CN111410343B - Ammonia nitrogen removal device and method for acid regeneration acid-containing wastewater - Google Patents
Ammonia nitrogen removal device and method for acid regeneration acid-containing wastewater Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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Abstract
The invention discloses an ammonia nitrogen removal device and method for acid regeneration acid-containing wastewater, wherein the method comprises the following steps of 1: acid regeneration wastewater flows into an adjusting tank (1), and water quality and water quantity are balanced in the adjusting tank; step 2: the acid regeneration wastewater is filtered, then is lifted by a primary lift pump (6) and enters an electrochemical oxidation reaction tank (7); and step 3: removing ammonia nitrogen after the wastewater reacts in an electrochemical oxidation reaction tank; and 4, step 4: wastewater in the electrochemical oxidation reaction tank flows into an electrochemical oxidation water production tank (8) and is lifted to an ion exchange resin adsorption tower (10) through a secondary lifting pump (9); and 5: cation exchange resin (101) is filled in the ion exchange resin adsorption tower, the ion exchange resin adsorption tower and the water production pool are circulated, ion exchange is carried out on the cation exchange resin and ammonia nitrogen substances, and the ammonia nitrogen is removed and flows into the water production pool. The invention can control the ammonia nitrogen in the acid-containing wastewater discharged by the acid regeneration unit to be below 8ppm, and can be directly discharged.
Description
Technical Field
The invention relates to a pickling device and a pickling method in the field of metallurgy, in particular to an ammonia nitrogen removal device and an ammonia nitrogen removal method for acid regeneration acid-containing wastewater.
Background
The hydrochloric acid pickling is widely applied to the production of cold-rolled strip steel due to the characteristics of high efficiency and high speed. The waste acid generated in the hydrochloric acid pickling process generates regenerated acid through an acid regeneration process, so that the cyclic use of hydrochloric acid is realized. At present, the hydrochloric acid regeneration technology mainly adopts a spray roasting technology, please refer to fig. 1, the main flow of the technology is that waste acid 100 after silicon removal firstly enters a preconcentrator 200, the waste acid after silicon removal and roasting furnace gas are evaporated and concentrated through direct heat exchange, the waste acid 100 concentrated by the preconcentrator is sent to a reaction roasting furnace 300, the waste acid 100 and oxygen in air fuel are subjected to chemical reaction to produce hydrogen chloride gas and ferric oxide powder 500, and the hydrogen chloride gas generated by the reaction passes through a double-cyclone dust collector 600, reaches the bottom of an absorption tower 700 and is absorbed by water to form regenerated hydrochloric acid 800. The waste gas from the absorption tower 700 enters the washing tower 400, the water is sprayed to absorb the residual hydrogen chloride in the steam, and the waste gas from the washing tower is discharged into the atmosphere through a chimney.
The silicon removing technology in the acid regeneration process mainly comprises the step of reacting waste acid in a pickling line with ammonia water to form Fe (OH)3Colloid, realize removing silicon impurity. Because the ammonium salt after reaction exists in the waste acid solution after silicon removal in the form of ions, the waste acid is heated and decomposed into NH in a roasting furnace 3Gas, after absorption in a scrubber, NH3The ammonia nitrogen dissolved in the water solution is discharged into a sewage pit, so that the ammonia nitrogen in the sewage pit exceeds the standard and can not reach the national water discharge standard. At present, the measure adopted for overcoming the standard exceeding of ammonia nitrogen in wastewater is to process industrial water into a sewage pit, dilute the ammonia nitrogen in the wastewater and realize the standard reaching of wastewater discharge. The silicon removal technology in the existing acid regeneration process has the following defects:
1. the ammonia nitrogen in the acid-containing wastewater from the acid regeneration process washing tower exceeds the national water discharge standard, and the direct discharge of the wastewater cannot be realized.
2. At present, the measure for reducing ammonia nitrogen in acid-containing wastewater from a washing tower is industrial water dilution, the method cannot reduce the total amount of ammonia nitrogen in the wastewater, causes a great deal of waste of water resources, and is not beneficial to water conservation and environmental protection.
The Chinese patent application CN201110427390.7 discloses a high ammonia nitrogen wastewater recycling technology, which removes solid impurities from wastewater through flocculation and solid-liquid separation, and obtains two parts after being treated by a membrane concentration system, wherein one part is purified water which is recycled after being oxidized by ammonia nitrogen through chlorine dioxide; the other part is that the concentrated solution is subjected to solid-liquid separation again after being adjusted by adding alkali to remove solids, and then enters an ammonia separation tower for deamination, the medicine intermediate urotropine with high added value is generated by the reaction of the concentrated solution and formaldehyde in a reaction kettle extracted by the ammonia separation tower, and the tower bottom water after deamination is directly discharged or discharged after being added with the medicine to deaminate and filtered. The application is a process for realizing the reutilization of sewage after ammonia nitrogen in the sewage is removed, realizes the standard discharge and cannot solve the problem of the removal of the ammonia nitrogen in the acidic wastewater.
The Chinese patent CN200310106515.1 discloses a membrane-based absorption method for treating high-concentration ammonia nitrogen wastewater resource technology, and relates to a membrane-based absorption technology for recovering ammonia in high-concentration ammonia nitrogen wastewater. The invention adopts a hollow fiber membrane contactor, high-concentration ammonia nitrogen wastewater flows through a tube pass of the contactor (a tube cavity of a hollow fiber), and absorption liquid (H2SO4) flows through a shell pass. The optimization and related parameters of the contactor structure are discussed, the optimal operation process conditions are selected, and the method is particularly applied to the treatment of high-concentration ammonia 'residual ammonia water' in a coking plant, so that the effect of standard emission in one-time treatment is achieved. However, in order to realize the direct discharge of acid-containing wastewater, the ammonia nitrogen content of the raw and cold acid wastewater must be below 8ppm, and the patent cannot solve the problems.
Disclosure of Invention
The invention aims to provide an ammonia nitrogen removal device and method for acid regeneration acid-containing wastewater, which can control ammonia nitrogen in the acid-containing wastewater discharged by an acid regeneration unit to be below 8ppm so as to achieve direct discharge of the acid-containing wastewater.
The invention is realized by the following steps:
an ammonia nitrogen removal device for acid regeneration acid-containing wastewater comprises a regulating reservoir, a water inlet pump, a filtering system, a primary lift pump, an electrochemical oxidation reaction tank, an electrochemical oxidation water production tank, a secondary lift pump, an ion exchange resin adsorption tower and a water production tank; the water outlet end of the adjusting tank is connected with the water inlet end of the filtering system through a water inlet pump, the water outlet end of the filtering system is connected with the water inlet end of the electrochemical oxidation reaction tank through a primary lifting pump, electrodes are arranged in the electrochemical oxidation reaction tank, the water outlet end of the electrochemical oxidation reaction tank is connected with the water inlet end of the electrochemical oxidation water production tank, the water outlet end of the electrochemical oxidation water production tank is connected with the water inlet end of the ion exchange resin adsorption tower through a secondary lifting pump, the water outlet end of the ion exchange resin adsorption tower is connected with the water inlet end of the water production tank, and the circulating water outlet end of the water production tank is connected with the circulating water inlet end of the ion exchange resin adsorption tower.
The filtration system include that microfiltration membrane filtering component, microfiltration circulating bath and microfiltration produce the pond, the play water end of equalizing basin is connected through the end of intaking of intake pump with the microfiltration circulating bath, the play water end of microfiltration circulating bath is connected through the end of intaking of circulating pump with microfiltration membrane filtering component, the play water end of microfiltration membrane filtering component is connected with the end of intaking in the microfiltration product pond and the return water end of microfiltration circulating bath, the play water end in the microfiltration product pond is connected through the end of intaking of one-level elevator pump with electrochemical oxidation reaction pond.
The ammonia nitrogen removal device for acid regeneration acid-containing wastewater also comprises a regeneration liquid regeneration system, wherein the regeneration liquid regeneration system comprises a regeneration water pump, a regeneration waste liquid water tank and a regeneration liquid water tank; the regeneration waste liquid water tank and the liquid outlet of the regeneration liquid water tank are connected with the regeneration liquid inlet of the ion exchange resin adsorption tower through a regeneration water pump, and the waste liquid outlet of the water production pool is connected with the liquid inlet of the regeneration waste liquid water tank; the liquid outlet of the regeneration waste liquid water tank is connected with the water inlet end of the regulating tank.
The ammonia nitrogen removal device for acid regeneration acid-containing wastewater also comprises a cleaning solution regeneration system, wherein the cleaning solution regeneration system comprises a cleaning water pump, a cleaning waste liquid water tank and a cleaning solution water tank; the liquid outlets of the cleaning waste liquid water tank and the cleaning liquid water tank are connected with a cleaning liquid inlet of the ion exchange resin adsorption tower through a cleaning water pump, and a waste liquid outlet of the water production pool is connected with a liquid inlet of the cleaning waste liquid water tank; the liquid outlet of the cleaning waste liquid water tank is connected with the water inlet end of the regulating tank.
An ammonia nitrogen removal method for acid regeneration acid-containing wastewater comprises the following steps:
step 1: acid regeneration wastewater discharged by the acid regeneration unit flows into the regulating reservoir, and water quality and water quantity are balanced in the regulating reservoir;
step 2: filtering the acid regeneration wastewater by a filter system, and lifting the acid regeneration wastewater by a primary lift pump to enter an electrochemical oxidation reaction tank;
and step 3: removing ammonia nitrogen after the wastewater reacts in an electrochemical oxidation reaction tank;
and 4, step 4: wastewater in the electrochemical oxidation reaction tank flows into the electrochemical oxidation water production tank and is lifted to the ion exchange resin adsorption tower through a secondary lift pump;
and 5: cation exchange resin is filled in the ion exchange resin adsorption tower, wastewater circulates between the ion exchange resin adsorption tower and the water production pool, ion exchange is carried out on the wastewater and ammonia nitrogen through the cation exchange resin, and the wastewater flows into the water production pool after the ammonia nitrogen is removed.
The step 2 comprises the following sub-steps:
step 2.1: pumping the acid regeneration wastewater into a microfiltration circulating tank by a water inlet pump, and lifting the acid regeneration wastewater to a microfiltration membrane filtering component by a circulating pump;
step 2.2: the produced water after being microfiltered by the microfiltration membrane filtering component enters a microfiltration water producing tank;
step 2.3: the mud-water mixed liquid in the microfiltration membrane filtering component returns to the circulation box of the microfiltration circulation tank;
Step 2.4: and lifting the water in the microfiltration product water tank by a primary lifting pump and then feeding the water into the electrochemical oxidation reaction tank.
The cation exchange resin is regenerated through regeneration liquid after being adsorbed and saturated, the using amount of the regeneration liquid is 2-3 times of the volume of the cation exchange resin, and the regeneration liquid is prepared by mixing regeneration waste liquid in a regeneration waste liquid water tank and new regeneration liquid in a regeneration liquid water tank.
The regeneration steps of the cation exchange resin are as follows: pumping the regenerated waste liquid in the regenerated waste liquid water tank and new regenerated liquid in the regenerated liquid water tank into an ion exchange resin adsorption tower through a regenerated water pump to regenerate cation exchange resin, and enabling the regenerated waste liquid to flow into the regenerated waste liquid water tank; the regenerated waste liquid in the regenerated waste liquid water tank flows into the regulating tank after being recycled.
And (3) after the regenerated liquid is discharged, cleaning an ion exchange column of the ion exchange resin adsorption tower, wherein the water volume of the cleaning liquid is 4-5 times of the volume of the cation exchange resin, and the cleaning liquid is prepared by mixing the cleaning waste liquid in the cleaning waste liquid water tank and the new cleaning liquid in the cleaning liquid water tank.
The regeneration steps of the cleaning solution are as follows: pumping the cleaning waste liquid in the cleaning waste liquid water tank and new cleaning liquid in the cleaning liquid water tank into an ion exchange resin adsorption tower through a cleaning water pump, and enabling the cleaning waste liquid after cleaning to flow into the cleaning waste liquid water tank; the washing waste liquid after being recycled in the washing waste liquid water tank flows into the regulating tank.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention can realize the standard discharge of ammonia nitrogen in acid regeneration wastewater, and chemical agents are not needed to be added in the treatment process, and only electricity is consumed in the electrochemical oxidation process; the ion exchange resin regeneration waste liquid is returned to the regulating tank for treatment, thereby fundamentally solving the problem of treatment of the ion exchange resin regeneration waste liquid.
2. The invention has the double effects of economy and environmental protection, and has good social benefit and environmental benefit.
Drawings
FIG. 1 is a block diagram of a prior art acid regeneration plant;
FIG. 2 is a structural diagram of an ammonia nitrogen removal device for acid regeneration of acid-containing wastewater according to the present invention;
FIG. 3 is a flow chart of the method for removing ammonia nitrogen from acid-regenerated acid-containing wastewater of the present invention.
In the figure, 100 waste acid, 200 preconcentrators, 300 reaction roasting furnaces, 400 washing towers, 500 ferric oxide powder, 600 double-cyclone dust collectors, 700 absorption towers, 800 regenerated hydrochloric acid, 1 adjusting tank, 2 water inlet pumps, 3 microfiltration membrane filtering components, 4 microfiltration circulating tanks, 5 microfiltration production water tanks, 6 primary lift pumps, 7 electrochemical oxidation reaction tanks, 8 electrochemical oxidation production water tanks, 9 secondary lift pumps, 10 ion exchange resin adsorption towers, 101 cation exchange resins, 11 production water tanks, 14 regenerated water pumps, 15 cleaning water pumps, 161 regenerated waste liquid water tanks, 162 regenerated liquid water tanks, 181 cleaning waste liquid water tanks and 182 cleaning liquid water tanks.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
Referring to the attached figure 2, the ammonia nitrogen removal device for acid regeneration acid-containing wastewater comprises an adjusting tank 1, a water inlet pump 2, a filtering system, a primary lifting pump 6, an electrochemical oxidation reaction tank 7, an electrochemical oxidation water production tank 8, a secondary lifting pump 9, an ion exchange resin adsorption tower 10 and a water production tank 11, wherein the acid regeneration acid-containing wastewater flows into the adjusting tank 1, the water outlet end of the adjusting tank 1 is connected with the water inlet end of the filtering system through the water inlet pump 2, the water outlet end of the filtering system is connected with the water inlet end of the electrochemical oxidation reaction tank 7 through the primary lifting pump 6, and the electrochemical oxidation reaction tank is connected with the water inlet end of the electrochemical oxidation reaction tank 77 an electrode is arranged in the chamber, wherein the anode adopts titanium-based lead dioxide (Ti/PbO)2) The cathode is made of titanium, the water outlet end of the electrochemical oxidation reaction tank 7 is connected with the water inlet end of the electrochemical oxidation water production tank 8, the water outlet end of the electrochemical oxidation water production tank 8 is connected with the water inlet end of the ion exchange resin adsorption tower 10 through the secondary lift pump 9, the water outlet end of the ion exchange resin adsorption tower 10 is connected with the water inlet end of the water production tank 11, and the circulating water outlet end of the water production tank 11 is connected with the circulating water inlet end of the ion exchange resin adsorption tower 10, so that wastewater can circulate between the ion exchange resin adsorption tower 10 and the water production tank 11 and can be subjected to repeated adsorption treatment to reach the emission standard.
Filtration system include microfiltration membrane filtering component 3, pond 5 is produced in microfiltration circulation 4 and microfiltration, the play water end of equalizing basin 1 is connected through the end of intaking of intake pump 2 with microfiltration circulation 4, the play water end of microfiltration circulation 4 is connected through the end of intaking of circulating pump with microfiltration membrane filtering component 3, the play water end of microfiltration membrane filtering component 3 is connected with the end of intaking in the pond 5 and the return water end of microfiltration circulation 4 of producing water in the pond 5 with the microfiltration, the play water end of pond 5 is produced in the microfiltration is held through the end of intaking of one-level elevator pump 6 with electrochemical oxidation reaction pond 7 and is connected.
The ammonia nitrogen removal device for acid regeneration acid-containing wastewater further comprises a regeneration liquid regeneration system, wherein the regeneration liquid regeneration system comprises a regeneration water pump 14, a regeneration waste liquid water tank 161 and a regeneration liquid water tank 162; the regeneration waste liquid water tank 161 and the regeneration liquid water tank 162 have liquid outlets connected to the regeneration liquid inlet of the ion exchange resin adsorption tower 10 via a regeneration water pump 14, and the waste liquid outlet of the water generating tank 11 is connected to the liquid inlet of the regeneration waste liquid water tank 161; the liquid outlet of the regeneration waste liquid tank 161 is connected with the water inlet end of the regulating reservoir 1.
The ammonia nitrogen removal device for acid regeneration acid-containing wastewater also comprises a cleaning solution regeneration system, wherein the cleaning solution regeneration system comprises a cleaning water pump 15, a cleaning waste liquid water tank 181 and a cleaning solution water tank 182; the cleaning waste liquid tank 181 and the cleaning liquid tank 182 have liquid outlets connected to a cleaning liquid inlet of the ion exchange resin adsorption tower 10 via a cleaning water pump 15, and a waste liquid outlet of the water production tank 11 is connected to a liquid inlet of the cleaning waste liquid tank 181; the liquid outlet of the cleaning waste liquid water tank 181 is connected with the water inlet end of the regulating tank 1.
Referring to fig. 3, a method for removing ammonia nitrogen from acid-regenerated acid-containing wastewater comprises the following steps:
step 1: acid regeneration wastewater discharged by the acid regeneration unit flows into the regulating reservoir 1, and water quality and water quantity are balanced in the regulating reservoir 1. Preferably, the hydraulic retention time of the adjusting tank 1 is 3-24 h.
Step 2: the acid regeneration wastewater is filtered by a filtering system and is lifted by a primary lift pump 6 to enter an electrochemical oxidation reaction tank 7. The content of suspended matters in the acid regeneration wastewater is high, mainly iron oxide powder and the like in the acid regeneration process, and a microfiltration membrane can be adopted for filtering in order to reduce the influence on the subsequent process.
Step 2.1: the water inlet pump 2 pumps the acid regeneration wastewater into the microfiltration circulating tank 4 and then lifts the acid regeneration wastewater to the microfiltration membrane filtering component 3 through the circulating pump. The micro-filtration membrane of the micro-filtration membrane filtration component 3 has small aperture and high filtration precision, can intercept tiny particles, and adopts a ceramic or organic sintered tubular micro-filtration membrane.
Step 2.2: the produced water after being microfiltered by the microfiltration membrane filtering component 3 enters a microfiltration water producing tank 5. Preferably, the microfiltration circulating tank 4 adopts cross flow filtration, the circulating amount of a microfiltration system is 5-100 times of the water yield, the microfiltration membrane filtration precision is 0.05-1 mu m, and the flux is 100-500L/m 2H, can reduce membrane fouling.
Step 2.3: and the mud-water mixed liquid in the microfiltration membrane filtering component 3 returns to the circulating tank of the microfiltration circulating tank 4, and when the concentration of suspended matters in the mixed liquid in the circulating tank reaches 3-10%, part of concentrated liquid is discharged, so that the concentration of the suspended matters in the microfiltration circulating tank 4 is kept stable.
Step 2.4: the water in the microfiltration water production tank 5 is lifted by a primary lift pump 6 and then enters an electrochemical oxidation reaction tank 7.
And step 3: the wastewater is reacted in an electrochemical oxidation reaction tank 7 to remove ammonia nitrogen, and the chemical reaction formula is as follows: 2NH4 ++ 3HClO → N2 + 3H2O + 5H+ + 3Cl-。
The reaction in the electrochemical oxidation reaction tank 7 includes:
1) cathodic reductionReaction: 2H+ + 2e- → H2↑ （1）
Cations in the electrooxidation reaction tank 7 move to the cathode under the action of current, H+Is reduced to H2Released in gaseous form, H+The pH value of the solution is increased due to consumption, and the subsequent removal of ammonia nitrogen is facilitated after the pH value is increased.
2) Anodic oxidation reaction: 2Cl- → Cl2↑+ 2e- （2）
Anions moving towards the anode under the action of an electric current, Cl-Is oxidized to Cl2。
3）Cl2Reaction in solution: cl2 + H2O → HClO + H+ + Cl- （3）
HClO + NH4 + → NH2Cl＋ H2O ＋ H+ （4）
HClO + NH2Cl → NHCl2 + H2O （5）
NHCl2 + H2O → NOH + 2H+ + 2Cl- （6）
NHCl2 + NOH → N2 + HClO + H+ + Cl- （7）
NH in the solution by the above reaction4 +Oxidation to N2Thereby realizing the regeneration of NH in the wastewater4 +And (4) removing.
The current density during the electro-oxidation is controlled to be 10-100 mA/cm2The voltage is controlled to be 5-30V, and the Hydraulic Retention Time (HRT) is controlled to be 30-300 min. After the electro-oxidation reaction treatment, the pH value of the acidic wastewater is increased to 5-7, and the removal rate of ammonia nitrogen reaches 80-95%.
After the electro-oxidation process treatment, most of ammonia nitrogen in the wastewater can be removed, on the other hand, the pH value of the wastewater is improved from 2-5 to 5-7, a near-neutral condition is achieved, and the effect of ammonia nitrogen adsorption is optimal under the neutral condition.
And 4, step 4: the wastewater in the electrochemical oxidation reaction tank 7 flows into an electrochemical oxidation water production tank 8 and is lifted to an ion exchange resin adsorption tower 10 through a secondary lift pump 9.
And 5: the ion exchange resin adsorption tower 10 is filled with strongly acidic cation exchange resin 101, wastewater circulates between the ion exchange resin adsorption tower 10 and the water production tank 11, ion exchange is carried out on the wastewater and ammonia nitrogen through the cation exchange resin 101, and the wastewater finally flows into the water production tank 11 after ammonia nitrogen is removed so as to reach the discharge standard.
The functional group of the strong-acid cation exchange resin 101 is SO3H，SO3H is strongly acidic and can be easily dissociated in aqueous solution+So that its adsorption effect is relatively little influenced by pH, H+Can react with residual NH in the water produced by electrooxidation4 +Ion exchange is carried out, so that ammonia nitrogen is removed.
Preferably, the retention time of the wastewater in the ion exchange resin adsorption tower 10 is 15-150 min, the flow rate is 1-10 m/h, the ammonia nitrogen of the effluent is less than 5mg/L, and the wastewater can be discharged up to the standard.
After the strong-acid cation exchange resin 101 is saturated by adsorption, regeneration needs to be carried out through a regeneration liquid, the regeneration liquid is preferably 3-5% hydrochloric acid, and the flow rate of the regeneration liquid is controlled to be 0.5-5 m/h in the regeneration process. The dosage of the regeneration liquid is 2-3 times of the volume of the cation exchange resin 101. In order to save the consumption of the regeneration liquid and improve the regeneration effect, the regeneration liquid can be reused, in the regeneration process, the regeneration liquid in the later period of the last period stored in the regeneration waste liquid water tank 161 is firstly used, the consumption of the regeneration liquid in the later period is 1-1.5 times of the volume of the cation exchange resin 101, the new regeneration liquid stored in the regeneration liquid water tank 162 is used, and the consumption of the new regeneration liquid is 1-1.5 times of the volume of the cation exchange resin 101 to prepare the regeneration liquid for reuse. The flow rate of the regenerated liquid which is repeatedly used is controlled to be 0.5-5 m/h.
The regenerated waste liquid and the regenerated liquid in the regenerated waste liquid water tank 161 and the regenerated liquid water tank 162 are pumped into the ion exchange resin adsorption tower 10 through the regenerated water pump 14, so that the cation exchange resin 101 is regenerated, and the regenerated waste liquid flows into the regenerated waste liquid water tank 161.
In the regeneration process of the regeneration liquid, the regeneration liquid can be recycled and regenerated for a plurality of times between the ion exchange resin adsorption tower 10 and the water production pool 11.
The ion exchange column of the ion exchange resin adsorption tower 10 may be cleaned after discharging the regeneration liquid. Preferably, the cleaning solution can be industrial water, and the water amount of the cleaning solution is 4-5 times of the volume of the cation exchange resin 101. The cleaning solution can be reused, in the cleaning process, the cleaning solution stored in the cleaning waste liquid water tank 181 at the later period of the previous period is firstly used, the using amount of the cleaning solution at the later period is 2-2.5 times of the volume of the cation exchange resin 101, and then the new cleaning solution stored in the cleaning solution water tank 182 is used, and the using amount of the new cleaning solution is 2-2.5 times of the volume of the cation exchange resin 101, so that the cleaning solution can be prepared into the reusable cleaning solution. The purge flow rate is initially equal to the regeneration flow rate and gradually increases to the operating flow rate.
The cleaning liquid in the cleaning waste liquid tank 181 and the cleaning liquid tank 182 is pumped into the ion exchange resin adsorption tower 10 by the cleaning water pump 15 for cleaning the ion exchange column, and the cleaning waste liquid after cleaning flows into the cleaning waste liquid tank 181.
The recycled regeneration waste liquid in the regeneration waste liquid water tank 161 can be recycled into the regulating tank 1, the recycled cleaning waste liquid in the cleaning waste liquid water tank 181 can be recycled into the regulating tank 1 and mixed with the acid regeneration waste water in the regulating tank 1, the formed mixed liquid is acidic and contains part of ammonia nitrogen, the water quality is close to that of the acid regeneration waste water, and therefore the part of the waste liquid can be returned into the regulating tank 1 of the acid regeneration waste water and is treated together with the acid regeneration waste water. The method can fundamentally solve the problem of treating the ion exchange resin regeneration waste liquid.
In the process of cleaning solution regeneration, the cleaning solution can be cyclically regenerated for a plurality of times between the ion exchange resin adsorption tower 10 and the water production tank 11.
Example 1:
the pH value of the wastewater generated by the acid regeneration process is 2.8, and the ammonia nitrogen content is 52 mg/L. Control conditions in the electrochemical oxidation reaction tank 7: the current density was 30mA/cm2The temperature of the waste water in the electrolytic cell is 32 ℃, and the retention time of the waste water in the electrolytic cell is 45 min. After the treatment of the electrooxidation process, the ammonia nitrogen content is 5.2mg/L, the ammonia nitrogen removal rate reaches 90%, and the pH value of effluent is 6.0. The effluent treated by the electro-oxidation process enters an ion exchange resin adsorption tower 10 for separationThe hydraulic retention time in the sub-exchange resin adsorption tower 10 is 30min, the flow rate is 1m/h, the ammonia nitrogen content of the effluent of the ion exchange resin adsorption tower 10 is 1.6mg/L, and the discharge standard of 5mg/L can be met.
Example 2:
the pH value of the wastewater generated by the acid regeneration process is 3.5, and the content of ammonia nitrogen is 19 mg/L. Control conditions in the electrochemical oxidation reaction tank 7: the current density is 25mA/cm2The temperature of the waste water in the electrolytic cell is 30 ℃, and the retention time of the waste water in the electrolytic cell is 30 min. The ammonia nitrogen content after the treatment of the electrooxidation process is 3.5mg/L, the ammonia nitrogen removal rate reaches 81.6 percent, and the pH value of effluent is 6.3. After being treated by the electro-oxidation process, the waste gas can meet the discharge standard of 5mg/L, does not need to be adsorbed by ion exchange resin, and can be directly discharged.
Example 3:
the pH value of the wastewater generated by the acid regeneration process is 2.0, and the content of ammonia nitrogen is 87 mg/L. Control conditions in the electrochemical oxidation reaction tank 7: the current density is 55mA/cm2The temperature of the waste water in the electrolytic cell is 35 ℃, and the retention time of the waste water in the electrolytic cell is 90 min. After the treatment of the electrooxidation process, the ammonia nitrogen content is 7.5mg/L, the ammonia nitrogen removal rate reaches 92.5%, and the pH value of effluent is 5.7. The effluent water after the electro-oxidation process enters an ion exchange resin adsorption tower 10, the hydraulic retention time in the ion exchange resin adsorption tower 10 is 60min, the flow rate is 1m/h, the ammonia nitrogen content of the effluent water of the ion exchange resin adsorption tower 10 is 0.75mg/L, and the discharge standard of 5mg/L can be met.
Claims (8)
1. The utility model provides an ammonia nitrogen desorption device that acid regeneration contains acid waste water which characterized by: comprises a regulating reservoir (1), a water inlet pump (2), a filtering system, a primary lift pump (6), an electrochemical oxidation reaction pool (7), an electrochemical oxidation water production pool (8), a secondary lift pump (9), an ion exchange resin adsorption tower (10) and a water production pool (11); the water outlet end of the adjusting tank (1) is connected with the water inlet end of the filtering system through a water inlet pump (2), the water outlet end of the filtering system is connected with the water inlet end of the electrochemical oxidation reaction tank (7) through a primary lifting pump (6), an electrode is arranged in the electrochemical oxidation reaction tank (7), the water outlet end of the electrochemical oxidation reaction tank (7) is connected with the water inlet end of the electrochemical oxidation water generating tank (8), the water outlet end of the electrochemical oxidation water generating tank (8) is connected with the water inlet end of the ion exchange resin adsorption tower (10) through a secondary lifting pump (9), the water outlet end of the ion exchange resin adsorption tower (10) is connected with the water inlet end of the water generating tank (11), and the circulating water outlet end of the water generating tank (11) is connected with the circulating water inlet end of the ion exchange resin adsorption tower (10);
Filtration system include microfiltration membrane filtering component (3), microfiltration circulating pool (4) and microfiltration product pond (5), the play water end of equalizing basin (1) is connected through intake pump (2) and the end of intaking of microfiltration circulating pool (4), the play water end of microfiltration circulating pool (4) is connected through the end of intaking of circulating pump with microfiltration membrane filtering component (3), the play water end of microfiltration membrane filtering component (3) is connected with the return water end of the end of intaking of microfiltration product pond (5) and microfiltration circulating pool (4), the play water end of microfiltration product pond (5) is connected through the end of intaking of one-level elevator pump (6) and electrochemical oxidation reaction pond (7).
2. The ammonia nitrogen removal device for acid regeneration acid-containing wastewater according to claim 1, which is characterized in that: the ammonia nitrogen removal device for acid regeneration acid-containing wastewater also comprises a regeneration liquid regeneration system, wherein the regeneration liquid regeneration system comprises a regeneration water pump (14), a regeneration waste liquid water tank (161) and a regeneration liquid water tank (162); the regeneration waste liquid water tank (161) and the liquid outlet of the regeneration liquid water tank (162) are connected with the regeneration liquid inlet of the ion exchange resin adsorption tower (10) through a regeneration water pump (14), and the waste liquid outlet of the water production tank (11) is connected with the liquid inlet of the regeneration waste liquid water tank (161); the liquid outlet of the regeneration waste liquid water tank (161) is connected with the water inlet end of the regulating reservoir (1).
3. The ammonia nitrogen removal device for acid regeneration acid-containing wastewater according to claim 1, which is characterized in that: the ammonia nitrogen removal device for acid regeneration acid-containing wastewater also comprises a cleaning solution regeneration system, wherein the cleaning solution regeneration system comprises a cleaning water pump (15), a cleaning waste liquid water tank (181) and a cleaning solution water tank (182); the cleaning waste liquid water tank (181) and the liquid outlet of the cleaning liquid water tank (182) are connected with the cleaning liquid inlet of the ion exchange resin adsorption tower (10) through a cleaning water pump (15), and the waste liquid outlet of the water generating tank (11) is connected with the liquid inlet of the cleaning waste liquid water tank (181); the liquid outlet of the cleaning waste liquid water tank (181) is connected with the water inlet end of the regulating tank (1).
4. An ammonia nitrogen removal method of an ammonia nitrogen removal device for regenerating acid-containing wastewater by using the acid of any one of claims 1 to 3, which is characterized in that: the method comprises the following steps:
step 1: acid regeneration wastewater discharged by the acid regeneration unit flows into the regulating tank (1), and water quality and water quantity are balanced in the regulating tank (1);
step 2: filtering the acid regeneration wastewater by a filtering system, and lifting the acid regeneration wastewater by a primary lifting pump (6) and then feeding the acid regeneration wastewater into an electrochemical oxidation reaction tank (7);
and step 3: the wastewater is reacted in an electrochemical oxidation reaction tank (7) to remove ammonia nitrogen;
And 4, step 4: wastewater in the electrochemical oxidation reaction tank (7) flows into an electrochemical oxidation water production tank (8) and is lifted to an ion exchange resin adsorption tower (10) through a secondary lifting pump (9);
and 5: cation exchange resin (101) is filled in the ion exchange resin adsorption tower (10), wastewater circulates between the ion exchange resin adsorption tower (10) and the water production tank (11), ion exchange is carried out on the wastewater and ammonia nitrogen through the cation exchange resin (101), and the wastewater flows into the water production tank (11) after the ammonia nitrogen is removed;
the step 2 comprises the following sub-steps:
step 2.1: the water inlet pump (2) pumps the acid regeneration wastewater into the microfiltration circulating tank (4) and then lifts the acid regeneration wastewater to the microfiltration membrane filtering component (3) through the circulating pump;
step 2.2: the produced water after being microfiltered by the microfiltration membrane filtering component (3) enters a microfiltration water producing tank (5); the micro-filtration circulating pool (4) adopts cross-flow filtration, the circulating amount of a micro-filtration system is 5-100 times of the water yield, the micro-filtration membrane filtration precision is 0.05-1 mu m, and the flux is 100-500L/m2H, reducing membrane fouling;
step 2.3: the mud-water mixed liquid in the microfiltration membrane filtering component (3) returns to the circulation box of the microfiltration circulation tank (4);
step 2.4: water in the microfiltration water production tank (5) is lifted by a primary lifting pump (6) and then enters an electrochemical oxidation reaction tank (7);
In the step 3, the current density during the electro-oxidation is controlled to be 10-100 mA/cm2The voltage is controlled to be 5-30V, and the Hydraulic Retention Time (HRT) is controlled to be 30-300 min.
5. The ammonia nitrogen removal method for acid regeneration acid-containing wastewater according to claim 4, which is characterized in that: the cation exchange resin (101) is adsorbed and saturated and then regenerated through a regeneration liquid, the using amount of the regeneration liquid is 2-3 times of the volume of the cation exchange resin (101), wherein the regeneration liquid is prepared by mixing regeneration waste liquid in a regeneration waste liquid water tank (161) and new regeneration liquid in a regeneration liquid water tank (162).
6. The ammonia nitrogen removal method for acid regeneration acid-containing wastewater according to claim 5, which is characterized in that: the regeneration steps of the cation exchange resin (101) are as follows: pumping the regenerated waste liquid in the regenerated waste liquid water tank (161) and new regenerated liquid in the regenerated liquid water tank (162) into the ion exchange resin adsorption tower (10) through a regenerated water pump (14) to regenerate the cation exchange resin (101), and enabling the regenerated waste liquid to flow into the regenerated waste liquid water tank (161); the regenerated waste liquid recycled in the regenerated waste liquid water tank (161) flows into the regulating tank (1).
7. The ammonia nitrogen removal method for acid regeneration acid-containing wastewater according to claim 6, which is characterized in that: and (3) after the regenerated liquid is discharged, cleaning the ion exchange column of the ion exchange resin adsorption tower (10), wherein the water volume of the cleaning liquid is 4-5 times of the volume of the cation exchange resin (101), and the cleaning liquid is prepared by mixing the cleaning waste liquid in the cleaning waste liquid water tank (181) and the new cleaning liquid in the cleaning liquid water tank (182).
8. The ammonia nitrogen removal method for acid regeneration acid-containing wastewater according to claim 7, which is characterized in that: the regeneration steps of the cleaning solution are as follows: the cleaning waste liquid in the cleaning waste liquid water tank (181) and the new cleaning liquid in the cleaning liquid water tank (182) are pumped into the ion exchange resin adsorption tower (10) through a cleaning water pump (15), and the cleaned cleaning waste liquid flows into the cleaning waste liquid water tank (181); the cleaning waste liquid in the cleaning waste liquid water tank (181) flows into the regulating tank (1) after being recycled.
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| CN105859028A (en) * | 2016-04-29 | 2016-08-17 | 红板（江西）有限公司 | Process for treating circuit board alkaline etching ammonia-nitrogen wastewater |
| CN206089294U (en) * | 2016-10-01 | 2017-04-12 | 辽宁中成永续水工科技有限公司 | Steel industry hydrochloric acid pickling liquid waste's processing recovery system |
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