CN111039803A - Method for preparing amino-substituted cyclohexanol from cyclohexane oxidation by-product - Google Patents
Method for preparing amino-substituted cyclohexanol from cyclohexane oxidation by-product Download PDFInfo
- Publication number
- CN111039803A CN111039803A CN201811190602.2A CN201811190602A CN111039803A CN 111039803 A CN111039803 A CN 111039803A CN 201811190602 A CN201811190602 A CN 201811190602A CN 111039803 A CN111039803 A CN 111039803A
- Authority
- CN
- China
- Prior art keywords
- light oil
- reaction
- amine
- micro
- amino
- 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
- 238000000034 method Methods 0.000 title claims abstract description 29
- -1 amino-substituted cyclohexanol Chemical class 0.000 title claims abstract description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000006227 byproduct Substances 0.000 title claims abstract description 10
- 230000003647 oxidation Effects 0.000 title claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000047 product Substances 0.000 claims abstract description 22
- 150000001412 amines Chemical class 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000005576 amination reaction Methods 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CCHNWURRBFGQCD-UHFFFAOYSA-N 2-chlorocyclohexan-1-one Chemical compound ClC1CCCCC1=O CCHNWURRBFGQCD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing amino-substituted cyclohexanol from cyclohexane oxidation byproducts, which comprises the steps of leading light oil and amine to a micro-channel reaction module from two inlets of a micro-channel reactor, controlling the feeding molar ratio of the epoxy cyclohexane to the amine in the light oil to be 1:1-15, staying and reacting reaction materials in the micro-channel reactor for 1-30 min at the temperature of 70-130 ℃, and rectifying and separating products to obtain the amino-substituted cyclohexanol. The invention takes light oil as a raw material, utilizes the epoxy cyclohexane amination reaction to prepare the amino-substituted cyclohexanol, adopts the microchannel reactor process, and has the advantages of mild and safe reaction conditions, rapid reaction, short retention time, less side reactions, high production efficiency and the like.
Description
Technical Field
The invention relates to a utilization method of cyclohexane oxidation by-product light oil, in particular to a method for preparing amino-substituted cyclohexanol by using cyclohexane oxidation by-product.
Background
The preparation of cyclohexanone by cyclohexane oxidation is one of the main methods for industrial production of cyclohexanone. When cyclohexane is used for preparing cyclohexanone, the light oil which is a byproduct distilled from the top of a light tower is a low-boiling-point mixture and contains various compounds such as cyclohexane, n-amyl alcohol, epoxy cyclohexane and the like, the yield of the light oil is about 1-3% of the yield of the cyclohexanone, and the content of the main components of the impurities in the light oil, namely the epoxy cyclohexane and the n-amyl alcohol, reaches 55-80 wt%. Because the components are relatively complex, the light oil is generally incinerated or sold as a low-grade solvent, the added value is low, and certain environmental risks are caused. The light oil has high reaction activity of the cyclohexene oxide, and can react with ammonia, alcohol, acid and the like to prepare related products, so that the recycling and utilization of the cyclohexene oxide in the light oil can generate certain economic benefit.
At present, some patents disclose technologies for recovering cyclohexene oxide from light oil byproducts, such as chinese patents CN 1059675C, CN 1060169C, CN106316990A, CN104098438B, and CN103508982A, mainly use methods such as chemical reaction to increase the boiling point difference of components difficult to separate, so as to achieve the separation purpose and then react to generate cyclohexene oxide; also, patents describe methods for preparing other chemicals using light oil as raw material, such as chinese patents CN102464579B, CN107540531A and CN1331068A, which describe methods for preparing chemicals such as adipic acid, o-chlorocyclohexanone and 2- (4-p-tert-butylphenoxy) cyclohexanol using light oil as raw material. Although the above patents describe some methods for light oil utilization, with the change of domestic chemical production energy and the change of downstream requirements, no matter cyclohexene oxide, adipic acid and the like, a surplus situation occurs, and the economical efficiency of light oil utilization is reduced.
The amino-substituted cyclohexanol is a fine chemical product with wide application range and great development value, and has high reactive groups such as amino, hydroxyl and the like, so that the amino-substituted cyclohexanol is used as a raw material in the fields of biological medicine, agriculture and the like to synthesize high-added-value products such as medicines or pesticides. Chinese patent CN102731325A discloses a method for preparing trans-aminocyclohexanol, which uses trans-benzyl cyclohexanol as raw material, and the raw material is prepared by the processes of reaction with dimethyl sulfate and hydrogenation, wherein the reaction conditions are harsh, and the cost of the used raw material is high. The invention provides a simple method for preparing amino-substituted cyclohexanol by using light oil as a raw material, adopting a microchannel reactor technology and utilizing the characteristics of efficient mixing, sufficient contact and the like of the microchannel reactor, and the method can be used for quickly and efficiently realizing high added value utilization of the light oil under mild conditions and has high economic benefit.
Disclosure of Invention
The invention aims to: the method comprises the following steps of (A) providing a method for refining and utilizing light oil; (2) provides a method for preparing amino-substituted cyclohexanol rapidly and efficiently at low cost.
The purpose of the invention is realized by the following technical scheme: a method for preparing amino-substituted cyclohexanol from cyclohexane oxidation byproducts comprises the steps of leading light oil and amine to a micro-channel reactor module from two inlets of the micro-channel reactor, controlling the feeding molar ratio of epoxy cyclohexane to amine in the light oil to be 1:1-15, reacting at 70-130 ℃, keeping reaction materials in the micro-channel reactor for 1-30 min, and rectifying and separating products to obtain the amino-substituted cyclohexanol.
In the above reaction, the molar ratio of the cyclohexene oxide to the amine in the light oil is preferably 1: 3-10.
The reaction temperature is preferably 90-110 ℃; the residence time of the reaction mass in the microchannel reactor is preferably from 3min to 20 min.
The pressure bearing capacity of the microchannel reactor module reaches 7.5 Mpa.
The amine is one of inorganic ammonia and organic amine, the inorganic ammonia is one of ammonia water or liquid ammonia, and the organic amine is one of methylamine, dimethylamine, ethanolamine and diethanolamine.
The invention discloses a method for refining and utilizing light oil as an oxidation byproduct of epoxy cyclohexane, which has low cost of raw materials and is realized by the following reaction of the epoxy cyclohexane and amine in a microchannel reactor:
wherein R is1And R2Selected from-H, -H; -H, -CH3；-CH3、-CH3；-H、-CH2CH2OH；-CH2CH2OH、-CH2CH2One of OH.
The invention has the remarkable characteristics that: the light oil is taken as a raw material, and the amino-substituted cyclohexanol is prepared by amination reaction, so that the aim of high value-added utilization of the light oil is fulfilled; the microchannel reactor process is adopted, so that the reaction condition is mild and the safe operation is facilitated; the reaction is rapid, the retention time is short, the side reaction is less, the utilization rate of raw materials is high, and the production efficiency is high.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples.
Example 1
Injecting light oil and liquid ammonia into a microchannel reactor through a metering pump for reaction, wherein the feeding molar ratio of the cyclohexene oxide to the liquid ammonia in the light oil is 1:1, the reaction temperature is 70 ℃, continuously collecting products after the reaction is carried out for 30min, and analyzing the composition of the products by adopting a chromatographic method, wherein the conversion rate of the cyclohexene oxide is 85.2%, and the selectivity is 82.1%.
Example 2
Injecting light oil and liquid ammonia into a microchannel reactor through a metering pump for reaction, wherein the feeding molar ratio of the cyclohexene oxide to the liquid ammonia in the light oil is 1:3, the reaction temperature is 90 ℃, the reaction is kept for 20min, then products are continuously collected, and the composition of the products is analyzed by adopting a chromatographic method, wherein the conversion rate of the cyclohexene oxide is 98.8%, and the selectivity is 91.1%.
Example 3
Injecting light oil and liquid ammonia into a microchannel reactor through a metering pump for reaction, wherein the feeding molar ratio of the cyclohexene oxide to the liquid ammonia in the light oil is 1:8, the reaction temperature is 100 ℃, continuously collecting products after the light oil and the liquid ammonia stay for reaction for 6min, and analyzing the composition of the products by adopting a chromatographic method, wherein the conversion rate of the cyclohexene oxide is 99.5%, and the selectivity is 96.2%.
Example 4
Injecting light oil and liquid ammonia into a microchannel reactor through a metering pump for reaction, wherein the feeding molar ratio of the cyclohexene oxide to the liquid ammonia in the light oil is 1:10, the reaction temperature is 110 ℃, continuously collecting products after the reaction is carried out for 3min, and analyzing the composition of the products by adopting chromatography, wherein the conversion rate of the cyclohexene oxide is 99.8%, and the selectivity is 97.1%.
Example 5
Injecting light oil and liquid ammonia into a microchannel reactor through a metering pump for reaction, wherein the feeding molar ratio of the cyclohexene oxide to the liquid ammonia in the light oil is 1:15, the reaction temperature is 90 ℃, continuously collecting products after the light oil and the liquid ammonia stay for reaction for 15min, and analyzing the composition of the products by adopting a chromatographic method, wherein the conversion rate of the cyclohexene oxide is 99.9%, and the selectivity is 98.1%.
Example 6
Injecting light oil and liquid ammonia into a microchannel reactor through a metering pump for reaction, wherein the feeding molar ratio of the cyclohexene oxide to the liquid ammonia in the light oil is 1:3, the reaction temperature is 130 ℃, continuously collecting products after the light oil and the liquid ammonia stay for reaction for 1min, and analyzing the composition of the products by adopting chromatography, wherein the conversion rate of the cyclohexene oxide is 97.2%, and the selectivity is 89.1%.
Example 7
Injecting light oil and dimethylamine into a microchannel reactor through a metering pump for reaction, wherein the feeding molar ratio of the cyclohexene oxide to the dimethylamine in the light oil is 1:8, the reaction temperature is 100 ℃, continuously collecting the product after the light oil is subjected to a residence reaction for 10min, and analyzing the composition of the product by adopting a chromatographic method, wherein the conversion rate of the cyclohexene oxide is 99.3%, and the selectivity is 99.5%.
Example 8
Injecting light oil and dimethylamine into a microchannel reactor through a metering pump for reaction, wherein the feeding molar ratio of epoxy cyclohexane to ethanolamine in the light oil is 1:8, the reaction temperature is 100 ℃, continuously collecting products after the reaction is carried out for 10min, and analyzing the composition of the products by adopting a chromatographic method, wherein the conversion rate of the epoxy cyclohexane is 99.5%, and the selectivity is 92.5%.
Claims (8)
1. A method for preparing amino-substituted cyclohexanol from cyclohexane oxidation byproducts, comprising: leading light oil and amine to a micro-channel reactor module from two inlets of the micro-channel reactor, controlling the feeding molar ratio of epoxy cyclohexane to amine in the light oil to be 1:1-15, reacting at 70-130 ℃, keeping the reaction material in the micro-channel reactor for 1-30 min, and rectifying and separating the product to obtain the amino substituted cyclohexanol.
2. The method of claim 1, wherein the light oil has a molar ratio of epoxy cyclohexane to amine of 1:3 to 10.
3. The method of claim 1, wherein the reaction temperature is 90-110 ℃.
4. The process of claim 1 wherein the residence time of the reaction mass in the microchannel reactor is from 3min to 20 min.
5. The method of claim 1 wherein the microchannel reactor module has a pressure capacity of 7.5 Mpa.
6. The method of claim 1, wherein the amine is one of inorganic ammonia and organic amines.
7. The method of claim 6, wherein the inorganic ammonia is one of aqueous ammonia or liquid ammonia.
8. The method of claim 6, wherein the organic amine is one of methylamine, dimethylamine, ethanolamine, and diethanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811190602.2A CN111039803A (en) | 2018-10-12 | 2018-10-12 | Method for preparing amino-substituted cyclohexanol from cyclohexane oxidation by-product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811190602.2A CN111039803A (en) | 2018-10-12 | 2018-10-12 | Method for preparing amino-substituted cyclohexanol from cyclohexane oxidation by-product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111039803A true CN111039803A (en) | 2020-04-21 |
Family
ID=70229753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811190602.2A Pending CN111039803A (en) | 2018-10-12 | 2018-10-12 | Method for preparing amino-substituted cyclohexanol from cyclohexane oxidation by-product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111039803A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100185012A1 (en) * | 2007-06-19 | 2010-07-22 | Toray Fine Chemicals Co., Ltd | Method for producing optically active trans-2-aminocyclohexanol and intermediate of optically active trans-2-aminocyclohexanol |
| CN102464579A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化学工业开发股份有限公司 | Method for preparing hexanedioic acid from cyclohexane oxidation byproducts |
| CN104557653A (en) * | 2014-12-31 | 2015-04-29 | 大连联化化学有限公司 | Preparation method for 7-methyl-aza-bicyclo[4,1,0]heptane |
| CN106831450A (en) * | 2017-01-05 | 2017-06-13 | 湖南理工学院 | The technique that a kind of 7-oxa-bicyclo[4.1.0 prepares 2 (N hydroxyalkyls) cyclohexanol and 2 (N, N dihydroxyalkyl) cyclohexanol |
| CN107011190A (en) * | 2017-04-01 | 2017-08-04 | 湖南理工学院 | A kind of 1,2 7-oxa-bicyclo[4.1.0 open loop prepares the new technology of β aminocyclohexanols |
| CN108440305A (en) * | 2018-05-10 | 2018-08-24 | 岳阳昌德化工实业有限公司 | The preparation method of 1,2- cyclohexanediamine |
-
2018
- 2018-10-12 CN CN201811190602.2A patent/CN111039803A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100185012A1 (en) * | 2007-06-19 | 2010-07-22 | Toray Fine Chemicals Co., Ltd | Method for producing optically active trans-2-aminocyclohexanol and intermediate of optically active trans-2-aminocyclohexanol |
| CN102464579A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化学工业开发股份有限公司 | Method for preparing hexanedioic acid from cyclohexane oxidation byproducts |
| CN104557653A (en) * | 2014-12-31 | 2015-04-29 | 大连联化化学有限公司 | Preparation method for 7-methyl-aza-bicyclo[4,1,0]heptane |
| CN106831450A (en) * | 2017-01-05 | 2017-06-13 | 湖南理工学院 | The technique that a kind of 7-oxa-bicyclo[4.1.0 prepares 2 (N hydroxyalkyls) cyclohexanol and 2 (N, N dihydroxyalkyl) cyclohexanol |
| CN107011190A (en) * | 2017-04-01 | 2017-08-04 | 湖南理工学院 | A kind of 1,2 7-oxa-bicyclo[4.1.0 open loop prepares the new technology of β aminocyclohexanols |
| CN108440305A (en) * | 2018-05-10 | 2018-08-24 | 岳阳昌德化工实业有限公司 | The preparation method of 1,2- cyclohexanediamine |
Non-Patent Citations (4)
| Title |
|---|
| 李俊辉: "环己烷氧化副产物的综合利用", 《化工环保》 * |
| 李俊辉: "环己烷氧化时副产的综合利用", 《浙江化工》 * |
| 贡长生等: "《绿色化学》", 30 June 2008, 华中科技大学出版社 * |
| 韩飞: "环氧环己烷的综合利用", 《精细石油化工》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108840310B (en) | Device and process for producing hydrogen chloride by deep analysis from dilute hydrochloric acid | |
| CN106631701B (en) | Method for synthesizing 4-terpineol by catalyzing 1, 4-cineole through supported acid catalyst | |
| CN109535103B (en) | Method for preparing cyclohexene oxide by oxidizing cyclohexene | |
| CN103159191A (en) | Preparation method of hydroxylamine salt | |
| CN105130778A (en) | Production process of methyl isobutyl ketone | |
| CN106588590A (en) | Refinement method for polyoxymethylene dimethyl ether | |
| CN1927795A (en) | Method of preparing resorcin by hydrolyzing m-phenylenediamine | |
| CN107987037B (en) | Method for preparing epoxypropane in unit mode | |
| CN1683326A (en) | Process for producing methyl carbamate | |
| CN111039803A (en) | Method for preparing amino-substituted cyclohexanol from cyclohexane oxidation by-product | |
| CN106608832B (en) | The process of liquid ammonia process for caustic soda purification and Ammonia Process co-producing ethanol amine | |
| CN115368207B (en) | Method for purifying hexafluoropropylene dimer | |
| CN208883750U (en) | A kind of serialization prepare glycine around pipe reaction device | |
| CN111039801A (en) | Utilization method of cyclohexane oxidation by-product light oil | |
| CN103497157A (en) | 2-imidazolidone synthesis method | |
| CN102633768A (en) | Method for transforming cisconfiguration of oxane compounds to transconfiguration | |
| CN102464633A (en) | Synthetic method for (methyl) glycidyl acrylate | |
| CN112358387B (en) | Method for continuously producing monochloroacetone by micro-droplet reactor | |
| CN105585451B (en) | A kind of method that cyclopentene direct hydration prepares cyclopentanol | |
| CN105585468B (en) | A method of cyclopentanone is prepared by raw material of cyclopentene | |
| CN107602420B (en) | Process for synthesizing dimethyl urethanene malonate by batch reaction rectification | |
| CN113200872A (en) | Method for preparing 1, 8-p-menthane diamine by one-step method | |
| CN116178106A (en) | Method for preparing benzyl alcohol by using micro-channel reactor without alkali | |
| CN111072495A (en) | Method for purifying 2-methyl-1, 2-propane diamine | |
| CN115636741B (en) | Method for separating formaldehyde from formaldehyde organic solution and application thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200421 |
|
| RJ01 | Rejection of invention patent application after publication |