CN101327431B - Process for preparing synthetic methanol catalyst - Google Patents
Process for preparing synthetic methanol catalyst Download PDFInfo
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- CN101327431B CN101327431B CN2008101505027A CN200810150502A CN101327431B CN 101327431 B CN101327431 B CN 101327431B CN 2008101505027 A CN2008101505027 A CN 2008101505027A CN 200810150502 A CN200810150502 A CN 200810150502A CN 101327431 B CN101327431 B CN 101327431B
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- nitrate
- methanol
- copper
- catalyst
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 34
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 33
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims abstract description 4
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000003068 static effect Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 238000003483 aging Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052596 spinel Inorganic materials 0.000 abstract description 2
- 239000011029 spinel Substances 0.000 abstract description 2
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000005303 weighing Methods 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 10
- 238000000975 co-precipitation Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012713 reactive precursor Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 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
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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)
Abstract
The present invention provides a preparation method of methanol synthesis catalyst. The catalyst has the preparation technical process as follows: firstly, copper-zinc coprecipitate is prepared; secondly, zinc-aluminium coprecipitate with a spinel structure is prepared; thirdly, copper-aluminium coprecipitate is prepared; then three coprecipitates are mixed and aged and then are washed, dried andcalcined; graphite is added into calcined material to be tabletted into the methanol synthesis catalyst. In weight percentage, the catalyst prepared by the present invention consists of 25 percent to65 percent of CuO, 15 percent to 45 percent of ZnO and 5 percent to 15 percent of Al2O3. The activity and the heat resistance of the catalyst prepared by the present invention are better than that ofthe catalyst prepared by the prior technical production method.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method, be specifically related to a kind of preparation method of catalst for synthesis of methanol.
Background technology
Methyl alcohol is important Organic Chemicals, and output is only second to synthetic ammonia, ethene, occupies the third place in the world.Along with the developing in methyl alcohol market, the output and the consumption figure of methyl alcohol increase gradually.The mesolow method is adopted in the production of methyl alcohol mostly, and the catalyst of mesolow method synthesizing methanol has many shortcomings: poor heat stability, life-span are short, by product is many.Improvement that concentrates on prepared by co-precipitation technology and optimization that the research of Preparation of Catalyst is more add the 4th component and improve activity of such catalysts and selectivity, improve carrier, improve the heat endurance of catalyst, prolong catalyst life.
Usually the catalst for synthesis of methanol preparation is to generate copper zinc mixing subcarbonate with coprecipitation, adds aluminium hydroxide then in pulping process, the slip that is generated through washing, drying, roasting, play the sheet moulding.Though the catalyst of this method preparation can satisfy commercial Application, the development need activity of the energy-saving and cost-reducing and methyl alcohol technology of commercial plant and stability is catalyst better.
Chinese patent CN1810357 adopts coprecipitation to make a kind of catalst for synthesis of methanol.The preparation method may further comprise the steps: at first with nitrate mixed solution and the Na of Cu, Zn, Al, Li
2CO
3Solution and stream are titrated in the deionized water that a small amount of high-speed stirred, and the pH that keeps solution simultaneously is between 7-8; Precipitate then that slip is aging, suction filtration, washing, dry catalyst precarsor, catalyst precarsor oven dry, roasting get finished product.This is the typical one-step technology of catalst for synthesis of methanol.Increased by the 4th component Li simultaneously.
Preparation method's technical process of the catalst for synthesis of methanol that Chinese patent CN1329938 introduces is: catalyst masterbatch is prepared separated into two parts, a part is to make the coprecipitate that contains copper, zinc, aluminium compound with coprecipitation, another part is to make the coprecipitate that contains copper, zinc compound with coprecipitation, but above-mentioned coprecipitate all thermal decomposition is the oxide of metal, with these two kinds of coprecipitates mixing, washing, dry, roasting, moulding makes a kind of high activated catalyst then.
The preparation method of the catalst for synthesis of methanol that Chinese patent CN1660490 relates to, be that coprecipitation prepares interpolation low quantity of surfactant OP in the methanol synthesis catalyst process, perhaps fractional precipitation prepares interpolation low quantity of surfactant OP in the methanol synthesis catalyst process.
Chinese patent CN1660493 relates to a kind of new catalyst for synthesizing copper based methanol and preparation method thereof.Main component is the big surface-active carrier of copper, zinc reactive precursor and submember heat endurance; The preparation method prepares the big surface-active carrier of copper, zinc reactive precursor and heat endurance respectively, mixes then and makes catalyst.It is two-step process that this technology also can be classified as.
The energy-saving and cost-reducing requirement and the fast development of methanol chemistry need be developed more efficiently catalst for synthesis of methanol, and the catalst for synthesis of methanol performance of above-mentioned patent introduction still has improved necessity so that further improve activity of such catalysts and selectivity.It is to make active ingredient copper divide spreading even with co-catalyst zinc and carrier aluminum better that catalst for synthesis of methanol prepares improved main thought, and this patent just is based on such guiding theory.
Summary of the invention
Technical problem to be solved by this invention is at above-mentioned deficiency of the prior art, provide a kind of technology simple, the preparation method of easy-operating catalst for synthesis of methanol is in order to the activity of raising catalst for synthesis of methanol and the service life of heat endurance and catalyst.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of catalst for synthesis of methanol, this method is following three kinds of coprecipitates to be mixed stir and ageing, the slip that makes is through washing, drying and roasting, material after the roasting adds graphite and water, compressing tablet makes catalst for synthesis of methanol, it is characterized in that the preparation process of described three kinds of coprecipitates is:
(a) preparation of copper zinc coprecipitate: adopt counter adding or parallel-flow precipitation, be in the aqueous slkali of 0.5～2M with concentration and the copper nitrate of same concentration and the mixed liquor of zinc nitrate, reaction temperature is 60～85 ℃, it is 7.0～7.5 that reaction finishes terminal point pH, and the mol ratio of copper nitrate and zinc nitrate is 2～5: 1 in the described mixed liquor;
(b) preparation of zinc-aluminium coprecipitate: adopt counter adding or parallel-flow precipitation, be in the aqueous slkali of 0.5～2M with concentration and the aluminum nitrate of same concentration and the mixed liquor of zinc nitrate, reaction temperature is 60～85 ℃, it is 7.0～7.5 that reaction finishes terminal point pH, and the mol ratio of zinc nitrate and aluminum nitrate is 0.5～2: 1 in the described mixed liquor;
(c) preparation of copper aluminium coprecipitate: adopt counter adding or parallel-flow precipitation, be in the aqueous slkali of 0.5～2M with concentration and the aluminum nitrate of same concentration and the mixed liquor of copper nitrate, it is 7.0～7.5 that reaction finishes terminal point pH, reaction temperature is 60～85 ℃, and the mol ratio of copper nitrate and aluminum nitrate is 4～6: 1 in the described mixed liquor.
Aqueous slkali is sodium carbonate, potash or sodium bicarbonate solution described in above-mentioned steps (a), step (b) and the step (c).
Parallel-flow precipitation is finished in having the reactor of stirring or is finished in pipeline static mixer described in above-mentioned steps (a), step (b) and the step (c).
Described mixing mixing time is 30min, and the ageing temperature is 70～75 ℃, and digestion time is 2 hours.
The metal oxide that contains following percentage by weight in the described catalyst: CuO 25～65%, ZnO15～45%, Al
2O
35～15%.
The present invention adopts three-step approach to prepare catalst for synthesis of methanol technology, at first prepares copper zinc coprecipitate, and purpose is to allow active ingredient copper and auxiliary agent zinc good dispersion; Next is the zinc-aluminium coprecipitate that preparation has spinel structure, improves the heat endurance of catalyst; The 3rd step preparation copper aluminium coprecipitate loads on the alumina catalyst support active ingredient copper.Subsequently with above-mentioned three kinds of coprecipitate mixing ageings, washing then, dry, roasting, compressing tablet makes a kind of catalst for synthesis of methanol.
The present invention compared with prior art has the following advantages: the catalyst of the present invention's preparation has the bigger specific surface of catalyst than the conventional method preparation, shows higher methyl alcohol synthesizing activity and heat endurance; Another characteristics of the present invention are to adopt static mixer to finish cocurrent cooling operation in coprecipitation process, have substituted traditional batch (-type) and have stirred precipitation reactor, make easy to controlly, and the catalyst favorable reproducibility helps controlling product quality.
Below by embodiment, technical scheme of the present invention is described in further detail.
The specific embodiment
In following examples, embodiment 1,2 and 3 is for adopting the catalst for synthesis of methanol of traditional handicraft preparation; Embodiment 4 and embodiment 5 are for adopting the catalst for synthesis of methanol of technology preparation of the present invention.
Embodiment 1
Take by weighing 182gCu (NO
3)
23H
2O and 75gZn (NO
3)
26H
2O is dissolved in wiring solution-forming A in the 850mL deionized water, is heated to 60～85 ℃; Take by weighing 106gNa
2CO
3Be dissolved in wiring solution-forming B in the 1000mL deionized water, be heated to 60～85 ℃; Under stirring condition, solution A is joined in the solution B, control terminal point pH is 7.0～7.5, continues to stir 30min precipitation color and becomes blue-green by blueness, keeps 60～85 ℃ of precipitation temperatures, leaves standstill 2～3 hours, adds 10gAl in the slip that makes
2O
3, then after filtration, wash to Na
+Content≤0.035% (w/w), the filter cake that obtains is 100～120 ℃ of oven dry, again 320 ℃ of roastings 4 hours, the material after the roasting adds an amount of graphite and becomes tablet with hydraulic pressure, is the catalst for synthesis of methanol sample.Sample number into spectrum is a.
Embodiment 2
Take by weighing 182gCu (NO
3)
23H
2O, 75gZn (NO
3)
26H
2O and 75gAl (NO
3)
39H
2O is dissolved in wiring solution-forming A in the 850mL deionized water, is heated to 60～85 ℃; Take by weighing 128gNa
2CO
3Be dissolved in wiring solution-forming B in the 1000mL deionized water, be heated to 60～85 ℃; Under stirring condition, solution A is joined in the solution B, control terminal point pH is 7.0～7.5, continues to stir 30min precipitation color and becomes blue-green by blueness, keeps 60～85 ℃ of precipitation temperatures, left standstill 2～3 hours, the slip that makes after filtration, wash to Na
+Content≤0.035% (w/w), the filter cake that obtains is 100～120 ℃ of oven dry, 320 ℃ of roastings 4 hours, the material after the roasting added an amount of graphite and water again, was pressed into tablet and was the catalst for synthesis of methanol sample.Sample number into spectrum is b.
Embodiment 3
Take by weighing 121gCu (NO
3)
23H
2O and 75gZn (NO
3)
26H
2O is dissolved in wiring solution-forming A in the 850mL deionized water, is heated to 60～85 ℃; Take by weighing 60gCu (NO
3)
23H
2O and 75gAl (NO
3)
39H
2O is dissolved in the 400mL deionized water, and wiring solution-forming B is heated to 60～85 ℃.Take by weighing 128gNa
2CO
3Be dissolved in wiring solution-forming C in the 1200mL deionized water, be heated to 60～85 ℃; Solution C is divided into two parts of C1, C2, and solution C 1 is 800mL, and solution C 2 is 400mL.Under stirring condition, solution A is joined in the solution C 1, controlling terminal point pH is 7.0～7.5, continues to stir 30min, the precipitation color becomes blue-green by blueness, keeps 60～85 ℃ of precipitation temperatures, gets slip D; Solution B is joined in the solution solution C 2, and control terminal point pH is 7.0～7.5, keeps 60～85 ℃ of precipitation temperatures, gets slip E.Then slip D and E are mixed and stir, left standstill 2～3 hours, the mixed slurry that makes after filtration, wash to Na
+Content≤0.035% (w/w), the filter cake that obtains is 100～120 ℃ of oven dry, 320 ℃ of roastings 4 hours, the material after the roasting added an amount of graphite and water again, was pressed into tablet and was the catalst for synthesis of methanol sample.Sample number into spectrum is c.
Embodiment 4
Take by weighing 121gCu (NO
3)
23H
2O and 50gZn (NO
3)
26H
2O is dissolved in wiring solution-forming A in the 550mL deionized water, is heated to 60-85 ℃; Take by weighing 25gZn (NO
3)
26H
2O and 37gAl (NO
3) 9H
2O is dissolved in the 200mL deionized water, and wiring solution-forming B is heated to 60-85 ℃; Take by weighing 60gCu (NO
3)
23H
2O and 37gAl (NO
3)
39H
2O is dissolved in the 300mL deionized water, and wiring solution-forming C is heated to 60-85 ℃.Take by weighing 128gNa
2CO
3Be dissolved in wiring solution-forming D in the 1200mL deionized water, be heated to 60-85 ℃; Solution D is divided into three parts of D1, D2, D3, and solution D 1 is 600mL, and solution D 2 is 400mL, and solution D 3 is 200mL.Under stirring condition, solution A is joined in the solution solution D 1, keep 60～85 ℃ of precipitation temperatures, control terminal point pH is 7.0～7.5, stirs 30min and makes the precipitation color become blue-green by blueness, gets slip E.Equally solution B is joined in the solution solution D 2, control terminal point pH is 7.0～7.5, and temperature gets slip F for 60～85 ℃.Solution C is joined in the solution D 3, and control terminal point pH is 7.0～7.5, and temperature gets slip G for 60～85 ℃.Then slip E, F and G are mixed stirring 30min, left standstill 2-3 hour, the mixed slurry that obtains is through filtering, washing to Na
+Content≤0.035% (w/w), the filter cake that obtains is in temperature 100-120 ℃ oven dry, again 320 ℃ of roastings 4 hours, the material after the roasting adds an amount of graphite and becomes tablet with hydraulic pressure, is the catalst for synthesis of methanol sample, sample number into spectrum is d.The content of Na+≤0.035% (w/w) in the catalyst.
Embodiment 5
Take by weighing 1210gCu (NO
3)
23H
2O and 500gZn (NO
3)
26H
2O is dissolved in wiring solution-forming A in the 5500mL deionized water, is heated to 60-85 ℃; Take by weighing 250gZn (NO
3)
26H
2O and 370gAl (NO
3)
39H
2O is dissolved in the 2000mL deionized water, and wiring solution-forming B is heated to 60-85 ℃; Take by weighing 600gCu (NO
3)
23H
2O and 370gAl (NO
3)
39H
2O is dissolved in the 3000mL deionized water, and wiring solution-forming C is heated to 60-85 ℃.Take by weighing 1280gNa
2CO
3Be dissolved in wiring solution-forming D in the 12000mL deionized water, be heated to 60-85 ℃, solution D is divided into three parts of D1, D2, D3, solution D 1 is 6000mL, and solution D 2 is 4000mL, and solution D 3 is 2000mL.With pump solution A and solution D 1 are driven in the static mixer simultaneously, the flow velocity of control pump makes that outlet slip pH is 7.0-7.5, in the reactor that slip importing band stirs, continues to stir, and keeps precipitation temperature 60-85 ℃, gets slip E.With pump solution B and solution D 2 are driven in the static mixer simultaneously, the flow velocity of control pump makes that outlet slip pH is 7.0-7.5, in the reactor that slip importing band stirs, continues to stir, and keeps precipitation temperature 60-85 ℃, gets slip F.With pump solution C and solution D 3 are driven in the static mixer simultaneously, the flow velocity of control pump makes that outlet slip pH is 7.0-7.5, in the reactor that slip importing band stirs, continues to stir, and keeps precipitation temperature 60-85 ℃ and gets slip G.Then slip E, F and G are mixed and stir 30min, left standstill 2-3 hour, mixed slurry after filtration, wash to Na
+Content≤0.035% (w/w), the filter cake that obtains is dried under temperature 100-120 ℃ condition, 320 ℃ of roastings of temperature 4 hours, the material after the roasting added an amount of graphite and water again, was pressed into tablet and was the catalst for synthesis of methanol sample, sample number into spectrum is e.Pipeline static mixer is SV type, SX type and SL type.Na in the catalyst
+Content≤0.035% (w/w).
Sample test
Catalyst sample granularity: 0.425～1.180mm.Loading amount: 4mL.
The sample activation: sample fed reducing gases (H before doing active and heat resistance
2: N
2=5: 95) reduction, 240 ℃ of reduction maximum temperatures activate.
The active testing condition: at pressure 5.0Mpa, 230～250 ℃ of temperature, air speed 10000～15000H
-1Down, synthesis gas composition (v/v) is: CO 13～15%, CO
24～6%, H
255～65%, surplus is N
2The initial activity of measuring catalyst (generates the space-time yield gmL of methyl alcohol
-1h
-1Promptly per hour every milliliter of catalyst produces the milliliter number of methyl alcohol).
Heat-resisting back active testing: after the sample determination initial activity, temperature of reactor rises to 400 ℃, keeps 5 hours, returns under the above-mentioned condition again, measures active (the space-time yield gmL of generation methyl alcohol in heat-resisting back
-1h
-1), compare the heat endurance of investigating catalyst with this activity and initial activity.
Can find out that by test result the catalyst of the technology preparation that the catalyst methanol yield of employing the present invention preparation and heat endurance are more traditional is greatly improved.
The catalst for synthesis of methanol active testing the results are shown in Table 1
Table 1
Claims (3)
1. the preparation method of a catalst for synthesis of methanol, this method is following three kinds of coprecipitates to be mixed stir and ageing, the slip that makes is through washing, drying and roasting, material after the roasting adds graphite and water, compressing tablet makes catalst for synthesis of methanol, it is characterized in that the preparation process of described three kinds of coprecipitates is:
(a) preparation of copper zinc coprecipitate: adopt counter adding or parallel-flow precipitation, be in the aqueous slkali of 0.5～2M with concentration and the copper nitrate of same concentration and the mixed liquor of zinc nitrate, reaction temperature is 60～85 ℃, it is 7.0～7.5 that reaction finishes terminal point pH, and the mol ratio of copper nitrate and zinc nitrate is 2～5: 1 in the described mixed liquor;
(b) preparation of zinc-aluminium coprecipitate: adopt counter adding or parallel-flow precipitation, be in the aqueous slkali of 0.5～2M with concentration and the aluminum nitrate of same concentration and the mixed liquor of zinc nitrate, reaction temperature is 60～85 ℃, it is 7.0～7.5 that reaction finishes terminal point pH, and the mol ratio of zinc nitrate and aluminum nitrate is 0.5～2: 1 in the described mixed liquor;
(c) preparation of copper aluminium coprecipitate: adopt counter adding or parallel-flow precipitation, be in the aqueous slkali of 0.5～2M with concentration and the aluminum nitrate of same concentration and the mixed liquor of copper nitrate, it is 7.0～7.5 that reaction finishes terminal point pH, reaction temperature is 60～85 ℃, and the mol ratio of copper nitrate and aluminum nitrate is 4～6: 1 in the described mixed liquor;
Aqueous slkali is sodium carbonate, potash or sodium bicarbonate solution described in step (a), step (b) and the step (c); The metal oxide that contains following percentage by weight in the described catalyst: CuO25～65%, ZnO 15～45%, Al
2O
35～15%.
2. according to the preparation method of the described catalst for synthesis of methanol of claim 1, it is characterized in that: parallel-flow precipitation is finished in having the reactor of stirring or is finished in pipeline static mixer described in step (a), step (b) and the step (c).
3. according to the preparation method of the described catalst for synthesis of methanol of claim 1, it is characterized in that: the mixing mixing time of described three kinds of coprecipitates is 30min, and the ageing temperature is 70～75 ℃, and digestion time is 2 hours.
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