CN103801321B - A kind of catalyst for the preparation of BDO and preparation method - Google Patents
A kind of catalyst for the preparation of BDO and preparation method Download PDFInfo
- Publication number
- CN103801321B CN103801321B CN201210440185.9A CN201210440185A CN103801321B CN 103801321 B CN103801321 B CN 103801321B CN 201210440185 A CN201210440185 A CN 201210440185A CN 103801321 B CN103801321 B CN 103801321B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- hours
- bdo
- roasting
- 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.)
- Active
Links
Abstract
The invention discloses a kind of Catalysts and its preparation method for the preparation of BDO.This catalyst take zinc oxide as carrier, and copper, nickel are active component, and M is auxiliary agent, Cu-Ni-Zn-M-O type catalyst, and wherein M is manganese or magnesium.In catalyst, the weight content of metallic element is: copper 30wt% ~ 60wt%, nickel element 2wt% ~ 10wt%, and Zn-ef ficiency is 20wt% ~ 40wt%, M element 2wt% ~ 10wt%.Preparation method comprises following content: the soluble-salt of Cu, Ni, Zn and M is made into mixed solution, mix with precipitant solution under stirring at 50 ~ 70 DEG C, control ph is 7 ~ 9, stirs 1 ~ 3 hour, is warming up to 80 ~ 90 DEG C, aging 2 ~ 10 hours, filtration is precipitated, and precipitates through washing, dries, roasting, shapingly obtains product.Catalyst of the present invention has that conversion ratio is high, product selectivity good, the life-span is long, low cost and other advantages, and preparation method is simple, is easy to operation.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of catalyst for the preparation of BDO and preparation method.
Background technology
BDO (BDO) is a kind of important Organic Chemicals, mainly for the production of polybutylene terephthalate (PBT) (PBT), polyurethane (PU), gamma-butyrolacton (GBL) and oxolane (THF).In recent years, due to increasing rapidly of thermoplastic elastic fiber and elastomer demand, as the polytetramethylene ether diol (PTMEG) of monomer and the in great demand of PTMG (PTMG), upstream raw material BDO demand is also increased fast.Therefore, the technology of Development and Production BDO has great importance.
The production line of BDO has following several: the Reppe method that (1) is raw material with acetylene and formaldehyde; (2) take cis-butenedioic anhydride as the hydrogenation technique of raw material; (3) the gas phase hydrogenation technique of maleate; (4) take propylene as the synthesis technique of raw material; (5) take butadiene as the synthesis technique of raw material.
CN1850328, CN101502803 disclose the catalyst of two kinds of one-part forms by maleate Hydrogenation BDO.But do not adopt pure dimethyl maleate raw material, but using the mixture of dimethyl maleate and methyl alcohol as raw material (methyl alcohol: dimethyl maleate=1:4).When same treatment amount, comparatively speaking, the productive rate of product is low, and the charging of device and separating energy consumption increase, and the energy consumption of whole device is increased greatly, and production cost raises.
CN1286142 discloses a kind of Cu-Zn-Mn-Al catalyst of succinic acid dialkyl ester Hydrogenation BDO, adopts one-part form reaction.But product BDO is high selectivity is 80.4%, await improving.
It is the method that raw material prepares BDO co-producing tetrahydrofuran and gamma-butyrolacton that CN101891592, CN101307042 disclose by dialkyl maleate, all adopts two-part hydrogenation technique.Main feature, in synthetic reaction section, adopts the catalyst that two kinds different, two kinds of catalyst layerings or point device filling.With one-part form reacting phase ratio, there is Catalyst Production and synthesis technique very complicated shortcoming.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of Catalysts and its preparation method for the preparation of BDO.Catalyst of the present invention has that conversion ratio is high, product selectivity good, the life-span is long, low cost and other advantages, and preparation method is simple, is easy to operation.
For the preparation of a catalyst for BDO, take zinc oxide as carrier, copper, nickel are active component, and M is auxiliary agent, Cu-Ni-Zn-M-O type catalyst, and wherein M is manganese or magnesium.In catalyst, the weight content of metallic element is: copper 30wt% ~ 60wt%, nickel element 2wt% ~ 10wt%, and Zn-ef ficiency is 20wt% ~ 40wt%, M element 2wt% ~ 10wt%.
The preparation method of a kind of catalyst for the preparation of BDO of the present invention, comprises following content:
The soluble-salt of Cu, Ni, Zn and M is made into mixed solution, mix with precipitant solution under stirring at 50 ~ 70 DEG C, control ph is 7 ~ 9, stirs 1 ~ 3 hour, is warming up to 80 ~ 90 DEG C, aging 2 ~ 10 hours, filtration is precipitated thing, and sediment, through washing, is dried, roasting, shapingly obtains product.
In the inventive method, soluble-salt mixed solution can directly mix with precipitant solution hybrid mode, also can adopt the mode that also drip adds.
Soluble-salt described in the present invention can be any one in nitrate, acetate, sulfate and oxalates.
Precipitating reagent described in the inventive method can be one or more in sodium carbonate, NaOH, ammonium carbonate, carbonic hydroammonium and ammoniacal liquor.
In the inventive method, drying condition is: dry 8 ~ 16 hours at 100 ~ 120 DEG C, roasting condition is: roasting 6 ~ 10 hours at 700 ~ 1000 DEG C.
Catalyst of the present invention can be applied to dimethyl maleate Hydrogenation and react for BDO.Catalyst application of the present invention prepares BDO reaction in dimethyl maleate, and good process conditions are: reaction pressure is 3 ~ 6MPa, and reaction temperature is 180 ~ 240 DEG C, and hydrogen ester mol ratio is 50:1 ~ 300:1, and the liquid hourly space velocity (LHSV) of ester is 0.2 ~ 2h
-1.Catalyst of the present invention needs reduction activation before use, the gas used that reduces be dilution after hydrogen (as H
2/ N
2, H
2/ Ar gaseous mixture), pressure is 0.1 ~ 2MPa, and temperature is 150 ~ 300 DEG C.
Catalyst of the present invention with the good copper of Hydrogenation, nickel for active component.Add the second active component nickel in the catalyst, catalyst hydrogenation performance is improved, especially selective hydrogenation ability improves, and is conducive to the generation of object product BDO, improves the activity, selective of catalyst.High-temperature roasting at 700 ~ 1000 DEG C, makes the acid resistance of catalyst improve, extends the service life of catalyst.When preparing BDO reaction for dimethyl maleate, the conversion ratio of ester close to 100%, alcohol selective average more than 80%.Catalyst was through the life experiment of 1500 hours, and the activity and selectivity of catalyst remains unchanged substantially.
embodiment
Further describe technology contents of the present invention and effect below by specific embodiment, but therefore do not limit the present invention.
Catalyst provided by the invention can use following method evaluation.
Catalyst powder after roasting makes material to 10 ~ 20 orders, investigates the activity of catalyst in micro fixed-bed reactor.Adopt reducing process in device, with H
2/ N
2gaseous mixture carries out activity rating after 180 DEG C of reduction.Enter after reaction raw materials is mixed with hot hydrogen in required ratio and answer device.With its composition of gas chromatographic analysis after product condensation.
Embodiment 1
By 11gCu (NO
3)
23H
2o, 9.8gZn (NO
3)
26H
2o, 2gNi (NO
3)
26H
2o and 1.5gMn (NO
3)
24H
2o is dissolved in 100mL water and is made into metal ion solution; 13.3gNa
2cO
3be dissolved in 120mL water and be precipitated agent solution.60 DEG C of water-baths, drip two kinds of solution under stirring, control ph is 7 ~ 9 simultaneously.Dropwise rear continuation stirring 2 hours, be warming up to 80 DEG C aging 2 hours.Then suction filtration, washing, 110 DEG C of dryings 10 hours, 900 DEG C of roastings 8 hours, obtained product A-1.In catalyst, each component element mass percentage is: Cu40wt%, Ni5.5wt%, Mn4.5wt%, Zn30wt%.
Comparative example 1
By 12gCu (NO
3)
23H
2o, 9.8gZn (NO
3)
26H
2o and 1.5gMn (NO
3)
24H
2o is dissolved in 100mL water and is made into metal ion solution; 13.3gNa
2cO
3be dissolved in 120mL water and be precipitated agent solution.60 DEG C of water-baths, drip two kinds of solution under stirring, control ph is 7 ~ 9 simultaneously.Dropwise rear continuation stirring 2 hours, be warming up to 80 DEG C aging 2 hours.Then suction filtration, washing, 110 DEG C of dryings 10 hours, 900 DEG C of roastings 8 hours, obtained product D-1.In catalyst, each component element mass percentage is: Cu45.5wt%, Mn4.6wt%, Zn30wt%.
Embodiment 2
By 10gCu (NO
3)
23H
2o, 9.8gZn (NO
3)
26H
2o, 2.5gNi (NO
3)
26H
2o and 2gMn (NO
3)
24H
2o is dissolved in 100mL water and is made into metal ion solution; 13.3gNa
2cO
3be dissolved in 120mL water, be precipitated agent solution.60 DEG C of water-baths, drip two kinds of solution under stirring, control ph is 7 ~ 9 simultaneously.Dropwise rear continuation stirring 2 hours, be warming up to 80 DEG C aging 2 hours.Then suction filtration, washing, 110 DEG C of dryings 10 hours, 900 DEG C of roastings 8 hours, obtained product A-2.In catalyst, each component element mass percentage is: Cu37wt%, Ni6.9wt%, Mn6.1wt%, Zn30wt%.
Embodiment 3
By 12.5gCu (NO
3)
23H
2o, 10.2gZn (NO
3)
26H
2o, 1.5gNi (NO
3)
26H
2o and 1gMn (NO
3)
24H
2o is dissolved in 100mL water and is made into metal ion solution; 13.3gNa
2cO
3be dissolved in 120mL water and be precipitated agent solution.60 DEG C of water-baths, drip two kinds of solution under stirring, control ph is 7 ~ 9 simultaneously.Dropwise rear continuation stirring 2 hours, be warming up to 80 DEG C aging 2 hours.Then suction filtration, washing, 110 DEG C of dryings 10 hours, 900 DEG C of roastings 8 hours, obtained product A-3.In catalyst, each component element mass percentage is: Cu43wt%, Ni3.9wt%, Mn2.9wt%, Zn30wt%.
Comparative example 2
By 12.5gCu (NO
3)
23H
2o, 10.2gZn (NO
3)
26H
2o, 1.5gNi (NO
3)
26H
2o and 1gMn (NO
3)
24H
2o is dissolved in 100mL water and is made into metal ion solution; 13.3gNa
2cO
3be dissolved in 120mL water and be precipitated agent solution.60 DEG C of water-baths, drip two kinds of solution under stirring, control ph is 7 ~ 9 simultaneously.Dropwise rear continuation stirring 2 hours, be warming up to 80 DEG C aging 2 hours.Then suction filtration, washing, 110 DEG C of dryings 10 hours, 450 DEG C of roastings 8 hours, obtained product D-2.In catalyst, each component element mass percentage is: Cu43wt%, Ni3.9wt%, Mn2.9wt%, Zn30wt%.
Embodiment 4
By 12.5gCu (NO
3)
23H
2o, 10.2gZn (NO
3)
26H
2o, 1gNi (NO
3)
26H
2o and 2.5gMn (NO
3)
24H
2o is dissolved in 100mL water and is made into metal ion solution, 13.3gNa
2cO
3be dissolved in 120mL water and be precipitated agent solution.60 DEG C of water-baths, drip two kinds of solution under stirring, control ph is 7 ~ 9 simultaneously.Dropwise rear continuation stirring 2 hours, be warming up to 80 DEG C aging 2 hours.Then suction filtration, washing, 110 DEG C of dryings 10 hours, 900 DEG C of roastings 8 hours, obtained product A-4.In catalyst, each component element mass percentage is: Cu41wt%, Ni2.5wt%, Mn7wt%, Zn28wt%.
Embodiment 5
By 20gCu (NO
3)
23H
2o, 10.2gZn (NO
3)
26H
2o, 2.0gNi (NO
3)
26H
2o and 2.5gMg (NO
3)
26H
2o is dissolved in 100mL water and is made into metal ion solution, 13.3gNa
2cO
3be dissolved in 120mL water and be precipitated agent solution.60 DEG C of water-baths, drip two kinds of solution under stirring, control ph is 7 ~ 9 simultaneously.Dropwise rear continuation stirring 3 hours, be warming up to 80 DEG C aging 2 hours.Then suction filtration, washing, 110 DEG C of dryings 10 hours, 900 DEG C of roastings, 8 hours A-5.In catalyst, each component element mass percentage is: Cu51wt%, Ni3.9wt%, Mg2.2wt%, Zn22wt%.
Embodiment 6
By 10gCu (NO
3)
23H
2o, 10.2gZn (NO
3)
26H
2o, 3gNi (NO
3)
26H
2o and 3gMn (NO
3)
2, be dissolved in 100mL water and be made into metal ion solution, 13.3gNa
2cO
3be dissolved in 120mL water, be precipitated agent solution.60 DEG C of water-baths, drip two kinds of solution under stirring, control ph is 7 ~ 9 simultaneously.Dropwise rear continuation stirring 2 hours, be warming up to 80 DEG C aging 2 hours.Then suction filtration, washing, 110 DEG C of dryings 10 hours, 900 DEG C of roastings 8 hours, obtained product A-6.In catalyst, each component element mass percentage is: Cu34wt%, Ni7.9wt%, Mn8.6wt%, Zn29wt%.
Embodiment 7
Take dimethyl maleate as raw material, gas phase hydrogenation reaction is carried out in fixed bed reaction, respectively catalyst A-1, A-2, A-3, A-4, A-5, A-6 and D-1 are evaluated, process conditions are: temperature 200 DEG C, pressure 5.0MPa, hydrogen ester mol ratio is 200:1, and the volume space velocity of dimethyl maleate is 0.3h
-1.Evaluation result is in table 1.
Embodiment 8
Be raw material with dimethyl maleate, in fixed bed reaction, carry out gas phase hydrogenation reaction.Carry out 1500 hours life experiments with catalyst A-3, D-2, process conditions are: pressure 5.0MPa, and hydrogen ester mol ratio is 200:1, and the volume space velocity of dimethyl maleate is 0.3h
-1.Appreciation condition the results are shown in Table 2.
Table 1 appreciation condition and result.
| Catalyst is numbered | Ester conversion rate (%) | Alcohol selective (%) |
| A-1 | 100 | 84.8 |
| A-2 | 100 | 84.2 |
| A-3 | 100 | 85.3 |
| A-4 | 100 | 82.7 |
| A-5 | 100 | 86.9 |
| A-6 | >99 | 79.2 |
| D-1 | >99 | 78.6 |
Table 2 appreciation condition and result.
| The duration of runs (h) | Reaction temperature (DEG C) | Reaction pressure (MPa) | Liquid hourly space velocity (LHSV) (h -1） | Hydrogen ester mol ratio (mol/mol) | A-3 ester conversion rate (%) | A-3 alcohol selective (%) | D-2 ester conversion rate (%) | D-2 alcohol selective (%) |
| 100 | 200 | 5.0 | 0.3 | 200 | 100 | 85.3 | 100 | 85.3 |
| 450 | 200 | 5.0 | 0.3 | 200 | 100 | 85.3 | 100 | 83.7 |
| 600 | 200 | 5.0 | 0.3 | 200 | 100 | 85.0 | >99 | 82.9 |
| 800 | 210 | 5.0 | 0.3 | 200 | 100 | 85.6 | >99 | 83.2 |
| 1000 | 210 | 5.0 | 0.3 | 200 | 100 | 85.2 | 98 | 82.6 |
| 1150 | 210 | 5.0 | 0.3 | 200 | 100 | 85.0 | 97 | 81.5 |
| 1300 | 220 | 5.0 | 0.3 | 200 | 100 | 85.6 | 97 | 81.2 |
| 1500 | 220 | 5.0 | 0.3 | 200 | 100 | 85.2 | 95 | 79.4 |
| 1650 | 225 | 5.0 | 0.3 | 200 | >99 | 85.3 | 95 | 78.8 |
Find out from table 1 and table 2 data, the conversion ratio of this catalyst is high, and selective good high, stable performance compared with prior art has raising by a relatively large margin.
Claims (9)
1. for the preparation of a catalyst for BDO, it is characterized in that: take zinc oxide as carrier, copper, nickel are active component, and M is auxiliary agent, Cu-Ni-Zn-M-O type catalyst, and wherein M is manganese or magnesium; In catalyst, the weight content of metallic element is: copper 30wt% ~ 60wt%, nickel element 2wt% ~ 10wt%, and Zn-ef ficiency is 20wt% ~ 40wt%, M element 2wt% ~ 10wt%.
2. the preparation method of a catalyst according to claim 1, it is characterized in that comprising following content: the soluble-salt of Cu, Ni, Zn and M is made into mixed solution, mix with precipitant solution under stirring at 50 ~ 70 DEG C, control ph is 7 ~ 9, stir 1 ~ 3 hour, be warming up to 80 ~ 90 DEG C, aging 2 ~ 10 hours, filter and be precipitated thing, sediment is through washing, dry, roasting, shapingly obtain product.
3. preparation method according to claim 2, is characterized in that: the mode that soluble-salt mixed solution and precipitant solution hybrid mode adopt also drip to add.
4. preparation method according to claim 2, is characterized in that: described soluble-salt is any one in nitrate, acetate, sulfate and oxalates.
5. preparation method according to claim 2, is characterized in that: described precipitating reagent is one or more in sodium carbonate, NaOH, ammonium carbonate, carbonic hydroammonium and ammoniacal liquor.
6. preparation method according to claim 2, is characterized in that: described drying condition is: dry 8 ~ 16 hours at 100 ~ 120 DEG C, roasting condition is: roasting 6 ~ 10 hours at 700 ~ 1000 DEG C.
7. the application of catalyst according to claim 1 in dimethyl maleate Hydrogenation reacts for BDO.
8. application according to claim 7, it is characterized in that hydrogenation process conditions is: reaction pressure is 3 ~ 6MPa, reaction temperature is 180 ~ 240 DEG C, and hydrogen ester mol ratio is 50:1 ~ 300:1, and the liquid hourly space velocity (LHSV) of ester is 0.2 ~ 2h
-1.
9. the application according to claim 7 or 8, it is characterized in that catalyst needs reduction before use, the gas used that reduces is the hydrogen after dilution, and pressure is 0.1 ~ 2Mpa, and temperature is 150 ~ 300 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210440185.9A CN103801321B (en) | 2012-11-07 | 2012-11-07 | A kind of catalyst for the preparation of BDO and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210440185.9A CN103801321B (en) | 2012-11-07 | 2012-11-07 | A kind of catalyst for the preparation of BDO and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103801321A CN103801321A (en) | 2014-05-21 |
| CN103801321B true CN103801321B (en) | 2016-01-20 |
Family
ID=50698993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210440185.9A Active CN103801321B (en) | 2012-11-07 | 2012-11-07 | A kind of catalyst for the preparation of BDO and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103801321B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108114727B (en) * | 2016-11-28 | 2020-08-11 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN111054324A (en) * | 2020-02-25 | 2020-04-24 | 贵州大学 | MnZnOx solid solution structure catalyst and preparation method thereof |
| CN114685242B (en) * | 2022-04-19 | 2023-08-22 | 天津大学 | Method for producing 1, 4-butanediol by one-step liquid-phase hydrogenation of dimethyl maleate |
| CN115368208A (en) * | 2022-07-25 | 2022-11-22 | 朱义峰 | Coupled electrolytic hydrogen production-storage system and process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1138018A (en) * | 1995-06-14 | 1996-12-18 | 中国石油化工总公司 | Catalyst(A) for preparation of 1,4-butanediol by gas-phase hydrogenation |
| CN1493569A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Method of preparing gamma-butyrolactone and/or 1,4-butanediol using chromium less catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58193738A (en) * | 1982-05-06 | 1983-11-11 | Mitsubishi Heavy Ind Ltd | Catalyst for production of gas enriched with hydrogen |
-
2012
- 2012-11-07 CN CN201210440185.9A patent/CN103801321B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1138018A (en) * | 1995-06-14 | 1996-12-18 | 中国石油化工总公司 | Catalyst(A) for preparation of 1,4-butanediol by gas-phase hydrogenation |
| CN1493569A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Method of preparing gamma-butyrolactone and/or 1,4-butanediol using chromium less catalyst |
Non-Patent Citations (1)
| Title |
|---|
| Pd（Ni）对铜基催化剂的调变及对顺酐选择性加氢产物的调控;卢伟京等;《催化学报》;20020930;第23卷(第5期);第409页2.1节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103801321A (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101954288B (en) | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof | |
| CN101607205B (en) | Glycol catalyst prepared by dimethyl oxalate hydrogenation and preparation method thereof | |
| CN105399940B (en) | A kind of preparation method of polyetheramine | |
| CN102233272A (en) | Catalyst for preparing ethylene diamine through amination of ethylene glycol and preparation method thereof | |
| CN101733123B (en) | Acid-proof catalyst for preparing gamma-valerolactone from levulinic acid, preparation method and application | |
| CN102091624B (en) | Catalyst for preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol and preparation method thereof | |
| CN106582652A (en) | Catalyst for ethylene glycol synthesis through gas phase hydrogenation of dimethyl oxalate, preparation method and applications thereof | |
| CN103801321B (en) | A kind of catalyst for the preparation of BDO and preparation method | |
| CN103100393B (en) | Hydrogenation catalyst and preparation method thereof | |
| CN101733109A (en) | Preparation method of copper-based catalyst | |
| CN113231069A (en) | Composite efficient catalyst for preparing succinic anhydride by maleic anhydride body hydrogenation and preparation method thereof | |
| CN104028267B (en) | A kind of method for making of benzene selective Hydrogenation cyclohexene noble metal Ru catalyst | |
| CN114054034B (en) | Multi-element copper-based non-noble metal hydrogenation catalyst, and preparation method and application thereof | |
| CN103769158B (en) | The preparation method of hydrogenation catalyst | |
| CN101786003A (en) | Catalyst used for preparing natural gas by methanation and preparation method thereof | |
| CN103801301B (en) | A kind of preparation method of Cu-contained catalyst | |
| CN103212420A (en) | Morpholine synthetic catalyst and preparation method thereof | |
| CN106140172A (en) | A kind of catalyst pressing liquid-phase hydrogenatin fatty alcohol be applicable to fatty acid methyl ester | |
| CN103801302B (en) | A kind of preparation method containing copper zinc catalyst | |
| CN109603837A (en) | A kind of preparation method of the Cu/Ce/Co catalyst for furfural liquid-phase hydrogenatin | |
| CN104759294B (en) | A kind of preparation method and applications of heteropolyanion Modified Cu base class hydrotalcite catalyst | |
| CN110862302A (en) | Method for preparing 1, 4-butanediol by combining slurry bed hydrogenation and fixed bed hydrogenation | |
| CN107537495A (en) | A kind of preparation method and application of synthesis gas ethanol Cu Co catalyst | |
| CN103769157B (en) | Preparation method of hydrogenation catalyst | |
| CN105709760B (en) | A kind of Cu-Cr catalyst and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |