CN106219692B - Tourmaline used as water body dephosphorization filter material and preparation method thereof - Google Patents
Tourmaline used as water body dephosphorization filter material and preparation method thereof Download PDFInfo
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- CN106219692B CN106219692B CN201610732106.XA CN201610732106A CN106219692B CN 106219692 B CN106219692 B CN 106219692B CN 201610732106 A CN201610732106 A CN 201610732106A CN 106219692 B CN106219692 B CN 106219692B
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
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- 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
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Abstract
The invention relates to an electrochemical stone as a water body dephosphorization filter material and a preparation method thereof, wherein the electrochemical stone comprises the following components in percentage by volume: 0.5 to 30 percent of metal material, 0.5 to 80 percent of binder, 1 to 40 percent of activator and 0.5 to 15 percent of catalyst; the preparation method of the filter material comprises the steps of carrying out micronization and nanocrystallization treatment on the components of the filter material, wherein the fineness of the components after the micronization and nanocrystallization treatment is not less than 300 meshes; uniformly mixing the micronized and nanocrystallized components; performing sintering-free extrusion (hydraulic) molding on the uniformly mixed material; and curing, drying and packaging the formed product. Compared with the prior art, the method well solves the problems of metal passivation, high manufacturing cost, lack of timeliness and the like in the phosphorus removal method.
Description
Technical Field
The invention relates to a filter material, in particular to an electrochemical stone used as a water body dephosphorization filter material and a preparation method thereof.
Background
The 'water eutrophication' is one of the well-known environmental pollution sources. The increasingly developed production and life activities of human beings provide rich N and P nutrient sources, namely eutrophication, for water bodies, and as a result, the excessive propagation of algae is caused. Particularly, the removal of the algae is mainly carried out the phosphorus removal, namely, the purification of the landscape water body is mainly carried out the phosphorus removal.
The phosphorus removal method comprises a physical and chemical method, a biochemical method, a biological method, natural treatment and the like. The physicochemical method is commonly used for chemical precipitation, ion exchange, electrolytic air flotation, adsorbent adsorption, deep filtration and the like, but the method has high cost and troublesome operation and is difficult to continue; the biochemical method is usually an activated sludge method, and can also adopt methods of culturing algae to absorb phosphorus and then separating the phosphorus, or culturing iron bacteria to precipitate high-iron phosphate, and the like, but the methods are limited by conditions such as C/N, C/P, sunlight and the like, and are difficult to continuously and effectively remove phosphorus; biological methods such as culturing algae eating insects and the like have obvious effects, but algae eating up insects die, so that the algae are difficult to continue, the seasonal problem also exists, and aquatic organisms can form secondary pollution due to decay; the natural treatment utilizes wetland or artificial wetland, soil adsorption and infiltration and the like, has good effect, but needs good management and has difficult searching condition.
Chinese patent CN104920465A discloses a composition for inhibiting algae growth, which is simple, efficient and widely applicable and superior to the above dephosphorization method, the composition takes metal raw materials such as scrap iron and the like and nonmetal such as active carbon and the like as main bodies, and is mixed with components such as a catalyst, an organic adhesive, a pore-forming agent and the like, and the components are processed by forming, drying, high-temperature anaerobic sintering and the like, so that the composition can perform supernormal electrochemical reaction and Fe by utilizing the principle of internal electrolysis when phosphorus-containing wastewater passes through the composition +3 +PO 4 -3 =FePO 4 ↓
3Fe +2 +2PO 4 -3 =Fe(PO 4 ) 2 ↓
……
The water-soluble orthophosphate is changed into water-insoluble metal phosphate to be separated out, so that the method can be applied to the wide fields of sewage treatment upgrading and reconstruction, landscape, riverway water algae removal and purification and the like. However, such compositions for inhibiting the growth of algae have the following disadvantages: the components are expensive, the processing procedure equipment is expensive, and the manufacturing cost of anaerobic sintering is too high; the metal elements are extremely easy to oxidize, namely passivate, in the presence of water and oxygen, need to be frequently acid-washed and regenerated, have short effective running time and short instantaneity, and are not easy to popularize and use.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, designs the tourmaline serving as the water body phosphorus removal filter material and the preparation method thereof, can effectively overcome the problems of passivation and timeliness, has excellent phosphorus removal effect, greatly reduces the manufacturing cost, and is beneficial to popularization and use.
In order to realize the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an electrochemical stone as a water body dephosphorization filter material, which comprises the following components in percentage by volume:
0.5 to 30 percent of metal material;
0.5 to 80 percent of binder;
1 to 40 percent of activating agent;
0.5 to 15 percent of catalyst.
Preferably, the metal material is at least one of iron, aluminum, and magnesium.
Preferably, the binder is at least one of cement, fine soil, water glass, activated carbon, and coke.
Preferably, the activator is at least one of strong acid salts of iron, aluminum, magnesium, zinc and copper;
preferably, the catalyst is a reduced support catalyst in which the support is an iron metal or non-metal particle and metallic copper is supported on the support.
Preferably, the shape of the above-mentioned electrified stone is an ellipsoid type or other body having a specific surface area as large as possible.
Preferably, the dosage proportion of the activating agent is less than 50%, and by adopting the activating agent, the partial PH value of the electrochemical reaction can be effectively reduced, so that the partial water body keeps acidity, the proper condition of the electrochemical reaction is created, metal elements for generating water-insoluble phosphate can be provided, and the water body is assisted to remove phosphorus:
Al 2 (SO 4 ) 3 =2AI 3+ +3SO 4 2-
Al 3+ +H 2 O=Al(OH) 2+ +H +
Al(OH) 2+ +H 2 O=Al(OH) + 2 +H +
Al(OH) + 2 +H 2 O=Al(OH) 3 +H +
Al 3+ +PO 4 -3 =AlPO 4 ↓
more preferably, the above-mentioned fossil is composed of, by volume:
metal material (b): 10-20% of iron powder, 5-10% of aluminum powder or 5-10% of magnesium powder;
adhesive: 10 to 20 percent of cement, 5 to 10 percent of fine soil, 5 to 10 percent of water glass and 10 to 20 percent of active carbon or coke;
activating agent: 10-30% of ferrous sulfate or 10-30% of aluminum sulfate;
catalyst: and 5 to 7 percent of metal copper is loaded.
In a second aspect, the invention further provides a preparation method of the filter material for removing phosphorus from the water body, which comprises the following steps:
step 1: micronizing and nano-treating the components of the electrified stone;
step 2: uniformly mixing the components treated in the step 1 with water;
and step 3: performing sintering-free extrusion (hydraulic) molding on the uniformly mixed material in the step 2;
and 4, step 4: and (4) curing, drying and packaging the formed product in the step (3).
Preferably, the above preparation method further comprises a preparation process of the reduced supported catalyst.
Preferably, the micronization and nanocrystallization treatment is performed by mechanical grinding, preferably ball milling or double-roll grinding, or by selecting commercially available products.
Preferably, the fineness of the component after the micronization and nanocrystallization treatment is not less than 300 mesh.
Preferably, the molding includes roll extrusion molding and hydroforming.
Preferably, the preparation process of the reduction carrier catalyst is an oxidation reduction copper removal process utilizing wastewater recovery treatment, and the reduction of copper ions to the carrier comprises two processing modes:
the first is the "fluidized bed electrode" technology with external power supply: the electrode is made of non-metal material and is in a particle state with air stirring. The electrolytic solution (i.e., copper-containing waste water) flows between the particle electrodes, and an electrode reaction (i.e., reduction of copper ions) occurs on the surface of the particle electrodes. When the reaction is finished, copper ions are converted into copper elements through electrons, and the copper elements are adsorbed on the surface of the particle electrode to form a thin layer, so that the required electroplating carrier catalyst is formed.
Reduction reaction formula of the particle cathode: cu 2+ +2e→Cu。
The second is redox "iron infiltration technique": the low-concentration copper-containing wastewater passes through a filter bed filled with scrap iron (strictly deoiling) under the condition that the pH value is less than or equal to 2.5 and the air is stirred, so that copper is separated out on the surface of the scrap iron to form a reduction carrier catalyst.
Reduction reaction formula on iron filings: cu 2+ +Fe→Cu+Fe 2+ 。
Compared with the prior art, the invention well solves the problems of metal passivation, high cost, lack of timeliness and the like in the dephosphorization method, and has the beneficial technical effects that:
the invention carries out micronization and nanocrystallization treatment on the material, so that the diameter of the particles is close to the nanometer level, various materials are uniformly and densely distributed after being mixed, and the distance between the cathode material and the anode material is extremely short, thereby effectively overcoming the problem that the bulk anode metal material is extremely easy to passivate; the current resistance between the cathode material and the anode material is small, and the reaction efficiency is high; moreover, the uniformly and densely distributed metal materials can be fully utilized and consumed, and the aging is long;
the invention adopts non-sintering extrusion (hydraulic) molding, saves energy, greatly reduces processing cost, does not generate toxic waste gas generated during sintering, is safe and is not limited by site conditions; the product has compact and firm structure, is waterproof and airtight, the reaction always starts from the surface layer and goes deep layer by layer, and the precious metal material can be fully utilized to avoid early passivation; has slow release function and ensures long time effect;
the invention adopts the activator which is a metal strong acid salt, has low cost, not only can provide local slightly acidic environment, avoid passivation and maintain long-acting effect, but also can provide more required metal elements to help water body dephosphorization.
The invention adopts the carrier catalyst to replace a transition metal catalyst, can recycle copper from the reduced copper residual liquid and the ineffective electrochemical stone, has no secondary pollution, can greatly reduce the manufacturing cost, and the metal iron used as the carrier is also an effective element for removing phosphorus.
Detailed Description
The technical scheme of the invention is an electrochemical stone used as a water body dephosphorization filter material and a preparation method thereof, and the electrochemical stone specifically comprises the following steps:
in a first aspect, the invention provides an electrochemical stone as a water body dephosphorization filter material, which comprises the following components in percentage by volume:
0.5 to 30 percent of metal material;
0.5 to 80 percent of binder;
1 to 40 percent of activating agent;
0.5 to 15 percent of catalyst.
In a preferred embodiment of the present invention, the metal material is at least one of iron, aluminum, and magnesium; the binder is at least one of cement, fine soil, water glass, activated carbon and coke; the activating agent is at least one of strong acid salts of iron, aluminum, magnesium, zinc and copper, and more specifically, the activating agent is at least one of ferrous sulfate and aluminum sulfate; the catalyst is a reduction carrier catalyst, wherein the carrier is iron metal or nonmetal particles, and metal copper is loaded on the carrier; the shape of the above-mentioned electrified stone is an ellipsoid type or other body with as large specific surface area as possible.
More preferably, the component and volume ratio of the electrochemical stone used as the water body dephosphorization filter material are as follows
Metal material: 10 to 20 percent of iron powder, 5 to 10 percent of aluminum powder or 5 to 10 percent of magnesium powder;
adhesive: 10 to 20 percent of cement, 5 to 10 percent of fine soil, 5 to 10 percent of water glass and 10 to 20 percent of active carbon or coke;
activating agent: 10 to 30 percent of ferrous sulfate or 10 to 30 percent of aluminum sulfate;
catalyst: 5 to 7 percent of load metal copper;
in a second aspect, the present invention provides a method for preparing any one of the above-mentioned filter materials for removing phosphorus from a water body, including:
step 1: micronizing and nano-treating the components of the electrified stone;
and 2, step: uniformly mixing the components treated in the step (1) with water;
and 3, step 3: performing sintering-free extrusion (hydraulic) molding on the uniformly mixed material in the step 2;
and 4, step 4: and (4) curing, drying and packaging the formed product in the step (3).
In a preferred embodiment of the present invention, the preparation method further comprises a preparation process of the catalyst. The fineness of the components after the micronization and nanocrystallization treatment is not less than 300 meshes, and the forming comprises roll extrusion forming and hydraulic forming.
The following examples are included to further describe specific embodiments of the present invention. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example one
The tourmaline serving as the water phosphorus removal filter material comprises the following components in percentage by volume:
metal material: 10 to 20 percent of iron powder;
adhesive: 10 to 20 percent of cement, 5 to 10 percent of fine soil, 5 to 10 percent of water glass and 10 to 20 percent of active carbon or coke;
activating agent: 10 to 30 percent;
catalyst: 5 to 7 percent of load metal copper;
the preparation method of the filter material for removing phosphorus in the water body comprises the following steps:
step 1: and a power supply is added, the electrodes are made of non-metallic materials and are in a particle state, and air stirring is carried out. The electrolytic solution (i.e., copper-containing waste water) flows between the particle electrodes, and an electrode reaction (i.e., reduction of copper ions) occurs on the surface of the particle electrodes. When the reaction is finished, copper ions are converted into copper elements through electrons and adsorbed on the surface of the particle electrode by a thin layer to prepare an electroplating carrier catalyst;
step 2: micronizing and nanocrystallizing the components of the electrified stone, and performing ball milling to obtain a material with fineness of not less than 300 meshes (or selecting a commercially available finished product);
and step 3: mixing the micronized and nanocrystallized components with a proper amount of water until the components are uniform;
and 4, step 4: performing sintering-free roll extrusion or hydraulic forming on the uniformly mixed material;
and 5: and (5) maintaining and drying the molded product.
Example two
The tourmaline component used as the water body dephosphorization filter material and the volume ratio thereof
Metal material: 5 to 10 percent of aluminum powder;
adhesive: 10 to 20 percent of cement, 5 to 10 percent of fine soil, 5 to 10 percent of water glass and 10 to 20 percent of active carbon or coke;
activating agent: 10 to 30 percent;
catalyst: 5 to 7 percent of load metal copper;
the preparation method of the filter material for removing phosphorus from water body is the same as the first embodiment.
EXAMPLE III
The invention relates to an electrochemical stone component used as a water body dephosphorization filter material and a volume ratio
Metal material: 5 to 10 percent of magnesium powder;
adhesive: 10 to 20 percent of cement, 5 to 10 percent of fine soil, 5 to 10 percent of water glass and 10 to 20 percent of active carbon or coke;
activating agent: 10 to 30 percent;
catalyst: 5 to 7 percent of load metal copper;
the preparation method of the filter material for removing phosphorus from the water body adopts a market catalyst or a preparation method of the following catalyst in the step 1: enabling low-concentration copper-containing wastewater to pass through a filter bed filled with scrap iron (strictly deoiling) under the conditions that the pH value is less than or equal to 2.5 and air stirring is carried out, and precipitating copper on the surface of the scrap iron to prepare a reduction carrier catalyst; the rest of the steps are the same as the first embodiment.
Example four
The tourmaline prepared in the first to third embodiments is applied to any device requiring water body phosphorus removal, and the phosphorus concentration in the water body is lower than 0.5mg/L.
The manufacturing cost of the electrified stones of the first embodiment to the fourth embodiment is far lower than that of the sintered algae inhibiting stones, and the operation effective time is longer than that of the algae inhibiting stones.
As can be seen from the first embodiment and the fourth embodiment, compared with the prior art, the method well solves the problems of metal passivation, high manufacturing cost, lack of timeliness and the like in the phosphorus removal method, and has excellent phosphorus removal effect.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications or alterations to this practice will occur to those skilled in the art and are intended to be within the scope of this invention. Accordingly, equivalent alterations and modifications are intended to be included within the scope of the present invention, without departing from the spirit and scope of the invention.
Claims (3)
1. The utility model provides an electrochemical stone as water dephosphorization filter material which characterized in that, the component and the volume ratio of the fossil of electricity are:
0.5 to 30 percent of metal material;
0.5 to 80 percent of binder;
1 to 40 percent of activating agent;
0.5 to 15 percent of catalyst;
the activating agent is at least one of strong acid salts of iron, aluminum, magnesium, zinc and copper;
the metal material is at least one of iron, aluminum and magnesium;
the catalyst is a reduction carrier catalyst, wherein the carrier is iron metal, and metal copper is loaded on the carrier;
the preparation method of the tourmaline used as the water body dephosphorization filter material comprises the following steps:
step 1: micronizing and nano-treating the components of the electrified stone; the fineness of the components subjected to micronization and nanocrystallization treatment is not less than 300 meshes;
step 2: uniformly mixing the components treated in the step (1) with water;
and step 3: performing sintering-free molding on the uniformly mixed material in the step 2; the sintering-free forming comprises double-roller extrusion forming and hydraulic forming;
and 4, step 4: and (4) curing, drying and packaging the formed product in the step (3).
2. The electrochemical stone according to claim 1, wherein the binder is at least one of cement, fine earth, water glass, activated carbon, and coke.
3. The electrochemical stone according to claim 1, characterized in that the shape of the electrified stone is ellipsoid and other shapes with large specific surface area.
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| CN108217863A (en) * | 2018-01-15 | 2018-06-29 | 上海山恒生态科技股份有限公司 | A kind of compound prescription of quick reduction river water body total nitrogen total phosphorus index |
| CN111943341B (en) * | 2020-08-12 | 2023-01-10 | 中冶一局环境科技有限公司 | Phosphorus removal composition and preparation method thereof, phosphorus removal product and preparation method thereof, and phosphorus removal method |
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