CN102950001A - High-temperature-resistant methanol catalyst and preparation method thereof - Google Patents
High-temperature-resistant methanol catalyst and preparation method thereof Download PDFInfo
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- CN102950001A CN102950001A CN201210389571XA CN201210389571A CN102950001A CN 102950001 A CN102950001 A CN 102950001A CN 201210389571X A CN201210389571X A CN 201210389571XA CN 201210389571 A CN201210389571 A CN 201210389571A CN 102950001 A CN102950001 A CN 102950001A
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- earth metal
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- methanol
- alkali
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 21
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 20
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 18
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 17
- 238000000975 co-precipitation Methods 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- VODBHXZOIQDDST-UHFFFAOYSA-N copper zinc oxygen(2-) Chemical class [O--].[O--].[Cu++].[Zn++] VODBHXZOIQDDST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 44
- 150000003839 salts Chemical class 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 43
- 239000003513 alkali Substances 0.000 claims description 35
- 238000001556 precipitation Methods 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 238000003786 synthesis reaction Methods 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 238000000748 compression moulding Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 3
- -1 rare-earth metal modified Copper-zinc oxide Chemical class 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 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
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002244 precipitate Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 6
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 abstract 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
- 238000004448 titration Methods 0.000 description 12
- 239000013049 sediment Substances 0.000 description 7
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
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- Catalysts (AREA)
Abstract
The invention discloses a high-temperature-resistant methanol catalyst and a preparation method thereof, belonging to the technical field of catalysts. The constituents of the high-temperature-resistant methanol catalyst comprise active constituents, a carrier and stabilizers, wherein the active constituents are copper-zinc oxides modified by rare-earth metal, the carrier is alumina modified by alkaline-earth metal, and the stabilizers are alkaline-earth metal oxides and rare-earth metal oxides. The catalyst comprises the constituents in the percentage by mass: 60-90% of copper-zinc oxides, 5-30% of alumina, 0.5-5% of alkaline-earth metal oxides, and 0.1-5% of rare-earth metal oxides. The preparation method for the catalyst comprises the following steps of: forming a modified active constituent precipitate by means of coprecipitation; forming a modified carrier precipitate by means of coprecipitation; and finally mixing, slurrying and ageing the active constituent precipitate with the carrier precipitate, filtering, washing, drying and roasting to obtaining synthetic methanol catalyst powder, and tabletting to obtain the synthetic methanol catalyst applicable to reaction. The catalyst is high in catalytic activity, and low in selectivity for dimethyl ether and ethanol.
Description
Technical field
The present invention relates to a kind of high temperature resistant catalyst for methanol and preparation method thereof, belong to catalyst technical field.
Background technology
Methyl alcohol is a kind of extremely important industrial chemicals, mainly for the production of methyl tertiary butyl ether(MTBE) (MTBE), dimethyl ether, formaldehyde, methyl formate, acetic acid and derivative thereof, rich horse ester (DMF), gasoline etc., also can be used as the fuel of potential vehicle alcohol ether fuel and fuel cell etc.In recent years, continuous rise along with International Crude Oil, national governments all show great attention to the clean energy resource problem of petroleum replacing, domestic and international energy company is numerous and confused search for oil substitute also, of many uses based on methyl alcohol, extensive petroleum replacing, it has very strong economy and realistic feasibility.
Usually the catalst for synthesis of methanol preparation is that coprecipitation prepares copper zinc mixings subcarbonate, then at pulping process adding carrier, the slurry that generates through washing, drying, roasting, play the sheet moulding.Although the catalyst of this method preparation can satisfy present commercial Application, but the development of the energy-saving and cost-reducing and methyl alcohol technology of commercial plant is the extensive future development of forward all, large-scale methanol production requires catalyst for methanol to have good resistance to elevated temperatures, will keep high activity, high stability and high selective under higher temperature, also there is the selective higher problem of high temperatures allowance below nominal size, accessory substance dimethyl ether and ethanol in present catalyst for methanol.
Publication number is that the China of CN101306369A applies for a patent and adopts the method for co-precipitation to make a kind of catalyst for methanol, the preparation method comprises Cu, Zn mixed liquor and alkali co-precipitation is prepared sediment 1, aluminum solutions and siliceous alkali lye co-precipitation prepare sediment 2, with aging at a certain temperature after sediment 1 and 2 mixing, filter, wash, dry and to get the catalyst precursor, the catalyst precursor gets finished product through roasting.Si has been introduced in the preparation of this catalyst, and purpose is in order to improve the activity of catalyst, but does not have to introduce the stability of catalyst and the impact of product selectivity.
Publication number is that the China of CN101327431A applies for a patent and adopts the method for co-precipitation to make a kind of catalyst for methanol, the preparation method comprise with Cu, Zn mixed liquor, Zn, Al mixed liquor, Cu, Al mixed liquor respectively with the alkali co-precipitation, prepare three kinds of sediments, then aging at a certain temperature after three kinds of sediments being mixed, filter, wash, dry and to get the catalyst precursor, the catalyst precursor gets finished product through roasting.The characteristics of this catalyst are the catalyst that has prepared bigger serface, make catalyst have high activity and stable.
Chinese patent CN1810357 adopts coprecipitation to make a kind of catalyst for methanol.The preparation method may further comprise the steps: at first the nitrate mixed solution of Cu, Zn, Al, Li and sodium carbonate liquor and stream are titrated in the deionized water that a small amount of high-speed stirred, keep simultaneously the PH of solution between 7-8; Then precipitate that slurry is aging, the catalyst precursor of suction filtration, washing, oven dry, the oven dry of catalyst precursor, roasting get finished product.This catalyst has increased Li, and purpose is in order to improve the resistance to elevated temperatures of catalyst.
The maximization of methyl alcohol product installation and energy-saving and cost-reducing requirement, require the more efficiently catalst for synthesis of methanol of exploitation, existing catalst for synthesis of methanol performance must further be improved, improve the selective of the stability of catalyst and product, the Main By product dimethyl ether of reduce synthesizing methanol and ethanol selective.It is to make the performance of active ingredient copper, zinc more stable that catalst for synthesis of methanol preparation improves main thought, reduces simultaneously side reaction that carrier may bring to the impact of catalyst selectivity, and this patent just is based on such guiding theory.
Summary of the invention
In order to overcome problems of the prior art, the invention provides a kind of high temperature resistant catalyst for methanol and preparation method thereof, by the modification to active component and carrier, provide a kind of Stability Analysis of Structures, surface acid alkaline equilibrium degree good, have activity stabilized, selective good catalst for synthesis of methanol.
The technical solution used in the present invention is: a kind of component of high temperature resistant catalst for synthesis of methanol comprises active component, carrier and stabilizing agent, described active component adopts rare-earth metal modified Copper-zinc oxide, carrier is the alkali-earth metal modified aluminium oxide of process, and stabilizing agent is the oxide of alkaline-earth metal and rare earth metal; The mass percent of each component in the described catalyst: described Copper-zinc oxide is that 60-90%, described aluminium oxide are that the oxide of 5-30%, described alkaline-earth metal is that the oxide of 0.5-5%, described rare earth metal is 0.1-5%.
Described alkaline-earth metal is one or more the mixture in magnesium, calcium, strontium, the barium.
Described rare earth metal is the mixture of a kind of in lanthanum, the cerium or two kinds.
The preparation method of described a kind of high temperature resistant catalst for synthesis of methanol comprises the following steps:
(1) nitrate of Cu, Zn and rare earth metal is mixed with the aqueous solution that the metal ion total mass concentration is 60-100g/L by the composition of catalyst, is designated as salt A solution; Get weak base and be mixed with the aqueous solution that mass concentration is 70-120g/L, be designated as alkali A solution; Under temperature 60-85 ℃, under agitation salt A solution and alkali A solution and stream are joined in the reactor, keeping pH value is co-precipitation under the condition of 7-8, stirs 0.5-2 hour after precipitation finishes, and is precipitated liquid 1;
(2) nitrate of Al and alkaline-earth metal is mixed with the aqueous solution that the metal ion total mass concentration is 50-85g/L by the composition of catalyst, is designated as salt B solution; Get weak base and be mixed with the aqueous solution that mass concentration is 70-120g/L, be designated as alkali B solution; Under temperature 20-50 ℃, under agitation salt B solution and alkali B solution and stream are joined in the reactor, keeping pH value is co-precipitation under the condition of 7-8, stirs 0.5-2 hour after precipitation finishes, and is precipitated liquid 2;
(3) precipitated liquid 2 is joined in the precipitated liquid 1,65-85 ℃ of lower the stirring aging 1-2 hour, filtration, washing, oven dry obtain the catalyst for methanol precursor, the catalyst precursor obtains the catalyst for methanol powder at 320-380 ℃ of roasting temperature 3-4h, and catalyst for methanol gets product behind compression molding.
Described weak base is selected from one or more the mixture in ammoniacal liquor, sodium carbonate, potash, ammonium carbonate, sodium acid carbonate, saleratus or the carbonic hydroammonium.
The invention has the beneficial effects as follows: the component of this high temperature resistant catalyst for methanol comprises active component, carrier and stabilizing agent, active component adopts rare-earth metal modified Copper-zinc oxide, carrier is the alkali-earth metal modified aluminium oxide of process, and stabilizing agent is the oxide of alkaline-earth metal and rare earth metal.The mass percent of each component in the catalyst: Copper-zinc oxide is that 60-90%, aluminium oxide are that the oxide of 5-30%, alkaline-earth metal is that the oxide of 0.5-5%, rare earth metal is 0.1-5%.The preparation method of catalyst comprises: adopt co-precipitation to form the active component sediment of modification; Adopt co-precipitation to form the carrier precipitation thing of modification; At last active component sediment and carrier precipitation thing are mixed making beating, aging, after filtration, washing, oven dry and roasting, obtain the catalst for synthesis of methanol powder, namely get the catalst for synthesis of methanol that can be used for reacting through compressing tablet.This catalyst has higher catalytic activity, and it is selective to have simultaneously lower dimethyl ether and ethanol.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1
With 628 gram Cu (NO
3)
33H
2O, 297.5 gram Zn (NO
3)
36H
2O and 2.3 gram La (NO
3)
36H
2O is made into the aqueous solution that concentration of metal ions is 1mol/L, is designated as salt A solution; Get the Na that an amount of concentration is 1mol/L
2CO
3The aqueous solution is designated as alkali A solution.Be 75 ℃ of lower parallel-flow precipitations with salt A liquid and alkali A liquid in temperature, pH value remains on 7.5 ~ 7.8, when salt A titration finishes, stirs 1 hour, is precipitated liquid 1.
With 210.6 gram Al (NO
3)
39H
2O and 22.2 gram Mg (NO
3)
26H
2O is made into the aqueous solution that aluminium ion concentration is 1mol/L, is designated as salt B solution; Get the ammoniacal liquor that an amount of concentration is 3mol/L, be designated as alkali B solution.Be 30 ℃ of lower parallel-flow precipitations with salt B liquid and alkali B liquid in temperature, pH value remains on 7.5 ~ 7.8, when salt B titration finishes, stirs 1 hour, is precipitated liquid 2.
Precipitation 2 obtained above is added in the precipitation 1,75 ~ 80 ℃ of lower stirrings aging 1 hour, filtration, washing, oven dry obtain the catalyst for methanol precursor, precursor obtains the catalyst for methanol powder at 340 ℃ of lower roasting 4h, and the oxide mass of active component, carrier, alkaline-earth metal, rare earth metal is than being 10.08:1:0.12:0.03 in the catalyst.The catalyst for methanol that gets product behind compression molding is designated as sample 1.
Adopt catalyst test apparatus that catalyst is estimated, unstripped gas forms CO:CO
2: N
2: H
2=16.2:7.2:8.0:68.6, temperature are that 270 ℃, pressure are that 5.0MPa, air speed are 20000h
-1The content of methyl alcohol, ethanol and dimethyl ether in the assay products, concrete evaluation result sees Table 1.
Embodiment 2
With 581 gram Cu (NO
3)
33H
2O, 240.0 gram Zn (NO
3)
36H
2O and 2.3 gram La (NO
3)
36H
2O is made into the aqueous solution that concentration of metal ions is 1mol/L, is designated as salt A solution; Get the Na that an amount of concentration is 1mol/L
2CO
3The aqueous solution is designated as alkali A solution.Be 75 ℃ of lower parallel-flow precipitations with salt A liquid and alkali A liquid in temperature, pH value remains on 7.5 ~ 7.8, when salt A titration finishes, stirs 1 hour, is precipitated liquid 1.
With 210.6 gram Al (NO
3)
39H
2O and 22.2 gram Mg (NO
3)
36H
2O is made into the aqueous solution that aluminium ion concentration is 1mol/L, is designated as salt B solution; Get the sodium carbonate liquor that an amount of concentration is 1mol/L, be designated as alkali B solution.Be 30 ℃ of lower parallel-flow precipitations with salt B liquid and alkali B liquid in temperature, pH value remains on 7.5 ~ 7.8, when salt B titration finishes, stirs 1 hour, is precipitated liquid 2.
Precipitation 2 obtained above is added in the precipitation 1,75 ~ 80 ℃ of lower stirrings aging 1 hour, filtration, washing, oven dry obtain the catalyst for methanol precursor, precursor obtains the catalyst for methanol powder at 320 ℃ of lower roasting 4h, and the oxide mass of active component, carrier, alkaline-earth metal, rare earth metal is than being 9.0:1.0:0.12:0.03 in the catalyst.The catalyst for methanol that gets product behind compression molding is designated as sample 2.
Sample 2 evaluation method samples 1, concrete evaluation result sees Table 1.
Embodiment 3
With 581 gram Cu (NO
3)
33H
2O, 240.0 gram Zn (NO
3)
36H
2O and 2.3 gram Ce (NO
3)
36H
2O is made into the aqueous solution that concentration of metal ions is 1mol/L, is designated as salt A solution; Get the Na that an amount of concentration is 1mol/L
2CO
3The aqueous solution is designated as alkali A solution.Be 75 ℃ of lower parallel-flow precipitations with salt A liquid and alkali A liquid in temperature, pH value remains on 7.5 ~ 7.8, when salt A titration finishes, stirs 1 hour, is precipitated liquid 1.
With 210.6 gram Al (NO
3)
39H
2O and 22.2 gram Mg (NO
3)
36H
2O is made into the aqueous solution that aluminium ion concentration is 1mol/L, is designated as salt B solution; Get the sodium carbonate liquor that an amount of concentration is 1mol/L, be designated as alkali B solution.Be 30 ℃ of lower parallel-flow precipitations with salt B liquid and alkali B liquid in temperature, pH value remains on 7.5 ~ 7.8, when salt B titration finishes, stirs 1 hour, is precipitated liquid 2.
Precipitation 2 obtained above is added in the precipitation 1,75 ~ 80 ℃ of lower stirrings aging 1 hour, filtration, washing, oven dry obtain the catalyst for methanol precursor, precursor obtains the catalyst for methanol powder at 350 ℃ of lower roasting 3h, and the oxide mass of active component, carrier, alkaline-earth metal, rare earth metal is than being 9.0:1.0:0.12:0.03 in the catalyst.The catalyst for methanol that gets product behind compression molding is designated as sample 3.
Sample 3 evaluation method samples 1, concrete evaluation result sees Table 1.
Embodiment 4
With 676.0 gram Cu (NO
3)
33H
2O, 335.0.0 gram Zn (NO
3)
36H
2O and 2.3 gram La (NO
3)
36H
2O is made into the aqueous solution that concentration of metal ions is 1mol/L, is designated as salt A solution; Get (the NH that an amount of concentration is 1mol/L
4)
2CO
3The aqueous solution is designated as alkali A solution.Be 70 ℃ of lower parallel-flow precipitations with salt A liquid and alkali A liquid in temperature, pH value remains on 7.5 ~ 7.8, when salt A titration finishes, stirs 1 hour, is precipitated liquid 1.
With 210.6 gram Al (NO
3)
39H
2O, 11.1 gram Mg (NO
3)
36H
2O and 4.2 gram Ca (NO
3)
34H
2O is made into the aqueous solution that aluminium ion concentration is 1mol/L, is designated as salt B solution; Get the sodium carbonate liquor that an amount of concentration is 1mol/L, be designated as alkali B solution.Be 30 ℃ of lower parallel-flow precipitations with salt B liquid and alkali B liquid in temperature, pH value remains on 7.5 ~ 7.8, when salt B titration finishes, stirs 1 hour, is precipitated liquid 2.
Precipitation 2 obtained above is added in the precipitation 1,75 ~ 80 ℃ of lower stirrings aging 1 hour, filtration, washing, oven dry obtain the catalyst for methanol precursor, precursor obtains the catalyst for methanol powder at 330 ℃ of lower roasting 3h, and the oxide mass of active component, carrier, alkaline-earth metal, rare earth metal is than being 11.0:1.0:0.11:0.03 in the catalyst.The catalyst for methanol that gets product behind compression molding is designated as sample 4.
Sample 4 evaluation methods are with sample 1, and concrete evaluation result sees Table 1.
Embodiment 5
With 628.0 gram Cu (NO
3)
33H
2O, 297.0.0 gram Zn (NO
3)
36H
2O and 4.6 gram La (NO
3)
36H
2O is made into the aqueous solution that concentration of metal ions is 1mol/L, is designated as salt A solution; Get the Na that an amount of concentration is 1mol/L
2CO
3The aqueous solution is designated as alkali A solution.Be 70 ℃ of lower parallel-flow precipitations with salt A liquid and alkali A liquid in temperature, pH value remains on 7.5 ~ 7.8, when salt A titration finishes, stirs 1 hour, is precipitated liquid 1.
With 210.6 gram Al (NO
3)
39H
2O, 22.2 gram Mg (NO
3)
36H
2O is made into the aqueous solution that aluminium ion concentration is 1mol/L, is designated as salt B solution; Get the sodium carbonate liquor that an amount of concentration is 1mol/L, be designated as alkali B solution.Be 30 ℃ of lower parallel-flow precipitations with salt B liquid and alkali B liquid in temperature, pH value remains on 7.5 ~ 7.8, when salt B titration finishes, stirs 1 hour, is precipitated liquid 2.
Precipitation 2 obtained above is added in the precipitation 1,75 ~ 80 ℃ of lower stirrings aging 1 hour, filtration, washing, oven dry obtain the catalyst for methanol precursor, precursor obtains the catalyst for methanol powder at 340 ℃ of lower roasting 3h, and the oxide mass of active component, carrier, alkaline-earth metal, rare earth metal is than being 10.08:1.0:0.12:0.06 in the catalyst.The catalyst for methanol that gets product behind compression molding is designated as sample 5.
Sample 5 evaluation methods are with sample 1, and concrete evaluation result sees Table 1.
Comparative Examples
With 628 gram Cu (NO
3)
33H
2O, 297.5 gram Zn (NO
3)
36H
2O is made into the aqueous solution that concentration of metal ions is 1mol/L, is designated as salt A solution; Get the Na that an amount of concentration is 1mol/L
2CO
3The aqueous solution is designated as alkali A solution.Be 75 ℃ of lower parallel-flow precipitations with salt A liquid and alkali A liquid in temperature, pH value remains on 7.5 ~ 7.8, when salt A titration finishes, stirs 1 hour, is precipitated liquid 1.
With 150.6 gram Al (NO
3)
39H
2O is made into the aqueous solution that aluminium ion concentration is 1mol/L, is designated as salt B solution; Get the ammoniacal liquor that an amount of concentration is 3mol/L, be designated as alkali B solution.Be 30 ℃ of lower parallel-flow precipitations with salt B liquid and alkali B liquid in temperature, pH value remains on 7.5 ~ 7.8, when salt B titration finishes, stirs 1 hour, is precipitated liquid 2.
Precipitation 2 obtained above is added in the precipitation 1,75 ~ 80 ℃ of lower stirrings aging 1 hour, filtration, washing, oven dry obtain the catalyst for methanol precursor, and precursor obtains the catalyst for methanol powder at 340 ℃ of lower roasting 4h, the catalyst for methanol that gets product behind compression molding is designated as Comparative Examples.
The Comparative Examples evaluation method is with sample 1, and concrete evaluation result sees Table 1.
Table 1 catalst for synthesis of methanol reactivity worth relatively
Annotate: industrial catalyst is the catalst for synthesis of methanol of generally using in the market.
By the evaluation result of table 1 as can be known, adopt rare earth metal to the active ingredient copper zinc of catalst for synthesis of methanol and adopt golden earth metal that the carrier of methanol synthesis catalyst is carried out modification, the catalyst for methanol that obtains has kept higher catalytic activity, the selective of methyl alcohol obviously improves simultaneously, and the selective of Main By product dimethyl ether and ethanol obviously reduces.
Claims (5)
1. high temperature resistant catalst for synthesis of methanol, it is characterized in that: the component of described catalyst comprises active component, carrier and stabilizing agent, described active component adopts rare-earth metal modified Copper-zinc oxide, carrier is the alkali-earth metal modified aluminium oxide of process, and stabilizing agent is the oxide of alkaline-earth metal and rare earth metal; The mass percent of each component in the described catalyst: described Copper-zinc oxide is that 60-90%, described aluminium oxide are that the oxide of 5-30%, described alkaline-earth metal is that the oxide of 0.5-5%, described rare earth metal is 0.1-5%.
2. a kind of high temperature resistant catalst for synthesis of methanol according to claim 1 is characterized in that: described alkaline-earth metal is one or more the mixture in magnesium, calcium, strontium, the barium.
3. a kind of high temperature resistant catalst for synthesis of methanol according to claim 1 is characterized in that: described rare earth metal is the mixture of a kind of in lanthanum, the cerium or two kinds.
4. the preparation method of a kind of high temperature resistant catalst for synthesis of methanol according to claim 1, it is characterized in that: described method comprises the following steps:
(1) nitrate of Cu, Zn and rare earth metal is mixed with the aqueous solution that the metal ion total mass concentration is 60-100g/L by the composition of catalyst, is designated as salt A solution; Get weak base and be mixed with the aqueous solution that mass concentration is 70-120g/L, be designated as alkali A solution; Under temperature 60-85 ℃, under agitation salt A solution and alkali A solution and stream are joined in the reactor, keeping pH value is co-precipitation under the condition of 7-8, stirs 0.5-2 hour after precipitation finishes, and is precipitated liquid 1;
(2) nitrate of Al and alkaline-earth metal is mixed with the aqueous solution that the metal ion total mass concentration is 50-85g/L by the composition of catalyst, is designated as salt B solution; Get weak base and be mixed with the aqueous solution that mass concentration is 70-120g/L, be designated as alkali B solution; Under temperature 20-50 ℃, under agitation salt B solution and alkali B solution and stream are joined in the reactor, keeping pH value is co-precipitation under the condition of 7-8, stirs 0.5-2 hour after precipitation finishes, and is precipitated liquid 2;
(3) precipitated liquid 2 is joined in the precipitated liquid 1,65-85 ℃ of lower the stirring aging 1-2 hour, filtration, washing, oven dry obtain the catalyst for methanol precursor, the catalyst precursor obtains the catalyst for methanol powder at 320-380 ℃ of roasting temperature 3-4h, and catalyst for methanol gets product behind compression molding.
5. the preparation method of a kind of high temperature resistant catalst for synthesis of methanol according to claim 4 is characterized in that: described weak base is selected from one or more the mixture in ammoniacal liquor, sodium carbonate, potash, ammonium carbonate, sodium acid carbonate, saleratus or the carbonic hydroammonium.
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| CN104722305B (en) * | 2013-12-23 | 2017-11-14 | 中国科学院上海高等研究院 | One kind is applied to multi component mixed gas catalst for synthesis of methanol and its preparation method and application |
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| CN113509937A (en) * | 2020-04-10 | 2021-10-19 | 中石化南京化工研究院有限公司 | Copper-containing catalyst and preparation method thereof |
| CN113509937B (en) * | 2020-04-10 | 2023-05-16 | 中国石油化工股份有限公司 | Copper-containing catalyst and preparation method thereof |
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