CN111348714A - Rapid composite water purification material for purifying slightly polluted surface water, preparation method and application thereof - Google Patents
Rapid composite water purification material for purifying slightly polluted surface water, preparation method and application thereof Download PDFInfo
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- CN111348714A CN111348714A CN201811572624.5A CN201811572624A CN111348714A CN 111348714 A CN111348714 A CN 111348714A CN 201811572624 A CN201811572624 A CN 201811572624A CN 111348714 A CN111348714 A CN 111348714A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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Abstract
The invention discloses a rapid composite water purification material for purifying slightly polluted surface water. The composite water purifying material is prepared by tabletting, calcining and granulating an environment repairing material, an oxygen release material, an auxiliary agent, activated carbon, a catalyst, high-efficiency magnetic powder and the like. The prepared repair material has excellent property, large surface area and better catalytic oxidation and adsorption effects; the oxygen release is fast and continuous, the efficiency is high, the energy consumption is low, the price is relatively low, the oxygen release is non-toxic and harmless, the secondary pollution is not generated, and the oxygen release can be independently used or can be used together with other technologies. The high efficiency of surface water purification is realized; the rapid surface water purification and restoration material realizes the multi-effect synergy of adsorption, chemical oxidation, catalytic oxidation and precipitation, overcomes the problems of single treatment function, poor regulation and control performance of treatment effect, secondary pollution and the like of the surface water purification material, achieves the aim of direct drinking after purification, and is a rapid surface water purification and restoration material which accords with the green sustainable restoration concept.
Description
Technical Field
The invention belongs to the technical field of surface water purification, and particularly relates to a rapid composite water purification material for purifying slightly polluted surface water, and a preparation method and application thereof.
Background
Surface water is an important component of fresh water resources and plays a very important role in the development of human society. However, the random stacking of industrial wastes, the large use of pesticides and fertilizers, and the leakage in the processes of oil exploitation, transportation, loading, unloading, storage, processing and use all cause serious surface pollution and pose a great threat to public health. The environmental protection department and the residential and construction department jointly transmit ' notice about publishing the national black and odorous water body investigation conditions in cities ' on a near day basis ' and report the investigation results after investigation. The investigation result shows that after 2 months and 16 days, in 295 places and above cities in the country, 218 cities find serious surface water pollution, and 1861 cities are counted. Wherein, the river 1595 accounts for 85.7%; 266 lakes and ponds and 14.3 percent. Therefore, the pollution of water resources in China is more and more serious, and the prevention and treatment of water pollution is urgent.
The traditional method for purifying the slightly polluted surface water body to be used as the domestic water comprises a physical method, a chemical method, a biological method, a combined technology and the like, wherein the physical and chemical methods have the defects of high treatment cost, complex operation, possibility of secondary pollution and the like, and the biological method has the problems of difficult domestication of flora, unstable treatment, long period and the like. In general, the above methods are difficult to achieve rapid purification to achieve the effect of direct living use or drinking. Filtration can effectively remove pollutants while maintaining the balance of elements required by humans, leaving water that humans can drink. Therefore, research on water purification materials has become a hotspot and difficulty in surface water purification research at home and abroad. The existing repair material applied to water purification has single function, the activity and efficiency of repair are to be improved urgently, and the repair material is high in price, large in using amount, slow in reaction, easy to form secondary pollution and the like.
Disclosure of Invention
The invention aims to provide a multi-effect composite repairing material for the purpose of quickly purifying the surface water quality to achieve the purpose of domestic use, and improve the environmental treatment efficiency.
The invention discloses a composite repairing material integrating multiple repairing functions of adsorption, precipitation, oxidation and the like, wherein oxygen release components can provide a quick and efficient solid oxygen supply source for repairing polluted surface water, and promote the purification speed of the surface water; meanwhile, the environment repairing material with the nano-aperture has good adsorption and oxidation capacity on organic pollutants; the catalytic capability of the catalyst to the oxidation reaction of the organic pollutants strengthens the treatment process of the organic pollutants; the active carbon has better effect on organic matters and heavy metals; the auxiliary agent provides a skeleton structure and a good reaction interface of the repair material; the high-efficiency magnetic powder has very strong adsorption effect on heavy metals, so that the heavy metals are precipitated.
In order to seek a green multi-effect repair material aiming at the purification of slightly polluted surface water and realize the effect of rapid purification and domestic use of the surface water, the invention creatively provides a preparation method of the multi-effect composite repair material which is used for the purification of slightly polluted surface water and has the advantages of adsorption, chemical oxidation, surface catalytic oxidation and magnetic precipitation.
The invention provides a rapid composite water purification material for purifying slightly polluted surface water, which comprises the following raw materials: environment repairing material, oxygen releasing material, assistant, active carbon, catalyst and efficient magnetic powder.
The environment restoration material shows good environment attributes such as surface restoration, pore channel effect and nanometer effect due to the special crystal structure and chemical characteristics prepared by synthesis, and can adsorb heavy metals and oxidize organic pollutants; the oxygen release material can provide a solid oxygen supply source to promote the rapid purification of surface water; the auxiliary agent, such as polylactic acid-glycolic acid copolymer has a better framework structure, plays a role in dispersion, provides a better reaction site, can be biodegraded, and has no secondary pollution risk; the natural sodium bentonite has adsorption performance and is a layered structure formed by natural octahedral sheets, and a good chemical reaction site is formed between layers; the active carbon has adsorption performance, plays a role in dispersion and inhibits powder agglomeration; the catalyst can catalyze and accelerate the degradation of organic matters; the high-efficiency magnetic powder can adsorb and precipitate heavy metals, so that the effect of removing the heavy metals is achieved.
Preferably, the raw materials of the rapid composite water purification material for purifying the slightly polluted surface water comprise the following components in parts by weight: 22-52 parts of an environment repairing material, 32-50 parts of an oxygen release material, 16-32 parts of an auxiliary agent, 15-42 parts of activated carbon, 5-18 parts of a catalyst and 10-25 parts of efficient magnetic powder.
Preferably, the environment repairing material is a synthetic manganese material which is formed by double-chain sharing oxygen top forming 2 × 2 type 2.
Preferably, the oxygen release material comprises one or more of sodium percarbonate, calcium peroxide and magnesium peroxide.
Preferably, the adjuvant is one or more of polylactic acid-glycolic acid copolymer, natural sodium bentonite, natural aluminosilicate ore and calcium carbonate.
Preferably, the activated carbon is biochar prepared from one or more of crop straws, peanut shells, shaddock peels, coconut shells and walnut shells.
Preferably, the catalyst is a modified catalyst of vanadium-doped ultrafine zinc oxide particles.
Preferably, the high-efficiency magnetic powder is CoxFe3-xO4Or modified cobalt ferrite CoxFe3-xO4(ii) a Wherein x is 1 or 2.
The invention also provides a preparation method of the rapid composite water purification material for purifying the slightly polluted surface water, which comprises the following steps:
(1) firstly, adsorbing an oxygen release material on the surface of active carbon, and then mixing and granulating the active carbon with an environment repairing material, an auxiliary agent, a catalyst and high-efficiency magnetic powder to prepare a spherical object;
(2) and (2) roasting the spherical object in the step (1) for 2-5h at 200-300 ℃ under the protection of inert gas, and cooling under the protection of inert gas to obtain the rapid composite water purifying material.
Preferably, the preparation method of the rapid composite water purification material for purifying the slightly polluted surface water comprises the following steps:
(1) preparing an environment repairing material:
①, adding a natural manganese mine product and a strong oxidant (the mol ratio is preferably 1:1.2-1:3.6) into deionized water, adding a phosphoric acid-disodium hydrogen phosphate buffer solution, stirring and mixing uniformly, adding concentrated nitric acid to adjust the pH of a reaction solution to be less than or equal to 1.5, transferring the reaction solution to a reaction kettle with a polyvinyl chloride liner, sealing the reaction kettle, heating to 200-350 ℃ and reacting for 12-36 hours, wherein the strong oxidant is preferably one of high-energy potassium, sodium persulfate, hydrogen peroxide and the like, and the pH value of the phosphoric acid-disodium hydrogen phosphate buffer solution is preferably 1.5-2.0;
② aging the mixture obtained in step ① for 12-24h, filtering, washing the filter cake with deionized water until the filtrate is neutral, and drying in an oven at 50-75 deg.C;
③, roasting the filter cake after drying in the step ② at the temperature of 250-600 ℃, and crushing and granulating the obtained product to obtain the environment repairing material;
(2) preparing activated carbon: cleaning biomass, soaking in strong alkali solution for 10-35h, taking out, cleaning, air drying, oven drying at 50-75 deg.C for 12h, baking the dried biomass at medium temperature for 5-10 hr to obtain activated carbon, pulverizing the activated carbon, and sealing; wherein the biomass is one or more of crop straws, peanut shells, shaddock peels, coconut shells and walnut shells;
(3) preparing a catalyst:
① putting zinc gluconate and sodium citrate (molar ratio is preferably 1:1-1:1.8) into a ball mill, high-speed ball milling for 30min, and transferring into a crucible;
② moving the crucible to a calcining furnace to be heated for 15-25min under the temperature of 300-500 ℃ in the absence of oxygen, and cooling under the protection of inert gas to obtain the ultramicro zinc oxide;
③, adding vanadium into the product obtained in the step ② (the mass ratio of the product to the vanadium is preferably 10:1-20:1), and placing the mixture into a ball mill for high-speed ball milling to obtain the modified catalyst of the vanadium-doped ultrafine zinc oxide particles;
(4) firstly, adsorbing an oxygen release material on the surface of active carbon, and then mixing and granulating the active carbon with an environment repairing material, an auxiliary agent, a catalyst and high-efficiency magnetic powder to prepare a spherical object;
(5) and (4) roasting the spherical objects in the step (4) at the temperature of 200-300 ℃ under the protection of inert gas, and cooling under the protection of inert gas to obtain the rapid composite water purifying material.
The invention also provides the rapid composite water purification material for purifying the slightly polluted surface water, which is obtained by the preparation method.
The invention also provides application of the rapid composite water purification material in water quality purification of slightly polluted surface water.
The invention also provides application of the rapid composite water purification material in remediation of slightly polluted underground water.
Compared with the prior art, the invention has the following advantages:
(1) the existing water purifying material has single function, and the use efficiency needs to be improved urgently. The invention can realize multiple purification functions of adsorption (precipitation) and catalysis/chemical oxidation of the slightly polluted surface water body by optimizing the combination of various functional materials, quickens the water purification process and achieves the effect of direct living use (or drinking).
(2) The composite material has the advantages of natural raw materials, low cost, simple preparation, adsorption, nano effect, catalytic oxidation and the like, and has a good purification effect on mild surface water bodies.
(3) The composite water purifying material provided by the invention has the advantages of rich raw materials, low price and simple preparation process, the used materials are natural materials, potential secondary pollution can not be caused by introducing surface water environment, no harm can be caused to human bodies, and the composite water purifying material conforms to the green sustainable restoration concept.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
A quick composite water purification material for purifying slightly polluted surface water comprises the following raw materials in parts by weight: 52 parts of environment-repairing material, 50 parts of sodium percarbonate, 32 parts of natural sodium bentonite, 42 parts of activated carbon, 18 parts of catalyst and high-efficiency magnetic powder CoFe2O4And 25 parts.
The environment repairing material is a synthetic manganese material which is formed by double-chain common-angle oxygen jacking and formed into a 2 × 2 type, wherein the preparation method comprises the following steps:
① adding natural manganese mine product and strong oxidant (potassium permanganate) (molar ratio is 1:1.2) into deionized water, adding phosphoric acid-disodium hydrogen phosphate buffer (pH is 2.0), stirring and mixing uniformly, adding 3-5ml of concentrated nitric acid to adjust the pH of the reaction solution to be less than or equal to 1.5, transferring to a reaction kettle of a polyvinyl chloride inner container, sealing the reaction kettle, heating to 350 ℃ and reacting for 12 hours;
② aging the mixture prepared in step ① for 12h, filtering, washing the filter cake with deionized water until the filtrate is neutral, and drying in an oven at 50 deg.C;
③, baking the filter cake after drying ② at 350 ℃, and crushing and granulating the obtained product to obtain the environment repairing material.
The preparation method of the activated carbon comprises the following steps: cleaning coconut shells, soaking in strong alkali solution for 30h, taking out, cleaning, air drying, drying in an oven at low temperature (50 ℃) for 12h, roasting the dried coconut shells at medium temperature (150 ℃) for 5h to obtain activated carbon, and crushing the activated carbon and sealing for later use.
The preparation method of the catalyst comprises the following steps:
① putting zinc gluconate and sodium citrate (molar ratio 1:1) into a ball mill, ball-milling at high speed for 30min, and transferring into a crucible;
② moving the crucible to a calcining furnace to be heated for 15-25min under the temperature of 300-500 ℃ in the absence of oxygen, and cooling under the protection of inert gas to obtain the ultramicro zinc oxide;
③ adding vanadium into the product obtained in the step ② (the mass ratio of the product to the vanadium is 10:1), and placing the product in a ball mill for high-speed ball milling to obtain the modified catalyst of the vanadium-doped ultrafine zinc oxide particles.
The preparation method of the rapid composite water purification material for purifying the slightly polluted surface water comprises the following steps:
(1) firstly, adsorbing an oxygen release material (sodium percarbonate) on the surface of active carbon, then mixing and granulating the active carbon with an environment repair material, an auxiliary agent (natural sodium bentonite), a catalyst and high-efficiency magnetic powder, and performing ball milling for 5 hours to prepare a spherical object;
(2) and (2) roasting the spherical object in the step (1) for 2 hours at 300 ℃ under the protection of inert gas, and cooling under the protection of inert gas to obtain the rapid composite water purifying material.
The prepared composite water purification material is placed in 80mg/LCOD lake water, and the dosage is 6 g/L. After 18 hours of reaction, the COD concentration in the solution was measured. The results show that the removal efficiency of COD reaches more than 94%.
Example 2
A quick composite water purification material for purifying slightly polluted surface water comprises the following raw materials in parts by weight: 22 parts of environment repairing material, 16 parts of calcium peroxide, 16 parts of magnesium peroxide, 8 parts of polylactic acid-glycolic acid copolymer, 8 parts of natural sodium bentonite, 15 parts of activated carbon, 5 parts of catalyst and high-efficiency magnetic powder CoFe2O410 parts.
The preparation method of the environment restoration material is the same as that of the embodiment 1.
The preparation method of the activated carbon comprises the following steps: cleaning walnut shells, soaking the walnut shells in a strong alkali solution for 30h, taking out the walnut shells, cleaning, air-drying the walnut shells, drying the walnut shells in an oven at a low temperature (50 ℃) for 12h, roasting the dried walnut shells at a medium temperature (200 ℃) for 5h to obtain activated carbon, and crushing the activated carbon and sealing the activated carbon for later use.
The preparation method of the catalyst is the same as that of the example 1.
The preparation method of the rapid composite water purification material for purifying the slightly polluted surface water comprises the following steps:
(1) firstly, absorbing oxygen release materials (calcium peroxide and magnesium peroxide) on the surface of active carbon, and then mixing the active carbon with an environment repairing material, polylactic acid-glycolic acid copolymer, natural sodium bentonite, a catalyst and high-efficiency magnetic powder CoFe2O4Mixing and granulating, and ball-milling for 5h to obtain a spherical object;
(2) and (2) roasting the spherical object in the step (1) for 2.5 hours at 300 ℃ under the protection of inert atmosphere, and cooling under the protection of inert gas to obtain the rapid composite water purifying material.
The prepared composite water purification material is placed in 120mg/LCOD river water body wastewater, and the dosage is 10 g/L. After 24 hours of reaction, the COD concentration in the solution was measured. The results show that: the removal rate of COD in the water body after the reaction reaches more than 90 percent.
Claims (10)
1. A quick composite water purification material for purifying slightly polluted surface water is characterized in that the raw materials comprise the following components in parts by weight: 22-52 parts of an environment repairing material, 32-50 parts of an oxygen release material, 16-32 parts of an auxiliary agent, 15-42 parts of activated carbon, 5-18 parts of a catalyst and 10-25 parts of efficient magnetic powder.
2. The rapid composite water purification material for purifying slightly polluted surface water as claimed in claim 1, wherein the environment restoration material is a synthetic manganese ore material of 2 × 2 type formed by double-chain common-angle oxygen top composed of octahedron common-edge, and the environment restoration material with nano-aperture grade is obtained after crushing and screening.
3. The rapid composite water purification material for purifying lightly polluted surface water as claimed in claim 1, wherein the oxygen release material comprises one or more of sodium percarbonate, calcium peroxide and magnesium peroxide.
4. The rapid composite water purification material for purifying slightly polluted surface water as claimed in claim 1, wherein the adjuvant is one or more of polylactic acid-glycolic acid copolymer, natural sodium bentonite, natural aluminosilicate ore and calcium carbonate.
5. The rapid composite water purification material for purifying slightly polluted surface water as claimed in claim 1, wherein the activated carbon is biochar prepared from one or more of crop straws, peanut shells, shaddock peels, coconut shells and walnut shells.
6. The rapid composite water purification material for purification of lightly polluted surface water as claimed in claim 1, wherein the catalyst is a catalyst of vanadium doped ultra micro zinc oxide particles.
7. The rapid composite water purification material for purifying slightly polluted surface water as claimed in claim 1, wherein the high-efficiency magnetic powder is cobalt ferrite CoxFe3-xO4Or modified cobalt ferrite CoxFe3-xO4Wherein x is 1 or 2.
8. The rapid composite water purification material for purifying lightly polluted surface water as claimed in claim 1, which is prepared by the following steps:
(1) preparing an environment repairing material:
① adding natural manganese mine products and strong oxidant into deionized water, adding phosphoric acid-disodium hydrogen phosphate buffer solution, stirring and mixing uniformly, adding concentrated nitric acid to adjust the pH of the reaction solution to be less than or equal to 1.5, transferring the reaction solution into a reaction kettle with a polyvinyl chloride liner, sealing the reaction kettle, heating to 200-350 ℃ and reacting for 12-36 hours;
② aging the mixture obtained in step ① for 12-24h, filtering, washing the filter cake with deionized water until the filtrate is neutral, and drying in an oven at 50-75 deg.C;
③, roasting the filter cake after drying in the step ② at the temperature of 250-600 ℃, and crushing and granulating the obtained product to obtain the environment repairing material;
(2) preparing activated carbon: cleaning biomass, soaking the biomass in a strong alkali solution for 10-35h, taking out, cleaning, air-drying, drying in a drying oven at a low temperature of 50-75 ℃ for 12h, roasting the dried biomass at a temperature of 150-350 ℃ for 5-10 h to obtain activated carbon, and crushing the activated carbon and sealing for later use; wherein the biomass is one or more of crop straws, peanut shells, shaddock peels, coconut shells and walnut shells;
(3) preparing a catalyst:
① putting zinc gluconate and sodium citrate into ball mill, high-speed ball milling for 30min, and transferring into crucible;
② moving the crucible to a calcining furnace to be heated for 15-25min under the temperature of 300-500 ℃ in the absence of oxygen, and cooling under the protection of inert gas to obtain the ultramicro zinc oxide;
③ adding vanadium into the product obtained in step ②, and placing the product in a ball mill for high-speed ball milling to obtain a modified catalyst of vanadium-doped ultrafine zinc oxide particles;
(4) firstly, adsorbing an oxygen release material on the surface of active carbon, and then mixing and granulating the active carbon with an environment repairing material, an auxiliary agent, a catalyst and high-efficiency magnetic powder to prepare a spherical object;
(5) and (4) roasting the spherical object in the step (4) for 2-5 hours at 200-300 ℃ under the protection of inert atmosphere, and cooling under the protection of inert gas to obtain the rapid composite water purifying material.
9. Use of the rapid composite water purification material according to any one of claims 1 to 7 in water purification of lightly polluted surface water.
10. The use of the rapid composite water purification material according to any one of claims 1 to 7 in the remediation of lightly polluted underground water bodies.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113683134A (en) * | 2021-08-31 | 2021-11-23 | 武汉千湖宝典生物科技有限公司 | Aquaculture water body bottom environment improver and preparation method thereof |
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| CN105036216A (en) * | 2015-08-17 | 2015-11-11 | 江苏金环环保设备有限公司 | Sodium-manganese water purifying material as well as preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113683134A (en) * | 2021-08-31 | 2021-11-23 | 武汉千湖宝典生物科技有限公司 | Aquaculture water body bottom environment improver and preparation method thereof |
| CN113683134B (en) * | 2021-08-31 | 2024-03-22 | 武汉千湖宝典生物科技有限公司 | Culture water body bottom environment improver and preparation method thereof |
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