CN102886272B - Supported catalyst, preparation method and application thereof - Google Patents
Supported catalyst, preparation method and application thereof Download PDFInfo
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- CN102886272B CN102886272B CN201210126248.3A CN201210126248A CN102886272B CN 102886272 B CN102886272 B CN 102886272B CN 201210126248 A CN201210126248 A CN 201210126248A CN 102886272 B CN102886272 B CN 102886272B
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Abstract
The invention relates to a supported catalyst, a preparation method and an application of the supported catalyst. Supported components of the supported catalyst is metal nickel or/and oxide of the metal nickel, wherein a carrier of the supported catalyst is a mesoporous molecular sieve MCM-41; based on 100% of total weight of the supported catalyst, the metal nickel or/or the oxide of the metal nickel is 2-20wt%; the supported catalyst is prepared by an impregnation method. The supported catalyst provided by the invention has a good catalytic activity and excellent thermal stability, and is suitable for a reaction for preparing methane by synthesis gas.
Description
Technical field
The present invention relates to a kind of loaded catalyst and its production and use, specifically, relate to a kind of nickel (Ni) base supported catalyst and its production and use.
Background technology
The reaction essence of preparing methane by synthetic gas is that co hydrogenation forms methane and water, in view of domestic and international, many mature industry catalyst are had to a small amount of the methanation of carbon monoxide process in hydrogen rich gas atmosphere, and also have Patents to report in oven gas and water gas methanation catalyst:
Chinese patent literature CN101185892A reports a kind of Ni/ZrO
2catalyst, carbon monoxide (CO) content in rich hydrogen system can be down to below 100ppm by it, but it is not suitable for the reaction system being prepared methane by the synthesis gas containing high concentration CO.
Chinese patent literature CN101371987A discloses a kind of Ni-Ru-B/ZrO
2catalyst, the exit concentration of CO in rich hydrogen system can be down to below 22ppm by it, can maintain extremely low CO simultaneously
2methane rate.But it is only only applicable to rich hydrogen system (namely the concentration of CO is very low), equally, it is not suitable for the reaction system being prepared methane by the synthesis gas containing high concentration CO yet.In addition, the Applicable temperature of the catalyst disclosed is 210 DEG C ~ 250 DEG C.
US Patent No. 3,787,468 provide a kind of Ru-WO
xand Pt-Ru-WO
xcatalyst, it goes for CO and carbon dioxide (CO
2) methanation.Because this catalyst adopts high-load noble metal (Ru and/or Pt) to be cause the cost of this catalyst significantly to rise for main active component.
Methanation is one of key reaction of coal preparing natural gas, belongs to strong exothermal reaction, and reaction heat can reach about 20% of forming gas calorific value, and strong exothermal reaction can cause the temperature of reaction system significantly to raise, and easily causes catalysqt deactivation.Therefore, development has good thermal stability methanation catalyst, is the technical issues that need to address of the present invention.
Summary of the invention
The present invention's object is, a kind of novel Supported Nickel Catalyst is provided, mainly metallic nickel is or/and its oxide for the load component (or claiming active component) of described Supported Nickel Catalyst, and the carrier of described Supported Nickel Catalyst is mesostructured material;
Wherein, in the gross weight of described Supported Nickel Catalyst for 100%, metallic nickel is or/and its oxide accounts for 2wt% ~ 20wt%.
Another object of the present invention is, a kind of method preparing above-mentioned Supported Nickel Catalyst is disclosed, the key step of described method is: at ambient temperature, mesostructured material be impregnated in the aqueous solution (as aqueous solution such as nickel nitrate, nickelous sulfate, nickel acetate, nickel oxalate or nickel chlorides) of the presoma of active component, take out the mesostructured material being loaded with loaded article, make it successively after drying and roasting, obtain object (Supported Nickel Catalyst of the present invention).
Another object of the present invention is, disclose a kind of purposes of above-mentioned Supported Nickel Catalyst, namely described Supported Nickel Catalyst can be used as by synthesis gas (CO+H
2) prepare the purposes of methane reaction catalyst.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of catalyst E,
The wherein XRD collection of illustrative plates of (a)-small-angle diffraction, the XRD collection of illustrative plates of (b)-wide-angle diffraction.
Fig. 2 is the TEM collection of illustrative plates of catalyst E.
Detailed description of the invention
In the present invention's preferred technical scheme, the load component (or claiming active component) of described Supported Nickel Catalyst also comprises metal molybdenum (Mo) or/and its oxide, in the gross weight of described Supported Nickel Catalyst for 100%, metal molybdenum (Mo) is or/and its oxide accounts for 0.1wt% ~ 10wt%.
In another preferred technical scheme of the present invention, the load component of described Supported Nickel Catalyst (or claiming active component) also comprises and to be selected from rare earth metal (general name of scandium, yttrium and lanthanide series) one or two or more kinds (containing two kinds) mixture or/and its oxide, in the gross weight of described Supported Nickel Catalyst for 100%, rare earth metal is or/and its oxide accounts for 0.1wt% ~ 5.0wt%;
Preferred technical scheme is: the load component of described Supported Nickel Catalyst (or claiming active component) also comprise be selected from lanthanide series a kind of or/and its oxide (this constituent content is the same);
Best technical scheme is: the load component (or claiming active component) of described Supported Nickel Catalyst also comprises lanthanum or/and its oxide (this constituent content is the same).
In a further preferred technical solution of the present invention, the load component of described Supported Nickel Catalyst (or claiming active component) also comprise be selected from alkaline-earth metal a kind of or/and its oxide, in the gross weight of described Supported Nickel Catalyst for 100%, alkaline-earth metal is or/and its oxide accounts for 0.1wt% ~ 5.0wt%;
Preferred technical scheme is: the load component (or claiming active component) of described Supported Nickel Catalyst also comprises magnesium (Mg) or/and its oxide (this constituent content is the same).
In addition, be used as the mesostructured material of carrier in the present invention, its specific area is 600m
2/ g ~ 1500m
2/ g, aperture is 2nm ~ 15nm.
The method of the preparation mentioned above Supported Nickel Catalyst of the present invention, it specifically comprises the steps:
(1) aqueous solution or the alcoholic solution of nickel salt, molybdenum salt, rare earth metal salt and the alkali salt of variable concentrations (concrete concentration is by described each active component content decision above) is prepared respectively;
Wherein, described nickel salt can be selected from: the one in the water such as nickel nitrate, nickelous sulfate, nickel acetate, nickel oxalate or nickel chloride or alcohol insoluble nickel salt; Described molybdenum salt is ammonium molybdate, nitric acid molybdenum or acetic acid molybdenum; Described rare earth metal salt can be selected from: the one in the water such as lanthanum nitrate, cerous nitrate, cerous nitrate, lanthanum chloride, cerium chloride, lanthanum acetate or cerous acetate or alcohol dissolubility rare earth metal salt; Described alkali salt can be selected from: a kind of in magnesium nitrate, magnesium sulfate, magnesium chloride, calcium chloride, calcium nitrate, strontium nitrate, strontium chloride, barium nitrate or barium chloride.
(2) equi-volume impregnating is adopted mesostructured material (carrier) to be impregnated in the nickel salt aqueous solution prepared by step (1), or itself and be selected from molybdenum salt, in the mixed liquor that in the aqueous solution (being prepared by step (1)) of rare earth metal salt or alkali salt, one or two or more kinds (containing two kinds) are combined into, room temperature in vacuo floods 2 little of 10 hours, by this solids in 40 DEG C ~ 80 DEG C oven dry, again that it is little of 10 hours 400 DEG C ~ 800 DEG C condition roastings 1, namely object (Supported Nickel Catalyst of the present invention) is obtained.
Supported Nickel Catalyst of the present invention can be used as by synthesis gas (CO+H
2) prepare the catalyst of methane reaction, its suitable reaction condition is synthesis gas volume space velocity is 3,000h
-1 ~ 30,000h
-1, H in synthesis gas
2/ CO ratio is 2 ~ 4, and the pressure of reaction system is normal pressure ~ 3.0Mpa, and the reaction temperature of reaction system is 250 ~ 550 DEG C.
Compared with prior art, catalyst provided by the invention not only has good catalytic activity and (in the temperature range of 250 DEG C ~ 550 DEG C, has activity, in the temperature range of wherein 350 DEG C ~ 450 DEG C, the activity of catalyst is best, CO conversion ratio can reach more than 99%, methane selectively reaches more than 85%), and there is good heat endurance (not declining through 700 DEG C of high-temperature calcinations, 2 hours catalytic activitys) and longer catalytic life (100 hours life test catalytic activitys are without decline).
Below by embodiment, the present invention is further elaborated.
Embodiment 1
Take 1.0g six water nickel nitrate to be dissolved in 5ml deionized water, be mixed with the aqueous solution of nickel nitrate.Then taking 2g specific area is 800m
2the mesostructured material of/g, adopts equi-volume impregnating to be impregnated in nickel nitrate aqueous solution by carrier MCM-41 at normal temperatures.Then ambient temperature in vacuum steeped overnight in vacuum drying oven is transferred them to, then by its vacuum drying under 40 DEG C ~ 80 DEG C conditions.The roasting 5 ~ 6 hours under (400 DEG C ~ 800 DEG C) in Muffle furnace by gained solid product, after mortar grinds, with the sieved filter of 100 order score sample, can obtain nickel loading is that the synthesis gas of 10wt% prepares methanation catalyst (referred to as catalyst A).The specific area 750m of catalyst A
2/ g, pore volume 0.66cm
3/ g, aperture 2.70nm.
Get the catalyst 0.5g of this example preparation, be seated in the fixed bed reactors of internal diameter 0.8mm.Use high-purity hydrogen reductase 12 h at a certain temperature, and then nitrogen protection drops to 350 DEG C, switches to synthesis gas, gas composition is 75%H
2, 25%CO, at ambient pressure, air speed 12000h
-1, CO conversion 97.87%, methane selectively 88.21%.
Embodiment 2
Divided by outside nickel nitrate in lanthanum nitrate and nickel nitrate alternate embodiment 1, obtain by the method similar to embodiment 1 that nickel loading is 10wt%, the synthesis gas of lanthanum load capacity 1wt% prepares methanation catalyst (referred to as catalyst B).The specific area of catalyst B is 783m
2/ g, pore volume 0.63cm
3/ g, aperture 2.70nm.
Evaluating catalyst method is identical with embodiment 1, and this catalyst is at pressure 1.0Mpa, air speed 12000h
-1, CO conversion is greater than 99.5%, and methane selectively is greater than 85%.
Embodiment 3
Divided by outside the nickel nitrate in ammonium molybdate and nickel nitrate alternate embodiment 1, obtain by the method similar to embodiment 1 and can obtain that nickel loading is 10wt%, the synthesis gas of molybdenum load capacity 3wt% prepares methanation catalyst (referred to as catalyst C).The specific area 762m of catalyst C
2/ g, pore volume 0.65cm
3/ g, aperture 2.70nm.
Evaluating catalyst method is identical with embodiment 1, this catalyst at ambient pressure, air speed 12000h
-1, CO conversion 99.36%, methane selectively 87.67%.
Embodiment 4
Divided by outside the nickel nitrate in ammonium molybdate, lanthanum nitrate and nickel nitrate alternate embodiment 1, obtain by the method similar to embodiment 1 that nickel loading is 10wt%, the synthesis gas of molybdenum load capacity 3wt%, lanthanum load capacity 1wt% prepares methanation catalyst (referred to as catalyst D).The specific area 760m of catalyst D
2/ g, pore volume 0.63cm
3/ g, aperture 2.70nm.
Evaluating catalyst method is identical with embodiment 1, this catalyst at ambient pressure, air speed 12000h
-1, CO conversion 99.70%, methane selectively 92.35%.
Embodiment 5
Divided by outside the nickel nitrate in ammonium molybdate, lanthanum nitrate, magnesium nitrate and nickel nitrate alternate embodiment 1, obtain by the method similar to embodiment 1 that nickel loading is 10wt%, the synthesis gas of molybdenum load capacity 3wt%, lanthanum load capacity 1wt%, magnesium-supported amount 3wt% prepares methanation catalyst (referred to as catalyst E).
Evaluating catalyst method is identical with embodiment 1, this catalyst at ambient pressure, air speed 12000h
-1, CO conversion 100.00%, methane selectively 90.08%.
Comparative example 1 ~ 5
Except adopting alundum (Al2O3) (Al
2o
3) or silica (SiO
2) outside mesostructured material in alternate embodiment 1 ~ 5, with the method similar to embodiment 1 ~ 5 obtained various catalyst (referred to as catalyst a ~ catalyst e) respectively, wherein the active component of all catalyst is Ni, and content is 10wt%.
At identical conditions, gas composition is 75%H
2, 25%CO, at ambient pressure, air speed 12000h
-1, reaction temperature 350 DEG C, its comparative result is in table 1:
Table 1
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (9)
1. a loaded catalyst, is characterized in that, the load group of described loaded catalyst is divided and comprised: metallic nickel is or/and its oxide and metal molybdenum are or/and its oxide, and the carrier of described loaded catalyst is mesostructured material;
Wherein, in the gross weight of described loaded catalyst for 100%, metallic nickel is or/and its oxide accounts for 2wt% ~ 20wt%, and metal molybdenum is or/and its oxide accounts for 0.1wt% ~ 10wt%.
2. loaded catalyst as claimed in claim 1, it is characterized in that, wherein said load component also comprises and is selected from one or two or more kinds mixture in rare earth metal or/and its oxide, and rare earth metal is or/and its oxide accounts for 0.1wt% ~ 5.0wt%.
3. loaded catalyst as claimed in claim 2, is characterized in that, wherein said rare earth metal is a kind of in lanthanide series.
4. loaded catalyst as claimed in claim 3, it is characterized in that, wherein said lanthanide series is lanthanum.
5. loaded catalyst as claimed in claim 2, is characterized in that, wherein said load component also comprises and is selected from alkaline-earth metal a kind of or/and its oxide, and alkaline-earth metal is or/and its oxide accounts for 0.1wt% ~ 5.0wt%.
6. loaded catalyst as claimed in claim 5, it is characterized in that, wherein said alkaline-earth metal is magnesium.
7. prepare the method as loaded catalyst as described in any one in claim 1 ~ 6 for one kind, its key step is: at ambient temperature, in the aqueous solution that mesostructured material be impregnated in the presoma of load component or alcoholic solution, take out the mesostructured material being loaded with loaded article, make it successively after drying and roasting, obtain object;
Wherein, the aqueous solution or the alcoholic solution of described presoma comprise: the water-soluble or aqueous solution of alcohol insoluble nickel salt or the mixed liquor of alcoholic solution and water-soluble molybdenum saline solution, or the mixture of the aqueous solution of above-mentioned mixed liquor and water-soluble dissolubility lanthanum salt and/or water-soluble magnesium salt.
8. prepared a method for methane by synthesis gas, it is characterized in that, preparing used catalyst in methane reaction at synthesis gas is loaded catalyst described in any one or following catalyst in claim 1 ~ 6:
A kind of loaded catalyst, mainly metallic nickel is or/and its oxide for the load component of described loaded catalyst, and the carrier of described loaded catalyst is mesostructured material;
Wherein, in the gross weight of described loaded catalyst for 100%, metallic nickel is or/and its oxide accounts for 2wt% ~ 20wt%.
9. method as claimed in claim 8, is characterized in that, the wherein said reaction temperature preparing methane reaction by synthesis gas is 250 ~ 550 DEG C, and reaction pressure is normal pressure ~ 3.0Mpa, and synthesis gas volume space velocity is 3,000h
-1~ 30,000h
-1, H in synthesis gas
2/ CO ratio is 2 ~ 4.
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Families Citing this family (9)
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| US9522391B2 (en) * | 2012-09-04 | 2016-12-20 | University Of Yamanashi | Co-selective methanation catalyst |
| CN103464192B (en) * | 2013-09-26 | 2015-11-18 | 中国石油大学(北京) | A kind of mesoporous nickel molybdenum oxide catalyst and its preparation method and application |
| CN104971763B (en) * | 2014-04-14 | 2017-10-31 | 华东理工大学 | A kind of preparation of catalyst for methanation in presence of sulfur based on SBA 16 and its application in SNG preparations |
| CN104084231B (en) * | 2014-07-15 | 2016-02-24 | 上海穗杉实业有限公司 | For removing H 2ni-based methanation catalyst of middle trace amounts of CO and preparation method thereof |
| CN105032470A (en) * | 2015-07-16 | 2015-11-11 | 湖北荟煌科技有限公司 | Catalyst for methane production from coke oven gas and preparation method thereof |
| CN105618131B (en) * | 2016-01-25 | 2019-02-01 | 华南农业大学 | A kind of Composite Double carried catalyst and the preparation method and application thereof |
| CN108452822B (en) * | 2018-03-23 | 2021-02-09 | 安徽理工大学 | Microwave-assisted catalyst for preparing high-carbon olefin by using MCM-41 as carrier and catalytic process |
| CN108568310B (en) * | 2018-04-12 | 2021-05-18 | 石家庄职业技术学院（石家庄广播电视大学） | Embedded microporous-mesoporous composite molecular sieve methanation catalyst and application thereof |
| CN110893339A (en) * | 2018-09-12 | 2020-03-20 | 华东理工大学 | Molybdenum-based sulfur-tolerant methanation catalyst and preparation method and application thereof |
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