CN110302840A - A kind of MnO2The preparation method and application of/Cu-Al-BTC ternary metal organic framework material - Google Patents
A kind of MnO2The preparation method and application of/Cu-Al-BTC ternary metal organic framework material Download PDFInfo
- Publication number
- CN110302840A CN110302840A CN201910475391.5A CN201910475391A CN110302840A CN 110302840 A CN110302840 A CN 110302840A CN 201910475391 A CN201910475391 A CN 201910475391A CN 110302840 A CN110302840 A CN 110302840A
- Authority
- CN
- China
- Prior art keywords
- btc
- mno
- preparation
- solution
- ternary metal
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 53
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910017767 Cu—Al Inorganic materials 0.000 claims abstract description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 12
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000411 inducer Substances 0.000 claims abstract description 7
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004411 aluminium Substances 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 6
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 6
- 229940038384 octadecane Drugs 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 3
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012697 Mn precursor Substances 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000011565 manganese chloride Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 4
- BXRRQHBNBXJZBQ-UHFFFAOYSA-L dichloromanganese;hydrate Chemical compound O.Cl[Mn]Cl BXRRQHBNBXJZBQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 2
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- -1 dipropyl Alkane Chemical class 0.000 claims 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001294 propane Substances 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000013148 Cu-BTC MOF Substances 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Substances CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/204—Carbon monoxide
-
- 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
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—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
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Electromagnetism (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to new type functional design of material and preparation technical fields, provide a kind of MnO2The preparation method and application of/Cu-Al-BTC ternary metal organic framework material.The present invention is using Microwave-assisted firing-dipping combination method as synthetic method, select benzoic acid and acetic acid mixture as stabilizer, synthesize the Cu-Al persursor material of high specific surface area as metal salt with chlorination dihydroxy-bis-tetramethyl ethylene diamine copper (II), (octadecane -9- alkenyl acetoacetate root conjunction-O1 ', O3) two propane -2- alcohol conjunction aluminium.Later, it selects FMES and OP-6 as molecule inducer, induces MnO2Into inside the skeleton structure of Cu-Al persursor material, the MnO with ternary metal active site is prepared2/ Cu-Al-BTC catalyst.The material achieves the denitration efficiency of 90%-96%, and stable structure can be kept until 340 DEG C.
Description
Technical field
The present invention relates to a kind of novel MnO2The preparation method of/Cu-Al-BTC ternary metal organic framework material and its
Application in terms of CO selective catalytic reduction reaction denitration (CO-SCR), belongs to new type functional design of material and technology of preparing is led
Domain.
Background technique
Nitrogen oxides (NOx) discharge will form the Environment Pollution Events such as acid rain, photochemical fog, to human health and
Ecological environment generates serious harm.Since the discharge of current China NOx is not yet perfectly controlled, the pollution for NOx
Control and emission reduction are current China's environmental area Important Problems to be solved.In many NOx removal methods, selective catalysis
Reduction method (Selective Catalytic Reduction, SCR) is denitration currently used widest in area and best effect
Technology.In SCR technology, it is often used NH3,CO,H2, hydrocarbon etc. is as reducing agent, wherein CO-SCR technology is due to tool
Have that catalyst life is long, can remove CO simultaneously, becomes the research tendency of SCR technology the advantages of two kinds of pollutants of NOx.For
For CO-SCR technology, the exploitation and selection of catalyst are the key that determine the reaction denitration performance.In terms of catalyst, SCR
Catalyst mainly includes noble metal catalyst, molecular sieve catalyst and metal oxide catalyst etc..But existing catalyst is deposited
The expensive, poor selectivity, poor stability the problems such as, therefore CO-SCR technology key scientific problems to be solved at present
Exactly developing one kind has preferable denitration efficiency, selective strong, thermal stability height, while cheap new catalytic
Agent.
In recent years, emerging MOFs series material is considered as a kind of ideal SCR catalyst.MOFs material mainly has
Following advantage: huge specific surface area can provide reacting environment for reaction；Unsatuated metal site can to reaction gas into
Row absorption, and it is catalyzed reaction；Regulatable topological structure can enhance the selectivity to gas simultaneously；With excellent thermostabilization
Property, these features are that the catalysis CO-SCR reaction of MOFs material lays the foundation.In MOFs material, different metal center ions exists
Improve denitration efficiency, enhancing stability, reduce reaction temperature etc. plays a different role.How to the metal of different function
Ion carries out selection and combination, can concerted catalysis CO-SCR reaction, improve catalyst performance, be that current MOFs material is de-
The research emphasis in nitre field.
The research of Jiang et al. has shown that Cu-BTC has certain SCR activity, meanwhile, trivalent metal cation such as Al3+
Ion can replace part Cu in the lattice of material2+, to increase the charge density of material, further promote metal active
The generation in site and evenly dispersed.Therefore, it selects Cu, Al as metal center ion first, synthesizes Cu-Al persursor material
It is feasible.And manganese-base oxide catalyst has been demonstrated to can be effectively reduced the light-off temperature of catalyst, therefore containing Cu,
The MOFs material of Al, Mn ternary metal may be a kind of new catalyst with preferable low temperature active and denitration efficiency.So
And currently, synthesis MOFs material has the following problems: common hydro-thermal method has that energy consumption is high, time-consuming；It is reported
Cu-BTC MOFs is the source of metal ion commonly using nitrate, but its that there are yields is not high, metal active site is dispersed
Difference, the problems such as catalytic efficiency is low；Uniformly, stablize, the MnO of high catalytic activity2/ Cu-Al-BTC ternary metal organic framework material
Synthesis and its CO-SCR application there is not yet report.
Summary of the invention
The present invention is using Microwave-assisted firing-dipping combination method as synthetic method, to use specific molecule inducer to induce
MnO2It is layout strategy inside into MOFs skeleton structure, proposes a kind of novel MnO2The organic bone of/Cu-Al-BTC ternary metal
The design and preparation method of frame material, and be applied to catalysis CO-SCR denitration technology in, the material have uniformly, stablize,
The characteristics of high catalytic activity,.
The present invention uses Microwave-assisted firing method to synthesize Cu-Al persursor material, the common water of effective solution first
The problem of energy consumption existing for thermal method is high, time-consuming.Select specific acid solution as stabilizer for the first time in the synthesis process,
The performance quality of synthesized material can be effectively improved.This method may be implemented quick multi-stage synthesis, improve yield, enhancing product
The purpose of selectivity, is a kind of efficient MOFs material synthesis method.
The raw materials such as common copper nitrate and aluminum nitrate are found in early-stage study, and deprotonation rate is low during the reaction, shadow
The synthesis rate of Cu-Al persursor material has been rung, so that material low yield, and it is unfavorable for point of Cu, Al metal active site
It dissipates, and then influences the catalytic efficiency of material.Therefore, it is explored by many experiments, the present invention has filtered out specific long-chain metal
Cu, Al salt effectively improve Cu-Al precursor synthesis efficiency.The experimental results showed that this method can be enhanced between Cu, Al metal
Interaction, and improve dispersion degree of Cu, Al metal ion in material, be conducive to the catalytic performance for improving material.
In addition, the researcher of this patent is it has furthermore been found that by MnO2It is introduced into the preparation process of Cu-Al presoma,
By the way that specific surfactant is added as molecule inducer, the dissolution and dispersion of Mn presoma can be effectively facilitated, sufficiently
Induction Mn element enters in Cu-Al precursor construction, finally synthesizes novel uniform, stable, with high catalytic performance
MnO2/ Cu-Al-BTC ternary metal organic framework compounds.
Technical solution of the present invention:
A kind of MnO2The preparation method of/Cu-Al-BTC ternary metal organic framework material, steps are as follows:
(1) preparation of Cu-Al presoma
By trimesic acid H3BTC is dissolved in dehydrated alcohol, benzoic acid, the acetic acid mixing that volume ratio is 25:3:2-35:4:1
In liquid, it is configured to the trimesic acid solution that concentration is 0.16-0.18mol/L, mixes to dissolution on magnetic stirring apparatus；It
Chlorination dihydroxy-bis-tetramethyl ethylene diamine copper (II) and (octadecane -9- alkenyl acetoacetate root conjunction-O1 ', O3) are added afterwards
Two propane -2- alcohol close aluminium and ultrapure water, continue stirring to being completely dissolved；Wherein mole of mantoquita, aluminium salt and trimesic acid
Than for 6.78:1.24:4.8-1.32:1.24:7.2, the volume ratio of dehydrated alcohol and ultrapure water is 0.71:1-1.4:1；It will be above-mentioned
Mixed system is placed in microwave reactor, is reacted 0.5-1.5h at 100 DEG C -160 DEG C, is obtained blue liquid；By reactant from
The heart is collected, and is successively purified with dehydrated alcohol and ultrapure water；Finally, reactant is dried in vacuo, blue powder is obtained
Last shape solid；
(2) preparation of Mn precursor solution
By four chloride hydrate manganese (MnCl2·4H2O) solid is put in dehydrated alcohol, and stirring is configured to Mn ion to dissolving
Concentration is the manganese chloride solution of 0.14-0.34mol/L；The methyl stearate polyethenoxy ether sulphonate being added into solution
(FMES) and the mixed liquor of octyl phenol polyoxyethylene ether (OP-6) two kinds of molecule inducers, magnetic agitation 0.5- at room temperature
1.5h；Wherein the molar ratio of FMES and OP-6 is 1:0.83-1:3.32, and the volume ratio of manganese chloride solution and inducer mixed liquor is
3.33:1-6:1；
(3)MnO2The preparation of/Cu-Al-BTC
Cu-Al persursor material is added into Mn precursor solution, being configured to concentration is the molten of 0.025-0.075g/mL
Liquid, at room temperature magnetic agitation 3-5h；Mixed liquor is filtered, filtered solid is taken, places it in baking oven, setting heating temperature
100-120 DEG C of degree, heating time 8-12h；It is taken out after solid sample is cooled to room temperature, in 240-260 DEG C, N2It is used under atmosphere
Tube furnace calcining sample 2-3h, prepares navy blue MnO2/ Cu-Al-BTC powdered samples.
In step (1), vacuum drying condition is 90-110 DEG C, 10-12h.
A kind of MnO2/ Cu-Al-BTC ternary metal organic framework material is in CO selective catalytic reduction reaction denitration (CO-
SCR the application in terms of).
Beneficial effects of the present invention: the present invention proposes to utilize Microwave-assisted firing-dipping joint preparation MnO2/Cu-Al-
The samples particle of the method for BTC material, acquisition is uniform, and partial size is about 0.2-0.5 μm, and pattern is complete, and specific surface area is
647m2g-1.CO-SCR test result shows, MnO2/ Cu-Al-BTC catalyst achieves 90- in 260-375 DEG C of temperature range
96% denitration efficiency, low temperature active is preferable, and thermal stability with higher.This method reaction time is short, low energy consumption, catalysis
Effect is good, is a kind of novel, efficient, convenient and fast MOFs method for preparing catalyst.
Detailed description of the invention
Fig. 1 is different proportion MnO2The XRD diagram of/Cu-Al-BTC material；
Fig. 2 is different proportion MnO2The SEM of/Cu-Al-BTC material schemes；(a)MnO2/Cu-Al-BTC(A),(b)MnO2/
Cu-Al-BTC(B)；
Fig. 3 is different proportion MnO2The N of/Cu-Al-BTC material2Adsorption desorption figure；
Fig. 4 is different proportion MnO2The TGA of/Cu-Al-BTC material schemes；
Fig. 5 is MnO2The H of/Cu-Al-BTC catalyst2- TPR figure；
Fig. 6 is different proportion MnO2The CO-SCR active testing curve of/Cu-Al-BTC catalyst.
Specific embodiment
The following contents is the specific implementation process of the invention patent.
The preparation method of embodiment 1:Cu-Al persursor material
Take 4.8mmol, 1.0293g trimesic acid (H3BTC) reagent and 25mL dehydrated alcohol, 3mL benzoic acid, 2mL second
Acid is put into 100mL beaker, and beaker is placed on magnetic stirring apparatus and mixes to dissolution；6.78mmol is added into beaker,
3.1488g chlorination dihydroxy-bis-tetramethyl ethylene diamine copper (II), 1.24mmol, 0.6159g (octadecane -9- alkenyl acetyl
Acetate conjunction-O1 ', O3) two propane -2- alcohol close aluminium and 35mL ultrapure water, and it is placed on magnetic stirring apparatus and 0.5h is mixed to molten
Solution；The beaker for filling mixed liquor is placed in microwave reactor, reacts 0.5h at 100 DEG C, after room temperature, from
The heart collects reactant, and the condition that is collected by centrifugation is revolving speed: 9000r/min, time: 5min.
The sample being collected into is washed 3 times respectively with 30mL dehydrated alcohol, is collected by centrifugation every time.Sample 50mL is surpassed again
Pure water is washed 3 times respectively, is also all collected by centrifugation every time.The sample of collection is put into vacuum oven, it is 10 dry at 90 DEG C
Hour, obtain blue powder shape solid.
The preparation method of embodiment 2:Mn precursor solution
Take 4.2mmol, tetra- chloride hydrate manganese (MnCl of 0.8312g2·4H2O) solid is put in 30mL dehydrated alcohol, is placed in
0.5h is mixed on magnetic stirring apparatus to dissolving, is configured to the solution that Mn ion concentration is 0.14mol/L.It is added into solution
5mL molar ratio is the mixed liquor of the FMES and OP-6 of 1:0.83, and 0.5h is stirred at room temperature.
Embodiment 3:MnO2The synthetic method of/Cu-Al-BTC
0.3g Cu-Al persursor material is taken to mix in beaker with 12ml Mn precursor solution, magnetic force stirs at room temperature
Mix 3h.Mixed liquor is filtered, filtered solid is taken to heat 8h at 100 DEG C.It is taken out after solid sample is cooled to room temperature,
240℃、N2Tube furnace calcining sample 2h is used under atmosphere, obtains navy blue MnO2/ Cu-Al-BTC powdered samples.
Embodiment 4:
In the embodiment of the present invention 1 by dehydrated alcohol, benzoic acid, acetic acid dosage adjust separately for 30mL, 3.5mL,
The dosage of 1.5mL, trimesic acid increase to 5.95mmol, other raw material dosages and experimental procedure remain unchanged, and are made deep
Blue MnO2/ Cu-Al-BTC material.
Embodiment 5:
The dosage of dehydrated alcohol, benzoic acid, acetic acid is adjusted separately as 35mL, 4mL, 1mL in the embodiment of the present invention 1,
The dosage of trimesic acid increases to 7.2mmol, other raw material dosages and experimental procedure remain unchanged, and navy blue is made
MnO2/ Cu-Al-BTC material.
Embodiment 6:
By chlorination dihydroxy-bis-tetramethyl ethylene diamine copper (II) and (octadecane -9- alkene in the embodiment of the present invention 1
Base acetoacetate root conjunction-O1 ', O3) two propane -2- alcohol close aluminium dosage adjust separately as 3.88mmol, 1.24mmol, ultrapure water
Dosage be changed to 30mL, microwave reaction temperature increases to 130 DEG C, and the reaction time increases to 1h, and vacuum drying temperature increases to 100
DEG C, drying time increases to 11h, other raw material dosages and experimental procedure remain unchanged, and navy blue MnO is made2/Cu-Al-
BTC material.
Embodiment 7:
By chlorination dihydroxy-bis-tetramethyl ethylene diamine copper (II) and (octadecane -9- alkene in the embodiment of the present invention 1
Base acetoacetate root conjunction-O1 ', O3) two propane -2- alcohol close aluminium dosage adjust separately as 1.32mmol, 1.24mmol, ultrapure water
Dosage be changed to 25mL, microwave reaction temperature increases to 160 DEG C, and the reaction time increases to 1.5h, and vacuum drying temperature increases to
110 DEG C, drying time increases to 12h, other raw material dosages and experimental procedure remain unchanged, and navy blue MnO is made2/Cu-
Al-BTC material.
Embodiment 8:
Four chloride hydrate manganese dosages are increased into 7.2mmol, the use of FMES and OP-6 mixed liquor in the embodiment of the present invention 2
Amount increases to 7mL, molar ratio is changed to 1:2.08, at room temperature magnetic agitation 1h, other raw material dosages and experimental procedure are kept
It is constant, navy blue MnO is made2/ Cu-Al-BTC material.
Embodiment 9:
Four chloride hydrate manganese dosages are increased into 10.2mmol in the embodiment of the present invention 2, FMES and OP-6 mixed liquor
Dosage increases to 9mL, molar ratio is changed to 1:3.32, at room temperature magnetic agitation 1.5h, other raw material dosages and experimental procedure
It remains unchanged, navy blue MnO is made2/ Cu-Al-BTC material.
Embodiment 10:
Cu-Al presoma dosage is increased into 0.6g in the embodiment of the present invention 3, the magnetic agitation time increases at room temperature
To 4h, other raw material dosages and experimental procedure are remained unchanged, and navy blue MnO is made2/ Cu-Al-BTC material.
Embodiment 11:
Cu-Al presoma dosage is increased into 0.9g in the embodiment of the present invention 3, the magnetic agitation time increases at room temperature
To 5h, other raw material dosages and experimental procedure are remained unchanged, and navy blue MnO is made2/ Cu-Al-BTC material.
Embodiment 12:
Heating temperature is increased to 110 DEG C in the embodiment of the present invention 3, heating time 10h.It will when being calcined using tube furnace
Calcination temperature increase to 250 DEG C, calcination time increase to 2.5h, other raw material dosages and experimental procedure remain unchanged, be made
Navy blue MnO2/ Cu-Al-BTC material.
Embodiment 13:
Heating temperature is increased to 120 DEG C in the embodiment of the present invention 3, heating time 12h.It will when being calcined using tube furnace
Calcination temperature increase to 260 DEG C, calcination time increase to 3h, other raw material dosages and experimental procedure remain unchanged, and are made deep
Blue MnO2/ Cu-Al-BTC material.
Claims (3)
1. a kind of MnO2The preparation method of/Cu-Al-BTC ternary metal organic framework material, which is characterized in that steps are as follows:
(1) preparation of Cu-Al presoma
By trimesic acid H3It is the dehydrated alcohol of 25:3:2-35:4:1, benzoic acid, in acetic acid mixture that BTC, which is dissolved in volume ratio,
It is configured to the trimesic acid solution that concentration is 0.16-0.18mol/L, mixes to dissolution on magnetic stirring apparatus；Later plus
Enter chlorination dihydroxy-bis-tetramethyl ethylene diamine copper (II) and (octadecane -9- alkenyl acetoacetate root conjunction-O1 ', O3) dipropyl
Alkane -2- alcohol closes aluminium and ultrapure water, continues stirring to being completely dissolved；Wherein the molar ratio of mantoquita, aluminium salt and trimesic acid is
The volume ratio of 6.78:1.24:4.8-1.32:1.24:7.2, dehydrated alcohol and ultrapure water is 0.71:1-1.4:1；By above-mentioned mixing
System is placed in microwave reactor, is reacted 0.5-1.5h at 100 DEG C -160 DEG C, is obtained blue liquid；Reactant is centrifuged and is received
Collection, and successively purified with dehydrated alcohol and ultrapure water；Finally, reactant is dried in vacuo, blue powder shape is obtained
Solid；
(2) preparation of Mn precursor solution
Four chloride hydrate manganese solids are put in dehydrated alcohol, to dissolving, being configured to Mn ion concentration is 0.14- for stirring
The manganese chloride solution of 0.34mol/L；The methyl stearate polyethenoxy ether sulphonate FMES and octylphenol polyethylene being added into solution
The mixed liquor of ethylene oxide ether two kinds of molecule inducers of OP-6, at room temperature magnetic agitation 0.5-1.5h；Wherein FMES and OP-6
Molar ratio is 1:0.83-1:3.32, and the volume ratio of manganese chloride solution and inducer mixed liquor is 3.33:1-6:1；
(3)MnO2The preparation of/Cu-Al-BTC
Cu-Al persursor material is added into Mn precursor solution, the solution that concentration is 0.025-0.075g/mL is configured to,
Magnetic agitation 3-5h at room temperature；Mixed liquor is filtered, filtered solid is taken, places it in baking oven, sets heating temperature
100-120 DEG C, heating time 8-12h；It is taken out after solid sample is cooled to room temperature, in 240-260 DEG C, N2Pipe is used under atmosphere
Formula furnace calcining sample 2-3h, prepares navy blue MnO2/ Cu-Al-BTC powdered samples.
2. preparation method according to claim 1, which is characterized in that in step (1), vacuum drying condition is 90-110
DEG C, 10-12h.
3. a kind of MnO2/ Cu-Al-BTC ternary metal organic framework material answering in terms of CO selective catalytic reduction reaction denitration
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910475391.5A CN110302840B (en) | 2019-06-03 | 2019-06-03 | MnO (MnO)2Preparation method and application of/Cu-Al-BTC ternary metal organic framework material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910475391.5A CN110302840B (en) | 2019-06-03 | 2019-06-03 | MnO (MnO)2Preparation method and application of/Cu-Al-BTC ternary metal organic framework material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110302840A true CN110302840A (en) | 2019-10-08 |
| CN110302840B CN110302840B (en) | 2021-04-16 |
Family
ID=68075058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910475391.5A Expired - Fee Related CN110302840B (en) | 2019-06-03 | 2019-06-03 | MnO (MnO)2Preparation method and application of/Cu-Al-BTC ternary metal organic framework material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110302840B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112138665A (en) * | 2020-10-21 | 2020-12-29 | 石河子大学 | CO-SCR low-temperature high-efficiency non-noble metal oxide catalyst and preparation method thereof |
| CN112625256A (en) * | 2020-11-24 | 2021-04-09 | 大连理工大学 | Preparation method and denitration application of mesoscale-regulated multilevel core-shell structure bimetal MOF-74(Co-Cu) |
| CN115888830A (en) * | 2022-07-08 | 2023-04-04 | 安徽工业大学 | Calcination-free octahedral Cu/Mn-BTC bimetallic MOF low-temperature SCR denitration catalyst, and preparation method and application thereof |
| CN116272986A (en) * | 2023-01-19 | 2023-06-23 | 石河子大学 | Cu-based SCR denitration catalyst and preparation method and application thereof |
| CN116351473A (en) * | 2023-02-27 | 2023-06-30 | 北京工业大学 | Metal organic frame-manganese dioxide composite material and application thereof in decomposing ozone |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920213A (en) * | 2010-07-23 | 2010-12-22 | 中环（中国）工程有限公司 | Low temperature SCR denitration catalyst taking organic metal framework as carrier and preparation method thereof |
| CN103752169A (en) * | 2014-01-10 | 2014-04-30 | 大连理工大学 | Metal-organic frame material Cu-BTC for removing nitric oxide with selective catalytic reduction method |
| CN105237586A (en) * | 2015-10-15 | 2016-01-13 | 大连理工大学 | Preparation and application of novel dual-core organic skeleton material MIL-100(Fe-Mn) |
| CN106345523A (en) * | 2016-09-18 | 2017-01-25 | 华南理工大学 | Low-temperature denitrification catalyst based on carbonized MOFs (metal organic frameworks) and preparation method thereof |
| CN109205567A (en) * | 2018-08-13 | 2019-01-15 | 浙江工业大学 | A method of metal oxide multilevel structure is prepared using the derivative bimetallic oxide template of MOF |
-
2019
- 2019-06-03 CN CN201910475391.5A patent/CN110302840B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920213A (en) * | 2010-07-23 | 2010-12-22 | 中环（中国）工程有限公司 | Low temperature SCR denitration catalyst taking organic metal framework as carrier and preparation method thereof |
| CN103752169A (en) * | 2014-01-10 | 2014-04-30 | 大连理工大学 | Metal-organic frame material Cu-BTC for removing nitric oxide with selective catalytic reduction method |
| CN105237586A (en) * | 2015-10-15 | 2016-01-13 | 大连理工大学 | Preparation and application of novel dual-core organic skeleton material MIL-100(Fe-Mn) |
| CN106345523A (en) * | 2016-09-18 | 2017-01-25 | 华南理工大学 | Low-temperature denitrification catalyst based on carbonized MOFs (metal organic frameworks) and preparation method thereof |
| CN109205567A (en) * | 2018-08-13 | 2019-01-15 | 浙江工业大学 | A method of metal oxide multilevel structure is prepared using the derivative bimetallic oxide template of MOF |
Non-Patent Citations (1)
| Title |
|---|
| YI-HONG QIN ET AL.: "Mixed-node A-Cu-BTC and porous carbon based oxides derived from A-Cu-BTC as low temperature NO-CO catalyst", 《INORGANIC CHEMISTRY COMMUNICATIONS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112138665A (en) * | 2020-10-21 | 2020-12-29 | 石河子大学 | CO-SCR low-temperature high-efficiency non-noble metal oxide catalyst and preparation method thereof |
| CN112138665B (en) * | 2020-10-21 | 2022-10-28 | 石河子大学 | CO-SCR low-temperature high-efficiency non-noble metal oxide catalyst and preparation method thereof |
| CN112625256A (en) * | 2020-11-24 | 2021-04-09 | 大连理工大学 | Preparation method and denitration application of mesoscale-regulated multilevel core-shell structure bimetal MOF-74(Co-Cu) |
| CN112625256B (en) * | 2020-11-24 | 2021-10-15 | 大连理工大学 | Preparation method and denitration application of mesoscale-regulated multilevel core-shell structure bimetal MOF-74(Co-Cu) |
| CN115888830A (en) * | 2022-07-08 | 2023-04-04 | 安徽工业大学 | Calcination-free octahedral Cu/Mn-BTC bimetallic MOF low-temperature SCR denitration catalyst, and preparation method and application thereof |
| CN116272986A (en) * | 2023-01-19 | 2023-06-23 | 石河子大学 | Cu-based SCR denitration catalyst and preparation method and application thereof |
| CN116351473A (en) * | 2023-02-27 | 2023-06-30 | 北京工业大学 | Metal organic frame-manganese dioxide composite material and application thereof in decomposing ozone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110302840B (en) | 2021-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110302840A (en) | A kind of MnO2The preparation method and application of/Cu-Al-BTC ternary metal organic framework material | |
| CN108927213A (en) | A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane | |
| WO2014173229A1 (en) | Fischer-tropsch synthesis catalyst for syngas to low carbon olefins, modified molecular sieve carrier and preparation method thereof | |
| CN102000572B (en) | Method for preparing denitration catalyst by performing selective catalytic reduction on CuMgAl composite oxide | |
| CN110449189B (en) | Catalyst for synthesizing dimethyl carbonate and preparation method thereof | |
| CN101439882B (en) | Method for synthesizing mesoporous ammonium nickel molybdate by using urea as precipitating agent | |
| CN105478157B (en) | A kind of quick method for preparing the methanation catalysts of Ni ZSM 5 | |
| CN106276963B (en) | A kind of synthetic method of metal-ZSM molecular sieve | |
| CN105879892A (en) | Solid base catalyst for synthesizing dimethyl carbonate through transesterification method and preparation method and application | |
| CN109589962A (en) | A kind of high resistance to SO_2 cerium based low-temperature denitration catalyst and preparation method thereof | |
| CN113967482B (en) | Method for preparing bimetallic hexahedral nanosheet Ti-Ni-MOF catalyst through mesoscale regulation and control and application | |
| CN106693985A (en) | Preparation method of sheet spinel structure cobalt-manganese composite oxide | |
| CN103212419B (en) | Preparation method and application of catalyst for treating acrylonitrile contained waste gas | |
| CN113817174A (en) | Preparation method and application of in-situ hydrazide three-dimensional MOFs material | |
| CN113231102A (en) | Glutaric acid selective polyacid catalyst based on micro-mesoporous Zr-MOF material and preparation method and application thereof | |
| CN107199051A (en) | A kind of copper heterogeneous catalyst of pyridine coordination and preparation method thereof | |
| CN112058291A (en) | Microspherical composite visible-light-driven photocatalyst and rapid preparation method and application thereof | |
| CN102814193B (en) | Copper-composite molecular sieve catalyst used for synthesis of diethyl carbonate through gas-phase oxidative carbonylation and its preparation method | |
| CN109647499B (en) | Catalyst for growing Cu-SSZ-13 molecular sieve by taking HT-SiC as carrier and preparation method thereof | |
| CN1750877A (en) | Process for preparing vanadyl pyrophosphate catalyst | |
| CN114789064A (en) | Catalyst for preparing methanol by partial oxidation of coal bed gas and preparation method and application thereof | |
| CN116726922A (en) | Catalyst for synthesizing dimethyl carbonate by liquid-phase oxidative carbonylation of methanol, preparation method and application | |
| CN115138386A (en) | Two-dimensional hexagonal boron nitride in CO catalysis 2 Application in cycloaddition reaction with epoxide | |
| CN107855132A (en) | A kind of method and its application using the system with molecular sieve for preparing of SAPO 34 for the catalyst of Fe/SAPO 34 | |
| CN113398912A (en) | Catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210416 |