KR20130115785A - Method and apparatus for treating fluoride ion contained wastewater and regenerating the wastewater - Google Patents
Method and apparatus for treating fluoride ion contained wastewater and regenerating the wastewater Download PDFInfo
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- KR20130115785A KR20130115785A KR1020120038424A KR20120038424A KR20130115785A KR 20130115785 A KR20130115785 A KR 20130115785A KR 1020120038424 A KR1020120038424 A KR 1020120038424A KR 20120038424 A KR20120038424 A KR 20120038424A KR 20130115785 A KR20130115785 A KR 20130115785A
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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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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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
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
Abstract
The present invention relates to a wastewater treatment and wastewater regeneration method for reducing the fluorine concentration to below the wastewater discharge allowance value in the treatment of wastewater containing fluorine,
Calcium ion removal step of substantially removing calcium ions in the wastewater by passing the fluorine-containing wastewater through a cation exchange resin, and filtering the residual ions by passing the fluorine-containing wastewater from which the calcium ions have been removed through a reverse osmosis membrane to remove ions. It provides a fluorine-containing wastewater treatment method comprising a treated water recovery step of recovering the treated water.
Therefore, by fluorine treatment from the fluorine-containing wastewater with a low-cost calcium-based fluorine treatment agent, the wastewater can be reused, thereby reducing water consumption, reducing wastewater emissions, and reducing costs.
Description
BACKGROUND OF THE
In general, for fluorine-containing wastewater, fluoride emission is strictly regulated by setting the wastewater discharge limit for fluorine concentration in wastewater to 3 mg / L in clean areas and 15 mg / L in other areas. In treating the wastewater, the wastewater is discharged by removing the fluorine ions in the wastewater below the standard, or the wastewater is recycled by removing the fluorine.
For example, a large amount of product cooling water is used in the regeneration process during the steelmaking process. At this time, fluorite (CaF 2 ) used in the product manufacturing process contains fluorine in the cooling water. If fluorine is contained in the waste water as described above, in order to remove fluorine ions, a fluorine treatment agent is usually added and coagulated and precipitated to remove fluorine with sludge as shown in FIG. Processing. At this time, in such a fluorine treatment step, a calcium fluorine treatment agent, an aluminum fluorine treatment agent, or an expensive rare earth fluorine treatment agent is generally used as the fluorine treatment agent.
Among the fluorine treatment agents, calcium-based fluorine treatment agents such as CaCl 2 and Ca (OH) 2 are inexpensive and economical. However, when the concentration of fluorine present in the wastewater to be treated is low, the fluorine treatment efficiency is low, and the emission is low. Difficult to handle within acceptance criteria.
Therefore, when treating with a calcium-based fluorine treatment agent for wastewater having a low fluorine concentration, it is common to treat the mixture with an aluminum-based treatment agent. However, such aluminum-based sludge is formed in a large amount of Al (OH) 3 sludge in the waste water is excessively increased sludge, causing a post-treatment problem that must be treated sludge produced.
On the other hand, the rare earth fluorine treatment agent can selectively treat only fluorine in the waste water irrespective of the concentration of fluorine ions in the waste water, the fluorine treatment efficiency is the most powerful and stable fluorine treatment, but rare earth metal as a raw material The high cost of the wastewater leads to a huge cost for wastewater treatment. Furthermore, such rare earth metals strongly inhibit resource exports from rare earth producing countries such as China, and thus supply and demand itself is unstable.
Due to the above characteristics of each of the fluorine treatment agents, the use of calcium, aluminum and rare earth systems as a fluorine treatment agent for the fluorine treatment from the effluent is mixed somewhat. In addition, the fluorine-treated effluent contains a large amount of ions supplied with the fluorine treatment agent and existing dissolved ions, making it difficult to reuse them. Therefore, most of the discharged water after treating fluorine is discharged as wastewater.
On the other hand, as a technique for removing fluorine in the wastewater, there is a technique for removing most ions such as fluorine ions in the wastewater by using a reverse osmosis membrane. However, when the wastewater to be treated contains calcium ions together with anions such as organic matter, suspended solids, and fluorine ions, the calcium ions form scales with anions such as fluorine ions to block or inactivate the reverse osmosis membrane and reverse osmosis. The performance of the permeation membrane is deteriorated, and frequent cleaning for the removal of the generated CaF 2 is necessary, and expensive reverse osmosis membranes need to be frequently exchanged, thereby rapidly decreasing the economical efficiency of the process.
Furthermore, since the reverse osmosis membrane does not remove ions but only separates, it is necessary to generate concentrated water containing high concentration ions, and a conventional wastewater treatment process is additionally required for the treatment of the concentrated water.
With regard to such fluorine-containing wastewater treatment and treated water reuse, the following techniques have been proposed.
Korean Patent Laid-Open Publication No. 2003-0016502 describing a method of reacting fluorine-containing wastewater with Al (OH) 3 by a wastewater treatment method, and then replacing it with slaked lime, and then recycling Al (OH) 3 again; Korean Patent Laid-Open Publication No. 1999-0028136, which describes a process for neutralizing fluorine-containing wastewater, treating fluorine by passing activated carbon and ion exchange resins, and then recycling the wastewater; The fluorine wastewater treatment method includes firstly treating the fluorine-containing wastewater with hydrated lime and a polymer flocculant, passing the multilayer media filter, and then passing the reverse osmosis membrane to reuse the treated water and coagulating sedimentation of the concentrated water. Korean Patent Publication No. 2001-0079251 described; Korean Patent Publication No. 1999-0053036, which discloses a technique of adding a flocculant to a pH-controlled acid wastewater to solidify residual fluorine and to treat a solid using a reverse osmosis membrane; Adjusting the pH of the hydrofluoric acid wastewater using a flocculant to solidify the fluorine ions contained in the hydrofluoric acid wastewater and to coarsen the solids formed by the flocculating aid; Separating the coarse solids in the step by microfiltration to discharge the solids containing the turbidity component and the treated water from which the solids are removed; Adsorbing and removing the organic matter contained in the treated water discharged in the step using activated carbon; And removing unreacted fluorine ions, other dissolved salts, and residual organic matters contained in the treated water from which the organic matter was removed using a reverse osmosis membrane to discharge the treated water for reuse. Korean Patent Laid-Open Publication No. 1998-0078119, which is disclosed in Korean Patent Application Publication No. 1998-0078119; And Korean Patent Laid-Open Publication No. 1996-0031480, which discloses a technique for producing recycled water that is almost pure water through ultraviolet / ozone sterilization, ion exchange resin, and the like after the reverse osmosis device.
Recently, the use of effluent is gradually increasing due to the development of membrane technology. However, there are not many cases of actual application due to high initial investment and operating costs. In particular, except for government-sponsored projects such as sewage reuse, the reuse of wastewater discharged from general enterprises is not economical and it is not easy to reuse wastewater using membranes.
In fluorine-containing wastewater treatment, a fluorine treatment agent is generally added, coagulated and precipitated to remove fluorine with sludge, and the treated water is generally discharged. In particular, when the rare earth flocculant is used as the fluorine treatment agent, the use of an expensive flocculant requires a huge wastewater treatment cost, and there is a problem in that the treated wastewater must also be discharged.
Therefore, economical fluorine treatment and wastewater reuse technology that can reduce water consumption, wastewater discharge, and cost by performing fluorine treatment from fluorine-containing wastewater and simultaneously recycling wastewater are required.
The present invention seeks to provide a method and a facility for treating fluorine from wastewater containing fluorine and fluorine treated effluent in a difficult and costly manner in which fluorine treatment is difficult or expensive.
It is also an object of the present invention to provide a method and a facility for performing fluorine treatment from fluorine-containing wastewater and at the same time recycling the effluent.
The present invention relates to a method for treating fluorine from fluorine-containing wastewater. According to a first embodiment of the present invention, a calcium ion removal step of removing calcium ions from wastewater by passing a fluorine-containing wastewater through a cation exchange resin, and The treated water recovery step of recovering the treated water from which the ions are removed by filtering the residual ions by passing the fluorine-containing wastewater from which the calcium ions have been removed through the reverse osmosis membrane.
According to the second embodiment of the present invention, the residual ions may further include a fluorine treatment step of coagulating fluorine in the concentrated water by adding a fluorine treatment agent to the concentrated concentrated water.
According to a third embodiment of the present invention, the concentrated water is preferably concentrated water containing more than 100mg / L fluorine anion.
According to a fourth embodiment of the present invention, the fluorine treatment agent may be a calcium-based fluorine treatment agent selected from CaCl 2 , Ca (OH) 2 , CaO, CaCO 3 and mixtures thereof.
According to a fifth embodiment of the present invention, the fluorine treatment agent may be added in a 1 to 10 times the concentration of fluorine ions as the weight-based calcium concentration.
According to a sixth embodiment of the present invention, part or all of the calcium-based fluorine treatment agent may be a fluorine treatment agent obtained from the calcium cation removed by the cation exchange resin and generated by regeneration of the cation exchange resin.
In addition, according to the seventh embodiment of the present invention, before the cation removal step may further comprise the step of removing the suspended solids by flocculation from the fluorine-containing waste water and the step of removing the suspended matter, organic matter or a mixture thereof by filtration. .
Furthermore, according to the eighth embodiment of the present invention, after the cation removing step, the fluorine-containing wastewater from which the cations have been removed may be further removed to remove suspended matter in the wastewater.
The present invention also relates to a fluorine treatment plant for treating fluorine from fluorine-containing wastewater, wherein the fluorine treatment plant filters ions from a cation exchange tower and a fluorine-containing wastewater to remove calcium ions present in the fluorine-containing wastewater. It includes a reverse osmosis membrane to discharge the treated water that does not substantially include a, to provide a concentrated solution of the ion concentration.
In the fluorine treatment plant of the present invention, a fluorine treatment tank may be included in which a fluorine treatment agent is added to a concentrated solution in which the ions are concentrated to aggregate the fluorine.
Furthermore, in the fluorine treatment facility of the present invention, the fluorine treatment agent may be a calcium-based fluorine treatment agent selected from CaCl 2 , Ca (OH) 2 , CaO, CaCO 3 and mixtures thereof.
According to any of the embodiments described in the present invention, fluorine-containing wastewater can be treated using only concentrated water as a low-cost calcium-based fluorine treatment agent instead of an expensive rare earth fluorine treatment agent, thereby significantly reducing the fluorine treatment cost.
On the other hand, it is possible to prevent the blockage of the reverse osmosis membrane due to the coexistence of fluorine and calcium ions in the waste water can reduce the cost required to reuse the waste water.
In addition, fluorine treatment can be used simultaneously with the effluent, thereby reducing water resources, reducing rare earth mineral resources, reducing wastewater emissions, and reducing sludge generation.
1 is a process diagram schematically showing a process for treating a conventional fluorine-containing wastewater using a rare earth fluorine treatment agent.
2 is a process diagram schematically showing a process of recycling fluorine treatment and effluent from fluorine-containing wastewater according to the present invention.
3 is a view showing a scale formation region according to the concentration of fluorine and calcium ions present in the wastewater.
4 is a graph showing the relationship between the fluorine concentration remaining in the wastewater according to the concentration of the calcium-based fluorine treatment agent when the wastewater is treated using the calcium-based fluorine treatment agent for the wastewater containing the low concentration of fluorine.
5 is a graph showing the relationship between the fluorine concentration remaining in the wastewater according to the rare earth charge concentration when the wastewater is treated with a rare earth fluorine treatment agent for the wastewater containing the low concentration of fluorine.
The present invention is to provide a method and equipment for treating fluorine-containing wastewater, which is effective and economical in treating fluorine from fluorine-containing wastewater, and reusable treated wastewater. And a separation recovery step of the concentrated water, and a fluorine treatment step from the concentrated water, and an apparatus configuration suitable for carrying out such a method.
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
2 is a process diagram schematically showing an example of a fluorine treatment and wastewater regeneration process from fluorine-containing wastewater according to the present invention.
In the present invention, a process for treating fluorine-containing wastewater may include pretreatment of the wastewater as needed before removing cations present in the wastewater. For example, in the case where the waste water contains suspended matter, organic matter, etc., these floats can increase the burden on the subsequent treatment process, thereby reducing the efficiency of the wastewater treatment or causing deterioration of the treatment equipment. Can be rough.
The pretreatment step is not particularly limited, but a low-density coagulant is added to the waste water in the coagulation tank to coagulate the suspended matter. Further, coagulation and precipitation of the coagulated suspended solid in the coagulation bath using a coagulant is followed by precipitation. The sludge can be treated. To this end, it may be provided with a precipitation tank.
In this case, the coagulant used is not particularly limited as long as it is generally applied to wastewater treatment, and includes alum, FeCl 3 , poly aluminum chloride (PAC), poly aluminum sulfate (PAS), and the like. The same aluminum type and iron salt type | system | group are mentioned. In addition, as the coagulant, a polymer coagulant commonly used may be used. For example, polyacrylamide, polyacrylic acid, or the like may be used alone or in combination thereof. The generated flocs can be coarsened, whereby impurities present in the wastewater can be easily removed.
Alternatively, the wastewater may be treated with a sand filtration device or an activated carbon adsorption column to filter out organic matter and suspended matter in the wastewater, and these may be appropriately selected or combined according to properties of suspended matter present in the wastewater to be treated. More specifically, the organic matter in the waste water can be removed by the adsorption column of activated carbon, and the suspended matter can be carried out by using filtration facilities such as sand filtration, micro filtration, ultra filtration and the like.
In order to remove the calcium cations present in the wastewater after removing the suspended matter or the organic matter present in the wastewater (influent water), the cation exchange column including a cation exchange membrane such as a cation exchange resin may be provided.
As will be described later, in the present invention, the reverse osmosis membrane is used to remove the ions in the waste water and reuse them as clean water. When calcium ions together with the fluorine ions are present in the waste water, the calcium ions and the fluorine ions are CaF 2. To form a scale. The CaF 2 thus produced has a fatal effect on the performance of the reverse osmosis membrane, thereby degrading the performance. Therefore, frequent reverse osmosis membranes are required for the removal of the generated scale, and expensive reverse osmosis membranes need to be frequently replaced, resulting in a drastic decrease in the economics of the process.
As can be seen from FIG. 3, when calcium ions and fluorine ions coexist, scales are formed in the reverse osmosis membrane, and these scales are generated even when very low concentrations of fluorine and calcium are present. It is desirable to remove from the wastewater in advance to inhibit the generation of this scale. In particular, since calcium ions react not only with fluorine ions but also with sulfate ions and carbonate ions to easily form scales, it is preferable to remove the ions to prevent the reverse osmosis membrane from being blocked.
Accordingly, the present invention aims to suppress the generation of scale in the reverse osmosis membrane by allowing the wastewater to pass through the cation exchange column to remove calcium ions rather than to remove fluorine ions in the water. The cation including the calcium cation present in the wastewater can be removed by the cation exchange resin. As the cation exchange resin, a cation exchange resin that is commonly used may be used, but is not limited thereto, and examples thereof include sulfone and carboxyl groups.
The fluorine-containing wastewater from which the cation has been removed is removed by filtering ions such as fluorine ions by a reverse osmosis membrane. As described above, when calcium ions coexist with fluorine ions by removing calcium ions from the wastewater, CaF 2 Is generated to block the reverse osmosis membrane, thereby preventing the function of the reverse osmosis membrane from being lowered.
Meanwhile, the calcium cations removed and collected by the cation exchange membrane may be regenerated through a separate regeneration procedure using a regeneration solution such as salt or hydrochloric acid to be used as a calcium-based fluorine treatment agent for the treatment of fluorine. As such, by utilizing the calcium recovered by the cation exchange membrane as a fluorine treatment agent for fluorine treatment, economics of the treatment process can be achieved and waste generation can be minimized.
The fluorine-containing wastewater from which the calcium cation has been removed by passing through the cation exchange resin may be subjected to a filtration step as necessary before treatment with the reverse osmosis membrane. The filtration step is to remove the fine suspended solids present in the waste water, even if the pre-treatment step may be there may be suspended solids not removed by it. Such fine suspension may cause a load on the reverse osmosis membrane of a later stage, and thus, it is preferable to remove the fine suspension in advance. In addition, it can be installed in a double with pretreatment if necessary to perform filtration.
The filtration step is not particularly limited as long as it is suitable for filtration and removal of fine suspended solids, for example, microfiltration, ultrafiltration, and the like, and may be applied alone or in combination thereof. After such a filtration step, by removing impurities such as fine suspended matter, the load on the reverse osmosis membrane can be minimized by minimizing the load on the reverse osmosis membrane, and the waste water can be reused by smoothly producing the treated water discharged from the reverse osmosis membrane. By obtaining a calcium-based fluorine treatment agent can be performed fluorine removal efficiency inexpensively and efficiently.
Impurities, such as the fine suspended solids filtered by the filtration step can maintain the performance by backwashing the filter medium, and in this case, since the backwash water partially contains fluorine ions, it is preferable to discharge the backwash water by fluorine treatment.
In the fluorine-containing wastewater from which the calcium cation has been removed, most ions such as fluorine ions are filtered out by the reverse osmosis membrane, whereby treated water from which most of the fluorine ions are removed and concentrated water with concentrated ions can be obtained. At this time, the treated water from which the fluorine ions have been removed is removed by the reverse osmosis membrane together with most of the ions such as chlorine ions and sulfate ions together with the fluorine ions, and thus can be reused as advanced industrial water.
In addition, the concentrated water containing a high concentration of ions by the reverse osmosis membrane is transferred to the next step including a fluorine treatment tank for the treatment of fluorine ions.
On the other hand, the concentrated water obtained by the reverse osmosis membrane contains most of the ions such as fluorine ions, and the concentrated water can be discharged after the fluorine concentration is reduced to below the discharge allowance using a fluorine treatment agent. . At this time, the backwash water by washing the filter medium of the filtration step as described above may be treated with the fluorine treatment agent together with the concentrated water.
As the fluorine treatment agent which can be used in the present invention, a treatment agent generally used for fluorine treatment can be suitably used. For example, a calcium fluorine treatment agent and an aluminum fluorine treatment agent, as well as a rare earth fluorine treatment agent can be used. . Mentioned specifically, not particularly limited, but aluminum-based as fluorine treatment Alum (Al 2 (SO 4) 3), PAC (Poly aluminum chloride), PAS (Poly aluminum sulfate), PASS (Poly aluminum silicate sulfate) , etc. And these may be used alone or in combination. The calcium-based fluorine treatment agent may include CaCl 2 , Ca (OH) 2 , CaO, CaCO 3 , and the like, and these may be used alone or in combination. Further, examples of the rare earth fluorine treatment agent include La, Ce, Nd, and Pr oxides, chlorides, and sulfur oxides, and these may be mixed and used.
However, in this invention, it is more preferable to apply a calcium-type fluorine treatment agent. That is, the fluorine ions of the concentrated water can be treated by applying an aluminum fluorine treatment agent and a rare earth fluorine treatment agent to the concentrated water obtained by the present invention. However, when the aluminum fluorine treatment agent is used, Additional post-treatment problems may occur, and rare earth-based fluorine treatment agents are expensive and have problems with supply and demand instability.
However, according to the method of the present invention, even when the fluorine concentration of the first fluorine-containing wastewater is low and a calcium-based fluorine treatment agent cannot be applied, a large amount of fluorine ions are concentrated in the concentrated water obtained by the present invention. Since it is a state, a calcium fluorine treatment agent can be used. Such calcium-based fluorine treatment agents exhibit fluorine treatment characteristics similar to rare earths in high concentrations of fluorine-containing solutions.
Therefore, when the fluorine ions are concentrated by the reverse osmosis membrane, the conventional aluminum fluorine treatment agent or the rare earth fluorine treatment agent can be applied, and the low-cost calcium fluorine treatment agent can be efficiently treated. desirable.
In addition, the cation exchange resin used to remove the calcium ions used in the entire process must be regularly regenerated, and the regeneration solution contains a large amount of calcium. Therefore, a substantial part of the regeneration solution can be reused as a fluorine treatment agent for treating fluorine. Therefore, it is possible to maximize the economics of the process to provide a useful means to reuse the effluent with fluorine treatment.
In the case of treating fluorine by applying the calcium-based fluorine treatment agent, the concentrated water preferably contains a high concentration of fluorine such as 100 mg / L or more. In the case where the calcium-based fluorine treatment agent is applied to the concentrated water having the fluorine concentration in the above range, the concentration of fluorine in the concentrated water can be lowered more effectively than the discharge allowable reference value, which is preferable. If the concentration of fluorine in the concentrated water exceeds the above range, the present invention can be suitably applied, and the upper limit thereof is not particularly limited.
By adding a fluorine treatment agent to the concentrated water, the fluorine ions in the concentrated water can be coagulated, and further, a polymer flocculant can be added together to aggregate and precipitate to sludge. The fluorine can be removed by separating the sludge from the liquid phase, and further, the wastewater can be collected and reused separately.
The fluorine treatment agent can be added in an amount sufficient to reduce the fluorine concentration in the concentrated water, it can be appropriately selected. For example, the fluorine treatment agent may be added at a concentration of 1 to 10 times the concentration of fluorine ions as a calcium concentration by weight. If it is less than 1 time, it is less than the theoretical amount, and it is insufficient in fluorine treatment, and if it is more than 10 times, it is not economical, and it is suitable to process fluorine ion concentration in concentrated water below the discharge tolerance standard by adding in the said range. In theory, the fluorine ion is Ca +2 + 2F - → CaF 2 is removed by, the weight ratio is 40:38 to remove, in a molar ratio of 1: 2 is removed at a. Thus, for example, when the fluorine ion is 100mg / L, the calcium-based fluorine treatment agent may be added at 100 ~ 1,000mg / L based on the calcium concentration.
As described above, after treating the fluorine from the concentrated water using a fluorine treatment agent to condense and precipitate the fluorine component, the precipitated sludge can be filtered to remove the fluorine. At this time, the fluorine can be condensed using the fluorine treatment agent, and the fluorine floc can be coarsened using the flocculant to increase the filtration efficiency.
The coagulant may be used as long as it is a polymer coagulant conventionally used in the art, but is not limited thereto. For example, polyacrylic acid, polyacryl amide-based cation, anion And nonionics.
Thus, in treating fluorine containing wastewater, when treating fluorine using this invention, even if a low cost calcium-based fluorine treatment agent is used instead of expensive rare earths, the fluorine treatment effect in wastewater can be remarkably improved. The cost of using a fluorine treatment agent can be reduced, and the recovery rate of water to be reused can be increased, thereby reducing the amount of water used, thereby significantly reducing the process cost of the fluorine treatment process.
Such a fluorine treatment facility suitable for applying the present invention will be easily understood by those skilled in the art from the description of the above process, and also easily modified and modulated therefrom. As the present invention can be carried out, such modifications and modifications do not depart from the scope of the present invention.
Example
Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are merely illustrative of the present invention, and the present invention is not limited thereto.
Example One
As the product cooling water (raw water) used in the regeneration process during the steelmaking process, in order to treat fluorine from fluorine-containing wastewater having a component as shown in Table 1, the wastewater treatment facility shown in the process diagram shown in FIG. Wastewater treatment was performed in sequence.
The wastewater as described in Table 2 introduced into the inflow tank was treated continuously at a flow rate of 1 ton / hr as raw water to confirm the results. Alum is added to the raw water at a concentration of (100) mg / L, and 1 mg / L of a polyacrylamide-based anionic flocculant is added as a polymer flocculant to flocculate suspended solids in the raw water, followed by precipitation. Sludge was filtered off.
Subsequently, the suspended solids and organic matters in the raw water were removed through the filter of the sand filter medium and the activated carbon adsorption tower, and then the calcium cations present in the wastewater were removed by passing through a cation exchange column including a sulfone-based cation exchange resin. The wastewater thus obtained was analyzed and the results are shown in Table 1 below.
As can be seen from Table 1, it can be seen that almost no organic matter, suspended solids and Ca ions in the wastewater passing through the filter, activated carbon adsorption column and cation exchange column.
The fluorine-containing wastewater obtained by the above process was filtered through a reverse osmosis membrane to obtain a treated water substantially free of ions and concentrated water containing ions such as fluorine ions. At this time, the obtained treated water was recovered to about 73% of the raw water. On the other hand, it can be seen that the concentrated water is concentrated by about 3.7 times the concentration of the ion compared to the influent. The components of the treated water and the concentrated water were analyzed and the results are shown in Table 1.
Meanwhile, in order to regenerate the ion exchange resin of the cation exchange column used to remove the calcium cation, 10% NaCl solution was regenerated using 10 L, and the obtained regenerated water was recovered and analyzed, and the results are shown in Table 1 below. It was.
As can be seen from Table 1, it can be seen that the regenerated water contains a high concentration of calcium. Therefore, it can be seen that it can be suitably used as a calcium-based fluorine treatment agent for treating fluorine contained in the concentrated water.
(uS / cm)
Example 2
The product cooling water used in the regeneration process during the steelmaking process was treated in the same manner as in Example 1 to obtain a reverse osmosis concentrated water having a fluorine concentration of 260 ppm.
Fluorine treatment was performed using the obtained reverse osmosis concentrated water as a fluorine treatment agent by using CaCl 2 35% and LaCl 2 in an amount as described in Table 2, and measuring the residual fluorine concentration according to the content of the treatment agent for each fluorine treatment agent. Treatment effects were tested. The test results are shown in Table 2.
(ppm)
As can be seen from Table 2, for the high concentration of wastewater having a high fluorine ion content, fluorine treatment using a calcium-based fluorine treatment agent (35% CaCl 2 ) and a rare earth-based fluorine treatment agent (17% LaCl 2 ) as the fluorine treatment agent. When the process is carried out, it can be seen that the fluorine treatment effect is equal to or higher than that of the rare earth-based fluorine treatment agent. Furthermore, when 5000 ppm of fluorine treatment agent was used, the discharge acceptance standard was satisfied.
Reference Example One
In order to confirm the effects of calcium treatment in the case of using a calcium fluorine treatment agent and a rare earth fluorine treatment agent for wastewater containing low concentrations of fluorine, CaCl 2 fluorine treatment agent and LaCl 2 in a low concentration wastewater containing 50 ppm of fluorine ions. Each of the fluorine treatment agents was used to measure the residual fluorine content in the wastewater according to the concentration of the fluorine treatment agent. The results are shown in Figs.
As can be seen from FIG. 4, it can be seen that when the wastewater containing low concentration of fluorine is treated with a calcium-based fluorine treatment agent, it is impossible to treat the concentration of fluorine ions in the wastewater within the emission limit. On the other hand, it can be seen from Fig. 5 that the treatment effect of the rare earth fluorine treatment agent has a high effect of treating fluorine ions regardless of the concentration of fluorine ions in the influent.
Therefore, as in the present invention, when the fluorine ions are concentrated by the reverse osmosis membrane, the conventional aluminum-based fluorine treatment agent or the rare earth fluorine treatment agent can be applied, and the low-cost calcium-based fluorine treatment agent can be efficiently treated. It can be seen that.
Claims (11)
And a treated water recovery step of recovering the treated water from which the ions have been removed by filtering the residual ions through the reverse osmosis membrane of the fluorine-containing wastewater from which the calcium ions have been removed.
The fluorine-containing wastewater treatment method further comprising the step of removing suspended solids, organic matter or a mixture thereof by filtration.
A fluorine-containing wastewater treatment facility comprising a reverse osmosis membrane for filtering ions from fluorine-containing wastewater to discharge treated water substantially free of ions, and providing a concentrated solution in which the ions are concentrated.
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