CN112742378A - Melanese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module, preparation method thereof and application of catalyst module in catalytic decomposition of hydrogen peroxide - Google Patents
Melanese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module, preparation method thereof and application of catalyst module in catalytic decomposition of hydrogen peroxide Download PDFInfo
- Publication number
- CN112742378A CN112742378A CN202110086632.4A CN202110086632A CN112742378A CN 112742378 A CN112742378 A CN 112742378A CN 202110086632 A CN202110086632 A CN 202110086632A CN 112742378 A CN112742378 A CN 112742378A
- Authority
- CN
- China
- Prior art keywords
- aluminum core
- manganese oxide
- honeycomb aluminum
- type manganese
- catalyst
- 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
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 650
- 239000003054 catalyst Substances 0.000 title claims abstract description 382
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims abstract description 311
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 302
- 238000002360 preparation method Methods 0.000 title claims abstract description 99
- 238000003421 catalytic decomposition reaction Methods 0.000 title claims abstract description 34
- 229910052700 potassium Inorganic materials 0.000 title description 7
- 239000011591 potassium Substances 0.000 title description 7
- HVCXHPPDIVVWOJ-UHFFFAOYSA-N [K].[Mn] Chemical compound [K].[Mn] HVCXHPPDIVVWOJ-UHFFFAOYSA-N 0.000 claims abstract description 174
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 113
- 239000000843 powder Substances 0.000 claims abstract description 87
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 47
- 238000001035 drying Methods 0.000 claims description 100
- 238000003756 stirring Methods 0.000 claims description 84
- 238000000034 method Methods 0.000 claims description 80
- 239000000725 suspension Substances 0.000 claims description 55
- 239000010935 stainless steel Substances 0.000 claims description 49
- 229910001220 stainless steel Inorganic materials 0.000 claims description 49
- 238000010438 heat treatment Methods 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 46
- 239000002002 slurry Substances 0.000 claims description 45
- 239000011162 core material Substances 0.000 claims description 40
- 239000011230 binding agent Substances 0.000 claims description 37
- 239000012153 distilled water Substances 0.000 claims description 37
- 238000007598 dipping method Methods 0.000 claims description 36
- 239000011148 porous material Substances 0.000 claims description 36
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 34
- 238000000498 ball milling Methods 0.000 claims description 28
- 239000010410 layer Substances 0.000 claims description 28
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 27
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 27
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 27
- 238000005303 weighing Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- 239000012778 molding material Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 20
- 239000002356 single layer Substances 0.000 claims description 19
- 238000012360 testing method Methods 0.000 claims description 19
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims description 18
- 238000005470 impregnation Methods 0.000 claims description 18
- 229940072033 potash Drugs 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 230000009471 action Effects 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 238000010411 cooking Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 235000015320 potassium carbonate Nutrition 0.000 claims description 10
- 238000007664 blowing Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005485 electric heating Methods 0.000 claims description 7
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 6
- 238000009434 installation Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical group O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 44
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004887 air purification Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000000499 gel Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000005265 energy consumption Methods 0.000 description 8
- 238000011031 large-scale manufacturing process Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000000969 carrier Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- YYGXPJNJHYORNC-UHFFFAOYSA-N potassium manganese(2+) oxygen(2-) Chemical compound [K+].[O-2].[Mn+2] YYGXPJNJHYORNC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000003622 immobilized catalyst Substances 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910003144 α-MnO2 Inorganic materials 0.000 description 1
- 229910006648 β-MnO2 Inorganic materials 0.000 description 1
- 229910006287 γ-MnO2 Inorganic materials 0.000 description 1
- 229910006364 δ-MnO2 Inorganic materials 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention provides a manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst module, a preparation method thereof and application thereof in catalytic decomposition of hydrogen peroxide. In addition, OMS-2 powder is adopted for catalyzing and decomposing hydrogen peroxide in a water phase and a gas phase at normal temperature and normal pressure for the first time, the concentration of the hydrogen peroxide in the water is reduced to below 1ppm, and a good effect is achieved on the catalytic decomposition of the hydrogen peroxide in the gas phase. Compared with the manganese oxide catalyst prepared by the prior art, OMS-2 has stronger hydrogen peroxide catalytic decomposition capacity, but has mild preparation conditions, simple and convenient preparation process and simple preparation equipment, thereby having very high practical application value. The molded catalyst module of the invention can be widely applied to the fields of hydrogen peroxide decomposition, air purification and the like.
Description
Technical Field
The invention relates to preparation of a manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module and application of the module in catalytic decomposition of hydrogen peroxide in a water phase and a gas phase, and belongs to the technical field of preparation of a formed catalyst.
Background
Hydrogen peroxide (H)2O2) Has strong oxidizing property and high water solubility, and can have oxidizing effect or reducing effect under different conditions. Generally, the method is divided into three types, namely medical use, military use and industrial use. Medical hydrogen peroxide (about 3% or less) is a good disinfectant. It is used for bleaching, strong oxidant, antichlor and fuel in industrial use (about 35%). 99 percent of military grade, mainly popularized and applied to space flight and aviation engines and manned flyers, and also applied to military satellites, carrier rockets and anti-bounce-channel missiles. In daily life and production, hydrogen peroxide is most commonly used as a disinfectant, but a small amount or trace amount of hydrogen peroxide often remains after sterilization with hydrogen peroxide, and the residual hydrogen peroxide must be removed to prevent adverse effects on human health and environmental quality.
The best way to remove the residual hydrogen peroxide is to decompose it. Manganese is a metal element with good oxidation-reduction property, and researches show that some manganese oxides have catalytic activity for decomposing hydrogen peroxide, so that the manganese oxides are widely concerned in the field of catalysis. At present, in practical application, the hydrogen peroxide decomposition catalyst is related to more crystal forms of manganese oxide, and due to the fact that the property identification of materials such as the crystal forms of the manganese oxide is not strict, the product characteristics of the manganese oxide which is actually adopted are greatly different, and the catalytic hydrogen peroxide decomposition effect is inconsistent. Further, the use of the potassium manganate-type manganese oxide (OMS-2) for the catalytic decomposition of hydrogen peroxide has not been reported.
When the manganese oxide powder catalyst is used for daily environmental treatment, the powder catalyst has large contact area and good mass transfer effect, so that the catalytic reaction efficiency is high and the speed is high, but the powder material has the defects of difficult recovery, easy loss, easy agglomeration in the reaction process, low repeated utilization rate and the like, and the practical application of the powder catalyst is greatly limited. To solve this problem, the powder material, or even the nanomaterial, may be immobilized on a support.
The traditional main carriers for immobilizing the powder catalyst comprise silica gel, molecular sieves, activated carbon, glass fibers, stainless steel, glass sheets, metal titanium sheets, ceramics and the like. Silica gel, molecular sieve and active carbon are granular carriers, necessary separation equipment and process are still needed for preparing the immobilized catalyst, glass fiber is soft material, the difficult problem of fixation exists in a narrow space, the carriers of glass and stainless steel have too smooth surfaces, the catalyst is easy to fall off, the cost of metal titanium sheets is high, the consumption of raw materials for preparing ceramics is large, high-temperature sintering is needed, and the ceramics generally have large specific gravity, so that the carriers are difficult to be used as carriers to prepare supported catalysts and are difficult to meet the requirements of practical application.
The microporous honeycomb aluminum core is prepared by bonding and laminating aluminum foils and then stretching and unfolding the aluminum foils into a regular hexagonal honeycomb shape, and the used aluminum alloy material generally contains 98% of aluminum, 1% of magnesium, a small amount of iron and silicon, and has light specific gravity and high strength. The existing honeycomb aluminum core is mainly applied to structural materials and has the functions of sound insulation, heat preservation, heat insulation, fire prevention, water prevention and shock prevention, the existing microporous honeycomb aluminum core adopted as a catalyst carrier has poor fastness for loading catalyst particles, the problem of serious powder falling exists, in addition, the difficulty of loading the catalyst particles is high due to the smooth surface of the aluminum core, the process is complex, the service life of the catalyst is seriously influenced, the service capacity of the catalyst is reduced, the cost is obviously increased, and the requirement of catalytic decomposition of hydrogen peroxide cannot be met.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provides a monopotassium manganese ore type manganese oxide microporous honeycomb aluminum core catalyst module, a preparation method thereof and application thereof in catalytic decomposition of hydrogen peroxide. The method adopts a slurry dipping, pulling and heat treatment method to load and fix the manganese-potassium ore type manganese oxide (OMS-2) powder catalyst on the microporous honeycomb aluminum core to prepare a shaped and easily-circulated catalyst module so as to avoid the defect of direct use of the powder catalyst, and in addition, the manganese-potassium ore type manganese oxide (OMS-2) powder catalyst adopted by the invention is firstly used for catalytically decomposing hydrogen peroxide. The research of the invention finds that the OMS-2 powder catalyst can effectively catalyze and decompose hydrogen peroxide in a water phase and a gas phase at normal temperature and normal pressure, can reduce the concentration of the hydrogen peroxide in the water to be less than 1ppm, has higher catalytic activity for decomposing the hydrogen peroxide in the gas phase, and is far superior to the prior art, thereby having very high practical application value. The invention utilizes the characteristics of the microporous honeycomb aluminum core that the microporous honeycomb aluminum core has the smallest micropores and the most dense parallel micropore pore canal structure, high void ratio, large specific surface area, light specific gravity, high strength, good toughness, straight appearance, green environmental protection, resource saving in the production process and the like to realize the firm loading of the powder catalyst and prepare the molded catalyst module. The catalyst module has simple preparation process and easy operation and control, and the special dipping-drawing machine is used to raise the yield of the formed catalyst module, ensure the quality and meet the practical production requirement. The formed catalyst module prepared by the technical scheme of the invention has the advantages of large specific surface area, more catalytic active sites, high utilization rate of active catalyst, short mass transfer distance of catalytic reaction, high catalytic activity, small wind resistance, large fluid flux, small pressure drop, light weight, high mechanical strength, good chemical stability, low production cost and the like, and can be widely applied to the fields of hydrogen peroxide decomposition, sterilization scenes taking hydrogen peroxide as a medium, air purification and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a manganese oxide catalyst for hydrogen peroxide decomposition, wherein the manganese oxide is a manganese potassium ore type manganese oxide, and the preparation method comprises the following steps:
a1. weighing 1872.3g of manganese acetate, dissolving in at least 6808.4mL of distilled water, and stirring at room temperature to fully dissolve the manganese acetate to form a solution A;
a2. weighing 851.0mL of glacial acetic acid, diluting in at least 6808.4mL of distilled water, and stirring at room temperature to fully and uniformly mix and dissolve different substances to form a buffer solution B;
a3. weighing 1106.4g of potassium permanganate, dissolving in at least 25531.4mL of distilled water, and stirring at room temperature to fully dissolve the potassium permanganate to form a solution C;
a4. adding the buffer solution B prepared in the step a2 into the solution A prepared in the step a1, and stirring at room temperature to fully mix the A, B two solutions; slowly adding the solution C prepared in the step a3 while stirring to enable the mixed solution to form gel, refluxing the obtained gel for not less than 24 hours under stirring, and then filtering and washing the obtained solid; carrying out centrifugal separation treatment on the mixture of the solid and water at the rotating speed of not less than 4000rpm for at least 5 minutes to realize solid-liquid separation, transferring the obtained solid into distilled water to be continuously washed, then continuously carrying out centrifugal separation treatment according to the conditions in the step, carrying out centrifugal separation-washing circulation treatment until the pH value of a washing liquid reaches 6-7, and then collecting the solid;
a5. placing the solid obtained by centrifugal separation and washing in the step a4 in an electric heating forced air drying oven, and drying at the temperature of not less than 80 ℃ for at least 10 hours to obtain solid powder; and then putting the dried solid powder into a muffle furnace, heating the furnace to a temperature of not higher than 450 ℃ at a heating rate of not higher than 2 ℃/min, preserving the temperature for at least 4 hours, calcining the solid powder, and then cooling the muffle furnace to the room temperature to obtain the powder catalyst, namely the manganese-potassium ore type manganese oxide.
In a preferred embodiment of the present invention, in the step a1, the manganese acetate is manganese acetate tetrahydrate.
As a preferred technical scheme of the invention, in the step a4, the centrifugal separation-washing cycle treatment times are at least 3.
The invention relates to a manganese oxide catalyst for hydrogen peroxide decomposition, which is prepared by adopting the preparation method of the manganese oxide catalyst for hydrogen peroxide decomposition.
A manganesium ore type manganese oxide micropore honeycomb aluminum core catalyst module takes micropore honeycomb aluminum core material as a carrier, manganesium ore type manganese oxide as catalyst active particle material, and manganesium ore type manganese oxide is loaded on the surface of a straight-through micropore pore channel of a micropore honeycomb aluminum core to form a composite catalyst for decomposing hydrogen peroxide.
As a preferred technical scheme of the invention, the manganese-potassium ore type manganese oxide powder catalyst is fixed on the surface of a straight-through microporous pore canal of a microporous honeycomb aluminum core by a slurry dip-coating and heat treatment method.
As the preferred technical scheme of the invention, the cross-sectional area of the straight-through micropore duct of the micropore honeycomb aluminum core is not more than 23.4cm2The length of a straight-through micropore duct of the micropore honeycomb aluminum core is not more than 40 mm; the thickness of the straight-through micropore channel wall of the straight-through micropore channel of the micropore honeycomb aluminum core is not more than 0.06 mm.
As a further preferable aspect of the present invention, the present invention is characterized in that: the thickness of the straight-through micropore channel wall of the micropore honeycomb aluminum core is 0.025-0.04 mm.
As the preferred technical scheme of the invention, the microporous honeycomb aluminum core has a parallel microporous pore channel structure to form a regular hexagonal honeycomb structure, and the side length of the hexagon is not more than 3 mm. As a further preferable technical scheme of the invention, the side length of the hexagon is not more than 1.0 mm.
As a preferred technical scheme of the invention, the shape of the microporous honeycomb aluminum core material is a cuboid module shape, the length of the microporous honeycomb aluminum core material is not more than 300mm, and the height of the microporous honeycomb aluminum core material is not more than 35 mm.
As a preferable technical scheme of the invention, the load of the powdered catalyst of the manganese potassium ore type manganese oxide particles of the microporous honeycomb aluminum core is not less than 1.45 to 10 by calculation according to the solidification amount of the powdered catalyst of the manganese potassium ore type manganese oxide of the unit surface area of the microporous honeycomb aluminum core-3g/cm2。
As a preferable technical scheme of the invention, in an ultrasonic shedding rate test, the shedding rate of the manganese-potassium ore type manganese oxide particle powder catalyst from the surface of the microporous honeycomb aluminum core is not higher than 0.003%.
The invention relates to a preparation method of a manganese-potassium ore type manganese oxide micropore honeycomb aluminum core catalyst module, which adopts a slurry dipping-pulling method and comprises the following steps:
b1. preparation of a potassium manganate ore type manganese oxide suspension:
adding at least 400g of a manganese-potassium ore type manganese oxide powder catalyst into 3600mL of distilled water, and adjusting the pH value with nitric acid in the adding process to form a manganese-potassium ore type manganese oxide suspension;
b2. dispersing treatment of the potassium manganate ore type manganese oxide suspension:
b, putting the manganic-potash ore type manganese oxide suspension obtained in the step b1 into a ball milling tank, and ball milling the manganic-potash ore type manganese oxide suspension at a ball milling rotating speed of not less than 50rpm for a ball milling time of not less than 16 hours to obtain uniform manganic-potash ore type manganese oxide suspension;
b3. preparing a mixed solution of the potassium manganate ore type manganese oxide:
after the ball milling is completed in the step b2, transferring the uniform manganese-potassium ore type manganese oxide suspension into a mixing stirrer, stirring at the rotating speed of not less than 600rpm, adding pseudo-boehmite sol, fully stirring for not less than 2 hours, and uniformly mixing to obtain a mixed solution of manganese-potassium ore type manganese oxide;
b4. preparation of a manganese potassium ore type manganese oxide catalyst slurry:
uniformly mixing the mixture in the step b3, stirring at the rotating speed of not less than 600rpm, adding a binder, fully stirring for not less than 12 hours, and standing for defoaming overnight to obtain a manganese-potassium ore type manganese oxide catalyst slurry;
b5. preparing a manganese-potassium ore type manganese oxide micropore honeycomb aluminum core molding material precursor:
b, adopting a microporous honeycomb aluminum core material as a carrier, and attaching the slurry of the manganese-potassium ore type manganese oxide catalyst prepared in the step b4 to the surface of a straight-through microporous pore passage of the microporous honeycomb aluminum core by using an impregnation and pulling machine and an auxiliary clamp through an impregnation-pulling method; then transferring the microporous honeycomb aluminum core attached with the catalyst slurry into a centrifugal drying machine, carrying out centrifugal drying treatment for at most 3 minutes at the rotating speed of not higher than 400rpm, then transferring the microporous honeycomb aluminum core onto a stainless steel net rack, putting the stainless steel net rack and the microporous honeycomb aluminum core into an electrothermal blowing drying box, carrying out drying treatment for at least 30 minutes at the temperature of not higher than 80 ℃, and removing moisture; then taking out the microporous honeycomb aluminum core material which is subjected to primary dipping, lifting, centrifugal drying and drying treatment and is primarily combined with the manganese-potassium ore type manganese oxide powder catalyst, and repeatedly carrying out dipping, lifting, centrifugal drying and drying treatment for at least 5 times in the same way as the primary dipping, lifting, centrifugal drying and drying treatment, thereby obtaining a manganese-potassium ore type manganese oxide microporous honeycomb aluminum core molding material precursor subjected to multiple dipping, lifting, centrifugal drying and drying treatment;
b6. preparing a molding material initial product:
after continuous multiple dipping and pulling, centrifugal drying and drying treatment are completed in the step b5, adopting a heat treatment method to raise the temperature of an electrothermal blowing drying box with a built-in loading stainless steel net rack to be not higher than 200 ℃, preserving heat at the temperature and carrying out heat treatment for not more than 30 minutes to completely remove the moisture of slurry on the surface of the microporous honeycomb aluminum core, and utilizing the temperature to fully play the roles of pseudo-boehmite gel and a binder to tightly bond the manganese potash ore type manganese oxide powder catalyst particles and the surface of the microporous honeycomb aluminum core together to obtain a manganese potash ore type manganese oxide microporous honeycomb aluminum core molding material initial product;
b7. preparation of a catalyst module product:
and c, after the heat preservation heat treatment in the step b6 is finished, naturally cooling the manganese-potassium ore type manganese oxide microporous honeycomb aluminum core to room temperature to obtain a manganese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module product.
The invention takes a microporous honeycomb aluminum core as a carrier, and fixes a manganese-potassium ore type manganese oxide (OMS-2) powder catalyst on the surface of the microporous honeycomb aluminum core through a slurry dipping, pulling and heat treatment method. The manganese-potassium ore type manganese oxide (OMS-2) adopted by the invention is a manganese-potassium ore type manganese oxide with the pore diameter of
Manganese oxide of one-dimensional tunnel structure of (1), manganese ion of Mn2+、Mn3+、Mn4+The mixed valence state exists in the OMS-2 skeleton structure and can provide great specific surface area and high humidity resistance, potassium ion is located in the one-dimensional tunnel of OMS-2 structure to neutralize excessive negative charge, and small amount of water molecule in the channel is used to maintain stable structure and is favorable to the catalytic decomposition of hydrogen peroxide. Compared with other hydrogen peroxide decomposition catalysts prepared in the prior art, the manganese-potassium ore type manganese oxide (OMS-2) has stronger hydrogen peroxide catalytic decomposition activity, and thus has higher practical application value.
The core layer of the micropore honeycomb aluminum core adopted by the invention is distributed and fixed in the whole plate surface, is not easy to deform, has stable plate, can resist bending and compression, and has high porosity and large specific surface area as the structure has the smallest micropores and the most dense parallel micropore pore channels, and also has the largest load surface area. Thus, the microporous honeycomb aluminum core can be used as a substrate for monolithic catalysts, and the prepared microporous honeycomb aluminum core catalyst module can be applied to air screens and some ventilation systems. The monolithic catalyst module taking the microporous honeycomb aluminum core as the base material has the characteristics of high porosity, parallel straight channels, large specific surface area, more catalytic active sites, short catalytic reaction mass transfer distance, high active catalyst utilization rate, high catalytic activity, large fluid flux, small wind resistance, small pressure drop, wide application range, lasting and stable effect, no secondary pollution and the like. Therefore, the invention can firmly load the manganese potassium ore type manganese oxide (OMS-2) powder catalyst on the surface of the microporous honeycomb aluminum core through the slurry dipping, pulling and heat treatment method, the process is simple and convenient, the equipment is simple, the actual operation is easy, the pollutant generation link is less, the invention is suitable for the actual industrial production, and the product manganese potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module can be used for the catalytic decomposition of residual hydrogen peroxide and the air purification in the hydrogen peroxide sterilization scene.
In a preferred embodiment of the present invention, in the step b1, the distilled water is distilled water without any binder or distilled water with a binder.
As a preferable technical scheme of the invention, in the step b1, the concentration of the nitric acid is not lower than 2 mol/L.
As a preferable embodiment of the present invention, in the step b1, the pH is adjusted to not less than 3.40.
As a preferred technical scheme of the invention, in the step b3, not less than 1333.3g of pseudo-boehmite sol is added to the uniform manganesite type manganese oxide suspension.
In a preferred embodiment of the present invention, in the step b4, the binder is at least one of hydroxyethyl cellulose sol and polyvinyl alcohol sol.
As a preferable technical scheme of the invention, in the step b4, not less than 2400mL of binder is added, the stirring time is not less than 12 hours, and the standing defoaming time is not less than 8 hours.
As a preferred technical solution of the present invention, in the step b5, the cross-sectional area of the straight-through microporous channel of the microporous honeycomb aluminum core is not more than 23.4cm2The length of a straight-through micropore duct of the micropore honeycomb aluminum core is not more than 40 mm; the thickness of the straight-through micropore channel wall of the micropore honeycomb aluminum core is not more than 0.06 mm.
As a preferred technical solution of the present invention, in the step b5, the microporous honeycomb aluminum core has a parallel microporous pore channel structure to form a regular hexagonal honeycomb shape, and the side length of the hexagon is not greater than 3 mm.
In the step b5, the shape of the microporous honeycomb aluminum core material is a cuboid module shape, the length of the microporous honeycomb aluminum core material is not more than 300mm, and the height of the microporous honeycomb aluminum core material is not more than 35 mm.
As a further preferable technical solution of the present invention, in the step b5, the shape of the microporous honeycomb aluminum core material is a honeycomb cuboid having a length of 150mm, a width of 150mm and a height of 30mm, the inner pore channels are regular hexagons having a side length of 0.8mm, and the thickness of the pore channel walls is 0.025 mm; or the microporous honeycomb aluminum core material is a honeycomb cuboid with the length of 150mm, the width of 150mm and the height of 30mm, the inner pore channel is a regular hexagon with the side length of 1.0mm, and the thickness of the pore channel wall is 0.04 mm.
In a preferred embodiment of the present invention, in the step b5, the dip-and-pull method uses a dip puller and an auxiliary jig, the dipping time per dip-and-pull is at least 1 minute, and the pulling rate per dip-and-pull is not more than 3 cm/min.
As a preferable technical solution of the present invention, in the step b5, the centrifugal spin-drying is performed at a centrifugal rotation speed of not less than 400rpm, and the centrifugal time per centrifugal spin-drying is not more than 3 minutes.
In the step b5, the dipping and pulling, centrifugal drying and drying treatment are repeated at least 6 times.
As a further preferable embodiment of the present invention, in the step b4, the method for preparing the hydroxyethyl cellulose sol as the binder comprises the steps of:
(1) weighing 5760mL of deionized water, pouring the deionized water into a stainless steel cylindrical barrel, placing the cylindrical barrel into a stainless steel cooking pot, stirring the cylindrical barrel with water in the pot at a rotating speed of not less than 300rpm, and adding at least 240g of hydroxyethyl cellulose into the stainless steel barrel while stirring to obtain hydroxyethyl cellulose suspension with the mass percentage concentration of not less than 4 wt.%;
(2) and (2) heating the stainless steel cooking pot filled with the hydroxyethyl cellulose suspension in the step (1) to a temperature not lower than 80 ℃, stirring at a rotating speed not lower than 300rpm, continuing to stir in a sealed manner for at least 4 hours, and cooling the feed liquid to room temperature after stirring is finished to obtain hydroxyethyl cellulose sol with the mass percentage concentration not lower than 4 wt.%.
As a further preferred embodiment of the present invention, in the step b4, the method for preparing the polyvinyl alcohol sol as the binder comprises the following steps:
weighing 4750mL of deionized water, pouring the deionized water into a stainless steel cylindrical barrel, placing the cylindrical barrel into a stainless steel cooking pot, stirring the water in the pot at a rotating speed of not less than 300rpm, and adding at least 250g of polyvinyl alcohol into the stainless steel barrel while stirring to obtain a polyvinyl alcohol suspension with the mass percentage concentration of not less than 5 wt.%;
heating the stainless steel cooking pot filled with the polyvinyl alcohol suspension liquid in the step I to be not less than 85 ℃, stirring at the rotating speed of not less than 300rpm, continuing to stir in a sealed manner for at least 4 hours, and cooling the feed liquid to room temperature after stirring is finished to obtain the polyvinyl alcohol sol with the mass percentage concentration of not less than 5 wt.%.
As a further preferable technical solution of the present invention, in the step b5, the side length of the hexagon of the regular hexagon honeycomb structure of the microcellular aluminum honeycomb core is not more than 1.0 mm.
In a further preferred embodiment of the present invention, in step b5, the thickness of the through-cell channel wall of the microcellular honeycomb aluminum core is 0.025-0.04 mm.
As a preferred embodiment of the present invention, in the step b3, the preparation method of the pseudo-boehmite sol comprises the following steps:
weighing 162.54mL of concentrated nitric acid with the mass percentage concentration of 65-68%, adding the concentrated nitric acid into at least 19837.46mL of distilled water, and preparing HNO with the mass percentage concentration of not higher than 1.14 wt%3A solution;
ii, 2229.35g of pseudoboehmite were weighed and added to the HNO in step i above3Obtaining a solid-liquid mixture with the pseudo-boehmite mass content of not less than 10 wt.% in the solution;
and iii, refluxing and stirring the solid-liquid mixture in the step ii for at least 1.5 hours, standing to form a colloidal solution, enabling the pH of the colloidal solution to be not lower than 1.64 and the viscosity of the colloidal solution to be not lower than 1.27mPa & s, then aging the colloidal solution, and standing and aging the sol formed after refluxing and stirring for at least 1 week to obtain the pseudoboehmite sol.
The invention relates to an application of a manganese-potassium ore type manganese oxide micropore honeycomb aluminum core catalyst module, which is characterized in that: under normal temperature and pressure, the manganese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module is applied to catalytic decomposition of hydrogen peroxide in water or air, and residual hydrogen peroxide in water or air is decomposed and removed.
As a preferred technical scheme of the invention, the initial concentration of the hydrogen peroxide in the water or air environment medium to be treated is not lower than 600ppm, and the hydrogen peroxide concentration in the environment medium is reduced to be not higher than 1ppm under the action of the manganese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module.
As a preferable technical scheme of the invention, a plurality of manganese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst modules are combined and installed according to the installation volume size of a catalyst unit to form a catalyst module assembly, and the catalyst module assembly is of a single-layer or multi-layer assembly structure.
The potassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module is tested by adopting the following ultrasonic shedding rate test method:
1. the test requirements are as follows:
the bonding firmness of the load coating and the substrate and the mechanical stability of the catalyst module are reflected by the falling rate of the catalyst coating loaded by the catalyst module after the specified ultrasonic treatment.
2. The test method comprises the following steps:
through weighing and observing the mass change of the catalyst module before and after ultrasonic treatment, the ultrasonic shedding rate of the catalyst module is calculated, and the specific calculation formula is as follows:
u＝(m0－m2)/m1*100％；
in the formula, m0Initial mass of prepared manganesite type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module, g; m is1Loading the mass increment, g, of the monopotassium manganese ore type manganese oxide (OMS-2) on the microporous honeycomb aluminum core module; m is2In order to carry out the specified ultrasonic treatment,mass of kalmanesite type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module, g.
3. The specific testing steps are as follows:
(1) weighing:
weighing the initial mass m of the prepared manganesite type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module on an analytical balance0The accuracy of the analytical balance is required to be +/-1 mg, and the time interval from taking out of the potassium manganate oxide (OMS-2) microporous honeycomb aluminum core catalyst module from the electrothermal blowing dry box to weighing when naturally cooling to room temperature after the heat treatment in the preparation process is not more than 2 minutes. Calculating the mass increment m of the module after the microporous honeycomb aluminum core module is loaded with the manganite type manganese oxide (OMS-2) through the known mass of the unsupported microporous honeycomb aluminum core module and the initial mass of the prepared manganite type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module1. Then weighing the mass m of the specified ultrasonically-treated manganese potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module by using an analytical balance2。
(2) Ultrasonic treatment:
after the manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module is subjected to heat treatment and naturally cooled to room temperature, the prepared manganese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module is immediately taken out of an electric hot blast drying oven and placed in a 5L plastic measuring cup, distilled water is poured into the plastic measuring cup to completely immerse the catalyst module, then the plastic measuring cup is placed in a water tank of an ultrasonic cleaning instrument, the ultrasonic action is started for 15 minutes, then the catalyst module subjected to ultrasonic treatment is taken out and placed in an electric hot blast drying oven, and the catalyst module is dried at 120 ℃ for at least 4 hours until the constant weight of the catalyst module is reached. Finally, the mass of the catalyst module was weighed out on an analytical balance.
Through the ultrasonic shedding rate test, the shedding rate of the surface of the matrix of the manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module is not higher than 0.003 percent.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the preparation method of the potassium manganese ore type manganese oxide (OMS-2) catalyst is simple, convenient and feasible, low in pollution, easy to control, low in equipment requirement, high in controllability, wide in raw material source and low in production cost;
2. the manganese-potassium ore type manganese oxide (OMS-2) powder catalyst prepared by the method can effectively catalyze and decompose hydrogen peroxide in water at normal temperature and normal pressure, can reduce the concentration of the hydrogen peroxide in the water to be below 1ppm, has higher catalytic activity on the decomposition of the hydrogen peroxide in a gas phase, is far superior to the prior art, has stronger catalytic decomposition capacity of the hydrogen peroxide, and has good practical application value;
3. the microporous honeycomb aluminum core molded catalyst module can efficiently catalyze and decompose hydrogen peroxide in a water phase and a gas phase, and the molded catalyst has the advantages of simple preparation method, high chemical and thermal stability, environmental friendliness, low cost and macroscopic form under the use condition, and thoroughly solves the problems of the powder catalyst: the traditional powder catalyst has the defects of difficult recovery, easy loss, easy agglomeration in the catalytic process, low repeated utilization rate and the like, thereby greatly limiting the practical application of the catalyst;
4. the invention utilizes the advantages of large specific surface area, light specific gravity, high strength, good toughness, straight appearance, resource saving in the green and environment-friendly production process and lower production cost of the microporous honeycomb aluminum core, and the catalyst module has simple preparation process and is easy to operate and control;
5. the invention utilizes a special dipping-drawing machine to improve the yield of the formed catalyst module, ensure the quality of the formed catalyst module and meet the actual production requirement;
6. the specific surface area of the supported catalyst prepared by the method is greatly increased. The surface area of the microporous honeycomb aluminum core with the same area is several times, even 10 times that of other materials;
7. the wind resistance of the supported catalyst prepared by the method is greatly reduced; because the aluminum foil of the microporous honeycomb aluminum core is not large in thickness and does not need much space, the pore space is increased, and the wind resistance is reduced;
8. the supported catalyst prepared by the method has the advantages of large fluid flux, light weight, high mechanical strength, good chemical stability and low production cost. Can be applied to the fields of hydrogen peroxide decomposition, air purification and the like.
Drawings
Fig. 1 is a schematic structural diagram of an octamicroporous honeycomb aluminum core according to a first embodiment, a third embodiment and an embodiment of the present invention.
FIG. 2 is a schematic diagram of a cryptomelane type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module according to an embodiment of the present invention.
FIG. 3 is a graph comparing the rate curves for catalytic decomposition of hydrogen peroxide in water for a manganese potassium ore type manganese oxide (OMS-2) powder catalyst and other manganese oxide powder catalysts in accordance with an embodiment of the present invention.
FIG. 4 is a comparison of XRD patterns of a manganese potassium ore type manganese oxide (OMS-2) powder catalyst of the present invention before and after ball milling.
FIG. 5 is a graph comparing catalytic decomposition curves of manganesite-type (OMS-2) microporous honeycomb aluminum core catalyst modules of different honeycomb sizes for hydrogen peroxide in water in accordance with the first and second examples of the present invention.
FIG. 6 is a graph of the decomposition efficiency and rate of hydrogen peroxide in water for 5 consecutive cycles of a honeycomb aluminum core shaped catalyst module of manganese potassium ore type manganese oxide (OMS-2) in accordance with an embodiment of the present invention.
FIG. 7 is a schematic diagram of a single layer assembly of a PMA-type manganese oxide (OMS-2) microporous honeycomb aluminum core shaped catalyst module according to a third and fourth embodiment of the present invention.
FIG. 8 is a schematic diagram of the assembly of two layers of hexagonal-kalmanesite type manganese oxide (OMS-2) microporous honeycomb aluminum core shaped catalyst modules in accordance with the fourth and fourth embodiments of the present invention.
Fig. 9 is a schematic structural diagram of a stainless steel support dedicated between two-layer assembled catalyst modules according to the fourth embodiment and the sixth embodiment of the present invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example one
In this example, the manganese potassium ore type manganese oxide (OMS-2) powder catalyst is fixed on the surface of the microporous honeycomb aluminum core by a slurry dip-coating heat treatment method, and the powder catalyst is tightly connected and fixed with the surface of the microporous honeycomb aluminum core by the binder. In the ultrasonic shedding rate test, the shedding rate of the manganese-potassium ore type manganese oxide (OMS-2) powder catalyst from the surface of the microporous honeycomb aluminum core is 0.003%. Due to the adoption of surface contact combination, the catalyst of the embodiment has firm load and is not easy to fall off, and the quality of the catalyst module formed by the manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core is ensured. The method comprises the following specific steps:
in this example, a method for preparing a manganese oxide catalyst for hydrogen peroxide decomposition, which is a potassium manganate-type manganese oxide, comprises the following steps:
a1. 1872.3g of Mn (CH) were weighed3COO)2·4H2Dissolving O in 6808.4mL of distilled water, and stirring at room temperature by electric power to fully dissolve manganese acetate to form a solution A;
a2. weighing 851.0mL of glacial acetic acid, diluting the glacial acetic acid in 6808.4mL of distilled water, and electrically stirring at room temperature to fully and uniformly mix and dissolve different substances to form a buffer solution B;
a3. 1106.4g of KMnO were weighed in4Dissolving in 25531.4mL of distilled water, and stirring at room temperature under electric action to fully dissolve potassium permanganate to form a solution C;
a4. adding the buffer solution B prepared in the step a2 into the solution A prepared in the step a1, and stirring the solution A at room temperature by an electric motor to fully mix the A, B two solutions; slowly adding the solution C prepared in the step a3 while stirring to enable the mixed solution to form gel, refluxing the obtained gel for 24 hours under stirring, and then filtering and washing the obtained solid; carrying out centrifugal separation treatment on the mixture of the solid and water at the rotating speed of 4000rpm for 5 minutes to realize solid-liquid separation, transferring the obtained solid into distilled water to be continuously washed, then continuously carrying out centrifugal separation treatment according to the conditions in the step, carrying out centrifugal separation-washing cumulative 3 times of circulating treatment until the pH value of a washing liquid reaches 6-7, and then collecting the solid;
a5. centrifuging and washing the solid obtained in step a4Drying in an electric heating forced air drying oven at 80 deg.C for 10 hr to obtain solid powder; and then putting the dried solid powder into a muffle furnace, heating the furnace to 450 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 4 hours, calcining the solid powder, and then cooling the muffle furnace to room temperature to obtain the powder catalyst manganese-potassium ore type manganese oxide (OMS-2). Referring to fig. 3 and 4, fig. 3 is a graph comparing the rate profiles of the kukolite-type manganese oxide (OMS-2) powder catalyst of this example with other manganese oxide powder catalysts for the catalytic decomposition of hydrogen peroxide in water. FIG. 4 is a comparison of XRD patterns of the POMANGANESE-TYPE MANGANESE OXIDE (OMS-2) POWDER CATALYST of this example before and after ball milling. The powdered catalyst of the manganese-potassium-ore-type manganese oxide (OMS-2) prepared in the example is applied to decompose hydrogen peroxide, the powdered catalyst of the manganese-potassium-ore-type manganese oxide (OMS-2) is applied to catalyze the decomposition of hydrogen peroxide in water or air at normal temperature and normal pressure, and the water and the residual hydrogen peroxide in the air are removed under the action of the prepared manganese oxide catalyst. Curve a in fig. 3 shows that the powdered catalyst of the manganese potassium ore type manganese oxide (OMS-2) prepared in this example can achieve 99% decomposition rate or removal rate of hydrogen peroxide having an initial concentration of 600ppm in water in 10 minutes and almost 100% decomposition rate or removal rate in 15 minutes. The potassium manganate type manganese oxide (OMS-2) catalyst can effectively catalyze and decompose hydrogen peroxide in water at normal temperature and normal pressure, can reduce the concentration of the hydrogen peroxide in the water to be below 1ppm, which is far superior to the prior art, and compared with the catalyst prepared in the prior art, curves b, c, d, e, f and g in a graph 3 are respectively powder catalysts delta-MnO2、α-MnO2、β-MnO2、γ-MnO2、γ-Mn3O4、α-Mn2O3Has stronger hydrogen peroxide decomposition capability and higher catalytic activity for the decomposition of hydrogen peroxide in a gas phase, thereby having good practical application value. The results of X-ray diffraction analysis of the OMS-2 powder catalyst before and after ball milling in the above process steps are shown in fig. 4. The powder catalyst before and after ball milling was mixed with standard PDF card (KMn) of manganese potassium ore type manganese oxide (OMS-2)8O16JCPDS 29-1020) are completely identical without any other impuritiesAnd (4) generating. The crystal structure of the OMS-2 catalyst is not changed in the ball milling process, the catalyst components are not changed in the ball milling process, and the process is stable and does not generate chemical reaction. The manganese oxide catalyst for hydrogen peroxide decomposition of this example was prepared by the method of preparing the manganese oxide catalyst for hydrogen peroxide decomposition of this example.
In this example, a method for preparing hydroxyethyl cellulose sol as a binder comprises the following steps:
(1) weighing 5760mL of deionized water, pouring the deionized water into a stainless steel cylindrical barrel, placing the cylindrical barrel into a stainless steel cooking pot with water in the pot, stirring at the rotating speed of 300rpm, and adding 240g of hydroxyethyl cellulose into the stainless steel barrel while stirring to obtain hydroxyethyl cellulose suspension with the mass percentage concentration of 4 wt.%;
(2) and (2) heating the stainless steel cooking pot filled with the hydroxyethyl cellulose suspension in the step (1) to 80 ℃, stirring at the rotating speed of 300rpm, continuing to stir in a sealed manner for 4 hours, and cooling the feed liquid to room temperature after stirring is finished to obtain hydroxyethyl cellulose sol with the mass percentage concentration of 4 wt.%.
In this embodiment, a method for preparing a pseudo-boehmite sol comprises the following steps:
weighing 162.54mL of concentrated nitric acid with the mass percentage concentration of 65-68%, adding the concentrated nitric acid into 19837.46mL of distilled water, and preparing HNO with the mass percentage concentration of 1.14 wt%3A solution;
ii, 2229.35g of pseudoboehmite were weighed and added to the HNO in step i above3Obtaining a solid-liquid mixture with the pseudo-boehmite mass content of 10 wt.% in the solution;
and iii, refluxing and stirring the solid-liquid mixture in the step ii for 1.5 hours, standing to form a colloidal solution, enabling the pH of the colloidal solution to be 1.64 and the viscosity of the colloidal solution to be 1.27mPa & s, then aging the colloidal solution, and standing and aging the sol formed after refluxing and stirring for 1 week to obtain the pseudo-boehmite sol.
In this embodiment, in the cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module, a microporous honeycomb aluminum core material is used as a carrier, a cryptomelane-type manganese oxide is used as a catalyst active particle material, and a cryptomelane-type manganese oxide is loaded on the surface of a through microporous pore passage of a microporous honeycomb aluminum core to form a composite catalyst for hydrogen peroxide decomposition. The manganese-potassium ore type manganese oxide powder catalyst is fixed on the surface of a straight-through micropore pore passage of a micropore honeycomb aluminum core through a slurry dip-lift-heat treatment method. See fig. 1 and 2.
In this embodiment, a preparation method of a cryptomelane type manganese oxide microporous honeycomb aluminum core catalyst module adopts a slurry dipping-pulling method and a slurry dipping-pulling-heat treatment method to prepare a cryptomelane type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst module, and includes the following steps:
a. preparation of a manganese potassium ore type manganese oxide (OMS-2) powder catalyst:
the preparation method thereof is as described in the preparation method of the manganese oxide catalyst for hydrogen peroxide decomposition of this example, see fig. 3 and 4;
b. preparing pseudo-boehmite sol:
the preparation method is as described in the preparation method of the pseudo-boehmite sol of the embodiment;
c. preparation of binder hydroxyethyl cellulose sol:
the preparation method is as described in the preparation method of hydroxyethyl cellulose sol as the binder in the embodiment;
d. preparation of a cryptomelane type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module:
d1. preparation of a potassium manganate ore type manganese oxide suspension:
adding 400g of a manganese-potassium ore type manganese oxide powder catalyst into 3600mL of distilled water, and adjusting the pH value with nitric acid in the adding process to form a manganese-potassium ore type manganese oxide suspension; the method specifically comprises the following steps:
firstly, distilled water is measured and poured into a stainless steel barrel, and HNO with the concentration of 2M is used3Dripping the solution into the distilled water, and adjusting the pH value to 3.40;
then, the powdered catalyst, manganese potassium ore type manganese oxide (OMS-2), was weighed and slowly added thereto with stirringIn the process of adding the powder into the distilled water with the adjusted pH value, in order to uniformly disperse the powder in the water, HNO with the concentration of 2M is synchronously and slowly dripped3A solution to stabilize the pH of the suspension at 3.40 throughout to form a potassium manganate-type oxide suspension;
d2. dispersing treatment of the potassium manganate ore type manganese oxide suspension:
putting the manganite type manganese oxide suspension obtained in the step d1 into a ball milling tank, and carrying out ball milling on the manganite type manganese oxide suspension for 16 hours at a ball milling rotating speed of 50rpm so as to obtain uniform manganite type manganese oxide suspension;
d3. preparing a mixed solution of the potassium manganate ore type manganese oxide:
after the ball milling is completed in the step d2, transferring the uniform manganese potassium ore type manganese oxide suspension into a mixing stirrer, stirring at the stirring frequency of 10.0Hz (597rpm), adding 1333.3g of pseudo-boehmite sol, fully stirring for 2 hours, and uniformly mixing to obtain a mixed solution of manganese potassium ore type manganese oxide;
d4. preparation of a manganese potassium ore type manganese oxide catalyst slurry:
after the mixture is uniformly mixed in the step d3, stirring at the stirring frequency of 10.0Hz (597rpm), adding 2400mL of hydroxyethyl cellulose sol binder, fully stirring for 12 hours, and then standing and defoaming the mixture overnight to obtain the manganese-potassium ore type manganese oxide catalyst slurry; is suitable for dipping-pulling for standby;
d5. preparing a manganese-potassium ore type manganese oxide micropore honeycomb aluminum core molding material precursor:
the method comprises the following steps of (1) taking a microporous honeycomb aluminum core material with regular size and shape as a carrier, wherein the microporous honeycomb aluminum core material is a honeycomb cuboid with the length of 150mm, the width of 150mm and the height of 30mm, an internal pore channel is a regular hexagon with the side length of 0.8mm, and the pore wall thickness of the pore channel is 0.025mm, and is shown in figure 1; adopting a microporous honeycomb aluminum core material as a carrier, and utilizing an impregnation and pulling machine and an auxiliary clamp to perform impregnation and pulling for 1 time by an impregnation and pulling method, wherein the impregnation time is 1 minute, and the pulling speed is 3 cm/min, so that the manganese-potassium ore type manganese oxide catalyst slurry prepared in the step d4 is attached to the surface of a straight-through microporous pore passage of the microporous honeycomb aluminum core; then transferring the microporous honeycomb aluminum core attached with the catalyst slurry into a centrifugal drying machine, carrying out centrifugal drying treatment for 3 minutes at the rotating speed of 400rpm, then transferring the microporous honeycomb aluminum core to a stainless steel net rack, putting the stainless steel net rack and the microporous honeycomb aluminum core into an electric heating blast drying oven, and carrying out drying treatment for 30 minutes at the temperature of 80 ℃ to remove moisture; then taking out the microporous honeycomb aluminum core material which is subjected to primary dipping, lifting, centrifugal drying and drying treatment and is primarily combined with the manganese-potassium ore type manganese oxide powder catalyst, and repeatedly carrying out dipping, lifting, centrifugal drying and drying treatment for 5 times in the same way as the primary dipping, lifting, centrifugal drying and drying treatment, thereby obtaining a manganese-potassium ore type manganese oxide microporous honeycomb aluminum core molding material precursor subjected to multiple dipping, lifting, centrifugal drying and drying treatment;
d6. preparing a molding material initial product:
after continuous multiple dipping and pulling, centrifugal drying and drying treatment are completed in the step d5, adopting a heat treatment method to raise the temperature of an electrothermal blowing drying box with a built-in loading stainless steel net rack to be not higher than 200 ℃, preserving heat at the temperature and carrying out heat treatment for not more than 30 minutes to completely remove the moisture of slurry on the surface of the microporous honeycomb aluminum core, and utilizing the temperature to fully play the roles of pseudo-boehmite gel and a binder to tightly bond the manganese potash ore type manganese oxide powder catalyst particles and the surface of the microporous honeycomb aluminum core together to obtain a manganese potash ore type manganese oxide microporous honeycomb aluminum core molding material initial product;
d7. preparation of a catalyst module product:
after the heat preservation heat treatment in the step d6 is finished, the monopotassium manganese ore type manganese oxide microporous honeycomb aluminum core is naturally cooled to the room temperature, so that a monopotassium manganese ore type manganese oxide microporous honeycomb aluminum core catalyst module product is obtained, as shown in fig. 2.
Experimental test analysis:
the potassium-manganese-ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module of the embodiment is tested by adopting the following ultrasonic shedding rate test method:
1. the test requirements are as follows:
the bonding firmness of the load coating and the substrate and the mechanical stability of the catalyst module are reflected by the falling rate of the catalyst coating loaded by the catalyst module after the specified ultrasonic treatment.
2. The test method comprises the following steps:
through weighing and observing the mass change of the catalyst module before and after ultrasonic treatment, the ultrasonic shedding rate of the catalyst module is calculated, and the specific calculation formula is as follows:
u＝(m0－m2)/m1*100％；
in the formula, m0Initial mass of prepared manganesite type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module, g; m is1Loading the mass increment, g, of the monopotassium manganese ore type manganese oxide (OMS-2) on the microporous honeycomb aluminum core module; m is2Mass g of a langasite type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module after specified ultrasonic treatment.
3. The specific testing steps are as follows:
(1) weighing:
weighing the initial mass m of the prepared manganesite type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module on an analytical balance0The accuracy of the analytical balance is required to be +/-1 mg, and the time interval from taking out of the potassium manganate oxide (OMS-2) microporous honeycomb aluminum core catalyst module from the electrothermal blowing dry box to weighing when naturally cooling to room temperature after the heat treatment in the preparation process is not more than 2 minutes. Calculating the mass increment m of the module after the microporous honeycomb aluminum core module is loaded with the manganite type manganese oxide (OMS-2) through the known mass of the unsupported microporous honeycomb aluminum core module and the initial mass of the prepared manganite type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module1. Then weighing the mass m of the specified ultrasonically-treated manganese potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module by using an analytical balance2。
(2) Ultrasonic treatment:
after the manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module is subjected to heat treatment and naturally cooled to room temperature, the prepared manganese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module is immediately taken out of an electric hot blast drying oven and placed in a 5L plastic measuring cup, distilled water is poured into the plastic measuring cup to completely immerse the catalyst module, then the plastic measuring cup is placed in a water tank of an ultrasonic cleaning instrument, the ultrasonic action is started for 15 minutes, then the catalyst module subjected to ultrasonic treatment is taken out and placed in an electric hot blast drying oven, and the catalyst module is dried at 120 ℃ for at least 4 hours until the constant weight of the catalyst module is reached. Finally, the mass of the catalyst module was weighed out on an analytical balance.
Through the ultrasonic shedding rate test, the shedding rate of the surface of the matrix of the module of the manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst in the embodiment is 0.003%.
Under normal temperature and pressure, applying the manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module to catalytic decomposition of hydrogen peroxide in water, and removing residual hydrogen peroxide in water under the action of the prepared manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module. The module of the manganese potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst prepared in this example was applied to catalytically decompose hydrogen peroxide in water, and the result is shown as a curve a in fig. 5. Curve a shows that the decomposition rate or removal rate of hydrogen peroxide with an initial concentration of 400ppm in water in 15 minutes can reach 99.6% by using the cryptomelane type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module prepared in this example. The monopotassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module prepared by the embodiment can effectively catalyze and decompose hydrogen peroxide in water. After the monopotassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module prepared in the embodiment is used as a hydrogen peroxide decomposition catalyst for continuous 5 times of recycling, as shown in FIG. 6, the catalytic decomposition rate of hydrogen peroxide with the initial concentration of 400ppm can still reach 98% within 15 minutes. The leaching percentage of the obtained Mn is only 0.23% through ICP analysis test, which proves that the cryptomelane type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module prepared by the embodiment has good stability and reusability. The preparation process of the monopotassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module is simple, low in energy consumption and cost and easy for large-scale production.
Example two
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of a monopotassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core forming module is to prepare the monopotassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core forming catalyst modules with different pore sizes by a slurry dip-heat treatment method, and specifically includes the following steps:
the preparation process of OMS-2 powder catalyst is the same as that of example one;
b. the preparation process of the pseudo-boehmite sol is the same as that of the first embodiment;
c. the preparation process of the binder hydroxyethyl cellulose sol is the same as that of the first embodiment;
d. preparation of potassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module
d1. The step is the same as the first embodiment;
d2. the step is the same as the first embodiment;
d3. the step is the same as the first embodiment;
d4. the step is the same as the first embodiment;
d5. preparing a manganese-potassium ore type manganese oxide micropore honeycomb aluminum core molding material precursor:
the method comprises the following steps of (1) taking a microporous honeycomb aluminum core material with a regular size and shape as a carrier, wherein the microporous honeycomb aluminum core material is a honeycomb cuboid with the length of 150mm, the width of 150mm and the height of 30mm, an internal pore channel is a regular hexagon with the side length of 1.0mm, and the pore wall thickness of the pore channel is 0.04 mm; adopting a microporous honeycomb aluminum core material as a carrier, and utilizing an impregnation and pulling machine and an auxiliary clamp to perform impregnation and pulling for 1 time by an impregnation and pulling method, wherein the impregnation time is 1 minute, and the pulling speed is 3 cm/min, so that the manganese-potassium ore type manganese oxide catalyst slurry prepared in the step d4 is attached to the surface of a straight-through microporous pore passage of the microporous honeycomb aluminum core; then transferring the microporous honeycomb aluminum core attached with the catalyst slurry into a centrifugal drying machine, carrying out centrifugal drying treatment for 3 minutes at the rotating speed of 400rpm, then transferring the microporous honeycomb aluminum core to a stainless steel net rack, putting the stainless steel net rack and the microporous honeycomb aluminum core into an electric heating blast drying oven, and carrying out drying treatment for 30 minutes at the temperature of 80 ℃ to remove moisture; then taking out the microporous honeycomb aluminum core material which is subjected to primary dipping, lifting, centrifugal drying and drying treatment and is primarily combined with the manganese-potassium ore type manganese oxide powder catalyst, and repeatedly carrying out dipping, lifting, centrifugal drying and drying treatment for 5 times in the same way as the primary dipping, lifting, centrifugal drying and drying treatment, thereby obtaining a manganese-potassium ore type manganese oxide microporous honeycomb aluminum core molding material precursor subjected to multiple dipping, lifting, centrifugal drying and drying treatment;
d6. the step is the same as the first embodiment;
d7. the procedure is the same as in the first embodiment.
Experimental test analysis:
through test analysis, the powder OMS-2 loading capacity of the microporous honeycomb aluminum core is 1.54-10 calculated by the OMS-2 solidification amount of unit surface area of the microporous honeycomb aluminum core-3g/cm2(ii) a The OMS-2 powder fully exerts the functions of the pseudo-boehmite gel and the binder by utilizing heat treatment, and the OMS-2 powder and the surface of the microporous honeycomb aluminum core material are tightly bonded together, so that a surface interface of a catalyst active site with a certain surface area is formed on the surface of the microporous honeycomb aluminum core. In the ultrasonic peeling rate test, the peeling rate of the OMS-2 powder from the surface of the microporous honeycomb aluminum core matrix is 0.003%.
Under normal temperature and pressure, applying the manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module to catalytically decompose hydrogen peroxide in water, and removing residual hydrogen peroxide in water under the action of the prepared manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module. The module of the langasite-type manganese oxide (OMS-2) microporous honeycomb aluminum core-formed catalyst prepared in this example was applied to catalytically decompose hydrogen peroxide in water, and the result is shown as a curve b in fig. 5. Curve b shows that the decomposition rate or removal rate of hydrogen peroxide with an initial concentration of 400ppm in water within 15 minutes can reach 97.1% by using the cryptomelane type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module prepared in this example. The monopotassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module prepared by the embodiment can effectively catalyze and decompose hydrogen peroxide in water. Meanwhile, under the normal operation condition, the catalyst has good stability and reusability, and the catalyst has the advantages of simple preparation process, low energy consumption, low cost and easy large-scale production.
EXAMPLE III
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of a kummerite type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst module includes steps of preparing kummerite type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst modules by a slurry dip-lift-heat treatment method, and forming a single-layer molded catalyst module unit in an arrangement manner of 3 × 3, that is, including 9 kummerite type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst modules:
the preparation process of OMS-2 powder catalyst is the same as that of example one;
b. the preparation process of the pseudo-boehmite sol is the same as that of the first embodiment;
c. the preparation process of the binder hydroxyethyl cellulose sol is the same as that of the first embodiment;
d. preparation of potassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module
d1. The step is the same as the first embodiment;
d2. the step is the same as the first embodiment;
d3. the step is the same as the first embodiment;
d4. the step is the same as the first embodiment;
d5. the step is the same as the first embodiment;
d6. the step is the same as the first embodiment;
d7. the procedure is the same as in the first embodiment.
In this embodiment, an application of the cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module is to apply the cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module to catalytically decompose hydrogen peroxide in water or air at normal temperature and pressure, and decompose and remove hydrogen peroxide remaining in water or air. And (3) assembling and installing a plurality of manganese-potassium ore type manganese oxide micropore honeycomb aluminum core catalyst modules according to the installation volume size of the catalyst units to form a catalyst module assembly, wherein the catalyst module assembly is of a single-layer assembly structure. In this example, the monopotassium manganese oxide (OMS-2) microporous honeycomb aluminum core formed catalyst modules were prepared according to the above steps d 1-d 7, and a single-layer formed catalyst module unit was formed in a3 × 3 arrangement, that is, the catalyst module unit included 9 monopotassium manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst modules, as shown in fig. 7.
Experimental test analysis:
under normal temperature and pressure, the single-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module unit is applied to catalytic decomposition of hydrogen peroxide in a gas phase, and residual hydrogen peroxide in the gas phase is removed under the action of the prepared single-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module unit. The single-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst module unit prepared in the embodiment is applied to catalytic decomposition of hydrogen peroxide in gas phase. The reactor is designed and installed in a pipeline system, the basic size of the reactor is designed to be 500mm multiplied by 300mm in length multiplied by width multiplied by height, and a silica gel flat pad is used for sealing treatment of a catalyst module unit and the reactor, so that the tightness of a corresponding space is ensured. Single-layer manganese-potassium-ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module unit (effective volume is 6.075 multiplied by 10) prepared by the embodiment-3m3) When subjected to transient (non-steady state) catalytic reaction performance tests, it was found that by controlling the initial hydrogen peroxide input concentration to 800ppmv and using different air flow rates (wind speeds), the reactor hydrogen peroxide output concentration was between 0.2ppmv and 3.0 ppmv. The results show that at this hydrogen peroxide input concentration, the gas space velocity is 13168.72h-1In this case, the decomposition rate (removal rate) of hydrogen peroxide in 240s reached 99.99%; when the gas space velocity is 16460.91h-1In this case, the decomposition rate (removal rate) of hydrogen peroxide in 240s reached 99.97%; when the gas space velocity is 23045.27h-1In this case, the decomposition rate (removal rate) of hydrogen peroxide in 240s was 99.90%; when the gas space velocity is 25514.40 h-1The decomposition rate of hydrogen peroxide in 240s (de)Removal rate) was 99.78%; when the gas space velocity is 29629.63h-1In this case, the decomposition rate (removal rate) of hydrogen peroxide in 240s was 99.68%; when the gas space velocity is 32921.81h-1In this case, the decomposition rate (removal rate) of hydrogen peroxide in 240s was 99.65%. The single-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core forming catalyst module unit prepared by the embodiment can effectively catalyze and decompose hydrogen peroxide in gas phase. Meanwhile, under the normal operation condition, the catalyst module unit has good stability and reusability, and the catalyst module is simple in preparation process, low in energy consumption, low in cost and easy for large-scale production.
Example four
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of a kummerite type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst module includes preparing kummerite type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst modules by a slurry dip-coating-heat treatment method, and forming a double-layer molded catalyst module unit in an arrangement of 3 × 3, that is, each layer includes 9 kummerite type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst modules, and the specific steps are as follows:
the preparation process of OMS-2 powder catalyst is the same as that of example one;
b. the preparation process of the pseudo-boehmite sol is the same as that of the first embodiment;
c. the preparation process of the binder hydroxyethyl cellulose sol is the same as that of the first embodiment;
d. preparation of potassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module
d1. The step is the same as the first embodiment;
d2. the step is the same as the first embodiment;
d3. the step is the same as the first embodiment;
d4. the step is the same as the first embodiment;
d5. the step is the same as the first embodiment;
d6. the step is the same as the first embodiment;
d7. the procedure is the same as in the first embodiment.
In this embodiment, an application of the cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module is to apply the cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module to catalytically decompose hydrogen peroxide in water or air at normal temperature and pressure, and decompose and remove hydrogen peroxide remaining in water or air. And (3) assembling and installing a plurality of manganese-potassium ore type manganese oxide micropore honeycomb aluminum core catalyst modules according to the installation volume size of the catalyst units to form a catalyst module assembly, wherein the catalyst module assembly is of a multilayer assembly structure. Preparing the monopotassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst module according to the steps d 1-d 7, forming a double-layer molded catalyst module according to the arrangement mode of 3 x 3, wherein each layer comprises 9 monopotassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst modules and has 2 layers in total, and as shown in figure 8, a special stainless steel frame is used between the layers to separate and support the molded catalyst module unit, as shown in figure 9.
Experimental test analysis:
under normal temperature and pressure, the double-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module unit is applied to catalytic decomposition of hydrogen peroxide in a gas phase, and residual hydrogen peroxide in the gas phase is removed under the action of the prepared double-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module unit. The double-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst module unit prepared in the embodiment is applied to catalytic decomposition of hydrogen peroxide in gas phase. The reactor is designed and installed in a pipeline system, the basic size of the reactor is designed to be 500mm multiplied by 300mm in length multiplied by width multiplied by height, and a silica gel flat pad is used for sealing treatment of a catalyst module unit and the reactor, so that the tightness of a corresponding space is ensured. The double-layer manganese-potassium-ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module unit (effective volume is 0.01215 m) prepared by the embodiment3) When the hydrogen peroxide is subjected to transient (non-steady state) catalytic reaction performance test, the initial input concentration of the hydrogen peroxide is controlled to be 800ppmv, and different air volumes (air speeds) are adopted) The reactor hydrogen peroxide output concentration is between 0.2ppmv and 0.5 ppmv. The results show that at this hydrogen peroxide input concentration, the gas space velocity is 13168.72h-1In this case, the decomposition rate (removal rate) of hydrogen peroxide in 240s reached 99.98%; when the gas space velocity is 16460.91h-1In this case, the decomposition rate (removal rate) of hydrogen peroxide in 240s reached 99.98%; when the gas space velocity is 23045.27h-1In this case, the decomposition rate (removal rate) of hydrogen peroxide in 240s was 99.97%; when the gas space velocity is 25514.40 h-1In this case, the decomposition rate (removal rate) of hydrogen peroxide in 240s was 99.95%; when the gas space velocity is 29629.63h-1In this case, the decomposition rate (removal rate) of hydrogen peroxide in 240s reached 99.93%; when the gas space velocity is 32921.81h-1In this case, the decomposition rate (removal rate) of hydrogen peroxide in 240s was 99.92%. The double-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core forming catalyst module unit prepared by the embodiment can effectively catalyze and decompose hydrogen peroxide in gas phase. Meanwhile, under the normal operation condition, the catalyst module unit in the reactor has good stability and reusability, and the catalyst module has the advantages of simple preparation process, low energy consumption, low cost and easy large-scale production.
EXAMPLE five
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of a kummerite type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst is to prepare kummerite type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst modules by a slurry dip-coating-heat treatment method, and form a single-layer molded catalyst unit in an arrangement manner of 3 × 3, that is, the method includes 9 kummerite type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst modules, and specifically includes the following steps:
the preparation process of OMS-2 powder catalyst is the same as that of example one;
b. the preparation process of the pseudo-boehmite sol is the same as that of the first embodiment;
c. the preparation process of the binder hydroxyethyl cellulose sol is the same as that of the first embodiment;
d. preparation of potassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module
d1. The step is the same as the first embodiment;
d2. the step is the same as the first embodiment;
d3. the step is the same as the first embodiment;
d4. the step is the same as the first embodiment;
d5. the step is the same as the first embodiment;
d6. the step is the same as the first embodiment;
d7. the procedure is the same as in the first embodiment.
In this embodiment, an application of the cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module is to apply the cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module to catalytically decompose hydrogen peroxide in water or air at normal temperature and pressure, and decompose and remove hydrogen peroxide remaining in water or air. And (3) assembling and installing a plurality of manganese-potassium ore type manganese oxide micropore honeycomb aluminum core catalyst modules according to the installation volume size of the catalyst units to form a catalyst module assembly, wherein the catalyst module assembly is of a single-layer assembly structure. In this example, the kummermate-type manganese oxide (OMS-2) microporous honeycomb aluminum core shaped catalyst modules prepared according to the above steps d 1-d 7 were assembled in a3 × 3 arrangement to form a single layer shaped catalyst unit, i.e., containing 9 kummermate-type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst modules, as shown in fig. 7.
Experimental test analysis:
under normal temperature and pressure, the single-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module unit is applied to catalytic decomposition of hydrogen peroxide in a gas phase, and residual hydrogen peroxide in the gas phase is removed under the action of the prepared single-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module unit. The single-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst module unit prepared in the embodiment is applied to catalytic decomposition of hydrogen peroxide in gas phase. The design is arranged in the hydrogen peroxide catalytic decomposition reactor, the reactor is designed and arranged in a pipeline system, the basic size of the reactor is designed to be the length multiplied by the width multiplied by the height multiplied by 500mm300mm, and a silica gel flat pad is used for sealing the catalyst module unit and the reactor, so that the tightness of the corresponding space is ensured. Single-layer manganese-potassium-ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module unit (effective volume is 6.075 multiplied by 10) prepared by the embodiment-3m3) When the catalyst is subjected to a steady-state catalytic reaction performance test, the gas space velocity is 13168.72h-1During the process, the hydrogen peroxide input concentration of the reactor is stably controlled to be 250-270 ppmv, and at the moment, the decomposition rate (removal rate) of the hydrogen peroxide in 240s reaches 99.65%; when the gas space velocity is 23045.27h-1Meanwhile, the input concentration of the hydrogen peroxide is stably controlled to be 168ppmv-185ppmv, and at the moment, the decomposition rate (removal rate) of the hydrogen peroxide in 240s reaches 97.32%; when the gas space velocity is 32921.81h-1Meanwhile, the input concentration of the hydrogen peroxide is stably controlled to be 158ppmv-170ppmv, and the decomposition rate (removal rate) of the hydrogen peroxide in 240s reaches 93.59%. The single-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core forming catalyst module unit prepared by the embodiment can effectively catalyze and decompose hydrogen peroxide in gas phase. Meanwhile, under the normal operation condition, the reactor catalyst module unit has good stability and reusability, and the catalyst module has the advantages of simple preparation process, low energy consumption, low cost and easy large-scale production.
EXAMPLE six
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of a kummerite type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst module, which is to prepare the kummerite type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst module by a slurry dip-lift-heat treatment method, and form a double-layer molded catalyst module unit in a3 × 3 arrangement manner, that is, each layer contains 9 kummerite type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst modules, and has 2 layers in total, specifically includes the following steps:
the preparation process of OMS-2 powder catalyst is the same as that of example one;
b. the preparation process of the pseudo-boehmite sol is the same as that of the first embodiment;
c. the preparation process of the binder hydroxyethyl cellulose sol is the same as that of the first embodiment;
d. preparation of potassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module
d1. The step is the same as the first embodiment;
d2. the step is the same as the first embodiment;
d3. the step is the same as the first embodiment;
d4. the step is the same as the first embodiment;
d5. the step is the same as the first embodiment;
d6. the step is the same as the first embodiment;
d7. the procedure is the same as in the first embodiment.
In this embodiment, an application of the cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module is to apply the cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module to catalytically decompose hydrogen peroxide in water or air at normal temperature and pressure, and decompose and remove hydrogen peroxide remaining in water or air. And (3) assembling and installing a plurality of manganese-potassium ore type manganese oxide micropore honeycomb aluminum core catalyst modules according to the installation volume size of the catalyst units to form a catalyst module assembly, wherein the catalyst module assembly is of a multilayer assembly structure. Preparing the manganesium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst module according to the steps d 1-d 7, forming a double-layer molded catalyst module unit according to a3 x 3 arrangement mode, wherein each layer comprises 9 manganesium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst modules and has 2 layers in total, and as shown in figure 8, a special stainless steel frame is used between the layers to separate and support the molded catalyst module unit, as shown in figure 9.
Experimental test analysis:
under normal temperature and pressure, the double-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module unit is applied to catalytic decomposition of hydrogen peroxide in a gas phase, and residual hydrogen peroxide in the gas phase is removed under the action of the prepared double-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module unit. The double-layer manganese-potassium ore type manganese oxide (OMS-2) microporous bee prepared in the exampleThe aluminum honeycomb core molded catalyst module unit is applied to catalytic decomposition of hydrogen peroxide in gas phase. The reactor is designed and installed in a pipeline system, the basic size of the reactor is designed to be 500mm multiplied by 300mm in length multiplied by width multiplied by height, and a silica gel flat pad is used for sealing treatment of a catalyst module unit and the reactor, so that the tightness of a corresponding space is ensured. The double-layer manganese-potassium-ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module unit (effective volume is 0.01215 m) prepared by the embodiment3) And carrying out stable test on catalytic decomposition performance of the double-layer formed catalyst module unit. The results show that when the gas space velocity is 13168.72h-1During the process, the hydrogen peroxide input concentration of the reactor is stably controlled to be 250-270 ppmv, and at the moment, the decomposition rate (removal rate) of the hydrogen peroxide in 240s reaches 99.81 percent; when the gas space velocity is 23045.27h-1Meanwhile, the input concentration of the hydrogen peroxide is stably controlled to be 168ppmv-185ppmv, and at the moment, the decomposition rate (removal rate) of the hydrogen peroxide in 240s reaches 99.66%; when the gas space velocity is 32921.81h-1Meanwhile, the input concentration of the hydrogen peroxide is stably controlled to be 158ppmv-170ppmv, and the decomposition rate (removal rate) of the hydrogen peroxide in 240s reaches 99.34%. The double-layer manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core forming catalyst module unit prepared by the embodiment can effectively catalyze and decompose hydrogen peroxide in gas phase. Meanwhile, under the normal operation condition, the reactor catalyst module unit has good stability and reusability, and the catalyst module has the advantages of simple preparation process, low energy consumption, low cost and easy large-scale production.
EXAMPLE seven
In this embodiment, a preparation method of a manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst module, which is prepared by a slurry dip-coating and heat treatment method, specifically includes the following steps:
the preparation process of OMS-2 powder catalyst is the same as that of example one;
b. the preparation process of the pseudo-boehmite sol is the same as that of the first embodiment;
c. the preparation process of the binder hydroxyethyl cellulose sol is the same as that of the first embodiment;
d. preparation of potassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module
d1. Preparation of a potassium manganate ore type manganese oxide suspension:
adding 400g of a manganese-potassium ore type manganese oxide powder catalyst into 3600mL of distilled water, and adjusting the pH value with nitric acid in the adding process to form a manganese-potassium ore type manganese oxide suspension; the method specifically comprises the following steps:
firstly, distilled water is measured and poured into a stainless steel barrel, and HNO with the concentration of 2M is used3Dripping the solution into distilled water mixed with a binder, and adjusting the pH value to 3.40;
then, the powdered catalyst, manganese potassium ore type manganese oxide (OMS-2), was weighed and slowly added with stirring to the above pH-adjusted distilled water mixed with a binder, and in the course of adding the powder, HNO with a concentration of 2M was slowly added dropwise in synchronization to disperse the powder uniformly in the water3A solution to stabilize the pH of the suspension at 3.40 throughout to form a potassium manganate-type oxide suspension;
d2. dispersing treatment of the potassium manganate ore type manganese oxide suspension:
putting the manganite type manganese oxide suspension obtained in the step d1 into a ball milling tank, and carrying out ball milling on the manganite type manganese oxide suspension for 16 hours at a ball milling rotating speed of 50rpm so as to obtain uniform manganite type manganese oxide suspension;
d3. preparing a mixed solution of the potassium manganate ore type manganese oxide:
after the ball milling is completed in the step d2, transferring the uniform manganese potassium ore type manganese oxide suspension into a mixing stirrer, stirring at the stirring frequency of 10.0Hz (597rpm), adding 1333.3g of pseudo-boehmite sol, fully stirring for 2 hours, and uniformly mixing to obtain a mixed solution of manganese potassium ore type manganese oxide;
d4. preparation of a manganese potassium ore type manganese oxide catalyst slurry:
after the mixture is uniformly mixed in the step d3, stirring at the stirring frequency of 10.0Hz (597rpm), adding 2400mL of hydroxyethyl cellulose sol binder, fully stirring for 12 hours, and then standing and defoaming the mixture overnight to obtain the manganese-potassium ore type manganese oxide catalyst slurry; is suitable for dipping-pulling for standby;
d5. preparing a manganese-potassium ore type manganese oxide micropore honeycomb aluminum core molding material precursor:
the method comprises the following steps of (1) taking a microporous honeycomb aluminum core material with a regular size and shape as a carrier, wherein the microporous honeycomb aluminum core material is a honeycomb cuboid with the length of 150mm, the width of 150mm and the height of 30mm, an internal pore channel is a regular hexagon with the side length of 0.8mm, and the pore wall thickness of the pore channel is 0.025 mm; adopting a microporous honeycomb aluminum core material as a carrier, and utilizing an impregnation and pulling machine and an auxiliary clamp to perform impregnation and pulling for 1 time by an impregnation and pulling method, wherein the impregnation time is 1 minute, and the pulling speed is 3 cm/min, so that the manganese-potassium ore type manganese oxide catalyst slurry prepared in the step d4 is attached to the surface of a straight-through microporous pore passage of the microporous honeycomb aluminum core; then transferring the microporous honeycomb aluminum core attached with the catalyst slurry into a centrifugal drying machine, carrying out centrifugal drying treatment for 3 minutes at the rotating speed of 400rpm, then transferring the microporous honeycomb aluminum core to a stainless steel net rack, putting the stainless steel net rack and the microporous honeycomb aluminum core into an electric heating blast drying oven, and carrying out drying treatment for 30 minutes at the temperature of 80 ℃ to remove moisture; then taking out the microporous honeycomb aluminum core material which is subjected to primary dipping, lifting, centrifugal drying and drying treatment and is primarily combined with the manganese-potassium ore type manganese oxide powder catalyst, and repeatedly carrying out dipping, lifting, centrifugal drying and drying treatment for 5 times in the same way as the primary dipping, lifting, centrifugal drying and drying treatment, thereby obtaining a manganese-potassium ore type manganese oxide microporous honeycomb aluminum core molding material precursor subjected to multiple dipping, lifting, centrifugal drying and drying treatment;
d6. preparing a molding material initial product:
after continuous multiple dipping and pulling, centrifugal drying and drying treatment are completed in the step d5, adopting a heat treatment method to raise the temperature of an electrothermal blowing drying box with a built-in loading stainless steel net rack to be not higher than 200 ℃, preserving heat at the temperature and carrying out heat treatment for not more than 30 minutes to completely remove the moisture of slurry on the surface of the microporous honeycomb aluminum core, and utilizing the temperature to fully play the roles of pseudo-boehmite gel and a binder to tightly bond the manganese potash ore type manganese oxide powder catalyst particles and the surface of the microporous honeycomb aluminum core together to obtain a manganese potash ore type manganese oxide microporous honeycomb aluminum core molding material initial product;
d7. preparation of a catalyst module product:
and d6, after the heat preservation heat treatment is finished, naturally cooling the manganese-potassium ore type manganese oxide microporous honeycomb aluminum core to room temperature, thereby obtaining a manganese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module product.
Under normal temperature and pressure, applying the manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module to catalytic decomposition of hydrogen peroxide in water, and removing residual hydrogen peroxide in water under the action of the prepared manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module. The monopotassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module prepared by the embodiment has good stability and reusability. The preparation process of the monopotassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module is simple, low in energy consumption and cost and easy for large-scale production.
Example eight
In this example, a method for preparing a polyvinyl alcohol sol as a binder includes the following steps:
weighing 4750mL of deionized water, pouring the deionized water into a stainless steel cylindrical barrel, placing the cylindrical barrel into a stainless steel cooking pot, stirring the cylindrical barrel with water in the pot at the rotating speed of 300rpm, and adding 250g of polyvinyl alcohol into the stainless steel barrel while stirring to obtain a polyvinyl alcohol suspension with the mass percentage concentration of 5 wt.%;
heating the stainless steel cooking pot filled with the polyvinyl alcohol suspension liquid in the step I to 85 ℃, stirring at the rotating speed of 300rpm, continuing to stir in a sealed manner for 4 hours, and cooling the feed liquid to room temperature after stirring is finished to obtain the polyvinyl alcohol sol with the mass percentage concentration of 5 wt.%.
In this embodiment, a preparation method of a manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core molded catalyst module, which is prepared by a slurry dip-coating and heat treatment method, specifically includes the following steps:
the preparation process of OMS-2 powder catalyst is the same as that of example one;
b. the preparation process of the pseudo-boehmite sol is the same as that of the first embodiment;
c. preparation of the adhesive polyvinyl alcohol sol:
the preparation method is as described in the preparation method of the polyvinyl alcohol sol as the binder in the embodiment;
d. preparation of potassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module
d1. Preparation of a potassium manganate ore type manganese oxide suspension:
adding 400g of a manganese-potassium ore type manganese oxide powder catalyst into 3600mL of distilled water, and adjusting the pH value with nitric acid in the adding process to form a manganese-potassium ore type manganese oxide suspension; the method specifically comprises the following steps:
firstly, distilled water is measured and poured into a stainless steel barrel, and HNO with the concentration of 2M is used3Dripping the solution into distilled water, and adjusting the pH value to 3.40;
then, a powder catalyst of manganese potassium ore type manganese oxide (OMS-2) is weighed and slowly added into the distilled water with the pH adjusted under the condition of stirring, and in the process of adding the powder, in order to uniformly disperse the powder in the water, HNO with the concentration of 2M is synchronously and slowly added dropwise3A solution to stabilize the pH of the suspension at 3.40 throughout to form a potassium manganate-type oxide suspension;
d2. dispersing treatment of the potassium manganate ore type manganese oxide suspension:
putting the manganite type manganese oxide suspension obtained in the step d1 into a ball milling tank, and carrying out ball milling on the manganite type manganese oxide suspension for 16 hours at a ball milling rotating speed of 50rpm so as to obtain uniform manganite type manganese oxide suspension;
d3. preparing a mixed solution of the potassium manganate ore type manganese oxide:
after the ball milling is completed in the step d2, transferring the uniform manganese potassium ore type manganese oxide suspension into a mixing stirrer, stirring at the stirring frequency of 10.0Hz (597rpm), adding 1333.3g of pseudo-boehmite sol, fully stirring for 2 hours, and uniformly mixing to obtain a mixed solution of manganese potassium ore type manganese oxide;
d4. preparation of a manganese potassium ore type manganese oxide catalyst slurry:
after the mixture is uniformly mixed in the step d3, stirring at the stirring frequency of 10.0Hz (597rpm), adding 2400mL of polyvinyl alcohol sol binder, fully stirring for 12 hours, and then standing and defoaming the mixture overnight to obtain the manganese-potassium ore type manganese oxide catalyst slurry; is suitable for dipping-pulling for standby;
d5. preparing a manganese-potassium ore type manganese oxide micropore honeycomb aluminum core molding material precursor:
the method comprises the following steps of (1) taking a microporous honeycomb aluminum core material with a regular size and shape as a carrier, wherein the microporous honeycomb aluminum core material is a honeycomb cuboid with the length of 150mm, the width of 150mm and the height of 30mm, an internal pore channel is a regular hexagon with the side length of 0.8mm, and the pore wall thickness of the pore channel is 0.025 mm; adopting a microporous honeycomb aluminum core material as a carrier, and utilizing an impregnation and pulling machine and an auxiliary clamp to perform impregnation and pulling for 1 time by an impregnation and pulling method, wherein the impregnation time is 1 minute, and the pulling speed is 3 cm/min, so that the manganese-potassium ore type manganese oxide catalyst slurry prepared in the step d4 is attached to the surface of a straight-through microporous pore passage of the microporous honeycomb aluminum core; then transferring the microporous honeycomb aluminum core attached with the catalyst slurry into a centrifugal drying machine, carrying out centrifugal drying treatment for 3 minutes at the rotating speed of 400rpm, then transferring the microporous honeycomb aluminum core to a stainless steel net rack, putting the stainless steel net rack and the microporous honeycomb aluminum core into an electric heating blast drying oven, and carrying out drying treatment for 30 minutes at the temperature of 80 ℃ to remove moisture; then taking out the microporous honeycomb aluminum core material which is subjected to primary dipping, lifting, centrifugal drying and drying treatment and is primarily combined with the manganese-potassium ore type manganese oxide powder catalyst, and repeatedly carrying out dipping, lifting, centrifugal drying and drying treatment for 5 times in the same way as the primary dipping, lifting, centrifugal drying and drying treatment, thereby obtaining a manganese-potassium ore type manganese oxide microporous honeycomb aluminum core molding material precursor subjected to multiple dipping, lifting, centrifugal drying and drying treatment;
d6. preparing a molding material initial product:
after continuous multiple dipping and pulling, centrifugal drying and drying treatment are completed in the step d5, adopting a heat treatment method to raise the temperature of an electrothermal blowing drying box with a built-in loading stainless steel net rack to be not higher than 200 ℃, preserving heat at the temperature and carrying out heat treatment for not more than 30 minutes to completely remove the moisture of slurry on the surface of the microporous honeycomb aluminum core, and utilizing the temperature to fully play the roles of pseudo-boehmite gel and a binder to tightly bond the manganese potash ore type manganese oxide powder catalyst particles and the surface of the microporous honeycomb aluminum core together to obtain a manganese potash ore type manganese oxide microporous honeycomb aluminum core molding material initial product;
d7. preparation of a catalyst module product:
and d6, after the heat preservation heat treatment is finished, naturally cooling the manganese-potassium ore type manganese oxide microporous honeycomb aluminum core to room temperature, thereby obtaining a manganese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module product.
Under normal temperature and pressure, applying the manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst to catalytically decompose hydrogen peroxide in water, and removing residual hydrogen peroxide in water under the action of the prepared manganese-potassium ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst. The monopotassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module prepared by the embodiment has good stability and reusability. The preparation process of the monopotassium manganese ore type manganese oxide (OMS-2) microporous honeycomb aluminum core catalyst module is simple, low in energy consumption and cost and easy for large-scale production.
In summary, the module of the manganese-potassium-ore-type manganese oxide microporous honeycomb aluminum core catalyst, the preparation method thereof and the application thereof in catalytic decomposition of hydrogen peroxide are provided. In addition, the OMS-2 powder catalyst is adopted in the embodiment to carry and fix the hydrogen peroxide in the water phase and the gas phase at normal temperature and normal pressure, the hydrogen peroxide concentration in the water is reduced to below 1ppm, and a good effect is achieved on the catalytic decomposition of the hydrogen peroxide in the gas phase. Compared with the manganese oxide catalyst prepared by the prior art, OMS-2 has stronger hydrogen peroxide catalytic decomposition capacity, but has mild preparation conditions, simple and convenient preparation process and simple preparation equipment, thereby having very high practical application value. The invention utilizes the characteristics of micropore and dense parallel micropore channel structure, high porosity, large specific surface area, light specific gravity, high strength, good toughness, flat and straight appearance, environmental protection and resource saving of micropore honeycomb aluminum core substrate micropores and dense parallel micropore channel structures to realize the load of the powder catalyst OMS-2 and prepare the formed catalyst module, and the module has simple preparation process and easy operation and control. Meanwhile, the embodiment utilizes a special dipping-pulling machine to carry out dipping-pulling operation, so that the yield of the formed catalyst module is improved, the quality of the formed catalyst module is ensured, and the actual production requirement can be met. The molded catalyst module prepared by the method has the advantages of large specific surface area, more catalytic active sites, high catalytic activity, high utilization rate of active powder catalyst, large fluid flux, small wind resistance, small pressure drop, high mechanical strength, good chemical stability, low production cost and the like, and can be widely applied to the fields of hydrogen peroxide decomposition, air purification and the like.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, as long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention without departing from the technical principle and inventive concept of the present invention.
Claims (22)
1. A preparation method of a manganese oxide catalyst for hydrogen peroxide decomposition is characterized in that the manganese oxide is a manganese-potassium ore type manganese oxide, and the preparation method comprises the following steps:
a1. weighing 1872.3g of manganese acetate, dissolving in at least 6808.4mL of distilled water, and stirring at room temperature to fully dissolve the manganese acetate to form a solution A;
a2. weighing 851.0mL of glacial acetic acid, diluting in at least 6808.4mL of distilled water, and stirring at room temperature to fully and uniformly mix and dissolve different substances to form a buffer solution B;
a3. weighing 1106.4g of potassium permanganate, dissolving in at least 25531.4mL of distilled water, and stirring at room temperature to fully dissolve the potassium permanganate to form a solution C;
a4. adding the buffer solution B prepared in the step a2 into the solution A prepared in the step a1, and stirring at room temperature to fully mix the A, B two solutions; slowly adding the solution C prepared in the step a3 while stirring to enable the mixed solution to form gel, refluxing the obtained gel for not less than 24 hours under stirring, and then filtering and washing the obtained solid; carrying out centrifugal separation treatment on the mixture of the solid and water at the rotating speed of not less than 4000rpm for at least 5 minutes to realize solid-liquid separation, transferring the obtained solid into distilled water to be continuously washed, then continuously carrying out centrifugal separation treatment according to the conditions in the step, carrying out centrifugal separation-washing circulation treatment until the pH value of a washing liquid reaches 6-7, and then collecting the solid;
a5. placing the solid obtained by centrifugal separation and washing in the step a4 in an electric heating forced air drying oven, and drying at the temperature of not less than 80 ℃ for at least 10 hours to obtain solid powder; and then putting the dried solid powder into a muffle furnace, heating the furnace to a temperature of not higher than 450 ℃ at a heating rate of not higher than 2 ℃/min, preserving the temperature for at least 4 hours, calcining the solid powder, and then cooling the muffle furnace to the room temperature to obtain the powder catalyst, namely the manganese-potassium ore type manganese oxide.
2. The method for preparing a manganese oxide catalyst for hydrogen peroxide decomposition according to claim 1, wherein: in the step a1, the manganese acetate is manganese acetate tetrahydrate;
alternatively, in step a4, the centrifugation-washing cycle is processed at least 3 times.
3. A manganese oxide catalyst for the decomposition of hydrogen peroxide, characterized by: the method for preparing a manganese oxide catalyst for hydrogen peroxide decomposition according to claim 1.
4. A manganesium ore type manganese oxide micropore honeycomb aluminum core catalyst module is characterized in that a micropore honeycomb aluminum core material is used as a carrier, a manganesium ore type manganese oxide is used as a catalyst active particle material, and the manganesium ore type manganese oxide is loaded on the surface of a straight-through micropore channel of a micropore honeycomb aluminum core to form a composite catalyst for decomposing hydrogen peroxide.
5. The cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module of claim 4, wherein: the manganese-potassium ore type manganese oxide powder catalyst is fixed on the surface of a straight-through micropore pore passage of a micropore honeycomb aluminum core through a slurry dip-lift-heat treatment method.
6. The cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module of claim 4, wherein: the cross-sectional area of the straight-through micropore channel of the micropore honeycomb aluminum core is not more than 23.4cm2The length of a straight-through micropore duct of the micropore honeycomb aluminum core is not more than 40 mm; the thickness of the straight-through micropore channel wall of the straight-through micropore channel of the micropore honeycomb aluminum core is not more than 0.06 mm.
7. The monopotassium manganese ore type manganese oxide microporous honeycomb aluminum core catalyst module of claim 6, wherein: the thickness of the straight-through micropore channel wall of the micropore honeycomb aluminum core is 0.025-0.04 mm.
8. The cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module of claim 4, wherein: the micropore honeycomb aluminum core has a parallel micropore pore channel structure to form a regular hexagon honeycomb structure, and the side length of the hexagon is not more than 3 mm.
9. The monopotassium manganite-type manganese oxide microporous honeycomb aluminum core catalyst module of claim 8, wherein: the side length of the hexagon of the regular hexagon honeycomb structure of the micropore honeycomb aluminum core is not more than 1.0 mm.
10. The cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module of claim 4, wherein: the shape of the micropore honeycomb aluminum core material is a cuboid module shape, the length of the micropore honeycomb aluminum core material is not more than 300mm, and the height of the micropore honeycomb aluminum core material is not more than 35 mm.
11. The cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module of claim 4, wherein: calculated by the solidification amount of the powder catalyst manganese-potassium ore type manganese oxide of unit surface area of the microporous honeycomb aluminum core, the load amount of the powder catalyst manganese-potassium ore type manganese oxide particles of the microporous honeycomb aluminum core is not less than 1.45 to 10-3g/cm2。
12. The cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module of claim 4, wherein: in the ultrasonic shedding rate test, the shedding rate of the manganese-potassium ore type manganese oxide particle powder catalyst from the surface of the microporous honeycomb aluminum core is not higher than 0.003%.
13. A preparation method of the manganesium ore type manganese oxide micropore honeycomb aluminum core catalyst module as claimed in claim 4, is characterized in that a slurry dipping-pulling method is adopted, and the steps are as follows:
b1. preparation of a potassium manganate ore type manganese oxide suspension:
adding at least 400g of a manganese-potassium ore type manganese oxide powder catalyst into 3600mL of distilled water, and adjusting the pH value with nitric acid in the adding process to form a manganese-potassium ore type manganese oxide suspension;
b2. dispersing treatment of the potassium manganate ore type manganese oxide suspension:
b, putting the manganic-potash ore type manganese oxide suspension obtained in the step b1 into a ball milling tank, and ball milling the manganic-potash ore type manganese oxide suspension at a ball milling rotating speed of not less than 50rpm for a ball milling time of not less than 16 hours to obtain uniform manganic-potash ore type manganese oxide suspension;
b3. preparing a mixed solution of the potassium manganate ore type manganese oxide:
after the ball milling is completed in the step b2, transferring the uniform manganese-potassium ore type manganese oxide suspension into a mixing stirrer, stirring at the rotating speed of not less than 600rpm, adding pseudo-boehmite sol, fully stirring for not less than 2 hours, and uniformly mixing to obtain a mixed solution of manganese-potassium ore type manganese oxide;
b4. preparation of a manganese potassium ore type manganese oxide catalyst slurry:
uniformly mixing the mixture in the step b3, stirring at the rotating speed of not less than 600rpm, adding a binder, fully stirring for not less than 12 hours, and standing for defoaming overnight to obtain a manganese-potassium ore type manganese oxide catalyst slurry;
b5. preparing a manganese-potassium ore type manganese oxide micropore honeycomb aluminum core molding material precursor:
b, adopting a microporous honeycomb aluminum core material as a carrier, and attaching the slurry of the manganese-potassium ore type manganese oxide catalyst prepared in the step b4 to the surface of a straight-through microporous pore passage of the microporous honeycomb aluminum core by using an impregnation and pulling machine and an auxiliary clamp through an impregnation-pulling method; then transferring the microporous honeycomb aluminum core attached with the catalyst slurry into a centrifugal drying machine, carrying out centrifugal drying treatment for at most 3 minutes at the rotating speed of not higher than 400rpm, then transferring the microporous honeycomb aluminum core onto a stainless steel net rack, putting the stainless steel net rack and the microporous honeycomb aluminum core into an electrothermal blowing drying box, carrying out drying treatment for at least 30 minutes at the temperature of not higher than 80 ℃, and removing moisture; then taking out the microporous honeycomb aluminum core material which is subjected to primary dipping, lifting, centrifugal drying and drying treatment and is primarily combined with the manganese-potassium ore type manganese oxide powder catalyst, and repeatedly carrying out dipping, lifting, centrifugal drying and drying treatment for at least 5 times in the same way as the primary dipping, lifting, centrifugal drying and drying treatment, thereby obtaining a manganese-potassium ore type manganese oxide microporous honeycomb aluminum core molding material precursor subjected to multiple dipping, lifting, centrifugal drying and drying treatment;
b6. preparing a molding material initial product:
after continuous multiple dipping and pulling, centrifugal drying and drying treatment are completed in the step b5, adopting a heat treatment method to raise the temperature of an electrothermal blowing drying box with a built-in loading stainless steel net rack to be not higher than 200 ℃, preserving heat at the temperature and carrying out heat treatment for not more than 30 minutes to completely remove the moisture of slurry on the surface of the microporous honeycomb aluminum core, and utilizing the temperature to fully play the roles of pseudo-boehmite gel and a binder to tightly bond the manganese potash ore type manganese oxide powder catalyst particles and the surface of the microporous honeycomb aluminum core together to obtain a manganese potash ore type manganese oxide microporous honeycomb aluminum core molding material initial product;
b7. preparation of a catalyst module product:
and c, after the heat preservation heat treatment in the step b6 is finished, naturally cooling the manganese-potassium ore type manganese oxide microporous honeycomb aluminum core to room temperature to obtain a manganese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module product.
14. The method of making a cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module of claim 13, wherein: in the step b1, the distilled water is distilled water without adding any binder or distilled water with adding a binder;
alternatively, in the step b1, the nitric acid concentration is not lower than 2 mol/L;
alternatively, in step b1, the pH is adjusted to not less than 3.40;
alternatively, in the step b3, not less than 1333.3g of pseudo-boehmite sol is added to the uniform manganesite-type manganese oxide suspension;
alternatively, in the step b4, the binder is at least one of hydroxyethyl cellulose sol and polyvinyl alcohol sol;
or, in the step b4, not less than 2400mL of binder is added, the stirring time is not less than 12 hours, and the standing and defoaming time is not less than 8 hours;
or, in the step b5, the cross-sectional area of the straight-through micropore channels of the micropore honeycomb aluminum core is not more than 23.4cm2The length of a straight-through micropore duct of the micropore honeycomb aluminum core is not more than 40 mm; the thickness of the straight-through micropore channel wall of the micropore honeycomb aluminum core is not more than 0.06 mm;
or in the step b5, the microporous honeycomb aluminum core has a parallel microporous pore channel structure to form a regular hexagonal honeycomb shape, wherein the side length of the hexagon is not more than 3 mm;
or, in the step b5, the shape of the microporous honeycomb aluminum core material is a cuboid module shape, the length of the microporous honeycomb aluminum core material is not more than 300mm, and the height of the microporous honeycomb aluminum core material is not more than 35 mm;
or, in the step b5, the dipping-pulling method utilizes a dipping-pulling machine and an auxiliary clamp, the dipping time of each dipping-pulling is at least 1 minute, and the pulling speed of each dipping-pulling is not more than 3 cm/minute;
or, in the step b5, the centrifugal spin-drying is carried out at a centrifugal rotating speed of not less than 400rpm, and the centrifugal time of each centrifugal spin-drying is not more than 3 minutes;
alternatively, in the step b5, the dipping and pulling-centrifugal drying-drying treatment is repeated at least 6 times.
15. The method for preparing a cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module as claimed in claim 14, wherein in step b4, the hydroxyethyl cellulose sol as a binder is prepared by the following steps:
(1) measuring 5760mL of deionized water, pouring the deionized water into a stainless steel cylindrical barrel, placing the cylindrical barrel into a stainless steel cooking pot, stirring the cylindrical barrel with water in the pot at a rotating speed of not less than 300rpm, and adding at least 240g of hydroxyethyl cellulose into the stainless steel barrel while stirring to obtain hydroxyethyl cellulose suspension with the mass percentage concentration of not less than 4 wt.%;
(2) and (2) heating the stainless steel cooking pot filled with the hydroxyethyl cellulose suspension in the step (1) to a temperature not lower than 80 ℃, stirring at a rotating speed not lower than 300rpm, continuing to stir in a sealed manner for at least 4 hours, and cooling the feed liquid to room temperature after stirring is finished to obtain hydroxyethyl cellulose sol with the mass percentage concentration not lower than 4 wt.%.
16. The method for preparing a cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module as claimed in claim 14, wherein in step b4, the polyvinyl alcohol sol as a binder is prepared by the following steps:
weighing 4750mL of deionized water, pouring the deionized water into a stainless steel cylindrical barrel, placing the cylindrical barrel into a stainless steel cooking pot, stirring the water in the pot at a rotating speed of not less than 300rpm, and adding at least 250g of polyvinyl alcohol into the stainless steel barrel while stirring to obtain a polyvinyl alcohol suspension with the mass percentage concentration of not less than 5 wt.%;
heating the stainless steel cooking pot filled with the polyvinyl alcohol suspension liquid in the step I to be not less than 85 ℃, stirring at the rotating speed of not less than 300rpm, continuing to stir in a sealed manner for at least 4 hours, and cooling the feed liquid to room temperature after stirring is finished to obtain the polyvinyl alcohol sol with the mass percentage concentration of not less than 5 wt.%.
17. The method of making a cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module of claim 14, wherein: in the step b5, the side length of the hexagon of the regular hexagon honeycomb structure of the micropore honeycomb aluminum core is not more than 1.0 mm.
18. The method of making a cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module of claim 14, wherein: in the step b5, the thickness of the straight-through micropore channel wall of the micropore honeycomb aluminum core is 0.025-0.04 mm.
19. The method of making a cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module of claim 13, wherein: in the step b3, the preparation method of the pseudo-boehmite sol comprises the following steps:
weighing 162.54mL of concentrated nitric acid with the mass percentage concentration of 65-68%, adding the concentrated nitric acid into at least 19837.46mL of distilled water, and preparing HNO with the mass percentage concentration of not higher than 1.14 wt%3A solution;
ii, 2229.35g of pseudoboehmite were weighed and added to the HNO in step i above3Obtaining a solid-liquid mixture with the pseudo-boehmite mass content of not less than 10 wt.% in the solution;
and iii, refluxing and stirring the solid-liquid mixture in the step ii for at least 1.5 hours, standing to form a colloidal solution, enabling the pH of the colloidal solution to be not lower than 1.64 and the viscosity of the colloidal solution to be not lower than 1.27mPa & s, then aging the colloidal solution, and standing and aging the sol formed after refluxing and stirring for at least 1 week to obtain the pseudoboehmite sol.
20. The use of the cryptomelane-type manganese oxide microporous honeycomb aluminum core catalyst module of claim 4, wherein: under normal temperature and pressure, the manganese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module is applied to catalytic decomposition of hydrogen peroxide in water or air, and residual hydrogen peroxide in water or air is decomposed and removed.
21. The use of a potassic manganese ore type manganese oxide microporous honeycomb aluminum core catalyst module as claimed in claim 20 wherein: the initial concentration of hydrogen peroxide in water or air environment medium to be treated is not lower than 600ppm, and the hydrogen peroxide concentration in the environment medium is reduced to be not higher than 1ppm under the action of the manganese-potassium ore type manganese oxide catalyst of the manganese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module.
22. The use of a potassic manganese ore type manganese oxide microporous honeycomb aluminum core catalyst module as claimed in claim 20 wherein: and (3) assembling and installing a plurality of manganese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst modules according to the installation volume size of the catalyst units to form a catalyst module assembly, wherein the catalyst module assembly is of a single-layer or multi-layer assembly structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110086632.4A CN112742378B (en) | 2021-01-22 | 2021-01-22 | Melanese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module, preparation method thereof and application of catalyst module in catalytic decomposition of hydrogen peroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110086632.4A CN112742378B (en) | 2021-01-22 | 2021-01-22 | Melanese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module, preparation method thereof and application of catalyst module in catalytic decomposition of hydrogen peroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112742378A true CN112742378A (en) | 2021-05-04 |
| CN112742378B CN112742378B (en) | 2023-04-18 |
Family
ID=75652889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110086632.4A Active CN112742378B (en) | 2021-01-22 | 2021-01-22 | Melanese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module, preparation method thereof and application of catalyst module in catalytic decomposition of hydrogen peroxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112742378B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117816253A (en) * | 2024-03-06 | 2024-04-05 | 无锡威孚环保催化剂有限公司 | Ozone decomposition catalyst and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101281821A (en) * | 2008-05-20 | 2008-10-08 | 中山大学 | Nano thread-shaped manganese dioxide load carbon silica aerogel as well as preparation method and application thereof |
| CN106378145A (en) * | 2016-11-18 | 2017-02-08 | 济南大学 | Catalyst for gaseous hydrogen peroxide and application thereof |
| CN107803205A (en) * | 2017-11-08 | 2018-03-16 | 绍兴上虞易诚工业设计有限公司 | A kind of manufacture method of material for water treatment |
| KR20180084276A (en) * | 2017-01-16 | 2018-07-25 | 한국과학기술연구원 | Methods of preparing catalysts for decomposition of hydrogen peroxide |
| US20190009253A1 (en) * | 2016-01-14 | 2019-01-10 | Korea Research Institute Of Chemical Technology | Solid-phase catalyst for decomposing hydrogen peroxide and method for producing same |
| CN109482175A (en) * | 2018-11-23 | 2019-03-19 | 华南理工大学 | A kind of yolk-shell structure cryptomelane-type manganese dioxide-catalyst and the preparation method and application thereof |
| CN110240203A (en) * | 2019-06-04 | 2019-09-17 | 上海大学 | The preparation method and applications for the manganese oxide catalyst that hydrogen peroxide decomposes |
| CN110975610A (en) * | 2019-12-27 | 2020-04-10 | 南通得力净化器材厂有限公司 | Ozone room temperature decomposition honeycomb module and preparation method thereof |
-
2021
- 2021-01-22 CN CN202110086632.4A patent/CN112742378B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101281821A (en) * | 2008-05-20 | 2008-10-08 | 中山大学 | Nano thread-shaped manganese dioxide load carbon silica aerogel as well as preparation method and application thereof |
| US20190009253A1 (en) * | 2016-01-14 | 2019-01-10 | Korea Research Institute Of Chemical Technology | Solid-phase catalyst for decomposing hydrogen peroxide and method for producing same |
| CN106378145A (en) * | 2016-11-18 | 2017-02-08 | 济南大学 | Catalyst for gaseous hydrogen peroxide and application thereof |
| KR20180084276A (en) * | 2017-01-16 | 2018-07-25 | 한국과학기술연구원 | Methods of preparing catalysts for decomposition of hydrogen peroxide |
| CN107803205A (en) * | 2017-11-08 | 2018-03-16 | 绍兴上虞易诚工业设计有限公司 | A kind of manufacture method of material for water treatment |
| CN109482175A (en) * | 2018-11-23 | 2019-03-19 | 华南理工大学 | A kind of yolk-shell structure cryptomelane-type manganese dioxide-catalyst and the preparation method and application thereof |
| CN110240203A (en) * | 2019-06-04 | 2019-09-17 | 上海大学 | The preparation method and applications for the manganese oxide catalyst that hydrogen peroxide decomposes |
| CN110975610A (en) * | 2019-12-27 | 2020-04-10 | 南通得力净化器材厂有限公司 | Ozone room temperature decomposition honeycomb module and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| OIHANE SANZ ET AL.: ""Stacked wire-mesh monoliths for VOCs combustion: Effect of the meshopening in the catalytic performance"", 《CATALYSIS TODAY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117816253A (en) * | 2024-03-06 | 2024-04-05 | 无锡威孚环保催化剂有限公司 | Ozone decomposition catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112742378B (en) | 2023-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102794115A (en) | Preparation method of metal organic framework ZIF-8 (zero insert force-9) film | |
| CN107824217B (en) | Preparation method of coating slurry and preparation method of coating type Cu molecular sieve SCR catalyst | |
| CN105833899A (en) | Preparation method for SCR catalyst for purifying oxynitride in motor vehicle exhaust | |
| CN106025178B (en) | It is a kind of to prepare the method for metal oxide and its application in lithium cell cathode material by template of MOF | |
| WO2011022888A1 (en) | Mesoporous composite titania and preparing method thereof | |
| CN112742378B (en) | Melanese-potassium ore type manganese oxide microporous honeycomb aluminum core catalyst module, preparation method thereof and application of catalyst module in catalytic decomposition of hydrogen peroxide | |
| CN101972663A (en) | New method for preparing LaCoO3/SBA-16 and LaMnO3/SBA-16 catalyst | |
| CN113694724B (en) | Used for capturing and catalyzing CO 2 Reaction system of | |
| CN113736432B (en) | Metal oxide heat storage material, metal oxide heat storage unit and preparation method | |
| CN105854592A (en) | Air purifying material and preparation method and application thereof | |
| CN114832811B (en) | Monolithic catalyst and preparation method and application thereof | |
| CN101444741B (en) | Preparation method of stainless steel carrier catalysts and coating process | |
| CN105116030B (en) | A kind of Cu2Nuclear-shell structured nano-composite materials of O@CuO half and preparation method thereof | |
| CN102728347B (en) | MnO2-TiO2 graphite-porous inorganic ceramic membrane low temperature catalyst denitration self-cleaning material and its preparation method | |
| CN110581265A (en) | Hollow spherical CeO for positive electrode of lithium-sulfur battery2-xPreparation method of @ C composite material | |
| CN112588257B (en) | Ordered mesoporous silicon-glass fiber paper composite material and preparation method and application thereof | |
| CN107744830A (en) | The method that one-step method prepares Cu based molecular sieve SCR catalysts | |
| CN111286408A (en) | Method for preparing biodiesel by catalyzing jatropha curcas oil through zirconium-based MOFs material loaded with ionic liquid | |
| CN106732499A (en) | A kind of preparation method of the aluminum oxide film layer carrier of monoblock type methyl hydride combustion catalyst | |
| CN106492813A (en) | A kind of three-dimensional ordered macroporous LaFeO of support type3/CeO2The preparation method of catalyst | |
| CN101607199B (en) | CO selective methanation monolithic catalyst and preparation method thereof | |
| CN103316652B (en) | The glass Catalysts and its preparation method of purifying tail gas of diesel vehicles carbon soot particles | |
| CN106179299B (en) | Load the Preparation equipment of the aerogels of nano-titanium oxide | |
| CN114082439A (en) | Preparation method and application of tar cracking catalyst | |
| CN113097467A (en) | Preparation method of lithium ion battery composite material with double-layer shell structure |
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 |