CN111153802A - Green nitration method based on strong acid proton type ionic liquid catalysis - Google Patents
Green nitration method based on strong acid proton type ionic liquid catalysis Download PDFInfo
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Abstract
The invention discloses a green nitration method based on strong acid proton type ionic liquid catalysis, which adopts benzene and nitric acid as raw materials and strong acid proton type ionic liquid as a catalyst to obtain a product through the steps of reaction, phase splitting, extraction, water washing, rectification, crystallization and the like. The strong acid proton type ionic liquid catalyst has high catalytic activity and good selectivity, can be regenerated by removing water through double-effect falling film evaporation, and can recycle wastewater generated by washing in the process. The process is simple, no waste water is generated, the total yield of the product is high, and the industrial application value is high.
Description
Technical Field
The invention belongs to the technical field of organic compound manufacturing, and particularly relates to a green nitration method based on strong-acid proton type ionic liquid catalysis.
Background
M-dinitrobenzene is an important organic chemical raw material and is mainly used in the fields of organic synthesis, dye intermediates, explosives and the like. The m-dinitrobenzene is industrially produced by the traditional process which takes sulfuric acid as a catalyst, nitric acid as a nitrating agent and benzene (patent CN 102311347) or nitrobenzene (patent CN 101343229) as raw materials, and the technology is mature. However, because the m-dinitrobenzene has high solubility in hot acidic aqueous solution, the subsequent treatment is difficult, a large amount of waste water is easily caused, and the environment is polluted. In recent years, with the strong market demand for resorcinol and m-aminophenol, the demand for m-dinitrobenzene as a starting material has been gradually increased. However, with the gradual improvement of domestic environmental protection requirements, the traditional process for producing m-dinitrobenzene can not meet the development requirements of current 'green production', so the development of a novel nitrating agent and a novel nitration process is very important.
The Ionic liquid is also called Room Temperature Ionic liquid (RTILs for short) which is a green solvent and catalyst. It is a liquid organic molten salt with a melting point lower than 100 ℃. Because of its characteristics of zero vapor pressure, high thermal stability, strong dissolving power, designable structure and function, etc., it can be extensively used in the organic reactions of esterification, alkylation, etherification and nitration, etc.
At present, patents and literature reports about ionic liquid participating in nitration are available, such as patents CN1469859, CN 10139293, CN101898968 and the like, but all adopt single ionic liquid, and have low catalytic activity, large using amount and high input cost. In 2014, a K.Matuszek team takes pyridine as a cation and hydrogen sulfate as an anion, a large number of anion clusters are formed through the hydrogen bond action between the anions, and a strong acid proton type ionic liquid is developed and used in esterification reaction, and has remarkable effect. On the basis, long-term research shows that the proton type ionic liquid catalyst which has double cation centers and double anion clusters and is stronger in acidity has higher catalytic activity and selectivity, low synthesis cost and good stability, is easy to phase separate with products, and is particularly suitable for preparing m-dinitrobenzene by continuous benzene nitration.
Disclosure of Invention
The invention provides a green nitration method for synthesizing m-dinitrobenzene by selecting novel strong acid proton type ionic liquid as a catalyst and nitric acid as a nitrating agent. The technical scheme is as follows:
the method takes nitric acid as a nitrating agent, strong acid proton type ionic liquid as a catalyst and benzene as a raw material to carry out nitration reaction. After the reaction is finished, phase separation is carried out, and the lower phase catalyst is extracted by nitrobenzene. And combining the extraction phase and the upper phase crude product after phase separation, washing, performing double-effect falling film evaporation on the raffinate phase, sending the evaporated water to the upper phase crude product after washing, and continuously reacting the evaporated lower phase catalyst. And the water phase obtained after the crude product of the upper phase is washed by water and is combined with the raffinate phase in the extraction step to enter the double-effect falling film evaporation. Washing the upper phase crude product with water to obtain a crude product, separating the crude product by a rectifying tower, returning the light component nitrobenzene to the reaction step, and crystallizing and separating the rectified heavy component mixed dinitrobenzene to obtain the product m-dinitrobenzene.
In general, the strongly acidic proton type ionic liquid cation used in the green nitration method for synthesizing m-dinitrobenzene is alkyl diamine or triamine, such as N, N ‒ tetramethyl ethylene diamine, N ‒ tetramethyl propylene diamine, N ‒ tetramethyl butylene diamine, N ‒ hexamethyl butylene triamine, N ‒ hexamethyl heptatriamine, etc., the anion is sulfuric acid, and the catalyst synthesis molar ratio is cation to sulfuric acid =1: 1-10.
In the reaction step of the green nitration method for synthesizing m-dinitrobenzene, the molar ratio of nitric acid to benzene is 2-2.08: 1, and the mass ratio of strong-acid proton type ionic liquid to benzene is 0.5-2: 1.
The reaction temperature of the green nitration method for synthesizing m-dinitrobenzene is 80-130 ℃, and the retention time is 1-3 hours.
In the green nitration method for synthesizing m-dinitrobenzene, in the nitrobenzene extraction step, the volume ratio (nitrobenzene: lower phase catalyst) is 0.5-1.5: 1, and the extraction temperature is 80-120 ℃.
In the green nitration method for synthesizing m-dinitrobenzene, the volume ratio (water: crude product of upper phase) is 0.5-1: 1 in the water washing step, and the water washing temperature is 80-120 ℃.
In the green nitration method for synthesizing m-dinitrobenzene, in the falling film evaporation step, the temperature of the one-effect falling film evaporation is 60-80 ℃, and the vacuum degree is 0.1 bar; the temperature of the double-effect falling film evaporation is 80-100 ℃, and the vacuum degree is 0.1 bar.
In the green nitration method for synthesizing m-dinitrobenzene, the rectifying tower is a packed tower or a plate tower in the rectifying part, the temperature of the top of the tower rectifying tower is 180-230 ℃, and the temperature of the bottom of the tower rectifying tower is 280-300 ℃.
The packing in the packed tower is one of ɵ ring packing and step ring packing, the height of the tower is 15-30m, and the extraction position of nitrobenzene is 1-2 m away from the top of the tower. The number of the plate tower plates of the plate tower is 40-60, and the position of the nitrobenzene extraction is 1-5 plates away from the tower top.
The green nitration method for synthesizing m-dinitrobenzene adopts an ethanol solvent for recrystallization.
Technical effects of the invention
The method adopts the strong acid proton type ionic liquid as the catalyst, has good catalytic effect and strong water absorption, the mixed dinitrobenzene has low solubility in the catalyst system, the product does not need to be washed by alkali, the generation of phenol byproducts is avoided, no waste water is generated, the process is green, and the method has great competitive advantage.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
The strong-acid proton type ionic liquid catalyst is N, N ‒ tetramethylethylenediamine sulfate, and the synthesis molar ratio of the catalyst is cation sulfuric acid =1: 1. The molar ratio of nitric acid to benzene is 2.08:1, the mass ratio of strong acid proton type ionic liquid to benzene is 2:1, the reaction temperature is 130 ℃, and the retention time is 3 hours. The volume ratio of nitrobenzene extraction (nitrobenzene: lower phase catalyst) is 1.5:1, and the extraction temperature is 80 ℃. The volume ratio of water washing (water: crude product of the upper phase) is 0.5:1, and the water washing temperature is 100 ℃. The temperature of the first-effect falling film evaporation is 60 ℃, and the vacuum degree is 0.1 bar. The double-effect falling film evaporation temperature is 80 ℃, and the vacuum degree is 0.1 bar. The rectifying tower is a packed tower, the temperature of the top of the tower is 230 ℃, and the temperature of the bottom of the tower is 300 ℃. The packing in the packed tower is ɵ rings, the height of the tower is 15 meters, and the extraction position of nitrobenzene is 1 meter away from the top of the tower. The yield of m-dinitrobenzene after secondary recrystallization of ethanol is 87 percent.
Example 2
The strong-acid proton type ionic liquid catalyst is N, N ‒ tetramethylpropanediamine sulfate, and the synthesis molar ratio of the catalyst is cation sulfuric acid =1: 5. The molar ratio of nitric acid to benzene is 2.05:1, the mass ratio of strong acid proton type ionic liquid to benzene is 1.5:1, the reaction temperature is 110 ℃, and the retention time is 2 hours. The volume ratio of nitrobenzene extraction (nitrobenzene: lower phase catalyst) is 1:1, and the extraction temperature is 90 ℃. The volume ratio of water washing (water: crude product of the upper phase) is 1:1, and the water washing temperature is 90 ℃. The temperature of the first-effect falling film evaporation is 60 ℃, and the vacuum degree is 0.1 bar. The double-effect falling film evaporation temperature is 90 ℃, and the vacuum degree is 0.1 bar. The rectifying tower is a packed tower, the temperature of the top of the tower is 200 ℃, and the temperature of the bottom of the tower is 280 ℃. The packing in the packed tower is a stepped ring, the height of the tower is 30 meters, and the extraction position of nitrobenzene is 2 meters away from the top of the tower. The yield of m-dinitrobenzene after secondary recrystallization of ethanol is 90 percent.
Example 3
The strong-acid proton type ionic liquid catalyst is N, N ‒ tetramethyl butanediamine sulfate, and the molar ratio of the catalyst to the cation is sulfuric acid =1: 10. The molar ratio of nitric acid to benzene is 2:1, the mass ratio of strong acid proton type ionic liquid to benzene is 0.5:1, the reaction temperature is 120 ℃, and the retention time is 1.5 hours. The volume ratio of nitrobenzene extraction (nitrobenzene: lower phase catalyst) is 1:1, and the extraction temperature is 100 ℃. The volume ratio of water washing (water: crude product of the upper phase) is 0.8:1, and the water washing temperature is 100 ℃. The temperature of the first-effect falling film evaporation is 70 ℃, and the vacuum degree is 0.1 bar. The double-effect falling film evaporation temperature is 90 ℃, and the vacuum degree is 0.1 bar. The rectifying tower is a plate tower, the temperature of the top of the tower is 180 ℃, and the temperature of the bottom of the tower is 290 ℃. The number of the plate tower plates is 40, and the nitrobenzene extraction position is at the 3 rd plate from the top of the tower. The yield of m-dinitrobenzene after secondary recrystallization of ethanol is 91 percent.
Example 4
The strongly acidic proton type ionic liquid catalyst is N, N, N ‒ hexamethyl butyl triamine sulfate, and the synthesis molar ratio of the catalyst is cation to sulfuric acid =1: 5. The molar ratio of nitric acid to benzene is 2.03:1, the mass ratio of strong acid proton type ionic liquid to benzene is 0.9:1, the reaction temperature is 80 ℃, and the retention time is 1 hour. The volume ratio of nitrobenzene extraction (nitrobenzene: lower phase catalyst) is 1:1, and the extraction temperature is 80 ℃. The volume ratio of water washing (water: crude product of the upper phase) is 0.5:1, and the water washing temperature is 80 ℃. The temperature of the first-effect falling film evaporation is 80 ℃, and the vacuum degree is 0.1 bar. The double-effect falling film evaporation temperature is 100 ℃, and the vacuum degree is 0.1 bar. The rectifying tower is a plate tower, the temperature of the top of the tower is 190 ℃, and the temperature of the bottom of the tower is 280 ℃. The number of the plate tower plates is 60, and the nitrobenzene extraction position is the 2 nd plate from the top of the tower. The yield of m-dinitrobenzene after secondary recrystallization of ethanol is 88 percent.
Example 5
The strongly acidic proton type ionic liquid catalyst is N, N, N ‒ hexamethyl heptatriamine sulfate, and the synthesis molar ratio of the catalyst is cation to sulfuric acid =1: 8. The molar ratio of nitric acid to benzene is 2.07:1, the mass ratio of strong acid proton type ionic liquid to benzene is 1.2:1, the reaction temperature is 90 ℃, and the retention time is 2.5 hours. The volume ratio of nitrobenzene extraction (nitrobenzene: lower phase catalyst) is 0.5:1, and the extraction temperature is 90 ℃. The volume ratio of water washing (water: crude product of the upper phase) is 0.5:1, and the water washing temperature is 90 ℃. The temperature of the first-effect falling film evaporation is 80 ℃, and the vacuum degree is 0.1 bar. The double-effect falling film evaporation temperature is 90 ℃, and the vacuum degree is 0.1 bar. The rectifying tower is a packed tower, the temperature of the top of the tower is 210 ℃, and the temperature of the bottom of the tower is 290 ℃. The packing in the packed tower is a step ring, the height of the tower is 18 m, and the extraction position of nitrobenzene is 1.5 m away from the top of the tower. The yield of m-dinitrobenzene after secondary recrystallization of ethanol is 92 percent.
Example 6
The strong-acid proton type ionic liquid catalyst is N, N ‒ tetramethylethylenediamine sulfate, and the synthesis molar ratio of the catalyst is cation sulfuric acid =1: 10. The molar ratio of nitric acid to benzene is 2:1, the mass ratio of strong acid proton type ionic liquid to benzene is 1.5:1, the reaction temperature is 80 ℃, and the retention time is 3 hours. The volume ratio of nitrobenzene extraction (nitrobenzene: lower phase catalyst) is 1.5:1, and the extraction temperature is 100 ℃. The volume ratio of water washing (water: crude product of the upper phase) is 1:1, and the water washing temperature is 100 ℃. The temperature of the first-effect falling film evaporation is 60 ℃, and the vacuum degree is 0.1 bar. The double-effect falling film evaporation temperature is 90 ℃, and the vacuum degree is 0.1 bar. The rectifying tower is a plate tower, the temperature of the top of the tower is 200 ℃, and the temperature of the bottom of the tower is 290 ℃. The number of the plate tower plates is 50, and the nitrobenzene extraction position is the 4 th plate from the top of the tower. The yield of m-dinitrobenzene after secondary recrystallization of ethanol is 92 percent.
Example 7
The strong-acid proton type ionic liquid catalyst is N, N ‒ tetramethylpropanediamine sulfate, and the synthesis molar ratio of the catalyst is cation sulfuric acid =1: 8. The molar ratio of nitric acid to benzene is 2.01:1, the mass ratio of strong acid proton type ionic liquid to benzene is 1.8:1, the reaction temperature is 130 ℃, and the retention time is 1.9 hours. The volume ratio of nitrobenzene extraction (nitrobenzene: lower phase catalyst) is 1:1, and the extraction temperature is 90 ℃. The volume ratio of water washing (water: crude product of the upper phase) is 1:1, and the water washing temperature is 90 ℃. The temperature of the first-effect falling film evaporation is 80 ℃, and the vacuum degree is 0.1 bar. The double-effect falling film evaporation temperature is 100 ℃, and the vacuum degree is 0.1 bar. The rectifying tower is a plate tower, the temperature of the top of the tower is 230 ℃, and the temperature of the bottom of the tower is 300 ℃. The number of the plate tower plates is 55, and the nitrobenzene extraction position is at the 3 rd plate from the top of the tower. The yield of m-dinitrobenzene after secondary recrystallization of ethanol is 89 percent.
Example 8
The strongly acidic proton type ionic liquid catalyst is N, N, N ‒ hexamethyl heptatriamine sulfate, and the synthesis molar ratio of the catalyst is cation to sulfuric acid =1: 4. The molar ratio of nitric acid to benzene is 2.08:1, the mass ratio of strong acid proton type ionic liquid to benzene is 2:1, the reaction temperature is 120 ℃, and the retention time is 2.5 hours. The volume ratio of nitrobenzene extraction (nitrobenzene: lower phase catalyst) is 1.5:1, and the extraction temperature is 110 ℃. The volume ratio of water washing (water: crude product of the upper phase) is 1:1, and the water washing temperature is 100 ℃. The temperature of the first-effect falling film evaporation is 90 ℃, and the vacuum degree is 0.1 bar. The double-effect falling film evaporation temperature is 100 ℃, and the vacuum degree is 0.1 bar. The rectifying tower is a plate tower, the temperature of the top of the tower is 220 ℃, and the temperature of the bottom of the tower is 300 ℃. The number of the plate tower plates is 45, and the nitrobenzene extraction position is at the 2 nd plate from the top of the tower. The yield of m-dinitrobenzene after secondary recrystallization of ethanol is 90 percent.
Example 9
The strongly acidic proton type ionic liquid catalyst is N, N, N ‒ hexamethyl butyl triamine sulfate, and the synthesis molar ratio of the catalyst is cation to sulfuric acid =1: 6. The molar ratio of nitric acid to benzene is 2.06:1, the mass ratio of strong acid proton type ionic liquid to benzene is 1.9:1, the reaction temperature is 110 ℃, and the retention time is 2.5 hours. The volume ratio of nitrobenzene extraction (nitrobenzene: lower phase catalyst) is 1.5:1, and the extraction temperature is 100 ℃. The volume ratio of water washing (water: crude product of the upper phase) is 0.8:1, and the water washing temperature is 90 ℃. The temperature of the first-effect falling film evaporation is 80 ℃, and the vacuum degree is 0.1 bar. The double-effect falling film evaporation temperature is 90 ℃, and the vacuum degree is 0.1 bar. The rectifying tower is a packed tower, the temperature of the top of the tower is 200 ℃, and the temperature of the bottom of the tower is 280 ℃. The packing in the packed tower is a stepped ring, the height of the tower is 20 meters, and the extraction position of nitrobenzene is 1.5 meters away from the top of the tower. The yield of m-dinitrobenzene after secondary recrystallization of ethanol is 90 percent.
Example 10
The strong-acid proton type ionic liquid catalyst is N, N ‒ tetramethyl butanediamine sulfate, and the molar ratio of the catalyst to the cation is sulfuric acid =1: 6. The molar ratio of nitric acid to benzene is 2.03:1, the mass ratio of strong acid proton type ionic liquid to benzene is 1:1, the reaction temperature is 90 ℃, and the retention time is 3 hours. The volume ratio of nitrobenzene extraction (nitrobenzene: lower phase catalyst) is 1.3:1, and the extraction temperature is 90 ℃. The volume ratio of water washing (water: crude product of the upper phase) is 0.8:1, and the water washing temperature is 90 ℃. The temperature of the first-effect falling film evaporation is 90 ℃, and the vacuum degree is 0.1 bar. The double-effect falling film evaporation temperature is 100 ℃, and the vacuum degree is 0.1 bar. The rectifying tower is a plate tower, the temperature of the top of the tower is 230 ℃, and the temperature of the bottom of the tower is 300 ℃. The number of the plate tower plates is 60, and the nitrobenzene extraction position is at the 5 th plate from the top of the tower. The yield of m-dinitrobenzene after secondary recrystallization of ethanol is 92 percent.
Claims (10)
1. A green nitration method based on strong acid proton type ionic liquid catalysis is characterized by comprising the following steps: benzene, nitric acid and a catalyst are continuously reacted; after the reaction is finished, phase splitting is carried out, the lower phase catalyst is extracted by nitrobenzene, and after the extraction is finished, the extraction phase and the crude product of the upper phase after the phase splitting are combined and washed by water; after extraction, carrying out double-effect falling film evaporation on the raffinate phase; the evaporated water is sent to wash the upper phase crude product, and the catalyst obtained after evaporation continuously participates in the reaction; the water phase obtained by washing the upper phase crude product after phase splitting and the raffinate phase in the nitrobenzene extraction step are combined and enter into double-effect falling film evaporation; and (3) washing the upper phase crude product to obtain a mixture of mixed dinitrobenzene and nitrobenzene, re-separating the mixture by a rectifying tower, returning the separated light component nitrobenzene to the reaction step, and crystallizing and separating the separated heavy component mixed dinitrobenzene to obtain the product m-dinitrobenzene.
2. The process according to claim 1, characterized in that the catalyst is a strongly acidic protic ionic liquid, the ionic liquid cation is an alkyl diamine or triamine selected from the group consisting of N, N ‒ tetramethylethylenediamine, N ‒ tetramethylpropylenediamine, N ‒ tetramethylbutanediamine, N ‒ hexamethylbutanetriamine, N ‒ hexamethylheptatriamine, the anion is sulfuric acid, the catalyst synthesis molar ratio is cation: sulfuric acid =1: 1-10.
3. The method according to claim 1, wherein the molar ratio of the nitric acid to the benzene is 2-2.08: 1, and the mass ratio of the strongly acidic proton type ionic liquid to the benzene is 0.5-2: 1.
4. The method according to claim 1, wherein the reaction temperature is 80 to 130 ℃ and the residence time is 1 to 3 hours.
5. The method according to claim 1, wherein the volume ratio of extraction (nitrobenzene: lower phase catalyst) is 0.5-1.5: 1, and the extraction temperature is 80-120 ℃.
6. The method according to claim 1, wherein the extraction volume ratio (water: crude product in the upper phase) is 0.5-1: 1, and the water washing temperature is 80-120 ℃.
7. The method according to claim 1, wherein the temperature of the single-effect falling film evaporation is 60-80 ℃ and the vacuum degree is 0.1 bar; the temperature of the double-effect falling film evaporation is 80-100 ℃, and the vacuum degree is 0.1 bar.
8. The method according to claim 1, wherein the rectifying tower is a packed tower or a plate tower, the tower rectifying tower has the top temperature of 180-230 ℃ and the bottom temperature of 280-300 ℃.
9. The method according to claim 8, characterized in that the packing in the packed tower is one of ɵ ring packing and ladder ring packing, the height of the tower is 15-30m, and the position of extracting nitrobenzene is 1-2 m from the top of the tower; the number of the plate tower plates of the plate tower is 40-60, and the nitrobenzene extraction position is 1-5 plates away from the tower top.
10. The process according to claim 1, characterized in that the crystallization solvent is ethanol.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5488187A (en) * | 1988-06-22 | 1996-01-30 | Olin Corporation | Process for the production of dinitrobenzene and mononitrobenzene |
| CN1469859A (en) * | 2000-10-10 | 2004-01-21 | ������˹��Ů����ѧ | Aromatic nitration reactions |
| CN102060715A (en) * | 2010-12-22 | 2011-05-18 | 南京大学 | Double quaternary ammonium carboxylate functional ionic liquid and preparation method thereof |
| CN102416347A (en) * | 2011-08-31 | 2012-04-18 | 中山大桥化工集团有限公司 | Multi-ionic liquid catalyst and application thereof in synthesizing acrylate compounds |
| 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 |
| CN103113232A (en) * | 2013-01-22 | 2013-05-22 | 南京理工大学 | Method for catalyzing and nitrifying methylbenzene in micro-reactor |
| CN103553925A (en) * | 2013-10-28 | 2014-02-05 | 河北工业大学 | Process for synthesizing nitrocyclohexane by liquid phase nitration |
-
2018
- 2018-11-08 CN CN201811325199.XA patent/CN111153802A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5488187A (en) * | 1988-06-22 | 1996-01-30 | Olin Corporation | Process for the production of dinitrobenzene and mononitrobenzene |
| CN1469859A (en) * | 2000-10-10 | 2004-01-21 | ������˹��Ů����ѧ | Aromatic nitration reactions |
| CN102060715A (en) * | 2010-12-22 | 2011-05-18 | 南京大学 | Double quaternary ammonium carboxylate functional ionic liquid and preparation method thereof |
| 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 |
| CN102416347A (en) * | 2011-08-31 | 2012-04-18 | 中山大桥化工集团有限公司 | Multi-ionic liquid catalyst and application thereof in synthesizing acrylate compounds |
| CN103113232A (en) * | 2013-01-22 | 2013-05-22 | 南京理工大学 | Method for catalyzing and nitrifying methylbenzene in micro-reactor |
| CN103553925A (en) * | 2013-10-28 | 2014-02-05 | 河北工业大学 | Process for synthesizing nitrocyclohexane by liquid phase nitration |
Non-Patent Citations (1)
| Title |
|---|
| PENG-CHENG WANG等: "Regioselectivity nitration of aromatics with N2O5 in PEG-based dicationic ionic liquid", 《TETRAHEDRON LETTERS》 * |
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Application publication date: 20200515 |
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