CN110937675A - Flocculation-oxidation composite material for improving water quality of black and odorous water body - Google Patents
Flocculation-oxidation composite material for improving water quality of black and odorous water body Download PDFInfo
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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
- C02F1/52—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
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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
- C02F1/722—Oxidation by peroxides
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
Abstract
The invention discloses a flocculation-oxidation composite material for improving the water quality of black and odorous water, belonging to the technical field of water treatment. In the treatment technology of the black and odorous water body, the reduction of the turbidity of the black and odorous water body is very important for treating the black and odorous water body, and the prior art does not have a method for removing the turbidity. The flocculation-oxidation composite material prepared by taking bentonite, calcium peroxide and lanthanum chloride as raw materials can quickly reduce the turbidity of black and odorous water in a short time, the lanthanum chloride effectively eliminates the problem that white foam can be formed on the water surface in the use process of the bentonite, the treated black and odorous water is transparent and colorless, meanwhile, the flocculation-oxidation composite material can effectively reduce the chromaticity, odor and total phosphorus of the water, improve the dissolved oxygen and oxidation-reduction potential of the water, and the total water quality can reach the standard of surface water II.
Description
Technical Field
The invention relates to a flocculation-oxidation composite material for improving the water quality of black and odorous water, belonging to the technical field of water treatment.
Background
Along with the development of economy, the water quality of river water areas deteriorates increasingly, and large-area black and odorous water bodies are formed. With the publication of ten items of water, the attention of national policies and the improvement of environmental awareness of citizens, the treatment of black and odorous water is urgent. When the water body is exploded to black and smelly, bad social influence can be caused, so that emergency treatment needs to be carried out on the water body.
The flocculation precipitation method is efficient and simple, and is a common method for removing turbidity, chromaticity and various toxic and harmful pollutants of water. The flocculating agents commonly used for water treatment are polyaluminium chloride and polyacrylamide, and the two flocculating agents are easy to generate secondary pollution and are not suitable for natural water bodies. The flocculant of natural material is natural, low in price and environment-friendly, and has attracted extensive attention. According to reports at home and abroad, the research on the aspect of water treatment for preparing the flocculating agent or coagulant aid by using chitosan, montmorillonite, attapulgite, bentonite, zeolite, diatomite, sepiolite and other minerals as raw materials has achieved certain results, but the screening research on the mineral flocculating agent for emergency treatment of black and odorous water bodies does not exist at present.
The oxidation method is to improve the oxidation-reduction potential of the water body by adding an oxidant into the water body, thereby improving the anaerobic environment of the water body, inhibiting the formation of sulfides, promoting the decomposition of pollutants in the water body and further improving the water quality. Currently, more and less environmentally harmful oxidizing agents are used, including ferrate, calcium peroxide and hydrogen peroxide. At present, no oxidant screening research aiming at water covering emergency treatment on black and odorous water is available.
In the treatment technology of black and odorous water, submerged plants are planted as an important method. However, the black and odorous water body generally has high turbidity, which affects sunlight entering the water body, so that submerged plants are difficult to grow, and the application of planting the submerged plants is limited. In addition, the turbidity substance can also generate adsorption and complexation with other pollutants in water, which affects the migration and transformation of pollutants, and is one of the causes of continuous deterioration of natural water body. Therefore, reducing the turbidity of the black and odorous water body is very important for treating the black and odorous water body, and the prior art does not aim at a turbidity removal method.
Disclosure of Invention
Aiming at the problems, the invention provides a flocculation-oxidation composite material for improving the water quality of black and odorous water, which can reduce the turbidity of the black and odorous water within several hours, simultaneously reduce the chroma, odor and total phosphorus of the water, and improve the dissolved oxygen and the oxidation-reduction potential.
The first purpose of the invention is to provide a flocculation-oxidation composite material, which is prepared from bentonite, calcium peroxide and lanthanum chloride.
In one embodiment of the present invention, the mass ratio of bentonite, calcium peroxide and lanthanum chloride in the flocculation-oxidation composite material is 8: (2-3): 1.
in one embodiment of the present invention, the mass ratio of bentonite, calcium peroxide and lanthanum chloride in the flocculation-oxidation composite material is 8: 2: 1.
in one embodiment of the present invention, the flocculation-oxidation composite is prepared by a mechanical method, and bentonite, calcium peroxide and lanthanum chloride are uniformly mixed by grinding.
A second object of the present invention is to provide a method for treating a black and odorous water body, which utilizes the above-mentioned flocculation-oxidation composite material.
In one embodiment of the invention, the method for treating the black and odorous water body comprises the following steps: mixing the ground composite material with deionized water to prepare a suspension solution, adding the suspension solution into a black and odorous water body, and stirring at normal temperature for 300 r.min-1-400r·min-1Stirring for 2-4min at stirring speed, and stirring at 50 r.min-1Stirring at stirring speed for 10-12min, standing for 30min-60min。
In one embodiment of the invention, the concentration of the prepared suspension solution is 100 g.L-1。
In one embodiment of the invention, 2-4 ml of suspension solution is added into 100ml of black odorous water.
In one embodiment of the invention, the temperature is 300 r.min at room temperature-1Stirring for 3min at stirring speed, and then stirring for 50r min-1Stirring for 10min at the stirring speed.
In one embodiment of the invention, the mixture is allowed to stand for 30min after stirring.
The invention has the beneficial effects that:
(1) the flocculant adopted by the invention is a natural material, and the added oxidant calcium peroxide also has little influence on the environment, thus conforming to the concept of environmental protection; the flocculation-oxidation composite material is prepared by adopting a mechanical method, and the preparation method is simple.
(2) The flocculation-oxidation composite material can quickly reduce the turbidity of black and odorous water in a short time, effectively reduce the chromaticity, odor and total phosphorus of the water, improve the dissolved oxygen and oxidation-reduction potential, and ensure that the total water quality can reach the standard of surface water class II.
(3) The invention effectively solves the problem that white foam can be formed on the water surface in the using process of bentonite by adding lanthanum chloride, and the black and odorous water body treated by the flocculation-oxidation composite material is transparent and colorless.
Drawings
FIG. 1 is a photograph showing the appearance of water in example 1 and comparative example 1; in which fig. 1(a) is raw water, fig. 1(b) is water treated with the flocculation-oxidation composite of example 1, and fig. 1(c) is water treated with the flocculation-oxidation composite of comparative example 1.
FIG. 2 is a representation of the flocculation-oxidation composite of example 1; fig. 2(a) is an appearance photograph of the composite material, fig. 2(b) is a fourier infrared spectrum of the composite material, and fig. 2(c) is a scanning electron micrograph of the composite material.
Detailed Description
The present invention is described in further detail below with reference to specific examples, but the embodiments of the present invention are not limited to these examples.
The black smelly water in the following examples is taken from a certain black smelly river channel (N31 degrees 33', E120 degrees 15') in the lakeside area of Wuxi city, the water quality indexes are shown in Table 1, and the appearance photos are shown in FIG. 1 (a). According to the standard method of Water and wastewater monitoring and analysis (fourth edition), Total Phosphorus (TP) was measured by MoSb spectrophotometry, chromaticity by the text description method and dilution factor method, and odor by the text description method. Two representative odor-causing substances, namely dimethyl sulfide (DMS) and 2, 4-di-tert-butylphenol (2,4-D), are simultaneously selected, and the concentration of the odor-causing substances is determined by a headspace solid phase microextraction-gas chromatography-mass spectrometry combined method, wherein the test method is described in the literature: chapter Cabernet Sauvignon, test research on removal of dimethyl sulfide and dimethyl trisulfide from water by potassium permanganate [ D ]. 2016. Turbidity was measured using a DR900 water quality analyzer from hash corporation; the Dissolved Oxygen (DO) is measured by adopting a Merterler-Tolyduo portable Seven Go dissolved oxygen measuring instrument; the oxidation-reduction potential (ORP) was measured using a Bell BPH-610CK model portable ORP meter.
TABLE 1 Water quality parameters of water covering on a tin-free, black and odorous river
Example 1
A flocculation-oxidation composite material is prepared from the following raw materials: CaO (CaO)2：LaCl3＝8：2：1。
The preparation method comprises the following steps: taking 0.8g of bentonite and CaO20.2g、LaCl30.1g, namely setting bentonite and CaO2And LaCl3The mass ratio of (A) to (B) is 8: 2: 1, grinding the raw materials in an agate mortar, and completely and uniformly mixing the raw materials to obtain the flocculation-oxidation composite material.
The characterization of the prepared flocculation-oxidation composite material is shown in fig. 2. Fig. 2(a) is a photograph showing the appearance of the composite material, and from this photograph, it can be seen that the flocculation-oxidation composite material was prepared as a pale yellow powder. FIG. 2(b) is a Fourier infrared spectrum of a composite illustrating bentonite and CaO2Is a composite material which combines physical force into a single material, the configuration of bentonite ions is not changed, and CaO2No new chemical bond is generated between the metal ion and the bentonite, and the metal ion in the bentonite is not replaced by Ca. FIG. 2(c) is a scanning electron micrograph of the material, from which CaO is seen in FIG. 2(c)2The crystals are attached to the surface of the bentonite.
Mixing the ground composite material with deionized water to prepare 100 g.L-1The suspension solution of (2 ml) was added to 100ml of black and odorous water and the mixture was stirred at room temperature for 300 r.min-1Stirring for 3min at stirring speed, and then stirring for 50r min-1Stirring at stirring speed for 10min, and standing for 30min. And taking supernatant liquor to measure water quality parameters.
The treatment effect of the flocculation-oxidation composite material obtained in the example on water quality is shown in table 2:
TABLE 2 Water quality parameters after addition of materials
As can be seen from Table 2, the removal rate of TP after the treatment in this example was 90% and the TP content was only 0.087 mg.L as compared with the blank group-1The standard of surface water class II is achieved; the turbidity is only 1FAU, and the removal rate of the turbidity reaches 95 percent; the ORP is 45mV, which is improved by 96% compared with the blank group; DO of 12.84 mg.L-1Compared with a blank group, the water quality is improved by 177 percent, and the standard of surface water and the like is achieved. In addition, the water body after treatment in this embodiment is changed from original dark brown to colorless, and is reduced from original odor degree 3 grade with obvious odor to 0 grade, two representative odor causing substances: the removal rates of dimethyl sulfide (DMS) and 2, 4-di-tert-butylphenol (2,4-D) respectively reach 58 percent and 65 percent. As can be seen from fig. 1(b), the black odorous water body treated by the composite material in this example becomes clear and transparent. Therefore, the flocculation-oxidation composite material in the embodiment can effectively reduce the turbidity of the black and odorous water bodyAnd deodorization, and the water quality after treatment is greatly improved.
Example 2
A flocculation-oxidation composite material comprises bentonite in the following material ratio: CaO (CaO)2：LaCl3＝8：2：1。
The preparation method is a sodium alginate embedding method: preparing 100ml of deionized water containing 3 percent of sodium alginate, 2 percent of bentonite and 0.5 percent of CaO2、0.25％LaCl3The mixed solution of (1). Then slowly dripping the mixed solution into CaCl with the mass concentration of 3 percent by using a 10ml syringe2Fixing the mixture in the solution to form black pellets with the diameter of 3-5 mm. Placing the pellet in CaCl2After crosslinking in solution for 8 hours, filtration was carried out, leaving beads. The pellets were then dried in an oven at 105 ℃ for 1h to constant weight to give a composite.
Mixing the obtained composite material with deionized water to prepare 100 g.L-1The suspension solution of (2 ml) was added to 100ml of black and odorous water and the mixture was stirred at room temperature for 300 r.min-1Stirring for 3min at stirring speed, and then stirring for 50r min-1Stirring at stirring speed for 10min, and standing for 30min. And taking supernatant liquor to measure water quality parameters.
The treatment effect of the flocculation-oxidation composite material obtained in this example on water quality is shown in table 3:
TABLE 3 Water quality parameters after addition of materials
As can be seen from Table 3, the removal rate of TP after the treatment in this example was 84%, and the TP content was 0.136 mg.L, as compared with the blank group-1The standard of surface water three types is achieved; the turbidity is 13FAU, and the turbidity removal rate is 41 percent; the ORP is 30mV, which is improved by 30% compared with the blank group; DO of 10.56 mg.L-1Compared with the blank group, the water quality is improved by 128 percent and reaches the standard of surface water and the like. In addition, the water body after treatment in this embodiment is changed from original dark brown to colorless, and is reduced from original odor degree 3 grade with obvious odor to grade 1, two representative odor causing substances: dimethyl sulfide (DMS) and 2, 4-di-tert-butylphenol (2,4-D) removalThe rate reaches 47 percent and 48 percent respectively.
Example 3
A flocculation-oxidation composite material is prepared from the following raw materials: CaO (CaO)2：LaCl3＝8：4：1。
The preparation method comprises the following steps: taking 0.8g of bentonite and CaO20.4g、LaCl30.1g of bentonite and CaO2And LaCl3The mass ratio of (A) to (B) is 8: 4: 1, grinding the raw materials in an agate mortar, and completely and uniformly mixing the raw materials to obtain the composite material. Mixing the obtained composite material with deionized water to prepare 100 g.L-1The suspension solution of (2 ml) was added to 100ml of black and odorous water and the mixture was stirred at room temperature for 300 r.min-1Stirring for 3min at stirring speed, and then stirring for 50r min-1Stirring at stirring speed for 10min, and standing for 30min. And taking supernatant liquor to measure water quality parameters.
The treatment effect of the flocculation-oxidation composite material obtained in this example on water quality is shown in table 4:
TABLE 4 Water quality parameters after addition of materials
As can be seen from Table 4, the removal rate of TP after the treatment in this example was 86% and the TP content was 0.125 mg.L, as compared with the blank group-1The standard of surface water three types is achieved; the turbidity is 4FAU, and the turbidity removal rate is 82%; the ORP is 33mV, which is improved by 43% compared with the blank group; DO of 9.89 mg.L-1Compared with the blank group, the water quality is improved by 114 percent, and the water quality reaches the standard of surface water and the like. In addition, the water body treated in this embodiment is changed from original dark brown to light yellow, and is reduced from original odor degree grade 3 with obvious odor to grade 0, and two representative odor-causing substances: the removal rates of dimethyl sulfide (DMS) and 2, 4-di-tert-butylphenol (2,4-D) respectively reach 54 percent and 60 percent.
Example 4
A flocculation-oxidation composite material is prepared from the following raw materials: CaO (CaO)2：LaCl3＝8：8：1。
The preparation method comprises the following steps: taking 0.8g of bentonite and CaO20.8g、LaCl30.1g of bentonite and CaO2And LaCl3The mass ratio of (A) to (B) is 8: 8: 1, grinding the raw materials in an agate mortar, and completely and uniformly mixing the raw materials to obtain the composite material.
Mixing the ground composite material with deionized water to prepare 100 g.L-1The suspension solution of (2 ml) was added to 100ml of black and odorous water and the mixture was stirred at room temperature for 300 r.min-1Stirring for 3min at stirring speed, and then stirring for 50r min-1Stirring at stirring speed for 10min, and standing for 30min. And taking supernatant liquor to measure water quality parameters.
The treatment effect of the flocculation-oxidation composite material obtained in this example on water quality is shown in table 5:
TABLE 5 Water quality parameters after addition of materials
As can be seen from Table 5, the removal rate of TP after the treatment in this example was 86% and the TP content was 0.123 mg.L in comparison with the blank group-1The standard of surface water three types is achieved; the turbidity is 5FAU, and the turbidity removal rate is 77%; the ORP is 34mV, which is increased by 48% compared with the blank group; DO of 9.78 mg.L-1Compared with a blank group, the water quality is improved by 111 percent, and the standard of surface water and the like is achieved. In addition, the water body treated in this embodiment is changed from original dark brown to light yellow, and is reduced from original odor degree grade 3 with obvious odor to grade 0, and two representative odor-causing substances: the removal rates of dimethyl sulfide (DMS) and 2, 4-di-tert-butylphenol (2,4-D) respectively reach 52 percent and 64 percent.
Example 5
A flocculation-oxidation composite material is prepared from the following raw materials: CaO (CaO)2：LaCl3＝2：8：1。
The preparation method comprises the following steps: taking 0.2g of bentonite and CaO20.8g、LaCl30.1g, namely setting bentonite and CaO2And LaCl3The mass ratio of (A) to (B) is 2: 8: 1, mixing the above raw materialsGrinding the materials in an agate mortar, and completely and uniformly mixing the materials to obtain the composite material.
Mixing the ground composite material with deionized water to prepare 100 g.L-1The suspension solution of (2 ml) was added to 100ml of black and odorous water and the mixture was stirred at room temperature for 300 r.min-1Stirring for 3min at stirring speed, and then stirring for 50r min-1Stirring at stirring speed for 10min, and standing for 30min. And taking supernatant liquor to measure water quality parameters.
The treatment effect of the flocculation-oxidation composite material obtained in this example on water quality is shown in table 6:
TABLE 6 Water quality parameters after addition of materials
As can be seen from Table 6, the TP removal rate after the treatment in this example was 91% and the TP content was 0.074 mg. L, as compared with the blank group-1The standard of surface water class II is achieved; the turbidity is 17FAU, and the turbidity removal rate is 23%; the ORP is 39mV, which is increased by 70% compared with the blank group; DO of 9.04 mg.L-1Compared with the blank group, the water quality is improved by 95 percent, and the standard of surface water and the like is reached. In addition, the water body treated in this embodiment is changed from original dark brown to light yellow, and is reduced from original odor degree grade 3 with obvious odor to grade 1, two representative odor causing substances: the removal rates of dimethyl sulfide (DMS) and 2, 4-di-tert-butylphenol (2,4-D) respectively reach 40 percent and 46 percent.
Comparative example 1
A flocculation-oxidation composite material is prepared from the following raw materials: CaO (CaO)2＝4：1
The preparation method comprises the following steps: taking 0.8g of bentonite and CaO20.4g, namely setting bentonite and CaO2The mass ratio of (A) to (B) is 4: 1, grinding the raw materials in an agate mortar, and completely and uniformly mixing the raw materials to obtain the composite material.
Mixing the ground composite material with deionized water to prepare 100 g.L-12ml of the suspension solution is added into 100ml of black and odorous water,at normal temperature at 300 r.min-1Stirring for 3min at stirring speed, and then stirring for 50r min-1Stirring at stirring speed for 10min, standing for 30min, and collecting supernatant to measure water quality parameters.
As can be seen from fig. 1(c), when the composite material in example 1 is used to treat black and odorous water, the treated water is clear and transparent, and when the composite material in comparative example 1 without lanthanum chloride is used to treat black and odorous water, a layer of white foam is covered on the surface of the water, and the white foam makes excessive suspended matters in the water not meet the water quality requirement.
Comparative example 2 comparative testing of various flocculants
Selecting a plurality of natural flocculants for carrying out a comparison experiment, wherein the selected natural flocculants are respectively towel gourd extract, zeolite, chitosan, attapulgite, diatomite, sepiolite and bentonite, adding the natural flocculants into a plurality of black and odorous water bodies of the same batch respectively, and carrying out comparison experiment at normal temperature at 300 r.min-1Stirring for 3min at stirring speed, and then stirring for 50r min-1Stirring at stirring speed for 10min, standing for 30min, and collecting supernatant to test turbidity. The conclusion can be drawn by comparative testing of various flocculants: the bentonite can obtain the best turbidity removal rate with the lowest adding cost.
TABLE 7 cost of different flocculants on turbidity removal and dosing
Comparative example 3 comparative testing of various oxidizers
A plurality of oxidants are selected for carrying out a comparison experiment, and the selected oxidants are ferrate, calcium peroxide and hydrogen peroxide respectively. Taking the copper cash in the same black and odorous river channel while taking the black and odorous water body, taking the copper cash out of the black and odorous river channel, selecting the copper cash with excellent growth vigor, firstly culturing the copper cash in the black and odorous water for 5 days, and equally dividing the cultured copper cash and the black and odorous water body into 3 parts.
Adding three different oxidants into herba Desmodii Styracifolii and black and odorous water respectively, and collecting part of black and odorous water at normal temperature for 300 r.min-1Stirring for 3min at stirring speed, and stirring again50r·min-1Stirring at stirring speed for 10min, standing for 30min, and collecting supernatant for water quality test. The cupreous johnsongrass added with the oxidant is continuously cultured for 5 days, then the fresh weight of the plants is weighed through an analytical balance, and the leaf area of the cupreous johnsongrass is measured through a Win Folia leaf analysis scanner to study whether the growth of the cupreous johnsongrass is influenced by the addition of the oxidant.
TABLE 8 Effect of different oxidants on Water quality and Christina loosestrife growth
The conclusion was drawn by comparative tests of various oxidants: the calcium peroxide has the best comprehensive removal effect on water quality and has the minimum influence on the environment.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The flocculation-oxidation composite material is characterized in that raw materials of the flocculation-oxidation composite material comprise bentonite, calcium peroxide and lanthanum chloride.
2. The flocculation-oxidation composite of claim 1, wherein the bentonite, calcium peroxide and lanthanum chloride are present in a mass ratio of 8: (2-3): 1.
3. the flocculation-oxidation composite of claim 1 wherein the mass ratio of bentonite, calcium peroxide and lanthanum chloride in the flocculation-oxidation composite is 8: 2: 1.
4. the flocculation-oxidation composite of claim 1 wherein the flocculation-oxidation composite is prepared by a mechanical method comprising mixing bentonite, calcium peroxide and lanthanum chloride uniformly by grinding.
5. A method of treating black and odorous water bodies using the flocculation-oxidation composite of claim 1.
6. The method for treating the black and odorous water body according to claim 5, wherein the method is specifically as follows: grinding the composite material of claim 1, mixing with deionized water to prepare a suspension solution, adding the suspension solution into black and odorous water, and stirring at normal temperature for 300 r-min-1-400r·min-1Stirring for 2-4min at stirring speed, and stirring at 50 r.min-1Stirring at stirring speed for 10-12min, and standing for 30-60 min.
7. The method for treating black and odorous water according to claim 6, wherein the concentration of the prepared suspension solution is 100 g-L-1。
8. The method for treating the black and odorous water body according to claim 6, wherein 2 to 4ml of the suspension solution is added to 100ml of the black and odorous water body.
9. The method for treating black and odorous water according to claim 6, wherein the temperature is 300 r-min at normal temperature-1Stirring for 3min at stirring speed, and then stirring for 50r min-1Stirring for 10min at the stirring speed.
10. The method for treating the black and odorous water body according to claim 6, wherein the stirring is followed by standing for 30min.
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| CN114534686A (en) * | 2022-03-01 | 2022-05-27 | 武汉理工大学 | Black and odorous water body and bottom mud in-situ remediation agent as well as preparation method and application thereof |
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| CN112939135A (en) * | 2021-01-26 | 2021-06-11 | 南京乐透思环保科技有限公司 | COD (chemical oxygen demand) and ammonia nitrogen remover for tail water treatment |
| CN114534686A (en) * | 2022-03-01 | 2022-05-27 | 武汉理工大学 | Black and odorous water body and bottom mud in-situ remediation agent as well as preparation method and application thereof |
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