CN100584455C - Method for preparing copper base catalyst - Google Patents
Method for preparing copper base catalyst Download PDFInfo
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- CN100584455C CN100584455C CN200610097873A CN200610097873A CN100584455C CN 100584455 C CN100584455 C CN 100584455C CN 200610097873 A CN200610097873 A CN 200610097873A CN 200610097873 A CN200610097873 A CN 200610097873A CN 100584455 C CN100584455 C CN 100584455C
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- precipitating reagent
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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
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Abstract
The invention relates to a preparation method of a copper-based catalyst, belonging to the technical field of catalyst. The catalyst is prepared by adopting coprecipitation, and the main components are CuO, ZnO, Al2O3, and assistant to form a catalyst system with a plurality of components; the steps mainly include: the mixed solution of Cu and Zn is added to the carbonate solution to deposit and obtain high activity mother substance. After being washed, appropriate amount of cleaned liquid aluminum salt and appropriate amount of assistant are added for beating, drying, calcining, and molding. The catalyst is used for making methanol with synthetic gas which comprises CO, CO2 and H2, which is especially applied to a methanol synthesis plant with low temperature low pressure.
Description
Technical field:
The invention belongs to catalyst technical field, relate to a kind of preparation method of catalyst for synthesizing copper based methanol.
Background technology:
Methyl alcohol is one of the most basic Organic Chemicals.Plant-scale methyl alcohol generally is with containing H
2, CO, CO
2The synthesis gas method production of under certain pressure and temperature and the condition that has catalyst to exist, reacting.In early days, people are that the catalyst of main active ingredient is produced methyl alcohol in order to the oxide of Zn, Cr, but this catalyst must just can have active preferably under the condition of high temperature (as 350 ℃) and high pressure (as 30.0MPa), thereby the methanol contaminant content height of producing, and energy consumption is also high.Afterwards, it is found that the Cu-Zn-Al series catalysts has good low-temp methanol synthesizing activity, because the methanol contaminant content that this system obtains at low temperatures is lower, and this catalyst also has the excellent methanol synthesizing activity under lower operating pressure, help energy-conservationly, this system is widely used.
Catalyst for methanol has manufacture method now: methanol synthesis catalyst is generally copper-zinc-aluminium system at present.Common reactive precursor preparation method is the soluble-salt mixed solution and the precipitating reagent reaction of copper, zinc, obtaining copper, zinc precipitation is reactive precursor, add alumina catalyst support again, parent combines with carrier after operations such as washing, filtration, oven dry, roasting, moulding are made catalyst.Methanol synthesis catalyst with the method preparation can meet the needs of production substantially, but apart from requirements at the higher level distance is arranged still.
Summary of the invention:
The objective of the invention is to propose a kind of new copper base catalyst for methanol preparation method.Catalyst for methanol with the inventive method preparation has higher methyl alcohol synthesizing activity and the heat endurance of catalyst for preparing than conventional method, can satisfy higher needs.
The present invention is achieved like this: 1L is contained 100g～200g Cu (NO
3)
2And 30g～120gZn (NO
3)
2Mixed solution, be heated to 60 ℃～90 ℃ stand-by, the acid carbonate solution of concentration range 30g/L～120g/L is made precipitating reagent, be heated to 60 ℃～90 ℃ stand-by, stir down above-mentioned mixed solution is joined in the precipitating reagent, N-process control temperature is at 60 ℃～90 ℃, and control endpoint pH 6.5～8.0 obtains high-activity mother body; To not contain Cl, S impurity, concentration range 5g/L～200g/L soluble aluminum salting liquid and concentration are 0.5%～20% precipitating reagent reaction, make the big surperficial carrier of heat endurance; With the carrier washes clean, mix making beating with high-activity mother body, in pulping process, add appropriate amount of addition agent, drying, calcining, moulding.
In the preparing carriers process, carrier is washed till traditional indicator nondiscolouring, carrier is fully combined with mother liquor; An amount of a little auxiliary agent that adds in parent is pulled an oar the process that combines with carrier, make parent and carrier obtain fully combining, thereby make active constituent decentralization height, have bigger surface area and suitable pore volume, bring into play the synergy of component better, obtain product catalyst and have the higher active and long life-span.
The used acid carbonate of the present invention can be that wherein a kind of of sodium acid carbonate, potassium, ammonium also can be two or three mixture solution wherein.Aluminum soluble salt of the present invention can be nitrate or acetate; Precipitating reagent can be an ammoniacal liquor.The used auxiliary agent of the present invention is one or more metal oxides or its carbonate or its acetate or its oxalates, one or more among preferred K, Mg, Mn, the V.
The specific embodiment:
Following embodiment is in order to further specify content of the present invention:
Embodiment 1
1L is contained 160gCu (NO
3)
2And 72gZn (NO
3)
2A solution, be heated to 60 ℃～88 ℃ stand-by.With 210g NaHCO
3Be dissolved in the 3L deionized water and make solution B, be heated to 60 ℃～88 ℃ stand-by.Under stirring solution A is added solution B, N-process control temperature is controlled endpoint pH 6.0～8.0 at 60 ℃～80 ℃.With 23.5g Al (NO
3)
39H
2O is dissolved in the 500ml deionized water, this Al (NO that neutralizes of the ammoniacal liquor with 0.5%～20%
3)
3Alumina gel is made in solution to pH=7.0～8.0, again this gel is cleaned the back and mixes with copper, zinc reactive precursor, adds 1% (w) auxiliary agent potassium oxalate, stirs.Then slip after filtration, washing, the filter cake that obtains is at 90 ℃～120 ℃ oven dry 20hr., again at 260 ℃～360 ℃ roasting 3hr., the catalyst after the roasting is admixed 0.5%～3% graphite and is pressed into tablet and is finished catalyst.
Embodiment 2
The preparation method is the same, adds to such an extent that auxiliary agent is the mixed aid of magnesium carbonate of the potash and 2.5% (W) of 0.5% (W).
Embodiment 3
The preparation method is the same, adds to such an extent that auxiliary agent is the MnO of 2% (W)
2Auxiliary agent.
Embodiment 4
The preparation method is the same, adds to such an extent that auxiliary agent is the V of the potassium acetate and 2% (W) of 0.5% (W)
2O
5Mixed aid.
Sample test
Catalyst sample: granularity is 0.425mm～1.180mm.
The sample activation: sample fed reducing gases (H before the test activity
2: N
2=3: 97) reduction, temperature programming to 210 ℃ activates.
The active testing condition: the sample after the reduction, feed synthesis gas, at pressure 5.0MPa, 210 ℃ of temperature, air speed 2.0 * 10
4h
-1Measure catalyst activity down.Synthetic gas density, % (v/v): CO 3.8～4.2, CO
20.7～0.9, H
255～65.To generate the space-time yield (gml of methyl alcohol
-1h
-1) the active height of expression.
Active testing the results are shown in table 1.Wherein sample 1,2,3,4 is the catalyst with this preparation method preparation, and sample X is certain domestic catalyst, is reference catalyst.
Table 1 sample active testing result
| Catalyst sample | X | 1 | 2 | 3 | 4 |
| Relative initial activity | 100 | 110 | 105 | 111 | 108 |
| Heat-resisting relatively activity | 100 | 108 | 110 | 103 | 107 |
Can be found out that by test result the catalyst methanol yield that adopts the inventive method preparation shows that apparently higher than the reference sample 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 contain CO, CO
2And H
2Synthesis gas make methyl alcohol, be particularly useful for low-temp low-pressure synthesizing methanol device.
Claims (2)
1. the preparation method of a copper-based catalysts is characterized in that it mainly may further comprise the steps, and 1L is contained 100g～200g Cu (NO
3)
2And 30g～120gZn (NO
3)
2Mixed solution, be heated to 60 ℃～90 ℃ stand-by, the acid carbonate solution of concentration range 30g/L～120g/L is made precipitating reagent, be heated to 60 ℃～90 ℃ stand-by, stir down above-mentioned mixed solution is joined in the precipitating reagent, N-process control temperature is at 60 ℃～90 ℃, and control endpoint pH 6.5～8.0 obtains high-activity mother body; To not contain Cl, S impurity, concentration range 5g/L～200g/L soluble aluminum salting liquid and concentration are 0.5%～20% precipitating reagent reaction, make the big surperficial carrier of heat endurance; With the carrier washes clean, mix making beating with high-activity mother body, in pulping process, add auxiliary agent, auxiliary agent is the metal oxide of K, Mg, Mn or V or in its carbonate or its acetate or its oxalates one or more, drying, calcining, moulding.
2. a Preparation of catalysts method according to claim 1 is characterized in that in the preparing carriers process, and carrier is washed till traditional indicator nondiscolouring, and carrier is fully mixed making beating with high-activity mother body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610097873A CN100584455C (en) | 2006-11-17 | 2006-11-17 | Method for preparing copper base catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610097873A CN100584455C (en) | 2006-11-17 | 2006-11-17 | Method for preparing copper base catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101185894A CN101185894A (en) | 2008-05-28 |
| CN100584455C true CN100584455C (en) | 2010-01-27 |
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ID=39478640
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|---|---|---|---|
| CN200610097873A Active CN100584455C (en) | 2006-11-17 | 2006-11-17 | Method for preparing copper base catalyst |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733109B (en) * | 2008-11-06 | 2012-09-05 | 南化集团研究院 | Preparation method of copper-based catalyst |
| CN102000578A (en) * | 2010-09-29 | 2011-04-06 | 大连理工大学 | Catalyst for preparing methyl alcohol by carbon dioxide catalytic hydrogenation and preparing method thereof |
| CN102451695A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工集团公司 | Preparation method of copper base catalyst for methanol synthesis |
| CN102125852A (en) * | 2010-12-31 | 2011-07-20 | 北京三聚环保新材料股份有限公司 | Preparation method of methanol synthesis catalyst |
| CN102259002B (en) * | 2011-06-13 | 2013-05-08 | 中国石油化工股份有限公司 | Method for preparing matrix capable of improving performance of catalyst for synthesizing methanol |
| CN102513113B (en) * | 2011-12-15 | 2013-10-09 | 太原理工大学 | Slurry catalyst for preparing ethanol from synthesis gas in slurry reactor and preparation method thereof |
| CN103480377B (en) * | 2012-06-15 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of copper based catalyst for methanol synthesis |
| 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 |
| CN103223344B (en) * | 2013-04-17 | 2014-07-09 | 太原理工大学 | Copper-based catalyst for synthesis of methanol in slurry bed, preparation method and application thereof |
| CN108786823B (en) * | 2018-04-25 | 2021-02-05 | 广西民族师范学院 | Preparation and application of strip-shaped catalyst for hydrogen production by methanol reforming |
| CN110898840A (en) * | 2018-09-18 | 2020-03-24 | 中国石油化工股份有限公司 | Methanol synthesis catalyst and preparation method thereof |
| CN111250098B (en) * | 2020-03-11 | 2023-03-31 | 上海兖矿能源科技研发有限公司 | Water hydrogenation catalyst for Fischer-Tropsch synthesis reaction and preparation method and application thereof |
| CN114669303A (en) * | 2022-03-24 | 2022-06-28 | 山东亮剑环保新材料有限公司 | Alkaline earth metal modified CO2Preparation method of hydrogenation catalyst |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: 210048 Jiangsu Province, Nanjing city Liuhe District Dachang geguan Road No. 699 Patentee before: Nanhua Group Research Institute |