CN102309965A - 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 from material, removes minimum gas impurity.Relate in particular a kind of carbon nano-tube modification copper-based catalysts, and its production and application, be applicable to the H that removes in the material trace
2, CO, CH
3Gaseous impurities such as OH
Background technology
At various industrial circles, micro-H
2, CO, CH
3OH, O
2Deng existence, often harmful, perhaps harmful to the security of system to reaction system, need remove as impurity.In the polyolefin industry of electronics industry and petrochemical field, require the content of carbon monoxide and oxygen in the streams even in ppb magnitude etc.
For removing of these microcomponents, generally can adopt modes such as catalytic oxidation, chemisorbed or transformation absorption to remove.Catalytic oxidation has advantages such as stable operation and small investment.Catalyst such as noble metal catalyst such as Pd, Pt and Au are generally arranged, or non-precious metal catalyst such as Cu series catalysts or adsorbent.Compare with noble metal catalyst; Cu is catalyst based often to have an anti-effect of poisoning, even as the cleanser of multiple poisonous substance, like (chemical industry and engineerings such as Wu Yongzhong; 2004; Vol (25) 3, and 39～43) think that copper is that cleanser can be used on dearsenification, desulfurization, dechlorination and takes off a plurality of fields such as CO.Existing Cu-series catalyst often only is used for removing of micro amount of oxygen or carbon monoxide; Promptly adopt the Cu that goes back ortho states to adsorb the oxygen of trace respectively separately; Perhaps adopt the Lattice Oxygen among the CuO of oxidation state to adsorb micro CO separately, all disclose copper oxide catalyst like US5625116, CN1044599C, WO 95/21146, US20050241478A1, WO 2007093532, DE102005061322 etc. and be used for trace amounts of CO and remove.Disclosed the type catalyst all is to utilize component CuO in the catalyst
xIn Lattice Oxygen come with streams in the CO reaction, rather than with carbon monoxide in the material and oxygen reaction; Lattice Oxygen in the catalyst can't be replenished under reaction temperature, thereby constantly reduces along with the use of catalyst is active, removes temperature and constantly raises; When bringing up to higher temperature (as 120 ℃), the CO that the Lattice Oxygen in the catalyst is not enough to remove in the material reaches requirement, and this moment, catalyst promptly need be regenerated in oxygen or air or other oxygen-containing gas.
In sum, also there is not a kind of catalyst can remove H simultaneously in the prior art
2, CO, O
2With the catalyst of volatile organic oxygen compound, therefore, necessary a kind of catalyst is provided, can remove H simultaneously
2, CO etc. goes back ortho states impurity and O
2Impurity not only can play the life cycle and the scope of application that prolong catalyst like this, and reach the effect that removes plurality of impurities simultaneously.
Summary of the invention
The inventor needs the problem of multiple catalyst when solving impurity such as removing micro-hydrogen, carbon monoxide, oxygen and volatile organic oxygen compound in the prior art; Carried out intensive research; It is unexpected that discovery use the carbon nano-tube modification copper-based catalysts; Can remove multiple minimum gas impurity simultaneously, simplify process for purifying, reduce operating cost.
First purpose of the present invention has just provided the above-mentioned copper-based catalysts that is used to remove minimum gas impurity, and this catalyst comprises oxide and the CNT of the first component CuO, the second component M; In the gross weight of catalyst, the content of CuO is 0.1wt%～99.9wt%, is preferably 30wt%～80wt%; The second component M is selected from one or more among Zn, Zr, Mn, Ce, Fe, Co, Ag, the Pd, and in the gross weight of catalyst, the content of the oxide of the 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 said copper-based catalysts is preferably 1～300m
2/ g, more preferably 5～200m
2/ g.
CuO crystal grain is preferably 1～30nm in the said catalyst, more preferably 3～30nm, more preferably 3～20nm.
The preferred multi-walled carbon nano-tubes of said CNT, its outer tube diameter are 5～100nm, and interior caliber is 1～10nm.
Second purpose of the present invention provided the above-mentioned preparation method who is used to remove the copper-based catalysts of minimum gas impurity, and this preparation method may further comprise the steps:
(1) formulations prepared from solutions: the mixed solution of preparation mantoquita and M salt, preparation 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 the salting liquid titration is added aqueous slkali, makes that the pH value of reaction system finally is 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 the 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 wore out 10～120 minutes down at 20～90 ℃, filtered and obtained sediment;
(4) washing: the sediment that washing step (3) obtains, 10～90 ℃ of wash temperatures;
(5) drying: the material that step (4) obtains is following dry 1～48 hour at 60～120 ℃;
(6) granulation: the material that step (5) is obtained rolled 0.5～12 hour;
(7) roasting: the material that step (6) is obtained obtains particle 200～800 ℃ of following roastings 1～12 hour;
(8) moulding: particle and adhesive that step (7) is obtained mix compression molding;
CNT can or add in a few step in any step of step (1) to step (8), except the step (7).
In the anti-addition co-precipitation described in the step (2), the pH value of preferred reaction system finally is 6.0～11.0, and precipitation temperature is preferably 40～90 ℃; In the described cocurrent process co-precipitation, preferably the pH value with reaction system is controlled at 6.0～11.0, and precipitation temperature is preferably 40～90 ℃; In step (7), sintering temperature is preferably 250～600 ℃.
Described CNT can the form with crystal seed add or when step (6) rolls, add when step (2) co-precipitation; Perhaps in step (8) moulding, add; Perhaps in other steps, add; Perhaps in a plurality of steps, add respectively, but can not when step (7) roasting, add.
In catalyst preparation process of the present invention, mantoquita is a soluble copper salt, like 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.The preparation aqueous slkali 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 set of dispense ratio of catalyst when changing, best preparation parameter also changes; That is to say,, have specific the best deposition pH value scope, precipitation temperature scope and aging temperature scope etc. for a certain specific catalyst set of dispense ratio.It should be noted that for the cocurrent process Preparation of Catalyst it is stable very necessary to control its pH, for example be controlled at ± 0.5 scope in, help preparing the catalyst of homogeneous grain size like this.
In washing step, washing is in order to remove anion such as the NO in the sediment
3 -With institute's remaining impurities cation such as Na
+After the washing, guarantee Na
2The content of O in catalyst is lower than 0.05wt%, otherwise can have a strong impact on activity of such catalysts.
In Preparation of catalysts process of the present invention, used adhesive can be various adhesives commonly used in the shaping of catalyst process, like graphite etc.
The 3rd purpose of the present invention provides a kind of application process of catalyst removal minimum gas impurity of the present invention, and this application process comprises:
In temperature is 20～240 ℃, and preferred 80～220 ℃, more preferably 120～200 ℃, reaction pressure is 0.1～10MPa, and preferred 1～8MPa more preferably under the condition of 2～6MPa, makes the H that contains trace
2, CO, CH
3The material of OH contacts with catalyst of the present invention and removes the H in the material
2, CO, CH
3OH; Described material is CO
2, C
2H
4, C
3H
6, N
2, air, inert gas be (like He, Ar), CH
4, natural gas or coal bed gas, H in the said material
2, CO, O
2And CH
3The content of OH is 0.01vol%～5vol%, preferred 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 preferred 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 the charging
2, CO, O
2And CH
3The content of OH is 0.01vol%～5vol%, preferred 0.01vol%～3vol%, and more preferably 0.01vol%～1vol% under the situation of reactive chemistry metering than permission, uses catalyst of the present invention can make micro-H in the material
2, CO, O
2And CH
3OH content deep removal is to 10ppm.
If H in the charging
2, CO, O
2And CH
3The content of OH is 0.01～500ppm, preferred 0.1～200ppm, and more preferably 0.1～5ppm under the situation of reactive chemistry metering than permission, uses catalyst of the present invention can make micro-H in the material
2, CO, O
2And CH
3OH content deep removal is to 10ppb.
H in the said charging
2, CO, O
2And CH
3OH when using catalyst removal of the present invention, surpasses the component of reactive chemistry metering ratio, can remove through other modes.
Catalyst of the present invention activity reduce or inactivation after can regenerate, regeneration temperature is 120～600 ℃, regeneration gas is that oxygen or air or other contain the mist of oxygen.
In specification of the present invention and claims, related content, for example %, ppm and ppb are by volumes.
Catalyst of the present invention has following beneficial effect:
(1) uses catalyst removal micro CO of the present invention, remove multiple minimum gas impurity simultaneously at 20～240 ℃ of following catalytic oxidations, like the H of trace
2, CO, CH
3OH etc. can with the O of trace
2Reaction removes multiple gases impurity simultaneously under the situation that stoichiometric proportion allows, simplify process for purifying, reduces operating cost.
(2) copper-based catalysts that adopts coprecipitation to prepare, catalyst has high activity and good stable property when adding CNT.
The specific embodiment
The method of testing of relevant data is following in the embodiments of the invention:
Specific surface test: adopt the physical adsorption appearance of the Nova 3000e of U.S. Kang Ta company, carry out specific surface area analysis.Under liquid nitrogen temperature-196 ℃, use N
2Determination of adsorption method surface area and pore-size distribution, sample vacuumize preliminary treatment to pressure less than 10 under 300 ℃
-3Pa, assay method are static method.Adopt the BET method to calculate specific surface based on adsorption isotherm.
The following example further describes and explains the preferred embodiment in the scope of the invention.
Embodiment 1
With the copper nitrate solution of 1 mol of 2000mL and the mixed solution of zirconium oxychloride; Add 0.18 gram CNT simultaneously; Sodium carbonate liquor with mixed liquor and 2000mL 1 mol also flows in the container that joins 5L to precipitate then; Precipitation temperature is 90 ℃, and the pH value is controlled at 8.5 ± 0.5.Under the strong agitation situation, wore out 2 hours then, aging temperature is 90 ℃.Filter then, under 80 ℃, spend deionised water at least six times, be washed till Na
2O content is lower than 0.05%.110 ℃ dry 12 hours down, roll the granulation of sieve powder afterwards, 400 ℃ of following roastings 6 hours, 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 are 240m
2/ g.
Embodiment 2
Like embodiment 1, adopt and the stream prepared by co-precipitation, in co-precipitation, add 0.8 gram 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 are 150m
2/ g.
Embodiment 3
Like embodiment 1, adopt and the stream prepared by co-precipitation, when rolling the granulation of sieve powder, add 1.78 gram 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 are 180m
2/ g.
Embodiment 4
Like embodiment 1, different is to adopt the anti-prepared by co-precipitation that adds, and promptly at first the sodium carbonate liquor of 2000mL 1 mol is added in 5 liters the container, afterwards again with the copper nitrate solution and the adding of manganese nitrate mixed solution of 1 mol.To in compression molding, add 7.8 gram CNTs, and make and contain 70wt%CuO and 25wt%Mn
2O
3Catalyst, content of carbon nanotubes is 5wt%, is labeled as 4
#Catalyst, specific surface are 125m
2/ g.
Embodiment 5
Like embodiment 1, adopt the anti-prepared by co-precipitation that adds, in co-precipitation, add 0.8 gram 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 are 140m
2/ g.
Comparative Examples
Except that not adding CNT, all the other adopt also stream prepared by co-precipitation like embodiment 2, make the CuO/ZnO catalyst that contains 30%CuO and 70%ZnO and are labeled as 6
#Catalyst, specific surface are 40m
2/ g.
Embodiment 7:
With embodiment 1～5 and the prepared catalyst of Comparative Examples, 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 controlled through the program temperature controller by thermocouple.After the catalyst filling, adopt high-purity nitrogen to purge 12 hours at 150 ℃.Material is CO
2, wherein containing CO is 0.5vol%, H
2Be 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 1000 hours evaluation.Gas-chromatography Varian 3800 is adopted in the analysis of raw material and product, band methanation nickel reburner, thermal conductivity detector (TCD) and hydrogen flame detector, and the CO lowest detection is limited to 0.1ppm, H
2And O
2Detection be limited to 0.01vol%.The micro anti-evaluation result of catalyst lists in table 1.
Embodiment 8:
With embodiment 1～5 and the prepared catalyst of Comparative Examples, 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 controlled through the program temperature controller by thermocouple.After the catalyst filling, adopt high-purity nitrogen to purge 12 hours at 120 ℃.Material is C
2H
2, wherein containing CO is 5ppm, H
2Be 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 1000 hours evaluation.Gas-chromatography Varian 3800 is adopted in the analysis of raw material and product, band methanation nickel reburner, thermal conductivity detector (TCD) and hydrogen flame detector, and the 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
2Be limited to 1ppm under detecting.After the content of reactor outlet CO is lower than 0.1ppm, switch and the detection of use micro CO analyzer.The micro anti-evaluation result of catalyst lists in table 2.
Table 1
| Catalyst | Form (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 | Form (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 represent instrument not detect
Can find out from the data of table 1 and table 2: 1) adding of CNT has increased the specific surface of catalyst; 2) when adding CNT in the copper-based catalysts, catalyst has good activity, according to stoichiometric proportion, can remove trace amount of foreign gas simultaneously; And the copper-based catalysts that does not add CNT does not almost have reactivity.
Embodiment 9
Present embodiment is used for explaining that catalyst of the present invention can remove the trace impurity in the various materials.
With embodiment 2 prepared 2
#Catalyst removes test.Fixed-bed tube reactor.Loaded catalyst is 100mL.
Experiment condition is following:
Treat that processed gas is respectively: propylene, nitrogen, helium and argon gas etc., it is 5ppm that these gases wherein all contain CO, H
2Be 5ppm, O
2Content is 5.5ppm.Treat processed gas methane, wherein containing CO is 0.5vol%, H
2Be 0.5vol%, CH
3OH content is 0.07vol%, O
2Content is 1.1vol%.For these appreciation conditions of treating processed gas be: 80 ℃ of reaction temperatures, reaction pressure 1.7MPa, air speed 10,000h
-1
Result of the test is listed in table 3 and the table 4.
Table 3.1
#Catalyst is in the experimental result of differential responses system
| Material is formed | 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 is formed | Outlet H 2 (％) | Outlet CO (%) | Outlet O 2 (％) | Outlet CH 3OH (％) |
| Methane (containing 5ppm sulphur) | 0.01 | 0.02 | 0.05 | 0.01 |
Find out from table 3 and table 4, when containing micro-H
2, CO and O
2Material not simultaneously, even when containing trace in the methane gas, the performance that removes of this catalyst does not receive tangible influence, has all obtained satisfied removal effect.
Claims (8)
1. a copper-based catalysts that removes minimum gas impurity is characterized in that, this catalyst is made up of oxide and the CNT of the first component CuO, the second component M;
Wherein, the weight content of CuO is 0.1wt%～99.9wt%;
The second component M is selected from one or more among Zn, Zr, Mn, Ce, Fe, Co, Ag, the Pd, and the weight content of the oxide of M is 0.01wt%～94.9wt%;
The weight content of CNT is 0.01wt%～5wt%;
Described weight content is a benchmark with the catalyst gross weight.
2. the copper-based catalysts that removes gaseous impurity as claimed in claim 1; It is characterized in that; The weight content of CuO is 30wt%～80wt% in this catalyst, and the weight content of the oxide of M is 19.5wt%～69.9wt%, and the weight content of CNT is 0.1wt%～1wt%.
3. the copper-based catalysts that removes gaseous impurity as claimed in claim 1 is characterized in that, described CNT is a multi-walled carbon nano-tubes, and its outer tube diameter is 5～100nm, and interior caliber is 1～10nm.
4. the copper-based catalysts that removes gaseous impurity as claimed in claim 1 is characterized in that, the specific surface of said catalyst is 1～300m
2/ g is preferably 5～200m
2/ g.
5. the copper-based catalysts that removes gaseous impurity as claimed in claim 1 is characterized in that, CuO crystal grain is 1～30nm in the said catalyst, preferred 3～30nm, more preferably 3～20nm.
6. like the preparation method of one of claim 1-5 described copper-based catalysts, it is characterized in that described catalyst adopts the coprecipitation method preparation, may further comprise the steps:
(1) formulations prepared from solutions: the mixed solution of preparation mantoquita and M salt, preparation 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 the salting liquid titration is added aqueous slkali, makes that the pH value of reaction system finally is 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 the 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 wore out 10～120 minutes down at 20～90 ℃, filtered and obtained sediment;
(4) washing: the sediment that washing step (3) obtains, 10～90 ℃ of wash temperatures;
(5) drying: the material that step (4) obtains is following dry 1～48 hour at 60～120 ℃;
(6) granulation: the material that step (5) is obtained rolled 0.5～12 hour;
(7) roasting: the material that step (6) is obtained obtains particle 200～800 ℃ of following roastings 1～12 hour;
(8) moulding: particle and adhesive that step (7) is obtained mix compression molding;
CNT can or add in a few step in any step of step (1) to step (8), except the step (7).
7. the method for the described catalyst removal gaseous impurity of one of claim 1-5 is characterized in that, is 20～240 ℃ in temperature, and pressure is under 0.1～6MP, makes the H that contains trace
2, CO, CH
3The material of OH contacts with the described catalyst of one of claim 1-5 and removes the H in the material
2, CO, CH
3OH; Described material is CO
2, C
2H
4, C
3H
6, N
2, air, inert gas, CH
4, natural gas or coal bed gas, H in the said material
2, CO, O
2And CH
3The content of OH is 0.01vol%～5vol%, preferred 0.01vol%～3vol%, more preferably 0.01vol%～1vol%.
8. the renovation process of the described catalyst of one of claim 1-5; Comprise with activity reduce or the catalyst of inactivation under 120～600 ℃ regeneration temperature; In regeneration gas, regenerate, wherein said regeneration gas is that oxygen or air or other contain the mist of oxygen.
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| CN109529871A (en) * | 2018-12-13 | 2019-03-29 | 重庆工商大学 | A kind of sea urchin shape copper-based catalysts and its preparation method and application |
| CN114029063A (en) * | 2021-12-16 | 2022-02-11 | 厦门大学 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method 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 |
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| 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 |
| CN114029063A (en) * | 2021-12-16 | 2022-02-11 | 厦门大学 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof |
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