CN105107513A - Method for preparing Cu-based water-gas shift catalyst by using mesoporous silicon as template - Google Patents
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Abstract
The present invention provides a method for preparing a Cu-based water-gas shift catalyst by using mesoporous silicon as a template. The method comprises: firstly dissolving a plurality of metal salts, comprising soluble copper salt and soluble cerium salt, in a first volatile organic solvent to prepare a first solution system; dissolving the mesoporous silica in a second volatile solvent to prepare a second solution system; and then mixing the first solution system and the second solution system and preparing and obtaining the Cu-based water-gas shift catalyst under a suitable condition. According to the present invention, in the process of catalyst preparation, the catalyst can be uniformly dispersed in a porous channel and on the surface of a templating agent, and the dispersity of active components in metal is greatly improved, meanwhile the sintering phenomenon of the catalyst at a high temperature is effectively avoided, the thermal stability is good, the shift activity is high, and therefore the Cu-based water-gas shift catalyst prepared by the present invention has the characteristics of a large specific surface area, a high dispersion degree of active components, a good high-temperature resistance property, high shift activity and the like.
Description
Technical field
The present invention relates to a kind of take mesoporous silicon as the method for Template preparation Cu based water gas converting catalyst, belongs to the preparation field of water gas converting catalyst.
Background technology
Water gas shift/WGS (CO+H
2o=CO
2+ H
2, WaterGasShift, is called for short WGS) and be the course of reaction of industrial extensive use, be mainly used in the hydrogen manufacturing in the industry such as synthetic ammonia and regulate synthesis gas to manufacture CO/H in process
2.Water gas shift reaction has extensive use in the purified treatment of industries, methanol-fueled CLC, vehicle exhaust, fuel cell electric vehicle and town gas industry etc.Up to now, except the electrolytic hydrogen production of minute quantity, water gas shift reaction is still the main path of cheap hydrogen manufacturing.Water gas shift reaction can make the CO in unstripped gas become H with steam reaction conversions
2and CO
2, not only effectively can reduce the concentration of CO, can H be improved simultaneously
2content.
At present, the water gas converting catalyst of industrial extensive use mainly contains three classes: iron system high temperature conversion catalyst (300-450 DEG C), copper system low temperature conversion catalyst (190-250 DEG C) and cobalt molybdenum system wide temperature shift catalyst (180-450 DEG C).Wherein, iron system high temperature conversion catalyst need add structural promoter Cr
2o
3improve its heat resistance, prevent from sintering the activity decrease caused, but its low temperature active is on the low side, and chromium is extremely toxic substance, cause the pollution to personnel and environment in production, use and processing procedure.Although cobalt-molybdenum series catalyst operating temperature range is large, complete resistant to sulfur, but need loaded down with trivial details sulfidation before use, and need in process gas to ensure that a certain amount of sulfur content and lower steam-to-gas ratio can reach optimum activity state, and easily there is non-uniform phenomenon in sulfuration.Although copper system low temperature catalyst is good at low temperature active, it is sulfur resistive, thermo-labile not, also limit its range of application.But, because copper is rare simultaneously to CO activation and H
2o Dissociative has highly active metal, and therefore, copper system low temperature conversion catalyst is study hotspot all the time.
Chinese patent literature CN104014345A discloses a kind of CuO-CeO for water gas shift reaction
2catalysts and its preparation method, it comprises the steps: (1) under agitation, dropwise adds in the water of 80 DEG C, after hybrid reaction by cerium solution and aqueous slkali simultaneously, through ageing, cooling, centrifugal, washing be precipitated, then drying obtain CeO
2carrier; (2) at room temperature, ammonia spirit is dropwise added in copper salt solution, obtain copper ammonia complexation solution; (3) by CeO obtained for step (1)
2carrier ultrasonic disperse, in water, then adds the copper ammonia complexation solution that step (2) obtains, and continues to stir 1h under 500-700r/min stirs; (4) under agitation, aqueous slkali is added in the mixed liquor of step (3) and react, after ageing, obtain CuO-CeO through cooling, centrifugal, washing, dry, roasting
2catalyst.But the catalyst that said method prepares, specific area is little, and the decentralization of active component is poor, and resistance to elevated temperatures is still poor.
Summary of the invention
It take mesoporous silicon as the method for Template preparation Cu based water gas converting catalyst that technical problem to be solved by this invention is to provide a kind of, and the Cu based water gas converting catalyst that described method prepares has that specific area is large, active component decentralization is high, resistance to elevated temperatures good, shift activity high.
For solving the problems of the technologies described above, technical scheme of the present invention is:
Take mesoporous silicon as a method for Template preparation Cu based water gas converting catalyst, it comprises the steps:
(1) take the soluble-salt of other transition metal outside soluble copper salt, solubility cerium salt and copper removal respectively and be dissolved in the first volatile organic solvent, obtain the first solution system, the mol ratio controlling other transition metal outside described soluble copper salt, solubility cerium salt and copper removal is 0.28-0.38:1:0.7-0.9;
(2) take mesopore silicon oxide and be dissolved in the second easy volatile solvent, obtaining the second solution system, the additional proportion controlling described mesopore silicon oxide and described second volatile organic solvent is 1:0.5-1:1.5g/ml;
(3) described first solution system and described second solution system are mixed to get mixed system, described mixed system is carried out fully stirring that the first volatile organic solvent of wherein containing and the second volatile organic solvent are volatilized completely at ambient temperature, residue system drying, roasting, obtain Cu based water gas converting catalyst.
In step (1), other transition metal outside copper removal are the mixture of one or more in soluble cobalt, soluble manganese salt and soluble ferric iron salt.
Described mesopore silicon oxide is nanometer mesoporous silicon oxide.
Described mesopore silicon oxide is the mixture of one or more in KIT-6, SBA-15, MCM-48.
The specific area of described mesopore silicon oxide is 400-500m
2/ g.
Described soluble copper salt is Cu (NO
3)
23H
2o, CuCl
22H
2o, Cu (CH
3oO)
2h
2the mixture of one or more in O, described solubility cerium salt is Ce (NO
3)
36H
2o, Ce (Cl)
37H
2o, Ce
2(SO
4)
38H
2the mixture of one or more in O.
Described first volatile organic solvent is the mixture of one or more in ethanol, methyl alcohol, carrene.
Described second volatile organic solvent is the mixture of one or more in ethanol, carrene, DMF.
In step (3), the temperature of carrying out described drying is 60-90 DEG C, and the time of described drying is 12-24h; The temperature of carrying out described roasting is 360-400 DEG C, and the time of described roasting is 2-6h.
The Cu based water gas converting catalyst that described method prepares.
Technique scheme of the present invention has the following advantages compared to existing technology:
(1) of the present invention take mesoporous silicon as the method for Template preparation Cu based water gas converting catalyst, first the various metals salt comprising soluble copper salt and solubility cerium salt to be dissolved in the first volatile organic solvent obtained first and to be dissolved in system, and mesopore silicon oxide is dissolved in obtained second solution system of the second easy volatile solvent, utilize described first solution system to mix with described second solution system afterwards and prepare Cu based water gas converting catalyst under the proper conditions, thus the inventive method is passed through with high specific surface area and mesoporous silica as template, further utilization comprises the first solution system of described mesopore silicon oxide and comprises soluble copper salt, second solution system of solubility cerium salt and copper removal other transition metal soluble-salts outer carries out stirring reaction, prepare with CuO is active component, with Fe
2o
3, MnO
2or CoO be auxiliary agent, with CeO
2for the catalyst of carrier, make to prepare in the duct and surface that catalyst can be dispersed in template, while increasing substantially the dispersiveness of metal active constituent, effectively avoid catalyst sintering phenomenon at high temperature, Heat stability is good, shift activity is high, thus the inventive method prepares Cu based water gas converting catalyst has that specific area is large, active component decentralization is high, resistance to elevated temperatures good, shift activity high.
(2) of the present invention take mesoporous silicon as the method for Template preparation Cu based water gas converting catalyst, its mesopore silicon oxide adopted is the mixture of one or more in KIT-6, SBA-15, MCM-48, above-mentioned mesopore silicon oxide has the pore passage structure be evenly distributed, larger specific area and good hydrothermal stability, thus above to state mesopore silicon oxide be that Template preparation obtains Cu based water gas converting catalyst, resistance to elevated temperatures is excellent, shift activity is high.
Detailed description of the invention
Embodiment 1
The present embodiment provides a kind of with the method for mesoporous silicon KIT-6 for Template preparation Cu based water gas converting catalyst, and it comprises the steps:
(1) 0.38gCu (NO is taken respectively
3)
23H
2o, 1.767gCe (NO
3)
36H
2o, 0.997gCo (NO
3)
26H
2o is also dissolved in 20ml absolute ethyl alcohol, at room temperature carries out stirring 1h, obtains the first solution system, wherein, and the mol ratio 0.38:1:0.84 of described soluble copper salt, solubility cerium salt and described soluble cobalt;
(2) take 0.5g mesopore silicon oxide KIT-6 and be dissolved in 5ml absolute ethyl alcohol, at room temperature carrying out stirring 0.5h, obtaining the second solution system, wherein, the specific area of described mesopore silicon oxide is 400m
2/ g, the additional proportion of described mesopore silicon oxide and described absolute ethyl alcohol is 1:1g/ml;
(3) described first solution system and described second solution system are mixed to get mixed system, carry out at ambient temperature fully stirring to make the absolute ethyl alcohol wherein contained volatilize completely to described mixed system, residue system is through 80 DEG C of dry 24h, 380 DEG C of roasting 3h, heating rate during roasting is 0.8 DEG C/min, obtains Cu based water gas converting catalyst.
Embodiment 2
The present embodiment provides a kind of with the method for mesoporous silicon SBA-15 for Template preparation Cu based water gas converting catalyst, and it comprises the steps:
(1) 0.28gCu (NO is taken respectively
3)
23H
2o, 1.767gCe (NO
3)
36H
2o, 0.831gCo (NO
3)
26H
2o is also dissolved in 20ml absolute methanol, at room temperature carries out stirring 1h, obtains the first solution system, wherein, and the mol ratio 0.28:1:0.7 of described soluble copper salt, solubility cerium salt and described soluble cobalt;
(2) take 0.5g mesoporous SBA-15 and be dissolved in 0.25mlN, dinethylformamide, at room temperature carrying out stirring 0.5h, obtaining the second solution system, wherein, the specific area of described mesopore silicon oxide is 450m
2/ g, the additional proportion of described mesopore silicon oxide and described DMF is 1:0.25g/ml;
(3) described first solution system and described second solution system are mixed to get mixed system, carry out at ambient temperature fully stirring to make the absolute ethyl alcohol wherein contained volatilize completely to described mixed system, residue system is through 90 DEG C of dry 12h, 400 DEG C of roasting 2h, heating rate during roasting is 1.5 DEG C/min, obtains Cu based water gas converting catalyst.
Embodiment 3
The present embodiment provides a kind of with the method for mesoporous silicon MCM-48 for Template preparation Cu based water gas converting catalyst, and it comprises the steps:
(1) 0.3gCu (NO is taken respectively
3)
23H
2o, 1.767gCe (NO
3)
36H
2o, 1.068gCo (NO
3)
26H
2o is also dissolved in 20ml carrene, at room temperature carries out stirring 1h, obtains the first solution system, wherein, and the mol ratio 0.3:1:0.9 of described soluble copper salt, solubility cerium salt and described soluble cobalt;
(2) take 0.5g mesopore silicon oxide MCM-48 and be dissolved in 7.5ml carrene, at room temperature carrying out stirring 0.5h, obtaining the second solution system, wherein, the specific area of described mesopore silicon oxide is 500m
2/ g, the additional proportion of described mesopore silicon oxide and described carrene is 1:1.5g/ml;
(3) described first solution system and described second solution system are mixed to get mixed system, carry out at ambient temperature fully stirring to make the absolute ethyl alcohol wherein contained volatilize completely to described mixed system, residue system is through 60 DEG C of dry 24h, 360 DEG C of roasting 6h, heating rate during roasting is 1 DEG C/min, obtains Cu based water gas converting catalyst.
Embodiment 4
The present embodiment provides a kind of with the method for mesoporous silicon SBA-15 for Template preparation Cu based water gas converting catalyst, and it comprises the steps:
(1) 0.38gCu (NO is taken respectively
3)
23H
2o, 1.767gCe (NO
3)
36H
2o, 0.915gMn (NO
3)
24H
2o is also dissolved in 20ml absolute ethyl alcohol, at room temperature carries out stirring 1h, obtains the first solution system, wherein, and the mol ratio 0.38:1:0.89 of described soluble copper salt, solubility cerium salt and described soluble manganese salt;
(2) take 0.5g mesoporous SBA-15 and be dissolved in 5ml absolute ethyl alcohol, at room temperature carrying out stirring 0.5h, obtaining the second solution system, wherein, the specific area of described mesopore silicon oxide is 420m
2/ g, the additional proportion of described mesopore silicon oxide and described absolute ethyl alcohol is 1:1g/ml;
(3) described first solution system and described second solution system are mixed to get mixed system, carry out at ambient temperature fully stirring to make the absolute ethyl alcohol wherein contained volatilize completely to described mixed system, residue system is through 80 DEG C of dry 24h, 380 DEG C of roasting 3h, heating rate during roasting is 1 DEG C/min, obtains Cu based water gas converting catalyst.
Comparative example 1
This comparative example provides a kind of method of Co deposited synthesis Cu based water gas converting catalyst, and it comprises the steps:
Take 0.38gCu (NO respectively
3)
23H
2o, 1.767gCe (NO
3)
36H
2o, 0.997gMn (NO
3)
24H
2o is also dissolved in 10ml deionized water, obtains mixed solution;
By above-mentioned mixed solution first 60 DEG C, carry out pretreatment 30min under stirring condition, more slowly drip 1.242gKOH wherein, and to maintain pH be 10, burin-in process 8h is carried out afterwards at 60 DEG C, carry out centrifugal after cooling, washing to pH is 7, namely obtains catalyst after oven dry.
Experimental example
In order to prove of the present inventionly have conversion and the carrier of adsorption cleaning performance and the technique effect of catalyst, the present invention is provided with the catalytic performance of experimental example to carrier and catalyst and tests.
Catalyst in embodiment 1-4 and comparative example 1 is numbered successively as A-E and carries out following test.
Specific surface area of catalyst and pore structure test experiments
In this experimental example specific surface area of catalyst and pore structure the U.S. of employing respectively Micrometrics company Ominisorp100cx type gas absorption pore size determination instrument on measure, test process and test condition as follows: take (the drying pretreatment of 0.10g sample, 20-40 order, 380 μm-830 μm), vacuumize under 200 DEG C of conditions and (be less than 10
-5torr) 4h is processed, with N
2for adsorbate, under liquid nitrogen temperature, (-196 DEG C) record adsorption desorption curve.Adsorptive value according to adsorption desorption curve adopts BET method calculated specific surface area, and desorption value adopts BJH method calculated pore volume and pore size distribution.
Specific area and the pore structure test result of catalyst are as shown in table 1.
The specific area of table 1-carrier and pore structure test result
| Sample | Specific area/(m 2/g) | Pore volume/(cm 3/g) | Pore radius/(nm) |
| A | 185 | 0.238 | 3.502 |
| B | 192 | 0.252 | 3.536 |
| C | 154 | 0.239 | 3.315 |
| D | 133 | 0.221 | 3.154 |
| E | 65 | 0.162 | 2.328 |
As can be seen from Table 1, catalyst (sample A-D) the specific area more greatly 192m for preparing of the inventive method
2/ g, pore volume is 0.252cm
3/ g, aperture is 3.536nm, is conducive to improving catalyst to the shift activity of CO; By comparison, the catalyst (sample E) adopting coprecipitation to prepare in comparative example, its specific area is only 65m
2/ g, pore volume is 0.162cm
3/ g, aperture is 2.328nm, thus poor to the shift activity of CO.
Catalyst for CO transformationreation active appraisal experiment
Experimental procedure is specific as follows:
(1) catalyst pretreatment:
First pass into H with 30ml/min flow velocity
2, at 350 DEG C, reduction 4h is carried out to catalyst;
(2) the shift activity test of catalyst:
Test condition:
Conversion unstripped gas composition: 10%CO, 5%CO
2, 5%H
2, all the other are N
2;
Loaded catalyst 30ml, pressure is normal pressure, air speed 6000h
-1, steam-to-gas ratio is 1:1;
Probe temperature interval is 150-350 DEG C, and heating rate is 5 DEG C/min, 50 DEG C, temperature interval, and each probe temperature point retention time is 4h.Adopt GC-2014 gas chromatographicanalyzer, six-way valve automatic sampling, the CO content before and after detection reaction.
Represent catalyst shift activity with the conversion ratio of CO, computing formula is as follows:
CO conversion ratio (%)=100% × (1-Vo/Vi)/(1+Vo)
In formula, Vi is the volume fraction of CO in unstripped gas, and Vo is the volume fraction of CO in conversion gas.
When transformationreation temperature is respectively 250 DEG C, 300 DEG C, 350 DEG C, calculate the CO conversion ratio of catalyst, result is as shown in table 2.
The CO conversion ratio of catalyst at the different transformationreation temperature of table 2-
| Sample | 150℃ | 200℃ | 250℃ | 300℃ | 350℃ |
| A | 1.34％ | 5.28％ | 41.33％ | 95.01％ | 92.27％ |
| B | 2.47％ | 6.38％ | 51.32％ | 95.15％ | 92.55％ |
| C | 3.78％ | 8.073％ | 59.87％ | 95.08％ | 92.23％ |
| D | 4.29％ | 5.23％ | 47.67％ | 93.87％ | 91.37％ |
| E | 0.98％ | 3.89％ | 9.69％ | 42.15％ | 73.59％ |
As can be seen from Table 2, catalyst of the present invention (sample A-D) Applicable temperature is wider, in the temperature range of 150-350 DEG C, to CO, all there is certain shift activity, and higher shift activity is kept under the high temperature of 300-350 DEG C, resistance to elevated temperatures is high, by comparison, catalyst (sample E) in comparative example, Applicable temperature narrow range, shift activity is poor, and resistance to elevated temperatures is poor.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not 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 exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. be a method for Template preparation Cu based water gas converting catalyst with mesoporous silicon, it comprises the steps:
(1) take the soluble-salt of other transition metal outside soluble copper salt, solubility cerium salt and copper removal respectively and be dissolved in the first volatile organic solvent, obtain the first solution system, the mol ratio controlling other transition metal outside described soluble copper salt, solubility cerium salt and copper removal is 0.28-0.38:1:0.7-0.9;
(2) take mesopore silicon oxide and be dissolved in the second easy volatile solvent, obtaining the second solution system, the additional proportion controlling described mesopore silicon oxide and described second volatile organic solvent is 1:0.5-1:1.5g/ml;
(3) described first solution system and described second solution system are mixed to get mixed system, described mixed system is carried out fully stirring that the first volatile organic solvent of wherein containing and the second volatile organic solvent are volatilized completely at ambient temperature, residue system drying, roasting, obtain Cu based water gas converting catalyst.
2. according to claim 1 take mesoporous silicon as the method for Template preparation Cu based water gas converting catalyst, it is characterized in that, in step (1), other transition metal outside copper removal are the mixture of one or more in soluble cobalt, soluble manganese salt and soluble ferric iron salt.
3. according to claim 1 and 2 take mesoporous silicon as the method for Template preparation Cu based water gas converting catalyst, and it is characterized in that, described mesopore silicon oxide is nanometer mesoporous silicon oxide.
4. take mesoporous silicon as the method for Template preparation Cu based water gas converting catalyst according to any one of claim 1-3, and it is characterized in that, described mesopore silicon oxide is the mixture of one or more in KIT-6, SBA-15, MCM-48.
5. take mesoporous silicon as the method for Template preparation Cu based water gas converting catalyst according to any one of claim 1-4, and it is characterized in that, the specific area of described mesopore silicon oxide is 400-500m
2/ g.
6. take mesoporous silicon as the method for Template preparation Cu based water gas converting catalyst according to any one of claim 1-5, and it is characterized in that, described soluble copper salt is Cu (NO
3)
23H
2o, CuCl
22H
2o, Cu (CH
3oO)
2h
2the mixture of one or more in O, described solubility cerium salt is Ce (NO
3)
36H
2o, Ce (Cl)
37H
2o, Ce
2(SO
4)
38H
2the mixture of one or more in O.
7. take mesoporous silicon as the method for Template preparation Cu based water gas converting catalyst according to any one of claim 1-6, and it is characterized in that, described first volatile organic solvent is the mixture of one or more in ethanol, methyl alcohol, carrene.
8. take mesoporous silicon as the method for Template preparation Cu based water gas converting catalyst according to any one of claim 1-7, and it is characterized in that, described second volatile organic solvent is ethanol, carrene, N
,the mixture of one or more in dinethylformamide.
9. take mesoporous silicon as the method for Template preparation Cu based water gas converting catalyst according to any one of claim 1-8, and it is characterized in that, in step (3), the temperature of carrying out described drying is 60-90 DEG C, and the time of described drying is 12-24h; The temperature of carrying out described roasting is 360-400 DEG C, and the time of described roasting is 2-6h.
10. the Cu based water gas converting catalyst that the method according to any one of claim 1-9 prepares.
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ID=54655755
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070179053A1 (en) * | 2006-02-02 | 2007-08-02 | Samsung Sdi Co., Ltd. | Composite oxide support, catalyst for low temperature water gas shift reaction and methods of preparing the same |
| CN101518737A (en) * | 2009-03-26 | 2009-09-02 | 上海大学 | Catalyst for shifting carbon monoxide by water gas reaction in hydrogen-rich fuel gas and preparation method thereof |
| WO2011146240A1 (en) * | 2010-05-18 | 2011-11-24 | Kellogg Brown & Root Llc | Gasification system and process for maximizing production of syngas and syngas-derived products |
| CN104437512A (en) * | 2014-11-02 | 2015-03-25 | 中国科学院福建物质结构研究所 | Transition-metal-modified Cu/CeO2 ordered mesopore material for NOx purification of stationary source |
-
2015
- 2015-08-12 CN CN201510492272.2A patent/CN105107513A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070179053A1 (en) * | 2006-02-02 | 2007-08-02 | Samsung Sdi Co., Ltd. | Composite oxide support, catalyst for low temperature water gas shift reaction and methods of preparing the same |
| CN101518737A (en) * | 2009-03-26 | 2009-09-02 | 上海大学 | Catalyst for shifting carbon monoxide by water gas reaction in hydrogen-rich fuel gas and preparation method thereof |
| WO2011146240A1 (en) * | 2010-05-18 | 2011-11-24 | Kellogg Brown & Root Llc | Gasification system and process for maximizing production of syngas and syngas-derived products |
| CN104437512A (en) * | 2014-11-02 | 2015-03-25 | 中国科学院福建物质结构研究所 | Transition-metal-modified Cu/CeO2 ordered mesopore material for NOx purification of stationary source |
Non-Patent Citations (1)
| Title |
|---|
| S. VARGHESE ET AL.: "CO oxidation and preferential oxidation of CO in the presence of hydrogen over SBA-15-templated CuO-Co3O4 catalysts", 《APPLIED CATALYSIS A: GENERAL》 * |
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