CN107199047A - A kind of Ni-based methanation catalyst being scattered in SBA-15 ducts and its preparation and application - Google Patents
A kind of Ni-based methanation catalyst being scattered in SBA-15 ducts and its preparation and application Download PDFInfo
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- CN107199047A CN107199047A CN201610151648.8A CN201610151648A CN107199047A CN 107199047 A CN107199047 A CN 107199047A CN 201610151648 A CN201610151648 A CN 201610151648A CN 107199047 A CN107199047 A CN 107199047A
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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
- B01J29/0333—Iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The present invention relates to a kind of Ni-based methanation catalyst being scattered in SBA-15 ducts and its preparation and application.In the catalyst, in terms of 100 parts by weight, the content of metal nickel element is 5~20 parts by weight, and the content of additive is 10~40 parts by weight, and remaining is mesoporous molecular sieve SBA-15.It is prepared, including：Prepare nickel salt solution and add additive；In nickel salt solution, SBA-15 is impregnated at room temperature after the mixed liquor of step A configurations, dipping first through vacuum, roasting, Ni-based methanation catalyst is made.The present invention is by adding additive, and the nickel based metal catalyst that active component is highly dispersed in carrier duct is prepared for for carrier using the mesoporous molecular sieve SBA-15 that chemical property is stable, heat-conductive characteristic is good, specific surface area is big, gained catalyst has the advantages that catalytic activity height, methane selectively is good, heat endurance is good and catalyst life is longer.The catalyst can reach CO conversion ratios 100%, methane selectively 99.9%, methane yield 99.9%, great industrial prospect in optimal conditions.
Description
Technical field
The invention belongs to catalyst and its preparing technical field, more particularly to a kind of Ni-based methanation catalyst being highly dispersed in SBA-15 ducts and its preparation and application.
Background technology
The energy resource structure of China is " rich coal, oil starvation, few gas ", positive Development of Coal synthetic natural gas (SNG) is used to substitute natural gas or town gas, the growing market demand is met, it is significant in terms of the energy security, energy-saving and emission-reduction to China.Synthesis gas (CO and H2) methanation is the most key ring of coal synthetic natural gas, and the methanation of high concentration CO is strong exothermal reaction, when heat can not be discharged in time, moment can cause very high temperature rise, so as to cause sintering of catalyst, carbon distribution.Therefore the methanation catalyst of research high temperature resistant and high activity is significant.Ni bases catalyst prepares the dominant catalyst of substitute natural gas methanation reaction as coal gasification because its price is relatively suitable, catalytic activity is higher.The preparation method of current nickel-base catalyst is typically to be co-precipitated or by its salt solution impregnation porous carrier with its esters and other metal salts, is then calcined and reduction obtains catalyst sample.Using these methods, active component Ni is difficult high degree of dispersion, and easily causes the reunion of W metal crystallite in follow-up high-temperature process and reduction process, so as to further reduce decentralization, influences catalytic activity.
In addition, for high-temperature methanation reaction system, stable carrier is very crucial.Ordered mesoporous material with its high-specific surface area, better heat stability, be easy to modification and to characteristics such as the preferable peptizaitons of metal active constituent, be widely used in field of catalytic chemistry.Because mesopore molecular sieve is mostly pure SiO2, without catalytic activity, therefore mix metal/metal oxide in these molecular sieves or they carried out surface to be modified to be that these molecular sieves are used for the effective ways of catalytic field at present.Metal/metal oxide can be loaded to by infusion process on mesopore molecular sieve, but metal/metal oxide is distributed in mesopore molecular sieve surface and is difficult to be uniformly dispersed mostly.There are some researches show prepare Ni/Al using infusion process2O3When, the addition of surfactant restrained effectively the eggshell type distribution of metal, so that metal is more uniform in the distribution of carrier surface.In addition, influence of the surfactant for metal dispersion in metallic catalyst and catalytic performance of also many scholar's research, but use mostly is deposition-precipitation method prepares catalyst, and this method is compared for infusion process, and preparation process is cumbersome, and cost is higher.
Chinese patent CN104549411A is disclosed a kind of " a kind of preparation of nickel-base catalyst based on SBA-15 and its application in SNG preparations ", but dry and roasting process in active component can migrate, it is difficult to be uniformly dispersed and active component Ni is gathered in the outer surface of mesopore molecular sieve mostly to ultimately result in metal in carrier surface.
It is, thus, sought for a kind of method simple to operation prepares high-dispersed nickel methanation catalyst, while high activity is ensured, in addition it is also necessary to possess excellent resistance to elevated temperatures and stability.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of Ni-based methanation catalyst being highly dispersed in SBA-15 ducts and its preparation and application.
The purpose of the present invention is achieved through the following technical solutions：
The first object of the present invention is a kind of Ni-based methanation catalyst being scattered in SBA-15 ducts of offer, and the catalyst is using mesoporous molecular sieve SBA-15 as carrier, using W metal as main active component；Wherein, in terms of 100 parts by weight, the content of metal nickel element is 5~20 parts by weight, and the content of additive is 10~40 parts by weight, and remaining is mesoporous molecular sieve SBA-15；The additive is the surfactants such as organic molecule, cetyl trimethylammonium bromide or the lauryl sodium sulfate such as citric acid.
The aperture size of the mesoporous molecular sieve SBA-15 4.6~30nm can modulation, 3~9nm of pore wall thickness, pore volume is 0.85cm3/g.The mesoporous molecular sieve SBA-15 is the larger molecular screen material of current aperture, because SBA-15 is while the two-dimentional hexagonal structure of high-sequential is kept, more traditional MCM-41 has bigger aperture size, thicker hole wall structure and more preferable hydrothermal stability, therefore, extensive potential application foreground is all shown in absorption, catalysis, biological medicine and new material processing and other fields.
The activity component metal nickel element is with NiO or Ni2O3Form exist.
The second object of the present invention is to provide a kind of preparation method for the Ni-based methanation catalyst being scattered in SBA-15 ducts, comprised the following steps：
(1) prepare nickel salt solution and add additive；The additive is the surfactants such as organic molecule, cetyl trimethylammonium bromide or the lauryl sodium sulfate such as citric acid；Wherein, the weight ratio of metal nickel element and additive is 5~20 in the nickel salt solution：10~40；
(2) in the nickel salt solution, mesoporous molecular sieve SBA-15 is impregnated in 2~12h of mixed liquor of step A configurations at room temperature, dipping is first vacuum dried after terminating, 30~80 DEG C of temperature, 5~12 hours time, then it is fired, temperature is 400~800 DEG C, 1~10 hour time, Ni-based methanation catalyst is made；Nickel loading is 10~20mol% in the catalyst.
Further, the nickel salt in the step (1) is nickel chloride, nickel sulfate, nickel acetate, nickel oxalate or nickel nitrate；The solvent of the nickel salt solution is deionized water, ethanol, acetic acid, chloroform or acetone.
Further, the dipping in the step (2) is using excessive infusion process.
Further, the dip time in the step (2) is 8~10 hours.
Further, the vacuum drying temperature in the step (2) is 40~60 DEG C, and the time is 6~8 hours.
Further, the temperature of the roasting in the step (2) is 500~600 DEG C, and the time is 5~6 hours.
Further, the catalyst obtained after roasting is milled into fine powder, filtered with the sub-sieve of 100 mesh.
It is still another object of the present invention to provide application of the above-mentioned Ni-based methanation catalyst being scattered in SBA-15 ducts in natural gas from coal is prepared.
Specifically, the synthesis gas volume space velocity of the catalyst treatment is 3000~30000h-1, pressure is normal pressure~3.0Mpa, and temperature is 200~600 DEG C, H in synthesis gas2/ CO ratios are 2~4.
Compared with prior art, the positive effect of the present invention is as follows：
(1) catalyst shows superior activity and methane selectively in preparing methane by synthetic gas reaction, it is all active in 200~600 DEG C of temperature range, within the temperature range of wherein 300~450 DEG C, catalyst it is active best, CO conversion ratios can reach more than 100%, and methane selectively reaches more than 92%；
(2) catalyst is using chemical property stabilization and the good mesoporous molecular sieve SBA-15 of heat conduction property as carrier, the catalyst of preparation has the advantages of high metal dispersity, catalytic activity height, heat endurance good (not declining by 700 DEG C of high-temperature calcination 2h catalytic activity) and catalyst life longer (100h life experiments catalytic activity is without decline)；
(3) catalyst does not contain noble metal component, and preparation method is simple and easy to apply, and catalytic performance is higher, there is larger advantage in cost performance.
(4) in catalyst preparation process, by adding these additives, the size of active component particles can be reduced, it is set uniformly to be scattered in the duct of carrier, can also it prevent it from sintering simultaneously because confinement is acted on during catalyst reduction, and then improve the decentralization of active component nickel in catalyst, the activity and stability of final influence catalyst.
Brief description of the drawings
Fig. 1 is catalyst XRD spectrum prepared by embodiment 1-4；Wherein, (A) small-angle diffraction, (B) wide-angle diffraction；
The TEM pictures that Fig. 2 is used carrier SBA-15 in the present invention；
Fig. 3 is catalyst 10%Ni/S15 (S1) prepared by embodiment 1 TEM pictures；
Fig. 4 is applied to the result curve figure of the catalytic performance, i.e. embodiment 5 in synthesis gas methanation reaction for the methanation catalyst in 1-4 of the embodiment of the present invention；Wherein, (A) CO conversion ratios, (B) CH4Yield.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it is to be understood that after the content of the invention lectured has been read, those skilled in the art can make various changes or modifications to the present invention, these equivalent form of values equally fall within the application appended claims limited range.
Raw materials used source is described as follows in following examples：
Mesoporous molecular sieve SBA-15：Laboratory is made by oneself, and detailed process is：Under 40 DEG C of constant temperatures, by 4.0g three block surfactant P123 (EO20PO70EO20, M=5800) and (being provided by Sigma-Aldrich companies) is dissolved in 125g deionized waters, then adds the HCl solution 23.6g that mass fraction is 36-38%.After being completely dissolved, 8.5g tetraethyl orthosilicate is slowly added to, holding is stirred vigorously 24h.Then, 46mg NH4F is dissolved in after 5mL deionized waters, add in solution, mixed liquor is transferred in polytetrafluoroethylene (PTFE) bottle again, the crystallization 24h at 110 DEG C, then filter, wash, dry, the product obtained by drying is finally calcined to 6h (heating rate is 1 DEG C/min) at 550 DEG C and removes template, that is, obtains carrier S BA-15 mesopore molecular sieve white powders.
Lauryl sodium sulfate, citric acid, Nickelous nitrate hexahydrate, four hydration nickel acetates：There is provided by Shanghai Ling Feng chemical reagent Co., Ltd
Embodiment
1
(1) 0.55g Nickelous nitrate hexahydrates and 0.55g lauryl sodium sulfate (SDS) are dissolved in 10g deionized waters；
(2) 1.0g SBA-15 white powders are weighed, SBA-15 white powders are added in solution and impregnate 10h, dipping takes out after terminating, 50 DEG C of vacuum drying 8h, then 5h is calcined in 500 DEG C of air, naturally cools to room temperature, that is, Ni/SBA-15 catalyst is made, 10%Ni/S15 (S1) is designated as, nickel loading is 10mol%.
10%Ni/S15 (S1) manufactured in the present embodiment, its small angle and wide-angle XRD spectrum are as shown in figure 1, shown in TEM pictures such as Fig. 2 (B).It can be seen that by Fig. 1 (A), sample, which has, compares clearly (100), (110) and (200) peak, these peaks are the characteristic peak of regular mesoporous molecular sieve SBA-15, illustrate that the introducing of metallic nickel does not have the destruction original ordered mesopore structure of carrier.It can be seen that by Fig. 1 (B), except showing the feature broad peak (15-35 °) of obvious silica on the wide-angle XRD spectra of sample, also there are characteristic diffraction peak (2 θ=37.5 ° of NiO particles, 43.7 °, 63.7 °) peak, can obtain catalyst surface NiO particle mean size with reference to Scherrer equations is 10nm or so.Can visually see SBA-15 pore passage structure from Fig. 2, and in (110) direction, one-dimensional straight hole road arrangement is close；As seen from Figure 3, the decentralization of active component nickel can be effectively improved by additive being added in maceration extract, be distributed nickel particle more uniform, particle is smaller.With reference to (specific surface area is obviously reduced) deducibility of BET results, nickel is distributed evenly in carrier S BA-15 duct in catalyst 10%Ni/S15 (S1).
Embodiment
2
Lauryl sodium sulfate in embodiment 1 is replaced with citric acid, remaining be the same as Example 1 is made Ni/SBA-15 catalyst, is designated as 10%Ni/S15 (CA), nickel loading is 10mol%.
Catalyst 10%Ni/S15 (CA) manufactured in the present embodiment, its small angle and wide-angle XRD spectrum are as shown in Figure 1.It can be seen that from Fig. 1 (A), the order of mesopore molecular sieve still exists after nickel metal is introduced；It can be seen that from Fig. 1 (B), compare catalyst 10%Ni/S15 (S1), the intensity of its NiO characteristic diffraction peak increased, and this illustrates that the granular size of the NiO in the catalyst has increased.
Embodiment
3
Nickel acetate is hydrated instead of the 0.55g Nickelous nitrate hexahydrates in embodiment 1 with 0.6g tetra-, remaining be the same as Example 1 is made Ni/SBA-15 catalyst, is designated as 10%Ni/S15 (AC), nickel loading is 10mol%.
It can be seen that by Fig. 1 (A), sample, which has, compares clearly (100), (110) and (200) peak, these peaks are the characteristic peak of regular mesoporous molecular sieve SBA-15, illustrate that the introducing of metallic nickel does not have the destruction original ordered mesopore structure of carrier.It can be seen that, except showing the feature broad peak (15-35 °) of obvious silica on the wide-angle XRD spectra of sample, also there is characteristic diffraction peak (2 θ=37.5 °, 43.7 °, 63.7 °) peak of NiO particles by Fig. 1 (B).
Embodiment
4
(1) 1.24g Nickelous nitrate hexahydrates and 0.18g lauryl sodium sulfate (SDS) are dissolved in 10g deionized waters；
(2) 1.0g SBA-15 white powders are weighed, SBA-15 white powders are added in solution and impregnate 2h, dipping takes out after terminating, 30 DEG C of vacuum drying 5h, then 1h is calcined in 400 DEG C of air, naturally cools to room temperature, that is, Ni/SBA-15 catalyst is made, 20%Ni/S15 (S2) is designated as, nickel loading is 20mol%.
It can be seen that by Fig. 1 (A), sample, which has, compares clearly (100), (110) and (200) peak, these peaks are the characteristic peak of regular mesoporous molecular sieve SBA-15, illustrate that the introducing of metallic nickel does not have the destruction original ordered mesopore structure of carrier.It can be seen that, except showing the feature broad peak (15-35 °) of obvious silica on the wide-angle XRD spectra of sample, also there is characteristic diffraction peak (2 θ=37.5 °, 43.7 °, 63.7 °) peak of NiO particles by Fig. 1 (B).
Respectively by Catalyst packing made from embodiment 1~4 in internal diameter 8mm fixed-bed micro-reactor, N is first used before reaction2Purging air, then at 500 DEG C, it is passed through pure H2Reducing catalyst 2 hours.Then the methanation reaction of unstripped gas is catalyzed with the catalyst obtained after reduction.The composition and catalytic reaction condition of unstripped gas are as follows：
Unstripped gas is constituted：CO：20%, H2：60%, N2：20%；
Loaded catalyst：500mg；
Reaction temperature：300~500 DEG C；
Reaction pressure：0.3Mpa；
Reaction velocity：15000h-1。
The composition and catalytic reaction condition of the applicable unstripped gas of the catalyst of the present invention can also be：Synthesis gas volume space velocity is 3000~30000h-1, pressure is normal pressure~3.0Mpa, and temperature is 200~600 DEG C, H in synthesis gas2/ CO ratios are 2~4.
Determine as follows and calculate CO conversion ratios and CH4Yield, is as a result shown in Fig. 4：
CO conversion ratios：XCO=(the CO amounts contained in the CO amounts/unstripped gas contained in 1- products) × 100%
CH4Yield：SCH4=(change into CH4CO amounts/unstripped gas in the CO amounts that contain) × 100%
Figure 4, it can be seen that with the increase of temperature, the trend for being first incremented by and successively decreasing afterwards is presented in the activity of all catalyst.When reaction temperature is 350 DEG C, catalyst 10%Ni/S15's (S1) is active optimal, and CO conversion ratios reach 100%, CH4Yield reaches 99.9%.
Application Example
The present embodiment is used to illustrate resistance to elevated temperatures of the different catalysts in synthesis preparing methane from coal reaction
Catalyst made from embodiment 1~4 and comparative example catalyst D1-D4 are seated in internal diameter 8mm fixed-bed micro-reactor, N is first used before reaction2Purging air, then use pure H2Reducing catalyst, unstripped gas is by CO and H2Mixing enters reactor after filtering, first measures catalyst activity at 400 DEG C of Optimal Temperature, then by catalyst under unstripped gas atmosphere 700 DEG C of calcining 2h, then reaction temperature is dropped back into 400 DEG C of investigation catalyst activities of Optimal Temperature.Reaction gained gas calculates CO conversion ratios and CH through gas-chromatography on-line analysis, and according to method same as Example 54Selectivity, is as a result listed in table 1.Test condition is：T=350 DEG C of temperature, pressure P=0.3Mpa, unstripped gas CO:H2=1:3, air speed 15000h-1。
Above-mentioned comparative example catalyst D1-D4, is described as follows：
Comparative example catalyst D1：Using 1.0g SBA-15 as carrier, 0.55g Nickelous nitrate hexahydrates are dissolved in 10g deionized waters；SBA-15 is impregnated in 12h in solution, dipping takes out after terminating, then 50 DEG C of vacuum drying 12h are calcined 5h in 500 DEG C of air, naturally cool to room temperature, Ni/SBA-15 catalyst is made, 10%Ni/S15 (D1) is designated as.
Comparative example catalyst D2：Using 1.0g MCM-41 as carrier, remaining is made Ni/M41 catalyst, is designated as 10%Ni/M41 (D2) with comparative catalyst D1.
Comparative example catalyst D3：With 1.0g Al2O3For carrier, Ni/Al is made with comparative catalyst D1 in remaining2O3Catalyst, is designated as 10%Ni/Al2O3(D3)。
Comparative example catalyst D4：With 1.0g SiO2For carrier, Ni/SiO is made with comparative catalyst D1 in remaining2Catalyst, is designated as 10%Ni/SiO2(D4)。
Table 1
As shown in Table 1, the catalyst prepared using the excessive infusion process for adding additive is in unstripped gas atmosphere after 700 DEG C of calcining 2h, and CO conversion ratios are still maintained at 100%, CH4The amplitude that yield declines is within 0.1%, and 10%Ni/S15 (D1), 10%Ni/M41 (D2), 10%Ni/Al in comparative example2O3And 10%Ni/SiO (D3)2(D4) activity have dropped 23.2%, 26.8%, 29.5% and 30.5% respectively, the catalyst n i/SBA-15 (S1) that this explanation is prepared using the excessive infusion process for adding additive is in addition to good catalytic activity, also with good resistance to elevated temperatures.
The present invention is on the basis of the preparation method (infusion process) of conventional methanation catalyst, by adding additive, and the nickel based metal catalyst that active component is highly dispersed in carrier duct is prepared for for carrier using the mesoporous molecular sieve SBA-15 that chemical property is stable, heat-conductive characteristic is good, specific surface area is big, gained catalyst has the advantages that catalytic activity height, methane selectively is good, heat endurance is good and catalyst life is longer.The catalyst can reach CO conversion ratios 100%, methane selectively 99.9%, methane yield 99.9%, great industrial prospect in optimal conditions.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.It should be understood by those skilled in the art that; the present invention is not limited to the above embodiments; merely illustrating the principles of the invention described in above-described embodiment and specification; various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, and these changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention is defined by appended claims and its equivalent.
Claims (10)
1. a kind of Ni-based methanation catalyst being scattered in SBA-15 ducts, it is characterised in that：The catalyst is with mesoporous point
Son sieve SBA-15 is carrier, using W metal as active component；Wherein, in terms of 100 parts by weight, the content of metal nickel element
For 5~20 parts by weight, the content of additive is 10~40 parts by weight, and remaining is mesoporous molecular sieve SBA-15；The addition
Agent is citric acid, cetyl trimethylammonium bromide or lauryl sodium sulfate.
2. a kind of Ni-based methanation catalyst being scattered in SBA-15 ducts according to claim 1, it is characterised in that：
The aperture size of the mesoporous molecular sieve SBA-15 is 4.6~30nm, and 3~9nm of pore wall thickness, pore volume is 0.85cm3/g.
3. a kind of Ni-based methanation catalyst being scattered in SBA-15 ducts according to claim 1, it is characterised in that：
The activity component metal nickel element is with NiO or Ni2O3Form exist.
4. a kind of preparation method for the Ni-based methanation catalyst being scattered in SBA-15 ducts, comprises the following steps：
(1) prepare nickel salt solution and add additive；The additive is citric acid, cetyl trimethylammonium bromide or 12
Sodium alkyl sulfate；Wherein, the weight ratio of metal nickel element and additive is 5~20 in the nickel salt solution：10~40；
(2) in the nickel salt solution, mesoporous molecular sieve SBA-15 is impregnated at room temperature step A configuration mixed liquor 2~
12h, first vacuum dried, 30~80 DEG C of temperature after dipping terminates, 5~12 hours time, then fired, temperature is 400~
800 DEG C, 1~10 hour time, Ni-based methanation catalyst is made.
5. a kind of preparation method of Ni-based methanation catalyst being scattered in SBA-15 ducts according to claim 4, its
It is characterised by：Nickel salt in the step (1) is nickel chloride, nickel sulfate, nickel acetate, nickel oxalate or nickel nitrate；It is described
The solvent of nickel salt solution is deionized water, ethanol, acetic acid, chloroform or acetone.
6. a kind of preparation method of Ni-based methanation catalyst being scattered in SBA-15 ducts according to claim 4, its
It is characterised by：Dipping in the step (2) is using excessive infusion process, and dip time is 8~10 hours.
7. a kind of preparation method of Ni-based methanation catalyst being scattered in SBA-15 ducts according to claim 4, its
It is characterised by：Vacuum drying temperature in the step (2) is 40~60 DEG C, and the time is 6~8 hours.
8. a kind of preparation method of Ni-based methanation catalyst being scattered in SBA-15 ducts according to claim 4, its
It is characterised by：The temperature of roasting in the step (2) be 500~600 DEG C, the time is 5~6 hours.
9. application of the Ni-based methanation catalyst in natural gas from coal is prepared according to claim any one of 1-3.
10. application according to claim 10, it is characterised in that：The synthesis gas volume space velocity of the catalyst treatment be 3000~
30000h-1, pressure is normal pressure~3.0Mpa, and temperature is 200~600 DEG C, H in synthesis gas2/ CO ratios are 2~4.
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