CN105879854B - A kind of catalyst for methanation in presence of sulfur and its preparation method and application - Google Patents
A kind of catalyst for methanation in presence of sulfur and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of catalyst for methanation in presence of sulfur and its application, the catalyst synthesizes to obtain using hydro-thermal method, wherein on the basis of 100 part by weight of catalyst, the catalyst contains the parts by weight of activated component of 15-50 (M1)AOB, 2-20 parts by weight support modification agent (M2)COD, 40-80 parts by weight carrier, wherein M1 is VI B race metallic element and/or V B race metallic element, and M2 is thulium and/or III B race metallic element.The present invention provides a kind of methods for preparing catalyst for methanation in presence of sulfur of the present invention, this method comprises: in the presence of aqueous solvent, carrier predecessor, active component predecessor, support modification agent predecessor are mixed with precipitating sustained release agent, in confined conditions, gained mixed solution is subjected to hydro-thermal process.Catalyst of the invention, preparation process is simple, reproducible, and has high methanation activity and high methane selectively under low temperature, high water vapor atmosphere.
Description
Technical field
The present invention relates to a kind of catalyst for methanation in presence of sulfur and a kind of preparation method of catalyst for methanation in presence of sulfur, with
And the application of catalyst for methanation in presence of sulfur of the invention in methanation reaction.
Background technique
Methanation reaction is the core of natural gas from coal technology, and the performance of methanation catalyst directly determines entire coal system
The economy and competitiveness of natural gas technology.Ni base catalyst is mostly used in existing methanation technology, it is known that Ni base
Catalyst is very sensitive to carbon distribution and sulfur species, is easy to rapid deactivation due to carbon distribution is with sulfur poisoning in reaction.
To delay catalyst because of inactivation caused by carbon distribution and sulfur poisoning during industrial application, the synthesis that coal gasification obtains
Gas must first pass through Water gas shift/WGS (WGS), sour gas separation, fine de-sulfur (sulphur < 0.1ppm) etc. before entering methanation reaction
H of the process to synthesis gas2When sulfur content carries out modulation to/CO, this causes entire natural gas from coal system process complicated and process
Long, investment cost is huge.
CN102029161A discloses a kind of method that hydro-thermal method prepares support type Ni methylmethane catalyst, party's legal system
Standby obtained support type Ni methylmethane catalyst is demonstrated by preferable hydrothermal stability.
CN102350375A discloses a kind of resistant to sulfur Mo-Ni methylmethane catalyst of magnesium aluminate spinel load, result
Show to be only capable of the Sulfur tolerance that appropriateness improves Ni base catalyst after adding Mo, when the activity of rear catalyst is added in the hydrogen sulfide of 50ppm
It significantly reduces immediately.
Compared to Ni base catalyst, MoS2Base catalyst has superior anti-carbon and resistance to sulphur property, therefore can be by coal
The obtained sulfur-bearing crude synthesis gas that gasifies is converted into methane.But the Mo base catalyst methane activity phase compared with Ni base catalyst
To lower.
US4833112 discloses a kind of cerium oxide carrying molybdenum oxide catalyst for methane production.Experiments have shown that: it is supported on
It is living that the methanation catalyst activity of molybdenum oxide catalyst on cerium oxide carrier is higher than its catalysis of load on the alumina support
Property, but as the trend gradually decreased is presented in the catalyst activity that carries out of reaction.
CN101745401B, which is disclosed, a kind of prepares support type Mo base catalyst for methanation in presence of sulfur using sol-gal process
Method, the catalyst low-temperature activity that this method is prepared is high, and stability is good, however sol-gal process preparation catalyst process is multiple
Miscellaneous, the period is long, and water consume is huge with energy consumption.
CN85109420A discloses one kind with ZrO2For carrier, Co or Ni are the Mo methylmethane catalyst of auxiliary agent.This is urged
Agent has relatively high low temperature methanation activity, but its stability is poor under low temperature.
CN103433026A discloses a kind of ZrO that Y is modified2The Mo methylmethane catalyst of load, active component Mo are logical
It crosses infusion process and is carried on Y-ZrO2On carrier.
It is found that the catalyst activity that the two discloses largely takes after reading CN85109420A and CN103433026A
Certainly in carrier ZrO2Specific surface area, however the ZrO of high-specific surface area2Preparation method is complex, industrially also rarely has height at present
Specific surface area ZrO2Application report.
Although it is living how to improve its methanation as described above, Mo base catalyst has the good characteristic of resistant to sulfur, anti-carbon
Property be still the catalyst in the significant challenge that faces of methanation field application, especially divide atmosphere in low temperature and high water vapor
Under, which is mainly shown as that water-gas shift side reaction activity is high, and methanation activity is greatly inhibited.
Summary of the invention
There can be the resistance to of high methanation activity under the conditions of low temperature, high liquid to steam ratio the purpose of the present invention is to provide a kind of
Sulphur methanation catalyst.
To realize foregoing purpose, in a first aspect, the catalyst is adopted the present invention provides a kind of catalyst for methanation in presence of sulfur
It synthesizes to obtain with hydro-thermal method, wherein on the basis of 100 part by weight of catalyst, the catalyst contains parts by weight of activated group of 15-50
Divide (M1)AOB, 2-20 parts by weight support modification agent (M2)COD, 40-80 parts by weight carrier, wherein M1 is VI B race metallic element
And/or V B race metallic element, M2 are thulium and/or III B race metallic element.
Second aspect, the present invention provides a kind of method for preparing catalyst for methanation in presence of sulfur of the present invention, the party
Method includes: to delay carrier predecessor, active component predecessor, support modification agent predecessor and precipitating in the presence of aqueous solvent
Agent mixing is released, in confined conditions, gained mixed solution is subjected to hydro-thermal process.
The third aspect, the present invention provides application of the catalyst of the present invention in methanation reaction.
Catalyst of the invention, preparation process is simple, reproducible, and has high first under low temperature, high water vapor atmosphere
Alkylating Activity and high methane selectively.
The carrier such as ZrO of method of the invention without using high-specific surface area2Catalyst is prepared, only by using carrier
Then the method according to the invention progress hydro-thermal process can be obtained with high methanation activity and high methane selectively predecessor
Methanation catalyst, this in industrial application have very big prospect.
And method of the invention carries out hydro-thermal process using carrier predecessor the method according to the invention, before carrier
When to drive object be substance containing Zr, ZrO in obtained catalyst2Predominantly monoclinic phase, i.e., method first passage hydro-thermal method of the invention
Synthesize obtained catalyst, carrier ZrO2Predominantly monoclinic phase.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 shows the XRD spectra of the catalyst of embodiment 2, embodiment 3, embodiment 6.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
As previously mentioned, the catalyst is synthesized using hydro-thermal method the present invention provides a kind of catalyst for methanation in presence of sulfur
It arrives, wherein on the basis of 100 part by weight of catalyst, the catalyst contains the parts by weight of activated component of 15-50 (M1)AOB, 2-20
Parts by weight support modification agent (M2)COD, 40-80 parts by weight carrier, wherein M1 is VI B race metallic element and/or V B race metal member
Element, M2 are thulium and/or III B race metallic element.
According to the present invention, M1 is active component element, and M2 is support modification agent element, and M3 is carrier element, but this is not
It should be construed to the introduction or hint of the potential mechanism of catalytic activity.It will be appreciated by those skilled in the art that no matter for which kind of
Design concept selection a certain kind or various metals, no matter how implementer defines and speculates the work of the metal in the catalyst
With, such as no matter state to select the metal as active component, the catalysis is introduced as support modification agent, or as auxiliary agent
Agent, all without the definition for considering the effect for metal, as long as its content falls into the range of each component of catalyst of the present invention
As fall into protection scope of the present invention.
Catalyst according to the invention, preferably on the basis of 100 part by weight of catalyst, the catalyst contains 20-40 weight
It measures part active component (M1)AOB；5-15 parts by weight support modification agent (M2)COD, 45-70 parts by weight carrier.
Catalyst according to the invention, the M1 for meeting aforementioned claim are used equally for the present invention, and for the present invention, preferably M1 is
One of Mo, W and V or a variety of.It is possible thereby to further increase the methanation activity and methane selectively of catalyst.Embodiment
In when to schematically illustrate M1 be Mo, advantage of the invention, but the present invention is not restricted to this.
Catalyst according to the invention, (M1)AOBIn A and the numerical value of B determined according to the valence state of M1, number both preferably
Value is selected finally to make (M1)AOBFor the steady oxide of M1, such as when M1 is Mo, A 1, B 3.
Catalyst according to the invention, the M2 for meeting aforementioned claim are used equally for the present invention, and for the present invention, preferably M2 is
One of La, Ce and Y or a variety of.It is possible thereby to further increase the methanation activity and methane selectively of catalyst.Implement
When to schematically illustrate M2 in example be Y and La, advantage of the invention, but the present invention is not restricted to this.
Catalyst according to the invention, (M2)CODIn C and the numerical value of D determined according to the valence state of M2, the choosing of the numerical value of the two
It is fixed finally to make (M2)CODFor the steady oxide of M2, such as when M2 is Y, C 2, D 3.
Catalyst according to the invention, optional wider range of the type of the carrier, is usually used in methanation catalyst
Carrier is used equally for the present invention, and for the present invention, the preferably described carrier is (M3)EOF, wherein preferred M3 is II A race element, III A
One of race's element, IV A race element, IV B race element and thulium are a variety of, and M3 is different from M2.
Catalyst according to the invention, preferably M3 are one of Al, Si and Zr or a variety of, and M3 is different from M2.
Catalyst according to the invention, preferred vector Al2O3、SiO2And ZrO2One of or a variety of, more preferable carrier
For ZrO2。
Catalyst according to the invention, wherein carrier ZrO2When, ZrO2With monoclinic phase for main phase, preferably greater than 80
The ZrO of weight %2For monoclinic phase, remaining is tetragonal phase.
Catalyst according to the invention, wherein the BET surface area of the preferred catalyst is not less than 100m2/ g, more preferably
For not less than 150m2/ g, more preferably 150-200m2/g。
The catalyst that hydro-thermal method of the invention is prepared under low temperature, high water vapor atmosphere have high methanation activity with
High methane selectively.
The present invention provides a kind of methods for preparing catalyst for methanation in presence of sulfur of the present invention, this method comprises:
In the presence of aqueous solvent, carrier predecessor, active component predecessor, support modification agent predecessor are mixed with precipitating sustained release agent,
In confined conditions, gained mixed solution is subjected to hydro-thermal process.
With the method for the invention it is preferred to it is 100 DEG C or more that the condition of hydro-thermal process, which includes: temperature, preferably 120-250
DEG C, more preferably 150-200 DEG C.It is possible thereby to further increase the methanation activity and methane selectively of catalyst.
With the method for the invention it is preferred to which the condition of hydro-thermal process includes: to be 5h or more, preferably 8-24h the time.Thus
It can be further improved the methanation activity and methane selectively of catalyst.
According to the method for the present invention, optional wider range of the type of the precipitating corrosion inhibiter, for the present invention, preferably institute
Stating precipitating sustained release agent is one of urea, ethylene glycol, butylamine and ethamine alcohol or a variety of.It is possible thereby to further increase catalyst
Methanation activity and methane selectively.
With the method for the invention it is preferred to this method further include: slurries obtained by hydro-thermal process are filtered, washed, dry and
Roasting.
The present invention without particular/special requirement, carries out the mode and condition that are filtered, washed, dry and roast in a conventional manner
?.
With the method for the invention it is preferred to which the dosage for precipitating sustained release agent is so that the metallic element in feeding intake all precipitates institute
Need 1-4 times of theoretical amount.
According to a preferred embodiment of the present invention, preferably the method comprise the steps that
In the presence of aqueous solvent, carrier predecessor, support modification agent predecessor are mixed to get solution A；Containing water-soluble
In the presence of agent, active component predecessor and precipitating sustained release agent are mixed to get B solution；The solution A and B solution are mixed to get
Gained mixed solution is carried out the hydro-thermal process in confined conditions by mixed solution.It is possible thereby to further increase catalyst
Methanation activity and methane selectively.
Aqueous solvent of the invention can be with all water, can also be according to needing to be added other cosolvents, and the present invention is to this
Without particular/special requirement.
According to the method for the present invention, the carrier predecessor is the substance for being capable of providing carrier, is for example, capable of providing
The salt compound of carrier, such as carrier are (M3)EOF, preferred vector be M3 salt compound, for example, the ammonium salt of M3, nitrate,
Chlorate, sulfate, carbonate etc., specifically can be according to being selected, and the type of M3 has been described in aforementioned, example
As in an embodiment of the present invention, when M3 is Zr, carrier predecessor can be the nitrate of zirconium.
According to the method for the present invention, the active component predecessor is the substance for being capable of providing active component, for example, can
Enough provide active component salt compound, the preferably described active component predecessor be M1 salt compound, for example, the ammonium salt of M1,
Nitrate, chlorate, sulfate, carbonate etc., specifically can according to being selected, the type of M1 it is aforementioned in detail
Description, such as in an embodiment of the present invention, when M1 is Mo, carrier predecessor can be the ammonium salt of Mo.
According to the method for the present invention, the support modification agent predecessor is the substance for being capable of providing support modification agent, such as
For the salt compound for being capable of providing support modification agent, the preferably described support modification agent predecessor is the salt compound of M2, for example,
Ammonium salt, nitrate, chlorate, sulfate, carbonate of M2 etc., specifically can be according to being selected, and the type of M2 is preceding
State and have been described in, such as in an embodiment of the present invention, when M2 be La and/or Y when, carrier predecessor can for La and/
Or the nitrate of Y.
The present invention provides application of the catalyst of the present invention in methanation reaction.
Catalyst of the invention preferably carries out presulfurization, the method and condition reference of presulfurization before for methanation reaction
The prior art carries out, and to this present invention without particular/special requirement, this is not described in detail here.
Advantage of the invention is further illustrated below by embodiment, but the present invention is not limited to this.
Comparative example 1
Conventional impregnation method, which prepares weight group, becomes 20MoO3/10Y2O3/70ZrO2Methanation catalyst D1.
Weigh 17.0g Y (NO3)3·6H2O is dissolved in 70ml water, weighs 70g monoclinic phase business ZrO2Carrier (specific surface area
For 90m2/ g) it is added in above-mentioned solution.After being evaporated extra suspension in a water bath, it is placed in oven drying, obtaining load has Y's
ZrO2Carrier.
Weigh 24.5g ammonium heptamolybdate ((NH4)6Mo7O24·4H2O it) is placed in 50ml water, dissolution is sufficiently stirred and obtains molybdic acid
Ammonium salt solution, by the aforementioned ZrO for loading and having Y2Carrier is added in ammonium molybdate solution.After being evaporated extra suspension in a water bath,
It is placed in oven drying.Under or over the decomposition temperature of ammonium molybdate, such as 600 DEG C, the sample after calcining impregnation drying obtains weight
Amount group becomes 20MoO3/10Y2O3/70ZrO2Methanation catalyst.
Comparative example 2
Conventional precipitation method, which prepares weight group, becomes 20Mo/80ZrO2Methanation catalyst D2.
Weigh the ammonium heptamolybdate ((NH of 24.5g4)6Mo7O24·4H2O) with the zirconyl nitrate ZrO (NO of 164.2g3)2·2H2O
It is placed in 500ml water, it is 6.5 that ammonium hydroxide to pH value is slowly added dropwise under the conditions of being then stirred at room temperature.By sediment slurry aging 12h
Afterwards, it filters, be filtered, washed.Filter cake is roasted after 120 DEG C of dryings in 600 DEG C, obtains weight group as 20Mo/80ZrO2's
Methanation catalyst.
Embodiment 1
Preparing weight group becomes 20MoO3/10Y2O3/70ZrO2Methanation catalyst C1.
Weigh 151.8g zirconyl nitrate (ZrO (NO3)2·2H2O), 17.0g Y (NO3)3·6H2O is dissolved in 1500ml water
Solution A is obtained, 24.5g ammonium heptamolybdate ((NH is weighed4)6Mo7O24·4H2O) be dissolved in 80g urea in 1500ml water obtain it is molten
Liquid B.Then it is transferred in water heating kettle after two solution being mixed and are sufficiently stirred, in 160 DEG C of hydro-thermal process 10h after closed water heating kettle.
After hydro-thermal rear slurry is filtered and is sufficiently washed, in 120 DEG C of drying and dehydratings, 600 DEG C of roastings obtain weight group as 20Mo/
10Y2O3/70ZrO2Methanation catalyst.
Embodiment 2
Preparing weight group becomes 30MoO3/10Y2O3/60ZrO2Methanation catalyst C2.
It prepares according to the method for embodiment 1, the difference is that by the 151.8g zirconyl nitrate (ZrO (NO in embodiment 13)2·
2H2O 130.1g, 24.5g ammonium heptamolybdate ((NH) are changed to4)6Mo7O24·4H2O it) is changed to 36.8g, remaining step and 1 phase of embodiment
Together.
Embodiment 3
Preparing weight group becomes 40MoO3/10Y2O3/50ZrO2Methanation catalyst C3.
It prepares according to the method for embodiment 1, the difference is that by the 151.8g zirconyl nitrate (ZrO (NO in embodiment 13)2·
2H2O 108.4g, 24.5g ammonium heptamolybdate ((NH) are changed to4)6Mo7O24·4H2O it) is changed to 49g, remaining step is same as Example 1.
Embodiment 4
Preparing weight group becomes 20MoO3/5Y2O3/75ZrO2Methanation catalyst C4.
It prepares according to the method for embodiment 1, the difference is that by 151.8g zirconyl nitrate (ZrO (NO in embodiment 13)2·
2H2O 162.6g, 17.0g Y (NO) are changed to3)3·6H2O is changed to 8.5g, remaining step is same as Example 1.
Embodiment 5
Preparing weight group becomes 40MoO3/15Y2O3/45ZrO2Methanation catalyst C5.
It is prepared according to the method for embodiment 3, the difference is that by 108.4g zirconyl nitrate (ZrO (NO in embodiment 33)2·
2H2O 97.5g, 17.0g Y (NO) are changed to3)3·6H2O is changed to 25.5g, remaining step is same as Example 3.
Embodiment 6
Preparing weight group becomes 20MoO3/10La2O3/70ZrO2Methanation catalyst C6.
It prepares according to the method for embodiment 1, the difference is that by 17.0g Y (NO in embodiment 13)3·6H2O is changed to 26.6g
Lanthanum nitrate hexahydrate (La (NO3)3·6H2O), remaining step is same as Example 1.
Embodiment 7
Preparing weight group becomes 20MoO3/10Y2O3/70ZrO2Methanation catalyst C7.
It prepares according to the method for embodiment 1, unlike, the temperature of hydro-thermal process is 200 DEG C, and hydrothermal conditions are
8h, remaining condition are all the same.
Embodiment 8
Preparing weight group becomes 20MoO3/10Y2O3/70ZrO2Methanation catalyst C8.
It prepares according to the method for embodiment 1, unlike, the temperature of hydro-thermal process is 150 DEG C, and hydrothermal conditions are
15h, remaining condition are all the same.
Embodiment 9
Preparing weight group becomes 20MoO3/10Y2O3/70ZrO2Methanation catalyst C9.
It prepares according to the method for embodiment 1, unlike, the temperature of hydro-thermal process is 130 DEG C, remaining condition is all the same.
Embodiment 10
Preparing weight group becomes 20MoO3/10Y2O3/70ZrO2Methanation catalyst C10.
It prepares according to the method for embodiment 1, unlike, weigh 151.8g zirconyl nitrate (ZrO (NO3)2·2H2O),
17.0g Y(NO3)3·6H2O, 24.5g ammonium heptamolybdate ((NH4)6Mo7O24·4H2O it) is dissolved in 3000ml water and obtains with 80g urea
It to mixed solution, is transferred in water heating kettle after being sufficiently stirred, in 160 DEG C of hydro-thermal process 10h after closed water heating kettle.By hydro-thermal rear slurry
After filtering and sufficiently washing, in 120 DEG C of drying and dehydratings, 600 DEG C of roastings obtain weight group as 20Mo/10Y2O3/70ZrO2's
Methanation catalyst.
Fig. 1 shows 2 (30MoO of embodiment3/10Y2O3/60ZrO2, 30MoO is reduced in figure3/10Y2O3/ZrO2), implement
3 (40MoO of example3/10Y2O3/50ZrO2, 40MoO is reduced in figure3/10Y2O3/ZrO2), 6 (20MoO of embodiment3/10La2O3/
70ZrO2, 20MoO is reduced in figure3/10La2O3/ZrO2) catalyst XRD spectra；
Carrier ZrO in the catalyst of embodiment 2 as seen from Figure 1, embodiment 3 and embodiment 62It is with monoclinic phase
It is main.
As seen from Figure 1, Mo phase and Y phase are not observed in the XRD spectra of catalyst of the invention, shows the present invention
Catalyst be in high degree of dispersion state.
Remaining catalyst of XRD spectra, ZrO similar with the XRD spectrum of the catalyst of embodiment 6 is not shown2It is predominantly single
Monoclinic phase.
Test case
Catalyst methane performance evaluation: prior to 400 DEG C, 5 volume %H2S/95 volume %H2Vulcanize 5h in gaseous mixture, so
Afterwards in H2/ CO (molar ratio)=1.0, the H containing 0.1 volume %2In the synthesis gas of S and 20 volume % vapor, in 400 DEG C,
3MPa, 5000h-1Methanation reaction test is carried out, the BET surface area and methanation reaction of catalyst the results are shown in Table 1.
Table 1
Catalyst methane activity of the invention is significantly better than the catalyst of comparative example it can be seen from the result of table 1.And
With the increase of active component such as Mo content, catalyst activity is first increased and is reduced afterwards, works as MoO3Content is between 30%-40%
When reach highest.As the increase catalyst stability of support modification agent such as Y content significantly increases, but activity is suppressed.
And catalyst BET surface area of the invention is in 100m2/ g or more reaches as high as 190m2/ g or more.
And the catalyst of the invention it can be seen from the data of table 1, stability is good, after reaction is after 100h, is still able to maintain
High methanation conversion ratio.
Claims (17)
1. a kind of catalyst for methanation in presence of sulfur, which is characterized in that the catalyst synthesizes to obtain using hydro-thermal method, wherein with 100
On the basis of part by weight of catalyst, the catalyst contains the parts by weight of activated component of 20-40 (M1)AOB, 5-15 parts by weight support modification
Agent (M2)COD, 45-70 parts by weight carrier；Wherein, one of M1 Mo, W and V or a variety of, M2 be thulium and/or
III B race metallic element, carrier ZrO2, ZrO2With monoclinic phase for main phase.
2. catalyst according to claim 1, wherein one of M2 La, Ce and Y or a variety of.
3. catalyst according to claim 1 or 2, wherein the BET surface area of the catalyst is not less than 100m2/g。
4. catalyst according to claim 3, wherein the BET surface area of the catalyst is not less than 150m2/g。
5. catalyst according to claim 3, wherein the BET surface area of the catalyst is 150-200m2/g。
6. a kind of method for preparing catalyst for methanation in presence of sulfur described in any one of claim 1-5, which is characterized in that should
Method includes: in the presence of aqueous solvent, by carrier predecessor, active component predecessor, support modification agent predecessor and precipitating
Gained mixed solution is carried out hydro-thermal process in confined conditions by sustained release agent mixing.
7. according to the method described in claim 6, wherein, the condition of hydro-thermal process includes: that temperature is 100 DEG C or more.
8. according to the method described in claim 7, wherein, the condition of hydro-thermal process includes: that temperature is 120-250 DEG C.
9. according to the method described in claim 7, wherein, the condition of hydro-thermal process includes: that temperature is 150-200 DEG C.
10. the method according to any one of claim 6-9, wherein the condition of hydro-thermal process include: the time be 5h with
On.
11. according to the method described in claim 10, wherein, the condition of hydro-thermal process include: be 8-24h the time.
12. the method according to any one of claim 6-9, wherein the precipitating sustained release agent be urea, ethylene glycol,
One of butylamine and ethamine alcohol are a variety of.
13. the method according to any one of claim 6-9, wherein this method further include: will be starched obtained by hydro-thermal process
Liquid is filtered, washed, dries and roasts.
14. the method according to any one of claim 6-9, wherein precipitate sustained release agent dosage be so that feeding intake in
Metallic element all precipitate needed for 1-4 times of theoretical amount.
15. the method according to any one of claim 6-9, wherein this method comprises:
In the presence of aqueous solvent, carrier predecessor, support modification agent predecessor are mixed to get solution A；It is deposited in aqueous solvent
Under, active component predecessor and precipitating sustained release agent are mixed to get B solution；The solution A and B solution are mixed to get mixing
Gained mixed solution is carried out the hydro-thermal process in confined conditions by solution.
16. the method according to any one of claim 6-9, wherein the carrier predecessor is to be capable of providing carrier
Salt compound, the active component predecessor is the substance for being capable of providing active component, and the support modification agent predecessor is
It is capable of providing the substance of support modification agent.
17. application of the catalyst in methanation reaction described in any one of claim 1-5.
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| CN111408399A (en) * | 2020-03-13 | 2020-07-14 | 中国华能集团清洁能源技术研究院有限公司 | Low-temperature sulfur-tolerant methanation catalyst with metal oxide and molecular sieve composite carrier and preparation method thereof |
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| JP2007252991A (en) * | 2006-03-20 | 2007-10-04 | Catalysts & Chem Ind Co Ltd | Honeycomb catalyst for carbon monoxide methanation, manufacturing method of the catalyst, and methanation method of carbon monoxide using the catalyst |
| CN102029161A (en) * | 2009-09-28 | 2011-04-27 | 中国科学院大连化学物理研究所 | Method for preparing complete methanation catalyst for hydrothermal chemical process |
| CN103386307A (en) * | 2012-05-08 | 2013-11-13 | 中国科学院过程工程研究所 | Preparation method for Ni-Mg/Al2O3 catalyst |
| CN103962123A (en) * | 2013-01-28 | 2014-08-06 | 神华集团有限责任公司 | ZrO2-loaded sulfur-tolerant methanation catalyst and preparation method thereof |
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