CN102872883A - Supported non-noble metal oxygen-containing coalbed methane deoxidation catalyst and preparation method and application thereof - Google Patents
Supported non-noble metal oxygen-containing coalbed methane deoxidation catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN102872883A CN102872883A CN2012103651147A CN201210365114A CN102872883A CN 102872883 A CN102872883 A CN 102872883A CN 2012103651147 A CN2012103651147 A CN 2012103651147A CN 201210365114 A CN201210365114 A CN 201210365114A CN 102872883 A CN102872883 A CN 102872883A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- coal bed
- noble metal
- bed gas
- oxygen
- 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 87
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 65
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000001301 oxygen Substances 0.000 title claims abstract description 62
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 72
- 239000007789 gas Substances 0.000 claims description 66
- 239000003245 coal Substances 0.000 claims description 54
- 239000010949 copper Substances 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000012752 auxiliary agent Substances 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 15
- 239000004005 microsphere Substances 0.000 claims description 14
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 238000006392 deoxygenation reaction Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract 2
- 230000000996 additive effect Effects 0.000 abstract 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 26
- 238000003756 stirring Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910017827 Cu—Fe Inorganic materials 0.000 description 9
- 238000007654 immersion Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000007084 catalytic combustion reaction Methods 0.000 description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000463 material 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
A supported non-noble metal oxygen-containing coalbed methane deoxidation catalyst comprises an active component, an additive, and a carrier; on an oxide basis, the catalyst comprises 0.5-30 wt% of the active component, 2-40 wt% of the additive, and the balance of the carrier. The active component is a composite oxide of Cu and Fe, and the weight ratio of CuO/Fe2O3 of the composite oxide of Cu and Fe is 1:1-10. The catalyst of the invention has the advantages of high catalytic activity, high stability, high mechanical strength, low price, and suitability for fluidized bed deoxidation process.
Description
Technical field
The invention belongs to a kind of Catalysts and its preparation method and application, be specifically related to a kind of supported non-noble metal oxygen-containing coal bed gas deoxidation catalyst and preparation method thereof and application.
Background technology
Coal bed gas has another name called gas, is the natural fuel gas of certainly storage formula in the ature of coal stratum.China's coal bed gas resource is abundant, occupies the third place in the world, and national shallow-layer coal bed gas resource amount is 36.8 tcms, and calorific value is equivalent to 52,000,000,000 tons of standard coals.In the situation that the current energy is becoming tight day by day, coal bed gas can be used for generating, heating, resident living and vehicle fuel etc. as a kind of high-quality and efficient clean energy resource, 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 mainly refers to the coal bed gas that extracts in the progress of coal mining from coal body and country rock, this coal bed gas causes the coal bed gas dilution owing to sneak into large quantity of air, is called coalbed methane containing oxygen or mixed empty coal bed gas, its CH
4Content is lower, and concentration is 20～60 vol.%, contains simultaneously N
2, O
2, CO, CO
2, SO
2And NO
xEtc. foreign gas.China every year amounts to more than pure methane 200 billion cubic meters because of the coalbed methane containing oxygen that discharges in the atmosphere of mining, and has caused the great wasting of resources.Develop this part coalbed methane containing oxygen resource, for adjusting China's energy resource structure, form coal bed gas novel energy industry, improve the Safety of Coal Mine Production condition, reducing gas accident and greenhouse gas emission, tool is of great significance.
Methane concentration in coalbed methane containing oxygen reaches 5～15 vol.%, oxygen concentration surpasses 12 vol.%, chance naked light or high temperature heat source are very easily blasted, and therefore fail or separate in the concentration process at pipe to have certain danger, have greatly restricted the recycling of coalbed methane containing oxygen.Therefore want safety, effectively realize that one of problem that the recovery of coalbed methane containing oxygen and utilizing at first will solve is exactly the oxygen that how to remove efficiently in the coalbed methane containing oxygen.
The coal bed gas deoxidation technology of report mainly contains physics and chemistry two class separation methods both at home and abroad at present.Physical method can be divided into pressure swing adsorption method, membrane separation process, low temperature processing; Chemical analysis method has reducing process, firing method, Production by Catalytic Combustion Process.Wherein the most direct, safest method is Production by Catalytic Combustion Process.Production by Catalytic Combustion Process refers to sacrifice a part of methane under catalyst action, allows itself and oxygen reaction generate carbon dioxide and water, reaches the deoxygenation purpose.
The essence of catalytic combustion technique is CH under the rich combustion oxygen-lean atmosphere
4Catalytic combustion, the key reaction of this process is:
CH
4 (g) + 2O
2 (g) = CO
2 (g) + 2H
2O (g) - 802.32 kJ/mol (1-1)
Except above key reaction, at a certain temperature, following side reaction and some association reactions etc. may occur also.
Side reaction may have:
CH
4+0.5O
2=CO+2H
2 (1-2)
CH
4=C+2H
2 (1-3)
CH
4+H
2O=CO+3H
2 (1-4)
CH
4+CO
2=2CO+2H
2 (1-5)
The association reaction may have:
CO+0.5O
2=CO
2 (1-6)
CO+H
2O=CO
2+H
2 (1-7)
This shows that the coal bed gas deoxidation reaction is comparatively complicated, and emit a large amount of heat in the course of reaction.Therefore oxygen removes catalyst is proposed higher requirement in the coalbed methane containing oxygen.
Main catalytic combustion dehydrogenation catalyst can be divided into following a few class at present:
In ZL02113628.9 " the methanol catalytic combustion deoxidization process of coal mine mash gas ", and the noble metals such as CN101664679A " a kind of coal bed gas deoxidation catalyst, its preparation method and application " employed Pt and Pd have the catalytic activity height, reaction temperature is low, oxygen after the deoxidation in the gas can eliminate substantially, technique is simple, the advantages such as side reaction is few, and initiation temperature is low.Weak point is that catalyst is expensive, and is responsive to the toxic gases such as hydrogen sulfide in the coal bed gas simultaneously, the easy inactivation of catalyst, and the while noble metal is easy sintering at high temperature, and high-temperature resistance is relatively poor.It is catalyst based that the southwest CN101139239A of chemical research institute " a kind of oxygen-containing coal bed gas deoxidation catalyst and preparation method thereof and application " discloses the strong Co of a kind of anti-sulphur ability, have the characteristics such as anti-sulphur ability is strong, but its reaction temperature is higher, air speed is less, and can only process the less coal bed gas of oxygen content, have larger limitation.
The deoxidation of coalbed methane containing oxygen catalytic combustion not only proposes higher requirement to catalyst, simultaneously, also reaction process is proposed baptism.Methyl hydride combustion is strong exothermal reaction, the oxygen of every consumption 1 vol.%, and about 90～100 ℃ of the caused bed adiabatic temperature rise of reaction heat, as remove the oxygen of 15 vol.%, the gas adiabatic temperature rise will be above 1000
oC must mix a deoxidation gas circulation part with the raw material coal bed gas, regulate and enter the oxygen content of gas reactor, thereby reach the purpose (CN 101613627A) of controlling reaction temperature.The coal bed gas catalytic deoxidation process all adopts bed technology at present.The fixed bed reactors technological design is ripe, and is simple to operate, but its heat transfer efficiency is low, and the oxygen concentration of reactor inlet gas must be controlled at about 3 vol.%, and circulation dilution tolerance reaches 3 ~ 5 times of material gas quantity, and the process energy consumption is high; The beds temperature difference is large, the poor selectivity of reaction; Easy local temperature runaway causes catalysqt deactivation, even sintering; Bed pressure drop is high, and it is little to cross bed gas gas speed, and disposal ability is low.
Fluid bed has the heat transfer efficiency height, fluidized particles can easily add or take out, process the advantages such as gas flow is large, is specially adapted to the coal bed gas deoxidation reaction of strong heat release.Fluid bed internal combustion liberated heat also shifts out with the form of steam easily simultaneously, is used for generating, heating, reaches the greenization recycling, reduces energy loss.
For the technological requirement of fluid bed, catalyst should possess following characteristics: (1) high catalytic activity, can realize CH at 400-750 ℃
4Conversion; (2) high stability has higher stability to impurity compositions such as water, carbon dioxide, sulfide, itrated compounds; (3) high mechanical properties reaches the fluidized bed applications requirement; (4) the particle particle will between 10-1500 μ m, be convenient to fluid bed and keep preferably fluidized state; (5) catalyst is regenerated easily; (6) low price, raw material sources are extensive, are convenient to a large amount of manufactures etc.
Summary of the invention
The purpose of this invention is to provide a kind of high catalytic activity, high stability, high mechanical properties, supported non-noble metal oxygen-containing coal bed gas deoxidation catalyst of low-cost suitable fluid bed deoxidization technique and preparation method thereof and application.
Catalyst of the present invention is comprised of active component, auxiliary agent and carrier, and in oxide, the weight percentage of active component is 0.5-30 wt%, and the content of auxiliary agent is 2-40 wt%, and all the other are carrier;
Described active component is the composite oxides of Cu and Fe, auxiliary agent is one or more in Mg, Mn, Mo, Ti, Ce, Zr, the Ca oxide, described carrier is aluminum oxide micro-sphere, molecular sieve microballoon or silicon dioxide microsphere, and the particle size range of carrier microballoons is 10-1500 μ m.
Aforesaid aluminum oxide micro-sphere carrier is alpha-aluminium oxide microballoon or gamma-alumina microballoon.
The CuO/Fe of aforesaid copper iron compound oxide
2O
3Weight ratio be between the 1:1-10.
The preparation method of catalyst of the present invention is equi-volume impregnating, the steps include:
(1) with the soluble-salt of the soluble-salt of active component and auxiliary agent by being mixed with the aqueous solution;
(2) carrier microballoons is slowly immersed in the aqueous solution of step (1), dipping is 12-48 hour under the normal temperature, 110-120
oDry 4-6 hour of C, 400-700
oC roasting 4-8 hour makes dehydrogenation catalyst.
The soluble-salt of described Cu active component is copper sulphate, Schweinfurt green or copper nitrate; The soluble-salt of Fe active component is any one or two kinds in ferric nitrate, ferrous nitrate, ferric oxalate, frerrous chloride, the ferrous sulfate.
The soluble-salt of described auxiliary agent is one or more of the solubility nitrate of Mg, Mn, Mo, Ce, Zr, Ca or Ti, Ca, Zr chloride salt.
Catalyst of the present invention be applicable to coalbed methane containing oxygen fluid bed deoxidization technique, the oxygen content of coalbed methane containing oxygen is in 4-14 vol.%(volume ratio) in the scope, the unstripped gas air speed is 1000-30000 h
-1, the temperature of catalyst deoxygenation is between 400-750
oC, pressure are under the condition of normal pressure, and oxygen outlet concentration of the present invention is less than 0.5 vol.%.
The present invention compared with prior art, dehydrogenation catalyst of the present invention has following substantive distinguishing features:
(1) compare with noble metal, catalyst of the present invention has selective height, and anti-sulphur is good, and is cheap, is easy to the advantages such as production.
(2) this catalyst has higher wear-resisting mechanical strength (wear rate is lower than 15 wt% in the 1000h) and less particle size (10-1500 μ m), have long life cycle and preferably mass transfer, heat-transfer capability, be specially adapted to coalbed methane containing oxygen fluid bed deoxidization technique.This catalyst has reaction temperature window wide (400-750 ℃) simultaneously, and heat-resisting ability is strong, the advantages such as long service life.It is large to have the gas treatment amount after the fluid bed deoxidization technique is combined, and it is hot good to move, the advantages such as processing ease.
The specific embodiment
The present invention is further elaborated below in conjunction with some specific embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment, the content of each component is weight percentage in the embodiments of the invention.
Embodiment 1
The oxygen-containing coal bed gas deoxidation catalyst of present embodiment is comprised of the active component of 2 wt%, the auxiliary agent of 20 wt% and the carrier of 78 wt%, and active component is comprised of the Cu-Fe composite oxides, and Cu is by CuO, and Fe presses Fe
2O
3Meter, CuO and Fe
2O
3Mass ratio be 1:1, the raw materials Cu (NO of copper
3)
23H
2O, the raw materials of iron are Fe (NO
3)
39H
2O, the raw materials of auxiliary agent is the manganese nitrate solution that is equivalent to 10 wt% manganese dioxide, is equivalent to the magnesian Mg (NO of 2 wt%
3)
26H
2O, and be equivalent to the Zr (NO of 8 wt% zirconium dioxides
3)
45H
2O.Carrier is the gamma-alumina microballoon of 78 wt%, particle size range 100-500 μ m.
The oxygen-containing coal bed gas deoxidation catalyst preparation method of present embodiment is:
(1) with the Cu (NO of 3.04g
3)
23H
2Fe (the NO of O, 5.06g
3)
39H
2O, 41.17g contain the solution of manganese nitrate 50 wt%, the Mg (NO of 12.72g
3)
26H
2Zr (the NO of O and 27.87g
3)
45H
2O is dissolved in the 100g water, is made into the aqueous solution under constantly stirring;
(2) with in the aqueous solution in the 78g gamma-alumina microballoon immersion step (1), stir 1h; Room temperature volumetric dipping 24h; Then 110
oThe dry 4h of C, 600
oC roasting 6h makes dehydrogenation catalyst, and catalyst weight percentage consists of: CuO
0.01(Fe
2O
3)
0.01MgO
0.02(MnO
2)
0.10(ZrO
2)
0.08(γ-Al
2O
3)
0.78
The catalyst of present embodiment preparation reacts in the normal pressure fluidized bed reactor, and reaction condition and Evaluation results see Table 1.
Embodiment 2
The oxygen-containing coal bed gas deoxidation catalyst of present embodiment is comprised of the active component of 5 wt%, the auxiliary agent of 25 wt% and the carrier of 70 wt%, and active component is comprised of the Cu-Fe composite oxides, and Cu is by CuO, and Fe presses Fe
2O
3Meter, CuO and Fe
2O
3Mass ratio be 1:4, the raw materials Cu (NO of copper
3)
23H
2O, the raw materials of iron are FeSO
47H
2O, the raw materials of coagent is the manganese nitrate solution that is equivalent to 10 wt% manganese dioxide, is equivalent to the Ce (NO of 10 wt% cerias
3)
36H
2O, and be equivalent to the TiCl of 5 wt% titanium dioxide
4Carrier is the gamma-alumina microballoon of 70 wt%, particle size range 100-500 μ m.
The oxygen-containing coal bed gas deoxidation catalyst preparation method of present embodiment is:
(1) with the Cu (NO of 3.04g
3)
23H
2The FeSO of O, 13.90g
47H
2O, 41.17g contain the solution of manganese nitrate 50 wt%, the Ce (NO of 25.25g
3)
36H
2O is dissolved in the 90g water, is made into the aqueous solution, then is cooled to 5
oBelow the C, dropwise add 11.87g TiCl
4Solution must keep water temperature to be lower than 5 in whole dropping process
oC in order to keep titanium tetrachloride not to be hydrolyzed, then constantly stirs and forms the uniform aqueous solution;
(2) with in the aqueous solution in the 70g gamma-alumina microballoon immersion step (1), stir 1 h; The room temperature volumetric floods 36 h; Then 115
oThe dry 4h of C, 700
oC roasting 4 h make dehydrogenation catalyst, and catalyst weight percentage consists of: CuO
0.01(Fe
2O
3)
0.04(MnO
2)
0.10(CeO
2)
0.10(TiO
2)
0.05(γ-Al
2O
3)
0.70
The catalyst of present embodiment preparation reacts in the normal pressure fluidized bed reactor, and reaction condition and Evaluation results see Table 1.
Embodiment 3
The oxygen-containing coal bed gas deoxidation catalyst of present embodiment is comprised of the active component of 10 wt%, the auxiliary agent of 20 wt% and the carrier of 70 wt%, and active component is comprised of the Cu-Fe composite oxides, and Cu is by CuO, and Fe presses Fe
2O
3Meter, CuO and Fe
2O
3Mass ratio be 3:7, the raw materials CuSO of copper
45H
2O, the raw materials of iron are FeSO
47H
2O, the raw materials of coagent are the Zr (NO that is equivalent to 10 wt% zirconium dioxides
3)
45H
2O and the TiCl that is equivalent to 10 wt% titanium dioxide
4Carrier is the gamma-alumina microballoon of 70 wt%, particle size range 100-500 μ m.
The oxygen-containing coal bed gas deoxidation catalyst preparation method of present embodiment is:
(1) with the CuSO of 9.42g
45H
2The FeSO of O, 24.32g
47H
2O, the Zr (NO of 34.84g
3)
45H
2O is dissolved in the 90g water, is made into the aqueous solution, then is cooled to 5
oBelow the C, dropwise add 23.74g TiCl
4Solution must keep water temperature to be lower than 5 in whole dropping process
oC in order to keep titanium tetrachloride not to be hydrolyzed, then constantly stirs and forms the uniform aqueous solution;
(2) with in the aqueous solution in the 70g gamma-alumina microballoon immersion step (1), stir 1h; Room temperature volumetric dipping 36h; Then 110 ℃ of dry 4h, 700 ℃ of roasting 6h make dehydrogenation catalyst, and percentage by weight consists of: Catalysts Cu O
0.03(Fe
2O
3)
0.07(ZrO
2)
0.10(TiO
2)
0.10(γ-Al
2O
3)
0.70
The catalyst of present embodiment preparation reacts in the normal pressure fluidized bed reactor, and reaction condition and Evaluation results see Table 1.
Embodiment 4
The oxygen-containing coal bed gas deoxidation catalyst of present embodiment is comprised of the active component of 10 wt%, the auxiliary agent of 20 wt% and the carrier of 70 wt%, and active component is comprised of the Cu-Fe composite oxides, and Cu is by CuO, and Fe presses Fe
2O
3Meter, CuO and Fe
2O
3Mass ratio be 5:5, the raw materials Cu (NO of copper
3)
23H
2O, the raw materials of iron are Fe (NO
3)
39H
2O, the raw materials of coagent are the Ce (NO that is equivalent to 10 wt% cerias
3)
36H
2O and the Zr (NO that is equivalent to 10 wt% zirconium dioxides
3)
45H
2O.Carrier is the gamma-alumina microballoon of 70 wt%, particle size range 100-500 μ m.
The oxygen-containing coal bed gas deoxidation catalyst preparation method of present embodiment is:
(1) with the Cu (NO of 15.20g
3)
23H
2Fe (the NO of O, 25.25g
3)
39H
2O, the Ce (NO of 25.25g
3)
36H
2Zr (the NO of O and 34.84g
3)
45H
2O is dissolved in the 90g water, constantly stirs to form the uniform aqueous solution;
(2) with in the aqueous solution in the 70g gamma-alumina microballoon immersion step (1), stir 1h; Room temperature volumetric dipping 36h; Then 115 ℃ of dry 4h, 500 ℃ of roasting 6h make dehydrogenation catalyst, and catalyst weight percentage consists of: CuO
0.05(Fe
2O
3)
0.05(CeO
2)
0.10(ZrO
2)
0.10(γ-Al
2O
3)
0.70
The catalyst of present embodiment preparation reacts in the normal pressure fluidized bed reactor, and reaction condition and Evaluation results see Table 1.
Embodiment 5
The oxygen-containing coal bed gas deoxidation catalyst of present embodiment is comprised of the active component of 8 wt%, the auxiliary agent of 22 wt% and the carrier of 70 wt%, and active component is comprised of the Cu-Fe composite oxides, and Cu is by CuO, and Fe presses Fe
2O
3Meter, CuO and Fe
2O
3Mass ratio be 2:6, the raw materials Cu (NO of copper
3)
23H
2O, the raw materials of iron are Fe (NO
3)
39H
2O, the raw materials of coagent are the Ce (NO that is equivalent to 10 wt% cerias
3)
36H
2O is equivalent to the Zr (NO of 10 wt% zirconium dioxides
3)
45H
2O and the Ca (NO that is equivalent to the calcium oxide of 2 wt%
3)
24H
2O.Carrier is the silicon dioxide microsphere of 70 wt%, particle size range 200-1000 μ m.
The oxygen-containing coal bed gas deoxidation catalyst preparation method of present embodiment is:
(1) with the Cu (NO of 6.08g
3)
23H
2Fe (the NO of O, 30.36g
3)
39H
2O, the Ce (NO of 25.25g
3)
36H
2O, the Zr (NO of 34.84g
3)
45H
2O and 8.44g Ca (NO
3)
24H
2O is dissolved in the 100g water, constantly stirs to form the uniform aqueous solution;
(2) with in the aqueous solution in the 70g silicon dioxide microsphere immersion step (1), stir 2h; Room temperature volumetric dipping 18h; Then 110
oThe dry 4h of C, 600
oC roasting 6h makes dehydrogenation catalyst, and catalyst weight percentage consists of: CuO
0.02(Fe
2O
3)
0.06CaO
0.02(CeO
2)
0.10(ZrO
2)
0.10(SiO
2)
0.70
The catalyst of present embodiment preparation reacts in the normal pressure fluidized bed reactor, and reaction condition and Evaluation results see Table 1.
Embodiment 6
The oxygen-containing coal bed gas deoxidation catalyst of present embodiment is comprised of the active component of 4 wt%, the auxiliary agent of 20 wt% and the carrier of 76 wt%, and active component is comprised of the Cu-Fe composite oxides, and Cu is by CuO, and Fe presses Fe
2O
3Meter, CuO and Fe
2O
3Mass ratio be 2:2, the raw materials Cu (NO of copper
3)
23H
2O, the raw materials of iron are Fe (NO
3)
39H
2O, the raw materials of coagent is the manganese nitrate solution that is equivalent to 10 wt% manganese dioxide, is equivalent to the magnesian Mg (NO of 2 wt%
3)
26H
2O, and be equivalent to the Zr (NO of 8 wt% zirconium dioxides
3)
45H
2O.Carrier is the silicon dioxide microsphere of 76 wt%, particle size range 100-800 μ m.
The oxygen-containing coal bed gas deoxidation catalyst preparation method of present embodiment is:
(1) with the Cu (NO of 6.08g
3)
23H
2Fe (the NO of O, 10.12g
3)
39H
2O, 41.17g contain the solution of manganese nitrate 50%, the Mg (NO of 12.72g
3)
26H
2Zr (the NO of O and 27.87g
3)
45H
2O is dissolved in the 100g water, is made into the aqueous solution under constantly stirring;
(2) with in the aqueous solution in the 76g silicon dioxide microsphere immersion step (1), stir 2h; Room temperature volumetric dipping 24h; Then 120
oThe dry 4h of C, 650
oC roasting 6h makes dehydrogenation catalyst, and catalyst weight percentage consists of: CuO
0.02(Fe
2O
3)
0.02MgO
0.02(MnO
2)
0.10(ZrO
2)
0.08(SiO
2)
0.76
The catalyst of present embodiment preparation reacts in the normal pressure fluidized bed reactor, and reaction condition and Evaluation results see Table 1.
Embodiment 7
The oxygen-containing coal bed gas deoxidation catalyst of present embodiment is comprised of the active component of 3 wt%, the auxiliary agent of 22 wt% and the carrier of 75 wt%, and active component is comprised of the Cu-Fe composite oxides, and Cu is by CuO, and Fe presses Fe
2O
3Meter, CuO and Fe
2O
3Mass ratio be 1:2, the raw materials Cu (NO of copper
3)
23H
2O, the raw materials of iron are FeSO
47H
2O, the raw materials of coagent are the Ce (NO that is equivalent to 10 wt% cerias
3)
36H
2O is equivalent to the TiCl of 10 wt% titanium dioxide
4(NH with the molybdenum dioxide that is equivalent to 2 wt%
4)
2Mo
2O
7Carrier is the silicon dioxide microsphere of 75 wt%, particle size range 50-600 μ m.
The oxygen-containing coal bed gas deoxidation catalyst preparation method of present embodiment is:
(1) with the Cu (NO of 3.04g
3)
23H
2The FeSO of O, 6.85g
47H
2Ce (the NO of O, 25.25g
3)
36H
2(the NH of O and 2.66g
4)
2Mo
2O
7Be dissolved in the 100g water, be made into the aqueous solution, then be cooled to below 5 ℃, dropwise add the TiCl of 23.74g
4Solution must keep water temperature to be lower than 5 ℃ in whole dropping process, in order to keep titanium tetrachloride not to be hydrolyzed; Constantly stir and form the uniform aqueous solution;
(2) with in the aqueous solution in the 75g silicon dioxide microsphere immersion step (1), stir 2h; Room temperature volumetric dipping 24h; Then 110 ℃ of dry 4h, 600 ℃ of roasting 4h make dehydrogenation catalyst, and catalyst weight percentage consists of: CuO
0.01(Fe
2O
3)
0.02(MoO
2)
0.02(CeO
2)
0.10(TiO
2)
0.08(SiO
2)
0.75
The catalyst of present embodiment preparation reacts in the normal pressure fluidized bed reactor, and reaction condition and Evaluation results see Table 1.
Embodiment 8
The oxygen-containing coal bed gas deoxidation catalyst of present embodiment is comprised of the active component of 4 wt%, the auxiliary agent of 20 wt% and the carrier of 76 wt%, and active component is comprised of the Cu-Fe composite oxides, and Cu is by CuO, and Fe presses Fe
2O
3Meter, CuO and Fe
2O
3Mass ratio be 2:2, the raw materials Cu (NO of copper
3)
23H
2O, the raw materials of iron are Fe (NO
3)
39H
2O, the raw materials of coagent are the Ce (NO that is equivalent to 10 wt% cerias
3)
36H
2O and the Zr (NO that is equivalent to 10 wt% zirconium dioxides
3)
45H
2O.Carrier is the alpha-aluminium oxide microballoon of 76 wt%, particle size range 100-1000 μ m.
The oxygen-containing coal bed gas deoxidation catalyst preparation method of present embodiment is:
(1) with the Cu (NO of 6.08g
3)
23H
2Fe (the NO of O, 10.10g
3)
39H
2O, the Ce (NO of 25.25g
3)
36H
2Zr (the NO of O and 34.84g
3)
45H
2O is dissolved in the 90g water, constantly stirs to form the uniform aqueous solution;
(3) with in the aqueous solution in the 76g alpha-aluminium oxide microballoon immersion step (1), stir 1h; Room temperature volumetric dipping 48h; Then 110 ℃ of dry 6h, 700 ℃ of roasting 6h make dehydrogenation catalyst.Catalyst weight percentage consists of: CuO
0.02(Fe
2O
3)
0.02(CeO
2)
0.10(ZrO
2)
0.10(α-Al
2O
3)
0.76
The catalyst of present embodiment preparation reacts in the normal pressure fluidized bed reactor, and reaction condition and Evaluation results see Table 1.
Embodiment 9
The oxygen-containing coal bed gas deoxidation catalyst of present embodiment is comprised of the active component of 11 wt%, the auxiliary agent of 20 wt% and the carrier of 69 wt%, and active component is comprised of the Cu-Fe composite oxides, and Cu is by CuO, and Fe presses Fe
2O
3Meter, CuO and Fe
2O
3Mass ratio be 1:10, the raw materials Cu (NO of copper
3)
23H
2O, the raw materials of iron are Fe (NO
3)
39H
2O, the raw materials of coagent are the Ce (NO that is equivalent to 10 wt% cerias
3)
36H
2O and the Zr (NO that is equivalent to 10 wt% zirconium dioxides
3)
45H
2O.Carrier is the silicon dioxide microsphere of 69 wt%, particle size range 200-1000 μ m.
The oxygen-containing coal bed gas deoxidation catalyst preparation method of present embodiment is:
(1) with the Cu (NO of 3.04g
3)
23H
2Fe (the NO of O, 50.50g
3)
39H
2O, the Ce (NO of 25.25g
3)
36H
2Zr (the NO of O and 34.84g
3)
45H
2O is dissolved in the 90g water, constantly stirs to form the uniform aqueous solution;
(2) with in the aqueous solution in the 69g silicon dioxide microsphere immersion step (1), stir 1h; Room temperature volumetric dipping 48h; Then 115 ℃ of dry 6h, 600 ℃ of roasting 6h make catalyst, and catalyst weight percentage consists of: CuO
0.01(Fe
2O
3)
0.10(CeO
2)
0.10(ZrO
2)
0.10(SiO
2)
0.69
The catalyst of present embodiment preparation reacts in the normal pressure fluidized bed reactor, and reaction condition and Evaluation results see Table 1.
Table 1 catalyst fluidized bed activity rating result
Remarks: the unstripped gas oxygen content is 4-14 vol.%(volume ratio), methane content 30-80 vol.%, all the other are nitrogen, the fluid bed evaluation
Claims (9)
1. supported non-noble metal oxygen-containing coal bed gas deoxidation catalyst, it is characterized in that catalyst is comprised of active component, auxiliary agent and carrier, in oxide, the weight percentage of active component is 0.5-30 wt%, the content of auxiliary agent is 2-40 wt%, and all the other are carrier.
2. a kind of supported non-noble metal oxygen-containing coal bed gas deoxidation catalyst as claimed in claim 1 is characterized in that described active component is the composite oxides of Cu and Fe, the CuO/Fe of copper iron compound oxide
2O
3Weight ratio be between the 1:1-10.
3. a kind of supported non-noble metal oxygen-containing coal bed gas deoxidation catalyst as claimed in claim 1 is characterized in that auxiliary agent is one or more in Mg, Mn, Mo, Ti, Ce, Zr, the Ca oxide.
4. a kind of supported non-noble metal oxygen-containing coal bed gas deoxidation catalyst as claimed in claim 1 is characterized in that described carrier is aluminum oxide micro-sphere, molecular sieve microballoon or silicon dioxide microsphere, and the particle size range of carrier microballoons is 10-1500 μ m.
5. a kind of supported non-noble metal oxygen-containing coal bed gas deoxidation catalyst as claimed in claim 1 is characterized in that described aluminum oxide micro-sphere carrier is alpha-aluminium oxide microballoon or gamma-alumina microballoon.
6. such as the preparation method of each described a kind of supported non-noble metal oxygen-containing coal bed gas deoxidation catalyst of claim 1-5, it is characterized in that equi-volume impregnating, the steps include:
(1) soluble-salt of active component and the soluble-salt of auxiliary agent are mixed with the aqueous solution by the catalyst composition;
(2) the carrier microballoons equal-volume slowly is impregnated in the aqueous solution of step (1), dipping is 12-48 hour under the normal temperature, 110-120
oDry 4-6 hour of C, 400-700
oC roasting 4-8 hour makes dehydrogenation catalyst.
7. the preparation method of a kind of supported non-noble metal oxygen-containing coal bed gas deoxidation catalyst as claimed in claim 6, the soluble-salt that it is characterized in that described Cu active component is copper sulphate, Schweinfurt green or copper nitrate; The soluble-salt of Fe active component is any one or two kinds in ferric nitrate, ferrous nitrate, ferric oxalate, frerrous chloride, the ferrous sulfate.
8. the preparation method of a kind of supported non-noble metal oxygen-containing coal bed gas deoxidation catalyst as claimed in claim 6, the soluble-salt that it is characterized in that described auxiliary agent is one or more of the solubility nitrate of Mg, Mn, Mo, Ce, Zr, Ca or Ti, Ca, Zr chloride salt.
9. such as the application of each described a kind of supported non-noble metal oxygen-containing coal bed gas deoxidation catalyst of claim 1-5, it is characterized in that for coalbed methane containing oxygen fluid bed deoxidization technique, the oxygen content of coalbed methane containing oxygen is in 4-14 vol.% scope, and the unstripped gas air speed is 1000-30000 h
-1, the temperature of catalyst deoxygenation is between 400-750
oC, pressure are under the condition of normal pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103651147A CN102872883A (en) | 2012-09-26 | 2012-09-26 | Supported non-noble metal oxygen-containing coalbed methane deoxidation catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103651147A CN102872883A (en) | 2012-09-26 | 2012-09-26 | Supported non-noble metal oxygen-containing coalbed methane deoxidation catalyst and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102872883A true CN102872883A (en) | 2013-01-16 |
Family
ID=47474528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103651147A Pending CN102872883A (en) | 2012-09-26 | 2012-09-26 | Supported non-noble metal oxygen-containing coalbed methane deoxidation catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102872883A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103432896A (en) * | 2013-08-23 | 2013-12-11 | 西南化工研究设计院有限公司 | Cleaning agent for removing impurity oxygen in reducing gases including synthesis gas and the like as well as preparation method and application of cleaning agent |
| CN103599792A (en) * | 2013-11-15 | 2014-02-26 | 四川大学 | Preparation method and application of catalyst for removing oxygen in oxygen-containing gas by using methanol |
| CN105107508A (en) * | 2015-07-21 | 2015-12-02 | 华烁科技股份有限公司 | Coalbed methane sulfur-tolerant deoxidizing monolithic catalyst and preparation method thereof |
| CN106378186A (en) * | 2016-10-26 | 2017-02-08 | 南京碳环生物质科技有限公司 | Preparation method of non-noble-metal biogas deoxidation catalyst |
| CN108928803A (en) * | 2017-05-27 | 2018-12-04 | 中国石油化工股份有限公司 | A kind of method of chloration hydro-oxidation production chlorine |
| CN109772440A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of coal gas layer catalyst for catalytic combustion and preparation method thereof |
| CN109772441A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of catalyst of core-shell structure and its preparation method and application |
| CN116116409A (en) * | 2023-01-12 | 2023-05-16 | 北京市飞达捷能气体分离技术有限公司 | A combustion type gas deoxidation catalyst and its preparation method |
| CN119281315A (en) * | 2024-12-12 | 2025-01-10 | 上海化工研究院有限公司 | A CO2 catalytic conversion catalyst and its preparation method and application |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050862A (en) * | 1989-09-19 | 1991-04-24 | 联合碳化化学品及塑料有限公司 | Oxidative coupling is produced the method for height ratio ethylene ratio ethane hydrocarbon |
| CN1623658A (en) * | 2003-12-04 | 2005-06-08 | 中国科学院兰州化学物理研究所 | Methane catalytic combustion solid solution catalyst and preparation method thereof |
| CN101301611A (en) * | 2008-07-07 | 2008-11-12 | 西南化工研究设计院 | Sulfur-tolerance deoxidation catalyst and preparation and use thereof |
| CN101322942A (en) * | 2008-07-29 | 2008-12-17 | 西南化工研究设计院 | Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications |
| CN101664679A (en) * | 2009-11-17 | 2010-03-10 | 中国科学院大连化学物理研究所 | Coal bed gas deoxidation catalyst as well as preparation method and application thereof |
| CN101912783A (en) * | 2010-08-31 | 2010-12-15 | 西南化工研究设计院 | Catalyst for combustion of ventilation air methane and preparation method thereof |
| CN101947457A (en) * | 2010-08-31 | 2011-01-19 | 西南化工研究设计院 | Ventilation air methane combustion catalyst and preparation method thereof |
| CN102266768A (en) * | 2010-07-29 | 2011-12-07 | 西南化工研究设计院 | Catalyst with functions of methane catalytic combustion and conversion, and preparation method thereof |
| CN102302931A (en) * | 2011-07-11 | 2012-01-04 | 大连瑞克科技有限公司 | Catalytic combustion deoxidation catalyst for oxygen-containing methane mixed gas, as well as preparation method and application thereof |
| CN102553585A (en) * | 2011-12-23 | 2012-07-11 | 新地能源工程技术有限公司 | Sulfur-tolerant catalyst for gas deoxidation as well as preparation method and application thereof |
-
2012
- 2012-09-26 CN CN2012103651147A patent/CN102872883A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050862A (en) * | 1989-09-19 | 1991-04-24 | 联合碳化化学品及塑料有限公司 | Oxidative coupling is produced the method for height ratio ethylene ratio ethane hydrocarbon |
| CN1623658A (en) * | 2003-12-04 | 2005-06-08 | 中国科学院兰州化学物理研究所 | Methane catalytic combustion solid solution catalyst and preparation method thereof |
| CN101301611A (en) * | 2008-07-07 | 2008-11-12 | 西南化工研究设计院 | Sulfur-tolerance deoxidation catalyst and preparation and use thereof |
| CN101322942A (en) * | 2008-07-29 | 2008-12-17 | 西南化工研究设计院 | Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications |
| CN101664679A (en) * | 2009-11-17 | 2010-03-10 | 中国科学院大连化学物理研究所 | Coal bed gas deoxidation catalyst as well as preparation method and application thereof |
| CN102266768A (en) * | 2010-07-29 | 2011-12-07 | 西南化工研究设计院 | Catalyst with functions of methane catalytic combustion and conversion, and preparation method thereof |
| CN101912783A (en) * | 2010-08-31 | 2010-12-15 | 西南化工研究设计院 | Catalyst for combustion of ventilation air methane and preparation method thereof |
| CN101947457A (en) * | 2010-08-31 | 2011-01-19 | 西南化工研究设计院 | Ventilation air methane combustion catalyst and preparation method thereof |
| CN102302931A (en) * | 2011-07-11 | 2012-01-04 | 大连瑞克科技有限公司 | Catalytic combustion deoxidation catalyst for oxygen-containing methane mixed gas, as well as preparation method and application thereof |
| CN102553585A (en) * | 2011-12-23 | 2012-07-11 | 新地能源工程技术有限公司 | Sulfur-tolerant catalyst for gas deoxidation as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 储伟主编: "《催化剂工程》", 30 September 2006, article "浸渍法" * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103432896A (en) * | 2013-08-23 | 2013-12-11 | 西南化工研究设计院有限公司 | Cleaning agent for removing impurity oxygen in reducing gases including synthesis gas and the like as well as preparation method and application of cleaning agent |
| CN103432896B (en) * | 2013-08-23 | 2015-09-09 | 西南化工研究设计院有限公司 | A kind of cleanser and Synthesis and applications thereof removing impurity oxygen in the reducibility gas such as synthesis gas |
| CN103599792A (en) * | 2013-11-15 | 2014-02-26 | 四川大学 | Preparation method and application of catalyst for removing oxygen in oxygen-containing gas by using methanol |
| CN105107508A (en) * | 2015-07-21 | 2015-12-02 | 华烁科技股份有限公司 | Coalbed methane sulfur-tolerant deoxidizing monolithic catalyst and preparation method thereof |
| CN106378186B (en) * | 2016-10-26 | 2019-01-04 | 南京碳环生物质科技有限公司 | A kind of preparation method of base metal type biogas dehydrogenation catalyst |
| CN106378186A (en) * | 2016-10-26 | 2017-02-08 | 南京碳环生物质科技有限公司 | Preparation method of non-noble-metal biogas deoxidation catalyst |
| CN108928803A (en) * | 2017-05-27 | 2018-12-04 | 中国石油化工股份有限公司 | A kind of method of chloration hydro-oxidation production chlorine |
| CN109772440A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of coal gas layer catalyst for catalytic combustion and preparation method thereof |
| CN109772441A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of catalyst of core-shell structure and its preparation method and application |
| 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 |
| CN116116409A (en) * | 2023-01-12 | 2023-05-16 | 北京市飞达捷能气体分离技术有限公司 | A combustion type gas deoxidation catalyst and its preparation method |
| CN119281315A (en) * | 2024-12-12 | 2025-01-10 | 上海化工研究院有限公司 | A CO2 catalytic conversion catalyst and its preparation method and application |
| CN119281315B (en) * | 2024-12-12 | 2025-03-21 | 上海化工研究院有限公司 | A CO2 catalytic conversion catalyst and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102872883A (en) | Supported non-noble metal oxygen-containing coalbed methane deoxidation catalyst and preparation method and application thereof | |
| CN101322942B (en) | Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications | |
| CN103373706B (en) | A kind of methane reforming hydrogen production process and device | |
| CN106238046B (en) | Preparation method and application of supported rhodium-based catalyst with perovskite as precursor | |
| CN101637726A (en) | Preparation method of catalyst for preparing synthesis gas by reforming methane-carbon dioxide | |
| Tian et al. | Using a hierarchically-structured CuO@ TiO2-Al2O3 oxygen carrier for chemical looping air separation in a paralleled fluidized bed reactor | |
| He et al. | Application of Fe2O3/Al2O3 composite particles as oxygen carrier of chemical looping combustion | |
| CN101301611A (en) | Sulfur-tolerance deoxidation catalyst and preparation and use thereof | |
| ZHANG | Recent advances in integrated carbon dioxide capture and methanation technology | |
| CN102674247B (en) | A kind of method of decarburization and the dual forced methane steam reforming hydrogen manufacturing of dehydrogenation and device | |
| CN101108350B (en) | Hydrocarbon steam conversion catalyst and preparation method thereof | |
| CN102302931A (en) | Catalytic combustion deoxidation catalyst for oxygen-containing methane mixed gas, as well as preparation method and application thereof | |
| CN111097447A (en) | Catalyst for low-temperature catalytic cracking of methane to produce hydrogen, preparation method thereof and low-temperature catalytic cracking method for methane to produce hydrogen | |
| CN101912783B (en) | Catalyst for combustion of ventilation air methane and preparation method thereof | |
| Li et al. | Integrated Carbon Dioxide Capture and Utilization for the Production of CH4, Syngas and Olefins over Dual‐Function Materials | |
| CN103816913A (en) | Catalyst for preparing synthetic gas by reforming of methane and carbon dioxide as well as preparation method and application of catalyst | |
| CN102600912B (en) | Pretreatment method for improving performance of methane and carbon dioxide dry reforming catalyst | |
| Waikar et al. | A review on Chemical Looping Water Splitting (CLWS) as a potential alternative to Steam Methane Reforming (SMR) for hydrogen production | |
| CN105080564A (en) | Catalyst used for preparation of carbon monoxide by conversion of carbon dioxide and use method thereof | |
| Min et al. | CO production via thermochemical CO2 splitting over Ni ferrite-based catalysts | |
| JP5897722B2 (en) | Method for preparing carbon dioxide methanation catalyst | |
| CN117504577A (en) | Preparation method of CaO-based dual-function material, caO-based dual-function material and application thereof | |
| CN101767031B (en) | Low temperature conversion catalyst for partial oxidation of methane to syngas | |
| CN105642289A (en) | Preparation method of catalyst for complete methanation of syngas | |
| CN103374431A (en) | Oxygen carrier, preparation method therefor, and applications thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130116 |