CN102125852A - Preparation method of methanol synthesis catalyst - Google Patents
Preparation method of methanol synthesis catalyst Download PDFInfo
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- CN102125852A CN102125852A CN2010106200751A CN201010620075A CN102125852A CN 102125852 A CN102125852 A CN 102125852A CN 2010106200751 A CN2010106200751 A CN 2010106200751A CN 201010620075 A CN201010620075 A CN 201010620075A CN 102125852 A CN102125852 A CN 102125852A
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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
Abstract
The invention provides a preparation method of a methanol synthesis catalyst. The preparation method comprises the following steps: co-precipitating soluble salts of copper, zinc and aluminum as well as an aqueous solution of an alkali metal salt to obtain a parent substance, and washing, drying, baking, tabletting, crushing and screening the parent substance to form particles; and preparing a salt solution of active components, dipping the particles in the solution in a vacuum environment by an isovolumetric mode, and drying and baking the dipped material to obtain the finished product of the methanol synthesis catalyst. By utilizing the preparation method of the methanol synthesis catalyst, the problems such as uneven distribution and high possibility of inactivation of surface active components of the catalyst obtained by the preparation method in the prior art are solved; and for the methanol synthesis catalyst obtained by the preparation method provided by the invention, the surface active components thereof are evenly distributed and not easily inactivated.
Description
Technical field
The invention belongs to the catalst for synthesis of methanol field, particularly relate to the preparation method of a kind of CO of being used for, CO2 and H2 catalst for synthesis of methanol.
Background technology
Methyl alcohol is one of the most basic Organic Chemicals.In recent years, methyl alcohol demand and production capacity sustainable growth, the purposes of methyl alcohol also has new development.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.Along with the continuous progress of synthesizing methanol production technology, it is found that the Cu-Zn-Al series catalysts has good low-temp methanol synthesizing activity.Publication number is the preparation method who discloses a kind of copper-based catalysts in the patent documentation of CN101185894A, the mixed solution and the carbonate coprecipitation that will contain copper, zinc obtain high-activity mother body, add the making beating of liquid aluminium salt and appropriate amount of addition agent again, drying, calcining, moulding make methanol synthesis catalyst; Publication number is to disclose a kind of preparation method who is used for methanol synthesis catalyst in the patent documentation of CN101274278A, with the soluble-salt co-precipitation of copper, zinc, aluminium, titanium, makes it aging then, dries, washs, dry, roasting obtains the powder catalyst.The above-mentioned method for preparing catalyst, in the time of the preparation parent auxiliary agent is added, this mode influences auxiliary agent and plays a role because the auxiliary agent that fixedly causes adding of parent crystal formation is difficult to reach evenly in the catalyst surface distribution, thereby influences the overall activity and the stability of catalyst.In the prior art, publication number is to disclose a kind of method of adding auxiliary agent of flooding among the preparation method of disclosed carbon monoxide room-temperature catalytic oxidation agent in the patent documentation of CN101422730A, carrier is soaked in a period of time in the maceration extract, makes the adjuvant component in the maceration extract enter carrier.Because dip time is longer, maceration extract is vulnerable to the influence of the oxygen in the environment, makes active the reduction or inactivation of adjuvant component in the maceration extract.
Summary of the invention
For this reason, technical problem to be solved by this invention is, the easy inactivation of adjuvant component in the method for preparing catalyst preparation process of the prior art, the catalyst surface auxiliary agent skewness that obtains, thereby a kind of preparation method of catalst for synthesis of methanol is provided, and adjuvant component is difficult for inactivation in the preparation process, the catalyst for methanol that makes surface auxiliary agent is evenly distributed.
For solving the problems of the technologies described above, the invention provides a kind of preparation method of catalst for synthesis of methanol, comprise the steps:
1) soluble-salt of copper, zinc and aluminium and the aqueous solution co-precipitation of alkali metal salt are obtained parent, parent washs through deionized water, and dry then, roasting are sieved into particle after compressing tablet, pulverizing;
2) preparation active component salting liquid, with 1) described in particle flood in vacuum environment with described solution, after the material drying behind the dipping, the roasting, obtain the finished product catalst for synthesis of methanol.
In the described step 1), the soluble-salt mixed solution of copper, zinc is joined in the sodium bicarbonate solution, control terminal point PH is 6.5, obtains copper zinc suspension after aging; Ammonium bicarbonate soln is joined in the soluble-salt solution of aluminium, mix obtaining parent then with described copper zinc suspension and stream.
Described active component comprises one or more in titanium, potassium, the manganese.
The salting liquid mass concentration of described active component is 1%～12%.
Described step 2) the dipping back is dry under 100 ℃～130 ℃ conditions in.
Described step 2) dried material roasting under 250 ℃～400 ℃ conditions in.
Described step 2) roasting time in is 1～5h.
Technique scheme of the present invention has the following advantages compared to existing technology,
The present invention is the impregnation catalyst agent aid under vacuum condition, make auxiliary agent be impregnated on the porous carrier and be penetrated into inner surface with the salting liquid form, form effective catalyst, maceration extract under the vacuum condition is difficult for inactivation, and can remove the impurity in the carrier space, increase the effective surface area of carrier, be impregnated into maceration extract on the carrier to greatest extent, save the consumption of maceration extract, efficiently added auxiliary agent potassium, titanium, manganese in the catalst for synthesis of methanol that has guaranteed simultaneously to make; And auxiliary agent is evenly distributed at catalyst surface, effectively promoted the dispersion of active component, simultaneously also being beneficial to active component evenly distributes at catalyst surface, prevent the sintering of catalyst, thereby the raising of higher degree the overall activity and the heat endurance of catalyst, reduce reduction temperature, reduced the technology use cost.
For large-scale production, infusion process technology is simple, and especially bead-type substrate infusion process treating capacity is big, the production capacity height; Active component is disperseed more even, and the utilization rate height can reduce the catalyst cost; Carrier through handling, helps improving catalyst activity and stability in advance.
The specific embodiment
Embodiment 1
1) will contain 30g copper nitrate and 11.8g zinc nitrate altogether solution join in the sodium bicarbonate solution and mix, the solution after mixed is neutralized to terminal point PH under 50 ℃ of conditions be 6.5, obtains copper zinc suspension after wearing out; Ammonium bicarbonate soln is joined in the solution that contains the 16.2g aluminum nitrate, and the neutralization back is also flowed to mix with the copper zinc solution and is obtained parent, and described parent washs through deionized water, is filtered to NaNO
3Disappear, through behind 3 pressure-filtering process repeatedly, 100 ℃ dry 12 hours down, prepare the compound that contains the copper zinc-aluminium after 5 hours 250 ℃ of following roastings then, through compressing tablet, pulverizing, sieve into 20～40 order particles, obtain precursor granule.
2) compound concentration is 1% solution of potassium carbonate, then under vacuum condition with this this precursor granule of solution incipient impregnation, the material behind the dipping is 110 ℃ of dryings, dried material obtains finished catalyst C1 behind 300 ℃ of roasting 2h.The physico-chemical property of C1 sees Table 1.
Embodiment 2
Use the precursor granule of preparation among the embodiment 1, compound concentration is 5.7% solution of potassium carbonate then, with this this precursor granule of solution incipient impregnation, the material behind the dipping is 130 ℃ of dryings under vacuum condition, and dried material obtains finished catalyst C2 behind 300 ℃ of roasting 4h.The physico-chemical property of C2 sees Table 1.
Embodiment 3
Use the precursor granule of preparation among the embodiment 1, compound concentration is 12% liquor potassic permanganate then, with this this precursor granule of solution incipient impregnation, the material behind the dipping is 120 ℃ of dryings under vacuum condition, and dried material obtains finished catalyst C3 behind 250 ℃ of roasting 5h.The physico-chemical property of C3 sees Table 1.
Embodiment 4
Use the precursor granule of preparation among the embodiment 1, compound concentration is 2.6% liquor potassic permanganate then, with this this precursor granule of solution incipient impregnation, the material behind the dipping is 100 ℃ of dryings under vacuum condition, and dried material obtains finished catalyst C4 behind 400 ℃ of roasting 1h.The physico-chemical property of C4 sees Table 1.
Embodiment 5
Use the precursor granule of preparation among the embodiment 1, compound concentration is 5.7% meta-titanium acid solution then, with this this precursor granule of solution incipient impregnation, the material behind the dipping is 130 ℃ of dryings under vacuum condition, and dried material obtains finished catalyst C5 behind 250 ℃ of roasting 4h.The physico-chemical property of C5 sees Table 1.
Embodiment 6
Use the precursor granule of preparation among the embodiment 1, compound concentration is 10.5% meta-titanium acid solution then, with this this precursor granule of solution incipient impregnation, the material behind the dipping is 120 ℃ of dryings under vacuum condition, and dried material obtains finished catalyst C6 behind 300 ℃ of roasting 2h.The physico-chemical property of C6 sees Table 1.
Comparative Examples 1
Use the precursor granule of preparation among the embodiment 1, compound concentration is 5.7% solution of potassium carbonate then, and this solution is sprayed on this precursor granule, and the material behind the dipping is 120 ℃ of dryings, and dried material obtains finished catalyst C7 behind 350 ℃ of roasting 3h.The physico-chemical property of C7 sees Table 1.
Comparative Examples 2
Use the precursor granule of preparation among the embodiment 1, compound concentration is 5% liquor potassic permanganate then, and this solution is sprayed on this precursor granule, and the material behind the dipping is 120 ℃ of dryings, and dried material obtains finished catalyst C8 behind 350 ℃ of roasting 3h.The physico-chemical property of C8 sees Table 1.
The active effect assessment of catalst for synthesis of methanol among the present invention: utilize self assembly methyl alcohol evaluating apparatus, the catalst for synthesis of methanol C1-C7 for preparing in 3ml embodiment 1-6, the Comparative Examples 1,2 is not loaded in the reacting furnace, under the condition of＞10MPa, tentatively reduce by hydrogen, the reduction back is by ready synthesis gas (CO:5%～15%CO
2: 3%～10%, H
2: 50%～70%, all the other are N
2) at 200 ℃, air speed is 10000-20000h
-1Environment is estimated the data that obtain the catalst for synthesis of methanol space-time yield down and is seen Table 1.Wherein C1-C6 is the product of the inventive method preparation, and C7-C8 is the product of additive method preparation.
By the data in the table 1 as can be seen, the contrast of the catalst for synthesis of methanol for preparing among the present invention and the evaluating data of like product, it is low that product of the present invention has a reduction temperature, the space-time yield height, the characteristics of Heat stability is good have the very strong market competitiveness.
Table 1
| Embodiment | Reduction temperature ℃ | Space-time yield g/ml/h | Heat-resisting back space-time yield g/ml/h |
| C1 | 200 | 1.42 | 1.26 |
| C2 | 200 | 1.35 | 1.20 |
| C3 | 200 | 1.32 | 1.18 |
| C4 | 200 | 1.27 | 1.09 |
| C5 | 200 | 1.33 | 1.15 |
| C6 | 200 | 1.29 | 1.11 |
| C7 | 250 | 1.20 | 1.00 |
| C8 | 280 | 1.17 | 0.95 |
Obviously, the foregoing description only is for example clearly is described, and is not the qualification to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give exhaustive to all embodiments.And conspicuous variation of being extended out thus or change still are among the protection domain of the invention.
Claims (7)
1. the preparation method of a catalst for synthesis of methanol comprises the steps:
1) soluble-salt of copper, zinc and aluminium and the aqueous solution co-precipitation of alkali metal salt are obtained parent, parent is through washing, dry, roasting, and compressing tablet, grinding screen are divided into particle then;
2) preparation active component salting liquid, with 1) described in particle flood in vacuum environment with described solution, after the material drying behind the dipping, the roasting, obtain the finished product catalst for synthesis of methanol.
2. the preparation method of catalst for synthesis of methanol according to claim 2 is characterized in that: in the described step 1), the soluble-salt mixed solution of copper, zinc is joined in the sodium bicarbonate solution, control terminal point PH is 6.5, obtains copper zinc suspension after aging; Ammonium bicarbonate soln is joined in the soluble-salt solution of aluminium, mix obtaining parent then with described copper zinc suspension and stream.
3. the preparation method of catalst for synthesis of methanol according to claim 1 and 2, it is characterized in that: described active component comprises one or more in titanium, potassium, the manganese.
4. the preparation method of catalst for synthesis of methanol according to claim 3, it is characterized in that: the salting liquid mass concentration of described active component is 1%～12%.
5. the preparation method of catalst for synthesis of methanol according to claim 4 is characterized in that: dipping back drying under 100 ℃～130 ℃ conditions described step 2).
6. the preparation method of catalst for synthesis of methanol according to claim 5 is characterized in that: dried material roasting under 250 ℃～400 ℃ conditions described step 2).
7. the preparation method of catalst for synthesis of methanol according to claim 6, it is characterized in that: the roasting time described step 2) is 1～5 hour.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383928A (en) * | 2014-11-18 | 2015-03-04 | 大连瑞克科技有限公司 | Preparing method of high-performance catalyst for hydrogenation of carbon dioxide for synthesizing methyl alcohol |
| CN104549299A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of copper based hydrogenation catalyst |
| CN104907073A (en) * | 2014-03-13 | 2015-09-16 | 中国石油化工股份有限公司 | Ester hydrogenation catalyst, preparation method and ester hydrogenation reaction method |
| CN106944069A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | Catalst for synthesis of methanol precursor, catalst for synthesis of methanol and preparation method thereof |
| CN107115895A (en) * | 2016-02-25 | 2017-09-01 | 中国石油化工股份有限公司 | A kind of preparation method of copper-zinc-based catalyst |
| CN109289854A (en) * | 2018-11-01 | 2019-02-01 | 四川天科技股份有限公司 | A kind of high stability high intensity catalst for synthesis of methanol and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493398A (en) * | 2003-08-29 | 2004-05-05 | 南化集团研究院 | Copper series carbon oxide low temperature conversion catalyst and its preparation method and use |
| CN101185894A (en) * | 2006-11-17 | 2008-05-28 | 南化集团研究院 | Method for preparing copper base catalyst |
| CN101327431A (en) * | 2008-07-31 | 2008-12-24 | 西北化工研究院 | Process for preparing synthetic methanol catalyst |
| CN101584986A (en) * | 2009-07-04 | 2009-11-25 | 太原理工大学 | Method for preparing methanol synthesizing catalyst |
-
2010
- 2010-12-31 CN CN2010106200751A patent/CN102125852A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493398A (en) * | 2003-08-29 | 2004-05-05 | 南化集团研究院 | Copper series carbon oxide low temperature conversion catalyst and its preparation method and use |
| CN101185894A (en) * | 2006-11-17 | 2008-05-28 | 南化集团研究院 | Method for preparing copper base catalyst |
| CN101327431A (en) * | 2008-07-31 | 2008-12-24 | 西北化工研究院 | Process for preparing synthetic methanol catalyst |
| CN101584986A (en) * | 2009-07-04 | 2009-11-25 | 太原理工大学 | Method for preparing methanol synthesizing catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 周岳贤等: "载体对Cu-Mn甲醇合成催化剂性能的影响", 《湖南化工》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549299A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of copper based hydrogenation catalyst |
| CN104907073A (en) * | 2014-03-13 | 2015-09-16 | 中国石油化工股份有限公司 | Ester hydrogenation catalyst, preparation method and ester hydrogenation reaction method |
| CN104907073B (en) * | 2014-03-13 | 2018-08-28 | 中国石油化工股份有限公司 | The method of ester through hydrogenation catalyst and preparation method thereof and ester through hydrogenation reaction |
| CN104383928A (en) * | 2014-11-18 | 2015-03-04 | 大连瑞克科技有限公司 | Preparing method of high-performance catalyst for hydrogenation of carbon dioxide for synthesizing methyl alcohol |
| CN106944069A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | Catalst for synthesis of methanol precursor, catalst for synthesis of methanol and preparation method thereof |
| CN106944069B (en) * | 2016-01-07 | 2019-06-11 | 中国石油化工股份有限公司 | Catalst for synthesis of methanol predecessor, catalst for synthesis of methanol and preparation method thereof |
| CN107115895A (en) * | 2016-02-25 | 2017-09-01 | 中国石油化工股份有限公司 | A kind of preparation method of copper-zinc-based catalyst |
| CN107115895B (en) * | 2016-02-25 | 2019-09-17 | 中国石油化工股份有限公司 | A kind of preparation method of copper-zinc-based catalyst |
| CN109289854A (en) * | 2018-11-01 | 2019-02-01 | 四川天科技股份有限公司 | A kind of high stability high intensity catalst for synthesis of methanol and preparation method thereof |
| CN109289854B (en) * | 2018-11-01 | 2020-10-27 | 西南化工研究设计院有限公司 | High-stability high-strength methanol synthesis catalyst and preparation method thereof |
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Application publication date: 20110720 |