CN101703933B - Bimetal methanation catalyst and preparation method thereof - Google Patents
Bimetal methanation catalyst and preparation method thereof Download PDFInfo
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- CN101703933B CN101703933B CN2009101754062A CN200910175406A CN101703933B CN 101703933 B CN101703933 B CN 101703933B CN 2009101754062 A CN2009101754062 A CN 2009101754062A CN 200910175406 A CN200910175406 A CN 200910175406A CN 101703933 B CN101703933 B CN 101703933B
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Abstract
The invention discloses a bimetal methanation catalyst for the removal of micro carbon monoxide from a hydrogen-rich gas and a preparation method thereof. The bimetal methanation catalyst contains active components, namely nickel oxide and ferric oxide, loaded on an oxide carrier and an assistant, wherein the assistant is at least one element selected from the main group I, the main group II, the subgroup I, the subgroup III, the subgroup VI and the subgroup VIII of the periodic table, and the oxide carrier is alumina, titanium dioxide, zirconium dioxide and silicon dioxide or a mixture thereof. The catalyst of the invention can allow the micro carbon monoxide to be removed from the hydrogen-rich gas at a relatively low temperature and has the advantages of low load, high activity, relatively low cost and wide application prospect.
Description
Technical field
The present invention relates to a kind of methanation catalyst, be specifically related to a kind of bimetal methanation catalyst and preparation method thereof, described catalyst can remove micro CO in the hydrogen-rich gas when lower temperature.
Background technology
Methanation catalyst is mainly used in ethylene unit, synthetic ammonia installation and the hydrogen fuel cell device; Micro CO carries out deep removal through methanation reaction in the unstrpped gas of these devices; Just with trace in the process gas of rich hydrogen (like 5000ppm, the ppm of unit representes * 10
-6(V/V)) CO passes through hydrogenation with CH
4And H
2The form of O removes, and poisons to prevent downstream catalyst.
In recent years; Continuous development along with converter technique; CO content constantly drops to more low-levelly in the unstripped gas, and methanation furnace reduces reaction focus temperature requirement naturally, and traditional high-temperature methanation catalyst is possibly can't to transform the trace amounts of CO in the hydrogen-rich gas at low temperatures fully.If reduce the serviceability temperature of catalyst, on the one hand, can practice thrift process energy consumption and reacting furnace cost greatly; On the other hand and since under lower serviceability temperature in the nickel catalyst metallic nickel crystal grain be not easy to assemble and grow up, also help improving the service life of catalyst, realize energy efficiency.Simultaneously, Proton Exchange Membrane Fuel Cells hydrogen source is methanol recapitalization, requires follow-uply to remove that the trace amounts of CO temperature is not higher than 230 ℃ of reforming temperatures in the reformation gas.Therefore, the exploitation of low temperature high activity methanation catalyst is significant.
The existing oxycarbide methanation catalyst that removes generally adopts Ni catalyst based, adds other cocatalyst component on this basis, and noble metal catalyst also has research.
Kustov etc. (Applied Catalysis A:General, Volume 320,22 March 2007, Pages 98-104) have prepared and have been carried on MgAl
2O
4And Al
2O
3The Ni-Fe catalyst, studied the total load amount and be 10% Ni-Fe/MgAl
2O
4And Ni-Fe/Al
2O
3Catalyst activity, find as Ni: Fe=1: catalyst activity is best in the time of 1, at reaction condition 2%CO, 98%H
2, air speed 50000h
-1, conversion ratio is respectively 40.5% and 38.2%, and this research focuses on Mathematical Modeling foundation and calculation optimization, the low temperature active that removes CO is fully studied.
Up to the present, the ferronickel bimetallic catalyst does not also come thoroughly to remove the trace amounts of CO impurity in the hydrogen-rich gas as Catalyst for Low-Temperature Methanation in 220 ℃～250 ℃ scopes.
Summary of the invention
The object of the present invention is to provide a kind of bimetal methanation catalyst and preparation method thereof, described catalyst can remove micro CO in the hydrogen-rich gas when lower temperature.
A kind of bimetal methanation catalyst provided by the invention, it contains active component nickel oxide, iron oxide and the auxiliary agent that is carried on the oxide carrier;
Described active component nickel oxide, in metallic element, its content is 5～40wt%, preferred 10～25wt%; Described
The active component iron oxide, in metallic element, its content is 5～40wt%, preferred 8～25wt%;
Described auxiliary agent, in metallic element, its content is 0.001～10wt%, preferred 0.1～7wt%; It is selected from periodic table I, II main group, at least a element in I, III, VI and the VIII subgroup, at least a in preferred potassium, magnesium, calcium, copper, silver, lanthanum, cerium, molybdenum, ruthenium, rhodium, palladium, the platinum element;
All the other are carrier, and described carrier can be aluminium oxide, titanium dioxide, zirconium dioxide or silica, or the mixture of any two kinds or three kinds in them;
Described content is benchmark with the gross mass of catalyst all.
The method of a kind of ferronickel methanation catalyst preparation provided by the invention specifically comprises the steps:
(1) getting specific surface is 110～400m
2/ g, average pore size are the oxide carrier of 5～20nm, and through conventional soluble-salt dipping, drying obtains containing the carrier of auxiliary agent after the roasting; Described soluble-salt is I, the nitrate of II main group metal, carbonate, nitrate, the chloride of I, III, VI and VIII subgroup metal, and at least a in the nitrate of rare earth metal, ammonium salt;
The carrier that (2) will contain auxiliary agent vacuumizes through 100～150 ℃ and handles 10～30min, or directly in 100～150 ℃ of convection oven, heats 1～10h, after to reduce to room temperature subsequent use;
(3) get the inorganic salts of nickel by ferronickel mol ratio 1: 0.3～3 and/or the inorganic salts and/or the organic salt of organic salt and iron is hybridly prepared into the mixing salt solution that ferronickel content is 0.05～0.2g/mL; The inorganic salts of said nickel are selected from least a in nickel nitrate, nickel chloride and the nickelous sulfate, and the organic salt of nickel is selected from least a in nickel formate, nickel acetate, nickel oxalate, the citric acid nickel; The inorganic salts of iron are selected from least a in ferric nitrate, iron chloride and the ferric sulfate, and the organic salt of iron is selected from least a in ferric oxalate, ferric acetate, the ironic citrate;
(4) ratio that the carrier that contains auxiliary agent in every gram is got 0.7～2mL ferronickel mixing salt solution to carrier, leaves standstill 20～120min, the elimination redundant solution with solution impregnation; Also can be to carrier with ferronickel mixing salt solution graded impregnation; Each dipping back is dry down at 80～200 ℃;
(5) bubbling air or nitrogen feed the reducibility gas reduction then and obtain catalyst at 400～550 ℃ of following roasting 1～50h afterwards; Also can directly feed the reducibility gas reduction without roasting process at 400～550 ℃; Described reducibility gas is carbon monoxide, hydrogen, hydrogen/nitrogen mixed gas or carbon monoxide/hydrogen mixed gas,
Catalyst after the reduction is subsequent use through the oxygen passivation.Catalyst after the reduction also can directly be packed into and used in the reactor or using after the activation under 400～550 ℃ of hydrogen atmospheres.
Catalyst of the present invention is the ferronickel bimetallic catalyst, adopts immersion process for preparing, and adds auxiliary agent, and catalyst is easy to reduction, the active component high degree of dispersion, thereby in methanation reaction, show high low temperature methanation activity.
Catalyst of the present invention can be in ethylene process the hydrogenation gas source purification, syngas for synthetic ammonia purifies and the application of hydrogen fuel cell raw material gas purifying in interior and purified hydrogen correlated process.Trace amounts of CO in the hydrogen-rich gas (5000ppm) is reduced to below the 1ppm.
The specific embodiment
Through embodiment technology of the present invention is elaborated below, but the present invention is not limited to these embodiment.Among the embodiment below, percentage all is that the gross weight with catalyst is the percentage by weight of benchmark, and CO content is represented with ppm.
The carrier specific surface that uses in the embodiment of the invention is 110～400m
2/ g, average pore size is 5～20nm, through broken screening 40～60 purpose particles; The alumina support that mixes titanium dioxide, zirconium dioxide, silica (takes by weighing corresponding oxide and alumina support powder by certain percentage by weight; Obtain the mixed oxide carrier through moulding, roasting after mechanical mixture is even), the about 200m of their specific area
2/ g; Other reagent is AR.
Embodiment 1
Get alumina support 100g through 150 ℃, 13.3Pa air pressure is handled 10min down, after to reduce to room temperature subsequent use; Take by weighing 49.4g Nickelous nitrate hexahydrate, 72.4g nine nitric hydrate iron, be mixed with the 200mL mixing salt solution; Get the mixing salt solution that 200mL prepared and be impregnated in the treated carrier of 100g, room temperature leaves standstill 2h; Back elimination excess solution, 120 ℃ of dry 6h are warming up to 450 ℃ of roasting 5h so that salt decomposes, and the back is at H
2In the stream under 400 ℃ of conditions reduction handle 10h, reduce to room temperature after the oxygen passivation obtain catalyst 1.
Embodiment 2
Get alumina support 100g through 150 ℃, 13.3Pa air pressure is handled 10min down, after to reduce to room temperature subsequent use; Take by weighing 24.7g Nickelous nitrate hexahydrate, 21.2g four hydration nickel acetates, 36.2g nine nitric hydrate iron, 22.1g four hydration ferric acetates are mixed with 200mL mixed Ni salting liquid; Get mixed Ni salt solution impregnation that 200mL prepared in the treated carrier of 100g, room temperature leaves standstill 2h; Back elimination excess solution, 120 ℃ of dry 6h are warming up to 450 ℃ of roasting 5h so that salt decomposes, and the back is at H
2In the stream under 400 ℃ of conditions reduction handle 10h, reduce to room temperature after the oxygen passivation obtain catalyst 2.
Embodiment 3
Get alumina support 100g through 150 ℃, 13.3Pa air pressure is handled 10min down, after to reduce to room temperature subsequent use; Take by weighing the 69.4g Nickelous nitrate hexahydrate, 43.4g nine nitric hydrate iron are mixed with 200mL mixed Ni salting liquid; Get mixed Ni salt solution impregnation that 200mL prepared in the treated carrier of 100g, room temperature leaves standstill 2h; Back elimination excess solution, 120 ℃ of dry 6h are warming up to 450 ℃ of roasting 5h so that salt decomposes, and the back is at 50%H
2/ 50%N
2In the stream under 400 ℃ of conditions reduction handle 10h, reduce to room temperature after the oxygen passivation obtain catalyst 3.
Embodiment 4
Get alumina support 100g through 150 ℃, 13.3Pa air pressure is handled 10min down, after to reduce to room temperature subsequent use; Take by weighing the 49.4g Nickelous nitrate hexahydrate, 57.9g four nitric hydrate iron are mixed with the 200mL mixing salt solution; Get the mixing salt solution that 200mL prepared and be impregnated in the treated carrier of 100g, room temperature leaves standstill 2h; Back elimination excess solution, 120 ℃ of dry 6h are warming up to 450 ℃ of roasting 5h so that salt decomposes, and the back is at H
2In the stream under 400 ℃ of conditions reduction handle 10h, reduce to room temperature after the oxygen passivation obtain catalyst 4.
Embodiment 5
Get alumina support,, obtain containing the carrier of cerium 3wt% after the roasting through solubility cerium salt dipping, drying; Get this carrier 100g through 150 ℃, 13.3Pa air pressure is handled 10min down, and it is subsequent use to reduce to room temperature; Take by weighing the 49.4g Nickelous nitrate hexahydrate, 57.9g four nitric hydrate iron are mixed with the 200mL mixing salt solution; Be impregnated in the treated carrier of 100g, room temperature leaves standstill 2h; The elimination excess solution, 120 ℃ of dry 6h are warming up to 450 ℃ of roasting 5h so that salt decomposes, then at H
2In the stream under 400 ℃ of conditions reduction handle 10h, reduce to room temperature after the oxygen passivation obtain catalyst 5.
Embodiment 6
Get alumina support, through conventional soluble magnesium salt dipping, drying obtains containing the carrier of magnesium 3wt% after the roasting; Get this carrier 100g, directly in 100～150 ℃ of baking ovens, heat 5h, after to reduce to room temperature subsequent use; Take by weighing the 49.4g Nickelous nitrate hexahydrate, 57.9g four nitric hydrate iron are mixed with the 200mL mixing salt solution; Get the mixing salt solution that 200mL prepared and be impregnated in the treated carrier of 100g, room temperature leaves standstill 2h; Back elimination excess solution, 120 ℃ of dry 6h are warming up to 450 ℃ of roasting 5h so that salt decomposes, and the back is at 50%H
2/ 50%N
2In the stream under 400 ℃ of conditions reduction handle 10h, reduce to room temperature after the oxygen passivation obtain catalyst 6.
Embodiment 7
Get alumina support, through conventional solubility cobalt salt dipping, drying obtains containing the carrier of cobalt 3wt% after the roasting; Get this carrier 100g through 150 ℃, 13.3Pa air pressure is handled 10min down, after to reduce to room temperature subsequent use; Take by weighing the 49.4g Nickelous nitrate hexahydrate, 57.9g four nitric hydrate iron are mixed with the 200mL mixing salt solution; Get the mixing salt solution that 200mL prepared and be impregnated in the treated carrier of 100g, room temperature leaves standstill 2h; Back elimination excess solution, 120 ℃ of dry 6h are warming up to 450 ℃ of roasting 5h so that salt decomposes, and the back is at H
2In the stream under 400 ℃ of conditions reduction handle 10h, reduce to room temperature after the oxygen passivation obtain catalyst 7.
Embodiment 8
Get alumina support 100g through 150 ℃, 0.1mmHg air pressure is handled 10min down, after to reduce to room temperature subsequent use; Take by weighing the 89.2g Nickelous nitrate hexahydrate, 86.8g four nitric hydrate iron are mixed with the 200mL mixing salt solution; Get the mixing salt solution that 200mL prepared and be impregnated in the treated carrier of 100g, room temperature leaves standstill 2h; Back elimination excess solution, 120 ℃ of dry 6h are warming up to 450 ℃ of roasting 5h so that salt decomposes, and the back is at H
2In the stream under 400 ℃ of conditions reduction handle 10h, reduce to room temperature after the oxygen passivation obtain catalyst 8.
Embodiment 9
Get alumina support, through conventional solubility cerium salt, magnesium salts dipping, drying obtains containing the carrier of cerium 4.5wt%, magnesium 4.5wt% after the roasting; Get this carrier 100g through 150 ℃, 0.1mmHg air pressure is handled 10min down, after to reduce to room temperature subsequent use; Take by weighing the 49.4g Nickelous nitrate hexahydrate, 57.9g four nitric hydrate iron are mixed with the 200mL mixing salt solution; Get the mixing salt solution that 200mL prepared and be impregnated in the treated carrier of 100g, room temperature leaves standstill 2h; Back elimination excess solution, 120 ℃ of dry 6h are warming up to 450 ℃ of roasting 5h so that salt decomposes, and the back is at 50%H
2/ 50%N
2In the stream under 400 ℃ of conditions reduction handle 10h, reduce to room temperature after the oxygen passivation obtain catalyst 9.
Embodiment 10
Get titania support and repeat embodiment 9 catalyst preparation process, obtain catalyst 10.
Embodiment 11
Get multiple embodiment 9 catalyst preparation process of aluminium oxide-titanium dioxide complex carrier body weight, obtain catalyst 11.
Embodiment 12
Get multiple embodiment 9 catalyst preparation process of aluminium oxide-zirconium dioxide complex carrier body weight, obtain catalyst 12.
Embodiment 13
Get multiple embodiment 9 catalyst preparation process of alumina silica complex carrier body weight, obtain catalyst 13.
Comparative example 1:
Get alumina support 100g through 15 ℃, 0.1mmHg air pressure is handled 10min down, or directly in 150 ℃ of convection oven, heats 3h, after to reduce to room temperature subsequent use; Take by weighing the 99.1g Nickelous nitrate hexahydrate and be mixed with the 200mL nickel salt solution; Get the nickel salt solution that 200mL prepared and be impregnated in the treated carrier of 100g, room temperature leaves standstill 2h; Back elimination excess solution, 120 ℃ of dry 6h are warming up to 450 ℃ of roasting 5h so that salt decomposes, and the back is at H
2In the stream under 400 ℃ of conditions reduction handle 10h, reduce to room temperature after the oxygen passivation obtain the comparative example catalyst A.
Comparative example 2
Get alumina support 100g through 15 ℃, 0.1mmHg air pressure is handled 10min down, or directly in 150 ℃ of convection oven, heats 3h, after to reduce to room temperature subsequent use; Take by weighing the 49.5g Nickelous nitrate hexahydrate, 42.4g four hydration nickel acetates are mixed with 200mL mixed Ni salting liquid; Get mixed Ni salt solution impregnation that 200mL prepared in the treated carrier of 100g, room temperature leaves standstill 2h; Back elimination excess solution, 120 ℃ of dry 6h are warming up to 450 ℃ of roasting 5h so that salt decomposes, and the back is at 50%H
2/ 50%N
2In the stream under 400 ℃ of conditions reduction handle 10h, reduce to room temperature after the oxygen passivation obtain the comparative example catalyst B.
Comparative example 3
Get alumina support 100g through 15 ℃, 0.1mmHg air pressure is handled 10min down, or directly in 150 ℃ of convection oven, heats 3h, after to reduce to room temperature subsequent use; Take by weighing 144.7g nine nitric hydrate iron and be mixed with the 200mL iron salt solutions; Get the iron salt solutions that 200mL prepared and be impregnated in the treated carrier of 100g, room temperature leaves standstill 2h; Back elimination excess solution, 120 ℃ of dry 6h are warming up to 450 ℃ of roasting 5h so that salt decomposes, and the back is at H
2In the stream under 400 ℃ of conditions reduction handle 10h, reduce to room temperature after the oxygen passivation obtain comparative example catalyst C.
Comparative example 4
Get alumina support 100g through 15 ℃, 0.1mmHg air pressure is handled 10min down, or directly in 150 ℃ of convection oven, heats 3h, after to reduce to room temperature subsequent use; Take by weighing 72.3g nine nitric hydrate iron, 44.1g four hydration ferric acetates are mixed with 200mL mixed molysite solution; Get mixed molysite solution impregnation that 200mL prepared in the treated carrier of 100g, room temperature leaves standstill 2h; Back elimination excess solution, 120 ℃ of dry 6h are warming up to 450 ℃ of roasting 5h so that salt decomposes, and the back is at 50%H
2/ 50%N
2In the stream under 400 ℃ of conditions reduction handle 10h, reduce to room temperature after the oxygen passivation obtain comparative example catalyst D.
Get the foregoing description 1-13 catalyst and comparative example 1-4 catalyst on fixed bed reactors, 180～400 ℃ of reaction temperatures, reaction pressure 0.1MPa, air speed 5000h
-1Under the condition, the complete conversion temperature of CO methanation is carried out record.Product behind the methanation reaction has been carried out chromatography, and the result sees table 1.
Table one catalyst is formed and the reactivity worth data
Claims (3)
1. the preparation method of a bimetal methanation catalyst is characterized in that, comprises the steps:
(1) getting specific surface is 110～400m
2/ g, average pore size are 5～20nm carrier, through soluble-salt dipping, drying, obtain containing the carrier of auxiliary agent after the roasting;
The carrier that (2) will contain auxiliary agent vacuumizes through 100～150 ℃ and handles 10～30min, and it is subsequent use to reduce to room temperature then;
(3) get the inorganic salts of nickel by ferronickel mol ratio 1: 0.3～3 and/or the inorganic salts and/or the organic salt of organic salt and iron is hybridly prepared into the mixing salt solution that the ferronickel total content is 0.05～0.2g/mL;
(4) ratio that the carrier that contains auxiliary agent in every gram is got 0.7～2mL ferronickel mixing salt solution to carrier, leaves standstill 20～120min, the elimination redundant solution with solution impregnation; Or with ferronickel mixing salt solution graded impregnation to carrier; Each dipping back is dry down at 80～200 ℃;
(5) dry back bubbling air or nitrogen feed the reducibility gas reduction then and obtain catalyst at 400～550 ℃ of following roasting 1～50h; Or directly feed the reducibility gas reduction without roasting process and obtain catalyst at 400～550 ℃;
Described carrier is aluminium oxide, titanium dioxide, zirconium dioxide or silica, or the mixture of any two kinds or three kinds in them.
Described soluble-salt is I, the nitrate of II main group metal, carbonate, nitrate, the chloride of I, III, VI and VIII subgroup metal, and at least a in the nitrate of rare earth metal, ammonium salt.
2. Preparation of catalysts method as claimed in claim 1; It is characterized in that; The inorganic salts of said nickel are selected from least a in nickel nitrate, nickel chloride and the nickelous sulfate, and the organic salt of nickel is selected from least a in nickel formate, nickel acetate, nickel oxalate, the citric acid nickel; The inorganic salts of iron are selected from least a in ferric nitrate, iron chloride and the ferric sulfate, and the organic salt of iron is selected from least a in ferric oxalate, ferric acetate, the ironic citrate.
3. Preparation of catalysts method as claimed in claim 1 is characterized in that, described reducibility gas is hydrogen, hydrogen/nitrogen mixed gas or carbon monoxide/hydrogen mixed gas.
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| CN2009101754062A CN101703933B (en) | 2009-11-06 | 2009-11-06 | Bimetal methanation catalyst and preparation method thereof |
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2009
- 2009-11-06 CN CN2009101754062A patent/CN101703933B/en not_active Expired - Fee Related
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