CN111635076B - Sulfur autotrophic denitrification treatment tank and treatment method of salt-containing wastewater - Google Patents

Sulfur autotrophic denitrification treatment tank and treatment method of salt-containing wastewater Download PDF

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CN111635076B
CN111635076B CN202010523028.9A CN202010523028A CN111635076B CN 111635076 B CN111635076 B CN 111635076B CN 202010523028 A CN202010523028 A CN 202010523028A CN 111635076 B CN111635076 B CN 111635076B
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salt
water
autotrophic denitrification
sulfur autotrophic
denitrification treatment
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CN111635076A (en
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张�浩
马江山
聂俊国
杜献亮
张朋浩
杨衍文
杨哲
程乐明
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Xindi Environmental Protection Technology Co ltd
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C01D3/06—Preparation by working up brines; seawater or spent lyes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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    • C01P2006/80—Compositional purity
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • 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
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • 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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Abstract

The invention belongs to the technical field of wastewater treatment, and particularly relates to a sulfur autotrophic denitrification treatment tank and a method for treating salt-containing wastewater. The sulfur autotrophic denitrification treatment tank comprises a tank body, a plurality of packed beds which are arranged in an inner cavity of the tank body and are used for filling sulfur particles and are distributed at intervals in the height direction of the tank body and horizontally arranged, and a rotating device which is fixedly connected with the packed beds and is used for driving the packed beds to rotate horizontally. The sulfur autotrophic denitrification treatment tank can improve the wastewater treatment efficiency and increase the alkalinity and NO in wastewater in the metabolic process of sulfur autotrophic organisms 3 ‑ The consumption of the method can reduce the discharge of carbon dioxide and the content of complex salt components in water, and the method is favorable for obtaining salt with higher purity and simultaneously improving the purity of the effluent. According to the method for treating the salt-containing wastewater, the sulfur autotrophic denitrification treatment tank and the mutual cooperation among the steps are adopted, so that monovalent salt and divalent salt can be effectively separated, the purity of the produced salt is higher, and the salt content in water is less.

Description

Sulfur autotrophic denitrification treatment tank and treatment method of salt-containing wastewater
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a sulfur autotrophic denitrification treatment tank and a method for treating salt-containing wastewater.
Background
Enterprises in coal chemical industry, pesticide, pharmaceutical enterprises, printing and dyeing, coal power and the like can generate a large amount of salt-containing wastewater. At present, the commonly adopted process flow for resource utilization of the salt-containing wastewater is pretreatment → advanced treatment → concentration treatment → evaporative crystallization so as to realize the recycling or zero discharge of salt and wastewater, wherein the process flow relates to technologies such as physicochemical treatment, flocculation precipitation, membrane treatment (such as ultrafiltration, nanofiltration and reverse osmosis), ion exchange, electrodialysis, evaporative crystallization and the like.
Typically, the high concentration salt-containing wastewater contains the following ions, such as: na (Na) + ，K + ，Ca 2+ ，Mg 2+ ，Fe 3+ ，Al 3+ ，NH 4 + And F - ，Cl - ，HCO 3 - ，CO 3 2- ，NO 3 - ，SO 4 2- ，PO 4 3- And the like. When the technology is used for treating the wastewater, the pretreatment part can remove NH by adding sodium hypochlorite 4 + Generating nitrogen, water and sodium chloride; removal of Mg as a precipitate by the double base method 2+ ，Fe 3+ ，Ca 2+ ，Al 3+ At the same time, alkalinity is introduced; removing F by adding calcium salt and iron salt to form precipitate - ，PO 4 3- . Then adding flocculating agents PAC and PAM into the water to form flocs together with the above precipitates, and separating the flocs from the water by a settling or filtering method. A decarbonizing tower is usually arranged for the alkalinity of water, and free CO in the water is removed by blowing off through a fan 2 Reduction of alkalinity ion HCO 3 - ，CO 3 2- . However, when the alkalinity of water is high, a large amount of greenhouse gas CO is generated 2 And is discharged to the atmosphere.
The prior membrane treatment technology has more applications and is used for intercepting various ions, such as nanofiltration membrane which can intercept SO 4 2- 、CO 3 2- Aliovalent of divalent ions, allowing Cl - 、NO 3 - When monovalent ions pass through, the reverse osmosis membrane can cut off most of salt. However, for salt-containing wastewater containing various monovalent and divalent ions, the separation effect of the currently applied membrane treatment technology is not ideal, and the obtained concentrated water still contains monovalent and divalent ions. Containing SO 4 2- 、CO 3 2- Concentrated nanofiltration water containing equal divalent ions and Cl - ，NO 3 - The concentrated water of the monovalent ions is the main water source for evaporation and crystallization, and if the ion composition in the concentrated water is complex, the ion composition in the concentrated water can directly influence the produced salt productMass and evaporator operation. In addition, inorganic ions are finally separated from water in a mixed solid form in the evaporation crystallization process, and if monovalent and divalent salts in a large amount of generated solid waste are not completely separated, the produced salts are difficult to be recycled, so that a new environmental problem can be formed.
The sulfur autotrophic denitrification treatment technology can reduce the alkalinity and NO 3 - However, the traditional sulfur autotrophic denitrification filter frequently has water flow dead zones and generates hydrogen sulfide, the treatment effect is not ideal, a large amount of sludge is generated in the treatment process, and the treatment system can normally operate only by frequent back flushing operation, so that the system is complicated to operate and has low treatment efficiency.
Disclosure of Invention
The invention aims to provide a sulfur autotrophic denitrification treatment tank and a treatment method of salt-containing wastewater, which can reduce the alkalinity and NO in the pretreated salt-containing wastewater 3 - Content, and the effect of obtaining salt with higher purity is achieved.
The invention also provides a method for treating the salt-containing wastewater, aiming at solving the problem that monovalent and divalent salts cannot be completely separated when the prior membrane separation technology is applied to treating the salt-containing wastewater.
In order to achieve the purpose, the invention adopts the technical scheme that: the sulfur autotrophic denitrification treatment pool comprises a pool body, a plurality of packed beds which are arranged in an inner cavity of the pool body and are distributed at intervals along the height direction of the pool body and horizontally arranged for filling sulfur particles, and a rotating device which is fixedly connected with the packed beds and is used for driving the packed beds to horizontally rotate; a water inlet of the sulfur autotrophic denitrification treatment tank is lower than the packed bed; a sludge outlet is formed in the bottom of the tank body; and the upper part of the inner wall of the tank body is provided with an overflow weir.
Preferably, the tank body is connected with a water inlet pipe, and the water inlet pipe extends into the tank body; the water inlet is provided with a plurality of, all is located on the inlet tube and the opening is down.
Preferably, a gas collecting device is further arranged in the tank body, a gas inlet of the gas collecting device is lower than the overflow weir, and the distance between the outer edge of the gas inlet and the inner wall of the tank body is 1-2 cm.
Preferably, the inner cavity of the tank body is divided into a first area and a second area from top to bottom, the first area is cylindrical, the second area is conical, the small-caliber end of the second area is positioned below the large-caliber end, and the large-caliber end is connected with the first area; the sludge outlet is located at the small-caliber end of the second area.
Preferably, the water inlet pipe is located in the second region.
Preferably, the inner wall of the tank body is provided with a three-phase separation mechanism extending towards the axis direction of the first region, the three-phase separation mechanism is higher than the packed bed and lower than the overflow weir, and the vertical projection of the gas inlet of the gas collection device covers the inner edge of the three-phase separation mechanism.
Preferably, rotary device includes the rotation axis and along a plurality of fixed establishment of rotation axis axle center direction interval setting, fixed establishment is for following a plurality of support of rotation axis circumference interval distribution, the rotation axis even has rotating electrical machines.
The sulfur autotrophic denitrification treatment tank provided by the invention has the beneficial effects that: the filler bed is filled with sulfur particles for the attachment and growth of microorganisms. The packed bed realizes horizontal rotation through the rotating device, so that the wastewater is fully contacted with the packing in the packed bed, and biofilm with water flow dead zones and recession is prevented from being accumulated among the packing, so that the problems of water flow dead zones and hydrogen sulfide generation frequently occurring in the traditional sulfur autotrophic denitrification treatment tank can be solved, the sludge production is low, and the operation of backwashing equipment can be omitted, so that the performance recovery stage after backwashing of the traditional sulfur autotrophic denitrification treatment tank does not exist, the use process can be simplified, the sulfur autotrophic denitrification treatment efficiency is improved, the wastewater treatment efficiency is improved, the consumption of alkalinity in the wastewater in the sulfur autotrophic biological metabolism process is increased, carbon is fixed in the form of biomass sludge, the carbon dioxide emission is reduced, and the NO is increased 3 - Consumption of (2) generating nitrogen, biomass and SO which is easily separated by the nanofiltration membrane 4 2- Decrease ofComplex content of salt in water. The sulfur autotrophic denitrification treatment tank is beneficial to obtaining saline water with higher purity, and simultaneously improves the purity of the effluent water, so that the effluent water is easier to recycle.
The embodiment of the invention also provides a method for treating the salt-containing wastewater, which comprises the step of treating the salt-containing wastewater by using the sulfur autotrophic denitrification treatment tank; the processing steps comprise:
s1, pretreating the salt-containing wastewater to remove non-target ions including ammonium ions, magnesium ions, iron ions, calcium ions, aluminum ions, heavy metal ions, fluoride ions, phosphate ions and the like;
s2, adjusting the salt concentration to a range which does not influence the metabolism of the microorganisms, and then carrying out sulfur autotrophic denitrification treatment by using the sulfur autotrophic denitrification treatment tank;
s3, concentrating the produced water after the sulfur autotrophic denitrification treatment;
s4, evaporating and crystallizing the concentrated water obtained by the concentration treatment.
The pretreatment method in S1 can remove ammonium ions by adding sodium hypochlorite to generate nitrogen, water and sodium chloride, and the reaction formula is as follows: 2NH 4 + +3ClO - ＝＝N 2 ↑+3Cl-+3H 2 O+2H + ；
Removing magnesium ions, iron ions, calcium ions and aluminum ions in a precipitation form by a double-alkali method, wherein the reaction formula is as follows: mg (magnesium) 2+ +2OH-＝＝Mg(OH) 2 ↓，Ca 2+ +CO 3 2- ＝＝CaCO 3 ↓，Fe 3+ +3OH-＝＝Fe(OH) 3 ↓，Al 3+ +3OH-＝＝Al(OH) 3 ↓；
Removing fluorinion and phosphate radical ion by calcium salt and ferric salt, wherein the reaction formula is as follows: ca 2+ +2F - ＝＝CaF 2 ↓，Fe 3+ +PO 4 3- ＝＝FePO 4 ↓；
And adding flocculating agents PAC and PAM into the water to enable the above precipitates to form flocs, and separating the flocs from the water by a settling or filtering method to obtain the clarified salt-containing wastewater.
After the pretreatment of oxidation, reduction, softening treatment and the like of S1 and sedimentation or filtration, the ion components in the wastewater to be treated are less, so that salt components with higher purity can be obtained after subsequent treatment.
The inhibition effect of the salt concentration on the microbial metabolism can be reduced by adjusting the salt concentration, and the microbes with stronger salt-tolerant function can be screened out through the relationship between the salt concentration and the treatment effect. According to the requirement of microorganisms in the sulfur autotrophic denitrification treatment process section on the salt content of the inlet water and the comprehensive consideration of the treatment efficiency, the salt concentration of 2000-2500 mg/L is preferably adopted.
The sulfur autotrophic denitrification treatment can reduce the alkalinity of the wastewater through the biochemical reaction process and reduce the emission of greenhouse gas carbon dioxide; simultaneously reducing NO in wastewater 3 - Sulfate ions which are easy to be separated by the nanofiltration membrane are generated, and the purity of the effluent is improved. The principle of the biochemical reaction process is expressed by the chemical reaction formula:
55S+20CO 2 +50NO 3 - +38H 2 O+4NH 4 + ＝＝4C 5 H 7 O 2 N+25N 2 ↑+55SO 4 2- +64H + 。
the evaporative crystallization treatment can be performed by using a multi-effect evaporator or an MVR evaporator.
According to the method for treating the salt-containing wastewater, the sulfur autotrophic denitrification treatment tank and the mutual cooperation among the steps are adopted, so that monovalent salt and divalent salt can be effectively separated, the purity of the obtained salt is higher, and the salt content in water is less. The treatment method can be used for various applications of salt-containing wastewater treatment, such as coal chemical industry salt-containing wastewater, water recycling or zero emission treatment of power plant desulfurization wastewater and the like.
Preferably, the fresh water produced by the concentration process and/or the steam condensate produced by evaporative crystallization are used to adjust the salt concentration in S2.
Preferably, the concentration treatment comprises Reverse Osmosis (RO) and Nanofiltration (NF) in that order. The fresh water produced by reverse osmosis and the permeate produced by nanofiltration may be used to adjust the salinity concentration in S2.
Preferably, S3 further comprises subjecting the produced water of the sulfur autotrophic denitrification treatment to a treatment for removing turbidity, suspended matter and hardness ions before the concentration treatment. Turbidity and suspended matter can be removed by ultrafiltration, and hardness ions such as calcium ions, magnesium ions and the like in water can be removed by ion exchange.
Preferably, the concentrated water generated by nanofiltration is subjected to sulfur autotrophic denitrification treatment again by using the sulfur autotrophic denitrification treatment tank, so that the alkalinity and NO in the concentrated water generated by nanofiltration can be further reduced 3 - And the content of the salt in the concentrated water is further improved.
Preferably, the concentration treatment further comprises concentrating the concentrated water generated by nanofiltration again so as to reduce the amount of nanofiltration effluent and reduce the crystallization cost. The re-concentration mode can be at least one mode selected from the group consisting of disc tube reverse osmosis, vibration reverse osmosis and electrodialysis.
Drawings
FIG. 1 is a side view showing the overall structure of a sulfur autotrophic denitrification treatment tank according to an embodiment of the present invention;
FIG. 2 is a top view of a sulfur autotrophic denitrification treatment tank in an embodiment of the present invention;
FIG. 3 is a schematic process flow diagram in example 2 of the present invention;
FIG. 4 is a schematic view of a part of the process flow for reducing the salt concentration and increasing the purity of the concentrate in example 2 of the present invention.
In the figure:
1. a tank body; 11. a water inlet; 12. an overflow weir; 13. a sludge outlet;
2. a rotating device 21, a rotating shaft; 22. a fixing mechanism; 23. a rotating electric machine;
3. a packed bed;
4. a gas collection device;
5. a water inlet pipe;
6. three phase separation mechanisms.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Referring to fig. 1 and 2 together, the sulfur autotrophic denitrification treatment tank according to the present invention will now be described.
The sulfur autotrophic denitrification treatment tank comprises:
the device comprises a tank body 1, a plurality of packed beds 3 which are arranged in the inner cavity of the tank body 1, are distributed at intervals along the height direction of the tank body 1 and are horizontally arranged and used for filling sulfur particles, and a rotating device 2 which is fixedly connected with the packed beds 3 and is used for driving the packed beds 3 to rotate horizontally, wherein a water inlet 11 of the sulfur autotrophic denitrification treatment tank is lower than the packed beds 3; the bottom of the tank body 1 is provided with a sludge outlet 13; the upper part of the inner wall of the tank body 1 is provided with an overflow weir 12.
The beneficial effects of the sulphur autotrophic denitrification treatment tank provided by the embodiment are as follows: the packed bed 3 is filled with sulfur particles for the attachment and growth of microorganisms. The packed bed 3 realizes horizontal rotation through the rotating device 2, so that the wastewater is fully contacted with the packing in the packed bed 3, the biofilm with water flow dead zones and recession is prevented from being accumulated among the packing, the problems of water flow dead zones and hydrogen sulfide generation frequently occurring in the traditional sulfur autotrophic denitrification treatment tank can be solved, the sludge production is low, and the operation of backwashing equipment can be omitted, so that the performance recovery stage after backwashing of the traditional sulfur autotrophic denitrification treatment tank does not exist, the use process can be simplified, the sulfur autotrophic denitrification treatment efficiency is improved, the wastewater treatment efficiency is improved, the consumption of alkalinity in the wastewater in the sulfur autotrophic biological metabolism process is increased, the carbon is fixed in the form of biomass sludge, the carbon dioxide emission is reduced, and the NO is increased 3 - Consumption of (2) generating nitrogen, biomass and SO which is easily separated by the nanofiltration membrane 4 2- And the content of complex salt components in water is reduced. The sulfur autotrophic denitrification treatment tank is beneficial to obtaining saline water with higher purity, and simultaneously improves the purity of the effluent water, so that the effluent water is easier to recycle.
As a specific implementation mode provided by the sulfur autotrophic denitrification treatment tank, the tank body 1 is connected with a water inlet pipe 5, and the water inlet pipe 5 extends into the tank body 1; the water inlet 11 is provided with a plurality of water inlets, which are all positioned on the water inlet pipe 5 and have downward openings, so that water can be uniformly distributed in the tank, and the water inlet 11 can be prevented from being blocked by foreign matters.
As a specific implementation mode provided by the sulfur autotrophic denitrification treatment tank, a gas collecting device 4 is further arranged in the tank body 1, and a gas inlet of the gas collecting device 4 is lower than the overflow weir 12 so as to ensure that the gas inlet is lower than the water surface in the tank body 1. The distance between the outer edge of the air inlet and the inner wall of the pool body 1 is 1-2 cm, so that the overflow of gases such as carbon dioxide can be avoided. As a specific embodiment provided by the sulfur autotrophic denitrification treatment tank of the present invention, the gas collection device 4 is a conical cylindrical mechanism connected with a gas pipeline, and the large-diameter end of the conical cylindrical mechanism is below the small-diameter end, i.e., the gas inlet of the gas collection device 4.
As a specific embodiment provided by the sulfur autotrophic denitrification treatment tank, the inner cavity of the tank body 1 is divided into a first area and a second area from top to bottom, the first area is cylindrical, the second area is conical, the small-caliber end of the second area is positioned below the large-caliber end, and the large-caliber end is connected with the first area; the sludge outlet 13 is located at the small-caliber end of the second zone. The shape can save the occupied space of the tank body 1, ensure the sedimentation, collection and discharge of sludge or sedimentation particles in the conical structure of the second area and realize solid-liquid separation. The depth and volume of the first zone are determined according to water retention time (HRT) and hydraulic load design, and the HRT 1-3 h is generally selected.
As a specific embodiment provided by the sulfur autotrophic denitrification treatment tank, the water inlet pipe 5 is positioned in the second area, so that the space of the packed bed 3 for sulfur autotrophic denitrification treatment is not occupied, and the water distribution in the first area is more uniform.
As a specific embodiment provided by the sulfur autotrophic denitrification treatment tank of the invention, the inner wall of the tank body 1 is provided with a three-phase separation mechanism 6 extending towards the axial direction of the first area, the three-phase separation mechanism 6 is higher than the packed bed 3 and lower than the overflow weir 12, and the vertical projection of the gas inlet of the gas collection device 4 covers the inner edge of the three-phase separation mechanism 6. The three-phase separation mechanism 6 can block the solid components which are not settled, reduce the overflow of the solid components, and simultaneously, lead the gas generated in the reaction process to be taken into the gas inlet of the gas collection device 4 as completely as possible, and reduce the overflow of the gas such as carbon dioxide and the like. As a specific implementation mode provided by the sulfur autotrophic denitrification treatment tank, the three-phase separation mechanism 6 is a mechanism with a triangular cross section, and one side of the three-phase separation mechanism is attached to the inner wall of the tank body 1.
As a specific embodiment provided by the sulfur autotrophic denitrification treatment tank, the packed bed 3 is detachably connected with the fixing mechanism 22, so that the packed bed 3 is convenient to maintain and replace the packing.
As a specific embodiment provided by the sulfur autotrophic denitrification treatment tank of the invention, the rotating device 2 comprises a rotating shaft 21 and a plurality of fixing mechanisms 22 arranged at intervals along the axial direction of the rotating shaft 21, the fixing mechanisms 22 are a plurality of supports distributed at intervals along the circumferential direction of the rotating shaft 21, and can stably support and fix the packed bed 3, and when the rotating device is started, the packed bed 3 can be driven to rotate in water, so that the wastewater can fully contact with the packing in the packed bed 3. The rotating shaft 21 is connected with a rotating motor 23, and the rotating speed of the rotating shaft 21 can be controlled by controlling the rotating motor 23, so that the rotating speed of the packed bed 3 is adjusted.
Example 2
This example provides a method for treating salt-containing wastewater, which uses the sulfur autotrophic denitrification treatment tank of example 1 to treat the salt-containing wastewater. The process flow schematic diagram is shown in fig. 3, and specifically comprises the following steps:
s1, pretreating the salt-containing wastewater to be treated: removing ammonium ions by sodium hypochlorite, removing magnesium ions, iron ions, calcium ions and aluminum ions by a double-alkali method, removing fluoride ions and phosphate ions by calcium salt and iron salt, adding flocculating agents PAC and PAM into water to enable the above precipitates to form flocs, separating the flocs from the water by sedimentation to obtain clear wastewater to be treated, wherein the flow of the pretreated wastewater is 10m 3 /h。
S2, adjusting the salt concentration, wherein the water quality composition and concentration after adjustment are pH7.5, TDS 2002mg/L, Na + 680mg/L，NH 4 + 5.5mg/L，Cl - 600.6mg/L，NO 3 - 200mg/L，SO 4 2- 380mg/L，HCO 3 - 130mg/L，CO 3 2- 0.5mg/L, about 5mg/L of other soluble substances, water temperature of 25 ℃, and 0.3mg/L of dissolved oxygen.
Inputting the wastewater with the concentration adjusted into the tank body 1 from the bottom of the sulfur autotrophic denitrification treatment tank through a water inlet 11 of a water inlet pipe 5, completing inoculation and domestication starting of microorganisms in the filter tank, and setting the hydraulic retention time in the tank body 1 for 3h (the volume of a first area is 30 m) after the operation effect is stable 3 ) And the rotating speed of the rotating disc is 1 r/min. The effluent obtained after the sulfur autotrophic denitrification treatment has the water quality of pH6, TDS 1947.27mg/L and Na + 682mg/L，NH 4 + 2mg/L，Cl - 578.82mg/L，NO 3 - 42.45mg/L，SO 4 2- 607.76mg/L，HCO 3 - 28.94mg/L, about 5.3mg/L of other soluble substances, about 0.1mg/L of dissolved oxygen and 25 ℃ of water.
S3, removing turbidity and suspended matters from effluent obtained after the sulfur autotrophic denitrification treatment by ultrafiltration, removing hardness ions in the water by ion exchange, inputting the water into reverse osmosis equipment, and using a Dow BW30-4040 element in a first-stage two-stage mode; the water yield of the produced concentrated water is 3m 3 Per hour, water TDS 6402.23mg/L, Na + 2245.43mg/L，NH 4 + 4.77mg/L，Cl - 1904.9mg/L，NO 3 - 126.13mg/L，SO 4 2- 2008.38mg/L，HCO 3 - 94.98mg/L, other soluble substances about 17.59 mg/L; the produced fresh water amount is 7m 3 Per hour, water TDS38.82mg/L, Na + 11.97mg/L，NH 4 + 0.81mg/L，Cl - 10.51mg/L，NO 3 - 6.58mg/L，SO 4 2- 7.51mg/L，HCO 3 - 1.4mg/L, about 0.5mg/L of other soluble substances;
treating the concentrated water obtained by reverse osmosis by a nanofiltration device to obtain 3m concentrated water 3 Treating the/L by nanofiltration equipment, and using a Dow nanofiltration NF270-4040 element to form a first-stage two-stage type; the water yield of the produced concentrated water is 0.9m 3 H, water quality pH6.73, TDS 16042.20mg/L, Na + 5486.53mg/L，NH 4 + 11.76mg/L，Cl - 3554.21mg/L，NO 3 - 114.54mg/L，SO 4 2- 6569.71mg/L，HCO 3 - 250.49mg/L，CO 3 2- 0.68mg/L, about 90mg/L of other soluble substances; the amount of permeated water was 2.1m 3 Per hour, water TDS 2268.08mg/L, Na + 855.49mg/L，NH 4 + 1.77mg/L，Cl - 1197.69mg/L，NO 3 - 131.1mg/L，SO 4 2- 52.57mg/L，HCO 3 - 27.89mg/L, other soluble substances about 1.86 mg/L.
S4, where the reverse osmosis output fresh water or the nanofiltration output permeate water can be optionally returned to S2 for adjusting the salt concentration of the raw water or recycling treatment to reduce the concentration of non-target ions (as shown in fig. 4), so as to reduce the salt concentration and improve the purity of the concentrated water. (ii) a
Further concentrating and nano-filtering to produce permeated water to obtain concentrated water I;
concentrated water produced by nanofiltration is further concentrated and reduced through the treatment of processes such as disc tube type reverse osmosis, vibration reverse osmosis or electrodialysis, and the like, so that concentrated water is obtained;
the concentrated water is treated by multi-effect evaporation or MVR and other crystallization processes to obtain the salt product with sodium chloride and sodium sulfate as main components.
In this example, non-target NH ions of raw water, nanofiltration concentrated water obtained, and permeated water 4 + 、NO 3 - 、HCO 3 - 、CO 3 2- And the other soluble substances account for 17%, 2.9% and 7.1% of the TDS, respectively.
Example 3
In the method for treating salt-containing wastewater provided by this embodiment, the sulfur autotrophic denitrification treatment tank in embodiment 1 is used for treating the salt-containing wastewater. The process flow schematic diagram is shown in fig. 3, and specifically comprises the following steps:
s1, pretreating the salt-containing wastewater to be treated: removing ammonium ions by sodium hypochlorite, removing magnesium ions, iron ions, calcium ions and aluminum ions by a double-alkali method, removing fluoride ions and phosphate ions by calcium salt and iron salt, adding flocculating agents PAC and PAM into water to precipitate to form flocs,separating from water by sedimentation to obtain clear wastewater to be treated, wherein the flow of the pretreated wastewater is 10m 3 /h。
S2, adjusting the salt concentration, wherein the water quality composition and concentration after adjustment are pH7.5, TDS 2454mg/L, Na + 857.47mg/L，NH 4 + 5.66mg/L，Cl - 752.5mg/L，NO 3 - 98.4mg/L，SO 4 2- 640.23mg/L，HCO 3 - 95.44mg/L，CO 3 2- 0.3mg/L, about 4mg/L of other soluble substances, water temperature of 25 ℃, and 0.3mg/L of dissolved oxygen.
Inputting the wastewater with the adjusted concentration into the tank body 1 from the bottom of the sulfur autotrophic denitrification treatment tank through the water inlet 11 of the water inlet pipe 5 to finish the inoculation and domestication start of microorganisms in the filter tank, and setting the hydraulic retention time in the tank body 1 for 3h (the volume of the first area is 30 m) after the operation effect is stable 3 ) And the rotating speed of the rotating disc is 1 r/min. The effluent obtained after the sulfur autotrophic denitrification treatment has the water quality of pH6, TDS 2416.08mg/L and Na + 855.89mg/L，NH 4 + 1.89mg/L，Cl - 750.60mg/L，NO 3 - 21.40mg/L，SO 4 2- 756.50mg/L，HCO 3 - 24.80mg/L, about 5.01mg/L of other soluble substances, about 0.1mg/L of dissolved oxygen and 25 ℃ of water.
S3, removing turbidity and suspended matters from effluent obtained after sulfur autotrophic denitrification treatment through ultrafiltration, removing hardness ions in the water through ion exchange, inputting the water into reverse osmosis equipment, and using a Dow BW30-4040 element in a first-stage two-stage mode; the water yield of the produced concentrated water is 3m 3 H, water TDS 7955.90mg/L, Na + 2820.81mg/L，NH 4 + 4.49mg/L，Cl - 2470.72mg/L，NO 3 - 61.39mg/L，SO 4 2- 2500.44mg/L，HCO 3 - 81.38mg/L, about 16.61mg/L of other soluble substances; the produced fresh water amount is 7m 3 H, water TDS43.82mg/L, Na + 14.21mg/L，NH 4 + 0.77mg/L，Cl - 13.79mg/L，NO 3 - 4.27mg/L，SO 4 2- 9.49mg/L，HCO 3 - 1.26mg/L, other soluble substances0.3mg/L；
Treating the concentrated water obtained by reverse osmosis by a nanofiltration device to obtain 3m concentrated water 3 Treating the/L by nanofiltration equipment, and using a Dow nanofiltration NF270-4040 element to form a first-stage two-stage type; the water yield of the produced concentrated water is 0.9m 3 H, water pH6.71, TDS 20095.18mg/L, Na + 6935.40mg/L，NH 4 + 11.14mg/L，Cl - 4643.09mg/L，NO 3 - 55.87mg/L，SO 4 2- 8182.01mg/L，HCO 3 - 215.57mg/L，CO 3 2- 0.72mg/L, about 51.39mg/L of other soluble substances; the amount of permeated water was 2.1m 3 Per hour, water TDS 2751.83mg/L, Na + 1056.95mg/L，NH 4 + 1.64mg/L，Cl - 1539.52mg/L，NO 3 - 63.76mg/L，SO 4 2- 64.84mg/L，HCO 3 - 23.42mg/L, other soluble substances about 1.7 mg/L.
The produced water was treated in the same manner as in example 2 to obtain sodium chloride and sodium sulfate.
In this example, non-target NH ions of raw water, nanofiltration concentrated water obtained, and permeated water 4 + 、NO 3 - 、HCO 3 - 、CO 3 2- And other soluble materials account for 8%, 1.7% and 3.3% of TDS, respectively.
Comparative example
The comparative example provides a method for treating salt-containing wastewater, which uses the traditional RO and NF processes to treat the salt-containing wastewater. The method specifically comprises the following steps:
s1, pretreating the saline wastewater to be treated according to the method of the embodiment 2: removing ammonium ions by sodium hypochlorite, removing magnesium ions, iron ions, calcium ions and aluminum ions by a double-alkali method, removing fluoride ions and phosphate ions by calcium salt and iron salt, adding flocculating agents PAC and PAM into water to enable the above precipitates to form flocs, separating the flocs from the water by sedimentation to obtain clear wastewater to be treated, wherein the flow of the pretreated wastewater is 10m 3 /h。
S2, adjusting the salt concentration, the adjusted water quality composition andthe concentration is pH7.5, TDS 2002mg/L, Na + 680mg/L，NH 4 + 5.5mg/L，Cl - 600.6mg/L，NO 3 - 200mg/L，SO 4 2- 380mg/L，HCO 3 - 130mg/L，CO 3 2- 0.5mg/L, about 5mg/L of other soluble substances, water temperature of 25 ℃, and 0.3mg/L of dissolved oxygen.
S3, removing hardness ions in the salt-containing wastewater with the adjusted salt concentration through ion exchange, inputting the salt-containing wastewater into reverse osmosis equipment, and using a Dow BW30-4040 element in a first-stage two-stage mode; the water yield of the produced concentrated water is 3m 3 H, water pH7.76, TDS 6552.46mg/L, Na + 2236.15mg/L，NH 4 + 14.05mg/L，Cl - 1982.93mg/L，NO 3 - 617.57mg/L，SO 4 2- 1258.57mg/L，HCO 3 - 421.13mg/L，CO 3 2- 5.44mg/L, other soluble substance 16.61 mg/L; the produced fresh water amount is 7m 3 H, water pH5.81, TDS 49.72mg/L, Na + 13.11mg/L，NH 4 + 1.84mg/L，Cl - 8.16mg/L，NO 3 - 21.05mg/L，SO 4 2- 3.49mg/L，HCO 3 - 2.04mg/L, about 1mg/L of other soluble substances; the TDS of the concentrate was higher than that of example 2, but Na was present in the concentrate + And Cl in fresh water - Below example 2, the results were formed, as analyzed, by: since the anions of the non-target ions permeated through the membrane are more in this comparative example, as more anions (non-target ions) permeated through the membrane into the fresh water, the corresponding anions in the concentrated water decreased, accompanied by the cation Na + A decrease in concentration; meanwhile, since the concentration of anions (non-target ions) in fresh water is high, the concentration of anion chloride ions is decreased to achieve charge balance.
3m of concentrated water obtained by reverse osmosis 3 Treating the/L by nanofiltration equipment, and using a Dow nanofiltration NF270-4040 element to form a first-stage two-stage type; the water yield of the produced concentrated water is 0.9m 3 Per hour, water TDS 14864.45mg/L, Na + 5032.24mg/L，NH 4 + 31.99mg/L，Cl - 3859.49mg/L，NO 3 - 634.58mg/L，SO 4 2- 4126.4mg/L，HCO 3 - 1103.34mg/L, other soluble substances about 49.1 mg/L; the amount of permeated water was 2.1m 3 H, water TDS 2987.54mg/L, Na + 1038.43mg/L，NH 4 + 6.37mg/L，Cl - 1179.24mg/L，NO 3 - 610.28mg/L，SO 4 2- 30.12mg/L，HCO 3 - 120.05mg/L, other soluble substances about 2.72 mg/L. Na in concentrated water + And Cl in fresh water - The concentration is lower than that of the embodiment 2, and the concentrated water and the fresh water obtained by reverse osmosis are the same.
The produced water was treated in the same manner as in example 2 to obtain sodium chloride and sodium sulfate.
Non-target ion NH of raw water, nanofiltration concentrated water obtained and permeated water in this comparative example 4 + 、NO 3 - 、HCO 3 - 、CO 3 2- And the other soluble substances account for 17%, 12.2% and 24.8% of the TDS, respectively.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (6)

1. A method for treating salt-containing wastewater is characterized by comprising the following steps: treating the salt-containing wastewater by using a sulfur autotrophic denitrification treatment tank;
the sulfur autotrophic denitrification treatment tank comprises a tank body, a plurality of packed beds which are arranged in an inner cavity of the tank body and are distributed at intervals along the height direction of the tank body and horizontally arranged for filling sulfur particles, and a rotating device which is fixedly connected with the packed beds and is used for driving the packed beds to horizontally rotate; the water inlet of the sulfur autotrophic denitrification treatment tank is lower than the packed bed; a sludge outlet is formed in the bottom of the tank body; an overflow weir is arranged at the upper part of the inner wall of the tank body; the tank body is connected with a water inlet pipe, and the water inlet pipe extends into the tank body; the water inlets are arranged in a plurality and are all positioned on the water inlet pipe, and the openings of the water inlets face downwards; a gas collecting device is further arranged in the tank body, a gas inlet of the gas collecting device is lower than the overflow weir, and the distance between the outer edge of the gas inlet and the inner wall of the tank body is 1-2 cm; the inner cavity of the pool body is divided into a first area and a second area from top to bottom, the first area is cylindrical, the second area is conical, the small-caliber end of the second area is positioned below the large-caliber end, and the large-caliber end is connected with the first area; the sludge outlet is positioned at the small-caliber end of the second area;
the treatment steps of the salt-containing wastewater comprise:
s1, pretreating the salt-containing wastewater to remove ammonium ions, magnesium ions, iron ions, calcium ions, aluminum ions, fluorine ions and phosphate ions;
s2, adjusting the salt concentration of the salt-containing wastewater to a range not influencing microbial metabolism, and then carrying out sulfur autotrophic denitrification treatment by using the sulfur autotrophic denitrification treatment tank;
s3, removing turbidity, suspended matters and hardness ions from the produced water after the sulfur autotrophic denitrification treatment, and then sequentially performing concentration treatment through reverse osmosis and nanofiltration equipment;
s4, further concentrating the concentrated water and the permeated water generated by nanofiltration through disc tube type reverse osmosis, vibration reverse osmosis or electrodialysis respectively, and crystallizing the concentrated water obtained by further concentration treatment through multi-effect evaporation or MVR.
2. The method for treating salt-containing wastewater according to claim 1, wherein: the water inlet pipe is located in the second area.
3. The method for treating salt-containing wastewater according to claim 1, wherein: the cell body inner wall be equipped with to the triphase separation mechanism that the axle center direction in first region extends, triphase separation mechanism is higher than the packed bed just is less than the overflow weir, the perpendicular projection of gas collection device's air inlet covers triphase separation mechanism's inward flange.
4. The method for treating salt-containing wastewater according to any one of claims 1 to 3, wherein: the rotating device comprises a rotating shaft and a plurality of fixing mechanisms arranged at intervals along the axis direction of the rotating shaft, the fixing mechanisms are a plurality of supports distributed at intervals along the circumferential direction of the rotating shaft, and the rotating shaft is connected with a rotating motor.
5. The method for treating salt-containing wastewater according to claim 1, wherein: the permeate produced by reverse osmosis in S3, the permeate produced by nanofiltration in S3 and/or the steam condensate produced by evaporative crystallization are used to adjust the salinity of the saline wastewater in S2.
6. The method according to claim 5, wherein:
and (4) carrying out sulfur autotrophic denitrification treatment on the concentrated water generated by nanofiltration by using the sulfur autotrophic denitrification treatment tank again.
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