CN109574851B - Method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under catalysis of ionic liquid - Google Patents
Method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under catalysis of ionic liquid Download PDFInfo
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract
The invention discloses a method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid, which comprises the following steps: mixing chlorobenzene and a catalyst, heating to 50-60 ℃, and stirring and mixing for 2-4 hours to obtain a mixture; respectively adding the mixture prepared in the last step and a nitric acid solution into a microchannel reactor, carrying out nitration reaction in the microchannel reactor, then flowing out from an outlet, standing for 24h, taking down the liquid at the lower layer, washing, neutralizing and drying the liquid to obtain 2, 4-dinitrochlorobenzene; the method does not generate a large amount of waste acid in the production process, is green and environment-friendly, has higher selectivity in the reaction, prepares the 2, 4-dinitrochlorobenzene with higher purity, and has higher yield in the reaction.
Description
Technical Field
The invention relates to the field of aromatic ring nitration, in particular to a method for preparing 2, 4-dinitrochlorobenzene by catalyzing chlorobenzene nitration by ionic liquid.
Background
Nitration is one of the most common, earliest discovered organic unit reactions, which introduces-NO to the C atom in the molecule of an organic compound2The reaction of (1). The nitration of aromatic compounds is an important organic reaction, and the nitration products of aromatic hydrocarbons are important chemical raw materials and can be used as intermediates of explosives, pesticides, medicines, dyes and the like. Dinitrochlorobenzene has 6 isomers, and 2, 4-dinitrochlorobenzene is industrially required in large quantities. 2, 4-dinitrochlorobenzene is an important organic chemical intermediate product, is mainly applied to the fields of dye preparation, medicine preparation, pesticide preparation, photographic auxiliaries and the like, and has a plurality of derivative products and higher added value.
The prior aromatic hydrocarbon nitration method generally adopts a traditional nitrated sulfuric acid mixed acid nitration method, but has some disadvantages: (1) the production process is unsafe, and the phenomena of temperature rising, material bleeding and even explosion are very easy to cause because the nitration reaction is a quick strong exothermic reaction process; (2) environmental pollution can be caused, and a large amount of acidic wastewater containing organic matters can be generated by the nitric-sulfuric acid mixing process, so that serious environmental pollution is caused; (2) the problem of regioselective nitration of aromatic hydrocarbons. Therefore, the selection of a nitrification system with more accurate control, stability and energy conservation and a high-selectivity green nitrification technology is the key for solving the problem of aromatic hydrocarbon nitrification.
The research of green nitration reaction has made many advances, and the main technologies include solid acid catalysis liquid phase green nitration, solid acid catalysis gas phase green nitration, lewis acid catalysis liquid phase green nitration, liquid acid/nitrate system liquid phase green nitration, green nitration reaction in ionic liquid, and the like. The solid acid catalyzes green nitration reaction, thoroughly eliminates waste acid pollution, is easy to separate and recover the solid acid catalyst, has obvious difference on the synergistic action of an acidic active site on the solid acid and a substrate or a nitrating agent, and has obvious influence on the regioselectivity of a nitration product, and the solid acid comprises a clay catalyst, a molecular sieve catalyst, a metal oxide catalyst and a heteropoly acid catalyst.
The ionic liquid is mainly salt which is composed of organic cation and inorganic or organic anion and is liquid at room temperature or close to room temperature, is a novel high-efficiency green catalyst and solvent, has the advantages of no volatility, high thermal stability, low melting point, high boiling point, high refractive index, easy cyclic utilization and the like, and is widely applied to various organic reactions. The ionic liquid has various types, and various ionic liquids can be designed by changing different combinations of cations and anions. The properties of the ionic liquid can be adjusted by changing or modifying the anions and cations, such as melting point, viscosity, hydrophobicity, acidity and the like. However, the research on the ionic liquid has many defects, and the large-scale production is not realized, so that the research on the ionic liquid to enable the ionic liquid to be suitable for large-scale industrial production has important significance.
Chinese patent CN201410243113.4 discloses a method for producing high-purity 2, 4-dinitrochlorobenzene, relating to the technical field of chemical industry, putting mixed acid of nitrosulfur into a nitration kettle, then dripping p-nitrochlorobenzene, uniformly stirring,after the dripping of the p-nitrochlorobenzene is finished, the temperature in the nitration kettle is raised to 105 ℃, the stirring is stopped, the mixture is statically layered, the waste acid is separated into an extraction kettle, the p-nitrochlorobenzene is added into the extraction kettle after the extraction is finished to react with the residual nitric acid in the waste acid, the organic matters in the acid are extracted, the mixture is statically layered after the extraction is finished, the waste acid is input into a concentration section to be used for concentration and application, the extracted p-nitrochlorobenzene is recovered to be used as next batch nitration feeding, the qualified nitration liquid separated from the nitration kettle is put into a neutralization water washing kettle, and the added Na2CO3·10H2Washing to neutral, stopping stirring, standing and layering to obtain the finished product. However, the method still generates waste acid, has some environmental protection problems, and cannot meet the current environmental protection requirements.
Disclosure of Invention
The invention aims to provide a method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid, which does not generate a large amount of waste acid in the production process, is green and environment-friendly, has higher selectivity in the reaction, can prepare 2, 4-dinitrochlorobenzene with higher purity, and has higher yield in the reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid comprises the following steps:
step A: mixing chlorobenzene and a catalyst, heating to 50-60 ℃, and stirring and mixing for 2-4 hours to obtain a mixture;
and B: respectively adding the mixture prepared in the last step and a nitric acid solution into a microchannel reactor, carrying out nitration reaction in the microchannel reactor, then flowing out from an outlet, standing for 24h, taking down the liquid at the lower layer, washing, neutralizing and drying the liquid to obtain 2, 4-dinitrochlorobenzene;
the preparation method of the catalyst comprises the following steps:
(1) adding NaMoO4Adding into water, dissolving completely, and adding Na2HPO4Stirring the aqueous solution uniformly, heating, carrying out reflux reaction for 45-60min, then cooling to 60-70 ℃, and adding WO into the aqueous solution under the stirring condition3And carbonReacting the mixed solution of sodium acid for 45-60min, adding sulfuric acid to adjust the pH value to 1-2, and cooling to room temperature under the condition of stirring to obtain a mixed solution;
(2) adding diethyl ether into the mixed solution prepared in the step (1), stirring uniformly, adding a sulfuric acid solution, continuously stirring for reacting for 15-20min, stopping stirring, standing for 1h, taking an intermediate layer, evaporating under reduced pressure to remove diethyl ether, adding water, mixing uniformly, drying, recrystallizing and drying to obtain phosphomolybdotungstic heteropoly acid;
(3) mixing pyridine and 1, 3-propane sultone, adding the mixture into a reaction kettle, controlling the temperature to be 30-50 ℃, continuously stirring for reaction until the mixture is completely solidified, washing the mixture with ethanol, drying the mixture in vacuum to prepare a white solid, then stirring and dropwise adding concentrated sulfuric acid to the solid, controlling the temperature to be 60-80 ℃, keeping the temperature for reaction for 2-3 hours, and drying the mixture in vacuum to prepare ionic liquid;
(4) mixing the ionic liquid and the prepared heteropoly acid, adding the ionic liquid and the prepared heteropoly acid into ethanol, controlling the temperature to be 60-70 ℃, continuously reacting for 36-48 hours, centrifugally separating after the reaction is finished, taking an upper layer substance, and drying to obtain the catalyst.
Preferably, chlorobenzene and the catalyst are used in a mass ratio of 10-17: 1.
Preferably, the mass concentration of the nitric acid solution in the method for preparing the dinitrochlorobenzene is 70-80 percent; the molar ratio of chlorobenzene to nitric acid is 1: 1.2-2.1.
Preferably, NaMoO4And Na2HPO4In a molar ratio of 10:1, NaMoO4And WO3Is used in a molar ratio of 5: 1.
Preferably, said WO3The concentration of sodium carbonate in the mixed solution of sodium carbonate is 0.7-1.5 mol/L.
Preferably, in the catalyst preparation method, the mass concentration of the sulfuric acid solution in the step (2) is 40%, and the volume ratio of the usage amount of the sulfuric acid solution to the mixed solution in the step (1) is 1:1.
Preferably, in the step (3) of the catalyst preparation method, the molar ratio of the pyridine to the 1, 3-propane sultone to the concentrated sulfuric acid is 1:1: 1.
Preferably, the ionic liquid and the heteropoly acid are used in a molar ratio of 5: 1.
The present invention has the following advantageous effects in that,
1. the catalyst is prepared from the heteropoly acid and the ionic liquid, has the catalytic action of the heteropoly acid and the ionic liquid, has higher selectivity in the nitration process, can be used for nitrating chlorobenzene into dinitrochlorobenzene through one-time reaction, has higher 2, 4-dinitrochlorobenzene ratio, and effectively improves the chlorobenzene conversion rate.
2. The preparation method of the heteropoly acid ionic liquid is simple, the recovery is simple and convenient, the heteropoly acid ionic liquid can be repeatedly used for many times, the production cost is saved, and the economic benefit is improved.
3. The method has the advantages that a large amount of waste acid is not generated in the nitration process, large-scale pollution cannot be generated, the method is green and environment-friendly, the environment-friendly requirement in industrial production can be met, and the method has a high industrial production prospect.
Detailed Description
In order to better understand the present invention, the following examples further illustrate the invention, the examples are only used for explaining the invention, not to constitute any limitation of the invention.
Example 1
A method for preparing dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid comprises the following steps:
(1) mixing chlorobenzene and a catalyst according to the mass ratio of 10:1, heating to 50 ℃, and stirring and mixing for 2 hours to obtain a mixture;
(2) respectively adding the mixture prepared in the last step and a nitric acid solution into a microchannel reactor, wherein the mass concentration of the nitric acid solution is 70%; the using molar ratio of the chlorobenzene nitrate to the nitric acid is 1:1.2, the temperature is controlled at 60 ℃, after nitration reaction is carried out in a microchannel reactor, the liquid flows out from an outlet, stands for 24 hours, and the lower layer liquid is taken out, washed, neutralized and dried to prepare the dinitrochlorobenzene;
the preparation method of the catalyst comprises the following steps:
(1) adding NaMoO4Adding into water, dissolving completely, and adding Na2HPO4Stirring the aqueous solution, heating, performing reflux reaction for 50min, cooling to 60 ℃, and adding WO into the aqueous solution under the stirring condition3And sodium carbonate with concentration of 0.9mol/L, NaMoO4And Na2HPO4In a molar ratio of 10:1, NaMoO4And WO3The using amount molar ratio of (1) is 5:1, after reacting for 50min, adding sulfuric acid to adjust the pH value to 2, and cooling to room temperature under the stirring condition to prepare a mixed solution;
(2) adding diethyl ether into the mixed solution prepared in the step (1), stirring uniformly, adding a sulfuric acid solution, wherein the mass concentration of the sulfuric acid solution is 40%, the volume ratio of the use amount of the sulfuric acid solution to the mixed solution in the step (1) is 1:1, continuously stirring for reacting for 20min, stopping stirring, standing for 1h, taking an intermediate layer, evaporating under reduced pressure to remove the diethyl ether, adding water, mixing uniformly, drying, recrystallizing and drying to obtain phosphomolybdotungstic heteropoly acid;
(3) mixing pyridine and 1, 3-propane sultone, adding into a reaction kettle, controlling the temperature to be 30-50 ℃, continuously stirring for reaction until the mixture is completely solidified, washing with ethanol, drying in vacuum to prepare a white solid, stirring and dropwise adding concentrated sulfuric acid to the solid, wherein the molar ratio of the pyridine to the 1, 3-propane sultone to the concentrated sulfuric acid is 1:1:1, controlling the temperature to be 70 ℃, preserving the temperature for reaction for 3 hours, and then drying in vacuum to prepare ionic liquid;
(4) mixing ionic liquid and prepared heteropoly acid, adding the ionic liquid and the prepared heteropoly acid into ethanol, controlling the usage amount molar ratio of the ionic liquid to the heteropoly acid to be 5:1, controlling the temperature to be 60 ℃, continuously reacting for 48 hours, centrifugally separating after the reaction is finished, taking an upper layer substance, and drying to obtain the catalyst.
The yield of the prepared dinitrochlorobenzene was 93.4%, wherein the mass fraction of 2, 4-dinitrochlorobenzene was 99.0%.
Example 2
A method for preparing dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid comprises the following steps:
(1) mixing chlorobenzene and a catalyst according to the mass ratio of 17:1, heating to 60 ℃, and stirring and mixing for 4 hours to obtain a mixture;
(2) respectively adding the mixture prepared in the last step and a nitric acid solution into a micro-channel reactor, wherein the mass concentration of the nitric acid solution is 80%; the using molar ratio of the chlorobenzene nitrate to the nitric acid is 1:2.1, the temperature is controlled at 80 ℃, after nitration reaction is carried out in a microchannel reactor, the liquid flows out from an outlet, stands for 24 hours, and the lower layer liquid is taken out, washed, neutralized and dried to prepare the dinitrochlorobenzene;
the preparation method of the catalyst is the same as that of the example 1.
The yield of the prepared dinitrochlorobenzene was 94.1%, wherein the mass fraction of 2, 4-dinitrochlorobenzene was 99.1%.
Example 3
A method for preparing dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid comprises the following steps:
(1) mixing chlorobenzene and a catalyst according to the mass ratio of 10:1, heating to 60 ℃, and stirring and mixing for 2 hours to obtain a mixture;
(2) respectively adding the mixture prepared in the last step and a nitric acid solution into a micro-channel reactor, wherein the mass concentration of the nitric acid solution is 80%; the using molar ratio of the chlorobenzene nitrate to the nitric acid is 1:1.2, the temperature is controlled at 80 ℃, after nitration reaction is carried out in a microchannel reactor, the liquid flows out from an outlet, stands for 24 hours, and the lower layer liquid is taken out, washed, neutralized and dried to prepare the dinitrochlorobenzene;
the preparation method of the catalyst is the same as that of the example 1.
The yield of the prepared dinitrochlorobenzene was 94.5%, wherein the mass fraction of 2, 4-dinitrochlorobenzene was 99.3%.
Example 4
A method for preparing dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid comprises the following steps:
(1) mixing chlorobenzene and a catalyst according to the mass ratio of 15:1, heating to 55 ℃, and stirring and mixing for 3 hours to obtain a mixture;
(2) respectively adding the mixture prepared in the last step and a nitric acid solution into a micro-channel reactor, wherein the mass concentration of the nitric acid solution is 75%; the using molar ratio of the chlorobenzene nitrate to the nitric acid is 1:1.8, the temperature is controlled at 70 ℃, after nitration reaction is carried out in a microchannel reactor, the liquid flows out from an outlet, stands for 24 hours, and the lower layer liquid is taken out, washed, neutralized and dried to prepare the dinitrochlorobenzene;
the preparation method of the catalyst is the same as that of the example 1.
The yield of the prepared dinitrochlorobenzene was 94.9%, wherein the mass fraction of 2, 4-dinitrochlorobenzene was 99.2%.
Example 5
A method for preparing dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid comprises the following steps:
(1) mixing chlorobenzene and a catalyst according to the mass ratio of 10:1, heating to 50 ℃, and stirring and mixing for 2 hours to obtain a mixture;
(2) respectively adding the mixture prepared in the last step and a nitric acid solution into a microchannel reactor, wherein the mass concentration of the nitric acid solution is 70%; the using molar ratio of the chlorobenzene nitrate to the nitric acid is 1:1.2, the temperature is controlled at 60 ℃, after nitration reaction is carried out in a microchannel reactor, the liquid flows out from an outlet, stands for 24 hours, and the lower layer liquid is taken out, washed, neutralized and dried to prepare the dinitrochlorobenzene;
the preparation method of the catalyst comprises the following steps:
(1) adding NaMoO4Adding into water, dissolving completely, and adding Na2HPO4Stirring the aqueous solution, heating, performing reflux reaction for 50min, cooling to 60 ℃, and adding WO into the aqueous solution under the stirring condition3And sodium carbonate with concentration of 0.9mol/L, NaMoO4And Na2HPO4In a molar ratio of 10:1, NaMoO4And WO3The using amount molar ratio of (1) is 5:1, after reacting for 50min, adding sulfuric acid to adjust the pH value to 2, and cooling to room temperature under the stirring condition to prepare a mixed solution;
(2) adding ether into the mixed solution prepared in the step (1), stirring uniformly, adding a sulfuric acid solution, wherein the mass concentration of the sulfuric acid solution is 40%, the volume ratio of the usage amount of the sulfuric acid solution to the mixed solution in the step (1) is 1:1, continuously stirring for reacting for 20min, stopping stirring, standing for 1h, taking an intermediate layer, evaporating under reduced pressure to remove ether, adding water, mixing uniformly, drying, recrystallizing, and drying to obtain the phosphomolybdotungstic heteropoly acid, namely the catalyst.
The yield of the prepared dinitrochlorobenzene is 50.5 percent, wherein the mass part of the 2, 4-dinitrochlorobenzene is 81.6 percent.
Example 6
A method for preparing dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid comprises the following steps:
(1) mixing chlorobenzene and a catalyst according to the mass ratio of 10:1, heating to 50 ℃, and stirring and mixing for 2 hours to obtain a mixture;
(2) respectively adding the mixture prepared in the last step and a nitric acid solution into a microchannel reactor, wherein the mass concentration of the nitric acid solution is 70%; the using molar ratio of the chlorobenzene nitrate to the nitric acid is 1:1.2, the temperature is controlled at 60 ℃, after nitration reaction is carried out in a microchannel reactor, the liquid flows out from an outlet, stands for 24 hours, and the lower layer liquid is taken out, washed, neutralized and dried to prepare the dinitrochlorobenzene;
the preparation method of the catalyst comprises the following steps:
mixing pyridine and 1, 3-propane sultone, adding into a reaction kettle, controlling the temperature to be 30-50 ℃, continuously stirring for reaction until the mixture is completely solidified, washing with ethanol, drying in vacuum to prepare a white solid, stirring and dropwise adding concentrated sulfuric acid to the solid, wherein the molar ratio of the pyridine to the 1, 3-propane sultone to the concentrated sulfuric acid is 1:1:1, controlling the temperature to be 70 ℃, preserving the temperature for reaction for 3 hours, and drying in vacuum to prepare the ionic liquid.
The yield of the prepared dinitrochlorobenzene was 40.7%, wherein the mass fraction of 2, 4-dinitrochlorobenzene was 73.9%.
Claims (8)
1. A method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid is characterized by comprising the following steps: the method comprises the following steps:
step A: mixing chlorobenzene and a catalyst, heating to 50-60 ℃, and stirring and mixing for 2-4 hours to obtain a mixture;
and B: respectively adding the mixture prepared in the last step and a nitric acid solution into a microchannel reactor, carrying out nitration reaction in the microchannel reactor, then flowing out from an outlet, standing for 24h, taking down the liquid at the lower layer, washing, neutralizing and drying the liquid to obtain 2, 4-dinitrochlorobenzene;
the preparation method of the catalyst comprises the following steps:
(1) adding NaMoO4Adding into water, dissolving completely, and adding Na2HPO4Stirring the aqueous solution uniformly, heating, carrying out reflux reaction for 45-60min, then cooling to 60-70 ℃, and adding WO into the aqueous solution under the stirring condition3Reacting with the mixed solution of sodium carbonate for 45-60min, adding sulfuric acid to adjust the pH value to 1-2, and cooling to room temperature under the condition of stirring to obtain a mixed solution;
(2) adding diethyl ether into the mixed solution prepared in the step (1), stirring uniformly, adding a sulfuric acid solution, continuously stirring for reacting for 15-20min, stopping stirring, standing for 1h, taking an intermediate layer, evaporating under reduced pressure to remove diethyl ether, adding water, mixing uniformly, drying, recrystallizing and drying to obtain phosphomolybdotungstic heteropoly acid;
(3) mixing pyridine and 1, 3-propane sultone, adding the mixture into a reaction kettle, controlling the temperature to be 30-50 ℃, continuously stirring for reaction until the mixture is completely solidified, washing the mixture with ethanol, drying the mixture in vacuum to prepare a white solid, then stirring and dropwise adding concentrated sulfuric acid to the solid, controlling the temperature to be 60-80 ℃, keeping the temperature for reaction for 2-3 hours, and drying the mixture in vacuum to prepare ionic liquid;
(4) mixing the ionic liquid and the prepared heteropoly acid, adding the ionic liquid and the prepared heteropoly acid into ethanol, controlling the temperature to be 60-70 ℃, continuously reacting for 36-48 hours, centrifugally separating after the reaction is finished, taking an upper layer substance, and drying to obtain the catalyst.
2. The method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid according to claim 1, wherein the ionic liquid is prepared from the following raw materials in percentage by weight: the mass ratio of the chlorobenzene to the catalyst is 10-17: 1.
3. The method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid according to claim 1, wherein the ionic liquid is prepared from the following raw materials in percentage by weight: in the method for preparing the dinitrochlorobenzene, the mass concentration of the nitric acid solution is 70-80 percent; the molar ratio of chlorobenzene to nitric acid is 1: 1.2-2.1.
4. The method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid according to claim 1, wherein the ionic liquid is prepared from the following raw materials in percentage by weight: NaMoO4And Na2HPO4In a molar ratio of 10:1, NaMoO4And WO3Is used in a molar ratio of 5: 1.
5. The method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid according to claim 1, wherein the ionic liquid is prepared from the following raw materials in percentage by weight: said WO3The concentration of sodium carbonate in the mixed solution of sodium carbonate is 0.7-1.5 mol/L.
6. The method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid according to claim 1, wherein the ionic liquid is prepared from the following raw materials in percentage by weight: the mass concentration of the sulfuric acid solution in the step (2) of the catalyst preparation method is 40%, and the volume ratio of the usage amount of the sulfuric acid solution to the mixed solution in the step (1) is 1:1.
7. The method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid according to claim 1, wherein the ionic liquid is prepared from the following raw materials in percentage by weight: in the preparation method of the catalyst, in the step (3), the molar ratio of the pyridine to the 1, 3-propane sultone to the concentrated sulfuric acid is 1:1: 1.
8. The method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under the catalysis of ionic liquid according to claim 1, wherein the ionic liquid is prepared from the following raw materials in percentage by weight: the molar ratio of the ionic liquid to the heteropoly acid is 5: 1.
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| CN114805078B (en) * | 2022-02-11 | 2023-09-29 | 上海农帆生物科技有限公司 | Method for preparing 2,3, 4-trichloronitrobenzene through microchannel nitration |
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| EP1357167A1 (en) * | 2002-04-18 | 2003-10-29 | Haldor Topsoe A/S | Process for production of high quality gasoline with low aromatic content |
| CN1211338C (en) * | 2003-04-03 | 2005-07-20 | 浙江工业大学 | Chemical method for sythesizing dipheny ether compound |
| CN102417457A (en) * | 2011-08-22 | 2012-04-18 | 盐城师范学院 | P-chlorobenzotrifluoride clean nitration reaction catalyzed by heteropoly acid ionic liquid |
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| CN102553624B (en) * | 2012-01-05 | 2013-10-16 | 中国科学院过程工程研究所 | Preparation method of catalyst for synthesizing methacrylic acid |
| CN104014369B (en) * | 2014-06-23 | 2016-08-24 | 山东大学 | One class heteropolyacid acid ionic liquid and the application in ester exchange reaction thereof |
| US10961480B2 (en) * | 2017-01-17 | 2021-03-30 | Exxonmobil Chemical Patents Inc. | High stability lubricating oil base stocks and processes for preparing the same |
| CN106975522B (en) * | 2017-04-17 | 2020-05-12 | 辽宁大学 | Preparation of phosphomolybdotungstic heteropoly acid and application thereof in catalyzing olefin epoxidation |
| CN108465487B (en) * | 2018-03-30 | 2020-12-04 | 东南大学成贤学院 | Polyion liquid-based heteropolyacid catalyst for olefin epoxidation reaction, preparation method and application thereof |
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