CN107497441A - A kind of carbon dioxide methanation catalyst and its application - Google Patents
A kind of carbon dioxide methanation catalyst and its application Download PDFInfo
- Publication number
- CN107497441A CN107497441A CN201710737300.1A CN201710737300A CN107497441A CN 107497441 A CN107497441 A CN 107497441A CN 201710737300 A CN201710737300 A CN 201710737300A CN 107497441 A CN107497441 A CN 107497441A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carbon dioxide
- content
- methanation catalyst
- dioxide methanation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 57
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 239000008246 gaseous mixture Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 235000015424 sodium Nutrition 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 37
- 230000004913 activation Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000003610 charcoal Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical class O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 150000001243 acetic acids Chemical class 0.000 description 3
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 3
- 235000011162 ammonium carbonates Nutrition 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of carbon dioxide methanation catalyst and its application, belong to heterogeneous catalysis field.Catalyst includes active component cobalt and the titania support by additive modification, and the content of the active component cobalt is 5%~40%, and the content of the auxiliary agent is 0.1%~15%.The catalyst of the present invention has preferable low temperature matching in carbon dioxide methanation reaction, reaction temperature for 140~500 DEG C when, titanium dioxide charcoal percent conversion is higher, and methane selectively is close to 100%.Catalyst synthesis processes are simple, easy to operate, and energy effective activation carbon dioxide molecule, reaction condition is gentleer, and reaction rate is good.The catalyst of the present invention can efficient for carbon dioxide discharge-reduction field, meet green chemical concept and be easily achieved industrialization.
Description
【Technical field】
The present invention relates to heterogeneous catalysis field, relates in particular to a kind of carbon dioxide methanation catalyst and its application.
【Background technology】
It is well known that due to industrial expansion and the frequent activity of the mankind, the discharge capacity of carbon dioxide increasingly increases in air
Greatly, caused global warming has threatened the inhabitation living environment of the mankind, and therefore, the discharge to carbon dioxide is controlled
It is the emphasis studied at present with conversion.It is considered as a kind of efficient carbon dioxide conversion side that hydrogenation of carbon dioxide, which is converted into methane,
Formula, it so can both alleviate the discharge capacity of carbon dioxide, can obtain methane product again.Methane is the main component of natural gas, is led to
The crisis of lack of energy in the world can be alleviated to a certain extent by crossing the mode synthesizing methane of hydrogenation of carbon dioxide.Therefore, develop
Efficient carbon dioxide methanation catalyst is most important.
In recent decades, the research of methanation catalyst is concentrated mainly on non-noble metal Ni and noble metal Ru, Rh, Pt etc.
For active component, with Al2O3、SiO2、ZrO2、CeO2And molecular sieve etc. is carrier, research shows, these common catalyst are equal
With more excellent methanation performance.Noble metal catalyst generally has a preferable low temperature active, and with Ni base catalyst phases
Than limiting its extensive use with more preferable anti-carbon performance, but because noble metal such as Ru, Rh, Pt etc. are expensive.It is non-
Noble metal such as Ni, Co not only have excellent activity, and price is cheap, therefore before there is wider researching value and commercial Application
Scape.
At present, on Co base catalyst in CO2The also rare report of application in methanation.Publication No. CN 102941098
A Chinese invention patent prepares composite oxides Eu using combustion method2O3-Co3O4-ZrO2, and it is used for CO2Methanation reaction, knot
Fruit shows CO2Conversion ratio be only 20%~30%, methane selectively be 95% or so；The A's of Publication No. CN 103551153
The Co bases catalyst of Chinese invention patent report is shown preferably in 400 DEG C of reaction temperature, 4.0~6.0MPa of reaction pressure
CO2Methanation activity, but reaction condition is more harsh, does not meet the policy of energy-saving and emission-reduction.
Although the Ni bases catalyst used in carbon dioxide methanation industrially has the application of small range, prior art
Still suffer from catalyst easily inactivate, severe reaction conditions and CO2The not high technical problem of conversion ratio.
【The content of the invention】
The goal of the invention of the present invention is：In view of the above-mentioned problems, a kind of carbon dioxide methanation catalyst is provided and its answered
With a kind of cobalt-base catalyst for carbon dioxide methanation of exploitation, to solve CO2Conversion ratio is not high and severe reaction conditions
The problems such as, also, the catalyst that the present invention uses can strengthen inert molecule CO to a certain extent2Activation capacity.
The present invention is achieved by the following technical solutions：
A kind of carbon dioxide methanation catalyst, including active component cobalt and the titania support by additive modification,
With elemental metal, the content of the active component cobalt is 5%~40%, and the content of the auxiliary agent is 0.1%~15%, described
Content on the basis of the weight of catalyst carrier.The preparation method of catalyst comprises the following steps：
(1) preparation of additive modification titania support
Sol-gal process：It is 1 by volume by butyl titanate and absolute ethyl alcohol:1~2 is hybridly prepared into mixed solution A；
It is 1~2 by volume by glacial acetic acid, absolute ethyl alcohol and deionized water:1~2:1 is mixed, and is added quality and is accounted for above-mentioned metatitanic acid four
The auxiliary agent of butyl ester quality 0.025%~3.75%, stirring and dissolving are configured to mixed solution B, in 400~600r/min stirring speed
Under degree, the mixed solution B is slowly dropped into the mixed solution A, persistently stirs 0.5~1h after dripping off, still aging 3~
10h forms gel, and gel is placed at 80~110 DEG C and dries 10~24h, is ground to below 100 mesh, 300 in Muffle furnace
3~5h is calcined at~700 DEG C and obtains the titania support of additive modification；
(2) preparation of catalyst
Deposition-precipitation method：It is 0.2~2 by mass ratio:1:50 cobalt nitrate hexahydrate, above-mentioned modifying titanium dioxide carrier and go
Ionized water is hybridly prepared into suspension, stirs 1~2h, then 0.5~1.0mol/L aqueous slkali is slowly dropped into above-mentioned suspension
In, until the pH value of solution increases to 9~10, continue 2~3h of stirring, then 1~2h is stood, the filter cake that filtered, washing obtains exists
10~24h is dried at 100~120 DEG C, is ground to 20~40 mesh, 3~5h is calcined in Muffle furnace 400~550 DEG C and is obtained
Catalyst.
Further, the content of the active component cobalt is 10%~30%；The content of the auxiliary agent is 0.5%~5%.
Further, described auxiliary agent is at least one of calcium, scandium, rubidium, strontium, yttrium, zirconium, cerium.
Further, the aqueous slkali is one in sodium hydroxide, potassium hydroxide, ammoniacal liquor, ammonium carbonate or sodium carbonate liquor
Kind.
Reagent specification used in the present invention is that analysis is pure.
A kind of application for carbon dioxide methanation catalyst：The catalyst of the mesh of 0.2g 20~40 is taken to be placed in fixed bed
In reactor, first by catalyst at 400 DEG C hydrogen reducing 3h, then switch to the mixing of unstripped gas hydrogen and carbon dioxide
Gas is reacted, and reaction condition is：Normal pressure, temperature are 140~500 DEG C, unstripped gas air speed is 2000~10000h-1, Yi Jiyuan
Expect that hydrogen and carbon dioxide volume ratio are 4 in gas:1.The product of the reaction is methane and carbon monoxide.
Compared with prior art, the device have the advantages that being：
1. the present invention uses active component of the base metal cobalt for catalyst, there is stronger anti-mistake compared to Ni base catalyst
Viability, price is cheaper compared with noble metal catalyst.
2. the present invention is modified using auxiliary agent to titania support, the specific surface area of carrier is increased, while make load
Body surface face produces more Lacking oxygens, and this can promote CO to a certain extent2The activation of molecule, so as to improve CO2Conversion ratio.
3. catalyst is in CO in the present invention2There is preferable low temperature matching in methanation reaction, be 140 in reaction temperature
At~500 DEG C, CO2Conversion ratio it is higher, methane selectively is close to 100%.
, can effective activation CO 4. catalyst synthesis processes are simple in the present invention, easy to operate2Molecule, reaction condition temperature
With reaction rate is good.
【Embodiment】
All features disclosed in this specification, or disclosed all methods or during the step of, except mutually exclusive
Feature and/or step beyond, can combine in any way.
Any feature disclosed in this specification (including any accessory claim, summary), unless specifically stated otherwise,
Replaced by other equivalent or with similar purpose alternative features.I.e., unless specifically stated otherwise, each feature is a series of
An example in equivalent or similar characteristics.
Embodiment 1
(1) a kind of 5%Co/0.1%Y-TiO2The preparation method of catalyst, comprises the following steps：
0.1%Y-TiO2Preparation：Measure 20mL butyl titanates respectively and 20mL absolute ethyl alcohols to be mixed to form mixing molten
Liquid A, then measure 10mL absolute ethyl alcohols, 10mL glacial acetic acids and 5mL water respectively and mixed, the nitric hydrate yttriums of 0.0048g six are added,
Stirring and dissolving is configured to mixed solution B.Mixed solution B is slowly dropped into mixed solution A in the case where rotating speed is 400r/min, dripped off
After continue to stir 30min, still aging 3h forms gel, then gel is placed at 80 DEG C and dries 10h, is ground to below 100 mesh,
3h is calcined in Muffle furnace 300 DEG C and obtains 0.5%Y-TiO2Carrier.
5%Co/0.1%Y-TiO2Preparation：0.46g cabaltous nitrate hexahydrates and 2.20g 0.1%Y-TiO are weighed respectively2Carry
Body, which is dissolved in 100mL deionized waters, is configured to mixing suspension, stirs 1h.Weigh 0.94g ammonium carbonates and be dissolved in 20mL deionized waters
In, obtain the sal volatile that concentration is 0.5mol/L, then this aqueous slkali is slowly dropped into above-mentioned mixing suspension until
PH is 9.0.Continuing to stir 2h, then stand 1h, the filter cake that filtered, washing obtains dries 10h at 100 DEG C, it is ground to 20~
40 mesh, it is to obtain 5%Co/0.1%Y-TiO that 3h is calcined in Muffle furnace 400 DEG C2Catalyst.
(2) activity rating of catalyst
Take the 5%Co/0.1%Y-TiO that 0.2g particle diameters are 20~40 mesh2Catalyst is placed in fixed bed reactors, first
With H2For also Primordial Qi, after reducing 3h at 400 DEG C, switch CO2And H2For unstripped gas, carbon dioxide methanation reaction, reaction are carried out
Condition is：Unstripped gas H2With CO2Volume ratio be 4: 1, reaction velocity 5000h-1, normal pressure, reaction temperature is 140~500 DEG C,
Tail gas passes through gas-chromatography on-line checking.At 350 DEG C, CO2Conversion ratio reach maximum, be 65.9%, methane selectively is
99.2%.
Embodiment 2
(1) a kind of 15%Co/2%Y-TiO2The preparation method of catalyst, comprises the following steps：
3%Y-TiO2Preparation：20mL butyl titanates are measured respectively and 24mL absolute ethyl alcohols are mixed to form mixed solution
A, then measure 5mL absolute ethyl alcohols, 10mL glacial acetic acids and 5mL water respectively and mixed, add the nitric hydrate yttriums of 0.096g six, stirring
Dissolving is configured to mixed solution B.Mixed solution B is slowly dropped into mixed solution A in the case where rotating speed is 550r/min, dripped off follow-up
Continuous stirring 1h, still aging 5h forms gel, then gel is placed at 100 DEG C and dries 12h, is ground to below 100 mesh, then at horse
5h is not calcined in stove at 500 DEG C and obtains 2%Y-TiO2Carrier.
15%Co/2%Y-TiO2Preparation：1.52g cabaltous nitrate hexahydrates and 2.15g 0.1%Y-TiO are weighed respectively2Carry
Body, which is dissolved in 100mL deionized waters, is configured to mixing suspension, stirs 2h.Weigh 1.88g ammonium carbonates and be dissolved in 20mL deionized waters
In, the sal volatile that concentration is 1mol/L is obtained, then this aqueous slkali is slowly dropped into above-mentioned mixing suspension until pH
For 10.0.Continue to stir 3h, then stand 2h, the filter cake that filtered, washing obtains dries 12h at 110 DEG C, is ground to 20~40
Mesh, it is to obtain 15%Co/2%Y-TiO that 5h is calcined in Muffle furnace 500 DEG C2Catalyst.
(2) according to the activity rating method in embodiment 1 to 15%Co/2%Y-TiO2Catalyst carries out CO2Methanation
Activity rating, at 300 DEG C, CO2Conversion ratio reach maximum, be 85.9%, methane selectively 99.5%.
Embodiment 3
The preparation method of the present embodiment catalyst is substantially the same manner as Example 2, except that 0.096g six is hydrated into nitre
Sour yttrium is substituted for the nitric hydrate zirconiums of 0.096g five, finally gives 15%Co/2%Zr-TiO2Catalyst；According in embodiment 1
Activity rating method is to 15%Co/2%Zr-TiO2Catalyst carries out CO2The activity rating of methanation, at 350 DEG C, CO2Turn
Rate reaches maximum, is 82.5%, methane selectively 99.2%.
Embodiment 4
The preparation method of the present embodiment catalyst is substantially the same manner as Example 2, except that 0.096g six is hydrated into nitre
Sour yttrium is substituted for the nitric hydrate zirconiums of 0.096g five, and 1.52g cobalt nitrate hexahydrates are substituted for 3.98g cabaltous nitrate hexahydrates, finally given
40%Co/2%Zr-TiO2Catalyst；According to the activity rating method in embodiment 1 to 40%Co/2%Zr-TiO2Catalyst enters
Row CO2The activity rating of methanation, at 350 DEG C, CO2Conversion ratio reach maximum, be 75.6%, methane selectively is
98.6%.
Embodiment 5
The preparation method of the present embodiment catalyst is substantially the same manner as Example 2, except that 0.096g six is hydrated into nitre
Sour yttrium is substituted for the nitric hydrate zirconiums of 0.72g five, finally gives 15%Co/15%Zr-TiO2Catalyst；According in embodiment 1
Activity rating method is to 15%Co/15%Zr-TiO2Catalyst carries out CO2The activity rating of methanation, at 350 DEG C, CO2's
Conversion ratio reaches maximum, is 85.4%, methane selectively 99.1%.
Embodiment 6
Using the preparation method of catalyst in embodiment 2,15%Co/2%Y-TiO is obtained2Catalyst, in unstripped gas H2With
CO2Volume ratio be 4: 1, reaction velocity 2000h-1, normal pressure, under conditions of reaction temperature is 140~500 DEG C, carry out CO2First
The activity rating of alkylation reaction, the results showed that, at 350 DEG C, CO2Conversion ratio reach maximum, be 91.6%, methane selectively
For 99.6%.
Embodiment 7
Using the preparation method of catalyst in embodiment 2,15%Co/2%Y-TiO is obtained2Catalyst, in unstripped gas H2With
CO2Volume ratio be 4: 1, reaction velocity 10000h-1, normal pressure, under conditions of reaction temperature is 140~500 DEG C, carry out CO2
The activity rating of methanation reaction, the results showed that, at 350 DEG C, CO2Conversion ratio reach maximum, be 76.5%, methane selection
Property is 98.9%.
Embodiment 8
A kind of 15%Co/2%Y-5%Zr-TiO2The preparation method of catalyst, comprises the following steps：
(1) 2%Y-5%Zr-TiO2Preparation：20mL butyl titanates are measured respectively and 40mL absolute ethyl alcohols are mixed to form
Mixed solution A, then measure 10mL absolute ethyl alcohols, 10mL glacial acetic acids and 10mL water respectively and mixed, add 0.096g six and be hydrated
Yttrium nitrate and the nitric hydrate zirconiums of 0.24g five, stirring and dissolving are configured to mixed solution B.B solution is delayed in the case where rotating speed is 600r/min
It is slow to instill in solution A, continue to stir 1h after dripping off, still aging 10h forms gel, then gel is placed at 110 DEG C and dries 24h
Overnight, then it is ground to below 100 mesh, is put into Muffle furnace roasting 4h at 700 DEG C and obtains 2%Y-5%Zr-TiO2Carry
Body.
15%Co/2%Y-5%Zr-TiO2Preparation：1.52g cabaltous nitrate hexahydrates and 2.15g 2%Y- are weighed respectively
5%Zr-TiO2Carrier, which is dissolved in 100mL deionized waters, is configured to mixing suspension, stirs 2h.1.51g ammonium carbonates are weighed to be dissolved in
In 20mL deionized waters, obtain concentration and be 0.8mol/L sal volatile, then this aqueous slkali is slowly dropped into above-mentioned mixing
Until pH is 10.0 in suspension.Continue to stir 3h, then stand 2h, the filter cake that filtered, washing obtains is dried at 120 DEG C
24h, 20~40 mesh are ground to, 4h is calcined in Muffle furnace 550 DEG C and obtains 15%Co/2%Y-5%Zr-TiO2Catalysis
Agent.
(2) according to activity rating method in embodiment 1 to 15%Co/2%Y-5%Zr-TiO2Catalyst carries out CO2Methane
The activity rating of change, at 300 DEG C, CO2Conversion ratio reach maximum, be 93.9%, methane selectively 99.8%.
Embodiment 9
The preparation method of the present embodiment catalyst is substantially the same manner as Example 6, except that 0.096g six is hydrated into nitre
Sour yttrium is substituted for the nitric hydrate ceriums of 0.14g six, finally gives 15%Co/3%Ce-5%Zr-TiO2Catalyst, and according to implementation
Activity rating method carries out CO in example 12The activity rating of methanation, at 350 DEG C, CO2Conversion ratio reach maximum, be
92.4%, methane selectively 99.5%.
The invention is not limited in foregoing embodiment.The present invention, which expands to, any in this manual to be disclosed
New feature or any new combination, and disclose any new method or process the step of or any new combination.
Claims (6)
1. a kind of carbon dioxide methanation catalyst, it is characterised in that including active component cobalt and the dioxy that passes through additive modification
Change titanium carrier, with elemental metal, the content of the active component cobalt is 5%~40%, the content of the auxiliary agent for 0.1%~
15%, on the basis of the quality of titania support, the preparation method of the catalyst comprises the following steps described content：
(1) preparation of additive modification titania support
Sol-gal process：It is 1 by volume by butyl titanate and absolute ethyl alcohol:1~2 is hybridly prepared into mixed solution A；By ice
Acetic acid, absolute ethyl alcohol and deionized water are 1~2 by volume:1~2:1 is mixed, and is added quality and is accounted for above-mentioned butyl titanate
The auxiliary agent of quality 0.025%~3.75%, stirring and dissolving are configured to mixed solution B, in 400~600r/min mixing speed
Under, the mixed solution B is slowly dropped into the mixed solution A, persistently stirs 0.5~1h after dripping off, still aging 3~
10h forms gel, and gel is placed at 80~110 DEG C and dries 10~24h, is ground to below 100 mesh, 300 in Muffle furnace
3~5h is calcined at~700 DEG C and obtains the titania support of additive modification；
(2) preparation of catalyst
Deposition-precipitation method：It is 0.2~2 by mass ratio:1:50 cobalt nitrate hexahydrate, above-mentioned modifying titanium dioxide carrier and deionization
Water is hybridly prepared into suspension, stirs 1~2h, then 0.5~1.0mol/L aqueous slkali is slowly dropped into above-mentioned suspension, directly
PH value to solution is 9~10, continues 2~3h of stirring, then stands 1~2h, and the filter cake that filtered, washing obtains is 100~120
10~24h is dried at DEG C, is ground to 20~40 mesh, 3~5h is calcined in Muffle furnace 400~550 DEG C and obtains catalyst.
A kind of 2. carbon dioxide methanation catalyst according to claim 1, it is characterised in that described auxiliary agent be calcium,
At least one of scandium, rubidium, strontium, yttrium, zirconium, cerium.
3. a kind of carbon dioxide methanation catalyst according to claim 1, it is characterised in that the active component cobalt
Content is 10%~30%.
4. a kind of carbon dioxide methanation catalyst according to claim 1, it is characterised in that the content of the auxiliary agent is
0.5%~15%.
5. a kind of carbon dioxide methanation catalyst according to claim 1, it is characterised in that the aqueous slkali is hydrogen-oxygen
Change one kind in sodium, potassium hydroxide, ammoniacal liquor, ammonium carbonate or sodium carbonate liquor.
6. the application of the carbon dioxide methanation catalyst described in a kind of any one of claim 1-5, it is characterised in that first will
Catalyst hydrogen reducing 3h at 400 DEG C, the gaseous mixture for then switching to unstripped gas hydrogen and carbon dioxide are reacted, reaction
Condition is：Normal pressure, temperature are 140~500 DEG C, unstripped gas air speed is 2000~10000h-1, and hydrogen and dioxy in unstripped gas
The volume ratio for changing carbon is 4:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710737300.1A CN107497441A (en) | 2017-08-24 | 2017-08-24 | A kind of carbon dioxide methanation catalyst and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710737300.1A CN107497441A (en) | 2017-08-24 | 2017-08-24 | A kind of carbon dioxide methanation catalyst and its application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107497441A true CN107497441A (en) | 2017-12-22 |
Family
ID=60692783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710737300.1A Pending CN107497441A (en) | 2017-08-24 | 2017-08-24 | A kind of carbon dioxide methanation catalyst and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107497441A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109261183A (en) * | 2018-11-14 | 2019-01-25 | 太原科技大学 | It is a kind of for the cobalt-base catalyst and preparation method of carbon dioxide methanation and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013035698A (en) * | 2011-08-04 | 2013-02-21 | Nippon Telegr & Teleph Corp <Ntt> | Method of reducing carbon dioxide |
| CN103894181A (en) * | 2014-03-26 | 2014-07-02 | 北京工业大学 | Low-temperature SCR (Selective Catalytic Reduction) catalyst taking La-doped TiO2 as carrier and preparation method |
| CN103962123A (en) * | 2013-01-28 | 2014-08-06 | 神华集团有限责任公司 | ZrO2-loaded sulfur-tolerant methanation catalyst and preparation method thereof |
| CN104148065A (en) * | 2013-05-14 | 2014-11-19 | 中国科学院大连化学物理研究所 | Catalyst used for methanation of carbon dioxide, preparation method therefor and applications thereof |
| CN106732626A (en) * | 2016-12-17 | 2017-05-31 | 段清 | A kind of Co Ce Cu catalyst, preparation method and the application in carbon dioxide methanation reaction |
-
2017
- 2017-08-24 CN CN201710737300.1A patent/CN107497441A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013035698A (en) * | 2011-08-04 | 2013-02-21 | Nippon Telegr & Teleph Corp <Ntt> | Method of reducing carbon dioxide |
| CN103962123A (en) * | 2013-01-28 | 2014-08-06 | 神华集团有限责任公司 | ZrO2-loaded sulfur-tolerant methanation catalyst and preparation method thereof |
| CN104148065A (en) * | 2013-05-14 | 2014-11-19 | 中国科学院大连化学物理研究所 | Catalyst used for methanation of carbon dioxide, preparation method therefor and applications thereof |
| CN103894181A (en) * | 2014-03-26 | 2014-07-02 | 北京工业大学 | Low-temperature SCR (Selective Catalytic Reduction) catalyst taking La-doped TiO2 as carrier and preparation method |
| CN106732626A (en) * | 2016-12-17 | 2017-05-31 | 段清 | A kind of Co Ce Cu catalyst, preparation method and the application in carbon dioxide methanation reaction |
Non-Patent Citations (3)
| Title |
|---|
| （美）史泰尔斯（STILES，ALVIN B.）等: "《催化剂载体与负载型催化剂》", 31 March 1992, 中国石化出版社 * |
| 徐蕾等: "《负载型多酸光催化材料及应用》", 31 March 2015, 东北师范大学出版社 * |
| 江琦: "负载型钴催化剂作用下的二氧化碳加氢甲烷化", 《煤炭转化》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109261183A (en) * | 2018-11-14 | 2019-01-25 | 太原科技大学 | It is a kind of for the cobalt-base catalyst and preparation method of carbon dioxide methanation and application |
| CN109261183B (en) * | 2018-11-14 | 2021-03-05 | 太原科技大学 | Cobalt-based catalyst for methanation of carbon dioxide and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102921426B (en) | Catalyst for catalytic conversion of biological cellulose and preparation method and applications of catalyst | |
| CN102962077B (en) | Cobalt-based Fischer-Tropsch synthetic catalyst as well as preparation method and application thereof | |
| CN108855109A (en) | A kind of chemical chain partial oxidation methane preparing synthetic gas carrier of oxygen and its preparation method and application | |
| CN106732647A (en) | A kind of perovskite type methyl hydride combustion catalyst and preparation method and application | |
| CN104258864A (en) | Nanocomposite catalyst and preparation method and application thereof | |
| CN104148086B (en) | Prepare the catalyst and method of ethanol | |
| CN110368933B (en) | Ruthenium-based ammonia synthesis catalyst with Ce-Ti composite oxide as carrier and preparation method thereof | |
| CN104475087B (en) | Preparation method for denitration catalyst | |
| CN104028270A (en) | Methanation catalyst and preparation method thereof | |
| CN109420484A (en) | A kind of metal oxide solid solution catalyst and preparation and application | |
| CN113634257A (en) | Application of bifunctional catalyst to CO in flue gas2Integration of capture and methanation | |
| CN102302931A (en) | Catalytic combustion deoxidation catalyst for oxygen-containing methane mixed gas, as well as preparation method and application thereof | |
| CN103143364A (en) | High-dispersion nano-composite catalyst, and preparation method and applications thereof | |
| CN101607201A (en) | Be difficult for water gas converting catalyst of spontaneous combustion and its production and application | |
| CN103962130A (en) | Catalyst for oxalate ester synthetic reaction and preparation method of catalyst | |
| CN102863335B (en) | Preparation method of diethyl succinate | |
| CN103706360A (en) | Ru/BaCeO3 ammonia synthesis catalyst and preparation method thereof | |
| CN102319570A (en) | The ternary compound oxides Catalysts and its preparation method of carbon monoxide oxidation | |
| CN104815701A (en) | Cobalt-based catalyst reduction processing method used for Fischer-Tropsch synthesis | |
| CN101912783B (en) | Catalyst for combustion of ventilation air methane and preparation method thereof | |
| CN102728381A (en) | Tourmalinite-containing composite methane catalyst | |
| CN113842914A (en) | Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof | |
| CN107497441A (en) | A kind of carbon dioxide methanation catalyst and its application | |
| CN109847747A (en) | A kind of low temperature steam transformation catalyst and preparation method | |
| CN110329992B (en) | Catalyst for preparing hydrogen by reforming methanol with low temperature water vapor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171222 |