CN106311268A - Method for improving performance of methanol synthesis catalyst - Google Patents
Method for improving performance of methanol synthesis catalyst Download PDFInfo
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- CN106311268A CN106311268A CN201510389909.5A CN201510389909A CN106311268A CN 106311268 A CN106311268 A CN 106311268A CN 201510389909 A CN201510389909 A CN 201510389909A CN 106311268 A CN106311268 A CN 106311268A
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- methanol synthesis
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- 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
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- 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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Abstract
The invention relates to a method for improving the performance of a methanol synthesis catalyst. The method comprises the following steps: settling a carrier by a step-by-step method, adding an auxiliary agent into a carrier settling agent, preparing a carrier precursor, and then continuously settling the precursor to obtain a high-performance carrier. Compared with a catalyst prepared by a conventional method, the methanol synthesis catalyst prepared by the method disclosed by the invention has the advantages that the carrier is settled by the step-by-step method, and the added auxiliary agent can improve the dispersivity and interaction of Cu and Zn, so that the activity and thermal stability of the catalyst are improved, and the market competitiveness of the catalyst can be effectively enhanced.
Description
Technical field
The invention belongs to catalyst preparation technical field, be specifically related to a kind of method improving methanol synthesis catalyst performance.
Background technology
Methanol is a kind of important Organic Chemicals, is also clean alternative fuel.In recent years, in succession made a breakthrough by demand pull Coal Chemical Industry domestic technology equipment, China's methanol demands amount improves constantly, methanol industry has evolved into the industry to national economy with material impact, and the economic benefit of methanol enterprise is in addition to being affected by market factors, it is heavily dependent on the quality of used catalyst for methanol performance.Therefore, the methanol synthesis catalyst of development & production function admirable technological progress and the lifting meaning highly significant of economic benefit to promoting methanol industry.
Methanol synthesis catalyst is mainly by CuO-ZnO-Al at present2O3Composition, common method for preparing catalyst is first to prepare copper zinc parent, then makes its load on the alumina support, scrubbed, filters, dries, the operation such as roasting and molding, prepares catalyst.For improving the performance of copper-based catalysts further, present invention research is by CuO-ZnO-Al2O3On the basis of three component formula, use method of fractional steps precipitophore, carrier precipitation agent adds auxiliary agent, first prepares support precursor, the method continuing precipitation this presoma acquisition carrier afterwards prepares the methanol synthesis catalyst of higher performance, to improve activity and the stability of catalyst.
Summary of the invention
The mesh of the present invention is to propose a kind of method improving methanol synthesis catalyst performance.
The present invention is mainly characterized by: use method of fractional steps precipitophore, adds auxiliary agent in alkalescence precipitant, first prepares support precursor, continues to precipitate this presoma with strong base solution afterwards and obtain high performance carrier.
The main technical schemes of the present invention: the method improving methanol synthesis catalyst performance, it is characterised in that by Cu (NO3)2With Zn (NO3)2Mixed solution and alkali liquor carry out co-precipitation and react and obtain Cu/Zn parent；Carrier uses step-by-step precipitation method to prepare, first it is co-precipitated with aluminum nitrate solution with the weak caustic solution that with the addition of auxiliary agent, prepare support precursor, continue to precipitate this presoma with strong base solution afterwards, obtain carrier, this carrier is mixed with Cu/Zn parent making beating, scrubbed, filter, dry, roasting, molding procedure make methanol synthesis catalyst.
During described preparation Cu/Zn parent, control mixing speed is 700 ~ 1200r/min, precipitation temperature 60 ~ 85 DEG C, endpoint pH 6.5 ~ 8.0, and precipitation terminates rear aging 20 ~ 60min, with 60～85 DEG C of water washing slips to NO3 -1Concentration≤50mg/L.
Weak caustic solution used by described preparation support precursor is the one in ammonia and sodium bicarbonate solution.
The described auxiliary agent added in weak caustic solution is Mn (NO3)2、Ca(NO3)2、Mg(NO3)2In one or both mixture solutions.
Described during preparation support precursor, control mixing speed is 600 ~ 1000r/min, precipitation temperature 35 ~ 60 DEG C, and endpoint pH is 6.5, aging 20 ~ 40min.
The strong base solution of described continuation precipitophore presoma is the one in sodium hydroxide and potassium hydroxide.
The endpoint pH of described carrier is 7.0 ~ 7.5.
In described carrier, auxiliary agent is 0.01 ~ 0.1 with the mol ratio of main carrier aluminum.
The catalyst that methanol synthesis catalyst prepared by the inventive method is prepared with traditional method is compared, use method of fractional steps precipitophore, the auxiliary agent added can improve dispersion and the interaction of Cu and Zn, thus improves activity and the heat stability of catalyst, can be effectively improved the market competitiveness of catalyst.
Detailed description of the invention
Example 1
Under the conditions of low whipping speed is 1050r/min, by the Cu (NO of 1L, Cu/Zn=2.73)2With Zn (NO3)2Mixed solution and concentration are that the sodium carbonate liquor of 1mol/L carries out parallel-flow precipitation, precipitation temperature 65 DEG C, endpoint pH 7.0, and precipitation terminates rear aging 30min, slip 65 DEG C of hot washes to NO3 -1Concentration≤50mg/L, prepares Cu/Zn binary parent standby.Then 40 DEG C, under the conditions of 700r/min with the addition of 3% (molar concentration)
Mn(NO3)2The ammonia spirit of auxiliary agent is co-precipitated with aluminum nitrate solution, and controlling endpoint pH is 6.5, aging 30min, prepares support precursor, continues to precipitate this presoma with the sodium hydroxide solution of 1mol/L afterwards, control endpoint pH 7.0, prepare carrier.This carrier is mixed with Cu/Zn parent making beating, scrubbed, filter, dry, roasting, the operation such as molding make methanol synthesis catalyst cat1.
Example 2
Cu/Zn parent preparation process with example 1, then 40 DEG C, under the conditions of 700r/min with the addition of 5%Mg (NO3)2The ammonia spirit of auxiliary agent is co-precipitated with aluminum nitrate solution, and controlling endpoint pH is 6.5, aging 30min, prepares support precursor, continues to precipitate this presoma with the sodium hydroxide solution of 1mol/L afterwards, control endpoint pH 7.5, prepare carrier.This carrier is mixed with Cu/Zn parent making beating, scrubbed, filter, dry, roasting, the operation such as molding make methanol synthesis catalyst cat2.
Example 3
Under the conditions of low whipping speed is 900r/min, by the Cu (NO of 1L, Cu/Zn=2.73)2With Zn (NO3)2Mixed solution and concentration are that the sodium carbonate liquor of 1mol/L carries out parallel-flow precipitation, precipitation temperature 75 DEG C, endpoint pH 7.5, and precipitation terminates rear aging 50min, slip 70 DEG C of hot washes to NO3 -1Concentration≤50mg/L, prepares Cu/Zn binary parent standby.Then 50 DEG C, under the conditions of 850r/min with the addition of 3%Mn (NO3)2With 4%Ca (NO3)2Sodium bicarbonate solution and the aluminum nitrate solution of mixed aid be co-precipitated, controlling endpoint pH is 6.5, aging 40min, prepares support precursor, continues to precipitate this presoma with the potassium hydroxide solution of 1mol/L afterwards, control endpoint pH 7.0, prepare carrier.This carrier is mixed with Cu/Zn parent making beating, scrubbed, filter, dry, roasting, the operation such as molding make methanol synthesis catalyst cat3.
Example 4
Cu/Zn parent preparation process with example 3, then 50 DEG C, under the conditions of 850r/min with the addition of 5%Mg (NO3)2With 5%Ca (NO3)2Sodium bicarbonate solution and the aluminum nitrate solution of mixed aid be co-precipitated, controlling endpoint pH is 6.5, aging 40min, prepares support precursor, continues to precipitate this presoma with the potassium hydroxide solution of 1mol/L afterwards, control endpoint pH 7.5, prepare carrier.This carrier is mixed with Cu/Zn parent making beating, scrubbed, filter, dry, roasting, the operation such as molding make methanol synthesis catalyst cat4.
Reference 1
Cu/Zn parent preparation process with example 1, then 40 DEG C, under the conditions of 700r/min, directly ammonia spirit is co-precipitated with aluminum nitrate solution, control endpoint pH 7.0, after aging 30min, prepare carrier.This carrier is mixed with Cu/Zn parent making beating, scrubbed, filter, dry, roasting, the operation such as molding make methanol synthesis catalyst cat5.
Reference 2
Cu/Zn parent preparation process is with example 1, then 40 DEG C, ammonia spirit is co-precipitated with aluminum nitrate solution under the conditions of 700r/min, controlling endpoint pH is 6.5, aging 30min, prepare support precursor, continue to precipitate this presoma with the sodium hydroxide solution of 1mol/L afterwards, control endpoint pH 7.5, prepare carrier.This carrier is mixed with Cu/Zn parent making beating, scrubbed, filter, dry, roasting, the operation such as molding make methanol synthesis catalyst cat6.
Sample test
Activity determination: catalyst sample granularity is 0.425-1.180mm.Using miniature continuous flow reactor of fixed bed, loadings 2mL of catalyst, granularity 16 mesh～40 mesh, the reduction of catalyst is at low hydrogen (H2: N2=5:95) in atmosphere, temperature programming (20 DEG C/h) is reduced 10 hours, and temperature rises to 230 DEG C.Reducing gases is switched to unstripped gas and carries out active testing.Active testing condition is reaction pressure 8.0MP, air speed 10000h-1, temperature 230 DEG C, synthesis gas forms: H2∶CO∶CO2∶N2=65:14:4:17(v/v).Catalyst, after 350 DEG C of heat treatment 20h, measures heat-resisting rear activity under these conditions, and activity value is to generate the space-time yield (gml of methanol-1h-1) represent, concrete test result is as shown in table 2.Wherein sample cat1, cat2, cat3, cat4 is for using the present invention to prepare, and cat5, cat6 are reference sample.
Table 1 active testing result
From the active testing result of table 1 catalyst sample it can be seen that at traditional CuO-ZnO-Al2O3In catalyst, use method of fractional steps precipitophore, first with the weak caustic solution precipitation aluminum nitrate solution that with the addition of Mn auxiliary agent, prepare support precursor, the methanol synthesis catalyst prepared with strong base solution continuation precipitation this presoma acquisition carrier the most again possesses higher initial activity and heat-resisting rear activity, can significantly improve the performance of catalyst.
Claims (8)
1. the method improving methanol synthesis catalyst performance, it is characterised in that by Cu (NO3)2With Zn (NO3)2Mixed solution and alkali liquor carry out co-precipitation and react and obtain Cu/Zn parent；Carrier uses step-by-step precipitation method to prepare, first it is co-precipitated with aluminum nitrate solution with the weak caustic solution that with the addition of auxiliary agent, prepare support precursor, continue to precipitate this presoma with strong base solution afterwards, obtain carrier, this carrier is mixed with Cu/Zn parent making beating, scrubbed, filter, dry, roasting, molding procedure make methanol synthesis catalyst.
The method improving methanol synthesis catalyst performance the most according to claim 1, during it is characterized in that preparing Cu/Zn parent, control mixing speed is 700 ~ 1200r/min, precipitation temperature 60 ~ 85 DEG C, endpoint pH 6.5 ~ 8.0, precipitation terminates rear aging 20 ~ 60min, with 60～85 DEG C of water washing slips to NO3 -1Concentration≤50mg/L.
The method improving methanol synthesis catalyst performance the most according to claim 1, it is characterised in that preparation weak caustic solution used by support precursor is the one in ammonia and sodium bicarbonate solution.
The method improving methanol synthesis catalyst performance the most according to claim 1, it is characterised in that the auxiliary agent added in weak caustic solution is Mn (NO3)2、Ca(NO3)2、Mg(NO3)2In one or both mixture solutions.
The method improving methanol synthesis catalyst performance the most according to claim 1, it is characterised in that during preparation support precursor, control mixing speed is 600 ~ 1000r/min, precipitation temperature 35 ~ 60 DEG C, and endpoint pH is 6.5, aging 20 ~ 40min.
The method improving methanol synthesis catalyst performance the most according to claim 1, it is characterised in that the strong base solution of described continuation precipitophore presoma is the one in sodium hydroxide and potassium hydroxide.
The method improving methanol synthesis catalyst performance the most according to claim 1, it is characterised in that the endpoint pH of carrier is 7.0 ~ 7.5.
The method improving methanol synthesis catalyst performance the most according to claim 1, it is characterised in that in carrier, auxiliary agent is 0.01 ~ 0.1 with the mol ratio of main carrier aluminum.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112169800A (en) * | 2019-07-02 | 2021-01-05 | 中石化南京化工研究院有限公司 | Methanol synthesis catalyst and preparation method thereof |
| CN116020469A (en) * | 2022-12-13 | 2023-04-28 | 南京邮电大学 | Preparation method of sintering-resistant copper-based methanol synthesis catalyst |
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| CN101497463A (en) * | 2009-03-06 | 2009-08-05 | 西南大学 | Method for preparing gamma-Fe2O3 nanoparticle by two-step precipitation |
| CN102701722A (en) * | 2012-02-13 | 2012-10-03 | 中国科学院上海硅酸盐研究所 | Method for producing yttrium aluminum garnet (YAG) nanopowder through fractional precipitation method |
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Patent Citations (4)
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| CN1356169A (en) * | 2000-11-30 | 2002-07-03 | 南化集团研究院 | Process for preparing Cu-series catalyst carrier for synthesizing methanol |
| CN1660490A (en) * | 2004-12-21 | 2005-08-31 | 中国科学院广州能源研究所 | Preparation method of synthesizing catalyst of methyl alcohol |
| CN101497463A (en) * | 2009-03-06 | 2009-08-05 | 西南大学 | Method for preparing gamma-Fe2O3 nanoparticle by two-step precipitation |
| CN102701722A (en) * | 2012-02-13 | 2012-10-03 | 中国科学院上海硅酸盐研究所 | Method for producing yttrium aluminum garnet (YAG) nanopowder through fractional precipitation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112169800A (en) * | 2019-07-02 | 2021-01-05 | 中石化南京化工研究院有限公司 | Methanol synthesis catalyst and preparation method thereof |
| CN116020469A (en) * | 2022-12-13 | 2023-04-28 | 南京邮电大学 | Preparation method of sintering-resistant copper-based methanol synthesis catalyst |
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