CN111774091B - Material for photocatalytic degradation of printing and dyeing wastewater and preparation method thereof - Google Patents
Material for photocatalytic degradation of printing and dyeing wastewater and preparation method thereof Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 60
- 238000004043 dyeing Methods 0.000 title claims abstract description 56
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 55
- 238000007639 printing Methods 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 32
- 239000000835 fiber Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 238000011282 treatment Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000011941 photocatalyst Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 7
- 230000001699 photocatalysis Effects 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003623 enhancer Substances 0.000 claims description 9
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
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- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
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- 230000015556 catabolic process Effects 0.000 description 5
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- 238000007254 oxidation reaction Methods 0.000 description 5
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- ZJOKNSFTHAWVKK-UHFFFAOYSA-K aluminum octadecanoate sulfate Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Al+3].S(=O)(=O)([O-])[O-] ZJOKNSFTHAWVKK-UHFFFAOYSA-K 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
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- 238000012512 characterization method Methods 0.000 description 2
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- 239000012535 impurity Substances 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
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- 238000000643 oven drying Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009999 singeing Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
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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
- 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
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/61—
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a material for photocatalytic degradation of printing and dyeing wastewater and a preparation method thereof, wherein a washing liquid prepared by mixing an alcohol organic solvent, water and sodium dodecyl benzene sulfonate is adopted to wash rush fibers, the washed rush fibers are sequentially subjected to alkalization and carboxymethylation treatment, and then the rush fibers are subjected to electrostatic self-assembly with graphene oxide or metal oxide and g-C 3 N 4 Combining to form the binary mixed modified rush composite photocatalyst. The invention utilizes the natural, regular and uniform three-dimensional reticular pore canal structure in the rush and the high specific surface area, and can greatly improve the loading capacity of the composite photocatalyst, thereby having stronger adsorption effect on harmful substances in the printing and dyeing wastewater so as to cooperatively improve the photocatalytic degradation performance on the printing and dyeing wastewater. The preparation method is simple to operate, the reaction conditions are easy to control, the cost is low, the purification efficiency is high, and the preparation method has potential industrial application prospect.
Description
Technical Field
The invention relates to the technical field of printing and dyeing wastewater treatment, in particular to a material for photocatalytic degradation of printing and dyeing wastewater and a preparation method thereof.
Background
At present, water resources in China are polluted to different degrees, and the situation is continuously aggravated. Especially in recent years, the textile industry develops rapidly, the yield and the quality of the textile industry are greatly improved, the textile industry becomes one of the industrial departments with the largest water consumption and the largest wastewater discharge in China, and the use of dyes is also developing towards the directions of photolysis resistance, oxidation resistance and biodegradation resistance, so that the generated printing and dyeing wastewater becomes one of the heavy-point pollution sources of the water environment. And the dye wastewater has the characteristics of complex composition, large water quantity and water quality change, high chromaticity, high salt content, poor biodegradability and the like, so that the dye wastewater has gradually developed into a major problem which is urgently needed to be solved in the current domestic and foreign water pollution control field.
The printing and dyeing wastewater refers to mixed wastewater discharged by each procedure in the printing and dyeing process. Mainly comprises desizing, scouring, bleaching and mercerizing wastewater discharged in a pretreatment stage (such as singeing, desizing, scouring, bleaching and mercerizing); dyeing wastewater discharged in the dyeing stage; printing wastewater and soaping wastewater discharged in the printing stage; and finishing wastewater discharged in the finishing stage. Before the 80 s, the biochemical property of the Chinese printing and dyeing wastewater is higher, and COD is higher cr The concentration is usually below 800mg/L, and the emission requirement can be met by adopting a traditional biological and physical and chemical combined treatment system. However, with the development of the printing and dyeing industry, the components in the printing and dyeing wastewater are more and more complex, and the traditional process is difficult to meet the requirement of wastewater treatment. Conventional printing and dyeing wastewater treatment processes typically transfer organic matter from a liquid phase to a solid or gas phase, which not only do not completely eliminate organic contaminants, but also require the consumption of large amounts of chemicals. Therefore, a large amount of waste is accumulated and secondary pollution is formed, thus limiting the application development thereof. Biological methods can remove BOD in printing and dyeing wastewater, but have no obvious removal effect on COD, especially toxic refractory organics and chromaticity, and the current treatment requirements on the printing and dyeing wastewater are difficult to meet by a single treatment method.
In recent years, physicochemical technologies such as ozone oxidation, high-temperature deep oxidation, photocatalytic oxidation, ultrasonic degradation and the like are continuously developed, and particularly, the use of photocatalytic oxidation technology is attracting attention. The most commonly used photocatalyst at present is TiO 2 But it is not highly efficient in solar energy. Most of the treating agents used by the existing wastewater are non-environment-friendly products, and the price is generally high, so that the long-term development of the environment-friendly industry in China is not facilitated.
Therefore, it is necessary to develop a novel environment-friendly photocatalyst which can improve the solar energy utilization rate and has low price and is all natural.
Disclosure of Invention
The invention aims at solving the problems existing in the prior art and provides a material for photocatalytic degradation of printing and dyeing wastewater and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method for photocatalytic degradation of printing and dyeing wastewater materials comprises the following steps:
s1, preparing a washing solution:
putting the sodium dodecyl benzene sulfonate surfactant into a mixed solvent formed by mixing an alcohol organic solvent and water, and uniformly stirring to prepare a washing liquid;
s2, rush fiber pretreatment:
placing rush fibers into the washing liquid prepared in the step S1 for washing and then drying for later use;
s3, carboxymethylation of rush:
washing the rush fibers treated in the step S2 to be neutral after alkali treatment, drying, soaking the rush fibers subjected to alkali treatment in sodium chloroacetate solution for carboxymethylation treatment, taking out, washing and drying after soaking;
s4, preparing a rush composite photocatalytic material:
photocatalytic enhancer and C 3 N 4 Dispersing in aluminum sulfate octadecatriend water solution, adding carboxymethyl rush prepared in the step S3, performing ultrasonic treatment, taking out, washing with deionized water, and oven drying to obtain photocatalyst/g-C 3 N 4 Modified rush composite photocatalytic material.
As a further limitation of the above technical scheme, in step S1, the concentration of the sodium dodecyl benzene sulfonate surfactant is 0.05-0.2 g/L; the volume ratio of the alcohol organic solvent to the water in the washing liquid is 10 percent to 90 percent to 50 percent.
As a further limitation of the above technical solution, in step S1, the alcohol-type organic solvent is one or more of ethanol, isopropanol or glycerol.
As a further limitation of the above technical scheme, in step S2, the bath ratio of the washing liquid is 1:20 to 1:80; the washing temperature is 40-100 ℃, the washing time is 60-120 min, the drying temperature is 60-85 ℃, and the drying time is 45-120 min.
As a further limitation of the above technical scheme, in step S3, the alkali treatment is to soak for 5-25 min with NaOH solution with a mass concentration of 2-15%.
As a further limitation of the above technical scheme, in the step S3, the concentration of the sodium chloroacetate solution is 80-200 g/L, and the soaking time is 15-40 min.
As a further limitation of the above technical solution, in step S4, the photocatalytic enhancer is graphene oxide, tungsten trioxide, vanadium pentoxide, ag 2 WO 4 One or more of titanium dioxide or molybdenum trioxide.
As a further limitation of the above technical scheme, in step S4, the amount of the aluminum sulfate octadecahydrate is 8% -16% of the mass of rush; the dosage of the photocatalytic enhancer is 10% -80% of the mass of rush; the g-C 3 N 4 The dosage of the composition is 50-200% of the mass of rush.
As a further limitation of the above technical scheme, in step S4, the carboxymethylated rush and g-C 3 N 4 The dosage ratio of (2) is 1:0.5-1:2.
The invention also aims to provide the photocatalytic degradation printing and dyeing wastewater material prepared by the preparation method for photocatalytic degradation printing and dyeing wastewater material.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention firstly adopts a washing liquid formed by mixing an alcohol organic solvent, water and sodium dodecyl benzene sulfonate to wash rush fibers, and sequentially carries out alkalization and carboxymethylation treatment on the washed rush fibers, and then combines the rush fibers with graphene oxide or metal oxide in an electrostatic self-assembly mode to form the binary mixed modified rush composite photocatalyst material. The natural, regular and uniform pore structure and the high specific surface area in the rush are utilized, the loading capacity of the composite photocatalyst can be greatly improved, and harmful components in the printing and dyeing wastewater are locked in the nano holes of the rush so as to avoid secondary pollution, thereby cooperatively improving the adsorption and degradation performances on the printing and dyeing wastewater.
(2) The invention puts rush fiber into a photocatalysis enhancer and g-C 3 N 4 Is treated by ultrasonic oscillation in the eighteen hydrated aluminum sulfate aqueous solution, which is favorable for nano photocatalyst and g-C 3 N 4 Uniformly distributed in holes of medulla Junci fiber, and improving its load fastness with medulla Junci hole structure to reduce nano photocatalyst and g-C 3 N 4 Is fallen off; meanwhile, the large specific surface area of the nano photocatalyst lamellar structure and the natural pore structure in the rush are beneficial to cooperatively improving the adsorption and degradation performances on printing and dyeing wastewater.
(3) The invention adopts the mixed solvent formed by alcohols and water, thereby effectively dissolving organic and inorganic impurities in rush fibers; the alkalization treatment is used as a necessary pretreatment step for rush carboxymethylation, so that the hydrophilicity of rush porous fibers can be improved on the premise of ensuring that the rush structure is not damaged, and the influence of impurities on the rush fibers is reduced, so that the adsorption and degradation performances of the rush fibers are improved.
(4) The preparation method for photocatalytic degradation of the printing and dyeing wastewater material is simple to operate, easy to control reaction conditions, low in cost and high in purification efficiency, and has potential industrial application prospects.
Drawings
FIG. 1 is a scanning electron microscope characterization diagram of the photocatalytic degradation printing and dyeing wastewater material prepared in example 1.
FIG. 2 is a graph showing the results of photocatalytic degradation of the material for photocatalytic degradation of printing and dyeing wastewater prepared in examples 1 to 5 according to the present invention.
FIG. 3 is a graph showing the results of photocatalytic degradation of the material for photocatalytic degradation of printing and dyeing wastewater obtained in example 1 and examples 6 to 8.
FIG. 4 is a graph showing the results of photocatalytic degradation of the material for dyeing wastewater obtained in examples 1 and 14.
FIG. 5 is a graph showing the comparative photocatalytic degradation performance of the photocatalytic degradation printing and dyeing wastewater materials prepared in example 1 and example 14.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples; it should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the invention; unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
In the following specific embodiments, the photocatalytic degradation performance of the photocatalytic degradation printing and dyeing wastewater material prepared by the invention is characterized by measuring the change condition of the absorbance of the solution before and after photocatalytic degradation by an ultraviolet spectrophotometer.
The invention will now be described in further detail by way of specific examples of embodiments in connection with the accompanying drawings.
Example 1
A preparation method for photocatalytic degradation of printing and dyeing wastewater materials comprises the following steps:
s1, preparing a washing solution:
the method comprises the steps of (1) placing a sodium dodecyl benzene sulfonate surfactant in a mixed solvent formed by mixing ethanol and water according to the volume ratio of 30% to 70%, and uniformly stirring to prepare a washing liquid of 0.1 g/L;
s2, rush fiber pretreatment:
placing rush fibers into the washing liquid prepared in the step S1 for washing and then drying for later use; controlling the bath ratio of the washing liquid to be 1:50; the washing temperature is 70 ℃, the washing time is 90min, the drying temperature is 70 ℃, and the drying time is 80min;
s3, carboxymethylation of rush:
soaking 0.5g of rush fibers treated in the step S2 in a NaOH solution with the mass concentration of 5% for 15min at room temperature, taking out, washing to be neutral, and drying at 80 ℃; then the dried alkali-treated rush is put into 100mL of 100g/L sodium chloroacetate to be soaked for 25min, taken out to be washed to be neutral and dried at 80 ℃;
s4, preparing a rush composite photocatalytic material:
mixing 0.2g graphene oxide with 1g g-C 3 N 4 Dispersing in 100mL 0.8g/L aluminum sulfate octadecanoate water solution, adding 0.5g of the carboxymethylated rush prepared in the step S3, performing ultrasonic treatment for 3h, taking out, cleaning the surface with deionized water, floating, and drying at 80 ℃ to obtain GO/g-C 3 N 4 Modified rush composite photocatalytic material.
FIG. 1 shows the GO/g-C obtained in this example 3 N 4 From the scanning electron microscope characterization diagram of the modified rush composite photocatalytic material, it can be seen from the diagram that a large amount of graphene oxide is uniformly loaded on the rush uniform three-dimensional reticular pore structure, thereby indicating that the embodiment successfully prepares GO/g-C 3 N 4 Modified rush composite photocatalytic material.
Examples 2 to 5
Embodiments 2-5 provide a preparation method for photocatalytic degradation of printing and dyeing wastewater materials, which is different from embodiment 1 in that the dosage ratio of graphene oxide to rush in step S4 is changed, and other operations are the same except the above differences, and detailed experimental condition parameters are not described herein.
The photocatalytic degradation performance of the photocatalytic degradation printing and dyeing wastewater materials prepared in examples 1 to 5 is shown in fig. 2, wherein curve Initial represents the ultraviolet-visible spectrum curve of 50mg/L of the Initial dye. As shown in the graph, with the increase of the graphene oxide dosage, the prepared GO/g-C 3 N 4 The photocatalytic degradation performance of the modified rush composite photocatalytic material is increased and then is almost unchanged, and when the graphene oxide dosage is 80% of the rush mass, the prepared GO/g-C is prepared 3 N 4 The photocatalytic degradation performance of the modified rush composite photocatalytic material is approaching to the maximum.
Examples 6 to 8
Embodiments 6-8 provide a preparation method for photocatalytic degradation of printing and dyeing wastewater materials, which is different from embodiment 1 in that the mass concentration of NaOH solution in step S3 is changed, and other operations except for the above differences are the same, and detailed experimental condition parameters are not described here.
| Examples | NaOH solution mass concentration (%) |
| 1 | 5 |
| 6 | 2 |
| 7 | 10 |
| 8 | 15 |
The photocatalytic degradation performance of the photocatalytic degradation printing and dyeing wastewater materials prepared in example 1 and examples 6 to 8 is shown in FIG. 3, and it is understood from the results in the graph that as the mass concentration of the NaOH solution in step S3 increases, the GO/g-C is prepared 3 N 4 The degradation efficiency of the modified rush composite photocatalytic material is increased and then reduced, and the GO/g-C is prepared when the mass concentration of the NaOH solution is 5 percent 3 N 4 The modified rush composite photocatalytic material has optimal photocatalytic degradation performance。
Examples 9 to 13
Examples 9 to 13 provide a process for the preparation of materials for photocatalytic degradation of printing and dyeing wastewater, which differs from example 1 in that the g-C in step S4 is changed 3 N 4 Except for the above differences, other operations are the same, and detailed experimental condition parameters and experimental results are shown in the following table.
As can be seen from comparing the results of example 1 with those of examples 9 to 11, following the g-C in step S4 3 N 4 The usage amount is increased, and the prepared GO/g-C 3 N 4 The efficiency of the modified rush composite photocatalytic material for photocatalytic printing and dyeing wastewater is increased, thereby showing that the g-C is increased within the limit of the invention 3 N 4 The dosage of the rush can synergistically improve the efficiency of photocatalytic degradation of the printing and dyeing wastewater.
Example 14
Example 14 provides a preparation method for photocatalytic degradation of printing and dyeing wastewater materials, which is different from example 1 in that step S4 specifically comprises the following steps: will be 1.2g g-C 3 N 4 Dispersing in 100mL 0.8g/L aluminum sulfate octadecanoate water solution, adding 0.5g of the carboxymethylated rush prepared in the step S3, performing ultrasonic treatment for 3h, taking out, cleaning the surface with deionized water, floating, and drying at 80 ℃ to obtain g-C 3 N 4 Modified rush composite photocatalytic material. Except for the above differences, the other operations are the same and will not be described in detail herein.
The photocatalytic degradation performance of the photocatalytic degradation printing and dyeing wastewater material prepared in example 1 and example 14 is shown in figures 4 to 5, and the results in the figures show that under the condition that other reaction conditions are the same, the graphene oxide is blended with g-C 3 N 4 Modified rush is prepared by oxidizing graphene and g-C 3 N 4 The combined action of the two can synergistically improve the photocatalytic degradation efficiency of rush to the printing and dyeing wastewater.
Examples 15 to 20
The embodiments 15-20 provide a preparation method for photocatalytic degradation of printing and dyeing wastewater materials, which is different from the embodiment 1 in that the concentration and the soaking time of the sodium chloroacetate solution in the step S3 are changed, and other operations except for the above differences are the same, and detailed experimental condition parameters and experimental results are not described herein.
As is clear from the results of comparative examples 1 and examples 15 to 18, as the concentration of the sodium chloroacetate solution increases in step S3, the photocatalytic degradation efficiency of the produced photocatalytic degradation printing and dyeing wastewater material increases first and then approaches equilibrium, thereby indicating that when the concentration of the sodium chloroacetate solution reaches 100g/L, the carboxymethylation treatment of rush has reached an equilibrium state, so that electrostatic adsorption between catalysts is not increased, and the effect on rush load is small.
As can be seen from the results of comparative examples 1 and 19 to 20, the photocatalytic degradation rate of the prepared material for photocatalytic degradation of printing and dyeing wastewater increases and approaches equilibrium as the treatment time of the sodium chloroacetate solution in step S3 increases.
Examples 21 to 25
Embodiments 21 to 25 provide a preparation method for photocatalytic degradation of printing and dyeing wastewater materials, which is different from embodiment 1 in that the type of the photocatalytic enhancer in step S4 is changed, and other operations except for the above differences are the same, and detailed experimental condition parameters and experimental results are not described herein.
| Examples | Photocatalytic enhancer | Photocatalytic degradation Rate (%) |
| 21 | Tungsten trioxide | 98.2 |
| 22 | Vanadium pentoxide | 98.0 |
| 23 | Ag 2 WO 4 | 98.0 |
| 24 | Titanium dioxide | 99.8 |
| 25 | Molybdenum trioxide | 98.0 |
As is clear from the results of comparative example 1 and examples 21 to 25, the present invention uses graphene oxide, tungsten trioxide, vanadium pentoxide, and Ag 2 WO 4 Nano catalyst such as titanium dioxide or molybdenum trioxide and g-C 3 N 4 The photocatalytic degradation printing and dyeing wastewater material prepared by modifying rush through blending has better photocatalytic degradation performance. And in the process of enhancing photocatalysis, titanium dioxide and graphene oxide are mixed with g-C 3 N 4 The blend of the nano catalyst has slightly better photocatalysis effect on the material for photocatalytic degradation of printing and dyeing wastewater, which is prepared by modifying rush, and the blend of the nano catalyst is used for photocatalytic degradation of the material for printing and dyeing wastewater, which is prepared by modifying rushThe photocatalysis effect can reach more than 98 percent. Therefore, in the practical application demand process, the high-efficiency photocatalytic degradation printing and dyeing wastewater material with different photocatalytic degradation efficiencies can be prepared by adjusting the types of the photocatalytic reinforcing agents.
The foregoing is merely illustrative of the embodiments of the present invention and is not intended to be limiting in any way or nature, and it should be noted that modifications and additions to the ordinary skill in the art without departing from the method of the present invention are also contemplated as falling within the scope of the present invention; equivalent embodiments of the present invention will be apparent to those skilled in the art having the benefit of the teachings disclosed herein, and modifications, to which the invention pertains; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the protection scope of the present invention.
Claims (5)
1. A preparation method for photocatalytic degradation of printing and dyeing wastewater material is characterized by comprising the following steps of
S1, preparing a washing solution:
putting the sodium dodecyl benzene sulfonate surfactant into a mixed solvent formed by mixing an alcohol organic solvent and water, and uniformly stirring to prepare a washing liquid;
s2, rush fiber pretreatment:
placing rush fibers into the washing liquid prepared in the step S1 for washing and then drying for later use;
s3, carboxymethylation of rush:
washing the rush fibers treated in the step S2 to be neutral after alkali treatment, drying, soaking the rush fibers subjected to alkali treatment in sodium chloroacetate solution for carboxymethylation treatment, taking out, washing and drying after soaking;
s4, preparing the rush composite photocatalytic material
Combining a photocatalytic enhancer with g-C 3 N 4 Dispersing in an aqueous solution of aluminum sulfate octadecatydrateAdding the carboxymethylated rush prepared in the step S3, performing ultrasonic treatment, taking out, washing with deionized water, and drying to obtain the photocatalyst/g-C 3 N 4 Modified rush composite photocatalytic material;
in step S4, the photocatalytic enhancer is graphene oxide, tungsten trioxide, vanadium pentoxide or Ag 2 W0 4 One or more of titanium dioxide or molybdenum trioxide;
in the step S4, the dosage of the aluminum sulfate octadecatriend is 8-16% of the mass of the carboxymethylated rush; the dosage of the photocatalytic enhancer is 10-80% of the mass of the carboxymethylated rush;
in step S4, the carboxymethylated rush and g-C 3 N 4 The dosage ratio is 1:0.5-1:2;
in the step S1, the concentration of the sodium dodecyl benzene sulfonate surfactant is 0.05-0.2 g/L; the volume ratio of the alcohol organic solvent to the water in the washing liquid is 10 percent to 90 percent to 50 percent;
in the step S3, the alkali treatment is to soak for 5 to 25 minutes by adopting NaOH solution with the mass concentration of 2 to 15 percent.
2. The method for preparing a material for photocatalytic degradation of printing and dyeing wastewater according to claim 1, wherein in step S1, the alcohol-based organic solvent is one or more of ethanol, isopropanol or glycerol.
3. The method for preparing a material for photocatalytic degradation of printing and dyeing wastewater according to claim 1, wherein in the step S2, the bath ratio of the washing liquid is 1:20 to 1:80; the washing temperature is 40-100 ℃, the washing time is 60-120 min, the drying temperature is 60-85 ℃, and the drying time is 45-120 min.
4. The preparation method of the material for photocatalytic degradation of printing and dyeing wastewater according to claim 1, wherein in the step S3, the concentration of the sodium chloroacetate solution is 80-200 g/L, and the soaking time is 15-40 min.
5. The photocatalytic degradation printing and dyeing wastewater material according to any one of claims 1 to 4.
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