CN106622386A - Preparation method of high-performance catalyst for producing sec-butyl alcohol - Google Patents
Preparation method of high-performance catalyst for producing sec-butyl alcohol Download PDFInfo
- Publication number
- CN106622386A CN106622386A CN201710017618.2A CN201710017618A CN106622386A CN 106622386 A CN106622386 A CN 106622386A CN 201710017618 A CN201710017618 A CN 201710017618A CN 106622386 A CN106622386 A CN 106622386A
- Authority
- CN
- China
- Prior art keywords
- acid
- catalyst
- butyl alcohol
- preparation
- heteropoly acid
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/76—Dehydrogenation
- B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a preparation method of a high-performance catalyst for producing sec-butyl alcohol. The preparation method comprises the step of reacting heteropoly acid, difluoroacetic acid water solution, polyvinyl alcohol, furandicarboxylic acid, 5,10,15,20-tetrakis-(4-N,N,N-trimethyl ammonio phenyl)-21,23H-porphyrin tetratosylate and octadecyl dimethyl amine oxide in a micro-channel reactor to obtain a hydration catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst, particularly a kind of preparation of the effective catalyst for producing sec-butyl alcohol
Method.
Background technology
At present, the method for industrial n-butylene hydration sec-butyl alcohol mainly have indirect hydration method with sulphuric acid as catalyst and
Two kinds of techniques of direct hydration method with ion exchange resin or heteropoly acid as catalyst.Sulfuric acid process n-butene indirect hydration technique is
The traditional method of production sec-butyl alcohol.The law technology is ripe, reaction condition temperature not harsh to raw material n-butene purity requirement
With process is simple is easy to control, and weak point is that substantial amounts of diluted acid is produced in production process, and equipment corrosion is serious, the three wastes
More, plant investment is larger.Resin method direct hydration technique.The method was succeeded in developing by German RWE-DEA companies in 1984, was
Produce the topmost method of sec-butyl alcohol both at home and abroad at present.With resin as catalyst, n-butene is generated secondary by proton catalysis effect
Butanol, the method technological process is simple, and Product recycling is refined easy, and the three wastes are few, little to equipment corrosion, and sec-butyl alcohol selectivity is high,
Weak point is higher to raw material n-butene requirement, typically requires that n-butene content is higher than 90% in C 4 fraction.In addition, tree
Fat catalyst resistance to elevated temperatures is poor, short life, easy in inactivation, and n-butene conversion per pass is relatively low（Not higher than 10%）.Heteropoly acid method
Direct hydration technique, n-butene direct hydration under heteropolyacid catalyst effect is obtained sec-butyl alcohol.Heteropolyacid catalyst it is main
Composition is molybdophosphate, while adding organo-metallic compound additive.The method technological process is simple, catalyst performance stabilised, the longevity
Life length, reacts for solution-air phase reaction, and reactor efficiency is higher, and high boiling point by-products produced not accumulate in reactor, weak point is
N-butene conversion per pass is low, and reaction needs to be carried out under high pressure and higher temperature.
CN101395111 discloses the preparation method of sec-butyl alcohol, is characterised by the preparation method of sec-butyl alcohol, and the method is to make
With heteropoly acid aqueous solution as catalyst, direct hydration n-butene, the method is characterized in that:Dissolved with oxygen used in raw water
Water.Raw water is preferably oxygen saturation water.
CN101481296 provides the production technology of preparing sec-butyl alcohol by mixed C 4 reaction distillation method.Raw material mixing carbon four enters
Enter tubular reactive distillation column;Vaporization mixing carbon four and 75%～85% sulphuric acid adverse current by packing layer 25～50 DEG C, 0.3
Occur to absorb esterification under～0.8MPA;Reaction heat is removed by the cooling water between tubulation, keeps reaction temperature;Reaction end gas
Cooling liquid is sent outside, and the esterifying liquid of bottom of towe enters hydrolysis tower after static mixer prehydrolysis;The stripping hydrolysis of Jing tower bottom steams,
Bottom of towe dilute sulfuric acid enters sulphuric acid concentration operation concentration and returns tubular reactive distillation column to 75%～85%, sec-butyl alcohol and water azeotropic mixture from
Hydrolysis tower top is separated and send sec-butyl alcohol cut light tower and de-heavy oil column, obtains sec-butyl alcohol product.
CN101289368 is related to a kind of process of continuously producing sec-butyl alcohol by direct hydration of n-butene, belongs to oil
Work technical field, in the presence of strong acid type ion exchanges heteropolyacid catalyst, fresh n-butene raw material mixes with circulation n-butene
Hydration reaction is carried out into hydration reactor, is separated subsequently into crude product separative element, set up n-butene refined unit,
The unreacted n-butene isolated by crude product separative element a, part is back to hydration reactor and continues as circulation n-butene
Hydration reaction is participated in, another part is sent to n-butene refined unit and refined, remove butane, reclaim n-butene, continue conduct
Fresh n-butene raw material is used.
Existing patent and technical literature use sulfur acid as catalyst, although n-butene conversion per pass is higher, but equipment
Seriously corroded, waste water is more, pollutes environment；Heteropolyacid catalyst is exchanged using strong acid type ion, there is n-butene conversion per pass again
The relatively low shortcoming of rate；Using traditional heteropoly acid solution compositing catalyst, better catalytic activity, equipment corrosion can control, but positive fourth
Alkene conversion per pass can only achieve less than 35%.
The content of the invention
The technical problem to be solved is to overcome the deficiencies in the prior art, there is provided a kind of to produce the efficient of sec-butyl alcohol
The preparation method of catalyst.
In order to solve above technical problem, following technical scheme is present invention employs：It is a kind of to produce the efficient of sec-butyl alcohol
The preparation method of catalyst, comprises the following steps：
By heteropoly acid, the difluoroacetic acid aqueous solution of heteropoly acid mass percentage content 500-1000（Mass percent concentration 0.1-
1）Mixing 2-10h, adds the polyvinyl alcohol of heteropoly acid mass percentage content 1-5, adds heteropoly acid mass percentage content
The furandicarboxylic acid of 0.5-2, adds the 5,10,15,20- tetra- of heteropoly acid mass percentage content 0.5-2（4- dimethylaminos）Benzene
Base porphyrin tetramethyl benzene sulfonate, adds the octadecyl dimethyl amine oxide of heteropoly acid mass percentage content 0.1-0.5,
0.5-2h is reacted in 40-80 DEG C in micro passage reaction, hydration catalyst is obtained.
Described heteropoly acid is by hetero atom（Such as P, Si, Fe, Co）And polyatom（Such as Mo, W, V, Nb, Ta）By one
The oxygen-containing polyacid of a class that fixed structure is consisted of oxygen atom ligand bridging, is optimized for 12 phosphotungstic acids, molybdophosphate, for commercially available product
Product.
Described furandicarboxylic acid is commercially available prod, such as the product of Quzhou Run Dong Chemical Co., Ltd.s production；Described 5,
10,15,20- tetra-（4- dimethylaminos）Phenyl porphyrin tetramethyl benzene sulfonate is commercially available prod, such as Hubei Ju Sheng Science and Technology Ltd.s
The product of production.Described octadecyl dimethyl amine oxide is commercially available prod.
The micro passage reaction is commercially available prod, such as the product of Dow Corning Corporation's production.
Compared with prior art, the invention has the advantages that：
Jing this patents hydration catalyst has the big ring conjugated structure of porphyrin and the caged polyelectron structure of heteropoly acid simultaneously, improves
Catalyst activity；And octadecyl dimethyl amine oxide activator is added, and the compatibility of catalyst and butylene is improve, it is micro- logical
Road reactor can make catalyst, and respectively composition is sufficiently mixed uniformly, and the catalyst significantly improves n-butene conversion per pass, most
Height can reach 52%.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is further elucidated, but these embodiments are only used for explaining of the invention, and not
It is for limiting the scope of the present invention.
Embodiment 1
The phosphotungstic acids of 100Kg 12, the difluoroacetic acid aqueous solution of 700Kg are added in 2000L reactors（Mass percent concentration
0.5）Mixing 6h, adds the polyvinyl alcohol of 3Kg, adds the furandicarboxylic acid of 1Kg, adds 5, the 10,15,20- tetra- of 1Kg
（4- dimethylaminos）Phenyl porphyrin tetramethyl benzene sulfonate, adds the octadecyl dimethyl amine oxide of 0.3Kg, in microchannel plate
Answer in device and react 1h in 60 DEG C, hydration catalyst, numbering RD-1 is obtained.
Embodiment 2
The phosphotungstic acids of 100Kg 12, the difluoroacetic acid aqueous solution of 500Kg are added in 2000L reactors（Mass percent concentration
0.1）Mixing 2h, adds the polyvinyl alcohol of 1Kg, adds the furandicarboxylic acid of 0.5Kg, adds the 5,10,15,20- of 0.5Kg
Four（4- dimethylaminos）Phenyl porphyrin tetramethyl benzene sulfonate, adds the octadecyl dimethyl amine oxide of 0.1Kg, in microchannel
0.5h is reacted in 40 DEG C in reactor, hydration catalyst is obtained.Numbering RD-2.
Embodiment 3
100Kg molybdophosphates, the difluoroacetic acid aqueous solution of 1000Kg are added in 2000L reactors（Mass percent concentration 1）It is mixed
10h is closed, the polyvinyl alcohol of 5Kg is added, the furandicarboxylic acid of 2Kg is added, 5, the 10,15,20- tetra- of 2Kg are added（4- front threes
Amino）Phenyl porphyrin tetramethyl benzene sulfonate, add 0.5Kg octadecyl dimethyl amine oxide, in micro passage reaction in
80 DEG C of reaction 2h, are obtained hydration catalyst.Numbering RD-3.
Comparative example 1
It is added without difluoroacetic acid solution, the other the same as in Example 1.Prepared hydration catalyst.Numbering RD-4.
Comparative example 2
It is added without polyvinyl alcohol, the other the same as in Example 1.Prepared hydration catalyst.Numbering RD-5.
Comparative example 3
It is added without furandicarboxylic acid, the other the same as in Example 1.Prepared hydration catalyst.Numbering RD-6.
Comparative example 4
It is added without 5,10,15,20- tetra-（4- dimethylaminos）Phenyl porphyrin tetramethyl benzene sulfonate, the other the same as in Example 1.Prepared water
Close catalyst.Numbering RD-7.
Comparative example 5
It is added without octadecyl dimethyl amine oxide, the other the same as in Example 1.Prepared hydration catalyst.Numbering RD-8.
Comparative example 6
Catalyst is made using 100Kg molybdophosphates.Numbering RD-8.
Embodiment 4
Hydration catalyst 100Kg obtained in embodiment 1-3 and comparative example 1-6 is added in the deionized water of 1500Kg, in
60 DEG C of stirring reactions 3h, are obtained reaction water；Carbon four will be mixed, reaction water is passed through in hydration reactor, mixes the positive fourth in carbon four
The mol ratio of alkene and water is 1:8,220 DEG C of temperature, pressure 20MPa, time of staying 2h, from reactor top extraction sec-butyl alcohol, make
Gas chromatographic detection content is used, n-butene conversion is calculated.
Table 1：The n-butene conversion of embodiment 1-3 and comparative example 1-6.
| Embodiment | N-butene conversion % |
| RD-1 | 50 |
| RD-2 | 48 |
| RD-3 | 52 |
| RD-4 | 45 |
| RD-5 | 40 |
| RD-6 | 39 |
| RD-7 | 37 |
| RD-8 | 24 |
Claims (5)
1. a kind of preparation method of the effective catalyst for producing sec-butyl alcohol, it is characterised in that comprise the following steps：
By heteropoly acid, difluoroacetic acid aqueous solution 2-10h of heteropoly acid mass percentage content 500-1000, heteropoly acid is added
The polyvinyl alcohol of mass percentage content 1-5, adds the furandicarboxylic acid of heteropoly acid mass percentage content 0.5-2, adds miscellaneous
The 5,10,15,20- tetra- of polyacid mass percentage content 0.5-2（4- dimethylaminos）Phenyl porphyrin tetramethyl benzene sulfonate, adds
The octadecyl dimethyl amine oxide of heteropoly acid mass percentage content 0.1-0.5, it is anti-in 40-80 DEG C in micro passage reaction
0.5-2h is answered, hydration catalyst is obtained.
2. a kind of according to claim 1 one preparation method of the effective catalyst for producing sec-butyl alcohol, it is characterised in that institute
The heteropoly acid stated is oxygen-containing more by the class that oxygen atom ligand bridging is constituted by certain structure by hetero atom P, Si, Fe, Co
Acid.
3. a kind of preparation method of effective catalyst for producing sec-butyl alcohol according to claim 1, it is characterised in that step
（1）Described in difluoroacetic acid aqueous solution weight percent concentration 0.1-1.
4. the preparation method of a kind of effective catalyst for producing sec-butyl alcohol according to claim 1, it is characterised in that described
Heteropoly acid it is oxygen-containing many by the class that oxygen atom ligand bridging is constituted by certain structure by polyatom Mo, W, V, Nb, Ta
Acid.
5. the preparation method of a kind of effective catalyst for producing sec-butyl alcohol according to claim 1, it is characterised in that use
Micro passage reaction can make catalyst, and respectively composition is sufficiently mixed uniformly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710017618.2A CN106622386A (en) | 2017-01-11 | 2017-01-11 | Preparation method of high-performance catalyst for producing sec-butyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710017618.2A CN106622386A (en) | 2017-01-11 | 2017-01-11 | Preparation method of high-performance catalyst for producing sec-butyl alcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106622386A true CN106622386A (en) | 2017-05-10 |
Family
ID=58843971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710017618.2A Pending CN106622386A (en) | 2017-01-11 | 2017-01-11 | Preparation method of high-performance catalyst for producing sec-butyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106622386A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60149536A (en) * | 1984-01-13 | 1985-08-07 | Idemitsu Petrochem Co Ltd | Production of secondary butanol |
| CN101395111A (en) * | 2006-03-02 | 2009-03-25 | 出光兴产株式会社 | Process for the preparation of sec-butanol |
| CN103459358A (en) * | 2011-01-10 | 2013-12-18 | 沙特阿拉伯石油公司 | Process for the hydration of mixed butenes to produce mixed alcohols |
| CN104203933A (en) * | 2012-03-30 | 2014-12-10 | 三菱化学株式会社 | Method for manufacturing epoxy compound, and catalyst composition for epoxylating reaction |
| CN104311390A (en) * | 2014-10-17 | 2015-01-28 | 深圳市飞扬实业有限公司 | Method for synthesizing sec-butyl alcohol |
-
2017
- 2017-01-11 CN CN201710017618.2A patent/CN106622386A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60149536A (en) * | 1984-01-13 | 1985-08-07 | Idemitsu Petrochem Co Ltd | Production of secondary butanol |
| CN101395111A (en) * | 2006-03-02 | 2009-03-25 | 出光兴产株式会社 | Process for the preparation of sec-butanol |
| CN103459358A (en) * | 2011-01-10 | 2013-12-18 | 沙特阿拉伯石油公司 | Process for the hydration of mixed butenes to produce mixed alcohols |
| CN104203933A (en) * | 2012-03-30 | 2014-12-10 | 三菱化学株式会社 | Method for manufacturing epoxy compound, and catalyst composition for epoxylating reaction |
| CN104311390A (en) * | 2014-10-17 | 2015-01-28 | 深圳市飞扬实业有限公司 | Method for synthesizing sec-butyl alcohol |
Non-Patent Citations (3)
| Title |
|---|
| 孟广耀，彭定坤主编: "《材料化学若干前沿研究》", 31 January 2013, 中国科学技术大学出版社 * |
| 张祯成: ""金属卟啉与杂多酸复合型催化剂的制备及其催化性能的研究"", 《万方数据知识服务平台》 * |
| 游效曾等主编: "《配位化学进展》", 31 August 2000, 高等教育出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101485990B (en) | Solid supported heteropoly acid catalyst and preparation method thereof | |
| CN105688985B (en) | A kind of preparation method of solid-carrying type ionic-liquid catalyst | |
| CN101157019A (en) | A catalyzer for preparing dimethyl ether by dewatering methanol as well as its preparing method | |
| CN107311868B (en) | Method for preparing p-tert-butyl methyl benzoate | |
| CN107814939B (en) | Method for synthesizing poly (ethylene glycol methyl phosphonate) by metal oxide catalysis | |
| CN110833844B (en) | Application of cobalt carbonate in preparing acetophenone by ethylbenzene catalytic oxidation under solvent-free catalysis of molecular oxygen | |
| CN109912413B (en) | Method for synthesizing butyl oleate by catalyzing oleic acid-based ionic liquid microemulsion | |
| CN105461515A (en) | Method for preparing cyclopentanol from cyclopentene | |
| CN109704902A (en) | Ionic liquid-catalyzed method of deoxidation during a kind of lignin derivative hydrogenation deoxidation | |
| CN109225312B (en) | Synthesis method of methyl p-toluenesulfonate | |
| CN115028584B (en) | Ionic liquid for producing glutaraldehyde | |
| CN102167657B (en) | Hdrogenation synthesis method for preparing 2-methyl allyl alcohol by using recyclable catalyst | |
| CN106622386A (en) | Preparation method of high-performance catalyst for producing sec-butyl alcohol | |
| CN110903181B (en) | Method for preparing p-benzoquinone compound by double-catalytic system | |
| CN113861084B (en) | Process for preparing 4,4' -dichlorodiphenyl sulfone by one-pot method | |
| CN102850185A (en) | Method for synthesizing isopropanol by using cation exchange resin as catalyst | |
| CN114213248A (en) | Preparation method of 4-benzyloxy phenyl ethyl n-decanoate | |
| CN109824491B (en) | Production method of 2,3,4, 4' -tetrahydroxybenzophenone | |
| CN108586193A (en) | A method of preparing 1,3-PD using 3- methoxy methyl propionates | |
| CN102731250A (en) | Method for synthesizing sec-butyl alcohol | |
| CN107556188B (en) | Method for synthesizing benzyl ester by phase transfer catalysis | |
| CN108250056B (en) | Catalytic synthesis method of benzaldehyde | |
| CN106632161A (en) | Method used for preparing gamma-valerolactone via high-selectivity catalysis | |
| CN111153794A (en) | Method for synthesizing ethyl palmitate by using dodecyl trimethyl ammonium chloride-based eutectic solvent catalyst | |
| CN111393402A (en) | Br nsted acid/quaternary ammonium salt composite catalytic CO2Method for preparing cyclic carbonate by cycloaddition with epoxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: The new school district 322000 town Zhejiang city Yiwu province 5 Building 1 unit 201 room Applicant after: Wang Yilin Address before: 402, building 19, building three, garden community, 324004 Garden Street, Zhejiang, Quzhou Applicant before: Wang Yilin |
|
| 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170510 |