CN107626314A - A kind of preparation method of the mesoporous Ni-based methanation catalyst of rule - Google Patents
A kind of preparation method of the mesoporous Ni-based methanation catalyst of rule Download PDFInfo
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- CN107626314A CN107626314A CN201710971485.2A CN201710971485A CN107626314A CN 107626314 A CN107626314 A CN 107626314A CN 201710971485 A CN201710971485 A CN 201710971485A CN 107626314 A CN107626314 A CN 107626314A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 15
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 7
- -1 polyoxyethylene Polymers 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000007790 solid phase Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052593 corundum Inorganic materials 0.000 abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 abstract description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 1
- 229960002380 dibutyl phthalate Drugs 0.000 abstract 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000003245 coal Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910011011 Ti(OH)4 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910001679 gibbsite Inorganic materials 0.000 description 3
- 235000011167 hydrochloric acid Nutrition 0.000 description 3
- 239000004579 marble Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N 1-butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 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
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method of the mesoporous Ni-based methanation catalyst of rule,It is using titanium dioxide and alundum (Al2O3) as complex carrier,Nickel oxide is active component,Nickel acetate is used as nickel source,Butyl Phthalate and the raw material that aluminium isopropoxide is complex carrier,Blocked polyethers F 127 and polyoxyethylene polyoxypropylene polyoxyethylene triblock copolymer P123 are composite mould plate agent,Finely dispersed collosol and gel is prepared into by hydrolysis,Through aging,Sintering,The Ni-based methanation catalyst of meso-hole structure is made,Product is powder granule,Being mixed with unstripped gas can quick methanation,The mesoporous of rule increases diffusivity and improves catalyst heat endurance,Effectively anti-agglomeration it can be gathered in caused hot environment during fast reaction,The operation of this preparation method is easy,Simple process is quick,Material mixture ratio is reasonable,Informative data is accurate,Product stability and resistive connection performance are good,It is the preparation method of very good regular mesoporous Ni-based methanation catalyst.
Description
Technical field
The preparation method of the mesoporous Ni-based methanation catalyst of rule of the invention, category natural gas catalyst manufactured by coal prepares and application
Technical field.
Background technology
China be one " rich coal, oil-poor, few gas " country, natural gas from coal not only has good in Waste Era of Oil
Economic benefit, and energy security and environmental protection to safeguarding China are significant.Methanation is natural gas from coal
Important step, it is key link therein to develop efficient methanation catalyst.
Current domestic methanation catalyst with Al2O3For main carriers, but limited in applying by carrier itself, be not easy
Regulating catalyst performance, whole structure is bad, and TiO2As transition metal oxide, there is the property of N-type semiconductor, can be with
The metal for being carried on its surface produces more strong electron interaction, and has influence on absorption and the catalytic performance of catalyst,
But TiO2The intensity of carrier is not high, and pore volume is small, and specific surface area is generally less than 50m2/ g, it is impossible to which good dispersed active metal meets
Catalyst requirement, and the Anatase TiO under high temperature2It is unstable, easily it is changed into Rutile Type, these all limit TiO2With
Make the application of catalyst carrier.Single A12O3Carrier specific surface area is high, intensity is big, good heat stability but activity and mithridatism
All have much room for improvement, single TiO2Carriers Active high and low temperature activity is good, anti-Poisoning is strong but has that intensity is weak, specific surface area
It is low, the shortcomings of pore volume is small, and heat endurance is poor, and finished product is expensive.Combine both, prepare complex carrier and be used for coal day
Right gas methanation catalyst, then can effectively make up these defects while respective advantage is retained.
The content of the invention
For the present invention in order to what is proposed the shortcomings that overcoming above-mentioned prior art to exist, its technical problem solved is to provide one
The preparation method of the mesoporous Ni-based methanation catalyst of kind rule.
In order to solve the above technical problems, the technical solution adopted by the present invention is to provide a kind of mesoporous Ni-based methanation of rule
The preparation method of catalyst.The preparation method of described regular mesoporous Ni-based methanation catalyst comprises the following steps：
（1）Nickel acetate, blocked polyethers F-127 and polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer P123 are added
Into absolute ethyl alcohol, stir until after solid whole dissolving, add concentrated hydrochloric acid and deionized water, stir up to being sufficiently mixed,
Nickel acetate mixed solution is formed, it is stand-by；
（2）Absolute ethyl alcohol is mixed with acetylacetone,2,4-pentanedione, is stirring evenly and then adding into aluminium isopropoxide, then butyl titanate is slowly added dropwise, after
Continue stirring until being well mixed, that is, form butyl titanate and aluminium isopropoxide mixed solution, it is stand-by；
（3）Nickel acetate mixed solution is added in butyl titanate and aluminium isopropoxide mixed solution, stirring is molten up to being fully hydrolyzed
Liquid gradually becomes viscous to form sol gel solution, and blocked polyethers F-127 and polyoxyethylene-poly-oxypropylene polyoxyethylene three are embedding
Section copolymer p 123 is dispersed in sol gel solution；
（4）Sol gel solution is poured into container, ensures that sol gel solution film thickness in below 1mm, is then placed in perseverance
Under constant temperature and humidity environment, temperature is maintained at 30 DEG C, and humidity keeps 60% ± 2%, and aging sol gel solution is until be in solid-phase mixture；
（5）Above-mentioned solid phase mixture is heated at high temperature in the following manner and decomposes roasting：
（Ⅰ）Solid-phase mixture is put under hot environment；
（Ⅱ）Solid-phase mixture is fully contacted with air, the temperature of hot environment is gradually increased to 100 DEG C ± 2 by 20 DEG C
DEG C, 4 DEG C/min of heating rate, constant temperature insulation then proceedes to heat up with 4 DEG C/min of speed until make dry materials, by 100 DEG C by
Edge up to 500 DEG C ± 2 DEG C, constant temperature insulation will carry out decomposition reaction in decomposable process, and treat anti-up to decomposing solid-phase mixture
After should terminating, stop heating, make reaction product naturally cool but to 25 DEG C；
（6）The fine powder then obtained is the mesoporous methanation catalyst of rule.
Further, prepare and obtain the invention provides a kind of preparation method of above-mentioned mesoporous Ni-based methanation catalyst of rule
Application of the regular mesoporous methanation catalyst obtained in methanation reaction.
Present invention also offers a kind of method of methanation, by a kind of above-mentioned mesoporous Ni-based methanation catalyst of rule
The regular mesoporous methanation catalyst that preparation method prepares is reduced, and the regular mesoporous methanation after reduction afterwards is urged
In the presence of agent, synthesis gas is subjected to methanation.
As a preferred scheme of a kind of above-mentioned method of methanation, the mesoporous methanation catalyst of rule is to pass through
What hydrogen was reduced, and reduction temperature is 450 DEG C.
As a kind of above-mentioned another preferred scheme of the method for methanation, the condition of the methanation includes：Temperature is
200-300 DEG C, H in synthesis gas2It is 3 with CO volume ratios.
As a kind of another preferred scheme of the hair method of above-mentioned methanation, the condition of the methanation includes：Temperature is
200-300 DEG C, the H in synthesis gas2And CO2Volume ratio is 4.
Compared with prior art, the beneficial effects of the invention are as follows：The product of the preparation method is powder granule, and aperture exists
Below 20nm, mixed with unstripped gas can quick methanation, it is regular it is mesoporous increase diffusivity and improve catalyst heat endurance,
Effectively anti-agglomeration it can be gathered in caused hot environment during fast reaction, the operation of this preparation method is easy, simple process
Fast, material mixture ratio is reasonable, informative data is accurate, product stability and resistive connection performance are good, is very good regular mesoporous nickel
The preparation method of methylmethane catalyst.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is that high temperature process furnances prepare catalyst condition figure.
Fig. 2 is high temperature process furnances heating-up temperature and time coordinate graph of a relation.
Fig. 3 is a kind of mesoporous Ni-based methanation catalyst product morphology figure of rule.
Fig. 4 is a kind of mesoporous Ni-based methanation catalyst x-ray diffraction intensity collection of illustrative plates of rule.
Fig. 5 is a kind of mesoporous Ni-based methanation catalyst N of rule2Adsorption desorption curve map.
Fig. 6 is a kind of mesoporous Ni-based methanation catalyst evaluation result figure of rule.
In figure：1- high temperature process furnances；2- marble experimental benches；3.- electric cabinets；4- temperature controllers；5- power regulating knobs；6-
Ammeter；7- power switches；8- heating starting buttons；9- voltmeters；10- heats stop button；11- electric power starting indicator lamps；
12- burner on lights；13- bodies of heater；14- refractory insulating layers；15- electrical heating wires；16- quartz ampoules；17- quartz boats；18- catalyst
Product；19- air compressor machines；20- air hoses；21- mass flowmenters；22- air inlet ball valves；23- check (non-return) valves；24- wash bottles；25-NaOH
The aqueous solution.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical scheme will be carried out below
Detailed description.Obviously, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are resulting on the premise of creative work is not made to be owned
Other embodiment, belong to the scope that the present invention is protected.
Technical scheme is described in detail below in conjunction with the accompanying drawings.
As shown in figure 1, the heating of catalyst, calcining, decomposition are carried out in high temperature process furnances, it is in heating, logical sky
Completed under gaseity；High temperature process furnances 1 are vertical, and high temperature process furnances 1 are placed on marble experimental bench 2, are tested in marble
The top of platform 2 is provided with electric cabinet 3, temperature controller 4, power regulating knob 5, ammeter 6, power switch 7, heating on the panel of electric cabinet 3
Start button 8, voltmeter 9, heating stop button 10, electric power starting indicator lamp 11, burner on light 12 couple, and temperature controller 4 is logical
Wire 26 is crossed with the thermocouple 27 in high temperature Muffle furnace 1 and heating furnace silk 15 to couple；The top of electric cabinet 3 is body of heater 13, body of heater
13 top and the bottom are refractory insulating layer 14, and the middle part of refractory insulating layer 14 is electrical heating wire 15, and the middle part of electrical heating wire 15 is quartz ampoule 16,
Quartz boat 17 is placed at the middle part of quartz ampoule 16, is catalyst product 18 in quartz boat 17；The left part of high temperature process furnances 1 is provided with air compressor machine
19, air compressor machine 19 couples with air hose 20, mass flowmenter 21, air inlet ball valve 22, quartz ampoule 16, check (non-return) valve 23, wash bottle 24, and
The input air into the quartz ampoule 16 of high temperature Muffle furnace 1, tail gas are absorbed by the NaOH aqueous solution 25 in wash bottle 24.
All chemical materials that the present invention uses（Selected material）Dosage it is as follows,（Respectively with gram, milliliter, cubic centimetre
For measurement unit, when industrialization is produced, using kilogram, rise, cubic meter is measurement unit）：
Blocked polyethers F-127：EO106PO70EO106 1.50g ±0.01g
Polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer P123：
EO20PO70EO20 0.50g±0.01g
Absolute ethyl alcohol：CH3CH2OH 35mL±1ml
Concentrated hydrochloric acid：HCl 2mL±0.1ml（Mass fraction 37%）
Deionized water：H2O 2mL±0.1ml
Acetylacetone,2,4-pentanedione：CH2(CH3CO)2 2mL±0.1ml
Butyl titanate：Ti(CH3CH2CH2CH2O)4 8.8ml±0.1ml
Aluminium isopropoxide：Al((CH3)2CHO)3 3.21g±0.01g
Nickel acetate：Ni (CH3COO)2·4H2O 4.00g±0.01g
Air：78%N2、21%O2, the 60000cm of other components 1%3±100cm3
The step of preparation method, is as follows：
（1）Prepare nickel acetate mixed solution
By 4.00g ± 0.01g nickel acetates, 1.5g ± 0.01g blocked polyethers F-127 and 0.5g ± 0.01g polyoxyethylene-poly-
Oxypropylene-polyoxyethylene triblock copolymer P123 is added in the beaker of 20mL ± 1ml absolute ethyl alcohols, and stirring 10min treats solid
After being completely dissolved, 2mL ± 0.1ml concentrated hydrochloric acids and 2mL ± 0.1ml deionized waters are then added, stirring 30min makes it fully mixed
Close, form nickel acetate mixed solution, it is stand-by；
（2）Prepare butyl titanate and aluminium isopropoxide mixed solution
15mL ± 0.1ml absolute ethyl alcohols and 2mL ± 0.1ml acetylacetone,2,4-pentanediones are added in beaker and are stirred 10min, is then added
3.21g ± 0.01g aluminium isopropoxides, then 8.8ml ± 0.1ml butyl titanate solution is slowly added dropwise, continue to stir 30min, treat fully
Butyl titanate and aluminium isopropoxide mixed solution are formed after mixing, it is stand-by；
（3）Using peristaltic pump with by nickel acetate mixed solution pump to butyl titanate and aluminium isopropoxide mixed solution, stirring
240min, it is fully hydrolyzed it, solution gradually becomes viscous, blocked polyethers F-127 and PULLRONIC F68-polyoxy second
Alkene triblock copolymer P123 is dispersed in sol gel solution, stand-by；
Hydrolysis equation is as follows：
Ti(CH3CH2CH2CH2O)4 +Al((CH3)2CHO)3 + 7H2O → 3(CH3)2CHOH + 4CH3CH2CH2CH2OH +
Ti(OH)4 ↓ + Al(OH)3↓
In formula：Ti(CH3CH2CH2CH2O)4：Butyl titanate
Al((CH3)2CHO)3：Aluminium isopropoxide
CH3CH2CH2CH2OH：N-butanol
(CH3)2CHOH：Isopropanol
Al(OH)3：Aluminium hydroxide
Ti(OH)4：Metatitanic acid
H2O：Water
（4）Aging
The sol gel solution is poured into stainless steel plate, keeps below sol gel solution film thickness 1mm, then
It is put into constant temperature humidity chamber, temperature is maintained at 30 DEG C, and humidity keeps 60% ± 2%, and aging 240h is in solid-phase mixture.
（5）High-temperature heating decomposes roasting
The high-temperature heating of solid-phase mixture decomposes to be carried out in tube furnace；
（Ⅰ）The high temperature section quartzy product boat for filling solid-phase mixture being put into high temperature process furnances；
（Ⅱ）Open high temperature process furnances, by air compressor into tube furnace input air, air input speed 100cm3/
Min, then begin to warm up, in-furnace temperature is gradually increased to 100 DEG C ± 2 DEG C, 4 DEG C/min of heating rate by 20 DEG C, constant temperature insulation
180min ± 5min, make dry materials, then proceed to 4 DEG C/min of heating rate, 500 DEG C ± 2 DEG C are gradually increased to by 100 DEG C,
Constant temperature is incubated 150min ± 5min, decomposes solid-phase mixture, decomposition reaction will be carried out in decomposable process, equation is as follows：
Ni(CH3COO)2·4H2O+EO20PO70EO20+ EO106PO70EO106+ Al(OH)3 + Ti(OH)4 + O2
NiO+H2O ↑+CO2↑+Al2O3+ TiO2
In formula：Al2O3:Alundum (Al2O3)
TiO2：Titanium dioxide
NiO：Nickel oxide
H2O：Vapor
CO2:Carbon dioxide
Stop heating after reaction, it is down to 25 DEG C with stove natural cooling；Described in Fig. 2, high temperature process furnances heating-up temperature with
Time coordinate graph of a relation, heat and started to warm up by 20 DEG C, be i.e. A points, with 4 DEG C/min speed, rise to 100 DEG C ± 2 DEG C, i.e. B points,
In this thermostatic, insulation 180min ± 2min, i.e. B-C sections, 500 DEG C ± 2 DEG C then are risen to 4 DEG C/min speed again,
That is D points, in this thermostatic, insulation 150min ± 2min, i.e. D-E sections, stop heat temperature raising, it is naturally cooled to stove
25 DEG C, i.e. F points；Heating-up temperature is directly proportional to the time.
（6）Close power supply and air compressor machine, quartzy product boat is taken out in blow-on, the fine powder thing in quartzy product boat, i.e.,：Rule is situated between
Hole methanation catalyst.
An also critically important step is exactly the storage of the product, to the grey-brown powder product storage of preparation in colourless
In bright glass container, sealed storage, be placed in dry, be shady and cool, clean environment, waterproof, sun-proof, anti-acid-alkali salt to corrode, storage
25 DEG C ± 2 DEG C of temperature, relative humidity≤10%.
The product that will be obtained, then detected, chemically examined, analyzed, characterized i.e.：
Color and luster, pattern, composition, chemicals rationality are carried out to the regular mesoporous methanation catalyst powder product to preparation of preparation
Energy, analysis and characterization；
Morphology analysis is carried out with SEM；Fig. 3 show the mesoporous Ni-based methanation catalyst product morphology figure of rule,
Aperture ＜ 20nm are understood in figure.
Crystal phase analysis is carried out with x-ray powder diffraction instrument；As shown in figure 4, it is the Ni-based methanation catalyst product X of high temperature resistant
Ray diffraction intensity collection of illustrative plates, Emission in Cubic NiO characteristic diffraction peak, anatase TiO are shown in figure2Characteristic diffraction peak and γ-
Al2O3Characteristic diffraction peak.
Shown in Fig. 5, for the mesoporous Ni-based methanation catalyst N of rule2Adsorption desorption curve map, in figure：Abscissa is p/po, indulge
Coordinate is adsorption desorption amount.
The performance measurement method of the mesoporous Ni-based methanation catalyst of rule is as follows：
Analytical instrument：GC-950 type gas chromatographs, thermal conductivity cell detector, chromatographic column TDX-01, carrier gas Ar, Main Analysis turn
Change the H in gas2、CO、CH4And CO2；Capillary chromatographic column is Agilent PLOT Al2O3, column internal diameter 0.35mm, column length 50m, point
C in analysis conversion gas2And above higher hydrocarbon；
Catalyst loading amount 1.0g, reactor inside diameter 1.00cm, height 2.50cm is loaded, at 450 DEG C of temperature, is arrived with hydrogen pressure-raising
For 1.0 MPa by catalyst reduction 2 hours, reduction air speed was 2000 h-1；After reduction terminates, hydrogen is disconnected, is passed through reaction in proportion
Gas volume fractions are：H2：CO=3, the total air speed of gaseous mixture are 20000h-1, reacting gas volume ratio is：H2：CO2=4,
The total air speed of gaseous mixture is 20000h-1, methanation reaction is carried out at 200-300 DEG C, evaluation result is as shown in fig. 6, Fig. 6 is situated between for rule
The Ni-based methanation catalyst in hole is in hydrogen and carbon monoxide（Carbon dioxide）Activity evaluation table in reacting gas, can in table
Know：CO conversion of the mesoporous Ni-based methanation catalyst of rule at a temperature of 260 DEG C reaches more than 99.0%, 280
Carbon dioxide conversion at a temperature of DEG C reaches more than 99.0%.
The catalyst of the present invention has good stability, has higher conversion ratio to carbon monoxide and carbon dioxide,
It can meet that the methanation reaction of producing synthesis gas from coal uses, improve the content of methane in product gas, while have compared with high carbon deposition resistance
Ability and anti-caking power, it is the preparation method of very good regular mesoporous Ni-based methanation catalyst.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (6)
- A kind of 1. preparation method of the mesoporous Ni-based methanation catalyst of rule, it is characterised in that：The preparation method includes following Step：Nickel acetate, blocked polyethers F-127 and polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer P123 are added to In absolute ethyl alcohol, stirring adds concentrated hydrochloric acid and deionized water until after solid whole dissolving, and stirring is until be sufficiently mixed, i.e., Nickel acetate mixed solution is formed, it is stand-by；Absolute ethyl alcohol is mixed with acetylacetone,2,4-pentanedione, is stirring evenly and then adding into aluminium isopropoxide, then butyl titanate is slowly added dropwise, continues to stir Mix until well mixed, that is, form butyl titanate and aluminium isopropoxide mixed solution, it is stand-by；Nickel acetate mixed solution is added in butyl titanate and aluminium isopropoxide mixed solution, stirring until be fully hydrolyzed, solution by The sticky formation sol gel solution of gradual change, blocked polyethers F-127 and polyoxyethylene-poly-oxypropylene polyoxyethylene three block are total to Polymers P123 is dispersed in the sol gel solution；Sol gel solution is poured into container, ensures sol gel solution film thickness in below 1mm, is then placed in constant temperature perseverance Under wet environment, temperature is maintained at 30 DEG C, and humidity keeps 60% ± 2%, and aging sol gel solution is until be in solid-phase mixture；Above-mentioned solid phase mixture is heated at high temperature in the following manner and decomposes roasting：（Ⅰ）Solid-phase mixture is put under hot environment；（Ⅱ）Solid-phase mixture is fully contacted with air, the temperature of hot environment is gradually increased to 100 DEG C ± 2 by 20 DEG C DEG C, 4 DEG C/min of heating rate, constant temperature insulation then proceedes to heat up with 4 DEG C/min of speed until make dry materials, by 100 DEG C by Edge up to 500 DEG C ± 2 DEG C, constant temperature insulation will carry out decomposition reaction in decomposable process, and treat anti-up to decomposing solid-phase mixture After should terminating, stop heating, make reaction product naturally cool but to 25 DEG C；The fine powder then obtained is the mesoporous methanation catalyst of rule.
- 2. the regular mesoporous first that a kind of preparation method of the mesoporous Ni-based methanation catalyst of rule described in claim 1 prepares Application of the Alkanizing catalyst in methanation reaction.
- A kind of 3. method of methanation, it is characterised in that by a kind of mesoporous Ni-based methanation catalyst of rule described in claim 1 The regular mesoporous methanation catalyst for preparing of preparation method reduced, the regular mesoporous methanation after reduction afterwards In the presence of catalyst, synthesis gas is subjected to methanation.
- A kind of 4. method of methanation according to claim 3, it is characterised in that the mesoporous methanation catalyst of rule Logical hydrogen is reduced, and reduction temperature is at 450 DEG C.
- 5. the method for a kind of methanation according to claim 3 or 4, it is characterised in that the condition of the methanation includes： Temperature is 200-300 DEG C, H in synthesis gas2It is 3 with CO volume ratios.
- 6. the method for a kind of methanation according to claim 3 or 4, it is characterised in that the condition of the methanation includes： Temperature is 200-300 DEG C, H in synthesis gas2And CO2Volume ratio is 4.
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