CN102247851A - Methanation process for removing a small amount of H2 from industrial CO gas and preparation method of catalyst - Google Patents
Methanation process for removing a small amount of H2 from industrial CO gas and preparation method of catalyst Download PDFInfo
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- CN102247851A CN102247851A CN2011101224398A CN201110122439A CN102247851A CN 102247851 A CN102247851 A CN 102247851A CN 2011101224398 A CN2011101224398 A CN 2011101224398A CN 201110122439 A CN201110122439 A CN 201110122439A CN 102247851 A CN102247851 A CN 102247851A
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Abstract
The invention discloses a preparation method of a catalyst for removing a small amount of H2 from industrial CO gas. The catalyst is prepared by an impregnation method, nickel is taken as an active ingredient, transition metal is taken as an auxiliary agent, and active alumina is taken as a carrier. The catalyst prepared by the method has the advantages that: the preparation method is simple, the active ingredient is uniformly loaded, the obtained catalyst has high catalytic property, and CO and the H2 in the industrial CO gas can be subjected to methanation reaction, so that the content of the H2 in reaction tail gas is less than 400ppm, and the problem of purifying the CO gas in the carbonyl synthesis industry can be effectively solved.
Description
Technical field
The present invention relates to a kind of employing CO catalytic production of methane reaction and remove small amount of H in the industrial CO gas
2Technology and method for preparing catalyst, belong to catalyst field.
Background technology
In conjunction with China's oil starvation, weak breath, the relative rich in natural resources present situation of coal resources, development is that the chemical industry technical meaning of raw material is very great with the coal.With the CO after the synthesis gas separation is the multiple large chemicals of feedstock production, become one of focus of domestic and international research in recent years as methyl alcohol, alkene, aromatic hydrocarbons, formaldehyde, aceticanhydride, metaformaldehyde, dimethyl ether, ethylene glycol, mixed alcohol etc., wherein, coal-ethylene glycol is an emerging technology of coal chemical technology in recent years, and great economic and social benefit is arranged.This technology is the technology source with Fujian Inst. of Matter Structure, Chinese Academy of Sciences, in conjunction with the through engineering approaches strength of Jiangsu pelletization Group Co.,Ltd and the fund input of Shanghai gold coal Technew SA, finished the operation of hundred tonnes of pilot scales and ton industry demonstration plant in succession since 2005, finish 200,000 tons of coal-ethylene glycol construction and succeed in the test run in December, 2009, indicate that coal-ethylene glycol formally goes on the road of large-scale industrial production.The coal-ethylene glycol process route mainly contains three reactions steps, and they are respectively that coal system water-gas obtains CO and H through the transformation adsorbing separation
2, CO catalytic coupling synthesis of oxalate and oxalate catalytic hydrogenation preparing ethylene glycol, wherein the CO gas raw material of a large amount of high purifications of process need of CO catalytic coupling synthesis of oxalate.Separate the industrial CO unstrpped gas that obtains by water-gas transformation adsorbing separation or cryogenics and unavoidably have certain amount of H
2Remnants have influenced follow-up carbongl group synthesis reaction, even the H about 1 %
2Remnants also can produce serious negative effect to the performance of catalyst, and, catalyst life many as accessory substance is short or the like.Therefore, how to make things convenient for and remove small amount of H in the industrial CO gas economically
2Thereby acquisition meets the important technology difficult problem that the CO gas of subsequent reactions requirement is development carbonyl compound probability.
Be used for removing CO gas small amount of H at present both at home and abroad
2Technology and Preparation of Catalyst report seldom, more typical example is the dehydrogenating process that uses in the coal-ethylene glycol process route, this method adopts noble metal catalyst by a small amount of O of adding
2Selective oxidation is removed the small amount of H among the industrial CO
2Though this dehydrogenation technology can be successful H residual in the CO gas
2Be removed to below 100 ppm, but, increased the production cost that removes hydrogen purification and whole coal-ethylene glycol technological process greatly because big commercial plant need be used a large amount of noble metal catalysts.In addition, CO and H
2Mist and O
2At high temperature mix and also have certain explosion danger, on commercial plant, should avoid this type of reaction as far as possible.Therefore, explore a kind of new more economical, more efficient, safer small amount of H in the industrial CO gas of removing
2Technology and efficient catalyst, significant.
The present invention proposes to remove a spot of H in the industrial CO gas with the technology of CO methanation
2, can avoid introducing new reactant.The carbon monoxide methanation reaction is a strong exothermal reaction, and its reaction equation is as follows:
Reaction equation (1) and (2) are main reactions, and (3) are side reactions.
CO adds H
2Synthesizing methane is well-known heterogeneously catalysed gas phase reactions, has carried out a large amount of research for many years, and 1902, Satatier and Senderenst at first reported CO and H
2Can be converted into methane under the Raney nickel effect, nineteen twenty-six F. Fischer and H. Tropsch have reported CO/H
2Can generate the hydrocarbon and the oxygenatedchemicals of the wide scope of molecular weight through catalyzed conversion, Here it is, and the known Fischer-Tropsch of people is synthetic.Recently decades, a spot of CO that methanation technology is applied in the removing process gas always (also comprises CO
2), the method is that use at most also is one of most reasonable approach at present.Be mainly used in the following aspects:
(1) in ammonia factory and hydrogen plant, methanation is the final step of gas purification.In the synthesis gas a spot of oxycarbide in the presence of methanation catalyst with H
2Reaction is converted into the water that is easy to remove and the methane of inertia, with protection synthetic ammonia and hydrogenation catalyst.
(2) utilize methanation technology to make natural gas (LPG).In addition, in the town gas of making by long flame coal gas, can add H to CO wherein
2Methanation makes in the coal gas CO concentration greatly reduce and is detoxified, and can improve the calorific value of town gas greatly.
(3) remove trace amounts of carbon oxide in the fuel cell hydrogen source with methanation reaction, can improve greatly fuel cell performance and life-span.
Yet domestic and international methanation process that adopts and catalyst technology are all concentrated and are used to remove rich H at present
2A small amount of CO in the environment (also comprises CO
2), remove small amount of H in the CO gas and almost be not used in
2With the technology of the CO gas that obtains to meet the subsequent reactions requirement and the report of method for preparing catalyst.
Summary of the invention
The purpose of this invention is to provide novel can be used for and remove small amount of H in the industrial CO gas
2Technology and method for preparing catalyst.
The present invention adopts following technical scheme:
1, small amount of H in the industrial CO gas is removed in a kind of employing CO catalytic production of methane reaction
2Catalyst, its chemical formula is: NiO-MO
x/ γ-Al
2O
3, with metallic nickel and metal oxide MO
xAuxiliary agent is an active component, is carrier with the pretreated activated alumina of process.
As item 1 described catalyst, it is characterized in that 2, used promoter metal ion M is second main group, first, the 5th, the 6th in the periodic table of elements, the 8th subgroup or lanthanide series, as Ba
2+, Cu
2+, Ag
+, Nb
5+, Mo
6+, W
6+, Fe
2+, Fe
3+, Co
2+, La
2+, Sm
3+, Ce
3+In one or more;
The also available sulfate of used nickel salt and promoter metal salt, phosphate, acetate or halide, corresponding acid solution can use hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid to replace.
3, a kind of as 1 or 2 a described Preparation of catalysts method, it is characterized in that: use immersion process for preparing, its preparation process is as follows, the salpeter solution of preparation certain pH value, load capacity according to active component and auxiliary agent, in salpeter solution, add a certain amount of nickel salt and soluble metal salt assitant, stirring and dissolving; Then treated active porous alumina support is soaked 4 ~ 24 h, put into baking oven and dry 3 ~ 24 h, put into muffle furnace heat treatment 3 ~ 24 h again, obtain catalyst after the cooling.
4, a kind of use 1 or 2 described catalyst are removed small amount of H in the industrial CO gas
2Method, it is characterized in that fixed bed reactors are adopted in this reaction, contain small amount of H
2CO gas with 500 ~ 4000 h
-1Air speed by bed, under the condition of 100 ~ 600 ℃ of pressure 0.1 ~ 3.0 MPa, temperature, react.
5, as the purposes of catalyst as described in item 1 or 2, this method can be used for but is not limited to industrial CO gas is feedstock production methyl alcohol, alkene, aromatic hydrocarbons, formaldehyde, formic acid, acetic acid, aceticanhydride, metaformaldehyde, dimethyl ether, oxalate, carbonic ester, toluene diisocyanate TDI, diphenyl methane diisocyanate MDI, and technical process such as dimethyl formamide.
6, as the experimental evaluation device of item 1 or 2 described catalyst, it is characterized by the air inlet of two-way gas, gas flow is controlled by mass flowmenter, reacting system pressure is jointly controlled by the pressure maintaining valve of a counterbalance valve and two-way gas import department, unstripped gas and product analysis adopt online gas chromatographic analysis, chromatogram adopts molecular sieve packed column, and thermal conductivity detector (TCD) detects.
Small amount of H in the industrial CO gas of removal of the present invention
2The preparation concrete steps of methanation dehydrogenation as follows:
(1) with particle diameter is the corundum crucible that the activated alumina particle of 1 ~ 6 mm is put into prior cleaning-drying, place muffle furnace to carry out roasting, slowly be raised to 400 ~ 800 ℃ from room temperature through temperature programming, cool off behind constant temperature 2 ~ 10 h, rare nitric acid that cooled carrying alumina body and function concentration is 1 ~ 5 % spends deionised water to neutral at 40 ~ 80 ℃ after soaking 3 ~ 12 h, puts into the baking oven oven dry and is placed on drier and preserves;
(2) soluble-salt with nickel salt and promoter metal is dissolved in rare nitric acid of pH=1 ~ 5, the total mol concentration of control nickel ion and auxiliary agent ion is 0.10 ~ 10.30 mol/l, the auxiliary agent ion that wherein mixes accounts for 1 ~ 30 % of total mol concentration, stirs;
(3) alumina particle of step (1) is put into step (2) solution that configures, dipping 3 ~ 24 h;
(4) filter out the filtrate of step (3), put into dry 3 ~ 24 h of baking oven through the alumina particle of dipping, dried sample is put into muffle furnace again, through temperature programming to 300 ~ 600 ℃, cool to room temperature behind constant temperature 3 ~ 12 h obtains required methanation dehydrogenation.
Technology of the present invention need not to add O
2, the risk of explosion of having avoided oxygenation dehydrogenation technology to cause, method for preparing catalyst is simple, and active constituent loading is even, and equipment is less demanding, and the gained catalyst catalytic performance is superior, can make CO and H in the industrial CO gas
2Methanation reaction takes place, and makes H in the reaction end gas
2Content is lower than 400 ppm, can effectively solve in the carbonyl compound probability CO gas cleaning problem.
Description of drawings
Fig. 1 is a methanation dehydrogenation reaction evaluating device schematic flow sheet.
The specific embodiment
The present invention selects Ba for use
2+, W
6+, Mo
6+, Nb
5+, Cu
2+, La
2+As auxiliary agent doping ion, in the configuration of step (2) maceration extract, soluble nickel salt can be selected nickelous sulfate, nickel phosphate, nickel nitrate, nickel acetate, nickel chloride, nickelous bromide etc. for use, solubility barium, niobium, copper, lanthanum salt can be selected nitrate, acetate, villaumite, bromine salt etc. for use, and soluble molybdenum (tungsten) salt can be selected the sour sodium of molybdenum (tungsten), the sour ammonium of molybdenum (tungsten) etc. for use.
Example 1:
With 20 g diameters is the corundum crucible that the activated alumina particle of 2 ~ 3 mm is put into prior cleaning-drying, place muffle furnace to carry out roasting, slowly be raised to 500 ℃ from room temperature through temperature programming, cool off behind constant temperature 6 h, rare nitric acid that cooled carrying alumina body and function concentration is 2 % spends deionised water to neutral at 60 ℃ after soaking 10 h, puts into the baking oven oven dry and is placed on drier and preserves; Take by weighing 0.75 g Ni (NO
3)
26H
2O and 0.15 g Ba (NO
3)
2Pouring 12 ml concentration into is in the dilute nitric acid solution of 1.0 %, make the metal ion aqueous solution after being stirred to whole dissolvings, in the above-mentioned aqueous solution, add the alumina support that 15 g handle well in advance, filter solution after flooding 8 h, impregnated catalyst sample is put into baking oven dry, put into muffle furnace behind the cool to room temperature, through temperature programming to 450 ℃ through 160 C, cool to room temperature behind constant temperature 6 h obtains required methanation dehydrogenation.Get 15 ml catalyst samples, the reaction tube of the evaluating apparatus of packing into, the hollow porcelain ring of upper strata preheating section filling 15 ~ 20 ml.Switch to H after with nitrogen reaction bed being purged 30 min
2, H
2Air speed is 700 h
-1, the speed with 2 ℃/min is warmed up to 400 ℃ from room temperature then, is cooled to 200 ℃ behind constant temperature 8 h, closes H
2Switch to unstripped gas, unstripped gas is mist (CO:98.5 %, H through demarcating
2: 1.5 %), air speed is 1200 h
-1, pressure is 0.30 MPa, is 463.6 ℃ in reaction temperature, H in the reaction end gas
2Content is 391 ppm.
Example 2:
In embodiment 1, change carrier sintering temperature in the catalyst preparation step into 600 ℃, i.e. the cost example.
The performance evaluation condition is 1200 h with embodiment 1 in air speed
-1, pressure is 0.30 MPa, is 361.7 ℃ in reaction temperature, H in the reaction end gas
2Content is 927 ppm.
Example 3:
In embodiment 1, change carrier sintering temperature in the catalyst preparation step into 400 ℃, i.e. the cost example.
The performance evaluation condition is 1200 h with embodiment 1 in air speed
-1, pressure is 0.30 MPa, is 463.7 ℃ in reaction temperature, H in the reaction end gas
2Content is 4222 ppm.
Example 4:
In embodiment 1, change active component into 0.75g Ni (NO
3)
26H
2O and 0.15g Na
2WO
4, i.e. cost example.The performance evaluation condition is 1200 h with embodiment 1 in air speed
-1, pressure is 0.30 MPa, is 471.0 ℃ in reaction temperature, H in the reaction end gas
2Content is 1371ppm.
Example 5:
In embodiment 1, change active component into 0.75 g Ni (NO
3)
26H
2O and 0.15 g Nb (NO
3)
5, i.e. cost example.The performance evaluation condition is 1200 h with embodiment 1 in air speed
-1, pressure is 0.30 MPa, is 373.4 ℃ in reaction temperature, H in the reaction end gas
2Content is 3810 ppm.
Example 6:
In embodiment 1, change active component into 0.75 g Ni (NO
3)
26H
2O and 0.15 g La (NO
3)
2, i.e. cost example.The performance evaluation condition is 1200 h with embodiment 1 in air speed
-1, pressure is 0.30 MPa, is 463.2 ℃ in reaction temperature, H in the reaction end gas
2Content is 5140 ppm.
Example 7:
In embodiment 1, change active component into 0.75 g Ni (NO
3)
26H
2O and 0.15 g Cu (NO
3)
23H
2O, i.e. cost example.The performance evaluation condition is 1200 h with embodiment 1 in air speed
-1, pressure is 0.30 MPa, is 454.1 ℃ in reaction temperature, H in the reaction end gas
2Content is 4930 ppm.
Example 8:
In embodiment 1, change active component into 0.75 g Ni (NO
3)
26H
2O and 0.15 g Na
2MoO
4, i.e. cost example.The performance evaluation condition is 1200 h with embodiment 1 in air speed
-1, pressure is 0.30 MPa, is 434.9 ℃ in reaction temperature, H in the reaction end gas
2Content is 7250 ppm.
Example 9:
In embodiment 1, change active component into 0.75 g Ni (NO
3)
26H
2O, i.e. cost example.The performance evaluation condition is 1200 h with embodiment 1 in air speed
-1, pressure is 0.30 MPa, is 458.0 ℃ in reaction temperature, H in the reaction end gas
2Content is 3950 ppm.
Claims (6)
1. one kind is adopted the reaction of CO catalytic production of methane to remove small amount of H in the industrial CO gas
2Catalyst, its chemical formula is: NiO-MO
x/ γ-Al
2O
3, with metallic nickel and metal oxide MO
xAuxiliary agent is an active component, is carrier with the pretreated activated alumina of process.
2. catalyst as claimed in claim 1 is characterized in that, used promoter metal ion M is second main group, first, the 5th, the 6th in the periodic table of elements, the 8th subgroup or lanthanide series, as Ba
2+, Cu
2+, Ag
+, Nb
5+, Mo
6+, W
6+, Fe
2+, Fe
3+, Co
2+, La
2+, Sm
3+, Ce
3+In one or more; The also available sulfate of used nickel salt and promoter metal salt, phosphate, acetate or halide, corresponding acid solution can use hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid to replace.
3. Preparation of catalysts method as claimed in claim 1 or 2, it is characterized in that: use immersion process for preparing, its preparation process is as follows, the salpeter solution of preparation certain pH value, load capacity according to active component and auxiliary agent, in salpeter solution, add a certain amount of nickel salt and soluble metal salt assitant, stirring and dissolving; Then treated active porous alumina support is soaked 4 ~ 24 h, put into baking oven and dry 3 ~ 24 h, put into muffle furnace heat treatment 3 ~ 24 h again, obtain catalyst after the cooling.
4. one kind is used claim 1 or 2 described catalyst to remove small amount of H in the industrial CO gas
2Method, it is characterized in that fixed bed reactors are adopted in this reaction, contain small amount of H
2CO gas with 500 ~ 4000 h
-1Air speed by bed, under the condition of 100 ~ 600 ℃ of pressure 0.1 ~ 3.0 MPa, temperature, react.
5. the purposes of catalyst as claimed in claim 1 or 2, this method can be used for but be not limited to industrial CO gas is feedstock production methyl alcohol, alkene, aromatic hydrocarbons, formaldehyde, formic acid, acetic acid, aceticanhydride, metaformaldehyde, dimethyl ether, oxalate, carbonic ester, toluene diisocyanate TDI, diphenyl methane diisocyanate MDI, and technical process such as dimethyl formamide.
6. the experimental evaluation device of catalyst as claimed in claim 1 or 2, it is characterized by the air inlet of two-way gas, gas flow is controlled by mass flowmenter, reacting system pressure is jointly controlled by the pressure maintaining valve of a counterbalance valve and two-way gas import department, unstripped gas and product analysis adopt online gas chromatographic analysis, chromatogram adopts molecular sieve packed column, and thermal conductivity detector (TCD) detects.
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| CN102583374A (en) * | 2012-02-09 | 2012-07-18 | 中国科学院福建物质结构研究所 | Purification process of industrial CO gas for preparing oxalate or carbonic ester |
| CN102600837A (en) * | 2012-02-09 | 2012-07-25 | 中国科学院福建物质结构研究所 | Ru/Al2O3 methanation dehydrogenation catalyst and preparation method thereof |
| CN103901131A (en) * | 2014-04-10 | 2014-07-02 | 中国科学院福建物质结构研究所 | Device and method device for evaluating catalyst during preparation of oxalate through three-channel automatic CO gas phase oxidative coupling |
| CN104418321A (en) * | 2013-09-04 | 2015-03-18 | 中国石油化工股份有限公司 | Method of removing H2 in CO raw material |
| CN104415760A (en) * | 2013-09-04 | 2015-03-18 | 中国石油化工股份有限公司 | Nickel-containing catalyst and method for removing H2 in CO raw material |
| CN104925808A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Method of removing hydrogen in carbon monoxide mixed gas |
| CN105032470A (en) * | 2015-07-16 | 2015-11-11 | 湖北荟煌科技有限公司 | Catalyst for methane production from coke oven gas and preparation method thereof |
| CN105110332A (en) * | 2015-07-21 | 2015-12-02 | 中国科学院福建物质结构研究所 | Technological method for removal of H2 from CO feed gas by CO2 hydrogenation and hydrogenation catalyst |
| CN105618042A (en) * | 2015-12-26 | 2016-06-01 | 中国科学院福建物质结构研究所 | Bimetallic oxide catalyst for removing hydrogen in CO gas and preparation method of bimetallic oxide catalyst |
| CN106946254A (en) * | 2017-03-17 | 2017-07-14 | 杨皓 | A kind of improved method of ethylene glycol production process CO gas catalytic dehydrogenation |
| CN109046398A (en) * | 2018-08-07 | 2018-12-21 | 中国科学院福建物质结构研究所 | A kind of CO dehydrogenation purification Mn base non-precious metal catalyst and preparation method thereof |
| CN111258345A (en) * | 2020-02-25 | 2020-06-09 | 北京首钢朗泽新能源科技有限公司 | Gas concentration stabilizing device and control method thereof |
| CN112129852A (en) * | 2020-08-31 | 2020-12-25 | 中国科学院福建物质结构研究所 | Reaction gas cyclic utilization and controllable CO dehydrogenation of atmosphere purifies catalyst evaluation device |
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| CN102600837B (en) * | 2012-02-09 | 2016-07-06 | 中国科学院福建物质结构研究所 | Ru/Al2O3Methanation dehydrogenation and preparation method thereof |
| CN102600837A (en) * | 2012-02-09 | 2012-07-25 | 中国科学院福建物质结构研究所 | Ru/Al2O3 methanation dehydrogenation catalyst and preparation method thereof |
| CN102583374A (en) * | 2012-02-09 | 2012-07-18 | 中国科学院福建物质结构研究所 | Purification process of industrial CO gas for preparing oxalate or carbonic ester |
| CN104418321A (en) * | 2013-09-04 | 2015-03-18 | 中国石油化工股份有限公司 | Method of removing H2 in CO raw material |
| CN104415760A (en) * | 2013-09-04 | 2015-03-18 | 中国石油化工股份有限公司 | Nickel-containing catalyst and method for removing H2 in CO raw material |
| CN104925808A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Method of removing hydrogen in carbon monoxide mixed gas |
| CN104925808B (en) * | 2014-03-17 | 2017-03-15 | 中国石油化工股份有限公司 | The method of hydrogen in removal of carbon monoxide gaseous mixture |
| CN103901131A (en) * | 2014-04-10 | 2014-07-02 | 中国科学院福建物质结构研究所 | Device and method device for evaluating catalyst during preparation of oxalate through three-channel automatic CO gas phase oxidative coupling |
| CN103901131B (en) * | 2014-04-10 | 2015-04-15 | 中国科学院福建物质结构研究所 | Device and method device for evaluating catalyst during preparation of oxalate through three-channel automatic CO gas phase oxidative coupling |
| CN105032470A (en) * | 2015-07-16 | 2015-11-11 | 湖北荟煌科技有限公司 | Catalyst for methane production from coke oven gas and preparation method thereof |
| CN105110332A (en) * | 2015-07-21 | 2015-12-02 | 中国科学院福建物质结构研究所 | Technological method for removal of H2 from CO feed gas by CO2 hydrogenation and hydrogenation catalyst |
| CN105618042A (en) * | 2015-12-26 | 2016-06-01 | 中国科学院福建物质结构研究所 | Bimetallic oxide catalyst for removing hydrogen in CO gas and preparation method of bimetallic oxide catalyst |
| CN106946254A (en) * | 2017-03-17 | 2017-07-14 | 杨皓 | A kind of improved method of ethylene glycol production process CO gas catalytic dehydrogenation |
| CN109046398A (en) * | 2018-08-07 | 2018-12-21 | 中国科学院福建物质结构研究所 | A kind of CO dehydrogenation purification Mn base non-precious metal catalyst and preparation method thereof |
| CN109046398B (en) * | 2018-08-07 | 2021-02-19 | 中国科学院福建物质结构研究所 | Mn-based non-noble metal catalyst for CO dehydrogenation and purification and preparation method thereof |
| CN111258345A (en) * | 2020-02-25 | 2020-06-09 | 北京首钢朗泽新能源科技有限公司 | Gas concentration stabilizing device and control method thereof |
| CN112129852A (en) * | 2020-08-31 | 2020-12-25 | 中国科学院福建物质结构研究所 | Reaction gas cyclic utilization and controllable CO dehydrogenation of atmosphere purifies catalyst evaluation device |
| CN112129852B (en) * | 2020-08-31 | 2021-08-10 | 中国科学院福建物质结构研究所 | Reaction gas cyclic utilization and controllable CO dehydrogenation of atmosphere purifies catalyst evaluation device |
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Application publication date: 20111123 |