CN101274278A - Method for preparing catalyst for synthesizing methanol - Google Patents
Method for preparing catalyst for synthesizing methanol Download PDFInfo
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- CN101274278A CN101274278A CNA2007100648809A CN200710064880A CN101274278A CN 101274278 A CN101274278 A CN 101274278A CN A2007100648809 A CNA2007100648809 A CN A2007100648809A CN 200710064880 A CN200710064880 A CN 200710064880A CN 101274278 A CN101274278 A CN 101274278A
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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
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Abstract
The invention provides a preparation method of a catalyst which is used for methanol synthesis. Mixed hydroxide at least containing copper and zinc or/and basic salt precipitation are hydrothermally treated under the temperature of 50-300 DEG C and pressure of 0.11-10Mpa for 0.5-240 hours, and dried and roasted so as to obtain the catalyst comprising copper oxide and zinc oxide. The preparation method provided by the invention modulates the structure of catalyst precipitation and greatly improves the performance of catalyst.
Description
Technical field
The invention belongs to catalysis material and synthesis gas transformation technology field, relate in particular to a kind of synthetic Preparation of catalysts method of methyl alcohol that is used for.
Background technology
Methyl alcohol is a kind of very important industrial chemicals and chemical products.Since the sixties in last century, Britain ICI company succeeded in developing low pressure gas-solid phase method methanol synthetizing technology technology, produced methyl alcohol industrialization for many years by synthesis gas low pressure.CuO-ZnO-Al
2O
3Series catalysts is present main low-pressure process methanol synthesis catalyst, also can add other yuan and usually improve CuO-ZnO-Al
2O
3The performance of series catalysts, antitoxin (S, the Cl) performance that adds the W rear catalyst as patent US 4483943 reports obviously improves; Patent EP 0483943 report adds the low temperature active that Zr, Mn etc. can obviously improve catalyst, and adds the poison resistance that Mo can improve catalyst.Patent EP 0101622, EP 0146165 etc. have reported the effect of adding rare earth element.Patent RU 2175886, JP 9253495, JP 6312138, DE 3238845, JP54053691, US 4111847, DE 2365001 etc. are seen in the interpolation of other element such as Ga, Cr, Mg, V, Ba, Ti, B, Ca etc.
The performance of methanol synthesis catalyst and the composition of catalyst, structure are closely related, rely on the Preparation of catalysts method consumingly.The obvious improvement of catalyst performance in the prior art, the main improvement that still relies on Preparation of catalysts method and technology.The preparation method of the methanol synthesis catalyst in the bibliographical information has infusion process, ball milling mixing method, coprecipitation, sol-gal process etc.Wherein, coprecipitation becomes industrial the most frequently used catalyst for methanol preparation method owing to the good and preparation cost of catalyst catalytic performance of preparation is lower.Coprecipitation is through constantly improving, and preparation technology reaches its maturity, and develops into two present step coprecipitations by one step of initial copper zinc-aluminium coprecipitation.The one step precipitation method are to adopt precipitating reagent will contain copper, zinc, aluminium or/and the soluble salts of other element is finished the technical process of precipitation simultaneously.Though step coprecipitation preparation is simple, the poor-performing of catalyst.Two step coprecipitations generally be with the mixing salt solution of the mixing salt solution of copper, zinc and zinc, aluminium earlier respectively with precipitating reagent reaction, and then the preparation method that two parts precipitation is mixed, the difference to some extent of concrete each bibliographical information of preparation process.The two-step precipitation method of patent UK 1296212 reports is that zinc-aluminium is precipitated, and then copper zinc is precipitated on it; 60122040 of patent JP precipitate aluminium and copper earlier, then copper zinc are precipitated; Patent CN 1660493 proposes a kind of new preparation method, the Heat stability is good for preparing copper zinc reactive precursor respectively and form by copper aluminium etc., and the active carrier that specific surface is big mixes the two then and prepares catalyst.It is reported that the two-step precipitation method generates ZnAl by increasing the decentralization of CuO
2O
4Spinelle improves the specific surface of catalyst, reduces catalyst density, improves pore canal structure of catalyst etc. and makes the aggregate level of catalyst significantly improve (Shanghai chemical industry,, 12 phases, 32 pages in 2000).The most two step coprecipitations that adopt of the catalyst for methanol of commercial Application prepare at present.
Though more than the catalyst performance of various improved precipitation preparation methods preparations good, preparation technology is loaded down with trivial details, and process control parameter is a lot, influence is complicated, and is wayward.Therefore, it is more simple and direct to be necessary to develop preparation process, the methanol synthesis catalyst preparation technology that technology controlling and process is more convenient.
Summary of the invention
The object of the present invention is to provide a kind of synthetic Preparation of catalysts method of high activity methyl alcohol that is used for, according to this method, by precipitating the hydrothermal treatment consists of carrying out under the certain condition to adopting a step coprecipitation method or two to go on foot the resulting mixed hydroxides (or/and basic salt) that contains copper and zinc of coprecipitations, can regulating catalyst the structure of precipitation, improve the performance of catalyst significantly.
Main points of the present invention are: mixed hydroxides (or/and basic salt) precipitation that will contain copper and zinc is carried out hydrothermal treatment consists, and process oven dry and roasting obtain containing the high activity methanol synthesis catalyst of cupric oxide and zinc oxide again.
Specifically, the synthetic Preparation of catalysts method of methyl alcohol that is used for provided by the invention, to contain the mixed hydroxides of copper and zinc at least or/and the basic salt precipitation is carried out hydrothermal treatment consists, hydrothermal treatment consists temperature be 50-300 ℃, pressure is 0.11-10Mpa, the hydrothermal treatment consists time is 0.5-240 hour, again through oven dry and roasting, obtains containing the catalyst of cupric oxide and zinc oxide;
Wherein, the mol ratio of copper and zinc is 3-6: 2-3.
Described preparation method, wherein, the temperature of hydrothermal treatment consists is 80-150 ℃.
Described preparation method, wherein, the time of hydrothermal treatment consists is 6-48 hour.
Described preparation method, wherein, the pressure 0.2-1.0Mpa in the hydrothermal treatment consists.
Described preparation method, wherein, the pressure of hydrothermal treatment consists adopts high pressure synthesis reactor or other sealing means to keep.
Described preparation method, wherein, contain copper and zinc mixed hydroxides or/and basic salt precipitate respectively with hydrothermal treatment consists after mix, again the oven dry and roasting.
Described preparation method wherein, contains in Al, Si, Cr, Mn, Zr, B, Ag, Ce, W, V, Ga, Mo, Mg, Ti, Ca and the rare earth element one or more in the catalyst; The mol ratio of itself and copper is 1-3: 6.
Specific embodiment
The synthetic Preparation of catalysts method of methyl alcohol alcohol that is used for provided by the invention, be that the mixed hydroxides (or/and basic salt) that will contain copper and zinc at least is deposited in and carries out hydrothermal treatment consists under uniform temperature and the certain pressure, obtain containing the methanol synthesis catalyst of cupric oxide and zinc oxide through oven dry and roasting again, and after reducing, use; The preparation that wherein contains the mixed hydroxides (or/and basic salt) of copper and zinc can adopt each component to precipitate respectively or coprecipitation method, perhaps adopts a kind of of these two kinds of intermediate processings in a plurality of steps respectively; The temperature range that hydrothermal treatment consists adopts is 50-300 ℃; Optimum range is 80-150 ℃; The time range that hydrothermal treatment consists adopts is 0.5-240h; Optimum range is 6-48h; Adopt high pressure synthesis reactor or other sealing means to keep certain pressure in the hydrothermal treatment consists, pressure limit is 0.11-10Mpa; Optimum range is 0.2-1.0Mpa; Catalyst also can contain one or more other elements outside copper removal and the zinc, as Al, Si, Cr, Mn, Zr, B, Ag, Ce, W, V, Ga, Mo, Mg, Ti, Ca and rare earth element etc.
By the following examples the present invention is made detailed description, but the present invention is not limited to these embodiment.
Embodiment 1:
Add deionized water in the synthesis reactor of 200ml, the temperature of keeping water in the synthesis reactor is at 80 ℃.Under agitation, with the mixed solution of copper nitrate and zinc nitrate (Cu: Zn=6: 3, mol) solution with natrium carbonicum calcinatum is added drop-wise in the synthesis reactor simultaneously, the flow velocity of control natrium carbonicum calcinatum, keeping the pH of solution in the still is 7.5-8.5.Continue after precipitation finishes to stir, aging 1h with the synthesis reactor sealing, puts into baking oven then, at 210 ℃, leaves standstill 200h under the 8.0Mpa condition, reduces to room temperature, and sample in the still is carried out suction filtration, wash, and 80 ℃ of dryings, 350 ℃ of roasting 4h obtain the powder catalyst A.
Embodiment 2:
Add deionized water in the synthesis reactor of 200ml, the temperature of keeping water in the synthesis reactor is at 80 ℃.Under agitation, with copper nitrate, zinc nitrate and aluminum nitrate (according to technical characterictic of the present invention, this aluminum nitrate also can be one or more in Si, Cr, Mn, Zr, B, Ag, Ce, W, V, Ga, Mo, Mg, Ti, Ca and the rare earth element) mixed solution (Cu: Zn: Al=6: 3: 1, mol) solution with natrium carbonicum calcinatum is added drop-wise in the synthesis reactor simultaneously, the flow velocity of control natrium carbonicum calcinatum, keeping the pH of solution in the still is 7.5-8.5.Continue after precipitation finishes to stir, aging 0.5h with the synthesis reactor sealing, puts into baking oven then, at 110 ℃, leaves standstill 12h under the 0.25Mpa condition, reduces to room temperature, and sample in the still is carried out suction filtration, wash, and 80 ℃ of dryings, 350 ℃ of roasting 2h obtain the powder catalyst B.
Embodiment 3:
Prepare respectively certain density zinc nitrate, silver nitrate mixed solution A (Zn: Ag=1: 3, mol) and the mixed solution B of copper nitrate, zinc nitrate (Cu: Zn=3: 1, mol).In the 200ml synthesis reactor, add deionized water, keep in the still water temperature at 60 ℃, adopt natrium carbonicum calcinatum to make precipitating reagent, under agitation solution A and Carbon Dioxide sodium solution are added drop-wise to simultaneously and carry out coprecipitation reaction in the synthesis reactor, keep in the precipitation process that pH value of solution is 7.5-8.5 in the still, after finishing, precipitation continues to stir, and aging.And then in another synthesis reactor, solution B and Carbon Dioxide sodium solution are carried out coprecipitation reaction, and keeping in the precipitation process that solution temperature is at 80 ℃ in the still, pH is 7.5-8.5; After finishing, precipitation continues to stir, and aging.Two parts precipitation is mixed, and baking oven is put in the synthesis reactor of packing into sealing, at 80 ℃, leaves standstill 40h under the 0.25Mpa condition, reduces to room temperature, and sample in the still is carried out suction filtration, washing, and 80 ℃ of dryings, 350 ℃ of roasting 2h obtain powder catalyst C.
Embodiment 4:
Catalyst A, B and the C of embodiment 1,2 and 3 preparations 250 ℃ of reduction down, estimate its methyl alcohol synthetic reaction activity through compression molding.Carry out the reaction that synthesis gas is produced methyl alcohol on the fixed bed reactors, reaction condition: 240 ℃ of temperature, H in the synthesis gas
2: CO is 2: 1, reaction velocity 3000h
-1, adopt online gas-chromatography to finish the product distributional analysis.Reaction result is as shown in table 1, and the CO conversion ratio of catalyst A is 27.47%, and the methyl alcohol yield is 0.15 (mol/mol CO).The CO conversion ratio of catalyst B is 29.27%, and the methyl alcohol yield is 0.17 (mol/mol CO).The CO conversion ratio of catalyst C is 35.37%, and the methyl alcohol yield is 0.22 (mol/mol CO).
The reaction result of table 1: embodiment 3
Comparative Examples 1:
One step of hydrothermal treatment consists in embodiment 1 preparation process is removed, and other step is constant, and the precipitation that obtains is directly carried out suction filtration, washing, and drying, roasting obtains powder catalyst D.
Comparative Examples 2:
One step of hydrothermal treatment consists in embodiment 2 preparation process is removed, and other step is constant, and the precipitation that obtains is directly carried out suction filtration, washing, and drying, roasting obtains powder catalyst E.
Comparative Examples 3:
The catalyst D of Comparative Examples 1 and 2 preparations and E 250 ℃ of reduction, estimate its methyl alcohol synthetic reaction activity through compression molding.Carry out the reaction that synthesis gas is produced methyl alcohol on the fixed bed reactors, reaction condition: 240 ℃ of temperature, H in the synthesis gas
2: CO is 2: 1, reaction velocity 3000h
-1, adopt online gas-chromatography to finish the product distributional analysis.Reaction result is as shown in table 1, and the CO conversion ratio of catalyst D is 10.47%, and the methyl alcohol yield is 0.03 (mol/mol CO).The CO conversion ratio of catalyst E is 30.71%, and the methyl alcohol yield is 0.18 (mol/mol CO).
Table 2: the reaction result of Comparative Examples 3
Claims (7)
1. one kind is used for the synthetic Preparation of catalysts method of methyl alcohol, to contain the mixed hydroxides of copper and zinc at least or/and the basic salt precipitation is carried out hydrothermal treatment consists, hydrothermal treatment consists temperature be 50-300 ℃, pressure is 0.11-10Mpa, the hydrothermal treatment consists time is 0.5-240 hour, through oven dry and roasting, obtain containing the catalyst of cupric oxide and zinc oxide again;
Wherein, the mol ratio of copper and zinc is 3-6: 2-3.
2. the described preparation method of claim 1, wherein, the temperature of hydrothermal treatment consists is 80-150 ℃.
3. the described preparation method of claim 1, wherein, the time of hydrothermal treatment consists is 6-48 hour.
4. the described preparation method of claim 1, wherein, the pressure 0.2-1.0Mpa in the hydrothermal treatment consists.
5. the described preparation method of claim 1, wherein, the pressure of hydrothermal treatment consists adopts high pressure synthesis reactor or other sealing means to keep.
6. the described preparation method of claim 1, wherein, contain copper and zinc mixed hydroxides or/and basic salt precipitate respectively with hydrothermal treatment consists after mix oven dry and roasting again.
7. the described preparation method of claim 1 wherein, contains in Al, Si, Cr, Mn, Zr, B, Ag, Ce, W, V, Ga, Mo, Mg, Ti, Ca and the rare earth element one or more in the catalyst, the mol ratio of itself and copper is 1-3: 6.
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| CNA2007100648809A CN101274278A (en) | 2007-03-28 | 2007-03-28 | Method for preparing catalyst for synthesizing methanol |
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| CNA2007100648809A CN101274278A (en) | 2007-03-28 | 2007-03-28 | Method for preparing catalyst for synthesizing methanol |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580753A (en) * | 2012-03-05 | 2012-07-18 | 昆明理工大学 | Catalyst for synthesizing methanol by taking multi-carbon sources in metallurgical fume as raw materials and preparation method of catalyst |
| CN103230799A (en) * | 2013-04-08 | 2013-08-07 | 中国科学院广州能源研究所 | Cu-Zn-based catalyst used in reverse water gas shift reaction, and preparation method and application thereof |
| CN104275184A (en) * | 2013-07-12 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method of low-impurity-content copper-based methanol synthesis catalyst |
| 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 |
| CN106179356A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of for CO2cuZnAl catalyst of preparing methanol by hydrogenation and preparation method thereof |
| CN106238062A (en) * | 2015-06-08 | 2016-12-21 | 中国石油化工股份有限公司 | Microreactor pressurizes the method preparing methanol synthesis catalyst continuously |
| CN106540709A (en) * | 2015-09-16 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of preparation method of auxiliary agent doping type methanol synthesis catalyst |
| CN109092312A (en) * | 2018-09-19 | 2018-12-28 | 昆明理工大学 | A kind of hydro-thermal method prepares the method and application of copper-based catalysts |
| CN114210334A (en) * | 2021-10-26 | 2022-03-22 | 山东科技大学 | CO (carbon monoxide)2Copper-zinc based catalyst for preparing methyl formate by hydrogenation and preparation method thereof |
| CN114618499A (en) * | 2022-03-24 | 2022-06-14 | 山东亮剑环保新材料有限公司 | Doped CO2Preparation method of hydrogenation catalyst |
-
2007
- 2007-03-28 CN CNA2007100648809A patent/CN101274278A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580753A (en) * | 2012-03-05 | 2012-07-18 | 昆明理工大学 | Catalyst for synthesizing methanol by taking multi-carbon sources in metallurgical fume as raw materials and preparation method of catalyst |
| CN103230799A (en) * | 2013-04-08 | 2013-08-07 | 中国科学院广州能源研究所 | Cu-Zn-based catalyst used in reverse water gas shift reaction, and preparation method and application thereof |
| CN103230799B (en) * | 2013-04-08 | 2016-06-08 | 中国科学院广州能源研究所 | A kind of Cu-Zn for reverse water-gas-shift reaction is catalyst based, its preparation method and application |
| CN104275184A (en) * | 2013-07-12 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method of low-impurity-content copper-based methanol synthesis catalyst |
| CN106179356B (en) * | 2015-05-07 | 2019-02-22 | 中国石油化工股份有限公司 | One kind being used for CO2CuZnAl catalyst of preparing methanol by hydrogenation and preparation method thereof |
| CN106179356A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of for CO2cuZnAl catalyst of preparing methanol by hydrogenation 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 |
| CN106238062A (en) * | 2015-06-08 | 2016-12-21 | 中国石油化工股份有限公司 | Microreactor pressurizes the method preparing methanol synthesis catalyst continuously |
| CN106540709A (en) * | 2015-09-16 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of preparation method of auxiliary agent doping type methanol synthesis catalyst |
| CN109092312A (en) * | 2018-09-19 | 2018-12-28 | 昆明理工大学 | A kind of hydro-thermal method prepares the method and application of copper-based catalysts |
| CN114210334A (en) * | 2021-10-26 | 2022-03-22 | 山东科技大学 | CO (carbon monoxide)2Copper-zinc based catalyst for preparing methyl formate by hydrogenation and preparation method thereof |
| CN114210334B (en) * | 2021-10-26 | 2024-01-30 | 山东科技大学 | CO (carbon monoxide) 2 Copper-zinc-based catalyst for preparing methyl formate by hydrogenation and preparation method thereof |
| CN114618499A (en) * | 2022-03-24 | 2022-06-14 | 山东亮剑环保新材料有限公司 | Doped CO2Preparation method of hydrogenation catalyst |
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Open date: 20081001 |