CN110947383A - Polyester fiber photodegradation catalyst and preparation method thereof - Google Patents
Polyester fiber photodegradation catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000000835 fiber Substances 0.000 title claims abstract description 35
- 229920000728 polyester Polymers 0.000 title claims abstract description 35
- 238000001782 photodegradation Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002243 precursor Substances 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 19
- 229910052796 boron Inorganic materials 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 150000003751 zinc Chemical class 0.000 claims description 17
- 150000001879 copper Chemical class 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000005083 Zinc sulfide Substances 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 229960004889 salicylic acid Drugs 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 125000005619 boric acid group Chemical group 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 238000004064 recycling Methods 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 238000002144 chemical decomposition reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/72—Copper
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a polyester fiber photodegradation catalyst and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of photodegradation catalysts, in particular to a polyester fiber photodegradation catalyst and a preparation method thereof.
Background
Currently, with the rapid development of economy and technology, the application of polyester fibers is increasingly widespread, and the polyester fiber wastes generated in the forms of clothing textiles, non-woven fabrics and the like are increased year by year. According to statistics, in 2013, the consumption of textile fibers is 3800 ten thousand tons in China every year, and the generated waste textiles are 2350 more than ten thousand tons. However, the main treatment mode of the waste textiles is burying or burning at present, the burying not only needs dozens of years or even hundreds of years for complete degradation, but also needs to waste a large amount of land; incineration causes serious air pollution, so that the recycling of the waste polyester fibers is a necessary trend.
In the past, the recycling technology of waste polyester fiber textiles mainly comprises two types of physical recycling and chemical recycling, wherein the physical recycling is to prepare the waste polyester clothes into secondary products such as household mops and the like through simple processing, and the method greatly reduces the value of fiber materials; the chemical method comprises chemical improvement and chemical degradation, wherein the chemical improvement mainly changes the original ester structure; chemical degradation is a research hotspot at present, and the method, whether neutral hydrolysis or amphoteric hydrolysis, has defects such as low efficiency, high pollution and the like.
Currently, publication No. CN106512983A discloses a preparation method of a catalyst for photodegradation of polyester fibers, which comprises: 1) soaking shell powder and attapulgite in acid liquor, filtering to obtain filter cake to obtain active substance; 2) placing soluble cerium salt, tantalum pentachloride, graphene oxide, hydrazine hydrate, water and an activator in a closed environment for hydrothermal reaction, and filtering to remove a filter cake to obtain a hydrothermal product; 3) and (3) putting the hydrothermal product into a molybdate aqueous solution for soaking, and then drying and roasting to obtain the catalyst for photodegrading the polyester fiber. Although the catalyst has excellent photodegradation efficiency for polyester fibers in the presence of visible light or infrared light, the catalyst has a disadvantage that the photodegradation efficiency of polyester fibers is rapidly reduced after the catalyst is recycled for 4 to 5 times.
Disclosure of Invention
In view of the above, the present invention aims to provide a polyester fiber photodegradation catalyst and a preparation method thereof, wherein the polyester fiber photodegradation catalyst has excellent stability and can be reused for multiple times, and the preparation method has the characteristics of easily available raw materials and convenient operation.
The preparation method of the polyester fiber photodegradation catalyst based on the aim comprises the following steps:
carrying out hydrothermal reaction on titanyl sulfate, urea, copper salt, zinc salt and water in a closed environment, and crushing a reaction product to obtain a precursor;
carrying out ball milling on a carbon source, a boron source and the precursor to obtain an intermediate;
and calcining the intermediate under the condition of protective gas to prepare the polyester fiber photodegradation catalyst.
Optionally, the use ratio of the titanyl sulfate to the urea to the copper salt to the zinc salt to the water is 2 mmol: 0.5-1 mmol: 0.002-0.008 mmol, 0.001-0.004 mmol, 1-2 mL.
Optionally, the reaction temperature of the hydrothermal reaction is 115-125 ℃, and the reaction time is 1.5-2 h.
Optionally, the molar ratio of the precursor to the carbon source to the boron source is 1: 0.005-0.01: 0.001 to 0.004.
Optionally, the ball milling speed is 1500-1800 rpm, and the ball milling time is 20-30 min.
Optionally, the zinc salt is a soluble zinc salt, and the soluble zinc salt is at least one of zinc sulfate, zinc sulfide and zinc nitrate.
Optionally, the copper salt is a soluble copper salt, and the soluble copper salt is at least one of copper sulfate, copper sulfide and copper nitrate.
Optionally, the carbon source is selected from at least one of ascorbic acid, salicylic acid, glucose, sucrose, oxalic acid and adipic acid; the boron source is boric acid and/or borax.
Optionally, the calcining temperature of the calcining is 800-850 ℃, and the calcining time is 2-3 h.
The polyester fiber photodegradation catalyst is prepared by the preparation method.
From the above, according to the preparation method of the polyester fiber photodegradation catalyst provided by the invention, firstly, the copper and zinc doped metatitanic acid is prepared by a uniform precipitation method, then, the carbon and boron are doped in a solid phase, and finally, the co-doped nano titanium dioxide is prepared by a calcination method, and the nano titanium dioxide has the characteristics of poisoning inhibition and pore channel blockage inhibition, so that the catalyst has excellent stability, and can be repeatedly used for many times.
Detailed Description
In the following description of the embodiments, the detailed description of the present invention, such as the manufacturing processes and the operation and use methods, will be further described in detail to help those skilled in the art to more fully, accurately and deeply understand the inventive concept and technical solutions of the present invention.
In order to solve the problem that the photodegradation efficiency of polyester fibers is sharply reduced after the catalyst for degrading the polyester fibers is recycled for 4-5 times in the prior art, the invention provides a preparation method of the catalyst for degrading the polyester fibers, which comprises the following steps:
carrying out hydrothermal reaction on titanyl sulfate, urea, copper salt, zinc salt and water in a closed environment, and crushing a reaction product to obtain a precursor;
carrying out ball milling on a carbon source, a boron source and the precursor to obtain an intermediate;
and calcining the intermediate under the condition of protective gas to prepare the polyester fiber photodegradation catalyst.
Firstly, a copper and zinc doped metatitanic acid precursor is prepared by a uniform hydrothermal precipitation method, then carbon and boron are doped in a solid phase, and finally co-doped nano titanium dioxide is prepared by a calcination method, and the nano titanium dioxide has the characteristics of inhibiting poisoning and pore channel blockage, so that the catalyst has excellent stability and can be repeatedly used.
In the above preparation method, the amount of each material may be selected within a wide range, but in order to further improve the catalytic performance and stability of the catalyst, it is preferable that the ratio of the amounts of titanyl sulfate, urea, copper salt, zinc salt and water is 2 mmol: 0.5-1 mmol: 0.002-0.008 mmol: 0.001-0.004 mmol: 1-2 mL.
In the above preparation method, the conditions of the hydrothermal reaction may be selected within a wide range, but in order to further improve the catalytic performance and stability of the catalyst, it is preferable that the hydrothermal reaction satisfies the following conditions: the reaction temperature is 115-125 ℃, and the reaction time is 1.5-2 h.
In the above-mentioned production method, the kind of the copper salt may be selected within a wide range, but in order to further improve the catalytic performance and the stability of the catalyst, it is preferable that the copper salt is soluble and is selected from at least one of copper sulfate, copper sulfide, and copper nitrate.
In the above-mentioned production method, the kind of the zinc salt may be selected from a wide range, but in order to further improve the catalytic performance and the stability of the catalyst, it is preferable that the zinc salt is soluble and is selected from at least one of zinc sulfate, zinc sulfide, and zinc nitrate.
In the above preparation method, the amount of each material may be selected within a wide range, but in order to further improve the catalytic performance and stability of the catalyst, it is preferable that the molar ratio of the precursor, the carbon source, and the boron source is 1: 0.005-0.01: 0.001 to 0.004.
In the above preparation method, the conditions for the ball milling may be selected within a wide range, but in order to further improve the catalytic performance and stability of the catalyst, it is preferable that the ball milling satisfies the following conditions: the rotating speed is 1500-1800 rpm, and the ball milling time is 20-30 min.
In the above production method, the kinds of the carbon source and the boron source may be selected within a wide range, but in order to further improve the catalytic performance and the stability performance of the catalyst, preferably, the carbon source is selected from at least one of ascorbic acid, salicylic acid, glucose, sucrose, oxalic acid, and adipic acid; the boron source is selected from boric acid and/or borax.
In the above preparation method, the conditions of calcination may be selected within a wide range, but for further catalytic performance and stability performance of the catalyst, it is preferable that calcination satisfies the following conditions: the calcination temperature is 800-850 ℃, and the calcination time is 2-3 h.
The invention also provides a polyester fiber photodegradation catalyst which is prepared by the preparation method. Has good catalytic performance and stability.
Specifically, the polyester fiber photodegradation catalyst in embodiment 1 of the present invention is prepared by the following preparation method, including the steps of: copper sulfate, soluble zinc salt: zinc sulfate and water were added as 2 mmol: 0.8 mmol: 0.006 mmol: 0.003 mmol: 1.5mL of the catalyst is subjected to hydrothermal reaction in a closed environment, the reaction temperature is 120 ℃, the reaction time is 1.8h, and a reaction product is crushed to obtain a precursor;
carbon source: ascorbic acid, boron source: boric acid and a precursor, wherein the molar ratio of the precursor to a carbon source to a boron source is 1: 0.008: ball milling is carried out for 0.003, the rotating speed is 1600rpm, and the ball milling time is 25min, so as to obtain an intermediate;
and calcining the intermediate under the condition of protective gas, wherein the calcining temperature is 830 ℃, and the calcining time is 2.5h to prepare the polyester fiber photodegradation catalyst 1.
Specifically, the polyester fiber photodegradation catalyst in embodiment 2 of the present invention is prepared by the following preparation method, in which titanyl sulfate, urea, and a soluble copper salt are: copper sulfide, soluble zinc salt: zinc sulphide and water were added as 2 mmol: 0.5 mmol: 0.002 mmol:0.001 mmol: 1mL of the precursor is subjected to hydrothermal reaction in a closed environment, the reaction temperature is 115 ℃, the reaction time is 2 hours, and a reaction product is crushed to obtain a precursor;
carbon source: salicylic acid, boron source: boric acid and a precursor, wherein the molar ratio of the precursor to a carbon source to a boron source is 1: 0.005: 0.001, performing ball milling at the rotating speed of 1500rpm for 30min to obtain an intermediate;
and calcining the intermediate under the condition of protective gas at 800 ℃ for 3h to obtain the polyester fiber photodegradation catalyst 2.
Specifically, the polyester fiber photodegradation catalyst in embodiment 3 of the present invention is prepared by the following preparation method, in which titanyl sulfate, urea, and a soluble copper salt are: copper nitrate, soluble zinc salt: zinc nitrate and water were added as 2 mmol:1 mmol: 0.008mmol: 0.004mmol: 2mL of the precursor is subjected to hydrothermal reaction in a closed environment at the reaction temperature of 125 ℃ for 1.5h, and the reaction product is crushed to obtain a precursor;
carbon source: adipic acid, boron source: boric acid and a precursor, wherein the molar ratio of the precursor to a carbon source to a boron source is 1: 0.01: ball milling is carried out for 0.004, the rotating speed is 1800rpm, and the ball milling time is 20min, so as to obtain an intermediate;
and calcining the intermediate under the condition of protective gas at 850 ℃ for 2h to obtain the polyester fiber photodegradation catalyst 3.
In comparative example 1, catalyst 4 was prepared by the method described in example 1 of patent publication No. CN 106512983A.
Comparative example 2, catalyst 5 prepared according to example 1, except that no carbon source was added.
Comparative example 3, catalyst 6 prepared according to example 1 except that no boron source was added.
Comparative example 4, catalyst 7 prepared according to example 1 except that no copper source was added.
Comparative example 5 catalyst 8, prepared according to example 1, except that no zinc source was added.
Comparative example 6, catalyst 9 prepared according to example 1 except that it was not calcined.
Application example 1
In the presence of visible light or infrared ray, polyester fiber, hexadecyl trimethyl ammonium bromide, the catalyst and water are mixed according to the proportion of 100: 30: 1: 500, filtering degradation products, washing and filtering a sodium hydroxide solution with the mass fraction of 10% to obtain a solid, weighing the final solid to calculate the degradation rate, performing repeated degradation catalysis under the same condition by adopting the catalyst, and calculating the degradation rate after repeated degradation, wherein the degradation rate is performed by adopting the following formula,
the specific degradation results and degradation conditions are shown in the table below.
As can be seen from the examples, the comparative examples and the application examples, the catalyst provided by the invention has excellent catalytic performance and stability for the photodegradation of polyester fibers.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also features in the above embodiments or in different embodiments may be combined, steps may be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The embodiments of the invention are intended to embrace all such alternatives, modifications and variances that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A preparation method of a polyester fiber photodegradation catalyst is characterized by comprising the following steps:
carrying out hydrothermal reaction on titanyl sulfate, urea, copper salt, zinc salt and water in a closed environment, and crushing a reaction product to obtain a precursor;
carrying out ball milling on a carbon source, a boron source and the precursor to obtain an intermediate;
and calcining the intermediate under the condition of protective gas to prepare the polyester fiber photodegradation catalyst.
2. The method according to claim 1, wherein the ratio of the titanyl sulfate, urea, copper salt, zinc salt and water is 2 mmol: 0.5-1 mmol: 0.002-0.008 mmol: 0.001-0.004 mmol: 1-2 mL.
3. The preparation method according to claim 1, wherein the reaction temperature of the hydrothermal reaction is 115 to 125 ℃ and the reaction time is 1.5 to 2 hours.
4. The method according to claim 1, wherein the molar ratio of the precursor to the carbon source to the boron source is 1: 0.005-0.01: 0.001 to 0.004.
5. The preparation method of claim 1, wherein the ball milling rotation speed is 1500-1800 rpm, and the ball milling time is 20-30 min.
6. The preparation method according to claim 1, wherein the zinc salt is a soluble zinc salt, and the soluble zinc salt is at least one of zinc sulfate, zinc sulfide and zinc nitrate.
7. The method according to claim 1, wherein the copper salt is a soluble copper salt, and the soluble copper salt is at least one of copper sulfate, copper sulfide, and copper nitrate.
8. The method according to claim 1, wherein the carbon source is at least one selected from the group consisting of ascorbic acid, salicylic acid, glucose, sucrose, oxalic acid and adipic acid; the boron source is boric acid and/or borax.
9. The preparation method according to claim 1, wherein the calcination temperature is 800-850 ℃ and the calcination time is 2-3 h.
10. A polyester fiber photodegradation catalyst, which is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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