CN110339856A - One kind is with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst and the preparation method and application thereof of carrier - Google Patents

One kind is with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst and the preparation method and application thereof of carrier Download PDF

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CN110339856A
CN110339856A CN201810290101.5A CN201810290101A CN110339856A CN 110339856 A CN110339856 A CN 110339856A CN 201810290101 A CN201810290101 A CN 201810290101A CN 110339856 A CN110339856 A CN 110339856A
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molecular sieve
mesoporous sio
carrier
kit
sieve kit
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辛忠
吕宇皓
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East China University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/396—Distribution of the active metal ingredient
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/617—500-1000 m2/g
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
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    • C07C1/0425—Catalysts; their physical properties
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    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself

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Abstract

The invention discloses one kind with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier, with mesoporous SiO2Molecular sieve KIT-6 is carrier, using W metal as active component；Wherein, on the basis of the catalyst of 100 parts by weight, with elemental metal, the content of nickel is 3~10 parts by weight, and surplus is mesoporous SiO2Molecular sieve KIT-6.The invention also discloses described in one kind with mesoporous SiO2The preparation method and the purposes in preparing methane by synthetic gas that molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier.It is of the invention with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier, is with chemical property is stable, large specific surface area and heat conduction property are good mesoporous SiO2Molecular sieve KIT-6 is carrier, and the catalyst of preparation has many advantages, such as that metal dispersity is high, catalytic activity is high, thermal stability is good and catalyst life is longer.

Description

One kind is with mesoporous SiO2Molecular sieve KIT-6 be carrier Ni-based methanation catalyst and its Preparation method and application
Technical field
The invention belongs to technical field of fine, are related to one kind with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based of carrier Methanation catalyst and the preparation method and application thereof.
Background technique
In recent years, as oil-fired increasingly depleted and industrial largely discharge pollutants causes ecological environment problem It gets worse, the synthesis gas of coal, biomass is subjected to methanation technology and is had been to be concerned by more and more people.Synthesis gas can lead to Progress methanation prepares methane and substitute natural gas (SNG) after crossing purification, adjusting hydrogen-carbon ratio.Natural gas from coal technology be by High-carbon energy had both improved effective utilization rate of thermal energy (53%), also to the height of coal resources to low-carbon, hydrogen-rich energy conversion in this way The clean comprehensive utilization of effect has great importance.
Ni base catalyst becomes coal gasification preparation substitute natural gas first since its price is relatively suitable, catalytic activity is higher The dominant catalyst of alkylation reaction.The preparation method of nickel-base catalyst is usually to be total to its esters and other metal salts at present It precipitates or by its salt solution impregnation porous carrier, then carries out roasting and reduction obtains catalyst sample.Using these sides Method, active component Ni are not easy high degree of dispersion, and the group of W metal crystallite is easily caused in subsequent high-temperature process and reduction process It is poly-, to further decrease dispersion degree, influence catalytic activity.
In addition, stable carrier is very crucial for high-temperature methanation reaction system.Ordered mesoporous material is with its height Specific surface area, better heat stability, be easy to modify and to characteristics such as the preferable peptizaitons of metal active constituent, in catalysisization Be widely used in field.Since mesopore molecular sieve is mostly pure SiO2, do not have catalytic activity, therefore in these molecular sieves Incorporation metal/metal oxide or to carry out surface modifications to them be to have efficacious prescriptions for what these molecular sieves were used for catalytic field at present Method.Metal/metal oxide can be loaded on mesopore molecular sieve by infusion process, but metal/metal oxide divides mostly It is distributed in mesopore molecular sieve surface and is difficult to be uniformly dispersed.Some researches show that prepare Ni/Al using infusion process2O3When, surface-active The addition of agent restrained effectively the eggshell type distribution of metal, to keep metal more uniform in the distribution of carrier surface.In addition, There are also many scholars to have studied influence of the surfactant for metal dispersion in metallic catalyst and catalytic performance, but fortune mostly It is that deposition-precipitation method prepares catalyst, this method is compared for infusion process, and preparation process is cumbersome, higher cost.Cause This, needs to find one kind method simple to operation and prepares high-dispersed nickel methanation catalyst, while guaranteeing high activity, Also need to have excellent high temperature resistance and stability.
Summary of the invention
In order to overcome, for active component in the defect of carrier surface bad dispersibility, it is an object of the invention to mention in the prior art For a kind of good dispersion, with excellent synthesis gas methanation activity with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based first of carrier Alkanizing catalyst.
It is a further object to provide described in one kind with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methane of carrier Change the preparation method of catalyst, this method is simple and convenient.
It is also another object of the present invention to provide described in one kind with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methane of carrier Change the application of catalyst.
To achieve the goals above, The technical solution adopted by the invention is as follows:
One aspect of the present invention provides one kind with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier Agent, with mesoporous SiO2Molecular sieve KIT-6 (Ia3d) is carrier, using W metal as active component；Wherein, urging with 100 parts by weight On the basis of agent, with elemental metal, the content of nickel is 3~10 parts by weight, and surplus is mesoporous SiO2Molecular sieve KIT-6.
It is described with mesoporous SiO2Molecular sieve KIT-6 be the specific surface area of the Ni-based methanation catalyst of carrier be 500~ 1000m2/ g, preferably 835m2/ g, aperture are 3~12nm, and preferably 6.0nm, pore volume is 0.4~1.4m3/ g, preferably 1cm3/g。
The mesoporous SiO2The specific surface area of molecular sieve KIT-6 is 500~1000m2/ g, preferably 600~835m2/ g, hole Diameter is 3~12nm, and preferably 4~10nm, hole wall is 2~6nm, and pore volume is 0.4~1.4cm3/ g, preferably 0.8~1cm3/ g；
The active component Ni is with NiO, Ni2O3Form exist.
Another aspect of the present invention provides described in one kind with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methane of carrier Change the preparation method of catalyst, comprising the following steps:
Nickel salt is dissolved in solvent, and the solution that additive is made into nickel salt is added, dry mesoporous SiO is then added2Point Son sieve KIT-6, using equi-volume impregnating by mesoporous SiO2Molecular sieve KIT-6 is impregnated in the solution of nickel salt, stood after stirring, It is dried in vacuo, roasts, grinds, sieves, obtain described with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier Agent.
The nickel salt is at least one of nickel chloride, nickel sulfate, nickel acetate, nickel oxalate, nickel nitrate.
The solvent is at least one of deionized water, methanol, ethyl alcohol, acetic acid, ethyl acetate, chloroform, acetone.
The additive be in the small organic molecules additive such as citric acid, glucose, ethylene glycol, glycerol, sorbierite extremely Few one kind.
The mass ratio of the additive and the nickel salt is (0.3~1.5): 1；And it can be removed in catalyst roasting process It goes, not in catalyst component.In catalyst preparation process, by the way that these additives are added, active component can reduce The size of grain, is scattered in it uniformly in the duct of carrier, simultaneously because molecular sieve pore passage has confinement effect, is urging Also its sintering can be prevented in agent reduction process, and then improves the dispersion degree of active component nickel in catalyst, it is final to influence catalysis The activity and stability of agent.
The nickel salt and mesoporous SiO2The mass ratio of molecular sieve KIT-6 is (0.1~0.6): 1.
The temperature of the equi-volume impregnating is room temperature, and the time is 2~12h, preferably 4~6h.
The vacuum drying temperature is 30~80 DEG C, and preferably 50~70 DEG C, the time is 1~12h, preferably 2~6h.
The temperature of the roasting be 400~800 DEG C, preferably 400~600 DEG C, the time be 0.5~10h, preferably 0.5 ~2h.
The screening is sieved by the sub-sieve of 200 mesh.
The mesoporous SiO of the drying2Molecular sieve KIT-6 is dry under conditions of temperature is 50~200 DEG C, the time 2 ~for 24 hours.
Another aspect of the invention additionally provides described in one kind with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based first of carrier Purposes of the Alkanizing catalyst in preparing methane by synthetic gas.
The condition of the preparing methane by synthetic gas is as follows: synthesis gas volume space velocity is 3000~30000h-1, pressure be normal pressure extremely 3.0MPa, temperature are 300~500 DEG C, H in synthesis gas2/ CO ratio is 2~4.
Due to the adoption of the above technical scheme, the present invention has the following advantages and beneficial effects:
It is of the invention with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier, in preparing methane by synthetic gas Superior activity and methane selectively are shown in reaction, it is all active in 300~500 DEG C of temperature range, wherein 300~ Within the temperature range of 400 DEG C, preferably, CO conversion ratio can achieve 100% to the activity of catalyst, and methane selectively reaches 99.9%, great industrial prospect.
It is of the invention with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier, is steady with chemical property Determine, the mesoporous SiO that large specific surface area and heat conduction property are good2Molecular sieve KIT-6 is carrier, and the catalyst of preparation is with metal point Divergence height, catalytic activity height, thermal stability good (not declining by 700 DEG C of high-temperature calcination 2h catalytic activity) and catalyst life The advantages that longer (100h life experiment catalytic activity is without decline), which does not contain noble metal component, and preparation method is simple Easy, Ni content is low, and catalytic performance is higher, there is biggish advantage in cost performance.
It is of the invention with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier, and nickel particle size is small, point It dissipates uniformly, metal large specific surface area, and metal component enters inside molecular sieve pore passage, for preparing methane by synthetic gas, this is strongly exothermic In reaction, have many advantages, such as that catalytic activity is high, methane selectively is good, thermal stability is good, catalyst life is longer.
It is of the invention with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier, mesopore molecular sieve carrier KIT-6 is three-dimensional column SiO2Molecular screen material, pore size is between more traditional MCM-41 and SBA-15, three-dimensional structure Keep material mass transfer effect more preferable, overcome active component blocking molecular sieve pore passage problem, in molecular sieve wall containing secondary mesoporous and Micropore can play active component and fall into domain effect, and active component thermophoresis under high temperature is prevented to be sintered.Its absorption, biological medicine, The fields such as new material processing especially catalysis all show extensive potential application foreground.
Detailed description of the invention
The TEM figure that Fig. 1 is 5Ni-KIT-6-CA in embodiment 1.
Fig. 2 is TEM figure of the 5Ni-KIT-6-CA after the lower 650 DEG C of roastings 2h of unstripped gas atmosphere in embodiment 8.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this The protection scope of invention.
In the following examples, the experimental methods for specific conditions are not specified, usually according to normal condition or according to institute, manufacturer It is recommended that condition.Unless otherwise stated, otherwise all percentage, ratio, ratio or number be by weight.
The unit in percent weight in volume in the present invention is well-known to those skilled in the art, such as is referred to The weight of solute in 100 milliliters of solution.
As used herein, " room temperature " refers to 15-30 DEG C, preferably 20-25 DEG C.
As used herein, " normal pressure " refers to 0.1MPa.
As used herein, if without particularly pointing out, mesoporous SiO2The synthetic method of molecular sieve KIT-6 is as follows: hydrothermal synthesis temperature Spend 100 DEG C of times for 24 hours, 80 DEG C of dry 12h, 550 DEG C of calcining 5h.
As used herein, if immersion solvent generally uses deionized water without particularly pointing out.
Unless otherwise defined, all professional and scientific terms as used herein and meaning familiar to those skilled in the art Justice is identical.In addition, any method similar to or equal to what is recorded and material can be applied to the method for the present invention.Wen Zhong The preferred implement methods and materials are for illustrative purposes only.
Solvent for use and material are as shown in table 1 in the embodiment of the present invention:
Table 1
Embodiment 1
It weighs 0.26g Nickelous nitrate hexahydrate to be dissolved in 1.9mL deionized water, and adds 0.18g monohydrate potassium, prepare At the aqueous solution of nickel nitrate.Then weighing 1g specific surface area is 835m2Mesoporous SiO2 molecular sieve KIT-6 (the mesoporous SiO of/g2Molecule The aperture size for sieving KIT-6 is 6nm, hole wall 4nm, pore volume 1cm3/ g), mesoporous SiO2Molecular sieve KIT-6 is to be in temperature Dry under conditions of 100 DEG C, carrier KIT-6 is impregnated in above-mentioned nitric acid using equi-volume impregnating at normal temperature by time 12h In the aqueous solution of nickel, 6h, 80 DEG C of dry 12h in baking oven are stored at room temperature after stirring.By obtained solid product in Muffle kiln roasting, The temperature of roasting is 500 DEG C, time 5h, after mortar is ground, and is sieved with 200 mesh sub-sieves, nickel loading, which can be obtained, is 5wt% with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier, is denoted as 5Ni/KIT-6-CA, TEM picture As shown in FIG. 1, FIG. 1 is the TEM pictures of 5Ni-KIT-6-CA in embodiment 1, to facilitate activity after the load of visual understanding catalyst Component dispersion and its influence to carrier ordered property.From figure 1 it appears that after carried metal carrier cellular structure according to So high-visible, wherein nickel particle size about 2-4nm, Ni dispersion degree are greatly improved.
With mesoporous SiO2Molecular sieve KIT-6 is that the specific surface area of the Ni-based methanation catalyst of carrier is 835m2/ g, aperture For 6.0nm, pore volume 1cm3/g。
Embodiment 2
The preparation method is the same as that of Example 1, institute the difference is that: additive is glucose, and gained catalyst is denoted as 5Ni/ KIT-6-Gl。
Embodiment 3
The preparation method is the same as that of Example 1, institute the difference is that: additive is sorbierite, and gained catalyst is denoted as 5Ni/ KIT-6-So。
Embodiment 4
The preparation method is the same as that of Example 1, the difference is that: with 0.3g tetra- be hydrated nickel acetate replace embodiment 1 in 0.26g Nickelous nitrate hexahydrate, the catalyst that the present embodiment is prepared are denoted as 5Ni/KIT-6-CA/AC.
Embodiment 5
The preparation method is the same as that of Example 1, the difference is that: the additive amount of Nickelous nitrate hexahydrate be 0.15g, gained catalysis The nickel loading of agent is 3%, is denoted as 3Ni/KIT-6-CA.
Embodiment 6
The preparation method is the same as that of Example 1, the difference is that: the additive amount of Nickelous nitrate hexahydrate be 0.55g, gained catalysis The nickel loading of agent is 10%, is denoted as 10Ni/KIT-6-CA.
Embodiment 7
Respectively by Catalyst packing made from Examples 1 to 6 in the fixed-bed micro-reactor that internal diameter is 8mm, reaction It is preceding first to use N2Purging air, then at 500 DEG C, it is passed through pure H2Reducing catalyst 2 hours.Then with the catalyst obtained after reduction The methanation reaction of unstripped gas is catalyzed.The composition and catalytic reaction condition of unstripped gas are as follows:
Unstripped gas composition: CO:20%, H2: 60%, N2: 20%；
Loaded catalyst: 200mg；
Reaction temperature: 300~500 DEG C；
Reaction pressure: 0.1MPa；
Reaction velocity: 15,000h-1。
The composition and catalytic reaction condition of the applicable unstripped gas of catalyst of the invention can be with are as follows: synthesis gas volume space velocity For 3000~30000h-1, pressure is normal pressure to 3.0MPa, and temperature is 300~500 DEG C, H in synthesis gas2/ CO ratio is 2~4.
It measures as follows and calculates CO conversion ratio and CH4Yield:
CO conversion ratio: XCO=(the CO amount contained in the CO amount/unstripped gas contained in 1- product) × 100%
CH4Yield: SCH4=(it is converted to CH4CO amount/unstripped gas in the CO amount that contains) × 100%
Embodiment 8
Embodiment 8 is used to illustrate heat-resisting quantity of the catalyst made from Examples 1 to 6 in preparing methane by synthetic gas reaction Energy.
By Catalyst packing made from Examples 1 to 6 in the fixed-bed micro-reactor that internal diameter is 8mm, before reacting first Use N2Purging air, then with pure H2Reducing catalyst, unstripped gas is by CO and H2Mixing enters reactor after filtering, first optimal At a temperature of measure catalyst activity, then by catalyst under unstripped gas atmosphere 650 DEG C of calcining 2h, then reaction temperature dropped back to optimal Temperature investigates catalyst activity.Gained gas is reacted through gas-chromatography on-line analysis, and according to method meter same as Example 7 Calculate CO conversion ratio and CH4Selectivity, is as a result listed in table 1.
Test condition are as follows: T=350 DEG C of temperature, unstripped gas H2: CO=3:1, air speed 15,000h-1.With 5Ni/KIT-6-CA For, the catalyst TEM picture after roasting is as shown in Fig. 2, Fig. 2 is that 5Ni-KIT-6-CA passes through raw material atmosphere in embodiment 8 TEM figure after enclosing lower 650 DEG C of roastings 2h, shadow whether to facilitate comparison roasting to reunite active component and its to carrier ordered property It rings.The cellular structure of carrier in Fig. 2 after carried metal is still high-visible, wherein nickel particle size still about 2-4nm, has no bright Aobvious Ni agglomeration, this illustrates the better heat stability of KIT-6 molecular sieve, and short grained Ni heat resistance is preferable, the group of being not easy It is poly-.
Comparative example
The methanation catalyst and its application in preparing methane by synthetic gas reaction that this comparative example is used to illustrate the prior art.
Respectively with KIT-6, MCM-41, Al2O3And SiO2For carrier, catalyst is obtained according to excessive infusion process, is denoted as 5Ni/ KIT-6、5Ni/MCM-41、5Ni/Al2O3、5Ni/SiO2, and answer catalyst obtained according to method same as Example 6 For synthesis gas methanation reaction, it is as a result listed in table 2.
Table 2
By the data of table 2 it is found that adding small organic molecule in dipping process, with equal actively catalyst prepared by infusion process In unstripped gas atmosphere after 650 DEG C of calcining 2h, CO conversion ratio and CH4Yield is held essentially constant, and the 5Ni/ in comparative example KIT-6、5Ni/MCM-41、5Ni/Al2O3And 5Ni/SiO2Activity have dropped 13.5%, 26.8%, 35.2% and respectively 31.7%, this explanation uses the excess catalyst prepared by infusion process that additive is added other than with good catalytic activity, Also there is good high temperature resistance.In addition, reaction pressure is 1MPa in catalytic activity examination by taking 5Ni/KIT-6-CA as an example When, under optimum reaction condition, CO conversion ratio is up to 100% and CH4Methane selectively illustrates methanation reaction up to 99.9% In be suitably pressurized with progress conducive to methane selectively.
The present invention is on the basis of preparation method (infusion process) of conventional methanation catalyst, by adding in dipping process Enter small organic molecule additive, and it is stable with chemical property, heat-conductive characteristic is good, large specific surface area mesoporous SiO2Molecular sieve KIT-6 is carrier, is prepared for the nickel based metal catalyst that active component is highly dispersed in carrier duct, and gained catalyst has The advantages that catalytic activity is high, methane selectively is good, thermal stability is good and catalyst life is longer.The catalyst is in optimal conditions Under can achieve CO conversion ratio 100%, methane selectively 99.9%, methane yield 99.9%, great industrial prospect.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this The principle of invention, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent defines.

Claims (10)

1. one kind is with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier, it is characterised in that: with mesoporous SiO2 Molecular sieve KIT-6 is carrier, using W metal as active component；Wherein, on the basis of the catalyst of 100 parts by weight, with metal member Element meter, the content of nickel are 3~10 parts by weight, and surplus is mesoporous SiO2Molecular sieve KIT-6.
2. according to claim 1 with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier, feature It is: with mesoporous SiO2Molecular sieve KIT-6 is that the specific surface area of the Ni-based methanation catalyst of carrier is 500~1000m2/ g, it is excellent It is selected as 835m2/ g, aperture are 3~12nm, and preferably 6.0nm, pore volume is 0.4~1.4m3/ g, preferably 1cm3/g。
3. according to claim 1 with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier, feature It is: the mesoporous SiO2The specific surface area of molecular sieve KIT-6 is 500~1000m2/ g, preferably 600~835m2/ g, aperture For 3~12nm, preferably 4~10nm, hole wall is 2~6nm, and pore volume is 0.4~1.4cm3/ g, preferably 0.8~1cm3/g；
The active component Ni is with NiO, Ni2O3Form exist.
4. a kind of claims 1 to 3 is described in any item with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier The preparation method of agent, it is characterised in that: the following steps are included:
Nickel salt is dissolved in solvent, and the solution that additive is made into nickel salt is added, dry mesoporous SiO is then added2Molecular sieve KIT-6, using equi-volume impregnating by mesoporous SiO2Molecular sieve KIT-6 is impregnated in the solution of nickel salt, is stood after stirring, vacuum It dries, roast, grind, sieve, obtain described with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier.
5. according to claim 4 with mesoporous SiO2Molecular sieve KIT-6 is the preparation side of the Ni-based methanation catalyst of carrier Method, it is characterised in that: the nickel salt is at least one of nickel chloride, nickel sulfate, nickel acetate, nickel oxalate, nickel nitrate.
6. according to claim 4 with mesoporous SiO2Molecular sieve KIT-6 is the preparation side of the Ni-based methanation catalyst of carrier Method, it is characterised in that: the solvent is deionized water, methanol, ethyl alcohol, acetic acid, ethyl acetate, chloroform, at least one in acetone Kind；
The additive is at least one of citric acid, glucose, ethylene glycol, glycerol, sorbierite.
7. according to claim 4 with mesoporous SiO2Molecular sieve KIT-6 is the preparation side of the Ni-based methanation catalyst of carrier Method, it is characterised in that: the mass ratio of the additive and the nickel salt is (0.3~1.5): 1；
The nickel salt and mesoporous SiO2The mass ratio of molecular sieve KIT-6 is (0.1~0.6): 1.
8. according to claim 4 with mesoporous SiO2Molecular sieve KIT-6 is the preparation side of the Ni-based methanation catalyst of carrier Method, it is characterised in that: the temperature of the equi-volume impregnating is room temperature, and the time is 2~12h, preferably 4~6h；
The vacuum drying temperature is 30~80 DEG C, and preferably 50~70 DEG C, the time is 1~12h, preferably 2~6h；
The temperature of the roasting is 400~800 DEG C, and preferably 400~600 DEG C, the time is 0.5~10h, preferably 0.5~2h；
The screening is sieved by the sub-sieve of 200 mesh；
The mesoporous SiO of the drying2Molecular sieve KIT-6 be it is dry under conditions of temperature is 50~200 DEG C, the time is 2~for 24 hours.
9. a kind of claims 1 to 3 is described in any item with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst of carrier Purposes of the agent in preparing methane by synthetic gas.
10. according to claim 9 with mesoporous SiO2Molecular sieve KIT-6 is that the Ni-based methanation catalyst of carrier is synthesizing Purposes in gas methane, it is characterised in that: the condition of the preparing methane by synthetic gas is as follows: synthesis gas volume space velocity be 3000~ 30000h-1, pressure is normal pressure to 3.0MPa, and temperature is 300~500 DEG C, H in synthesis gas2/ CO ratio is 2~4.
CN201810290101.5A 2018-04-03 2018-04-03 One kind is with mesoporous SiO2Molecular sieve KIT-6 is the Ni-based methanation catalyst and the preparation method and application thereof of carrier Pending CN110339856A (en)

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