CN114405546A - Manganese-loaded fiber catalyst for catalytic oxidation of ozone and preparation method and application thereof - Google Patents
Manganese-loaded fiber catalyst for catalytic oxidation of ozone and preparation method and application thereof Download PDFInfo
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- CN114405546A CN114405546A CN202210101234.XA CN202210101234A CN114405546A CN 114405546 A CN114405546 A CN 114405546A CN 202210101234 A CN202210101234 A CN 202210101234A CN 114405546 A CN114405546 A CN 114405546A
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- fiber
- manganese
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- oxidation
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- 239000000835 fiber Substances 0.000 title claims abstract description 210
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000011572 manganese Substances 0.000 title claims abstract description 133
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 133
- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 111
- 230000003647 oxidation Effects 0.000 title claims abstract description 108
- 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 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002657 fibrous material Substances 0.000 claims abstract description 72
- 229920002972 Acrylic fiber Polymers 0.000 claims abstract description 64
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 41
- 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 16
- 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 manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 48
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 39
- 230000015556 catabolic process Effects 0.000 claims description 39
- 238000006731 degradation reaction Methods 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 26
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- 238000010438 heat treatment Methods 0.000 claims description 17
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- 239000007789 gas Substances 0.000 claims description 16
- 125000003277 amino group Chemical group 0.000 claims description 15
- 239000004744 fabric Substances 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
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 229910052760 oxygen 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
- 150000001555 benzenes Chemical class 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 210000002268 wool Anatomy 0.000 claims description 7
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000007363 ring formation reaction Methods 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
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- 230000000052 comparative effect Effects 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 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
- 230000010355 oscillation Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
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- 239000002994 raw material Substances 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
- 239000000758 substrate Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000002791 soaking Methods 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
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 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
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 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 Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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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
-
- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
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- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
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- Health & Medical Sciences (AREA)
- Textile Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a manganese-loaded fiber material. The invention particularly selects the soft texture with rich shapeThe acrylic fiber material is used as a matrix and is prepared by functionalization, preoxidation and KMnO4The in-situ oxidation process is a specific preparation route, particularly a pre-oxidation step is adopted, and the finally obtained fiber-based catalyst is convenient to fill, large in manganese carrying capacity, rich in nitrogen-containing groups on the surface, stable in thermal oxidation resistance, particularly in thermal ozone catalytic oxidation resistance, and excellent in catalytic performance, and has important significance for making up the defects of the existing catalyst. The preparation method of the manganese-loaded fiber catalyst has the advantages of simple process, mild conditions, low energy consumption and the like, and is beneficial to industrial popularization and application. The manganese-loaded fiber catalyst provided by the invention can be used for catalyzing ozone oxidation to degrade pollutants, the structure of the manganese-loaded fiber catalyst is not influenced by ozone oxidation, the selection of the form is not limited, and the use depth and the use width of the catalyst are greatly widened.
Description
Technical Field
The invention belongs to the technical field of manganese-loaded materials, relates to a manganese-loaded fiber material, and a preparation method and application thereof, and particularly relates to a manganese-loaded fiber catalyst for catalytic oxidation of ozone, and a preparation method and application thereof.
Background
The research in the field of functionalizing common textile fibers (synthetic fibers and natural fibers) to maintain the original characteristics and advantages of the fibers and having various special properties and purposes has been receiving increasing attention in recent years. The textile fiber has sufficient supply, various varieties and proper price, and is a good raw material source for obtaining new materials. Chemical modification is an important means for functionalizing fibers, and the fibers have new surface chemical properties through chemical reaction of active chemical groups carried by the fibers and certain molecules or ions or through chemical reaction under the assistance of ultrasound, microwaves or heat, so that the fibers have new functions of static resistance, water absorption and moisture retention, adsorption separation, antibiosis, deodorization, catalysis and the like. The chemical modification can be realized by different treatment methods and processes by using different fibers as raw materials.
At present, the supported metal oxide catalyst mostly uses metal oxide or molecular sieve and other porous substances as a substrate, although the catalyst prepared by using the substrate materials has excellent stability and dispersibility, the form of the catalyst is not easy to change, the catalyst is difficult to fill in industrial application, the resistance of a catalyst bed layer is large, most of active sites of the molecular sieve or metal oxide based catalyst are positioned in particles, the influence of an internal diffusion process on the catalytic performance of the catalyst is large in an actual reaction, and meanwhile, particles generated by the reaction are easy to block catalyst pore channels, so that the activity of the catalyst is reduced. Therefore, how to design a new catalyst supporting metal oxide to solve the above problems of the existing catalyst has become one of the focuses of common attention of many research and development enterprises and prospective researchers in the field.
Disclosure of Invention
The invention aims to solve the technical problem of providing a manganese-loaded fiber material, in particular to a manganese-loaded fiber catalyst for catalytic oxidation of ozone, and the manganese-loaded fiber catalyst provided by the invention has the characteristics of convenience in filling, rich nitrogen-containing groups on the surface, stable thermal oxidation resistance, especially thermal ozone catalytic oxidation resistance, excellent catalytic performance and the like, and has important significance for making up 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 beneficial to industrial popularization and application.
In order to realize the purpose of the invention, the adopted specific technical scheme is as follows:
the invention provides a preparation method of a manganese-loaded fiber material, which comprises the following steps:
1) swelling and grafting reaction are carried out on acrylic fiber by utilizing a polyamino compound to obtain amino fiber;
2) carrying out 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 step by adopting a potassium permanganate in-situ oxidation method to obtain the manganese-loaded fiber material.
Preferably, the polyamino compound comprises one or more of ethylenediamine, diethylenetriamine, triethylenetetramine and polyethylene polyamine;
the polyamine-based compound also 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 polyamino compound is 1: (5-200);
the mass ratio of the polyamine compound solution to the acrylic fiber is (20-200): 1;
the swelling temperature of the fiber is 60-80 ℃;
the swelling time of the fiber is 4-12 h;
the reaction temperature 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 by heat treatment 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 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;
the temperature of the oxidation 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, the manganese-loaded fiber material contains 50-250 mg/g of manganese;
the manganese-loaded fiber material is in a form of one or more of a fiber form, a wool form, a needle punched cloth form and a knitted cloth form.
Preferably, the manganese-loaded fiber material is obtained by oxidizing and grafting a manganese oxide in situ by potassium permanganate from a pre-oxidized amino fiber;
the pre-oxidized amino fiber is obtained by thermally oxidizing amino functionalized fiber;
the amino functional fiber is acrylic fiber grafted with amino groups.
Preferably, the amino group is grafted on the acrylic fiber through the reaction of a polyamine compound and a-CN group in the acrylic fiber;
the pre-oxidized amino fiber contains a nitrogen-containing functional group;
the manganese-loaded fiber material contains a nitrogen-containing functional group;
the nitrogen-containing functional group comprises a nitrogen heterocycle and/or an amine group;
the nitrogen heterocycle is generated after cyclization of one or more of a cyano group, a carbonyl group and an amine group.
Preferably, the manganese-loaded fiber material comprises a manganese-loaded fiber catalyst;
the manganese-loaded fiber catalyst comprises a catalyst for catalytic oxidation by ozone;
the manganese-loaded fiber material is brown to black in color.
The invention also provides the application of the manganese-loaded fiber material in any one of the technical schemes or the manganese-loaded fiber material prepared by the preparation method in 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 comprises ozone oxidation degradation of benzene series in the gas phase;
the benzene series comprises toluene and/or benzene;
the degradation temperature is 90-140 ℃;
the catalyst has the degradation rate of catalyzing ozone oxidation degradation of benzene and/or toluene of not less than 99% at the space velocity 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 existing metal oxide catalyst mostly takes metal oxide or porous substances such as molecular sieve and the like as a substrate, the catalyst form is difficult to change, the filling is difficult in industrial application, most active sites are positioned in particles, the influence of an internal diffusion process on the catalytic performance is large, and reaction products are easy to block catalyst pore channels to cause the reduction of the catalyst activity. The invention particularly selects organic fiber materials as catalyst carriers for research, and the prior art hasAlthough there are a few published reports on organic fiber catalysts in the literature, taking fiber materials incorporating oxides of manganese as an example, the study on the preparation of fiber-supported oxides of manganese catalysts and their formaldehyde degradation performance at room temperature (Beijing university of construction, academic thesis 2015) in KMnO4Using methanol to reduce KMnO in situ as precursor4Preparation of MnOxAnd the manganese-loaded oxide fiber catalyst for formaldehyde degradation is prepared by loading the manganese-loaded oxide fiber catalyst on filter cotton (PET), and the oxidative degradation performance of the manganese-loaded oxide fiber catalyst on formaldehyde in the air at room temperature is reported. The patent with the application number of 202010651686.6 discloses a method for manufacturing catalytic oxidative decomposition cationic dye fiber, which comprises the steps of synthesizing polymethacrylate by a solution polymerization method, spinning polymethacrylate fiber with rich hydroxyl on the surface by a wet spinning technology, finally reducing potassium permanganate to generate manganese oxide by using an oxidation-reduction reaction between the hydroxyl on the surface of the fiber and potassium permanganate under an alkaline condition, oxidizing the hydroxyl to generate carboxyl, firmly combining the manganese oxide on the surface of the fiber based on the complexation between the manganese oxide and the carboxyl, preparing a manganese oxide-loaded fiber catalyst for catalytic oxidative decomposition cationic dye, and reporting the catalytic degradation performance of the manganese oxide-loaded fiber catalyst on the cationic dye in an aqueous solution. However, in these documents, the manganese oxide is supported by a direct oxidation-reduction method (the former is external reduction, and the latter is internal group reduction), the catalytic reaction type does not involve ozone catalytic oxidation, and the matrix material is limited to polyester fibers (PET) and polymethacrylate fibers. Although the fiber catalyst prepared by directly carrying out potassium permanganate in-situ oxidation on organic fibers with matrix materials loads manganese oxides on the surfaces of the fibers through the complexation between carboxyl and the manganese oxides, part of the loaded manganese oxides are usually wrapped by carboxyl on the surfaces of the fibers and other organic fragments, so that part of the manganese oxides lose activity in the preparation process, and therefore the catalytic activity of the catalyst prepared by the method is usually low. The catalytic oxidation of ozone, especially at higher temperature, has stronger oxidative degradation performance on organic matters, and the catalyst prepared from organic fibersThe skeleton belongs to organic matter and is easy to be degraded by catalytic oxidation of ozone, thereby destroying the fiber form. Therefore, further research needs to be carried out on how to further optimize the types of organic fibers and the preparation route of the catalyst, so that the organic fibers can be applied to the ozone catalytic oxidation reaction, especially the ozone catalytic oxidation (the oxidation reaction temperature is usually more than 120 ℃) reaction of benzene or toluene and other benzene series with low ozone selectivity, and the heat-resistant ozone catalytic oxidation stability of the manganese-loaded fiber catalyst and the catalytic performance of the manganese-loaded fiber catalyst on the benzene series degraded by ozone oxidation.
Compared with the prior art, the invention has the following positive beneficial effects:
the invention creatively designs a manganese-loaded fiber material with a specific structure and composition. The invention particularly selects acrylic fiber materials with rich forms and soft texture as a matrix, and the acrylic fiber materials are functionalized, pre-oxidized and KMnO4The in-situ oxidation is a specific preparation route, particularly a pre-oxidation step is adopted, and the finally obtained fiber-based catalyst is convenient to fill, large in manganese carrying capacity, rich in nitrogen-containing groups on the surface, stable in thermal oxidation resistance, particularly in thermal ozone catalytic oxidation resistance, and excellent in catalytic performance, and has important significance for making up the defects of the existing catalyst. The manganese-loaded fiber catalyst which is resistant to temperature and catalytic oxidation by ozone and has rich nitrogen-containing groups is prepared through functionalization, pre-oxidation and in-situ oxidation, the rich nitrogen-containing groups on the surface of the catalyst can play a role in catalyzing the oxidation reaction of ozone with manganese oxide in a synergistic manner, and the preparation method has the advantages of simple process, mild conditions, low energy consumption and the like, and is beneficial to industrial popularization and application.
The invention directly takes commercial acrylic fiber as a base material, rich amino functional groups are grafted on the surface of the acrylic fiber by a chemical grafting method to prepare amino fiber, then the amino fiber is put in a tubular furnace to be heated and oxidized in the air atmosphere to obtain amino oxide fiber (namely, pre-oxidized amino fiber), and the pre-oxidized amino fiber is prepared by a potassium permanganate in-situ oxidation method to obtain 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, has no limitation on the selection of forms, can be in any form of disordered fibers, wool, needle punched cloth, knitted cloth and the like, and greatly widens the use depth and the use range of the catalyst.
Experimental results show that the manganese-loaded fiber catalyst prepared by the invention has the degradation rate of catalyzing ozone oxidation degradation benzene and/or toluene, and the degradation rate is not lower than 99% at the airspeed of 60000 mL/(g.h) and the temperature of 110 ℃.
Drawings
FIG. 1 is an infrared spectrum of four fibers in the preparation of a manganese-loaded fiber catalyst according to the present invention;
FIG. 2 is a photograph of a sample of various forms of manganese oxide-loaded fibrous materials prepared in accordance with the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a manganese oxide-loaded fiber material prepared in example 2 of the invention at different magnifications;
FIG. 4 is a Scanning Electron Microscope (SEM) image at different magnifications of a manganese oxide-loaded fibrous material prepared in comparative example 1 of the present invention.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention, and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs a purity which is conventional in the field of analytical purification or 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 invention, the manganese content in the manganese-loaded fiber material is preferably 50-250 mg/g, more preferably 90-210 mg/g, and even more preferably 130-170 mg/g. Wherein, the manganese content is calculated by manganese element.
In the present invention, the supporting means 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 wool form, a needle-punched cloth form, and a knitted cloth form, and more preferably a fibrous form, a wool form, a needle-punched cloth form, or a knitted cloth form. The manganese-loaded fiber material provided by the invention not only can adopt the original random fiber shape, but also can adopt the states of various fiber products, such as a wool shape, a needle punched cloth shape or a knitted cloth shape.
In the invention, the manganese-loaded fiber material is preferably prepared by pre-oxidizing amino fibers, and carrying out in-situ oxidation grafting on manganese oxide by potassium permanganate to obtain modified acrylic fibers and manganese oxide loaded on the modified acrylic fibers. Among them, since most of the cyano groups in the acrylic fiber are on the fiber surface, they are also referred to as surface modification or surface grafting in the art.
In the present invention, the pre-oxidized amino fiber is preferably obtained by thermally oxidizing amino functionalized fiber.
In the present invention, the amino-functionalized fiber is preferably an acrylic fiber grafted with an amino group.
In the present invention, the amino group is preferably grafted on the acrylic fiber by reacting a polyamine compound with a-CN group in the acrylic fiber.
In the present invention, the pre-oxidized amine-based 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 a nitrogen heterocycle, more preferably an amine group and a nitrogen heterocycle.
In the present invention, the nitrogen heterocycle is preferably generated after cyclization of one or more of a cyano group, a carbonyl group and an amine group.
Specifically, in the present invention, the pre-oxidized amine-based fiber should preferably contain an — N ═ N-bond. The modified acrylic fiber of the manganese-loaded fiber material preferably contains-N-bond.
In the invention, the length of the acrylic fiber is preferably 30-120 mm, more preferably 50-100 mm, and even more preferably 70-80 mm.
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 5 dtex.
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 catalytic oxidation by ozone.
In the present invention, the manganese-loaded fiber material preferably has a color of brown to black.
The invention provides a preparation method of a manganese-loaded fiber material, which comprises the following steps:
1) swelling and grafting reaction are carried out on acrylic fiber by utilizing a polyamino compound to obtain amino fiber;
2) carrying out 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 step by adopting a potassium permanganate in-situ oxidation method to obtain the manganese-loaded fiber material.
The invention firstly soaks the acrylic fiber in the polyamine group compound, and the fiber swells and then reacts to obtain the amino fiber.
In the present invention, the polyamino compound preferably includes one or more of ethylenediamine, diethylenetriamine, triethylenetetramine and polyethylenepolyamine, and more preferably ethylenediamine, diethylenetriamine, triethylenetetramine or polyethylenepolyamine.
In the present invention, the polyamine-based compound preferably further includes a polyamine-based compound solution. Namely, the acrylic fiber is reacted with the acrylic fiber in the form of a polyamine-based compound solution. Specifically, the solvent in the polyamino 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 by using an organic amine compound as it is or by using a solvent.
In the present invention, the mass ratio of the acrylic fiber to the polyamino compound is preferably 1: (5-200), more preferably 1: (45-160), more preferably 1: (85-120).
In the invention, the mass ratio of the polyamine compound solution to the acrylic fiber is preferably (20-200): 1, more preferably (60 to 160): 1, more preferably (100 to 120): 1.
in the invention, the swelling temperature of the fiber is preferably 60-80 ℃, more preferably 64-76 ℃, and even more preferably 68-72 ℃.
In the invention, the swelling time of the fiber is preferably 4-12 h, more preferably 5-11 h, more preferably 6-10 h, and more preferably 7-9 h.
In the present invention, the base exchange capacity in the amino fiber is preferably 3 to 6mmol/g, more preferably 3.5 to 5.5mmol/g, and still more preferably 4 to 5 mmol/g.
The amino fiber obtained in the step is subjected to thermal oxidation treatment to obtain the pre-oxidized amino fiber.
In the present invention, the thermal oxidation treatment is preferably performed by performing a heat treatment 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, even more preferably 200 to 400mL/min, and even more preferably 250 to 350 mL/min.
In the present invention, the temperature rise rate of the thermal oxidation treatment is preferably 2 to 20 ℃/min, more preferably 6 to 16 ℃/min, and still more preferably 10 to 12 ℃/min.
In the present invention, the temperature of the thermal oxidation treatment is preferably 200 to 250 ℃, more preferably 210 to 240 ℃, and still more preferably 220 to 230 ℃.
In the present invention, the time for the thermal oxidation treatment is preferably 0.5 to 4 hours, more preferably 1 to 3.5 hours, even more preferably 1.5 to 3 hours, and even more preferably 2 to 2.5 hours.
Finally, carrying out in-situ oxidation on the pre-oxidized amino fiber obtained in the step by adopting a potassium permanganate in-situ oxidation method to obtain the manganese-loaded fiber material.
In the potassium permanganate in-situ oxidation method, the concentration of the potassium permanganate solution is preferably 20-100 mmol/L, more preferably 30-90 mmol/L, further preferably 40-80 mmol/L, and more preferably 50-70 mmol/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 invention, the temperature of the oxidation is preferably 10-40 ℃, more preferably 15-35 ℃, and even more preferably 20-30 ℃.
In the invention, the time for oxidation is preferably 0.5-12 h, more preferably 1.5-10 h, more preferably 2.5-8 h, and more preferably 3.5-6 h.
The invention is a complete and refined integral technical scheme, better ensures the composition, structure and performance of the manganese-loaded fiber material, and improves the subsequent catalytic performance in catalytic application, and the preparation method of the manganese-loaded fiber catalyst can specifically comprise the following steps:
(1) the process for preparing the amino fiber by chemical grafting comprises the following steps:
soaking acrylic fibers 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 heating to 100-150 ℃, reacting for 1-12 h, washing the fibers to neutrality with deionized water, drying at 60 ℃ to constant weight to obtain amino fibers, and sealing and storing;
(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) in a tube furnace, introducing air into a roasting tube at a rate of 100-500 mL/min, heating to 200-250 ℃ at a rate of 2-20 ℃/min, and keeping for 0.5-4 h to prepare the pre-oxidized amino fiber, and sealing and storing.
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:
soaking a certain amount of the pre-oxidized amino fiber prepared in the step (2) in a potassium permanganate solution, and carrying out constant-temperature oscillation reaction for 0.5-12 h at 10-40 ℃, wherein the liquid-solid ratio is 20-200: 1, and the concentration of the potassium permanganate solution is 20-100 mmol/L; after the reaction is finished, the manganese-loaded fiber material is obtained, washed by deionized water until the eluate is neutral, dried at 60 ℃ to constant weight, and sealed for storage.
The manganese-loaded fiber material prepared by the method and the intermediate product in the preparation process are characterized.
Referring to fig. 1, fig. 1 is an infrared spectrum of four fibers in the preparation process of the manganese-loaded fiber catalyst of the present invention. Wherein, (a) acrylic fiber, (b) amino fiber, (c) preoxidized fiber, and (d) manganese-loaded fiber catalyst.
As can be seen from fig. 1, the infrared absorption peaks of the acrylic fibrils in the figure are labeled as: 3437.2cm-1(γO-H)，2929.2cm-1And 2867.8cm-1(CH3，CH2Gammac C-H) symmetrical and asymmetrical in the group) 1449.6cm-1(δs C-H)，1357.3cm-1(δs CH2)，2241.7cm-1(γCN)，1729.8cm-1(γ C ═ O), where γ represents stretching vibration, δsRepresenting shear vibrations.
2241.7cm in amino fiber after graft modification of polyamine compound-1The absorption peak of gamma CN almost disappears, which shows that the grafting reaction mainly occurs on the-CN group of the acrylic fiber; 3000 + 3700cm-1A broad absorption peak appears in the range due to-NH-and-NH2The middle N-H absorption peak and the-OH absorption peak are superposed; 1729.8cm-1The absorption peak of the carbonyl group disappears, which shows that the ester group in the second monomer acrylate is hydrolyzed along with the reaction; 1627.6cm-1A stretching vibration absorption peak of C ═ N or C ═ O and an N-H deformation vibration absorption peak of amide or secondary amine groupOverlapping peaks, wherein C ═ O is due to swelling of the acrylic fiber, hydrolysis, partial-CN in the crosslinking stage and hydrolysis of the-C ═ N group formed by the reaction; 1550.9cm-1The absorption peak of N-H deformation vibration of amide or secondary amine.
3000 + 3700cm in the fiber after pre-oxidation-1The amine group absorption peak in the range was significantly weakened and 1536cm-1The 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 damaged; and 1627.6cm-1Infrared absorption peak enhancement at and 1433cm-1The occurrence of the peak at-N-stretching vibration absorption indicates that the C-N, C-O and N-H groups undergo cyclization reaction during pre-oxidation, accompanied by the formation of-N-; 2929.2cm-1And 2867.8cm-1The attenuation of the gamma C-H absorption peak indicates that the fiber is subjected to dehydrogenation and cyclization reactions in the pre-oxidation process.
2929.2cm in manganese-loaded fiber catalyst-1And 2867.8cm-1The absorption peak at the gamma C-H is completely disappeared, which shows that the fiber is continuously subjected to dehydrogenation reaction in the potassium permanganate oxidation process; and 1428.1cm-1、1625.9cm-1、1547.6cm-1And 3000 + 3700cm-1The obvious reduction of the absorption peak indicates that part of nitrogen-containing groups of the fiber are also removed by oxidation in the potassium permanganate oxidation process, but nitrogen-containing basic groups still remain in the fiber.
According to the structural changes of four fibers in the preparation process of the manganese-loaded fiber catalyst, an alkaline group is introduced into the fibers through amination reaction 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 pre-oxidation process, nitrogen heterocycles are generated in the fiber structure, and the nitrogen heterocycles are reserved in the prepared manganese-loaded fiber catalyst, and the group can play a role in concerted 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 plurality of forms of manganese oxide-loaded fiber materials prepared according to the present invention.
As shown in FIG. 2, the present inventionSelecting acrylic fiber material with rich shape and soft texture as matrix, and performing functionalization, preoxidation and KMnO4The fiber-based catalyst which is convenient to fill, rich in nitrogen-containing groups on the surface, stable in thermal oxidation resistance, especially thermal ozone catalytic oxidation resistance and excellent in catalytic performance is prepared in the in-situ oxidation process, and the preparation method has the advantages of being simple, mild in condition, low in energy consumption and the like.
The invention provides application of the manganese-loaded fiber material in any one of the technical schemes or the manganese-loaded fiber material prepared by the preparation method in any one of the technical schemes in the field of catalysis.
In the present invention, the catalyst preferably includes a catalyst in an ozone oxidation process. Specifically, the ozone oxidation preferably comprises ozone oxidation degradation of benzene series in the gas phase.
In the present invention, the benzene series preferably includes toluene and/or benzene, more preferably toluene or benzene.
In the invention, the degradation temperature is preferably 90-140 ℃, more preferably 100-130 ℃, and even more preferably 110-120 ℃.
In the present invention, the degradation rate of benzene and toluene by catalytic ozonation of the catalyst is preferably not less than 99%, more preferably not less than 99.5%, and still more preferably not less than 99.7% at a space velocity of 60000mL/(g · h) and a temperature of 110 ℃.
The invention provides a manganese-loaded fiber catalyst for catalytic oxidation of ozone, and a preparation method and application thereof. The invention particularly selects acrylic fiber materials with rich forms and soft texture as a matrix, and the acrylic fiber materials are functionalized, pre-oxidized and KMnO4The in-situ oxidation process is a specific preparation route, particularly a pre-oxidation step is adopted, and the finally obtained fiber-based catalyst is convenient to fill, large in manganese carrying capacity, rich in nitrogen-containing groups on the surface, stable in thermal oxidation resistance, particularly in thermal ozone catalytic oxidation resistance, and excellent in catalytic performance, and has important significance for making up the defects of the existing catalyst. The invention prepares the manganese-loaded fiber catalyst which is temperature resistant and rich in nitrogen-containing groups through functionalization, pre-oxidation and in-situ oxidationThe agent and the rich 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 conditions, low energy consumption and the like, and is beneficial to industrial popularization and application.
The invention can directly take commercial acrylic fiber as a base material, graft abundant amino functional groups on the surface of the acrylic fiber by a chemical grafting method to prepare amino fiber, then place the amino fiber in a tubular furnace to carry out heating and thermal oxidation in the air atmosphere to obtain pre-oxidized amino fiber, and prepare the manganese-loaded fiber catalyst from the pre-oxidized amino fiber by 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, the selection of the form is not limited, the manganese-loaded fiber catalyst can be in any form of disordered fibers, wool yarns, needle punched cloth, knitted fabrics and the like, and the use depth and the use range of the catalyst are greatly expanded.
Experimental results show that the manganese-loaded fiber catalyst prepared by the invention has the degradation rate of catalyzing ozone oxidation degradation benzene and/or toluene, and the degradation rate is not lower than 99% at the airspeed of 60000 mL/(g.h) and the temperature of 110 ℃.
For further illustration of the present invention, the following will describe in detail a manganese-loaded fiber material and its preparation method and application in conjunction with the following examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given only for further illustration of the features and advantages of the present invention, not for 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
Washing the commercial acrylic fiber with deionized water for three times, and drying at 60 ℃ to constant weight. Adding 200mL of triethylene tetramine solution into a three-neck flask, weighing 2g of pretreated acrylic fibers, immersing the acrylic fibers in the triethylene tetramine solution at 60 ℃ for swelling for 12 hours, heating to 150 ℃ for reaction for 1 hour, cooling, washing, and drying at 60 ℃ to constant weight to obtain amino fibers, wherein the exchange capacity is measured to be 4.63 mmol/g; placing 2g of the prepared amino fiber in a tubular furnace, introducing air into the tubular furnace at a rate of 200mL/min for balancing for 30min, then heating to 200 ℃ at a rate of 10 ℃/min and keeping the temperature for 4h, cooling, and sealing for storage to obtain pre-oxidized amino fiber; and (2) putting 1g of the pre-oxidized amino fiber into a triangular flask containing 200mL of 20mmol/L potassium permanganate solution, carrying out constant-temperature oscillation reaction at 40 ℃ for 0.5h, taking out, washing with water until eluate is colorless, and drying at 60 ℃ to constant weight to obtain the manganese-loaded fiber catalyst.
The manganese-loaded fiber material prepared in the embodiment 1 of the invention is detected and tested.
The results showed that the manganese content of the fibers was measured to be 56 mg/g.
The manganese-loaded fiber catalyst is used for catalyzing toluene in ozone oxidation degradation gas, and when the experimental conditions are as follows: the air speed is 60000 mL/(g.h), the toluene concentration is 80ppm, the reaction temperature is 110 ℃, the ozone concentration is 6.0-7.0 mg/L, the degradation rate of the toluene is more than 99%, and the attenuation phenomenon does not occur within 3h of experimental investigation. Under the same conditions, when the manganese-loaded fiber catalyst is not used, the toluene degradation rate is only 3.1 percent.
Example 2
Washing the commercial acrylic fiber with deionized water for three times, and drying at 60 ℃ to constant weight. Adding 400mL of diethylenetriamine solution into a three-neck flask, weighing 2g of pretreated acrylic fiber, immersing the acrylic fiber in the diethylenetriamine solution at 80 ℃ for swelling for 4h, heating to 100 ℃ for reaction for 12h, cooling, washing, and drying at 60 ℃ to constant weight to obtain amino fiber, wherein the measured exchange capacity of the amino fiber is 6.08 mmol/g; placing 2g of the prepared amino fiber in a tubular furnace, introducing air into the tubular furnace at a rate of 100mL/min for balancing for 30min, then heating to 250 ℃ at a rate of 20 ℃/min and keeping the temperature for 0.5h, cooling, and sealing for storage to obtain pre-oxidized amino fiber; and (2) putting 1g of the pre-oxidized amino fiber into a triangular flask containing 20mL of a potassium permanganate solution with the concentration of 100mmol/L, carrying out constant-temperature oscillation reaction at 10 ℃ for 12h, taking out, washing with water until an eluate is colorless, and drying at 60 ℃ to constant weight to obtain 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 fiber 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 a manganese oxide-loaded fiber material prepared in comparative example 1 of the present invention at different magnifications.
As can be seen from the comparison between FIG. 3 and FIG. 4, the fiber catalyst prepared by the present invention has many surface ravines, uniform particle distribution, and no obvious boundary between the particles and the fiber main body skeleton, and is obtained by grafting through chemical reaction; the fiber catalyst prepared in the comparative example 1 has uneven surface particle distribution, and the particles are in an aggregated and stacked state; the difference of the framework surfaces, the particle forms and the particle distribution of the two fiber catalysts is large, and the forms of the active sites formed by the same transition metal or the oxide thereof are closely related to the structures of the active sites, which shows that the fiber catalysts prepared by the invention have larger difference with the comparative examples in the form structures and the molecular structures of active species. This also explains the reason why the fiber catalyst prepared by the invention has obviously better effect on the ozone catalytic oxidation degradation of toluene in gas than the comparative example.
The manganese-loaded fiber material prepared in the embodiment 2 of the invention is detected and tested.
The results show that the manganese content in the fiber was measured to be 241 mg/g.
The manganese-loaded fiber catalyst is used for catalyzing toluene in ozone oxidation degradation gas, and when the experimental conditions are as follows: the air speed is 60000 mL/(g.h), the toluene concentration is 80ppm, the reaction temperature is 110 ℃, and the ozone concentration is 6.0-7.0 mg/L, the degradation rate of the toluene is 100%, and the attenuation phenomenon does not occur within 3h of experimental investigation. Under the same conditions, when the manganese-loaded fiber catalyst is not used, the toluene degradation rate is only 3.1 percent.
Example 3
Washing the commercial acrylic fiber with deionized water for three times, and drying at 60 ℃ to constant weight. Adding 40mL of ethylenediamine solution into a three-neck flask, weighing 2g of pretreated acrylic fiber, immersing the acrylic fiber in the ethylenediamine solution at 60 ℃ for swelling for 12h, heating to 130 ℃ for reaction for 4h, cooling, washing, and drying at 60 ℃ to constant weight to obtain amino fiber, wherein the exchange capacity is measured to be 3.57 mmol/g; placing 2g of the prepared amino fiber in a tubular furnace, introducing air into the tubular furnace at a rate of 500mL/min for balancing for 30min, then heating to 220 ℃ at a rate of 2 ℃/min, keeping the temperature for 2h, cooling, and sealing for storage to obtain pre-oxidized amino fiber; and (2) putting 1g of the pre-oxidized amino fiber into a triangular flask containing 100mL of 50mmol/L potassium permanganate solution, carrying out constant-temperature oscillation reaction at 25 ℃ for 6h, taking out, washing with water until eluate is colorless, and drying at 60 ℃ to constant weight to obtain the manganese-loaded fiber catalyst.
The manganese-loaded fiber material prepared in the embodiment 3 of the invention is detected and tested.
The results show that the manganese content in the fiber was measured to be 113 mg/g.
The manganese-loaded fiber catalyst is used for catalyzing toluene in ozone oxidation degradation gas, and when the experimental conditions are as follows: the air speed is 60000 mL/(g.h), the toluene concentration is 80ppm, the reaction temperature is 110 ℃, the ozone concentration is 6.0-7.0 mg/L, the degradation rate of the toluene is more than 99%, and the attenuation phenomenon does not occur within 3h of experimental investigation. Under the same conditions, when the manganese-loaded fiber catalyst is not used, the toluene degradation rate is only 3.1 percent.
Example 4
Washing the commercial acrylic fiber with deionized water for three times, and drying at 60 ℃ to constant weight. Adding 400mL of diethylenetriamine solution into a three-neck flask, weighing 2g of pretreated acrylic fiber, immersing the acrylic fiber in the diethylenetriamine solution at 80 ℃ for swelling for 4h, heating to 100 ℃ for reaction for 12h, cooling, washing, and drying at 60 ℃ to constant weight to obtain amino fiber, wherein the measured exchange capacity of the amino fiber is 6.08 mmol/g; placing 2g of the prepared amino fiber in a tubular furnace, introducing air into the tubular furnace at a rate of 100mL/min for balancing for 30min, then heating to 250 ℃ at a rate of 20 ℃/min and keeping the temperature for 0.5h, cooling, and sealing for storage to obtain pre-oxidized amino fiber; and (2) putting 1g of the pre-oxidized amino fiber into a triangular flask containing 20mL of a potassium permanganate solution with the concentration of 100mmol/L, carrying out constant-temperature oscillation reaction at 10 ℃ for 12h, taking out, washing with water until an eluate is colorless, and drying at 60 ℃ to constant weight to obtain the manganese-loaded fiber catalyst.
The manganese-loaded fiber material prepared in the embodiment 4 of the invention is detected and tested.
The results show that the manganese content in the fiber was measured to be 241 mg/g.
The manganese-loaded fiber catalyst is used for catalyzing benzene in ozone oxidation degradation gas, and when the experimental conditions are as follows: the air speed is 60000 mL/(g.h), the benzene concentration is 80ppm, the reaction temperature is 110 ℃, the ozone concentration is 6.0-7.0 mg/L, the degradation rate of benzene is more than 99%, and the attenuation phenomenon does not occur within 3h of experimental investigation. Under the same conditions, when the manganese-loaded fiber catalyst is not used, the benzene degradation rate is only 1.5 percent.
Comparative example 1
The importance of the pre-oxidation step in the preparation method is proved, and the manganese-loaded fiber catalyst is prepared by adopting a method of directly oxidizing amino fibers by potassium permanganate.
Washing the commercial acrylic fiber with deionized water for three times, and drying at 60 ℃ to constant weight. Adding 400mL of diethylenetriamine solution into a three-neck flask, weighing 2g of pretreated acrylic fiber, immersing the acrylic fiber in the diethylenetriamine solution at 80 ℃ for swelling for 4h, heating to 100 ℃ for reaction for 12h, cooling, washing, and drying at 60 ℃ to constant weight to obtain amino fiber, wherein the measured exchange capacity of the amino fiber is 6.08 mmol/g; and (2) putting 1g of amino fiber into a triangular flask containing 20mL of a potassium permanganate solution with the concentration of 100mmol/L, carrying out constant-temperature oscillation reaction at 10 ℃ for 12h, taking out, washing with water until an eluate is colorless, and drying at 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 of 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 show that the manganese content in the fiber was measured to be 262 mg/g.
The manganese-loaded fiber catalyst is used for catalyzing toluene in ozone oxidation degradation gas, and when the experimental conditions are as follows: the space velocity of 60000 mL/(g.h), the toluene concentration of 80ppm, the reaction temperature of 110 ℃ and the ozone concentration of 6.0-7.0 mg/L, the toluene degradation rate is less than 43%. Under the same conditions, when the manganese-loaded fiber catalyst is not used, the toluene degradation rate is 3.1%.
Comparative example 2
Preparation and Properties of Carboxylic acid type ion exchange fibers according to the reference "Wangjintao, Yuan Kuo, Zhao Lin, et al [ J ] synthetic fiber industry, 2001 (6): 13-17, preparing a carboxyl fiber material by using acrylic fibers as matrix fibers, and measuring the exchange capacity of the carboxyl fiber material to be 6.43 mmol/g; and (2) putting 1g of carboxyl fiber into a triangular flask containing 20mL of a potassium permanganate solution with the concentration of 100mmol/L, carrying out constant-temperature oscillation reaction at 10 ℃ for 12h, taking out, washing with water until an eluate is colorless, and drying at 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 show that the manganese content in the fiber was measured to be 137 mg/g.
The manganese-loaded fiber catalyst is used for catalyzing toluene in ozone oxidation degradation gas, and when the 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 the toluene is less than 19% when the ozone concentration is 6.0-7.0 mg/L. Under the same conditions, when the manganese-loaded fiber catalyst is not used, the toluene degradation rate is 3.1%.
While the present invention has been described in detail with respect to the preparation and application of a manganese-loaded fiber catalyst for catalytic oxidation of ozone, and with reference to specific examples set forth herein, the principles and implementations of the present invention are explained with the aid of examples that are presented only to facilitate an understanding of the methods of the present invention and their core concepts, including the best mode, and 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, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention 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 languages of the claims.
Claims (10)
1. The preparation method of the manganese-loaded fiber material is characterized by comprising the following steps of:
1) swelling and grafting reaction are carried out on acrylic fiber by utilizing a polyamino compound to obtain amino fiber;
2) carrying out 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 step by adopting a potassium permanganate in-situ oxidation method to obtain the manganese-loaded fiber material.
2. The method according to claim 1, wherein the polyamine-based compound comprises one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, and polyethylenepolyamine;
the polyamine-based compound also 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 polyamino compound is 1: (5-200);
the mass ratio of the polyamine compound solution to the acrylic fiber is (20-200): 1;
the swelling temperature of the fiber is 60-80 ℃; the swelling time of the fiber is 4-12 h;
the reaction temperature is 100-150 ℃; the reaction time is 1-12 h;
the alkali exchange capacity in the amino fiber is 3-6 mmol/g.
3. The production method according to claim 1, wherein the thermal oxidation treatment is carried out by heat treatment 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 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;
the temperature of the in-situ oxidation is 10-40 ℃; the time of the in-situ oxidation is 0.5-12 h.
4. The manganese-loaded fiber material is characterized by comprising modified acrylic fibers and manganese oxides loaded on the modified acrylic fibers.
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 manganese-loaded fiber material is in a form of one or more of a fiber form, a wool form, a needle punched cloth form and a knitted cloth form.
6. The manganese-loaded fiber material of claim 4, wherein the manganese-loaded fiber material is prepared by pre-oxidizing amino fibers, in-situ oxidizing and grafting 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 thermally oxidizing 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 group is grafted on the acrylic fiber through the reaction of a polyamine compound and a-CN group in the acrylic fiber;
the pre-oxidized amino fiber contains a nitrogen-containing functional group;
the nitrogen-containing functional group comprises a nitrogen heterocycle and/or an amine group;
the nitrogen heterocycle is generated after cyclization of one or more of a cyano group, a carbonyl group and an amine group.
8. The manganese-loaded fibrous material according to claim 6, wherein the manganese-loaded fibrous material comprises a manganese-loaded fibrous catalyst;
the manganese-loaded fiber catalyst comprises a catalyst for catalytic oxidation by ozone;
the manganese-loaded fiber material is brown to black in color.
9. The manganese-loaded fiber material prepared by the preparation method of any one of claims 1 to 3 or the manganese-loaded fiber material of any one of claims 4 to 8 or the application of the manganese-loaded fiber material in the field of catalysts.
10. The use of claim 9, wherein the catalyst comprises a catalyst in an ozone oxidation process;
the ozone oxidation comprises ozone oxidation degradation of benzene series in the gas phase;
the degradation temperature is 90-140 ℃;
the catalyst has the degradation rate of catalyzing ozone oxidation degradation of benzene and/or toluene of not less than 99% at the space velocity of 60000 mL/(g.h) and the temperature of 110 ℃.
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