CN111925060A - Sewage treatment agent and preparation method and application thereof - Google Patents
Sewage treatment agent and preparation method and application thereof Download PDFInfo
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- CN111925060A CN111925060A CN202010808892.3A CN202010808892A CN111925060A CN 111925060 A CN111925060 A CN 111925060A CN 202010808892 A CN202010808892 A CN 202010808892A CN 111925060 A CN111925060 A CN 111925060A
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- 239000010865 sewage Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000000843 powder Substances 0.000 claims abstract description 101
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 55
- 239000002994 raw material Substances 0.000 claims abstract description 36
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 19
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 16
- 229910021536 Zeolite Inorganic materials 0.000 claims description 33
- 239000010457 zeolite Substances 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 241000193830 Bacillus <bacterium> Species 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000004005 microsphere Substances 0.000 claims description 13
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004806 packaging method and process Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000004065 wastewater treatment Methods 0.000 claims description 7
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 4
- 235000019792 magnesium silicate Nutrition 0.000 claims description 4
- 239000000391 magnesium silicate Substances 0.000 claims description 4
- 239000008055 phosphate buffer solution Substances 0.000 claims description 2
- 239000010840 domestic wastewater Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 8
- 239000011574 phosphorus Substances 0.000 abstract description 8
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 6
- 239000000975 dye Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 239000008363 phosphate buffer Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 102000030523 Catechol oxidase Human genes 0.000 description 1
- 108010031396 Catechol oxidase Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/166—Nitrites
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
Abstract
The invention provides a sewage treatment agent and a preparation method and application thereof, and relates to the technical field of sewage treatment, wherein the sewage treatment agent consists of a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 20-40 parts of biological modified zeolite powder and 10-23 parts of non-ionic polyacrylamide; the component B comprises the following raw materials in parts by weight: 8-18 parts of carbon-doped modified titanium dioxide, 5-10 parts of polyaluminium chloride, 3-8 parts of amino trimethylene phosphonic acid and 8-15 parts of silicate, the sewage treatment agent has excellent removal effect on dyes, organic pollutants, ammonia nitrogen, suspended matters, total phosphorus, heavy metals and the like in sewage, the treated sewage can reach a first-level discharge standard, and the preparation method is simple and is convenient to popularize and apply.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a sewage treatment agent and a preparation method and application thereof.
Background
Water resources are one of important resources for sustainable development of modern society, and protection of water environment and continuous utilization of water resources are the primary environmental resource problems in China at present. With the economic development and the rapid increase of the population worldwide, the shortage of water resources has become an urgent problem to be solved. At present, the regeneration and utilization of water resources are taken as an important strategy for relieving the shortage of water resources in many water-deficient countries in the world, and the use of fresh water is controlled, so that the contradiction between water supply and water use is solved to a certain extent, and obvious social, environmental and economic benefits are obtained.
The sewage treatment has been in the history of hundreds of years in western countries, along with the improvement of living standard, people have higher and higher requirements on water quality, the sewage treatment rate and the sewage treatment depth are increased, and the removal of suspended matters and organic matters in the sewage is increased from the first consideration to the removal of nitrogen and phosphorus substances in the sewage in the seventh and eighty years of the twentieth century. Since the eighties of the twentieth century, a large amount of water bodies have eutrophicated, so that nitrogen and phosphorus removal is promoted to be listed as another execution requirement of sewage treatment in various countries.
The urban domestic sewage is all drainage collected through a sewer pipeline and is mixed water of various domestic sewage, industrial wastewater and urban rainfall runoff drained into the sewer pipeline system. Domestic sewage is water discharged in daily life, and the water is characterized by containing higher organic matters, such as starch, protein, grease and the like, inorganic matters, such as nitrogen, phosphorus and the like, and also containing pathogenic microorganisms and more suspended matters. The industrial wastewater is wastewater discharged in the industrial production process, circulating cooling water flushing wastewater and comprehensive wastewater, and the wastewater contains mineral particle suspended matters, acid, alkali, inorganic salts, heavy metal ions, heavy metal toxic substances, organic toxic substances, dye pollutants and the like.
At present, the traditional sewage treatment methods in China mainly comprise physical methods, chemical methods, biological treatment methods and the like. The methods have respective advantages, but the problems of too complicated process, higher cost of the sewage treatment agent, too high cost of sewage treatment, incomplete sewage treatment and the like are not avoided in the actual sewage treatment. Therefore, the problem to be solved in the field at present is to provide a sewage treatment agent which is simple in use method, can efficiently remove impurities such as organic pollutants, pigments, ammonia nitrogen, heavy metal ions and the like in sewage and is low in cost.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a sewage treatment agent, a preparation method and application thereof, the sewage treatment agent has excellent removal effect on dyes, organic pollutants, ammonia nitrogen, suspended matters, total phosphorus, heavy metals and the like in sewage, the treated wastewater can reach the first-level discharge standard, and the preparation method is simple and is convenient for popularization and application.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
a sewage treatment agent is composed of a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 20-40 parts of biological modified zeolite powder and 10-23 parts of non-ionic polyacrylamide; the component B comprises the following raw materials in parts by weight: 8-18 parts of carbon-doped modified titanium dioxide, 5-10 parts of polyaluminium chloride, 3-8 parts of aminotrimethylene phosphonic acid and 8-15 parts of silicate.
Further, the component A comprises the following raw materials in parts by weight: 25-35 parts of biological modified zeolite powder and 15-20 parts of non-ionic polyacrylamide; the component B comprises the following raw materials in parts by weight: 10-15 parts of carbon-doped modified titanium dioxide, 6-9 parts of polyaluminium chloride, 4-7 parts of aminotrimethylene phosphonic acid and 10-12 parts of silicate.
Further, the component A comprises the following raw materials in parts by weight: 30 parts of biological modified zeolite powder and 16 parts of non-ionic polyacrylamide; the component B comprises the following raw materials in parts by weight: 12 parts of carbon-doped modified titanium dioxide, 8 parts of polyaluminium chloride, 6 parts of aminotrimethylene phosphonic acid and 11 parts of silicate.
Further, the preparation method of the modified zeolite powder comprises the following steps:
1) adding a natural zeolite powder raw material into a dodecyl trimethyl ammonium bromide solution, reacting for 24 hours at the temperature of 30-40 ℃ and the stirring speed of 120-;
2) adding the modified zeolite powder obtained in the step 1 into bacillus strain suspension taking phosphate buffer solution as a solvent, reacting for 2 hours at the temperature of 30-40 ℃ and at the stirring speed of 80-120r/min, standing, filtering out supernatant after the modified zeolite powder is precipitated, and drying the lower modified zeolite powder in a drying box at the temperature of 30-37 ℃ to obtain the biological modified zeolite powder.
Further, in the step 1), the concentration of the dodecyl trimethyl ammonium bromide solution is 0.03-0.05mol/L, and the drying temperature in a drying oven is 60-70 ℃.
Further, in the step 2), the concentration of bacillus in the bacillus suspension is 1.6 x 109cfu/mL, pH 7-7.5, mass/body of modified zeolite powder and bacillus suspensionThe product ratio is 0.8-1 g: 70-90 mL.
Further, the preparation method of the carbon-doped modified titanium dioxide comprises the following steps:
1) adding polyacrylonitrile thermal expansion microspheres into 75 wt% sulfuric acid solution, hydrolyzing at 65 ℃ for 15min, taking out the polyacrylonitrile thermal expansion microspheres, washing with water to neutrality, and soaking the polyacrylonitrile thermal expansion microspheres in tetrabutyl titanate and 45% ethanol according to a volume ratio of 1: 1 for 10 hours, taking out, then placing the mixture into water and 45% ethanol according to a volume ratio of 1: 1, soaking for 1h, and centrifugally drying to obtain a solid for later use;
2) calcining the solid obtained in the step 1) at 480 ℃ for 1.5h under the protection of nitrogen to obtain the carbon-doped modified titanium dioxide.
Further, the silicate is one of aluminum silicate, iron silicate and magnesium silicate or a mixture of the silicate and the iron silicate in any proportion.
The preparation method of the sewage treatment agent comprises the following steps:
1) mixing the biological modified zeolite powder and the non-ionic polyacrylamide according to a proportion, uniformly stirring to obtain a component A, and packaging for later use;
2) mixing carbon-doped modified titanium dioxide, polyaluminium chloride, aminotrimethylene phosphonic acid and silicate in proportion, stirring uniformly to obtain a component B, and packaging for later use;
3) when the sewage treatment agent is used, the component A is firstly put into sewage and treated for 4-6 hours, and then the component B is put into the sewage and continuously treated for 10-12 hours, wherein the mass ratio of the component A to the component B in the sewage treatment agent is 1: 2, the addition amount of the sewage treatment agent is 0.03 wt%.
The sewage treatment agent is mainly used for treating urban domestic sewage.
(III) advantageous effects
The invention provides a sewage treatment agent, a preparation method and application thereof, and the biologically modified zeolite powder in the raw materials of the sewage treatment agent has good removal effect on pigment, ammonia nitrogen and nitrite in sewage. The zeolite powder has large specific surface area, strong adsorbability and ion exchange characteristic, and a series of metabolic activities of the bacillus lead the bacillus to have strong bioremediation capability, so the invention adopts the biological modified zeolite powder as one of the raw materials of the sewage treatment agent, and improves the treatment effect on sewage.
When the biological modified zeolite powder is prepared, firstly, dodecyl trimethyl ammonium bromide is adopted to modify the natural zeolite powder, the surface charge of zeolite can be changed, so that the adsorption rate of zeolite to anions and organic matters is enhanced, then the modified zeolite powder is used for adsorbing bacillus to form the biological modified zeolite powder for sewage treatment, the zeolite powder can adsorb a part of organic matters, and simultaneously, as the bacillus can generate a polyphenol oxidase, the biological modified zeolite powder can degrade stubborn organic matters adsorbed by the zeolite powder, and can remove pigments, ammonia nitrogen, nitrite and the like in sewage.
The invention selects the non-ionic polyacrylamide as the flocculant, has good stability and water solubility, simultaneously has lower cost, good flocculation performance on suspended matters in sewage, red mud and the like, and excellent compatibility, not only can not influence other components to play the role, but also can have the synergistic effect when being compatible with other components.
The carbon-doped modified titanium dioxide selected from the raw materials can degrade organic pollutants and the like in sewage through photocatalysis, and has good degradation effect and high removal rate. When the carbon-doped modified titanium dioxide is prepared, the polyacrylonitrile expanded microspheres with low cost are used as a carbon source, and the introduction of carbon doping can improve the specific surface area, the photoresponse intensity and the light absorption range of the titanium dioxide, improve the light utilization rate, ensure that the photocatalysis effect is better and the degradation performance is higher.
The sewage treatment agent disclosed by the invention exists in the form of A, B two components, and the two components have the effects of mutual matching and synergy when in use. When the composite material is used, the component A is firstly added into sewage, so that part of suspended matters in the sewage can be settled, pigments, ammonia nitrogen, nitrite and the like in the sewage are removed, bioremediation is started, after the component B is added, polluted organic matters in the sewage can be removed through photocatalysis, and polymeric aluminum chloride, amino trimethylene phosphonic acid and silicate are compounded for removing phosphorus in the sewage and are simultaneously complexed with heavy metal ions in the sewage to form complex precipitates, so that the heavy metal ions in the sewage are removed. The sewage treatment agent disclosed by the invention has an excellent sewage treatment effect, is simple in preparation method, non-toxic, convenient to use and low in cost, and is worthy of large-scale popularization and application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The sources of the raw materials used in the examples of the present invention are shown in table 1.
Table 1:
example 1:
a sewage treatment agent is composed of a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 30 parts of biological modified zeolite powder and 16 parts of non-ionic polyacrylamide; the component B comprises the following raw materials in parts by weight: 12 parts of carbon-doped modified titanium dioxide, 8 parts of polyaluminium chloride, 6 parts of amino trimethylene phosphonic acid, aluminum silicate, iron silicate and magnesium silicate in a mass ratio of 1: 1 to obtain 11 parts of a mixture.
The preparation method of the modified zeolite powder comprises the following steps:
1) adding a natural zeolite powder raw material into a dodecyl trimethyl ammonium bromide solution with the concentration of 0.04mol/L, reacting for 24 hours at the temperature of 35 ℃ and the stirring speed of 150r/min, taking out the zeolite powder, washing the zeolite powder by using distilled water until the zeolite powder does not contain the dodecyl trimethyl ammonium bromide, and drying the zeolite powder in a drying box at the temperature of 70 ℃ for later use to obtain modified zeolite powder;
2) adding the modified zeolite powder obtained in the step 1 into phosphate buffer as a solvent, wherein the concentration of bacillus is 1.6 x 109cfu/mL of bacillus strain suspension with the pH value of 7-7.5, reacting for 2 hours at the temperature of 40 ℃ and the stirring speed of 100r/min, standing, filtering the supernatant after the modified zeolite powder is precipitated, and drying the lower modified zeolite powder in a drying box at the temperature of 37 ℃ to obtain the biological modified zeolite powder. The mass/volume ratio of the modified zeolite powder to the bacillus suspension is 1 g: 90 mL.
The preparation method of the carbon-doped modified titanium dioxide comprises the following steps:
1) adding polyacrylonitrile thermal expansion microspheres into 75 wt% sulfuric acid solution, hydrolyzing at 65 ℃ for 15min, taking out the polyacrylonitrile thermal expansion microspheres, washing with water to neutrality, and soaking the polyacrylonitrile thermal expansion microspheres in tetrabutyl titanate and 45% ethanol according to a volume ratio of 1: 1 for 10 hours, taking out, then placing the mixture into water and 45% ethanol according to a volume ratio of 1: 1, soaking for 1h, and centrifugally drying to obtain a solid for later use;
2) calcining the solid obtained in the step 1) at 480 ℃ for 1.5h under the protection of nitrogen to obtain the carbon-doped modified titanium dioxide.
The preparation method of the sewage treatment agent comprises the following steps:
1) mixing the biological modified zeolite powder and the non-ionic polyacrylamide according to a proportion, uniformly stirring to obtain a component A, and packaging for later use;
2) mixing carbon-doped modified titanium dioxide, polyaluminium chloride, aminotrimethylene phosphonic acid and silicate in proportion, stirring uniformly to obtain a component B, and packaging for later use;
3) when the sewage treatment agent is used, the component A is firstly put into sewage for treatment for 6 hours, and then the component B is put into the sewage for continuous treatment for 12 hours, wherein the mass ratio of the component A to the component B in the sewage treatment agent is 1: 2, the addition amount of the sewage treatment agent is 0.03 wt%.
Example 2:
a sewage treatment agent is composed of a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 25 parts of biological modified zeolite powder and 15 parts of non-ionic polyacrylamide; the component B comprises the following raw materials in parts by weight: 16 parts of carbon-doped modified titanium dioxide, 8 parts of polyaluminium chloride, 8 parts of aminotrimethylene phosphonic acid and 10 parts of aluminum silicate.
The preparation method of the modified zeolite powder comprises the following steps:
1) adding a natural zeolite powder raw material into a dodecyl trimethyl ammonium bromide solution with the concentration of 0.05mol/L, reacting for 24 hours at the temperature of 30 ℃ and the stirring speed of 160r/min, taking out the zeolite powder, washing the zeolite powder by using distilled water until the zeolite powder does not contain the dodecyl trimethyl ammonium bromide, and drying the zeolite powder in a drying box at the temperature of 65 ℃ for later use to obtain modified zeolite powder;
2) adding the modified zeolite powder obtained in the step 1 into phosphate buffer as a solvent, wherein the concentration of bacillus is 1.6 x 109cfu/mL of bacillus strain suspension with the pH value of 7-7.5, reacting for 2 hours at the temperature of 35 ℃ and the stirring speed of 80r/min, standing, filtering the supernatant after the modified zeolite powder is precipitated, and drying the lower modified zeolite powder in a drying box at the temperature of 35 ℃ to obtain the biological modified zeolite powder. The mass/volume ratio of the modified zeolite powder to the bacillus suspension is 0.8 g: 70 mL.
The preparation method of the carbon-doped modified titanium dioxide comprises the following steps:
1) adding polyacrylonitrile thermal expansion microspheres into 75 wt% sulfuric acid solution, hydrolyzing at 65 ℃ for 15min, taking out the polyacrylonitrile thermal expansion microspheres, washing with water to neutrality, and soaking the polyacrylonitrile thermal expansion microspheres in tetrabutyl titanate and 45% ethanol according to a volume ratio of 1: 1 for 10 hours, taking out, then placing the mixture into water and 45% ethanol according to a volume ratio of 1: 1, soaking for 1h, and centrifugally drying to obtain a solid for later use;
2) calcining the solid obtained in the step 1) at 480 ℃ for 1.5h under the protection of nitrogen to obtain the carbon-doped modified titanium dioxide.
The preparation method of the sewage treatment agent comprises the following steps:
1) mixing the biological modified zeolite powder and the non-ionic polyacrylamide according to a proportion, uniformly stirring to obtain a component A, and packaging for later use;
2) mixing carbon-doped modified titanium dioxide, polyaluminium chloride, aminotrimethylene phosphonic acid and silicate in proportion, stirring uniformly to obtain a component B, and packaging for later use;
3) when the sewage treatment agent is used, the component A is firstly put into sewage for treatment for 5 hours, and then the component B is put into the sewage for continuous treatment for 10 hours, wherein the mass ratio of the component A to the component B in the sewage treatment agent is 1: 2, the addition amount of the sewage treatment agent is 0.03 wt%.
Example 3:
a sewage treatment agent is composed of a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 20 parts of biological modified zeolite powder and 12 parts of non-ionic polyacrylamide; the component B comprises the following raw materials in parts by weight: 18 parts of carbon-doped modified titanium dioxide, 6 parts of polyaluminium chloride, 4 parts of aminotrimethylene phosphonic acid and 15 parts of ferric silicate.
The preparation method of the modified zeolite powder comprises the following steps:
1) adding a natural zeolite powder raw material into a dodecyl trimethyl ammonium bromide solution with the concentration of 0.03mol/L, reacting for 24 hours at the temperature of 40 ℃ and the stirring speed of 140r/min, taking out the zeolite powder, washing the zeolite powder by using distilled water until the zeolite powder does not contain the dodecyl trimethyl ammonium bromide, and drying the zeolite powder in a drying box at the temperature of 60 ℃ for later use to obtain modified zeolite powder;
2) adding the modified zeolite powder obtained in the step 1 into phosphate buffer as a solvent, wherein the concentration of bacillus is 1.6 x 109cfu/mL of bacillus strain suspension with the pH value of 7-7.5, reacting for 2 hours at the temperature of 40 ℃ and the stirring speed of 110r/min, standing, filtering the supernatant after the modified zeolite powder is precipitated, and drying the lower modified zeolite powder in a drying box at the temperature of 35 ℃ to obtain the biological modified zeolite powder. The mass/volume ratio of the modified zeolite powder to the bacillus suspension is 0.9 g: 80 mL.
The preparation method of the carbon-doped modified titanium dioxide and the preparation method of the sewage treatment agent are the same as the example 1.
Example 4:
a sewage treatment agent is composed of a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 35 parts of biological modified zeolite powder and 10 parts of non-ionic polyacrylamide; the component B comprises the following raw materials in parts by weight: 8 parts of carbon-doped modified titanium dioxide, 5 parts of polyaluminium chloride, 3 parts of amino trimethylene phosphonic acid and 12 parts of magnesium silicate.
The preparation method of the modified zeolite powder comprises the following steps:
1) adding a natural zeolite powder raw material into a dodecyl trimethyl ammonium bromide solution with the concentration of 0.04mol/L, reacting for 24 hours at the temperature of 35 ℃ and the stirring speed of 180r/min, taking out the zeolite powder, washing the zeolite powder by using distilled water until the zeolite powder does not contain the dodecyl trimethyl ammonium bromide, and drying the zeolite powder in a drying box at the temperature of 65 ℃ for later use to obtain modified zeolite powder;
2) adding the modified zeolite powder obtained in the step 1 into phosphate buffer as a solvent, wherein the concentration of bacillus is 1.6 x 109cfu/mL, pH 7-7.5, reacting for 2h at 30 deg.C under stirring speed of 120r/min, standing, filtering to remove supernatant, and oven drying the lower modified zeolite powder in a oven at 30 deg.C to obtain the biological modified zeolite powder. The mass/volume ratio of the modified zeolite powder to the bacillus suspension is 0.8 g: 90 mL.
The preparation method of the carbon-doped modified titanium dioxide and the preparation method of the sewage treatment agent are the same as the example 1.
Example 5:
a sewage treatment agent is composed of a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 40 parts of biological modified zeolite powder and 23 parts of non-ionic polyacrylamide; the component B comprises the following raw materials in parts by weight: 10 parts of carbon-doped modified titanium dioxide, 9 parts of polyaluminium chloride, 5 parts of aminotrimethylene phosphonic acid, aluminum silicate and ferric silicate in a mass ratio of 2: 1, 8 parts of a mixture.
The preparation method of the modified zeolite powder comprises the following steps:
1) adding a natural zeolite powder raw material into a dodecyl trimethyl ammonium bromide solution with the concentration of 0.03mol/L, reacting for 24 hours at the temperature of 30 ℃ and the stirring speed of 120r/min, taking out the zeolite powder, washing the zeolite powder by using distilled water until the zeolite powder does not contain the dodecyl trimethyl ammonium bromide, and drying the zeolite powder in a drying box at the temperature of 65 ℃ for later use to obtain modified zeolite powder;
2) adding the modified zeolite powder obtained in the step 1 into phosphate buffer as a solvent, wherein the concentration of bacillus is 1.6 x 109cfu/mL of bacillus strain suspension with the pH value of 7-7.5, reacting for 2 hours at the temperature of 35 ℃ and the stirring speed of 90r/min, standing, filtering the supernatant after the modified zeolite powder is precipitated, and drying the lower modified zeolite powder in a drying box at the temperature of 32 ℃ to obtain the biological modified zeolite powder. The mass/volume ratio of the modified zeolite powder to the bacillus suspension is 1 g: 80 mL.
The preparation method of the carbon-doped modified titanium dioxide and the preparation method of the sewage treatment agent are the same as the example 1.
Comparative example 1:
unlike example 1, component a of the wastewater treatment agent did not contain the biologically modified zeolite powder.
Comparative example 2:
different from the embodiment 1, the component B of the sewage treatment agent does not contain carbon-doped modified titanium dioxide.
Comparative example 3:
different from the embodiment 1, the component A of the sewage treatment agent does not contain non-ionic polyacrylamide, and the component B of the sewage treatment agent does not contain carbon-doped modified titanium dioxide.
The sewage treatment tests were performed on the sewage from the same sewage treatment plant using the sewage treatment agents prepared in examples 1 to 5 of the present invention and comparative examples 1 to 3, respectively, test groups 1 to 5 and control groups 1 to 3. Carrying out chroma determination on the sewage according to a method in a standard GB/11903-89; measuring COD in the sewage according to the standard HJ/T399-2007; measuring suspended matters in the sewage according to a standard GB/11901-89, and detecting the content of ammonia nitrogen in the sewage according to a standard GB/7478-87; detecting the alkalinity of the total phosphorus content in the sewage according to the standard GB/11893-89; and carrying out heavy metal detection on the sewage according to the standards GB/7475-87, GB/7466-87 and GB/6920-86. The results are shown in Table 2. The contents of the substances in the table are (mg/L)
Table 2:
in summary, the embodiment of the invention has the following beneficial effects: the sewage treatment agent prepared in the embodiments 1 to 5 of the present invention has excellent removal effects on dyes, organic pollutants, ammonia nitrogen, suspended matters, total phosphorus, heavy metals, and the like in sewage, and the treated wastewater can reach a first-level discharge standard, and especially, the biological modified zeolite powder, the carbon-doped modified titanium dioxide, and the non-ionic polyacrylamide in the raw materials have significant effects on removal of the dyes, the organic pollutants, the ammonia nitrogen, the suspended matters, and the like in sewage.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The sewage treatment agent consists of a component A and a component B, and is characterized in that the component A comprises the following raw materials in parts by weight: 20-40 parts of biological modified zeolite powder and 10-23 parts of non-ionic polyacrylamide; the component B comprises the following raw materials in parts by weight: 8-18 parts of carbon-doped modified titanium dioxide, 5-10 parts of polyaluminium chloride, 3-8 parts of aminotrimethylene phosphonic acid and 8-15 parts of silicate.
2. The sewage treatment agent according to claim 1, wherein the component A comprises the following raw materials in parts by weight: 25-35 parts of biological modified zeolite powder and 15-20 parts of non-ionic polyacrylamide; the component B comprises the following raw materials in parts by weight: 10-15 parts of carbon-doped modified titanium dioxide, 6-9 parts of polyaluminium chloride, 4-7 parts of aminotrimethylene phosphonic acid and 10-12 parts of silicate.
3. The sewage treatment agent according to claim 2, wherein the component A comprises the following raw materials in parts by weight: 30 parts of biological modified zeolite powder and 16 parts of non-ionic polyacrylamide; the component B comprises the following raw materials in parts by weight: 12 parts of carbon-doped modified titanium dioxide, 8 parts of polyaluminium chloride, 6 parts of aminotrimethylene phosphonic acid and 11 parts of silicate.
4. The wastewater treatment agent according to any one of claims 1 to 3, wherein the preparation method of the modified zeolite powder comprises the following steps:
1) adding a natural zeolite powder raw material into a dodecyl trimethyl ammonium bromide solution, reacting for 24 hours at the temperature of 30-40 ℃ and the stirring speed of 120-;
2) adding the modified zeolite powder obtained in the step 1 into bacillus strain suspension taking phosphate buffer solution as a solvent, reacting for 2 hours at the temperature of 30-40 ℃ and at the stirring speed of 80-120r/min, standing, filtering out supernatant after the modified zeolite powder is precipitated, and drying the lower modified zeolite powder in a drying box at the temperature of 30-37 ℃ to obtain the biological modified zeolite powder.
5. The sewage treatment agent according to claim 4, wherein the concentration of the dodecyl trimethyl ammonium bromide solution in the step 1) is 0.03-0.05mol/L, and the drying temperature in the drying box is 60-70 ℃.
6. The wastewater treatment agent of claim 4, wherein in step 2), the concentration of Bacillus in the Bacillus suspension is 1.6 x 109cfu/mL, pH value of 7-7.5, quality of modified zeolite powder and bacillus suspensionVolume ratio of 0.8-1 g: 70-90 mL.
7. The wastewater treatment agent according to any one of claims 1 to 3, wherein the carbon-doped modified titanium dioxide is prepared by a method comprising the steps of:
1) adding polyacrylonitrile thermal expansion microspheres into 75 wt% sulfuric acid solution, hydrolyzing at 65 ℃ for 15min, taking out the polyacrylonitrile thermal expansion microspheres, washing with water to neutrality, and soaking the polyacrylonitrile thermal expansion microspheres in tetrabutyl titanate and 45% ethanol according to a volume ratio of 1: 1 for 10 hours, taking out, then placing the mixture into water and 45% ethanol according to a volume ratio of 1: 1, soaking for 1h, and centrifugally drying to obtain a solid for later use;
2) calcining the solid obtained in the step 1) at 480 ℃ for 1.5 hours under the protection of nitrogen to obtain the carbon-doped modified titanium dioxide.
8. The wastewater treatment agent according to any one of claims 1 to 3, wherein the silicate is one of aluminum silicate, iron silicate, magnesium silicate or a mixture thereof in any proportion.
9. A method of preparing the wastewater treatment agent according to any of claims 1 to 3, comprising the steps of:
1) mixing the biological modified zeolite powder and the non-ionic polyacrylamide according to a proportion, uniformly stirring to obtain a component A, and packaging for later use;
2) mixing carbon-doped modified titanium dioxide, polyaluminium chloride, aminotrimethylene phosphonic acid and silicate in proportion, stirring uniformly to obtain a component B, and packaging for later use;
3) when the sewage treatment agent is used, the component A is firstly put into sewage and treated for 4-6 hours, and then the component B is put into the sewage and continuously treated for 10-12 hours, wherein the mass ratio of the component A to the component B in the sewage treatment agent is 1: 2, the addition amount of the sewage treatment agent is 0.03 wt%.
10. Use of a wastewater treatment agent as claimed in any of claims 1 to 3 for the treatment of municipal domestic wastewater.
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