CN106316787A - Preparation method of difluoroethanol - Google Patents
Preparation method of difluoroethanol Download PDFInfo
- Publication number
- CN106316787A CN106316787A CN201610460277.1A CN201610460277A CN106316787A CN 106316787 A CN106316787 A CN 106316787A CN 201610460277 A CN201610460277 A CN 201610460277A CN 106316787 A CN106316787 A CN 106316787A
- Authority
- CN
- China
- Prior art keywords
- preparation
- reactor
- triethylamine
- filled
- ethanol
- 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
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
Abstract
The invention provides a preparation method of difluoroethanol. According to the method, hydrogenation reduction reaction is carried out on the raw material ethyl difluorochloroacetate by using Raney nickel as a catalyst, triethylamine as an acid-binding agent and ethanol as a solvent. F atoms have high electronegativity in the ethyl difluorochloroacetate hydrogenation process and can not generate HF, but the C-Cl bond can be easily hydrogenated to generate HCl; and therefore, the HCl generated by adding the acid-binding agent triethylamine for neutralization promotes the forward proceeding of the reaction, thereby enhancing the conversion rate of the ethyl difluorochloroacetate. Therefore, the method provided by the invention solves the problems of complex reaction technique, high investment, inapplicability to small-scale production in the field of fine chemical engineering and the like in the traditional ester hydrogenation process, and has the advantages of higher ester conversion rate, higher alcohol selectivity and high raw material conversion rate.
Description
Technical field
The present invention relates to technical field of catalytic chemistry, particularly relate to the preparation method of a kind of difluoroethanol.
Background technology
Fluorinated alcohols belongs to aliphatic fluoro-containing intermediate, is widely used in the field such as pesticide, medicine synthesis, material, dyestuff, tool
There is the best DEVELOPMENT PROSPECT, if difluoroethanol, trifluoroethanol, hexafluoro butanol etc. are all have high added value important organic
Synthetic intermediate.Difluoroethanol is the alcohol in organic synthesis, especially for agriculture chemistry and pharmaceutical field.At present,
Through propose synthesis difluoroethanol multiple method, especially can be by with hydride reduction difluoroacetic acid chloride [AL.Henne and
RL.Pelley-JACS, 74 (1952), 1426-8] or by catalytic hydrogenation reduced [Asahi Chemical, 24/05/
Patent JP61268639 of 85] or by with sodium borohydride reduction ethyl difluoro [M.Lewis and E.deClerck-J
Chem Res., Miniprint 8 (2001), 844-56] prepare difluoroethanol.
Cu catalyst is the catalyst that current commercial Application most widely prepares difluoroethanol, but, Cu catalyst is adding
There is the biggest gap than aspect in hydrogen activity, selectivity, hydrogen ester, it is difficult to adapts to what raw materials quality in actual industrial production often fluctuated
Requirement.Therefore, hydrogenation catalyst need to have low hydrogen ester ratio, preferably activity and a selectivity, thus extends catalyst service life.
On the other hand, preparing difluoroethanol and use tradition ester through hydrogenation fixed-bed process flow process, it operates complexity, and equipment cost is higher, throws
Money is big, and can not effectively reclaim catalyst, is not suitable for field of fine chemical small-scale production.
It is considered as desirable by the inventor to, it is provided that the preparation method of a kind of difluoroethanol, utilize slurry bed system ester through hydrogenation to react, improve ester and add
Feed stock conversion during hydrogen.
Summary of the invention
Present invention solves the technical problem that the preparation method being to provide a kind of difluoroethanol, technique is simple, and raw material converts
Rate is high.
In view of this, the invention provides the preparation method of a kind of difluoroethanol, comprise the following steps: step a) is by thunder Buddhist nun
Nickel, difluoro ethyl chloroacetate, ethanol and triethylamine are poured in reactor successively, tighten kettle cover；Step b) is in described reactor
It is filled with H2And check whether gas leakage；Described reactor is heated to 150-200 DEG C in silicone oil bath by step c), and the response time is 5-
10h, obtains difluoroethanol.
Preferably, the mass ratio of described Raney's nickel, difluoro ethyl chloroacetate, ethanol and triethylamine is 1:3-10:10-30:
1-3。
Preferably, the mass ratio of described Raney's nickel, difluoro ethyl chloroacetate, ethanol and triethylamine is 1:5-10:15-30:
1.4-2.8。
Preferably, tightening kettle cover described in makes reactor be in air-tight state.
Preferably, in step b, in described reactor, it is filled with the H of 5-8MPa2And check whether gas leakage.
Preferably, in step b, in described reactor, it is filled with the H of 5-7MPa2And check whether gas leakage.
Preferably, described step b is particularly as follows: be filled with H in described reactor2Check whether gas leakage, air tight then hydrogen
Gas is released, and in triplicate, is the most again flushed with hydrogen gas.
Preferably, in step c, reaction is carried out under the stirring of magnetic stirring apparatus.
Preferably, described step c particularly as follows: described reactor is heated to 150-200 DEG C in silicone oil bath, the response time
For 5-10h, after having reacted, it is cooled to room temperature, opens vent valve venting, then turn on kettle cover, be dried to clean with dropper sampling
In sample bottle, carry out chromatography.
Preferably, described reactor is heated to 180-200 DEG C in silicone oil bath.
The invention provides the preparation method of a kind of difluoroethanol, comprise the following steps: by Raney's nickel, difluoro monoxone second
Ester, ethanol and triethylamine are poured in reactor successively, tighten kettle cover；It is filled with H in described reactor2And check whether gas leakage；
Described reactor is heated in silicone oil bath 150-200 DEG C, and the response time is 5-10h, obtains difluoroethanol.With prior art
Compare, the present invention with difluoro ethyl chloroacetate as raw material, Raney's nickel as catalyst, triethylamine as acid binding agent, ethanol enters for solvent
Row hydrogenation reduction.Owing in difluoro ethyl chloroacetate hydrogenation process, F atom has bigger electronegativity, it is impossible to generate HF, but
C-Cl key is easily hydrogenated with, and easily generates HCl, thus the present invention is by the HCl adding in acid binding agent triethylamine and generate, and advances reaction
Carry out to forward, improve the conversion ratio of difluoro ethyl chloroacetate.Therefore, the present invention solves tradition ester through hydrogenation process reaction technique
Complexity, investment greatly, are not suitable for the problems such as field of fine chemical small-scale production, have higher ester conversion rate and alcohol selectivity,
Feed stock conversion is high.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but
Should be appreciated that these describe simply as to further illustrate the features and advantages of the present invention rather than to the claims in the present invention
Limit.
The embodiment of the invention discloses the preparation method of a kind of difluoroethanol, comprise the following steps: step a) by Raney's nickel,
Difluoro ethyl chloroacetate, ethanol and triethylamine are poured in reactor successively, tighten kettle cover；Step b) is filled with in described reactor
H2And check whether gas leakage；Described reactor is heated to 150-200 DEG C in silicone oil bath by step c), and the response time is 5-10h,
Obtain difluoroethanol.
The present invention with difluoro ethyl chloroacetate as raw material, Raney's nickel as catalyst, triethylamine as acid binding agent, ethanol is as solvent
Carry out hydrogenation reduction, select suitable reaction conditions, solve tradition ester through hydrogenation process reaction complex process, investment greatly, no
It is suitable for the problems such as field of fine chemical small-scale production, it is thus achieved that higher ester conversion rate and alcohol selectivity.
Preferably, the mass ratio of described Raney's nickel, difluoro ethyl chloroacetate, ethanol and triethylamine is preferably 1:3-
10:10-30:1-3, more preferably 1:5-10:15-30:1.4-2.8.
Wherein, the present invention is with triethylamine as acid binding agent.In difluoro ethyl chloroacetate hydrogenation process, just have relatively due to F atom
Big electronegativity, C-F key is stronger, it is impossible to generate HF.But C-Cl key is easily hydrogenated with, generates HCl, HCl and there is highly acid, perishable
Erosion equipment.Therefore, the present invention is by the HCl adding in acid binding agent triethylamine and generate, and meanwhile, reaction can be advanced to enter to forward
OK, the conversion ratio of difluoro ethyl chloroacetate is improved.Course of reaction is as follows:
Preferably, in step a, the present invention makes reactor be in air-tight state by tightening kettle cover, otherwise can leak
Gas, and then affect being smoothed out of reaction.
Preferably, in step b, the present invention is filled with the H of 5-8MPa in described reactor2And check whether Lou
Gas, is more preferably filled with the H of 5-7MPa2.Described step b is particularly as follows: be filled with H in described reactor2Check whether gas leakage, do not leak
Gas is then released hydrogen, in triplicate, is the most again flushed with hydrogen gas.When checking whether gas leakage, pressure used can be more than reaction
Pressure 5MPa, after a period of time, sees whether its reading diminishes, and diminishes and leaks gas exactly.And it is possible to checking H2Instrument inspection
Leakage, and judge Gas leak position, make respective handling.
Preferably, in step c, reaction is carried out under the stirring of magnetic stirring apparatus.Described step c is particularly as follows: incite somebody to action
Described reactor is heated to 150-200 DEG C in silicone oil bath, and the response time is 5-10h, is cooled to room temperature, opens after having reacted
Vent valve is exitted, then turns on kettle cover, with in dropper sampling to the clean sample bottle being dried, carries out chromatography.Preferably, by institute
State reactor in silicone oil bath, be heated to 180-200 DEG C.Wherein, the present invention to exit, if temperature is the highest after it cools down again
Just venting will make the liquid in reactor together erupt with gas.
From above scheme it can be seen that the present invention provides a kind of slurry bed system ester through hydrogenation reaction, on the one hand improve ester through hydrogenation
During feed stock conversion, on the other hand improve the selectivity of product fluorinated alcohols and fluoroester.Invention simultaneously uses reactor
Technological process replaces tradition ester through hydrogenation fixed-bed process flow process, simplifies operating process, reduces equipment cost, and can be effective
Recovery noble metal catalyst, effective solution tradition slurry reactor complex process, investment greatly, are not suitable for field of fine chemical little
The deficiencies such as scale is raw, and reduce production cost.
In order to be further appreciated by the present invention, the technical scheme provided the present invention below in conjunction with embodiment is carried out specifically
Bright, protection scope of the present invention is not limited by the following examples.
Raw material and chemical reagent that the embodiment of the present invention uses are commercial.
Embodiment 1
Magnetitum is first placed into reactor, then weighs catalyst Raney's nickel 1.0g, difluoro ethyl chloroacetate with electronic balance
5g, ethanol 15g, triethylamine 1.4g pour into successively in reactor, tighten kettle cover.The hydrogen inspection being filled with 3MPa in reactor is
No gas leakage, air tight, hydrogen is released, in triplicate, is the most again flushed with hydrogen gas 1.0MPa.Reactor is moved into and has reached 165
DEG C silicone oil bath in, open magnetic stirring apparatus, react 5h.Treat after having reacted that it is cooled to the receptible scope of hands, open venting
Valve is exitted, then turns on kettle cover, with in dropper sampling to the clean sample bottle being dried, carries out chromatography, and result is as shown in table 1.
Embodiment 2
Magnetitum is first placed into reactor, weighs Raney's nickel 1.0g, difluoro ethyl chloroacetate 10g, ethanol with electronic balance
30g, triethylamine 2.8g pour into successively in reactor, tighten kettle cover.The hydrogen being filled with 3MPa in reactor checks whether gas leakage,
Air tight, hydrogen is released, in triplicate, is the most again flushed with hydrogen gas 2.0MPa.Reactor is moved into the silicon having reached 180 DEG C
In oil bath, open magnetic stirring apparatus, react 5h.Treat after having reacted that it is cooled to the receptible scope of hands, open vent valve venting,
Turning on kettle cover again, with in dropper sampling to the clean sample bottle being dried, carry out chromatography, result is as shown in table 1.
Embodiment 3
Magnetitum is first placed into reactor, weighs Raney's nickel 1.0g, difluoro ethyl chloroacetate 10g, ethanol with electronic balance
30g, triethylamine 2.8g pour into successively in reactor, tighten kettle cover.The hydrogen being filled with 3MPa in reactor checks whether gas leakage,
Air tight, hydrogen is released, in triplicate, is the most again flushed with hydrogen gas 2.0MPa.Reactor is moved into the silicon having reached 180 DEG C
In oil bath, open magnetic stirring apparatus, react 10h.Treat after having reacted that it is cooled to the receptible scope of hands, open vent valve and put
Gas, then turn on kettle cover, with in dropper sampling to the clean sample bottle being dried, carrying out chromatography, result is as shown in table 1.
Comparative example 1
Magnetitum is first placed into reactor, then weighs catalyst Raney's nickel 1.0g, ethanol 15g, difluoro chlorine with electronic balance
Ethyl acetate 3g, triethylamine 1.4g, pours into successively in reactor, tightens kettle cover.The hydrogen inspection of 4.0MPa it is filled with in reactor
Test and whether leak gas, air tight, hydrogen is released, in triplicate, is the most again flushed with hydrogen gas 2.0MPa.Reactor is moved into and reaches
In the silicone oil baths of 80 DEG C, open magnetic stirring apparatus, react 5h.Treat after having reacted that it is cooled to the receptible scope of hands, open
Vent valve is exitted, and is turning on kettle cover, with in dropper sampling to the clean sample bottle being dried, carries out chromatography, and detection target is produced
Thing difluoroethanol, result is as shown in table 1.
Comparative example 2
Magnetitum is first placed into reactor, weighs catalyst Raney's nickel 1.0g, ethanol 15g, difluoro chloroethene with electronic balance
Acetoacetic ester 5g, triethylamine 1.4g, pour into successively in reactor, tighten kettle cover.The hydrogen inspection being filled with 4MPa in reactor is
No gas leakage, air tight, hydrogen is released, in triplicate, is the most again flushed with hydrogen gas 2.0MPa.Reactor is moved into and has reached 80
DEG C silicone oil bath in, open magnetic stirring apparatus, react 10h.Treat after having reacted that it is cooled to the receptible scope of hands, open venting
Valve is exitted, and is turning on kettle cover, with in dropper sampling to the clean sample bottle being dried, carries out chromatography, and result is as shown in table 1.
Comparative example 3
Magnetitum is first placed into reactor, then weighs catalyst Raney's nickel 1.0g, ethanol 15g, difluoro chlorine with electronic balance
Ethyl acetate 5g, pours into successively in reactor, tightens kettle cover.The hydrogen being filled with 4MPa in reactor checks whether gas leakage, no
Gas leakage is then released hydrogen, in triplicate, is the most again flushed with hydrogen gas 2.0MPa.Reactor is moved into the silicone oil bath having reached 80 DEG C
In, open magnetic stirring apparatus, react 5h.Treat after having reacted that it is cooled to the receptible scope of hands, open vent valve venting, twisting
Opening kettle cover, with in dropper sampling to the clean sample bottle being dried, carry out chromatography, result is as shown in table 1.
Comparative example 4
Magnetitum is first placed into reactor, then weighs catalyst Raney's nickel 1.0g, difluoro ethyl chloroacetate with electronic balance
5g, ethanol 15g, triethylamine 1.4g pour into successively in reactor, tighten kettle cover.The hydrogen inspection of 3.0MPa it is filled with in reactor
Whether leak gas, air tight, hydrogen is released, in triplicate, is the most again flushed with hydrogen gas 1.0MPa.Reactor is moved into and reaches
In the silicone oil bath of 80 DEG C, open magnetic stirring apparatus, react 10h.Treat after having reacted that it is cooled to the receptible scope of hands, open and put
Air valve is exitted, then turns on kettle cover, with in dropper sampling to the clean sample bottle being dried, carries out chromatography, result such as table 1 institute
Show.
Raw material that table 1 embodiment of the present invention and comparative example use and product
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It is right to it should be pointed out that,
For those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out
Some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (10)
1. the preparation method of a difluoroethanol, it is characterised in that comprise the following steps:
Raney's nickel, difluoro ethyl chloroacetate, ethanol and triethylamine are poured in reactor by step a) successively, tighten kettle cover；
Step b) is filled with H in described reactor2And check whether gas leakage；
Described reactor is heated to 150-200 DEG C in silicone oil bath by step c), and the response time is 5-10h, obtains difluoroethanol.
Preparation method the most according to claim 1, it is characterised in that described Raney's nickel, difluoro ethyl chloroacetate, ethanol and
The mass ratio of triethylamine is 1:3-10:10-30:1-3.
Preparation method the most according to claim 2, it is characterised in that described Raney's nickel, difluoro ethyl chloroacetate, ethanol and
The mass ratio of triethylamine is 1:5-10:15-30:1.4-2.8.
Preparation method the most according to claim 1, it is characterised in that described in tighten kettle cover and make reactor be in sealed shape
State.
Preparation method the most according to claim 1, it is characterised in that in step b, is filled with 5-8MPa in described reactor
H2And check whether gas leakage.
Preparation method the most according to claim 5, it is characterised in that in step b, is filled with 5-7MPa in described reactor
H2And check whether gas leakage.
Preparation method the most according to claim 1, it is characterised in that described step b particularly as follows:
It is filled with H in described reactor2Check whether gas leakage, air tight, hydrogen is released, in triplicate, is the most again flushed with hydrogen
Gas.
Preparation method the most according to claim 1, it is characterised in that in step c, reaction is under the stirring of magnetic stirring apparatus
Carry out.
9. according to the preparation method described in claim 1-8 any one, it is characterised in that described step c particularly as follows:
Described reactor is heated in silicone oil bath 150-200 DEG C, and the response time is 5-10h, is cooled to room after having reacted
Temperature, opens vent valve venting, then turns on kettle cover, with in dropper sampling to the clean sample bottle being dried, carries out chromatography.
Preparation method the most according to claim 1, it is characterised in that described reactor is heated in silicone oil bath
180-200℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610460277.1A CN106316787A (en) | 2016-06-21 | 2016-06-21 | Preparation method of difluoroethanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610460277.1A CN106316787A (en) | 2016-06-21 | 2016-06-21 | Preparation method of difluoroethanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106316787A true CN106316787A (en) | 2017-01-11 |
Family
ID=57725193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610460277.1A Pending CN106316787A (en) | 2016-06-21 | 2016-06-21 | Preparation method of difluoroethanol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106316787A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105859553A (en) * | 2016-04-26 | 2016-08-17 | 南通宝凯化工有限公司 | Preparation technique of ethyl difluoroacetate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5455376A (en) * | 1993-12-10 | 1995-10-03 | Bayer Aktiengesellschaft | Process for the preparation of aliphatic omega-difluorocarboxyl compounds |
| WO2007093567A1 (en) * | 2006-02-13 | 2007-08-23 | Solvay (Societe Anonyme) | Process for the manufacture of fluorinated alcohols |
| CN101687740A (en) * | 2007-09-18 | 2010-03-31 | 中央硝子株式会社 | Processes for production of 2-bromo-2,2-difluoroethanol and 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfonic acid salt |
| CN102553614A (en) * | 2011-12-26 | 2012-07-11 | 浙江师范大学 | Catalyst for producing difluoroethanol by hydrogenation of difluoro carboxylate and preparation method thereof |
-
2016
- 2016-06-21 CN CN201610460277.1A patent/CN106316787A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5455376A (en) * | 1993-12-10 | 1995-10-03 | Bayer Aktiengesellschaft | Process for the preparation of aliphatic omega-difluorocarboxyl compounds |
| WO2007093567A1 (en) * | 2006-02-13 | 2007-08-23 | Solvay (Societe Anonyme) | Process for the manufacture of fluorinated alcohols |
| CN101687740A (en) * | 2007-09-18 | 2010-03-31 | 中央硝子株式会社 | Processes for production of 2-bromo-2,2-difluoroethanol and 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfonic acid salt |
| CN102553614A (en) * | 2011-12-26 | 2012-07-11 | 浙江师范大学 | Catalyst for producing difluoroethanol by hydrogenation of difluoro carboxylate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张迪等: "2,2-二氟乙醇的合成研究进展", 《有机氟工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105859553A (en) * | 2016-04-26 | 2016-08-17 | 南通宝凯化工有限公司 | Preparation technique of ethyl difluoroacetate |
| CN105859553B (en) * | 2016-04-26 | 2019-05-21 | 南通宝凯化工有限公司 | A kind of preparation process of ethyl difluoro |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101691332B (en) | Method for preparing 4-amino diphenylamine by catalytic hydrogenation | |
| CN106866589B (en) | A kind of preparation method of gamma-valerolactone | |
| CN103333075A (en) | Production method of 2,5-dichloroaniline | |
| CN105693659B (en) | A kind of preparation method of tetrahydrofurfuryl alcohol | |
| CN103626240B (en) | Lower concentration complexity prepares the method for ruthenium trichloride containing ruthenium waste liquid | |
| CN102816045A (en) | Method for synthesizing chloromethane by tail gas generated during chloroacetic acid production | |
| CN106316787A (en) | Preparation method of difluoroethanol | |
| CN110227449A (en) | A kind of high-temperature catalyst, preparation method and application | |
| CN109879728A (en) | A kind of method of catalysis of phenol and methanol-fueled CLC methyl phenyl ethers anisole | |
| CN106316795A (en) | Method for preparing difluoroethanol through catalytic hydrogenation | |
| CN101544569B (en) | Method for preparing 1,5-diaminonaphthalene through catalytic hydrogenation | |
| CN102976897A (en) | Method for purifying tetrafluoro propanol | |
| CN101264447A (en) | Nickel-boehmite composite catalyst for ethylene glycol liquid phase reforming reaction and preparation thereof | |
| CN106008227A (en) | Solvent-free catalytic hydrogenation method for preparation of 2,4-dichloro-5-isopropoxy aniline | |
| CN107164099A (en) | A kind of method that utilization way of distillation extracts wormwood essential oil | |
| CN111215079B (en) | Method for preparing alcohol by hydrogenation of aldehydes by adopting nickel-based heterogeneous catalyst | |
| CN105080545B (en) | The catalyst of CO Hydrogenation isobutanols and a kind of CO Hydrogenations for isobutanol method | |
| CN108658787B (en) | The preparation method of ethamine | |
| CN106831841A (en) | A kind of method that chloride impurity in industrial trimethyl aluminium is removed by sodium-potassium eutectic | |
| CN103894232B (en) | A kind of Catalysts and its preparation method of methyl nitrite formylated synthesis methyl formate and application | |
| CN103433059B (en) | Catalyst used in hydrogenation reaction of m-dinitrobenzene to synthesize m-phenylenediamine and application of catalyst | |
| CN109897019A (en) | A method of preparing furfuryl alcohol by furfural liquid phase hydrogenation is carried out using copper-based catalysts | |
| CN101786607B (en) | Method for preparing hydrogen fluoride from byproduct generated in the process of producing silane | |
| CN108435187A (en) | The technique of acetic acid hydrogenation catalyst and synthesis gas and acetic acid one step methanol and ethyl alcohol | |
| CN101544571B (en) | A method for preparing o-chloro PPD |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170111 |