CN113060870A - Triple-box type desulfurization wastewater treatment method - Google Patents
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- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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Abstract
The invention provides a triple-box type desulfurization wastewater treatment method. The triple-box desulfurization wastewater treatment method comprises the following steps: A) adding barium salt into the desulfurization wastewater in the neutralization tank, stirring, adding alkali liquor as required to ensure that the reaction is carried out at a pH value of more than 8.5, and feeding the effluent into a reaction tank; B) adding organic sulfide into the reaction tank, reacting under the stirring condition, and then allowing effluent to enter a flocculation tank; C) and adding a flocculating agent into the flocculation tank for reaction, and allowing the effluent to enter a clarification tank for clarification. The desulfurization wastewater treatment method can effectively remove sulfate radicals, heavy metals and suspended matters in the desulfurization wastewater, and can realize standard discharge of the desulfurization wastewater on the premise of not increasing equipment investment and operation cost; in addition, under the requirement of zero emission of the desulfurization wastewater, the method can also avoid scaling of subsequent evaporation crystallization or membrane concentration treatment facilities, reduce subsequent investment and operation investment, and has the advantages of being more economic and effective and the like.
Description
Technical Field
The invention relates to the technical field of desulfurization wastewater, in particular to a triple-box type desulfurization wastewater treatment method.
Background
The limestone-gypsum wet desulphurization process has the advantages of high desulphurization efficiency, high operation reliability, wide applicable coal range, high utilization rate of the absorbent, high equipment operation rate, low price and easy obtainment of the absorbent and the like, and is a sulfur dioxide removal technology which is widely applied and has mature technology in the world at present. To prevent the slurry from being too concentrated in soluble chloride ions and fine dust particles, a certain amount of wastewater needs to be discharged from the system to maintain the balance of the materials in the desulfurization unit.
The impurities contained in the desulfurization wastewater mainly comprise solid suspended matters, supersaturated sulfite, sulfate, chloride and trace heavy metals. The traditional treatment method of the desulfurization wastewater is mainly a chemical precipitation method, which is commonly called a 'triple box' method. The 'triple-box' method desulfurization wastewater treatment system generally comprises a wastewater pool triple-box (a neutralization box, a reaction box and a flocculation box are collectively called as a triple-box), a clarification tank, a clean water pool, a sludge treatment device, a dosing device and the like; the desulfurization wastewater flows into a neutralization box through a pipeline, and qualified lime slurry is added in proportion to precipitate heavy metal ions. The neutralization treatment is used for carrying out acid-base neutralization reaction on one hand, so as to adjust the pH value to a neutral range, and achieve the emission standard of pH 6-9; on the other hand, the method is used for precipitating part of heavy metal to enable the heavy metal to generate hydroxide precipitate. However, not all heavy metals, such as cadmium and mercury, form good precipitates by reacting with lime slurry.
In addition, the desulfurization wastewater treated by the triple-header treatment process needs to be further treated if zero discharge or resource utilization is required, mainly because the effluent contains high calcium and magnesium ion concentration and salt content, and serious pollution and blockage can be caused to subsequent concentration, evaporation and crystallization equipment and pipelines if the treatment is not carried out. At present, lime, soda ash and a flocculating agent as well as sodium hydroxide and soda ash are mainly adopted for softening treatment. However, both routes consume large amounts of chemicals and produce large amounts of sludge, increasing the cost of softening equipment and operation, as well as increasing wastewater zero discharge and sludge treatment costs.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a triple-box type desulfurization wastewater treatment method, which can realize standard discharge of desulfurization wastewater on the premise of not increasing equipment investment and operation cost; in addition, under the requirement of zero emission of the desulfurization wastewater, the method can avoid scaling of subsequent evaporation crystallization or membrane concentration treatment facilities, and reduce subsequent investment and operation investment.
The invention provides a triple-box type desulfurization wastewater treatment method, which comprises the following steps:
A) adding barium salt into the desulfurization wastewater in the neutralization tank, stirring, adding alkali liquor as required to ensure that the reaction is carried out at a pH value of more than 8.5, and feeding the effluent into a reaction tank;
B) adding organic sulfide into the reaction tank, reacting under the stirring condition, and then allowing effluent to enter a flocculation tank;
C) and adding a flocculating agent into the flocculation tank for reaction, and allowing the effluent to enter a clarification tank for clarification.
The inventor finds out through research that: mg (magnesium)2+Can be controlled by pH adjustment and the formation of Mg (OH)2The scale is easy to clean; ca2+CaSO formed4Scale is difficult to clean and can cause serious contamination of the membrane module, so if CaSO can be prevented4And scale formation can play a role in protecting the membrane module. The desulfurization wastewater is not softened, and only sulfate radicals are removed by selecting a proper sulfate radical removing agent, so that calcium sulfate scaling substances can be prevented from being formed in the subsequent concentration process, the pretreatment operation cost is greatly reduced, the wastewater concentration multiple is increased, the volume of the subsequent crystallization treatment wastewater is reduced, and the treatment cost of a wastewater zero discharge system is further reduced; based on this, the present invention has been completed.
In step a) of the present invention, the type and amount of added barium salt are not limited, for example, barium chloride, barium hydroxide, etc. may be used as barium salt, and the barium salt may be added in the form of barium salt solution, and the concentration of the barium salt solution may be 1 to 20%, preferably 5 to 15%, and more preferably 10%. In addition, the molar ratio of barium ions in the added barium salt to sulfate ions in the desulfurization wastewater can be controlled to be (1-1.05): 1.
with the addition of barium salt, the pH value of the desulfurization wastewater in the neutralization tank is increased; in order to ensure the precipitation effect of the heavy metal ions, the pH value of the desulfurization wastewater in the neutralization tank can be controlled to be 8.5-9.5, and the pH value range is favorable for the precipitation of most heavy metal ions. Specifically, the pH value of the desulfurization wastewater can be adjusted to 8.5-9.5 by adding an alkali solution according to needs; as the alkali solution, a slaked lime solution, a caustic soda solution or the like can be used, and the concentration of the alkali solution may be 1 to 10%, preferably 4 to 6%, more preferably 5%.
Further, in the step A), the reaction time can be controlled to be 30-90 min. Because the desulfurization waste water contains a certain amount of metal ions such as magnesium, iron, aluminum and the like, hydroxide precipitates can be generated under the alkaline condition; meanwhile, due to the introduction of barium ions, sulfate radicals are removed, insoluble barium sulfate precipitate is generated, hydroxide and barium sulfate precipitate are generated, part of suspended matters are precipitated, and the precipitate is discharged through a bottom sludge discharge pipe. After the neutralization treatment, the concentration of sulfate ions in the effluent of the neutralization tank is lower than 20 ppm.
In step B) of the present invention, the organic sulfide is mainly used for precipitating heavy metals such as cadmium and mercury, and is not strictly limited, for example, organic sulfide TMT-15 or the like can be used; the concentration of the organic sulfide may be 1-5%.
Further, in the step B), the reaction time can be controlled to be 5-30 min; after the treatment, the cadmium content in the effluent of the reaction tank is lower than 0.1ppm, the mercury content is lower than 0.05ppm, and simultaneously the precipitate can be discharged through a bottom sludge discharge pipe.
In step C) of the present invention, the flocculant to be used is not particularly limited, and for example, at least one of polyacrylamide and iron salt; the mass concentration of the flocculating agent can be 0.1-0.3%; the hydraulic retention time of the desulfurization wastewater in the flocculation tank can be 5-10 min. The flocculant can improve the settleability of particles, shorten the precipitation time and further reduce the SS content in the desulfurization wastewater.
In the step D), the retention time of the desulfurization wastewater in the clarification tank can be controlled to be 30-120 min; after clarification, the content of suspended substances in the effluent of the clarification tank is lower than 70 ppm.
Further, step D) may be included after step C): and (4) the effluent of the clarification tank enters a pH value adjusting tank, and the pH value of the effluent is adjusted to 6-9 and then discharged.
If zero discharge and resource utilization of the desulfurization wastewater are required, a step E) can be included after the step C): the effluent of the clarification tank sequentially enters an ultrafiltration device and a reverse osmosis device for ultrafiltration and reverse osmosis treatment, reverse osmosis concentrated water enters a crystallizer for crystallization or enters a flue for evaporation, and reverse osmosis effluent is recycled, so that zero discharge of desulfurization wastewater is realized.
The implementation of the invention has at least the following advantages:
1. according to the invention, the pH value, the sulfate radical and the heavy metal concentration are controlled by adding the barium salt and the organic sulfide, so that the function of the traditional triple box for treating the desulfurization wastewater is inherited, the heavy metal and suspended matters can be removed, the effluent is discharged up to the standard, and the scaling in the subsequent concentration and crystallization process can be prevented under the condition of no softening treatment.
2. On the basis of the traditional triple box, the desulfurization wastewater treatment method can realize the effect of desulfurization wastewater anti-scaling treatment without changing the specific structure of the triple box or additionally adding softening equipment, reduces subsequent investment and operation investment, and has the advantages of being more economical, more effective and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a process flow diagram of a triple-chamber desulfurization wastewater treatment method in example 1 of the present invention;
FIG. 2 is a process flow diagram of the triple-chamber desulfurization wastewater treatment method of embodiment 2 of the present invention.
Description of reference numerals:
1: a neutralization pond; 2: a reaction tank; 3: a flocculation tank; 4: a clarification tank; 5: a sludge discharge pipe; 6: a stirrer; 7: a pH adjusting tank; 8: an ultrafiltration device; 9: a reverse osmosis device.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
As shown in fig. 1, the desulfurization wastewater treatment system adopted in this embodiment includes a neutralization pond 1, a reaction pond 2, a flocculation pond 3, a clarification tank 4 and a pH adjusting pond 7, which are arranged in sequence, a sludge discharge pipe 5 is arranged at the bottom of the neutralization pond 1, the reaction pond 2, the flocculation pond 3 and the clarification tank 4, and a stirrer 6 is arranged in the neutralization pond 1, the reaction pond 2 and the flocculation pond 3.
The triple-box desulfurization wastewater treatment method of the embodiment comprises the following steps:
the desulfurization wastewater of a certain power plant is connected into the treatment system of the embodiment, and the flow rate of the wastewater is 20 t/h. Conveying the desulfurization wastewater into a neutralization tank 1, adding a medicament A, namely 10% barium hydroxide, into the neutralization reaction tank 1, wherein the molar ratio of barium ions in the added barium hydroxide to sulfate ions in the desulfurization wastewater is 1: 1, simultaneously starting a stirrer 6 for stirring; with the addition of barium hydroxide, the pH value of the desulfurization wastewater in the neutralization tank is increased, then a reagent B, namely 5% caustic soda, is added according to the requirement, the pH value of the desulfurization wastewater is adjusted to 9.5 for reaction, after the reaction is carried out for 30min, the concentration of sulfate radicals in the effluent is lower than 20ppm, and precipitates are discharged through a sludge discharge pipe 5 at the bottom.
The effluent of the neutralization tank 1 enters a reaction tank 2, and a medicament C, namely 3% organic sulfide TMT-15, is added into the reaction tank 2; starting the stirrer 6, reacting for 15min under stirring, reducing the content of cadmium and mercury in the effluent to be lower than 0.1ppm and 0.05ppm respectively, and discharging the precipitate through a bottom sludge discharge pipe 5.
The effluent of the reaction tank 2 enters a flocculation tank 3, a flocculating agent D, namely a polyacrylamide solution with the mass concentration of 0.1 percent, is added into the flocculation tank 3, and the hydraulic retention time in the flocculation tank is controlled to be 5 min.
The effluent of the flocculation tank 3 then enters a clarification tank 4, the retention time in the clarification tank 4 is 60min, the suspended solids SS of the effluent is less than 70ppm, and the precipitated sludge is discharged through a sludge discharge pipe 5.
And the effluent of the clarification tank 4 enters a pH adjusting tank 7, hydrochloric acid is added into the pH adjusting tank 7 to adjust the pH value of the effluent to 8.0, and the effluent can reach the standard and be discharged.
Example 2
As shown in fig. 2, the desulfurization wastewater treatment system adopted in this embodiment includes a neutralization pond 1, a reaction pond 2, a flocculation pond 3, a clarification tank 4, an ultrafiltration device 8 and a reverse osmosis device 9, which are sequentially arranged, a sludge discharge pipe 5 is arranged at the bottom of the neutralization pond 1, the reaction pond 2, the flocculation pond 3 and the clarification tank 4, and a stirrer 6 is arranged in the neutralization pond 1, the reaction pond 2 and the flocculation pond 3.
The triple-box desulfurization wastewater treatment method of the embodiment comprises the following steps:
the desulfurization wastewater of a certain power plant is connected into the treatment system of the embodiment, and the flow rate of the wastewater is 20 t/h. Conveying the desulfurization wastewater into a neutralization tank 1, adding a medicament A, namely 10% barium hydroxide, into the neutralization tank 1, wherein the molar ratio of barium ions in the added barium hydroxide to sulfate radicals in the wastewater is 1: 1, simultaneously starting a stirrer 6 for stirring; with the addition of barium hydroxide, the pH value of the desulfurization wastewater in the neutralization tank 1 is increased, a medicament B, namely 5% caustic soda, can be added according to needs, the pH value of the desulfurization wastewater is adjusted to 9.5 for reaction, after the reaction is carried out for 30min, the concentration of sulfate radicals in the effluent is lower than 20ppm, and precipitates are discharged through a bottom sludge discharge pipe 5.
The effluent of the neutralization tank 1 enters a reaction tank 2, and a medicament C, namely 3% organic sulfide TMT-15, is added into the reaction tank 2; starting the stirrer 6, reacting for 20min under stirring, reducing cadmium and mercury in the effluent to be lower than 0.1ppm and 0.05ppm respectively, and discharging the precipitate through a bottom sludge discharge pipe 5.
The effluent of the reaction tank 2 enters a flocculation tank 3, a flocculating agent D, namely a polyacrylamide solution with the mass concentration of 0.1 percent, is added into the flocculation tank 3, and the hydraulic retention time in the flocculation tank 3 is controlled to be 5 min.
The effluent of the flocculation tank 3 then enters a clarification tank 4, the retention time in the clarification tank 4 is 60min, the suspended solids SS of the effluent is less than 70ppm, and the precipitated sludge is discharged through a sludge discharge pipe 5.
And the effluent of the clarification tank 4 enters an ultrafiltration device 8 for ultrafiltration treatment, wherein the effluent SDI value of the ultrafiltration device 8 is 5, and the turbidity is less than 0.8 NTU.
The effluent of the ultrafiltration device 8 enters a reverse osmosis device 9 for reverse osmosis treatment, reverse osmosis concentrated water enters a crystallizer for crystallization or enters a flue for evaporation, and reverse osmosis effluent can be directly recycled, so that zero emission of desulfurization wastewater is realized.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A triple-box desulfurization wastewater treatment method is characterized by comprising the following steps:
A) adding barium salt into the desulfurization wastewater in the neutralization tank, stirring, adding alkali liquor as required to ensure that the reaction is carried out at a pH value of more than 8.5, and feeding the effluent into a reaction tank;
B) adding organic sulfide into the reaction tank, reacting under the stirring condition, and then allowing effluent to enter a flocculation tank;
C) and adding a flocculating agent into the flocculation tank for reaction, and allowing the effluent to enter a clarification tank for clarification.
2. The triple-box desulfurization wastewater treatment method according to claim 1, wherein in the step A), the molar ratio of barium ions in the added barium salt to sulfate ions in the desulfurization wastewater is controlled to be (1-1.05): 1;
preferably, the barium salt is barium chloride or barium hydroxide;
preferably, the barium salt is added in the form of a barium salt solution;
preferably, the concentration of the barium salt solution is controlled to be 1 to 20%, more preferably 5 to 15%, and still more preferably 10%.
3. The triple-box desulfurization wastewater treatment method according to claim 1, characterized in that in step A), alkali liquor is added as required to ensure reaction at pH 8.5-9.5;
preferably, the pH value of the desulfurization wastewater is adjusted to 8.5-9.5 by adding alkali solution;
preferably, the alkali solution is a slaked lime solution or a caustic soda solution;
preferably, the concentration of the alkali solution is controlled to be 1 to 10%, more preferably 4 to 6%, and still more preferably 5%.
4. The triple-box desulfurization wastewater treatment method according to claim 3, wherein in the step A), the reaction time is controlled to be 30-90 min;
preferably, the concentration of sulfate ions in the effluent of the neutralization tank is controlled to be less than 20 ppm.
5. The triple-box desulfurization wastewater treatment method according to claim 1, wherein in step B), the organic sulfide is TMT-15;
preferably, the concentration of the organic sulfide is controlled to be 1-5%;
preferably, in the step B), the reaction time is controlled to be 5-30 min;
preferably, the cadmium content in the effluent water of the reaction tank is controlled to be lower than 0.1ppm, and the mercury content is controlled to be lower than 0.05 ppm.
6. The triple-box desulfurization wastewater treatment method according to claim 1, wherein in step C), the flocculant is at least one of polyacrylamide and ferric salt;
preferably, the mass concentration of the flocculating agent is controlled to be 0.1-0.3%.
7. The triple-box desulfurization wastewater treatment method according to claim 1, wherein in the step C), the hydraulic retention time of the desulfurization wastewater in the flocculation tank is controlled to be 5-10 min.
8. The triple-box desulfurization wastewater treatment method according to claim 1, wherein in the step D), the retention time of the desulfurization wastewater in the clarification tank is controlled to be 30-120 min;
preferably, the effluent from the clarifier is controlled to have a level of suspended matter below 70 ppm.
9. The triple-box desulfurization wastewater treatment method according to claim 1, further comprising a step D) after the step C): and (4) the effluent of the clarification tank enters a pH value adjusting tank, and the pH value of the effluent is adjusted to 6-9 and then discharged.
10. The triple-box desulfurization wastewater treatment method according to claim 1, further comprising a step E) after the step C): the effluent of the clarification tank sequentially enters an ultrafiltration device and a reverse osmosis device for ultrafiltration and reverse osmosis treatment, reverse osmosis concentrated water enters a crystallizer for crystallization or enters a flue for evaporation, and reverse osmosis effluent is recycled.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115231743A (en) * | 2022-09-23 | 2022-10-25 | 大唐环境产业集团股份有限公司 | Low-cost desulfurization wastewater treatment method and system |
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Application publication date: 20210702 |