CN103372440B - Preparation method of methanol synthesis catalyst - Google Patents
Preparation method of methanol synthesis catalyst Download PDFInfo
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- CN103372440B CN103372440B CN201210442896.XA CN201210442896A CN103372440B CN 103372440 B CN103372440 B CN 103372440B CN 201210442896 A CN201210442896 A CN 201210442896A CN 103372440 B CN103372440 B CN 103372440B
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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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- 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 methanol synthesis catalyst. The method comprises the step of adding a copper and zinc metal salt solution, a sodium metaaluminate solution and CO2 gas in a parallel flow mode and gelling to prepare the methanol synthesis catalyst. The method has the beneficial effects of increasing the specific surface area of the catalyst, improving the dispersibility of an active phase, increasing the quantity of active centers, preventing copper particles from being sintered and suffering from carbon deposit, 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 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 specific surface area of catalyst of the method gained is higher, and it is more even that active ingredient copper and co-catalyst zinc distribute, and improves the activity of catalst for synthesis of methanol and the service life of heat endurance and catalyst.
Found by a large amount of experiments, when copper, zinc metal salt solution and sodium metaaluminate plastic, pass into CO
2gas, carries out precipitation reaction and prepares catalst for synthesis of methanol, can increase the specific area of catalyst, makes CuO and ZnO uniform load to carrier A l
2o
3on, active phase crystal grain is little, and decentralization is high, and activity is combined closely with carrier, which adds the effect that ZnO promotes Cu dispersion, substantially increases catalyst activity, simultaneously Al
2o
3the increase of specific area, increases activated centre quantity, and can hinder copper particle sintered, carbon deposit, improves the heat resistance of catalyst.
The preparation method of catalst for synthesis of methanol of the present invention, comprises the following steps:
(1), by wiring solution-forming A soluble in water for the soluble-salt of Cu, Zn, preparation sodium aluminate solution B;
(2), by solution A, solution B and CO
2gas stream add plastic in retort, aging;
(3), the material that obtains of step (2) through washing, filtration, drying, roasting, compression molding, obtain catalst for synthesis of methanol.
Cu, Zn soluble-salt described in step (1) is nitrate and/or acetate, copper (Cu in solution A
2+) concentration is 1.0 ~ 6.0mol/L, is preferably 2.0 ~ 4.0mol/L, zinc (Zn in solution A
2+) concentration is 0.5 ~ 5.0mol/L, be preferably 1.0 ~ 3.0mol/L, copper/zinc atom mol ratio is 0.1 ~ 10.0, and be preferably 0.2 ~ 5.0, (copper+zinc)/aluminium atomic molar ratio is 0.1 ~ 10.0, is preferably 3.0 ~ 8.0.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, be preferably 40 ~ 85 DEG C, pH value is 6.0 ~ 11.0, and be preferably 7.0 ~ 9.0, 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 ~ 3.0 hour.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%.
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 ~ 24.0 hour drying time, is preferably 1 ~ 16 hour drying time.The condition of described roasting is as follows: 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 175gCu (NO respectively
3)
23H
2o and 83gZn (NO
3)
26H
2o dissolves, and preparating acid sex work solution A, adds 500mL water in dissolving tank 2, and then add sodium metaaluminate 52 grams dissolving, prepare alkaline working solution B, add 350mL water in retort, temperature rises to 65 DEG C.When stirring, by solution A, solution B and CO
2and stream adds plastic in retort, CO
2concentration is 90v%, plastic reaction temperature 65 DEG C, gelation time 1 hour, 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 3.5.Be 8.0 ± 0.2 at pH after plastic, temperature is under 75 DEG C of conditions aging 2 hours, after material filtering, spend deionized water 3 times, filter cake is in 80 DEG C of dryings, 300 DEG C of roastings 4 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 56%; ZnO is 31%; Al
2o
3be 13%.The character of catalyst: specific area is 158m
2/ g, pore volume is 0.367cm
3/ g.
Embodiment 2
In dissolving tank 1, add 500mL water, add 185gCu (NO respectively
3)
23H
2o and 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 58 grams dissolving, prepare alkaline working solution B, add 400mL 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 80v%, plastic reaction temperature 70 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 4.0.Be 8.2 ± 0.2 at pH after plastic, temperature is under 80 DEG C of conditions aging 2 hours, after material filtering, spend deionized water 3 times, filter cake is in 100 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 B.
The composition of catalyst B, in mass fraction, as follows: CuO is 58%; ZnO is 28%; Al
2o
3be 14%.The character of catalyst: specific area is 169 m
2/ g, pore volume is 0.384cm
3/ g.
Embodiment 3
In dissolving tank 1, add 500mL water, add 195gCu (NO respectively
3)
23H
2o and 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 63 grams dissolving, prepare alkaline working solution B, add 350mL water in retort, temperature rises to 60 DEG C.When stirring, by solution A, solution B and CO
2and stream adds plastic in retort, CO
2concentration is 85v%, plastic reaction temperature 60 DEG C, gelation time 1.5 hours, and the pH value being controlled to rubber cement liquid is 7.3 ± 0.2.CO is added in plastic process
2al in the total amount of gas and alkaline working solution B
2o
3mol ratio is 5.0.Be 7.8 ± 0.2 at pH after plastic, temperature is under 85 DEG C of conditions aging 2 hours, after material filtering, spend deionized water 2 times, filter cake 120 DEG C of dryings after 5 hours, 340 DEG C of roastings 6 hours, 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 60%; ZnO35 is %; Al
2o
3be 15%.The character of catalyst: specific area is 145m
2/ g, pore volume is 0.360 cm
3/ g.
Embodiment 4
In dissolving tank 1, add 500mL water, add 188gCu (NO respectively
3)
23H
2o and 83gZn (NO
3)
26H
2o dissolves, and preparating acid sex work solution A, adds 500mL water in dissolving tank 2, and then add sodium metaaluminate 48 grams dissolving, prepare alkaline working solution B, add 350mL water in retort, temperature rises to 77 DEG C.When stirring, by solution A, solution B and CO
2and stream adds plastic in retort, CO
2concentration is 70v%, plastic reaction temperature 77 DEG C, gelation time 1.2 hours, 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 3.5.Be 8.6 ± 0.2 at pH after plastic, temperature is under 77 DEG C of conditions aging 3 hours, after material filtering, spend deionized water 4 times, filter cake 100 DEG C of dryings 6 hours, 350 DEG C of roastings 4 hours, 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 59%; ZnO is 29%; Al
2o
3be 12%.The character of catalyst: specific area is 182 m
2/ g, pore volume is 0.415 cm
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
2o85g, 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
2o185g, 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 in reaction be 7.8 ± 0.2.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, as follows: CuO is 58%; ZnO is 28%; Al
2o
3be 14%.The character of catalyst: specific area is 75m
2/ g, pore volume is 0.120cm
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
2o185g, 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 3 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, as follows: CuO is 58%; ZnO is 28%; Al
2o
3be 14%.The character of catalyst: specific area is 81m
2/ g, pore volume is 0.117cm
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 every milliliter of catalyst per hour produces the grams of methyl alcohol, 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 | 91.33 | 85.46 | 86.17 | 77.31 | 2.99 | 95.12 |
| B | 92.54 | 83.73 | 85.82 | 75.94 | 3.01 | 96.45 |
| C | 93.11 | 84.56 | 86.02 | 76.64 | 3.08 | 94.37 |
| D | 94.29 | 86.27 | 87.43 | 79.23 | 3.15 | 94.98 |
| E | 81.36 | 74.45 | 67.21 | 60.12 | 1.89 | 80.65 |
| F | 82.89 | 75.59 | 65.30 | 58.95 | 1.74 | 81.39 |
Claims (9)
1. a preparation method for catalst for synthesis of methanol, comprises the following steps:
(1), by wiring solution-forming A soluble in water for the soluble-salt of Cu, Zn, preparation sodium aluminate solution B;
(2), by solution A, solution B and CO
2gas stream add plastic in retort, aging; Add 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%;
(3), the material that obtains of step (2) through washing, filtration, drying, roasting, compression molding, obtain catalst for synthesis of methanol;
Gelation Conditions described in step (2): reaction temperature is 30 ~ 90 DEG C, 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 Cu, Zn soluble-salt described in step (1) is nitrate and/or acetate, in solution A, copper concentration is 1.0 ~ 6.0mol/L, and 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, copper concentration is 2.0 ~ 4.0mol/L, 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 solution A, copper/zinc atom mol ratio is 0.1 ~ 10.0, and (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 described solution A, copper/zinc atom mol ratio is 0.2 ~ 5.0, and (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, 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 ~ 85 DEG C, pH value is 7.0 ~ 9.0, and gelation time is 0.5 ~ 3 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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| 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 |
| CN107790138B (en) * | 2016-08-31 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of copper zinc catalyst and preparation method thereof |
| CN110270384B (en) * | 2018-03-13 | 2021-08-13 | 中国石油化工股份有限公司 | Preparation method of methanol synthesis catalyst |
| CN110314688A (en) * | 2018-03-28 | 2019-10-11 | 国家能源投资集团有限责任公司 | Methanol synthesis catalyst and preparation method thereof |
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| CN1398787A (en) * | 2002-05-31 | 2003-02-26 | 中国石油化工集团公司 | Prepn of gamma-alumina |
| CN1660490A (en) * | 2004-12-21 | 2005-08-31 | 中国科学院广州能源研究所 | Preparation method of synthesizing catalyst of methyl alcohol |
| CN101574649A (en) * | 2009-05-25 | 2009-11-11 | 来安县迅能催化剂有限公司 | Methanol catalyst preparation method |
| CN101927194A (en) * | 2010-08-30 | 2010-12-29 | 淄博泰通催化技术有限公司 | Preparation method of aluminum hydroxide powder containing lanthanum, phosphorus and titanium elements |
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2012
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398787A (en) * | 2002-05-31 | 2003-02-26 | 中国石油化工集团公司 | Prepn of gamma-alumina |
| CN1660490A (en) * | 2004-12-21 | 2005-08-31 | 中国科学院广州能源研究所 | Preparation method of synthesizing catalyst of methyl alcohol |
| CN101574649A (en) * | 2009-05-25 | 2009-11-11 | 来安县迅能催化剂有限公司 | Methanol catalyst preparation method |
| CN101927194A (en) * | 2010-08-30 | 2010-12-29 | 淄博泰通催化技术有限公司 | Preparation method of aluminum hydroxide powder containing lanthanum, phosphorus and titanium elements |
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