CN105618061A - Slurry bed carbon dioxide methanation bimetallic catalyst and preparation method and application thereof - Google Patents
Slurry bed carbon dioxide methanation bimetallic catalyst and preparation method and application thereof Download PDFInfo
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- CN105618061A CN105618061A CN201610062032.3A CN201610062032A CN105618061A CN 105618061 A CN105618061 A CN 105618061A CN 201610062032 A CN201610062032 A CN 201610062032A CN 105618061 A CN105618061 A CN 105618061A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 38
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 28
- 239000002002 slurry Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229920000428 triblock copolymer Polymers 0.000 claims description 4
- PKQYSCBUFZOAPE-UHFFFAOYSA-N 1,2-dibenzyl-3-methylbenzene Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=CC=1CC1=CC=CC=C1 PKQYSCBUFZOAPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 2
- 230000008020 evaporation Effects 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 238000000802 evaporation-induced self-assembly Methods 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 30
- 230000000694 effects Effects 0.000 description 11
- 239000000523 sample Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000001338 self-assembly Methods 0.000 description 5
- 238000000935 solvent evaporation Methods 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/647—
-
- 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
Abstract
The invention relates to a bimetallic catalyst applied to slurry bed carbon dioxide methanation, a preparation method of the bimetallic catalyst and application of the bimetallic catalyst in slurry bed carbon dioxide methanation. A regular-mesoporous nickel-cobalt bimetallic alumina catalyst is prepared in one step through an evaporation induced self-assembly method. The bimetallic catalyst is composed of, by mass, 20-60 wt.% of active component Ni, 0.1-8 wt.% of active component Co and 39-78 wt.% of alumina carrier, specific surface area of the prepared catalyst is 100-500 m<2>/g, pore volume is 0.2-1.0 cm<3>/g, and pore diameter is 5-15 nm. The bimetallic catalyst is simple in preparation process, the active components nickel and cobalt in the catalyst are dispersed on the carrier surface and in pores more uniformly, and interaction between the active components and the carrier is enhanced; when the catalyst is applied under reaction conditions of slurry bed carbon dioxide methanation, CO2 conversion rate can be up to 81.5%, CH4 selectivity can be up to 99.7% or above.
Description
Technical field
The present invention relates to a kind of bimetallic catalyst being applied to slurry bed system carbon dioxide methanation, belong to gas chemical industry and technical field of coal chemical industry. Moreover, it relates to the preparation method of this bimetallic catalyst, and its application in slurry bed system carbon dioxide methanation reacts.
Background technology
Methane is a kind of important fuel and chemical intermediate. In recent years, along with increasing sharply of China's natural gas demand, the insufficiency of supply-demand of domestic natural gas resource is gradually increased. Converting coal into synthesis gas and to prepare synthetic natural gas by methanation reaction be alleviate one of important channel of natural gas breach, in this process, methanation technology is crucial. Coke-stove gas is the mixing gas produced after the dry distillation of coal, wherein contains higher hydrogen content 5560%, methane 2327%, carbon monoxide 5.08.0%, carbon dioxide 2.04.0%, nitrogen 2.06.0% and other a small amount of gases, resource had both been wasted in coke-stove gas burning and exhausting or directly discharge, contaminated environment again, carry out methanation reaction hence with the supplementary carbon dioxide wherein of the hydrogen of high-load in coke-stove gas and produce natural gas, it is possible not only to improve the calorific value of coke-stove gas, it is also possible to significantly improve resource utilization. The reaction equation of hydrogenation of carbon dioxide synthesizing methane is as follows:
CO2+4H2=CH4+2H2O��H0=-165kJ/mol
At present, the research for synthesis gas or CO methanation reaction is a lot, and most of methanation catalyst is also develop for synthesis gas or CO methanation reaction system, but to CO2It is less that hydrogenation synthesis methane reaction is then studied, and is especially adapted for use in slurry bed system CO2The research of the catalyst of hydrogenation synthesis methane is then relatively less.
Ni-Co bimetallic catalyst is widely used to energy conversion field at present, and especially CO is hydrogenated with methanation, CH4Reformation CO2Reaction. Reacting for carbon dioxide methanation, nickel cobalt bimetallic catalyst is compared with monometallic nickel-base catalyst, and bimetallic catalyst can be remarkably reinforced CO2The methanation activity of hydrogenation and stability. At present, cobalt improved Ni/SiO prepared by infusion process is adopted2Though catalyst can improve the fixing bed CO of catalyst2Methanation activity, but catalyst prepared by this method there is also some defects, as active component interacts weak with carrier, granule is relatively big and less stable during catalyst longtime running. For intensively stirred slurry bed system methanation reaction, it is easy to fall off that active component is easily caused active component when interacting more weak with carrier, reduces the stability of catalyst.
Summary of the invention
The present invention seeks to the situation for background technology and deficiency, prepare with aluminium oxide for carrier by solvent evaporation induced self-assembly one step, with metallic nickel and metallic cobalt for catalyst activity component, regular mesoporous nickel cobalt bimetallic catalyst suitable in slurry bed system carbon dioxide methanation and stable in catalytic performance, the method is simple, drastically increases the utilization ratio of the energy.
To achieve these goals, the invention provides following technical scheme.
The bimetallic catalyst of a kind of slurry bed system carbon dioxide methanation, it consists of by mass percentage: Ni active component 2060wt.%, Co active component 0.18wt.%, alumina support 3978wt.%; Described catalyst is prepared by solvent evaporation induced self-assembly one step.
The bimetallic catalyst of slurry bed system carbon dioxide methanation as above, wherein: nickel active component is prepared by evaporation induced self-assembly one step by a kind of precursor salt in nickel nitrate, nickel acetate or nickel acetylacetonate; Cobalt active component is prepared by evaporation induced self-assembly method by a kind of precursor salt in cobalt nitrate, cobalt acetate and acetylacetone cobalt (II); Alumina support is prepared by evaporation induced self-assembly method by aluminum isopropylate. or aluminium secondary butylate precursor salt.
The preparation method of the bimetallic catalyst of a kind of slurry bed system carbon dioxide methanation, comprises the steps:
(1) it is 3 by qualityIt is 60 that the template of 4 parts is dissolved in qualityIn the dehydrated alcohol of 65 parts, at room temperature stir 46h obtains mixed solution, adds 13 in above-mentioned mixed solution14 parts of mass percents are the salpeter solution of 65%, and the pH value controlling solution is 23, obtain mixed solution (1);
(2) weighing quality is 37 parts of aluminum isopropylate. or aluminium secondary butylate add mixed solution (1), be stirred well to aluminum isopropylate. or aluminium secondary butylate is completely dissolved, obtain white clear solution (2);
(3) it is 2 by quality10 parts of nickel precursor salt and 0.011 portion of cobalt precursor salt joins in (2) solution, stirs 5 under room temperature10h, is transferred to above-mentioned solution baking oven afterwards and dries 48 at 60 DEG C60h, obtains after solid sample 450Roasting at 750 DEG C, grinds the sample after roasting, is screened to 80250 orders, obtain catalyst precursor;
(4) catalyst precursor of above-mentioned preparation is carried out in fixed bed reactors reduction 310h, namely obtains the regular mesoporous nickel cobalt bimetallic catalyst that active component is W metal and metal Co.
The preparation method of the bimetallic catalyst of slurry bed system carbon dioxide methanation as above, template adopts triblock copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer (P123); Described nickel salt presoma selects a kind of compound in nickel nitrate, nickel acetate or nickel acetylacetonate; Described cobalt salt presoma selects a kind of compound in cobalt nitrate, cobalt acetate and acetylacetone cobalt (II).
The preparation method of the bimetallic catalyst of slurry bed system carbon dioxide methanation as above, described reducing gas is consisted of 30 by volume90% hydrogen and 1070% nitrogen, is 1000 in air speedReduce under 6000ml/(g h) condition.
Above-mentioned bimetallic catalyst is applied to paste state bed reactor and carries out carbon dioxide methanation reaction, it is characterized in that, synthetic conduction oil dibenzyl toluene big with heat conductivity, that thermal capacitance is big, boiling point is high is solvent, add a certain amount of catalyst, control the ratio of suitable unstripped gas, then according to following reaction condition carries out methanation reaction: the addition of catalyst is 0.00830.04gCatalyst/mlSolvent; Unstripped gas H2/CO2Volume ratio is 3.55; Reaction temperature 220350 DEG C; Reaction pressure 1.04.0MPa; Air speed 10006000mL/(g h); Stir speed (S.S.) is 5001200 rpms.
A kind of method that the invention discloses regular mesoporous nickel cobalt bimetallic catalyst utilizing solvent evaporation induced self-assembly method one step to prepare, active high stability good feature, be particularly suited for paste state bed reactor carbon dioxide methanation reaction. Compared with preparing nickel-base catalyst preparation process with traditional infusion process or sol-gal process, the substantive distinguishing features that the present invention has and progress are in that:
(1) present invention adopts solvent evaporation induced self-assembly method one step to prepare the regular mesoporous nickel cobalt bimetallic catalyst of alumina load type, confinement effect due to aluminium oxide duct, the growth of nanoparticles on carrier can be controlled, can effectively stop the reunion of active component crystal grain, improve the dispersion of active component.
(2) solvent evaporation induced self-assembly method of the present invention is adopted to prepare catalyst, with nonionic surfactant for template, one-step synthesis ordered mesoporous aluminium oxide loaded catalyst, the interaction of catalyst carrier and active component can be strengthened, due to problem that the continuously stirred active component caused comes off when solving slurry reactor.
(3) compared with the single metallic nickel based metal catalysts prepared by sol-gal process, catalyst prepared by the inventive method is by adding the second active component cobalt, make generation synergism between nickel and cobalt, promote the dispersion of W metal, strengthen the interaction of carrier and active component, when further increasing slurry reactor, CO2The catalysis activity of methanation catalyst, CO2Conversion ratio may be up to 81.5%, CH4Selectivity reaches more than 99.7%, and catalysis activity is substantially better than the catalyst prepared by sol-gal process before tradition infusion process or improvement.
Detailed description of the invention
Further describe the preparation method disclosed in this patent below by specific embodiment, but the present invention is not by the restriction of following embodiment. The present invention is with the performance probe reaction that reaction is catalyst of carbon dioxide and hydrogen synthesizing methane.
Embodiment 1
Being be completely dissolved in after quality is 64 parts of dehydrated alcohol under 4.1 parts of P123 room temperatures by quality, be added thereto to the nitric acid that quality is 14 part 65%, the pH value controlling solution is 23, then be that 8.5 parts of aluminium secondary butylates add in above solution by quality, stir under room temperature and be completely dissolved to it. Being subsequently adding quality is stirring 5h under 1.8 parts of nickel acetates and 0.84 part of cobalt nitrate room temperature, moves into afterwards after drying 48h at 60 DEG C in baking oven, puts into 550 DEG C of roasting 6h in Muffle furnace, the sample after roasting grinds pelletize to 140200 orders, in fixing bed 500 DEG C, volume consists of 30%H2With 70%N2, air speed is reduction 6h under 6000mL/(g h) condition, namely obtains methanation nickel-base catalyst. The quality group of this catalyst components becomes: active component Ni20wt.%, active component Co8wt.%, Al2O372wt.%. The specific surface area of prepared catalyst is 436m2/ g, pore volume is 0.57cm3/ g, aperture 10.8nm.
Catalyst activity rating actual conditions in carbon dioxide methane reaction and result see attached list 1. Specifically comprise the following steps that
The above-mentioned catalyst of certain mass and 120mL dibenzyl toluene mixed liquor are injected in the reactor of 250mL paste state bed reactor. At ambient temperature, N is used2It is pressurized to reaction pressure to system, is then warming up to reaction temperature with 5 DEG C/min, then pass into 20mL/minCO to reactor simultaneously2With a certain amount of H2, and under certain stir speed (S.S.), start reaction, terminate after reaction a period of time.
Embodiment 2
Being be completely dissolved in after quality is 64 parts of dehydrated alcohol under 4.0 parts of P123 room temperatures by quality, be added thereto to the nitric acid that quality is 14 part 65%, the pH value controlling solution is 23. It is that 6 parts of aluminum isopropylate. add in above solution by quality again, stirs under room temperature and be completely dissolved to it. Being subsequently adding quality is stirring 6h under 3.15 parts of nickel nitrates and 0.45 part of cobalt acetate room temperature, moves into afterwards after drying 60h at 60 DEG C in baking oven, puts into 500 DEG C of roasting 8h in Muffle furnace, the sample after roasting grinds pelletize to 100140 orders, in fixing bed 600 DEG C, volume consists of 40%H2With 60%N2, air speed is reduction 4h under 4500mL/(g h) condition, namely obtains methanation nickel-base catalyst. This catalyst consists of: active component Ni30wt.%, active component Co5wt.%, Al2O365wt.%. The specific surface area of prepared catalyst is 392m2/ g, pore volume is 0.59cm3/ g, aperture 7.7nm.
Catalyst preparing methane by synthetic gas react in activity rating actual conditions and result see attached list 1. Concrete steps are as described in Example 1.
Embodiment 3
Being be completely dissolved in after quality is 63 parts of dehydrated alcohol under 3.9 parts of P123 room temperatures by quality, be added thereto to the nitric acid that quality is 14 part 65%, the pH value controlling solution is 23. It is that 6.15 parts of aluminium secondary butylates add in above solution by quality again, stirs under room temperature and be completely dissolved to it. Being subsequently adding quality is stirring 7h under 3.7 parts of nickel acetylacetonates and 1.9 parts of acetylacetone cobalt room temperatures, moves into afterwards after drying 50h at 60 DEG C in baking oven, puts into 650 DEG C of roasting 6h in Muffle furnace, the sample after roasting grinds pelletize to 200250 orders, in fixing bed 650 DEG C, volume consists of 60%H2With 40%N2, air speed is reduction 4h under 3000mL/(g h) condition, namely obtains methanation nickel-base catalyst. This catalyst consists of: active component Ni40wt.%, active component Co2wt.%, Al2O358wt.%. The specific surface area of prepared catalyst is 352m2/ g, pore volume is 0.71cm3/ g, aperture 8.6nm.
Catalyst preparing methane by synthetic gas react in activity rating actual conditions and result see attached list 1. Concrete steps are as described in Example 1.
Embodiment 4
Being be completely dissolved in after quality is 62 parts of dehydrated alcohol under 3.9 parts of P123 room temperatures by quality, be added thereto to the nitric acid that quality is 13.6 part 65%, the pH value controlling solution is 23. It is that 4.3 parts of aluminum isopropylate. add in above solution by quality again, stirs under room temperature and be completely dissolved to it. Being subsequently adding quality is stirring 8h under 4.7 parts of nickel acetylacetonates and 0.07 part of cobalt acetate room temperature, moves into afterwards after drying 48h at 60 DEG C in baking oven, puts into 450 DEG C of roasting 6h in Muffle furnace, the sample after roasting grinds pelletize to 80100 orders, in fixing bed 700 DEG C, volume consists of 75%H2With 25%N2, air speed is reduction 4h under 2000mL/(g h) condition, namely obtains methanation nickel-base catalyst. This catalyst consists of: active component Ni50wt.%, active component Co0.8wt.%, Al2O349.2wt.%. The specific surface area of prepared catalyst is 237m2/ g, pore volume is 0.57cm3/ g, aperture 5.6nm.
Catalyst preparing methane by synthetic gas react in activity rating actual conditions and result see attached list 1. Concrete steps are as described in Example 1.
Embodiment 5
Being be completely dissolved in after quality is 60 parts of dehydrated alcohol under 3.8 parts of P123 room temperatures by quality, be added thereto to the nitric acid that quality is 13.4 part 65%, the pH value controlling solution is 23. It is that 3.4 parts of aluminum isopropylate. add in above solution by quality again, stirs under room temperature and be completely dissolved to it. Being subsequently adding quality is stirring 10h under 6.3 parts of nickel nitrates and 0.03 part of acetylacetone cobalt room temperature, moves into afterwards after drying 60h at 60 DEG C in baking oven, puts into 750 DEG C of roasting 3h in Muffle furnace, the sample after roasting grinds pelletize to 140200 orders, in fixing bed, 600 DEG C, volume consists of 90%H2With 10%N2, air speed is reduction 6h under 1000mL/(g h) condition, namely obtains methanation nickel-base catalyst. This catalyst consists of: active component Ni60wt.%, active component Co0.3wt.%, Al2O339.7wt.%. The specific surface area of prepared catalyst is 186m2/ g, pore volume is 0.32cm3/ g, aperture 7.9nm.
Catalyst preparing methane by synthetic gas react in activity rating actual conditions and result see attached list 1. Concrete steps are as described in Example 1.
Table 1
Claims (8)
1. a regular mesoporous nickel cobalt bimetallic catalyst for slurry bed system carbon dioxide methanation, by mass percentage, it consists of: active component nickel 2060wt.%, active component cobalt 0.18wt.%, alumina support 3978wt.%; The specific surface area of described catalyst is 100500m2/ g, pore volume is 0.21.0cm3/ g, aperture 515nm��
2. the regular mesoporous nickel cobalt bimetallic catalyst of slurry bed system carbon dioxide methanation according to claim 1, it is characterised in that in described catalyst, the precursor salt of nickel active component is the one in nickel nitrate, nickel acetate or nickel acetylacetonate; The precursor salt of cobalt active component is the one in cobalt nitrate, cobalt acetate and acetylacetone cobalt (II); The precursor salt of alumina support is aluminum isopropylate. or aluminium secondary butylate.
3. a preparation method for the regular mesoporous nickel cobalt bimetallic catalyst of slurry bed system carbon dioxide methanation described in claim 1, comprises the steps:
1) it is 3.5 by qualityIt is 60 that the template of 4.5 parts is dissolved in qualityIn the dehydrated alcohol of 65 parts, at room temperature stir 46h obtains mixed solution, adds 13 in above-mentioned mixed solution14 parts of mass percents are the salpeter solution of 65%, and the pH value controlling solution is 23, obtain mixed solution;
2) weighing quality is 37 parts of aluminum isopropylate. or aluminium secondary butylate add step 1) gained mixed solution, are stirred well to and are completely dissolved, obtain white clear solution;
3) it is 1.5 by quality7 parts of nickel precursor salt and 0.012 portions of cobalt precursor salt join step 2) in gained solution, it is stirred well under room temperature and is completely dissolved, afterwards above-mentioned solution evaporation is fallen solvent, obtain solid sample, then again by gained solid sample roasting, grinding, sieve, obtain catalyst precursor;
4) catalyst precursor prepared by step 3) is carried out in fixed bed reactors reduction 46h, namely obtains the regular mesoporous nickel cobalt bimetallic catalyst that active component is W metal and metal Co.
4. the preparation method of the regular mesoporous nickel cobalt bimetallic catalyst of slurry bed system carbon dioxide methanation according to claim 3, it is characterized in that, in step 3), described template adopts triblock copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer (P123); In step 3), described nickel salt presoma selects the one in nickel nitrate, nickel acetate or nickel acetylacetonate, and described cobalt salt presoma selects the one in cobalt nitrate, cobalt acetate and acetylacetone cobalt (II).
5. the preparation method of the regular mesoporous nickel cobalt bimetallic catalyst of slurry bed system carbon dioxide methanation according to claim 3, it is characterised in that in step 3), the time of described stirring is 510h, the described dry process evaporating solvent dries 48 for solution is transferred to baking oven at 60 DEG C60h, the temperature of the roasting of described solid sample is 450750 grades
6. the preparation method of the regular mesoporous nickel cobalt bimetallic catalyst of slurry bed system carbon dioxide methanation according to claim 3, it is characterised in that described reducing gas is consisted of 30 by volume90% hydrogen and 1070% nitrogen, is 1000 in air speedUnder 6000mL/(g h) condition, reduction prepares.
7. the preparation method of the regular mesoporous nickel cobalt bimetallic catalyst of slurry bed system carbon dioxide methanation according to claim 3, it is characterised in that the granularity of described catalyst is 80250 orders, the specific surface area of prepared catalyst is 100500m2/ g, pore volume is 0.21.0cm3/ g, aperture 515nm��
8. the application of the regular mesoporous nickel cobalt bimetallic catalyst of slurry bed system carbon dioxide methanation described in a claim 1, it is characterized in that, inertia synthetic conduction oil dibenzyl toluene big with heat conductivity, that thermal capacitance is big, boiling point is high is solvent, add a certain amount of catalyst, control the ratio of suitable unstripped gas, then according to following reaction condition carries out methanation reaction: the addition of catalyst is 0.0050.05gCatalyst/mLSolvent; Unstripped gas H2/CO2Volume ratio is 3.55; Reaction temperature 220350 DEG C; Reaction pressure 1.04.0MPa; Air speed 10006000mL/(g h); Stir speed (S.S.) is 5001200 rpms.
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