CN114573185A - Treatment method of fluorine-containing wastewater of photovoltaic enterprise - Google Patents
Treatment method of fluorine-containing wastewater of photovoltaic enterprise Download PDFInfo
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a method for treating fluorine-containing wastewater of photovoltaic enterprises, and belongs to the technical field of fluorine-containing wastewater treatment. The treatment method comprises physicochemical treatment and biochemical treatment; in the physicochemical treatment stage, calcium sulfate sludge is mainly used for removing fluorine in high-concentration fluorine-containing wastewater, and then a fluorine removing agent, a coagulant and a flocculating agent are used for further removing fluorine ions in the fluorine-containing wastewater of photovoltaic enterprises; then the biological treatment process of ammoniation, nitrification and denitrification of microorganisms is carried out to achieve the purpose of removing the total nitrogen in the fluorine-containing wastewater. The invention adopts the common industrial waste calcium sulfate sludge to remove fluorine, can greatly reduce the operation cost of photovoltaic enterprises, improve the economic profit obtained by the photovoltaic enterprises, realize the recycling of the waste, achieve the purpose of treating waste by waste, and have better social benefit, environmental benefit and economic benefit.
Description
Technical Field
The invention relates to the technical field of fluorine-containing wastewater treatment, in particular to a method for treating fluorine-containing wastewater of photovoltaic enterprises.
Background
The production process of the solar crystalline silicon cell mainly comprises the working procedures of texturing, phosphorus diffusion, etching, printing and the like, and because chemical medicines such as nitric acid, hydrofluoric acid and the like are used in a large amount in the production working procedures, main pollutants in the produced wastewater comprise fluoride ions, total nitrogen, ammonia nitrogen and the like; the fluorine ion concentration is high, the corrosivity is strong, and the method is a serious difficulty in wastewater treatment in the photovoltaic industry.
At present, the common treatment methods for the fluorine-containing wastewater of photovoltaic enterprises mainly comprise a chemical precipitation method, a coagulating precipitation method, an adsorption method, an electrodialysis method, an electrocoagulation method, a reverse osmosis method and the like, and the chemical precipitation method, the coagulating precipitation method and the adsorption method are high in practicability and can be used together frequently to achieve a better treatment effect. Such as the method of combining chemical precipitation method and coagulating precipitation method to treat the industrial waste water containing fluorine of a certain fluorine chemical enterprise. The results show that: by adding a calcium source, the fluoride ion concentration in the wastewater can be reduced from 576mg/L to 10mg/L by adopting a chemical-coagulative precipitation method, and the fluoride ion concentration of the effluent meets the primary discharge standard of wastewater discharge standard (GB 8978-2002). The study of Xujinlan and the like finds that if the high-concentration fluorine-containing wastewater cannot be reduced to a lower level by using a lime precipitation method, the fluoride ion concentration in the wastewater can be reduced from about 3000mg/L to below 10mg/L by adopting a lime precipitation and coagulating sedimentation combined process, and the fluoride ions in the effluent can stably reach the discharge standard value. As known in the literature, chemical precipitation is widely used for treating high-concentration fluorine-containing wastewater. The defluorination principle of the chemical precipitation method is mainly to add chemical drugs such as calcium chloride, limestone, calcium hydroxide and the like into the wastewater, so that calcium ions in the added drugs and fluoride ions in the wastewater generate calcium fluoride precipitates, thereby achieving the defluorination aim. If the chemical precipitation method is adopted for removing fluorine, not only a large amount of chemicals are consumed, but also the fluorine removal is not thorough.
Disclosure of Invention
The invention aims to provide a method for treating fluorine-containing wastewater of photovoltaic enterprises. Common industrial waste calcium sulfate sludge is adopted to replace calcium chloride and limestone for defluorination, experiments prove that the defluorination effect of the calcium sulfate sludge can reach a design standard value, and meanwhile, the defluorination of the calcium sulfate sludge does not influence the removal of other pollutants in the wastewater.
In order to achieve the purpose, the invention provides the following technical scheme:
the method for treating the fluorine-containing wastewater of the photovoltaic enterprise comprises physicochemical treatment and biochemical treatment;
wherein the materialization treatment comprises the following steps: injecting the photovoltaic enterprise fluorine-containing wastewater regulated by the regulating water tank into a primary reaction tank, adding a calcium sulfate suspension for defluorination, then adding alkali for regulating the pH value to 6-9, reacting, then entering a primary sedimentation tank, and enabling sediments to enter a sludge tank; the supernatant enters a secondary reaction tank, a defluorinating agent, a coagulant and a flocculating agent are added, the mixture enters a secondary sedimentation tank after reaction, and the sediment enters a sludge tank; detecting the content of fluorine ions in the supernatant, if the content of the fluorine ions meets the fluorine ion discharge standard, enabling the supernatant to enter an intermediate water tank, if the content of the fluorine ions does not meet the fluorine ion discharge standard, enabling the supernatant to enter a third-stage reaction tank, adding a defluorinating agent, a coagulant and a flocculant, enabling the supernatant to enter a third-stage sedimentation tank after reaction, enabling sediments to enter a sludge tank, detecting whether the concentration of the fluorine ions in the supernatant meets the fluorine ion discharge standard, enabling the supernatant to enter the intermediate water tank if the concentration of the fluorine ions meets the fluorine ion discharge standard, and repeating the operation in the third-stage reaction tank until the supernatant meets the fluorine ion discharge standard, and enabling the supernatant to enter the intermediate water tank;
the biochemical treatment comprises the following steps: sequentially carrying out an ammoniation reaction, a nitration reaction and a denitrification reaction on the wastewater in the intermediate water tank under the action of microorganisms to remove total nitrogen in the wastewater;
the preparation method of the calcium sulfate suspension comprises the following steps: and (3) directly adding the calcium sulfate sludge into water, and stirring to obtain a calcium sulfate suspension.
Because the waste water is acidic, after calcium sulfate suspension is added, the dissolution of calcium can be promoted, and fluoride ions in the waste water react with calcium ions to generate calcium fluoride precipitate, and the dissolution of calcium sulfate can also be promoted. Meanwhile, the temperature of the wastewater in the primary reaction tank is 40-50 ℃, and the dissolution of the calcium sulfate suspension in the wastewater is also facilitated.
Preferably, the base is sodium hydroxide.
Preferably, the fluorine removal agent is a deep fluorine removal agent GMS-F4; the coagulant is polyaluminium chloride (PAC); the flocculant is Polyacrylamide (PAM).
Only calcium sulfate sludge is adopted, so that the fluorine ions of the treated wastewater can not reach the discharge standard, and after primary physicochemical treatment, a fluorine removal agent, PAC (polyaluminium chloride) and PAM (polyacrylamide) agent are further added to carry out advanced treatment on the wastewater, so that the concentration of the fluorine ions of the effluent reaches the discharge standard.
Preferably, the adding amount of the calcium sulfate sludge is 7.22kg/m3(ii) a The addition amount of the fluorine removal agent is 0.31kg/m3(ii) a The addition amount of the coagulant is 0.79kg/m3(ii) a The addition amount of the flocculant is 0.011kg/m3。
Preferably, the ammoniation reaction is that ammoniation functional bacteria decompose and convert nitrogen-containing organic matters in the wastewater into NH4 +The process of (1).
Preferably, the nitration reaction is carried out in an aerobic state, and NH in the wastewater is converted by nitrifying bacteria4 +Conversion to NO2 -Then reoxidized to NO3 -The process of (1).
Preferably, the denitrification reaction is that NO in the wastewater is treated by denitrifying bacteria under the anoxic state2 -、NO3 -Reduction to nitrogen.
More preferably, the ammoniation reaction is carried out in an anoxic tank, the nitrification reaction is carried out in an aerobic tank, and the denitrification reaction is carried out in the anoxic tank; the nitrogen removal process can be a single-stage or multi-stage series treatment system of an anoxic pond and an aerobic pond, or a single-stage or multi-stage parallel treatment system of the anoxic pond and the aerobic pond (the minimum unit of series connection and parallel connection is a system formed by connecting the first-stage anoxic pond and the aerobic pond).
Preferably, the calcium sulfate content in the calcium sulfate sludge is not more than 60%.
Preferably, the carbon-nitrogen ratio of the wastewater in the intermediate water tank is adjusted to 4:1 by adding a carbon source before biochemical treatment.
The purpose of adjusting the carbon-nitrogen ratio is to satisfy the nutrient substances required by the microorganisms in the denitrification process, and the ratio not only can satisfy the requirement of the denitrification of the microorganisms, but also can make the effluent COD meet the discharge standard.
The invention has the following beneficial technical effects:
the main component of the calcium sulfate sludge is CaSO4The calcium source has high content and can be used for removing fluorine.
In order to make the wastewater reach the discharge standard, the Cl in the wastewater needs to be strictly controlled-The concentration of (c). If CaCl is added in the physicochemical treatment stage2And limestone chemicals to remove fluorine, which can lead to Cl in wastewater-The concentration is increased, and the invention adopts calcium sulfate sludge to replace calcium chloride and limestone to remove fluorine, which is beneficial to Cl in wastewater-The concentration of (2) is controlled so that the effluent Cl-The concentration reaches the design standard value.
The main component of the calcium sulfate sludge selected by the invention is calcium sulfate, which belongs to neutrality and approaches to neutrality, and the calcium sulfate sludge is added in the physical and chemical treatment stage, so that the removal of pollutants such as TN (total nutrient) in the biological stage can not be influenced.
The invention adopts the common industrial waste calcium sulfate sludge to remove fluorine, can greatly reduce the operation cost of photovoltaic enterprises, improve the economic profit obtained by the photovoltaic enterprises, realize the recycling of the waste, achieve the purpose of treating waste by waste, and have better social benefit, environmental benefit and economic benefit.
Drawings
FIG. 1 is a flow chart of a treatment process of wastewater containing fluorine according to example 1.
FIG. 2 is a graph showing the change of pH value in the treatment of the fluorine-containing wastewater in example 1.
FIG. 3 shows F after first-stage physicochemical treatment of the fluorine-containing wastewater in example 1-The change in concentration.
FIG. 4 shows F after physicochemical and biochemical treatments of the fluorine-containing wastewater in example 1-The concentration changes.
FIG. 5 shows the change of TN concentration of the influent TN of the wastewater and after the first A/O process treatment in the fluorine-containing wastewater treatment process of example 1.
FIG. 6 shows the change of TN and TN concentration of effluent after the treatment of the two-stage A/O process in the treatment process of the wastewater containing fluorine in example 1.
FIG. 7 shows Cl in wastewater during treatment of fluorine-containing wastewater in example 1-And COD concentration changes.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every intervening value, to the extent any stated value or intervening value in a stated range, and any other stated or intervening value in a stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The analysis of the components of part of the calcium sulfate sludge used in example 1 of the present invention is shown in table 1:
table 1 calcium sulfate sludge composition analysis table
The defluorinating agent used in the invention is a deep defluorinating agent GMS-F4 which is purchased from ecological technology limited of Shandong girui.
Example 1
The embodiment treats the fluorine-containing wastewater in a certain photovoltaic industrial park in a metropolis, and the daily treated water amount is 12500m3And mainly treats waste water produced by the production processes of workshop wool making, etching, SCRUBBER and the like and washing water of a waste gas absorption tower for 24-hour continuous operation. And (3) treating the solar crystalline silicon cell production wastewater in the photovoltaic industrial park by a wastewater treatment station to reach corresponding discharge standards, and then discharging the wastewater into a municipal pipe network system. The processing steps are as follows:
(1) physical and chemical treatment: corresponding waste liquid collecting tanks are used for collecting concentrated alkali waste liquid, mixed acid waste liquid, concentrated fluorine waste water, dilute alkali waste water and dilute fluorine waste water (the treatment water amount is 11395 m)3) Then, the five collected waste liquids are mixed and adjusted in an adjusting tank (the pH of the inlet water after adjustment is 1.49; f-610.71 mg/L; cl-423.02 mg/L; TN is 118.67 mg/L; COD is 62.02mg/L), and the regulated wastewater is pumped to a first-stage reaction tank by a lifting pump (the water temperature is 40-50 ℃); 82.28t of calcium sulfate sludge (the calcium sulfate sludge is added in a suspension form, the suspension is prepared by directly adding the calcium sulfate sludge into water, wherein the mass-volume ratio of the calcium sulfate sludge to the water is 2:1) instead of the raw material is added into the first-stage reaction tank for defluorination, 1.7t of sodium hydroxide is added after 30min to adjust the pH value of the wastewater to 7.21, and the CaF is generated by reaction in the first-stage reaction tank2Precipitating, flowing into the first-stage sedimentation tank together with the wastewater, and generating CaF2Settling to the bottom of the tank by natural settling, pumping the settled sludge discharged from the mud scraper in the primary settling tank into a physicochemical sludge concentration tank by a lift pump, and collecting the supernatant (pH 7.21; F)-8.54 mg/L; cl-578.61mg/L) flows into a secondary reaction tank, 3.04t of defluorinating agent deep defluorinating agent (GMS-F4) is added into the secondary reaction tank to carry out deep treatment on fluoride ions, 7.71t of coagulant PAC and 107.5kg of flocculant PAM are matched to form obvious alum floc for further removing the fluoride ions, the generated wastewater flows into the secondary sedimentation tank along with sedimentation, settled sludge is pumped into a materialized sludge concentration tank, and supernatant (the pH is 7.48; f-6.40mg/L) flows into a three-stage reaction tank for third-stage physical and chemical treatment, and is added with 494.2kg of deep defluorinating agent (GMS-F4), 17.5kg of PAM, 1.26t of PAC and 1.2 t of sodium hydroxide02.06kg, the waste water and the sediment after the reaction enter a third-stage sedimentation tank, the settled sludge is pumped into a materialized sludge concentration tank, and the supernatant (pH is 7.70; F)-6.08mg/L) into an intermediate water tank.
(2) Biochemical treatment: pumping the wastewater after the three-stage physicochemical treatment in the intermediate water tank into a biochemical system by a lifting pump. The biochemical system consists of two sets of two-stage A/O processes (one set is three-stage and one set is four-stage), and the treatment processes adopted by the two sets of biochemical systems are completely consistent. The wastewater pumped in through the intermediate water tank firstly flows into the first-stage anoxic tank for ammoniation reaction (nitrogen-containing organic matters in the wastewater are decomposed and converted into NH under the metabolic action of ammoniation functional bacteria4 +The process) and the wastewater after the ammoniation reaction flows into a primary aerobic tank for nitration reaction (in an aerobic state, nitrifying bacteria use inorganic nitrogen in the wastewater as a nitrogen source to react NH4 +Conversion to NO2 -Then reoxidized to NO3 -The process (a) is carried out, after the nitrification reaction, the sewage flows back to the first-level anoxic tank to carry out denitrification reaction (in an anoxic state, the process of reducing nitrite nitrogen and nitrate nitrogen into nitrogen by denitrifying bacteria), and after the denitrification reaction, the sewage flows into the first-level aerobic tank (the residence time in the operation process is as follows: the first-stage anoxic pond stays: 4.02h, then entering a first-stage aerobic tank for staying: and (3) 12.04h, then refluxing to the first-stage anoxic tank for staying: 4.02h, and then entering the next stage A/O process through a second stage aerobic tank; the second-stage anoxic tank stays for 4.02h, and then enters the second-stage aerobic tank to stay: and (4) returning to the secondary anoxic tank for staying for 12.04 h: 4.02h, finally, the wastewater is converged into a biochemical sedimentation tank through a secondary aerobic tank), thereby realizing the removal of nitrogen in the wastewater. The wastewater after the primary biochemical treatment flows into a secondary A/O process treatment pool which is the same as the primary biochemical treatment, and the nitrogen in the wastewater is subjected to advanced treatment again according to the process. The waste water after the second-stage biochemical treatment flows into a biochemical sedimentation tank, sludge is separated from the waste water in the biochemical sedimentation tank through the action of natural sedimentation or flocculation sedimentation, part of the sludge is pumped into a biochemical sludge concentration tank by a lift pump, the other part of the sludge flows back to a first-stage anoxic tank to supplement microorganisms, the waste water flows into a high-efficiency sedimentation tank to be sedimentated again, and the water flows sedimentated through the high-efficiency sedimentation tankAnd (4) entering a clean water tank and finally discharging into a municipal pipe network system.
In the biochemical treatment stage, a carbon supplement agent is required to be added before the A/O process treatment, the carbon supplement agent added in the embodiment is a WT-312 composite carbon supplement agent with the COD equivalent of 20 ten thousand mg/L, C: N is adjusted to be 4:1, and the actual dosage of the WT-312 composite carbon supplement agent is 30.95 t.
Indexes after the first-stage A/O process treatment (third stage): the pH was 7.48; f-5.93 mg/L; TN is 6.35 mg/L; COD was 54.26 mg/L.
Indexes after the second-level A/O process treatment (third stage): the pH was 7.53; f-5.93 mg/L; TN is 5.02 mg/L; COD was 58.14 mg/L.
Indexes after the first-stage A/O process treatment (fourth stage): the pH was 7.54; f-6.20 mg/L; TN is 15.60 mg/L; the COD was 37.21 mg/L.
Indexes after the second-stage A/O process treatment (fourth stage): the pH was 7.49; f-6.20 mg/L; TN is 14.35 mg/L; the COD was 44.19 mg/L.
Final effluent index: the pH was 7.65; f-6.05 mg/L; TN is 9.20 mg/L; the COD is 52.33 mg/L; cl-It was 777.97 mg/L.
(3) And discharging the sludge generated in the materialized stage into a materialized sludge concentration tank, removing partial water in the sludge through a plate-and-frame filter press, compressing into a sludge cake with the water content of less than 60 percent, and transporting out of a factory. And (3) discharging sludge generated in the biochemical stage into a biochemical sludge concentration tank, compressing the sludge by a spiral-stacked filter press until the water content is less than 80%, and then transporting the sludge out of a factory.
The flow of the fluorine-containing wastewater treatment process of example 1 of the present invention is shown in FIG. 1.
The parameters of the wastewater treatment process of example 1 were monitored, and the measurement items and analysis methods are shown in Table 2.
TABLE 2 wastewater determination items and analysis method
The monitoring result of the water quality of the fluorine-containing wastewater in the photovoltaic industrial park in 2021 and 9 months is as follows: the pH value is 1.49-2.77; f-378.96-698.90 mg/L; cl-370.71-505.68 mg/L; TN is 92.42-131.58 mg/L; the COD is 25.34-62.02 mg/L.
The effluent quality designed in the embodiment is implemented according to the standards of the discharge Standard of pollutants for the Battery industry (GB 30484-2013 Indirect discharge Limit of solar cell) and the discharge Standard of Water saving pollutants for Sichuan (DB 51/190-93W-level Standard), wherein Cl is-The method is carried out according to the discharge standard of the water-saving pollutants in Sichuan (DB 51/190-93W standard).
The specific indexes are as follows: the pH value is 6-9; f-≤8.0mg/L；Cl-≤1000mg/L；TN≤40mg/L；COD≤150mg/L。
Example 1 the pH of the wastewater during the treatment of fluorine-containing wastewater varies as shown in fig. 2. As can be seen from the figure 2, the pH value of the inlet water of the wastewater treatment station is low, the wastewater is acidic, the pH value of the inlet water can be adjusted to 6-9 after the first-stage materialization treatment is finished by adding sodium hydroxide, and the pH value of the inlet water can be controlled to 7-8 after the second-stage materialization treatment and the third-stage materialization treatment, so that the pH value of the outlet water finally reaches the discharge standard.
Example 1F of wastewater after first-stage physicochemical treatment of fluorine-containing wastewater-The concentration changes are shown in FIG. 3; f after physicochemical treatment and biochemical treatment-The concentration changes are shown in FIG. 4. As can be seen from FIGS. 3 and 4, F in the fluorine-containing waste water-The concentration is very high and can reach 700 mg/L. In the first-stage physicochemical treatment stage, after calcium sulfate sludge is added for treatment, the concentration of fluorine ions in the effluent can be reduced to about 10mg/L, which is close to the requirement of discharge standard, the removal rate is about 97 percent, F-The removal effect is good; after the advanced treatment of secondary and tertiary materialization, the effluent F-The concentration can be controlled below 7mg/L, and the effluent stably reaches the discharge standard. Therefore, the calcium sulfate sludge is adopted for removing fluorine, the fluorine removal effect can still be ensured, and the concentration of the fluorine ions in the final effluent meets the designed effluent standard requirement.
In the process of treating the fluorine-containing wastewater, the TN concentration change of the wastewater after the TN inlet water and the first-stage A/O process treatment is shown in FIG. 5; the TN and effluent TN concentration changes after the two-stage A/O process treatment are shown in FIG. 6. As can be seen from FIGS. 5 and 6, the TN concentration of the influent water is about 115mg/L, the TN concentration can be reduced to about 12mg/L after the treatment of the first-stage A/O process, the removal rate can reach 95%, and the effluent can stably reach the discharge standard after the advanced treatment of the second-stage A/O process. Therefore, the adoption of the calcium sulfate sludge for fluorine removal does not influence the treatment of TN in the subsequent working section.
Example 1 Cl of wastewater during treatment of wastewater containing fluorine-And COD concentration changes are shown in FIG. 7. As can be seen from FIG. 7, the feed water Cl-The concentration is relatively high, so that strict control of Cl in the wastewater is required to meet the discharge standard-If CaCl is added in the physicochemical treatment stage2And limestone chemicals to remove fluorine, which can lead to Cl in wastewater-The concentration is increased, and the embodiment 1 adopts calcium sulfate sludge to replace calcium chloride and limestone to remove fluorine, which is beneficial to Cl in wastewater-Concentration control of (2) so that the effluent Cl-The concentration reaches the design standard value; cl of effluent from wastewater treatment station-The concentration can be controlled below 850mg/L, and the requirement of the designed emission standard is met. Therefore, the adoption of the calcium sulfate sludge for removing fluorine is beneficial to Cl in the wastewater-The concentration of (4) is controlled. As the COD value of the inlet water is only between 20 and 65mg/L, the carbon source required in the microbial denitrification process at the biochemical treatment process is not satisfied, and the carbon source is required to be additionally added as a nutrient substance of the microorganisms, the WT-312 composite carbon supplement agent with the COD equivalent of 20 ten thousand mg/L is selected in the embodiment 1, and the carbon source required in the microbial denitrification process is satisfied by adding the WT-312 composite carbon supplement agent according to the proportion of C: N-4: 1. Finally, the COD concentration of the effluent meets the standard.
Example 1 benefit analysis of the actual run:
(1) social benefit analysis
Discharging 440KgCO per one ton of limestone produced2785.7KgCO discharged in the production of one ton of calcium chloride2Taking 2325.41 tons of calcium sulfate sludge consumed in 9 months in 2021 as an example, if general industrial waste calcium sulfate sludge is used for removing fluorine, 407.1 tons of calcium chloride and 407.1 tons of limestone can be saved711.47 tons, the emission of carbon dioxide can be reduced by about 738.13 tons each month. Therefore, the calcium sulfate sludge is adopted to replace calcium chloride and limestone for defluorination, so that the waste calcium sulfate sludge is changed into valuable, the emission of carbon dioxide is effectively reduced, and the method has good social benefit.
(2) Environmental benefit analysis
In 9 months in 2021, a wastewater treatment station adopts a three-stage materialization fluorine removal and two-stage A/O nitrogen removal process to co-treat 352984m of wastewater3The concentration of pollutants such as fluorinion, TN and the like in the sewage is reduced, the water quality is obviously improved, and the environmental benefit is better achieved.
(3) Analysis of economic benefits
In 9 months in 2021, 2325.41 tons of calcium sulfate sludge are consumed, and 407.1 tons of calcium chloride and 711.47 tons of limestone can be saved. Since 2021 the next half year, because of the global inflation, the price of calcium chloride, limestone rises, according to the market price estimate after rising, the price of calcium chloride is calculated as 1300 yuan/ton, the price of limestone is calculated as 400 yuan/ton, according to the actual raw material purchase contract related to outsourcing operation, this calcium sulfate mud is sent to the waste water treatment station by the related enterprise for free, therefore its calcium sulfate mud cost is zero, then the economic benefits that can be saved for the company every month is about 80 ten thousand yuan.
Example 2
Sources of calcium sulfate sludge:
sulfuric acid is an important basic chemical raw material and is widely applied to the fields of metallurgy, steel, titanium dioxide and the like, but in the application process, wastewater containing sulfuric acid is generated, the environment is seriously polluted, and the biological growth and human life are seriously harmed. Therefore, the waste water must be treated to reach the standard and then can be discharged. At present, the domestic and foreign treatment methods of waste acid mostly adopt a neutralization method, the adopted medicines are generally lime, calcium hydroxide and the like, and the main principle is SO in wastewater4 2-With addition of Ca in the medicine+Reaction to produce CaSO4Precipitating to adjust the acidity of the wastewater, and discharging the treated wastewater when the pH value reaches about 7. A large amount of chemicals is used in the neutralization treatment stage, and thus a large amount of calcium sulfate sludge is producedIf it is not properly treated, it will cause environmental pollution. Calcium sulfate sludge contains rich calcium source, so that the calcium sulfate sludge can be used for removing fluorine ions in wastewater.
The economic comparison analysis of the calcium sulfate sludge and limestone and calcium chloride for treating the fluorine-containing wastewater:
calcium sulfate sludge and limestone and calcium chloride are used for removing fluorine by utilizing Ca in the calcium sulfate sludge and the limestone and the calcium chloride+With F in the waste water-Reaction to CaF2Precipitating, thereby achieving the purpose of reducing the concentration of the fluorinion in the wastewater. The main component of the calcium sulfate sludge is CaSO4(ii) a The main component of limestone is CaCO3The main component of the calcium chloride is CaCl2. In the actual treatment process of the fluorine-containing wastewater, no matter calcium sulfate sludge or limestone and calcium chloride are adopted for removing fluorine, the operation cost is the most important consideration of enterprises and comprises the following aspects:
(1) and comparing the prices of the raw materials. The calcium chloride selling price is 1300 yuan/ton and the limestone selling price is 400 yuan/ton according to the market conditions at present, and the calcium sulfate sludge can be basically supplied free as waste residues generated in the production links of industries such as titanium dioxide, pyrite, printing and dyeing and the like, and has great superiority in terms of material price.
(2) And comparing the material transportation cost. Because the calcium sulfate sludge has certain water content (generally not exceeding 30 percent), the adding amount is about 2.3 times of that of limestone and 1.7 times of that of calcium chloride. Therefore, the transportation cost of the calcium sulfate sludge is higher than that of limestone and calcium chloride, but the calcium sulfate sludge adopted by the project is freely delivered to the wastewater treatment station by related enterprises, so that the transportation cost is zero.
(3) And comparing the running cost of the equipment. The calcium chloride is directly prepared into mixed liquor, the limestone is prepared into mixed liquor by adding water, the calcium sulfate sludge is prepared into mixed liquor by adding water, and the prepared mixed liquor is used for treating wastewater. According to estimates, the operating cost for treating the wastewater with limestone + calcium chloride is about 4.35 yuan/ton, and the operating cost for treating the wastewater with calcium sulfate sludge is 3.74 yuan/ton. The calcium sulfate sludge treatment of the fluorine-containing wastewater has more advantages in terms of operation cost. However, calcium sulfate sludge contains considerable water and occupies a large area, so that the calcium sulfate sludge occupies a large amount of land of a treatment station due to stacking, and the management cost is increased.
The comparative analysis is integrated, the economic comparative analysis advantage of adopting the calcium sulfate sludge to replace limestone and calcium chloride to treat the fluorine-containing wastewater is obvious, the calcium sulfate sludge can be comprehensively utilized, and the problems of land occupation and treatment cost in the calcium sulfate sludge treatment process are also solved. Therefore, the advantage of adopting calcium sulfate sludge to remove fluorine is obvious.
Influence of the content of calcium sulfate sludge components on the defluorination effect.
The test principle is as follows: the main component of the calcium sulfate sludge is CaSO4The content of calcium source is high, and Ca in the calcium sulfate sludge is utilized+With F in the waste water-Survival by reaction CaF2And precipitation can achieve the purpose of reducing the concentration of fluorine ions in the wastewater.
The test contents are as follows:
the raw water quality condition of the fluorine-containing wastewater selected in the test is as follows: the pH was 1.84; f-It was 473.89 mg/L.
The calcium sulfate sludge medicines with different component contents selected in the method have the following code numbers:
group a calcium sulfate sludge: CaSO4The content of the components is 48.4 percent.
Calcium sulfate sludge of group B: CaSO4The content of the components is 59.5 percent.
Calcium sulfate sludge of group C CaSO4The content of the components is 65.7 percent.
The test contents are as follows:
three 100mL beakers were numbered 1, 2, and 3. Adding 100mL of fluorine-containing wastewater into each beaker, adding sodium hydroxide to adjust the pH value of the wastewater to 7-8, heating the wastewater to 40-50 ℃, then slowly adding the same amount of calcium sulfate sludge medicines (the adding amount of each group is 0.722g) into the beakers respectively, adding A group of calcium sulfate sludge into the No. 1 beaker, adding B group of calcium sulfate sludge into the No. 2 beaker, and adding C group of calcium sulfate sludge into the No. 3 beaker, continuously stirring the beakers in the medicine adding process, standing the beakers for 40min after the medicine adding is finished, taking the supernatant of the beaker, and measuring F-And (4) content.
Test results and discussion:
TABLE 3 calcium sulfate sludge pairs of different component contents F-Removing effect influence
As can be seen from table 3: with the increase of the calcium content in the calcium sulfate sludge, the concentration of the fluorinion in the wastewater is in a descending trend, and when the CaSO in the calcium sulfate sludge4When the component content is 59.5%, the concentration of fluorine ions in the treated wastewater is the lowest, and the treatment effect is better. If the calcium content in the calcium sulfate sludge component continues to increase, F in the treated wastewater-The concentration tends to rise, and the treatment effect is reduced.
The above-described embodiments are only intended to illustrate the preferred embodiments of the present invention, and not to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (9)
1. A treatment method of fluorine-containing wastewater of photovoltaic enterprises is characterized by comprising physicochemical treatment and biochemical treatment;
wherein the materialization treatment comprises the following steps: injecting the photovoltaic enterprise fluorine-containing wastewater regulated by the regulating water tank into a primary reaction tank, adding a calcium sulfate suspension for defluorination, then adding alkali for regulating the pH value to 6-9, reacting, then entering a primary sedimentation tank, and enabling sediments to enter a sludge tank; the supernatant enters a secondary reaction tank, a defluorinating agent, a coagulant and a flocculating agent are added, the mixture enters a secondary sedimentation tank after reaction, and the sediment enters a sludge tank; detecting the content of fluorine ions in the supernatant, if the content of the fluorine ions meets the fluorine ion discharge standard, enabling the supernatant to enter an intermediate water tank, if the content of the fluorine ions does not meet the fluorine ion discharge standard, enabling the supernatant to enter a third-stage reaction tank, adding a fluorine removing agent, a coagulant and a flocculant, enabling the supernatant to enter a third-stage sedimentation tank after reaction, enabling sediments to enter a sludge tank, detecting whether the concentration of the fluorine ions in the supernatant meets the fluorine ion discharge standard, enabling the supernatant to enter the intermediate water tank if the concentration of the fluorine ions meets the fluorine ion discharge standard, and repeating the operation in the third-stage reaction tank until the supernatant meets the fluorine ion discharge standard, and enabling the supernatant to enter the intermediate water tank;
the biochemical treatment comprises the following steps: sequentially carrying out an ammoniation reaction, a nitration reaction and a denitrification reaction on the wastewater in the intermediate water tank under the action of microorganisms to remove total nitrogen in the wastewater;
the preparation method of the calcium sulfate suspension comprises the following steps: and (3) directly adding the calcium sulfate sludge into water, and stirring to obtain a calcium sulfate suspension.
2. The method for treating fluorine-containing wastewater of photovoltaic enterprises according to claim 1, wherein the alkali is sodium hydroxide.
3. The method for treating fluorine-containing wastewater of photovoltaic enterprises according to claim 1, wherein the fluorine removal agent is a deep fluorine removal agent GMS-F4; the coagulant is polyaluminium chloride; the flocculant is polyacrylamide.
4. The method for treating fluorine-containing wastewater of photovoltaic enterprises according to claim 1, wherein the addition amount of the calcium sulfate sludge is 7.22kg/m3(ii) a The addition amount of the fluorine removal agent is 0.31kg/m3(ii) a The addition amount of the coagulant is 0.79kg/m3(ii) a The addition amount of the flocculant is 0.011kg/m3。
5. The method for treating fluorine-containing wastewater of photovoltaic enterprises as claimed in claim 1, wherein the ammoniation reaction is to decompose and convert nitrogen-containing organic matters in wastewater into NH by using ammoniation functional bacteria4 +The process of (2).
6. The photovoltaic enterprise fluorine-containing waste of claim 1The method for treating water is characterized in that the nitrification reaction is that nitrifying bacteria react NH in the wastewater in an aerobic state4 +Conversion to NO2 -Then reoxidized to NO3 -The process of (1).
7. The method for treating fluorine-containing wastewater of photovoltaic enterprises as claimed in claim 1, wherein the denitrification reaction is to remove NO in wastewater by denitrifying bacteria under anoxic condition2 -、NO3 -Reduction to nitrogen.
8. The method for treating fluorine-containing wastewater of photovoltaic enterprises according to claim 1, wherein the calcium sulfate content in the calcium sulfate sludge is not more than 60%.
9. The method for treating fluorine-containing wastewater of photovoltaic enterprises as claimed in claim 1, wherein the carbon-nitrogen ratio of wastewater in the intermediate pool is adjusted to 4:1 by adding carbon source before biochemical treatment.
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| CN109879550A (en) * | 2019-04-08 | 2019-06-14 | 重庆港力环保股份有限公司 | Photovoltaic cell produces waste water purification system |
| CN110776142A (en) * | 2019-11-12 | 2020-02-11 | 张家港宏昌钢板有限公司 | Physicochemical coagulation defluorination and precipitation integrated wastewater treatment method |
| CN112919690A (en) * | 2021-03-26 | 2021-06-08 | 四川省创飞格环保技术有限公司 | Fluorine-containing wastewater defluorination device and process |
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| CN109879550A (en) * | 2019-04-08 | 2019-06-14 | 重庆港力环保股份有限公司 | Photovoltaic cell produces waste water purification system |
| CN110776142A (en) * | 2019-11-12 | 2020-02-11 | 张家港宏昌钢板有限公司 | Physicochemical coagulation defluorination and precipitation integrated wastewater treatment method |
| CN112919690A (en) * | 2021-03-26 | 2021-06-08 | 四川省创飞格环保技术有限公司 | Fluorine-containing wastewater defluorination device and process |
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| CN116282699A (en) * | 2023-03-06 | 2023-06-23 | 武汉天源环保股份有限公司 | Semiconductor wastewater treatment method and system |
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