CN102451695A - Preparation method of copper base catalyst for methanol synthesis - Google Patents
Preparation method of copper base catalyst for methanol synthesis Download PDFInfo
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- CN102451695A CN102451695A CN2010105169484A CN201010516948A CN102451695A CN 102451695 A CN102451695 A CN 102451695A CN 2010105169484 A CN2010105169484 A CN 2010105169484A CN 201010516948 A CN201010516948 A CN 201010516948A CN 102451695 A CN102451695 A CN 102451695A
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- alkali lye
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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
- 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
Abstract
A preparation method of a copper base catalyst for methanol synthesis belongs to the technical field of catalyst. A coprecipitation method is employed to prepare a three-component catalyst system, mainly comprising ingredients of copper, zinc and aluminium. The preparation method comprises steps of: (1) adding Al liquid slowly into aqueous alkali emulsified by an auxiliary agent to prepare a carrier precursor; (2) carrying out parallel flow coprecipitation on a mixed solution of Cu and Zn and alkali liquor, adding the mixture into the carrier precursor from the step (1), ageing, washing, filtering, drying, calcining and moulding to prepare the catalyst for methanol synthesis. The catalyst prepared by the method of the invention has high specific surface area and activity; the preparation technology is simple, accurate and suitable for methanol preparation from synthetic gas containing CO, CO2 and H2, especially suitable for a low temperature and low pressure methanol synthesis apparatus.
Description
Technical field: the invention belongs to the fine chemistry industry catalyst technical field, be specifically related to a kind of preparation method of catalyst for synthesizing copper based methanol.
Background technology: methyl alcohol is widely used in organic synthesis, dyestuff, medicine, agricultural chemicals, coating, automobile and the national defense industry as a kind of important basic Organic Chemicals and clean fuel.Its downstream product mainly contains formaldehyde, acetic acid, methyl tertiary butyl ether(MTBE), methyl acetate, dimethyl ether, methyl formate, gasoline additive etc.It can make synthesis gas through partial oxidation or steam reforming by gas raw material natural gas and casing-head gas, liquid charging stock naphtha and residual oil and solid material coal etc., again through purify, synthetic, rectifying makes.Industrial methanol generally is with containing H
2, CO, CO
2Synthesis gas in certain pressure and temperature and have that reaction produces under the condition that catalyst exists.Catalyst adopts the Cu-Zn-Al system; Wherein copper, zinc oxide are called as reactive precursor; Aluminium oxide is a carrier, and this System Catalyst not only has good low-temp methanol synthesizing activity under lower operating pressure, and synthetic methanol contaminant content is lower; Help energy-conservationly, so this system is widely used.
It is generally acknowledged that during the Cu radical synthesizing methanol was urged, Cu/Zn was the active material of synthesizing methanol, Al
2O
3As the carrier of catalyst, play the effect that support is provided for the catalyst activity material, when the uniform individual layer of active material is an effective rate of utilization when reaching maximum attached to the carrier surface of high dispersive, it is maximum that activity of such catalysts also reaches.
Summary of the invention: the objective of the invention is to propose a kind of new Cu base methanol synthetic catalyst preparation method.
Methanol synthesis catalyst with the inventive method preparation has higher methyl alcohol synthesizing activity and the hear resistance of catalyst than the conventional method preparation, is dispersed in the Al of high dispersive in the catalyst between copper, zinc component
2O
3Carrier surface, catalyst have better physical and chemical performance, can satisfy higher needs.
Catalyst of the present invention mainly consists of the copper zinc-aluminium, and the weight percentage of copper zinc-aluminium is conventionally known to one of skill in the art, and the preparation method mainly is: earlier alkali lye is slowly joined in the Al liquid after the emulsification, obtain the higher support precursor of decentralization; Cu, Zn mixed solution and alkali lye also flow co-precipitation and join in the support precursor, and aging then, washing, filtration, drying, calcining, moulding make the high activity catalst for synthesis of methanol.The copper zinc-aluminium content of the content of copper zinc-aluminium and traditional catalst for synthesis of methanol is suitable.
Usually, Preparation of catalysts method according to the invention may further comprise the steps:
Step (1): compound concentration is copper, the zinc mixed nitrate solution of 0.1～1mol/L;
Step (2): compound concentration is the aluminium nitrate solution of 0.01～0.02mol/L;
Step (3): compound concentration is 1～1.5mol/L aqueous slkali;
Step (4): the emulsion adjuvant that in the aluminum salt solution that step (2) prepares, adds earlier 1～3% (w) carries out emulsion reaction, constantly slowly dripping the alkali lye that step (3) prepares under the stirring condition, obtains support precursor then;
Step (5): step (1) is mixed liquid and step (3) alkali lye under stirring condition; 60～90 ℃ and flow in co-precipitation to step (4) support precursor; Keep pH value of solution value 6～9; And stream finishes the aging 30～120min in back, leaves standstill deionized water then and washs to 10 of diphenylamine sulfate solution not bluely, and suction filtration, drying and calcining, moulding make catalst for synthesis of methanol.
The emulsion adjuvant that said emulsification AI liquid adds is one or more in triethyl group hexyl phosphoric acid, diethylamine, triethylamine, polyacrylamide, guar gum, ethylene glycol, polyethylene glycol, fatty acid polyethylene glycol ester, the glycerine.
The emulsifying temperature of said Al liquid is controlled to be 20～60 ℃, and the time is controlled to be 5～60min, and the pH value of titration end-point is controlled to be 7～8, and titration finishes the aging 30～120min of back carrier and obtains support precursor
Used deposition alkali lye is one or more in NaOH, sodium carbonate, sodium acid carbonate or the saleratus in the preparation process.
The specific embodiment: following combination instance further specifies content of the present invention:
Instance 1-1: 196mL is contained 126g Al (NO
3)
3Solution and 0.6g ethylene glycol are mixed and heated to 40 ℃, and emulsification 15min under stirring condition obtains latex A.80gNaOH is dissolved in to process solution B in the 2L deionized water for use.Stir the decline solution B and slowly be added drop-wise among the A, N-process control temperature is 35～40 ℃, control endpoint pH 6.5～8.0, and neutralization finishes aging 30～40min.
Instance 1-2: the preparation process is with routine 1-1, but in N-process, adds the 2.52g polyethylene glycol.
Instance 1-3: the preparation process is with routine 1-1, but in N-process, adds the 4.28g polyethylene glycol.
Instance 2-1: 196mL is contained 126g Al (NO
3)
3Solution and 1.26g diethylamine are mixed and heated to 50 ℃, and emulsification 15min under stirring condition obtains latex A.80gNaOH is dissolved in to process solution B in the 2L deionized water for use.Stir the decline solution B and slowly be added drop-wise among the A, N-process control temperature is 45～50 ℃, control endpoint pH 6.5～8.0, and neutralization finishes aging 30～60min.
Instance 2-2: the preparation process is with routine 2-1, but the Hybrid Heating temperature is 45 ℃, and N-process control temperature is 40～45 ℃.
Instance 3: 196mL is contained 126g Al (NO
3)
3Solution and 1.26g triethylamine are mixed and heated to 45 ℃, and emulsification 15min under stirring condition obtains latex A.With 168gNaHCO
3Be dissolved in that to process solution C in the 2L deionized water for use.Under stirring solution C slowly is added drop-wise among the A, N-process control temperature is 40～45 ℃, control endpoint pH 6.5～8.0, and neutralization finishes the 30～40min that wears out.
Instance 4: 196mL is contained 126g Al (NO
3)
3Solution and 1.26g polyethylene glycol are mixed and heated to 45 ℃, and emulsification 15min under stirring condition obtains latex A.With 106gNa2CO
3Be dissolved in that to process solution D in the 2L deionized water for use.Stir the decline solution D and slowly be added drop-wise among the A, N-process control temperature is 40～45 ℃, control endpoint pH 6.5～8.0, and neutralization finishes aging 30～40min.
1.8L is contained 315gCu (NO
3)
2And 110gZn (NO
3)
2E solution, be heated to 60-90 ℃ for use.With 530gNa
2CO
3Be dissolved in and process solution F in the 5L deionized water, be heated to 60-90 ℃ for use.Stir down solution E and F and flow in the high dispersive support precursor that above-mentioned instance makes; N-process control pH value 7.5～8; 60～90 ℃ of temperature, and the aging 30～60min in stream end back are processed the Cu-series catalyst for synthesizing methanol sample through operations such as washing, filtration, oven dry, roasting, moulding.
Comparison example
1.8L is contained 315gCu (NO
3)
2And 110gZn (NO
3)
2E solution, be heated to 60-90 ℃ for use.With 530gNa
2CO
3Be dissolved in and process solution F in the 5L deionized water, be heated to 60-90 ℃ for use.Stir down solution E is made reactive precursor with F and stream, N-process control pH value 7.5～8,60～90 ℃ of temperature, and the stream 30～60min that wears out after finishing.
In the reactive precursor that above-mentioned instance makes, add alumina support, process the Cu-series catalyst for synthesizing methanol sample through operations such as washing, filtration, oven dry, roasting, moulding.
Sample test
Catalyst sample: granularity is 0.425-1.180mm.
The active detection: adopt miniature continuous flow reactor of fixed bed, the loadings 2mL of catalyst, granularity 16 orders～40 orders, the reduction of catalyst is at low hydrogen (H
2: N
2=5: 95) in the atmosphere, (20 ℃/h) reduced 10 hours, temperature rises to 230 ℃ in temperature programming.Reducing gases is switched to unstripped gas carry out active testing.The active testing condition is reaction pressure 8.0MP, air speed 10000h
-1, 230 ℃ of temperature, synthesis gas is formed: H
2: CO: CO
2: N
2=65: 14: 4: 17 (v/v).Catalyst is behind 350 ℃ of heat treatment 20h, and it is active to measure heat-resisting back under these conditions, and activity value is to generate the space-time yield (gml of methyl alcohol
-1h
-1) expression.And come the height of comparative sample heat endurance with the active ratio in heat-resisting back with initial activity.
The active testing result is in shown in the table 1.Wherein sample 1-1,1-2,1-3,2-1,2-2,3,4 are preparation method's preparation of the present invention, and comparative sample is the reference of conventional method preparation.
Table 1 active testing result
Above-mentioned catalyst sample is carried out materialization characterize, the result sees table 2.
Table 2 materialization characterization result
| Sample number into spectrum | Specific area (m 2/g) | Pore volume (ml/g) | Average pore size (nm) |
| 1-1 | 109 | 0.29 | 5.20 |
| 1-2 | 107 | 0.32 | 6.70 |
| 1-3 | 107 | 0.28 | 6.30 |
| 2-1 | 109 | 0.28 | 5.29 |
| 2-2 | 105 | 0.31 | 5.36 |
| 3 | 108 | 0.29 | 6.00 |
| 4 | 106 | 0.29 | 5.31 |
| Comparison sample | 104 | 0.28 | 5.00 |
Can find out by table 1; Adopt the inventive method to prepare the methanol synthesis catalyst methanol yield apparently higher than the reference sample; Can find out that by table 2 specific area of catalyst, pore volume, average pore size show that all greater than reference the present invention has compared tangible progress with existing method; Promptly higher methyl alcohol synthesizing activity can satisfy higher needs.
The catalyst of the inventive method preparation is applicable to and contains CO, CO
2And H
2Synthesising gas systeming carbinol, be particularly suited for low-temp low-pressure synthesizing methanol device.
Claims (5)
1. the preparation method of a catalyst for synthesizing copper based methanol, catalyst mainly consists of the copper zinc-aluminium, and the weight percentage of copper zinc-aluminium is known, it is characterized in that earlier alkali lye is slowly joined in the Al liquid after the emulsification, obtains the higher support precursor of decentralization; Cu, Zn mixed solution and alkali lye also flow co-precipitation and join in the support precursor, and aging then, washing, filtration, drying, calcining, moulding make the high activity catalst for synthesis of methanol.
2. according to the said Preparation of catalysts method of claim 1, it is characterized in that Preparation of catalysts may further comprise the steps:
Step (1): compound concentration is copper, the zinc mixed nitrate solution of 0.1～1mol/L;
Step (2): compound concentration is the aluminium nitrate solution of 0.01～0.02mol/L;
Step (3): compound concentration is 1～1.5mol/L aqueous slkali;
Step (4): the emulsion adjuvant that in the aluminum salt solution that step (2) prepares, adds earlier 1～3% (w) carries out emulsion reaction, constantly slowly dripping the alkali lye that step (3) prepares under the stirring condition, obtains support precursor then;
Step (5): step (1) is mixed liquid and step (3) alkali lye under stirring condition; 60～90 ℃ and flow in co-precipitation to step (4) support precursor; Keep pH value of solution value 6～9; And stream finishes the aging 30～120min in back, leaves standstill deionized water then and washs to 10 of diphenylamine sulfate solution not bluely, and suction filtration, drying and calcining, moulding make catalst for synthesis of methanol.
3. according to claim 1 or 2 said Preparation of catalysts methods, the emulsion adjuvant that it is characterized in that the interpolation of emulsification AI liquid is one or more in triethyl group hexyl phosphoric acid, diethylamine, triethylamine, polyacrylamide, guar gum, ethylene glycol, polyethylene glycol, fatty acid polyethylene glycol ester, the glycerine.
4. according to claim 1 or 2 said one-tenth Preparation of catalysts methods, it is characterized in that deposition alkali lye used in the preparation process is one or more in NaOH, sodium carbonate, sodium acid carbonate or the saleratus.
5. according to claim 1 or 2 said Preparation of catalysts methods; The emulsifying temperature that it is characterized in that Al liquid is controlled to be 20～60 ℃; Time is controlled to be 5～60min, and the pH value of titration end-point is controlled to be 7～8, and titration finishes the aging 30～120min of back carrier and obtains support precursor
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480378A (en) * | 2012-06-15 | 2014-01-01 | 中国石油化工股份有限公司 | Preparation method of improved copper base catalyst for methanol synthesis |
| CN103506170A (en) * | 2012-06-30 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method of low-sodium copper-based dehydrogenation catalyst |
| CN103623833A (en) * | 2013-11-07 | 2014-03-12 | 青岛文创科技有限公司 | Novel methanol synthesis catalyst and preparation method thereof |
| CN105964267A (en) * | 2016-06-03 | 2016-09-28 | 沈阳三聚凯特催化剂有限公司 | Copper-based methanol synthesis catalyst and preparation method thereof |
| CN106179519A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for synthesizing copper based methanol high performance carrier materials |
| CN106179357A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of synthesis gas another name for catalyst |
| CN111167459A (en) * | 2020-02-12 | 2020-05-19 | 中国科学院上海高等研究院 | Catalyst for preparing methanol from mixed gas and preparation method and application thereof |
| 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 |
| CN113509936A (en) * | 2020-04-10 | 2021-10-19 | 中石化南京化工研究院有限公司 | Preparation method of methanol synthesis catalyst loaded on composite gel carrier |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480378B (en) * | 2012-06-15 | 2016-08-10 | 中国石油化工股份有限公司 | The preparation method of Modified Copper-based Catalysts for Methanol |
| CN103480378A (en) * | 2012-06-15 | 2014-01-01 | 中国石油化工股份有限公司 | Preparation method of improved copper base catalyst for methanol synthesis |
| CN103506170A (en) * | 2012-06-30 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method of low-sodium copper-based dehydrogenation catalyst |
| CN103506170B (en) * | 2012-06-30 | 2015-07-01 | 中国石油化工股份有限公司 | Preparation method of low-sodium copper-based dehydrogenation catalyst |
| CN103623833A (en) * | 2013-11-07 | 2014-03-12 | 青岛文创科技有限公司 | Novel methanol synthesis catalyst and preparation method thereof |
| CN103623833B (en) * | 2013-11-07 | 2016-05-18 | 青岛文创科技有限公司 | A kind of novel carbinol synthetic catalyst and preparation method thereof |
| CN106179357A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of synthesis gas another name for catalyst |
| CN106179519A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for synthesizing copper based methanol high performance carrier materials |
| CN105964267A (en) * | 2016-06-03 | 2016-09-28 | 沈阳三聚凯特催化剂有限公司 | Copper-based methanol synthesis catalyst and preparation method thereof |
| CN105964267B (en) * | 2016-06-03 | 2018-09-18 | 沈阳三聚凯特催化剂有限公司 | A kind of Cu-series catalyst for synthesizing methanol and preparation method thereof |
| CN111167459A (en) * | 2020-02-12 | 2020-05-19 | 中国科学院上海高等研究院 | Catalyst for preparing methanol from mixed gas and preparation method and application thereof |
| 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 |
| CN113509936A (en) * | 2020-04-10 | 2021-10-19 | 中石化南京化工研究院有限公司 | Preparation method of methanol synthesis catalyst loaded on composite gel carrier |
| 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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Application publication date: 20120516 |