CN111268751B - Preparation method of polyacid-based yarn for catalyzing organic pollutants - Google Patents
Preparation method of polyacid-based yarn for catalyzing organic pollutants Download PDFInfo
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- CN111268751B CN111268751B CN201911200202.XA CN201911200202A CN111268751B CN 111268751 B CN111268751 B CN 111268751B CN 201911200202 A CN201911200202 A CN 201911200202A CN 111268751 B CN111268751 B CN 111268751B
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- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003607 modifier Substances 0.000 claims abstract description 7
- -1 quaternary ammonium salt cation Chemical class 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 229910001868 water Inorganic materials 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229920000447 polyanionic polymer Polymers 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000000149 penetrating effect Effects 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims 1
- 238000011068 loading method Methods 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 239000004744 fabric Substances 0.000 abstract description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009956 embroidering Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000013460 polyoxometalate Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- D06M11/36—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 oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- 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
- D06M13/46—Compounds containing quaternary nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Silicon Compounds (AREA)
- Catalysts (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a preparation method of polyacid-based yarns for catalyzing organic pollutants, which comprises the steps of carrying out cation modification on yarns and loading poly tungstate with catalytic performance; the principle comprises two parts, namely, firstly, carrying out cation modification on the yarn, namely, putting the yarn into a container, and then adding a micromolecular quaternary ammonium salt cation modifier to carry out modification treatment on the yarn; mixing the modified yarn with a polyacid precursor, and loading polyacid on the yarn under the action of electrostatic attraction; the functional yarn prepared by the method shows high-efficiency catalytic performance, can catalyze and degrade organic pollutants, can be recycled by further processing the yarn prepared by the method to form a fabric, is used for catalyzing and degrading the organic pollutants, and has practical value.
Description
Technical Field
The invention belongs to the development of functional yarns, and relates to a method for preparing polyacid modified yarns.
Background
Under the condition, the photocatalysis technology comes along with the operation, and the environment pollution crisis can be relieved by selecting a proper catalyst to catalyze organic wastewater.
The polyoxometalate anion (polyacid for short) is a compound formed from0The complex formed by connecting V, Nb, Ta, Mo, W and other atoms in electronic configuration through oxygen atoms has high reaction activity in a homogeneous catalysis system due to the unique molecular structure, and is non-toxic and pollution-free; most organic pollutants can be completely mineralized into CO by polyacid2、H2O、Cl-And (3) inorganic small molecules, but the homogeneous system has obvious defects: the specific surface area is small, the thermal stability of part of polyacid is poor, most polyacid is easily dissolved in a polar solvent, and the separation is difficult; one of the methods to solve this problem is to find a suitable carrier to carry the polyacid. Therefore, a proper load material is urgently needed to prepare the polyacid composite material with high catalytic activity and repeatability.
The yarn is a textile used for various products such as weaving, knitting, embroidering and the like, can be used as a novel carrier material, can be further processed into functional fabric after being subjected to multi-acid functional modification, and is used for catalyzing and degrading organic pollutants.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a preparation method of polyacid-based yarn for catalyzing organic pollutants, aiming at solving the defects in the prior art, cation modification is carried out on the yarn, and poly tungstate with catalytic performance is loaded; the principle comprises two parts, specifically as follows:
firstly, performing cationic modification on the yarn. Putting the yarns into a container, and then adding a small molecular quaternary ammonium salt cationic modifier to modify the yarns;
and secondly, mixing the modified yarn with polyacid, and loading the polyacid on the yarn through the action of electrostatic attraction.
The technical scheme is as follows: in order to achieve the aim, the invention provides a preparation method of a polyacid-based yarn for catalyzing organic pollutants, which comprises the following specific steps:
step 1, soaking the yarn with ethanol, removing surface attachments, washing with water, and airing for later use;
step 2, dissolving 0.5-5 g/L of sodium hydroxide, 2-10 g/L of penetrating agent and 10-100 g/L of quaternary ammonium salt cation modifier in deionized water, and stirring and mixing uniformly to obtain a mixed solution;
step 3, adding the yarns obtained in the step 1 into the mixed solution obtained in the step 2, heating the mixed solution to 60-80 ℃, preserving heat for 10 seconds, firstly carrying out two-dipping and two-rolling on the yarns, and then drying the yarns, wherein the dried yarns are reserved;
and 4, mixing the cation-modified yarn obtained in the step 3 with 10-50 g/L polyacid precursor solution, combining positive charges on the yarn with the polyanion of the polyacid through ionic bonds, permeating the polyanion of the polyacid into molecules through gaps, loading the polyanion of the polyacid on the yarn, stirring for 5-8 hours at room temperature, taking out, washing, and evaporating and airing at room temperature.
Preferably, the polyacid precursor in the polyacid precursor solution in step 4 is K4[PW11Fe(H2O)O39]·6H2O，K5[SiW11Fe(H2O)O39]·9H2O，K6[BW11Fe(H2O)O39]·9H2O and K4[PW11Mn(H2O)O39]·6H2O。
Preferably, the solvent used for washing in step 4 is water and diethyl ether.
Has the advantages that: according to the preparation method of the polyacid-based yarn for catalyzing organic pollutants, the functional yarn prepared by the method shows high-efficiency catalytic performance, can catalyze and degrade the organic pollutants, and the yarn prepared by the method is further processed into a fabric, can be recycled, is used for catalyzing and degrading the organic pollutants, and has practical value.
Detailed Description
Example 1
A preparation method of polyacid-based yarn for catalyzing organic pollutants comprises the following specific steps:
step 1, soaking the yarn with ethanol, removing surface attachments, washing with water, and airing for later use;
step 2, dissolving 4 g/L of sodium hydroxide, 5 g/L of penetrating agent and 50 g/L of quaternary ammonium salt modifier in deionized water, and stirring and mixing uniformly to obtain a mixed solution;
step 3, adding the yarns obtained in the step 1 into the mixed solution obtained in the step 2, heating to 80 ℃, preserving heat for 10 seconds, soaking twice, rolling twice, and drying for later use;
and 4, mixing the cation-modified yarn obtained in the step 3 with 20 g/L polyacid precursor solution, combining positive charges on the yarn with the polyanion of the polyacid through ionic bonds, permeating the polyanion of the polyacid into molecules through gaps, loading the polyanion of the polyacid on the yarn, stirring for 8 hours at room temperature, taking out, washing with water and ether, and evaporating and airing at room temperature.
Further in this embodiment, the polyacid precursor in the polyacid precursor solution in step 4 is K4[PW11Fe(H2O)O39]·6H2O，K5[SiW11Fe(H2O)O39]·9H2O，K6[BW11Fe(H2O)O39]·9H2O and K4[PW11Mn(H2O)O39]·6H2O。
Example 2
Step 1, soaking the yarn with ethanol, removing surface attachments, washing with water, and airing for later use;
step 2, dissolving 4 g/L of sodium hydroxide, 5 g/L of penetrating agent and 20 g/L of quaternary ammonium salt modifier in deionized water, and stirring and mixing uniformly to obtain a mixed solution;
step 3, adding the yarns obtained in the step 1 into the mixed solution obtained in the step 2, heating to 80 ℃, preserving heat for 10 seconds, soaking twice, rolling twice, and drying for later use;
and 4, mixing the cation-modified yarn obtained in the step 3 with 20 g/L polyacid precursor solution, combining positive charges on the yarn with the polyanion of the polyacid through ionic bonds, permeating the polyanion of the polyacid into molecules through gaps, loading the polyanion of the polyacid on the yarn, stirring for 8 hours at room temperature, taking out, washing with water and ether, and evaporating and airing at room temperature.
Further in this embodiment, the polyacid precursor in the polyacid precursor solution in step 4 is K4[PW11Fe(H2O)O39]·6H2O，K5[SiW11Fe(H2O)O39]·9H2O，K6[BW11Fe(H2O)O39]·9H2O and K4[PW11Mn(H2O)O39]·6H2O。
Example 3
Step 1, soaking the yarn with ethanol, removing surface attachments, washing with water, and airing for later use;
step 2, dissolving 5 g/L of sodium hydroxide, 5 g/L of penetrating agent and 20 g/L of quaternary ammonium salt modifier in deionized water, and stirring and mixing uniformly to obtain a mixed solution;
step 3, adding the yarns obtained in the step 1 into the mixed solution obtained in the step 2, heating to 80 ℃, preserving heat for 10 seconds, soaking twice, rolling twice, and drying for later use;
and 4, mixing the cation-modified yarn obtained in the step 3 with 30 g/L polyacid precursor solution, combining positive charges on the yarn with the polyanion of the polyacid through ionic bonds, permeating the polyanion of the polyacid into molecules through gaps, loading the polyanion of the polyacid on the yarn, stirring for 8 hours at room temperature, taking out, washing with water and ether, and evaporating and airing at room temperature.
Further in this embodiment, the polyacid precursor in the polyacid precursor solution in step 4 is K4[PW11Fe(H2O)O39]·6H2O，K5[SiW11Fe(H2O)O39]·9H2O，K6[BW11Fe(H2O)O39]·9H2O and K4[PW11Mn(H2O)O39]·6H2O。
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (2)
1. A preparation method of polyacid-based yarn for catalyzing organic pollutants is characterized by comprising the following steps: the method comprises the following specific steps:
step 1, soaking the yarn with ethanol to remove surface attachments, washing with water, and airing for later use;
step 2, dissolving 0.5-5 g/L of sodium hydroxide, 2-10 g/L of penetrating agent and 10-100 g/L of quaternary ammonium salt cation modifier in deionized water, and stirring and mixing uniformly to obtain a mixed solution;
step 3, adding the yarns obtained in the step 1 into the mixed solution obtained in the step 2, heating the mixed solution to 60-80 ℃, preserving heat for 10 seconds, firstly carrying out two-dipping and two-rolling on the yarns, and then drying the yarns, wherein the dried yarns are reserved;
step 4, mixing the cation-modified yarn obtained in the step 3 with 10-50 g/L polyacid precursor solution, enabling positive charges on the yarn to be combined with the polyanion of the polyacid through ionic bonds, enabling the polyanion of the polyacid to permeate into molecules through gaps, enabling the polyanion of the polyacid to be loaded on the yarn, stirring for 5-8 hours at room temperature, taking out, washing, and evaporating and airing at room temperature; the polyacid precursor in the polyacid precursor solution is K4[PW11Fe(H2O)O39]·6H2O，K5[SiW11Fe(H2O)O39]·9H2O，K6[BW11Fe(H2O)O39]·9H2O and K4[PW11Mn(H2O)O39]·6H2O。
2. The method for preparing the polyacid-based yarn for catalyzing organic pollutants as claimed in claim 1, wherein: the solvents adopted in the washing in the step 4 are water and diethyl ether.
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| CN201911200202.XA CN111268751B (en) | 2019-11-29 | 2019-11-29 | Preparation method of polyacid-based yarn for catalyzing organic pollutants |
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| CN112227068A (en) * | 2020-08-24 | 2021-01-15 | 南通花园布业有限公司 | Preparation method of flame-retardant yarn based on polyoxometallate |
| CN112844429B (en) * | 2021-01-11 | 2021-11-19 | 吉林医药学院 | Preparation method of supported dimer heteropoly acid quaternary ammonium salt catalyst |
| CN112900098A (en) * | 2021-01-22 | 2021-06-04 | 南通大学 | Photocatalytic self-cleaning functional cotton fabric and preparation method thereof |
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| CN101884917A (en) * | 2010-06-29 | 2010-11-17 | 于建强 | Method for preparing composite fiber material for visible light photocatalytic degradation of organic pollutants |
| CN103111335B (en) * | 2013-01-11 | 2014-10-08 | 长春理工大学 | Ionic crystal type visible-light-induced photocatalyst based on Dawson type poly-tungstate and preparation method thereof |
| CN106179262B (en) * | 2016-07-08 | 2018-07-20 | 苏州大学 | Composite material and preparation method and purposes with absorption-visible light photocatalytic degradation synergistic effect |
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Address after: 226000 No.88, hantongdao, Binjiang New District, Tongzhou District, Nantong City, Jiangsu Province Patentee after: Nantong Hongwei Textile Co.,Ltd. Address before: 226000 No.88, hantongdao, Binjiang New District, Tongzhou District, Nantong City, Jiangsu Province Patentee before: TIANHONGYINHAI INDUSTRY Co.,Ltd. |