CN112439410A - Catalyst for synthesizing aromatic ketone and method for catalytically synthesizing aromatic ketone by using same - Google Patents
Catalyst for synthesizing aromatic ketone and method for catalytically synthesizing aromatic ketone by using same Download PDFInfo
- Publication number
- CN112439410A CN112439410A CN202011404704.7A CN202011404704A CN112439410A CN 112439410 A CN112439410 A CN 112439410A CN 202011404704 A CN202011404704 A CN 202011404704A CN 112439410 A CN112439410 A CN 112439410A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acid
- aromatic ketone
- aromatic
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/48—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation involving decarboxylation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for synthesizing aromatic ketone and a method for catalytically synthesizing aromatic ketone by using the catalyst, wherein the catalyst is simple to prepare, low in cost and capable of being activated for recycling; the process for continuously synthesizing the aromatic ketone by high-temperature catalysis is green and environment-friendly, has high utilization rate of raw materials, less three-waste emission and great industrialization prospect.
Description
Technical Field
The invention relates to a catalyst for synthesizing aromatic ketone and a method for synthesizing aromatic ketone by catalyzing the same.
Technical Field
The aromatic ketone compounds are both photoinitiators and important intermediates for synthesizing other photoinitiators, for example, benzophenone, 4-chlorobenzophenone and 4-methylbenzophenone are important photoinitiator varieties per se, phenylcyclohexyl ketone is an important intermediate for the photoinitiator UV184, isobutyrophenone is an important intermediate for synthesizing the photoinitiator UV1173, and other alpha-amino ketone photoinitiators also need to be used as aromatic ketone intermediates.
In the production of industrial aromatic ketone compounds, aromatic hydrocarbon and acyl chloride are mostly prepared through Friede-Crafts acylation reaction, the process needs to prepare an acyl chloride intermediate firstly, and then react with aromatic hydrocarbon at low temperature by taking metal halide as a catalyst for synthesis, the defects of long reaction time, high energy consumption and high equipment requirement generally exist, and in addition, the production process also has serious hidden danger of environmental protection: the reaction is accompanied by the production of a large amount of acidic waste gas; the catalyst has large dosage and is difficult to recycle, and a large amount of solid by-products and waste water are generated, thereby being a non-environment-friendly technical route.
Based on the above, the invention provides a novel aromatic ketone synthesis catalyst and a method for catalytically synthesizing aromatic ketone, so as to solve the problems in the technical scheme.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalyst which is low in price, good in selectivity and high in catalytic efficiency and can be used for synthesizing aromatic ketone by continuous reaction and a method for synthesizing aromatic ketone by catalytic synthesis of the catalyst.
The technical scheme for realizing the first purpose of the invention is a catalyst for catalytically synthesizing aromatic ketone, wherein the catalyst is a magnesium-manganese bimetallic catalyst, and the preparation method comprises the following steps: dissolving magnesium chloride and manganous chloride in deionized water to prepare a mixed solution, simultaneously dripping the mixed solution and a sodium hydroxide solution into a three-neck flask under normal temperature stirring, heating to 60 ℃ after dripping, carrying out heat preservation reaction for 2 hours, filtering, washing a filter cake with the deionized water until the pH value is 7, extruding the filter cake into granules, drying in vacuum, and roasting at high temperature for 2 hours in a nitrogen atmosphere.
Wherein the molar ratio of the magnesium chloride to the manganous chloride used in the preparation method of the catalyst is 0.05-0.5: 1.
The molar equivalent of the sodium hydroxide is 2-2.5 times of the sum of the molar equivalents of the magnesium chloride and the manganous chloride.
The high-temperature roasting temperature of the catalyst is 450-500 ℃.
The technical scheme for realizing the second purpose of the invention is a method for catalytically synthesizing aromatic ketone, which comprises the following steps:
filling a catalyst into a high-temperature-resistant quartz tube reactor, and heating to a reaction temperature under the protection of nitrogen;
secondly, mixing and melting two organic acid raw materials, and then continuously feeding the mixture into a reactor for reaction along with a certain amount of high-temperature steam by a pump;
thirdly, the reacted materials are collected after condensation, the product ketone and the unreacted organic acid are separated, and the organic acid repeatedly enters the reactor for reaction.
The optimal reaction temperature in the step I is 280-350 ℃.
In the step (II), the organic acid raw material can be the same aromatic acid or a mixture of the aromatic acid and another aromatic acid or fatty acid.
In the second step, the feeding speed of the two organic acid raw materials is controlled to be 80-120 kg/h, and the feeding speed of the high-temperature steam is controlled to be 10-15 kg/h.
Also includes the step of recovering the catalyst; during recovery, the deactivated catalyst is dissolved in dilute hydrochloric acid, sodium sulfite solution is added for reduction, insoluble matters are removed by filtration, and the filtrate is continuously reacted with sodium hydroxide solution according to claim 1 and subjected to subsequent treatment to obtain the activated catalyst.
If the raw materials are two different organic acids, the mass ratio of the two organic acids is 0.8-1.2: 1; if fatty acids are present in the feedstock, it is preferred to have an excess of fatty acids.
The invention has the following positive effects:
(1) the catalyst preparation has the advantages of low raw material price, simple preparation method and low production cost;
(2) the process for catalytically synthesizing the aromatic ketone is green and environment-friendly, water and carbon dioxide are byproducts, and three wastes are not generated;
(3) the magnesium salt is added into the catalyst, so that the selectivity of the target ketone generated by mutual decarboxylation of two different organic acids is improved, and the difficulty in post-treatment and separation of the product is reduced;
(4) the service life of the catalyst can be effectively prolonged by introducing high-temperature water vapor into the reactor, so that the service life of the catalyst is prolonged from 7 days to 15 days, and the use cost of the catalyst is greatly reduced;
(5) the catalyst and the method for catalytically synthesizing aromatic ketone provided by the invention can realize continuous production and are beneficial to improving the production efficiency.
Detailed Description
The following examples illustrate the invention in detail, but the following examples are not intended to limit the invention thereto.
Example 1: preparation of phenylcyclohexyl methanones
a. Preparation of the catalyst
Weighing 47.5g of magnesium chloride and 126g of manganous chloride, dissolving the magnesium chloride and the manganous chloride in 300ml of deionized water, stirring the mixture at normal temperature until the magnesium chloride and the manganous chloride are completely dissolved, then dripping the mixture into a three-neck flask with stirring together with 800g of 15% sodium hydroxide solution to react to generate a large amount of white to light red solids, heating the mixture to 60 ℃ after dripping, carrying out heat preservation reaction for 2 hours, filtering the mixture, washing filter cakes with 100ml of deionized water for 3 times respectively, extruding the filter cakes into granules through an extruder, drying the granules in a vacuum drying oven to remove moisture, then putting the granules into a high-temperature box, and roasting the granules at 500 ℃
b. Synthesis of phenylcyclohexyl ketone
Filling the catalyst prepared in the step a into a quartz tube, heating to 340 ℃ by using an electric heating zone under the protection of nitrogen, mixing and melting the cyclohexanecarboxylic acid and the benzoic acid according to the molar ratio of 1.2:1, controlling the flow rate by using a peristaltic pump to continuously feed, and controlling the flow rate by using another pump to continuously pump high-temperature steam; reacting the mixed acid through a catalyst layer, discharging the reacted mixed acid, cooling the reacted mixed acid in a condenser, collecting the cooled mixed acid, continuously feeding the collected mixed acid into a rectifying tower to separate the incompletely reacted mixed acid and a product, continuously performing the reaction for 17 hours, accumulating 1800g of feeding materials (wherein 1012.5g of cyclohexanecarboxylic acid and 787.5g of benzoic acid), finally collecting 1036.1g of phenylcyclohexyl ketone, recovering 229.55g of cyclohexanecarboxylic acid, recovering 118.02g of benzoic acid, and obtaining 25.46g of a small amount of dicyclohexyl ketone byproduct; the utilization rate of benzoic acid is about 99.6%.
Example 2: preparation of isobutyrophenone
a. Preparation of catalyst reference example 1 step a;
b. synthesis of isobutyrophenone
Filling the catalyst prepared in the step a into a quartz tube, heating to 340 ℃ by using an electric heating zone under the protection of nitrogen, mixing and melting isobutyric acid and benzoic acid according to the molar ratio of 1.2:1, controlling the flow rate by using a peristaltic pump to continuously feed, and controlling the flow rate by using another pump to continuously pump high-temperature steam; reacting the mixed acid through a catalyst layer, discharging the reacted mixed acid, cooling the reacted mixed acid in a condenser, collecting the cooled mixed acid, continuously feeding the collected mixed acid into a rectifying tower to separate the mixed acid and products which are not completely reacted, continuously carrying out the reaction for 2 hours, accumulating 227.6g of feed (wherein the feed contains 106g of isobutyric acid and 121.56g of benzoic acid), finally collecting 126.2g of isobutyrylbenzene, recovering 27.3g of isobutyric acid, recovering 7g of benzoic acid and carrying out 2.5g of a small amount of byproduct diisopropyl ketone; the utilization rate of benzoic acid is about 92.0%.
Example 3: preparation of benzophenone
a. Preparation of catalyst reference example 1 step a;
b. synthesis of benzophenone
Filling the catalyst prepared in the step a into a quartz tube, heating to 340 ℃ by using an electric heating zone under the protection of nitrogen, continuously feeding benzoic acid at a flow rate controlled by a peristaltic pump after the benzoic acid is molten, and continuously pumping high-temperature steam at the flow rate controlled by another pump; reacting the mixed acid through a catalyst layer, discharging the material, cooling the material in a condenser, collecting the material, continuously feeding the material into a rectifying tower to separate the mixed acid and the product which are not completely reacted, continuously performing the reaction for 2 hours, accumulating 252.7g of the fed benzoic acid, finally collecting 162.2g of the benzophenone product, recovering 34.2g of the benzoic acid, generating almost no by-product, and ensuring that the utilization rate of the benzoic acid is 99.47 percent
Example 4: preparation of p-chlorobenzene butanone
a. Preparation of catalyst reference example 1 step a;
b. synthesis of p-chlorobenzene butanone
Filling the catalyst prepared in the step a into a quartz tube, heating to 340 ℃ by using an electric heating zone under the protection of nitrogen, mixing and melting n-butyric acid and p-chlorobenzoic acid according to the molar ratio of 1.2:1, controlling the flow rate by using a peristaltic pump to continuously feed, and controlling the flow rate by using another pump to continuously pump high-temperature steam; the mixed acid is discharged after reaction through a catalyst layer, enters a condenser for cooling, is collected and then continuously enters a rectifying tower to separate the mixed acid and products which are not completely reacted, the reaction is continuously carried out for 2 hours, 308.4g of the mixed acid is accumulated and fed (wherein 124.2g of n-butyric acid and 184.2g of p-chlorobenzoic acid), 195.1g of p-chlorobenzoic butanone is finally separated, 15.9g of p-chlorobenzoic acid, 25.8g of n-butyric acid, 3.66g of byproducts are recovered, and the utilization rate of the benzoic acid is 99.3%.
Claims (10)
1. A catalyst for catalytic synthesis of aromatic ketone is characterized in that the catalyst is a magnesium-manganese bimetallic catalyst, and the preparation method comprises the following steps: dissolving magnesium chloride and manganous chloride in deionized water to prepare a mixed solution, simultaneously dripping the mixed solution and a sodium hydroxide solution into a three-neck flask under normal temperature stirring, heating to 60 ℃ after dripping, carrying out heat preservation reaction for 2 hours, filtering, washing a filter cake with the deionized water until the pH value is 7, extruding the filter cake into granules, drying in vacuum, and roasting at high temperature for 2 hours in a nitrogen atmosphere.
2. The catalyst for catalytic synthesis of aromatic ketones according to claim 1, characterized in that: the molar ratio of the magnesium chloride to the manganous chloride used in the preparation method is 0.05-0.5: 1.
3. The catalyst for catalytic synthesis of aromatic ketones according to claim 1, characterized in that: the molar equivalent of the sodium hydroxide used in the preparation method is 2-2.5 times of the sum of the molar equivalents of the magnesium chloride and the manganous chloride.
4. The catalyst for catalytic synthesis of aromatic ketones according to claim 1, characterized in that: the high-temperature roasting temperature of the catalyst in the preparation method is 450-500 ℃.
5. The method for catalytically synthesizing the aromatic ketone is characterized by comprising the following steps of:
filling a catalyst into a high-temperature-resistant quartz tube reactor, and heating to a reaction temperature under the protection of nitrogen;
melting the organic acid raw material, continuously feeding the melted raw material into a reactor along with high-temperature steam by a pump for reaction;
thirdly, the reacted materials are collected after condensation, the product ketone and the unreacted organic acid are separated, and the organic acid repeatedly enters the reactor for reaction.
6. The method of claim 5, wherein the step of catalytically synthesizing the aromatic ketone comprises: the reaction temperature in the step I is 280-350 ℃.
7. The method of claim 5, wherein the step of catalytically synthesizing the aromatic ketone comprises: in the step (II), the organic acid raw material can be the same aromatic acid or a mixture of the aromatic acid and another aromatic acid or fatty acid.
8. The method of claim 5, wherein the step of catalytically synthesizing the aromatic ketone comprises: secondly, the feeding speed of the organic acid is controlled to be 80-120 kg/h, and the feeding speed of the high-temperature steam is controlled to be 10-15 kg/h.
9. The method of claim 5, wherein the step of catalytically synthesizing the aromatic ketone comprises: also includes the step of recovering the catalyst; during recovery, the deactivated catalyst is dissolved in dilute hydrochloric acid, sodium sulfite solution is added for reduction, insoluble matters are removed by filtration, and the filtrate is continuously reacted with sodium hydroxide solution according to claim 1 and subjected to subsequent treatment to obtain the activated catalyst.
10. The method of claim 7, further comprising: if the raw materials are two different organic acids, the mass ratio of the two organic acids is 0.8-1.2: 1; if fatty acids are present in the feedstock, it is preferred to have an excess of fatty acids.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011404704.7A CN112439410A (en) | 2020-12-03 | 2020-12-03 | Catalyst for synthesizing aromatic ketone and method for catalytically synthesizing aromatic ketone by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011404704.7A CN112439410A (en) | 2020-12-03 | 2020-12-03 | Catalyst for synthesizing aromatic ketone and method for catalytically synthesizing aromatic ketone by using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112439410A true CN112439410A (en) | 2021-03-05 |
Family
ID=74740512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011404704.7A Pending CN112439410A (en) | 2020-12-03 | 2020-12-03 | Catalyst for synthesizing aromatic ketone and method for catalytically synthesizing aromatic ketone by using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112439410A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1030003A (en) * | 1962-05-07 | 1966-05-18 | Snia Viscosa Societa' Nazionale Industria Applicazioni Viscosa S.P.A. | |
| FR2612181A1 (en) * | 1987-03-11 | 1988-09-16 | Elf Aquitaine | Process for the preparation of diketones by the reaction of an organometallic compound with a compound carrying two carbonyl groups, in a solvent |
| CN101743222A (en) * | 2007-07-16 | 2010-06-16 | 埃克森美孚化学专利公司 | The method of oxidizing alkylaromatic compounds |
| CN102875343A (en) * | 2012-10-31 | 2013-01-16 | 南京林业大学 | Method for preparing aromatic aldehyde compound by catalyzing and degrading lignin with loaded solid acid |
| CN107513012A (en) * | 2016-06-15 | 2017-12-26 | 江苏英力科技发展有限公司 | A kind of continuous method for preparing 1 (4 chlorphenyl) 1 butanone |
| CN108187688A (en) * | 2018-01-25 | 2018-06-22 | 北京科技大学 | It is a kind of can be at room temperature by the preparation method of the catalyst of formaldehyde complete catalysts oxidation |
| CN109926040A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of heterogeneous catalyst preparing isophorone and its preparation and application |
| CN110922313A (en) * | 2019-12-19 | 2020-03-27 | 连云港德洋化工有限公司 | Method for continuously producing aromatic ketone |
| CN110975884A (en) * | 2019-12-17 | 2020-04-10 | 南京工程学院 | Preparation method of transition metal-containing catalyst for preparing benzaldehyde by selectively oxidizing toluene |
-
2020
- 2020-12-03 CN CN202011404704.7A patent/CN112439410A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1030003A (en) * | 1962-05-07 | 1966-05-18 | Snia Viscosa Societa' Nazionale Industria Applicazioni Viscosa S.P.A. | |
| FR2612181A1 (en) * | 1987-03-11 | 1988-09-16 | Elf Aquitaine | Process for the preparation of diketones by the reaction of an organometallic compound with a compound carrying two carbonyl groups, in a solvent |
| CN101743222A (en) * | 2007-07-16 | 2010-06-16 | 埃克森美孚化学专利公司 | The method of oxidizing alkylaromatic compounds |
| CN102875343A (en) * | 2012-10-31 | 2013-01-16 | 南京林业大学 | Method for preparing aromatic aldehyde compound by catalyzing and degrading lignin with loaded solid acid |
| CN107513012A (en) * | 2016-06-15 | 2017-12-26 | 江苏英力科技发展有限公司 | A kind of continuous method for preparing 1 (4 chlorphenyl) 1 butanone |
| CN109926040A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of heterogeneous catalyst preparing isophorone and its preparation and application |
| CN108187688A (en) * | 2018-01-25 | 2018-06-22 | 北京科技大学 | It is a kind of can be at room temperature by the preparation method of the catalyst of formaldehyde complete catalysts oxidation |
| CN110975884A (en) * | 2019-12-17 | 2020-04-10 | 南京工程学院 | Preparation method of transition metal-containing catalyst for preparing benzaldehyde by selectively oxidizing toluene |
| CN110922313A (en) * | 2019-12-19 | 2020-03-27 | 连云港德洋化工有限公司 | Method for continuously producing aromatic ketone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4048196A (en) | Manufacture of butanediol and/or tetrahydrofuran from maleic and/or succinic anhydride via γ- butyrolactone | |
| KR102364274B1 (en) | Continuous process for the preparation of 2-methylallyl alcohol | |
| CN108911960A (en) | A kind of preparation method of photoinitiator 1- hydroxycyclohexyl phenyl ketone | |
| CN111662185B (en) | Synthesis method of N-methyl o-fluoroaniline | |
| CN101575269B (en) | Preparation method of aromatic methyl ether compound | |
| CN115894229A (en) | Selective synthesis process of monoethyl adipate | |
| CN101125810A (en) | Method for preparing isooctanoic acid | |
| CN112439410A (en) | Catalyst for synthesizing aromatic ketone and method for catalytically synthesizing aromatic ketone by using same | |
| CN114835564B (en) | Method for producing photoinitiator UV-1173 by condensation method | |
| CN114907234B (en) | Preparation method of 2-fluoro-5-formylbenzonitrile | |
| CN111099975A (en) | Preparation method of 5-bromo-2-chloro-4' -ethoxy benzophenone | |
| US6162946A (en) | Processing for producing allyl 2-hydroxyisobutyrate | |
| CN1197792A (en) | Liquid phase oxidation and carbonylation process synthesizing dimethyl carbonate | |
| CN104098438B (en) | A kind of method of Separation and Recovery Pentyl alcohol from pimelinketone by-product lightweight oil | |
| CN107602408B (en) | Synthesis method of acetamino diethyl malonate | |
| CN106565438A (en) | Preparation method of isophthalaldehyde | |
| CN110655442A (en) | Novel chlorination process of o-chlorotrifluoromethylene | |
| CN114085132B (en) | Preparation method of 2, 6-dihydroxytoluene | |
| CN101665420A (en) | Method for preparing vanilline | |
| CN115246772B (en) | Preparation method of isobutyryl methyl acetate | |
| CN101658802B (en) | Supported ionic liquid catalyst and preparation and applications thereof | |
| CN112174801B (en) | Method for coproducing glycolic acid and 1,1,1, 2-tetrafluoroethane by one-pot method | |
| JPH11171825A (en) | Production of benzoyl chloride | |
| CN115368217B (en) | Synthesis method of 3,4, 5-trimethoxytoluene | |
| CN112661737A (en) | Method for synthesizing coumarin-3-carboxylic acid by low-temperature co-melting liquid catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210305 |
|
| WD01 | Invention patent application deemed withdrawn after publication |