CN108358740A - A kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols - Google Patents
A kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols Download PDFInfo
- Publication number
- CN108358740A CN108358740A CN201810135369.1A CN201810135369A CN108358740A CN 108358740 A CN108358740 A CN 108358740A CN 201810135369 A CN201810135369 A CN 201810135369A CN 108358740 A CN108358740 A CN 108358740A
- Authority
- CN
- China
- Prior art keywords
- parts
- auxiliary agent
- alcohols
- preparing isobutene
- powder
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols, is related to technical field of petrochemical industry, it is characterised in that：Material including following parts by weight is made, 37 parts of attapulgite, 9 14 parts of modified meerschaum powder, 13 parts of ammonium metavanadate, 35 parts of 1-hydroxy ethylidene-1,1-diphosphonic acid, 14 parts of casein, 14 parts of end amino polybasic alcohol ester, 27 parts of polyethylene wax, 6 10 parts of ceramic powder, 29 parts of EDETATE SODIUM, 10 parts of adjuvant.The method of the present invention is reasonable, at low cost, high catalytic efficiency.
Description
Technical field
The present invention relates to technical field of petrochemical industry, and in particular to a kind of to prepare helping for isobutene for isobutyl dehydration of alcohols
Agent.
Background technology
Isobutene is a kind of important industrial chemicals, mainly for the preparation of butyl rubber, polyisobutene, methacrylonitrile,
Antioxidant, tertiary butyl phenol, tertbutyl ether etc..Currently, the method for production isobutene mainly has the separation of light oil C 4 fraction, the tert-butyl alcohol de-
Water, etherificate cracking etc..
Isobutanol is generated when preparing 2-Ethylhexyl Alcohol for the carbongl group synthesis reaction of raw material using aqueous gas and propylene
By-product.In order to make the by-product isobutanol rationally be utilized, the present invention uses it for the preparation of isobutene.Patent CN
104640627A using molybdenum, tungsten, tantalum, niobium, titanium composite oxides as catalyst, but its catalyst preparation process is complicated, needs
It is made by high-temperature process, although the conversion ratio of isobutanol can reach 100%, the yield of isobutene reaches 89.6%, urges
Agent manufacturing cost is high, and catalyst preparation metal belongs to noble metal, and dosage is limited, is not suitable for industrializing extensive preparation
Isobutene.
Invention content
Technical problem to be solved by the present invention lies in overcome existing technological deficiency provide a kind of method rationally, cost
A kind of low, high catalytic efficiency auxiliary agent preparing isobutene for isobutyl dehydration of alcohols.
The technical problems to be solved by the invention are realized using technical solution below：
A kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols, it is characterised in that：Include the material system of following parts by weight
At,
3-7 parts of attapulgite, 1-3 parts of ammonium metavanadate, 3-5 parts of 1-hydroxy ethylidene-1,1-diphosphonic acid, is done 9-14 parts of modified meerschaum powder
1-4 parts of casein, 1-4 parts of the amino polybasic alcohol ester in end, 2-7 parts of polyethylene wax, 6-10 parts of ceramic powder, 2-9 parts of EDETATE SODIUM, adjuvant
5-10 parts；
The preparation method of the modified meerschaum powder is：Sepiolite is ground to and crossed 300-400 mesh sieve, is then added bicyclic
Pentadiene is stirred 10min at normal temperatures, then heats to 80-85 DEG C of heat preservation grinding 30min, adds water stirring and be made and contain admittedly
Amount reaches the solution of 25-35%, and gained mixed liquor is sent into spray dryer and is dried, the spheric granules of obtained 20-40 mesh, and in
It is dried at 100-110 DEG C；
The mass ratio of the dicyclopentadiene and sepiolite not 1：4.1；
The adjuvant is made up of the following materials in parts by weight,
4 parts of carboxymethyl cellulose, 6 parts of methenamine, N, the bromo- 2- nitros -1,3- of 7 parts of N "-ethylene bis stearamides, 2- third
2 parts of glycol, 5 parts of zeolite powder, 7 parts of octadecanoid acid, 9 parts of antioxidant A；
Preparation method is：Above-mentioned material is sequentially placed into equipment, heat preservation grinding 30min at a temperature of 50-60 DEG C,
Then the microwave reflow treatment 5min under microwave frequency 2450MHz, output power 700W；
A kind of preparation method of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols is：
I is put into attapulgite, modified meerschaum powder, ammonium metavanadate, 1-hydroxy ethylidene-1,1-diphosphonic acid, casein in reaction kettle,
1 hour is mixed at a temperature of 55-65 DEG C；
II is put into remaining material in reaction kettle, is warming up to 85-95 DEG C, and the reaction was continued 1.5 hours；
III material is sufficiently mixed after stand 30min, and microwave returns under microwave frequency 2450MHz, output power 700W
Then stream process 5min adds water stirring and the solution that solid content reaches 25-35% is made, gained mixed liquor is sent into spray dryer
Middle drying, is made the spheric granules of 20-40 mesh, and is dried at 100-110 DEG C.
Beneficial effects of the present invention are：It can be used in isobutyl dehydration of alcohols using the auxiliary agent of the present invention and prepare isobutene, it can
Reduce the temperature of dehydration, additionally it is possible to increase the conversion ratio of isobutanol, and product is without side reaction, nontoxic irritation
It is small, it is of low cost, the yield of isobutene can be increased.
Specific implementation mode
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention be easy to understand, below into
One step illustrates the present invention.
Embodiment 1
A kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols, it is characterised in that：Include the material system of following parts by weight
At,
3 parts of attapulgite, 9 parts of modified meerschaum powder, 1 part of ammonium metavanadate, 3 parts of 1-hydroxy ethylidene-1,1-diphosphonic acid, 1 part of casein,
Hold 1 part of amino polybasic alcohol ester, 2 parts of polyethylene wax, 6 parts of ceramic powder, 2 parts of EDETATE SODIUM, 5 parts of adjuvant；
The preparation method of the modified meerschaum powder is：Sepiolite is ground to and crossed 300-400 mesh sieve, is then added bicyclic
Pentadiene is stirred 10min at normal temperatures, then heats to 80-85 DEG C of heat preservation grinding 30min, adds water stirring and be made and contain admittedly
Amount reaches the solution of 25-35%, and gained mixed liquor is sent into spray dryer and is dried, the spheric granules of obtained 20-40 mesh, and in
It is dried at 100-110 DEG C；
The mass ratio of the dicyclopentadiene and sepiolite not 1：4.1；
The adjuvant is made up of the following materials in parts by weight,
4 parts of carboxymethyl cellulose, 6 parts of methenamine, N, the bromo- 2- nitros -1,3- of 7 parts of N "-ethylene bis stearamides, 2- third
2 parts of glycol, 5 parts of zeolite powder, 7 parts of octadecanoid acid, 9 parts of antioxidant A；
Preparation method is：Above-mentioned material is sequentially placed into equipment, heat preservation grinding 30min at a temperature of 50-60 DEG C,
Then the microwave reflow treatment 5min under microwave frequency 2450MHz, output power 700W；
A kind of preparation method of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols is：
I is put into attapulgite, modified meerschaum powder, ammonium metavanadate, 1-hydroxy ethylidene-1,1-diphosphonic acid, casein in reaction kettle,
1 hour is mixed at a temperature of 55-65 DEG C；
II is put into remaining material in reaction kettle, is warming up to 85-95 DEG C, and the reaction was continued 1.5 hours；
III material is sufficiently mixed after stand 30min, and microwave returns under microwave frequency 2450MHz, output power 700W
Then stream process 5min adds water stirring and the solution that solid content reaches 25-35% is made, gained mixed liquor is sent into spray dryer
Middle drying, is made the spheric granules of 20-40 mesh, and is dried at 100-110 DEG C.
Embodiment 2
A kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols, it is characterised in that：Include the material system of following parts by weight
At,
7 parts of attapulgite, 14 parts of modified meerschaum powder, 3 parts of ammonium metavanadate, 5 parts of 1-hydroxy ethylidene-1,1-diphosphonic acid, 4 parts of casein,
Hold 4 parts of amino polybasic alcohol ester, 7 parts of polyethylene wax, 10 parts of ceramic powder, 9 parts of EDETATE SODIUM, 10 parts of adjuvant；
The preparation method of the modified meerschaum powder is：Sepiolite is ground to and crossed 300-400 mesh sieve, is then added bicyclic
Pentadiene is stirred 10min at normal temperatures, then heats to 80-85 DEG C of heat preservation grinding 30min, adds water stirring and be made and contain admittedly
Amount reaches the solution of 25-35%, and gained mixed liquor is sent into spray dryer and is dried, the spheric granules of obtained 20-40 mesh, and in
It is dried at 100-110 DEG C；
The mass ratio of the dicyclopentadiene and sepiolite not 1：4.1；
The adjuvant is made up of the following materials in parts by weight,
4 parts of carboxymethyl cellulose, 6 parts of methenamine, N, the bromo- 2- nitros -1,3- of 7 parts of N "-ethylene bis stearamides, 2- third
2 parts of glycol, 5 parts of zeolite powder, 7 parts of octadecanoid acid, 9 parts of antioxidant A；
Preparation method is：Above-mentioned material is sequentially placed into equipment, heat preservation grinding 30min at a temperature of 50-60 DEG C,
Then the microwave reflow treatment 5min under microwave frequency 2450MHz, output power 700W；
A kind of preparation method of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols is：
I is put into attapulgite, modified meerschaum powder, ammonium metavanadate, 1-hydroxy ethylidene-1,1-diphosphonic acid, casein in reaction kettle,
1 hour is mixed at a temperature of 55-65 DEG C；
II is put into remaining material in reaction kettle, is warming up to 85-95 DEG C, and the reaction was continued 1.5 hours；
III material is sufficiently mixed after stand 30min, and microwave returns under microwave frequency 2450MHz, output power 700W
Then stream process 5min adds water stirring and the solution that solid content reaches 25-35% is made, gained mixed liquor is sent into spray dryer
Middle drying, is made the spheric granules of 20-40 mesh, and is dried at 100-110 DEG C.
Embodiment 3
A kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols, it is characterised in that：Include the material system of following parts by weight
At,
6 parts of attapulgite, 11 parts of modified meerschaum powder, 2 parts of ammonium metavanadate, 4 parts of 1-hydroxy ethylidene-1,1-diphosphonic acid, 3 parts of casein,
Hold 2 parts of amino polybasic alcohol ester, 5 parts of polyethylene wax, 8 parts of ceramic powder, 7 parts of EDETATE SODIUM, 7 parts of adjuvant；
The preparation method of the modified meerschaum powder is：Sepiolite is ground to and crossed 300-400 mesh sieve, is then added bicyclic
Pentadiene is stirred 10min at normal temperatures, then heats to 80-85 DEG C of heat preservation grinding 30min, adds water stirring and be made and contain admittedly
Amount reaches the solution of 25-35%, and gained mixed liquor is sent into spray dryer and is dried, the spheric granules of obtained 20-40 mesh, and in
It is dried at 100-110 DEG C；
The mass ratio of the dicyclopentadiene and sepiolite not 1：4.1；
The adjuvant is made up of the following materials in parts by weight,
4 parts of carboxymethyl cellulose, 6 parts of methenamine, N, the bromo- 2- nitros -1,3- of 7 parts of N "-ethylene bis stearamides, 2- third
2 parts of glycol, 5 parts of zeolite powder, 7 parts of octadecanoid acid, 9 parts of antioxidant A；
Preparation method is：Above-mentioned material is sequentially placed into equipment, heat preservation grinding 30min at a temperature of 50-60 DEG C,
Then the microwave reflow treatment 5min under microwave frequency 2450MHz, output power 700W；
A kind of preparation method of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols is：
I is put into attapulgite, modified meerschaum powder, ammonium metavanadate, 1-hydroxy ethylidene-1,1-diphosphonic acid, casein in reaction kettle,
1 hour is mixed at a temperature of 55-65 DEG C；
II is put into remaining material in reaction kettle, is warming up to 85-95 DEG C, and the reaction was continued 1.5 hours；
III material is sufficiently mixed after stand 30min, and microwave returns under microwave frequency 2450MHz, output power 700W
Then stream process 5min adds water stirring and the solution that solid content reaches 25-35% is made, gained mixed liquor is sent into spray dryer
Middle drying, is made the spheric granules of 20-40 mesh, and is dried at 100-110 DEG C.
Comparative example：
One kind being used for isobutanol dehydrating agent, is prepared according to 1 the method for patent CN 104640627A embodiments.
It is utilized respectively embodiment 1, embodiment 2, embodiment 3, comparative example the method and prepares isobutene using isobutanol, and
Conversion ratio, the isobutanol for measuring isobutanol are converted into the selection rate and isobutene yield of isobutene, and the results are shown in Table 1.
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Conversion ratio/% | 100 | 99.7 | 99.9 | 99.1 |
| Selection rate/% | 96.4 | 96.2 | 94.4 | 90.1 |
| Yield/% | 95.6 | 96.2 | 95.4 | 89.2 |
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (4)
1. a kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols, it is characterised in that：Material including following parts by weight is made,
3-7 parts of attapulgite, 9-14 parts of modified meerschaum powder, 1-3 parts of ammonium metavanadate, 3-5 parts of 1-hydroxy ethylidene-1,1-diphosphonic acid, casein
1-4 parts, end 1-4 parts of amino polybasic alcohol ester, 2-7 parts of polyethylene wax, 6-10 parts of ceramic powder, 2-9 parts of EDETATE SODIUM, adjuvant 5-10
Part.
2. a kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols according to claim 1, it is characterised in that：It is described to change
The preparation method of property sepiolite powder is：Sepiolite is ground to and crossed 300-400 mesh sieve, dicyclopentadiene then is added at normal temperatures
It is stirred 10min, then heats to 80-85 DEG C of heat preservation grinding 30min, stirring is added water solid content is made and reach 25-35%
Solution, gained mixed liquor is sent into dry in spray dryer, the spheric granules of 20-40 mesh is made, and dried at 100-110 DEG C
It is dry.
3. a kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols according to claim 1, it is characterised in that：It is described auxiliary
Auxiliary agent is made up of the following materials in parts by weight,
4 parts of carboxymethyl cellulose, 6 parts of methenamine, N, the bromo- 2- nitros -1,3- propylene glycol of 7 parts of N "-ethylene bis stearamides, 2-
2 parts, 5 parts of zeolite powder, 7 parts of octadecanoid acid, 9 parts of antioxidant A.
4. a kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols according to claim 1, it is characterised in that：Described one
The preparation method of kind of the auxiliary agent for preparing isobutene for isobutyl dehydration of alcohols is：
I is put into attapulgite, modified meerschaum powder, ammonium metavanadate, 1-hydroxy ethylidene-1,1-diphosphonic acid, casein in reaction kettle, in 55-
1 hour is mixed at a temperature of 65 DEG C；
II is put into remaining material in reaction kettle, is warming up to 85-95 DEG C, and the reaction was continued 1.5 hours；
III material is sufficiently mixed after stand 30min, and under microwave frequency 2450MHz, output power 700W at microwave reflux
5min is managed, stirring is then added water and the solution that solid content reaches 25-35% is made, gained mixed liquor is sent into spray dryer and is done
It is dry, the spheric granules of 20-40 mesh is made, and dried at 100-110 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810135369.1A CN108358740A (en) | 2018-02-09 | 2018-02-09 | A kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810135369.1A CN108358740A (en) | 2018-02-09 | 2018-02-09 | A kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108358740A true CN108358740A (en) | 2018-08-03 |
Family
ID=63005457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810135369.1A Pending CN108358740A (en) | 2018-02-09 | 2018-02-09 | A kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108358740A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101439295A (en) * | 2008-12-23 | 2009-05-27 | 南京工业大学 | Catalyst for preparing ethylene by ethanol dehydration and preparation method and application thereof |
| CN104640627A (en) * | 2012-09-18 | 2015-05-20 | 国立大学法人北海道大学 | Catalyst for producing isobutylene, and method for producing isobutylene using same |
| CN105396615A (en) * | 2015-10-18 | 2016-03-16 | 任丘市华北石油科林环保有限公司 | Catalyst for preparing low carbon olefins from methanol |
| CN106458786A (en) * | 2014-05-07 | 2017-02-22 | 三菱丽阳株式会社 | Method for producing isobutylene from isobutanol |
| EP3162763A1 (en) * | 2015-10-30 | 2017-05-03 | Total Research & Technology Feluy SA | Simultaneous dehydration and skeletal isomerisation of isobutanol on ti-containing zeolite catalysts |
| CN107001178A (en) * | 2014-09-26 | 2017-08-01 | Ifp 新能源公司 | Based on the catalyst comprising iron type zeolite by 2 methods being dehydrated by alkyl-substituted primary alconol starting isomericization |
| CN107118069A (en) * | 2017-06-17 | 2017-09-01 | 安徽海德石油化工有限公司 | A kind of method that utilization isobutyl dehydration of alcohols prepares isobutene |
| CN107405601A (en) * | 2015-04-22 | 2017-11-28 | 三菱化学株式会社 | For manufacturing the catalyst of isobutene and the manufacture method of isobutene |
-
2018
- 2018-02-09 CN CN201810135369.1A patent/CN108358740A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101439295A (en) * | 2008-12-23 | 2009-05-27 | 南京工业大学 | Catalyst for preparing ethylene by ethanol dehydration and preparation method and application thereof |
| CN104640627A (en) * | 2012-09-18 | 2015-05-20 | 国立大学法人北海道大学 | Catalyst for producing isobutylene, and method for producing isobutylene using same |
| CN106458786A (en) * | 2014-05-07 | 2017-02-22 | 三菱丽阳株式会社 | Method for producing isobutylene from isobutanol |
| CN107001178A (en) * | 2014-09-26 | 2017-08-01 | Ifp 新能源公司 | Based on the catalyst comprising iron type zeolite by 2 methods being dehydrated by alkyl-substituted primary alconol starting isomericization |
| CN107405601A (en) * | 2015-04-22 | 2017-11-28 | 三菱化学株式会社 | For manufacturing the catalyst of isobutene and the manufacture method of isobutene |
| CN105396615A (en) * | 2015-10-18 | 2016-03-16 | 任丘市华北石油科林环保有限公司 | Catalyst for preparing low carbon olefins from methanol |
| EP3162763A1 (en) * | 2015-10-30 | 2017-05-03 | Total Research & Technology Feluy SA | Simultaneous dehydration and skeletal isomerisation of isobutanol on ti-containing zeolite catalysts |
| CN107118069A (en) * | 2017-06-17 | 2017-09-01 | 安徽海德石油化工有限公司 | A kind of method that utilization isobutyl dehydration of alcohols prepares isobutene |
Non-Patent Citations (1)
| Title |
|---|
| 李亚男等: ""乙醇催化脱水制乙烯沸石催化剂研究现状"", 《化工进展》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107118069A (en) | A kind of method that utilization isobutyl dehydration of alcohols prepares isobutene | |
| CN105921161B (en) | A kind of catalyst and preparation method thereof preparing 2,5- chlorophenesic acids for paracide hydroxylating | |
| CN105562041B (en) | The preparation method of solid base catalyst and its reaction method for catalyzing and synthesizing irisone system fragrance intermediates | |
| CN106635110B (en) | A kind of agriculture and forestry organic waste material microwave catalysis thermal cracking is prepared rich in phenols, the method for alcohol-based liquid product | |
| CN103113195A (en) | Novel method for rapidly preparing hydroxytyrosol | |
| CN108043407A (en) | A kind of Co/ sepiolites catalyst and its preparation method and application | |
| CN105001027A (en) | Fluorne compound preparing method | |
| CN105294409A (en) | Eugenol synthesis method | |
| CN113004895A (en) | Preparation method of biomass carbon dots based on sulfonic acid type eutectic solvent | |
| CN108358740A (en) | A kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols | |
| CN106140234A (en) | Solid phosphoric acid catalyst for producing adiponitrile and preparation method thereof | |
| CN105622419B (en) | A kind of method that carbohydrate prepares ethyl glycolate | |
| CN110437231B (en) | Preparation method of valaciclovir hydrochloride anhydrous crystal form I | |
| CN102698813B (en) | Method for preparing multifunctional solid superacid catalyst and method using waste cooking oil as raw material to synthesize biodiesel | |
| CN115650938B (en) | Continuous method and equipment for simultaneously extracting furfural and 5-hydroxymethylfurfural from biomass | |
| CN104387347B (en) | 2-methyl maleic anhydride and the preparation method of double (citraconimidomethyl) benzene of 1,3- | |
| CN101823955B (en) | Method for extracting ferulic acid from maize peels | |
| CN100391955C (en) | Synthetic method for strotium renelate intermediate | |
| CN213060776U (en) | Rose essential oil processing is with oil-water separator | |
| CN105503790A (en) | Method for preparing furfural from corncobs and corn straw serving as raw materials | |
| CN103896810B (en) | The synthetic method of bufexamac | |
| CN106518671A (en) | Preparation method of butylparaben | |
| CN102838482A (en) | Preparation method of 3,6-dichlorosalicylic acid | |
| CN100584861C (en) | Preparation of carboxymethylstach sodium by microwave alcohol-free solid-phase one-step alkali-adding method | |
| CN109266434A (en) | A kind of cortex cinnamomi deep working method |
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: 20180803 |
|
| RJ01 | Rejection of invention patent application after publication |