CN114405546B - Manganese-loaded fiber catalyst for ozone catalytic oxidation and preparation method and application thereof - Google Patents
Manganese-loaded fiber catalyst for ozone catalytic oxidation and preparation method and application thereof Download PDFInfo
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- CN114405546B CN114405546B CN202210101234.XA CN202210101234A CN114405546B CN 114405546 B CN114405546 B CN 114405546B CN 202210101234 A CN202210101234 A CN 202210101234A CN 114405546 B CN114405546 B CN 114405546B
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- 239000000835 fiber Substances 0.000 title claims abstract description 205
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000011572 manganese Substances 0.000 title claims abstract description 118
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 118
- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 104
- 230000003647 oxidation Effects 0.000 title claims abstract description 99
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002657 fibrous material Substances 0.000 claims abstract description 70
- 229920002972 Acrylic fiber Polymers 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000011065 in-situ storage Methods 0.000 claims abstract description 28
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 90
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 75
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 57
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 45
- 239000012286 potassium permanganate Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 29
- 229920000768 polyamine Polymers 0.000 claims description 27
- 230000015556 catabolic process Effects 0.000 claims description 24
- 238000006731 degradation reaction Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 16
- 230000008961 swelling Effects 0.000 claims description 16
- 125000003277 amino group Chemical group 0.000 claims description 14
- 239000004744 fabric Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000007363 ring formation reaction Methods 0.000 claims description 6
- 150000001555 benzenes Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- -1 cyano, carbonyl Chemical group 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims 1
- 238000007306 functionalization reaction Methods 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 2
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- 230000000052 comparative effect Effects 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 229960001124 trientine Drugs 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010525 oxidative degradation reaction Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000011835 investigation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 229920000193 polymethacrylate Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003335 secondary amines Chemical group 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Chemical group 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
-
- 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
- B01D53/8678—Removing components of undefined structure
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- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
-
- B01J35/58—
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/332—Di- or polyamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/90—Odorous compounds not provided for in groups B01D2257/00 - B01D2257/708
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
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- 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
Abstract
The invention provides a preparation method of a manganese-loaded fiber material. The invention particularly selects the soft acrylic fiber material with rich forms as the matrix through functionalization, preoxidation and KMnO 4 The fiber-based catalyst which is convenient to fill, large in manganese carrying capacity, rich in nitrogen-containing groups on the surface, stable in heat-resistant oxidation performance, particularly heat-resistant ozone catalytic oxidation performance and excellent in catalytic performance is finally obtained in the in-situ oxidation process, and has important significance for overcoming the defects of the existing catalyst. The preparation method of the manganese-loaded fiber catalyst has the advantages of simple process, mild condition, low energy consumption and the like, and is favorable for industrialized popularization and application. The manganese-loaded fiber catalyst provided by the invention can be used for catalyzing ozone to oxidize and degrade pollutants, the structure of the catalyst is not affected by ozone oxidation, the shape is not limited, and the use depth and the breadth of the catalyst are greatly widened.
Description
Technical Field
The invention belongs to the technical field of manganese-carrying materials, relates to a manganese-carrying fiber material, a preparation method and application thereof, and in particular relates to a manganese-carrying fiber catalyst for ozone catalytic oxidation, a preparation method and application thereof.
Background
The common textile fibers (synthetic fibers and natural fibers) are functionalized, so that the original characteristics and advantages of the fibers are maintained, and the fibers have various special properties and purposes. The textile fiber is sufficient in supply, various in variety and proper in price, and is a good raw material source for obtaining new materials. Chemical modification is an important means for functionalization of fibers, and the fibers have new surface chemical characteristics by chemical reaction of active chemical groups carried by the fibers with certain molecules or ions or chemical reaction by ultrasonic, microwave or heat assistance, so that the fibers have new functions of antistatic, water absorption and moisture retention, adsorption and separation, antibacterial and deodorization, catalysis and the like. The chemical modification can be achieved by using different fibers as raw materials and by different treatment methods and processes.
At present, most of supported metal oxide catalysts take porous substances such as metal oxide or molecular sieve as substrates, and although the catalysts prepared from the substrate materials have excellent stability and dispersibility, the morphology of the catalysts is not easy to change, the catalyst is difficult to fill in industrial application, the catalyst bed resistance is large, most of active sites of the molecular sieve or metal oxide-based catalysts are positioned in particles, the catalytic performance of the catalysts is greatly influenced in the internal diffusion process in actual reaction, and meanwhile, the catalyst pore channels are easily blocked by particles generated in the reaction, so that the activity of the catalysts is reduced. Therefore, how to design a new metal oxide supported catalyst, to solve the above-mentioned problems of the existing catalyst, has become one of the common focuses of research and development enterprises and prospective researchers in the field.
Disclosure of Invention
The invention aims to solve the technical problems of providing a manganese-carrying fiber material, in particular to a manganese-carrying fiber catalyst for ozone catalytic oxidation, which has the characteristics of convenient filling, rich nitrogen-containing groups on the surface, stable heat-resistant oxidation performance, particularly stable heat-resistant ozone catalytic oxidation performance, excellent catalytic performance and the like, and has important significance for overcoming the defects of the existing catalyst. Meanwhile, the manganese-loaded fiber catalyst has the advantages of simple preparation process, mild conditions, low energy consumption and the like, and is favorable for industrial popularization and application.
In order to achieve the purpose of the invention, the following specific technical scheme is adopted:
the invention provides a preparation method of a manganese-loaded fiber material, which comprises the following steps:
1) Swelling and grafting the acrylic fiber by using a polyamine-based compound to obtain an amino fiber;
2) Performing thermal oxidation treatment on the amino fiber obtained in the step to obtain pre-oxidized amino fiber;
3) And (3) carrying out in-situ oxidation on the pre-oxidized amino fiber obtained in the steps by adopting a potassium permanganate in-situ oxidation method to obtain the manganese-loaded fiber material.
Preferably, the polyamine-based compound includes one or more of ethylenediamine, diethylenetriamine, triethylenetetramine and polyethylenepolyamine;
the polyamine-based compound further includes a polyamine-based compound solution;
the solvent in the polyamine-based compound solution comprises one or more of water, ethylene glycol, propylene glycol and glycerol;
the mass ratio of the acrylic fiber to the polyamine-based compound is 1: (5-200);
the mass ratio of the polyamine-based compound solution to the acrylic fiber is (20-200): 1, a step of;
the swelling temperature of the fiber is 60-80 ℃;
the swelling time of the fiber is 4-12 h;
the temperature of the reaction is 100-150 ℃;
the reaction time is 1-12 h;
the alkali exchange capacity in the amino fiber is 3-6 mmol/g.
Preferably, the thermal oxidation treatment is performed in an oxygen-containing gas;
the flow rate of the oxygen-containing gas is 100-500 mL/min;
the heating rate of the thermal oxidation treatment is 2-20 ℃/min;
the temperature of the thermal oxidation treatment is 200-250 ℃;
the time of the thermal oxidation treatment is 0.5-4 h;
in the potassium permanganate in-situ oxidation method, the concentration of the potassium permanganate solution is 20-100 mmol/L;
in the potassium permanganate in-situ oxidation method, the liquid-solid mass ratio of the pre-oxidized amino fiber in the potassium permanganate solution is (20-200): 1, a step of;
the temperature of the oxidization is 10-40 ℃;
the oxidation time is 0.5-12 h.
The invention provides a manganese-loaded fiber material, the surface of which is rich in nitrogen-containing groups and manganese oxide.
Preferably, in the manganese-loaded fiber material, the manganese content is 50-250 mg/g;
the morphology of the manganese-loaded fiber material includes one or more of fibrous, mao Xianzhuang, needled cloth, and knitted cloth.
Preferably, the manganese-loaded fiber material is prepared by oxidizing and grafting manganese oxide in situ through potassium permanganate by pre-oxidizing amino fiber;
the pre-oxidized amino fiber is obtained by thermal oxidation of amino functionalized fiber;
the amino functional fiber is acrylic fiber grafted with amino groups.
Preferably, the amine groups are grafted onto the acrylic fiber by reacting the polyamine-based compound with the-CN groups in the acrylic fiber;
the pre-oxidized amino fiber contains nitrogen-containing functional groups;
the manganese-loaded fiber material contains nitrogen-containing functional groups;
the nitrogen-containing functional group comprises an nitrogen heterocycle and/or an amine group;
the nitrogen heterocycle is produced after cyclization of one or more of cyano, carbonyl and amine groups.
Preferably, the manganese-loaded fiber material comprises a manganese-loaded fiber catalyst;
the manganese-loaded fiber catalyst comprises a catalyst for ozone catalytic oxidation;
the manganese-loaded fiber material has a brown to black color.
The invention also provides the application of the manganese-loaded fiber material prepared by any one of the technical schemes or the preparation method of any one of the technical schemes in the field of catalysts.
Preferably, the catalyst comprises a catalyst in an ozone oxidation process;
the ozone oxidation includes ozone oxidation to degrade benzene based compounds in the gas phase;
the benzene series comprises toluene and/or benzene;
the degradation temperature is 90-140 ℃;
the catalyst catalyzes the ozone oxidation to degrade benzene and/or toluene, and the degradation rate is not lower than 99% at the air speed of 60000 mL/(g.h) and the temperature of 110 ℃.
The invention provides a manganese-loaded fiber material. Compared with the prior art, the invention aims at the defects that the prior metal oxide catalyst mostly takes porous substances such as metal oxide or molecular sieve and the like as a substrate, the catalyst form is not easy to change, the filling is difficult in industrial application, most active sites are positioned in particles, the influence on the catalytic performance in the internal diffusion process is large, the catalyst pore canal is easy to be blocked by a reaction product, and the activity of the catalyst is reduced. The invention selects organic fiber material as catalyst carrier for research, although there is a little report about organic fiber catalyst in the prior literature, taking fiber material with manganese oxide as an example, for example, "preparation of fiber-supported manganese oxide catalyst and research on its formaldehyde degradation performance at room temperature" (Beijing university of architecture, academic paper, 2015) uses KMnO 4 In situ reduction of KMnO with methanol as precursor 4 Preparation of MnO x And is loaded on filter cotton (PET) to prepare the manganese oxide-loaded fiber catalyst for formaldehyde degradation, and the oxidative degradation performance of the manganese oxide-loaded fiber catalyst for formaldehyde in air at room temperature is reported. The patent with application number 202010651686.6 discloses a method for preparing cationic dye fiber by catalytic oxidative decomposition, which comprises synthesizing polymethacrylate by solution polymerization, spinning polymethacrylate fiber with hydroxyl group on surface by wet spinning technique, and oxidizing under alkaline condition by oxidation between hydroxyl group on fiber surface and potassium permanganateThe original reaction, the reduction of potassium permanganate to form manganese oxide, the oxidation of hydroxyl to form carboxyl, based on the complexation between manganese oxide and carboxyl, makes manganese oxide firmly combined on the fiber surface, prepares a manganese oxide-loaded fiber catalyst for catalyzing oxidative decomposition of cationic dye, and reports the catalytic degradation performance of the catalyst on cationic dye in aqueous solution. However, in these documents disclosed in the prior art, the direct oxidation-reduction method (the former is external reduction, and the latter is internal radical reduction) is used for loading manganese oxide, and the type of catalytic reaction is not related to ozone catalytic oxidation, and the substrate material is limited to polyester fibers (PET) and polymethacrylate fibers. The organic fiber is directly connected with the fiber catalyst prepared by the potassium permanganate in-situ oxidation method, and although the organic fiber is loaded with the manganese oxide on the surface of the fiber through the complexation between carboxyl and manganese oxide, the loaded part of the manganese oxide is generally wrapped by carboxyl and other organic matter fragments on the surface of the fiber, so that part of the manganese oxide is deactivated in the preparation process, and the catalytic activity of the catalyst prepared by the method is generally lower. Ozone catalytic oxidation, especially at higher temperature, has stronger oxidative degradation performance on organic matters, and the self skeleton of the catalyst prepared by the organic fibers also belongs to the organic matters and is easily damaged by ozone catalytic oxidative degradation, so that the fiber morphology is damaged. Therefore, how to further optimize the types of the organic fibers and the preparation route of the catalyst, so that the catalyst can be applied to the ozone catalytic oxidation reaction, especially the ozone catalytic oxidation reaction of benzene or toluene and other benzene compounds with low ozone selectivity (the oxidation reaction temperature is usually more than 120 ℃), the heat-resistant ozone catalytic oxidation stability and the catalytic performance on the ozone oxidative degradation of benzene compounds of the manganese-loaded fiber catalyst are improved, and further more research is needed.
Compared with the prior art, the invention has the following positive and beneficial effects:
the invention creatively designs a manganese-loaded fiber material with specific structure and composition. The invention particularly selects the acrylic fiber material with rich forms and soft texture as the matrix, and performs functionalization and pre-oxygenationChemical and KMnO 4 The fiber-based catalyst which is convenient to fill, large in manganese carrying amount, rich in nitrogen-containing groups on the surface, stable in heat-resistant oxidation performance, particularly heat-resistant ozone catalytic oxidation performance and excellent in catalytic performance is finally obtained by adopting a pre-oxidation step in the in-situ oxidation specific preparation route, and has important significance for overcoming the defects of the existing catalyst. The manganese-loaded fiber catalyst which is resistant to temperature and has rich nitrogen-containing groups is prepared through functionalization, pre-oxidation and in-situ oxidation, the nitrogen-containing groups on the surface of the catalyst can play a role in synergetic catalysis with the manganese oxide on the ozone oxidation reaction, and the preparation method has an important role in improving the catalytic performance of the catalyst, has the advantages of simple process, mild condition, low energy consumption and the like, and is beneficial to industrial popularization and application.
The preparation method directly takes commercial acrylic fiber as a matrix material, and is characterized in that the amino fiber is prepared by grafting rich amino functional groups on the surface of the acrylic fiber through a chemical grafting method, then the amino fiber is placed in a tube furnace to be subjected to temperature rising oxidation under the air atmosphere to obtain an amino oxide fiber (namely a pre-oxidized amino fiber), and the pre-oxidized amino fiber is subjected to in-situ oxidation by adopting a potassium permanganate method to prepare the modified acrylic fiber manganese oxide-loaded fiber catalyst. Furthermore, the manganese-loaded fiber catalyst provided by the invention can be used for catalyzing ozone to oxidize and degrade pollutants such as volatile organic compounds, malodorous pollutants and the like, is not limited in form selection, can be any form such as disordered fibers, knitting yarns, needled cloth and knitted cloth, and greatly widens the use depth and breadth of the catalyst.
Experimental results show that the degradation rate of catalyzing ozone to oxidize and degrade benzene and/or toluene by adopting the manganese-loaded fiber catalyst prepared by the invention is not lower than 99% when the airspeed is 60000 mL/(g.h) and the temperature is 110 ℃.
Drawings
FIG. 1 is an infrared spectrogram of four fibers in the preparation process of the manganese-loaded fiber catalyst of the invention;
FIG. 2 is a photograph of a physical form of a manganese oxide-loaded fibrous material of various forms prepared in accordance with the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the manganese oxide-loaded fibrous material prepared in example 2 of the present invention at different magnifications;
fig. 4 is a Scanning Electron Microscope (SEM) image of the manganese oxide-loaded fibrous material prepared in comparative example 1 of the present invention at different magnifications.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further the features and advantages of the invention and are not limiting of the patent claims of the invention.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
The purity of all the raw materials of the present invention is not particularly limited, and the present invention is preferably carried out using analytically pure or conventional purities in the field of metal oxide catalyst materials.
The invention provides a manganese-loaded fiber material, which comprises modified acrylic fibers and manganese oxides loaded on the modified acrylic fibers.
In the present invention, the manganese content in the manganese-carrying fiber material is preferably 50 to 250mg/g, more preferably 90 to 210mg/g, and even more preferably 130 to 170mg/g. Wherein the manganese content is calculated by manganese element.
In the present invention, the means of loading preferably includes chemical bond grafting.
In the present invention, the form of the manganese-loaded fiber material preferably includes one or more of a fibrous form, a Mao Xianzhuang form, a needled cloth form, and a knitted cloth form, and more preferably a fibrous form, a Mao Xianzhuang form, a needled cloth form, or a knitted cloth form. The manganese-loaded fiber material provided by the invention can be not only in the original random fiber shape, but also in various fiber product states, such as Mao Xianzhuang, needled cloth or knitted cloth, and the like.
In the invention, the manganese-loaded fiber material is preferably prepared by oxidizing and grafting manganese oxide on pre-oxidized amino fiber through potassium permanganate in situ to obtain modified acrylic fiber and manganese oxide loaded on the modified acrylic fiber. Among them, since cyano groups in acrylic fibers are mostly on the surface of the fibers, they are also called surface modification or surface grafting in the field.
In the present invention, the pre-oxidized amino fibers are preferably obtained from an amino-functionalized fiber after thermal oxidation.
In the present invention, the amine-based functional fiber is preferably an acrylic fiber grafted with an amine group.
In the present invention, the amine groups are preferably grafted onto the acrylic fiber by reacting a polyamine-based compound with the-CN groups in the acrylic fiber.
In the present invention, the pre-oxidized amino fiber preferably contains a nitrogen-containing functional group.
In the present invention, the manganese-loaded fiber material preferably contains a nitrogen-containing functional group.
In the present invention, the nitrogen-containing functional group preferably includes an amine group and/or an azacycle, more preferably an amine group and an azacycle.
In the present invention, the nitrogen heterocycle is preferably produced after cyclization of one or more of cyano, carbonyl and amine groups.
Specifically, in the present invention, the pre-oxidized amino fiber should preferably contain-n=n-bonds. The modified acrylic fiber of the manganese-loaded fiber material should preferably contain-n=n-bonds.
In the present invention, the acrylic fiber preferably has a length of 30 to 120mm, more preferably 50 to 100mm, and still more preferably 70 to 80mm.
In the present invention, the linear density of the acrylic fiber is preferably 1.4 to 10dtex, more preferably 2.0 to 7dtex, and still more preferably 3 to 5dtex.
In the present invention, the manganese-loaded fiber material preferably includes a manganese-loaded fiber catalyst.
In the present invention, the manganese-loaded fiber catalyst preferably includes a catalyst for ozone catalytic oxidation.
In the present invention, the manganese-loaded fiber material is preferably brown to black in color.
The invention provides a preparation method of a manganese-loaded fiber material, which comprises the following steps:
1) Swelling and grafting the acrylic fiber by using a polyamine-based compound to obtain an amino fiber;
2) Performing thermal oxidation treatment on the amino fiber obtained in the step to obtain pre-oxidized amino fiber;
3) And (3) carrying out potassium permanganate in-situ oxidation on the pre-oxidized amino fiber obtained in the steps by adopting a potassium permanganate in-situ oxidation method to obtain the manganese-carrying fiber material.
According to the invention, acrylic fiber is soaked in a polyamine-based compound, and the fiber is swelled and then reacts to obtain the amino fiber.
In the present invention, the polyamine-based compound preferably includes one or more of ethylenediamine, diethylenetriamine, triethylenetetramine and polyethylenepolyamine, more preferably ethylenediamine, diethylenetriamine, triethylenetetramine or polyethylenepolyamine.
In the present invention, the polyamine-based compound preferably further includes a polyamine-based compound solution. I.e., in the form of a solution of a polyamine-based compound, with acrylic fibers. Specifically, the solvent in the polyamine-based compound solution preferably includes one or more of water, ethylene glycol, propylene glycol, and glycerol, more preferably water, ethylene glycol, propylene glycol, or glycerol. The swelling of the fibers may be carried out directly with an organic amine compound or with a solvent.
In the present invention, the mass ratio of the acrylic fiber to the polyamine-based compound is preferably 1: (5 to 200), more preferably 1: (45 to 160), more preferably 1: (85-120).
In the present invention, the mass ratio of the polyamine-based compound solution to acrylic fiber is preferably (20 to 200): 1, more preferably (60 to 160): 1, more preferably (100 to 120): 1.
in the present invention, the temperature at which the fibers swell is preferably 60 to 80 ℃, more preferably 64 to 76 ℃, and even more preferably 68 to 72 ℃.
In the present invention, the time for swelling the fibers is preferably 4 to 12 hours, more preferably 5 to 11 hours, still more preferably 6 to 10 hours, still more preferably 7 to 9 hours.
In the present invention, the alkali exchange capacity of the amine-based fiber is preferably 3 to 6mmol/g, more preferably 3.5 to 5.5mmol/g, and even more preferably 4 to 5mmol/g.
The invention further carries out thermal oxidation treatment on the amino fiber obtained in the steps to obtain the pre-oxidized amino fiber.
In the present invention, the thermal oxidation treatment is preferably performed in an oxygen-containing gas such as oxygen or air.
In the present invention, the flow rate of the oxygen-containing gas is preferably 100 to 500mL/min, more preferably 150 to 450mL/min, still more preferably 200 to 400mL/min, and still more preferably 250 to 350mL/min.
In the present invention, the heating rate of the thermal oxidation treatment is preferably 2 to 20℃per minute, more preferably 6 to 16℃per minute, and still more preferably 10 to 12℃per minute.
In the present invention, the temperature of the thermal oxidation treatment is preferably 200 to 250 ℃, more preferably 210 to 240 ℃, and even more preferably 220 to 230 ℃.
In the present invention, the time of the thermal oxidation treatment is preferably 0.5 to 4 hours, more preferably 1 to 3.5 hours, still more preferably 1.5 to 3 hours, and still more preferably 2 to 2.5 hours.
Finally, the manganese-carrying fiber material is obtained by in-situ oxidation of the pre-oxidized amino fiber obtained by the steps by adopting a potassium permanganate in-situ oxidation method.
In the in-situ oxidation method of potassium permanganate, the concentration of the potassium permanganate solution is preferably 20 to 100mmol/L, more preferably 30 to 90mmol/L, still more preferably 40 to 80mmol/L, and still more preferably 50 to 70mmol/L.
In the invention, the liquid-solid mass ratio of the pre-oxidized amino fiber in the potassium permanganate solution is preferably (20-200): 1, more preferably (60 to 160): 1, more preferably (100 to 120): 1.
in the present invention, the temperature of the oxidation is preferably 10 to 40 ℃, more preferably 15 to 35 ℃, and even more preferably 20 to 30 ℃.
In the present invention, the time of the oxidation is preferably 0.5 to 12 hours, more preferably 1.5 to 10 hours, still more preferably 2.5 to 8 hours, still more preferably 3.5 to 6 hours.
The invention is a complete and refined integral technical scheme, better ensures the composition, structure and performance of the manganese-loaded fiber material, improves the subsequent catalytic performance in catalytic application, and the preparation method of the manganese-loaded fiber catalyst specifically comprises the following steps:
(1) The process for preparing the amino fiber by chemical grafting comprises the following steps:
firstly, soaking acrylic fiber in one or more solutions of ethylenediamine, diethylenetriamine or triethylenetetramine (specifically, the liquid-solid ratio can be 20-200:1), swelling for 4-12 h at 60-80 ℃, then raising the temperature to 100-150 ℃ for reaction for 1-12 h, washing the fiber to neutrality by deionized water, drying at 60 ℃ to constant weight to obtain amino fiber, and sealing and preserving;
(2) The preparation method of the pre-oxidized amino fiber comprises the following steps:
placing 1-8 g of the amino fiber prepared in the step (1) into a tube furnace, introducing air into a roasting tube at a speed of 100-500 mL/min, heating to 200-250 ℃ at a speed of 2-20 ℃/min, and preserving for 0.5-4 h to prepare the pre-oxidized amino fiber, and sealing and preserving.
In this process, small amounts of uncrosslinked CN groups, grafted amine groups and carbonyl groups undergo cyclization.
(3) The preparation method of the manganese-loaded fiber catalyst comprises the following steps:
taking a certain amount of the pre-oxidized amino fibers prepared in the step (2), soaking the pre-oxidized amino fibers in a potassium permanganate solution, carrying out constant-temperature oscillation reaction for 0.5-12 h at the temperature of 10-40 ℃, wherein the liquid-solid ratio is 20-200:1, and the concentration of the potassium permanganate solution is 20-100 mmol/L; and after the reaction is finished, obtaining the manganese-loaded fiber material, washing the manganese-loaded fiber material with deionized water until the eluate is neutral, drying the manganese-loaded fiber material at 60 ℃ until the weight of the manganese-loaded fiber material is constant, and sealing and preserving the manganese-loaded fiber material.
The manganese-loaded fiber material prepared by the invention is characterized by an intermediate product in the preparation process.
Referring to fig. 1, fig. 1 is an infrared spectrogram of four fibers in the preparation process of the manganese-loaded fiber catalyst. Wherein, (a) acrylic fiber, (b) amino fiber, (c) pre-oxidized fiber, (d) manganese-loaded fiber catalyst.
As can be seen in FIG. 1, the infrared absorption peaks of acrylic fibrils can be marked as: 3437.2cm -1 (γO-H)，2929.2cm -1 And 2867.8cm -1 (CH 3 ，CH 2 Symmetrical and asymmetrical gammac-H in the radical), 1449.6cm -1 (δ s C-H)，1357.3cm -1 (δ s CH 2 )，2241.7cm -1 (γCN)，1729.8cm -1 (γc=o), wherein γ represents stretching vibration, δ s Representing shear vibration.
2241.7cm in the amino fiber grafted and modified by the polyamine compound -1 The gamma CN absorption peak at the sites almost disappeared, which suggests that the grafting reaction mainly occurs on the-CN groups of the acrylic fiber; 3000-3700cm -1 A broader absorption peak occurs in the range due to-NH-and-NH- 2 The N-H absorption peak and the-OH absorption peak are superposed; 1729.8cm -1 The carbonyl absorption peak at the position disappears, which indicates that the ester group in the second monomer acrylate is hydrolyzed along with the progress of the reaction; 1627.6cm -1 A telescopic vibration absorption peak of c=n or c=o, wherein c=o is generated by swelling of acrylic fiber, hydrolysis, crosslinking stage partial-CN and hydrolysis of the-c=n group generated by the reaction, and an N-H deformation vibration absorption peak of amide or secondary amine group; 1550.9cm -1 N-H deformation vibration absorption peaks which are amide or secondary amine groups.
3000-3700cm of pre-oxidized fiber -1 The amine absorption peak in the range is obviously weakened and 1536cm -1 The N-H deformation vibration absorption peak at the wave number is weakened, which indicates that the nitrogen-containing group is changed in the pre-oxidation process and the hydrogen bond in the fiber molecule is destroyed; and 1627.6cm -1 Enhancement of infrared absorption peak at 1433cm -1 The occurrence of the-n=n-stretching vibration absorption peak, which indicates that the c= N, C =o and N-H groups undergo cyclization during the pre-oxidation process, accompanied by the formation of-n=n-; 2929.2cm -1 And 2867.8cm -1 Attenuation of the gamma C-H absorption peak indicates dehydrogenation and cyclization of the fiber during preoxidationAnd (5) carrying out chemical reaction.
2929.2cm in manganese-loaded fiber catalyst -1 And 2867.8cm -1 The complete disappearance of the gamma C-H absorption peak indicates that the fiber continuously undergoes dehydrogenation reaction in the oxidation process of potassium permanganate; and 1428.1cm -1 、1625.9cm -1 、1547.6cm -1 3000-3700cm -1 The significant decrease in the absorption peak indicates that some of the nitrogen-containing groups of the fiber are also removed by oxidation during oxidation of the potassium permanganate, but that the nitrogen-containing basic groups remain in the fiber.
The structural change of the four fibers in the preparation process of the manganese-loaded fiber catalyst can be known, and the amination reaction leads to the introduction of alkaline groups into the fibers and can be reserved in the pre-oxidation and potassium permanganate oxidation processes, so that the prepared manganese-loaded fiber catalyst has rich nitrogen-containing groups; through the preoxidation process, nitrogen heterocycle is generated in the fiber structure, and the nitrogen heterocycle is reserved in the prepared manganese-loaded fiber catalyst, and the group can play a role in synergetic catalysis with manganese oxide, so that the catalytic performance of the manganese-loaded fiber catalyst is obviously improved.
Referring to fig. 2, fig. 2 is a photograph of a manganese oxide-loaded fibrous material prepared according to the present invention in various forms.
As shown in figure 2, the invention selects the acrylic fiber material with rich form and soft texture as the matrix through functionalization, pre-oxidation and KMnO 4 In-situ oxidation process, the fiber-based catalyst which is convenient to fill, has the surface rich in nitrogen-containing groups, has stable heat-resistant oxidation performance, particularly heat-resistant ozone catalytic oxidation performance and excellent catalytic performance, and has the advantages of simple method, mild condition, low energy consumption and the like.
The invention provides the manganese-loaded fiber material prepared by any one of the technical schemes or the preparation method of any one of the technical schemes, and the application of the manganese-loaded fiber material in the catalysis field.
In the present invention, the catalyst preferably includes a catalyst in an ozone oxidation process. Specifically, the ozone oxidation preferably includes ozone oxidation to degrade benzene-based compounds in the gas phase.
In the present invention, the benzene series preferably includes toluene and/or benzene, more preferably toluene or benzene.
In the present invention, the degradation temperature is preferably 90 to 140 ℃, more preferably 100 to 130 ℃, and even more preferably 110 to 120 ℃.
In the present invention, the catalyst is preferably used for catalyzing the oxidative degradation of benzene and toluene by ozone, and the degradation rate is preferably not less than 99%, more preferably not less than 99.5%, and even more preferably not less than 99.7% at a space velocity of 60000 mL/(g.h) and a temperature of 110 ℃.
The invention provides a manganese-loaded fiber catalyst for ozone catalytic oxidation, and a preparation method and application thereof. The invention particularly selects the acrylic fiber material with rich forms and soft texture as the matrix, and adopts functionalization, pre-oxidation and KMnO 4 The fiber-based catalyst which is convenient to fill, large in manganese carrying capacity, rich in nitrogen-containing groups on the surface, stable in heat-resistant oxidation performance, particularly heat-resistant ozone catalytic oxidation performance and excellent in catalytic performance is finally obtained in the in-situ oxidation process, and has important significance for overcoming the defects of the existing catalyst. The manganese-loaded fiber catalyst which is resistant to temperature and rich in nitrogen-containing groups is prepared through functionalization, pre-oxidation and in-situ oxidation, the nitrogen-containing groups on the surface of the catalyst play an important role in improving the catalytic performance of the catalyst, and the preparation method has the advantages of simple process, mild condition, low energy consumption and the like, and is beneficial to industrial popularization and application.
The preparation method can directly take commercial acrylic fiber as a matrix material, prepare the amino fiber by grafting rich amino functional groups on the surface of the acrylic fiber through a chemical grafting method, then place the amino fiber in a tubular furnace to perform heating thermal oxidation in an air atmosphere to obtain the pre-oxidized amino fiber, and prepare the manganese-loaded fiber catalyst by adopting a potassium permanganate in-situ oxidation method. Furthermore, the manganese-loaded fiber catalyst provided by the invention can be used for catalyzing ozone to oxidize and degrade pollutants such as volatile organic compounds, malodorous pollutants and the like, is not limited in form selection, can be any form such as disordered fibers, knitting yarns, needled cloth and knitted cloth, and greatly widens the use depth and breadth of the catalyst.
Experimental results show that the degradation rate of catalyzing ozone to oxidize and degrade benzene and/or toluene by adopting the manganese-loaded fiber catalyst prepared by the invention is not lower than 99% when the airspeed is 60000 mL/(g.h) and the temperature is 110 ℃.
For further explanation of the present invention, the following details of a manganese-loaded fiber material, a preparation method and application thereof are described in conjunction with examples, but it should be understood that these examples are implemented on the premise of the technical scheme of the present invention, and detailed implementation and specific operation procedures are given only for further explanation of the features and advantages of the present invention, and not limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
The commercial acrylic fiber is washed three times with deionized water and dried to constant weight at 60 ℃. Adding 200mL of triethylene tetramine solution into a three-neck flask, weighing 2g of pretreated acrylic fiber immersed in the triethylene tetramine solution, swelling for 12h at 60 ℃, heating to 150 ℃ for reaction for 1h, cooling, washing, drying at 60 ℃ to constant weight, and obtaining amino fiber, wherein the exchange capacity is measured to be 4.63mmol/g; placing 2g of the prepared amino fiber in a tube furnace, introducing air into the tube furnace at a speed of 200mL/min for balancing for 30min, heating to 200 ℃ at a speed of 10 ℃/min, keeping the temperature for 4h, cooling, and sealing and preserving to obtain the pre-oxidized amino fiber; and (3) putting 1g of the pre-oxidized amino fiber into a triangular flask containing 200mL of potassium permanganate solution with the concentration of 20mmol/L, carrying out constant-temperature oscillation reaction for 0.5h at 40 ℃, taking out, washing until the eluate is colorless, and drying at 60 ℃ until the weight is constant, thus obtaining the manganese-loaded fiber catalyst.
The manganese-loaded fiber material prepared in example 1 of the present invention was tested and applied.
The results showed that the manganese content of the fiber was measured to be 56mg/g.
The manganese-loaded fiber catalyst is used for catalyzing the ozone to oxidize and degrade toluene in the gas, and when experimental conditions are as follows: the space velocity is 60000 mL/(g.h), the toluene concentration is 80ppm, the reaction temperature is 110 ℃, the degradation rate of toluene is more than 99% when the ozone concentration is 6.0-7.0 mg/L, and no attenuation phenomenon occurs in 3h of experimental investigation. Under the same conditions, the toluene degradation rate is only 3.1% when the manganese-loaded fiber catalyst is not used.
Example 2
The commercial acrylic fiber is washed three times with deionized water and dried to constant weight at 60 ℃. Adding 400mL of diethylenetriamine solution into a three-necked flask, weighing 2g of pretreated acrylic fiber immersed in the diethylenetriamine solution, swelling for 4 hours at 80 ℃, heating to 100 ℃ for reaction for 12 hours, cooling, washing, drying at 60 ℃ to constant weight to obtain amino fiber, and measuring the exchange capacity of the amino fiber to be 6.08mmol/g; placing 2g of the prepared amino fiber in a tube furnace, introducing air into the tube furnace at a speed of 100mL/min for balancing for 30min, heating to 250 ℃ at a speed of 20 ℃/min, keeping the temperature for 0.5h, cooling, and sealing and preserving to obtain the pre-oxidized amino fiber; putting 1g of pre-oxidized amino fiber into a triangular flask containing 20mL of potassium permanganate solution with the concentration of 100mmol/L, carrying out constant-temperature oscillating reaction for 12h at the temperature of 10 ℃, taking out, washing until the eluate is colorless, and drying at the temperature of 60 ℃ until the weight is constant, thus obtaining the manganese-loaded fiber catalyst.
The manganese-loaded fiber catalyst prepared in example 2 of the present invention was characterized.
Referring to fig. 3, fig. 3 is a Scanning Electron Microscope (SEM) image of the manganese oxide-loaded fibrous material prepared in example 2 of the present invention at different magnifications.
Referring to fig. 4, fig. 4 is a Scanning Electron Microscope (SEM) image of the manganese oxide-loaded fibrous material prepared in comparative example 1 according to the present invention at different magnifications.
As can be seen from the comparison of FIG. 3 and FIG. 4, the fiber catalyst prepared by the invention has more surface ravines, uniform particle distribution, no obvious limit between the particles and the fiber main body skeleton, and is obtained by grafting through chemical reaction; the surface particles of the fiber catalyst prepared in the comparative example 1 are unevenly distributed, and the particles are in an aggregation and stacking state; the two fiber catalysts have large differences in skeleton surface, particle morphology and particle distribution, and the active site morphology formed by the same transition metal or oxide thereof is closely related to the structure thereof, which indicates that the fiber catalysts prepared by the invention have large differences in morphology and structure and active species molecular structure. This also explains why the effect of the fiber catalyst prepared by the invention on the ozone catalytic oxidation degradation of toluene in gas is significantly better than that of the comparative example.
The manganese-loaded fiber material prepared in example 2 of the present invention was tested and applied.
The results showed that the manganese content of the fiber was found to be 241mg/g.
The manganese-loaded fiber catalyst is used for catalyzing the ozone to oxidize and degrade toluene in the gas, and when experimental conditions are as follows: the space velocity is 60000 mL/(g.h), the toluene concentration is 80ppm, the reaction temperature is 110 ℃, the degradation rate of toluene is 100% when the ozone concentration is 6.0-7.0 mg/L, and no attenuation phenomenon occurs in 3h of experimental investigation. Under the same conditions, the toluene degradation rate is only 3.1% when the manganese-loaded fiber catalyst is not used.
Example 3
The commercial acrylic fiber is washed three times with deionized water and dried to constant weight at 60 ℃. Adding 40mL of ethylenediamine solution into a three-neck flask, weighing 2g of pretreated acrylic fiber, immersing in the ethylenediamine solution, swelling for 12h at 60 ℃, heating to 130 ℃ for reaction for 4h, cooling, washing, drying at 60 ℃ to constant weight, and obtaining amino fiber, wherein the exchange capacity is measured to be 3.57mmol/g; placing 2g of the prepared amino fiber in a tube furnace, introducing air into the tube furnace at 500mL/min for balancing for 30min, heating to 220 ℃ at 2 ℃/min, keeping the temperature for 2h, cooling, and sealing and preserving to obtain the pre-oxidized amino fiber; putting 1g of pre-oxidized amino fiber into a triangular flask containing 100mL of potassium permanganate solution with the concentration of 50mmol/L, carrying out constant-temperature oscillating reaction for 6 hours at 25 ℃, taking out, washing until the eluate is colorless, and drying at 60 ℃ until the weight is constant, thus obtaining the manganese-loaded fiber catalyst.
The manganese-loaded fiber material prepared in example 3 of the present invention was tested and applied.
The results showed that the manganese content of the fiber was 113mg/g.
The manganese-loaded fiber catalyst is used for catalyzing the ozone to oxidize and degrade toluene in the gas, and when experimental conditions are as follows: the space velocity is 60000 mL/(g.h), the toluene concentration is 80ppm, the reaction temperature is 110 ℃, the degradation rate of toluene is more than 99% when the ozone concentration is 6.0-7.0 mg/L, and no attenuation phenomenon occurs in 3h of experimental investigation. Under the same conditions, the toluene degradation rate is only 3.1% when the manganese-loaded fiber catalyst is not used.
Example 4
The commercial acrylic fiber is washed three times with deionized water and dried to constant weight at 60 ℃. Adding 400mL of diethylenetriamine solution into a three-necked flask, weighing 2g of pretreated acrylic fiber immersed in the diethylenetriamine solution, swelling for 4 hours at 80 ℃, heating to 100 ℃ for reaction for 12 hours, cooling, washing, drying at 60 ℃ to constant weight to obtain amino fiber, and measuring the exchange capacity of the amino fiber to be 6.08mmol/g; placing 2g of the prepared amino fiber in a tube furnace, introducing air into the tube furnace at a speed of 100mL/min for balancing for 30min, heating to 250 ℃ at a speed of 20 ℃/min, keeping the temperature for 0.5h, cooling, and sealing and preserving to obtain the pre-oxidized amino fiber; putting 1g of pre-oxidized amino fiber into a triangular flask containing 20mL of potassium permanganate solution with the concentration of 100mmol/L, carrying out constant-temperature oscillating reaction for 12h at the temperature of 10 ℃, taking out, washing until the eluate is colorless, and drying at the temperature of 60 ℃ until the weight is constant, thus obtaining the manganese-loaded fiber catalyst.
The manganese-loaded fiber material prepared in example 4 of the present invention was tested and applied.
The results showed that the manganese content of the fiber was found to be 241mg/g.
The manganese-loaded fiber catalyst is used for catalyzing the ozone to oxidize and degrade benzene in gas, and when experimental conditions are as follows: the space velocity is 60000 mL/(g.h), the benzene concentration is 80ppm, the reaction temperature is 110 ℃, the degradation rate of benzene is more than 99% when the ozone concentration is 6.0-7.0 mg/L, and no attenuation phenomenon occurs in 3h of experimental investigation. Under the same conditions, the benzene degradation rate is only 1.5% when the manganese-loaded fiber catalyst is not used.
Comparative example 1
Proved by the importance of the pre-oxidation step in the preparation method, the manganese-loaded fiber catalyst is prepared by adopting a method for directly oxidizing the amino fiber by potassium permanganate.
The commercial acrylic fiber is washed three times with deionized water and dried to constant weight at 60 ℃. Adding 400mL of diethylenetriamine solution into a three-necked flask, weighing 2g of pretreated acrylic fiber immersed in the diethylenetriamine solution, swelling for 4 hours at 80 ℃, heating to 100 ℃ for reaction for 12 hours, cooling, washing, drying at 60 ℃ to constant weight to obtain amino fiber, and measuring the exchange capacity of the amino fiber to be 6.08mmol/g; and (3) putting 1g of amino fiber into a triangular flask containing 20mL of potassium permanganate solution with the concentration of 100mmol/L, carrying out constant-temperature oscillating reaction for 12h at the temperature of 10 ℃, taking out, washing until the eluate is colorless, and drying at the temperature of 60 ℃ to constant weight to obtain the manganese-loaded fiber catalyst.
The manganese-loaded fiber catalyst prepared in comparative example 1 of the present invention was characterized.
Referring to fig. 4, fig. 4 is a Scanning Electron Microscope (SEM) image of the manganese-loaded fiber material prepared in comparative example 1 according to the present invention at different magnifications.
The manganese-loaded fiber material prepared in comparative example 1 of the present invention was tested and applied.
The results showed that the manganese content of the fiber was 262mg/g.
The manganese-loaded fiber catalyst is used for catalyzing the ozone to oxidize and degrade toluene in the gas, and when experimental conditions are as follows: the space velocity is 60000 mL/(g.h), the toluene concentration is 80ppm, the reaction temperature is 110 ℃, and the degradation rate of toluene is less than 43% when the ozone concentration is 6.0-7.0 mg/L. Under the same conditions, the toluene degradation rate is 3.1% when the manganese-loaded fiber catalyst is not used.
Comparative example 2
Preparation and Properties of Carboxylic acid ion exchange fibers [ J ]. Synthetic fiber industry, 2001 (6): 13-17- "carboxyl fiber material is prepared by taking acrylic fiber as matrix fiber, and the exchange capacity is measured to be 6.43mmol/g; putting 1g of carboxyl fiber into a triangular flask containing 20mL of potassium permanganate solution with the concentration of 100mmol/L, carrying out constant-temperature oscillating reaction for 12h at the temperature of 10 ℃, taking out, washing until the eluate is colorless, and drying at the temperature of 60 ℃ to constant weight to obtain the manganese-loaded fiber catalyst.
The manganese-loaded fiber material prepared in comparative example 2 of the present invention was tested and applied.
The results showed that the manganese content of the fiber was 137mg/g.
The manganese-loaded fiber catalyst is used for catalyzing the ozone to oxidize and degrade toluene in the gas, and when experimental conditions are as follows: the space velocity is 60000 mL/(g.h), the toluene concentration is 80ppm, the reaction temperature is 11 ℃ and the degradation rate of toluene is less than 19% when the ozone concentration is 6.0-7.0 mg/L. Under the same conditions, the toluene degradation rate is 3.1% when the manganese-loaded fiber catalyst is not used.
The present invention provides a manganese-loaded fiber catalyst for ozone catalytic oxidation, a preparation method and application thereof, and specific examples are set forth herein to illustrate the principles and embodiments of the present invention, and the description of the examples is only for the purpose of aiding in understanding the method and its core concept, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems, and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (11)
1. The preparation method of the manganese-loaded fiber material is characterized by comprising the following steps of:
1) Swelling and grafting the acrylic fiber by using a polyamine-based compound to obtain an amino fiber;
the polyamine-based compound comprises one or more of ethylenediamine, diethylenetriamine, triethylenetetramine and polyethylenepolyamine;
the mass ratio of the acrylic fiber to the polyamine-based compound is 1: (5-200);
the temperature of the grafting reaction is 100-150 ℃; the grafting reaction time is 1-12 h;
2) Performing thermal oxidation treatment on the amino fiber obtained in the step to obtain pre-oxidized amino fiber;
the thermal oxidation treatment is carried out in an oxygen-containing gas;
the temperature of the thermal oxidation treatment is 200-250 ℃; the time of the thermal oxidation treatment is 0.5-4 hours;
3) And (3) carrying out in-situ oxidation on the pre-oxidized amino fiber obtained in the steps by adopting a potassium permanganate in-situ oxidation method to obtain the manganese-loaded fiber material.
2. The method of producing according to claim 1, wherein the polyamine-based compound further comprises a polyamine-based compound solution;
the solvent in the polyamine-based compound solution comprises one or more of water, ethylene glycol, propylene glycol and glycerol;
the mass ratio of the polyamine-based compound solution to the acrylic fiber is (20-200): 1, a step of;
the swelling temperature of the fibers is 60-80 ℃; the swelling time of the fibers is 4-12 hours;
the alkali exchange capacity of the amino fiber is 3-6 mmol/g.
3. The preparation method according to claim 1, wherein the flow rate of the oxygen-containing gas is 100-500 mL/min;
the heating rate of the thermal oxidation treatment is 2-20 ℃/min;
in the potassium permanganate in-situ oxidation method, the concentration of a potassium permanganate solution is 20-100 mmol/L;
in the potassium permanganate in-situ oxidation method, the liquid-solid mass ratio of the pre-oxidized amino fiber in the potassium permanganate solution is (20-200): 1, a step of;
the in-situ oxidation temperature is 10-40 ℃; the in-situ oxidation time is 0.5-12 h.
4. A manganese-loaded fibrous material according to any one of claims 1 to 3, comprising modified acrylic fibres and oxides of manganese loaded on said modified acrylic fibres.
5. The manganese-loaded fiber material according to claim 4, wherein the manganese content in the manganese-loaded fiber material is 50-250 mg/g;
the morphology of the manganese-loaded fiber material includes one or more of fibrous, mao Xianzhuang, needled cloth, and knitted cloth.
6. The manganese-loaded fiber material according to claim 4, wherein the manganese-loaded fiber material is prepared from pre-oxidized amino fibers through in-situ oxidation grafting of manganese oxide by potassium permanganate to obtain modified acrylic fibers and manganese oxide loaded on the modified acrylic fibers;
the pre-oxidized amino fiber is obtained by thermal oxidation of amino functionalized fiber;
the amino functional fiber is acrylic fiber grafted with amino groups.
7. The manganese-loaded fiber material according to claim 6, wherein the amine groups are grafted onto the acrylic fiber by reacting a polyamine-based compound with-CN groups in the acrylic fiber;
the pre-oxidized amino fiber contains nitrogen-containing functional groups;
the nitrogen-containing functional group comprises an nitrogen heterocycle and/or an amine group;
the nitrogen heterocycle is produced after cyclization of one or more of cyano, carbonyl and amine groups.
8. The manganese-loaded fiber material according to claim 6, wherein the manganese-loaded fiber material comprises a manganese-loaded fiber catalyst;
the manganese-loaded fiber catalyst comprises a catalyst for ozone catalytic oxidation.
9. The manganese-loaded fiber material prepared by the preparation method according to any one of claims 1 to 3 or the application of the manganese-loaded fiber material according to any one of claims 4 to 8 in the field of catalysts.
10. The use according to claim 9, wherein the catalyst comprises a catalyst in an ozone oxidation process;
the ozone oxidation includes ozone oxidation degrading benzene series in the gas phase.
11. The use according to claim 10, wherein the degradation temperature is 90-140 ℃;
the degradation rate of the catalyst for catalyzing the ozone oxidation to degrade benzene and/or toluene is not less than 99% at the air speed of 60000 mL/(g.h) and the temperature of 110 ℃.
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|---|
| 羧酸基腈纶纤维负载MnOx的制备与应用;寇立栋 等;《2018中国环境科学会科学技术年会论文集》;第2卷;第1574-1578页 * |
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