CN105709748B - CO methanation catalysts and its preparation method and application with water-gas shift function - Google Patents
CO methanation catalysts and its preparation method and application with water-gas shift function Download PDFInfo
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Abstract
The invention discloses a kind of CO methanation catalysts and its preparation method and application with water-gas shift function.The catalyst is the first auxiliary agent using nickel zinc alloy as active component, with rare earth metal Ce, La, Yb etc., with alkali metal K, alkaline-earth metal Ca, Mg etc. for the second auxiliary agent, with γ Al2O3For carrier.Catalyst provided by the invention has methanation reaction and CO water gas shift reations difunctional simultaneously, can be in low H2Enter full methanation reactor, reaction process not carbon distribution, to widen the H of methanation reaction under the conditions of/C ratios2/ C is than action pane and operating flexibility.
Description
Technical field
The invention belongs to catalytic synthetic techniques fields, more particularly to a kind of CO methanation catalysts with water-gas shift function
Agent and its preparation method and application.
Background technology
Methanation reaction is a kind of important hydrogenation reaction, is the core using synthesis gas manufacture substitute natural gas (SNG)
Process.The key reaction 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) is key reaction in methanation system, wherein reaction (2) can be decomposed into reaction (1) and
(4).Due in reaction system with the presence of water, so transformationreation (4) will necessarily occur.It is methanation system to react (5) and (6)
In analysis carbon reaction.When reaction temperature is relatively low, analysis carbon mainly occurs with reaction (5)；When reaction temperature is relatively high, with anti-
(6) are answered to occur.It is totally unfavorable to catalyst to analyse carbon reaction：Carbon blocking catalyst duct, leads to catalyst inactivation.Gas methanation
Thermodynamic analysis of process shows that CO (Boudouard Reaction) disproportionated reactions (5) are to cause to accumulate in methanation reaction system
The main reason for carbon, and the reaction is H2/ C is than, the function of temperature and pressure.It is by calculation of thermodynamics it is found that complete in synthesis gas
Under full methanation reaction temperature (260-700 DEG C) and reaction pressure (1-3MPa), the H in reaction system2The molar ratio of/C needs
More than 3, just can guarantee will not occur to analyse carbon reaction (5) in methanation reaction.Therefore synthesis gas for the purpose of to produce SNG is complete
In methanation process, need to carry out synthesis controlled atmosphere ratio in advance, i.e., by CO water gas shift reations, by H in synthesis gas2Mole of/C
Than being adjusted to be more than 3, reactor feed gas could enter the methanation workshop section of next step.Even so, under the conditions of long period of operation,
Carbon distribution still inevitably occurs for methanation catalyst, to cause catalyst inactivation.Therefore, development one kind can be in low H2/ C ratios
It is lower operation, anti-carbon synthesis gas methanation catalyst be of great significance.
CO water gas shift reations (4) are that CO and steam reaction generate H2And CO2Isometric reaction, due in synthesis gas
Conversion gas washes workshop section by low-temp methanol in production SNG techniques can remove CO2Equal sour gas, therefore objectively play increase
H2Effect and be used for synthesize controlled atmosphere ratio.In synthesis gas methanation workshop section, due to vapour gas molar ratio (steam/ in reaction system
Gas) usually 0.2 or so, therefore the CO water gas shift reations (4) of part can still occur.Although the reaction does not generate CH4, but should
Reaction is conducive to increase the H in reaction system2Content inhibits the generation of analysis carbon reaction.There are CO water in methanation reaction system
Vapour transformationreation, can be in low H to develop one kind2/ C is than lower operation, anti-carbon, multi-functional coupling with water-gas shift effect
Synthesis gas methanation catalyst provides possibility.In fact, foreign study person is when studying CO water gas shift reation processes,
It was found that on certain catalyst, there are the response competitions of CO water-gas shifts and CO methanations, such as Ru/ZrO2Catalyst (US
20020114762)、Pt/CeO2Catalyst (WO 0226618,2002-04-04) etc..
Invention content
The object of the present invention is to provide one kind can be in low H2/ C than lower operation, anti-carbon, with the more of water-gas shift effect
Synthesis gas methanation catalyst of Function Coupling and its preparation method and application.
The present invention concrete scheme be：
A kind of CO methanation catalysts with water-gas shift function, the catalyst is by active component, auxiliary agent and vehicle group
At, wherein：
Active component is nickel-zinc alloy, and content is the 35-60% of total catalyst weight in terms of metal oxide；
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 in terms of metal oxide, be total catalyst weight 3~
15%；
Auxiliary agent two is alkali metal K, alkaline-earth metal Ca or Mg, and Content is overall catalyst weight in terms of metal oxide
The 3~15% of amount；
Catalyst surplus is carrier γ-Al2O3。
In terms of metal oxide, active nickel-kirsite content is preferably the 45~55% of total catalyst weight；Nickel-zinc
Nickel in 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.
A kind of preparation method of the CO methanation catalysts with water-gas shift function, follows the steps below：
(1) according to the stoichiometric ratio of catalyst component, the soluble predecessor aqueous solution containing auxiliary agent one is prepared, is placed in
In stirred tank and carrier γ-Al are added2O3, neutralization precipitation is carried out with alkaline precipitating agent under stirring conditions, precipitation is filtered,
It washs, catalyst intermediate powder is roasted 3 hours to obtain at 16 hours, 500~700 DEG C dry at 100~150 DEG C, through being crushed, making
Catalyst intermediate A is obtained after grain, molding procedure；
(2) according to the stoichiometric ratio of catalyst component, the soluble predecessor aqueous solution containing auxiliary agent two is prepared, is used
The mode of dipping supports auxiliary agent two on above-mentioned catalyst intermediate A, 8 hours, 500~700 DEG C dry at 100~150 DEG C
Lower roasting obtains catalyst intermediate B in 3 hours；
(3) according to the stoichiometric ratio of catalyst component, the soluble predecessor water containing catalyst activity component is prepared
Solution or mixed water solution are supported catalyst activity component on above-mentioned catalyst intermediate B by the way of dipping, 100
3 hours are roasted at~150 DEG C at drying 8 hours, 500~700 DEG C up to catalyst of the present invention.
The nitrate of the active component nickel, the predecessor preferably solubility of zinc；
The predecessor of the auxiliary agent is preferably the nitrate of solubility.
Alkaline precipitating agent described in step (1) is Na2CO3、NH4HCO3, NaOH, ammonium hydroxide or urea；
The alkaline precipitating agent is more preferably ammonium hydroxide or urea；Still more preferably it is urea.
Neutralization-precipitation reaction described in step (1) can carry out at 40~90 DEG C；More preferably implement certain
In scheme, neutralization-precipitation reaction temperature is 80~90 DEG C.
Dipping active component sequence described in step (3) is nickel after first zinc；After being in other embodiments first nickel
Zinc；It is nickel, zinc mixing co-impregnation in other highly preferred embodiments.
A kind of application of the CO methanation catalysts with water-gas shift function, the catalyst are used for synthesis gas high temperature first
In alkylation reaction, 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) molar ratio be more than 0.8；Under the reaction conditions, CO, CO2Conversion ratio connects
The equilibrium conversion of proximal response system, CH4Selectively close to 100%.
In the certain preferred embodiments of catalyst of the present invention, active component nickel can partly with active component zinc shape
At solid solution, alloy or eutectic mixture to improve catalyst activity.Zinc oxide (ZnO) belongs to n-type semiconductor oxide,
Under certain condition, the non-stoichiometric ZnOx crystal structures of anoxic are easily formed, H is conducive to2, CO on nickel, zinc eutectoid content and send out
Raw surface reaction, becomes the activity unit for being conducive to CO water gas shift reations and methanation reaction.
In the certain preferred embodiments of catalyst of the present invention, active component nickel, zinc can be formed partly with carrier
Spinelle type composite oxides prevent active component crystal grain from reuniting to improve catalyst activity and stability.
In certain embodiments of catalyst of the present invention, rare-earth additive can be used as Structure promoter partly or entirely
With carrier γ-Al2O3Composite oxides are formed to improve stability of the carrier under high temperature hydrothermal condition.It is more excellent at other
In the embodiment of choosing, rare-earth additive can receive the electronics of oxygen atom in reactant CO as electron type auxiliary agent, be conducive to CO and exist
Nickel, zinc surface dissociate to form active surface carbon species, are conducive to CO water gas shift reations and the work of methanation reaction to become
Property unit.
In certain embodiments of catalyst of the present invention, alkali metal or/and base earth metal promoter can also be used as structure
Type Aid Portions or fully with carrier γ-Al2O3Composite oxides are formed to improve stabilization of the carrier under high temperature hydrothermal condition
Property；In some preferred embodiments, alkali metal or/and base earth metal promoter can neutralize carrier γ-Al2O3Surface acid
Property, start the effect for inhibiting catalyst surface carbon distribution；In other highly preferred embodiments, alkali metal or/and alkaline earth
Metal promoter can partly inhibit the methanation reaction of CO in reaction process, to play in regulation system CO methanation reactions and
The effect of CO water gas shift reation speed.
Catalyst of the present invention has the following advantages：Bimetallic nickel-kirsite catalyst has methanation reaction and CO simultaneously
Water gas shift reation is difunctional, can be in low H2Enter full methanation reactor under the conditions of/C ratios, reaction process not carbon distribution, from
And the H of methanation reaction is widened2/ C is than action pane and operating flexibility.
Specific implementation mode
The present invention is described in further details with embodiment below, but this should not be interpreted as to aforesaid right of the present invention and wanted
The range asked is only limitted to following embodiments.Meanwhile embodiment has been merely given as realizing the part Experiment condition of the invention, but not
Mean that must satisfy these conditions can be only achieved the purpose of the present invention.The catalyst provided in specific embodiment is formed, is prepared
Method, reaction condition are the illustration to representing many possible specific implementations that the present invention applies.
Unless otherwise noted, all numbers occurred in description of the invention and claims, such as dry, roasting
It is absolutely accurate to indicate that the numerical value such as the mass percent of catalyst composition are not construed as temperature, operation temperature and pressure
Value, the numerical value are in that those of ordinary skill in the art is understood, the permitted error range of known technology.
Embodiment 1：
(1-1) takes the NaOH of 30g to be dissolved in (being labeled as solution I) spare in 150ml deionized waters.Take the La (NO of 88g3)3·
6H2O is dissolved in 300ml deionized waters and (is labeled as solution II), under stirring conditions by the γ-Al of 100g2O3Powder slowly adds
Enter into above-mentioned solution II, stirring 10min is allowed to evenly dispersed, and it is anti-to be then slow added into alkaline solution I progress neutralization precipitations
It answers, stirring ageing 60min is further continued for after the completion of precipitation reaction, be then filtered, washed filter cake, it is 14 hours dry at 120 DEG C, 500
Catalyst intermediate powder is roasted 3 hours to obtain at DEG C, and catalyst intermediate A, shape ruler are obtained after broken, granulation, molding procedure
It is very little to be
(1-2) takes the KNO of 20g3It is dissolved in 50ml deionized waters, by above-mentioned KNO by the way of dipping3Solution is impregnated into
On catalyst intermediate A, catalyst intermediate B is roasted 3 hours to obtain at 8 hours, 500 DEG C dry at 120 DEG C.
(1-3) takes the Ni (NO of 180g3)2·6H2Zn (the NO of O and 120g3)2·6H2O is dissolved under 50 DEG C, stirring condition
In 120ml deionized waters, above-mentioned mixed solution is impregnated at twice on catalyst intermediate B, it is 8 hours dry at 120 DEG C,
3 hours are roasted at 600 DEG C up to catalyst of the present invention, the final group of the catalyst becomes 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 methanator, with pure H2Reductase 12 is small under the conditions of 500 DEG C
When, then pressure is 3.0MPa, temperature is 620 DEG C, air speed 15000h-1、H2/(3CO+4CO2) molar ratio be 0.8
Under the conditions of evaluated.Under the reaction conditions, CO conversion ratios are 79.4%, CO2Conversion ratio is 19.2%, CO, CO2Conversion ratio
Close to the equilibrium conversion of reaction system, CH4Selectivity 99.5%.
Embodiment 2：
(2-1) takes the NaOH of 8.0g to be dissolved in (being labeled as solution I) spare in 200ml deionized waters.Take (the NH of 24g4)2Ce
(NO3)6It is dissolved in 300ml deionized waters and (is labeled as solution II), under stirring conditions by the γ-Al of 80g2O3Powder is slow
It is added in above-mentioned solution II, stirring 10min is allowed to evenly dispersed, is then slow added into alkaline solution I and carries out neutralization precipitation
Reaction is further continued for stirring ageing 60min after the completion of precipitation reaction, is then filtered, washed filter cake, 14 hours dry at 120 DEG C,
Catalyst intermediate powder is roasted 3 hours to obtain at 500 DEG C, and catalyst intermediate A, shape are obtained after broken, granulation, molding procedure
Size is
(2-2) takes the Mg (NO of 50g3)2·6H2O is dissolved in 50ml deionized waters, by above-mentioned Mg by the way of dipping
(NO3)2Solution is impregnated on catalyst intermediate A, is roasted 3 hours and is obtained among catalyst at 8 hours, 500 DEG C dry at 120 DEG C
Body B.
(2-3) takes the Ni (NO of 380g3)2·6H2Zn (the NO of O and 150g3)2·6H2O is dissolved under 50 DEG C, stirring condition
In 120ml deionized waters, above-mentioned mixed solution is impregnated at twice on catalyst intermediate B, it is 8 hours dry at 120 DEG C,
3 hours are roasted at 600 DEG C up to catalyst of the present invention, the final group of the catalyst becomes 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 methanator, with pure H2Reductase 12 is small under the conditions of 500 DEG C
When, then pressure is 3.0MPa, temperature is 600 DEG C, air speed 20000h-1、H2/(3CO+4CO2) molar ratio be 0.9
Under the conditions of evaluated.Under the reaction conditions, CO conversion ratios are 82.8%, CO2Conversion ratio is 20.5%, CO, CO2Conversion ratio
Close to the equilibrium conversion of reaction system, CH4Selectivity 99.5%.
Embodiment 3：
(3-1) takes the Yb (NO of 50g3)3·5H2O is dissolved in 150ml deionized waters, under stirring conditions by the γ-of 67g
Al2O3Powder is slowly added into above-mentioned solution, and stirring 10min is allowed to evenly dispersed, and it is a concentration of to be then slow added into 55ml
12.5% ammonium hydroxide carries out neutralization-precipitation reaction, and stirring ageing 60min is further continued for after the completion of precipitation reaction, is then filtered, washed
Filter cake roast 3 hours to obtain catalyst intermediate powder at 14 hours, 500 DEG C dry at 120 DEG C, through it is broken, be granulated, be molded work
Catalyst intermediate A is obtained after sequence, appearance and size is
(3-2) takes the Mg (NO of 70g3)2·6H2O is dissolved in 50ml deionized waters, by above-mentioned Mg by the way of dipping
(NO3)2Solution is impregnated on catalyst intermediate A, is roasted 3 hours and is obtained among catalyst at 8 hours, 500 DEG C dry at 120 DEG C
Body B.
(3-3) takes the Ni (NO of 300g3)2·6H2Zn (the NO of O and 85g3)2·6H2O is dissolved under 50 DEG C, stirring condition
In 150ml deionized waters, above-mentioned mixed solution is impregnated at twice on catalyst intermediate B, it is 8 hours dry at 120 DEG C,
3 hours are roasted at 500 DEG C up to catalyst of the present invention, the final group of the catalyst becomes 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 methanator, with pure H2Reductase 12 is small under the conditions of 500 DEG C
When, then pressure is 2.0MPa, temperature is 450 DEG C, air speed 20000h-1、H2/(3CO+4CO2) molar ratio be 0.9
Under the conditions of evaluated.Under the reaction conditions, CO conversion ratios are 99.9%, CO2Conversion ratio is 83.5%, CO, CO2Conversion ratio
Close to the equilibrium conversion of reaction system, CH4Selectivity 99.5%.
Embodiment 4：
(4-1) takes (NH of the urea of 20g, 24g4)2Ce(NO3)6It is dissolved in 500ml deionized waters, under stirring conditions
By the γ-Al of 80g2O3Powder is slowly added into above-mentioned solution, and stirring 10min is allowed to evenly dispersed, and then heated solution, makes
Solution is to slowly warm up to 90 DEG C and maintains to carry out within 2 hours neutralization-precipitation reaction, and stirring ageing is further continued for after the completion of precipitation reaction
Then 60min is filtered, washed filter cake, catalyst intermediate powder is roasted 3 hours to obtain at being dried 14 hours, 500 DEG C at 120 DEG C,
Catalyst intermediate A is obtained after broken, granulation, molding procedure, appearance and size is
Remaining steps (4-2), (4-3) are with (2-2), (2-3) the step of embodiment 2 to get catalyst of the present invention, the catalysis
The final group of agent becomes 41.6%NiO-17.5%ZnO/3.3%MgO/3.2%CeO2/ 34.2% γ-Al2O3(urea), label
For embodiment 4.
Above-mentioned CATALYST EXAMPLE 4 is filled in methanator, with pure H2Reductase 12 is small under the conditions of 500 DEG C
When, then pressure is 3.0MPa, temperature is 450 DEG C, air speed 40000h-1、H2/(3CO+4CO2) molar ratio be 0.8
Under the conditions of evaluated.Under the reaction conditions, CO conversion ratios are 98.5%, CO2Conversion ratio is 81.2%, CO, CO2Conversion ratio
Close to the equilibrium conversion of reaction system, CH4Selectivity 99.1%.
Embodiment 5：
Step (5-1), (5-2) are the same as (1-1), (1-2) the step of embodiment 1.
(5-3) takes the Ni (NO of 180g3)2·6H2O is dissolved under 50 DEG C, stirring condition in 80ml deionized waters；It will be above-mentioned
Solution is impregnated on catalyst intermediate B, and catalyst intermediate C is roasted 3 hours to obtain at 8 hours, 500 DEG C dry at 120 DEG C.
(5-4) takes the Zn (NO of 120g3)2·6H2O is dissolved under 50 DEG C, stirring condition in 50ml deionized waters；It will be above-mentioned
Solution is impregnated on catalyst intermediate C, and 3 hours catalyst of the present invention to obtain the final product are roasted at 8 hours, 500 DEG C dry at 120 DEG C,
The final group of the catalyst becomes 20.9%NiO-14.8%ZnO/4.2%K2O/15.0%La2O3/ 45.1% γ-Al2O3(Zn/
Ni), it is labeled as embodiment 5.
Above-mentioned CATALYST EXAMPLE 5 is filled in methanator, with pure H2Reductase 12 is small under the conditions of 500 DEG C
When, then pressure is 3.0MPa, temperature is 620 DEG C, air speed 15000h-1、H2/(3CO+4CO2) molar ratio be 0.9
Under the conditions of evaluated.Under the reaction conditions, CO conversion ratios are 80.2%, CO2Conversion ratio is 19.7%, CO, CO2Conversion ratio
Close to the equilibrium conversion of reaction system, CH4Selectivity 99.3%.
Embodiment 6：
Step (6-1), (6-2) are the same as (1-1), (1-2) the step of embodiment 1.
(6-3) takes the Zn (NO of 120g3)2·6H2O is dissolved under 50 DEG C, stirring condition in 50ml deionized waters；It will be above-mentioned
Solution is impregnated on catalyst intermediate B, and catalyst intermediate C is roasted 3 hours to obtain at 8 hours, 500 DEG C dry at 120 DEG C.
(6-4) takes the Ni (NO of 180g3)2·6H2O is dissolved under 50 DEG C, stirring condition in 80ml deionized waters；It will be above-mentioned
Solution is impregnated on catalyst intermediate C, and 3 hours catalyst of the present invention to obtain the final product are roasted at 8 hours, 500 DEG C dry at 120 DEG C,
The final group of the catalyst becomes 20.9%NiO-14.8%ZnO/4.2%K2O/15.0%La2O3/ 45.1% γ-Al2O3(Ni/
Zn), it is labeled as embodiment 6.
Above-mentioned CATALYST EXAMPLE 6 is filled in methanator, with pure H2Reductase 12 is small under the conditions of 500 DEG C
When, then pressure is 3.0MPa, temperature is 400 DEG C, air speed 20000h-1、H2/(3CO+4CO2) molar ratio be 0.85
Under the conditions of evaluated.Under the reaction conditions, CO conversion ratios are 99.0%, CO2Conversion ratio is 83.4%, CO, CO2Conversion ratio
Close to the equilibrium conversion of reaction system, CH4Selectivity 99.4%.
Comparative example 1：
(1) NaOH of 30g is taken to be dissolved in (being labeled as solution I) spare in 200ml deionized waters.Take (the NH of 74g4)2Ce
(NO3)6It is dissolved in 300ml deionized waters and (is labeled as solution II), under stirring conditions by the γ-Al of 80g2O3Powder is slow
It is added in above-mentioned solution II, stirring 10min is allowed to evenly dispersed, is then slow added into alkaline solution I and carries out neutralization precipitation
Reaction is further continued for stirring ageing 60min after the completion of precipitation reaction, is then filtered, washed filter cake, 14 hours dry at 120 DEG C,
Catalyst intermediate powder is roasted 3 hours to obtain at 500 DEG C, and catalyst intermediate A, shape are obtained after broken, granulation, molding procedure
Size is
(2) Mg (NO of 40g are taken3)2·6H2O is dissolved in 50ml deionized waters, by above-mentioned Mg (NO by the way of dipping3)2
Solution is impregnated on catalyst intermediate A, and catalyst intermediate B is roasted 3 hours to obtain at 8 hours, 500 DEG C dry at 120 DEG C.
(3) Ni (NO of 350g are taken3)2·6H2O is dissolved under 50 DEG C, stirring condition in 150ml deionized waters, will be above-mentioned
Mixed solution is impregnated at twice on catalyst intermediate B, and 3 hours are roasted at 8 hours, 600 DEG C dry at 120 DEG C up to this hair
Bright comparative example catalyst is labeled as comparative example 1.The final group of the catalyst becomes 45.2%NiO/3.1%MgO/11.6%
CeO2/ 40.0% γ-Al2O3。
Above-mentioned COMPARATIVE CATALYST EXAMPLE 1 is filled in methanator, with pure H2Reductase 12 is small under the conditions of 500 DEG C
When, then pressure is 3.0MPa, temperature is 620 DEG C, air speed 20000h-1、H2/(3CO+4CO2) molar ratio be 0.8
Under the conditions of evaluated.Under the reaction conditions, initial CO conversion rate is 83.8%, CO2Conversion ratio is 20.7%, CO, CO2Turn
Rate is close to the equilibrium conversion of reaction system, CH4Selectivity 99.5%.
Embodiment 7：
The present embodiment is that thermogravimetry burns carbon experiment, it is therefore an objective to compare each embodiment and comparative example catalysis after methanation reaction
The carbon distribution situation of agent.
By after methanation reaction 200hrs each embodiment and comparative example catalyst in N2Protection drop to room temperature, sample into
Row thermogravimetric analysis (TGA), temperature elevating range are room temperature to 750 DEG C, and heating rate is 5 DEG C/min.Sample goes out between 400-700 DEG C
Existing weightless peak, each CATALYST EXAMPLE of calculating and the carbon distribution situation of comparative example see the table below 1：
As shown in Table 1, catalyst of the present invention is in low H2Carbon accumulation resisting ability under conditions of/C ratios is significantly larger than comparative example and urges
Agent.
Claims (11)
1. a kind of CO methanation catalysts with water-gas shift function, it is characterised in that the catalyst is by active component, auxiliary agent
It is formed with carrier, wherein：
Active component is nickel-zinc alloy, and content is the 35-60% of total catalyst weight in terms of metal oxide；Nickel-zinc
Nickel in alloy, zinc atomic ratio be 1~8：1；
Auxiliary agent one is rare earth metal Ce, La or Yb；Its content is the 3~15% of total catalyst weight in terms of metal oxide；
Auxiliary agent two be alkali metal K, alkaline-earth metal Ca or Mg, content in terms of metal oxide, be total catalyst weight 3~
15%；
Catalyst surplus is carrier γ-Al2O3；
In the active component nickel-kirsite, active component nickel partly forms solid solution, alloy or total with active component zinc
Brilliant mixture or active component nickel, zinc partly form spinelle type composite oxides with carrier.
2. the CO methanation catalysts with water-gas shift function according to claim 1, it is characterised in that aoxidized with metal
Object meter, active nickel-kirsite content are the 45~55% of total catalyst weight；Nickel in nickel-zinc alloy, zinc atomic ratio be 3
~5：1.
3. a kind of preparation method of the CO methanation catalysts with water-gas shift function as described in claim 1, feature exist
In following the steps below：
(1) according to the stoichiometric ratio of catalyst component, the soluble predecessor aqueous solution containing auxiliary agent one is prepared, stirring is placed in
In kettle and carrier γ-Al are added2O3, neutralization precipitation is carried out with alkaline precipitating agent under stirring conditions, precipitation is filtered, washed,
Roast 3 hours to obtain catalyst intermediate powder at 100~150 DEG C at dry 16 hours, 500~700 DEG C, through broken, granulation, at
Catalyst intermediate A is obtained after type process；
(2) according to the stoichiometric ratio of catalyst component, the soluble predecessor aqueous solution containing auxiliary agent two is prepared, using dipping
Mode auxiliary agent two is supported on above-mentioned catalyst intermediate A, roasted at dry 8 hours, 500~700 DEG C at 100~150 DEG C
Burn 3 hours to obtain catalyst intermediate B；
(3) according to the stoichiometric ratio of catalyst component, the soluble predecessor aqueous solution containing catalyst activity component is prepared
Or mixed aqueous solution, catalyst activity component is supported on above-mentioned catalyst intermediate B by the way of dipping, 100~
3 hours are roasted at 150 DEG C at drying 8 hours, 500~700 DEG C up to the CO methanation catalysts with water-gas shift function.
4. the preparation method of the CO methanation catalysts according to claim 3 with water-gas shift function, feature exist
In the nitrate that the predecessor of the active component nickel, zinc is solubility；
The predecessor of the auxiliary agent is the nitrate of solubility.
5. the preparation method of the CO methanation catalysts according to claim 3 with water-gas shift function, feature exist
In the alkaline precipitating agent described in step (1) is Na2CO3、NH4HCO3, NaOH, ammonium hydroxide or urea.
6. the preparation method of the CO methanation catalysts according to claim 3 with water-gas shift function, feature exist
Alkaline precipitating agent described in step (1) is ammonium hydroxide or urea.
7. the preparation method of the CO methanation catalysts according to claim 6 with water-gas shift function, feature exist
Alkaline precipitating agent described in step (1) is urea.
8. the preparation method of the CO methanation catalysts according to claim 3 with water-gas shift function, feature exist
Neutralization-precipitation reaction described in step (1) carries out at 40~90 DEG C.
9. the preparation method of the CO methanation catalysts according to claim 3 with water-gas shift function, feature exist
Neutralization-precipitation reaction temperature described in step (1) is 80~90 DEG C.
10. the preparation method of the CO methanation catalysts according to claim 3 with water-gas shift function, feature exist
In the dipping active component sequence described in step (3) is nickel after first zinc；Or it is zinc after first nickel；Or it is mixed altogether for nickel, zinc
Dipping.
11. a kind of application of the CO methanation catalysts with water-gas shift function as described in the appended claim 1, it is characterised in that
The catalyst is in the reaction of synthesis gas high-temperature methanation, full methanation reaction condition to be as follows：Pressure be 1.0~
5.0MPa, temperature are 260~700 DEG C, air speed is 10000~40000h-1、H2/(3CO+4CO2) molar ratio be more than 0.8；
Under the reaction conditions, CO, CO2Conversion ratio is close to the equilibrium conversion of reaction system, CH4Selectively close to 100%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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| JP4197073B2 (en) * | 1999-08-27 | 2008-12-17 | 株式会社コスモ総合研究所 | Deep desulfurization catalyst, method for producing the same, and desulfurization method using the same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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