CN110586176A - Electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst and preparation method thereof - Google Patents
Electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst and preparation method thereof Download PDFInfo
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- CN110586176A CN110586176A CN201910924200.9A CN201910924200A CN110586176A CN 110586176 A CN110586176 A CN 110586176A CN 201910924200 A CN201910924200 A CN 201910924200A CN 110586176 A CN110586176 A CN 110586176A
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- electrolytic manganese
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- manganese slag
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000011572 manganese Substances 0.000 title claims abstract description 74
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 67
- 239000002893 slag Substances 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 46
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 25
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 11
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical class [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002808 molecular sieve Substances 0.000 abstract description 17
- 239000012855 volatile organic compound Substances 0.000 abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003517 fume Substances 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000003921 oil Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000000779 smoke Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000003337 fertilizer Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst and a preparation method thereof, wherein the catalyst is represented by the following general formula (1), CeO2The general formula of the/Mn-H-ZSM-5 … is shown in the specification (1), wherein Mn-H-ZSM-5 is used as a carrier, H-ZSM-5 is micro-mesoporous ZSM-5, and Mn is manganese. The molecular sieve is mainly prepared by taking solid waste electrolytic manganese slag as a main material without extracting Si and Al components, mixing and roasting with sodium hydroxide, adding a certain amount of tetrapropylammonium hydroxide (TPAOH), cerium nitrate and polydienedimethylammonium chloride (PDADMAC) solution, performing one-step hydrothermal synthesis, and filtering, washing, drying and roasting. CeO (CeO)2The specific surface area of/Mn-H-ZSM-5 is 325-458m2The mesoporous volume range is 0.067-0.550cm3The mesoporous aperture size is 2-16nm, and the average aperture is 2.25-5.58nm. The molecular sieve not only has adjustable aperture, but also can improve the utilization value of the electrolytic manganese residues, and simultaneously has better activity and stability in catalyzing oil fume VOCs.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of resources and environmental pollution control, in particular to an electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst and a preparation method thereof.
Background
China is the biggest world for producing, consuming and exporting electrolytic manganese metal, and the capacity of China exceeds 200 million tons, which accounts for 98 percent of the total production capacity of the electrolytic manganese. The electrolytic manganese slag is the filtered acid slag generated after the metal manganese is electrolyzed, and is a key pollutant in the electrolytic manganese industry. The production of electrolytic manganese slag reaches 7-11 tons per ton of manganese, the production per year is about 2000 ten thousand tons, the annual accumulation is more than 8000 ten thousand tons, and the stock is huge. At present, enterprises do not find a method for properly treating electrolytic manganese slag, and the electrolytic manganese slag is generally transported to a storage yard to be built into a dam for stacking. The domestic manganese slag tailing dam occupies a large area, has low safety coefficient, and pollutes large cultivated land and underground water sources under the effect of weathering eluviation for a long time, thus causing serious damage to the ecological environment.
The accumulation of a large amount of electrolytic manganese slag brings great pressure to the environmental protection work of China. The electrolytic manganese slag is recycled, so that the problem of environmental pollution can be solved, benefits can be created for enterprises, and the production cost is reduced. At present, the electrolytic manganese slag is mainly recycled in the following ways:
(1) and recovering the valuable metals. The manganese resource in the electrolytic manganese slag accounts for 9-13%. However, this method has a complicated process, high cost and causes secondary pollution, resulting in limited applications.
(2) And (4) preparing a complete fertilizer. The electrolytic manganese slag is rich in organic substances and a large amount of nutrient elements required by plants, such as manganese, selenium, potassium, sodium, iron, boron and the like, which provides possibility for preparing the complete fertilizer by utilizing the electrolytic manganese slag. At present, although the full-value fertilizer prepared by electrolytic manganese slag can increase certain fertilizer efficiency, the fertilizer efficiency is inferior to that of common nitrogen fertilizer and phosphate fertilizer. In addition, the electrolytic manganese residues also contain a plurality of harmful elements, promote the growth of crops and pollute soil, thus being harmful to human health.
(3) Used as cement additive. The doping amount of the electrolytic manganese slag is too small, so that enterprises can hardly reasonably utilize the electrolytic manganese slag through self-building cement plants.
(4) Producing wall materials and roadbed materials. The main problems of the electrolytic manganese slag in the field of preparing wall materials are as follows: firstly, the manganese slag is relatively less in doping proportion, and the strength of the brick body is reduced due to the increase of the doping amount; and secondly, heavy metal and toxic impurities in the manganese slag need to be further removed.
In conclusion, an application approach with higher added value and environmental protection is urgently needed for the electrolytic manganese slag. The mesoporous ZSM-5 molecular sieve prepared by the method not only can improve the utilization value of the molecular sieve, but also can provide more molecular sieve catalysts for the market.
In addition, the harmfulness of non-methane hydrocarbons (alkanes, alkenes, alkynes, aromatics, etc.) and oxygen-containing organic substances (aldehydes, ketones, alcohols, ethers, etc.)) in lampblack is not inferior to SOx and NOx, and is one of the important factors for forming photochemical smog, and is an important precursor for forming haze. Haze formation is closely related to the VOC in the atmosphere. Atmospheric organic aerosols, which are an important component of PM2.5, can be present in proportions of up to 90% in densely populated urban areas, and VOCs are precursors to organic aerosols. Meanwhile, VOCs are also important precursors for forming ozone. VOCs (benzene series, aldehyde ketone, alkane and the like) in the oil smoke are harmful to human bodies, and serious diseases can be caused by long-time inhalation.
The cooking oil smoke VOCs treatment method mainly comprises a physical method and a chemical method, wherein the physical method comprises the following steps: mechanical separation, adsorption, condensation, absorption, electrostatic methods; the chemical method comprises the following steps: catalytic oxidation, direct combustion, plasma purification, photocatalysis, biological purification. Wherein, the physical method can only remove oil drops in the oil smoke, but can not completely eliminate VOCs in the oil smoke; in chemical methods (except catalytic oxidation), the reaction speed is slow (photocatalysis and biological purification methods), high voltage (plasma purification) or high concentration reaction (direct combustion) is needed, the catalytic oxidation method is particularly suitable for treating VOCs gases which have no recovery value or are difficult to recover, in oil fume treatment, the reaction speed is high, high-voltage discharge is not needed, and in single treatment method, the catalytic oxidation has greater research value than other methods. However, catalytic combustion is mainly performed by using a catalyst, and for eliminating macromolecular chains and low-concentration VOCs in oil smoke, a mesoporous catalyst is required to improve the expansion efficiency and prolong the catalytic life.
Disclosure of Invention
The invention provides an electrolytic manganese residue-based micro-mesoporous ZSM-5 catalyst and a preparation method thereof.
The invention provides the following scheme:
an electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst, comprising:
represented by the following general formula (1),
CeO2/Mn-H-ZSM-5 … general formula (1)
Wherein Mn-H-ZSM-5 is a carrier, H-ZSM-5 is micro-mesoporous ZSM-5, and Mn is manganese.
A preparation method of an electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst comprises the following steps:
adding NaOH solution into electrolytic manganese slag according to a certain mass ratio, uniformly mixing, and roasting to obtain a roasted product;
mixing the roasted product with a tetrapropylammonium hydroxide solution and a cerium nitrate solution according to a certain proportion, heating and stirring for a certain time to obtain a mixed solution;
adding a certain amount of polydiene dimethyl ammonium chloride solution into the mixed solution, mixing and heating for a certain time to obtain a mixture;
and transferring the mixture to a reaction kettle, crystallizing for a certain time at a certain temperature, filtering, washing, drying and roasting to obtain the catalyst.
Preferably: the mass ratio of the electrolytic manganese slag to the NaOH solution is determined by analyzing the content of silicon and aluminum in the electrolytic manganese slag.
Preferably: the mass ratio of the electrolytic manganese slag to the NaOH solution is 1:2, the roasting temperature is 600-700 ℃, and the roasting time is 2-4 hours.
Preferably: mixing the roasted product with tetrapropylammonium hydroxide and cerium nitrate solution according to a certain proportion,the mol ratio is SiO2:TPAOH＝100:20；SiO2:H2O100: 2000, Ce: Si ═ x (x ═ 0 to 0.1), where SiO is2Silicon-oxygen compounds in the electrolytic manganese slag; the heating temperature is 40-50 ℃, the stirring speed is 300-500r/min, and the stirring time is 2-3 hours.
Preferably: adding a polydiene dimethyl ammonium chloride solution in a certain proportion into the mixed solution, wherein the mass ratio of the polydiene dimethyl ammonium chloride solution to the mixed solution is PDADMAC: SiO 220.04-0.30, heating at 50-70 deg.C for 2-4 hr, and stirring at 300-.
Preferably: the mixture is transferred to a reaction kettle and crystallized for 2 to 3 days at the temperature of 150 ℃ and 200 ℃.
Preferably: the reaction kettle is a stainless steel reaction kettle containing a polytetrafluoroethylene lining.
Preferably: crystallizing for a certain time at a certain temperature, filtering, washing, drying to obtain solid powder, roasting for 4 hours at the temperature of 350-400 ℃, and then roasting for 4-6 hours at the temperature of 500-600 ℃ to obtain the catalyst.
According to the specific embodiment provided by the invention, the invention discloses the following technical effects:
the invention can realize an electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst and a preparation method thereof, and in one implementation mode, the catalyst is represented by the following general formula (1), and CeO2The general formula of the/Mn-H-ZSM-5 … is shown in the specification (1), wherein Mn-H-ZSM-5 is used as a carrier, H-ZSM-5 is micro-mesoporous ZSM-5, and Mn is manganese. The molecular sieve is mainly prepared by taking solid waste electrolytic manganese slag as a main material without extracting Si and Al components, mixing and roasting with sodium hydroxide, adding a certain amount of tetrapropylammonium hydroxide (TPAOH), cerium nitrate and polydienedimethylammonium chloride (PDADMAC) solution, performing one-step hydrothermal synthesis, and filtering, washing, drying and roasting. CeO (CeO)2The specific surface area of/Mn-H-ZSM-5 is 325-458m2The mesoporous volume range is 0.067-0.550cm3The pore size of the mesoporous is 2-16nm, and the average pore size is 2.25-5.58 nm. The molecular sieve not only has adjustable aperture, but also can improve the utilization value of the electrolytic manganese residues, and simultaneously has better activity and stability in catalyzing oil fume VOCs.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Examples
The embodiment of the invention provides an electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst, which is represented by the following general formula (1),
CeO2/Mn-H-ZSM-5 … general formula (1)
Wherein Mn-H-ZSM-5 is a carrier, H-ZSM-5 is micro-mesoporous ZSM-5, and Mn is manganese.
The embodiment of the application also provides a preparation method of the electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst, which comprises the following steps:
the content of added NaoH is determined by analyzing the content of elements such as Si, Al and the like in the electrolytic manganese slag, and roasting is carried out after uniform mixing. Specifically, the electrolytic manganese slag and NaOH are uniformly mixed according to a certain mass ratio of 1-2, and then are roasted for 2-4 hours at the temperature of 600-700 ℃, so as to obtain a calcined product.
Mixing the roasted product with tetrapropyl ammonium hydroxide solution and deionized water in certain proportion, heating and stirring for certain period. Specifically, the roasted product is mixed with tetrapropylammonium hydroxide and cerium nitrate solution according to a certain proportion, and the molar ratio is SiO2:TPAOH＝100:20；SiO2:H2O100: 2000, Ce: Si ═ x (x ═ 0 to 0.1), where SiO is2Silicon-oxygen compounds in the electrolytic manganese slag; the heating temperature is 40-50 ℃, the stirring speed is 300-500r/min, and the stirring time is 2-3 hours.
Adding a certain amount of polydiene dimethyl ammonium chloride solution into the mixed solution, mixing and heating for a certain time. Concretely, polydiene dimethyl ammonium chloride (PDADMAC) solution with a certain proportion is added into the mixed solutionThe mass ratio is PDADMAC: SiO 220.04-0.30, heating at 50-70 deg.C for 2-4 hr, and stirring at 300-.
And transferring the mixture to a stainless steel reaction kettle with a polytetrafluoroethylene lining, crystallizing for a certain time at a certain temperature, filtering, washing, drying and roasting to obtain the polytetrafluoroethylene ceramic. Specifically, the mixture solution is transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining and crystallized for 2 to 3 days at the temperature of 150-. Taking out and cooling to room temperature, filtering, washing with deionized water to neutrality, drying, roasting at 400 deg.C for 4 hr at 500 deg.C for 600 hr to obtain CeO2/Mn-H-ZSM-5。
The preparation method takes electrolytic manganese residue, sodium hydroxide, tetrapropylammonium hydroxide (TPAOH) and poly dimethyl diallyl ammonium chloride (PDADMAC) as main raw materials. Mixing and roasting the electrolytic manganese slag and sodium hydroxide, mixing tetrapropyl ammonium hydroxide (TPAOH) and poly dimethyl diallyl ammonium chloride (PDADMAC) with a roasted product step by step, and heating and stirring for a certain time. After hydrothermal reaction for 2-3 days in a hydrothermal reaction kettle, filtering, washing, drying and roasting to obtain CeO2/Mn-H-ZSM-5。
In order to achieve the purpose, the invention adopts the following technical method:
first, the alkali-fusion activation method: mixing electrolytic manganese slag and NaOH according to a certain mass ratio of 1:2, after being uniformly mixed, roasting for 2-4 hours at the temperature of 600-700 ℃, and reacting the silicon-aluminum component which is difficult to dissolve in the electrolytic manganese slag with sodium hydroxide to form the easy-to-dissolve nepheline (NaAl-SiO)2) Thereby improving the utilization rate of the silicon-aluminum component in the electrolytic manganese slag.
Second, one-step hydrothermal synthesis without phase separation: when the micro-mesoporous molecular sieve is synthesized, a phase separation phenomenon is easy to occur, so that the micro-mesoporous molecular sieve is difficult to synthesize. Therefore, polydimethyldiallyl ammonium chloride (PDADMAC) with high charge is selected, and after micelles are formed in a solution, the surface of the micelles has high positive charge, and molecular sieve units can be firmly adsorbed on the surface of the micelles, so that the possibility of phase separation is reduced. The mesoporous volume and the pore size can be adjusted by controlling the addition amount of poly dimethyl diallyl ammonium chloride (PDADMAC). Specifically, a certain amount of polydiene dimethyl ammonium chloride solution is added into a mixed solution of TPAOH, cerium nitrate and a roasting product, and the mixed solution is mixed and heated for a certain time. Heating at 50-70 deg.C for 2-4 hr with stirring rate of 300-500 r/min. Then, the mixed solution is transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining and crystallized for 2 to 3 days at the temperature of 150-.
Thirdly, the step roasting method: the step firing can completely remove the mesoporous template (poly dimethyl diallyl ammonium chloride (PDADMAC)) and the structural template (tetrapropyl ammonium hydroxide (TPAOH)). Specifically, the crystallized product is filtered, washed and dried, then roasted for 4 hours at the temperature of 350-2/Mn-H-ZSM-5。
In the specific implementation:
first, the electrolytic manganese slag is activated. Mixing electrolytic manganese slag and NaOH according to a certain mass ratio of 1:2, after mixing evenly, roasting for 2-4 hours at 600-700 ℃.
Secondly, hydro-thermal synthesis. Mixing the roasted product with tetrapropylammonium hydroxide solution and cerium nitrate in certain proportion, heating and stirring for certain time. Specifically, the roasted product is mixed with tetrapropylammonium hydroxide and cerium nitrate solution according to a certain proportion, and the molar ratio is SiO2:TPAOH＝100:20；SiO2:H2O100: 2000, Ce: Si ═ x (x ═ 0 to 0.1), where SiO is2Silicon-oxygen compounds in the electrolytic manganese slag; the heating temperature is 40-50 ℃, the stirring speed is 300-500r/min, and the stirring time is 2-3 hours. Adding a polydiene dimethyl ammonium chloride (PDADMAC) solution in a certain proportion into the mixed solution, wherein the mass ratio of PDADMAC: SiO 220.04-0.30, heating at 50-70 deg.C for 2-4 hr, and stirring at 300-. Transferring the mixture solution to a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 2-3 days at the temperature of 150-.
Finally, the crystallized product is filtered, washed and dried, and then is roasted for 4 hours at the temperature of 350-2/Mn-H-ZSM-5。
Example 1
The prepared electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst is subjected to mesoporous test and scanning electron microscope test, and shows that the micro-mesoporous ZSM-5 molecular sieve catalyst has an obvious mesoporous structure, the absorption and desorption curve of nitrogen conforms to the IV type, and the hysteresis loop conforms to the H type3The size of the mesoporous aperture is 2-16 nm; the microscopic particles are spheres formed by intersecting lamellar layers, and a large number of mesoporous structures exist among the lamellar layers.
Example 2
The prepared micro-mesoporous ZSM-5 molecular sieve catalyst is used for evaluating the catalytic activity of valeraldehyde and hexane in oil smoke. At the temperature of 200 ℃ and 240 ℃, the catalytic conversion rate of the valeraldehyde reaches 95 percent; at 300-360 deg.c, the hexane converting rate reaches 90%. In the catalytic stability experiment, the conversion of the valeraldehyde is maintained to be unchanged for 50 hours at 90-95 percent at 200 ℃; the hexane conversion was maintained at 90-95% for 50 hours at 360 ℃. The molecular sieve has good catalytic activity and stability for catalytic oxidation of oil fume VOCs, and 5-10 vol.% of H is added2After O, the catalyst still keeps higher catalytic activity and stability, has certain water resistance and is suitable for the oil smoke rich water environment.
The invention has the advantages that:
the method has the advantages that the electrolytic manganese slag is used as an aluminum source and a silicon source required by the preparation of the micro-mesoporous ZSM-5 molecular sieve, a new path is developed for the utilization of the electrolytic manganese slag, and the utilization value of the electrolytic manganese slag is improved.
The method has the advantages that a one-step hydrothermal synthesis method is adopted, the synthesis time of the micro mesoporous ZSM-5 is saved, the production efficiency is improved, and meanwhile, the cerium nitrate jointly participates in the hydrothermal reaction, so that the dispersion degree of the active components is improved.
The method has the advantages that the Mn element in the electrolytic manganese slag is utilized, the requirement of Mn atom doping can be met without adding the Mn element externally, and the VOCs catalytic effect of the micro-mesoporous ZSM-5 molecular sieve is further improved.
The method has the advantages that the micro-mesoporous ZSM-5 molecular sieve catalyst is prepared by adopting the electrolytic manganese residues as the raw material and is applied to the low-temperature catalytic oxidation of the oil smoke VOCs, so that the waste is produced by using waste.
The molecular sieve mainly adopts solid waste electrolytic manganese slag asThe main material is prepared without extracting Si and Al components, and is prepared by mixing and roasting with sodium hydroxide, adding a certain amount of tetrapropylammonium hydroxide (TPAOH), cerium nitrate and polydienedimethylammonium chloride (PDADMAC) solution, performing one-step hydrothermal synthesis, filtering, washing, drying and roasting. CeO (CeO)2The specific surface area of/Mn-H-ZSM-5 is 325-458m2The mesoporous volume range is 0.067-0.550cm3The pore size of the mesoporous is 2-16nm, and the average pore size is 2.25-5.58 nm. The molecular sieve not only has adjustable aperture, but also can improve the utilization value of the electrolytic manganese residues, and simultaneously has better activity and stability in catalyzing oil fume VOCs.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (9)
1. An electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst is characterized by being represented by the following general formula (1),
CeO2/Mn-H-ZSM-5 … general formula (1)
Wherein Mn-H-ZSM-5 is a carrier, H-ZSM-5 is micro-mesoporous ZSM-5, and Mn is manganese.
2. The preparation method of the electrolytic manganese slag-based micro-mesoporous ZSM-5 catalyst is characterized by comprising the following steps of:
adding NaOH solution into electrolytic manganese slag according to a certain mass ratio, uniformly mixing, and roasting to obtain a roasted product;
mixing the roasted product with a tetrapropylammonium hydroxide solution and a cerium nitrate solution according to a certain proportion, heating and stirring for a certain time to obtain a mixed solution;
adding a certain amount of polydiene dimethyl ammonium chloride solution into the mixed solution, mixing and heating for a certain time to obtain a mixture;
and transferring the mixture to a reaction kettle, crystallizing for a certain time at a certain temperature, filtering, washing, drying and roasting to obtain the catalyst.
3. The method of claim 2, wherein the mass ratio of the electrolytic manganese slag to the NaOH solution is determined by analyzing the content of silicon and aluminum in the electrolytic manganese slag.
4. The method as claimed in claim 3, wherein the mass ratio of the electrolytic manganese slag to the NaOH solution is 1:2, the roasting temperature is 600-700 ℃, and the roasting time is 2-4 hours.
5. The method of claim 2, wherein the calcined product is mixed with a solution of tetrapropylammonium hydroxide and cerium nitrate in a molar ratio of SiO2:TPAOH＝100:20；SiO2:H2O100: 2000, Ce: Si ═ x (x ═ 0 to 0.1), where SiO is2Silicon-oxygen compounds in the electrolytic manganese slag; the heating temperature is 40-50 ℃, the stirring speed is 300-500r/min, and the stirring time is 2-3 hours.
6. The method of claim 2, wherein a certain proportion of polydiene dimethyl ammonium chloride solution is added to the mixed solutionThe mass ratio is PDADMAC: SiO 220.04-0.30, heating at 50-70 deg.C for 2-4 hr, and stirring at 300-.
7. The method as claimed in claim 2, wherein the mixture is transferred to a reaction vessel and crystallized at 150 ℃ and 200 ℃ for 2 to 3 days.
8. The method of claim 7, wherein the reaction vessel is a stainless steel reaction vessel comprising a polytetrafluoroethylene liner.
9. The method as claimed in claim 2, wherein the catalyst is obtained by crystallizing at a certain temperature for a certain time, filtering, washing, drying the obtained solid powder, and calcining at 400 ℃ for 4 hours at 350-.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113751053A (en) * | 2021-10-11 | 2021-12-07 | 中国环境科学研究院 | Catalyst suitable for low-concentration large-air-volume organic volatile matters and preparation method thereof |
| CN113856744A (en) * | 2021-11-04 | 2021-12-31 | 中国环境科学研究院 | Atom-doped modified double-shell monolithic hollow catalyst, and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6147425A (en) * | 1984-08-10 | 1986-03-07 | Sumitomo Chem Co Ltd | Method of dealkylation selectively in para-position |
| CN102515198A (en) * | 2011-11-21 | 2012-06-27 | 浙江大学 | Integral-type heteroatom replacing hierarchical porous molecular sieve and synthesis method thereof |
| CN102674390A (en) * | 2011-11-21 | 2012-09-19 | 浙江大学 | Method for directly synthesizing heteroatom substituted multistage ordered mesoporous molecular sieve |
| WO2013060341A1 (en) * | 2011-10-24 | 2013-05-02 | Haldor Topsøe A/S | Catalyst composition for use in selective catalytic reduction of nitrogen oxides |
| CN104437604A (en) * | 2014-10-29 | 2015-03-25 | 复旦大学 | Mn-Ce-ZSM-11 catalyst as well as preparation method and application of Mn-Ce-ZSM-11 catalyst |
| CN109908951A (en) * | 2019-04-12 | 2019-06-21 | 中国环境科学研究院 | A kind of micro--mesoporous low temperature catalyst of multistage and preparation method thereof |
-
2019
- 2019-09-27 CN CN201910924200.9A patent/CN110586176B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6147425A (en) * | 1984-08-10 | 1986-03-07 | Sumitomo Chem Co Ltd | Method of dealkylation selectively in para-position |
| WO2013060341A1 (en) * | 2011-10-24 | 2013-05-02 | Haldor Topsøe A/S | Catalyst composition for use in selective catalytic reduction of nitrogen oxides |
| CN102515198A (en) * | 2011-11-21 | 2012-06-27 | 浙江大学 | Integral-type heteroatom replacing hierarchical porous molecular sieve and synthesis method thereof |
| CN102674390A (en) * | 2011-11-21 | 2012-09-19 | 浙江大学 | Method for directly synthesizing heteroatom substituted multistage ordered mesoporous molecular sieve |
| CN104437604A (en) * | 2014-10-29 | 2015-03-25 | 复旦大学 | Mn-Ce-ZSM-11 catalyst as well as preparation method and application of Mn-Ce-ZSM-11 catalyst |
| CN109908951A (en) * | 2019-04-12 | 2019-06-21 | 中国环境科学研究院 | A kind of micro--mesoporous low temperature catalyst of multistage and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| JIAN LI ET AL.: ""Hierarchical ZSM‑5 based on fly ash for the low‑temperature purification of odorous volatile organic compound in cooking fumes"", 《REACTION KINETICS, MECHANISMS AND CATALYSIS》 * |
| 于守武等: "《高分子材料改性原理及技术》", 31 May 2015, 知识产权出版社 * |
| 吉林市革命委员会科学技术局编: "《钢铁化学讲义》", 31 December 1973, 吉林市革命委员会科学技术局 * |
| 曹孝仁等: "《高炉锰铁冶炼》", 30 June 1979, 新余钢铁厂 * |
| 王运正等编: "《现代锰冶金》", 30 September 2015, 冶金工业出版社 * |
| 贺丽芳等: ""制备方法对Mn-Ce/ZSM-5催化剂低温选择性催化还原NO 性能的影响"", 《高等学校化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113751053A (en) * | 2021-10-11 | 2021-12-07 | 中国环境科学研究院 | Catalyst suitable for low-concentration large-air-volume organic volatile matters and preparation method thereof |
| CN113751053B (en) * | 2021-10-11 | 2022-08-12 | 中国环境科学研究院 | Catalyst suitable for low-concentration large-air-volume organic volatile matters and preparation method thereof |
| CN113856744A (en) * | 2021-11-04 | 2021-12-31 | 中国环境科学研究院 | Atom-doped modified double-shell monolithic hollow catalyst, and preparation method and application thereof |
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