CN103372443A - Preparation method of copper-based catalyst - Google Patents
Preparation method of copper-based catalyst Download PDFInfo
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- CN103372443A CN103372443A CN2012104431093A CN201210443109A CN103372443A CN 103372443 A CN103372443 A CN 103372443A CN 2012104431093 A CN2012104431093 A CN 2012104431093A CN 201210443109 A CN201210443109 A CN 201210443109A CN 103372443 A CN103372443 A CN 103372443A
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- 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
Abstract
The invention discloses a preparation method of a copper-based catalyst. The method comprises the steps of filling pure water into a reaction tank, introducing a certain amount of CO2, then adding a zinc metal salt solution and a sodium metaaluminate solution in parallel for gelling, aging under the condition of stirring, and adding basic copper carbonate during aging to prepare the copper-based catalyst. The method has the beneficial effects of improving the physical and chemical properties of the catalyst, increasing the specific surface area of the catalyst, improving the synergism between the main active metal component copper and the cocatalyst metal component zinc, improving the dispersibility of an active phase, and improving the activity and stability of the catalyst. The catalyst is especially suitable to serve as a methanol synthesis catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of copper-based catalysts, be specifically related to a kind of preparation method for the synthesis of the copper-based catalysts of methyl alcohol with high activity, good heat resistance.
Background technology
Methyl alcohol is a kind of extremely important industrial chemicals, be widely used in organic synthesis, dyestuff, fuel, medicine, coating and national defense industry, its output is only second to synthetic ammonia and ethene, occupies the third place in the world, in recent years methyl alcohol demand and the production capacity sustainable growth along with industrial development.
Industrial methyl alcohol is general with containing H
2, CO, CO
2Synthesis gas under certain pressure, temperature and catalyst existence condition, produce.In generally adopting in the world at present, low-pressure vapor phase method synthesizing methanol, catalyst system therefor is essentially the mixed oxide of copper, zinc, aluminium.CuO, ZnO, Al in the catalst for synthesis of methanol
2O
3The effect of three components is variant, and CuO is main active component, ZnO and Al
2O
3Be auxiliary agent.Method for preparing catalyst is generally the mixing subcarbonate of using first coprecipitation (comprise and flow, instead add, just adding coprecipitation) to generate copper zinc, and then add aluminium hydroxide in the pulping process, the slurry that generates through washing, drying, roasting, compression molding.The research of at present catalyst preparation mainly concentrates on optimization and the improvement of preparation method and technique, improve catalyst activity by the ratio that changes catalytic component, the size of crystal grain, size and the pore-size distribution of specific area, improve the copper-based catalysts poor heat stability, selective hanging down and short problem of life-span.Method for preparing catalyst is different, and it is larger that the performance of gained catalyst can differ.
CN 1810357A adopts a traditional step coprecipitation to prepare a kind of catalst for synthesis of methanol.Nitrate mixed solution and NaCO with Cu, Zn, Al, Li
3Solution and stream are titrated in the deionized water of a small amount of high-speed stirred, keep simultaneously the pH of solution between 7 ~ 8, and is aging, suction filtration, washing, dries to get catalyst precarsor, and catalyst precarsor oven dry, roasting get finished product.The method is to adopt a typical step coprecipitation to prepare catalyst for methanol, has added LiNO in preparation process
3
CN 1329938A discloses a kind of preparation method of catalst for synthesis of methanol, and this catalyst is comprised of the oxide of copper, zinc, aluminium.Preparation process: a part is to make the coprecipitate that contains copper, zinc, aluminium compound with coprecipitation, and another part is to make the coprecipitate that contains copper, zinc compound with co-precipitation.The equal thermal decomposition of above-mentioned coprecipitate is the oxide of metal, and then with these two kinds of co-precipitation mixing, washing, dry, roasting, moulding makes catalyst.
CN 1660490A discloses a kind of preparation method of catalst for synthesis of methanol, its preparation process is: coprecipitation prepares adds a small amount of Surfactant OP in the methanol synthesis catalyst process, perhaps fractional precipitation prepares a small amount of Surfactant OP of interpolation in the methanol synthesis catalyst process, makes a kind of catalst for synthesis of methanol.
CN 101574649A discloses a kind of preparation method of catalst for synthesis of methanol, step is the mixed aqueous solution reaction with the aqueous solution of aluminum soluble salt and alkali metal hydroxide-carbonate, generate a kind of transparent meta-aluminate aqueous solution, then with its with contain the copper of water-soluble high-molecular compound, the transparent aqueous solution of zinc salt carries out coprecipitation reaction, generate the mixing co-precipitation of a kind of copper, zinc, aluminium, then through washing, drying, granulation processing, roasting, play the sheet moulding and can make a kind of highly active catalst for synthesis of methanol.
The catalst for synthesis of methanol method of above-mentioned patent Introduction is by adding new auxiliary agent (Li and surfactant), change catalyst preparation process the presoma of (step process changes two step or three step process into) and change Al, come structure, surface acid alkalescence, the electronic property of regulating catalyst, with the activity of improving existing catalyst, selective or life-span.Be to increase the more even of the specific area of catalyst and active ingredient copper and the distribution of co-catalyst zinc but improve catalst for synthesis of methanol the key active and life-span, above patent does not all relate to.
Summary of the invention
For above-mentioned deficiency of the prior art, the invention provides that a kind of technique is simple, the preparation method of easy-operating copper-based catalysts.The method can be improved the physico-chemical property of catalyst, increases the specific area of catalyst, increases the coordinative role between main active metal component copper and the promoter metal component zinc, improves the dispersiveness of active phase, improves the active and stable of catalyst.
Different aluminium sources is different with the composite oxide of metal grain size that precipitating reagent obtains, and then the specific area of catalyst is had considerable influence, and the adding mode of active component also has a significant impact coordinative role between active component dispersiveness, the active metal component.The inventor finds that by a large amount of experiments the zinc metal salt solution passes into CO when becoming glue with sodium metaaluminate
2Gas carries out precipitation reaction, add basic copper carbonate when aging and prepare catalst for synthesis of methanol, can improve the physico-chemical property of catalyst, increase the specific area of catalyst, increase coordinative role between main metal component copper and the promoter metal component zinc, improve the dispersiveness of active metal component copper, allow reactive metal plays one's part to the full in the catalyst, improve the active and stable of catalyst.
The preparation method of copper-based catalysts of the present invention comprises:
(1), with the soluble-salt of Zn wiring solution-forming A soluble in water, preparation sodium aluminate solution B;
(2), the water purification of packing in the retort, pass into CO
2, add CO
2The total amount of gas and the aluminium in the solution B are (with Al
2O
3Meter) mol ratio is 2～8, is preferably 3～6;
(3), solution A, solution B and stream are added step (2) and pass into CO
2Retort in become glue, then aging under stirring condition, add basic copper carbonate when aging;
(4), the resulting material of step (3) through washing, filter, dry, roasting, compression molding obtains copper-based catalysts.
The soluble-salt of Zn can be nitrate and/or acetate described in the step (1), zinc (Zn in the solution A
2+) concentration is 0.5～5.0mol/L, is preferably 1.0～3.0mol/L, sodium metaaluminate concentration is 1.0～6.0mol/L in the solution B, is preferably 2.0～4.0mol/L.
The water purification of packing in the retort in the step (2) passes into CO
2, add CO
2The total amount of gas and the aluminium in the solution B are (with Al
2O
3Meter) mol ratio is 2～8.Logical CO
2The afterreaction tank preferably seals.The CO that passes into
2The volumetric concentration of gas is 20v%～99v%, is preferably 40v%～95v%.Described water purification typically refers to the water that does not contain heteroion, such as deionized water.
In the described copper-based catalysts, copper/zinc atom mol ratio is 0.1～10, is preferably 0.2～5, and (copper+zinc)/aluminium atomic molar ratio is 0.1～10, is preferably 3～8.
Become the adhesive tape part as follows described in the step (3): reaction temperature is 30～90 ℃, is preferably 40～80 ℃.The pH value is controlled to be 6.0 ~ 11.0 when becoming glue, is preferably 7.0 ~ 10.0, and gelation time is 0.2 ~ 4.0 hour, is preferably 0.5 ~ 3.0 hour.Aging temperature is 50～100 ℃ behind the one-tenth glue, is preferably 60～90 ℃, and aging pH value is controlled to be 6.0 ~ 11.0, is preferably 7.0 ~ 10.0, and ageing time is 0.5 ~ 5.0 hour, is preferably 1.0 ~ 3.0 hours.
The described washing of step (4) is washed with deionized water, and wash temperature is controlled at 30～90 ℃, is preferably 40～70 ℃.Filter cake is dry under 50 ~ 150 ℃ of conditions, and preferably 60 ~ 120 ℃ of baking temperatures, are preferably 1 ~ 16 hour drying time at 0.5 ~ 24 hour drying time.300～360 ℃ of roastings 1 ~ 16 hour, be preferably 2 ~ 10 hours.
Copper-based catalysts of the present invention, take the weight of catalyst as benchmark, the composition of catalyst comprises, is 15%～50%, Al take mass fraction: CuO as 20%～75%, ZnO
2O
3Be 5%～30%; Being preferably CuO is that 30%～60%, ZnO is 20%～40%, Al
2O
3Be 6%～30%.
Than method of the prior art, adopt the prepared copper-based catalysts of method of the present invention to have higher activity, the characteristics of Heat stability is good, this catalyst is suitable to catalst for synthesis of methanol especially.
The specific embodiment
Further specify the solution of the present invention and effect below by embodiment.Among the present invention, wt% is mass fraction.
Among the present invention, specific area and pore volume are to adopt the low temperature liquid nitrogen determination of adsorption method.
Embodiment 1
To dissolving tank 1 interior adding 500mL water, add 93gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 32 gram dissolvings, prepares alkaline working solution B.Add 800mL water in the retort, in water purification, pass into the CO that volumetric concentration is 90v%
2, hermetically sealed can, temperature rises to 68 ℃, solution A, solution B and stream is added in the retort that seals become glue, becomes 68 ℃ of glue temperature, gelation time 1 hour, the pH value of slurries is controlled to be 8.0 when becoming glue.CO in the water purification neutralization reaction tank
2Al among the total amount of gas and the alkaline working solution B
2O
3Mol ratio is 4.8.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 164 grams, pH is 8.2 when aging, temperature is 80 ℃, aging 2 hours, behind material filtering, wash with water 4 times, filter cake is in the 340 ℃ of roastings 5 hours after 6 hours of 100 ℃ of dryings, the material after the roasting add an amount of graphite and hydraulic pressure in blocks, compressing tablet obtains final catalyst A.
The composition of catalyst A, in mass fraction, as follows: CuO is 57%; ZnO is 33%; Al
2O
3Be 10%.The character of catalyst: specific area is 151m
2/ g, pore volume are 0.378cm
3/ g.
Embodiment 2
To dissolving tank 1 interior adding 500mL water, add 101gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 36 gram dissolvings, prepares alkaline working solution B.Add 1000mL water in the retort, in water purification, pass into the CO that volumetric concentration is 95v%
2, hermetically sealed can, temperature rises to 75 ℃, solution A, solution B and stream is added in the retort that seals become glue, becomes 75 ℃ of glue temperature, gelation time 1.5 hours, the pH value of slurries is controlled to be 7.6 when becoming glue.CO in the water purification neutralization reaction tank
2Al among the total amount of gas and the alkaline working solution B
2O
3Mol ratio is 3.5.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 152 grams, pH is 8.2 when aging, temperature is 80 ℃, aging 3 hours, behind material filtering, wash with water 4 times, filter cake is in the 360 ℃ of roastings 4 hours after 5 hours of 90 ℃ of dryings, the material after the roasting add an amount of graphite and hydraulic pressure in blocks, compressing tablet obtains final catalyst B.
The composition of catalyst B, in mass fraction, as follows: CuO is 55%; ZnO is 35%; Al
2O
3Be 11%.The character of catalyst: specific area is 174m
2/ g, pore volume are 0.411cm
3/ g.
Embodiment 3
To dissolving tank 1 interior adding 500mL water, add 97gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 44 gram dissolvings, prepares alkaline working solution B.Add 1000mL water in the retort, in water purification, pass into the CO that volumetric concentration is 90v%
2, hermetically sealed can, temperature rises to 78 ℃, solution A, solution B and stream is added in the retort that seals become glue, becomes 78 ℃ of glue temperature, gelation time 2 hours, the pH value of slurries is controlled to be 7.2 when becoming glue.CO in the water purification neutralization reaction tank
2Al among the total amount of gas and the alkaline working solution B
2O
3Mol ratio is 4.0.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 146 grams, pH is 7.6 when aging, temperature is 80 ℃, aging 2 hours, behind material filtering, wash with water 4 times, filter cake is in the 350 ℃ of roastings 4 hours after 8 hours of 110 ℃ of dryings, the material after the roasting add an amount of graphite and hydraulic pressure in blocks, compressing tablet obtains final catalyst C.
The composition of catalyst C, in mass fraction, as follows: CuO is 53%; ZnO is 34%; Al
2O
3Be 13%.The character of catalyst: specific area is 185m
2/ g, pore volume are 0.427cm
3/ g.
Embodiment 4
To dissolving tank 1 interior adding 500mL water, add 87gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 48 gram dissolvings, prepares alkaline working solution B.Add 1000mL water in the retort, in water purification, pass into the CO that volumetric concentration is 88v%
2, hermetically sealed can, temperature rises to 65 ℃, solution A, solution B and stream is added in the retort that seals become glue, becomes 65 ℃ of glue temperature, gelation time 1 hour, the pH value of slurries is controlled to be 8.0 when becoming glue.CO in the water purification neutralization reaction tank
2Al among the total amount of gas and the alkaline working solution B
2O
3Mol ratio is 5.5.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 158 grams, pH is 8.5 when aging, temperature is 70 ℃, aging 2 hours, behind material filtering, wash with water 4 times, filter cake is in the 330 ℃ of roastings 6 hours after 10 hours of 80 ℃ of dryings, the material after the roasting add an amount of graphite and hydraulic pressure in blocks, compressing tablet obtains final catalyst D.
The composition of catalyst D, in mass fraction, as follows: CuO is 55%; ZnO is 31%; Al
2O
3Be 14%.The character of catalyst: specific area is 141m
2/ g, pore volume are 0.369cm
3/ g.
Comparative Examples 1
Press the disclosed method for preparing catalyst of CN 101574649A, preparation forms identical reference agent E with the catalyst of embodiment 2.
Take by weighing Al (NO
3)
39H
2O64g adds deionized water 200mL stirring and dissolving, takes by weighing NaOH40g, NaCO
350g is total in molten and the 500mL deionized water.Under 35 ℃ condition, with NaOH-NaCO
350g solution slowly adds Al (NO
3)
3, control terminal point pH 〉=12, it is for subsequent use to obtain a kind of water white sodium aluminate solution.
Take by weighing Cu (NO
3)
23H
2O188g, Zn (NO
3)
26H
2O101g is dissolved in the 250mL deionized water; Take by weighing the 1g polyvinyl alcohol, be dissolved in the 250mL deionized water.Then these two kinds of solution are mixed, make a kind of blue clear solution.
To contain solution also stream reaction under 70 ℃ condition of sodium metaaluminate and copper nitrate-zinc nitrate, the control ph value of reaction is 7.8.React complete continuation and stirred 60 minutes under reaction temperature, material is through washing, then in baking oven in 110 ℃ of dryings 4 hours, 350 ℃ of lower roastings are 4 hours in Muffle furnace, the cold deflocculated graphite of rear adding 2% and 3% the deionized water of going played sheet moulding, gained catalyst sample E after being mixed.
The composition of catalyst E, in mass fraction, CuO is 55%; ZnO is 35%; Al
2O
3Be 11%.The character of catalyst: specific area is 87m
2/ g, pore volume are 0.110cm
3/ g.
Comparative Examples 2
Comparative Examples 2 adopts the catalst for synthesis of methanol of traditional handicraft preparation, and preparation forms identical reference agent F with the catalyst of embodiment 2.
Take by weighing Cu (NO
3)
23H
2O188g, Zn (NO
3)
26H
2O101g is dissolved in wiring solution-forming A in the 850mL deionized water, is heated to 70 ℃; Take by weighing 106 gram Na
2CO
3Be dissolved in wiring solution-forming B in the 1000mL deionized water, be heated to 70 ℃; Under the condition that stirs, solution A and solution B and stream added be equipped with in the retort of 500mL deionized water, gelation time is 1 hour, the control endpoint pH is 7.8, continues to stir 30min precipitation color and becomes blue-green by blueness,, keep 80 ℃ of precipitation temperatures; Static 2 hours, add 19gAl (OH) in the slip that makes
3, then after filtration, wash to Na
+Content≤0.035wt%, the filter cake that obtains is 100～120 ℃ of oven dry, again 320 ℃ of roastings 4 hours, the material after the roasting add an amount of graphite and hydraulic pressure in blocks, obtain catalyst F.
The composition of catalyst F, in mass fraction, CuO is 55%; ZnO is 35%; Al
2O
3Be 11%.The character of catalyst: specific area is 81m
2/ g, pore volume are 0.105cm
3/ g.
Embodiment 5
Catalst for synthesis of methanol is pulverized the order for 16-40, adopt before use low-concentration hydrogen (H
2/ N
2=3/97) hydrogen nitrogen mixed gas reduction 16～20h, the highest reduction temperature is 235 ℃.Carry out the activity rating of catalyst at miniature fixed-bed reactor.Loaded catalyst is 5mL, and unstripped gas consists of CO/H
2/ CO
2/ N
2=12/70/3/15(volume ratio), reaction pressure is 5.0MPa, and air speed is 10000h
-1, reaction temperature is 250 ℃, measures CO and CO
2Conversion ratio be the catalyst initial activity.Then with catalyst in synthetic atmosphere with 450 ℃ of heat treatment 5h, drop to again 250 ℃ and measure CO and CO
2Conversion ratio be active after the heat treatment, i.e. heat resistance.Product gas chromatograph analysis, the space-time yield gmL of methanol
-1H
-1Namely every milliliter of grams of producing methyl alcohol per hour the results are shown in Table 1.Find out that from result of the test methanol synthesis catalyst of the present invention has the selective of high activity, heat resistance and excellence.
The evaluation of table 1 catalyst activity and heat resistance experimental result
| Catalyst | Initial activity, % | Initial activity, % | Heat-resisting rear activity, % | Heat-resisting rear activity, % | The methyl alcohol space-time yield, (gmL -1·h -1） | Methyl alcohol is selective, % |
| CO | CO 2 | CO | CO 2 | |||
| A | 95.32 | 87.21 | 86.85 | 80.21 | 2.98 | 95.32 |
| B | 93.41 | 84.67 | 87.82 | 78.83 | 3.05 | 96.47 |
| C | 94.98 | 85.19 | 86.96 | 78.41 | 3.10 | 97.23 |
| D | 95.14 | 86.55 | 87.05 | 79.54 | 3.14 | 96.46 |
| E | 80.16 | 73.45 | 68.21 | 60.54 | 1.98 | 84.65 |
| F | 81.25 | 75.59 | 65.19 | 57.74 | 1.87 | 82.39 |
Claims (11)
1. the preparation method of a copper-based catalysts comprises:
(1), with the soluble-salt of Zn wiring solution-forming A soluble in water, preparation sodium aluminate solution B;
(2), the water purification of packing in the retort, pass into CO
2, add CO
2The total amount of gas and the aluminium in the solution B are with Al
2O
3The mol ratio of meter is 2～8;
(3), solution A, solution B and stream are added step (2) and pass into CO
2Retort in become glue, then aging under stirring condition, add basic copper carbonate when aging;
(4), the resulting material of step (3) through washing, filter, dry, roasting, compression molding obtains copper-based catalysts.
2. in accordance with the method for claim 1, it is characterized in that the Zn soluble-salt described in the step (1) is nitrate and/or acetate, zinc concentration is 0.5～5.0mol/L in the solution A; Sodium metaaluminate concentration is 1.0～6.0mol/L in the solution B.
3. in accordance with the method for claim 1, it is characterized in that zinc concentration is 1.0～3.0mol/L in step (1) solution A; Sodium metaaluminate concentration is 2.0～4.0mol/L in the solution B.
4. in accordance with the method for claim 1, it is characterized in that in the step (2) CO that passes into
2The volumetric concentration of gas is 20v%～99v%.
5. in accordance with the method for claim 1, it is characterized in that in the step (2), add CO
2The total amount of gas and the aluminium in the solution B are with Al
2O
3The mol ratio of meter is 3～6.
6. in accordance with the method for claim 1, it is characterized in that in the described copper-based catalysts that copper/zinc atom mol ratio is 0.1～10.0, (copper+zinc)/aluminium atomic molar ratio is 0.1～10.0.
7. in accordance with the method for claim 1, it is characterized in that in the described copper-based catalysts that copper/zinc atom mol ratio is 0.2～5.0, (copper+zinc)/aluminium atomic molar ratio is 3.0～8.0.
8. in accordance with the method for claim 1, it is characterized in that becoming the adhesive tape part described in the step (3): reaction temperature is 30～90 ℃, and the pH value is 6.0 ~ 11.0, and gelation time is 0.2 ~ 4.0 hour; Aging temperature is 50～100 ℃ behind the one-tenth glue, and aging pH value is controlled to be 6.0 ~ 11.0, and ageing time is 0.5 ~ 5.0 hour.
9. in accordance with the method for claim 1, it is characterized in that becoming the adhesive tape part described in the step (3): reaction temperature is 40～80 ℃, and the pH value is 7.0 ~ 10.0, and gelation time is 0.5 ~ 3.0 hour; Aging temperature is 60～90 ℃ behind the one-tenth glue, and aging pH value is controlled to be 7.0 ~ 10.0, and ageing time is 1.0 ~ 3.0 hours.
10. the temperature that in accordance with the method for claim 1, it is characterized in that the described washing of step (4) is controlled at 30～90 ℃; Filter cake is dry under 50 ~ 150 ℃ of conditions, and 0.5 ~ 24.0 hour drying time was 300～360 ℃ of roastings 1 ~ 16 hour.
11. in accordance with the method for claim 1, it is characterized in that described copper-based catalysts, take the weight of catalyst as benchmark, the composition of catalyst comprises, is 15%～50%, Al take mass fraction: CuO as 20%～75%, ZnO
2O
3Be 5%～30%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107774262A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | The preparation method of copper zinc catalyst |
| CN107774263A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of preparation method of catalst for synthesis of methanol |
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| JPH10277392A (en) * | 1997-04-11 | 1998-10-20 | Kansai Electric Power Co Inc:The | Catalyst for synthesis of methanol |
| CN1256970A (en) * | 1998-11-16 | 2000-06-21 | 中国石油化工集团公司 | Processf or preparing copper-containing catalyst |
| CN1398787A (en) * | 2002-05-31 | 2003-02-26 | 中国石油化工集团公司 | Prepn of gamma-alumina |
| CN101574649A (en) * | 2009-05-25 | 2009-11-11 | 来安县迅能催化剂有限公司 | Methanol catalyst preparation method |
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|---|---|---|---|---|
| JPH10277392A (en) * | 1997-04-11 | 1998-10-20 | Kansai Electric Power Co Inc:The | Catalyst for synthesis of methanol |
| CN1256970A (en) * | 1998-11-16 | 2000-06-21 | 中国石油化工集团公司 | Processf or preparing copper-containing catalyst |
| CN1398787A (en) * | 2002-05-31 | 2003-02-26 | 中国石油化工集团公司 | Prepn of gamma-alumina |
| CN101574649A (en) * | 2009-05-25 | 2009-11-11 | 来安县迅能催化剂有限公司 | Methanol catalyst preparation method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107774262A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | The preparation method of copper zinc catalyst |
| CN107774263A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of preparation method of catalst for synthesis of methanol |
| CN107774263B (en) * | 2016-08-31 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of preparation method of catalst for synthesis of methanol |
| CN107774262B (en) * | 2016-08-31 | 2019-11-15 | 中国石油化工股份有限公司 | The preparation method of copper zinc catalyst |
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