CN115231648B - Industrial sewage treatment agent and preparation method thereof - Google Patents
Industrial sewage treatment agent and preparation method thereof Download PDFInfo
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- 239000010865 sewage Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 61
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920002472 Starch Polymers 0.000 claims abstract description 31
- 235000019698 starch Nutrition 0.000 claims abstract description 31
- 239000008107 starch Substances 0.000 claims abstract description 31
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 27
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 27
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 27
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 27
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 26
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims abstract description 26
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims abstract description 23
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 23
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 21
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 21
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims description 69
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 44
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 239000000706 filtrate Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000012047 saturated solution Substances 0.000 claims description 20
- 235000007340 Hordeum vulgare Nutrition 0.000 claims description 17
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 14
- 238000005286 illumination Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 229940115440 aluminum sodium silicate Drugs 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 240000005979 Hordeum vulgare Species 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 33
- 231100000719 pollutant Toxicity 0.000 abstract description 33
- 230000000694 effects Effects 0.000 abstract description 24
- 239000002245 particle Substances 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 4
- 241000209219 Hordeum Species 0.000 description 16
- 229920000881 Modified starch Polymers 0.000 description 9
- 239000004368 Modified starch Substances 0.000 description 9
- 235000019426 modified starch Nutrition 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 239000005445 natural material Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 230000002186 photoactivation Effects 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- -1 silver ions Chemical class 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- 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
- C02F1/28—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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Sludge (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The application provides an industrial sewage treatment agent and a preparation method thereof, and relates to the technical field of industrial sewage. The industrial sewage treatment agent comprises the following raw materials in parts by weight: 0.1-0.3 part of titanium dioxide, 0.01-0.05 part of silver nitrate, 5-10 parts of starch, 1-2 parts of epoxypropyl trimethyl ammonium chloride, 5-10 parts of montmorillonite, 5-7.5 parts of aluminum hydroxide, 2-3 parts of sodium silicate, 0.2-0.6 part of acrylamide, 0.5-1.2 parts of dimethyl diallyl ammonium chloride, 0.01-0.03 part of sodium tripolyphosphate, 0.05-0.1 part of azobisisobutyronitrile, 0.01-0.03 part of ammonium sulfate and 2-3 parts of polyaluminum ferric chloride. The industrial sewage treatment agent can neutralize the surface charge of pollutants in industrial sewage and reduce the repulsive force of pollutant particles, so that the aggregation of floccules is enhanced, the specific surface area of the pollutants is reduced, the pollutants are settled, and the effect of purifying the sewage is achieved.
Description
Technical Field
The application relates to the technical field of industrial sewage, in particular to an industrial sewage treatment agent and a preparation method thereof.
Background
Industrial sewage is a heavy sewage in modern society, and along with the development of industry, more and more industrial sewage is discharged and recycled and treated. Industrial sewage is different from domestic sewage, contains a plurality of heavy metals, is more serious to environmental pollution, and threatens human health. Therefore, the treatment of industrial sewage needs to be more important than the treatment of municipal sewage.
Industrial sewage contains a lot of pollutants, including a large amount of solid pollutants, which are toxic to the environment and human bodies, and the pollutants are small in particles and can increase the turbidity of water after being dissolved in the water, so that the water body is polluted, meanwhile, the particles are small and are difficult to remove, and the pollutants in the water can permeate into soil to pollute the soil. When sewage is treated, a sewage treatment agent is needed, and the existing sewage treatment agent can not treat impurities contained in the sewage better at present, so that the impurities contained in the sewage can not be thoroughly treated when the sewage is treated, the impurities are still contained after the sewage treatment, and the treatment effect of the sewage treatment agent is reduced.
Disclosure of Invention
The application aims to provide an industrial sewage treatment agent which has the advantage of good sewage treatment effect.
Another object of the present application is to provide a method for preparing an industrial sewage treatment agent to obtain the sewage treatment agent.
The application solves the technical problems by adopting the following technical scheme.
On one hand, the embodiment of the application provides an industrial sewage treatment agent, which comprises the following raw materials in parts by weight: 0.1-0.3 part of titanium dioxide, 0.01-0.05 part of silver nitrate, 5-10 parts of starch, 1-2 parts of epoxypropyl trimethyl ammonium chloride, 5-10 parts of montmorillonite, 5-7.5 parts of aluminum hydroxide, 2-3 parts of sodium silicate, 0.2-0.6 part of acrylamide, 0.5-1.2 parts of dimethyl diallyl ammonium chloride, 0.01-0.03 part of sodium tripolyphosphate, 0.05-0.1 part of azobisisobutyronitrile, 0.01-0.03 part of ammonium sulfate and 2-3 parts of polyaluminum ferric chloride.
On the other hand, the embodiment of the application provides a preparation method of an industrial sewage treatment agent, which comprises the following steps:
mixing titanium dioxide with ethylene glycol under illumination, adjusting the pH value to 8, and performing ultrasonic treatment to obtain a titanium dioxide solution;
preparing saturated solution by adding absolute ethyl alcohol into silver nitrate, mixing the saturated solution with titanium dioxide solution, stirring, taking out, washing with absolute ethyl alcohol, and drying to obtain a product 1;
adding epoxypropyl trimethyl ammonium chloride into a sodium hydroxide solution, adding starch, stirring, using absolute ethyl alcohol for 3-5 times, drying and crushing to obtain a product 2;
mixing montmorillonite, water and sulfuric acid, heating, filtering to obtain filtrate, adding sulfuric acid into the filtrate, adding aluminum hydroxide and sodium silicate, drying and pulverizing to obtain a product 3;
mixing acrylamide, dimethyl diallyl ammonium chloride and sodium tripolyphosphate, adding water, mixing, stirring under an anaerobic condition, adding azodiisobutyl cyanide, stirring for reaction, adding a product 1, a product 2, a product 3 and polyaluminium ferric chloride, and stirring to obtain a finished product of the industrial sewage treatment agent.
Compared with the prior art, the embodiment of the application has at least the following advantages or beneficial effects:
the industrial sewage treatment agent disclosed by the application can neutralize the surface charge of pollutants in industrial sewage, and reduce the repulsive force of pollutant particles, so that the aggregation effect of floccules is enhanced, the specific surface area of the pollutants is reduced, the pollutants are settled, and the effect of purifying the sewage is achieved.
According to the application, titanium dioxide is used as a raw material, has excellent photodegradation and photocatalytic activity, based on the photoactivation points existing on the surface of the titanium dioxide, cations on a crystal lattice of the titanium dioxide can lose 2 electrons to become oxygen atoms under illumination, and released electrons are reduced to trivalent titanium by tetravalent titanium replenishment, so that free radicals of hydroxyl groups and peroxy hydroxyl groups can be generated, but based on the fact that the titanium dioxide has less response to light, pollutants cannot be fully degraded, the titanium dioxide is selected to be treated with ethylene glycol under illumination conditions, and then is doped with silver ions, so that effective separation of electron and hole pairs can be effectively realized, the service life of photo-generated electrons is prolonged, and the photocatalytic activity of the titanium dioxide is better. The hydroxyl of the starch is replaced by the epoxypropyl trimethyl ammonium chloride, so that the modified starch has good effect of capturing pollutants, and the modified starch is a natural material and still has good biocompatibility, so that the treating agent is environment-friendly. By modifying montmorillonite (containing silicon dioxide and aluminum oxide) with sulfuric acid and then treating, the montmorillonite can have good adsorption effect on impurities such as oil bodies, colloids, suspended matters and the like in sewage. And then grafting the acrylamide and the modified starch to form a netlike macromolecular polymer which has outstanding electric neutralization capacity and also has outstanding adsorption flocculation effect, and simultaneously, the added product 1, the product 3 and the polyaluminium ferric chloride are uniformly dispersed in the netlike macromolecular polymer, so that the pollutant treatment capacity of the whole treating agent is enhanced. The added polyaluminum ferric chloride has good effect of removing pollutants and low required dosage.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings to be used in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the comparative treatment removal rate of the experimental example of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to specific examples.
The application provides an industrial sewage treatment agent which comprises the following raw materials in parts by weight: 0.1-0.3 part of titanium dioxide, 0.01-0.05 part of silver nitrate, 5-10 parts of starch, 1-2 parts of epoxypropyl trimethyl ammonium chloride, 5-10 parts of montmorillonite, 5-7.5 parts of aluminum hydroxide, 2-3 parts of sodium silicate, 0.2-0.6 part of acrylamide, 0.5-1.2 parts of dimethyl diallyl ammonium chloride, 0.01-0.03 part of sodium tripolyphosphate, 0.05-0.1 part of azobisisobutyronitrile, 0.01-0.03 part of ammonium sulfate and 2-3 parts of polyaluminum ferric chloride. The industrial sewage treatment agent disclosed by the application can neutralize the surface charge of pollutants in industrial sewage, and reduce the repulsive force of pollutant particles, so that the aggregation effect of floccules is enhanced, the specific surface area of the pollutants is reduced, the pollutants are settled, and the effect of purifying the sewage is achieved.
In some embodiments, the industrial sewage treatment agent comprises the following raw materials in parts by weight: 0.1-0.2 part of titanium dioxide, 0.02-0.03 part of silver nitrate, 8-10 parts of starch, 1-1.5 parts of epoxypropyl trimethyl ammonium chloride, 6-8 parts of montmorillonite, 6-7 parts of aluminum hydroxide, 2.1-2.5 parts of sodium silicate, 0.3-0.5 part of acrylamide, 0.6-1 part of dimethyl diallyl ammonium chloride, 0.01-0.02 part of sodium tripolyphosphate, 0.07-0.09 part of azodiisobutyl cyanide, 0.01-0.02 part of ammonium sulfate and 2.2-2.8 parts of polyaluminium ferric chloride.
In some embodiments, the starch is highland barley starch. The inventor discovers that highland barley starch is selected for modification, the purifying effect on pollutants is better than that of common corn starch in the market, and highland barley has low price, and the highland barley can reduce the production cost of the treating agent as a raw material.
The application also provides a preparation method of the industrial sewage treatment agent, which comprises the following steps:
mixing titanium dioxide with ethylene glycol under illumination, adjusting the pH value to 8, and performing ultrasonic treatment to obtain a titanium dioxide solution;
preparing saturated solution by adding absolute ethyl alcohol into silver nitrate, mixing the saturated solution with titanium dioxide solution, stirring, taking out, washing with absolute ethyl alcohol, and drying to obtain a product 1;
adding epoxypropyl trimethyl ammonium chloride into a sodium hydroxide solution, adding starch, stirring, using absolute ethyl alcohol for 3-5 times, drying and crushing to obtain a product 2;
mixing montmorillonite, water and sulfuric acid, heating, filtering to obtain filtrate, adding sulfuric acid into the filtrate, adding aluminum hydroxide and sodium silicate, drying and pulverizing to obtain a product 3;
mixing acrylamide, dimethyl diallyl ammonium chloride and sodium tripolyphosphate, adding water, mixing, stirring under an anaerobic condition, adding azodiisobutyl cyanide, stirring for reaction, adding a product 1, a product 2, a product 3 and polyaluminium ferric chloride, and stirring to obtain a finished product of the industrial sewage treatment agent. According to the method, titanium dioxide is used as a raw material, the titanium dioxide has excellent photodegradation and photocatalytic activity, based on the photoactivation points existing on the surface of the titanium dioxide, 2 electrons can be lost to form oxygen atoms by cations on a crystal lattice of the titanium dioxide under illumination, the released electrons are reduced to trivalent titanium by tetravalent titanium replenishment, hydroxyl free radicals and peroxy hydroxyl free radicals can be generated, but the titanium dioxide cannot fully degrade pollutants based on less response of the titanium dioxide to light, and silver ions are used for doping the titanium dioxide after the titanium dioxide is treated with ethylene glycol under illumination conditions, so that effective separation of electrons and hole pairs can be effectively realized, the service life of photo-generated electrons is prolonged, and the photocatalytic activity of the titanium dioxide is better. The modified starch has good capturing effect on pollutants by using the epoxypropyl trimethyl ammonium chloride to replace the hydroxyl groups of the starch, and the modified starch is a natural material and still has good biocompatibility, so that the treatment agent is environment-friendly. By modifying montmorillonite (containing silicon dioxide and aluminum oxide) with sulfuric acid and then treating, the montmorillonite can have good adsorption effect on impurities such as oil bodies, colloids, suspended matters and the like in sewage. And then grafting the acrylamide and the modified starch to form a netlike macromolecular polymer which has outstanding electric neutralization capacity and outstanding adsorption flocculation effect, and uniformly dispersing the added product 1, product 3 and polyaluminium ferric chloride therein, thereby enhancing the pollutant treatment capacity of the whole treating agent. The added polyaluminum ferric chloride has good effect of removing pollutants and low required dosage.
In some embodiments, the ratio of titania to ethylene glycol is 1:100, the pH value is regulated by sodium hydroxide, and the ultrasonic treatment time is 20-40min.
In some embodiments, the weight ratio of the saturated solution to titanium dioxide is 1: (3.5-4.5), and stirring the saturated solution and titanium dioxide at 55-60 ℃ for 7-10h.
In some embodiments, the ratio of the solution of epoxypropyl trimethyl ammonium chloride to sodium hydroxide is 1: (8-14), wherein the concentration of the sodium hydroxide solution is 0.1mol/L, and the epoxypropyl trimethyl ammonium chloride is mixed with the sodium hydroxide solution, then the mixture is kept stand for 15-20min, starch is added, and the mixture is stirred for 150-200min at the temperature of 40-45 ℃.
In some embodiments, the volume concentration of the sulfuric acid is 98%, and the montmorillonite, water, and sulfuric acid are mixed according to a ratio of 1:1: mixing 0.3 weight ratio, heating at 105-115 ℃ for 3-5h, wherein the weight ratio of the filtrate to the sulfuric acid is (32-34): (7-9), and still standing for 2-3h after adding the aluminum hydroxide and sodium silicate.
In some embodiments, the acrylamide, dimethyldiallylammonium chloride and sodium tripolyphosphate are mixed according to 1: mixing the feed liquid ratio of (100-150) with water, wherein the stirring time is 50-80min after the acrylamide, the dimethyl diallyl ammonium chloride and the sodium tripolyphosphate are mixed with the water.
In some embodiments, the azo-bis-isocyanide is added and then stirred for 3-5 hours at 50-80 ℃.
In some embodiments, the above product 1, product 2, product 3, and polyaluminum ferric chloride are stirred for 30-50 minutes after addition.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
The preparation method of the industrial sewage treatment agent is characterized by comprising the following steps of:
raw materials: titanium dioxide 0.1g, silver nitrate 0.01g, highland barley starch 5g, epoxypropyl trimethyl ammonium chloride 1g, montmorillonite 5g, aluminum hydroxide 5g, sodium silicate 2g, acrylamide 0.2g, dimethyl diallyl ammonium chloride 0.5g, sodium tripolyphosphate 0.01g, azodiisobutyl cyanide 0.05g, ammonium sulfate 0.01g and polyaluminium ferric chloride 2g.
Under illumination conditions, the following is true for 1: mixing titanium dioxide and ethylene glycol according to a feed liquid ratio of 100, adjusting the pH value to 8, and performing ultrasonic treatment for 20min to obtain a titanium dioxide solution;
preparing saturated solution by adding absolute ethyl alcohol into silver nitrate according to the following proportion of 1:3.5, mixing the saturated solution and the titanium dioxide solution in a weight ratio, stirring for 7 hours at 55 ℃, taking out, washing with absolute ethyl alcohol, and drying to obtain a product 1;
according to 1: adding epoxypropyl trimethyl ammonium chloride into a sodium hydroxide solution with the concentration of 0.1mol/L according to the feed liquid ratio of 8, standing for 15min, adding highland barley starch, stirring for 150min at 40 ℃, using absolute ethanol for 3 times, drying and crushing to obtain a product 2;
montmorillonite, water and sulfuric acid (98% by volume) were mixed according to a 1:1: mixing in a weight ratio of 0.3, heating at 105-115 ℃ for 3-5h, filtering to obtain filtrate, and mixing the filtrate with the filtrate according to the weight ratio of 32: adding sulfuric acid into the filtrate according to the weight ratio of 7, adding aluminum hydroxide and sodium silicate, standing for 2 hours, drying, and crushing to obtain a product 3;
after mixing acrylamide, dimethyldiallylammonium chloride and sodium tripolyphosphate, the following steps were followed: mixing the feed liquid ratio of 100 with water, stirring for 50min under anaerobic condition, adding azodiisobutyl cyanide, stirring at 50 ℃ for reaction for 3h, adding the product 1, the product 2, the product 3 and polyaluminium ferric chloride, and stirring for 30min to obtain the industrial sewage treatment agent finished product.
Example 2
The preparation method of the industrial sewage treatment agent is characterized by comprising the following steps of:
raw materials: titanium dioxide 0.1g, silver nitrate 0.02g, highland barley starch 8g, epoxypropyl trimethyl ammonium chloride 1g, montmorillonite 6g, aluminum hydroxide 6g, sodium silicate 2.1g, acrylamide 0.3g, dimethyl diallyl ammonium chloride 0.6g, sodium tripolyphosphate 0.01g, azodiisobutyl cyanide 0.07g, ammonium sulfate 0.01g and polyaluminium ferric chloride 2.2g.
Under illumination conditions, the following is true for 1: mixing titanium dioxide and ethylene glycol according to a feed liquid ratio of 100, adjusting the pH value to 8, and performing ultrasonic treatment for 30min to obtain a titanium dioxide solution;
preparing saturated solution by adding absolute ethyl alcohol into silver nitrate according to the following proportion of 1:4, mixing the saturated solution with the titanium dioxide solution in a weight ratio, stirring for 8 hours at 58 ℃, taking out, washing with absolute ethyl alcohol, and drying to obtain a product 1;
according to 1:10, adding epoxypropyl trimethyl ammonium chloride into a sodium hydroxide solution with the concentration of 0.1mol/L, standing for 18min, adding highland barley starch, stirring for 180min at 43 ℃, using absolute ethanol for 4 times, drying and crushing to obtain a product 2;
montmorillonite, water and sulfuric acid (98% by volume) were mixed according to a 1:1: mixing in a weight ratio of 0.3, heating at 110 ℃ for 4 hours, filtering to obtain filtrate, and mixing the filtrate according to 33:8, adding sulfuric acid into the filtrate in a weight ratio, adding aluminum hydroxide and sodium silicate, standing for 2.5h, drying, and crushing to obtain a product 3;
after mixing acrylamide, dimethyldiallylammonium chloride and sodium tripolyphosphate, the following steps were followed: 130, stirring for 70min under anaerobic condition, adding azodiisobutyl cyanide, stirring at 70 ℃ for 3-5h, adding the product 1, the product 2, the product 3 and polyaluminium ferric chloride, and stirring for 30-50min to obtain the industrial sewage treatment agent finished product.
Example 3
The preparation method of the industrial sewage treatment agent is characterized by comprising the following steps of:
raw materials: titanium dioxide 0.15g, silver nitrate 0.025g, highland barley starch 9g, epoxypropyl trimethyl ammonium chloride 1.3g, montmorillonite 7g, aluminum hydroxide 6.5g, sodium silicate 2.3g, acrylamide 0.4g, dimethyl diallyl ammonium chloride 0.8g, sodium tripolyphosphate 0.015g, azodiisobutyl cyanide 0.08g, ammonium sulfate 0.015g and polyaluminium ferric chloride 2.5g.
Under illumination conditions, the following is true for 1: mixing titanium dioxide and ethylene glycol according to a feed liquid ratio of 100, adjusting the pH value to 8, and performing ultrasonic treatment for 30min to obtain a titanium dioxide solution;
preparing saturated solution by adding absolute ethyl alcohol into silver nitrate according to the following proportion of 1:4, mixing the saturated solution with the titanium dioxide solution in a weight ratio, stirring for 9 hours at 58 ℃, taking out, washing with absolute ethyl alcohol, and drying to obtain a product 1;
according to 1:12, adding epoxypropyl trimethyl ammonium chloride into a sodium hydroxide solution with the concentration of 0.1mol/L, standing for 18min, adding highland barley starch, stirring for 180min at 43 ℃, using absolute ethanol for 4 times, drying and crushing to obtain a product 2;
montmorillonite, water and sulfuric acid (98% by volume) were mixed according to a 1:1: mixing in a weight ratio of 0.3, heating at 110 ℃ for 4 hours, filtering to obtain filtrate, and mixing the filtrate according to 33:8, adding sulfuric acid into the filtrate in a weight ratio, adding aluminum hydroxide and sodium silicate, standing for 2.5h, drying, and crushing to obtain a product 3;
after mixing acrylamide, dimethyldiallylammonium chloride and sodium tripolyphosphate, the following steps were followed: 130, stirring for 70min under anaerobic condition, adding azodiisobutyl cyanide, stirring at 70 ℃ for reaction for 4h, adding the product 1, the product 2, the product 3 and polyaluminium ferric chloride, and stirring for 40min to obtain the industrial sewage treatment agent finished product.
Example 4
The preparation method of the industrial sewage treatment agent is characterized by comprising the following steps of:
raw materials: titanium dioxide 0.2g, silver nitrate 0.03g, highland barley starch 10g, epoxypropyl trimethyl ammonium chloride 1.5g, montmorillonite 8g, aluminum hydroxide 7g, sodium silicate 2.5g, acrylamide 0.5g, dimethyl diallyl ammonium chloride 1g, sodium tripolyphosphate 0.02g, azobisisobutyronitrile 0.09g, ammonium sulfate 0.02g and polyaluminum ferric chloride 2.8g.
Under illumination conditions, the following is true for 1: mixing titanium dioxide and ethylene glycol according to a feed liquid ratio of 100, adjusting the pH value to 8, and performing ultrasonic treatment for 20-40min to obtain a titanium dioxide solution;
preparing saturated solution by adding absolute ethyl alcohol into silver nitrate according to the following proportion of 1:4.5, mixing the saturated solution and the titanium dioxide solution in a weight ratio, stirring for 10 hours at 60 ℃, taking out, washing with absolute ethyl alcohol, and drying to obtain a product 1;
according to 1:14, adding epoxypropyl trimethyl ammonium chloride into a sodium hydroxide solution with the concentration of 0.1mol/L, standing for 20min, adding highland barley starch, stirring for 200min at 45 ℃, using absolute ethanol for 5 times, drying and crushing to obtain a product 2;
montmorillonite, water and sulfuric acid (98% by volume) were mixed according to a 1:1: mixing in a weight ratio of 0.3, heating at 115 ℃ for 5 hours, filtering to obtain filtrate, and mixing the filtrate according to 34: adding sulfuric acid into the filtrate according to the weight ratio of 9, adding aluminum hydroxide and sodium silicate, standing for 3 hours, drying, and crushing to obtain a product 3;
after mixing acrylamide, dimethyldiallylammonium chloride and sodium tripolyphosphate, the following steps were followed: 150, mixing the solution with water, stirring for 80min under anaerobic condition, adding azodiisobutyl cyanide, stirring at 80 ℃ for reaction for 5h, adding the product 1, the product 2, the product 3 and polyaluminium ferric chloride, and stirring for 50min to obtain the industrial sewage treatment agent finished product.
Example 5
The preparation method of the industrial sewage treatment agent is characterized by comprising the following steps of:
raw materials: titanium dioxide 0.3g, silver nitrate 0.05g, highland barley starch 10g, epoxypropyl trimethyl ammonium chloride 2g, montmorillonite 10g, aluminum hydroxide 7.5g, sodium silicate 3g, acrylamide 0.6g, dimethyl diallyl ammonium chloride 1.2g, sodium tripolyphosphate 0.03g, azodiisobutyl cyanide 0.1g, ammonium sulfate 0.03g and polyaluminium ferric chloride 3g.
Under illumination conditions, the following is true for 1: mixing titanium dioxide and ethylene glycol according to a feed liquid ratio of 100, adjusting the pH value to 8, and performing ultrasonic treatment for 40min to obtain a titanium dioxide solution;
preparing saturated solution by adding absolute ethyl alcohol into silver nitrate according to the following proportion of 1:4.5, mixing the saturated solution and the titanium dioxide solution in a weight ratio, stirring for 10 hours at 60 ℃, taking out, washing with absolute ethyl alcohol, and drying to obtain a product 1;
according to 1:14, adding epoxypropyl trimethyl ammonium chloride into a sodium hydroxide solution with the concentration of 0.1mol/L, standing for 20min, adding highland barley starch, stirring for 200min at 45 ℃, using absolute ethanol for 5 times, drying and crushing to obtain a product 2;
montmorillonite, water and sulfuric acid (98% by volume) were mixed according to a 1:1: mixing in a weight ratio of 0.3, heating at 115 ℃ for 5 hours, filtering to obtain filtrate, and mixing the filtrate according to 34: adding sulfuric acid into the filtrate according to the weight ratio of 9, adding aluminum hydroxide and sodium silicate, standing for 3 hours, drying, and crushing to obtain a product 3;
after mixing acrylamide, dimethyldiallylammonium chloride and sodium tripolyphosphate, the following steps were followed: 150, mixing the solution with water, stirring for 80min under anaerobic condition, adding azodiisobutyl cyanide, stirring at 80 ℃ for reaction for 5h, adding the product 1, the product 2, the product 3 and polyaluminium ferric chloride, and stirring for 50min to obtain the industrial sewage treatment agent finished product.
Comparative example 1
This comparative example is substantially identical to example 3, except that: highland barley starch is replaced by corn starch.
Experimental example
The papermaking wastewater is selected for experiments, and contains a large amount of suspended matters, COD and partial toxic substances. Experiments were carried out by taking examples 2 to 4 and comparative example 1, respectively, and putting them into sewage at 20℃to examine the removal of COD at an addition amount of 30mg/L, and the results are shown in Table 1.
TABLE 1
Comparison shows that the removing effect of the example 3 is optimal, and comparison of the comparative example 1 and the example 3 shows that the highland barley starch has better sewage treatment effect.
The papermaking wastewater was treated with the treating agents of example 3 in different amounts, and the specific treatment results are shown in fig. 1.
As can be seen from the observation of FIG. 1, the removal rate increased with the increase of the amount added, and the removal effect was optimal when the amount was 30mg/L, and the subsequent removal rate was gradually deteriorated. This may be because too much treating agent is added, resulting in an increase in charge density, so that charge repulsion between contaminants is large, adsorption is deteriorated, and thus sewage treatment effect is deteriorated.
In conclusion, the industrial sewage treatment agent disclosed by the application can neutralize the surface charge of pollutants in industrial sewage, reduce the repulsive force of pollutant particles, further enhance the aggregation of floccules, reduce the specific surface area of the pollutants, and further enable the pollutants to settle, thereby playing a role in purifying sewage.
According to the application, titanium dioxide is used as a raw material, has excellent photodegradation and photocatalytic activity, based on the photoactivation points existing on the surface of the titanium dioxide, cations on a crystal lattice of the titanium dioxide can lose 2 electrons to become oxygen atoms under illumination, and released electrons are reduced to trivalent titanium by tetravalent titanium replenishment, so that free radicals of hydroxyl groups and peroxy hydroxyl groups can be generated, but based on the fact that the titanium dioxide has less response to light, pollutants cannot be fully degraded, the titanium dioxide is selected to be treated with ethylene glycol under illumination conditions, and then is doped with silver ions, so that effective separation of electron and hole pairs can be effectively realized, the service life of photo-generated electrons is prolonged, and the photocatalytic activity of the titanium dioxide is better. The hydroxyl of the starch is replaced by the epoxypropyl trimethyl ammonium chloride, so that the modified starch has good effect of capturing pollutants, and the modified starch is a natural material and still has good biocompatibility, so that the treating agent is environment-friendly. By modifying montmorillonite (containing silicon dioxide and aluminum oxide) with sulfuric acid and then treating, the montmorillonite can have good adsorption effect on impurities such as oil bodies, colloids, suspended matters and the like in sewage. And then grafting the acrylamide and the modified starch to form a netlike macromolecular polymer which has outstanding electric neutralization capacity and outstanding adsorption flocculation effect, and uniformly dispersing the added product 1, product 3 and polyaluminium ferric chloride therein, thereby enhancing the pollutant treatment capacity of the whole treating agent. The added polyaluminum ferric chloride has good effect of removing pollutants and low required dosage.
The embodiments described above are some, but not all embodiments of the application. The detailed description of the embodiments of the application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden on the person of ordinary skill in the art based on embodiments of the present application, are within the scope of the present application.
Claims (9)
1. The industrial sewage treatment agent is characterized by comprising the following raw materials in parts by weight: 0.1-0.3 part of titanium dioxide, 0.01-0.05 part of silver nitrate, 5-10 parts of starch, 1-2 parts of epoxypropyl trimethyl ammonium chloride, 5-10 parts of montmorillonite, 5-7.5 parts of aluminum hydroxide, 2-3 parts of sodium silicate, 0.2-0.6 part of acrylamide, 0.5-1.2 parts of dimethyl diallyl ammonium chloride, 0.01-0.03 part of sodium tripolyphosphate, 0.05-0.1 part of azobisisobutyronitrile, 0.01-0.03 part of ammonium sulfate and 2-3 parts of polyaluminum ferric chloride;
the starch is highland barley starch;
the preparation method of the industrial sewage treatment agent comprises the following steps:
mixing titanium dioxide with ethylene glycol under illumination, adjusting the pH value to 8, and performing ultrasonic treatment to obtain a titanium dioxide solution;
preparing saturated solution by adding absolute ethyl alcohol into silver nitrate, mixing the saturated solution with titanium dioxide solution, stirring, taking out, washing with absolute ethyl alcohol, and drying to obtain a product 1;
adding epoxypropyl trimethyl ammonium chloride into a sodium hydroxide solution, adding starch, stirring, washing with absolute ethyl alcohol for 3-5 times, drying and crushing to obtain a product 2;
mixing montmorillonite, water and sulfuric acid, heating, filtering to obtain filtrate, adding sulfuric acid into the filtrate, adding aluminum hydroxide and sodium silicate, drying and pulverizing to obtain a product 3;
mixing acrylamide, dimethyl diallyl ammonium chloride and sodium tripolyphosphate, adding water, mixing, stirring under an anaerobic condition, adding azodiisobutyl cyanide, stirring for reaction, adding a product 1, a product 2, a product 3 and polyaluminium ferric chloride, and stirring to obtain a finished product of the industrial sewage treatment agent.
2. The industrial sewage treatment agent according to claim 1, which is characterized by comprising the following raw materials in parts by weight: 0.1-0.2 part of titanium dioxide, 0.02-0.03 part of silver nitrate, 8-10 parts of starch, 1-1.5 parts of epoxypropyl trimethyl ammonium chloride, 6-8 parts of montmorillonite, 6-7 parts of aluminum hydroxide, 2.1-2.5 parts of sodium silicate, 0.3-0.5 part of acrylamide, 0.6-1 part of dimethyl diallyl ammonium chloride, 0.01-0.02 part of sodium tripolyphosphate, 0.07-0.09 part of azodiisobutyl cyanide, 0.01-0.02 part of ammonium sulfate and 2.2-2.8 parts of polyaluminium ferric chloride.
3. The industrial sewage treatment agent according to claim 1, wherein the feed liquid ratio of titanium dioxide to ethylene glycol is 1:100, the pH value is regulated by sodium hydroxide, and the ultrasonic treatment time is 20-40min.
4. The industrial sewage treatment agent according to claim 1, wherein the weight ratio of the saturated solution to titanium dioxide is 1: (3.5-4.5), and stirring the saturated solution and the titanium dioxide solution for 7-10 hours at 55-60 ℃.
5. The industrial sewage treatment agent according to claim 1, wherein the ratio of the material to the liquid of the epoxypropyl trimethyl ammonium chloride to the sodium hydroxide solution is 1: (8-14), wherein the concentration of the sodium hydroxide solution is 0.1mol/L, and the epoxypropyl trimethyl ammonium chloride is mixed with the sodium hydroxide solution, then the mixture is kept stand for 15-20min, starch is added, and the mixture is stirred for 150-200min at the temperature of 40-45 ℃.
6. The industrial sewage treatment agent according to claim 1, wherein the volume concentration of sulfuric acid is 98%, and the montmorillonite, water and sulfuric acid are mixed according to the following formula 1:1: mixing in a weight ratio of 0.3, heating at 105-115 ℃ for 3-5h, wherein the weight ratio of the filtrate to sulfuric acid is (32-34): (7-9), and still standing for 2-3h after adding the aluminum hydroxide and sodium silicate.
7. The industrial sewage treatment agent according to claim 1, wherein the acrylamide, the dimethyldiallylammonium chloride and the sodium tripolyphosphate are mixed according to the following formula 1: mixing the feed liquid ratio of (100-150) with water, wherein the stirring time is 50-80min after the acrylamide, the dimethyl diallyl ammonium chloride and the sodium tripolyphosphate are mixed with the water.
8. The industrial sewage treatment agent according to claim 1, wherein the azobisisobutyronitrile is stirred and reacted for 3-5 hours at 50-80 ℃ after being added.
9. The industrial sewage treatment agent according to claim 1, wherein the product 1, the product 2, the product 3 and the polyaluminum ferric chloride are stirred for 30-50min after being added.
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