CN103372439A - Preparation method of methanol synthesis catalyst - Google Patents
Preparation method of methanol synthesis catalyst Download PDFInfo
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- CN103372439A CN103372439A CN2012104426818A CN201210442681A CN103372439A CN 103372439 A CN103372439 A CN 103372439A CN 2012104426818 A CN2012104426818 A CN 2012104426818A CN 201210442681 A CN201210442681 A CN 201210442681A CN 103372439 A CN103372439 A CN 103372439A
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Abstract
The invention discloses a preparation method of a methanol synthesis catalyst. The method comprises the steps of adding a zinc metal salt solution, a sodium metaaluminate solution and CO2 gas in parallel flow mode and gelling, aging under the condition of stirring, and adding basic copper carbonate while aging to prepare the methanol synthesis 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.
Description
Technical field
The present invention relates to a kind of preparation method of catalst for synthesis of methanol, be specifically related to a kind of preparation method with catalst for synthesis of methanol of 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 catalst for synthesis of methanol.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 catalst for synthesis of methanol 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), with solution A, solution B and CO
2Gas and stream add one-tenth glue in the retort, and is then aging under stirring condition, adds basic copper carbonate when aging;
(3), the resulting material of step (2) is through washing, filtration, drying, roasting, compression molding, obtains catalst for synthesis of methanol.
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.
Become the adhesive tape part described in the step (2): reaction temperature is 30～90 ℃, is preferably 40～80 ℃.The pH value is 6.0 ~ 11.0, 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.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, CO
2Gas concentration is 20v%～99v%, is preferably 40v%～95v%.
In the catalst for synthesis of methanol of the present invention, used 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.
The described washing of step (3) 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.
Catalst for synthesis of methanol 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 catalyst of the prepared synthesizing methanol of method of the present invention to have higher activity, the characteristics of Heat stability is good.
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 88gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 46 gram dissolvings, prepares alkaline working solution B, adds 450mL water in retort, and temperature rises to 60 ℃.In situation about stirring, solution A, solution B and CO
2And stream adds one-tenth glue in the retort, CO
2Concentration is 85v%, becomes 60 ℃ of glue reaction temperatures, gelation time 1 hour, and the pH value that is controlled to rubber cement liquid is 7.8 ± 0.2.Become in the glue process and add CO
2Al among the total amount of gas and the alkaline working solution B
2O
3Mol ratio is 3.8.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 171 grams, pH is 8.0 ± 0.2 when aging, temperature is 80 ℃, aging 2 hours, behind material filtering, with deionized water washing 3 times, filter cake is in the 320 ℃ of roastings 5 hours after 8 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 A.
The composition of catalyst A, in mass fraction, as follows: CuO is 55%; ZnO is 32%; Al
2O
3Be 13%.The character of catalyst: specific area is 141m
2/ g, pore volume are 0.372cm
3/ g.
Embodiment 2
To dissolving tank 1 interior adding 500mL water, add 78gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 53 gram dissolvings, prepares alkaline working solution B, adds 350mL water in retort, and temperature rises to 65 ℃.In situation about stirring, solution A, solution B and CO
2And stream adds one-tenth glue in the retort, CO
2Concentration is 75v%, becomes 65 ℃ of glue reaction temperatures, gelation time 1.5 hours, and the pH value that is controlled to rubber cement liquid is 7.5 ± 0.2.Become in the glue process and add CO
2Al among the total amount of gas and the alkaline working solution B
2O
3Mol ratio is 4.3.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 174 grams, pH is 8.2 ± 0.2 when aging, temperature is 80 ℃, aging 2 hours, behind material filtering, with deionized water washing 3 times, filter cake is in the 300 ℃ of roastings 6 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 B.
The composition of catalyst B, in mass fraction, as follows: CuO is 57%; ZnO is 29%; Al
2O
3Be 14%.The character of catalyst: specific area is 156m
2/ g, pore volume are 0.383cm
3/ g.
Embodiment 3
To dissolving tank 1 interior adding 500mL water, add 81gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 38 gram dissolvings, prepares alkaline working solution B, adds 500mL water in retort, and temperature rises to 75 ℃.In situation about stirring, with solution A, solution B and CO
2And stream adds one-tenth glue in the retort, CO
2Concentration is 90v%, becomes 75 ℃ of glue reaction temperatures, gelation time 1 hour, and the pH value that is controlled to rubber cement liquid is 8.0 ± 0.2.Become in the glue process and add CO
2Al among the total amount of gas and the alkaline working solution B
2O
3Mol ratio is 4.5.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 189 grams, pH is 8.5 ± 0.2 when aging, temperature is 75 ℃, aging 2 hours, behind material filtering, with deionized water washing 3 times, filter cake is in the 360 ℃ of roastings 4 hours after 5 hours of 120 ℃ 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 58%; ZnO is 30%; Al
2O
3Be 12%.The character of catalyst: specific area is 1841m
2/ g, pore volume are 0.412cm
3/ g.
Embodiment 4
To dissolving tank 1 interior adding 500mL water, add 95gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 33 gram dissolvings, prepares alkaline working solution B, adds 450mL water in retort, and temperature rises to 70 ℃.In situation about stirring, with solution A, solution B and CO
2And stream adds one-tenth glue in the retort, CO
2Concentration is 85v%, becomes 70 ℃ of glue reaction temperatures, gelation time 1.5 hours, and the pH value that is controlled to rubber cement liquid is 7.5 ± 0.2.Become in the glue process and add CO
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) 165 grams, pH is 7.5 ± 0.2 when aging, temperature is 85 ℃, aging 1.5 hours, behind material filtering, with deionized water washing 43 times, filter cake is in the 340 ℃ of roastings 5 hours after 10 hours of 60 ℃ 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 56 %; ZnO is 34 %; Al
2O
3Be 10%.The character of catalyst: specific area is 173m
2/ g, pore volume are 0.395cm
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
2O66g 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 water white sodium aluminate solution.
Take by weighing Cu (NO
3)
23H
2O201g, Zn (NO
3)
26H
2O78g 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 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 2wt% and the deionized water of 3wt% of going played sheet moulding, gained catalyst sample E after being mixed.
The composition of catalyst E, in mass fraction, CuO is 57%; ZnO is 29%; Al
2O
3Be 14%.The character of catalyst: specific area is 75m
2/ g, pore volume are 0.122cm
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
2O201g, Zn (NO
3)
26H
2O78g 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 22gAl (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 57%; ZnO is 29%; Al
2O
3Be 14%.The character of catalyst: specific area is 81m
2/ g, pore volume are 0.141cm
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(volume ratio)) 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 | 92.12 | 82.26 | 86.29 | 76.59 | 2.99 | 95.32 |
| B | 93.23 | 83.85 | 85.35 | 75.23 | 3.01 | 94.25 |
| C | 94.06 | 84.32 | 86.21 | 76.12 | 3.25 | 96.54 |
| D | 94.41 | 84.56 | 87.36 | 79.12 | 3.15 | 96.01 |
| E | 80.36 | 73.45 | 68.21 | 60.54 | 1.98 | 84.65 |
| F | 82.89 | 75.59 | 65.19 | 57.74 | 1.87 | 82.39 |
Claims (11)
1. the preparation method of a catalst for synthesis of methanol comprises:
(1), with the soluble-salt of Zn wiring solution-forming A soluble in water, preparation sodium aluminate solution B;
(2), with solution A, solution B and CO
2Gas and stream add one-tenth glue in the retort, and is then aging under stirring condition, adds basic copper carbonate when aging;
(3), the resulting material of step (2) is through washing, filtration, drying, roasting, compression molding, obtains catalst for synthesis of methanol.
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 described catalst for synthesis of methanol that copper/zinc atom mol ratio is 0.1～10.0, (copper+zinc)/aluminium atomic molar ratio is 0.1～10.0.
5. in accordance with the method for claim 1, it is characterized in that in the described catalst for synthesis of methanol that copper/zinc atom mol ratio is 0.2～5.0, (copper+zinc)/aluminium atomic molar ratio is 3.0～8.0.
6. in accordance with the method for claim 1, it is characterized in that becoming the adhesive tape part described in the step (2): 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.
7. 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 2～8, CO
2Gas concentration is 20v%～99v%.
8. 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.
9. in accordance with the method for claim 1, it is characterized in that becoming the adhesive tape part described in the step (2): 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 (3) 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. according to the arbitrary described method of claim 1 ~ 10, it is characterized in that described catalst for synthesis of methanol, 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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| CN106944069A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | Catalst for synthesis of methanol precursor, catalst for synthesis of methanol and preparation method thereof |
| 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 |
| 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 |
| CN107790137A (en) * | 2016-08-31 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of preparation method of copper zinc catalyst |
| CN110935456A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing methanol |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944069A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | Catalst for synthesis of methanol precursor, catalst for synthesis of methanol and preparation method thereof |
| CN106944069B (en) * | 2016-01-07 | 2019-06-11 | 中国石油化工股份有限公司 | Catalst for synthesis of methanol predecessor, catalst for synthesis of methanol and preparation method thereof |
| 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 |
| 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 |
| CN107790137A (en) * | 2016-08-31 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of preparation method of copper zinc catalyst |
| CN107790137B (en) * | 2016-08-31 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of preparation method of copper zinc catalyst |
| 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 |
| CN110935456A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing methanol |
| CN110935456B (en) * | 2018-09-25 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing methanol |
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