CN111774091A - 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 64
- 238000004043 dyeing Methods 0.000 title claims abstract description 61
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000011941 photocatalyst Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 33
- 230000001699 photocatalysis Effects 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 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
- 239000003623 enhancer Substances 0.000 claims description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 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
- 239000003960 organic solvent Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 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
- 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
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
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- 230000015556 catabolic process Effects 0.000 description 6
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- 238000004140 cleaning Methods 0.000 description 2
- 238000009990 desizing Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- LFHXPRTYXDXTDD-UHFFFAOYSA-H bis(2,2-dioxo-1,3,2,4-dioxathialumetan-4-yl) sulfate octahydrate Chemical compound 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 LFHXPRTYXDXTDD-UHFFFAOYSA-H 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 230000010355 oscillation Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000009999 singeing Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/61—Surface area
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a material for photocatalytic degradation of printing and dyeing wastewater and a preparation method thereof3N4And combining to form the binary mixed modified rush composite photocatalyst. The invention utilizes the natural, regular and uniform three-dimensional net-shaped pore canal structure and height in the rushThe specific surface area can greatly improve the loading capacity of the composite photocatalyst, so that the composite photocatalyst has a stronger adsorption effect on harmful substances in the printing and dyeing wastewater, and the photocatalytic degradation performance of the printing and dyeing wastewater is synergistically improved. The preparation method is simple to operate, reaction conditions are easy to control, the cost is low, the purification efficiency is high, and the method has a potential industrial application prospect.
Description
Technical Field
The invention relates to the technical field of printing and dyeing sewage 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 is developed rapidly, the yield and the quality of the textile industry are greatly improved, the textile industry becomes one of industrial departments with the largest water consumption and the largest waste water discharge amount in China, the use of dyes is developing towards the direction of photolysis resistance, oxidation resistance and biological degradation resistance, and the printing and dyeing wastewater generated by the dye is one of the important pollution sources of the water environment. And the dye wastewater has the characteristics of complex composition, large water quantity and water quality change, high chroma, high salt content, poor biodegradability and the like, and is gradually developed into a great problem to be solved urgently in the field of domestic and foreign water pollution control.
The printing and dyeing wastewater refers to mixed wastewater discharged from each process in the printing and dyeing processing 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; finishing wastewater discharged in the finishing stage. Before 80 s, the biodegradability of Chinese printing and dyeing wastewater is high, and the COD iscrThe concentration is usually below 800mg/L, and the requirement of discharge can be met by adopting the traditional biological and physical-chemical combined treatment system. However, with the development of the printing and dyeing industry, the components in the printing and dyeing wastewater become more and more complex, and the traditional process is difficult to meet the requirement of wastewater treatment. The traditional printing and dyeing wastewater treatment process generally transfers organic matters from a liquid phase to a solid phase or a gas phase, not only does not completely eliminate organic pollutants,it also requires the consumption of large amounts of chemicals. Therefore, a large amount of waste is accumulated and secondary pollution is generated, thereby limiting the development of applications thereof. The biological method can remove BOD in the printing and dyeing wastewater, but the removal effect on COD, particularly toxic and nondegradable organic matters and chromaticity is not obvious, and the single treatment method is difficult to meet the current treatment requirement on the printing and dyeing wastewater.
In recent years, physicochemical techniques such as an ozone oxidation method, a high-temperature deep oxidation method, a photocatalytic oxidation method, and an ultrasonic degradation method have appeared, and particularly, the use of the photocatalytic oxidation technique has attracted attention. The most commonly used photocatalyst at present is TiO2But it does not have a high solar energy utilization. Most of the treatment agents used by the existing wastewater are non-environment-friendly products, and the price is generally higher, so that the treatment agents are not beneficial to the long-term development of the environmental protection industry of China.
Therefore, there is a need to develop a novel, low-cost and all-natural photocatalyst for environmental protection, which can improve the utilization rate of solar energy.
Disclosure of Invention
The invention aims to solve the problems 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 purpose, the invention adopts the technical scheme that:
a preparation method of a material for photocatalytic degradation of printing and dyeing wastewater comprises the following steps:
s1, preparation of a washing solution:
placing the sodium dodecyl benzene sulfonate surfactant in a mixed solvent formed by mixing an alcohol organic solvent and water, and preparing a washing solution after uniformly stirring;
s2, pretreatment of rush fibers:
placing rush fibers into the washing solution prepared in the step S1, washing and drying for later use;
s3, carboxymethylation of rush:
performing alkali treatment on the rush fiber treated in the step S2, washing to be neutral, drying, soaking the rush subjected to alkali treatment in a sodium chloroacetate solution for carboxymethylation, taking out after soaking, washing and drying;
s4, preparing the rush composite photocatalytic material:
mixing the photocatalytic enhancer with C3N4Dispersing in aluminum sulfate octadecahydrate aqueous solution, adding the carboxymethylated rush prepared in the step S3, performing ultrasonic treatment, taking out, washing with deionized water, and drying to obtain the photocatalyst/g-C3N4The modified rush composite photocatalytic material.
As a further limitation of the above technical solution, in step S1, the concentration of the sodium dodecylbenzenesulfonate 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, 90 percent to 50 percent and 50 percent.
As a further limitation of the above technical solution, in step S1, the alcohol organic solvent is one or a combination of more of ethanol, isopropanol and glycerol.
As a further limitation of the above technical solution, 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 solution, in step S3, the alkali treatment is performed by soaking in a 2-15% NaOH solution for 5-25 min.
As a further limitation of the 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, or Ag2WO4One or more of titanium dioxide or molybdenum trioxide.
As a further limitation of the above technical solution, in step S4, the amount of the aluminum sulfate octadecahydrate is 8% -16% of the mass of the rush; the dosage of the photocatalytic enhancer is 10-80% of the mass of the rush; the g to C3N4The dosage of the Chinese herbal medicine is 50 to 20 percent of the mass of the rush0％。
As a further limitation of the above technical solution, in step S4, the carboxymethylated rush and g-C3N4The dosage ratio of the components 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) firstly, washing rush fibers by using a washing solution formed by mixing an alcohol organic solvent, water and sodium dodecyl benzene sulfonate, sequentially carrying out alkalization and carboxymethylation on the washed rush fibers, and combining the rush fibers with graphene oxide or a metal oxide in an electrostatic self-assembly manner 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 load capacity of the composite photocatalyst can be greatly improved, and harmful ingredients in the printing and dyeing wastewater are locked in the nano holes of the rush, so that secondary pollution is avoided, and the adsorption and degradation performance of the printing and dyeing wastewater is synergistically improved.
(2) The rush fiber is placed between the photocatalysis reinforcing agent and g-C3N4The aluminum sulfate octadecahydrate aqueous solution is treated by ultrasonic oscillation, which is beneficial to the nanometer photocatalyst and g-C3N4Uniformly distributed in the holes of rush fiber, and has improved load fastness with rush hole structure to reduce nanometer photocatalyst and g-C3N4The falling off of (1); meanwhile, the large specific surface area of the nano photocatalyst lamellar structure and the natural hole structure in the rush are utilized to be beneficial to synergistically improving the adsorption and degradation performance of the printing and dyeing wastewater.
(3) The invention adopts the mixed solvent formed by alcohol and water, thereby effectively dissolving organic and inorganic impurities in rush fibers; the alkalization treatment is used as a necessary pretreatment step for the carboxymethylation of the rush, the hydrophilicity of rush porous fibers can be improved on the premise of ensuring that the structure of the rush is not damaged, and the influence of impurities on the rush fibers is reduced, so that the adsorption degradation performance of the rush fibers is improved.
(4) The preparation method for the material for photocatalytic degradation of printing and dyeing wastewater is simple to operate, easy to control reaction conditions, low in cost, high in purification efficiency and has potential industrial application prospects.
Drawings
FIG. 1 is a scanning electron microscope characterization chart of the photocatalytic degradation printing and dyeing wastewater material prepared in example 1.
FIG. 2 is a graph showing the results of photocatalytic degradation performance of the photocatalytic degradation printing and dyeing wastewater material prepared in examples 1 to 5 of the present invention.
FIG. 3 is a graph showing the results of photocatalytic degradation performance of the photocatalytic degradation printing and dyeing wastewater materials prepared in examples 1 and 6 to 8.
FIG. 4 is a graph showing the results of photocatalytic degradation performance of the photocatalytic degradation printing and dyeing wastewater materials obtained in examples 1 and 14.
FIG. 5 is a graph comparing the photocatalytic degradation performance of the photocatalytic degradation printing and dyeing wastewater materials obtained in example 1 and example 14.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly apparent, the present invention is further described in detail with reference to the following embodiments; it should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention; reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
In the following specific embodiment, the change of the absorbance of the solution before and after photocatalytic degradation is measured by an ultraviolet spectrophotometer to characterize the photocatalytic degradation performance of the photocatalytic degradation printing and dyeing wastewater material prepared by the invention.
The present invention will be described in further detail below with reference to specific embodiments and with reference to the attached drawings.
Example 1
A preparation method of a material for photocatalytic degradation of printing and dyeing wastewater comprises the following steps:
s1, preparation of a washing solution:
placing the sodium dodecyl benzene sulfonate surfactant into a mixed solvent formed by mixing ethanol and water according to the volume ratio of 30% to 70%, and preparing 0.1g/L washing liquid after uniformly stirring;
s2, pretreatment of rush fibers:
placing rush fibers into the washing solution prepared in the step S1, washing and 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 80 min;
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 the rush fibers, washing the rush fibers to be neutral, and drying the rush fibers at 80 ℃; then, putting the dried alkali-treated rush into 100mL of 100g/L sodium chloroacetate, soaking for 25min, taking out, washing to be neutral, and drying at 80 ℃;
s4, preparing the rush composite photocatalytic material:
0.2g of graphene oxide was mixed with 1g g-C3N4Dispersing in 100mL of 0.8g/L aluminum sulfate octadecahydrate aqueous solution, adding 0.5g of carboxymethylated rush prepared in step S3, performing ultrasonic treatment for 3h, taking out, cleaning the surface with deionized water, floating and sinking, and drying at 80 ℃ to obtain GO/g-C3N4The modified rush composite photocatalytic material.
FIG. 1 shows GO/g-C made in this example3N4The characterization drawing of the scanning electron microscope of the modified rush composite photocatalytic material shows that a large amount of graphene oxide is uniformly loaded on the uniform three-dimensional reticular pore structure of rush, thereby demonstrating that GO/g-C is successfully prepared in the embodiment3N4The modified rush composite photocatalytic material.
Examples 2 to 5
Examples 2 to 5 provide a method for preparing a material for photocatalytic degradation of printing and dyeing wastewater, which is different from example 1 in that the amount ratio of graphene oxide to rush in step S4 is changed, and other operations are the same except for the above differences, and are not repeated herein, and specific experimental condition parameters are shown in the following table.
The photocatalytic degradation performance of the photocatalytic degradation printing and dyeing wastewater material prepared in the embodiments 1 to 5 is shown in fig. 2, wherein the Initial curve in the graph represents the ultraviolet-visible spectrum curve of the Initial dye of 50 mg/L. As can be seen from the results in the figure, with the increase of the dosage of the graphene oxide, the prepared GO/g-C3N4The photocatalytic degradation performance of the modified rush composite photocatalytic material is increased firstly and then is approximately unchanged, and when the amount of graphene oxide is 80% of the mass of rush, the prepared GO/g-C3N4The photocatalytic degradation performance of the modified rush composite photocatalytic material is approaching to the maximum.
Examples 6 to 8
Examples 6 to 8 provide a method for preparing a material for photocatalytic degradation of printing and dyeing wastewater, which is different from example 1 in that the mass concentration of the NaOH solution in step S3 is changed, and other operations are the same except for the above differences, and are not repeated herein, and specific experimental condition parameters are shown in the following table.
| 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 the embodiments 1 and 6 to 8 is shown in FIG. 3, and the results in the graph show that the GO/g-C prepared with the increase of the mass concentration of the NaOH solution in the step S33N4The degradation efficiency of the modified rush composite photocatalytic material is increased and then reduced, and GO/g-C is prepared when the mass concentration of NaOH solution is 5%3N4The modified rush composite photocatalytic material has the best photocatalytic degradation performance.
Examples 9 to 13
Examples 9 to 13 provide a production method for photocatalytic degradation of a printing and dyeing wastewater material, which is different from example 1 in that g-C described in step S4 was changed3N4Except for the above differences, the other operations are the same and are not repeated herein, and the specific experimental condition parameters and experimental results are shown in the following table.
Comparing the results of examples 1 and 9-11, it can be seen that the g-C in step S4 is followed3N4Increased amount of GO/g-C3N4The efficiency of the modified rush composite photocatalytic material for photocatalytic printing and dyeing wastewater is increased, thereby illustrating that the g-C is increased within the range defined by the invention3N4The usage amount of the rush can synergistically improve the efficiency of photocatalytic degradation of printing and dyeing wastewater.
Example 14
Example 14 provides a method for preparing a material for photocatalytic degradation of printing and dyeing wastewater, which is different from example 1 in that step S4 specifically includes the following steps: 1.2g g-C3N4Dispersed in 100mL of 0.8g/L tenAdding 0.5g of carboxymethylated rush prepared in step S3 into the aqueous solution of aluminum sulfate octahydrate, performing ultrasonic treatment for 3h, taking out, cleaning the surface with deionized water, and drying at 80 ℃ to obtain g-C3N4The modified rush composite photocatalytic material. Except for the above differences, other operations are the same and are not described herein again.
The photocatalytic degradation performance of the photocatalytic degradation printing and dyeing wastewater materials prepared in the embodiments 1 and 14 is shown in fig. 4-5, and the results in the figures show that under the same other reaction conditions, the g-C is blended by graphene oxide3N4Modified rush, by oxidation of graphene, g-C3N4The combined action of the two can synergistically improve the photocatalytic degradation efficiency of rush to printing and dyeing wastewater.
Examples 15 to 20
Examples 15 to 20 provide a method for preparing a material for photocatalytic degradation of printing and dyeing wastewater, which is different from example 1 in that the concentration of the sodium chloroacetate solution and the soaking time in step S3 are changed, and other operations are the same except for the above differences, and are not repeated herein, and specific experimental condition parameters and experimental results are shown in the following table.
Comparing the results of example 1 and examples 15 to 18, it can be seen that, as the concentration of the sodium chloroacetate solution in step S3 increases, the photocatalytic degradation efficiency of the prepared photocatalytic degradation printing and dyeing wastewater material increases first and then approaches to the equilibrium, thus indicating that when the concentration of the sodium chloroacetate solution reaches 100g/L, the carboxymethylation treatment of rush reaches the equilibrium state, so that the electrostatic adsorption between the catalysts is not increased, and the influence on the loading capacity of rush is small.
As is clear from the results of comparative example 1 and examples 19 to 20, the photocatalytic degradation rate of the produced photocatalytic degradation printing and dyeing wastewater material increased and then reached equilibrium as the treatment time of the sodium chloroacetate solution in step S3 was increased.
Examples 21 to 25
Examples 21 to 25 provide a method for preparing a material for photocatalytic degradation of printing and dyeing wastewater, which is different from example 1 in that the kind of the photocatalytic enhancer used in step S4 is changed, and other operations are the same except for the above differences, and are not repeated herein, and specific experimental condition parameters and experimental results are shown in the following table.
| Examples | Photocatalytic enhancer | Photocatalytic degradation ratio (%) |
| 21 | Tungsten trioxide | 98.2 |
| 22 | Vanadium pentoxide | 98.0 |
| 23 | Ag2WO4 | 98.0 |
| 24 | Titanium dioxide | 99.8 |
| 25 | Molybdenum trioxide | 98.0 |
Comparing the results of examples 1 and 21-25, it can be seen that the present invention uses graphene oxide, tungsten trioxide, vanadium pentoxide, and Ag2WO4Titanium dioxide or molybdenum trioxide and g-C3N4The blending is used for modifying rush to prepare the photocatalytic degradation printing and dyeing wastewater material which has better photocatalytic degradation performance. And in the process of enhancing photocatalysis, titanium dioxide and graphene oxide are reacted with g-C3N4The blending body has a slightly good photocatalytic effect on the photocatalytic degradation printing and dyeing wastewater material prepared by modifying rush, and the photocatalytic effect of the photocatalytic degradation printing and dyeing wastewater material prepared by modifying rush through the blending system of the nano-catalyst can reach more than 98%. Therefore, in the process of actual application requirements, 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.
While the invention has been described with respect to specific embodiments thereof, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention; those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and alterations of the above embodiments according to the spirit and techniques of the present invention are also within the scope of the present invention.
Claims (10)
1. A preparation method of a material for photocatalytic degradation of printing and dyeing wastewater is characterized by comprising the following steps:
s1, preparation of a washing solution:
placing the sodium dodecyl benzene sulfonate surfactant in a mixed solvent formed by mixing an alcohol organic solvent and water, and preparing a washing solution after uniformly stirring;
s2, pretreatment of rush fibers:
placing rush fibers into the washing solution prepared in the step S1, washing and drying for later use;
s3, carboxymethylation of rush:
performing alkali treatment on the rush fiber treated in the step S2, washing to be neutral, drying, soaking the rush subjected to alkali treatment in a sodium chloroacetate solution for carboxymethylation, taking out after soaking, washing and drying;
s4, preparing the rush composite photocatalytic material:
mixing the photocatalytic enhancer with g-C3N4Dispersing in aluminum sulfate octadecahydrate aqueous solution, adding the carboxymethylated rush prepared in the step S3, performing ultrasonic treatment, taking out, washing with deionized water, and drying to obtain the photocatalyst/g-C3N4The modified rush composite photocatalytic material.
2. The method for preparing a material for photocatalytic degradation of printing and dyeing wastewater according to claim 1, wherein in step S1, the concentration of the sodium dodecylbenzenesulfonate surfactant is 0.05 to 0.2 g/L; the volume ratio of the alcohol organic solvent to the water in the washing liquid is 10 percent, 90 percent to 50 percent and 50 percent.
3. The method for preparing the material for photocatalytic degradation of printing and dyeing wastewater according to claim 1 or 2, wherein in step S1, the alcohol organic solvent is one or more of ethanol, isopropanol or glycerol.
4. The preparation method of the material for photocatalytic degradation of printing and dyeing wastewater according to claim 1, characterized in that in step S2, the bath ratio of the washing solution is 1: 20-1: 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.
5. The method for preparing a material for photocatalytic degradation of printing and dyeing wastewater according to claim 1, wherein in step S3, the alkali treatment is soaking for 5-25 min with a NaOH solution with a mass concentration of 2-15%.
6. The method for preparing the material for photocatalytic degradation of printing and dyeing wastewater according to claim 1, wherein in step S3, the concentration of the sodium chloroacetate solution is 80-200 g/L, and the soaking time is 15-40 min.
7. The method as claimed in claim 1, wherein in step S4, the photocatalytic enhancer is selected from graphene oxide, tungsten trioxide, vanadium pentoxide, Ag2WO4One or more of titanium dioxide or molybdenum trioxide.
8. The method for preparing the material for photocatalytic degradation of printing and dyeing wastewater according to claim 1, characterized in that in step S4, the amount of aluminum sulfate octadecahydrate is 8-16% of the mass of rush; the dosage of the photocatalytic enhancer is 10-80% of the mass of the rush; the g to C3N4The dosage of the rush is 50 to 200 percent of the mass of the rush.
9. The method for preparing a material for photocatalytic degradation of printing and dyeing wastewater according to claim 1, wherein in step S4, the carboxymethylated rush and g-C are3N4The dosage ratio of the components is 1: 0.5-1: 2.
10. The photocatalytic degradation printing and dyeing wastewater material prepared by the preparation method for photocatalytic degradation printing and dyeing wastewater material according to any one of claims 1 to 9.
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