CN113666561B - High-salt sulfur-containing fluorine-containing wastewater treatment process - Google Patents
High-salt sulfur-containing fluorine-containing wastewater treatment process Download PDFInfo
- Publication number
- CN113666561B CN113666561B CN202110988489.8A CN202110988489A CN113666561B CN 113666561 B CN113666561 B CN 113666561B CN 202110988489 A CN202110988489 A CN 202110988489A CN 113666561 B CN113666561 B CN 113666561B
- Authority
- CN
- China
- Prior art keywords
- wastewater
- fluorine
- salt
- ion exchange
- calcium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/041—Treatment of water, waste water, or sewage by heating by distillation or evaporation by means of vapour compression
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
Abstract
The invention relates to a high-salt sulfur-containing fluorine-containing wastewater treatment process, which comprises the following steps of: firstly, oxidizing sulfite into sulfate by forced oxidation of high-salt sulfur-containing fluorine-containing wastewater, then adjusting pH to below 4, and removing carbonate in the wastewater; and secondly, adjusting the pH value of the wastewater to 5-10, adding a defluorinating agent to remove fluorine ions in the solution, separating the generated suspension by a ceramic membrane to remove solid impurities, finally, adsorbing the wastewater after the removal of the solid by an ion exchange resin to remove calcium ions in the wastewater, returning the wastewater regenerated by the ion exchange resin to a defluorinating reaction kettle as the defluorinating agent, introducing the wastewater after the decalcification to MVR, recovering crude salt, and separating the solid impurities separated by the ceramic membrane by filter pressing through a box filter press, wherein the separated wastewater returns to a membrane separation tank. The invention improves and shortens the process flow of the traditional high-salt fluorine-containing wastewater, reduces the addition amount of the medicament and the sludge production amount, and solves the technical problem of exceeding the standard of sewage discharge.
Description
Technical Field
The invention relates to a high-salt sulfur-containing fluorine-containing wastewater treatment process, and belongs to the technical field of fluoride wastewater treatment.
Background
Along with the development of modern industry, a large amount of fluorine-containing industrial wastewater is generated in the production process of fluorine-containing industry, the composition of the fluorine-containing wastewater is complex, but fluorine in the fluorine-containing wastewater still exists in the form of oxyfluoric acid, fluosilicic acid and soluble fluoride salt, and due to the development of industrial technology, a large amount of fluorine-containing wastewater is generated in each industry, and the difference of the concentration of fluorine ions in the fluorine-containing wastewater is large due to the different characteristics of each industry. Since the wastewater is industrial wastewater, the fluorine-containing wastewater usually contains other pollutants such as inorganic salts and organic matters in addition to fluorine, and many enterprises have no perfect water treatment facilities for treating the wastewater and then discharge the wastewater into the nature. The environment in which the human beings depend to survive is seriously polluted, and the health of the human beings is greatly threatened. The method for removing fluorine is based on the quality, quantity, emission standard, treatment method, cost and economic value. The traditional industrial wastewater treatment methods are classified into physical treatment methods, chemical treatment methods, biochemical methods and physicochemical treatment methods according to principles.
At present, a great deal of work has been carried out on the aspect of researching the treatment of fluorine-containing wastewater at home and abroad, and CN201910865251.9 discloses the recycling of deep fluorine-removing resin desorption liquid, namely, fluorine-containing wastewater is firstly adsorbed by fluorine-removing resin, and then is desorbed by alkali liquor; adding alkali liquor into the desorption liquid to carry out carbonization treatment, adding a small amount of calcium oxide or calcium hydroxide into the desorption liquid to precipitate and remove fluorine, and carrying out solid-liquid separation; adding calcium oxide or calcium hydroxide into the solution obtained after solid-liquid separation to carry out causticization reaction, and then softening the supernatant fluid obtained after solid-liquid separation through resin to remove calcium, wherein high-concentration alkali obtained by the causticization reaction can be used as a desorption agent, so that the resource recycling of the deeply treated resin desorption liquid of fluorine-containing wastewater is effectively realized; CN202010690536.6 uses an external electric field to gather fluoride ions, separates wastewater in a region enriched with fluoride ions and wastewater in a region less in fluoride ions, uses chemical precipitation to remove fluoride from wastewater enriched with fluoride ions, uses an external electrostatic field to gather and separate fluoride ions again after removing fluoride, separates, uses chemical precipitation, circulates, improves the efficiency of removing fluoride, and reduces the cost of removing fluoride.
CN202010472584.8 discloses that pH of fluorine-containing wastewater is adjusted to 3-8, a chemical defluorinating agent is added for reaction, alkali is added for adjusting the pH of reaction liquid to 6-9 after the reaction, polyacrylamide is added for flocculation reaction, and primary purifying liquid and primary filter residue are obtained after solid-liquid separation; and (3) deeply removing fluorine in the primary purifying liquid by adopting modified strong-alkaline anion resin, and then deeply treating fluorine in the wastewater by adopting a chemical precipitation method and the modified strong-alkaline anion resin, wherein the fluorine stability of the final effluent is lower than 1mg/L.
In recent years, the requirements on environmental protection are more and more strict, but the current treatment processes are obvious in long flow, large in dosage of the medicaments and restrained in the development of enterprises, so that development of an advanced treatment method with simple process and excellent effect is urgently needed.
Disclosure of Invention
The invention aims to provide a high-salt sulfur-containing and fluorine-containing wastewater treatment process, which aims to solve the problems of long treatment process flow, large dosage of agents and the like in the prior art.
The aim of the invention can be achieved by the following technical scheme:
a high-salt sulfur-containing and fluorine-containing wastewater treatment process comprises the following steps:
(1) Carrying out forced oxidation on the high-salt sulfur-containing fluorine-containing wastewater, adjusting the pH value to be less than 4, and then adjusting the pH value to be 5-10;
(2) Adding a defluorinating agent into the treated wastewater after the pH is adjusted in the step (1), and carrying out defluorinating precipitation reaction;
(3) Carrying out solid-liquid separation (ceramic membrane filtration can be adopted) on the suspension obtained in the step (2), and sending the obtained liquid phase into an ion exchange resin tower for ion exchange adsorption to obtain softened wastewater; concentrating and press-filtering the solid phase to obtain a mixture of calcium fluoride and calcium sulfate; (4) And sending the obtained softened wastewater into an MVR system, and separating coarse salt and water to finish the process.
Further, in the step (1), the forced oxidation method is one or two methods of air blowing, ozone blowing or hydrogen peroxide adding;
when the mode of bubbling air or ozone is adopted, the aeration time is controlled to be 14-18 hours, and the aeration rate is 200-800ml/min;
when the mode of adding hydrogen peroxide is adopted, the addition amount of the hydrogen peroxide satisfies the following conditions: the concentration of the catalyst in the wastewater is 1.5-3.0 wt%, and the reaction time after adding hydrogen peroxide is 30-50 min.
Further, in the step (2), the fluorine removing agent is calcium chloride.
In the step (2), when the pH of the treated wastewater is adjusted back to 5-7, the addition amount of the fluorine removing agent satisfies the following conditions: the molar ratio of calcium ions to fluoride ions in the wastewater is (1.5-2.0): 1;
when the pH of the treated wastewater is adjusted back to 7-10, the molar ratio of calcium ions to fluoride ions in the wastewater is (2.0-3.0): 1.
Further, in the step (2), the solid-liquid separation process is performed in a ceramic membrane separation tank, a ceramic membrane component for solid-liquid separation is arranged in the ceramic membrane separation tank, and an aeration component is arranged at the bottom 30-50mm of the ceramic membrane component.
In the step (2), the solid phase obtained by solid-liquid separation is concentrated and then sent to a filter press for filter pressing, and the liquid discharged by the filter press is returned to the step (2) for defluorination.
Furthermore, in the step (2), after the ceramic membrane separation tank is operated for a set time, the ceramic membrane component is subjected to backflushing regeneration or chemical cleaning.
More preferably, in the step (2), EDTA or aluminum trichloride is used as a cleaning agent in the chemical cleaning.
Further, in the step (3), the ion exchange resin is a chelate resin (used when the TDS is more than 50000) for removing calcium and magnesium from high-salt water, and the ion exchange resin is a product conventionally and commercially available in the field.
In the step (3), the ion exchange resin needs to be regenerated by 4% -8% hydrochloric acid after adsorption saturation, the using amount of the regenerant hydrochloric acid is 2-5 times of the resin volume, and the regenerated resin is neutralized by sodium hydroxide to convert the H-type resin into Na-type resin.
The invention converts sulfite in the high-salt sulfur-containing fluorine-containing wastewater into normal salt by utilizing forced oxidation, thereby preventing SO from being generated when the carbonate is removed by pH adjustment and acidification 2 Overflowing to pollute the environment, acidifying the wastewater obtained after forced oxidation to remove carbon, adjusting the pH value, adding a fluorine removing agent, and chemically precipitating to remove fluorine to generate suspension. The suspension enters a ceramic membrane separation tank, an aeration device is arranged at the bottom 30-50mm of a membrane component of the ceramic membrane separation tank, aeration disturbance cleans the surface of a membrane, and the ceramic membrane separates a solid phase from a liquid phase. The solid phase obtained by ceramic membrane separation is concentrated by a concentration tank and then enters a box type filter press for recovery, and the solid phase is mainly calcium fluoride which can be recycled, and the liquid from the filter press returns to a defluorination reaction kettle; the obtained liquid phase wastewater enters an ion exchange resin tower for decalcification treatment, excessive calcium ions added in the defluorination reaction are removed, and calcium and magnesium ions in the wastewater are exchanged and adsorbed in the ion exchange resin tower, so that the wastewater reaches the softened water index. And the obtained softened wastewater enters an MVR system, coarse salt is separated, part of the separated water is recycled, and the other part is directly discharged. And after the ceramic membrane is separated and operated for a period of time, backflushing regeneration or chemical cleaning is carried out, and wastewater generated by regenerating the ion exchange resin is returned to the defluorination reaction kettle to be used as a defluorination agent. The invention utilizes the coupling process technology of forced oxidation, ceramic membrane separation and ion exchange resin, shortens the process flow, reduces the addition amount of chemical agents and solid waste generation, recycles calcium ions, ensures that MVR can run for a long period and reduces energy consumption.
For dioxygenThe water limit is determined according to the sulfite content in the wastewater, the calcium chloride addition is determined according to the fluoride ion concentration in the wastewater after the defluorination reaction, and excessive calcium chloride is added to waste calcium chloride medicament, increase the running cost and increase Ca 2+ Scaling can also occur in subsequent MVR evaporation desalination, increasing energy consumption.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts the ceramic membrane and the ion exchange resin which can be recycled to use the green environment-friendly material, reduces the addition amount of the medicament, reduces the sludge production amount, and is green and economical.
(2) The invention creatively combines the integrated processes of forced oxidation, chemical precipitation defluorination, ceramic membrane separation, ion exchange decalcification, shortens the traditional process flow and improves the efficiency.
(3) The solid phase of the invention is mainly calcium fluoride after ceramic membrane separation, which can be used as resource, improves the utilization rate of byproducts and reduces the generation of solid waste.
(4) The solution obtained by regenerating the ion exchange resin by the hydrochloric acid mainly contains calcium chloride and can be returned to a defluorination reaction kettle to serve as a defluorination agent, so that the utilization rate of calcium ions is improved.
Drawings
Fig. 1 is a schematic flow chart of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
As shown in FIG. 1, the invention provides a high-salt sulfur-containing and fluorine-containing wastewater treatment process, which comprises the following steps:
(1) Converting sulfite in the wastewater into normal salt through forced oxidation of the wastewater containing sulfur and fluorine;
(2) The pH value of the wastewater after forced oxidation is adjusted to be less than 4, carbonate ions in the wastewater are removed, and then the pH value of the wastewater is adjusted back to 5-10;
(3) Pumping the wastewater with the pH value regulated back into a defluorination reaction kettle, and injecting a defluorination agent into the defluorination reaction kettle to generate calcium fluoride, calcium sulfate and the like;
(4) The suspension generated by the defluorination reaction enters a ceramic membrane separation tank, an aeration device is arranged at the bottom 30-50mm of a membrane component of the ceramic membrane separation tank, aeration is disturbed to clean the surface of the membrane, the ceramic membrane separates a solid phase from a liquid phase, and the solid phase enters a box filter press after being concentrated by a concentration tank; the wastewater from the ceramic membrane separation liquid phase enters an ion exchange resin tower for decalcification treatment, and the liquid from the filter press returns to a defluorination reaction kettle; the ceramic membrane is separated and operated for a period of time to carry out backflushing regeneration or chemical cleaning;
(5) The calcium and magnesium ions in the wastewater are exchanged and adsorbed in an ion exchange resin tower, so that the wastewater reaches the softened water index;
(6) And (3) introducing the wastewater softened by the ion exchange resin into an MVR system, separating out crude salt, and recycling a part of separated water and directly discharging a part of separated water.
The invention utilizes the coupling process technology of forced oxidation, ceramic membrane separation and ion exchange resin, shortens the process flow, reduces the addition amount of chemical agents and solid waste generation, recycles calcium ions, ensures that MVR can run for a long period and reduces energy consumption. The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
The process flow is described below in connection with more specific embodiments.
In the following examples, unless otherwise specified, the starting materials or processing steps employed are those conventionally used in commercial products or conventional techniques.
Example 1
Based on the above-mentioned process flow as shown in fig. 1, the process parameters of this embodiment are as follows:
adding 2% hydrogen peroxide (2% refers to the mass content of the added hydrogen peroxide in the wastewater) into sulfur-containing fluorine-containing wastewater with the concentration of sulfite of 1.5% and the concentration of fluoride ion of 499mg/L for reaction for 30min, wherein the conversion rate of sulfite ion is 99%, adding hydrochloric acid, and adjusting the pH valueAdjusting the pH to be 3.5, removing carbonate in the wastewater, adjusting the pH to be 5.5, adding calcium chloride, and meeting the requirement of [ Ca ] 2+ /F - ]=1.5, F in wastewater after ceramic membrane separation -1 The concentration of the calcium ions in the wastewater after the ceramic membrane separation is 20mg/L, and the concentration of the calcium ions in the wastewater after the calcium removal is 25mg/L through ion exchange resin, so that the wastewater reaches the softened water index.
Example 2
Based on the above-mentioned process flow as shown in fig. 1, the process parameters of this embodiment are as follows:
adding 2.5% hydrogen peroxide (2.5% refers to the mass content of the added hydrogen peroxide in the wastewater) into sulfur-containing and fluorine-containing wastewater with the concentration of sulfite of 1.5% and the concentration of fluoride ions of 499mg/L for reaction for 30min, wherein the conversion rate of sulfite ions is 100%, adding hydrochloric acid to adjust the pH value to 3.5, removing carbonate in the wastewater, adjusting the pH value to 5.5, adding calcium chloride, and meeting the requirements of [ Ca 2+ /F - ]=1.5, F in wastewater after ceramic membrane separation -1 The concentration of the calcium ions in the wastewater after the ceramic membrane separation is 18mg/L, and the concentration of the calcium ions in the wastewater after the calcium removal is 27mg/L through ion exchange resin, so that the wastewater reaches the softened water index.
Example 3
Based on the above-mentioned process flow as shown in fig. 1, the process parameters of this embodiment are as follows:
adding 3% hydrogen peroxide for reaction for 40min, adding hydrochloric acid to adjust pH value to 3, removing carbonate radical in the wastewater, adjusting pH value to 6.5, adding calcium chloride to meet [ Ca 2+ /F - ]=2.0, F in wastewater after ceramic membrane separation -1 The concentration of the calcium ions in the wastewater after ceramic membrane separation is 12mg/L, and the concentration of the calcium ions in the wastewater after calcium removal is 35mg/L through ion exchange resin, so that the wastewater reaches the softened water index.
Example 4
Based on the above-mentioned process flow as shown in fig. 1, the process parameters of this embodiment are as follows:
the concentration of sulfite in the sulfur-containing and fluorine-containing wastewater is 1.5 percent, and the fluorine isThe ion concentration is 800mg/L, aeration oxidation is carried out for 14 hours, the aeration amount is 200ml/min, the conversion rate of sulfite ions is 99 percent, then hydrochloric acid is added, the pH value is adjusted to 3.5, carbonate in the wastewater is removed, the pH value is adjusted to 7, and calcium chloride and [ Ca ] are added 2+ /F - ]=2, F in wastewater after ceramic membrane separation -1 The concentration of the calcium ions is 20mg/L, and the calcium ions in the wastewater after calcium removal are removed by ion exchange resin, and the concentration of the calcium ions in the wastewater after calcium removal is 40mg/L, so that the softened water index is reached.
Example 5
Based on the above-mentioned process flow as shown in fig. 1, the process parameters of this embodiment are as follows:
the concentration of sulfite in the sulfur-containing and fluorine-containing wastewater is 2.0%, the concentration of fluoride ions is 800mg/L, the aeration and oxidation are carried out for 14 hours, the aeration amount is 200ml/min, the conversion rate of sulfite ions is 99%, then hydrochloric acid is added, the pH value is adjusted to 3.5, carbonate in the wastewater is removed, the pH value is adjusted back to 7, and calcium chloride and [ Ca ] are added 2+ /F - ]=2, F in wastewater after ceramic membrane separation -1 The concentration is 20mg/L, the calcium ions are removed through ion exchange resin, and the concentration of the calcium ions in the wastewater after calcium removal is 42mg/L, thereby reaching the softened water index.
Example 6
Based on the above-mentioned process flow as shown in fig. 1, the process parameters of this embodiment are as follows:
the concentration of sulfite in the sulfur-containing and fluorine-containing wastewater is 2.0%, the concentration of fluoride ions is 800mg/L, the aeration and oxidation are carried out for 14 hours, the aeration amount is 200ml/min, the conversion rate of sulfite ions is 99%, then hydrochloric acid is added, the pH value is adjusted to 3.5, carbonate in the wastewater is removed, the pH value is adjusted back to 8, and calcium chloride and [ Ca ] are added 2+ /F - ]=2, F in wastewater after ceramic membrane separation -1 The concentration is 28mg/L, the calcium ions are removed through ion exchange resin, and the calcium ion concentration of the wastewater after calcium removal is 45mg/L, thereby reaching the softened water index.
Example 7
Based on the above-mentioned process flow as shown in fig. 1, the process parameters of this embodiment are as follows:
the concentration of sulfite radical in the sulfur-containing and fluorine-containing wastewater is 2.0 percent, and the concentration of fluoride ion is 800mgand/L, performing aeration oxidation for 14 hours, wherein the aeration amount is 200ml/min, the conversion rate of sulfite ions is 99%, then adding hydrochloric acid, adjusting the pH value to 3.5, removing carbonate in wastewater, adjusting the pH value to 8, and adding calcium chloride [ Ca ] 2+ /F - ]=2.5, F in wastewater after ceramic membrane separation -1 The concentration of the calcium ions is 21mg/L, and the calcium ions in the wastewater after calcium removal are 48mg/L through ion exchange resin exchange, so that the softened water index is reached.
Example 8
Based on the above-mentioned process flow as shown in fig. 1, the process parameters of this embodiment are as follows:
the concentration of sulfite in the sulfur-containing and fluorine-containing wastewater is 2.0%, the concentration of fluoride ions is 800mg/L, the aeration and oxidation are carried out for 14 hours, the aeration amount is 200ml/min, the conversion rate of sulfite ions is 99%, then hydrochloric acid is added, the pH value is adjusted to 3.5, carbonate in the wastewater is removed, the pH value is adjusted back to 9, and calcium chloride and [ Ca ] are added 2+ /F - ]=3, F in wastewater after ceramic membrane separation -1 The concentration is 15mg/L, the calcium ions are removed through ion exchange resin, and the calcium ion concentration of the wastewater after calcium removal is 52mg/L, thereby reaching the softened water index.
Example 9
In comparison with example 1, the same procedure was followed except that 1.5% hydrogen peroxide was added.
Example 10
In comparison to example 1, which is largely identical, the pH is adjusted back to 5, except for the addition of calcium chloride.
Example 11
In comparison to example 8, which is largely identical, the pH is adjusted back to 10 before the addition of calcium chloride.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (7)
1. A high-salt sulfur-containing and fluorine-containing wastewater treatment process is characterized by comprising the following steps of:
(1) Carrying out forced oxidation on the high-salt sulfur-containing fluorine-containing wastewater, regulating the pH value to be less than 4, and then regulating the pH value to be 5-10;
(2) Adding a defluorinating agent into the treated wastewater after the pH is adjusted in the step (1), and carrying out defluorinating precipitation reaction;
(3) Carrying out solid-liquid separation on the suspension obtained in the step (2), and sending the liquid phase into an ion exchange resin tower to carry out ion exchange to adsorb calcium and magnesium ions, so as to obtain softened wastewater; concentrating and press-filtering the solid phase to obtain a mixture of calcium fluoride and calcium sulfate, and delivering the mixture;
(4) The obtained softened wastewater is sent into an MVR system, and coarse salt and water are separated by evaporation, thus the process is completed;
in the step (2), the solid-liquid separation process is carried out in a ceramic membrane separation tank, a ceramic membrane component for solid-liquid separation is arranged in the ceramic membrane separation tank, and an aeration component is arranged at the bottom 30-50mm of the ceramic membrane component;
in the step (2), solid phase obtained by solid-liquid separation is concentrated and then is sent to a filter press for filter pressing, and liquid discharged by the filter press is returned to the step (2) for defluorination reaction;
in the step (3), the ion exchange resin is regenerated by adopting 4% -8% hydrochloric acid after adsorption saturation, the consumption of the regenerated hydrochloric acid is 2-5 times of the volume of the ion exchange resin, the regenerated ion exchange resin is neutralized by sodium hydroxide, and the wastewater generated by regeneration of the ion exchange resin is returned to the step (2) to be used as a fluorine removing agent.
2. The process for treating high-salt sulfur-containing and fluorine-containing wastewater according to claim 1, wherein in the step (1), the forced oxidation method is one or a combination of two methods of bubbling air, bubbling ozone or adding hydrogen peroxide;
when the mode of bubbling air or ozone is adopted, the aeration time is controlled to be 14-18 hours, and the aeration rate is 200-800ml/min;
when the mode of adding hydrogen peroxide is adopted, the addition amount of the hydrogen peroxide satisfies the following conditions: the concentration of the catalyst in the wastewater is 1.5-3.0 wt%, and the reaction time after adding hydrogen peroxide is 30-50 min.
3. The process for treating high-salt sulfur-containing and fluorine-containing wastewater according to claim 1, wherein in the step (2), the fluorine scavenger is calcium chloride.
4. The process for treating high-salt sulfur-containing and fluorine-containing wastewater according to claim 1 or 3, wherein in the step (2), when the pH of the treated wastewater is adjusted back to 5-7, the addition amount of the fluorine removing agent satisfies the following conditions: the molar ratio of calcium ions to fluoride ions in the wastewater is (1.5-2.0): 1;
when the pH of the treated wastewater is adjusted back to 7-10, the molar ratio of calcium ions to fluoride ions in the wastewater is (2.0-3.0): 1.
5. The process for treating wastewater containing sulfur and fluorine with high salt content according to claim 1, wherein in the step (2), after the ceramic membrane separation tank is operated for a set time, the ceramic membrane assembly is subjected to back flushing regeneration or chemical cleaning.
6. The process for treating wastewater containing sulfur and fluorine with high salt content according to claim 5, wherein EDTA or aluminum trichloride with concentration of 0.1-0.2 mol/L is adopted as the cleaning agent in the chemical cleaning process in the step (2).
7. The process for treating high-salt sulfur-containing and fluorine-containing wastewater according to claim 1, wherein in the step (3), the ion exchange resin is a chelate resin for removing calcium and magnesium from high-salt water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110988489.8A CN113666561B (en) | 2021-08-26 | 2021-08-26 | High-salt sulfur-containing fluorine-containing wastewater treatment process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110988489.8A CN113666561B (en) | 2021-08-26 | 2021-08-26 | High-salt sulfur-containing fluorine-containing wastewater treatment process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113666561A CN113666561A (en) | 2021-11-19 |
| CN113666561B true CN113666561B (en) | 2023-06-09 |
Family
ID=78546658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110988489.8A Active CN113666561B (en) | 2021-08-26 | 2021-08-26 | High-salt sulfur-containing fluorine-containing wastewater treatment process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113666561B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340221A (en) * | 2022-09-14 | 2022-11-15 | 深圳市环境科学研究院 | Deep defluorination treatment process and recycling system |
| CN115448522B (en) * | 2022-10-17 | 2024-01-30 | 北京国润伟业科技中心(有限合伙) | System and method for purifying water quality of high-salt wastewater |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5609767A (en) * | 1994-05-11 | 1997-03-11 | Eisenmann; Erhard T. | Method for regeneration of electroless nickel plating solution |
| WO2012141896A1 (en) * | 2011-04-13 | 2012-10-18 | Molycorp Minerals, Llc | Rare earth removal of hydrated and hydroxyl species |
| CN105800886A (en) * | 2016-05-23 | 2016-07-27 | 北京今大禹环境技术股份有限公司 | Resource recycling and treatment technology of high-concentration degradation-resistant salt-containing organic waste water |
| CN110204123A (en) * | 2019-04-16 | 2019-09-06 | 南京工业大学 | A kind of Resource comprehensive utilization method of Fipronil production abraum salt |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9719179B2 (en) * | 2012-05-23 | 2017-08-01 | High Sierra Energy, LP | System and method for treatment of produced waters |
| US9259703B2 (en) * | 2012-08-13 | 2016-02-16 | Enviro Water Minerals Company, Inc. | System for removing selenium from a feed stream |
| CN104445717B (en) * | 2014-11-13 | 2016-04-27 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | A kind of lead-zinc smelting wastewater reverse osmosis dope is synchronously except fluorine deliming treatment process |
| CN105502782B (en) * | 2015-12-07 | 2019-09-27 | 湖南湘牛环保实业有限公司 | A kind of coal chemical industry coking wastewater water resource and salt recovery process |
| SE539432C2 (en) * | 2015-12-21 | 2017-09-19 | Easymining Sweden Ab | Method and arrangement for recovery of salt |
| CN105800885B (en) * | 2016-05-23 | 2019-02-22 | 北京今大禹环境技术股份有限公司 | The resource utilization of high-concentration hardly-degradable salt-containing organic wastewater utilizes processing system |
| CN111362283B (en) * | 2018-12-26 | 2023-05-19 | 金科环境股份有限公司 | Viscose wastewater recycling treatment method |
| CN110683709A (en) * | 2019-07-15 | 2020-01-14 | 衢州市鼎盛化工科技有限公司 | Zero-discharge treatment method for fluorine-containing wastewater |
| CN110590012B (en) * | 2019-09-12 | 2020-09-22 | 南京大学 | Resource utilization method of deep defluorination resin desorption solution |
| CN110606612A (en) * | 2019-11-04 | 2019-12-24 | 江苏中电创新环境科技有限公司 | Coal coking high-salinity wastewater recycling treatment process |
| CN113003845B (en) * | 2019-12-19 | 2022-12-20 | 山东湘硕化工有限公司 | Zero-emission treatment process and system for sewage with high sulfate content and high COD (chemical oxygen demand) |
| CN111170544A (en) * | 2020-02-29 | 2020-05-19 | 北京中航泰达环保科技股份有限公司 | Zero discharge system and method for pretreatment wastewater of active coke desulfurization and denitrification and salt preparation from rich gas |
| CN111762963B (en) * | 2020-06-23 | 2022-08-05 | 烟台金正环保科技有限公司 | High-salt high-COD sewage treatment zero-discharge process |
| CN112266099A (en) * | 2020-10-12 | 2021-01-26 | 内蒙古晶泰环境科技有限责任公司 | Mine fluorine-containing wastewater resource utilization system and process |
| CN112624447A (en) * | 2020-12-21 | 2021-04-09 | 杭州蓝然环境技术股份有限公司 | Zero-discharge comprehensive utilization treatment process for graphite wastewater |
| CN112939321A (en) * | 2021-02-04 | 2021-06-11 | 上海宝汇环境科技有限公司 | Steel wastewater zero-discharge treatment technology |
-
2021
- 2021-08-26 CN CN202110988489.8A patent/CN113666561B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5609767A (en) * | 1994-05-11 | 1997-03-11 | Eisenmann; Erhard T. | Method for regeneration of electroless nickel plating solution |
| WO2012141896A1 (en) * | 2011-04-13 | 2012-10-18 | Molycorp Minerals, Llc | Rare earth removal of hydrated and hydroxyl species |
| CN105800886A (en) * | 2016-05-23 | 2016-07-27 | 北京今大禹环境技术股份有限公司 | Resource recycling and treatment technology of high-concentration degradation-resistant salt-containing organic waste water |
| CN110204123A (en) * | 2019-04-16 | 2019-09-06 | 南京工业大学 | A kind of Resource comprehensive utilization method of Fipronil production abraum salt |
Non-Patent Citations (1)
| Title |
|---|
| 化学沉淀法处理离子交换含盐废水试验;王晓晖;徐晓;卜二军;朱文玲;;化工生产与技术(第01期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113666561A (en) | 2021-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10662075B2 (en) | Method and apparatus for the recovery and deep treatment of polluted acid | |
| CN105541017B (en) | Method and device for zero emission of strong brine | |
| CN113666561B (en) | High-salt sulfur-containing fluorine-containing wastewater treatment process | |
| CN105314773A (en) | Wet desulphurization wastewater recycling method and apparatus thereof | |
| CN101838749A (en) | Ion exchange extraction vanadium method of vanadium-containing solution | |
| CN113003846B (en) | Zero-emission treatment process and system for sewage with high salt content and high COD (chemical oxygen demand) | |
| CN106630027A (en) | Method and system for treating high-chlorine desulfurization waste water by electrolytic method and performing flue gas mercury pollution control | |
| CN110282783B (en) | Ammonium phosphate chemical wastewater treatment system and method | |
| CN110038647B (en) | Method for efficiently regenerating resin by using electrolytic salt solution | |
| CN106977013B (en) | Purification treatment method of high-chlorine thallium-containing wastewater and application thereof | |
| CN112794500B (en) | Coking wastewater strong brine near-zero emission treatment system and treatment method thereof | |
| CN110981013A (en) | Method for treating waste liquid after extraction of thiamine | |
| RU2589139C2 (en) | Method of cleaning drainage water of solid domestic waste landfills | |
| CN205442916U (en) | Contain salt effluent disposal system | |
| CN108793558B (en) | Method for treating wastewater generated in activated carbon production by phosphoric acid activation method | |
| CN104005050A (en) | Method for treating and recycling divalent manganese in electrolytic manganese wastewater | |
| CN107226572B (en) | Zero-emission system and method for advanced treatment of mercury-containing wastewater | |
| JP3334142B2 (en) | Treatment method for fluorine-containing water | |
| CN106977034B (en) | Method for recovering hydrogen fluoride from high-concentration fluorine-containing wastewater | |
| CN111606496A (en) | Coking wastewater treatment device and method | |
| CN110937735A (en) | Coal-fired power plant desulfurization wastewater recycling treatment system and method | |
| CN106746100A (en) | A kind of processing method of ethene waste lye of refining | |
| CN210796035U (en) | High salt water recycling system that polycrystalline silicon production process produced | |
| CN110467312B (en) | Recycling treatment process for white carbon black production wastewater | |
| CN204490648U (en) | The complexes of a kind of electrolytic manganese ammonia nitrogen waste water process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |