CN106268858A - The catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation and preparation method and application - Google Patents
The catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation and preparation method and application Download PDFInfo
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Abstract
The catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation is made up of main active component, noble metal active component, structural promoter, rare-earth additive, carrier, its percentage by weight consists of main active component 45 ~ 60%, noble metal active component 5 ~ 15%, structural promoter 2 ~ 8%, rare-earth additive 5 ~ 15%, remaining weight is carrier.The present invention has good carbon dioxide methanation reactivity worth, thus effectively reduces the advantage of hydrogen component in methanation product.
Description
Technical field
The invention belongs to preparation method and the application thereof of a kind of methanation catalyst, particularly relate to a kind of high-performance carbon dioxide and add
Hydrogen methanation catalyst and preparation method and application.
Background technology
Methane is a kind of important fuel and chemical intermediate, can be used for the conjunction of the multiple compounds such as ethylene, acetylene, formaldehyde
Become.In recent years, along with increasing sharply of China's natural gas demand, the insufficiency of supply-demand of domestic natural gas resource is gradually increased.With
Producing synthesis gas from coal is raw material, and is to improve domestic natural gas to supply the effective of situation by methanation reaction production substitute natural gas
Approach, synthesis gas methanation is the core link of this technological process.
The main component of producing synthesis gas from coal is CO and hydrogen, permissible by methanation reaction under conditions of catalyst participates in
Generate CH4During, primary response is,
CO+3H2=CH4+H2O (1)
The most often converting 1molCO and need to consume 3mol hydrogen, product includes CH4And H2O。
The side reaction of this process is as follows,
2CO+2H2=CH4+CO2 (2)
CO+H2O=CO2+H2 (3)
Reaction equation (2) often converts 1molCO only need to consume 1mol hydrogen, by-product CO2.Reaction equation is become by steam in (3)
Changing reaction, CO and steam react generation CO2And hydrogen.
During real reaction, if feeding intake, then according to the stoichiometric proportion shown in the primary response formula (1) of methanation
In the middle of actual production, unstripped gas CO is all consumed, and H2Some residual occurs.Due to H2Be there is corruption in metal gas pipeline
Erosion, so the product gas of synthesis need to be through pressure-variable adsorption flow process to remove hydrogen.This process increases equipment investment and technique
Energy consumption, makes technological process become complicated, reduces product gas price competitiveness.By the optimization of methanation process, make full use of
Following reaction,
CO2+4H2=CH4+2H2O (4)
Make hydrogen convert the economy that can be effectively improved technical process completely, be the developing direction of methanation process.Base
In existing industry methanation technology, methanation technology as strange in Shandong and Top's rope methanation technology, its latter end methanation fixed bed
In feed gas, CO content is the most relatively low, and CO2Content is of a relatively high.Thus exploitation has higher CO2The latter end of methanation activity
Methanation catalyst has important value.
Summary of the invention
It is an object of the present invention to provide one and there is good carbon dioxide methanation reactivity worth, thus effectively reduce methanation
The methanation catalyst of hydrogen component and preparation method and application in product.
For reaching above-mentioned purpose, the present invention prepares methanation catalyst by the method for step impregnation.
The catalyst of the present invention is by main active component, noble metal active component, structural promoter, rare-earth additive, vehicle group
Become, its percentage by weight consists of: main active component 45～60%, noble metal active component 5～15%, structural promoter 2～
8%, rare-earth additive 5～15%, remaining weight is carrier.
Main active component as above is nickel and ferrum, and wherein nickel accounts for the 70～95% of main active component weight, ferrum
Account for the 5～30% of main active component weight.
Noble metal active component as above includes ruthenium and platinum or palladium, and wherein ruthenium accounts for the 51 of noble metal active composition weight
～99%, platinum or palladium account for the 1～49% of noble metal active composition weight.
Structural promoter as above is manganese dioxide.
Rare-earth additive as above includes the one in cerium oxide, and Disamarium trioxide, dysprosia or holmia, wherein oxygen
Changing cerium and account for the 50～90% of rare-earth additive weight, Disamarium trioxide, dysprosia or holmia account for the 10～50% of rare-earth additive weight.
Carrier as above includes aluminium oxide and zirconium dioxide, and wherein aluminium oxide accounts for the 55～80% of vehicle weight, two
Zirconium oxide accounts for the 20～45% of vehicle weight.
The concrete preparation method of the present invention is as follows
(1) coprecipitation is used to prepare aluminium oxide and zirconium dioxide complex carrier: according to aluminium oxide in carrier and titanium dioxide
The ratio of zirconium weighs aluminum nitrate and zirconyl nitrate, adds deionized water and is formulated as solution, and metal ion in solution total concentration is 0.5
～2mol/L, this ie in solution A；Preparing sal volatile with deionized water, wherein cation concn is 0.5～2mol/L, and this is i.e.
Solution B；The mode used by two kinds of solution and flow is added dropwise to fill in the reactor of deionized water, and controls the liquid in reactor
PH value controls 8～9, and precipitation process is carried out under room temperature and stirring condition, in 50～80 DEG C of water-baths and stirring after having precipitated
Under the conditions of be aged 1～3h, collect precipitation, and be 7～7.2 with deionized water by washing of precipitate to pH value, 80～120 will be deposited in
DEG C temperature be dried 8～20h, then in 400～600 DEG C of roastings 2～6h, obtain aluminium oxide and zirconium dioxide complex carrier；
(2) compound concentration be 0.5～1.3g/ml main active component, structural promoter, rare-earth additive soluble-salt molten
Liquid, is added thereto to the support powder of 60～100 mesh, under agitation dipping 12～24h, dipping terminate after by suspension in
Under 60～90 DEG C of water bath condition, heating concentrates, and subsequently in 450～650 DEG C of roastings 6～24h, the catalyst precursor after roasting grinds
It is milled to 60～100 mesh；
(3) compound concentration is the soluble salt solutions of noble metal active component of 0.1～0.4g/ml, is added thereto to step
Suddenly the catalyst precursor powder after (2) grind, under agitation dipping 4～8h, dipping terminate after by suspension in 60～
Under 90 DEG C of water bath condition heating concentrate, subsequently in 350～450 DEG C of roastings 6～24h, after roasting, grind, granulating and forming, subsequently,
Carry out reducing 6～48h fixed bed 500～650 DEG C by reducing gases, i.e. obtain, catalyst.Catalyst is placed in inert gas environment
Middle sealing preserves.
Main active component as above, structural promoter, rare-earth additive, the soluble-salt of noble metal active component are gold
Genus nitrobacter.
Reducing gases as above is made up of nitrogen and hydrogen, and volume consists of hydrogen 5～15%, nitrogen 85～95%,
Reducing gases air speed is 1000～12000L kg-1·h-1。
Catalyst as above is for fixed bed methanation reaction, and reaction velocity is 5000～50000L kg-1·h-1, reaction pressure is 1～5MPa, and reaction temperature is 400～600 DEG C, H in unstripped gas2/(CO+CO2) mol ratio be 2.6～
0.2:1。
The technical advantage of the present invention is as follows:
The present invention discloses multicomponent support type methanation catalyst prepared by a kind of method impregnated by distribution.With existing
Industrial catalyst and/or single nickel component methanation catalyst compare, the substantive distinguishing features that the present invention has and progressive be:
(1) in the methanation catalyst with nickel as main active component, introduce noble metal component, catalyst can be improved
Absorbability to hydrogen, improves the catalyst catalyzed conversion performance to hydrogen.
(2) method using step impregnation, make the relatively low noble metal component of content be uniformly distributed at catalyst external surface and
Fully expose so that it is the absorption stronger to hydrogen and catalyzed conversion ability can give full play to.
(3) use the rare-earth additive based on cerium oxide to be not only able to play the effect of structural promoter, promote nickel component
Dispersion, and cerium can+between trivalent and+4 valencys occur variation of valence, CO can be promoted2Absorption and dissociate.
(4) using aluminium oxide and the complex carrier of zirconium dioxide, wherein aluminium oxide and nickel component adhesion are relatively strong, Ke Yijia
The stability of strong nickel component, hinders it to reunite and sintering, and zirconium dioxide is amphoteric oxide, to CO2Absorbability relatively strong,
Promote CO2Catalyzed conversion.
Detailed description of the invention
Below by specific embodiment, the detailed description of the invention of the present invention is further described in detail.
Embodiment 1
Preparing alumina-zirconia complex carrier, its weight forms: aluminium oxide is 60%, and zirconium dioxide is 40%.Root
Weigh aluminum nitrate and zirconyl nitrate according to the ratio of aluminium oxide in carrier and zirconium dioxide, add deionized water and be formulated as metal ion
Total concentration is the solution of 0.5mol/L；Meanwhile, preparing sal volatile with deionized water, wherein cation concn is 1.2mol/
L.The mode used by two kinds of solution and flow is added dropwise to fill in the beaker of appropriate amount of deionized water, controls the liquid pH value in beaker
Control 8.Precipitation process is carried out under room temperature and stirring condition.It is aged under 60 DEG C of water-baths and stirring condition after having precipitated
1h.Collect precipitation, and be 7.2 with deionized water by washing of precipitate to pH value.The temperature being deposited in 100 DEG C is dried 12h, then
At 450 DEG C of roasting 4h, the product obtained is complex carrier, is ground to 60～100 mesh standby.
Weigh 105.69g nickel nitrate, 135.06g ferric nitrate, 3.84g manganese nitrate, 8.4g cerous nitrate, 4.26g samaric nitrate,
214.38ml water fully dissolves, is added thereto to complex carrier powder 10g, impregnate 20h under agitation, after dipping terminates
Suspension heats under 70 DEG C of water bath condition concentration, and subsequently at 450 DEG C of roasting 12h, the catalyst precursor after roasting grinds
To 60～100 mesh.
Weigh 7.44g nitric acid ruthenium, 2.13g platinum nitrate subsequently, fully dissolve in 23.93ml water, be added thereto to grind
After above-mentioned precursor powder 20g, impregnate 6h under agitation, suspension is added after terminating under 90 DEG C of water bath condition by dipping
Heat concentrates, and subsequently at 450 DEG C of roasting 24h, the catalyst precursor after roasting grinds, granulating and forming.Subsequently, in fixed bed 600
DEG C carry out reductase 12 4h by reducing gases, i.e. obtain loaded catalyst.Reducing gases hydrogen volume content is 5%, nitrogen volume content
Being 95%, reduction air speed is 10000L kg-1·h-1.Catalyst is placed in nitrogen environment sealing and preserves.Catalyst weight percentage
Ratio consists of: nickel, and 32%；Ferrum, 28%；Ruthenium, 10%；Platinum, 5.5%；Manganese dioxide, 2%；Cerium oxide, 5%；Disamarium trioxide,
2.5%；Aluminium oxide, 9%；Zirconium dioxide, 6%.
Catalyst carries out methanation catalyst reaction after having prepared in fixed bed reactors.Feed gas volume percentage ratio group
Become: H2-23%, CO-4%, CO2-5%, CH4-68%, reaction temperature is 400 DEG C, and reaction pressure is 2MPa, and reaction velocity is
5000L·kg-1·h-1.Product gas after removing condensed water amasss percentage ratio and consists of CO2-1.9%, CH4-98.0%, H2Contain
Amount is 20ppm for 30ppm, CO content.
Embodiment 2
Preparing alumina-zirconia complex carrier, its weight forms: aluminium oxide is 70%, and zirconium dioxide is 30%.Root
Weigh aluminum nitrate and zirconyl nitrate according to the ratio of aluminium oxide in carrier and zirconium dioxide, add deionized water and be formulated as metal ion
Total concentration is the solution of 2mol/L；Meanwhile, preparing sal volatile with deionized water, wherein cation concn is 1.5mol/L.
The mode used by two kinds of solution and flow is added dropwise to fill in the beaker of appropriate amount of deionized water, controls the liquid pH value control in beaker
System is 8.Precipitation process is carried out under room temperature and stirring condition.Under 80 DEG C of water-baths and stirring condition, 3h it is aged after having precipitated.
Collect precipitation, and be 7 with deionized water by washing of precipitate to pH value.The temperature being deposited in 80 DEG C is dried 15h, then 550
DEG C roasting 2h, the product obtained is complex carrier, is ground to 60～100 mesh standby.
Weigh 235.96g nickel nitrate, 103.37g ferric nitrate, 11g manganese nitrate, 16.82g cerous nitrate, 9.33g Dysprosium trinitrate,
289.6ml water fully dissolves, is added thereto to complex carrier powder 10g, impregnate 24h under agitation, after dipping terminates
Suspension heats under 90 DEG C of water bath condition concentration, and subsequently at 550 DEG C of roasting 24h, the catalyst precursor after roasting grinds
To 60～100 mesh.
Weigh 4.64g nitric acid ruthenium, 1.34g Palladous nitrate. subsequently, fully dissolve in 29.9ml water, after being added thereto to grind
Above-mentioned precursor powder 20g, impregnate 4h under agitation, suspension is heated after terminating under 60 DEG C of water bath condition by dipping
Concentrating, subsequently at 400 DEG C of roasting 12h, the catalyst precursor after roasting grinds, granulating and forming.Subsequently, fixed bed 500 DEG C
Carry out reduction 48h by reducing gases, i.e. obtain loaded catalyst.Reducing gases hydrogen volume content is 10%, nitrogen volume content
Being 90%, reduction air speed is 12000L kg-1·h-1.Catalyst is placed in nitrogen environment sealing and preserves.Catalyst weight percentage
Ratio consists of: nickel, and 50%；Ferrum, 15%；Ruthenium, 6.7%；Palladium, 2.8%；Manganese dioxide, 4%；Cerium oxide, 7%；Dysprosia,
4%；Aluminium oxide, 7.4%；Zirconium dioxide, 3.1%.
Catalyst carries out methanation catalyst reaction after having prepared in fixed bed reactors.Feed gas volume percentage ratio group
Become: H2-23%, CO-4.5%, CO2-4.5%, CH4-68%, reaction temperature is 450 DEG C, and reaction pressure is 3MPa, reaction sky
Speed is 50000L kg-1·h-1.Product gas after removing condensed water amasss percentage ratio and consists of CO2-1.6%, CH4-98.5%,
H2Content be 35ppm, CO content be 25ppm.
Embodiment 3
Preparing alumina-zirconia complex carrier, its weight forms: aluminium oxide is 80%, and zirconium dioxide is 20%.Root
Weigh aluminum nitrate and zirconyl nitrate according to the ratio of aluminium oxide in carrier and zirconium dioxide, add deionized water and be formulated as metal ion
Total concentration is the solution of 0.5mol/L；Meanwhile, preparing sal volatile with deionized water, wherein cation concn is 1mol/L.
The mode used by two kinds of solution and flow is added dropwise to fill in the beaker of appropriate amount of deionized water, controls the liquid pH value control in beaker
System is 9.Precipitation process is carried out under room temperature and stirring condition.Under 50 DEG C of water-baths and stirring condition, 2h it is aged after having precipitated.
Collect precipitation, and be 7.1 with deionized water by washing of precipitate to pH value.The temperature being deposited in 120 DEG C is dried 10h, then exists
600 DEG C of roasting 5h, the product obtained is complex carrier, is ground to 60～100 mesh standby.
Weigh 65.01g nickel nitrate, 11.86g ferric nitrate, 4.73g manganese nitrate, 2.07g cerous nitrate, 1.38g holmium nitrate,
170.1ml water fully dissolves, is added thereto to the alumina-zirconia complex carrier powder 10g of 60～100 mesh, wherein
Aluminium oxide accounts for 80%, and zirconium dioxide accounts for 20%.Impregnate 12h under agitation, dipping terminate after by suspension in 60 DEG C of water-baths
Under the conditions of heating concentrate, subsequently at 650 DEG C of roasting 6h, the catalyst precursor after roasting is ground to 60～100 mesh.
Weigh 10.42g nitric acid ruthenium, 1.15g platinum nitrate subsequently, fully dissolve in 38.57ml water, be added thereto to grind
After above-mentioned precursor powder 20g, impregnate 8h under agitation, suspension is added after terminating under 80 DEG C of water bath condition by dipping
Heat concentrates, and subsequently at 350 DEG C of roasting 6h, the catalyst precursor after roasting grinds, granulating and forming.Subsequently, fixed bed 650 DEG C
Carry out reduction 6h by reducing gases, i.e. obtain loaded catalyst.Reducing gases hydrogen volume content is 15%, and nitrogen volume content is
85%, reduction air speed is 1000L kg-1·h-1.Catalyst is placed in nitrogen environment sealing and preserves.Catalyst weight percent
Consist of: nickel, 40%；Ferrum, 5%；Ruthenium, 14.2%；Platinum, 0.3%；Manganese dioxide, 5%；Cerium oxide, 2.5%；Holmia,
2.5%；Aluminium oxide, 24.4%；Zirconium dioxide, 6.1%.
Catalyst carries out methanation catalyst reaction after having prepared in fixed bed reactors.Feed gas volume percentage ratio group
Become: H2-22.5%, CO-4.5%, CO2-5%, CH4-68%, reaction temperature is 600 DEG C, and reaction pressure is 4MPa, reaction sky
Speed is 10000L kg-1·h-1.Product gas after removing condensed water amasss percentage ratio and consists of CO2-2.1%, CH4-97.8%,
H2Content be 35ppm, CO content be 20ppm.
Embodiment 4
Preparing alumina-zirconia complex carrier, its weight forms: aluminium oxide is 56%, and zirconium dioxide is 44%.Root
Weigh aluminum nitrate and zirconyl nitrate according to the ratio of aluminium oxide in carrier and zirconium dioxide, add deionized water and be formulated as metal ion
Total concentration is the solution of 1.4mol/L；Meanwhile, preparing sal volatile with deionized water, wherein cation concn is 1.2mol/
L.The mode used by two kinds of solution and flow is added dropwise to fill in the beaker of appropriate amount of deionized water, controls the liquid pH value in beaker
Control 8.2.Precipitation process is carried out under room temperature and stirring condition.It is aged under 70 DEG C of water-baths and stirring condition after having precipitated
1h.Collect precipitation, and be 7.1 with deionized water by washing of precipitate to pH value.The temperature being deposited in 90 DEG C is dried 12h, then
At 500 DEG C of roasting 3h, the product obtained is complex carrier, is ground to 60～100 mesh standby.
Weigh 84.58g nickel nitrate, 35.3g ferric nitrate, 11.26g manganese nitrate, 16.62g cerous nitrate, 1.86g samaric nitrate,
149.62ml water fully dissolves, is added thereto to complex carrier powder 10g, impregnate 15h under agitation, after dipping terminates
Suspension heats under 80 DEG C of water bath condition concentration, and subsequently at 500 DEG C of roasting 18h, the catalyst precursor after roasting grinds
To 60～100 mesh.
Weigh 4.39g nitric acid ruthenium, 2.77g Palladous nitrate. subsequently, fully dissolve in 17.9ml water, after being added thereto to grind
Above-mentioned precursor powder 20g, impregnate 5h under agitation, suspension is heated after terminating under 70 DEG C of water bath condition by dipping
Concentrating, subsequently at 400 DEG C of roasting 18h, the catalyst precursor after roasting grinds, granulating and forming.Subsequently, fixed bed 550 DEG C
Carry out reduction 12h by reducing gases, i.e. obtain loaded catalyst.Reducing gases hydrogen volume content is 10%, nitrogen volume content
Being 90%, reduction air speed is 5000L kg-1·h-1.Catalyst is placed in nitrogen environment sealing and preserves.Catalyst weight percentage
Ratio consists of: nickel, and 35%；Ferrum, 10%；Ruthenium, 6%；Palladium, 5.5%；Manganese dioxide, 8%；Cerium oxide, 13.5%；Disamarium trioxide,
1.5%；Aluminium oxide, 11.5%；Zirconium dioxide, 9%.
Catalyst carries out methanation catalyst reaction after having prepared in fixed bed reactors.Feed gas volume percentage ratio group
Become: H2-22.5%, CO-5%, CO2-4.5%, CH4-68%, reaction temperature is 500 DEG C, and reaction pressure is 5MPa, reaction sky
Speed is 30000L kg-1·h-1.Product gas after removing condensed water amasss percentage ratio and consists of CO2-2.7%, CH4-97.2%,
H2Content be 50ppm, CO content be 15ppm.
Embodiment 5
Preparing alumina-zirconia complex carrier, its weight forms: aluminium oxide is 60%, and zirconium dioxide is 40%.Root
Weigh aluminum nitrate and zirconyl nitrate according to the ratio of aluminium oxide in carrier and zirconium dioxide, add deionized water and be formulated as metal ion
Total concentration is the solution of 1mol/L；Meanwhile, preparing sal volatile with deionized water, wherein cation concn is 1mol/L.Will
Two kinds of solution uses and the mode that flows is added dropwise to fill in the beaker of appropriate amount of deionized water, controls the liquid pH value in beaker and controls
8.8.Precipitation process is carried out under room temperature and stirring condition.It is aged under 50 DEG C of water-baths and stirring condition after having precipitated
1.5h.Collect precipitation, and be 7.1 with deionized water by washing of precipitate to pH value.The temperature being deposited in 90 DEG C is dried 10h, so
After be complex carrier at 600 DEG C of roasting 2h, the product obtained, be ground to 60～100 mesh standby.
Weigh 190.57g nickel nitrate, 25.32g ferric nitrate, 4.04g manganese nitrate, 17.63g cerous nitrate, 2.35g holmium nitrate,
Fully dissolving in 218.1ml water, be added thereto to complex carrier powder 10g, impregnate 20h under agitation, dipping terminates
After suspension is heated concentration under 70 DEG C of water bath condition, subsequently at 600 DEG C of roasting 8h, catalyst precursor after roasting grinds
To 60～100 mesh.
Weigh 5.46g nitric acid ruthenium, 1.21g platinum nitrate subsequently, fully dissolve in 22.23ml water, be added thereto to grind
After above-mentioned precursor powder 20g, impregnate 7h under agitation, suspension is added after terminating under 70 DEG C of water bath condition by dipping
Heat concentrates, and subsequently at 450 DEG C of roasting 20h, the catalyst precursor after roasting grinds, granulating and forming.Subsequently, in fixed bed 600
DEG C with reducing gases carry out reduce 36h, i.e. obtain loaded catalyst.Reducing gases hydrogen volume content is 5%, nitrogen volume content
Being 95%, reduction air speed is 8000L kg-1·h-1.Catalyst is placed in nitrogen environment sealing and preserves.Catalyst weight percentage
Ratio consists of: nickel, and 55%；Ferrum, 5%；Ruthenium, 8.2%；Platinum, 3.5%；Manganese dioxide, 2%；Cerium oxide, 10%；Holmia,
2%；Aluminium oxide, 8.6%；Zirconium dioxide, 5.7%.
Catalyst carries out methanation catalyst reaction after having prepared in fixed bed reactors.Feed gas volume percentage ratio group
Become: H2-23%, CO-5%, CO2-4%, CH4-68%, reaction temperature is 550 DEG C, and reaction pressure is 1MPa, and reaction velocity is
20000L·kg-1·h-1.Product gas after removing condensed water amasss percentage ratio and consists of CO2-1.2%, CH4-98.7%, H2Contain
Amount is 30ppm for 25ppm, CO content.
Claims (10)
1. the catalyst of a high-performance hydrogenation of carbon dioxide methanation, it is characterised in that the catalyst of the present invention is by chief active
Component, noble metal active component, structural promoter, rare-earth additive, carrier form, and its percentage by weight consists of: chief active group
Dividing 45 ~ 60%, noble metal active component 5 ~ 15%, structural promoter 2 ~ 8%, rare-earth additive 5 ~ 15%, remaining weight is carrier.
The catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation the most as claimed in claim 1, it is characterised in that described
Main active component is nickel and ferrum, and wherein nickel accounts for the 70 ~ 95% of main active component weight, and ferrum accounts for the 5 of main active component weight
~30%。
The catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation the most as claimed in claim 1, it is characterised in that described
Noble metal active component includes ruthenium and platinum or palladium, and wherein ruthenium accounts for your gold the 51 ~ 99% of noble metal active composition weight, platinum or palladium account for
Belong to the 1 ~ 49% of active component weight.
The catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation the most as claimed in claim 1, it is characterised in that described
Structural promoter is manganese dioxide.
The catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation the most as claimed in claim 1, it is characterised in that described
Rare-earth additive includes the one in cerium oxide, and Disamarium trioxide, dysprosia or holmia, and wherein cerium oxide accounts for rare-earth additive weight
50 ~ 90%, Disamarium trioxide, dysprosia or holmia account for the 10 ~ 50% of rare-earth additive weight.
The catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation the most as claimed in claim 1, it is characterised in that described
Carrier includes aluminium oxide and zirconium dioxide, and wherein aluminium oxide accounts for the 55 ~ 80% of vehicle weight, zirconium dioxide account for vehicle weight 20 ~
45%。
7. the preparation side of the catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation as described in any one of claim 1-6
Method, it is characterised in that comprise the steps:
(1) coprecipitation is used to prepare aluminium oxide and zirconium dioxide complex carrier: according to aluminium oxide in carrier and zirconium dioxide
Ratio weighs aluminum nitrate and zirconyl nitrate, adds deionized water and is formulated as solution, and metal ion in solution total concentration is 0.5 ~
2mol/L, this ie in solution A；Preparing sal volatile with deionized water, wherein cation concn is 0.5 ~ 2mol/L, this ie in solution
B；The mode used by two kinds of solution and flow is added dropwise to fill in the reactor of deionized water, the liquid pH value control in control reactor
System is 8 ~ 9, and precipitation process is carried out under room temperature and stirring condition, old under 50 ~ 80 DEG C of water-baths and stirring condition after having precipitated
Changing 1 ~ 3h, collect precipitation, and be 7 ~ 7.2 with deionized water by washing of precipitate to pH value, the temperature that will be deposited in 80 ~ 120 DEG C is dry
Dry 8 ~ 20h, then at 400 ~ 600 DEG C of roasting 2 ~ 6h, obtains aluminium oxide and zirconium dioxide complex carrier；
(2) compound concentration be 0.5～1.3g/ml main active component, structural promoter, the soluble salt solutions of rare-earth additive, to
Wherein add the support powder of 60 ~ 100 mesh, impregnate 12 ~ 24h under agitation, dipping terminate after by suspension in 60 ~ 90 DEG C
Under water bath condition, heating concentrates, and subsequently at 450 ~ 650 DEG C of roasting 6 ~ 24h, the catalyst precursor after roasting is ground to 60 ~ 100
Mesh；
(3) compound concentration is the soluble salt solutions of noble metal active component of 0.1～0.4g/ml, is added thereto to step (2)
Catalyst precursor powder after grinding, impregnates 4 ~ 8h under agitation, dipping terminate after by suspension in 60 ~ 90 DEG C of water-baths
Under the conditions of heating concentrate, subsequently at 350 ~ 450 DEG C of roasting 6 ~ 24h, after roasting, grind, granulating and forming, subsequently, in fixed bed 500
~ 650 DEG C carry out reducing 6 ~ 48h by reducing gases, i.e. obtain catalyst.
The preparation method of the catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation the most as claimed in claim 7, its feature
It is that described main active component, structural promoter, rare-earth additive, the soluble-salt of noble metal active component are metal nitrate
Salt.
The preparation method of the catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation the most as claimed in claim 7, its feature
Being that described reducing gases is made up of nitrogen and hydrogen, volume consists of hydrogen 5～15%, nitrogen 85～95%, reducing gases air speed
It is 1000 ~ 12000L kg-1·h-1。
10. the application of the catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation as described in any one of claim 1-6, its
Be characterised by described catalyst for fixed bed methanation reaction, reaction velocity is 5000 ~ 50000L kg-1·h-1, reaction
Pressure is 1 ~ 5MPa, and reaction temperature is 400 ~ 600 DEG C, H in unstripped gas2/(CO+CO2) mol ratio be 2.6 ~ 0.2:1.
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| CN109954507A (en) * | 2019-04-16 | 2019-07-02 | 宁夏大学 | Ni-Rh/αβ-MoXC composite catalyst and preparation and application |
| WO2022224993A1 (en) * | 2021-04-21 | 2022-10-27 | 大阪瓦斯株式会社 | Molded body of carbon dioxide methanation catalyst and method for producing the same |
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| CN106268858B (en) | 2019-01-25 |
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