CN103372440A - Preparation method of methanol synthesis catalyst - Google Patents
Preparation method of methanol synthesis catalyst Download PDFInfo
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- CN103372440A CN103372440A CN201210442896XA CN201210442896A CN103372440A CN 103372440 A CN103372440 A CN 103372440A CN 201210442896X A CN201210442896X A CN 201210442896XA CN 201210442896 A CN201210442896 A CN 201210442896A CN 103372440 A CN103372440 A CN 103372440A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000010949 copper Substances 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000003292 glue Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 9
- 238000001879 gelation Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002390 adhesive tape Substances 0.000 claims description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 238000000975 co-precipitation Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000012224 working solution Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal hydroxide-carbonate Chemical class 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- MBLVQSMBXDINOI-UHFFFAOYSA-N copper zinc dinitrate Chemical compound [N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-].[Cu+2] MBLVQSMBXDINOI-UHFFFAOYSA-N 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 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 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 improved the activity of catalst for synthesis of methanol and the service life of heat endurance and catalyst.
Find that by a large amount of experiments copper, zinc metal salt solution pass into CO when becoming glue with sodium metaaluminate
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, has so just increased ZnO and has promoted the effect that Cu disperses, and has greatly improved 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 energy.
The preparation method of catalst for synthesis of methanol of the present invention may further comprise the steps:
(1), with the soluble-salt of Cu, 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, aging in the retort;
(3), the material that obtains of step (2) is through washing, filtration, drying, roasting, compression molding, obtains catalst for synthesis of methanol.
Cu described in the step (1), Zn soluble-salt are nitrate and/or acetate, copper (Cu in the solution A
2+) concentration is 1.0～6.0mol/L, is preferably 2.0～4.0mol/L, zinc (Zn in the solution A
2+) concentration is 0.5～5.0mol/L, is preferably 1.0～3.0mol/L, copper/zinc atom mol ratio is 0.1～10.0, is preferably 0.2～5.0, (copper+zinc)/aluminium atomic molar ratio is 0.1～10.0, is preferably 3.0～8.0.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 40～85 ℃, and the pH value is 6.0 ~ 11.0, is preferably 7.0 ~ 9.0, 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 ~ 3.0 hour.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%.
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 ~ 24.0 hour drying time.The condition of described roasting is as follows: 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 respectively 175gCu (NO
3)
23H
2O and 83gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 52 gram dissolvings, prepares alkaline working solution B, adds 350mL water in retort, and temperature rises to 65 ℃.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 65 ℃ of glue reaction temperatures, gelation time 1 hour, 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 3.5.Becoming behind the glue at pH is 8.0 ± 0.2, and temperature is under 75 ℃ of conditions aging 2 hours, behind material filtering, with deionized water washing 3 times, filter cake is in the 300 ℃ of roastings 4 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 56%; ZnO is 31%; Al
2O
3Be 13%.The character of catalyst: specific area is 158m
2/ g, pore volume are 0.367cm
3/ g.
Embodiment 2
To dissolving tank 1 interior adding 500mL water, add respectively 185gCu (NO
3)
23H
2O and 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 58 gram dissolvings, prepares alkaline working solution B, adds 400mL 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 80v%, becomes 70 ℃ 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 4.0.Becoming behind the glue at pH is 8.2 ± 0.2, and temperature is under 80 ℃ of conditions 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 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 58%; ZnO is 28%; Al
2O
3Be 14%.The character of catalyst: specific area is 169 m
2/ g, pore volume are 0.384cm
3/ g.
Embodiment 3
To dissolving tank 1 interior adding 500mL water, add respectively 195gCu (NO
3)
23H
2O and 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 63 gram dissolvings, prepares alkaline working solution B, adds 350mL water in retort, and temperature rises to 60 ℃.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 60 ℃ of glue reaction temperatures, gelation time 1.5 hours, and the pH value that is controlled to rubber cement liquid is 7.3 ± 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 5.0.Becoming behind the glue at pH is 7.8 ± 0.2, and temperature is under 85 ℃ of conditions aging 2 hours, behind material filtering, with deionized water washing 2 times, filter cake is 120 ℃ of dryings after 5 hours, 340 ℃ of roastings 6 hours, 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 60%; ZnO35 is %; Al
2O
3Be 15%.The character of catalyst: specific area is 145m
2/ g, pore volume are 0.360 cm
3/ g.
Embodiment 4
To dissolving tank 1 interior adding 500mL water, add respectively 188gCu (NO
3)
23H
2O and 83gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 48 gram dissolvings, prepares alkaline working solution B, adds 350mL water in retort, and temperature rises to 77 ℃.In situation about stirring, with solution A, solution B and CO
2And stream adds one-tenth glue in the retort, CO
2Concentration is 70v%, becomes 77 ℃ of glue reaction temperatures, gelation time 1.2 hours, 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 3.5.Becoming behind the glue at pH is 8.6 ± 0.2, and temperature is under 77 ℃ of conditions aging 3 hours, behind material filtering, with deionized water washing 4 times, filter cake is 100 ℃ of dryings 6 hours, 350 ℃ of roastings 4 hours, 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 59%; ZnO is 29%; Al
2O
3Be 12%.The character of catalyst: specific area is 182 m
2/ g, pore volume are 0.415 cm
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
2O85g 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 obtain water white sodium aluminate solution, and are for subsequent use.
Take by weighing Cu (NO
3)
23H
2O185g, 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 in reaction is 7.8 ± 0.2.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, as follows: CuO is 58%; ZnO is 28%; Al
2O
3Be 14%.The character of catalyst: specific area is 75m
2/ g, pore volume are 0.120cm
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
2O185g, 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, keeps 80 ℃ of precipitation temperatures; Static 3 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, as follows: CuO is 58%; ZnO is 28%; Al
2O
3Be 14%.The character of catalyst: specific area is 81m
2/ g, pore volume are 0.117cm
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 catalyst 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 | 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 (11)
1. the preparation method of a catalst for synthesis of methanol may further comprise the steps:
(1), with the soluble-salt of Cu, 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, aging in the retort;
(3), the material that obtains 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 Cu described in the step (1), Zn soluble-salt are nitrate and/or acetate, copper concentration is 1.0～6.0mol/L in the solution A, and zinc concentration is 0.5～5.0mol/L; 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 copper concentration is 2.0～4.0mol/L in step (1) solution A, zinc concentration is 1.0～3.0mol/L; 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 solution A 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 solution A 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 40～85 ℃, and the pH value is 7.0 ~ 9.0, and gelation time is 0.5 ~ 3 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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| 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 |
| CN107790138A (en) * | 2016-08-31 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of copper zinc catalyst and preparation method thereof |
| CN110270384A (en) * | 2018-03-13 | 2019-09-24 | 中国石油化工股份有限公司 | A kind of preparation method of methanol synthesis catalyst |
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