CN1171677C - A Noble Metal Catalyst for Selective Oxidation Purification of Trace Carbon Monoxide in Methanol Reformed Gas - Google Patents
A Noble Metal Catalyst for Selective Oxidation Purification of Trace Carbon Monoxide in Methanol Reformed Gas Download PDFInfo
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- CN1171677C CN1171677C CNB011389087A CN01138908A CN1171677C CN 1171677 C CN1171677 C CN 1171677C CN B011389087 A CNB011389087 A CN B011389087A CN 01138908 A CN01138908 A CN 01138908A CN 1171677 C CN1171677 C CN 1171677C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 18
- 230000003647 oxidation Effects 0.000 title claims abstract description 17
- 238000000746 purification Methods 0.000 title claims abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract 7
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract 7
- 239000010970 precious metal Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002808 molecular sieve Substances 0.000 claims abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims abstract 2
- 238000001035 drying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 38
- 239000007789 gas Substances 0.000 abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 230000009257 reactivity Effects 0.000 abstract description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000002803 maceration Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
一种用于甲醇重整气中微量一氧化碳选择氧化净化的贵金属催化剂，其特征在于：该催化剂为复合载体多活性组分的担载型催化剂，通式为M1M2/S1S2；其中M1为主要活性组分贵金属Pt，M2为金属元素Fe、Co、Ni、Cu、Zn之一种或几种；S1为MD型分子筛，S2为ZrO2、TiO2的一种或两种；M1含量为催化剂总量的0.2～1.0%wt，M2含量为催化剂总量的0.2～5.0%wt，载体含量为催化剂总量的94.0～99.6%(wt)，其中S1/S2＝1～3.5。本发明催化剂具有反应活性高、稳定性好，选择性好的特点。本发明催化剂在还原气氛下，反应前不需预还原，反应后不需通气保护，多次启动性能无衰变。本发明催化剂操作的温度范围宽，易于车载氢源净化的操作控制。A precious metal catalyst for selective oxidation and purification of trace amounts of carbon monoxide in methanol reformed gas, characterized in that the catalyst is a supported catalyst with multiple active components on a composite carrier, and the general formula is M 1 M 2 /S 1 S 2 ; Among them, M 1 is the main active component noble metal Pt, M 2 is one or more of metal elements Fe, Co, Ni, Cu, Zn; S 1 is MD type molecular sieve, S 2 is a kind of ZrO 2 , TiO 2 or two; M1 content is 0.2-1.0%wt of the total catalyst, M2 content is 0.2-5.0%wt of the total catalyst, and the carrier content is 94.0-99.6% (wt) of the total catalyst, wherein S1 /S 2 =1 to 3.5. The catalyst of the invention has the characteristics of high reactivity, good stability and good selectivity. In the reducing atmosphere, the catalyst of the present invention does not need pre-reduction before the reaction, does not need ventilating protection after the reaction, and has no decay in the performance of multiple start-ups. The catalyst of the invention has a wide operating temperature range, and is easy to operate and control the purification of vehicle-mounted hydrogen sources.
Description
Technical field:
The present invention relates to the methanol recapitalization technology, a kind of noble metal catalyst that is used for the methanol reformed gas selective oxidation cleaning of micro CO is provided especially.
Background technology:
CO is the poisonous substance of proton exchange membrane fuel cell electrode catalyst.External report current battery electrode can the content of anti-CO be 100～1000ppm, and domestic research level has determined that fuel cell can only anti-CO be below the 10ppm.For adapting to present situation, must invent a kind of practical technique that trace amounts of CO in the fuel cell hydrogen source can be reduced to below the 10ppm, its key is Study of Catalyst.According to reported in literature, at present, adopt the noble metal supported catalyst, but bullion content is up to about 5% more.Once on Applied Catalysis A (General 159 (1997) 159-169), delivered one piece of article as people such as Hiroshi Igarashi, be intended to remove the kinetic reaction of catalyst, investigate the selection of catalysts oxidation susceptibility by micro CO to the fuel cell enriched gas source.The author is with Pt/ zeolite and Pt/Al
2O
3, catalyst contrasts, and the catalyst Pt loading is 6.0 ± 0.2% (wt%), catalyst loading amount 0.1 gram, it is CO=1%, O that unstripped gas is formed (vol%)
2=0.5～3%, H
2=96～98.5%.As a result, at H
2Excessive and O
2Under the very low situation of content, the CO oxidation selectivity ratios Pt/Al of Pt/ zeolite catalyst
2O
3Catalyst height, selectivity depend on O in catalyst carrier and the gas
2Content, selectivity is along with O
2The reduction of content and improving.In all Pt/ zeolite catalysts, the Pt/ mordenite catalyst has the highest CO conversion ratio.When adopting two-stage reactor, O
2It is minimum that addition can reduce to.
Technology contents:
The invention provides a kind of noble metal catalyst that is used for the methanol reformed gas selective oxidation cleaning of micro CO, it is characterized in that: this catalyst is the supported catalyst of complex carrier multiple active components, and general formula is M
1M
2/ S
1S
2Wherein
M
1Be main active component precious metals pt, M
2Be one or more of metallic element Fe, Co, Ni, Cu, Zn; S
1Be MD type molecular sieve, S
2Be ZrO
2, TiO
2One or both;
M
1Content is 0.2～1.0%wt of catalyst total amount, is good with 0.4～1.0wt%, M
2Content is 0.2～5.0%wt of catalyst total amount, is good with 0.5～4.5wt%, and vector contg is 94.0～99.6%wt of catalyst total amount, wherein S
1/ S
2=1～3.5, be good with 2～3.0.
The present invention also provides a kind of above-mentioned preparation method who is used for the noble metal catalyst of methanol reformed gas selective oxidation cleaning of micro CO, it is characterized in that preparation process is as follows:
Take by weighing 120～160 order S respectively according to weight proportion
1, S
2Powder mixes it, and adding forming agent, to be rolled onto φ 1～3mm spherical, and room temperature was placed after 4～5 hours, placed 110 ℃ of dryings of drying box 4～5 hours, and 500 ℃ of roastings of baking oven 4 hours are taken out after reducing to room temperature;
Carrier is poured in the maceration extract, stir 1 hour at a slow speed under the room temperature condition after, placed 48 hours, placed 110 ℃ of dryings of drying box 4～5 hours, 500 ℃ of roastings of baking oven 4 hours are taken out after reducing to room temperature, promptly make catalyst.
Catalyst of the present invention is a kind of supported catalyst of complex carrier multiple active components, and its catalytic action is respectively: M
1Be main catalyst component; M
2For helping catalyst component, mainly be to improve CO oxidation selectivity; S
1Be molecular sieve, mainly act as the decentralization that improves noble metal; S
2Mainly act as the stability that improves catalyst.
Catalyst of the present invention is used for 5KW level fuel cell hydrogen source, and (gas production is 12m
3/ hr)---and the cleaning system of trace amounts of CO in the preparing hydrogen by reforming methanol gas, catalyst loading amount 3～6 liters, it is H that unstripped gas is formed (vol%)
2: 46～49; N
2: 29～32; CO:0.6～1.60; CH
4: 0.09～0.26; CO
2: 20～21; Except said components, also contain methyl alcohol, dimethyl ether and the C of trace in the unstripped gas
2,, C
3, C
4Deng hydrocarbons, its content changes with the condition of oxidation and reformation of methanol reaction.Reaction condition is: system pressure 0.24MPa, 56～230 ℃ of reaction temperatures, air speed 2000～12000h
-1Reaction result: tail gas CO content is below the 10ppm, H
2Content (vol%) is 43～46.Up to now, do not see the report of the catalyst that this kind performance is arranged.
Catalyst selectivity of the present invention is good, and consumption hydrogen is few, suppresses the hydrogen-oxygen oxidation reaction, improves the CO oxidation activity.
Catalyst of the present invention does not need prereduction before the reaction under reducing atmosphere, the protection of need not ventilating after the reaction, and repeatedly startability does not have decay, is applicable to the gas purification of onboard hydrogen source.
The temperature range of catalyst operation of the present invention is wide, is easy to the operation control that on-board hydrogen source CO purifies.The good stability of catalyst of the present invention has passed through the life test more than 1000 hours, and activity is not found to descend.
In a word, the present invention has developed a kind of well behaved methanol reformed gas selective oxidation cleaning of micro CO catalyst that is used for, and this catalyst has reactivity height, good stability, the characteristics that selectivity is good.Catalyst of the present invention does not need prereduction before the reaction under reducing atmosphere, the protection of need not ventilating after the reaction, and repeatedly startability does not have decay.The temperature range of catalyst operation of the present invention is wide, is easy to the operation control that on-board hydrogen source purifies.
The specific embodiment:
Preparation of Catalyst all adopts following method preparation in the embodiment of the invention, and do not limit the present invention certainly: used catalyst component is except that Pt, and all the other nitrate that adopt them substantially are raw material, and the activity of such catalysts component is a step impregnation.Be specially the preparation of (1) carrier: take by weighing a certain amount of S respectively according to above-mentioned weight proportion
1, S
2Powder (through 500 ℃ of roastings 1 hour, 120～160 orders) mixes it, add forming agent and be rolled onto that spherical (φ 1～3mm), and room temperature was placed after 4～5 hours, placed 110～120 ℃ of dryings of drying box 4～5 hours, 500 ℃ of roastings of baking oven 4 hours are taken out after reducing to room temperature.(2) Preparation of catalysts: 1. take by weighing a certain amount of carrier,, calculate the content of Pt, calculate the weight of corresponding salt then, it is dissolved in a certain amount of deionized water according to above-mentioned active component content ratio.2. maceration extract is adjusted to PH6～8, carrier is poured in the maceration extract, stir 1 hour at a slow speed under 100 ℃ of water bath condition after, placed 48 hours, placed 110～120 ℃ of dryings of drying box 4～5 hours, 500 ℃ of roastings of baking oven 4 hours are taken out after reducing to room temperature.3. calculate the various content that help catalyst component by the carrier amount, calculate the weight of corresponding nitrate then, it is dissolved in a certain amount of deionized water.Pour the catalyst that 2. makes in the maceration extract (incipient impregnation), room temperature condition was placed 48 hours down, placed 110～120 ℃ of dryings of drying box 4～5 hours, and 500 ℃ of roastings of baking oven 4 hours are reduced to take out after the room temperature and promptly made catalyst.
Embodiment 1
Make catalyst according to above-mentioned preparation method.M wherein
1(precious metals pt) content is 0.2% (wt) of catalyst total amount; M
2(metal Ni) content is 0.2% (wt) of catalyst total amount; Carrier S (S
1+ S
2) content is 99.6% (wt), wherein S of catalyst total amount
1Be molecular sieve MD, S
2Be ZrO
2, S
1/ S
2=1.
Embodiment 2
Get embodiment 1 catalyst 10ml (8.5 gram), the internal diameter of packing into is the reactor constant temperature zone of 12mm.Methanol reformed gas feeds reactor, and it is H that unstripped gas is formed (vol%)
2: 49～52; N
2: 23～28; CO:0.5～2.2; CH
4: 0.2～0.3; CO
2: 20～23; Except above-mentioned product, also contain methyl alcohol, dimethyl ether and the C of trace in the gas
2, C
3, C
4Deng hydrocarbons, its content changes with the condition of oxidation and reformation of methanol reaction.Methyl alcohol and C
2, C
3, C
4Lower Deng hydrocarbons content, be about tens to hundreds of ppm, dimethyl ether content is higher relatively, is about 1.2～1.5%.System pressure is normal pressure 0.2MPa; Air speed is 2200～3000h
-1When reaction temperature is 80～160 ℃ the outlet tail gas in CO content be below the 10ppm.When reaction temperature was 125 ± 3 ℃, reaction was through tens of inferior tests that stop, open, and accumulative total is after more than 1000 hour, and catalyst activity does not reduce trend, has good stability.
Embodiment 3
Press embodiment 1 same quadrat method, make catalyst.M wherein
1(precious metals pt) content is 0.2% (wt) of catalyst total amount; M
2(metal Cu) content is 0.2% (wt) of catalyst total amount; Carrier S (S
1+ S
2) content is 99.6% (wt), wherein S of catalyst total amount
1Be molecular sieve MD, S
2Be ZrO
2, S
1/ S
2=1.
Embodiment 4
Get embodiment 3 catalyst 1ml (0.84 gram), the internal diameter of packing into is the reactor constant temperature zone of 6mm.The steel cylinder distribution feeds reactor, and it is H that unstripped gas is formed (vol%)
2: 41.59; N
2: 27.47; CO:1.53; CH
4: 1.10; CO
2: 28.13; CH
3OCH
3: 0.4010; O
2/ CO:1.21.System pressure is normal pressure 0.1MPa; Air speed is 4000h
-1When reaction temperature is 80～160 ℃ the outlet tail gas in CO content be below the 10ppm.When reaction temperature was 145 ± 3 ℃, reaction stopped, opens test through tens times, and accumulative total is after nearly 120 hours, and catalyst activity does not reduce trend, has good stability.
Embodiment 5
Press embodiment 1 same quadrat method, make catalyst.M wherein
1(precious metals pt) content is 0.2% (wt) of catalyst total amount; M
2(metal Ni) content is 5.0% (wt) of catalyst total amount; Carrier S (S
1+ S
2) content is 94.8% (wt), wherein S of catalyst total amount
1Be molecular sieve MD, S
2Be ZrO
2, S
1/ S
2=3.5.
Embodiment 6
Get embodiment 5 catalyst 1ml (0.85 gram), carry out catalyst performance evaluation, export when reaction temperature is 85～154 ℃ that CO content is below the 10ppm in the tail gas with example 4 same reaction devices.When reaction temperature was 125 ± 3 ℃, reaction stopped, opens test through tens times, and accumulative total is after nearly 100 hours, and catalyst activity does not reduce trend, has good stability.
Embodiment 7
Press embodiment 1 same quadrat method, make catalyst.M wherein
1(precious metals pt) content is 0.2% (wt) of catalyst total amount; M
2(metal Ni) content is 5.0% (wt) of catalyst total amount; Carrier S (S
1+ S
2) content is 94.8% (wt), wherein S of catalyst total amount
1Be molecular sieve MD, S
2Be ZrO
2, S
1/ S
2=3.5.
Embodiment 8
Get embodiment 7 catalyst 1ml (0.83 gram), carry out catalyst performance evaluation, export when reaction temperature is 105～174 ℃ that CO content is below the 10ppm in the tail gas with example 4 same reaction devices.
Embodiment 9
Press embodiment 1 same quadrat method, make catalyst.M wherein
1(precious metals pt) content is 1.0% (wt) of catalyst total amount; M
2(metal Ni) content is 0.2% (wt) of catalyst total amount; Carrier S (S
1+ S
2) content is 98.8% (wt), wherein S of catalyst total amount
1Be molecular sieve MD, S
2Be TiO
2, S
1/ S
2=1.
Embodiment 10
Get embodiment 9 catalyst 1ml (0.87 gram), carry out catalyst performance evaluation, export when reaction temperature is 79～143 ℃ that CO content is below the 10ppm in the tail gas with example 4 same reaction devices.When reaction temperature was 120 ± 4 ℃, reaction was through stopping, open test several times, and accumulative total is after nearly 60 hours, and catalyst activity does not reduce trend, has good stability.
Embodiment 11
Press embodiment 1 same quadrat method, make catalyst.M wherein
1(precious metals pt) content is 0.2% (wt) of catalyst total amount; M
2(metal Cu) content is 0.2% (wt) of catalyst total amount; Carrier S (S
1+ S
2) content is 99.6% (wt), wherein S of catalyst total amount
1Be molecular sieve MD, S
2Be TiO
2, S
1/ S
2=1.
Embodiment 12
Get embodiment 11 catalyst 1ml (0.85 gram), carry out catalyst performance evaluation, export when reaction temperature is 83～153 ℃ that CO content is below the 10ppm in the tail gas with example 4 same reaction devices.
Embodiment 13
Press embodiment 1 same quadrat method, make catalyst.M wherein
1(precious metals pt) content is 1.0% (wt) of catalyst total amount; M
2(metal Ni) content is 5.0% (wt) of catalyst total amount; Carrier S (S
1+ S
2) content is 94.0% (wt), wherein S of catalyst total amount
1Be molecular sieve MD, S
2Be TiO
2, S
1/ S
2=3.5.
Embodiment 14
Get embodiment 13 catalyst 1ml (0.86 gram), carry out catalyst performance evaluation, export when reaction temperature is 105～173 ℃ that CO content is below the 10ppm in the tail gas with example 4 same reaction devices.When reaction temperature was 145 ± 3 ℃, reaction was through stopping, open test several times, and accumulative total is after nearly 60 hours, and catalyst activity does not reduce trend, has good stability.
Embodiment 15
Press embodiment 1 same quadrat method, make catalyst.M wherein
1(precious metals pt) content is 1.0% (wt) of catalyst total amount; M
2(metal Cu) content is 5.0% (wt) of catalyst total amount; Carrier S content is 94.0% (wt), wherein S of catalyst total amount
1/ S
2=3.5.
Embodiment 16
Get embodiment 15 catalyst 6L (5.1 kilograms), the internal diameter of packing into is the reactor constant temperature zone of 150mm.Preparing hydrogen by reforming methanol gas feeds reactor, and it is H that unstripped gas is formed (vol%)
2: 46～49; N
2: 29～32; CO:0.6～1.60; CH
4: 0.09～0.26; CO
2: 20～21; In addition, the methyl alcohol, dimethyl ether and the C that also contain trace in the gas
2, C
3, C
4Deng hydrocarbons, reactor takes segmentation to advance O
2Method.System pressure is 0.24MPa; Air speed is 2000～4000h
-1Reaction temperature is 132～230 ℃.Reaction result: CO content is below the 2ppm in the outlet tail gas.Reaction is through stopping, open test several times, and accumulative total is after nearly 90 hours, and catalyst activity does not reduce trend, has good stability.H before and after purifying in the gas
2Reduce by 3 percentage points, selection of catalysts is better.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011389087A CN1171677C (en) | 2001-12-25 | 2001-12-25 | A Noble Metal Catalyst for Selective Oxidation Purification of Trace Carbon Monoxide in Methanol Reformed Gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011389087A CN1171677C (en) | 2001-12-25 | 2001-12-25 | A Noble Metal Catalyst for Selective Oxidation Purification of Trace Carbon Monoxide in Methanol Reformed Gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1428198A CN1428198A (en) | 2003-07-09 |
| CN1171677C true CN1171677C (en) | 2004-10-20 |
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|---|---|---|---|
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101193163B1 (en) | 2005-10-21 | 2012-10-19 | 삼성에스디아이 주식회사 | Catalyst for oxidizing carbon monoxide and method of producing the same |
| CN101121502B (en) * | 2006-08-11 | 2011-11-16 | 比亚迪股份有限公司 | System for preparing hydrogen from methanol and fuel battery device containing the same |
| FR2958185B1 (en) * | 2010-03-30 | 2012-04-20 | Arkema France | PROCESS FOR SELECTIVE OXIDATION OF CARBON MONOXIDE |
| CN104923220A (en) * | 2015-06-13 | 2015-09-23 | 常州大学 | Method for removing carbon monoxide by using oxidized graphene loading gold platinum catalyst |
| CN111036233B (en) * | 2018-10-12 | 2022-11-29 | 中国石油化工股份有限公司 | Wide-temperature methanol synthesis catalyst and preparation method and application thereof |
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2001
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