CN106362720A - Deoxidating catalyst with core-shell structure, and preparation method and application of deoxidating catalyst - Google Patents
Deoxidating catalyst with core-shell structure, and preparation method and application of deoxidating catalyst Download PDFInfo
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- CN106362720A CN106362720A CN201610835101.XA CN201610835101A CN106362720A CN 106362720 A CN106362720 A CN 106362720A CN 201610835101 A CN201610835101 A CN 201610835101A CN 106362720 A CN106362720 A CN 106362720A
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- dehydrogenation catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims description 21
- 239000011258 core-shell material Substances 0.000 title abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims description 57
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 48
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 40
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 38
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 24
- 239000005751 Copper oxide Substances 0.000 claims description 24
- 229910000431 copper oxide Inorganic materials 0.000 claims description 24
- 239000004408 titanium dioxide Substances 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 9
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- 150000000703 Cerium Chemical class 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000012695 Ce precursor Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 239000007789 gas Substances 0.000 abstract description 24
- 239000003245 coal Substances 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 17
- 238000006555 catalytic reaction Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 239000004480 active ingredient Substances 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000006396 nitration reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 238000013019 agitation Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000007084 catalytic combustion reaction Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HHRMPLKWNSRPMC-UHFFFAOYSA-N cerium ethanol Chemical compound C(C)O.[Ce] HHRMPLKWNSRPMC-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 229960004424 carbon dioxide Drugs 0.000 description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 3
- BBGVVPLPLBJJLS-UHFFFAOYSA-N copper ethanol dinitrate Chemical compound C(C)O.[N+](=O)([O-])[O-].[Cu+2].[N+](=O)([O-])[O-] BBGVVPLPLBJJLS-UHFFFAOYSA-N 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000011026 diafiltration Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000012691 Cu precursor Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- MWTXLMFPCZIOHL-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].[Cu+2].C(C)O Chemical compound S(=O)(=O)([O-])[O-].[Cu+2].C(C)O MWTXLMFPCZIOHL-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PQZQLYZNFTUOKV-UHFFFAOYSA-N [Cu].[Cu].C(C)O Chemical compound [Cu].[Cu].C(C)O PQZQLYZNFTUOKV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- ZVHSWYOCXJTJHW-UHFFFAOYSA-K cerium(3+) ethanol trichloride Chemical compound C(C)O.[Cl-].[Ce+3].[Cl-].[Cl-] ZVHSWYOCXJTJHW-UHFFFAOYSA-K 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- SCGJLFGXXZTXSX-UHFFFAOYSA-N copper;ethanol Chemical compound [Cu].CCO SCGJLFGXXZTXSX-UHFFFAOYSA-N 0.000 description 1
- YDRFJPRPCBJKCM-UHFFFAOYSA-L dichlorocopper ethanol Chemical compound C(C)O.[Cu](Cl)Cl YDRFJPRPCBJKCM-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011435 rock 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/397—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/12—Regeneration of a solvent, catalyst, adsorbent or any other component used to treat or prepare a fuel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a deoxidating catalyst with a core-shell structure, and belongs to the technical field of catalysis of oxygen-bearing coal bed gas. A core portion of the deoxidating catalyst comprises CuO and CeO2, and a shell portion of the deoxidating catalyst comprises TiO2. A shell is used for protecting active ingredients of metal Cu in an inner layer, and sintering of the active ingredients can be prevented effectively; the probability of collision between reaction molecules and active centers is increased through confinement effect of the shell, and low-temperature catalytic deoxidation activity and high-temperature performance of the catalyst are improved; the catalyst has the advantages of high heat stability, high low-temperature activity, ignition temperature being 400 DEG C, wide deoxidation temperature window (400-800 DEG C), high wear strength and service life as long as 1000h; the deoxidating catalyst has high stability to impurity ingredients such as water, carbon dioxide, sulfide and nitration products and high mechanical strength, can meet application requirements of fluidized beds, and has the advantages of high gas treatment quantity, high heat transfer performance and easiness in operation after being combined with a deoxidation process of the fluidized beds.
Description
Technical field
The present invention relates to coalbed methane containing oxygen catalysis technical field, more particularly, to a kind of coalbed methane containing oxygen with nucleocapsid structure
Dehydrogenation catalyst.
Background technology
China's coal bed gas resource enriches, and occupies third place in the world, and national shallow-layer Coal bed gas project is 36.8 tcms,
Calorific value is equivalent to 52,000,000,000 tons of standard coals.In the case that the current energy is increasingly becoming tight, coal bed gas is as a kind of high-quality and efficient cleaning
The energy, can be used for generating electricity, heats, resident living and vehicle fuel etc., and it utilizes economic worth huge on a large scale.
Coalbed methane containing oxygen is the important component part of coal bed gas resource, it be primarily referred to as in progress of coal mining from coal body and
In country rock extract coal bed gas, this coal bed gas due to be mixed into large quantity of air cause coal bed gas dilute, referred to as coalbed methane containing oxygen or
Mixed sky coal bed gas, its ch4Content is relatively low, and concentration is 20%～60%, contains n simultaneously2、o2、h2s、co、co2, the impurity gas such as water
Body.China converts into more than pure methane 200 billion cubic meter because of the coalbed methane containing oxygen of discharge in air of mining every year, causes greatly
The wasting of resources.Develop this part coalbed methane containing oxygen resource, for adjustment China energy resource structure, form coal bed gas New Energy
Source industry, Safety of Coal Mine Production condition of improving, minimizing gas accident and greenhouse gas emission, tool is of great significance.
When the methane concentration in coalbed methane containing oxygen reaches 5%～15%, and oxygen concentration is more than 12%, meet naked light or high temperature
Thermal source easily explodes, therefore manage defeated or separate concentration process in there is certain danger, significantly constrain oxygen-containing
The recycling of coal bed gas.Therefore to safely, effectively realize the recovery of coalbed methane containing oxygen and using the problem first having to solve
It is how the oxygen in efficient removal coalbed methane containing oxygen.
The coal bed gas deoxidation technology of report mainly has physics and chemical two class separation methods both at home and abroad at present.Physical method can
It is divided into pressure swing adsorption method, membrane separation process, low temperature processing；Chemical analysis method has reducing process, combustion method, Production by Catalytic Combustion Process, its
Middle Production by Catalytic Combustion Process is the most direct, safest method.Production by Catalytic Combustion Process refers to, under catalyst action, consume a part of first
Alkane, generates carbon dioxide and water with oxygen reaction, reaches removing oxygen purpose, the dominant response of this process is:
ch4(g)+2o2(g)=co2(g)+2h2o(g)-802.32kj/mol (1-1)
It is also possible to there is following side reaction and association reaction in addition to above dominant response, such as side reaction may have:
ch4+0.5o2=co+2h2(1-2)
ch4=c+2h2(1-3)
ch4+h2O=co+3h2(1-4)
ch4+co2=2co+2h2(1-5)
Association reaction may have:
co+0.5o2=co2(1-6)
co+h2O=co2+h2(1-7)
Coal bed gas deoxidation reaction is complex as can be seen here, and releases substantial amounts of heat in course of reaction.Therefore oxygen-containing coal seam
In gas, oxygen removing proposes higher requirement to catalyst.
Catalytic combustion deoxygenation catalyst main at present can be divided into following a few class: as cn1495247a,
Cn101664679a discloses the precious metal catalyst combustion deoxidizing catalyst such as pt and pd and has catalysis activity height, and reaction temperature is low,
Oxygen in gas after deoxidation can eliminate substantially, process is simple, and side reaction is few, the low advantage of initiation temperature, and these deoxidations are urged
Agent is disadvantageous in that noble metal easily sinters at high temperature, and high-temperature resistance is poor, and under low temperature, deoxy activity is low,
Cn101139239a discloses a kind of strong co base catalyst of sulfur resistive ability, have sulfur resistive ability strong the features such as, but its reaction temperature
Degree is higher, has larger limitation.
Content of the invention
In view of this, it is an object of the invention to provide a kind of dehydrogenation catalyst with nucleocapsid structure, improve deoxidation and urge
The low-temperature catalyzed deoxy activity of agent, resistance to elevated temperatures.
In order to realize foregoing invention purpose, present invention offer technical scheme below:
A kind of dehydrogenation catalyst with nucleocapsid structure, core includes cuo and ceo2, shell sections include tio2.
Preferably, the particle diameter of the described dehydrogenation catalyst with nucleocapsid structure is 10 μm～1000 μm.
Preferably, on the basis of the gross mass of catalyst, the weight/mass percentage composition of described cuo is 5～15%, ceo2Matter
Amount percentage composition is 10～50%, balance of tio2.
Preferably, on the basis of the gross mass of catalyst, the weight/mass percentage composition of described cuo is 7～10%, ceo2Matter
Amount percentage composition is 15～40%, balance of tio2.
What the present invention provided has the dehydrogenation catalyst of nucleocapsid structure using this special construction of nucleocapsid structure, using shell
Internal layer cu metal active constituent is protected, not only can effectively prevent the sintering of active component, more utilize the confinement effect of shell to increase
Add the collision probability in reaction molecular and active center, enhance the low temperature catalyst activity of catalyst.The tool that the present invention provides
It is good that the dehydrogenation catalyst having nucleocapsid structure has a heat stability high and low temperature activity, and initiation temperature is 400 DEG C, deoxidation temperature window
Wide (400-800 DEG C), wear strength is good, and service life is up to 1000h.
The present invention provides the preparation method of the dehydrogenation catalyst described in above technical scheme with nucleocapsid structure, including following
Step:
(1) copper oxide precursor, cerium oxide precursor, template and hydrogen peroxide are mixed, hydro-thermal reaction obtains hydrothermal product；
(2) hydrothermal product obtaining described step (1) is mixed with titanium dioxide precursor, and hydro-thermal reaction obtains deoxidation catalysis
Agent presoma；
(3) the dehydrogenation catalyst presoma roasting obtaining described step (2), obtains the deoxidation catalysis with nucleocapsid structure
Agent.
Preferably, described copper oxide precursor is soluble copper salt, and cerium oxide precursor is solubility cerium salt, and template comprises ten
The template agent composition of one or more of six alkyl trimethyl ammonium bromides, hexamethylenetetramine, ethylenediamine and n-butylamine, two
Precursors of titanium oxide comprises the titanium dioxide precursor mixture of one or more of butyl titanate, titanium chloride and titanium sulfate.
Preferably, in described step (1), copper oxide precursor, cerium oxide precursor, template add in the form of a solution, described oxygen
The molar concentration changing the solution of copper precursors is 0.1～1.0mol/l, the molar concentration of the solution of cerium oxide precursor is 0.1～
3.0mol/l, the molar concentration of the solution of template is 0.05～0.1mol/l；
Described hydrogen peroxide is added in the form of hydrogen peroxide, and the mass fraction of described hydrogen peroxide is 5～15%, described oxidation
The volume ratio of the solution of the solution of copper precursors and template is 1:1～1:10, the solution of copper oxide precursor and the volume of hydrogen peroxide
Than for 3:1～1:1.
Preferably, in described step (2), the mass fraction of the solution of titanium dioxide precursor is 20～40%, described copper oxide
The volume ratio of the solution of the solution of precursor and titanium dioxide precursor is 1:3～1:1.
Preferably, in described step (3), the temperature of roasting is 500～800 DEG C.
In the present invention, the raw material of employing is cheap and easy to get, and the preparation process of dehydrogenation catalyst is simple to be produced it is easy to amplify,
Suitable industrialized production.
The present invention provide above technical scheme described in there is the described preparation side of dehydrogenation catalyst of nucleocapsid structure or more
Application in the deoxidation catalysis of coalbed methane containing oxygen fluid bed for the dehydrogenation catalyst of what method obtained have nucleocapsid structure.
The catalyst that the present invention provides is used in the deoxidation catalysis of coalbed methane containing oxygen fluid bed, and using nucleocapsid structure, this is special
Different structure, core includes cuo and ceo2, shell sections include tio2, using shell, internal layer cu metal active constituent is protected
Shield, not only can effectively prevent the sintering of active component, more increased reaction molecular and active center using the confinement effect of shell
Collision probability, enhance catalyst low temperature catalyst activity, ch can be realized at 400～800 DEG C4Conversion, to water, two
The impurity compositions such as carbonoxide, sulfide, itrated compound have higher stability, high mechanical strength, can reach answering of fluid bed
With requiring, there is gas treatment amount greatly after being combined with fluid bed deoxidization technique, move hot good, the advantage of processing ease.
Brief description
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
[cuo] that Fig. 1 embodiment of the present invention 1 is obtained0.05[ceo2]0.20@[tio2]0.75Scanning electron microscope (SEM) photograph.
Specific embodiment
The invention provides a kind of dehydrogenation catalyst with nucleocapsid structure, core includes cuo and ceo2, shell portion
Divide and include tio2.
In the present invention, the particle diameter of the described dehydrogenation catalyst with nucleocapsid structure is preferably 10 μm～1000 μm, more excellent
Elect 200 μm～800 μm as, most preferably 400 μm～600 μm.
In the present invention, the particle diameter of the described dehydrogenation catalyst core with nucleocapsid structure is preferably 1.5 μm～650
μm, more preferably 2.2 μm～500 μm, most preferably 2.8 μm～390 μm, the thickness of shell is preferably 3.5 μm～850 μm, more
It is preferably 5.0 μm～780 μm, most preferably 7.2 μm～610 μm.
In the present invention, on the basis of the gross mass of catalyst, the weight/mass percentage composition of described cuo is preferably 5～15%,
More preferably 7～10%, most preferably 8～9%；Described ceo2Weight/mass percentage composition be preferably 10～50%, more preferably
15～40%, most preferably 20～30%；Balance of tio2.
What the present invention provided has the dehydrogenation catalyst of nucleocapsid structure using this special construction of nucleocapsid structure, using shell
Internal layer cu metal active constituent is protected, not only can effectively prevent the sintering of active component, more utilize the confinement effect of shell to increase
Add the collision probability in reaction molecular and active center, enhance the low temperature catalyst activity of catalyst.The tool that the present invention provides
It is good that the dehydrogenation catalyst having nucleocapsid structure has a heat stability high and low temperature activity, and initiation temperature is 400 DEG C, deoxidation temperature window
Wide (400-800 DEG C), wear strength is good, and service life is up to 1000h.
The present invention provides the preparation method of the dehydrogenation catalyst described in technique scheme with nucleocapsid structure, including following
Step:
(1) copper oxide precursor, cerium oxide precursor, template and hydrogen peroxide are mixed, hydro-thermal reaction obtains hydrothermal product；
(2) hydrothermal product obtaining described step (1) is mixed with titanium dioxide precursor, and hydro-thermal reaction obtains deoxidation catalysis
Agent presoma；
(3) the dehydrogenation catalyst presoma roasting obtaining described step (2), obtains the deoxidation catalysis with nucleocapsid structure
Agent.
Copper oxide precursor, cerium oxide precursor, template and hydrogen peroxide are mixed by the present invention, and hydro-thermal reaction obtains hydro-thermal and produces
Thing.In the present invention, described copper oxide precursor is preferably soluble copper salt, more preferably comprises copper chloride, copper nitrate, copper sulfate
With the mixture of the mixture of one or more in Schweinfurt green, most preferably copper chloride and copper nitrate, copper nitrate and Schweinfurt green
Mixture, the present invention does not limit to the mass ratio of each soluble copper salt in described mixture, and those skilled in the art can basis
It is actually needed the mixture of the soluble copper salt selecting any mass ratio；
In the present invention, described cerium oxide precursor is preferably solubility cerium salt, more preferably comprises cerous nitrate, cerous nitrate
In ammonium, cerous acetate and cerium chloride, the mixture of the mixture of one or more, most preferably cerous nitrate and cerium chloride, nitric acid are sub-
Cerium and the mixture of cerous acetate, the present invention does not limit to the mass ratio of solubility cerium salt each in described mixture, this area skill
Art personnel can select the mixture of the solubility cerium salt of any mass ratio according to actual needs.
In the present invention, described template preferably comprises cetyl trimethylammonium bromide, hexamethylenetetramine, ethylenediamine
With the template agent composition of one or more of n-butylamine, the mixing of described template agent composition preferably two kinds of template
The mixture of thing, more preferably cetyl trimethylammonium bromide and hexamethylenetetramine, cetyl trimethylammonium bromide and
The mixture of ethylenediamine.The present invention does not limit to the mass ratio of each template in described mixture, and those skilled in the art can
Select the mixture of the template of any mass ratio according to actual needs.
In the present invention, described copper oxide precursor and the mass ratio of cerium oxide precursor are preferably 1:2～1:10, more preferably
1:4～1:6, most preferably 1:5～1:6；Described copper oxide precursor is preferably 1:1～20:1 with the mol ratio of template, more excellent
Elect 1:5～1:15, most preferably 1:8～1:12 as.
In the present invention, described copper oxide precursor, cerium oxide precursor and template preferably add in the form of a solution, specifically
, the molar concentration of the solution of described copper oxide precursor is preferably 0.1～1.0mol/l, more preferably 0.2～0.8mol/l,
It is preferably 0.3～0.6mol/l；The molar concentration of the solution of described cerium oxide precursor is preferably 0.1～3.0mol/l, more preferably
For 0.5～2.5mol/l, most preferably 1.0～2.0mol/l；The molar concentration of the solution of described template be preferably 0.05～
0.1mol/l, more preferably 0.06～0.09mol/l, most preferably 0.07～0.08mol/l.The present invention is molten to formation solution
The species of agent there is not particular determination, using the solvent of the conventional copper oxide precursor of those skilled in the art, cerium oxide precursor,
Alcohol solvent is preferably employed in the embodiment of the present invention.
In the present invention, the volume ratio of the solution of the solution of copper oxide precursor and template is preferably 1:1～1:10, more excellent
Elect 1:2～1:8, most preferably 1:4～1:7 as.
In the present invention, described hydrogen peroxide is added preferably in the form of hydrogen peroxide, and the mass fraction of described hydrogen peroxide is excellent
Elect 5～15%, more preferably 7～14%, most preferably 9～12% as.In the present invention, the solution of described copper oxide precursor and
The volume ratio of hydrogen peroxide is preferably 3:1～1:1, more preferably 2.5:1～1.5:1, most preferably 2.0:1～1.8:1.
The present invention does not have special restriction to the mode of described mixing, using hybrid mode well known to those skilled in the art
?；In an embodiment of the present invention, it is preferred to use alr mode mixes, the present invention does not have particular/special requirement to alr mode, presses
It is stirred according to the technological means known to those skilled in the art, the rotating speed of described stirring is preferably 200～800rpm, more excellent
Elect 400～600rpm, most preferably 500～550rpm as.
In the present invention, in described step (1), the temperature of hydro-thermal reaction is preferably 50～100 DEG C, and more preferably 60～80
DEG C, most preferably 70～75 DEG C；The time of described hydro-thermal reaction preferably 4～20h, more preferably 6～15h, most preferably 8～
12h.
In the present invention, the equipment described hydro-thermal reaction being adopted does not have special restriction, using those skilled in the art
Known to reactor.
After obtaining hydrothermal product, described hydrothermal product is mixed by the present invention with titanium dioxide precursor, and hydro-thermal reaction is taken off
VPO catalysts presoma.In the present invention, described titanium dioxide precursor comprises butyl titanate, tetraethyl titanate and metatitanic acid 4 third
The mixture of one or more of ester, is specifically preferably the mixture of two kinds of titanium dioxide precursor, more preferably metatitanic acid four
The mixture of the mixture of butyl ester and tetraethyl titanate, butyl titanate and metatitanic acid orthocarbonate.In the present invention, in mixture
The mass ratio of each titanium dioxide precursor does not limit, and those skilled in the art can select the two of any mass ratio according to actual needs
The mixture of precursors of titanium oxide.
In the present invention, described copper oxide precursor and the mass ratio of titanium dioxide precursor are preferably 1:2～1:6, more preferably
For 1:3～1:5, most preferably 1:4～1:4.5.
In the present invention, described titanium dioxide precursor is preferably mixed with hydrothermal product as a solution, described titanium dioxide
The mass fraction of the solution of titanium precursor is preferably 20～40%, more preferably 25～35%, most preferably 28～32%.At this
In bright, the volume ratio of the solution of described copper oxide precursor and the solution of titanium dioxide precursor is preferably 1:3～1:1, more preferably
1:2.5～1:1.5, most preferably 1:2.3～1:1.8.
In the present invention, mode hydrothermal product being mixed with titanium dioxide precursor does not have special restriction, using ability
Hybrid mode known to field technique personnel, in an embodiment of the present invention, it is preferred to use alr mode mixes, described stirring
Rotating speed be preferably 500～1200rpm, more preferably 700～900rpm, most preferably 750～850rpm, described stirring when
Between be preferably 2～15h, more preferably 5～10h, most preferably 7～9h.
In the present invention, in described step (2), the temperature of hydro-thermal reaction is preferably 100～200 DEG C, more preferably 120～
160 DEG C, most preferably 140～150 DEG C；The time of described hydro-thermal reaction is preferably 5～20h, more preferably 6～15h, most preferably
For 8～12h.
After the hydro-thermal reaction of step (2), the hydro-thermal reaction obtaining product is preferably washed and is dried by the present invention, obtains
Dehydrogenation catalyst precursor.In the present invention, the detailed process of described washing is preferably: with water, dehydrogenation catalyst presoma is entered
Row filtration washing, the number of times of described washing preferably 3～8 times, more preferably 4～7 times, most preferably 5～6 times；
The temperature of described drying is preferably 100～130 DEG C, more preferably 110～120 DEG C, most preferably 115～118 DEG C；
The time being dried is preferably 2～7h, more preferably 3～6h, most preferably 4～5h.In the present invention, to dehydrogenation catalyst forerunner
The mode that body is dried does not have special restriction, using drying mode well known to those skilled in the art, in the present invention
Embodiment in, it is preferred to use the dry case of vacuum is dried.
After obtaining dehydrogenation catalyst presoma, the present invention obtains described dehydrogenation catalyst presoma roasting with nucleocapsid
The dehydrogenation catalyst of structure.In the present invention, the temperature of described roasting is preferably 500～800 DEG C, and more preferably 550～700
DEG C, most preferably 600～650 DEG C；The time of described roasting is preferably 2～10h, more preferably 4～8h, most preferably 5～7h.
In the present invention, there is no particular/special requirement to the mode of described roasting, according to roasting technology known to those skilled in the art
Means, preferably employ Muffle furnace in embodiments of the present invention and carry out roasting.
In the present invention, the raw material of employing is cheap and easy to get, and the preparation process of dehydrogenation catalyst is simple to be produced it is easy to amplify,
Suitable industrialized production.
The present invention provide above technical scheme described in there is the described preparation side of dehydrogenation catalyst of nucleocapsid structure or more
Application in the deoxidation catalysis of coalbed methane containing oxygen fluid bed for the dehydrogenation catalyst of what method obtained have nucleocapsid structure.
In the present invention, the dehydrogenation catalyst with nucleocapsid structure contains when coalbed methane containing oxygen fluid bed carries out deoxidation catalysis
In oxygen coal seam, oxygen content is 4-14vol.%, methane content 30-80vol.%, and remaining is nitrogen.
The catalyst that the present invention provides is used in the deoxidation catalysis of coalbed methane containing oxygen fluid bed, and using nucleocapsid structure, this is special
Internal layer cu metal active constituent is protected using shell, not only can effectively be prevented the sintering of active component by different structure, more utilizes shell
The confinement effect of layer increased the collision probability in reaction molecular and active center, enhances the low temperature catalyst activity of catalyst,
Ch can be realized at 400-800 DEG C4Conversion, the impurity compositions such as water, carbon dioxide, sulfide, itrated compound are had higher
Stability, high mechanical strength, the application requirement of fluid bed can be reached, after being combined with fluid bed deoxidization technique, there is gas treatment
Amount is big, moves hot good, the advantage of processing ease.
With reference to embodiment, the preparation method of the brominated epoxy resin that the present invention provides is described in detail, but
They can not be interpreted as limiting the scope of the present invention.
Embodiment 1
The nucleocapsid catalyst core of the present embodiment is by 5.0wt%cuo, 20.0wt%ceo2Form, remaining quality is
Nucleocapsid part tio2Quality.It is named as catalyst-1.
The preparation method of the present embodiment is:
(1) by the chlorination of the copper nitrate ethanol solution of 50ml molar concentration 0.6mol/l, 50ml molar concentration 0.6mol/l
The cerous nitrate ethanol solution of copper copper ethanol solution and 370ml molar concentration 3.0mol/l mixes in proportion, and adds 20ml
0.1mol/l cetyl trimethylammonium bromide aqueous solution and the aqueous hydrogen peroxide solution of 40ml mass fraction 5wt%, 60 DEG C of conditions
Lower stirring 8h, agitation revolution 500rpm, stand-by；
(2) and then by 304g butyl titanate ethanol solution it is added dropwise over (1) above-mentioned solution, under the high revolution of 1000rpm, 25
DEG C uniform stirring 2～6h, loads in stainless steel cauldron afterwards, stirs 6h under 110 DEG C of hydrothermal conditions.Filtration washing, 110 DEG C of dryings
6h, 700 DEG C of high-temperature roasting 4h, you can obtain the coalbed methane containing oxygen catalytic combustion deoxygenation catalyst with nucleocapsid structure.
Catalyst [cuo] manufactured in the present embodiment0.05[ceo2]0.20@[tio2]0.75The normal pressure fluidized bed reactor is carried out
Reaction, reaction condition and Evaluation results are shown in Table 1.
Embodiment 2
The nucleocapsid catalyst core of the present embodiment is by 10.0wt%cuo, 10.0wt%ceo2Form, remaining quality is
Nucleocapsid part tio2Quality.It is named as catalyst-2.
The preparation method of the present embodiment is:
(1) by the nitre of the copper chloride ethanol solution of 100ml molar concentration 0.3mol/l and 70ml molar concentration 0.2mol/l
Acid Asia cerium ethanol solution mixes in proportion, addition 10ml 0.05mol/l cetyl trimethylammonium bromide aqueous solution,
10ml 0.05mol/l hexa-methylene time amine and the aqueous hydrogen peroxide solution of 30ml mass fraction 10wt%, agitation revolution 200rpm,
6h is stirred under the conditions of 60 DEG C, stand-by；
(2) and then by 81g butyl titanate ethanol solution it is added dropwise over (1) above-mentioned solution, under the high revolution of 800rpm, 25 DEG C
Uniform stirring 2h, loads in stainless steel cauldron afterwards, stirs 6h, agitation revolution 400rpm under 120 DEG C of hydrothermal conditions.Cross diafiltration
Wash, 120 DEG C are dried 6h, 750 DEG C of high-temperature roasting 6h, you can the coalbed methane containing oxygen catalysis combustion deoxidizing obtaining having nucleocapsid structure is urged
Agent.
Catalyst [cuo] manufactured in the present embodiment0.10[ceo2]0.10@[tio2]0.80The normal pressure fluidized bed reactor is carried out
Reaction, reaction condition and Evaluation results are shown in Table 1.
Embodiment 3
The nucleocapsid catalyst core of the present embodiment is by 5.0wt%cuo, 30.0wt%ceo2Form, remaining quality is
Nucleocapsid part tio2Quality.It is named as catalyst-3.
The preparation method of the present embodiment is:
(1) by the nitric acid of the Schweinfurt green ethanol solution of 40ml molar concentration 0.3mol/l, 60ml molar concentration 0.6mol/l
The cerous nitrate ethanol solution of copper ethanol solution and 166ml molar concentration 0.5mol/l mixes in proportion, and adds 10ml
0.08mol/l cetyl trimethylammonium bromide aqueous solution, 10ml0.05mol/l ethylenediamine and 30ml mass fraction 15wt%'s
Aqueous hydrogen peroxide solution, agitation revolution 400rpm, stir 12h under the conditions of 70 DEG C, stand-by；
(2) and then by 62g butyl titanate ethanol solution, that 70g tetraethyl titanate ethanol solution is added dropwise over (1) is above-mentioned molten
Liquid, under the high revolution of 500rpm, 25 DEG C of uniform stirring 4h, load afterwards in stainless steel cauldron, under 130 DEG C of hydrothermal conditions, stir 4h,
Agitation revolution 600rpm.Filtration washing, 120 DEG C are dried 4h, 750 DEG C of high-temperature roasting 4h, you can obtain thering is containing of nucleocapsid structure
Oxygen coal bed gas catalytic combustion deoxygenation catalyst.
Catalyst [cuo] manufactured in the present embodiment0.05[ceo2]0.30@[tio2]0.65The normal pressure fluidized bed reactor is carried out
Reaction, reaction condition and Evaluation results are shown in Table 1.
Embodiment 4
The nucleocapsid catalyst core of the present embodiment is by 10.0wt%cuo, 40.0wt%ceo2Form, remaining quality is
Nucleocapsid part tio2Quality.It is named as catalyst-4.
The preparation method of the present embodiment is:
(1) by the nitre of the copper nitrate ethanol solution of 100ml molar concentration 0.45mol/l and 64ml molar concentration 0.8mol/l
Acid Asia cerium ethanol solution, the cerium chloride ethanol solution of 40ml molar concentration 0.8mol/l mix in proportion, and add 30ml
0.09mol/l cetyl trimethylammonium bromide aqueous solution, and the aqueous hydrogen peroxide solution of 60ml mass fraction 7wt%, stirring turns
Number 600rpm, stirs 4h under the conditions of 100 DEG C, stand-by；
(2) and then by 36g tetrabutyl titanate ethanol solution, that 40g metatitanic acid orthocarbonate ethanol solution is added dropwise over (1) is above-mentioned
Solution, under the high revolution of 500rpm, 25 DEG C of uniform stirring 4h, load afterwards in stainless steel cauldron, stir under 130 DEG C of hydrothermal conditions
4h, agitation revolution 500rpm.Filtration washing, 120 DEG C are dried 6h, 800 DEG C of high-temperature roasting 5h, you can obtain thering is nucleocapsid structure
Coalbed methane containing oxygen catalytic combustion deoxygenation catalyst.
Catalyst [cuo] manufactured in the present embodiment0.10[ceo2]0.40@[tio2]0.50The normal pressure fluidized bed reactor is carried out
Reaction, reaction condition and Evaluation results are shown in Table 1.
Embodiment 5
The nucleocapsid catalyst core of the present embodiment is by 8.0wt%cuo, 20.0wt%ceo2Form, remaining quality is
Nucleocapsid part tio2Quality.It is named as catalyst-5.
The preparation method of the present embodiment is:
(1) by the nitre of the copper sulfate ethanol solution of 50ml molar concentration 0.9mol/l and 260ml molar concentration 0.8mol/l
Acid Asia cerium ethanol solution mixes in proportion, and adds 30ml 0.07mol/l cetyl trimethylammonium bromide aqueous solution, and
The aqueous hydrogen peroxide solution of 30ml mass fraction 15wt%, agitation revolution 600rpm, stir 4h under the conditions of 75 DEG C, stand-by；
(2) and then by 137g butyl titanate ethanol solution it is added dropwise over (1) above-mentioned solution, under the high revolution of 700rpm, 25
DEG C uniform stirring 8h, loads in stainless steel cauldron afterwards, stirs 4h, agitation revolution 500rpm under 130 DEG C of hydrothermal conditions.Cross diafiltration
Wash, 120 DEG C are dried 6h, 500 DEG C of high-temperature roasting 6h, you can the coalbed methane containing oxygen catalysis combustion deoxidizing obtaining having nucleocapsid structure is urged
Agent.
Catalyst [cuo] manufactured in the present embodiment0.08[ceo2]0.20@[tio2]0.72The normal pressure fluidized bed reactor is carried out
Reaction, reaction condition and Evaluation results are shown in Table 1.
Embodiment 6
The nucleocapsid catalyst core of the present embodiment is by 8.0wt%cuo, 20.0wt%ceo2Form, remaining quality is
Nucleocapsid part tio2Quality.It is named as catalyst-5.
The preparation method of the present embodiment is:
(1) by the nitre of the copper nitrate ethanol solution of 50ml molar concentration 0.9mol/l and 130ml molar concentration 0.8mol/l
Acid Asia cerium ethanol solution, the cerous acetate ethanol solution of 130ml molar concentration 0.8mol/l mix in proportion, and add 30ml
0.06mol/l cetyl trimethylammonium bromide aqueous solution, and the aqueous hydrogen peroxide solution of 30ml mass fraction 15wt%, stirring turns
Number 600rpm, stirs 4h under the conditions of 90 DEG C, stand-by；
(2) and then by 137g butyl titanate ethanol solution it is added dropwise over (1) above-mentioned solution, under the high revolution of 700rpm, 25
DEG C uniform stirring 8h, loads in stainless steel cauldron afterwards, stirs 4h, agitation revolution 500rpm under 130 DEG C of hydrothermal conditions.Cross diafiltration
Wash, 120 DEG C are dried 6h, 600 DEG C of high-temperature roasting 6h, you can the coalbed methane containing oxygen catalysis combustion deoxidizing obtaining having nucleocapsid structure is urged
Agent.
Catalyst [cuo] manufactured in the present embodiment0.08[ceo2]0.20@[tio2]0.72The normal pressure fluidized bed reactor is carried out
Reaction, reaction condition and Evaluation results are shown in Table 1.
Comparative example 1
Using supported non-noble metal oxygen-containing coal bed gas deoxidation catalyst disclosed in cn102872883a in the normal pressure fluidized bed
Reacted in reactor, reaction condition and Evaluation results are shown in Table 1.
Table 1 different model catalyst fluidized bed Activity evaluation
Remarks: unstripped gas oxygen content is 4-14vol.%, methane content 30-80vol.%, remaining is nitrogen.
From the data of table 1, the oxygen-containing coal bed gas deoxidation catalyst of what the present invention was obtained have nucleocapsid structure with common
Loaded catalyst contrasts, and initiation temperature is 450 DEG C, and the initiation temperature of nucleocapsid catalyst is 400 DEG C, have heat stability high,
Low temperature active is good, deoxidation temperature window width (400-800 DEG C), the high advantage of dehydrogenation catalyst activity.
The above is only the preferred embodiment of the present invention it is noted that ordinary skill people for the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. there is the dehydrogenation catalyst of nucleocapsid structure it is characterised in that core includes cuo and ceo2, shell sections include
tio2.
2. dehydrogenation catalyst according to claim 1 is it is characterised in that the described dehydrogenation catalyst with nucleocapsid structure
Particle diameter is 10 μm～1000 μm.
3. dehydrogenation catalyst according to claim 1 is it is characterised in that on the basis of the gross mass of catalyst, described cuo
Weight/mass percentage composition be 5～15%, ceo2Weight/mass percentage composition be 10～50%, balance of tio2.
4. dehydrogenation catalyst according to claim 3 it is characterised in that described cuo weight/mass percentage composition be 7～
10%, ceo2Weight/mass percentage composition be 15～40%, balance of tio2.
5. there is described in Claims 1 to 4 any one the preparation method of the dehydrogenation catalyst of nucleocapsid structure, walk including following
Rapid:
(1) copper oxide precursor, cerium oxide precursor, template and hydrogen peroxide are mixed, hydro-thermal reaction obtains hydrothermal product；
(2) hydrothermal product obtaining described step (1) is mixed with titanium dioxide precursor, before hydro-thermal reaction obtains dehydrogenation catalyst
Drive body；
(3) the dehydrogenation catalyst presoma roasting obtaining described step (2), obtains the dehydrogenation catalyst with nucleocapsid structure.
6. preparation method according to claim 5, it is characterised in that described copper oxide precursor is soluble copper salt, aoxidizes
Cerium precursor is solubility cerium salt, and template comprises cetyl trimethylammonium bromide, hexamethylenetetramine, ethylenediamine and n-butylamine
One or more of template agent composition, titanium dioxide precursor comprises in butyl titanate, titanium chloride and titanium sulfate
Plant or several titanium dioxide precursor mixture.
7. preparation method according to claim 5 is it is characterised in that before copper oxide precursor in described step (1), cerium oxide
Body, template add in the form of a solution, and the molar concentration of the solution of described copper oxide precursor is 0.1～1.0mol/l, cerium oxide
The molar concentration of the solution of precursor is 0.1～3.0mol/l, and the molar concentration of the solution of template is 0.05～0.1mol/l；
Described hydrogen peroxide is added in the form of hydrogen peroxide, and the mass fraction of described hydrogen peroxide is 5～15%, before described copper oxide
The volume ratio of the solution of the solution of body and template is 1:1～1:10, and the solution of copper oxide precursor and the volume ratio of hydrogen peroxide are
3:1～1:1.
8. preparation method according to claim 5 it is characterised in that in described step (2) titanium dioxide precursor solution
Mass fraction be 20～40%, the volume ratio of the solution of described copper oxide precursor and the solution of titanium dioxide precursor be 1:3～
1:1.
9. preparation method according to claim 5 it is characterised in that in described step (3) roasting temperature be 500～
800℃.
10. described in Claims 1 to 4 any one there is the dehydrogenation catalyst of nucleocapsid structure or claim 5～9 is any one
What the described preparation method of item obtained has the dehydrogenation catalyst of nucleocapsid structure in the deoxidation of coalbed methane containing oxygen fluid bed is catalyzed
Application.
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| CN109772441B (en) * | 2017-11-14 | 2022-01-04 | 中国石油化工股份有限公司 | Catalyst with shell-core structure and preparation method and application thereof |
| CN112958098A (en) * | 2021-02-08 | 2021-06-15 | 清华大学 | Sulfur-mercury oxidation resistant catalyst, preparation method thereof and flow electrode device |
| CN115041178A (en) * | 2021-03-08 | 2022-09-13 | 上海睿筑环境科技有限公司 | Titanium-coated tin-cobalt core-shell catalyst capable of stably catalyzing and purifying sulfur-containing volatile organic pollutants and preparation method thereof |
| CN115041178B (en) * | 2021-03-08 | 2023-05-09 | 上海睿筑环境科技有限公司 | Titanium-coated tin-cobalt core-shell catalyst capable of stably catalyzing and purifying sulfur-containing volatile organic pollutants and preparation method thereof |
| CN116273022A (en) * | 2023-03-21 | 2023-06-23 | 昆明理工大学 | Catalytic material with hollow core-shell structure and preparation method and application thereof |
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