WO2023090993A1 - Procédé de production d'un catalyseur - Google Patents

Procédé de production d'un catalyseur Download PDF

Info

Publication number
WO2023090993A1
WO2023090993A1 PCT/MY2022/050112 MY2022050112W WO2023090993A1 WO 2023090993 A1 WO2023090993 A1 WO 2023090993A1 MY 2022050112 W MY2022050112 W MY 2022050112W WO 2023090993 A1 WO2023090993 A1 WO 2023090993A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
organic framework
around
metal organic
hours
Prior art date
Application number
PCT/MY2022/050112
Other languages
English (en)
Inventor
Zhe Phak CHAN
Akbar ABU SEMAN
Nor Hafizah YASIN
Nor Hafizah BERAHIM @ JUSOH
Oliver Michael LINDER-PATTON
Christopher James SUMBY
Christian James DOONAN
Original Assignee
Petroliam Nasional Berhad (Petronas)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petroliam Nasional Berhad (Petronas) filed Critical Petroliam Nasional Berhad (Petronas)
Publication of WO2023090993A1 publication Critical patent/WO2023090993A1/fr

Links

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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J23/80—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 zinc, cadmium or mercury
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
    • B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
    • 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
    • B01J23/72—Copper
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a method for producing a catalyst, in particular for use in hydrogenation of carbon dioxide to methanol.
  • methanol is commercially produced by reacting carbon monoxide and hydrogen over a catalyst, typically a mixture of copper and zinc oxides supported by alumina.
  • An alternative method is to use carbon dioxide instead, using Cu/ZnO/silica as a catalyst, which has the added benefit of utilising carbon emissions and increasing carbon offset efforts.
  • An aim of the invention therefore is to provide a method for producing a catalyst suitable for use in hydrogenation of carbon dioxide to methanol which overcomes at least some of the above issues.
  • a method for producing a catalyst comprising the steps of: mixing a metal precursor with an organic ligand and a solvent to form a precursor solution; heating the precursor solution at a predetermined temperature and time to form a metal organic framework; and washing and drying the metal organic framework; characterised in that a solution containing zinc and copper ions is added to the metal organic framework by incipient wetness impregnation, whereby the resulting loaded support is dried and then calcined to form the catalyst.
  • the incipient wetness impregnation ensures that the volume of precursor solution added to the dried metal organic framework is substantially equal to the pore volume thereof, whereby capillary action draws the solution into the pores, such that when dried and calcined to remove volatile components, the zinc/copper is deposited on the surface within the pores, resulting in a more structured and homogenous catalyst with a significantly higher surface area (and thus activity) compared to the prior art.
  • the metal organic framework comprises UiO-66, wherein the metal precursor comprises ZrOCh or ZrOfNCh , the organic ligand comprises 1,4-benzene dicarboxylic acid (H2BDC), and the solvent comprises dimethylformamide (DMF), and further includes a modulator such as formic acid (FA).
  • the metal precursor comprises ZrOCh or ZrOfNCh
  • the organic ligand comprises 1,4-benzene dicarboxylic acid (H2BDC)
  • the solvent comprises dimethylformamide (DMF)
  • FA formic acid
  • the predetermined temperature and time for heating the precursor solution for UiO-66 is about 100-150°C and around 12-48 hours respectively, typically about 120°C and around 24 hours respectively.
  • the metal organic framework comprises NU-1000, wherein the metal precursor comprises ZrOCh or ZrO(NO3)2, the organic ligand comprises 4,4',4",4"'-(pyrene-l,3,6,8-tetrayl)tetrabenzoic acid (FUTBAPy), and the solvent comprises dimethylformamide (DMF), and further includes a modulator such as benzoic acid (BA).
  • the metal precursor comprises ZrOCh or ZrO(NO3)2
  • the organic ligand comprises 4,4',4",4"'-(pyrene-l,3,6,8-tetrayl)tetrabenzoic acid (FUTBAPy)
  • the solvent comprises dimethylformamide (DMF)
  • BA benzoic acid
  • the predetermined temperature and time for heating the precursor solution for NU-1000 is about 80-120°C and around 12-48 hours respectively, typically about 100°C and around 24 hours respectively.
  • the metal organic framework comprises MIP-206, wherein the metal precursor comprises ZrC’h.
  • the organic ligand comprises isophthalic acid (IP A), and the solvent comprises formic acid (FA) or acetic acid.
  • the solvent further comprises water.
  • the predetermined temperature and time for heating the precursor solution for MIP-206 is about 100-200°C and around 12-48 hours respectively, typically about 180°C and around 24 hours respectively.
  • the metal organic framework is washed with dimethylformamide and acetone.
  • the washed metal organic framework is dried by centrifugation or fdtration, and then solvent removal under reduced pressure, typically in a vacuum desiccator for 2 hours.
  • the metal organic framework undergoes anion exchange to remove chloride ions in between the washing and drying steps.
  • anion exchange prevents catalyst poisoning due to the presence of chloride (which would significantly reduce the yield) as well as contamination/leaching which can cause corrosion at downstream processing.
  • UiO-66 and NU-1000 may use chloride-free precursors, such that the anion exchange is not required.
  • the anion exchange is conducted by dispersing the metal organic framework in methanol, and solvent exchanging with ammonium formate in methanol.
  • the loaded support is dried at about 80°C for around 24 hours, but it will be appreciated that other temperatures and times could be used.
  • the solution containing zinc and copper ions comprises copper nitrate and zinc nitrate.
  • the solution further comprises ammonium niobate oxalate, zirconium nitrate, and manganese nitrate.
  • the loaded support is calcined at about 200°C-400°C for around 2-6 hours. Typically where the temperature is >250°C, oxidative catalyst is formed. In addition copper sintering may occur if the temperature is >300°C.
  • the resulting pristine precatalyst can be reduced in situ using 5% H2/N2 or Fh/Ar at about 250°C for around 2-6 hours to form pristine catalyst.
  • pristine catalyst is dosed with F ⁇ CCh in the ratio range of 3: 1 to 10: 1, typically 3: 1, at about 250°C and around 40 bar for about 5 hours to form reductive catalyst.
  • the temperature of the process is about 200-300°C
  • the pressure is around 20-100 bar
  • the FtCCh ratio is 3-10: 1.
  • the temperature of the process is about 225°C, the pressure is around 40 bar, and the FtCCh ratio is 3: 1, for about 5 hours.
  • the temperature of the process is about 225°C, the pressure is around 80 bar, and the F ⁇ CCh ratio is 3: 1 in a continuous flow system.
  • This compares favourably with the alternative method using Cu/ZnO/silica as a catalyst, where the temperature of the process is about 200°C, the pressure is around 40 bar, and the TtCCh ratio is 3: 1, for about 5 hours.
  • the yield of the alternative method is ⁇ 1%
  • the yield for the invention is >20% because of the improved catalyst.
  • Figure 1 is a schematic view of the methods of making a catalyst according to an embodiment of the invention.
  • the precursors comprising a metal precursor, an organic ligand and a solvent modulator are mixed 2 and then heated 4 in a Teflon-lined sealed reactor, in this example at 180°C for 24 hours.
  • the resulting metal organic framework (MOF) is then washed 6 with DMF and acetone. If chloride ions are present, the product is anion exchanged 8 in methanol with ammonium formate. Then product is then dried.
  • the MOF was then loaded 10 with Cu/Zn solution using incipient wet impregnation (IWI), dried at 80°C overnight, and then calcined 12 at 250°C for 2 hours, resulting in a catalyst 14 such as UiO-66, NU-1000 or MIP-206.
  • IWI incipient wet impregnation
  • ZrO(NO3)2 (1.803 g, 7.8 mmol) was added into a solvent mixture of DMF/formic acid (40 ml/ 15 ml) in a round-bottom flask and sonicated for 15 minutes.
  • the solution was separated evenly between six 20 ml Teflon capped vials. The vials were then transferred to a pre-heated oven and kept at 120°C for 16 h (overnight).
  • the white crystalline material was collected via centrifugation, washed three times with DMF (50 ml x 3) and then the bulk sample was solvent exchanged with acetone (30 ml x 4) and left solvated until ready for use.
  • ZrO(NO3)2 (90.15 g, 0.39 mol) was added into a solvent mixture of DMF/formic acid (200 ml/ 75 ml) in a round-bottom flask and stirred for 15 minutes.
  • the solution was heated at 120°C for 16 h (overnight), whilst stirring constantly.
  • the white crystalline material was collected via filtration, washed three times with DMF (100 ml x 3) and then the bulk sample was solvent exchanged with acetone (60 ml x 4) and left solvated until ready for use.
  • MIP-206 was synthesized solvothermally by the reaction of ZrC’h and isophthalic acid (IP A) in formic acid.
  • IP A isophthalic acid
  • IPA 1.1 g, 6.6 mmol
  • formic acid 5 mb
  • ZrCU 2 g, 8.6 mmol
  • Dried MIP-206 was dispersed in methanol (30 ml / 1 g of MOF), centrifuged and was then solvent exchanged with ammonium formate in methanol (0.05 M, 30 ml x 5), centrifuging in between washes to ensure solvent removal.
  • the MOF was washed with methanol (30 ml x 3) and stored in methanol prior to use.
  • a stock solution of Cu(NO3)2 6H2O : Zn(NC>3)2 6H2O (70 : 30, 1.08 M) in methanol was prepared using 262 mg and 109 mg of Cu and Zn salts per 1 ml of methanol, respectively.
  • MOF supports are dried in a desiccator to remove solvent (2 h under vacuum) and the dried MOF supports were weighed in 20 ml vials and 1.38 ml of the stock solution was added to the dried MOF per gram of MOF support.
  • the resultant slurry was stirred until homogeneous, and air dried at 80°C for 24 h and then calcined at 250°C for 2 h and stored in a dry desiccator prior to analysis. Acetone was used as the solvent for MIP-206 samples.
  • Samples were dried from acetone in a vacuum desiccator for 1 h then transferred into sorption analysis tubes, the samples were then dried under a high vacuum (1 pbar) at 120°C for 3 h to yield activated samples.
  • Oxidative MOF-derived catalyst (Cu/ZnO@MOF (Ox. MDC)) preparation:
  • Reductive MOF-derived catalyst Cu/ZnO@MOF (Red. MDC)
  • Reaction monitoring was conducted using a residual gas analyser and gas chromatography .
  • the reaction is held at 30°C for 1 h (to establish a background for the RGA) and then the reaction cell is heated to the reaction temperature (200 - 250°C) and held at constant temperature for 120-300 min.
  • the reaction mixture is analysed in real time via RGA (by pulsing a small amount of gas into the vacuum chamber, 2 x 10‘ 6 Torr) to follow methanol production. After the reaction has concluded the gaseous reaction mixture was analysed via gas chromatography (GC-FID/TCD).
  • Cu/ZnO@MOF (Red. MDC) samples are formed by reducing Cu/ZnO@MOF catalysts in situ (1 bar 5% PF/ Ar at 250°C for 2 h), and then exposed these samples to reductive reaction conditions (250°C, 40 bar, 3: 1 F ⁇ CCh) for 5 h.
  • Table 1 illustrates the catalyst performance data where under comparative conditions, the invention with an MOF support achieves a yield of >20%, whereas the alternative silica support (which has a ratio of Nb:Mn:Zr (1: 1: 1) with 0.09 wt% of overall Cu/Zn weight) has a yield of ⁇ 1%.
  • the only yield identified in the prior art literature requires a much higher pressure of 360 bar, which is expensive and impractical.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'un catalyseur comprenant les étapes consistant à mélanger un précurseur métallique avec un ligand organique et un solvant pour former une solution de précurseur ; faire chauffer la solution de précurseur à une température et pendant un temps prédéfinis pour former une structure organométallique ; et laver et faire sécher la structure organométallique ; une solution contenant du zinc et des ions cuivre étant ajoutée à la structure organométallique par imprégnation à humidité naissante, le support chargé obtenu étant ainsi séché et ensuite calciné pour former le catalyseur.
PCT/MY2022/050112 2021-11-19 2022-11-17 Procédé de production d'un catalyseur WO2023090993A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI2021006906 2021-11-19
MYPI2021006906 2021-11-19

Publications (1)

Publication Number Publication Date
WO2023090993A1 true WO2023090993A1 (fr) 2023-05-25

Family

ID=86397559

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/MY2022/050112 WO2023090993A1 (fr) 2021-11-19 2022-11-17 Procédé de production d'un catalyseur

Country Status (1)

Country Link
WO (1) WO2023090993A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110105776A1 (en) * 2003-11-24 2011-05-05 Basf Aktiengesellschaft Method for electrochemical production of a crystalline porous metal organic skeleton material
US20200079796A1 (en) * 2018-09-06 2020-03-12 The Board Of Trustees Of The University Of Alabama Methods of making nanostructured metal-organic frameworks

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110105776A1 (en) * 2003-11-24 2011-05-05 Basf Aktiengesellschaft Method for electrochemical production of a crystalline porous metal organic skeleton material
US20200079796A1 (en) * 2018-09-06 2020-03-12 The Board Of Trustees Of The University Of Alabama Methods of making nanostructured metal-organic frameworks

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SUN SHUJIAN, WEI CAIFENG, XIAO YALI, LI GUANGQIN, ZHANG JIANYONG: "Zirconium-based metal–organic framework gels for selective luminescence sensing", RSC ADVANCES, vol. 10, no. 73, 21 December 2020 (2020-12-21), pages 44912 - 44919, XP093066957, DOI: 10.1039/D0RA09035B *
WANG SUJING, CHEN LIYU, WAHIDUZZAMAN MOHAMMAD, TISSOT ANTOINE, ZHOU LIN, IBARRA ILICH A., GUTIÉRREZ-ALEJANDRE AÍDA, LEE JI SUN, CH: "A Mesoporous Zirconium-Isophthalate Multifunctional Platform", MATTER, CELL PRESS, US, vol. 4, no. 1, 1 January 2021 (2021-01-01), US , pages 182 - 194, XP093066960, ISSN: 2590-2385, DOI: 10.1016/j.matt.2020.10.009 *
YANG YANG, XU YANAN, DING HENG, YANG DONG, CHENG ENPING, HAO YIMING, WANG HONGTAO, HONG YANZHEN, SU YUZHONG, WANG YANLIANG, PENG L: "Cu/ZnO x @UiO-66 synthesized from a double solvent method as an efficient catalyst for CO 2 hydrogenation to methanol", CATALYSIS SCIENCE & TECHNOLOGY, ROYAL SOCIETY OF CHEMISTRY, UK, vol. 11, no. 13, 5 July 2021 (2021-07-05), UK , pages 4367 - 4375, XP093066955, ISSN: 2044-4753, DOI: 10.1039/D0CY02450C *

Similar Documents

Publication Publication Date Title
CN110270348B (zh) 一种贵金属单原子催化剂及其制备和应用
CN111229218B (zh) 一种单原子钯复合催化剂及其制备方法和用途
Vrijburg et al. Ceria–zirconia encapsulated Ni nanoparticles for CO 2 methanation
US4275052A (en) Process for preparing high surface area aluminas
CN110575828A (zh) 用于乙醇和乙醛反应合成1，3-丁二烯的高效催化剂及其制备方法
CN115382541B (zh) 一种调控铑基催化剂中Rh物种存在形式的方法
CN115155600B (zh) 一种合成甲醇用的催化剂及其制备方法与应用
Guan et al. Tuneable oxidation of styrene to benzaldehyde and benzoic acid over Co/ZSM-5
CN112844486A (zh) 一种用于CO2化学固定的高稳定性催化剂ZIF-8/CeO2复合材料及其制备方法
Bennici et al. Bulk and surface properties of dispersed CuO phases in relation with activity of NO x reduction
Lázaro et al. MOF nanoparticles as heterogeneous catalysts for direct amide bond formations
NO314292B1 (no) Fremgangsmåte for omdannelse av syntesegass i n¶rv¶r av en katalysator somomfatter kobolt og ytterligere elementer
EA027378B1 (ru) Активированный катализатор реакции синтеза фишера-тропша и способ производства углеводородов
WO2023090993A1 (fr) Procédé de production d'un catalyseur
CN115337926B (zh) 一种铑基催化剂及其制备方法和应用
CN112316985A (zh) 一种二氧化碳加氢制甲醇的催化材料及其制备方法
CN108033462B (zh) 一种多级孔ltl分子筛及其合成方法和应用
CN112892570B (zh) 多级孔Co-N-C复合材料及其制备方法与应用
CN110560123B (zh) 无金属无孔催化剂材料的制备方法及应用
Liberman et al. Synthesis, structure, and properties of a Au/MnO x–CeO 2 nanocatalyst for low-temperature oxidation of carbon monoxide
CN113663722A (zh) 苯加氢烷基化制备环己基苯的催化剂及其制备方法和应用
CN112844482A (zh) 一种酸碱双功能核壳结构非均相催化剂及制备方法和一种裂解回收丙烯酸丁酯重组分的方法
CN112844469A (zh) 一种固体碱催化剂及其制备方法和在合成苯甲醚中的应用
CN113713840B (zh) 一种氮化钴-镍镓液态合金复合催化剂及其制备方法和应用
JP2013209743A (ja) Ｕｓｙゼオライトを担体とした自発的高分散化による金ナノ粒子の調製方法、金ナノ粒子

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22896188

Country of ref document: EP

Kind code of ref document: A1