CN103331166A - Copper-based catalyst for synthesizing methanol and preparation method and application of copper-based catalyst - Google Patents
Copper-based catalyst for synthesizing methanol and preparation method and application of copper-based catalyst Download PDFInfo
- Publication number
- CN103331166A CN103331166A CN2013102421496A CN201310242149A CN103331166A CN 103331166 A CN103331166 A CN 103331166A CN 2013102421496 A CN2013102421496 A CN 2013102421496A CN 201310242149 A CN201310242149 A CN 201310242149A CN 103331166 A CN103331166 A CN 103331166A
- Authority
- CN
- China
- Prior art keywords
- solution
- copper
- precipitation
- catalyst
- precipitate
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a copper-based catalyst for synthesizing methanol. The catalyst comprises the following metallic oxides in molar ratio based on metallic elements: 60 to 70% of Cu, 25 to 35% of Zn, and 2 to 10% of Al. The copper-based catalyst has the advantages of being long in service life and high in activity.
Description
Technical field
The invention belongs to a kind of Preparation of catalysts methods and applications, be specifically related to a kind of preparation method and application that starch attitude bed synthesising gas systeming carbinol copper-based catalysts.
Background technology
Methyl alcohol is a kind of important basic chemical industry raw material.Coal based synthetic gas methyl alcohol processed is one of important channel of coal high-efficiency clean utilization.At present, the catalyst that methanol synthesis in slurry reactor research is adopted is mainly the fixed bed industrial catalyst, and its life-span is shorter, does not reach industrialization demands.Can form CuO-ZnO single phase solid solution (Cu after the catalyst high-temperature roasting that raising catalyst activity and the key in life-span are to prepare
x Zn
1-
x O), active component Cu crystal grain meeting high degree of dispersion is combined in the ZnO lattice after the reduction, and while and ZnO produce synergy, make it both have greater activity, and difficult reunion is grown up and caused the catalyst heat inactivation again.
Document (Bems, B., et al.,
Chemistry – A European Journal, 2003. 9 (9): 2039) report, the catalyst precursor composition is mainly aurichalcite (Zn
5-x, Cu
x) (CO
3)
2(OH)
6Crystal and cuprozincite (Cu
2-x, Zn
x) (CO
3) (OH)
2Crystal, wherein after the aurichalcite roasting, copper can fully contact formation (Cu with ZnO
x Zn
1-
x O), produce well synergy, be conducive to improve activity of such catalysts and stability.But because active component Cu amount is less in the aurichalcite, Cu/ (Cu+Zn)≤50mol%, therefore simple aurichalcite thing mutually for the catalyst activity of presoma roasting be not very high (Fujita, S.-i., et al.,
Catalysis Today, 1998. 45 (1-4): 241).Chinese patent (CN 101584986A, CN 1810357A, CN 101306369A) report thinks that Cu/ (Cu+Zn) is when 60～70 mol% in the catalyst, and catalytic activity is best.
When adopting traditional co-precipitation method to prepare catalyst with Cu/ (Cu+Zn)=2/3 proportioning, exist the aurichalcite become crystal formation and cuprozincite thing mutually in the presoma simultaneously, and Zn/ (Cu+Zn)≤30mol% in the cuprozincite, there are not enough ZnO and all Cu to act synergistically after the roasting, simultaneously because the restriction of crystal structure, body mutually in not with ZnO form synergistic Cu also be difficult to the roasting of aurichalcite crystal after ZnO produce good synergy.Document (Li, Z., et al.,
Fuel, 2013,106:178) adopt under the microwave radiation and flow the mode of co-precipitation, promoted the generation of catalyst precursor medium green copper zinc mineral phase, suppressed the growing amount of cuprozincite thing phase simultaneously, improved activity of such catalysts.But still there is part cuprozincite thing phase in the presoma, still exists portion C u species not disperse to be combined in the ZnO lattice in the roasting rear catalyst, do not form synergy with ZnO.
Summary of the invention
It is long to the purpose of this invention is to provide a kind of life-span, the preparation method and application of the slurry attitude bed synthesising gas systeming carbinol copper-based catalysts that activity is high.
Improve catalyst activity and the key in life-span and be to increase on the one hand (Zn in the presoma
5-x, Cu
x) (CO
3)
2(OH)
6The amount of thing phase reaches wherein Cu
xContent, and this portion C u also must fully contact in conjunction with forming Cu with ZnO
x Zn
1-
x O solid solution produces synergy.The present invention at first adopts the copper acetate method of substitution to prepare (Zn
2.5, Cu
2.5) (CO
3)
2(OH)
6Crystal makes Cu content in its crystal reach the upper limit that the isomorphous replaces, and adopts the slurry mixing method by a certain percentage with the Cu of dispersed then
2(CO
3) (OH)
2Be coated on (Zn
2.5, Cu
2.5) (CO
3)
2(OH)
6The surface makes Cu/ in the catalyst precursor (Cu+Zn) in 60～70 mol% scopes, makes itself and zinc form Cu by high-temperature roasting
x Zn
1-
x O solid solution.
Catalyst of the present invention is made up of metal oxide, and in metallic element, its mole consists of Cu 60～70%, and Zn 25～35%, and Al 2～12%.
Catalyst of the present invention is prepared by following method:
(1) zinc nitrate, aluminum nitrate are mixed with the solution M of total concentration of metal ions 0.1～0.5 mol/L
A, element mol ratio Zn:AL=(50～70): (2～10) are made into isoconcentration solution P with alkaline precipitating agent
A
(2) copper acetate is configured to the solution of 0.05～0.15 mol/L;
(3) 60～80 ℃ of temperature, under the stirring condition, with metal salt solution M
AWith alkaline sedimentation agent solution P
AAnd the stream co-precipitation, control precipitation pH value is 6.5～8.0;
(4) after precipitation is finished, press element mol ratio Cu:Zn=0.5～0.7:1, copper acetate solution is slowly splashed in the precipitation with peristaltic pump, isomorphous substitution reaction takes place with Zn in the precipitation in the Cu ion, under 60～80 ℃, stirs the 0.5～3h that wears out;
(5) will precipitate suction filtration, washing 4～5 times, the copper acetate that flush away is excessive and the metal ion of alkaline precipitating agent at 105～115 ℃ of down dry 8～14h, get precipitate A;
(6) copper nitrate is mixed with the solution M of 0.1～2.0 mol/L
B, precipitating reagent is made into isoconcentration solution P
B
(7) with precipitate A as in the reactor, after adding certain distilled water pulp, 20～80 ℃ of temperature, under the stirring condition, simultaneously copper nitrate solution and precipitant solution are squeezed in the reactor with peristaltic pump and stream respectively, be 6.5～8.0 to carry out precipitation reaction in the pH value, the precipitation of generation evenly is coated on the surface of A, and the amount that adds copper nitrate is calculated Cu:Al=(25～45 with the element mol ratio): (2～10);
(8) will precipitate suction filtration, washing 4～5 times, at 105～115 ℃ of down dry 8～14h, 300～600 ℃ of following roasting 3～5h obtain CuZnAl catalyst.
Aforesaid precipitating reagent is a kind of in sodium carbonate, potash, NaOH, potassium hydroxide, ammoniacal liquor, sodium acid carbonate, the saleratus.
The prepared catalyst of said method of the present invention is the technology for the paste state bed reactor synthesizing methanol, and its application technology condition is: 200～280 ℃ of reaction temperatures, reaction pressure 2.0～8MPa, (H
2-CO
2)/(CO+CO
2) mol ratio is 1～4, air speed 500～12000 L/ (kg
Cat H).
Technical advantage of the present invention is as follows:
The present invention is by copper acetate method of substitution preparation (Zn
5-x, Cu
x) (CO
3)
2(OH)
6, make (Zn
5-x, Cu
x) (CO
3)
2(OH)
6Middle Cu content reaches maximum, has obviously increased (Cu in the catalyst
x Zn
1-
x O) content; And (Zn
5-x, Cu
x) (CO
3)
2(OH)
6The Cu of thing phase and dispersed
2(CO
3) (OH)
2Between ratio quantitatively controlled, baking mixed back Cu/ (Cu+Zn) is in 60～70 mol% scopes, and this portion C u also must fully contact in conjunction with forming Cu with ZnO
x Zn
1-
x O solid solution produces synergy, thereby has further improved activity of such catalysts and stability.
The specific embodiment
Comparative Examples 1
Copper nitrate, zinc nitrate, aluminum nitrate are mixed with the solution of total concentration of metal ions 1.0 mol/L, and element mol ratio Cu:Zn:Al=64:32:4 is made into isoconcentration solution with precipitating reagent; 70 ℃ of water-baths, under the stirring condition, simultaneously 200ml metal salt solution and precipitant solution are squeezed in the reactor with peristaltic pump respectively, and the stream co-precipitation, by adjusting the peristaltic pump rotating speed, control precipitation pH value is 7.5; After precipitation is finished, under 80 ℃, stir aging 1.5h; To precipitate suction filtration, washing 5 times, 105 ℃ of following dry 12h, 350 ℃ of following roasting 4h get finished catalyst in metal, and its constitutive molar ratio is Cu:Zn:Al=64:32:4.Application of Catalyst condition and the results are shown in Table 1.
Embodiment 1
(1) presses element mol ratio Zn:Al=63:7, zinc nitrate, aluminum nitrate are mixed with the solution M of total concentration of metal ions 0.5mol/L
A,, sodium carbonate is made into isoconcentration solution P
A
(2) copper acetate is configured to the solution of 0.1 mol/L;
(3) 70 ℃ of water-baths, under the stirring condition, simultaneously with 200ml metal salt solution M
AWith an amount of sodium carbonate liquor P
ASqueeze in the reactor with peristaltic pump respectively, and the stream co-precipitation, control precipitation pH value is 7.5;
(4) after precipitation is finished, 600ml copper acetate solution is slowly splashed in the precipitation with peristaltic pump, under 70 ℃, stir aging 1.5h;
(5) will precipitate suction filtration, washing 5 times, 105 ℃ of following dry 12h get precipitate A;
(6) copper nitrate is mixed with the solution M of 0.5mol/L
B, sodium carbonate is made into isoconcentration solution P
B
(7) with precipitate A as in the reactor, add the pulp of 100ml distilled water after, 50 ℃ of water-baths, under the stirring condition, simultaneously with 100ml copper nitrate solution M
BWith an amount of sodium carbonate liquor P
BSqueeze in the reactor with peristaltic pump and stream respectively, by adjusting the peristaltic pump rotating speed, control precipitation pH value is 7.5;
(8) will precipitate suction filtration, washing 5 times, 105 ℃ of following dry 12h, 350 ℃ of following roasting 4h get finished catalyst.In metal, its constitutive molar ratio is Cu:Zn:Al=63.3:30:6.7.
Application of Catalyst condition and the results are shown in Table 1.
Embodiment 2
(1) presses element mol ratio Zn:Al=66.5:3.5, zinc nitrate, aluminum nitrate are mixed with the solution M of total concentration of metal ions 1.0mol/L
A,, potash is made into isoconcentration solution P
A
(2) copper acetate is configured to the solution of 0.15 mol/L;
(3) 70 ℃ of water-baths, under the stirring condition, simultaneously with 200ml metal salt solution M
AWith an amount of solution of potassium carbonate P
ASqueeze in the reactor with peristaltic pump respectively, and the stream co-precipitation, control precipitation pH value is 7.5;
(4) after precipitation is finished, 700ml copper acetate solution is slowly splashed in the precipitation with peristaltic pump, under 70 ℃, stir aging 1.5h;
(5) will precipitate suction filtration, washing 5 times, 105 ℃ of following dry 12h get precipitate A;
(6) copper nitrate is mixed with the solution M of 0.5mol/L
B, potash is become isoconcentration solution P
B
(7) with precipitate A as in the reactor, add the pulp of 100ml distilled water after, 50 ℃ of water-baths, under the stirring condition, simultaneously with 200ml copper nitrate solution M
BWith an amount of solution of potassium carbonate P
BSqueeze in the reactor with peristaltic pump and stream respectively, by adjusting the peristaltic pump rotating speed, control precipitation pH value is 7.5;
(8) will precipitate suction filtration, washing 5 times, 105 ℃ of following dry 12h, 350 ℃ of following roasting 4h get finished catalyst.In metal, its constitutive molar ratio is Cu:Zn:Al=65:31.7:3.3.
Application of Catalyst condition and the results are shown in Table 1.
Embodiment 3
(1) presses element mol ratio Zn:Al=64:8, zinc nitrate, aluminum nitrate are mixed with the solution M of total concentration of metal ions 0.5mol/L
A,, sodium acid carbonate is made into isoconcentration solution P
A
(2) copper acetate is configured to the solution of 0.1 mol/L;
(3) 70 ℃ of water-baths, under the stirring condition, simultaneously with 200ml metal salt solution M
AWith an amount of sodium bicarbonate solution P
ASqueeze in the reactor with peristaltic pump respectively, and the stream co-precipitation, control precipitation pH value is 7.0;
(4) after precipitation is finished, 600ml copper acetate solution is slowly splashed in the precipitation with peristaltic pump, under 80 ℃, stir aging 1.5h;
(5) will precipitate suction filtration, washing 5 times, 110 ℃ of following dry 10h get precipitate A;
(6) copper nitrate is mixed with the solution M of 0.5mol/L
B, sodium acid carbonate is made into isoconcentration solution P
B
(7) with precipitate A as in the reactor, add the pulp of 100ml distilled water after, 50 ℃ of water-baths, under the stirring condition, simultaneously with 80ml copper nitrate solution M
BWith an amount of sodium bicarbonate solution P
BSqueeze in the reactor with peristaltic pump and stream respectively, by adjusting the peristaltic pump rotating speed, control precipitation pH value is 7.5;
(8) will precipitate suction filtration, washing 5 times, 110 ℃ of following dry 10h, 450 ℃ of following roasting 4h get finished catalyst.In metal, its constitutive molar ratio is Cu:Zn:Al=60.3:31.8:7.9.
Application of Catalyst condition and the results are shown in Table 1.
Embodiment 4
(1) presses element mol ratio Zn:Al=56.7:10, zinc nitrate, aluminum nitrate are mixed with the solution M of total concentration of metal ions 0.5mol/L
A,, saleratus is made into isoconcentration solution P
A
(2) copper acetate is configured to the solution of 0.1 mol/L;
(3) 70 ℃ of water-baths, under the stirring condition, simultaneously with 200ml metal salt solution M
AWith an amount of potassium bicarbonate solution P
ASqueeze in the reactor with peristaltic pump respectively, and the stream co-precipitation, control precipitation pH value is 7.5;
(4) after precipitation is finished, 600ml copper acetate solution is slowly splashed in the precipitation with peristaltic pump, under 80 ℃, stir aging 1.5h;
(5) will precipitate suction filtration, washing 5 times, 105 ℃ of following dry 12h get precipitate A;
(6) copper nitrate is mixed with the solution M of 0.5mol/L
B, sodium carbonate is made into isoconcentration solution P
B
(7) with precipitate A as in the reactor, add the pulp of 100ml distilled water after, 50 ℃ of water-baths, under the stirring condition, simultaneously with 100ml copper nitrate solution M
BWith an amount of sodium carbonate liquor P
BSqueeze in the reactor with peristaltic pump and stream respectively, by adjusting the peristaltic pump rotating speed, control precipitation pH value is 8.0;
(8) will precipitate suction filtration, washing 5 times, 105 ℃ of following dry 12h, 500 ℃ of following roasting 4h get finished catalyst.In metal, its constitutive molar ratio is Cu:Zn:Al=61.7:28.3:10.
Application of Catalyst condition and the results are shown in Table 1.
Embodiment 5
(1) presses element mol ratio Zn:Al=50:2, zinc nitrate, aluminum nitrate are mixed with the solution M of total concentration of metal ions 0.5mol/L
A,, NaOH is made into isoconcentration solution P
A
(2) copper acetate is configured to the solution of 0.1 mol/L;
(3) 70 ℃ of water-baths, under the stirring condition, simultaneously with 200ml metal salt solution M
AWith an amount of sodium hydroxide solution P
ASqueeze in the reactor with peristaltic pump respectively, and the stream co-precipitation, control precipitation pH value is 7.5;
(4) after precipitation is finished, 600ml copper acetate solution is slowly splashed in the precipitation with peristaltic pump, under 70 ℃, stir aging 1.5h;
(5) will precipitate suction filtration, washing 5 times, 105 ℃ of following dry 12h get precipitate A;
(6) copper nitrate is mixed with the solution M of 0.5mol/L
B, NaOH is made into isoconcentration solution P
B
(7) with precipitate A as in the reactor, add the pulp of 100ml distilled water after, 50 ℃ of water-baths, under the stirring condition, simultaneously with 100ml copper nitrate solution M
BWith an amount of sodium hydroxide solution P
BSqueeze in the reactor with peristaltic pump and stream respectively, by adjusting the peristaltic pump rotating speed, control precipitation pH value is 7.5;
(8) will precipitate suction filtration, washing 5 times, 105 ℃ of following dry 12h, 500 ℃ of following roasting 4h get finished catalyst.In metal, its constitutive molar ratio is Cu:Zn:Al=65.3:32:2.7.
Application of Catalyst condition and the results are shown in Table 1.
Embodiment 6
(1) presses element mol ratio Zn:Al=70:2, zinc nitrate, aluminum nitrate are mixed with the solution M of total concentration of metal ions 0.5mol/L
A,, potassium hydroxide is made into isoconcentration solution P
A
(2) copper acetate is configured to the solution of 0.1 mol/L;
(3) 70 ℃ of water-baths, under the stirring condition, simultaneously with 200ml metal salt solution M
AWith an amount of potassium hydroxide solution P
ASqueeze in the reactor with peristaltic pump respectively, and the stream co-precipitation, control precipitation pH value is 7.5;
(4) after precipitation is finished, 600ml copper acetate solution is slowly splashed in the precipitation with peristaltic pump, under 80 ℃, stir aging 1.5h;
(5) will precipitate suction filtration, washing 5 times, 105 ℃ of following dry 12h get precipitate A;
(6) copper nitrate is mixed with the solution M of 0.5mol/L
B, potassium hydroxide is made into isoconcentration solution P
B
(7) with precipitate A as in the reactor, add the pulp of 100ml distilled water after, 40 ℃ of water-baths, under the stirring condition, simultaneously with 150ml copper nitrate solution M
BWith an amount of potassium hydroxide solution P
BSqueeze in the reactor with peristaltic pump and stream respectively, by adjusting the peristaltic pump rotating speed, control precipitation pH value is 7.5;
(8) will precipitate suction filtration, washing 5 times, 105 ℃ of following dry 12h, 500 ℃ of following roasting 4h get finished catalyst.In metal, its constitutive molar ratio is Cu:Zn:Al=65.7:32.3:2.
Application of Catalyst condition and the results are shown in Table 1.
Embodiment 7
(1) presses element mol ratio Zn:Al=50:10, zinc nitrate, aluminum nitrate are mixed with the solution M of total concentration of metal ions 0.5mol/L
A,, sodium carbonate is made into isoconcentration solution P
A
(2) copper acetate is configured to the solution of 0.1 mol/L;
(3) 70 ℃ of water-baths, under the stirring condition, simultaneously with 200ml metal salt solution M
AWith an amount of sodium carbonate liquor P
ASqueeze in the reactor with peristaltic pump respectively, and the stream co-precipitation, control precipitation pH value is 7.0;
(4) after precipitation is finished, 600ml copper acetate solution is slowly splashed in the precipitation with peristaltic pump, under 80 ℃, stir aging 1.5h;
(5) will precipitate suction filtration, washing 5 times, 110 ℃ of following dry 10h get precipitate A;
(6) copper nitrate is mixed with the solution M of 0.5mol/L
B, sodium carbonate is made into isoconcentration solution P
B
(7) with precipitate A as in the reactor, add the pulp of 100ml distilled water after, 30 ℃ of water-baths, under the stirring condition, simultaneously with 100ml copper nitrate solution M
BWith an amount of sodium carbonate liquor P
BSqueeze in the reactor with peristaltic pump and stream respectively, by adjusting the peristaltic pump rotating speed, control precipitation pH value is 7.5;
(8) will precipitate suction filtration, washing 5 times, 105 ℃ of following dry 12h, 450 ℃ of following roasting 4h get finished catalyst.In metal, its constitutive molar ratio is Cu:Zn:Al=61.1:27.8:11.1.
Application of Catalyst condition and the results are shown in Table 1.
Table 1 slurry attitude bed synthesising gas systeming carbinol catalyst application conditions and result
Claims (4)
1. copper-based catalysts for the synthesis of methyl alcohol is characterized in that catalyst is made up of metal oxide, and in metallic element, its mole consists of Cu 60～70%, and Zn 25～35%, and Al 2～12%.
2. the preparation method of a kind of copper-based catalysts for the synthesis of methyl alcohol as claimed in claim 1 is characterized in that comprising the steps:
(1) zinc nitrate, aluminum nitrate are mixed with the solution M of total concentration of metal ions 0.1～0.5 mol/L
A, element mol ratio Zn:AL=50～70:2～10 are made into isoconcentration solution P with alkaline precipitating agent
A
Copper acetate is configured to the solution of 0.05～0.15 mol/L;
(3) 60～80 ℃ of temperature, under the stirring condition, with metal salt solution M
AWith alkaline sedimentation agent solution P
AAnd the stream co-precipitation, control precipitation pH value is 6.5～8.0;
(4) after precipitation is finished, press element mol ratio Cu:Zn=0.5～0.7:1, copper acetate solution is slowly splashed in the precipitation with peristaltic pump, isomorphous substitution reaction takes place with Zn in the precipitation in the Cu ion, under 60～80 ℃, stirs the 0.5～3h that wears out;
(5) will precipitate suction filtration, washing 4～5 times, the copper acetate that flush away is excessive and the metal ion of alkaline precipitating agent at 105～115 ℃ of down dry 8～14h, get precipitate A;
Copper nitrate is mixed with the solution M of 0.1～2.0 mol/L
B, precipitating reagent is made into isoconcentration solution P
B
(7) with precipitate A as in the reactor, after adding certain distilled water pulp, 20～80 ℃ of temperature, under the stirring condition, simultaneously copper nitrate solution and precipitant solution are squeezed in the reactor with peristaltic pump and stream respectively, be 6.5～8.0 to carry out precipitation reaction in the pH value, the precipitation of generation evenly is coated on the surface of A, and the amount that adds copper nitrate is calculated Cu:Al=25～45:2～10 with the element mol ratio;
(8) will precipitate suction filtration, washing 4～5 times, at 105～115 ℃ of down dry 8～14h, 300～600 ℃ of following roasting 3～5h obtain CuZnAl catalyst.
3. the preparation method of a kind of copper-based catalysts for the synthesis of methyl alcohol as claimed in claim 2 is characterized in that described precipitating reagent is a kind of in sodium carbonate, potash, NaOH, potassium hydroxide, ammoniacal liquor, sodium acid carbonate, the saleratus.
4. the application of a kind of copper-based catalysts for the synthesis of methyl alcohol as claimed in claim 1 is characterized in that catalyst is for the paste state bed reactor synthesizing methanol, and its application technology condition is: 200～280 ℃ of reaction temperatures, reaction pressure 2.0～8MPa, (H
2-CO
2)/(CO+CO
2) mol ratio is 1～4, air speed 500～12000 L/ (kg
Cat 
H).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310242149.6A CN103331166B (en) | 2013-06-19 | 2013-06-19 | Copper-based catalyst for synthesizing methanol and preparation method and application of copper-based catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310242149.6A CN103331166B (en) | 2013-06-19 | 2013-06-19 | Copper-based catalyst for synthesizing methanol and preparation method and application of copper-based catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103331166A true CN103331166A (en) | 2013-10-02 |
| CN103331166B CN103331166B (en) | 2014-12-03 |
Family
ID=49239411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310242149.6A Expired - Fee Related CN103331166B (en) | 2013-06-19 | 2013-06-19 | Copper-based catalyst for synthesizing methanol and preparation method and application of copper-based catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103331166B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769112A (en) * | 2014-01-22 | 2014-05-07 | 新疆大学 | Copper-base catalyst for synthesizing methanol and preparation method thereof |
| CN111215084A (en) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | Copper-based catalyst for preparing methanol by carbon dioxide hydrogenation, preparation and application thereof |
| US20220144630A1 (en) * | 2018-10-15 | 2022-05-12 | Research Institute Of Institute Science & Technology | Catalyst for water gas shift reaction at middle temperature, preparation method thereof, and hydrogen preparation method using same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1000658A2 (en) * | 1998-11-16 | 2000-05-17 | China Petrochemical Corporation | A copper-containing catalyst, a process for the preparation and use thereof |
| CN101584986A (en) * | 2009-07-04 | 2009-11-25 | 太原理工大学 | Method for preparing methanol synthesizing catalyst |
-
2013
- 2013-06-19 CN CN201310242149.6A patent/CN103331166B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1000658A2 (en) * | 1998-11-16 | 2000-05-17 | China Petrochemical Corporation | A copper-containing catalyst, a process for the preparation and use thereof |
| CN101584986A (en) * | 2009-07-04 | 2009-11-25 | 太原理工大学 | Method for preparing methanol synthesizing catalyst |
Non-Patent Citations (2)
| Title |
|---|
| CEN YAQING ET AL.: "Preparation of Copper-Based Catalysts for Methanol Synthesis by Acid–Alkali-Based Alternate Precipitation Method", 《CHINESE JOURNAL OF CATALYSIS 》, vol. 27, no. 3, 31 March 2006 (2006-03-31), pages 210 - 216, XP022857690, DOI: doi:10.1016/S1872-2067(06)60014-4 * |
| 房德仁 等: "超细低压甲醇合成催化剂性能评价", 《工业催化》, vol. 11, no. 6, 30 June 2003 (2003-06-30), pages 41 - 43 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769112A (en) * | 2014-01-22 | 2014-05-07 | 新疆大学 | Copper-base catalyst for synthesizing methanol and preparation method thereof |
| CN103769112B (en) * | 2014-01-22 | 2016-01-20 | 新疆大学 | Synthesizing methanol copper-based catalysts and preparation method thereof |
| US20220144630A1 (en) * | 2018-10-15 | 2022-05-12 | Research Institute Of Institute Science & Technology | Catalyst for water gas shift reaction at middle temperature, preparation method thereof, and hydrogen preparation method using same |
| CN111215084A (en) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | Copper-based catalyst for preparing methanol by carbon dioxide hydrogenation, preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103331166B (en) | 2014-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101367044B (en) | Method for preparing nano-catalyst copper chromite and copper ferrite | |
| CN103084178B (en) | Copper-contained hydrotalcite-based catalyst for preparing mixed alcohol by using synthesis gas as well as preparation method and application thereof | |
| CN102002402B (en) | Preparation method of renewable manganese high-temperature gas desulfurizer | |
| CN107597125B (en) | Sec-butyl alcohol dehydrogenation catalyst containing solid potassium and preparation method thereof | |
| CN103447026B (en) | Wet type catalyzed oxidation manganese-based catalyst and preparation method thereof | |
| CN105854888A (en) | Copper-based low-temperature conversion catalyst and preparation method thereof | |
| CN103331166B (en) | Copper-based catalyst for synthesizing methanol and preparation method and application of copper-based catalyst | |
| CN105214672A (en) | A kind of preparation method of the catalyst for methanol that maximizes | |
| CN102463121A (en) | High-stability Cu-based catalyst and preparation method thereof | |
| CN108682849A (en) | A kind of preparation method for mixing aluminium cobalt acid lithium | |
| CN1219445A (en) | New synthetic copper methoxide series catalysts and their preparation method | |
| CN105435799A (en) | Catalyst for ethanol preparation by ethyl acetate hydrogenation and preparation method for catalyst | |
| CN106622256A (en) | Preparation method of high-concentration CO methanation catalyst | |
| CN103223344B (en) | Copper-based catalyst for synthesis of methanol in slurry bed, preparation method and application thereof | |
| CN109205684A (en) | A kind of preparation method of small grain size cobaltosic oxide | |
| CN102179251A (en) | Catalyst for synthesizing methanol by fluidized bed and preparation method thereof | |
| CN105964267A (en) | Copper-based methanol synthesis catalyst and preparation method thereof | |
| CN103801302B (en) | A kind of preparation method containing copper zinc catalyst | |
| CN104028276B (en) | A kind of preparation method of compound molded breadth temperature methanation catalyst | |
| CN102950001A (en) | High-temperature-resistant methanol catalyst and preparation method thereof | |
| CN104549300A (en) | Preparation method of low-sodium copper-based methanol synthesis catalyst | |
| CN103480378B (en) | The preparation method of Modified Copper-based Catalysts for Methanol | |
| CN100444432C (en) | Nickel oxide mixed with cobalt manganese hydroxy base and preparation method thereof | |
| CN110237845B (en) | Method for preparing Cu-ZnO catalyst by using microreactor | |
| CN104841435A (en) | Alkali metal-doped modified coal-to-natural gas methane synthesis catalyst and preparation method 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141203 Termination date: 20150619 |
|
| EXPY | Termination of patent right or utility model |