CN103372441A - Preparation method of methanol synthesis catalyst - Google Patents
Preparation method of methanol synthesis catalyst Download PDFInfo
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- CN103372441A CN103372441A CN2012104429318A CN201210442931A CN103372441A CN 103372441 A CN103372441 A CN 103372441A CN 2012104429318 A CN2012104429318 A CN 2012104429318A CN 201210442931 A CN201210442931 A CN 201210442931A CN 103372441 A CN103372441 A CN 103372441A
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- zinc
- methanol
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Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 34
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000010949 copper Substances 0.000 claims abstract description 28
- 239000011701 zinc Substances 0.000 claims abstract description 28
- 230000032683 aging Effects 0.000 claims abstract description 27
- 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 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 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 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 10
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000003292 glue Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 13
- 239000012065 filter cake Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 10
- 238000001879 gelation Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 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
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-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
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 34
- 230000000694 effects Effects 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 239000012266 salt solution Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 28
- 238000000975 co-precipitation Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000012224 working solution Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000004568 cement Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229960004643 cupric oxide Drugs 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
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 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
- 239000003153 chemical reaction reagent 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
- 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
- 150000007513 acids Chemical class 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
- 229910052799 carbon Inorganic materials 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
- 238000001816 cooling Methods 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle 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 steps of adding a soluble salt solution of zinc, a sodium metaaluminate solution and CO2 gas in a parallel flow mode and gelling, aging under the condition of stirring, adding basic copper carbonate while aging, soaking the product in organic solvents after washing and filtration, and then forming to prepare the methanol synthesis catalyst. The method has the beneficial effects of improving the physical and chemical properties of the catalyst, increasing the specific surface area of the catalyst, improving the synergism between the main active metal component copper and the cocatalyst metal component zinc, improving the dispersibility of an active phase, and improving the activity and stability of the catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of catalst for synthesis of methanol, be specifically related to a kind of preparation method with catalst for synthesis of methanol of high activity, good heat resistance.
Background technology
Methyl alcohol is a kind of extremely important industrial chemicals, be widely used in organic synthesis, dyestuff, fuel, medicine, coating and national defense industry, its output is only second to synthetic ammonia and ethene, occupies the third place in the world, in recent years methyl alcohol demand and the production capacity sustainable growth along with industrial development.
Industrial methyl alcohol is general with containing H
2, CO, CO
2Synthesis gas under certain pressure, temperature and catalyst existence condition, produce.In generally adopting in the world at present, low-pressure vapor phase method synthesizing methanol, catalyst system therefor is essentially the mixed oxide of copper, zinc, aluminium.CuO, ZnO, Al in the catalst for synthesis of methanol
2O
3The effect of three components is variant, and CuO is main active component, ZnO and Al
2O
3Be auxiliary agent.Method for preparing catalyst is generally the mixing subcarbonate of using first coprecipitation (comprise and flow, instead add, just adding coprecipitation) to generate copper zinc, and then add aluminium hydroxide in the pulping process, the slurry that generates through washing, drying, roasting, compression molding.The research of at present catalyst preparation mainly concentrates on optimization and the improvement of preparation method and technique, improve catalyst activity by the ratio that changes catalytic component, the size of crystal grain, size and the pore-size distribution of specific area, improve the copper-based catalysts poor heat stability, selective hanging down and short problem of life-span.Method for preparing catalyst is different, and it is larger that the performance of gained catalyst can differ.
CN 1810357A adopts a traditional step coprecipitation to prepare a kind of catalst for synthesis of methanol.Nitrate mixed solution and NaCO with Cu, Zn, Al, Li
3Solution and stream are titrated in the deionized water of a small amount of high-speed stirred, keep simultaneously the pH of solution between 7 ~ 8, and is aging, suction filtration, washing, dries to get catalyst precarsor, and catalyst precarsor oven dry, roasting get finished product.The method is to adopt a typical step coprecipitation to prepare catalyst for methanol, has added LiNO in preparation process
3
CN 1329938A discloses a kind of preparation method of catalst for synthesis of methanol, and this catalyst is comprised of the oxide of copper, zinc, aluminium.Preparation process: a part is to make the coprecipitate that contains copper, zinc, aluminium compound with coprecipitation, and another part is to make the coprecipitate that contains copper, zinc compound with co-precipitation.The equal thermal decomposition of above-mentioned coprecipitate is the oxide of metal, and then with these two kinds of co-precipitation mixing, washing, dry, roasting, moulding makes catalyst.
CN 1660490A discloses a kind of preparation method of catalst for synthesis of methanol, its preparation process is: coprecipitation prepares adds a small amount of Surfactant OP in the methanol synthesis catalyst process, perhaps fractional precipitation prepares a small amount of Surfactant OP of interpolation in the methanol synthesis catalyst process, makes a kind of catalst for synthesis of methanol.
CN 101574649A discloses a kind of preparation method of catalst for synthesis of methanol, step is the mixed aqueous solution reaction with the aqueous solution of aluminum soluble salt and alkali metal hydroxide-carbonate, generate a kind of transparent meta-aluminate aqueous solution, then with its with contain the copper of water-soluble high-molecular compound, the transparent aqueous solution of zinc salt carries out coprecipitation reaction, generate the mixing co-precipitation of a kind of copper, zinc, aluminium, then through washing, drying, granulation processing, roasting, play the sheet moulding and can make a kind of highly active catalst for synthesis of methanol.
The catalst for synthesis of methanol method of above-mentioned patent Introduction is by adding new auxiliary agent (Li and surfactant), change catalyst preparation process the presoma of (step process changes two step or three step process into) and change Al, come structure, surface acid alkalescence, the electronic property of regulating catalyst, with the activity of improving existing catalyst, selective or life-span.Be to increase the more even of the specific area of catalyst and active ingredient copper and the distribution of co-catalyst zinc but improve catalst for synthesis of methanol the key active and life-span, above patent does not all relate to.
Summary of the invention
For above-mentioned deficiency of the prior art, the invention provides that a kind of technique is simple, the preparation method of easy-operating catalst for synthesis of methanol.The 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.
The inventor finds that by a large amount of experiments the zinc metal salt solution passes into CO when becoming glue with sodium metaaluminate
2Gas carries out precipitation reaction, add basic copper carbonate when aging and prepare catalst for synthesis of methanol, can improve the physico-chemical property of catalyst, increase the specific area of catalyst, increase coordinative role between main metal component copper and the promoter metal component zinc, improve the dispersiveness of active metal component copper, allow reactive metal plays one's part to the full in the catalyst, improve the active and stable of catalyst.
The preparation method of catalst for synthesis of methanol of the present invention may further comprise the steps:
(1), with the soluble-salt of Zn wiring solution-forming A soluble in water, preparation sodium aluminate solution B;
(2), with solution A, solution B and CO
2Gas and stream add one-tenth glue in the retort, and is then aging under stirring condition, adds basic copper carbonate when aging;
(3), the resulting material of step (2) soaks in the solution of filter cake at organic solvent through washing, after filtering, and is dry after filtering, roasting, compression molding obtains catalst for synthesis of methanol.
The soluble-salt of Zn can be nitrate and/or acetate described in the step (1), zinc (Zn in the solution A
2+) concentration is 0.5～5.0mol/L, is preferably 1.0～3.0mol/L, sodium metaaluminate concentration is 1.0～6.0mol/L in the solution B, is preferably 2.0～4.0mol/L.
Become the adhesive tape part described in the step (2): reaction temperature is 30～90 ℃, is preferably 40～80 ℃, and the pH value is 6.0 ~ 11.0, is preferably 7.0 ~ 10.0, and gelation time is 0.2 ~ 4.0 hour, is preferably 0.5 ~ 4.0 hour.Aging temperature is 50～100 ℃ behind the one-tenth glue, is preferably 60～90 ℃, and aging pH value is controlled to be 6.0 ~ 11.0, is preferably 7.0 ~ 10.0, and ageing time is 0.5 ~ 5.0 hour, is preferably 1.0 ~ 3.0 hours.Add CO
2The total amount of gas and the aluminium in the solution B are (with Al
2O
3Meter) mol ratio is 2～8, is preferably 3～6, CO
2Gas concentration is 20v%～99v%, is preferably 40v%～95v%.
In the catalst for synthesis of methanol of the present invention, used copper/zinc mol ratio is 0.1～10, is preferably 0.2～5, and (copper+zinc)/al mole ratio is 0.1～10, is preferably 3～8.
The described washing of step (3) is washed with deionized water, and wash temperature is controlled at 30～90 ℃, is preferably 40～70 ℃.Filter cake is dry under 50 ~ 150 ℃ of conditions, and preferably 60 ~ 120 ℃ of baking temperatures, are preferably 2 ~ 16 hours drying time at 0.5 ~ 24 hour drying time.Described roasting condition is as follows: 300～360 ℃ of roastings 1 ~ 16 hour, be preferably 2 ~ 10 hours.
The described organic solvent of step (3) is one or more in oxygen-containing organic compound and/or the organic compounds containing nitrogen.Wherein said oxygen-containing organic compound is one or more in Organic Alcohol and the organic acid, such as: one or more in ethylene glycol, glycerine, diethylene glycol, butanediol, the aminotriacetic acid etc., in the preferred organic amine of organic compounds containing nitrogen one or more, such as: one or more in ethylenediamine, EDTA, tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, the softex kw etc.Take the mol ratio of copper, zinc and the aluminium sum of oxide as 0.1 ~ 3.0, be preferably 0.3 ~ 2.0 in described organic solvent and the catalyst.Solid-liquid volume ratio when soaking with organic solvent is 1.0 ~ 4.0, is preferably 1.0 ~ 2.5, and organic solvent can soak behind the dilute with water.Soak time is 0.5～12 hour, preferred 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%.
Decomposing oxidation copper after the basic copper carbonate roasting in the inventive method, organic reagent can make the cupric oxide crystal grain of generation little and even, the particle I of cupric oxide is to increase widely the activity of catalyst, allow simultaneously cupric oxide in catalyst, evenly distribute, the coordinative role between main metal component copper and the promoter metal component zinc be can strengthen, catalyst activity and heat resistance also improved.
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 90gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 66 gram dissolvings, prepares alkaline working solution B, adds 450mL 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 80v%, becomes 65 ℃ of glue reaction temperatures, gelation time 1 hour, and the pH value that is controlled to rubber cement liquid is 7.6 ± 0.2.Become in the glue process and add CO
2Al among the total amount of gas and the alkaline working solution B
2O
3Mol ratio is 4.5.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 128 grams, pH is 8.2 ± 0.2 when aging, temperature is 75 ℃, aging 2 hours, behind material filtering, with water purification washing 3 times, filter cake is immersed in the 210 gram tetraethylammonium bromide solution, the solid-liquid volume ratio is 1.2, filter cake soaked after 7 hours, 80 ℃ of dryings 12 hours, 330 ℃ of roastings 5 hours, the material of gained 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 46%; ZnO is 33%; Al
2O
3Be 54%.The character of catalyst: specific area is 146m
2/ g, pore volume are 0.388cm
3/ g.
Embodiment 2
To dissolving tank 1 interior adding 500mL water, add 86gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 28 gram dissolvings, prepares alkaline working solution B, adds 450mL water in retort, and temperature rises to 70 ℃.In situation about stirring with solution A, solution B and CO
2And stream adds one-tenth glue in the retort, CO
2Concentration is 85v%, becomes 70 ℃ of glue reaction temperatures, gelation time 1.5 hours, and the pH value that is controlled to rubber cement liquid is 7.2 ± 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 3.2.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 188 grams, pH is 7.8 ± 0.2 when aging, temperature is 78 ℃, aging 3 hours, behind material filtering, with water purification washing 4 times, filter cake is immersed in the 182 gram softex kw solution, the solid-liquid volume ratio is 1.0, filter cake soaked after 6 hours, 120 ℃ of dryings 6 hours, 360 ℃ of roastings 4 hours, the material of gained 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 60%; ZnO is 32%; Al
2O
3Be 8%.The character of catalyst: specific area is 154m
2/ g, pore volume are 0.392cm
3/ g.
Embodiment 3
To dissolving tank 1 interior adding 500mL water, add 88gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 41 gram dissolvings, prepares alkaline working solution B, adds 600mL water in retort, and temperature rises to 75 ℃.In situation about stirring, with solution A, solution B and CO
2And stream adds one-tenth glue in the retort, CO
2Concentration is 90v%, becomes 75 ℃ of glue reaction temperatures, gelation time 2 hours, and the pH value that is controlled to rubber cement liquid is 8.2 ± 0.2.Become in the glue process and add CO
2Al among the total amount of gas and the alkaline working solution B
2O
3Mol ratio is 3.8.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 150 grams, pH is 8.4 ± 0.2 when aging, temperature is 80 ℃, aging 2 hours, behind material filtering, with water purification washing 5 times, filter cake is dipped in the aqueous solution that contains 176 gram butanediols, the solid-liquid volume ratio is 1.5, filter cake soaked after 6 hours, 90 ℃ of dryings 7 hours, 350 ℃ of roastings 6 hours, the material of gained 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 54%; ZnO is 33%; Al
2O
3Be 13%.The character of catalyst: specific area is 169m
2/ g, pore volume are 0.408cm
3/ g.
Embodiment 4
To dissolving tank 1 interior adding 500mL water, add 103gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 38 gram dissolvings, prepares alkaline working solution B, adds 700mL water in retort, and temperature rises to 80 ℃.In situation about stirring, with solution A and CO
2And stream adds one-tenth glue in the retort, CO
2Concentration is 85v%, becomes 80 ℃ of glue reaction temperatures, gelation time 1 hour, and the pH value that is controlled to rubber cement liquid is 7.0 ± 0.2.Become in the glue process and add CO
2Al among the total amount of gas and the alkaline working solution B
2O
3Mol ratio is 4.0.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 162 grams, pH is 7.6 ± 0.2 when aging, temperature is 80 ℃, aging 2 hours, behind material filtering, with water purification washing 3 times, filter cake is immersed in the aqueous solution that contains 242 gram aminotriacetic acids, the solid-liquid volume ratio is 1.1, soak after 8 hours 120 ℃ of dryings 5 hours, 340 ℃ of roastings 6 hours, the material of gained 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 55%; ZnO is 35%; Al
2O
3Be 10%.The character of catalyst: specific area is 193m
2/ g, pore volume are 0.422cm
3/ g.
Comparative Examples 1
Preparation forms identical reference agent E with the catalyst of embodiment 1, does not add organic reagent in the preparation process, and other step is identical.
To dissolving tank 1 interior adding 500mL water, add 90gZn (NO
3)
26H
2The O dissolving, preparating acid sex work solution A to dissolving tank 2 interior adding 500mL water, then adds sodium metaaluminate 66 gram dissolvings, prepares alkaline working solution B, adds 450mL 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 80v%, becomes 65 ℃ of glue reaction temperatures, gelation time 1 hour, and the pH value that is controlled to rubber cement liquid is 7.6 ± 0.2.Become in the glue process and add CO
2Al among the total amount of gas and the alkaline working solution B
2O
3Mol ratio is 4.5.Begin to wear out in the situation about stirring, add basic copper carbonate (Cu
2(OH)
2CO
3) 128 grams, pH is 8.2 ± 0.2 when aging, temperature is 75 ℃, aging 2 hours, behind material filtering, with water purification washing 3 times, 80 ℃ of dryings of filter cake 12 hours, 330 ℃ of roastings 5 hours, the material of gained add an amount of graphite and hydraulic pressure in blocks, compressing tablet obtains final catalyst E.
The composition of catalyst A, in mass fraction, as follows: CuO is 46%; ZnO is 33%; Al
2O
3Be 54%.The character of catalyst: specific area is 141m
2/ g, pore volume are 0.378cm
3/ g.
Comparative Examples 2
Press the disclosed method for preparing catalyst of CN 101574649A, preparation forms identical reference agent F with the catalyst of embodiment 2.
Take by weighing Al (NO
3)
39H
2O54g adds deionized water 200mL stirring and dissolving, takes by weighing NaOH40g, NaCO
350g is total in molten and the 500mL deionized water.Under 35 ℃ condition, with NaOH-NaCO
350g solution slowly adds Al (NO
3)
3, control terminal point pH 〉=12, it is for subsequent use to obtain water white sodium aluminate solution.
Take by weighing Cu (NO
3)
23H
2O208g, Zn (NO
3)
26H
2O86g 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.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, add the deflocculated graphite of 2wt% and the deionized water of 3wt% after the cooling, play sheet moulding, gained catalyst sample F after being mixed.
The composition of catalyst F, in mass fraction, as follows: CuO is 60%; ZnO is 32%; Al
2O
3Be 8%.The character of catalyst: specific area is 78m
2/ g, pore volume are 0.109cm
3/ g.
Comparative Examples 3
Comparative Examples 3 adopts the catalst for synthesis of methanol of traditional handicraft preparation, and preparation forms identical reference agent G with the catalyst of embodiment 2.
Take by weighing Cu (NO
3)
23H
2O208g, Zn (NO
3)
26H
2O86g is dissolved in wiring solution-forming A in the 850mL deionized water, is heated to 60～85 ℃; 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 70, continues to stir 30min precipitation color and becomes blue-green by blueness, keeps 80 ℃ of precipitation temperatures; Static 2 hours, add 16gAl (OH) in the slip that makes
3, then after filtration, wash to Na
+Content≤0.035wt%, the filter cake that obtains is 110 ℃ 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 G.
The composition of catalyst G, in mass fraction, as follows: CuO is 60%; ZnO is 32%; Al
2O
3Be 8%.The character of catalyst: specific area is 98m
2/ g, pore volume are 0.124cm
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) hydrogen nitrogen mixed gas reduction 16～20h, the highest reduction temperature is 235 ℃.Carry out the activity rating of catalyst at miniature fixed-bed reactor.Loaded catalyst is 5mL, and unstripped gas consists of CO/H
2/ CO
2/ N
2=12/70/3/15(volume ratio), reaction pressure is 5.0MPa, and air speed is 10000h
-1, reaction temperature is 250 ℃, measures CO and CO
2Conversion ratio be the catalyst initial activity.Then with catalyst in synthetic atmosphere with 450 ℃ of heat treatment 5h, drop to again 250 ℃ and measure CO and CO
2Conversion ratio be active after the heat treatment, i.e. heat resistance.Product gas chromatograph analysis, the space-time yield gmL of methanol
-1H
-1Namely every milliliter of grams of producing methyl alcohol per hour the results are shown in Table 1.Find out that from result of the test methanol synthesis catalyst of the present invention has the selective of high activity, heat resistance and excellence.
The evaluation of table 1 catalyst activity and heat resistance experimental result
| Catalyst | Initial activity, % | Initial activity, % | Heat-resisting rear activity, % | Heat-resisting rear activity, % | The methyl alcohol space-time yield, (gmL -1·h -1） | Methyl alcohol is selective, % |
| CO | CO 2 | CO | CO 2 | |||
| A | 97.69 | 86.98 | 88.02 | 78.91 | 3.10 | 95.69 |
| B | 96.58 | 87.54 | 87.85 | 79.37 | 3.25 | 94.15 |
| C | 97.01 | 86.91 | 88.47 | 80.15 | 3.09 | 95.47 |
| D | 96.99 | 86. 35 | 86.74 | 81.69 | 3.34 | 94.73 |
| E | 88.14 | 81.25 | 79.63 | 73.28 | 2.57 | 88.78 |
| F | 75.69 | 69.45 | 67.52 | 59.54 | 1.75 | 75.39 |
| G | 79.36 | 71.69 | 66.25 | 56.34 | 1.69 | 76.74 |
Claims (16)
1. the preparation method of a catalst for synthesis of methanol comprises:
(1), with the soluble-salt of Zn wiring solution-forming A soluble in water, preparation sodium aluminate solution B;
(2), with solution A, solution B and CO
2Gas and stream add one-tenth glue in the retort, and is then aging under stirring condition, adds basic copper carbonate when aging;
(3), the resulting material of step (2) soaks in the solution of filter cake at organic solvent through washing, after filtering, after filtering dry, roasting, compression molding obtains catalst for synthesis of methanol.
2. in accordance with the method for claim 1, it is characterized in that the Zn soluble-salt described in the step (1) is nitrate and/or acetate, zinc concentration is 0.5～5.0mol/L in the solution A; Sodium metaaluminate concentration is 1.0～6.0mol/L in the solution B.
3. in accordance with the method for claim 1, it is characterized in that zinc concentration is 1.0～3.0mol/L in step (1) solution A; Sodium metaaluminate concentration is 2.0～4.0mol/L in the solution B.
4. in accordance with the method for claim 1, it is characterized in that in the described catalst for synthesis of methanol that used copper/zinc atom mol ratio is 0.1～10, (copper+zinc)/aluminium atomic molar ratio is 0.1～10.
5. in accordance with the method for claim 1, it is characterized in that in the described catalst for synthesis of methanol that copper/zinc atom mol ratio is 0.2～5.0, (copper+zinc)/aluminium atomic molar ratio is 3.0～8.0.
6. in accordance with the method for claim 1, it is characterized in that becoming the adhesive tape part described in the step (2): reaction temperature is 30～90 ℃, and the pH value is 6.0 ~ 11.0, and gelation time is 0.2 ~ 4.0 hour; Aging temperature is 50～100 ℃ behind the one-tenth glue, and aging pH value is controlled to be 6.0 ~ 11.0, and ageing time is 0.5 ~ 5.0 hour.
7. in accordance with the method for claim 1, it is characterized in that in the step (2), add CO
2The total amount of gas and the aluminium in the solution B are with Al
2O
3The mol ratio of meter is 2～8, CO
2Gas concentration is 20v%～99v%.
8. in accordance with the method for claim 1, it is characterized in that in the step (2), add CO
2The total amount of gas and the aluminium in the solution B are with Al
2O
3The mol ratio of meter is 3～6.
9. in accordance with the method for claim 1, it is characterized in that becoming the adhesive tape part described in the step (2): reaction temperature is 40～80 ℃, and the pH value is 7.0 ~ 10.0, and gelation time is 0.5 ~ 4.0 hour; Aging temperature is 60～90 ℃ behind the one-tenth glue, and aging pH value is controlled to be 7.0 ~ 10.0, and ageing time is 1.0 ~ 3.0 hours.
10. in accordance with the method for claim 1, it is characterized in that the described organic solvent of step (3) is one or more in oxygen-containing organic compound and/or the organic compounds containing nitrogen.
11. in accordance with the method for claim 10, it is characterized in that described oxygen-containing organic compound is one or more in Organic Alcohol and the organic acid, organic compounds containing nitrogen is one or more in the organic amine.
12. in accordance with the method for claim 10, it is characterized in that oxygen-containing organic compound is one or more in ethylene glycol, glycerine, diethylene glycol, butanediol, the aminotriacetic acid, organic compounds containing nitrogen is one or more in ethylenediamine, EDTA, tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, the softex kw.
13. in accordance with the method for claim 1, it is characterized in that in described organic solvent and the catalyst that mol ratio take copper, zinc and the aluminium sum of oxide is as 0.1 ~ 3.0.
14. in accordance with the method for claim 1, it is characterized in that in the step (3), the solid-liquid volume ratio when soaking with organic solvent is 1.0 ~ 4.0, soak time is 0.5～12 hour.
Be controlled at 30～90 ℃ 15. it is characterized in that in accordance with the method for claim 1, the temperature of the described washing of step (3); Filter cake is dry under 50 ~ 150 ℃ of conditions, and 0.5 ~ 24.0 hour drying time, described roasting condition was as follows: 300～360 ℃ of roastings 1 ~ 16 hour.
16. in accordance with the method for claim 1, 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 |
| CN107774262A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | The preparation method of copper zinc catalyst |
| CN107790137A (en) * | 2016-08-31 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of preparation method of copper zinc catalyst |
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| CN110935456A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing methanol |
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| 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 |
| 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 |
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