CN105709748A - CO methanation catalyst with water-vapor conversion function and preparation method and application thereof - Google Patents
CO methanation catalyst with water-vapor conversion function and preparation method and application thereof Download PDFInfo
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Abstract
The present invention discloses a CO methanation catalyst with water-vapor conversion function and a preparation method and application thereof. The CO methanation catalyst comprises an active component, first additives, second additives and a carrier, a nickel-zinc alloy is used as the active component, rare earth metals Ce, La, Yb and the like are used as the first additives, alkali metals K, alkaline earth metals Ca, Mg and the like are used as the second additives, and gamma-Al2O3 is used as the carrier. The CO methanation catalyst has both methanation and CO water-vapor conversion dual functions, and can completely enter a methanation reactor under low H2 / C ratio condition, carbon is deposited in the reaction process, and methanation reaction H2/ C ratio operating window and operating flexibility are widened.
Description
Technical field
The invention belongs to catalytic synthetic techniques field, particularly relate to a kind of CO methanation catalyst with water-gas shift function and its preparation method and application.
Background technology
Methanation reaction is a kind of important hydrogenation reaction, is the core process utilizing synthesis gas to manufacture substitute natural gas (SNG).The dominant response that synthesis gas produces the generation of substitute natural gas technical process by methanation reaction is as follows:
CO+3H2→CH4+H2O△H0=-206kJ/mol (1)
2CO+2H2→CH4+CO2△H0=-247kJ/mol (2)
CO2+4H2→CH4+2H2O△H0=-165kJ/mol (3)
CO+H2O→H2+CO2△H0=-41kJ/mol (4)
2CO→C↓+CO2△H0=-173kJ/mol (5)
CH4→C↓+2H2△H0=75kJ/mol (6)
Reaction (1)-(3) are the dominant response in methanation system, and wherein reaction (2) can be decomposed into reaction (1) and (4).Owing to reaction system there being water exist, so transformationreation (4) will necessarily be there is.Reaction (5) and (6) is the analysis carbon reaction in methanation system.When reaction temperature is relatively low, analysis carbon is mainly to react (5) appearance；When reaction temperature is higher, to react (6) appearance.Analysis carbon reaction is totally unfavorable to catalyst: carbon blocking catalyst duct, causes catalysqt deactivation.Gas methanation thermodynamic analysis of process shows, CO (BoudouardReaction) dismutation reaction (5) is the main cause causing carbon distribution in methanation reaction system, and this reaction is H2The function of/C ratio, temperature and pressure.By calculation of thermodynamics it can be seen that under synthesis gas full methanation reaction temperature (260-700 DEG C) and reaction pressure (1-3MPa), the H in reaction system2The mol ratio of/C needs more than 3, and analysis carbon reaction (5) will not occur in guarantee methanation reaction.Therefore to produce in the synthesis gas full methanation technique for the purpose of SNG, it is necessary to carry out synthesis controlled atmosphere ratio in advance, namely by CO water gas shift reation, by H in synthesis gas2The mol ratio of/C adjusts more than 3, and reactor feed gas could enter next step methanation workshop section.Even so, when long period of operation, still inevitably there is carbon distribution in methanation catalyst, thus causing catalysqt deactivation.Therefore, development one can at low H2/ C is more significant than lower operation, anti-carbon synthesis gas methanation catalyst.
CO water gas shift reation (4) is CO and steam reaction generation H2And CO2Equal-volume reaction, CO can be removed owing to producing conversion gas in SNG technique at synthesis gas through low-temperature rectisol workshop section2Deng sour gas, therefore objectively serve increase H2Effect and be used to synthesis controlled atmosphere ratio.In synthesis gas methanation workshop section, owing in reaction system, vapour gas mol ratio (steam/gas), therefore still can the CO water gas shift reation (4) of generating portion generally about 0.2.Although this reaction does not generate CH4, but this reaction is conducive to increasing the H in reaction system2Content, it is suppressed that the generation of analysis carbon reaction.Methanation reaction system exists CO water gas shift reation, can at low H for developing one2/ C provides possibility than lower operation, anti-carbon, the synthesis gas methanation catalyst of multi-functional coupling with water-gas shift effect.It is true that foreign study person is when studying CO water gas shift reation process, it has been found that on some catalyst, there is the response competition of CO water-gas shift and CO methanation, such as Ru/ZrO2Catalyst (US20020114762), Pt/CeO2Catalyst (WO0226618,2002-04-04) etc..
Summary of the invention
It is an object of the invention to provide one can at low H2/ C is than lower operation, anti-carbon, the synthesis gas methanation catalyst of multi-functional coupling with water-gas shift effect and its preparation method and application.
The present invention the specific scheme is that
A kind of CO methanation catalyst with water-gas shift function, this catalyst is made up of active component, auxiliary agent and carrier, wherein:
Active component is nickel-zinc alloy, and its content is in metal-oxide, for the 35-60% of total catalyst weight；Nickel in nickel-zinc alloy, zinc atomic ratio be 1～8:1；
Auxiliary agent one is rare earth metal Ce, La or Yb；Its content is in metal-oxide, for the 3～15% of total catalyst weight；
Auxiliary agent two is alkali metal K, alkaline-earth metal Ca or Mg, and its Content is in metal-oxide, for the 3～15% of total catalyst weight；
Catalyst surplus is carrier γ-Al2O3。
In metal-oxide, active nickel-kirsite content is preferably the 45～55% of total catalyst weight；Nickel in nickel-zinc alloy, zinc atomic ratio be preferably 3～5:1.
Active component nickel partly can form solid solution, alloy or eutectic mixture with active component zinc.
Active component nickel, zinc partly can form spinelle type composite oxides with carrier.
The preparation method of a kind of CO methanation catalyst with water-gas shift function, carries out according to following steps:
(1) stoichiometric proportion according to catalyst component, the preparation solubility predecessor aqueous solution containing auxiliary agent one, it is placed in stirred tank and adds carrier γ-Al2O3, it is neutralized precipitation when stirring with alkaline precipitating agent, by precipitation filtration, washing, dries 16 hours at 100～150 DEG C, at 500～700 DEG C, roasting obtains catalyst intermediate powder body in 3 hours, obtains catalyst intermediate A after broken, pelletize, molding procedure；
(2) stoichiometric proportion according to catalyst component, the preparation solubility predecessor aqueous solution containing auxiliary agent two, auxiliary agent two is supported on above-mentioned catalyst intermediate A by the mode adopting dipping, dries 8 hours at 100～150 DEG C, and at 500～700 DEG C, roasting obtains catalyst intermediate B in 3 hours；
(3) stoichiometric proportion according to catalyst component, preparation contains solubility predecessor aqueous solution or the mixed water solution of catalyst activity component, catalyst activity component is supported on above-mentioned catalyst intermediate B by the mode adopting dipping, drying 8 hours at 100～150 DEG C, at 500～700 DEG C, namely roasting obtains catalyst of the present invention in 3 hours.
Described active component nickel, zinc predecessor be preferably the nitrate of solubility；
The predecessor of described auxiliary agent is preferably the nitrate of solubility.
Alkaline precipitating agent described in step (1) is Na2CO3、NH4HCO3, NaOH, ammonia or carbamide；
Described alkaline precipitating agent more preferably ammonia or carbamide；Further it is preferably carbamide.
Neutralization-precipitation reaction described in step (1) can carry out at 40～90 DEG C；In some highly preferred embodiment, neutralization-precipitation reaction temperature is 80～90 DEG C.
Impregnated activated component order described in step (3) is nickel after first zinc；It is zinc after first nickel in other embodiments；In other highly preferred embodiments, for nickel, the mixed co-impregnation of zinc.
A kind of application of the CO methanation catalyst with water-gas shift function, described catalyst is in the reaction of synthesis gas high-temperature methanation, and full methanation reaction condition is as follows: pressure is 1.0～5.0MPa, temperature is 260～700 DEG C, air speed is 10000～40000h-1、H2/(3CO+4CO2) mol ratio be more than 0.8；Under the reaction conditions, CO, CO2Conversion ratio is all close to the equilibrium conversion of reaction system, CH4Selectivity is close to 100%.
In some preferred embodiment of catalyst of the present invention, active component nickel partly can form solid solution, alloy or eutectic mixture to improve catalyst activity with active component zinc.Zinc oxide (ZnO) belongs to n-type conductor oxidate, under certain condition, is easily formed the non-stoichiometric ZnOx crystal structure of anoxia, is conducive to H2, CO co-adsorption and surface reaction occurs on nickel, zinc, become the activity unit being conducive to CO water gas shift reation and methanation reaction.
In some preferred embodiment of catalyst of the present invention, active component nickel, zinc partly can form spinelle type composite oxides with carrier, it is prevented that active component crystal grain is reunited to improve catalyst activity and stability.
In some embodiment of catalyst of the present invention, rare-earth additive can as Structure promoter partly or entirely with carrier γ-Al2O3Form composite oxides to improve carrier stability under high-temperature water heat condition.In other highly preferred embodiments, rare-earth additive is as the electronics of oxygen atom in electron type auxiliary agent energy acceptable response thing CO, CO is conducive to dissociate form active surface carbon species at nickel, zinc surface, thus becoming the activity unit being conducive to CO water gas shift reation and methanation reaction.
In some embodiment of catalyst of the present invention, alkali metal or/and base earth metal promoter can also as Structure promoter partly or entirely with carrier γ-Al2O3Form composite oxides to improve carrier stability under high-temperature water heat condition；In some preferred embodiments, alkali metal is or/and base earth metal promoter can neutralize carrier γ-Al2O3Surface acidity, start suppress catalyst surface carbon distribution effect；In other highly preferred embodiments, alkali metal is or/and base earth metal promoter can partly suppress the methanation reaction of CO in course of reaction, thus playing the effect of CO methanation reaction and CO water gas shift reation speed in regulation system.
Catalyst of the present invention has the advantage that bimetallic nickel-kirsite catalyst has methanation reaction simultaneously and CO water gas shift reation is difunctional, it is possible at low H2/ C enters full methanation reactor than under condition, and course of reaction not carbon distribution, thus having widened the H of methanation reaction2/ C is than action pane and operating flexibility.
Detailed description of the invention
By embodiment, the present invention is described in further details below, but this should not being interpreted as, the scope of the claims of the present invention is only limitted to following embodiment.Meanwhile, embodiment has been merely given as the part Experiment condition realizing this invention, but is not meant to must be fulfilled for these conditions and can be only achieved the purpose of the present invention.In specific embodiment, the catalyst composition of offer, preparation method, reaction condition are simply to the many possible illustration being embodied as representing present invention application.
Unless otherwise noted, the all numerals occurred in specification and claims of the present invention, such as dry, sintering temperature, operation temperature and pressure, the numerical value such as the mass percent of expression catalyst composition are all not construed as absolute exact value, in the range of error that this numerical value is understood one of ordinary skilled in the art, known technology allows.
Embodiment 1:
(1-1) NaOH taking 30g is dissolved in standby in 150ml deionized water (being labeled as solution I).Take the La (NO of 88g3)3·6H2O is dissolved in 300ml deionized water and (is labeled as solution II), when stirring by the γ-Al of 100g2O3Powder body is slowly added in above-mentioned solution II, 10min is so as to dispersed in stirring, then it is slow added into alkaline solution I and is neutralized precipitation, precipitation is further continued for stirring ageing 60min after completing, then filtration, washing leaching cake, dry 14 hours at 120 DEG C, and at 500 DEG C, roasting obtains catalyst intermediate powder body in 3 hours, obtaining catalyst intermediate A after broken, pelletize, molding procedure, overall dimensions is
(1-2) KNO of 20g is taken3It is dissolved in 50ml deionized water, adopts the mode of dipping by above-mentioned KNO3Solution impregnation, to catalyst intermediate A, dries 8 hours at 120 DEG C, and at 500 DEG C, roasting obtains catalyst intermediate B in 3 hours.
(1-3) Ni (NO of 180g is taken3)2·6H2Zn (the NO of O and 120g3)2·6H2O, 50 DEG C, be dissolved in 120ml deionized water under stirring condition, above-mentioned mixed solution is impregnated on catalyst intermediate B at twice, at 120 DEG C dry 8 hours, at 600 DEG C, namely roasting obtains catalyst of the present invention in 3 hours, this catalyst finally consist of 20.9%NiO-14.8%ZnO/4.2%K2O/15.0%La2O3/ 45.1% γ-Al2O3, it is labeled as embodiment 1.
Above-mentioned CATALYST EXAMPLE 1 is filled in the middle of methanator, uses pure H2Reductase 12 hour under 500 DEG C of conditions, then pressure to be 3.0MPa, temperature be 620 DEG C, air speed be 15000h-1、H2/(3CO+4CO2) mol ratio be evaluated when being 0.8.Under the reaction conditions, CO conversion ratio is 79.4%, CO2Conversion ratio is 19.2%, CO, CO2Conversion ratio is all close to the equilibrium conversion of reaction system, CH4Selectivity 99.5%.
Embodiment 2:
(2-1) NaOH taking 8.0g is dissolved in standby in 200ml deionized water (being labeled as solution I).Take (the NH of 24g4)2Ce(NO3)6It is dissolved in 300ml deionized water and (is labeled as solution II), when stirring by the γ-Al of 80g2O3Powder body is slowly added in above-mentioned solution II, 10min is so as to dispersed in stirring, then it is slow added into alkaline solution I and is neutralized precipitation, precipitation is further continued for stirring ageing 60min after completing, then filtration, washing leaching cake, dry 14 hours at 120 DEG C, and at 500 DEG C, roasting obtains catalyst intermediate powder body in 3 hours, obtaining catalyst intermediate A after broken, pelletize, molding procedure, overall dimensions is
(2-2) Mg (NO of 50g is taken3)2·6H2O is dissolved in 50ml deionized water, adopts the mode of dipping by above-mentioned Mg (NO3)2Solution impregnation, to catalyst intermediate A, dries 8 hours at 120 DEG C, and at 500 DEG C, roasting obtains catalyst intermediate B in 3 hours.
(2-3) Ni (NO of 380g is taken3)2·6H2Zn (the NO of O and 150g3)2·6H2O, 50 DEG C, be dissolved in 120ml deionized water under stirring condition, above-mentioned mixed solution is impregnated on catalyst intermediate B at twice, dry 8 hours at 120 DEG C, at 600 DEG C, namely roasting obtains catalyst of the present invention in 3 hours, this catalyst finally consist of 41.6%NiO-17.5%ZnO/3.3%MgO/3.2%CeO2/ 34.2% γ-Al2O3, it is labeled as embodiment 2.
Above-mentioned CATALYST EXAMPLE 2 is filled in the middle of methanator, uses pure H2Reductase 12 hour under 500 DEG C of conditions, then pressure to be 3.0MPa, temperature be 600 DEG C, air speed be 20000h-1、H2/(3CO+4CO2) mol ratio be evaluated when being 0.9.Under the reaction conditions, CO conversion ratio is 82.8%, CO2Conversion ratio is 20.5%, CO, CO2Conversion ratio is all close to the equilibrium conversion of reaction system, CH4Selectivity 99.5%.
Embodiment 3:
(3-1) Yb (NO of 50g is taken3)3·5H2O is dissolved in 150ml deionized water, when stirring by the γ-Al of 67g2O3Powder body is slowly added in above-mentioned solution, 10min is so as to dispersed in stirring, then it is slow added into the ammonia that 55ml concentration is 12.5% and is neutralized precipitation, precipitation is further continued for stirring ageing 60min after completing, then filtration, washing leaching cake, dry 14 hours at 120 DEG C, and at 500 DEG C, roasting obtains catalyst intermediate powder body in 3 hours, obtaining catalyst intermediate A after broken, pelletize, molding procedure, overall dimensions is
(3-2) Mg (NO of 70g is taken3)2·6H2O is dissolved in 50ml deionized water, adopts the mode of dipping by above-mentioned Mg (NO3)2Solution impregnation, to catalyst intermediate A, dries 8 hours at 120 DEG C, and at 500 DEG C, roasting obtains catalyst intermediate B in 3 hours.
(3-3) Ni (NO of 300g is taken3)2·6H2Zn (the NO of O and 85g3)2·6H2O, 50 DEG C, be dissolved in 150ml deionized water under stirring condition, above-mentioned mixed solution is impregnated on catalyst intermediate B at twice, dry 8 hours at 120 DEG C, at 500 DEG C, namely roasting obtains catalyst of the present invention in 3 hours, this catalyst finally consist of 38.6%NiO-11.6%ZnO/5.5%MgO/10.9%Y2O3/ 33.4% γ-Al2O3, it is labeled as embodiment 3.
Above-mentioned CATALYST EXAMPLE 3 is filled in the middle of methanator, uses pure H2Reductase 12 hour under 500 DEG C of conditions, then pressure to be 2.0MPa, temperature be 450 DEG C, air speed be 20000h-1、H2/(3CO+4CO2) mol ratio be evaluated when being 0.9.Under the reaction conditions, CO conversion ratio is 99.9%, CO2Conversion ratio is 83.5%, CO, CO2Conversion ratio is all close to the equilibrium conversion of reaction system, CH4Selectivity 99.5%.
Embodiment 4:
(4-1) (the NH of the carbamide of 20g, 24g is taken4)2Ce(NO3)6It is dissolved in 500ml deionized water, when stirring by the γ-Al of 80g2O3Powder body is slowly added in above-mentioned solution, 10min is so as to dispersed in stirring, then heated solution, making solution be to slowly warm up to 90 DEG C and maintain 2 hours and be neutralized precipitation, precipitation is further continued for stirring ageing 60min after completing, and then filters, washing leaching cake, dry 14 hours at 120 DEG C, at 500 DEG C, roasting obtains catalyst intermediate powder body in 3 hours, obtains catalyst intermediate A after broken, pelletize, molding procedure, and overall dimensions is
Remaining steps (4-2), (4-3), with the step (2-2) of embodiment 2, (2-3), obtain catalyst of the present invention, this catalyst finally consist of 41.6%NiO-17.5%ZnO/3.3%MgO/3.2%CeO2/ 34.2% γ-Al2O3(carbamide), is labeled as embodiment 4.
Above-mentioned CATALYST EXAMPLE 4 is filled in the middle of methanator, uses pure H2Reductase 12 hour under 500 DEG C of conditions, then pressure to be 3.0MPa, temperature be 450 DEG C, air speed be 40000h-1、H2/(3CO+4CO2) mol ratio be evaluated when being 0.8.Under the reaction conditions, CO conversion ratio is 98.5%, CO2Conversion ratio is 81.2%, CO, CO2Conversion ratio is all close to the equilibrium conversion of reaction system, CH4Selectivity 99.1%.
Embodiment 5:
Step (5-1), (5-2) are with the step (1-1) of embodiment 1, (1-2).
(5-3) Ni (NO of 180g is taken3)2·6H2O, 50 DEG C, be dissolved in 80ml deionized water under stirring condition；In above-mentioned solution impregnation to catalyst intermediate B, drying 8 hours at 120 DEG C, at 500 DEG C, roasting obtains catalyst intermediate C in 3 hours.
(5-4) Zn (NO of 120g is taken3)2·6H2O, 50 DEG C, be dissolved in 50ml deionized water under stirring condition；Will in above-mentioned solution impregnation to catalyst intermediate C, at 120 DEG C dry 8 hours, at 500 DEG C, namely roasting obtained catalyst of the present invention in 3 hours, this catalyst finally consist of 20.9%NiO-14.8%ZnO/4.2%K2O/15.0%La2O3/ 45.1% γ-Al2O3(Zn/Ni) embodiment 5, it is labeled as.
Above-mentioned CATALYST EXAMPLE 5 is filled in the middle of methanator, uses pure H2Reductase 12 hour under 500 DEG C of conditions, then pressure to be 3.0MPa, temperature be 620 DEG C, air speed be 15000h-1、H2/(3CO+4CO2) mol ratio be evaluated when being 0.9.Under the reaction conditions, CO conversion ratio is 80.2%, CO2Conversion ratio is 19.7%, CO, CO2Conversion ratio is all close to the equilibrium conversion of reaction system, CH4Selectivity 99.3%.
Embodiment 6:
Step (6-1), (6-2) are with the step (1-1) of embodiment 1, (1-2).
(6-3) Zn (NO of 120g is taken3)2·6H2O, 50 DEG C, be dissolved in 50ml deionized water under stirring condition；In above-mentioned solution impregnation to catalyst intermediate B, drying 8 hours at 120 DEG C, at 500 DEG C, roasting obtains catalyst intermediate C in 3 hours.
(6-4) Ni (NO of 180g is taken3)2·6H2O, 50 DEG C, be dissolved in 80ml deionized water under stirring condition；Will in above-mentioned solution impregnation to catalyst intermediate C, at 120 DEG C dry 8 hours, at 500 DEG C, namely roasting obtained catalyst of the present invention in 3 hours, this catalyst finally consist of 20.9%NiO-14.8%ZnO/4.2%K2O/15.0%La2O3/ 45.1% γ-Al2O3(Ni/Zn) embodiment 6, it is labeled as.
Above-mentioned CATALYST EXAMPLE 6 is filled in the middle of methanator, uses pure H2Reductase 12 hour under 500 DEG C of conditions, then pressure to be 3.0MPa, temperature be 400 DEG C, air speed be 20000h-1、H2/(3CO+4CO2) mol ratio be evaluated when being 0.85.Under the reaction conditions, CO conversion ratio is 99.0%, CO2Conversion ratio is 83.4%, CO, CO2Conversion ratio is all close to the equilibrium conversion of reaction system, CH4Selectivity 99.4%.
Comparative example 1:
(1) NaOH taking 30g is dissolved in standby in 200ml deionized water (being labeled as solution I).Take (the NH of 74g4)2Ce(NO3)6It is dissolved in 300ml deionized water and (is labeled as solution II), when stirring by the γ-Al of 80g2O3Powder body is slowly added in above-mentioned solution II, 10min is so as to dispersed in stirring, then it is slow added into alkaline solution I and is neutralized precipitation, precipitation is further continued for stirring ageing 60min after completing, then filtration, washing leaching cake, dry 14 hours at 120 DEG C, and at 500 DEG C, roasting obtains catalyst intermediate powder body in 3 hours, obtaining catalyst intermediate A after broken, pelletize, molding procedure, overall dimensions is
(2) Mg (NO of 40g is taken3)2·6H2O is dissolved in 50ml deionized water, adopts the mode of dipping by above-mentioned Mg (NO3)2Solution impregnation, to catalyst intermediate A, dries 8 hours at 120 DEG C, and at 500 DEG C, roasting obtains catalyst intermediate B in 3 hours.
(3) Ni (NO of 350g is taken3)2·6H2O, 50 DEG C, be dissolved in 150ml deionized water under stirring condition, above-mentioned mixed solution is impregnated on catalyst intermediate B at twice, at 120 DEG C dry 8 hours, at 600 DEG C, namely roasting obtains comparative example catalyst of the present invention for 3 hours, is labeled as comparative example 1.This catalyst finally consist of 45.2%NiO/3.1%MgO/11.6%CeO2/ 40.0% γ-Al2O3。
Above-mentioned COMPARATIVE CATALYST EXAMPLE 1 is filled in the middle of methanator, uses pure H2Reductase 12 hour under 500 DEG C of conditions, then pressure to be 3.0MPa, temperature be 620 DEG C, air speed be 20000h-1、H2/(3CO+4CO2) mol ratio be evaluated when being 0.8.Under the reaction conditions, initial CO conversion rate is 83.8%, CO2Conversion ratio is 20.7%, CO, CO2Conversion ratio is all close to the equilibrium conversion of reaction system, CH4Selectivity 99.5%.
Embodiment 7:
The present embodiment is that DTG burns carbon test, it is therefore an objective to the carbon distribution situation of each embodiment and comparative example catalyst after comparing methanation reaction.
By each embodiment after methanation reaction 200hrs and comparative example catalyst at N2Protection drops to room temperature, and sampling carries out thermogravimetric analysis (TGA), temperature elevating range be room temperature to 750 DEG C, heating rate is 5 DEG C/min.Sample occurs that between 400-700 DEG C weightless peak, each CATALYST EXAMPLE of calculating and the carbon distribution situation of comparative example are shown in table 1 below:
As shown in Table 1, catalyst of the present invention is at low H2Carbon accumulation resisting ability when/C ratio is significantly larger than comparative example catalyst.
Claims (11)
1. a CO methanation catalyst with water-gas shift function, it is characterised in that this catalyst is made up of active component, auxiliary agent and carrier, wherein:
Active component is nickel-zinc alloy, and its content is in metal-oxide, for the 35-60% of total catalyst weight；Nickel in nickel-zinc alloy, zinc atomic ratio be 1～8:1；
Auxiliary agent one is rare earth metal Ce, La or Yb；Its content is in metal-oxide, for the 3～15% of total catalyst weight；
Auxiliary agent two is alkali metal K, alkaline-earth metal Ca or Mg, and its Content is in metal-oxide, for the 3～15% of total catalyst weight；
Catalyst surplus is carrier γ-Al2O3。
2. there is the CO methanation catalyst of water-gas shift function according to claim 1, it is characterised in that in metal-oxide, active nickel-kirsite content is preferably the 45～55% of total catalyst weight；Nickel in nickel-zinc alloy, zinc atomic ratio be preferably 3～5:1.
3. there is the CO methanation catalyst of water-gas shift function according to claim 1, it is characterised in that active component nickel partly can form solid solution, alloy or eutectic mixture with active component zinc.
4. the CO methanation catalyst with water-gas shift function according to claim 1, it is characterised in that active component nickel, zinc partly can form spinelle type composite oxides with carrier.
5. the preparation method of a CO methanation catalyst as claimed in claim 1 with water-gas shift function, it is characterised in that carry out according to following steps:
(1) stoichiometric proportion according to catalyst component, the preparation solubility predecessor aqueous solution containing auxiliary agent one, it is placed in stirred tank and adds carrier γ-Al2O3, it is neutralized precipitation when stirring with alkaline precipitating agent, by precipitation filtration, washing, dries 16 hours at 100～150 DEG C, at 500～700 DEG C, roasting obtains catalyst intermediate powder body in 3 hours, obtains catalyst intermediate A after broken, pelletize, molding procedure；
(2) stoichiometric proportion according to catalyst component, the preparation solubility predecessor aqueous solution containing auxiliary agent two, auxiliary agent two is supported on above-mentioned catalyst intermediate A by the mode adopting dipping, dries 8 hours at 100～150 DEG C, and at 500～700 DEG C, roasting obtains catalyst intermediate B in 3 hours；
(3) stoichiometric proportion according to catalyst component, preparation contains solubility predecessor aqueous solution or the mixed water solution of catalyst activity component, catalyst activity component is supported on above-mentioned catalyst intermediate B by the mode adopting dipping, drying 8 hours at 100～150 DEG C, at 500～700 DEG C, namely roasting obtains catalyst of the present invention in 3 hours.
6. the preparation method of the CO methanation catalyst with water-gas shift function according to claim 5, it is characterised in that described active component nickel, zinc predecessor be preferably the nitrate of solubility；
The predecessor of described auxiliary agent is preferably the nitrate of solubility.
7. the preparation method of the CO methanation catalyst with water-gas shift function described according to claim 5, it is characterised in that the alkaline precipitating agent described in step (1) is Na2CO3、NH4HCO3, NaOH, ammonia or carbamide.
8. the preparation method of the CO methanation catalyst with water-gas shift function according to claim 7, it is characterised in that the alkaline precipitating agent more preferably ammonia described in step (1) or carbamide；Further it is preferably carbamide.
9. the preparation method of the CO methanation catalyst with water-gas shift function according to claim 5, it is characterised in that the neutralization-precipitation reaction described in step (1) can carry out at 40～90 DEG C；In some highly preferred embodiment, neutralization-precipitation reaction temperature is 80～90 DEG C.
10. the preparation method of the CO methanation catalyst with water-gas shift function according to claim 5, it is characterised in that the impregnated activated component order described in step (3) is nickel after first zinc；It is zinc after first nickel in other embodiments；In other highly preferred embodiments, for nickel, the mixed co-impregnation of zinc.
11. the application of a CO methanation catalyst as described in the appended claim 1 with water-gas shift function, in it is characterized in that described catalyst reacts for synthesis gas high-temperature methanation, full methanation reaction condition is as follows: pressure is 1.0～5.0MPa, temperature is 260～700 DEG C, air speed is 10000～40000h-1、H2/(3CO+4CO2) mol ratio be more than 0.8；Under the reaction conditions, CO, CO2Conversion ratio is all close to the equilibrium conversion of reaction system, CH4Selectivity is close to 100%.
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| JP2001062297A (en) * | 1999-08-27 | 2001-03-13 | Cosmo Research Inst | Deep desulfurization catalyst, its production and desulfurization method using same |
| CN101716513A (en) * | 2009-09-28 | 2010-06-02 | 中国科学院大连化学物理研究所 | Coal gasification catalyst completely methanated by synthesis gas and preparation and application thereof |
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| CN103551153A (en) * | 2013-10-29 | 2014-02-05 | 西南化工研究设计院有限公司 | Copper-based catalyst for methanation of carbon dioxide and preparation method of copper-based catalyst |
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| JP2001062297A (en) * | 1999-08-27 | 2001-03-13 | Cosmo Research Inst | Deep desulfurization catalyst, its production and desulfurization method using same |
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| CN102029162A (en) * | 2009-09-28 | 2011-04-27 | 中国科学院大连化学物理研究所 | Wide-temperature full methanation catalyst and preparation method thereof |
| CN102247850A (en) * | 2011-05-26 | 2011-11-23 | 肖天存 | Methanation catalyst, preparation process thereof and methanation reaction device |
| CN102259003A (en) * | 2011-05-31 | 2011-11-30 | 武汉科林精细化工有限公司 | Coke-oven gas methanation catalyst and preparation method thereof |
| CN103551153A (en) * | 2013-10-29 | 2014-02-05 | 西南化工研究设计院有限公司 | Copper-based catalyst for methanation of carbon dioxide and preparation method of copper-based catalyst |
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