CN106278926B - The method that bianry alloy catalyzes and synthesizes 3- amino-4-methoxyacetanilide - Google Patents
The method that bianry alloy catalyzes and synthesizes 3- amino-4-methoxyacetanilide Download PDFInfo
- Publication number
- CN106278926B CN106278926B CN201610629622.XA CN201610629622A CN106278926B CN 106278926 B CN106278926 B CN 106278926B CN 201610629622 A CN201610629622 A CN 201610629622A CN 106278926 B CN106278926 B CN 106278926B
- Authority
- CN
- China
- Prior art keywords
- methoxyacetanilide
- reaction
- solution
- bianry alloy
- amino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of Nanometer Copper/silver bianry alloy catalyst to catalyzing hydrogenating 3- nitro -4- p-methoxyacetanilide (NMA) synthesis 3- amino-4-methoxyacetanilide methods, belong to nano-catalytic field.Reaction of the present invention carries out in autoclave, and under catalyst action, providing hydrogen is hydrogen source.The catalyst has high activity in reaction process, highly selective, and catalyst not easy in inactivation, has good stability in use.
Description
Technical field
The present invention relates to a kind of Nanometer Copper/silver bianry alloy catalyst to catalyzing hydrogenating 3- nitro -4- p-methoxyacetanilides
(NMA) method for synthesizing 3- amino-4-methoxyacetanilide, belongs to nano-catalytic field.
Background technique
3- amino-4-methoxyacetanilide is the important centre for synthesizing organic azo-type disperse dyes and some drugs
Body can be used for preparing the intermediate and disperse dark blue of the dyestuffs such as C.I. Disperse Blue-79, C.I. disperse blue 301 and disperse violet 58
The coupling component of HGL, while can also be used in the synthesis of acid dyes, reactive dye and pigment, it occupies an important position in the industry.
China is that maximum 3- amino-4-methoxyacetanilide producing country, being in great demand at home and abroad have good in the world
Market prospects.
Traditional industry production synthesis 3- amino-4-methoxyacetanilide route is to first pass through nitrification, ether from chlorobenzene
Change, reduction, acylated synthesis methacetin, then nitrify, iron powder reducing obtains 3- amino 4- p-methoxyacetanilide.It adopts
Intermediate product 3- nitro -4- p-methoxyacetanilide synthetic product 3- amino-4-methoxyl acetophenone is restored with iron powder reducing method
Amine, although its simple process, applicable surface is wider, does not need high-tension apparatus, operation also relatively safety, iron powder use so that
A large amount of iron cement waste residue and acid waste water are generated in reaction process, seriously pollute environment, therefore, this synthesis 3- amino -4- methoxy
The technique of base antifebrin is urgently improved.
Currently, in the industrial production of aromatic amine compound, catalytic hydrogenation method used catalyst be mainly Raney-Ni and Pt,
The rare precious metals such as Pd, Ru and Rh.However, it is amino that commercialization Raney-Ni, which is not only catalyzed nitro hydrogenation, but also it is catalyzed phenyl ring and adds
Hydrogen leads to have by-product generation, reduces major product purity.With the rapid development of nanotechnology, metallic catalyst is being urged
Change in nitro-aromatic selective hydrogenation reaction and shows excellent catalytic performance.But that there are stability is poor for metallic catalyst,
The disadvantages of easy to reunite.And carrier nanometer catalyst, in activation process, nano-noble metal is easy to be reduced and is easy to be grown to
Large-sized metallic particles causes the dispersibility of active component low low with catalytic activity.
The shortcomings that for unitary metallic catalyst, is converted into bianry alloy for unitary is nanocrystalline, can prepare high work
The metallic catalyst of property.The alloying of metal not only increases the ability of the anti-sintering of particle, and it is living to have changed simultaneously catalyst
The Electronic Performance and geometry of property component.Compared with unitary metallic catalyst, binary alloy nano metallic catalyst exists
More excellent catalytic activity and selectivity are shown in catalysis nitro-aromatic selective hydrogenation reaction.Therefore, Nanometer Copper/silver is studied
Bianry alloy catalysis 3- nitro -4- p-methoxyacetanilide synthetic product 3- amino-4-methoxyacetanilide has important grind
Study carefully meaning.
Summary of the invention
Nanometer Copper/silver bianry alloy catalyst to catalyzing hydrogenating 3- nitro -4- is utilized the purpose of the present invention is to provide a kind of
The method of p-methoxyacetanilide synthesis 3- amino-4-methoxyacetanilide.Reaction of the present invention is in autoclave
It carries out, under catalyst action, providing hydrogen is hydrogen source.The catalyst has high activity in reaction process, highly selective, and urges
Agent not easy in inactivation has good stability in use.
The present invention is achieved through the following technical solutions:
A kind of Nanometer Copper/silver bianry alloy catalyst to catalyzing hydrogenating 3- nitro -4- p-methoxyacetanilide synthesis 3- amino -
The method of 4- p-methoxyacetanilide carries out as steps described below:
Step A, the methanol solution of certain density 3- nitro -4- p-methoxyacetanilide is added in a high pressure reaction kettle,
A certain amount of Nanometer Copper/silver bianry alloy catalyst is added, reaction unit is installed, leads to N2It is emptied, then is passed through high-purity
Hydrogen arranges N2, it is then turned on agitating device.
Step B, system obtained by step A is heated to reaction temperature；It is passed through certain pressure hydrogen to be reacted, reaction terminates
Afterwards, 45 DEG C are cooled to hereinafter, reaction product is diluted, using efficient liquid phase chromatographic analysis and calculated result.
In step A, the 3- nitro -4- p-methoxyacetanilide concentration of methanol solution is 0.05~0.3mol/L.
In step A, Nanometer Copper/silver bianry alloy catalyst dosage is every 150mL3- nitro -4- p-methoxyacetanilide
Methanol solution uses 0.1~1.0g.
In step A, the volume ratio of the 3- nitro -4- p-methoxyacetanilide methanol solution and autoclave is
1.5:5, stirring rate 400rpm.
In step B, the Hydrogen Vapor Pressure is 0.4~1.2MPa, and reaction temperature is 80~160 DEG C；Reaction time is 3h.
In step B, the dilution processing of the reaction product, which refers to, carries out dilute twice to the solution after reaction, uses first
Then the solution that pipette pipettes after 1ml reaction pipettes dilution of 1ml extremely with methanol constant volume to 25ml volumetric flask again
25ml volumetric flask, uses methanol constant volume；Solution after reaction includes the complete raw material of unreacted and reaction product.
Nanometer Copper described in above scheme/silver bianry alloy catalyst is with Tween-80, cetyl trimethyl bromine
Change ammonium (CTAB) or citric acid (CA) to be prepared under conditions of organic modifier by wet-chemical reduction method, specifically prepares
Method carries out as steps described below:
Step 1: the presoma of Cu and organic modifier are dissolved in dehydrated alcohol, ultrasound all dissolutions are then heated to
60 DEG C, dropwise be added dropwise NaOH ethanol solution come adjust solution ph be 8, obtain mixed liquor A.
Step 2: taking hydrazine hydrate to be dissolved in dehydrated alcohol is made hydrazine hydrate dilute solution, dropwise by the hydrazine hydrate dilute solution
It is added in mixed liquor A, forms mixed liquid B, and reacted, the Nanometer Copper of preparation is cooled to 30 DEG C after reaction.
Step 3: the presoma of Ag is dissolved in dehydrated alcohol, mixed liquor C is formed, and step 2 is added dropwise in C solution
It is reacted in resulting product, reacts after a certain period of time that the Nanometer Copper of preparation/silver bianry alloy is cooling under magnetic stirring
It to room temperature and is stored in ethanol solution, needs to pre-process before use, repeatedly washed, be centrifugated with dehydrated alcohol.
In the step 1, the presoma of Cu is nitrate trihydrate copper, and the molar concentration of copper nitrate ethanol solution is 0.2mol/
L。
In the step 1, organic modifier is cetyl trimethylammonium bromide (CTAB), citric acid in mixed liquor A
(CA) or Tween-80 (Tween-80), quality are that the concentration of 10%, the NaOH ethanol solution of nitrate trihydrate copper mass is
1.5mol/L。
In the step 2, when preparing hydrazine hydrate dilute solution, the volume ratio of hydrazine hydrate and dehydrated alcohol is 3:25.The water
The mass concentration for closing hydrazine is 85%, and the volume ratio of hydrazine hydrate alcohol dilute solution and copper nitrate ethanol solution is 7:5；Reaction time is
2h；Reaction temperature is still maintained at 60 DEG C.
In the step 3, the presoma of the Ag is silver nitrate, and the molar concentration of silver nitrate ethanol solution is
The volume ratio of 0.08mol/L, silver nitrate ethanol solution and copper nitrate ethanol solution is 1:2, and the reaction temperature is 30 DEG C, reaction
Time is 1h.
The distinctive technical characteristic of the present invention is:
By changing organic modifier type, different structure is prepared, Nanometer Copper/silver bianry alloy of different-shape is urged
Agent realizes complementation, cooperation between nano metal on catalytic performance, improves the catalytic activity and selectivity of nano metal, obtain
Unexpected catalytic effect, this is a big characteristic of the invention.
Specific embodiment
The following are presently preferred embodiments of the present invention, the present invention better understood when, but the embodiment of the present invention is not limited to
This, while its shown data does not represent the limitation to feature of present invention range.
Embodiment 1
The preparation of catalyst:
In the presence of organic modifier CTAB, using nitrate trihydrate copper, silver nitrate, hydrazine hydrate as raw material, using wet-chemical
Reduction method for preparing nanometer copper/silver bianry alloy catalyst.
1.93g nitrate trihydrate copper and 0.193g CTAB are dissolved in the dehydrated alcohol of 40ml, ultrasonic 30min all dissolves
Mixed liquor is formed, when mixed liquor is warming up to 60 DEG C, 1.5mol/L NaOH ethanol solution is added dropwise dropwise, adjusts mixed liquor pH value
It is 8；Then hydrazine hydrate alcohol dilute solution (hydrazine hydrate of 6ml 85%/50ml dehydrated alcohol) is added dropwise dropwise, and in magnetic agitation
Lower reaction 2h, is cooled to 30 DEG C for the Nanometer Copper of preparation after reaction；It weighs 0.27g silver nitrate and is dissolved in 20ml dehydrated alcohol
In, nanometer copper-silver bianry alloy Cu- is prepared into after the mixed liquor that silver nitrate ethanol solution is added dropwise to after cooling is carried out reaction 1h
Ag.Finally it is stored in ethanol solution.It needs to pre-process before use, is repeatedly washed, is centrifugated with dehydrated alcohol.
3- nitro -4- p-methoxyacetanilide catalytic hydrogenation reaction:
Take the 3- nitro -4- p-methoxyacetanilide of certain mass that 500mL is added with the reaction solution that methanol is configured to 150mL
Autoclave in, add 0.6g Nanometer Copper/silver bianry alloy catalyst, wherein 3- nitro -4- p-methoxyacetanilide
Concentration is 0.2mol/L；Reaction unit is installed, nitrogen purging 10min is passed through and is emptied, then be passed through High Purity Hydrogen row N2, then
Agitating device is opened, stirring rate 400rpm is passed through 0.8MPa H when reaction temperature rises to 120 DEG C2React 3h；Reaction knot
Shu Hou is cooled to 45 DEG C hereinafter, reaction product is diluted, using efficient liquid phase chromatographic analysis and calculates, the results are shown in Table 1.
Embodiment 2
Nanometer Copper/silver bianry alloy catalyst is prepared using the same method of embodiment 1, only changes organic modifier difference
For CA, Tween-80, the process of catalyst to catalyzing hydrogenating 3- nitro -4- p-methoxyacetanilide is using same as Example 1
Method can be obtained different modifying agent and prepare Nanometer Copper/silver bianry alloy catalyst and urges 3- nitro -4- p-methoxyacetanilide
The influence for changing hydrogenation reaction, the results are shown in Table 1.
1 different modifying agent of table prepares Nanometer Copper/silver bianry alloy catalyst and is catalyzed to 3- nitro -4- p-methoxyacetanilide
The influence of hydrogenation reaction
Embodiment 3
Using the same method preparing nano Cu-Ag catalyst of embodiment 1, it is catalyzed 3- nitro -4- p-methoxyacetanilide
Add hydrogen, only changing kettle interior reaction temperature is respectively 80 DEG C, 100 DEG C, 140 DEG C and 160 DEG C, and reaction temperature can be obtained to 3- nitre
The influence of base -4- p-methoxyacetanilide catalytic hydrogenation reaction, the results are shown in Table 2.
Influence of 2 reaction temperature of table to 3- nitro -4- p-methoxyacetanilide catalytic hydrogenation reaction
Embodiment 4
Using the same method preparing nano Cu-Ag catalyst of embodiment 1, it is catalyzed 3- nitro -4- p-methoxyacetanilide
Add hydrogen, the concentration for only changing 3- nitro -4- p-methoxyacetanilide is respectively 0.05mol/L, 0.1mol/L, 0.3mol/L, i.e.,
Influence of the material concentration to 3- nitro -4- p-methoxyacetanilide catalytic hydrogenation reaction can be obtained, the results are shown in Table 3.
3 3- nitro -4- p-methoxyacetanilide concentration of table is to 3- nitro -4- p-methoxyacetanilide catalytic hydrogenation reaction
Influence
Embodiment 5
Using the same method preparing nano Cu-Ag catalyst of embodiment 1, it is catalyzed 3- nitro -4- p-methoxyacetanilide
Add hydrogen, only changing Hydrogen Vapor Pressure is respectively 0.4MPa and 1.2MPa, and Hydrogen Vapor Pressure can be obtained to 3- nitro -4- methoxyl group acetyl
The influence of aniline catalytic hydrogenation reaction, the results are shown in Table 4.
Influence of 4 Hydrogen Vapor Pressure of table to 3- nitro -4- p-methoxyacetanilide catalytic hydrogenation reaction
Embodiment 6
Using the same method preparing nano Cu-Ag catalyst of embodiment 1, it is catalyzed 3- nitro -4- p-methoxyacetanilide
Add hydrogen, only changing catalyst amount is respectively 0.1g, 0.2g and 1.0g, and catalyst amount can be obtained to 3- nitro -4- methoxy
The influence of base antifebrin catalytic hydrogenation reaction, the results are shown in Table 5.
Influence of 5 catalyst amount of table to 3- nitro -4- p-methoxyacetanilide catalytic hydrogenation reaction
Embodiment 7
Using the same method preparing nano Cu-Ag catalyst of embodiment 1, it is catalyzed 3- nitro -4- p-methoxyacetanilide
Add hydrogen, catalyst and catalytic hydrogenation product are centrifugated, is washed with dehydrated alcohol, is dry, used the 2nd time, the 3rd time, the 4th
Secondary, the 5th can obtain recycling performance of the catalyst in 3- nitro -4- p-methoxyacetanilide catalytic hydrogenation reaction, as a result
It is shown in Table 6,
Influence of the 6 catalyst access times of table to 3- nitro -4- p-methoxyacetanilide catalytic hydrogenation reaction
Claims (8)
1. the method that bianry alloy catalyzes and synthesizes 3- amino-4-methoxyacetanilide, it is characterised in that in accordance with the following steps into
Row:
Step A, it is added the methanol solution of certain density 3- nitro -4- p-methoxyacetanilide in a high pressure reaction kettle, then plus
Enter a certain amount of Nanometer Copper/silver bianry alloy catalyst, install reaction unit, leads to N2It is emptied, then is passed through High Purity Hydrogen row
N2, it is then turned on agitating device；
Step B, system obtained by step A is heated to reaction temperature；Certain pressure hydrogen is passed through to be reacted, after reaction,
45 DEG C are cooled to hereinafter, reaction product is diluted, using efficient liquid phase chromatographic analysis and calculated result；
The Nanometer Copper/silver bianry alloy catalyst is with Tween-80, cetyl trimethylammonium bromide (CTAB) or lemon
Lemon acid (CA) is is prepared by wet-chemical reduction method under conditions of organic modifier, specific preparation method is according to following steps
It is rapid to carry out:
Step 1: the presoma of Cu and organic modifier are dissolved in dehydrated alcohol, ultrasound all dissolutions then heat to 60
DEG C, dropwise be added dropwise NaOH ethanol solution come adjust solution ph be 8, obtain mixed liquor A；
Step 2: taking hydrazine hydrate to be dissolved in dehydrated alcohol is made hydrazine hydrate dilute solution, the hydrazine hydrate dilute solution is added dropwise
Into mixed liquor A, mixed liquid B is formed, and reacted, the Nanometer Copper of preparation is cooled to 30 DEG C after reaction；
Step 3: the presoma of Ag is dissolved in dehydrated alcohol, mixed liquor C is formed, and C solution is added dropwise obtained by step 2
Product in reacted, react the Nanometer Copper of preparation/silver bianry alloy is cooled to room after a certain period of time under magnetic stirring
Temperature is simultaneously stored in ethanol solution, is needed to pre-process before use, is repeatedly washed, is centrifugated with dehydrated alcohol.
2. the method that bianry alloy as described in claim 1 catalyzes and synthesizes 3- amino-4-methoxyacetanilide, feature exist
In: in step A, the 3- nitro -4- p-methoxyacetanilide concentration of methanol solution is 0.05~0.3mol/L；Nanometer Copper/silver
The dosage of bianry alloy catalyst is that every 150mL3- nitro -4- p-methoxyacetanilide methanol solution uses 0.1~1.0g；Institute
The volume ratio of the 3- nitro -4- p-methoxyacetanilide methanol solution and autoclave stated is 1.5:5, and stirring rate is
400rpm。
3. the method that bianry alloy as claimed in claim 2 catalyzes and synthesizes 3- amino-4-methoxyacetanilide, feature exist
In: the 3- nitro -4- p-methoxyacetanilide concentration of methanol solution is 0.1mol/L, Nanometer Copper/silver bianry alloy catalyst
Dosage be every 150mL3- nitro -4- p-methoxyacetanilide methanol solution use 0.6g.
4. the method that bianry alloy as described in claim 1 catalyzes and synthesizes 3- amino-4-methoxyacetanilide, feature exist
In: in step B, the Hydrogen Vapor Pressure is 0.4~1.2MPa, and reaction temperature is 80~160 DEG C；Reaction time is 3h；It is described
Reaction product dilution processing refer to after reaction solution carry out dilute twice, first with pipette pipette 1ml reaction after
Solution then pipetted dilution of 1ml again with methanol constant volume to 25ml volumetric flask to 25ml volumetric flask, used methanol constant volume；
Solution after reaction includes the complete raw material of unreacted and reaction product.
5. the method that bianry alloy as claimed in claim 4 catalyzes and synthesizes 3- amino-4-methoxyacetanilide, feature exist
In: reaction temperature is 140 DEG C, and the Hydrogen Vapor Pressure is 0.8MPa.
6. the method that bianry alloy as described in claim 1 catalyzes and synthesizes 3- amino-4-methoxyacetanilide, feature exist
In: in the step 1, the presoma of Cu is nitrate trihydrate copper, and the molar concentration of copper nitrate ethanol solution is 0.2mol/L；It is mixed
Closing organic modifier in liquid A is cetyl trimethylammonium bromide, and quality is 10%, the NaOH ethyl alcohol of nitrate trihydrate copper mass
The concentration of solution is 1.5mol/L.
7. the method that bianry alloy as described in claim 1 catalyzes and synthesizes 3- amino-4-methoxyacetanilide, feature exist
In: in the step 2, when preparing hydrazine hydrate dilute solution, the volume ratio of hydrazine hydrate and dehydrated alcohol is 3:25；The hydrazine hydrate
Mass concentration be 85%, the presoma of Cu and organic modifier are dissolved in dehydrated alcohol in hydrazine hydrate alcohol dilute solution and step 1
Obtained in copper nitrate ethanol solution volume ratio be 7:5；Reaction time is 2h；Reaction temperature is still maintained at 60 DEG C.
8. the method that bianry alloy as described in claim 1 catalyzes and synthesizes 3- amino-4-methoxyacetanilide, feature exist
In: in the step 3, the presoma of the Ag is silver nitrate, and the molar concentration of silver nitrate ethanol solution is 0.08mol/L, nitre
It is molten that the presoma and organic modifier of sour silver ethanol solution and Cu in step 1 are dissolved in copper nitrate ethyl alcohol obtained in dehydrated alcohol
The volume ratio of liquid is 1:2, and the reaction temperature is 30 DEG C, reaction time 1h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610629622.XA CN106278926B (en) | 2016-08-03 | 2016-08-03 | The method that bianry alloy catalyzes and synthesizes 3- amino-4-methoxyacetanilide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610629622.XA CN106278926B (en) | 2016-08-03 | 2016-08-03 | The method that bianry alloy catalyzes and synthesizes 3- amino-4-methoxyacetanilide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106278926A CN106278926A (en) | 2017-01-04 |
| CN106278926B true CN106278926B (en) | 2019-04-30 |
Family
ID=57664632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610629622.XA Expired - Fee Related CN106278926B (en) | 2016-08-03 | 2016-08-03 | The method that bianry alloy catalyzes and synthesizes 3- amino-4-methoxyacetanilide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106278926B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107746380B (en) * | 2017-11-06 | 2020-04-07 | 宁夏中盛新科技有限公司 | Industrial production method of 2-amino-4-acetamino anisole |
| CN110252383A (en) * | 2019-05-17 | 2019-09-20 | 江苏大学 | A kind of Cu@Ru/MCM-41 nanocatalyst and its preparation method and application |
| CN113578346A (en) * | 2021-08-13 | 2021-11-02 | 江苏大学 | Copper/silver alloy nano catalyst and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565383A (en) * | 2009-05-08 | 2009-10-28 | 江苏大学 | Method for synthesizing 3-amino-4-methacetin by catalytic hydrogenation |
| CN103638947B (en) * | 2013-12-09 | 2015-08-26 | 江苏大学 | A kind of Ni/Ag/Cu/TiO 2the preparation of composite catalyst and application thereof |
-
2016
- 2016-08-03 CN CN201610629622.XA patent/CN106278926B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN106278926A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101007281B (en) | Novel preparation method of amorphous alloy catalyst | |
| CN108941599B (en) | Continuous preparation method of nano-copper | |
| CN101972651B (en) | Metal palladium nano-material catalyst and preparation and application thereof | |
| CN102921422B (en) | Preparation of magnetic nano Cu-Fe3O4/grapheme composite catalyst and application of composite catalyst in reduction of nitro-compounds | |
| CN106278926B (en) | The method that bianry alloy catalyzes and synthesizes 3- amino-4-methoxyacetanilide | |
| CN110743544B (en) | Palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof | |
| CN106242991A (en) | A kind of method of synthesis 3 amino 4 p-methoxyacetanilides | |
| CN111153768B (en) | Synthesis method of isohexide | |
| CN107497448B (en) | Rhodium/copper alloy nano catalyst and preparation method and application thereof | |
| CN102921419B (en) | A kind of for the direct hydroxylating of benzene Nanometer Copper-graphene composite catalyst preparing phenol and preparation method thereof | |
| CN103495420B (en) | Method for preparing ZnO-CuO composite metal oxide powder | |
| CN114160145A (en) | Catalyst for preparing ethanol by acetic acid hydrogenation and preparation method thereof | |
| CN113019393A (en) | Platinum nano catalyst, preparation method thereof and method for synthesizing aromatic amine by selective hydrogenation of aromatic nitro compound | |
| CN109453762A (en) | A kind of preparation method and application of modified clay mine loaded palladium catalyst | |
| CN101565383A (en) | Method for synthesizing 3-amino-4-methacetin by catalytic hydrogenation | |
| CN110202127B (en) | Synthesis method and application of sub-10 nanometer twin-crystal icosahedral PdCuPt nanometer alloy | |
| CN101935054B (en) | Method for preparing ammonia | |
| CN105457641A (en) | Preparation of copper, zinc and aluminum methanol synthesizing catalyst by virtue of reduction deposition method | |
| CN106881131A (en) | A kind of supported non-precious metal catalyst and its preparation and the application in nitrile synthesis | |
| CN110975921B (en) | Preparation method and application of nitrogen-doped cobalt-based carbon material with magnetic porous structure | |
| CN102229587B (en) | Method for generating succinic anhydride through maleic anhydride hydrogenation catalyzed by Nano-Ni | |
| CN109822090A (en) | A kind of preparation method of the copper nanoparticle of in-stiu coating organic matter | |
| CN107442134B (en) | Rhodium/nickel alloy nano catalyst and preparation method and application thereof | |
| CN106334572A (en) | Cu/Co@NPC compound used for catalytic reduction of p-nitrophenol | |
| CN103272611B (en) | Co-M-B amorphous alloy nanotube catalyst, and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190430 Termination date: 20200803 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |