CN103372439B - The preparation method of catalst for synthesis of methanol - Google Patents

The preparation method of catalst for synthesis of methanol Download PDF

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Publication number
CN103372439B
CN103372439B CN201210442681.8A CN201210442681A CN103372439B CN 103372439 B CN103372439 B CN 103372439B CN 201210442681 A CN201210442681 A CN 201210442681A CN 103372439 B CN103372439 B CN 103372439B
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solution
catalyst
methanol
synthesis
catalst
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CN103372439A (en
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王海涛
刘东香
徐学军
冯小萍
王继锋
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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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
    • 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

Abstract

The invention discloses a kind of preparation method of catalst for synthesis of methanol.The method is by zinc metal salt solution, sodium aluminate solution and CO 2gas also flows plastic, aging under agitation, adds basic copper carbonate to prepare catalst for synthesis of methanol time aging.The method can improve the physico-chemical property of catalyst, increases the specific area of catalyst, increases coordinative role between main active metal component copper and promoter metal component zinc, improve the dispersiveness of active phase, improves activity and the stability of catalyst.

Description

The preparation method of catalst for synthesis of methanol
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 of catalst for synthesis of methanol 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 third place in the world, methanol demands amount and the production capacity sustainable growth along with industrial development in recent years.
Industrial methyl alcohol is generally with containing H 2, CO, CO 2synthesis gas produce under certain pressure, temperature and catalyst existence condition.In generally adopting in the world at present, low-pressure vapor phase method synthesizing methanol, used catalyst is essentially the mixed oxide of copper, zinc, aluminium.CuO, ZnO, Al in catalst for synthesis of methanol 2o 3the effect of three components is variant, and CuO is main active component, ZnO and Al 2o 3for auxiliary agent.Method for preparing catalyst is generally the mixing subcarbonate first using coprecipitation to generate (comprise and flow, instead to add, just add coprecipitation) copper zinc, and then add aluminium hydroxide in pulping process, generate slurry through washing, drying, roasting, compression molding.The research of current catalyst preparing mainly concentrates on optimization and the improvement of preparation method and technique, catalyst activity is improved by changing the ratio of catalytic component, the size of crystal grain, the size of specific area and pore-size distribution, improve copper-based catalysts poor heat stability, the selective low problem short with the life-span.Method for preparing catalyst is different, and the performance of gained catalyst can differ larger.
CN 1810357A adopts a traditional step coprecipitation to prepare a kind of catalst for synthesis of methanol.By the nitrate mixed solution of Cu, Zn, Al, Li and NaCO 3solution stream is titrated in the deionized water of a small amount of high-speed stirred, keeps the pH of solution between 7 ~ 8 simultaneously, aging, suction filtration, washing, dries to obtain catalyst precarsor, and catalyst precarsor is dried, roasting obtains finished product.The method adopts a typical step coprecipitation to prepare catalyst for methanol, in preparation process, with the addition of LiNO 3.
CN 1329938A discloses a kind of preparation method of catalst for synthesis of methanol, and this catalyst is made up of the oxide of copper, zinc, aluminium.Preparation process a: part makes coprecipitate containing copper, zinc, aluminium compound by coprecipitation, another part makes coprecipitate containing copper, zinc compound with co-precipitation.The equal thermal decomposition of above-mentioned coprecipitate is the oxide of metal, then by these two kinds of co-precipitation mixing, washing, dry, roasting, and shaping obtained catalyst.
CN 1660490A discloses a kind of preparation method of catalst for synthesis of methanol, its preparation process is: coprecipitation is prepared in methanol synthesis catalyst process and added a small amount of Surfactant OP, or fractional precipitation is prepared in methanol synthesis catalyst process and is added a small amount of Surfactant OP, obtained a kind of catalst for synthesis of methanol.
CN 101574649A discloses a kind of preparation method of catalst for synthesis of methanol, step is reacted by the mixed aqueous solution of the aqueous solution of aluminum soluble salt and alkali metal hydroxide-carbonate, generate a kind of transparent meta-aluminate aqueous solution, then it is carried out coprecipitation reaction with containing the copper of water-soluble high-molecular compound, the transparent aqueous solution of zinc salt, generate the mixing co-precipitation of a kind of copper, zinc, aluminium, then through washing, drying, granulation process, roasting, beat that sheet is shaping can obtain 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), changing the presoma of catalyst preparation process (step process changes two steps or three step process into) and change Al, come the structure of regulating catalyst, surface acidic-basic property, electronic property, to improve the activity of existing catalyst, selective or life-span.But improve catalst for synthesis of methanol key that the is active and life-span be to increase the specific area of catalyst and active ingredient copper and co-catalyst zinc distribute more evenly, above patent does not all relate to.
Summary of the invention
For above-mentioned deficiency of the prior art, the invention provides the preparation method of simple, the easy-operating catalst for synthesis of methanol of a kind of technique.The method can improve the physico-chemical property of catalyst, increases the specific area of catalyst, increases the coordinative role between main active metal component copper and promoter metal component zinc, improve the dispersiveness of active phase, improves activity and the stability of catalyst.
Different aluminium sources is different with the composite oxide of metal grain size that precipitating reagent obtains, and then has considerable influence to the specific area of catalyst, and the feed postition of active component also has a significant impact coordinative role between active component dispersiveness, active metal component.Inventor is found by a large amount of experiments, passes into CO when zinc metal salt solution and sodium metaaluminate plastic 2gas carries out precipitation reaction, add basic copper carbonate time aging and prepare catalst for synthesis of methanol, the physico-chemical property of catalyst can be improved, increase the specific area of catalyst, increase coordinative role between main metal component copper and promoter metal component zinc, improve the dispersiveness of active metal component copper, allow active metal in catalyst play one's part to the full, improve activity and the stability of catalyst.
The preparation method of catalst for synthesis of methanol of the present invention, comprising:
(1), by wiring solution-forming A soluble in water for the soluble-salt of Zn, preparation sodium aluminate solution B;
(2), by solution A, solution B and CO 2gas stream adds plastic in retort, then aging under agitation, add basic copper carbonate time aging;
(3), the material that obtains of step (2) through washing, filtration, drying, roasting, compression molding, obtain catalst for synthesis of methanol.
Described in step (1), the soluble-salt of Zn can be nitrate and/or acetate, zinc (Zn in solution A 2+) concentration is 0.5 ~ 5.0mol/L, be preferably 1.0 ~ 3.0mol/L, in solution B, sodium metaaluminate concentration is 1.0 ~ 6.0mol/L, is preferably 2.0 ~ 4.0mol/L.
Gelation Conditions described in step (2): reaction temperature is 30 ~ 90 DEG C, is preferably 40 ~ 80 DEG C.PH value is 6.0 ~ 11.0, and be preferably 7.0 ~ 10.0, gelation time is 0.2 ~ 4.0 hour, is preferably 0.5 ~ 3.0 hour.Aging temperature 50 ~ 100 DEG C after plastic, is preferably 60 ~ 90 DEG C, and it is 6.0 ~ 11.0 that aging pH value controls, and be preferably 7.0 ~ 10.0, ageing time is 0.5 ~ 5.0 hour, is preferably 1.0 ~ 3.0 hours.Add CO 2aluminium in the total amount of gas and solution B is (with Al 2o 3meter) mol ratio be 2 ~ 8, be preferably 3 ~ 6, CO 2gas concentration is 20v% ~ 99v%, is preferably 40v% ~ 95v%.
In catalst for synthesis of methanol of the present invention, copper used/zinc atom mol ratio is 0.1 ~ 10, and be preferably 0.2 ~ 5, (copper+zinc)/aluminium atomic molar ratio is 0.1 ~ 10, is preferably 3 ~ 8.
Step (3) described washing spends deionized water, and wash temperature controls at 30 ~ 90 DEG C, is preferably 40 ~ 70 DEG C.Filter cake is dry under 50 ~ 150 DEG C of conditions, and baking temperature preferably 60 ~ 120 DEG C, 0.5 ~ 24 hour drying time, is preferably 1 ~ 16 hour drying time.300 ~ 360 DEG C of roastings 1 ~ 16 hour, be preferably 2 ~ 10 hours.
Catalst for synthesis of methanol of the present invention, with the weight of catalyst for benchmark, the composition of catalyst comprises, in mass fraction: CuO is 20% ~ 75%, ZnO is 15% ~ 50%, Al 2o 3be 5% ~ 30%; Preferably CuO is 30% ~ 60%, ZnO is 20% ~ 40%, Al 2o 3be 6% ~ 30%.
Compared to method of the prior art, the catalyst of synthesizing methanol prepared by method of the present invention is adopted to have higher activity, the feature of Heat stability is good.
Detailed description of the invention
The solution of the present invention and effect is further illustrated below by embodiment.In the present invention, wt% is mass fraction.
In the present invention, specific area and pore volume adopt low temperature liquid nitrogen determination of adsorption method.
Embodiment 1
In dissolving tank 1, add 500mL water, add 88gZn (NO 3) 26H 2o dissolves, and preparating acid sex work solution A, adds 500mL water in dissolving tank 2, and then add sodium metaaluminate 46 grams dissolving, prepare alkaline working solution B, add 450mL water in retort, temperature rises to 60 DEG C.When stirring, solution A, solution B and CO 2and stream adds plastic in retort, CO 2concentration is 85v%, plastic reaction temperature 60 DEG C, gelation time 1 hour, and the pH value being controlled to rubber cement liquid is 7.8 ± 0.2.CO is added in plastic process 2al in the total amount of gas and alkaline working solution B 2o 3mol ratio is 3.8.Start aging when stirring, add basic copper carbonate (Cu 2(OH) 2cO 3) 171 grams, time aging, pH is 8.0 ± 0.2, and temperature is 80 DEG C, aging 2 hours, after material filtering, spend deionized water 3 times, filter cake is in 80 DEG C of dryings, 320 DEG C of roastings 5 hours after 8 hours, and the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, and 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 is 0.372cm 3/ g.
Embodiment 2
In dissolving tank 1, add 500mL water, add 78gZn (NO 3) 26H 2o dissolves, and preparating acid sex work solution A, adds 500mL water in dissolving tank 2, and then add sodium metaaluminate 53 grams dissolving, prepare alkaline working solution B, add 350mL water in retort, temperature rises to 65 DEG C.When stirring, solution A, solution B and CO 2and stream adds plastic in retort, CO 2concentration is 75v%, plastic reaction temperature 65 DEG C, gelation time 1.5 hours, and the pH value being controlled to rubber cement liquid is 7.5 ± 0.2.CO is added in plastic process 2al in the total amount of gas and alkaline working solution B 2o 3mol ratio is 4.3.Start aging when stirring, add basic copper carbonate (Cu 2(OH) 2cO 3) 174 grams, time aging, pH is 8.2 ± 0.2, and temperature is 80 DEG C, aging 2 hours, after material filtering, spend deionized water 3 times, filter cake is in 100 DEG C of dryings, 300 DEG C of roastings 6 hours after 6 hours, and the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, and 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 is 0.383cm 3/ g.
Embodiment 3
In dissolving tank 1, add 500mL water, add 81gZn (NO 3) 26H 2o dissolves, and preparating acid sex work solution A, adds 500mL water in dissolving tank 2, and then add sodium metaaluminate 38 grams dissolving, prepare alkaline working solution B, add 500mL water in retort, temperature rises to 75 DEG C.When stirring, by solution A, solution B and CO 2and stream adds plastic in retort, CO 2concentration is 90v%, plastic reaction temperature 75 DEG C, gelation time 1 hour, and the pH value being controlled to rubber cement liquid is 8.0 ± 0.2.CO is added in plastic process 2al in the total amount of gas and alkaline working solution B 2o 3mol ratio is 4.5.Start aging when stirring, add basic copper carbonate (Cu 2(OH) 2cO 3) 189 grams, time aging, pH is 8.5 ± 0.2, and temperature is 75 DEG C, aging 2 hours, after material filtering, spend deionized water 3 times, filter cake is in 120 DEG C of dryings, 360 DEG C of roastings 4 hours after 5 hours, and the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, and 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 is 0.412cm 3/ g.
Embodiment 4
In dissolving tank 1, add 500mL water, add 95gZn (NO 3) 26H 2o dissolves, and preparating acid sex work solution A, adds 500mL water in dissolving tank 2, and then add sodium metaaluminate 33 grams dissolving, prepare alkaline working solution B, add 450mL water in retort, temperature rises to 70 DEG C.When stirring, by solution A, solution B and CO 2and stream adds plastic in retort, CO 2concentration is 85v%, plastic reaction temperature 70 DEG C, gelation time 1.5 hours, and the pH value being controlled to rubber cement liquid is 7.5 ± 0.2.CO is added in plastic process 2al in the total amount of gas and alkaline working solution B 2o 3mol ratio is 4.0.Start aging when stirring, add basic copper carbonate (Cu 2(OH) 2cO 3) 165 grams, time aging, pH is 7.5 ± 0.2, and temperature is 85 DEG C, aging 1.5 hours, after material filtering, spend deionized water 43 times, filter cake is in 60 DEG C of dryings, 340 DEG C of roastings 5 hours after 10 hours, and the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, and 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 is 0.395cm 3/ g.
Comparative example 1
By method for preparing catalyst disclosed in CN 101574649A, preparation forms identical reference agent E with the catalyst of embodiment 2.
Take Al (NO 3) 39H 2o66g, adds deionized water 200ml stirring and dissolving, takes NaOH40g, NaCO 350g is molten with 500ml deionized water altogether.Under the condition of 35 DEG C, by NaOH-NaCO 350g solution slowly adds Al (NO 3) 3, control terminal pH>=12, obtain water white sodium aluminate solution for subsequent use.
Take Cu (NO 3) 23H 2o201g, Zn (NO 3) 26H 2o78g is dissolved in 250ml deionized water; Take 1g polyvinyl alcohol, be dissolved in 250ml deionized water.Then by these two kinds of solution mixing, blue-tinted transparent solution is made.
Solution containing sodium metaaluminate and copper nitrate-zinc nitrate is flowed reaction under the condition of 70 DEG C, and to control ph value of reaction be 7.8.React complete continuation and stir 60 minutes at the reaction temperatures, material passes through washing, then in an oven in 110 DEG C of dryings 4 hours, roasting 4 hours at 350 DEG C in Muffle furnace, cold go after add the deflocculated graphite of 2wt% and the deionized water of 3wt%, beat sheet after being mixed shaping, gained catalyst sample E.
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 is 0.122cm 3/ g.
Comparative example 2
The catalst for synthesis of methanol that comparative example 2 adopts traditional handicraft to prepare, preparation forms identical reference agent F with the catalyst of embodiment 2.
Take Cu (NO 3) 23H 2o201g, Zn (NO 3) 26H 2o78g is dissolved in wiring solution-forming A in 850mL deionized water, is heated to 70 DEG C; Take 106 grams of Na 2cO 3be dissolved in wiring solution-forming B in 1000ml deionized water, be heated to 70 DEG C; Under the condition stirred, by solution A and solution B and stream adds in the retort that 500ml deionized water is housed, gelation time is 1 hour, and controlling endpoint pH is 7.8, continues to stir 30min and precipitates color and become blue-green from blueness, keep precipitation temperature 80 DEG C; Static 2 hours, in obtained slip, add 22gAl (OH) 3, then after filtration, wash to Na +content≤0.035wt%, the filter cake obtained is 100 ~ 120 DEG C of oven dry, then 320 DEG C of roastings 4 hours, the material after roasting adds appropriate graphite and hydraulic pressure is in blocks, obtains 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 is 0.141cm 3/ g.
Embodiment 5
Catalst for synthesis of methanol is pulverized for 16-40 order, adopt low-concentration hydrogen (H before use 2/ N 2=3/97(volume ratio)) hydrogen nitrogen mixed gas reduction 16 ~ 20h, the highest reduction temperature is 235 DEG C.Miniature fixed-bed reactor carries out the activity rating of catalyst.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 DEG C, measures CO and CO 2conversion ratio be catalyst initial activity.Then catalyst is being synthesized by 450 DEG C of heat treatment 5h in atmosphere, then dropping to 250 DEG C of mensuration CO and CO 2conversion ratio be active after heat treatment, i.e. heat resistance.Product chromatographic, the space-time yield gmL of methanol -1h -1namely the grams of every milliliter of product methyl alcohol per hour, the results are shown in Table 1.Find out 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, % 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 (9)

1. a preparation method for catalst for synthesis of methanol, comprising:
(1), by wiring solution-forming A soluble in water for the soluble-salt of Zn, preparation sodium aluminate solution B;
(2), by solution A, solution B and CO 2gas stream adds plastic in retort, then aging under agitation, add basic copper carbonate time aging;
(3), the material that obtains of step (2) through washing, filtration, drying, roasting, compression molding, obtain catalst for synthesis of methanol; Wherein, copper/zinc atom mol ratio is 0.1 ~ 10.0, and (copper+zinc)/aluminium atomic molar ratio is 0.1 ~ 10.0, Gelation Conditions described in step (2): reaction temperature is 30 ~ 90 DEG C, and pH value is 6.0 ~ 11.0, and gelation time is 0.2 ~ 4.0 hour; Aging temperature 50 ~ 100 DEG C after plastic, it is 6.0 ~ 11.0 that aging pH value controls, and ageing time is 0.5 ~ 5.0 hour.
2. in accordance with the method for claim 1, it is characterized in that the Zn soluble-salt described in step (1) is nitrate and/or acetate, in solution A, zinc concentration is 0.5 ~ 5.0mol/L; In solution B, sodium metaaluminate concentration is 1.0 ~ 6.0mol/L.
3. in accordance with the method for claim 1, it is characterized in that in step (1) solution A, zinc concentration is 1.0 ~ 3.0mol/L; In solution B, sodium metaaluminate concentration is 2.0 ~ 4.0mol/L.
4. in accordance with the method for claim 1, it is characterized in that in described catalst for synthesis of methanol, copper/zinc atom mol ratio is 0.2 ~ 5.0, and (copper+zinc)/aluminium atomic molar ratio is 3.0 ~ 8.0.
5. in accordance with the method for claim 1, it is characterized in that, in step (2), adding CO 2aluminium in the total amount of gas and solution B is with Al 2o 3the mol ratio of meter is 2 ~ 8, CO 2gas concentration is 20v% ~ 99v%.
6. in accordance with the method for claim 1, it is characterized in that, in step (2), adding CO 2aluminium in the total amount of gas and solution B is with Al 2o 3the mol ratio of meter is 3 ~ 6.
7. in accordance with the method for claim 1, it is characterized in that Gelation Conditions described in step (2): reaction temperature is 40 ~ 80 DEG C, pH value is 7.0 ~ 10.0, and gelation time is 0.5 ~ 3.0 hour; After plastic, aging temperature is 60 ~ 90 DEG C, and it is 7.0 ~ 10.0 that aging pH value controls, and ageing time is 1.0 ~ 3.0 hours.
8. in accordance with the method for claim 1, it is characterized in that the temperature of step (3) described washing controls at 30 ~ 90 DEG C; Filter cake is dry under 50 ~ 150 DEG C of conditions, and 0.5 ~ 24.0 hour drying time, 300 ~ 360 DEG C of roastings 1 ~ 16 hour.
9., according to the arbitrary described method of claim 1 ~ 8, it is characterized in that described catalst for synthesis of methanol, with the weight of catalyst for benchmark, the composition of catalyst comprises, in mass fraction: CuO is 20% ~ 75%, ZnO is 15% ~ 50%, Al 2o 3be 5% ~ 30%.
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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
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
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
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
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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GB1369475A (en) * 1970-12-31 1974-10-09 Mitsubishi Gas Chemical Co Process for preparing a catalyst for methanol synthesis
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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GB1369475A (en) * 1970-12-31 1974-10-09 Mitsubishi Gas Chemical Co Process for preparing a catalyst for methanol synthesis
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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