CN107555661B - Deep purification method for phosphorus and fluorine coexisting wastewater - Google Patents
Deep purification method for phosphorus and fluorine coexisting wastewater Download PDFInfo
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Abstract
The invention discloses a deep purification method of phosphorus and fluorine coexisting wastewater, which adopts the dissolution-reprecipitation and ion exchange reaction of Fred salt to control the removal of fluorine in polluted water; the removal of phosphorus in the polluted water is controlled by adopting chemical precipitation of calcium ions and complex precipitation of a Fe-Al-Ca phosphorus removal agent; the dissolution-reprecipitation and ion exchange reaction of Fred salt, the chemical precipitation of calcium ions and the complex precipitation of Fe-Al-Ca phosphorus removal agent are completed in the same reactor under the same pH value change condition, so that a plurality of phosphorus removal and defluorination reactions are synchronously carried out. The invention initiates a phosphorus and fluorine synchronous removal technology which takes Fred salt as an absorbent for controlling fluorine removal and takes Fe-Al-Ca phosphorus removal agent and lime milk to control the absorption of phosphorus, thereby realizing the synchronous operation of a plurality of phosphorus removal and fluorine removal reactions under the condition of the same pH value change in the same reactor.
Description
Technical Field
The invention belongs to the technical field of inorganic chemical industrial water body pollution treatment, and particularly relates to a method for synchronously removing phosphorus and fluorine in an inorganic phosphorus chemical polluted water body by combining Fred salt and a Fe-Al-Ca phosphorus removing agent.
Background
In the process of developing and utilizing phosphorite in China, over 100 million tons of fluorine enter the environment every year, and most of the fluorine is discharged into the water environment from a waste water way. With the promulgation of inorganic chemical industry pollutant emission standard (GB31573-2015), the method is fully implemented from 7 and 1 in 2017; the national standard of the emission standard of inorganic phosphorus chemical industry pollutants is also in the approval and will be implemented in 2018. The national water pollution control and management of phosphorus and fluorine is stricter, and the water pollutant discharge standards of two standards are stipulated as follows: f is less than 6 mg/L; p is less than 5 mg/L; the special discharge standard of water pollutants in the two standards is that F is less than 2 mg/L; p is less than 0.5 mg/L.
For years, phosphorus chemical enterprises always follow the Integrated wastewater discharge Standard (GB L, P-1996), and F is less than 10mg/L, P and less than 15mg/L for wastewater treatment; due to the large sewage discharge amount, especially in the Yuanduan areas with Karster landforms, regional underground river water is seriously polluted by phosphorus and fluorine due to leakage caused by the change of the geological condition of the phosphogypsum storage yard. The phosphorus and fluorine in rivers and lakes exceed the standard and eutrophication is caused by the two reasons, so that the physical health of people is directly threatened, and the ecological balance is damaged.
With the continuous development of water pollutant removing phosphorus and defluorination technology, the treatment method includes adsorption, electrocoagulation, reverse osmosis, ion exchange, chemical precipitation, coagulation and precipitation, etc. From the economic operation perspective, the common methods are mainly three, namely a chemical precipitation method, a coagulating precipitation method and an adsorption method. However, under the coexistence of phosphorus and fluorine, the removal of fluorine is often critical to the water treatment process.
1. The existing dephosphorization and defluorination technology
At present, the mature treatment process of phosphorus and fluorine coexisting wastewater in China is mainly based on the chemical precipitation method and combines the coagulation precipitation method and the adsorption method; the flow has been developed from one stage to three stage in series:
(1) the traditional one-stage lime precipitation method has the advantages of single pH adjustment and control, large lime adding amount, sewage treatment along the flow, less reuse and CaF2And Ca3(PO4)2The precipitated particles are very fine, the phosphorus and fluorine treatment is unstable, the effluent is easy to exceed the drainage standard by slight disturbance, the system sludge production is large, and the sludge treatment cost is increased. Relevant researches on fluorine and phosphorus removal by a lime precipitation method show that lime milk needs to be added excessively to ensure the treatment effect, particularly in the fluorine removal reaction, the adding amount of lime is often required to be excessive by more than 50%, and Ca is added2+The addition amount is 2-3 times of the F-content.
The method is often used with an inorganic coagulant and an organic flocculant.
(2) The method of 'calcium chloride partially replacing lime' is adopted to treat the wastewater containing fluorine and phosphorus. The inlet water is subjected to two-stage pH adjustment, calcium chloride is introduced to partially replace lime, and phosphorus and fluorine are subjected to graded treatment, so that the pH change interval of the inlet water can be fully utilized, the lime adding amount and the reaction pH value are more accurately controlled, the inlet water is subjected to various reactions in different pH value intervals, the lime adding amount is reduced, the precipitation is promoted to be carried out towards a more complete trend, the water quality and the water quantity can be more effectively adjusted by two-stage pH adjusting tanks, and the adaptability of the system to the change of the inlet water quality and the inlet water quantity is improved.
Introduced CaCl2Is strong electrolyte, has high solubility, and can be completely ionized into Ca in solution2+To make Ca in the solution2+The molar ratio of calcium salt to fluorinion is between 15: 1 and 20: 1, which promotes the reaction to be more complete. The phosphorus removal and defluorination rate reaches 98 percent.
(3) Three-stage reaction precipitation-flocculation dephosphorization and defluorination are adopted, the process route is more complicated, and the method is generally suitable for wastewater with the phosphorus and fluorine content of more than 300 mg/L.
Lime is added into the first-stage reaction tank to neutralize the wastewater, the pH value reaches about 11.5, and excessive CaCl is added at the same time2Strong electrolyte for promoting PO in waste water4 3-With Ca2+A precipitate formed.
The pH of the second-stage reaction tank is controlled to be 9.0-10.0, and PO which cannot be completely precipitated in the first-stage reaction tank4 3-With Ca2+The reaction is continued and the pH value is gradually reduced to be alkalescent.
The third-stage reaction tank is mainly used for precipitating F-Adjusting the pH value to 8.0-8.5, and adding excessive CaCl again2Make Ca be2+And F-The reaction of (3) is accelerated to promote F-And (4) removing.
2. Restriction point of prior art
The main process route is F-、HPO4 2-、PO4 3-With Ca2+Based on the chemical precipitation reaction:
2F-+Ca2+→CaF2↓ ①
Ksp＝2.7×10-11the optimum precipitation pH value is 7.5-8.5
HPO4 2-+2Ca2++2OH-→2Ca2HPO4(OH)2+HPO4 2-+Ca2+→Ca5(PO4)3OH↓+3H2O ②
Ksp＝1×10-7The optimum precipitation pH value is 8.0-9.0 Ksp ═ 1.6 × 10-58The optimum precipitation pH value is more than 10.0
2PO4 3-+3Ca2+→Ca3(PO4)2↓ ③
Ksp＝2.07×10-33The optimum precipitation pH value is more than 11.0
Ca5(PO4)3OH+F-→Ca5(PO4)3F↓+OH-④
Ksp＝2.8×10-61The optimum precipitation pH value is 6.5-7.5
2HF+Ca(OH)2→CaF2↓+2H2O ⑤
Ksp＝2.7×10-11The optimum precipitation pH value is 7.5-8.0
2F-+Ca(OH)2→CaF2↓+2OH- ⑥
Ksp＝2.7×10-11The optimum precipitation pH value is 7.5-8.0
In addition to this, Ca2+And PO4 3-Ca formed3(PO4)2Can also adsorb CaF2And the generated fluorapatite is precipitated, so that the coprecipitation effect is realized.
3Ca3(PO4)2+CaF2→3Ca3(PO4)2·CaF2↓ ⑦
Ksp＝1.6×10-58
The method has the advantages that under the condition of coexistence of phosphorus and fluorine, the removal of the fluorine cannot reach the standard and becomes a key constraint due to the control of the solubility product of a reaction precipitation product. As the solubility product of the calcium salt sediment of phosphorus is usually higher than 20 orders of magnitude of calcium fluoride, when competing for calcium ions with phosphorus, phosphorus is usually precipitated first, and fluorine is difficult to reduce to the standard of F < 6mg/L, so that the strict requirement of national standard of inorganic chemical industry pollutant emission standard-2015 cannot be met, and the special emission standard of water pollutant F < 2mg/L cannot be met particularly.
TABLE 1 treatment result of calcium chloride partial substitution lime two-stage process for wastewater containing fluorine and phosphorus
TABLE 2 fluorine and phosphorus removal analysis of the three stage procedure
The core of the coexistence of fluoride ions and phosphate ions in the acid wastewater by using the slaked lime for neutralizing and adding calcium chloride to precipitate phosphorus and fluorine is the control of the pH value of the wastewater and the fractional precipitation of phosphorus and fluorine in the wastewater treatment process. Because the difference of the optimal precipitation pH values of calcium fluoride and calcium phosphate (including calcium hydrophosphate, calcium hydroxy phosphate and calcium fluophosphate) is not large, the operation flexibility is reduced, and the process control is difficult.
In general, the defects of the existing treatment technology for wastewater with coexisting phosphorus and fluorine are as follows: the process is increasingly complex, the pumping and stirring energy consumption is high, the pH value operation elasticity is small, the medicament utilization rate is low, the defluorination and the reduction of the standard are not easy, and the like.
Disclosure of Invention
The invention aims to provide a deep purification method of phosphorus and fluorine coexisting wastewater, which has relatively simple flow and low treatment cost and can fully utilize the three phosphorus and fluorine removing mechanisms so as to solve the problems in the prior art.
The invention is realized by the following steps:
the invention is a deep purification method of waste water coexisting with phosphorus and fluorine, which adopts the dissolution-reprecipitation and ion exchange reaction of Fred salt to control the removal of fluorine in the polluted water; the removal of phosphorus in the polluted water is controlled by adopting chemical precipitation of calcium ions and complex precipitation of a Fe-Al-Ca phosphorus removal agent; based on the combination of the reactions, the dissolution-reprecipitation and ion exchange reaction of Fred salt, the chemical precipitation of calcium ions and the complex precipitation of Fe-Al-Ca phosphorus removal agent are completed in the same reactor and under the same pH value change condition, so that the synchronous proceeding of a plurality of phosphorus removal and defluorination reactions is realized.
Furthermore, a method of adding a combined medicament in the reactor is adopted to realize synchronous operation of a plurality of phosphorus removal and defluorination reactions, wherein the combined medicament comprises any two or three of three medicaments of auxiliary agents of lime milk, Fred salt and Fe-Al-Ca phosphorus removal agent.
Further, when the phosphorus content and the fluorine content in the phosphorus and fluorine coexisting wastewater are not more than 500mg/L and not more than 60mg/L, the using amounts of the three combined medicament components in the wastewater per unit volume are respectively as follows: 0-1g/L of auxiliary lime milk and 0-3g/L, Fe g/L of Fred salt-0-2.5 g/L of Al-Ca phosphorus removal agent.
In detail, the method comprises the following steps: adding the combined agent into the same reactor in sequence according to the sequence of the auxiliary agents of lime milk, Fred salt and Fe-Al-Ca phosphorus removal agent, fully stirring, controlling the pH value of the mixture at the end of the reaction to be 8-9, standing and settling for 30min, and then separating the clear from the turbid; the pH value of clear water after the separation of clear and turbid is less than 9, and the total phosphorus P of the clear water is less than 5 mg/L; the fluoride is less than 6.0mg/L of inorganic chemical industrial water pollutant discharge standard; or reach the special discharge standard of inorganic chemical industrial water pollutants, namely: : p is less than 0.5 mg/L; f is less than 2.0 mg/L.
Wherein, the wastewater containing phosphorus and fluorine is polluted water containing phosphorus and fluorine which is directly or indirectly discharged outside the normal limit of the existing inorganic chemical enterprises. Preferably, the phosphorus and fluorine coexisting wastewater is polluted phosphorus and fluorine-containing water which is directly or indirectly discharged outside the normal boundary of the existing inorganic phosphorus chemical industry enterprises.
The invention innovates and improves the prior dephosphorization and defluorination water treatment process technology. Compared with the prior art, the innovation and the improvement of the invention lie in the following points:
1. fred salt with anion exchange capacity is used as an absorbent for controlling defluorination and is found to be used for F-and PO in the treatment process of wastewater containing phosphorus and fluorine4 3-Dissolution-reprecipitation, complex precipitation and ion exchange mechanisms of (a);
2. the method initiates a phosphorus and fluorine synchronous removal technology which takes Fred salt as an absorbent for controlling fluorine removal and controls the absorption of phosphorus by a Fe-Al-Ca phosphorus removal agent and lime milk, and realizes the synchronous operation of a plurality of phosphorus removal and fluorine removal reactions under the condition of the same pH value change in the same reactor;
3. the method for synchronously removing phosphorus and fluorine in the wastewater by combining the Fe-Al-Ca phosphorus removing agent and the Fe-Al-Ca phosphorus removing agent is used for carrying out enhanced flocculation treatment on the wastewater containing phosphorus and fluorine, has obvious phosphorus removing and fluorine removing effects, and can reduce the phosphorus in the polluted water from 10mg/L in the prior art to P less than 5 mg/L; the removal of F is reduced from 7mg/L in the prior art to F less than 6 mg/L; or reach the special discharge standard of inorganic chemical industrial water pollutants, namely: p is less than 0.5 mg/L; f is less than 2.0 mg/L. . The implementation of the technology of the patent provides reliable technical support for the requirements of executing the regulations of special emission limits of water pollutants in the emission standard of inorganic phosphorus chemical industry pollutants (Table 3. total phosphorus is less than 0.5mg/L, and fluoride is less than 2.0 mg/L).
Drawings
FIG. 1 is a BEI-SEM image and EDS detection of a Fred salt defluorinated precipitate at pH3.0 and pH 7.5;
in fig. 1: BEI-SEM images and EDS measurements of the defluorinated precipitates of Fred's salt at pH3.0 and pH7.5 are shown respectively (upper FIG. 1, lower FIG. 1). The results show that the molar ratio of F: Al: Ca in the aluminium hydroxide floc formed at both pH values is around 11:1:4(pH 3.0 spectrum 3; pH7.5 spectrum 3), which corresponds to exactly one part of AlF3And four parts of CaF2。
FIG. 2 shows adsorption of Fredde salts F at different pH values-Front and back XRD patterns;
in fig. 2: XRD pattern showed complete dissolution of the Friedel salt after defluorination, representing d of the layered structure of the Friedel salt002And d020The diffraction peak completely disappeared or decreased (see fig. 2b), and the peaks for the production of fresh aluminum hydroxide (see inset i of fig. 2) and calcium carbonate (carbonate at 2 θ ═ 29.399 °) were greatly enhanced. In particular, a new peak at 2 θ ═ 26.66 ° is ascribed to aluminum fluoride (see ii in fig. 2), and the right part in fig. 2 is an enlarged view of the i site in the left part.
FIG. 3 shows adsorption of Fredde salts F at different pH values-Front and rearFT-IR spectroscopy;
in fig. 3: the fingerprint regions of the FT-IR spectrum before and after defluorination of the Fredt salt were observed, the most obvious change being observed at 965cm after adsorption of fluorine by the Fredt salt-1New peaks are generated (fig. 3b, c). 965cm-1The absorption peak is formed by AlF in the floc3、AlF2 +Or AlF2+Plasma induced, which corresponded to the XRD pattern identifying a new peak attributed to aluminum fluoride at 26.66 deg.. The right part of fig. 3 is an enlarged illustration of the position circled by an ellipse in the left part.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and embodiments. Wherein, the related numerical values, parts or proportions are mass numerical values, parts or proportions if not labeled.
Research and water treatment experience have shown that the defluorination of nascent aluminum hydroxide is a complex adsorption mechanism, the defluorination and the dephosphorization of layered double hydroxides are ion exchange mechanisms, and the defluorination and the dephosphorization of calcium salt are chemical precipitation mechanisms.
The three mechanisms are synchronously realized in the continuous process of one reactor, thereby achieving high removal efficiency (F is less than 2mg/L, P is less than 0.5mg/L, and pH value is less than 9); a new way of economic feasibility (the cost of medicament is slightly increased, the cost of energy consumption and labor is reduced, and the comprehensive cost is kept level or slightly reduced).
The primary condition for achieving this new approach is pharmaceutical agents. We combine the elements required for the three mechanisms described above in one structure-Ca-Al double hydroxide-abbreviated Ca-Al LDH (commonly known as Fred's salt); the calcium ions required by F, P chemical precipitation and the nascent aluminum ions required by F complex adsorption precipitation are provided by dissolving the calcium ions in the acidic phosphorus and fluorine coexisting wastewater; the chloride ions in the layered structure and the fluoride ions in the solution are used for ion exchange with phosphate radicals. The final complex adsorption precipitation of P is controlled by the combination of milk of lime and Al-Fe-Ca phosphorous removal agent.
The process of realizing the three mechanisms in the same reactor is as follows:
stirring and adding properly metered auxiliary agent lime milk (preferably adjusting the pH value of the wastewater to 8-9), sequentially adding two agents of Fred salt and Fe-Al-Ca phosphorus removal agent into the reactor under the condition of not changing the pH value, fully stirring, and synchronously performing chemical precipitation of phosphorus and fluorine; p, F, complexing, adsorbing and precipitating; and the ion exchange reaction of fluoride ions with phosphate and Fred salt. The mixed condensed water is subjected to decontamination and separation in a natural sedimentation mode.
In the technical scheme of the invention, Fred salt synthesized by the method disclosed by Chinese patent ZL201110048719.9 is used as an absorbent for defluorination control; the method adopts the method of Chinese patent ZL201310146980.1 to synthesize the Fe-Al-Ca phosphorus removing agent and lime milk to control the absorption of phosphorus, thus ensuring that the pollutant of the treated water reaches F less than 6 mg/L; p is less than 5 mg/L; or the standard F reaching the special discharge limit value of water pollutants is less than 2 mg/L; p is less than 0.5 mg/L.
Example 1:
imported raw water of a sewage treatment station of a certain phosphorization factory in Guizhou: the pH value is 6.30, the P content is 230.35mg/L, and the fluorine concentration is 13.95 mg/L. The treatment method provided by the invention is used for deeply purifying the wastewater with coexisting phosphorus and fluorine, and the results are shown in Table 1.
TABLE 1 results of treatment of the wastewater of example 1 with Fred salts in combination with Al-Fe-Ca phosphorous removal agent
Example 2, No. 34 # spring of wujiang, guizhou, was imported from a sewage treatment station with contaminated spring: the pH value is 6.55, the P content is 37.17mg/L, and the fluorine concentration is 5.16 mg/L. The treatment method provided by the invention is used for deeply purifying the wastewater with coexisting phosphorus and fluorine, and the results are shown in Table 2.
TABLE 2 results of treatment of the wastewater of example 2 with Fred salts in combination with Al-Fe-Ca phosphorous removal agent
Example 3. import of sewage treatment station of fertilizer company of Guizhou is polluted spring water: the pH value is 7.22, the P content is 8.95mg/L, and the fluorine concentration is 9.61 mg/L. The treatment method provided by the invention is used for deeply purifying the wastewater with coexisting phosphorus and fluorine, and the results are shown in Table 3.
TABLE 3 results of treatment of the wastewater of example 3 with Fred salts in combination with Al-Fe-Ca phosphorous removal agent
Completely meets the index of the recycled water of the company.
Example 4. sewage treatment station two-sink tank water of a certain mineral fertilizer company in Guizhou: pH 7.95; p is 11.69 mg/L; f is 23.06 mg/L. The treatment method provided by the invention is used for deeply purifying the wastewater with coexisting phosphorus and fluorine, and the results are shown in Table 4.
TABLE 4 results of Fredde salt + Al-Fe-Ca phosphorous removal agent treatment of wastewater from EXAMPLE 4
| Per L of raw water | 1 | 2 | 3 | 4 | 5 | 6 |
| Fredde salt dosage mg | 2.0 | 2.0 | 2.0 | 2.5 | 2.5 | 3.0 |
| Phosphorus removing agent dosage mL | 1.0 | 1.5 | 2.0 | 1.5 | 2.0 | 2.0 |
| pH | 8.20 | 8.03 | 7.86 | 8.36 | 8.18 | 8.49 |
| F mg/L | 7.24 | 4.6 | 4.88 | 4.76 | 3.91 | 4.17 |
| Removal rate% | 68.60 | 80.05 | 78.83 | 79.35 | 83.04 | 81.91 |
| P mg/L | Not detected out | 0.051 | 0.021 | 0.017 | 0.017 | 0.015 |
| Removal rate% | ＞99.9 | 99.56 | 99.82 | 99.85 | 99.85 | 99.87 |
The index of the recycled water of the company is reached.
Of course, the above is only a specific application example of the present invention, and other embodiments of the present invention are also within the scope of the present invention.
Claims (6)
1. A deep purification method of phosphorus and fluorine coexisting wastewater is characterized by comprising the following steps: controlling the removal of fluorine in the polluted water by adopting the dissolution-reprecipitation and ion exchange reaction of Fred salt; the removal of phosphorus in the polluted water is controlled by adopting chemical precipitation of calcium ions and complex precipitation of a Fe-Al-Ca phosphorus removal agent; based on the combination of the reactions, the dissolution-reprecipitation and ion exchange reaction of Fred salt, the chemical precipitation of calcium ions and the complex precipitation of Fe-Al-Ca phosphorus removal agent are completed in the same reactor and under the same pH value change condition, so that the synchronous proceeding of a plurality of phosphorus removal and defluorination reactions is realized.
2. The method for deeply purifying wastewater coexisting with phosphorus and fluorine according to claim 1, wherein: the method for putting the combined medicament in the reactor is adopted to realize the synchronous operation of a plurality of phosphorus removal and defluorination reactions, and the combined medicament comprises any two or three of three medicaments of auxiliary agents of lime milk, Fred salt and Fe-Al-Ca phosphorus removal agent.
3. The method for deeply purifying wastewater coexisting with phosphorus and fluorine according to claim 2, wherein: when the phosphorus content and the fluorine content in the phosphorus and fluorine coexisting wastewater are not more than 500mg/L and not more than 60mg/L, the using amounts of the three combined medicament components in the wastewater per unit volume are respectively as follows: 0-1g/L of auxiliary lime milk and 0-3g/L, Fe g/L of Fred salt-0-2.5 g/L of Al-Ca phosphorus removal agent.
4. The method for deeply purifying wastewater coexisting with phosphorus and fluorine according to any one of claims 1 to 3, characterized in that it comprises the steps of: adding the combined agent into the same reactor in sequence according to the sequence of the auxiliary agents of lime milk, Fred salt and Fe-Al-Ca phosphorus removal agent, fully stirring, controlling the pH value of the mixture at the end of the reaction to be 8-9, standing and settling for 30min, and then separating the clear from the turbid; the pH value of clear water after the separation of clear and turbid is less than 9, and the total phosphorus P of the clear water is less than 5 mg/L; the fluoride is less than 6.0mg/L of inorganic chemical industrial water pollutant discharge standard; or reach the special discharge standard of inorganic chemical industrial water pollutants, namely: p is less than 0.5 mg/L; f is less than 2.0 mg/L.
5. The method for deeply purifying wastewater coexisting with phosphorus and fluorine according to claim 1, wherein: the phosphorus and fluorine coexisting wastewater is polluted phosphorus and fluorine-containing water which is directly or indirectly discharged outside the normal limit of the existing inorganic chemical enterprises.
6. The method for deeply purifying wastewater coexisting with phosphorus and fluorine according to claim 5, wherein: the phosphorus and fluorine coexisting wastewater is polluted phosphorus and fluorine-containing water which is directly or indirectly discharged outside the normal boundary of the existing inorganic phosphorus chemical industry enterprises.
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| CN110282783B (en) * | 2019-07-23 | 2021-10-22 | 格丰科技材料有限公司 | Ammonium phosphate chemical wastewater treatment system and method |
| CN111569818A (en) * | 2020-05-06 | 2020-08-25 | 三峡大学 | Drinking water defluorinating agent and preparation method and application thereof |
| CN112759057A (en) * | 2021-01-06 | 2021-05-07 | 贵州大学 | Auxiliary agent feeding device for treating high-concentration ammonia nitrogen wastewater and using method |
| CN117303536B (en) * | 2023-11-29 | 2024-02-20 | 河北协同水处理技术有限公司 | Coking wastewater liquid defluorinating agent and preparation method and application thereof |
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