CN102019181A - Mesoporous material and preparation method thereof and synthesis methanol catalyst and preparation method thereof - Google Patents
Mesoporous material and preparation method thereof and synthesis methanol catalyst and preparation method thereof Download PDFInfo
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- CN102019181A CN102019181A CN2010105251597A CN201010525159A CN102019181A CN 102019181 A CN102019181 A CN 102019181A CN 2010105251597 A CN2010105251597 A CN 2010105251597A CN 201010525159 A CN201010525159 A CN 201010525159A CN 102019181 A CN102019181 A CN 102019181A
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Abstract
The invention relates to a mesoporous material and a preparation method thereof, and a synthesis methanol catalyst and a preparation method thereof, the mesoporous material is composed of the following components by weight percentage: 1%-30% of CuO, 0.5%-20% of Zn and 50%-98.5% of Al2O3; the preparation method of the mesoporous material comprises the following steps: dissolving soluble salts of cupper, zinc and aluminum in deionized water, uniformly mixing the solution with template agent to form blended solution, adjusting pH value, and then, transferring the blended solution to a reaction kettle to generate blue floccus, washing the floccus with water, and filtering to get filter cakes, drying, baking for 2-100 hours, and getting the mesoporous material; the synthesis methanol catalyst is composed of the following components by weight percentage: 30%-70% of CuO, 15%-40% of Zn and 5%-30% of Al2O3; the preparation method of the synthesis methanol catalyst comprises the following steps: using the mesoporous material as a carrier, depositing the Cu and the Zn on a surface of the carrier by a deposition precipitation method to form the parent substance of the synthesis methanol catalyst, and orderly washing, drying, prilling, roasting and shaping the parent substance to get the synthesis methanol catalyst.
Description
Technical field
The present invention relates to a kind of mesoporous material and preparation method thereof and catalst for synthesis of methanol its preparation method, belong to the organic chemistry synthesis technical field.
Background technology
Cu-Zn-Al
2O
3Catalyst is widely used in industrial processes such as low pressure methanol synthesis reaction, CO water gas shift reaction, hydrogen production from methanol-steam reforming, is class purposes catalyst very widely, is class purposes catalyst very widely; Along with the maximization of industrial installation and the raising of automatization level, to Cu-Zn-Al
2O
3The performance of catalyst has proposed more and more higher requirement, develop high performance catalyst and have extremely-huge economic and social benefit undoubtedly, especially along with the development of Coal Chemical Industry, more and more higher requirement, the Cu-Zn-Al that it is used have been proposed for the performance of catalst for synthesis of methanol
2O
3Catalyst generally prepares with coprecipitation.A kind of preparation method of catalst for synthesis of methanol is for example disclosed among the DD296855, they are with the aqueous solution of the soluble-salt of copper, zinc, aluminium and alkali carbonate co-precipitation, scope at 20～60 ℃, two stages of precipitation, precipitate under lower pH (4.5-5.5) condition earlier, the reaction later stage will be precipitated the pH value and mention 6～8.The Can1011325 patent disclosure a kind of technology of preparing of catalst for synthesis of methanol, they are that the preparation with catalyst masterbatch is divided into two parts: at first prepare zinc-aluminium coprecipitation mixture, in addition with the aqueous solution of the soluble-salt of copper-zinc and the subcarbonate that alkali-metal carbonate coprecipitation generates a kind of copper-zinc, then two kinds of material making beating are mixed, through washing, drying, roasting, play the sheet moulding, it is said that the catalyst that makes with this law has the better heat-resisting performance.The performance of the catalyst of coprecipitation preparation is not fully up to expectations, and for example specific surface is less, causes activity of such catalysts lower.Owing to be subjected to preparation method's restriction itself, be difficult to the performance of catalyst is carried out significant improvement with coprecipitation, must seek new method for preparing catalyst.
Mesopore molecular sieve is the new function material that a class has regular pore passage structure, and its specific area is generally at 500m
2More than/the g, the major obstacle that present mesoporous material exists as catalyst is hole wall thin (2-3nm), and heat endurance is relatively poor, and structure is caved in easily; The another one shortcoming is content of heteroatoms lower (generally being lower than 20%), is difficult to form constitutionally stable mesoporous material when content of heteroatoms is high, and consequently the active site in the mesoporous material of Xing Chenging is less, causes the catalyst overall activity lower; How improving the thermal stability and the content of heteroatoms thereof of mesoporous material, is the key point that is applied to catalytic field.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of mesoporous material and preparation method thereof and catalst for synthesis of methanol and preparation method thereof are provided, improve its stability, the purpose that specific area is big to reach.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of mesoporous material, described mesoporous material is made up of each raw material of following percentage by weight: CuO 1%～30%, ZnO 0.5%～20% and Al
2O
350%～98.5%.
The beneficial effect of medium catalyst of the present invention is: mesoporous material of the present invention, promptly mesoporous Cu-Zn-Al
2O
3Have fabulous heat endurance and bigger specific area, and its compound with regular structure, active site is many.
The another technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of preparation method of mesoporous material may further comprise the steps:
1) the solubility salt with copper, zinc, aluminium is dissolved in the deionized water altogether, and the template agent is dissolved in the deionized water in another container, then these two kinds of aqueous solution is fully mixed under strong mixing, generates a kind of even mixed solution;
2) with alkaline solution the pH value of above-mentioned mixed solution is adjusted between 6～14, continue again to stir 0.5～1 hour, then mixed solution is transferred to and under 5 ℃～200 ℃ synthesis temperature, continued reaction 2～720 hours in the stainless steel cauldron, after reaction finishes, be cooled to room temperature, take out the blue floccule that generates in the reactor;
3) the blue floccule that will take out is washed, is filtered and obtain filter cake, and filter cake is carried out drying under 10 ℃～200 ℃ temperature, then with dried filter cake in air in 250 ℃～650 ℃ roasting temperature 2～100 hours, promptly.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the solubility salt of the copper described in the described step 1), zinc, aluminium can be nitrate, sulfate, chloride or acetate.
Further, the aluminium salt described in the described step 1) also can be the polymeric aluminum colloidal sol of aluminium polychloride, polyaluminium sulfate or polymerization aluminum nitrate.
Further, the template agent described in the described step 1) is a kind of or any several mixture in cationic surfactant, anion surfactant, non-ionic surface active agent, the amphoteric surfactant.
Further, the alkaline solution described step 2) is NaOH, NaHCO
3, Na
2CO
3, KOH, KHCO
3Or K
2CO
3The aqueous solution.
Further, the pH value described step 2) is preferably 7～12.
Further, described step 2) synthesis temperature in the reactor is preferably 15 ℃～150 ℃, and the reaction time is preferably 10～300 hours.
Further, filter cake is preferable over 20 ℃～150 ℃ dryings in the described step 3).
Further, filter cake is preferable over 300 ℃～550 ℃ in the described step 3), roasting 3～30 hours.
The another technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of catalyst for methanol, to make by above-mentioned described mesoporous material, and described catalyst for methanol is made up of each raw material of following percentage by weight: CuO 30%～70%, and ZnO 15%～40%, Al
2O
3Content is 5%～30%.
The beneficial effect of catalyst for methanol of the present invention is: this catalyst surface area is big, and Stability Analysis of Structures, has fabulous catalytic activity.
The technical scheme again that the present invention solves the problems of the technologies described above is as follows: the preparation method of catalst for synthesis of methanol, use above-mentioned mesoporous material as carrier, adopt deposition-precipitation method that Cu and Zn are deposited on formation catalst for synthesis of methanol parent on the carrier surface, parent is more successively through washing, drying, granulation, roasting, moulding, promptly.
Further, described deposition-precipitation method is for to be deposited on the mesoporous material with the soluble-salt of alkaline aqueous solution with Cu and Zn.
Further, described deposition-precipitation method is for to be deposited on the mesoporous material with the soluble-salt of alkaline aqueous solution with Cu and Zn.
Further, described alkaline solution is meant NaOH, NaHCO
3, Na
2CO
3, KOH, KHCO
3Or K
2CO
3The aqueous solution.
Further, the solubility salt of described Cu and Zn is nitrate, sulfate, chloride or acetate.
The specific area of mesoporous material of the present invention is greater than 500m
2/; The specific area of described catalyst for methanol is greater than 150 m
2/ g.
Description of drawings
Fig. 1 represents the XRD spectra that mesoporous material of the present invention is measured with xrd method, and abscissa is represented diffraction peak intensity among the figure, and ordinate is represented the angle of diffraction.
The specific embodiment
Below in conjunction with accompanying drawing principle of the present invention and feature are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
Embodiment
Embodiment 1
Take by weighing Cu (NO respectively
3)
23H
2O 2.5g, Zn (NO
3)
26H
2O 1.5g, Al (NO
3)
39H
2O 20g, miscible in the 100mL deionized water; Take by weighing 1g trimethyl cetyl ammonium bromide and be dissolved in the 100mL deionized water, under vigorous stirring, two kinds of solution are mixed then, the pH value is adjusted to 8.5, continue to stir 60 minutes with the 1M NaOH aqueous solution.The pasty material that generates is transferred in the stainless steel synthesis reactor of 300mL and be warmed up to 120 ℃ and continue reaction 100 hours, reaction finishes to be cooled to room temperature, material is drawn off and repeatedly wash with centrifuge, filter cake is at room temperature dry, then in tube furnace under air atmosphere 550 ℃ of roastings 3 hours, obtain a kind of solid matter, measuring its specific area with nitrogen adsorption method (BET method) is 520 m
2/ g, xrd method measure it and have meso-hole structure, illustrate that prepared material is a mesoporous material of the present invention.
Above-mentioned mesoporous material with the making beating of 200mL deionized water, is taken by weighing Cu (NO respectively then
3)
23H
2O 20g, Zn (NO
3)
26H
2O 10g is dissolved in wherein, under agitation the pH value is adjusted to 8.5 with the 1M NaOH aqueous solution, continue to stir 3 hours, then the washing, suction filtration, material in 120 ℃ of dryings 10 hours, is crushed to 10～20 orders in baking oven, in Muffle furnace in 350 ℃ of roastings 5 hours, be pressed into sheet with tablet press machine at last, promptly obtain a kind of catalst for synthesis of methanol A.
Embodiment 2
Take by weighing Cu (NO respectively
3)
23H
2O 3g, Zn (NO
3)
26H
2O 1.5g, aluminium polychloride (contains Al
2O
320%) 10g, miscible in the 100mL deionized water; Take by weighing the 2g dodecyl sodium sulfate and be dissolved in the 100mL deionized water, under vigorous stirring, two kinds of solution are mixed then, the pH value is adjusted to 7.5, continue to stir 30 minutes with the 1M KOH aqueous solution.The pasty material that generates is transferred in the stainless steel synthesis reactor of 300mL and be warmed up to 30 ℃ and continue reaction 250 hours, reaction finishes, material is drawn off and repeatedly wash with centrifuge, filter cake is following dry 10 hours at 180 ℃, then in tube furnace under air atmosphere 250 ℃ of roastings 90 hours, obtain a kind of solid matter, measuring its specific area with nitrogen adsorption method (BET method) is 510 m
2/ g, xrd method measure it and have meso-hole structure, illustrate that prepared material is a mesoporous material of the present invention.
Above-mentioned mesoporous material with the making beating of 200mL deionized water, is taken by weighing Cu (NO respectively then
3)
23H
2O 50g, Zn (NO
3)
26H
2O 40g is dissolved in wherein, under agitation uses 1M Na
2CO
3The aqueous solution adjusts to 7.5 with the pH value, continues to stir 5 hours, then washing, suction filtration, material in 100 ℃ of dryings 15 hours, is crushed to 10～20 orders in baking oven, in Muffle furnace in 320 ℃ of roastings 6 hours, be pressed into sheet with tablet press machine at last, promptly obtain a kind of catalst for synthesis of methanol B.
Embodiment 3
Take by weighing Cu (NO respectively
3)
23H
2O 0.5g, Zn (NO
3)
26H
2O 3.5g, aluminium polychloride (contains Al
2O
320%) 20g, miscible in the 100mL deionized water; Take by weighing the 2g betaine and be dissolved in the 100mL deionized water, under vigorous stirring, two kinds of solution are mixed then, the pH value is adjusted to 10.5, continue to stir 60 minutes with the 1M KOH aqueous solution.The pasty material that generates is transferred in the stainless steel synthesis reactor of 300mL and be warmed up to 150 ℃ and continue reaction 10 hours, reaction finishes to be cooled to room temperature, material is drawn off and repeatedly wash with centrifuge, filter cake was 100 ℃ of dryings 5 hours, then in tube furnace under air atmosphere 350 ℃ of roastings 25 hours, obtain a kind of solid matter, measuring its specific area with nitrogen adsorption method (BET method) is 525 m
2/ g, xrd method measure it and have meso-hole structure, illustrate that prepared material is a mesoporous material of the present invention.
According to the mesoporous material that embodiment 3 identical methods prepare, the embodiment 5-9 that the soluble-salt of described copper, zinc, aluminium and alkaline solution kind and the pH that adjusts with alkaline solution are different is as shown in table 1 below.
Table 1
The mesoporous material that the foregoing description 3 makes is pulled an oar with the 200mL deionized water, take by weighing Cu (NO then respectively
3)
23H
2O 100g, Zn (NO
3)
26H
2O 35g is dissolved in wherein, under agitation uses 1M Na
2CO
3The aqueous solution adjusts to 9.5 with the pH value, continues to stir 2 hours, then washing, suction filtration, material in 150 ℃ of dryings 2 hours, is crushed to 10～20 orders in baking oven, in Muffle furnace in 450 ℃ of roastings 5 hours, be pressed into sheet with tablet press machine at last, promptly obtain a kind of catalst for synthesis of methanol C.
Embodiment 9
Take by weighing Cu (NO respectively
3)
23H
2O 2g, Zn (NO
3)
26H
2O 0.5g, the polymerization aluminum nitrate (contains Al
2O
320%) 20g, miscible in the 100mL deionized water; Take by weighing the 2g sodium laurate and be dissolved in the 100mL deionized water, under vigorous stirring, two kinds of solution are mixed then, the pH value is adjusted to 9.5, continue to stir 60 minutes with the 1M KOH aqueous solution.The pasty material that generates is transferred in the stainless steel synthesis reactor of 300mL and be warmed up to 100 ℃ and continue reaction 150 hours, reaction finishes to be cooled to room temperature, material is drawn off and repeatedly wash with centrifuge, filter cake was 150 ℃ of dryings 15 hours, then in tube furnace under air atmosphere 320 ℃ of roastings 10 hours, obtain a kind of solid matter, measuring its specific area with nitrogen adsorption method (BET method) is 515 m
2/ g, xrd method measure it and have meso-hole structure, illustrate that prepared material is a mesoporous material of the present invention.
Use the feedstock production mesoporous material identical with embodiment 9, the embodiment 5-9 that described other parameters are different is as shown in table 2 below.
Table 2
The mesoporous material that the foregoing description 9 makes is pulled an oar with the 200mL deionized water, take by weighing Cu (NO then respectively
3)
23H
2O 45g, Zn (NO
3) 26H
2O 45g is dissolved in wherein, under agitation uses 1M Na
2CO
3The aqueous solution adjusts to 7.5 with the pH value, continues to stir 5 hours, then washing, suction filtration, material in 120 ℃ of dryings 10 hours, is crushed to 10～20 orders in baking oven, in Muffle furnace in 450 ℃ of roastings 5 hours, be pressed into sheet with tablet press machine at last, promptly obtain a kind of catalst for synthesis of methanol D.
According to the catalst for synthesis of methanol that embodiment 9 identical methods prepare, diverse embodiment 10-13 is as shown in table 3 below for described alumino-silicate, adhesive and ammonium salt aqueous solution.
Table 3
The sample number into spectrum of embodiment 11,12,13 and 14 prepared catalst for synthesis of methanol correspondences is E, F, G, H
As seen the XRD spectra that the mesoporous material that the foregoing description is produced is measured with xrd method has formed really from Fig. 1 and to have stablized regular meso-hole structure, is a kind of desirable mesoporous material.
The comparative example 1
Take by weighing Cu (NO
3)
23H
2O 45g, Zn (NO
3)
26H
2O 20g is dissolved in the 250mL deionized water; Take by weighing Na
2CO
355g is dissolved in the 500mL deionized water.With the also stream reaction under 70 ℃～90 ℃ condition of two kinds of solution, the control pH value in reaction is 7.0～9.0, reacts the adding Al (OH) that finishes
35g continue to stir 60 minutes, material after washing in baking oven in 100 ℃～150 ℃ dryings 4 hours, be crushed to below 10 orders, in Muffle furnace,, cool off the deflocculated graphite of back adding 2% and 3% deionized water in 300 ℃ of roastings 4 hours, play the sheet moulding behind the mixing, the gained catalyst is called sample I.
The comparative example 2
Take by weighing Cu (NO
3)
23H
2O 55g, Zn (NO
3)
26H
2O 30g, Al (NO
3)
39H
2O 15g is dissolved in the 350mL deionized water; Take by weighing Na
2CO
355g is dissolved in the 500mL deionized water.With the also stream reaction under 40 ℃～60 ℃ condition of two kinds of solution, beginning to control pH value in reaction is 4.5～5.4, the reaction proceed to the salt consumption 1/3rd after, pH value in reaction is adjusted into 6～8, reinforced finishing continues to stir 60 minutes, material after washing in baking oven in 100 ℃～150 ℃ dryings 4 hours, be crushed to below 10 orders, in Muffle furnace in 300 ℃ of roastings 4 hours, the deflocculated graphite of cooling back adding 2% and 5% deionized water, play the sheet moulding behind the mixing, the gained catalyst is called sample J.
Concrete experimental example
For the catalst for synthesis of methanol that proves above-mentioned mesoporous material preparation has advantages of high catalytic activity, the spy has done two catalst for synthesis of methanol that the traditional coprecipitation of usefulness prepares, and carries out the energy comparative determination.
Experimental example 1
Above sample is estimated its reactivity and heat resistance with the pressurization evaluating apparatus.Evaluation method is: earlier catalyst sample is crushed to 40～60 orders, measures 5mL and dilute by 1:1 with quartz sand.Use 5%H earlier
2/ N
2Carry out temperature programmed reduction, then 240 ℃ of reaction temperatures, pressure 5.0MPa, air speed is 10000h
-1Condition under carry out activity rating.Reactor feed gas consists of CO 11～13%, CO
22～4%, N
24～5%, CH
44～5%, surplus is H
2Collect the methyl alcohol that produces with cold-trap, calculate the space-time yield of methyl alcohol.The heat-resistance test condition is: handled 5 hours in 400 ℃ under the synthesis gas atmosphere, and then measure its reactivity, other condition is the same, and the result is as shown in table 4.
Table 4 activity rating and heat resistance experimental result
Data declaration in the table 4, the low-temperature reactivity of catalyst of the present invention and heat resistance obviously are better than the catalyst of existing industrial process preparation.
Experimental example 2
With the BET determination of nitrogen adsorption specific area of each sample, the result is as shown in table 4.
The specific area result of table 5 embodiment and Comparative Examples
| Catalyst | A | B | C | D | E | F | G | H | I | J |
| Specific surface/m2g -1 | 152.3 | 156.2 | 154.3 | 151.5 | 150.8 | 153.6 | 155.2 | 151.3 | 78.9 | 69.8 |
The above only is preferred embodiment of the present invention, and is in order to restriction the present invention, within the spirit and principles in the present invention not all, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (14)
1. a mesoporous material is characterized in that, described mesoporous material is made up of each raw material of following percentage by weight: CuO 1%～30%, ZnO 0.5%～20% and Al
2O
350%～98.5%.
2. the preparation method of mesoporous material according to claim 1 is characterized in that, may further comprise the steps:
1) the solubility salt with copper, zinc, aluminium is dissolved in the deionized water altogether, and the template agent is dissolved in the deionized water in another container, then these two kinds of aqueous solution is fully mixed under strong mixing, generates a kind of even mixed solution;
2) with alkaline solution the pH value of above-mentioned mixed solution is adjusted between 6～14, continue again to stir 0.5～1 hour, then mixed solution is transferred to and under 5 ℃～200 ℃ synthesis temperature, continued reaction 2～720 hours in the stainless steel cauldron, after reaction finishes, be cooled to room temperature, take out the blue floccule that generates in the reactor;
3) the blue floccule that will take out is washed, is filtered and obtain filter cake, and filter cake is carried out drying under 10 ℃～200 ℃ temperature, then with dried filter cake in air in 250 ℃～650 ℃ roasting temperature 2～100 hours, promptly.
3. the preparation method of mesoporous material according to claim 2 is characterized in that, the solubility salt of the copper described in the described step 1), zinc, aluminium is nitrate, sulfate, chloride or acetate.
4. the preparation method of mesoporous material according to claim 2 is characterized in that, the aluminium salt described in the described step 1) is the polymeric aluminum colloidal sol of aluminium polychloride, polyaluminium sulfate or polymerization aluminum nitrate.
5. according to the preparation method of each described mesoporous material of claim 2 to 4, it is characterized in that the template agent described in the described step 1) is a kind of or any several mixture in cationic surfactant, anion surfactant, non-ionic surface active agent, the amphoteric surfactant.
6. according to the preparation method of each described mesoporous material of claim 2 to 4, it is characterized in that described step 2) described in alkaline solution be NaOH, NaHCO
3, Na
2CO
3, KOH, KHCO
3Or K
2CO
3The aqueous solution.
7. according to the preparation method of each described mesoporous material of claim 2 to 4, it is characterized in that described step 2) in the pH value be 7～12.
8. according to the preparation method of each described mesoporous material of claim 2 to 4, it is characterized in that described step 2) in synthesis temperature in the reactor be 15 ℃～150 ℃, the reaction time is 10～300 hours.
9. according to the preparation method of each described mesoporous material of claim 2 to 4, it is characterized in that, in the described step 3) filter cake in 20 ℃～150 ℃ dryings, then in 300 ℃～550 ℃, roasting 3～30 hours.
10. a catalst for synthesis of methanol is characterized in that, is made by the described mesoporous material of claim 1, and described catalst for synthesis of methanol is made up of each raw material of following percentage by weight: CuO 30%～70%, and ZnO 15%～40%, Al
2O
3Content is 5%～30%.
11. the preparation method of catalst for synthesis of methanol according to claim 10, it is characterized in that: mesoporous material as claimed in claim 1 is as carrier, adopt deposition-precipitation method that Cu and Zn are deposited on formation catalst for synthesis of methanol parent on the carrier surface, parent is more successively through washing, drying, granulation, roasting, moulding, promptly.
12. the preparation method of catalst for synthesis of methanol according to claim 11 is characterized in that: described deposition-precipitation method is for to be deposited on the mesoporous material with the soluble-salt of alkaline aqueous solution with Cu and Zn.
13. the preparation method according to claim 11 or 12 described catalst for synthesis of methanol is characterized in that: described alkaline solution is meant NaOH, NaHCO
3, Na
2CO
3, KOH, KHCO
3Or K
2CO
3The aqueous solution.
14. the preparation method of catalst for synthesis of methanol according to claim 12 is characterized in that: the solubility salt of described Cu and Zn is nitrate, sulfate, chloride or acetate.
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Cited By (9)
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|---|---|---|---|---|
| CN102614937A (en) * | 2012-03-09 | 2012-08-01 | 烟台大学 | Mesoporous material and preparation method thereof and catalyst and preparation method thereof |
| CN102614936A (en) * | 2012-03-09 | 2012-08-01 | 烟台大学 | Mesoporous material and preparation method thereof as well as catalyst and preparation method thereof |
| CN102688769A (en) * | 2012-06-14 | 2012-09-26 | 烟台大学 | Mesoporous material and preparation method thereof as well as catalyst and preparation method thereof |
| CN102698814A (en) * | 2012-06-14 | 2012-10-03 | 烟台大学 | Mesoporous material and preparation method thereof as well as catalyst and preparation method thereof |
| CN103611542A (en) * | 2013-11-07 | 2014-03-05 | 青岛文创科技有限公司 | Methanol synthesis catalyst and preparation method thereof |
| CN108114739A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | Support type multi-stage porous HZSM-5 catalyst |
| CN110624599A (en) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | Methanol synthesis catalyst and preparation method thereof |
| CN112169801A (en) * | 2019-07-02 | 2021-01-05 | 中石化南京化工研究院有限公司 | High, medium and low pressure methanol synthesis catalyst and preparation method thereof |
| CN113209974A (en) * | 2021-05-06 | 2021-08-06 | 淮阴工学院 | Mesoporous Cu-ZnO/Al2O3-ZrO2Composite catalyst and preparation method and application thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614937A (en) * | 2012-03-09 | 2012-08-01 | 烟台大学 | Mesoporous material and preparation method thereof and catalyst and preparation method thereof |
| CN102614936A (en) * | 2012-03-09 | 2012-08-01 | 烟台大学 | Mesoporous material and preparation method thereof as well as catalyst and preparation method thereof |
| CN102698814B (en) * | 2012-06-14 | 2015-06-24 | 烟台大学 | Mesoporous material and preparation method thereof as well as catalyst and preparation method thereof |
| CN102698814A (en) * | 2012-06-14 | 2012-10-03 | 烟台大学 | Mesoporous material and preparation method thereof as well as catalyst and preparation method thereof |
| CN102688769B (en) * | 2012-06-14 | 2015-01-14 | 烟台大学 | Mesoporous material and preparation method thereof as well as catalyst and preparation method thereof |
| CN102688769A (en) * | 2012-06-14 | 2012-09-26 | 烟台大学 | Mesoporous material and preparation method thereof as well as catalyst and preparation method thereof |
| CN103611542A (en) * | 2013-11-07 | 2014-03-05 | 青岛文创科技有限公司 | Methanol synthesis catalyst and preparation method thereof |
| CN103611542B (en) * | 2013-11-07 | 2016-08-17 | 青岛文创科技有限公司 | A kind of methanol synthesis catalyst and preparation method thereof |
| CN108114739A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | Support type multi-stage porous HZSM-5 catalyst |
| CN108114739B (en) * | 2016-11-28 | 2020-05-15 | 中国石油化工股份有限公司 | Supported multi-stage pore HZSM-5 catalyst |
| CN110624599A (en) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | Methanol synthesis catalyst and preparation method thereof |
| CN112169801A (en) * | 2019-07-02 | 2021-01-05 | 中石化南京化工研究院有限公司 | High, medium and low pressure methanol synthesis catalyst and preparation method thereof |
| CN112169801B (en) * | 2019-07-02 | 2023-06-20 | 中国石油化工股份有限公司 | High-medium-low pressure methanol synthesis catalyst and preparation method thereof |
| CN113209974A (en) * | 2021-05-06 | 2021-08-06 | 淮阴工学院 | Mesoporous Cu-ZnO/Al2O3-ZrO2Composite catalyst and preparation method and application thereof |
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