CN1772722A - Methyl heptenone preparing and refining process - Google Patents
Methyl heptenone preparing and refining process Download PDFInfo
- Publication number
- CN1772722A CN1772722A CN 200410068045 CN200410068045A CN1772722A CN 1772722 A CN1772722 A CN 1772722A CN 200410068045 CN200410068045 CN 200410068045 CN 200410068045 A CN200410068045 A CN 200410068045A CN 1772722 A CN1772722 A CN 1772722A
- Authority
- CN
- China
- Prior art keywords
- reaction
- acetone
- tower
- sodium hydroxide
- rectifying
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The methyl heptenone preparing and refining process includes the following steps: the condensation of chloroisoamylene and acetone inside sodium hydroxide aqua in the presence of ammonium cetyl trimethyl bromide as catalyst via stirring and filtering to eliminate reaction produced sodium chloride solid grain; letting the reaction product stand to laminate for separate oil phase and water phase; concentrating water phase for reuse; recovering unreacted acetone in an acetone recovering and rectifying tower to obtain reused acetone from the tower top; feeding the caldron material of the acetone recovering and rectifying tower to a reaction and refining tower for double acetol decomposition and refining in sodium hydroxide aqua; eliminating heavy component impurity from the caldron material of reaction and refining tower in a heavy component eliminating rectifying tower; and eliminating light component impurity of the tower top material from the heavy component eliminating rectifying tower and obtain the product.
Description
Technical field
The present invention relates to a kind of preparation and purified method of Sulcatone, is raw material with chloroisoamylene and acetone particularly, prepares the method for Sulcatone in aqueous sodium hydroxide solution by condensation reaction.
Background technology
Sulcatone has very strong chemical reaction ability, can be derivatized to many kinds of Chemicals, be medicine, essence and spices synthetic important intermediate, Sulcatone also is the main raw material of preparation phantol, citral and citrylideneacetone, and the latter can further prepare vitamin A, vitamin-E, vitamin K1 and multiple spices and essence etc.
The isoprene method is to make one of main operational path of Sulcatone, and isoprene at first generates chloroisoamylene with the hydrogenchloride addition reaction, and chloroisoamylene carries out condensation reaction generation Sulcatone with acetone in the presence of alkali lye then.Introduce adopting various amine compound or quaternary ammonium salt as patent JP40-22251 is that catalyzer carries out above-mentioned condensation reaction and prepares Sulcatone, the yield of Sulcatone is about 50%, JP56-115734 and JP56-6139 use chlorination triethylbenzene ammonium methyl and iodate triethyl isopentene group ammonium to carry out above-mentioned condensation reaction as catalyzer to prepare Sulcatone, the yield of Sulcatone reaches about 70%, also shortens to 3 hours with the reaction time.Existing chloroisoamylene and acetone prepare defective of method ubiquity of Sulcatone by condensation reaction, and promptly the yield of Sulcatone is on the low side, generally is no more than 75%.
Summary of the invention
The invention provides a kind of preparation and process for purification of Sulcatone, the technical problem that it will solve is to improve the yield of Sulcatone by the technology adjustment, and, reclaim the unreacted material and obtain colory refining Sulcatone product by refining step.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of preparation of Sulcatone and process for purification, this method comprises following process:
1) be raw material with chloroisoamylene and acetone, in aqueous sodium hydroxide solution, carry out condensation reaction, the content of sodium hydroxide is 42～55wt% in the aqueous sodium hydroxide solution, chloroisoamylene, the molar ratio of acetone and sodium hydroxide is 1: (6.5～8.4): (7.4～9.6), condensation reaction is catalyzer with the cetyl trimethylammonium bromide, catalyst consumption is counted 0.2～1.0wt% with the amount of chloroisoamylene, temperature of reaction is 20～70 ℃, reaction pressure is a normal pressure, reaction times is 2～6 hours, impose stirring in the reaction process, and in the process of reaction, remove by filter the solid particle of sodium chloride that generates in the reaction solution;
2) the reaction product standing demix that obtains of process 1 carries out profit and is separated;
3) the water material that obtains of process 2 is applied mechanically to returning the feed proportioning system after the content of sodium hydroxide is 42～55wt% through evaporation concentration;
4) oil phase material that obtains of process 2 enters acetone and reclaims rectifying tower and reclaim unreacted acetone, and control tower still temperature is 60～80 ℃, and pressure is normal pressure, and reflux ratio is 1～3, and cat head obtains the acetone material, and this material returns the feed proportioning system and applies mechanically;
5) process 4 acetone reclaim material that rectifying Tata still obtains and enter reaction fractionating tower carry out Pyranton decomposition reaction and rectifying in the presence of aqueous sodium hydroxide solution, the content of sodium hydroxide is 42～55wt% in the aqueous sodium hydroxide solution, aqueous sodium hydroxide solution is 0.01～0.05 with the feed weight ratio of material, the tower still temperature of control reaction fractionating tower is 60～100 ℃, reaction pressure is 0.01～0.1MPa, the trim the top of column ratio is 1～3, and the oil phase material that cat head material and process 2 obtain merges the acetone that enters process 4 and reclaims rectifying tower;
6) the tower still material that obtains of process 5 enters and takes off heavy rectifying tower and remove heavy component impurity, and control tower still temperature is 110～130 ℃, and rectifying pressure is 0.001～0.01MPa, and reflux ratio is 0.5～2, and tower still material is discharged out-of-bounds;
7) the cat head material that obtains of process 6 enters and takes off light rectifying tower and remove light component impurity, and control tower still temperature is 90～100 ℃, and rectifying pressure is 0.001～0.01MPa, and reflux ratio is 2～4, and the cat head material is discharged out-of-bounds, and the tower still must be made with extra care the Sulcatone product.
The molar ratio of said process 1 described chloroisoamylene, acetone and sodium hydroxide is preferably 1: (7.5～8.0): (8.5～9.2); Catalyst consumption is preferably 0.4～0.5wt% in the amount of chloroisoamylene; Temperature of reaction is preferably 55～62 ℃; In the reaction process, reaction solution can remove by filter the solid particle of sodium chloride that reaction generates by continuous outer circulation.
Chloroisoamylene and acetone can produce by product sodium-chlor when carrying out condensation reaction in aqueous sodium hydroxide solution, will form solid particulate and separate out after sodium-chlor in the reaction solution reaches certain concentration.Because sodium-chlor forms solid and separates out, be considered to usually can not cause adverse influence to the balance that reaction is carried out towards positive dirction.But the contriver finds in experiment, because this condensation reaction must be carried out liquid-liquid biphase mass transfer when carrying out, therefore it is very important in the reaction process reaction solution being stirred, the existence of solid particle of sodium chloride will increase the stirring resistance greatly in the reaction solution, under same power of agitator, the effect of stirring obviously descends.
In addition, the existence of solid particulate also can produce adverse influence to the carrying out of liquid-liquid two-phase mass transfer in the reaction solution.Therefore; carrying out along with reaction; the difficulty that becomes that after the solid particle of sodium chloride in the reaction solution builds up to certain degree, makes condensation reaction; can increase the generation of by product simultaneously; as if this obviously out in the cold in the prior art; just because this, existing this Sulcatone preparation method finally makes the yield of Sulcatone be restricted.
Key of the present invention is to remove by filter the solid particle of sodium chloride that generates in the reaction solution in the process that condensation reaction is carried out, and the operation of this process is to realize easily, can adopt the successive mode to carry out usually, also can adopt mode intermittently to carry out.Continuous mode can be in the process that condensation reaction is carried out, and partial reaction liquid is carried out outer circulation continuously by a strainer, and by removing by filter solid particle of sodium chloride, filtrate is returned condensation reactor.Mode intermittently can be regular all reaction solutions is filtered in the process that condensation reaction is carried out, and removes solid particle of sodium chloride.
Compared with prior art, advantage of the present invention is the yield that has obviously improved Sulcatone, and the Sulcatone yield of general condensation reaction can reach about 80%.The reaction product that condensation reaction obtains is through follow-up treating process, and the purity of the refining Sulcatone product that obtains is more than 99%.By treating process, unreacted acetone and sodium hydroxide recovery set usefulness, the Pyranton of by-product also is fully utilized after being decomposed into acetone, so whole process of preparation has lower production cost.
Below will the invention will be further described by specific embodiment and comparative example.
In embodiment and comparative example:
Embodiment
[embodiment 1～6]
In the four-hole boiling flask that whipping appts, thermometer, reflux exchanger and balance minim pipette are housed, add the catalyzer cetyl trimethylammonium bromide in the desired amount, and add raw material chloroisoamylene and acetone by required feed ratio.Start stirring, stirring velocity is 50r/min, slowly is heated to required temperature of reaction, the aqueous sodium hydroxide solution that simultaneously quick dropping prepares in advance, and the content of sodium hydroxide is 42～55wt% in the aqueous sodium hydroxide solution.To timing occurring having refluxed, taking out the upper oil phase reaction solution every 10min is that the sintered filter funnel suction filtration of 15～20 μ m is removed the sodium-chlor that is generated with the aperture, and filtrate is returned in the former four-hole boiling flask, repeats this operation, until reacting end.Reaction finishes the back and takes out all reaction solution standing demix, obtains oil phase and forms with gc analysis, calculates transformation efficiency and yield.
[comparative example 1～2]
The cancellation suction filtration is removed this operation of sodium-chlor that is generated, and all the other are with embodiment 1～6.
It is 1 listed that the concrete processing condition of each embodiment and comparative example see Table, and reaction result sees Table 2.
Table 1.
| Feed ratio (mol ratio) | Catalyst levels (wt%) | Temperature of reaction (℃) | Reaction times (hour) | |
| Embodiment 1 | 1∶6.5∶9.6 | 1.0 | 70 | 2 |
| Embodiment 2 | 1∶7.5∶9.2 | 0.4 | 62 | 3 |
| Embodiment 3 | 1∶8∶9 | 0.5 | 55 | 4 |
| Embodiment 4 | 1∶8.4∶7.4 | 0.2 | 65 | 4 |
| Embodiment 5 | 1∶8∶9 | 0.4 | 60 | 4 |
| Embodiment 6 | 1∶7∶8.5 | 0.4 | 20 | 6 |
| Comparative example 1 | 1∶8∶9 | 0.4 | 60 | 3 |
| Comparative example 2 | 1∶8∶9 | 0.4 | 60 | 4 |
Annotate: feed ratio is a chloroisoamylene: acetone: sodium hydroxide; Catalyst consumption is in the amount of chloroisoamylene.
Table 2.
| Transformation efficiency (%) | Yield (%) | |
| Embodiment 1 | 98.3 | 79.3 |
| Embodiment 2 | 99.9 | 81.6 |
| Embodiment 3 | 98.9 | 80.6 |
| Embodiment 4 | 98.6 | 80.2 |
| Embodiment 5 | 99.9 | 82.1 |
| Embodiment 6 | 99.2 | 79.1 |
| Comparative example 1 | 98.1 | 71.4 |
| Comparative example 2 | 98.3 | 70.3 |
[embodiment 7～12]
Enter the quantizer standing demix and carry out profit after reaction product that embodiment 1～6 obtains merges and be separated, water material evaporation concentration to the content of sodium hydroxide is to return the feed proportioning system behind 42～55wt% to apply mechanically.
Oil phase material enters acetone recovery rectifying tower and reclaims unreacted acetone, and the theoretical plate number of rectifying tower is 21.Rectifying pressure is normal pressure, and cat head obtains concentration and is the acetone material greater than 98wt%, and this cat head material returns the feed proportioning system and applies mechanically.The concrete rectifying condition of each embodiment sees Table 3.
The tower still material of acetone recovery rectifying tower enters a reaction fractionating tower and carry out Pyranton decomposition reaction and rectifying in the presence of aqueous sodium hydroxide solution, and the theoretical plate number of reaction fractionating tower is 14.The content of sodium hydroxide is 42～55wt% in the aqueous sodium hydroxide solution, and other concrete reactive distillation condition of each embodiment sees Table 4.The oil phase material merging that the cat head material of reaction fractionating tower and above profit are separated and obtain enters above-mentioned acetone recovery rectifying tower then and carries out the acetone recovery.
The tower still material that reaction fractionating tower obtains enters one and takes off heavy rectifying tower and remove heavy component impurity, and the theoretical plate number of taking off heavy rectifying tower is 19, and the concrete rectifying condition of each embodiment sees Table 5.Take off heavily rectifying Tata still material discharge out-of-bounds.
Take off cat head material that heavy rectifying tower obtains and enter and take off light rectifying tower and remove light component impurity, the theoretical plate number of taking off light rectifying tower is 20, and the concrete rectifying condition of each embodiment sees Table 6.Take off the cat head material of light rectifying tower and discharge out-of-bounds, the tower still must be made with extra care the Sulcatone product, and the purity of each embodiment product is with listing in table 6.
Table 3.
| Tower still temperature (℃) | Reflux ratio | |
| Embodiment 7 | 60 | 1 |
| Embodiment 8 | 80 | 1.5 |
| Embodiment 9 | 70 | 3 |
| Embodiment 10 | 70 | 1 |
| Embodiment 11 | 60 | 1.5 |
| Embodiment 12 | 80 | 3 |
Table 4.
| Charge ratio | Tower still temperature (℃) | Reaction pressure (MPa) | Reflux ratio | |
| Embodiment 7 | 0.01 | 60 | 0.01 | 1 |
| Embodiment 8 | 0.03 | 90 | 0.02 | 2 |
| Embodiment 9 | 0.03 | 60 | 0.01 | 2 |
| Embodiment 10 | 0.05 | 100 | 0.1 | 3 |
| Embodiment 11 | 0.01 | 90 | 0.01 | 2 |
| Embodiment 12 | 0.01 | 100 | 0.02 | 3 |
Annotate: charge ratio=aqueous sodium hydroxide solution: tower still material (weight ratio).
Table 5.
| Tower still temperature (℃) | Reaction pressure (MPa) | Reflux ratio | |
| Embodiment 7 | 110 | 0.001 | 0.5 |
| Embodiment 8 | 120 | 0.001 | 1 |
| Embodiment 9 | 120 | 0.005 | 1 |
| Embodiment 10 | 130 | 0.01 | 2 |
| Embodiment 11 | 125 | 0.001 | 0.5 |
| Embodiment 12 | 130 | 0.001 | 2 |
Table 6.
| Tower still temperature (℃) | Reaction pressure (MPa) | Reflux ratio | Product purity (%) | |
| Embodiment 7 | 90 | 0.001 | 2 | 98.6 |
| Embodiment 8 | 95 | 0.001 | 3 | 99.4 |
| Embodiment 9 | 95 | 0.005 | 3 | 99.1 |
| Embodiment 10 | 100 | 0.01 | 4 | 98.6 |
| Embodiment 11 | 90 | 0.005 | 2 | 98.2 |
| Embodiment 12 | 100 | 0.001 | 4 | 99.3 |
Claims (5)
1, a kind of preparation of Sulcatone and process for purification, this method comprises following process:
1) be raw material with chloroisoamylene and acetone, in aqueous sodium hydroxide solution, carry out condensation reaction, the content of sodium hydroxide is 42～55wt% in the aqueous sodium hydroxide solution, chloroisoamylene, the molar ratio of acetone and sodium hydroxide is 1: (6.5～8.4): (7.4～9.6), condensation reaction is catalyzer with the cetyl trimethylammonium bromide, catalyst consumption is counted 0.2～1.0wt% with the amount of chloroisoamylene, temperature of reaction is 20～70 ℃, reaction pressure is a normal pressure, reaction times is 2～6 hours, impose stirring in the reaction process, and in the process of reaction, remove by filter the solid particle of sodium chloride that generates in the reaction solution;
2) the reaction product standing demix that obtains of process 1 carries out profit and is separated;
3) the water material that obtains of process 2 is applied mechanically to returning the feed proportioning system after the content of sodium hydroxide is 42～55wt% through evaporation concentration;
4) oil phase material that obtains of process 2 enters acetone and reclaims rectifying tower and reclaim unreacted acetone, and control tower still temperature is 60～80 ℃, and pressure is normal pressure, and reflux ratio is 1～3, and cat head obtains the acetone material, and this material returns the feed proportioning system and applies mechanically;
5) process 4 acetone reclaim material that rectifying Tata still obtains and enter reaction fractionating tower carry out Pyranton decomposition reaction and rectifying in the presence of aqueous sodium hydroxide solution, the content of sodium hydroxide is 42～55wt% in the aqueous sodium hydroxide solution, aqueous sodium hydroxide solution is 0.01～0.05 with the feed weight ratio of material, the tower still temperature of control reaction fractionating tower is 60～100 ℃, reaction pressure is 0.01～0.1MPa, the trim the top of column ratio is 1～3, and the oil phase material that cat head material and process 2 obtain merges the acetone that enters process 4 and reclaims rectifying tower;
6) the tower still material that obtains of process 5 enters and takes off heavy rectifying tower and remove heavy component impurity, and control tower still temperature is 110～130 ℃, and rectifying pressure is 0.001～0.01MPa, and reflux ratio is 0.5～2, and tower still material is discharged out-of-bounds;
7) the cat head material that obtains of process 6 enters and takes off light rectifying tower and remove light component impurity, and control tower still temperature is 90～100 ℃, and rectifying pressure is 0.001～0.01MPa, and reflux ratio is 2～4, and the cat head material is discharged out-of-bounds, and the tower still must be made with extra care the Sulcatone product.
2, the preparation of Sulcatone according to claim 1 and process for purification is characterized in that the molar ratio of process 1 described chloroisoamylene, acetone and sodium hydroxide is 1: (7.5～8.0): (8.5～9.2).
3, the preparation of Sulcatone according to claim 1 and process for purification is characterized in that process 1 described catalyst consumption counts 0.4～0.5wt% with the amount of chloroisoamylene.
4, the preparation of Sulcatone according to claim 1 and process for purification is characterized in that process 1 described temperature of reaction is 55～62 ℃.
5, the preparation of Sulcatone according to claim 1 and process for purification is characterized in that in the process 1 described reaction process, and reaction solution removes by filter the solid particle of sodium chloride that reaction generates by continuous outer circulation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100680459A CN100482630C (en) | 2004-11-11 | 2004-11-11 | Methyl heptenone preparing and refining process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100680459A CN100482630C (en) | 2004-11-11 | 2004-11-11 | Methyl heptenone preparing and refining process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1772722A true CN1772722A (en) | 2006-05-17 |
| CN100482630C CN100482630C (en) | 2009-04-29 |
Family
ID=36759885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100680459A Active CN100482630C (en) | 2004-11-11 | 2004-11-11 | Methyl heptenone preparing and refining process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100482630C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664556A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of methyl heptenone |
| CN109180450A (en) * | 2018-10-09 | 2019-01-11 | 南通天泽化工有限公司 | A kind of preparation method of methyl heptenone |
| CN109232212A (en) * | 2018-09-28 | 2019-01-18 | 万华化学集团股份有限公司 | A method of by prenol synthesizing methyl heptenone |
| CN109516906A (en) * | 2018-11-29 | 2019-03-26 | 厦门金达威维生素有限公司 | A kind of method and apparatus of catalytic reaction rectification synthesis butanone alcohol |
| CN109824498A (en) * | 2018-12-22 | 2019-05-31 | 江门谦信化工发展有限公司 | A kind of efficient process units of diacetone alcohol serialization and production technology |
| CN111825538A (en) * | 2020-07-13 | 2020-10-27 | 万华化学集团股份有限公司 | Method for continuously producing pseudo ionone |
| CN113999100A (en) * | 2021-10-29 | 2022-02-01 | 万华化学集团股份有限公司 | Preparation of methyl heptenone and method for mechanically applying raw materials |
-
2004
- 2004-11-11 CN CNB2004100680459A patent/CN100482630C/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664556A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Preparation method of methyl heptenone |
| CN109232212A (en) * | 2018-09-28 | 2019-01-18 | 万华化学集团股份有限公司 | A method of by prenol synthesizing methyl heptenone |
| CN109232212B (en) * | 2018-09-28 | 2021-09-03 | 万华化学集团股份有限公司 | Method for synthesizing methyl heptenone from isopentenol |
| CN109180450A (en) * | 2018-10-09 | 2019-01-11 | 南通天泽化工有限公司 | A kind of preparation method of methyl heptenone |
| CN109180450B (en) * | 2018-10-09 | 2021-12-28 | 南通天泽化工有限公司 | Preparation method of methyl heptenone |
| CN109516906A (en) * | 2018-11-29 | 2019-03-26 | 厦门金达威维生素有限公司 | A kind of method and apparatus of catalytic reaction rectification synthesis butanone alcohol |
| CN109824498A (en) * | 2018-12-22 | 2019-05-31 | 江门谦信化工发展有限公司 | A kind of efficient process units of diacetone alcohol serialization and production technology |
| CN109824498B (en) * | 2018-12-22 | 2021-12-14 | 谦信化工集团有限公司 | Diacetone alcohol continuous production device and production process |
| CN111825538A (en) * | 2020-07-13 | 2020-10-27 | 万华化学集团股份有限公司 | Method for continuously producing pseudo ionone |
| CN111825538B (en) * | 2020-07-13 | 2022-08-05 | 万华化学集团股份有限公司 | Method for continuously producing pseudo ionone |
| CN113999100A (en) * | 2021-10-29 | 2022-02-01 | 万华化学集团股份有限公司 | Preparation of methyl heptenone and method for mechanically applying raw materials |
| CN113999100B (en) * | 2021-10-29 | 2023-10-13 | 万华化学集团股份有限公司 | Method for preparing methyl heptenone and applying raw materials |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100482630C (en) | 2009-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1848679A1 (en) | Method for preparing trimethylolpropane | |
| CN1167665C (en) | Process for preparing 4-aminodiphenylamines | |
| CN1061772A (en) | From carbonylation process stream, remove the method for carbonyl impurities | |
| CN1247181A (en) | One-step synthesizing process of 2,5-dimethyl-2,5-hexanediol | |
| CN101045962A (en) | Method of reclaiming platinum from selenium-containing waste liquid using hydrazine | |
| EP0686623A1 (en) | Process for producing methyl methacrylate | |
| CN102417442A (en) | Preparation method for high-purity methylal | |
| CN1271034C (en) | Waste water treatment in method for producing formic acid within is free of water | |
| CN1039994C (en) | Process for the preparation of 2-alkyl-6-methyl-N-(1'-methoxy-2'-propyl)-aniline and a process for the preparation of their chloracetanilides | |
| CN1772722A (en) | Methyl heptenone preparing and refining process | |
| CN1304350C (en) | Method for cleaning off-gas flows | |
| CN1095826C (en) | Esterification of (meth) acrylic acid with alkanol | |
| RU2764524C2 (en) | Method for obtaining indancarbaldehyde | |
| RU2369595C1 (en) | Method of obtaining 4-aminodiphenylamine and intermediate products of its synthesis | |
| CN1751015A (en) | Method for producing aromatic carboxylic acid | |
| CN100361950C (en) | Method for preparing methylheptenone | |
| CN112585112A (en) | Process for the catalytic production of a purified enal product from an aldehyde feed stream using a single enclosed apparatus | |
| CN102822137B (en) | Process for preparing unsymmetrical secondary tert-butylamines in the liquid phase | |
| CN1280255C (en) | Process for comprehensive utilization of waste sulfuric acid from 3,3'-dichloro benzidine hydrochloride | |
| JP2008184409A (en) | Distillation method of alkylamine-containing mixture and method for producing alkylamines | |
| CN104968638A (en) | Method for removing acrolein from the process gas of a heterogeneously catalysed oxidation of propene | |
| CN1578759A (en) | Method for processing water medium containing cylohexanone oxime and cyclohexanone | |
| CN1133679C (en) | Processes for producing polyester and producing sorbic acid | |
| JP4197763B2 (en) | Method for producing anhydrous 2-amino-1-methoxypropane | |
| CN1242996C (en) | Method for synthesizing 1H-1, 2,3 triazole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |