CN102309965B - Cu-based catalyst for removing trace gas impurity as well as preparation method and application thereof - Google Patents
Cu-based catalyst for removing trace gas impurity as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Cu-based catalyst for removing trace gas impurities, which is characterized by comprising first component CuO, the oxide of a second component M and a carbon nano tube, wherein the weight content of CuO is 0.1-99.9 percent by weight; the second component M is selected from one or several components of Zn, Zr, Mn, Ce, Fe, Co, Ag and Pd; the weight content of the oxide of M is 0.01-94.9 percent by weight; and the weight content of the carbon nano tube is 0.01-5 percent by weight; and the weight content is based on catalyst gross weight. The catalyst can simultaneously remove various trace gas impurities, simplifies the purifying process and reduces the operating cost.
Description
Technical field
The present invention relates to a kind of catalyst that removes minimum gas impurity from material, and its preparation method and application.Relate in particular a kind of carbon nano-tube modification copper-based catalysts, and its preparation method and application, be applicable to remove in material the H of trace
2, CO, CH
3the gaseous impurities such as OH
Background technology
At various industrial circles, micro-H
2, CO, CH
3oH, O
2deng existence, often harmful to reaction system, or harmful to the security of system, need to remove as impurity.In the polyolefin industry of electronics industry and petrochemical field, require the content of carbon monoxide in material flow and oxygen even in ppb magnitude etc.
For removing of these microcomponents, generally can adopt the modes such as catalytic oxidation, chemisorbed or pressure-variable adsorption to remove.Catalytic oxidation, has the advantage such as stable operation and small investment.Generally have noble metal catalyst as catalyst such as Pd, Pt and Au, or non-precious metal catalyst is as Cu series catalysts or adsorbent.Compared with noble metal catalyst, Cu is catalyst based often has anti-poisoning effect, even as the cleanser of multiple poisonous substance, as (chemical industry and engineerings such as Wu Yongzhong, 2004, vol (25) 3,39～43) to think, copper is that cleanser can be used on multiple fields such as dearsenification, desulfurization, dechlorination and de-CO.Often removing for micro amount of oxygen or carbon monoxide only of existing Cu-series catalyst, adopt separately respectively the Cu of reduction-state to adsorb micro-oxygen, or adopt separately the Lattice Oxygen in the CuO of oxidation state to adsorb micro CO, as US5625116, CN1044599C, WO 95/21146, US20050241478A1, WO 2007093532, DE102005061322 etc. all disclose copper oxide catalyst and removed for trace amounts of CO.Published the type catalyst is all to utilize Components of Catalysts CuO
xin Lattice Oxygen react with CO in material flow, rather than by the carbon monoxide in material and oxygen reaction; Lattice Oxygen in catalyst cannot be supplemented under reaction temperature, thereby along with the use activity of catalyst constantly reduces, removes temperature and constantly raise; Until while bringing up to higher temperature (as 120 ℃), the CO that the Lattice Oxygen in catalyst is not enough to remove in material reaches requirement, now catalyst need to regenerate in oxygen or air or other oxygen-containing gas.
In sum, in prior art, also do not have a kind of catalyst can remove H simultaneously
2, CO, O
2with the catalyst of volatile organic oxygen compound, therefore, necessaryly provide a kind of catalyst, can remove H simultaneously
2, reduction-state impurity and the O such as CO
2impurity, not only can play life cycle and the scope of application of extending catalyst like this, and has reached the effect that simultaneously removes plurality of impurities.
Summary of the invention
The inventor needs the problem of multiple catalysts while removing the impurity such as trace hydrogen, carbon monoxide, oxygen and volatile organic oxygen compound in order to solve in prior art, have conducted intensive studies, unexpected discovery carbon nano-tube modification copper-based catalysts, can remove lot of trace gaseous impurity simultaneously, simplify process for purifying, reduced operating cost.
First object of the present invention has just been to provide above-mentioned for removing the copper-based catalysts of minimum gas impurity, and this catalyst comprises oxide and the CNT of the first component CuO, second component M; In the gross weight of catalyst, the content of CuO is 0.1wt%～99.9wt%, is preferably 30wt%～80wt%; Second component M is selected from one or more in Zn, Zr, Mn, Ce, Fe, Co, Ag, Pd, and in the gross weight of catalyst, the content of the oxide of second component M is 0.01wt%～94.9wt%, is preferably 19.5wt%～69.9wt%; In the gross weight of catalyst, the content of CNT is 0.01wt%～5wt%, is preferably 0.1wt%～1wt%.
The specific surface of described copper-based catalysts is preferably 1～300m
2/ g, more preferably 5～200m
2/ g.
In described catalyst, CuO crystal grain is preferably 1～30nm, more preferably 3～30nm, more preferably 3～20nm.
The preferred multi-walled carbon nano-tubes of described CNT, its outer tube diameter is 5～100nm, interior caliber is 1～10nm.
Second object of the present invention has been to provide above-mentioned for removing the preparation method of copper-based catalysts of minimum gas impurity, and this preparation method comprises the following steps:
(1) solution preparation: prepare the mixed solution of mantoquita and M salt, prepare aqueous slkali;
(2) co-precipitation: adopt anti-addition co-precipitation or cocurrent process co-precipitation to obtain catalyst precursor;
Described anti-addition co-precipitation is that salting liquid titration is added to aqueous slkali, and the pH value that makes reaction system is finally 5.0～12.0, and precipitation temperature is 20～90 ℃;
Described cocurrent process co-precipitation is that salting liquid and aqueous slkali are added in container simultaneously, and the pH value of reaction system is controlled at 5.0～11.0, and precipitation temperature is 20～90 ℃;
(3) aging: the catalyst precursor that step (2) is obtained at 20～90 ℃ aging 10～120 minutes, filters and is precipitated thing;
(4) washing: the sediment that washing step (3) obtains, 10～90 ℃ of wash temperatures;
(5) dry: the material that step (4) is obtained is dried 1～48 hour at 60～120 ℃;
(6) granulation: the material that step (5) is obtained rolls 0.5～12 hour;
(7) roasting: the material that step (6) is obtained roasting 1～12 hour at 200～800 ℃, obtains particle;
(8) moulding: the particle that step (7) is obtained mixes with adhesive, compression molding;
CNT can be in step (1) to any step of step (8) or add in a few step, except step (7).
In anti-addition co-precipitation described in step (2), the pH value of preferred reaction system is finally 6.0～11.0, and precipitation temperature is preferably 40～90 ℃; In described cocurrent process co-precipitation, preferably the pH value of reaction system is controlled to 6.0～11.0, precipitation temperature is preferably 40～90 ℃; In step (7), sintering temperature is preferably 250～600 ℃.
Described CNT can add with the form of crystal seed or add when step (6) rolls in the time of step (2) co-precipitation, or add in step (8) moulding, or add in other steps, or in multiple steps, add respectively, but can not in the time of step (7) roasting, add.
In catalyst preparation process of the present invention, mantoquita is soluble copper salt, as copper nitrate, copper sulphate, Schweinfurt green, cupric oxalate, copper citrate or copper chloride etc.M salt is zirconium nitrate, zirconium sulfate, zirconium oxychloride, zirconium carbonate or acetic acid zirconium, zinc nitrate, silver nitrate, cobalt nitrate, cobalt acetate, manganese nitrate, cerous nitrate, ferric nitrate and ferric sulfate etc.Prepare aqueous slkali and can use sodium carbonate, sodium acid carbonate, NaOH, potassium hydroxide, ammoniacal liquor, carbonic hydroammonium or urea etc.
In coprecipitation process of the present invention, adopt cocurrent process or anti-addition.When the present invention the component proportion of catalyst while changing, best preparation parameter also changes; That is to say, for a certain specific catalytic component proportioning, have specific best precipitation pH value scope, precipitation temperature scope and aging temperature scope etc.It should be noted that for the preparation of cocurrent process catalyst, control its pH stable very necessary, for example, in be controlled at ± 0.5 scope, be conducive to like this prepare the catalyst of homogeneous grain size.
In washing step, washing is in order to remove anion in sediment as NO
3 -with residual impurity cationic as Na
+.After washing, guarantee Na
2the content of O in catalyst is lower than 0.05wt%, otherwise can have a strong impact on the activity of catalyst.
In the preparation process of catalyst of the present invention, adhesive used can be various adhesives conventional in shaping of catalyst process, as graphite etc.
The 3rd object of the present invention is to provide a kind of application process of catalyst removal minimum gas impurity of the present invention, and this application process comprises:
Be 20～240 ℃ in temperature, preferably 80～220 ℃, more preferably 120～200 ℃, reaction pressure is 0.1～10MPa, and preferably 1～8MPa more preferably, under the condition of 2～6MPa, makes containing micro-H
2, CO, CH
3the material of OH contacts and removes the H in material with catalyst of the present invention
2, CO, CH
3oH; Described material is CO
2, C
2h
4, C
3h
6, N
2, air, inert gas (as He, Ar), CH
4, natural gas or coal bed gas, H in described material
2, CO, O
2and CH
3the content of OH is 0.01vol%～5vol%, preferably 0.01vol%～3vol%, more preferably 0.01vol%～1vol%.
In the method for catalyst removal carbon monoxide of the present invention, reaction temperature is 0～150 ℃, and preferably 20～220 ℃, more preferably 80～220 ℃, more preferably 120～200 ℃, reaction pressure is 0.1～5Mpa, and air speed is 100～100,000h
-1(gas-phase reaction) or 1～200h
-1(liquid phase reactor).
If H in charging
2, CO, O
2and CH
3the content of OH is 0.01vol%～5vol%, preferably 0.01vol%～3vol%, and more preferably 0.01vol%～1vol%, in the situation that reactive chemistry metering ratio allows, uses catalyst of the present invention can make micro-H in material
2, CO, O
2and CH
3oH content deep removal is to 10ppm.
If H in charging
2, CO, O
2and CH
3the content of OH is 0.01～500ppm, preferably 0.1～200ppm, and more preferably 0.1～5ppm, in the situation that reactive chemistry metering ratio allows, uses catalyst of the present invention can make micro-H in material
2, CO, O
2and CH
3oH content deep removal is to 10ppb.
H in described charging
2, CO, O
2and CH
3oH, while using catalyst removal of the present invention, exceedes the component of reactive chemistry metering ratio, can remove by other means.
Catalyst of the present invention can be regenerated after activity decreased or inactivation, and regeneration temperature is 120～600 ℃, and regeneration gas is oxygen or air or other mists that contains oxygen.
In description of the present invention and claims, related content, for example %, ppm and ppb are by volume.
Catalyst of the present invention has following beneficial effect:
(1) use catalyst removal micro CO of the present invention, at 20～240 ℃, catalytic oxidation removes lot of trace gaseous impurity simultaneously, as micro-H
2, CO, CH
3oH etc. can with micro-O
2reaction removes multiple gases impurity in the situation that stoichiometric proportion allows simultaneously, simplifies process for purifying, reduces operating cost.
(2) copper-based catalysts that adopts coprecipitation to prepare, in the time adding CNT, catalyst has high activity and good stability.
The specific embodiment
In embodiments of the invention, the method for testing of relevant data is as follows:
Specific surface test: adopt the physical adsorption appearance of the Nova 3000e of Kang Ta company of the U.S., carry out specific surface area analysis.At liquid nitrogen temperature-196 ℃, use N
2determination of adsorption method surface area and pore-size distribution, sample vacuumizes pretreatment to pressure and is less than 10 at 300 ℃
-3pa, assay method is static method.Adopt BET method to calculate specific surface according to adsorption isotherm.
The following example further describes and demonstrates the preferred embodiment in the scope of the invention.
Embodiment 1
By the copper nitrate solution of 1 mol/L of 2000mL and the mixed solution of zirconium oxychloride, add 0.18 gram of CNT simultaneously, then the sodium carbonate liquor of mixed liquor and 2000mL 1 mol/L stream are joined in the container of 5L to precipitate, precipitation temperature is 90 ℃, and pH value is controlled at 8.5 ± 0.5.Then in strong agitation situation aging 2 hours, aging temperature was 90 ℃.Then filter, at 80 ℃, with deionized water washing at least six times, be washed till Na
2o content is lower than 0.05%.At 110 ℃, be dried 12 hours, roll afterwards the granulation of sieve powder, roasting 6 hours at 400 ℃, compression molding afterwards.Make and contain 70wt%CuO and 29.9wt%ZrO
2cuO/ZrO
2catalyst, content of carbon nanotubes is 0.1wt%, is labeled as 1
#catalyst, specific surface is 240m
2/ g.
Embodiment 2
As embodiment 1, adopt co-precipitation preparation, in co-precipitation, add 0.8 gram of CNT, make the CuO/ZnO catalyst that contains 30wt%CuO and 69.5wt%ZnO, content of carbon nanotubes is 0.5wt%, is labeled as 2
#catalyst, specific surface is 150m
2/ g.
Embodiment 3
As embodiment 1, adopt co-precipitation preparation, in rolling the granulation of sieve powder, add 1.78 grams of CNTs, make and contain 70wt%CuO, 10wt%ZnO and 19wt%ZrO
2cuO/ZnO/ZrO
2catalyst, content of carbon nanotubes is 1wt%, is labeled as 3
#catalyst, specific surface is 180m
2/ g.
Embodiment 4
As embodiment 1, different is adopts the anti-co-precipitation preparation that adds, and first the sodium carbonate liquor of 2000mL 1 mol/L is added in the container of 5 liters, the copper nitrate solution of 1 mol/L and manganese nitrate mixed solution is added afterwards again.Contain 70wt%CuO and 25wt%Mn by adding 7.8 grams of CNTs in compression molding, making
2o
3catalyst, content of carbon nanotubes is 5wt%, is labeled as 4
#catalyst, specific surface is 125m
2/ g.
Embodiment 5
As embodiment 1, adopt the anti-co-precipitation preparation that adds, in co-precipitation, add 0.8 gram of CNT, make the CuO/ZnO catalyst that contains 30%CuO and 79.5%ZnO, content of carbon nanotubes is 0.5wt%, is labeled as 5
#catalyst, specific surface is 140m
2/ g.
Comparative example
Except not adding CNT, all the other adopt co-precipitation preparation as embodiment 2, make the CuO/ZnO catalyst that contains 30%CuO and 70%ZnO and are labeled as 6
#catalyst, specific surface is 40m
2/ g.
Embodiment 7:
With embodiment 1～5 and the prepared catalyst of comparative example, carry out the evaluation of catalytic oxidation.Evaluating catalyst carries out in fixed bed continuous-flow tubular reactor.Loaded catalyst 1mL, reactor inside diameter is Ф 8mm, loading height is 30mm.Reaction temperature is passed through the control of program temperature controller by thermocouple.After Catalyst packing, adopt high-purity nitrogen to purge 12 hours at 150 ℃.Material is CO
2, be wherein 0.5vol% containing CO, H
2for 0.5vol%, CH
3oH content is 0.07vol%, O
2content is 1.1vol%.Reaction pressure is that 1.7MPa, reaction temperature are 180 ℃, and air speed is 2,0000hr
-1, carry out the evaluation of 1000 hours.The analysis of raw material and product adopts gas-chromatography Varian 3800, band methanation nickel reburner, thermal conductivity detector (TCD) and hydrogen flame detector, and CO lowest detection is limited to 0.1ppm, H
2and O
2detection be limited to 0.01vol%.The micro anti-evaluation of catalyst the results are shown in table 1.
Embodiment 8:
With embodiment 1～5 and the prepared catalyst of comparative example, carry out the evaluation of catalytic oxidation.Evaluating catalyst carries out in fixed bed continuous-flow tubular reactor.Loaded catalyst 1mL, reactor inside diameter is Ф 8mm, loading height is 30mm.Reaction temperature is passed through the control of program temperature controller by thermocouple.After Catalyst packing, adopt high-purity nitrogen to purge 12 hours at 120 ℃.Material is C
2h
2, be wherein 5ppm containing CO, H
2for 5ppm, O
2content is 5.5ppm.Reaction pressure is that 1.7MPa, reaction temperature are 50 ℃, and air speed is 1,0000hr
-1, carry out the evaluation of 1000 hours.The analysis of raw material and product adopts gas-chromatography Varian 3800, band methanation nickel reburner, thermal conductivity detector (TCD) and hydrogen flame detector, and CO lowest detection is limited to 0.1ppm; The CO that the TR3000 type micro CO analyzer of AMETEK company detects is limited to 10ppb under detecting, and resolution ratio is 0.1ppb.The O that the TEAU300 type trace oxygen analyzer of Teledyne company detects
2under detection, be limited to 1ppm.After the content of reactor outlet CO is lower than 0.1ppm, switches and use micro CO analyzer to detect.The micro anti-evaluation of catalyst the results are shown in table 2.
Table 1
| Catalyst | Composition (wt%) | Specific surface m 2/g | Outlet H2 (%) | Outlet CO (%) | Outlet O 2 (％) | Outlet CH3OH (%) |
| 1 # | 0.1CNT/70CuO30ZrO 2 | 240 | 0.01 | 0.01 | 0.05 | 0.05 |
| 2 # | 0.5CNT/30CuO69.5ZnO | 150 | 0.05 | 0.01 | 0.05 | 0.05 |
| 3 # | 1CNT/70CuO10ZnO19ZrO 2 | 180 | 0.01 | 0.02 | 0.05 | 0.03 |
| 4 # | 5CNT/70CuO20Mn 2O 3 | 125 | 0.01 | 0.02 | 0.05 | 0.02 |
| 5 # | 0.5CNT/30CuO69.5ZnO | 140 | 0.01 | 0.01 | 0.05 | 0.03 |
| 6 # | 30CuO70ZnO | 40 | 0.35 | 4469 | 1.01 | 0.06 |
* CNT represents carbon nanometer tube
Table 2
| Catalyst | Composition (wt%) | Outlet H 2Amount (ppm) | Outlet CO amount (ppb) | Outlet O 2Amount (ppm) |
| 1 # | 0.1CNT/70CuO30ZrO 2 | 0.1 | 10 | 0 |
| 2 # | 0.5CNT/30CuO69.5ZnO | 0.2 | 25 | 0 |
| 3 # | 1CNT/70CuO10ZnO19ZrO 2 | 0.1 | 15 | 0 |
| 4 # | 5CNT/70CuO20Mn 2O 3 | 0.1 | 26 | 0 |
| 5 # | 0.5CNT/30CuO69.5ZnO | 0.2 | 20 | 0 |
| 6 # | 30CuO70ZnO | 5 | 4800 | 5.48 |
* 0 represents that instrument does not detect
Can find out from the data of table 1 and table 2: 1) CNT add the specific surface that has increased catalyst; 2) in the time adding CNT in copper-based catalysts, catalyst has good activity, according to stoichiometric proportion, can remove trace amount of foreign gas simultaneously; And do not add the copper-based catalysts of CNT almost there is no reactivity.
Embodiment 9
The present embodiment is used for illustrating that catalyst of the present invention can remove the trace impurity in various materials.
With embodiment 2 prepared 2
#catalyst, removes test.Fixed-bed tube reactor.Loaded catalyst is 100mL.
Experiment condition is as follows:
Treat that processed gas is respectively: propylene, nitrogen, helium and argon gas etc., these gases are all wherein 5ppm containing CO, H
2for 5ppm, O
2content is 5.5ppm.Treating processed gas methane, is wherein 0.5vol% containing CO, H
2for 0.5vol%, CH
3oH content is 0.07vol%, O
2content is 1.1vol%.The appreciation condition for the treatment of processed gas for these is: 80 ℃ of reaction temperatures, reaction pressure 1.7MPa, air speed 10,000h
-1.
Result of the test is listed in table 3 and table 4.
Table 3.1
#catalyst is in the experimental result of differential responses system
| Material composition | Outlet H 2Amount (ppm) | Outlet CO amount (ppb) | Outlet O 2Amount (ppm) |
| Propylene | 0.1 | 10 | 0.2 |
| Nitrogen | 0.15 | 25 | 0.2 |
| Helium | 0.1 | 15 | 0.2 |
| Argon gas | 0.3 | 28 | 0.1 |
Table 4.1
#catalyst is in the experimental result of sulfur-containing methane gas
| Material composition | Outlet H 2 (％) | Outlet CO (%) | Outlet O 2 (％) | Outlet CH 3OH (％) |
| Methane (containing 5ppm sulphur) | 0.01 | 0.02 | 0.05 | 0.01 |
As seen from Table 3 and Table 4, when containing micro-H
2, CO and O
2material when different, while even containing trace in methane gas, the performance that removes of this catalyst is not subject to obvious impact, has all obtained satisfied removal effect.
Claims (6)
1. a preparation method who removes the copper-based catalysts of minimum gas impurity, is characterized in that, copper-based catalysts adopts coprecipitation method preparation, comprises the following steps:
(1) solution preparation: prepare the mixed solution of mantoquita and M salt, prepare aqueous slkali;
(2) co-precipitation: adopt anti-addition co-precipitation or cocurrent process co-precipitation to obtain catalyst precursor;
Described anti-addition co-precipitation is that salting liquid titration is added to aqueous slkali, and the pH value that makes reaction system is finally 5.0～12.0, and precipitation temperature is 20～90 ℃;
Described cocurrent process co-precipitation is that salting liquid and aqueous slkali are added in container simultaneously, and the pH value of reaction system is controlled at 5.0～11.0, and precipitation temperature is 20～90 ℃;
(3) aging: the catalyst precursor that step (2) is obtained at 20～90 ℃ aging 10～120 minutes, filters and is precipitated thing;
(4) washing: the sediment that washing step (3) obtains, 10～90 ℃ of wash temperatures;
(5) dry: the material that step (4) is obtained is dried 1～48 hour at 60～120 ℃;
(6) granulation: the material that step (5) is obtained rolls 0.5～12 hour;
(7) roasting: the material that step (6) is obtained roasting 1～12 hour at 200～800 ℃, obtains particle;
(8) moulding: the particle that step (7) is obtained mixes with adhesive, compression molding;
CNT can be in step (1) to any step of step (8) or add in a few step, except step (7);
In the copper-based catalysts of preparation, the weight content of CuO is 0.1wt%～99.9wt%; The weight content of the oxide of M is 0.01wt%～94.9wt%, and M is selected from one or more in Zn, Zr, Mn, Ce, Fe, Co, Ag, Pd; The weight content of CNT is 0.01wt%～5wt%, and CNT is multi-walled carbon nano-tubes, and its outer tube diameter is 5～100nm, and interior caliber is 1～10nm; Described weight content is take catalyst gross weight as benchmark, and above constituent content sum is 100%.
2. preparation method as claimed in claim 1, is characterized in that, the specific area of copper-based catalysts is 1～300m
2/ g.
3. preparation method as claimed in claim 2, is characterized in that, the specific area of copper-based catalysts is 5～200m
2/ g.
4. preparation method as claimed in claim 1, is characterized in that, in copper-based catalysts, CuO crystal grain is 1～30nm.
5. preparation method as claimed in claim 4, is characterized in that, in copper-based catalysts, CuO crystal grain is 3～30nm.
6. preparation method as claimed in claim 5, is characterized in that, in copper-based catalysts, CuO crystal grain is 3～20nm.
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| CN104338532B (en) * | 2013-08-09 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of Cu-Zr catalyst, preparation method and application |
| CN105312064B (en) * | 2015-06-30 | 2017-12-01 | 金华氟特催化科技有限公司 | A kind of catalyst for the middle carbon monoxide that removes smoke |
| WO2017024421A1 (en) * | 2015-08-12 | 2017-02-16 | 华北电力大学（保定） | Multi-walled carbon nanotube catalyst, preparation method therefor and use thereof |
| CN107570167A (en) * | 2017-09-11 | 2018-01-12 | 中国科学技术大学 | A kind of application of carbon nanometer tube loaded type catalyst and preparation method thereof and CO catalytic oxidation under low temperature |
| CN109529871B (en) * | 2018-12-13 | 2021-10-22 | 重庆工商大学 | Sea urchin-shaped copper-based catalyst and preparation method and application thereof |
| CN114181033A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Method for recovering methane from ethylene waste gas produced in preparation of ethylene through oxidative coupling of methane |
| CN114029063B (en) * | 2021-12-16 | 2023-03-28 | 厦门大学 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof |
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Non-Patent Citations (2)
| Title |
|---|
| Dengsong Zhang et al..Pyridine-thermal synthesis and high catalytic activity of CeO2/CuO/CNT nanocomposites.《Applied Surface Science》.2010,第256卷 |
| Pyridine-thermal synthesis and high catalytic activity of CeO2/CuO/CNT nanocomposites;Dengsong Zhang et al.;《Applied Surface Science》;20100429;第256卷;6795-6800 * |
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