WO2024066032A1 - Procédé de préparation d'un catalyseur hopcalite modifié et son utilisation - Google Patents
Procédé de préparation d'un catalyseur hopcalite modifié et son utilisation Download PDFInfo
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- WO2024066032A1 WO2024066032A1 PCT/CN2022/136499 CN2022136499W WO2024066032A1 WO 2024066032 A1 WO2024066032 A1 WO 2024066032A1 CN 2022136499 W CN2022136499 W CN 2022136499W WO 2024066032 A1 WO2024066032 A1 WO 2024066032A1
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- hopcalite catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011572 manganese Substances 0.000 claims abstract description 43
- 239000010949 copper Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract 2
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000000975 co-precipitation Methods 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 229910052596 spinel Inorganic materials 0.000 abstract description 5
- 239000011029 spinel Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 37
- 239000007789 gas Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002131 composite material Substances 0.000 description 12
- 229910018657 Mn—Al Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910018565 CuAl Inorganic materials 0.000 description 2
- 229910016583 MnAl Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 208000002381 Brain Hypoxia Diseases 0.000 description 1
- 208000001408 Carbon monoxide poisoning Diseases 0.000 description 1
- 229910017566 Cu-Mn Inorganic materials 0.000 description 1
- 229910017871 Cu—Mn Inorganic materials 0.000 description 1
- 206010019468 Hemiplegia Diseases 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 201000007201 aphasia Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Definitions
- the present invention relates to the technical field of catalysts for catalytic combustion of CO.
- the catalysts that are maturely used in CO catalytic combustion are mainly precious metal catalysts.
- the high cost has greatly limited the market application of precious metal catalysts. Therefore, the development of non-precious metal catalysts with high and low temperature activity, high stability and low cost will greatly promote the market application of catalytic combustion.
- hopcalite catalysts with Cu, Mn oxides and their composite oxides as main components have shown high reactivity in catalytic combustion activity studies.
- Hopcalite catalysts with MnO 2 and CuO as main components are widely used in submarine closed compartments. They can catalyze CO to CO 2 at high temperature in a 320°C burner environment. The reaction has the advantages of no secondary toxic pollutants (Christopher et al. Applied Catalysis B: Environmental, 2017, (203) 533-540).
- hopcalite catalysts are composed of CuMn 2 O 4 spinel formed by Cu and Mn, which makes most of the Cu and Mn elements mainly exist in the catalyst in the form of carriers, while only a small amount of Cu 2+ and Mn 4+ can be dispersed and freed on the catalyst surface to form catalytic reaction active centers, making it difficult for hopcalite catalysts to obtain good low-temperature catalytic activity.
- the object of the present invention is to provide a modified hopcalite catalyst, wherein the doping of Al forms a new spinel structure with Cu and Mn, thereby playing the role of a carrier, so that more Cu 2+ and Mn 4+ are dispersed on the catalyst surface.
- the structure is stable, the low-temperature catalytic activity is good, and the catalytic stability is high.
- the object of the present invention is also to provide a method for preparing the above catalyst, which has a simple process and high product stability.
- the present invention also aims to provide an application method of the catalyst.
- a modified hopcalite catalyst comprises the following components: a composite oxide consisting of CuAl 2 O 4 , MnAl 2 O 4 and oxides of Cu and Mn.
- the oxide of Cu and Mn is CuMnO 2 .
- the molar ratio of the Cu element, the Mn element and the Al element is 1-10:1-10:0.2-5.
- the molar ratio of the Cu element, the Mn element and the Al element is 5:1:0.2-3, and more preferably 5:1:0.5-1.
- the present invention provides the following technical solutions:
- the preparation method of the catalyst comprises the following steps: co-precipitating a mixed solution containing Cu ions, Mn ions and Al ions, and calcining the obtained precipitate.
- the mixed solution is an acid solution containing a Cu compound, a Mn compound and an Al compound.
- the acid solution is a nitric acid solution.
- the calcination temperature is 300-500°C.
- the calcination time is 6 to 10 hours.
- the coprecipitation is carried out under alkaline conditions.
- the coprecipitation uses an alkali as a precipitant, and the alkali is selected from one or more of sodium hydroxide, sodium carbonate and ammonia water.
- the concentration of the base is 0.3 to 3 mol ⁇ L -1 .
- the concentration of the base is 1.5 to 2.5 mol ⁇ L -1 .
- the coprecipitation temperature is 10 to 30 °C.
- the coprecipitation temperature is 15-20°C.
- the mixed solution is allowed to stand for 10 to 20 hours after the coprecipitation.
- the molar ratio of the Cu element, the Mn element and the Al element is 1-10:1-10:0.2-5.
- the molar ratio of the Cu element, the Mn element and the Al element is 5:1:0.5-1.
- the total concentration of metal ions in the mixed solution is 0.5 to 1.5 mol ⁇ L -1 .
- the Cu compound is selected from copper nitrate (Cu(NO 3 ) 2 ⁇ 3H 2 O) and/or copper sulfate (CuSO 4 ).
- the Mn compound is selected from manganese nitrate (MnN 2 O 6 ⁇ 4H 2 O) and/or manganese nitrate solution (Mn(NO 3 ) 2 ).
- the Al compound is selected from aluminum nitrate (Al(NO 3 ) 3 ⁇ 9H 2 O).
- the preparation of the mixed solution includes: dissolving the copper source, the manganese source, and the aluminum source in distilled water in sequence to obtain the mixed solution.
- the present invention provides the following technical solutions:
- the catalyst or the catalyst prepared according to the preparation method is applied to CO catalytic combustion.
- the particle size of the catalyst is 20-60 mesh.
- the CO low temperature oxidation temperature is 20°C.
- the present invention obtains a novel hopcalite catalyst for catalytic combustion of CO;
- the present invention further doped Al 2 O 3 in the existing hopcalite catalyst, which not only improved the dispersion of the active center components Cu 2+ and Mn 4+ , but also the doping effect of metal ions further promoted the bonding strength between CO and Cu and Mn, so that the low-temperature activity and catalytic efficiency of the catalyst were significantly improved;
- the catalyst of the present invention has better low-temperature activity in the CO catalytic combustion reaction than the traditional hopcalite catalyst, and can achieve 100% conversion of CO at room temperature of 20°C;
- FIG. 1 is an XRD spectrum of Example 5
- FIG. 2 is a comparison chart of H2-TPR of Example 5 and commercial Hojalat catalyst.
- the catalyst used in the following examples was obtained by the following preparation process:
- the pH value of the reaction solution is adjusted by adjusting the dripping rate of the two.
- stop adding the NaOH precipitant immediately, continue stirring at room temperature for 2h, and let it stand for aging for 15h.
- the activity of CO catalytic combustion reaction was investigated on commercial hopcalite catalyst.
- a mixed gas consisting of 1.6% CO, 21.4% oxygen and 77.0% nitrogen was introduced at a rate of 30 mL min -1 , a reaction space velocity of 360 h -1 , normal pressure and a reaction temperature of 15 °C, and the CO catalytic combustion reaction was carried out. After the temperature stabilized, the data were collected 15 minutes later, and the TCD detector was used for online analysis on the SC-2000 gas chromatograph.
- the formula for evaluating the CO conversion rate of the reactant is as follows:
- the sampling at this temperature is terminated, and the average conversion rate of three samplings is taken as the conversion rate at this temperature. Then the temperature is increased by 5°C/time until the CO conversion rate reaches 100% and the reaction is terminated.
- a mixed gas consisting of 1.6% CO, 21.4% oxygen and 77.0% nitrogen was introduced into a fixed bed reactor at a rate of 30 mL ⁇ min -1 , a reaction space velocity of 360 h -1 , normal pressure and a reaction temperature of 15°C to carry out a CO catalytic combustion reaction. After the temperature stabilized, the sample was collected 15 minutes later and the online analysis was carried out using a TCD detector on an SC-2000 gas chromatograph.
- a mixed gas consisting of 1.6% CO, 21.4% oxygen and 77.0% nitrogen was introduced into a fixed bed reactor at a rate of 30 mL ⁇ min -1 , a reaction space velocity of 360 h -1 , normal pressure and a reaction temperature of 15°C to carry out a CO catalytic combustion reaction. After the temperature stabilized, the sample was collected 15 minutes later and the online analysis was carried out using a TCD detector on an SC-2000 gas chromatograph.
- a mixed gas consisting of 1.6% CO, 21.4% oxygen and 77.0% nitrogen was introduced into a fixed bed reactor at a rate of 30 mL ⁇ min -1 , a reaction space velocity of 360 h -1 , normal pressure and a reaction temperature of 15°C to carry out a CO catalytic combustion reaction. After the temperature stabilized, the sample was collected 15 minutes later and the online analysis was carried out using a TCD detector on an SC-2000 gas chromatograph.
- a mixed gas consisting of 1.6% CO, 21.4% oxygen and 77.0% nitrogen was introduced into a fixed bed reactor at a rate of 30 mL ⁇ min -1 , a reaction space velocity of 360 h -1 , normal pressure and a reaction temperature of 15°C to carry out a CO catalytic combustion reaction. After the temperature stabilized, the sample was collected 15 minutes later and the online analysis was carried out using a TCD detector on an SC-2000 gas chromatograph.
- a mixed gas consisting of 1.6% CO, 21.4% oxygen and 77.0% nitrogen was introduced into a fixed bed reactor at a rate of 30 mL ⁇ min -1 , a reaction space velocity of 360 h -1 , normal pressure and a reaction temperature of 15°C to carry out a CO catalytic combustion reaction. After the temperature stabilized, the sample was collected 15 minutes later and the online analysis was carried out using a TCD detector on an SC-2000 gas chromatograph.
- the commercial Hojalat catalyst and the Cu-Mn-Al composite oxide prepared with the molar ratio of Cu:Mn:Al of 5:1:0.2, 5:1:0.4, 5:1:0.6, 5:1:0.8 and 5:1:1 were mainly investigated.
- the catalyst in Example 5 with the best low temperature activity was characterized by X-ray diffraction, and the XRD spectrum shown in Figure 1 was obtained.
- the main crystal form in the Cu-Mn-Al catalyst is a spinel structure formed by the combination of Cu, Mn and Al elements, and a part of CuMnO 2 composite oxide was observed, which indicates that in the newly generated Cu-Mn-Al composite oxide catalyst after the addition of Al element, Al as a carrier makes the CuMn 2 O 4 spinel structure replaced by CuAl 2 O 4 and MnAl 2 O 4 , which increases the dispersion of Cu and Mn and thus obtains better catalytic activity.
- the results of H 2 -TPR also verify this rule.
- the catalyst in Example 5 and the commercial hopcalite catalyst were characterized by H 2 programmed temperature reduction, and the H 2 -TPR comparison spectrum shown in Figure 2 was obtained.
- Al doping makes the Cu-Mn catalyst easier to reduce, which further proves the increase in the dispersion of Cu 2+ and Mn 2+ in the catalyst.
- Al doping effectively reduces the interaction between the active components and the carrier, so that the dispersion of the active components free Cu 2+ and Mn 4+ on the catalyst surface is increased, the low-temperature reducibility of the catalyst is enhanced, and thus the reaction activity of catalytic combustion is improved.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
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Abstract
La présente invention concerne un catalyseur hopcalite modifié, son procédé de préparation et son utilisation. Le procédé de préparation du catalyseur hopcalite modifié comprend : le mélange de solutions contenant une source de cuivre, une source de manganèse et une source d'aluminium pour obtenir une solution mixte; la co-précipitation de la solution mélangée dans une condition alcaline pour obtenir un précipité; et la torréfaction du précipité obtenu pour obtenir finalement un catalyseur hopcalite modifié. Selon le catalyseur hopcalite modifié fourni par la présente invention, par dopage Al, Al, Cu et Mn forment une nouvelle structure de spinelle qui fonctionne comme un support, de telle sorte qu'une quantité supérieure de Cu2 + et de Mn4 + est dispersée sur la surface du catalyseur. Le catalyseur a une structure stable, une bonne activité catalytique à basse température et une stabilité catalytique élevée. Le procédé de préparation selon la présente invention présente un procédé simple et une stabilité de produit élevée.
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CN202211177646.8 | 2022-09-27 | ||
CN202211177646.8A CN115445634A (zh) | 2022-09-27 | 2022-09-27 | 改性霍加拉特催化剂及其制备方法、应用 |
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CN109621967A (zh) * | 2018-12-26 | 2019-04-16 | 西安向阳航天材料股份有限公司 | 一种铜系低温变换催化剂的制备方法 |
WO2019204127A1 (fr) * | 2018-04-20 | 2019-10-24 | Aether Catalyst Solutions, Inc. | Catalyseur d'oxydes métalliques mixtes à base de cuivre-cobalt-aluminium, son procédé de préparation et son utilisation dans un convertisseur catalytique |
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US20140336044A1 (en) * | 2013-05-10 | 2014-11-13 | Cdti | Copper-Manganese Spinel Catalysts and Methods of Making Same |
CN103599793A (zh) * | 2013-11-28 | 2014-02-26 | 天津市环境保护科学研究院 | 室温去除甲醛的负载型铜锰复合氧化物催化剂及制备方法 |
CN111266115A (zh) * | 2018-12-04 | 2020-06-12 | 河北工程大学 | 一种制备霍加拉特催化剂的方法 |
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WO2019204127A1 (fr) * | 2018-04-20 | 2019-10-24 | Aether Catalyst Solutions, Inc. | Catalyseur d'oxydes métalliques mixtes à base de cuivre-cobalt-aluminium, son procédé de préparation et son utilisation dans un convertisseur catalytique |
CN109621967A (zh) * | 2018-12-26 | 2019-04-16 | 西安向阳航天材料股份有限公司 | 一种铜系低温变换催化剂的制备方法 |
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