CN106824252A - A kind of Ni-based meso-porous titanium dioxide carbon methanation catalyst and preparation method thereof - Google Patents
A kind of Ni-based meso-porous titanium dioxide carbon methanation catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000000969 carrier Substances 0.000 claims abstract description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 18
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 22
- 239000001569 carbon dioxide Substances 0.000 abstract description 16
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 239000002245 particle Substances 0.000 description 8
- WITQLILIVJASEQ-UHFFFAOYSA-N cerium nickel Chemical compound [Ni].[Ce] WITQLILIVJASEQ-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001868 water Inorganic materials 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—Iron group metals or copper
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of Ni-based meso-porous titanium dioxide carbon methanation catalyst and preparation method thereof, prepares Ni-based meso-porous titanium dioxide carbon methanation catalyst by the way of vacuum baking first.Have the beneficial effect that：Ni-based meso-porous titanium dioxide carbon methanation catalyst is prepared using the method for vacuum baking, the catalyst for obtaining has the meso-hole structure of high-sequential, and active component Ni is highly dispersed in the duct of the carriers of SBA 16 in the form of nano particle；Reacted using the catalyst carbon dioxide methanation of above-mentioned preparation（CO2+4H2=CH4+2H2O）, the high conversion rate of carbon dioxide, and it is strong to the selectivity of methane；The step of preparation, is simple, and raw material sources are wide, and economic worth is high.
Description
Technical field
The present invention relates to catalyst preparation technical field, specifically a kind of Ni-based meso-porous titanium dioxide carbon methanation catalyst and
Its preparation method.
Background technology
At present, energy and environment problem has turned into the focus of whole world concern.One is fossil energy discharges a large amount of greenhouses
Greenhouse effects caused by gas, thus cause global warming, ecology, economy, all sectors of society are produced comprehensive negative
Face rings.With the change of global climate, countries in the world are increasingly paid close attention to global greenhouse effect problem.Combustion of fossil fuel is arranged
The a large amount of CO put2It is the main cause for causing Global climate change, its contribution rate to global warming has exceeded 60%.Its
Two is the unsafe factor of the clean energy resource such as nuclear power energy, and production and existence to the mankind bring unprecedented challenge.
How the CO of industrial discharge is effectively reduced2 And convert it into available resources and be particularly important, wherein titanium dioxide
Carbon methanation reaction（CO2+4H2=CH4+2H2O）It is considered as most have one of reaction of application prospect.Methanation reaction is heat release
Reaction, therefore there is reaction equilibrium conversion higher under low temperature, be conducive to CH4Generation.Ni base catalyst can be used for methane
Change reaction.At present, in the prior art, to be primarily present low temperature active for methanation reaction low for Ni bases catalyst, and easily occurs inverse
Water-gas side reaction（CO2+H2=CO+H2O）, the shortcoming of reaction selectivity difference.Current carbon dioxide methanation catalyst needs solution badly
Problem certainly is how to improve the activity and selectivity of catalyst.
Prior art such as Authorization Notice No. is the Chinese invention patent of CN102416324B, discloses a kind of carbon dioxide first
Alkanizing catalyst and its production and use, the catalyst is by biomass power plant ash hybrid metal nickel compound through high-temperature roasting
Form, wherein the percentage by weight of metallic nickel composition is 2~20%.Its preparation method is as follows：1) metallic nickel compounds are prepared
Into the aqueous solution that mass concentration is 5~30%；2) biomass power plant ash is calcined at a temperature of 300~400 DEG C 20~
40min ；3) by catalyst nickel composition percentage by weight convert raw material dosage, take step 1) prepare metallic nickel chemical combination
The biomass power plant ash that the thing aqueous solution is calcined with step 2 mixes, and stirring 5~10h of upset, dipping is uniform；4) by the life after dipping
Material Power Plant Ash dries 0.5~1.5h at a temperature of 110~150 DEG C；5) by dried biomass power plant ash 400 ~
3~6h is calcined at a temperature of 500 DEG C.The method " turns waste into wealth ", and Power Plant Ash twice laid is made into carbon dioxide methane
Change catalyst, but the catalyst activity and selectivity of the method preparation all have much room for improvement.
The content of the invention
It is an object of the invention to provide a kind of meso-hole structure with high-sequential, active particle is small, and decentralization is high, urges
Change activity big, carbon dioxide conversion high Ni-based meso-porous titanium dioxide carbon methanation catalyst and its system strong to methane selectively
Preparation Method.
The problem mentioned for background technology of the present invention, the technical scheme taken is：
A kind of Ni-based meso-porous titanium dioxide carbon methanation catalyst and preparation method thereof, concretely comprises the following steps：
10%Ni-10%CeO2The preparation of/SBA-16 catalyst：Weigh 0.6 ~ 0.8 part of Ni (NO3)2·6H2O, 0.3 ~ 0.5 part of Ce
(NO3)3·6H2O, 0.5 ~ 0.7 part of deionized water and 0.9 ~ 1.2 part of acetone, after mixing, add 1 ~ 2 part of SBA-16, are allowed to fill
Share in the benefit wet；It is put into 55 ~ 65 DEG C of electric drying oven with forced convection, dries 0.8 ~ 1.2h；Load in quartz ampoule after drying, use vavuum pump
It is evacuated, is put into tube type resistance furnace, is warming up to 400 ~ 600 DEG C of 3 ~ 5h of roasting.After being cooled to room temperature, vacuum baking is obtained
10%Ni-10%CeO2/ SBA-16 catalyst.The finished product of the synthesis still meso-hole structure with SBA-16 high-sequentials, and it is living
Property composition Ni is highly dispersed in the duct of SBA-16 carriers in the form of nano particle；Urged using the catalyst of above-mentioned preparation
Change carbon dioxide methanation reaction（CO2+4H2=CH4+2H2O）, the high conversion rate of carbon dioxide, and to the selectivity of methane
By force.
Compared with prior art, the advantage of the invention is that：The finished product of synthesis still Jie with SBA-16 high-sequentials
Pore structure, and active component Ni is highly dispersed in the duct of SBA-16 carriers in the form of nano particle；Using above-mentioned
The catalyst carbon dioxide methanation reaction of preparation（CO2+4H2=CH4+2H2O）, the high conversion rate of carbon dioxide, and it is right
The selectivity of methane is strong；The step of preparation, is simple, and raw material sources are wide, and economic worth is high.
Brief description of the drawings
Fig. 1 is the carbon dioxide conversion comparison diagram of vacuum and the catalyst of roasting under air atmosphere；
Fig. 2 is the methane selectively comparison diagram of vacuum and the catalyst of roasting under air atmosphere；
Fig. 3 is the XRD spectra of the catalyst of vacuum 600 DEG C of roastings lower with air atmosphere.
Description of symbols：Curve 1 is 10%Ni-10%CeO2/ SBA-16-V, curve 2 is 10%Ni-10%CeO2/SBA-16-
Air, curve 3 is 10%Ni-10%CeO2/ SBA-16-V, curve 4 is 10%Ni-10%CeO2/ SBA-16-Air, curve 5 is 10%
Ni-10%CeO2/ SBA-16- Air, curve 6 is 10%Ni-10%CeO2/SBA-16- V。
Specific embodiment
Technical solution of the present invention is described further below by drawings and Examples：
Embodiment 1：
A kind of Ni-based meso-porous titanium dioxide carbon methanation catalyst and preparation method thereof, concretely comprises the following steps：
1）The preparation of SBA-16 carriers：Weigh 10 ~ 15 parts of F127（Triblock copolymer）, 25 ~ 35 parts of n-butanols, 400 ~ 600 parts
Distilled water, 43 ~ 47 DEG C of constant temperature blender with magnetic force stir 0.8 ~ 1.2h to well mixed.Add 15 ~ 20 portions of salt of concentration 35 ~ 40%
Acid, is slowly added dropwise 40 ~ 60 parts of TEOS（Tetraethyl orthosilicate）, 20 ~ 25h is stirred under 43 ~ 47 DEG C of constant temperatures.By mixed solution
It is transferred in reactor, 105 ~ 120 DEG C of 20 ~ 25h of hydro-thermal reaction, is cooled to room temperature, suction filtration is washed 2 ~ 5 times.By white powder
Surface plate is transferred to, 75 ~ 90 DEG C of 10 ~ 15h of drying are put into Muffle furnace, and firing rate is set as 1 ~ 1.5 DEG C/min, from room temperature
550 ~ 600 DEG C are raised to, 3 ~ 5h is calcined, target product SBA-16 carriers are obtained.Carrier not only have pore volume high, high-specific surface area and
Narrow pore distribution, can allow in catalyst activity particle access aperture, make the superincumbent metal dispersity of load high, and aperture
Good heat endurance can be reconciled with wall thickness；The anti-agglutinatting property of catalytic active component is increased, so as to extend catalyst in height
Service life under temperature；
2）10%Ni-10%CeO2The preparation of/SBA-16 catalyst：Weigh 0.6 ~ 0.8 part of Ni (NO3)2·6H2O, 0.3 ~ 0.5 part
Ce(NO3)3·6H2O, 0.5 ~ 0.7 part of deionized water and 0.9 ~ 1.2 part of acetone, after mixing, add 1 ~ 2 part of SBA-16, are allowed to
Fully wetting, factor data is in non-linear, and under the ratio, active component Ni is highly dispersed SBA-16 in the form of nano particle
In the duct of carrier；Ni contents are low, and activity is high, and anti-agglutinatting property is strong, and stability is high, the high conversion rate of carbon dioxide, and side reaction is produced
The yield of thing methane is few；It is put into 55 ~ 65 DEG C of electric drying oven with forced convection, dries 0.8 ~ 1.2h；Load quartz ampoule after drying
It is interior, it is evacuated with vavuum pump, it is put into tube type resistance furnace, it is warming up to 400 ~ 600 DEG C of 3 ~ 5h of roasting.After being cooled to room temperature, obtain
To vacuum baking 10%Ni-10%CeO2/ SBA-16 catalyst.The finished product of the synthesis still mesoporous knot with SBA-16 high-sequentials
Structure, and active component Ni is highly dispersed in the duct of SBA-16 carriers in the form of nano particle；Use above-mentioned preparation
Catalyst carbon dioxide methanation reaction（CO2+4H2=CH4+2H2O）, the high conversion rate of carbon dioxide, and to methane
Selectivity it is strong.
Embodiment 2：
A kind of Ni-based meso-porous titanium dioxide carbon methanation catalyst and preparation method thereof, optimization step is：
1）The preparation of SBA-16 carriers：Weigh 10.0gF127（Triblock copolymer）, 30.0g n-butanols, the distilled water of 475ml,
45 DEG C of constant temperature blender with magnetic force stir 1h to well mixed.The hydrochloric acid of 17.5ml concentration 37% is added, 47.3gTEOS is slowly added dropwise
（Tetraethyl orthosilicate）, 24h is stirred under 45 DEG C of constant temperatures.Mixed solution is transferred in reactor, 110 DEG C of hydro-thermal reactions
24h, is cooled to room temperature, carries out suction filtration, is first washed with deionized 3 times, then is washed 3 times with 5% ethanol, the white powder for obtaining.
White powder is transferred to surface plate, 80 DEG C dry 12h, are put into Muffle furnace, and firing rate is set as 1 DEG C/min, from room temperature
4h is calcined after being raised to 600 DEG C, target product SBA-16 carriers are obtained.
2）10%Ni-10%CeO2The preparation of/SBA-16 catalyst：Weigh 0.6192gNi (NO3)2·6H2O、0.3156g
Ce(NO3)3·6H2O, 0.57ml deionized water and 0.91ml acetone, after mixing, add 1.0gSBA-16, are allowed to fully profit
It is wet；It is put into 60 DEG C of electric drying oven with forced convection, dries 1h；Load in quartz ampoule after drying, be evacuated with vavuum pump, be put into
In tube type resistance furnace, 600 DEG C of roasting 4h are warming up to.After being cooled to room temperature, 600 DEG C of vacuum baking 10%Ni-10%CeO are obtained2/
SBA-16 catalyst（It is designated as 10%Ni-10%CeO2/SBA-16-V）.
Vacuum baking is made into be calcined in atmosphere, above-mentioned experiment is repeated, 10%Ni-10%CeO is obtained2/ SBA-16 is catalyzed
Agent（It is designated as 10%Ni-10%CeO2/SBA-16-Air）.The catalyst for obtaining in vacuum baking as shown in Figure 1 is to carbon dioxide
Conversion ratio is higher；The catalyst for obtaining in vacuum baking as shown in Figure 2 is higher to the selectivity of methane；Vacuum roasting as shown in Figure 3
Burning catalyst diffraction peak intensity is weaker, and half-peak breadth is larger, and nickel cerium particle is smaller in illustrating vacuum baking catalyst, nickel cerium particle
Decentralization is higher, and catalytic effect is more preferable.
Embodiment 3：
A kind of Ni-based meso-porous titanium dioxide carbon methanation catalyst and preparation method thereof, further Optimization Steps are：
1）The preparation of SBA-16 carriers：Weigh 10.0gF127（Triblock copolymer）, 30.0g n-butanols, the distilled water of 475ml,
45 DEG C of constant temperature blender with magnetic force stir 1h to well mixed.The hydrochloric acid of 17.5ml concentration 37% is added, 47.3gTEOS is slowly added dropwise
（Tetraethyl orthosilicate）, 24h is stirred under 45 DEG C of constant temperatures.Mixed solution is transferred in reactor, 110 DEG C of hydro-thermal reactions
24h, is cooled to room temperature, carries out suction filtration, is first washed with deionized 3 times, then is washed 3 times with 5% ethanol, the white powder for obtaining.
White powder is transferred to surface plate, 80 DEG C dry 12h, are put into Muffle furnace, and firing rate is set as 1 DEG C/min, from room temperature
4h is calcined after being raised to 600 DEG C, target product SBA-16 carriers are obtained.
2）10%Ni-10%CeO2The preparation of/SBA-16 catalyst：Weigh 0.6192gNi (NO3)2·6H2O、0.3156g
Ce(NO3)3·6H2O, 0.57ml deionized water and 0.91ml acetone, n-propylamine and β -4- amino benzoyl second dimethylamine（Third
Ketone, n-propylamine and β -4- amino benzoyl second dimethylamine ratio 2：1：1）, n-propylamine and β -4- amino benzoyl second diformazans
Amine is obviously promoted high degree of dispersion nickel cerium, and nickel cerium particle is smaller, and the decentralization of nickel cerium particle is higher, and catalytic effect is more preferably blended
Afterwards, 1.0gSBA-16 is added, fully wetting is allowed to；It is put into 60 DEG C of electric drying oven with forced convection, dries 1h；Load stone after drying
In English pipe, it is evacuated with vavuum pump, is put into tube type resistance furnace, is warming up to 600 DEG C of roasting 4h.After being cooled to room temperature, obtain
600 DEG C of vacuum baking 10%Ni-10%CeO2/ SBA-16 catalyst（It is designated as 10%Ni-10%CeO2/SBA-16-V）.
Vacuum baking is made into be calcined in atmosphere, above-mentioned experiment is repeated, 10%Ni-10%CeO is obtained2/ SBA-16 is catalyzed
Agent（It is designated as 10%Ni-10%CeO2/SBA-16-Air）.The catalyst for obtaining in vacuum baking as shown in Figure 1 is to carbon dioxide
Conversion ratio is higher；The catalyst for obtaining in vacuum baking as shown in Figure 2 is higher to the selectivity of methane；Vacuum roasting as shown in Figure 3
Burning catalyst diffraction peak intensity is weaker, and half-peak breadth is larger, and nickel cerium particle is smaller in illustrating vacuum baking catalyst, nickel cerium particle
Decentralization is higher, and catalytic effect is more preferable.
Catalyst performance is tested：
Above-mentioned catalyst 50mg is taken, is fitted into quartz tube reactor.It is passed through the H of 10ml/min2With the N of 40ml/min2, from 25 DEG C
450 DEG C are warming up to the heating rate of 10 DEG C/min, 40min is reduced.After reduction, 200 degree are cooled to, switching gas is 40ml/
The H of min2, 50ml/min N2With the CO of 10ml/min2Start reaction.Reaction temperature is 200 ~ 450 degree, 50 degree/step, is often walked
Reaction 80min.Reacted tail gas and unstripped gas composition are analyzed using day U.S.'s GC-7900 types gas chromatograph, are detected
Device is thermal conductivity detector (TCD).Test result shows 10%Ni-10%CeO prepared by vacuum baking2/ SBA-16-V better performances, 400 DEG C
Carbon dioxide conversion reaches more than 60%, and methane selectively is higher than 98%.
Routine operation in operating procedure of the invention is well known to those skilled in the art, and is not repeated herein.
Embodiment described above has been described in detail to technical scheme, it should be understood that the above is only
It is specific embodiment of the invention, is not intended to limit the invention, all any modifications made in spirit of the invention,
Supplement or similar fashion replacement etc., should be included within the scope of the present invention.
Claims (8)
1. a kind of Ni-based meso-porous titanium dioxide carbon methanation catalyst, it is characterised in that：10%Ni and 10%CeO are dispersed in mesoporous SiO2
In carrier S BA-16.
2. a kind of Ni-based meso-porous titanium dioxide carbon methanation catalyst according to claim 1, it is characterised in that：Described urges
The preparation process of agent is：Ni(NO3)2·6H2O and Ce (NO3)3·6H2Deionized water, acetone are added in O, after stirring, is added
SBA-16 carriers, dry, vacuum baking, and cooling obtains vacuum baking 10%Ni-10%CeO2/ SBA-16 catalyst.
3. a kind of preparation method of Ni-based meso-porous titanium dioxide carbon methanation catalyst according to claim 2, its feature exists
In：Described Ni (NO3)2·6H2O：Ce(NO3)3·6H2O：Deionized water：The mass volume ratio of acetone is 1g：（0.4~0.6）
g：（0.8~1.1）ml：（1.5~2.0）ml.
4. a kind of preparation method of Ni-based meso-porous titanium dioxide carbon methanation catalyst according to claim 2, its feature exists
In：Stir speed (S.S.) is 200 ~ 400r/min in described step.
5. a kind of preparation method of Ni-based meso-porous titanium dioxide carbon methanation catalyst according to claim 2, its feature exists
In：Described Ni (NO3)2·6H2O：SBA-16 mass ratioes are 1:1.6~1:2.0.
6. a kind of preparation method of Ni-based meso-porous titanium dioxide carbon methanation catalyst according to claim 2, its feature exists
In：Described drying process is that 0.8 ~ 1.2h is dried in 55 ~ 65 DEG C of electric drying oven with forced convection.
7. a kind of preparation method of Ni-based meso-porous titanium dioxide carbon methanation catalyst according to claim 2, its feature exists
In：Described vacuum baking temperature is 400 ~ 600 DEG C, and roasting time is 3 ~ 5h.
8. a kind of preparation method of Ni-based meso-porous titanium dioxide carbon methanation catalyst according to claim 2, its feature exists
In：Described cooling down operation is to naturally cool to room temperature.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110339855A (en) * | 2018-04-03 | 2019-10-18 | 华东理工大学 | A kind of nickel-base catalyst and the preparation method and application thereof |
| CN111514897A (en) * | 2020-05-11 | 2020-08-11 | 泰州禾益新材料科技有限公司 | Application of high-dispersion carbon-doped mesoporous silicon nanotube nickel-based catalyst in carbon dioxide methanation reaction |
| CN113351211A (en) * | 2021-04-20 | 2021-09-07 | 南昌大学 | Cerium dioxide fibrous catalyst containing nickel particles and preparation method thereof |
| CN113351211B (en) * | 2021-04-20 | 2022-11-08 | 南昌大学 | Cerium dioxide fibrous catalyst containing nickel particles and preparation method thereof |
| CN113368862A (en) * | 2021-06-04 | 2021-09-10 | 上海应用技术大学 | Carbon dioxide methanation catalyst and preparation method and application thereof |
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