art, nitric acid and sulfuric acid with high concentration are mostly adopted for preparing nitrochlorobenzene as a nitrating agent and a catalyst, the method is simple and easy to implement, but reactants, intermediate products and final products all contain a large amount of toxic and harmful components, and a lot of cost is additionally increased in discharge and recovery, for example, the preparation method of the high-purity nitrochlorobenzene, disclosed by application number 202110307845.5, adopts mixed acid prepared from the nitric acid and the sulfuric acid for synthesizing the nitrochlorobenzene;
solid acid as a mature catalytic substance can also play a good catalytic effect in the process of producing nitrochlorobenzene, however, the nitrochlorobenzene needs to be stirred sufficiently and rapidly to promote the reaction due to the problems of large heat production and low reactant solubility in the production, so that the solid catalyst is often crushed in the process, which is not convenient for the recovery and use of the catalyst and also can damage equipment.
Disclosure of Invention
The invention aims to provide a clean nitrochlorobenzene production process, which solves the following technical problems:
(1) the nitrating agent and the catalyst adopted in the prior art are heavy pollution and strong corrosion problems caused by nitric acid and sulfuric acid;
(2) solves the problem that the solid catalyst is easy to be stirred and crushed at high speed and difficult to be recycled in the reaction.
The purpose of the invention can be realized by the following technical scheme:
a clean production process of nitrochlorobenzene comprises the steps of reacting chlorobenzene, a nitrating agent, a water absorbent and a modified solid acid catalyst to generate a nitrochlorobenzene mixture;
the modified solid acid catalyst is prepared by the following steps:
s1, preparing zirconium oxychloride into an aqueous solution, cleaning the artificial zeolite powder, adding the cleaned artificial zeolite powder into the aqueous solution, uniformly mixing, dropwise adding ammonia water into the aqueous solution until the pH value of the solution is 3-6, uniformly stirring, standing and aging for 6-10 hours;
s2, drying the solution after S1 standing at the temperature of 100-220 ℃, heating the obtained product at the temperature of 630-680 ℃ for 2-3h, and grinding and sieving to obtain a powder material;
s3, mixing materials: adding the powder material obtained in the step S2 into silica sol, uniformly mixing, and adjusting the pH value to 8-11 to form gel;
s4, drying: freeze drying the gel obtained in S3 to form a solid acid catalyst;
s5, modification: and (3) adding the solid acid catalyst obtained in the step (S4) into anhydrous ethanol containing a silane coupling agent, stirring uniformly, standing, adding high-molecular water-absorbing resin, fully reacting, and drying to obtain the modified solid acid catalyst.
The application adopts a zirconium oxychloride sedimentation method to prepare zirconium hydroxide hydrosol, artificial zeolite powder is added before the solution is dissolved, the dispersion coefficient of the artificial zeolite powder in the solution is improved, a stable sol system is conveniently and jointly formed, the sol is dried and heated in S2, the artificial zeolite powder with zirconium oxide modified on the surface is finally obtained, the obtained artificial zeolite powder is added into silica sol, freeze drying is carried out to obtain aerogel adsorbing the artificial zeolite powder, namely the modified solid acid catalyst, the catalyst carrier is aerogel, the surface area is large, more catalysts can be carried, the artificial zeolite powder modified by zirconium oxide can cooperate with zirconium dioxide besides the catalytic performance of the artificial zeolite powder, the reaction rate and the yield of nitrochlorobenzene are jointly improved, meanwhile, carbon tetrachloride serving as a polar solvent can promote the polar chlorobenzene and the nitrochlorobenzene to be dissolved to improve the reaction rate, meanwhile, the artificial zeolite can easily attract polar groups to promote the reaction;
the silane coupling agent is adopted to combine the high-molecular water-absorbent resin with the solid acid catalyst taking silicon dioxide as a framework, the reaction of generated water is carried out on the solid acid, so that the water absorption efficiency of the reaction can be effectively improved, the high-molecular water-absorbent resin can also play a good buffering effect after absorbing water, finally, the expanded high-molecular water-absorbent resin can also be used as an excellent representation of the reaction progress in terms of a liquid phase or a broken solid phase dispersed in a reaction system, and the expanded modified solid acid catalyst can also be better separated and recovered after the reaction is finished.
As a further scheme of the invention: the production process of the present application further comprises the steps of:
filtering and settling: filtering the liquid phase after reaction to obtain a modified solid acid catalyst, placing the filtrate in a settling kettle for settling, and separating out a nitrochlorobenzene mixture;
acid-base neutralization: adding an alkaline reagent into the acidic nitrochlorobenzene mixture to adjust the pH value;
washing and drying: washing and drying the neutralized nitrochlorobenzene mixture for many times to obtain a crude nitrochlorobenzene mixture;
and (3) crystallization and rectification: crystallizing the dried crude nitrochlorobenzene mixture, separating out p-nitrochlorobenzene crystals, transferring the liquid phase into a rectifying tower, and rectifying and separating out carbon tetrachloride, meta-position oil rich in m-nitrochlorobenzene, o-nitrochlorobenzene and high-boiling-point organic matter waste liquid.
This application can be filtered modified solid acid catalyst and get to put into use once more after the reaction, and the carbon tetrachloride that the solvent adopted is difficult for mixing with the big difference of product boiling point, is convenient for retrieve and put into use once more.
As a further scheme of the invention: the nitrating agent is one of ferric nitrate or cupric nitrate.
As a further scheme of the invention: the particle size of the artificial zeolite powder is 10-300 mu m.
As a further scheme of the invention: the solution in S2 is kept under ultrasonic wave when being dried.
As a further scheme of the invention: the product obtained by heating in S2 is ground and sieved with 300-400 meshes.
As a further scheme of the invention: the mass of the powder material is 1-4% of the mass of the silica sol; the mass ratio of the artificial zeolite powder to the zirconium dioxide is 0.5-1.7: 0.3-1.2.
As a further scheme of the invention: the dosage of the modified solid acid catalyst in the nitration reaction is 50-200% of the mass of chlorobenzene.
As a further scheme of the invention: the high-molecular water-absorbing resin is one of polyacrylic resin, polyacrylamide resin or acrylic acid-acrylamide copolymer resin, and the mass of the high-molecular water-absorbing resin is 5-42% of that of the nitrating agent.
As a further scheme of the invention: in the preparation of the modified solid acid catalyst, the solid acid catalyst is obtained in step S4 and then is crushed into particles of 5-50 meshes.
The invention has the beneficial effects that:
(1) the chlorobenzene nitration reaction does not adopt heavy-pollution and strong-corrosion reaction substances such as sulfuric acid and nitric acid, so that the chlorobenzene nitration reaction is more friendly to reaction equipment and environment, and the yield and the reaction speed are not inferior to those of a mixed acid reaction.
(2) The application adopts a zirconium oxychloride sedimentation method to prepare zirconium hydroxide hydrosol, artificial zeolite powder is added before the solution is dissolved, the dispersion coefficient of the artificial zeolite powder in the solution is improved, a stable sol system is conveniently and jointly formed, the sol is dried and heated in S2, the artificial zeolite powder with zirconium oxide modified on the surface is finally obtained, the obtained artificial zeolite powder is added into silica sol, freeze drying is carried out to obtain aerogel adsorbing the artificial zeolite powder, namely the modified solid acid catalyst, the catalyst carrier is aerogel, the surface area is large, more catalysts can be carried, the artificial zeolite powder modified by zirconium oxide can cooperate with zirconium dioxide besides the catalytic performance of the artificial zeolite powder, the reaction rate and the yield of nitrochlorobenzene are jointly improved, meanwhile, carbon tetrachloride serving as a polar solvent can promote the polar chlorobenzene and the nitrochlorobenzene to be dissolved to improve the reaction rate, meanwhile, the artificial zeolite can easily attract polar groups to promote the reaction, silica components contained in the artificial zeolite can form silica bonds in silica sol to improve the binding force of the artificial zeolite and the silica sol, and the silica sol can be tightly connected to form silica aerogel to improve the adhesive force of the catalyst on a carrier; the silane coupling agent is adopted to combine the high-molecular water-absorbent resin with the solid acid catalyst taking silicon dioxide as a framework, the reaction of generated water is carried out on the solid acid, so that the water absorption efficiency of the reaction can be effectively improved, the high-molecular water-absorbent resin can also play a good buffering effect after absorbing water, finally, the expanded high-molecular water-absorbent resin can also be used as an excellent representation of the reaction progress in terms of a liquid phase or a broken solid phase dispersed in a reaction system, and the expanded modified solid acid catalyst can also be better separated and recovered after the reaction is finished.
(3) The carbon tetrachloride and the modified solid acid catalyst adopted by the application can be recovered after the chlorobenzene nitration, thereby saving materials and better realizing the purpose of clean production.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The artificial zeolite used in the following examples and comparative examples of this application was 1318-02-1Permutit CP, 97 artificial zeolite available from Shanghai-derived leaf Biotech Co.
The pH value regulator is 2 wt% ammonia water.
Example 1
The modified solid acid catalyst is prepared by the following steps:
s1, preparing zirconium oxychloride into an aqueous solution, cleaning artificial zeolite powder with the particle size of 10 microns, adding the artificial zeolite powder into the aqueous solution, uniformly mixing, dropwise adding ammonia water into the aqueous solution until the pH value of the solution is 3, uniformly stirring, standing and aging for 10 hours;
s2, drying the solution after S1 is kept still at 100 ℃, heating the obtained product at 680 ℃ for 2 hours, and grinding the product through a 400-mesh sieve to obtain a powder material;
s3, mixing materials: adding the powder material obtained in the step S2 into silica sol, uniformly mixing, and adjusting the pH value to 11 to form gel;
s4, drying: freeze-drying the gel obtained in S3 to form a solid acid catalyst, and pulverizing the solid acid catalyst into fine particles having a particle size of 5 mesh;
s5, modification: and (3) adding the solid acid catalyst obtained in the step (S4) into anhydrous ethanol containing a silane coupling agent, stirring uniformly, standing, adding polyacrylic resin, fully reacting, and drying to obtain the modified solid acid catalyst.
Example 2
The modified solid acid catalyst is prepared by the following steps:
s1, preparing zirconium oxychloride into an aqueous solution, washing 300 mu m of artificial zeolite powder, adding the washed artificial zeolite powder into the aqueous solution, uniformly mixing, dropwise adding ammonia water into the aqueous solution until the pH value of the solution is 6, uniformly stirring, standing and aging for 6 hours;
s2, drying the solution after S1 is stood at 220 ℃, heating the obtained product at 630 ℃ for 3 hours, and grinding and sieving the product with a 300-mesh sieve to obtain a powder material;
s3, mixing materials: adding the powder material obtained in the step S2 into silica sol, uniformly mixing, and adjusting the pH value to 8 to form gel;
s4, drying: freeze-drying the gel obtained in S3 to form a solid acid catalyst, and pulverizing the solid acid catalyst into fine particles having a particle size of 50 mesh;
s5, modification: and (3) adding the solid acid catalyst obtained in the step (S4) into anhydrous ethanol containing a silane coupling agent, stirring uniformly, standing, adding polyacrylic resin, fully reacting, and drying to obtain the modified solid acid catalyst.
Example 3
The modified solid acid catalyst is prepared by the following steps:
s1, preparing zirconium oxychloride into an aqueous solution, cleaning 50 mu m of artificial zeolite powder, adding the cleaned artificial zeolite powder into the aqueous solution, uniformly mixing, dropwise adding ammonia water into the aqueous solution until the pH value of the solution is 6, uniformly stirring, standing and aging for 6 hours;
s2, drying the solution after S1 is stood at 120 ℃, heating the obtained product at 650 ℃ for 3 hours, and grinding and sieving the product with a 300-mesh sieve to obtain a powder material;
s3, mixing materials: adding the powder material obtained in the step S2 into silica sol, uniformly mixing, and adjusting the pH value to 8 to form gel;
s4, drying: freeze-drying the gel obtained in S3 to form a solid acid catalyst, and pulverizing the solid acid catalyst into fine particles having a particle size of 20 mesh;
s5, modification: and (3) adding the solid acid catalyst obtained in the step (S4) into anhydrous ethanol containing a silane coupling agent, stirring uniformly, standing, adding acrylic acid-acrylamide copolymer resin, fully reacting, and drying to obtain the modified solid acid catalyst.
Comparative example 1
Grinding zirconium dioxide and artificial zeolite powder, sieving with a 400-mesh sieve, adding into an aqueous solution, and adjusting the pH value to 11 to form gel; the resulting gel was then freeze dried to form the solid acid catalyst.
Comparative example 2
Is prepared from zirconium dioxide and artificial zeolite powder through grinding and sieving with 400-mesh sieve.
Test example 1
The modified solid acid catalyst prepared in example 1 and acetic anhydride 5 times the volume of chlorobenzene were added to chlorobenzene to react at 25 ℃ for 6 hours,
through filtration and sedimentation: filtering the liquid phase after reaction to obtain a modified solid acid catalyst, placing the filtrate in a settling kettle for settling, and separating out a nitrochlorobenzene mixture;
acid-base neutralization: adding an alkaline reagent into the acidic nitrochlorobenzene mixture to adjust the pH value;
washing and drying: washing and drying the neutralized nitrochlorobenzene mixture for many times to obtain a crude nitrochlorobenzene mixture;
and (3) crystallization and rectification: crystallizing the dried crude nitrochlorobenzene mixture, separating out p-nitrochlorobenzene crystals, transferring the liquid phase into a rectifying tower, and rectifying and separating out carbon tetrachloride, meta-position oil rich in m-nitrochlorobenzene, o-nitrochlorobenzene and high-boiling-point organic matter waste liquid.
The dosage of the modified solid acid catalyst in the nitration reaction is 50 percent of the mass of the chlorobenzene, the volume of the acetic anhydride is 5 times of that of the chlorobenzene, and the molar ratio of the nitrating agent to the chlorobenzene is 1.2: 1.
Test example 2
The modified solid acid catalyst prepared in example 2 was added to chlorobenzene to react at 25 ℃ for 6h,
filtering and settling: filtering the liquid phase after reaction to obtain a modified solid acid catalyst, placing the filtrate in a settling kettle for settling, and separating out a nitrochlorobenzene mixture;
acid-base neutralization: adding an alkaline reagent into the acidic nitrochlorobenzene mixture to adjust the pH value;
washing and drying: washing and drying the neutralized nitrochlorobenzene mixture for many times to obtain a crude nitrochlorobenzene mixture;
and (3) crystallization and rectification: crystallizing the dried crude nitrochlorobenzene mixture, separating out p-nitrochlorobenzene crystals, transferring the liquid phase into a rectifying tower, and rectifying and separating out carbon tetrachloride, meta-position oil rich in m-nitrochlorobenzene, o-nitrochlorobenzene and high-boiling-point organic matter waste liquid.
The dosage of the modified solid acid catalyst in the nitration reaction is 200% of the mass of the chlorobenzene, and the molar ratio of the nitrating agent to the chlorobenzene is 1.1: 1.
Test example 3
The modified solid acid catalyst prepared in example 3 was added to chlorobenzene and reacted at 25 ℃ for 6h,
through filtration and sedimentation: filtering the liquid phase after reaction to obtain a modified solid acid catalyst, placing the filtrate in a settling kettle for settling, and separating out a nitrochlorobenzene mixture;
acid-base neutralization: adding an alkaline reagent into the acidic nitrochlorobenzene mixture to adjust the pH value;
washing and drying: washing and drying the neutralized nitrochlorobenzene mixture for multiple times to obtain a crude nitrochlorobenzene mixture;
and (3) crystallization and rectification: crystallizing the dried crude nitrochlorobenzene mixture, separating out p-nitrochlorobenzene crystals, transferring the liquid phase into a rectifying tower, and rectifying and separating out carbon tetrachloride, meta-position oil rich in m-nitrochlorobenzene, o-nitrochlorobenzene and high-boiling-point organic matter waste liquid.
The dosage of the modified solid acid catalyst in the nitration reaction is 100 percent of the mass of the chlorobenzene, the volume of the acetic anhydride is 1 time of that of the chlorobenzene, and the molar ratio of the nitrating agent to the chlorobenzene is 1.4: 1.
Test example 4
The product obtained in comparative example 1 was added to chlorobenzene and reacted at 25 ℃ for 6h,
through filtration and sedimentation: filtering the liquid phase after reaction to obtain a product of a comparative example 1, placing the filtrate in a settling kettle for settling, and separating out a nitrochlorobenzene mixture;
acid-base neutralization: adding an alkaline reagent into the acidic nitrochlorobenzene mixture to adjust the pH value;
washing and drying: washing and drying the neutralized nitrochlorobenzene mixture for many times to obtain a crude nitrochlorobenzene mixture;
and (3) crystallization and rectification: crystallizing the dried crude nitrochlorobenzene mixture, separating out p-nitrochlorobenzene crystals, transferring the liquid phase into a rectifying tower, and rectifying and separating out carbon tetrachloride, meta-position oil rich in m-nitrochlorobenzene, o-nitrochlorobenzene and high-boiling-point organic matter waste liquid.
Test example 5
The product obtained in comparative example 2 and acetic anhydride 5 times the volume of chlorobenzene were added to chlorobenzene to react for 6 hours at 25 c,
filtering and settling: filtering the liquid phase after the reaction to obtain a product of a comparative example 2, placing the filtrate in a settling kettle for settling, and separating out a nitrochlorobenzene mixture;
acid-base neutralization: adding an alkaline reagent into the acidic nitrochlorobenzene mixture to adjust the pH value;
washing and drying: washing and drying the neutralized nitrochlorobenzene mixture for many times to obtain a crude nitrochlorobenzene mixture;
and (3) crystallization and rectification: crystallizing the dried crude nitrochlorobenzene mixture, separating out p-nitrochlorobenzene crystals, transferring the liquid phase into a rectifying tower, and rectifying to separate out carbon tetrachloride, meta-position oil rich in m-nitrochlorobenzene, o-nitrochlorobenzene and high-boiling-point organic matter waste liquid.
The yield was calculated by crystallizing and fractionating the product, wherein the groups of test example 1 and comparative example 5 added acetic anhydride of 5 times the volume of chlorobenzene as a dehydrating agent, the mass of the solid acid catalyst was 60% of that of chlorobenzene, and the mass of the nitrating agent was 150% of that of chlorobenzene, and examples 1 to 3 and comparative example 1 were respectively designated as test examples 1 to 4; comparative example 2 was divided into two groups and recorded as 5-6, wherein test example 5 added only 350% by mass of mixed acid of chlorobenzene, and test example 6 added 150% by mass of acetic anhydride of chlorobenzene based on test example 5, and the experimental results are shown in table 1.
| Test example 1 | Test example 2 | Test example 3 | Test example 4 | Test example 5 | Test example 6 | |
| Yield/% | 70.3 | 69.8 | 68.2 | 45.1 | 32.2 | 33.7 |
The experimental results show that the catalytic effect of the modified solid acid catalyst obtained in each group of examples of the application on the nitration reaction of chlorobenzene is higher than that of the existing mixed acid catalyst, and the catalytic effect of each group of examples of the application is also better than that of the simply added zirconium dioxide-artificial zeolite mixed powder; and it can be seen from the analysis of test examples 1 and 2 that the presence or absence of the water absorbing agent has no substantial influence on the catalytic reaction of the solid acid catalyst modified with the polymeric water absorbent resin of the present application.
Catalyst recovery experiment
The solid matter obtained by filtration in test examples 1 to 6 was collected, washed with deionized water and absolute ethanol, and dried, and the catalyst recovery rate before and after the reaction was calculated as follows:
wherein: x is catalyst recovery (%)
M1 mass of catalyst added before reaction
M2 is the mass of catalyst collected after reaction, washed and dried
The results are shown in the following table
| Test example 1 | Test example 2 | Test example 3 | Test example 4 | Test example 5 | Test example 6 | |
| Percent recovery% | 99.3 | 98.7 | 99.1 | 53.7 | 33.1 | 41.7 |
While one embodiment of the present invention has been described in detail, the description is only a preferred embodiment of the present invention and should not be taken as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (10)
1. A clean production process of nitrochlorobenzene is characterized in that the process comprises the steps of enabling chlorobenzene chloride, a nitrating agent and a modified solid acid catalyst to react in carbon tetrachloride to generate a nitrochlorobenzene mixture;
the modified solid acid catalyst is prepared by the following steps:
s1, preparing zirconium oxychloride into an aqueous solution, cleaning the artificial zeolite powder, adding the cleaned artificial zeolite powder into the aqueous solution, uniformly mixing, dropwise adding ammonia water into the aqueous solution until the pH value of the solution is 3-6, uniformly stirring, standing and aging for 6-10 hours;
s2, drying the solution after S1 standing at the temperature of 100-220 ℃, heating the obtained product at the temperature of 630-680 ℃ for 2-3h, and grinding and sieving to obtain a powder material;
s3, mixing materials: adding the powder material obtained in the step S2 into silica sol, uniformly mixing, and adjusting the pH value to 8-11 to form gel;
s4, drying: freeze drying the gel obtained in S3 to form a solid acid catalyst;
s5, modification: and (3) adding the solid acid catalyst obtained in the step (S4) into anhydrous ethanol containing a silane coupling agent, stirring uniformly, standing, adding high-molecular water-absorbing resin, fully reacting, and drying to obtain the modified solid acid catalyst.
2. The clean nitrochlorobenzene production process according to claim 1, characterized in that it comprises the following steps:
filtering and settling: filtering the liquid phase after reaction to obtain a modified solid acid catalyst, placing the filtrate in a settling kettle for settling, and separating out a nitrochlorobenzene mixture;
acid-base neutralization: adding an alkaline reagent into the acidic nitrochlorobenzene mixture to adjust the pH value;
washing and drying: washing and drying the neutralized nitrochlorobenzene mixture for many times to obtain a crude nitrochlorobenzene mixture;
and (3) crystallization and rectification: crystallizing the dried crude nitrochlorobenzene mixture, separating out p-nitrochlorobenzene crystals, transferring the liquid phase into a rectifying tower, and rectifying and separating out carbon tetrachloride, meta-position oil rich in m-nitrochlorobenzene, o-nitrochlorobenzene and high-boiling-point organic matter waste liquid.
3. The clean nitrochlorobenzene production process according to claim 1, wherein the nitrating agent is one of ferric nitrate or cupric nitrate.
4. The clean nitrochlorobenzene production process according to claim 1, wherein the artificial zeolite powder has a particle size of 10-300 μm.
5. The clean nitrochlorobenzene production process according to claim 1, wherein the solution in S2 is dried and continuously subjected to ultrasonic vibration.
6. The clean nitrochlorobenzene production process as claimed in claim 1, wherein the product obtained by heating in S2 is ground and sieved with a sieve of 300-400 meshes.
7. The clean nitrochlorobenzene production process according to claim 1, wherein the mass of the powder material is 1-4% of the mass of the silica sol; the mass ratio of the artificial zeolite powder to the zirconium dioxide is 0.5-1.7: 0.3-1.2.
8. The clean nitrochlorobenzene production process according to claim 1, wherein the modified solid acid catalyst is used in the nitration reaction in an amount of 50-200% by mass of chlorobenzene.
9. The clean nitrochlorobenzene production process according to claim 1, wherein the high molecular water-absorbing resin is one of polyacrylic resin, polyacrylamide resin or acrylic acid-acrylamide copolymer resin, and the mass of the high molecular water-absorbing resin is 5-42% of that of the nitrating agent.
10. The clean nitrochlorobenzene production process according to claim 1, wherein the modified solid acid catalyst is prepared by crushing the solid acid catalyst into particles of 5-50 meshes after the solid acid catalyst is obtained in step S4.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115259328A (en) * | 2022-07-08 | 2022-11-01 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Preparation method of cationic flocculant |
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