CN210915600U - Recycling device of RO strong brine - Google Patents
Recycling device of RO strong brine Download PDFInfo
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- CN210915600U CN210915600U CN201920437262.2U CN201920437262U CN210915600U CN 210915600 U CN210915600 U CN 210915600U CN 201920437262 U CN201920437262 U CN 201920437262U CN 210915600 U CN210915600 U CN 210915600U
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Abstract
The utility model relates to a device of recycling of RO strong brine belongs to chemical industry technical field. The method comprises the following steps: the device for removing the cationic impurities is used for removing the cationic impurities from the concentrated water obtained by the reverse osmosis filtration treatment of the circulating water of the power plant by adopting a precipitation method; the separation membrane device is used for filtering and removing the precipitate obtained in the cation impurity removing device; the ion exchange resin column is used for carrying out ion exchange impurity cation removal treatment on the filtrate obtained by the separation membrane device; the organic membrane is used for filtering the produced water obtained by the ion exchange resin column; and the ionic membrane electrolytic cell is connected to the permeation side of the organic membrane and is used for carrying out ionic membrane electrolytic treatment on the purified brine obtained by the organic membrane. The utility model discloses a recycling method and device of RO strong brine can solve the difficult problem that chemical industry power plant circulating water RO concentrate can't be used because of having organic pollutant effectively.
Description
Technical Field
The utility model relates to a device of recycling of RO strong brine, in particular to be applied to device is recycled to power plant's circulating water RO concentrate embrane method of chemical industry belongs to chemical industry technical field.
Background
The thermal power plant is a large household for industrial water and mainly comprises a furnace water vapor system, a circulating cooling water system, a generator internal cooling water system, a wastewater treatment system and the like, wherein the water consumption of the circulating cooling water system is the largest and accounts for more than 75-90% of the total water consumption of the power plant. The circulating water system of the power plant is mainly used as cooling water of a condenser and is also used as cooling water of auxiliary equipment such as a hydrogen cooler, an oil cooler and the like of some power plants. With the requirements of national energy conservation and emission reduction, the water taking cost of a power plant is continuously increased, and the water saving of circulating water becomes the main work of saving water of the power plant.
The reverse osmosis method is a common membrane separation method, can be applied to removing harmful components such as hardness and microorganisms in circulating cooling water of a power plant, and has high desalination rate, and the water recovery rate can reach 75-90%. As the RO concentration process in the circulating water recycling system of the power plant is a common disposal means, the amount of the generated RO strong brine is remarkable. With the development of the environmental protection industry, policy control and pursuit of the national people on green water hills, 2-25% of strong brine generated in the RO process is difficult to treat due to the characteristics of high concentration and high salinity of the organic matters, and the direct discharge has adverse effect on the environment. At present, RO strong brine treatment methods mainly comprise electrodialysis, membrane distillation, thermal evaporation concentration and the like, and have the problems of large initial investment, high energy consumption, complex operation and the like; advanced oxidation may be the most promising treatment process for treating high-concentration brine due to its good effect, but it also has the problems of high cost and incomplete treatment. The main stream of the industrial treatment idea is to adopt an oxidation method to lead the wastewater to reach the standard and discharge, but inorganic salt resources in the wastewater cause loss; the thermal evaporation method realizes zero emission, but has the problems of high investment, large energy consumption and the like, thereby limiting the application of the thermal evaporation method.
CN108640395A discloses a thermal power plant circulating water zero discharge system, is equipped with the circulating water import, and the circulating water import meets the coagulating sedimentation tank, and the coagulating sedimentation tank meets with the coagulant storage tank through first valve, the water outlet of coagulating sedimentation tank meets with ultrafiltration device through multi-media filter equipment, is equipped with the germicide storage tank, the germicide storage tank connects between multi-media filter equipment and ultrafiltration device through the second valve, and the water outlet of ultrafiltration device meets with reverse osmosis unit, and reverse osmosis unit's dense water outlet meets with the evaporation crystallization device, and reverse osmosis unit's pure water outlet meets with the circulating water system, the evaporation crystallization device meets with the steam discharge pipe through the third valve. CN102464412A discloses a recycling treatment process and a device system for power plant circulating water, which are characterized in that the power plant circulating water is sequentially subjected to mechanical accelerated clarification, variable pore filtration, immersed ultrafiltration and reverse osmosis membrane treatment, and treated clear water is used as a power plant industrial water source.
However, the treatment process of the reverse osmosis concentrated solution is not well realized in the treatment process of the method.
In addition, patent CN 103819019A's utility model discloses a dense water graded oxidation treatment discharge to reach standard of RO method, makes the play water organic matter content reduce to discharge to reach standard through the process route of "ozone oxidation-sodium hypochlorite oxidation". The utility model of patent CN102190392A discloses a method for treating RO concentrated water for reclaimed water to reach the discharge standard, which adopts electrolysis-flocculation precipitation-sand filtration-carbon filtration-precise filtration to treat RO concentrated water to reach the discharge standard, but the above method causes waste of water resource and inorganic salt resource.
Based on the situation, the application is made for the resource utilization of the RO strong brine.
Disclosure of Invention
The utility model aims at: the method can effectively remove cationic impurities, ammonia nitrogen, total organic carbon content and the like in the RO strong brine of the power plant, obtain sodium chloride brine for brine extraction of brine by ionic membrane caustic soda, realize primary purification of the RO strong brine, and then purify the RO strong brine in an organic membrane system, thereby realizing resource utilization of the strong brine.
The technical scheme is as follows:
a recycling method of RO strong brine comprises the following steps:
step 1, removing cationic impurities from RO strong brine by a precipitation method;
step 2, performing solid-liquid separation on the saline water obtained in the step 1 by adopting a microfiltration/ultrafiltration membrane;
step 3, adsorbing the separation membrane permeate obtained in the step 2 by using resin to further reduce the content of cationic impurities;
and 4, sending the concentrated brine obtained in the step 3 into an organic membrane system for purification treatment to obtain clean sodium chloride brine.
In the step 1, the RO strong brine is the strong brine obtained by the reverse osmosis filtration treatment of the circulating water of the power plant.
In the step 1, RO strong brine is brine mainly containing NaCl; the COD range in the saline water is 1-500 ppm; the TOC range of the brine is 1-150 ppm; the ammonia nitrogen content in the brine is 1-1000 ppm; the sulfate radical content in the brine is 1-5000 ppm.
The cationic impurities are selected from Ca2+、Mg2+、Cs+Or Ni+Ions; the cationic impurities are removed by a precipitation method, which means that: adding CO into waste brine3 2-And/or OH-The ion is used as a precipitator, and is subjected to precipitation reaction with cation impurities in the brine to generate precipitate, and the precipitate is filtered through a separation membrane to remove the precipitate, so that the treated brine is obtained on the permeation side of the separation membrane.
The cation in the precipitant is the same as the cation of the main component in the brine; adding a precipitant selected from NaOH and Na2CO3And each precipitant is added in an amount equal to or slightly greater than the amount required to completely precipitate the impurity cations.
The adopted separation membrane is a microfiltration membrane or an ultrafiltration membrane; the average pore diameter of the separation membrane is 0.002-1 μm, or the cut-off molecular weight is 10000-5000000 Da.
Sequentially carrying out Fenton oxidation, activated carbon and electric flocculation treatment on the RO strong brine, and then sending the electric flocculation effluent to the step 1.
In the Fenton oxidation process, Fe2+And H2O2The concentration is 40-250 mg/L and 100-600 mg/L respectively, the pH value of the system is 3-4, and the reaction temperature isThe temperature is 10-60 ℃, and the reaction time is 15-120 min.
In the electric flocculation process, the operation parameters of the electric flocculation are as follows: the electrode plate is an aluminum plate, and the current density is 200-300A/m2The retention time is 40-100 min.
After the electric flocculation treatment, the produced water is added with magnetic nano zirconium hydroxide particles and then sent to the step 1.
The adding amount of the magnetic nano zirconium hydroxide particles is 1-5 g/L.
In one embodiment, the resin type is LSC-100 or S-930 or D463.
In one embodiment, the membrane module adopted by the organic membrane is a roll-up membrane module, and the membrane material is selected from one or a combination of several of PVC, PEEK, PES, PS, PP, PET, PVDF and the like.
In one embodiment, the brine obtained in step 4 is fed to an ionic membrane electrolysis process.
In one embodiment, the temperature of the ion membrane electrolysis process is 70-90 ℃, and the operating current density is 1.0-5.0 kA/m2。
A RO strong brine reuse device, comprising:
the device for removing the cationic impurities is used for removing the cationic impurities from the concentrated water obtained by the reverse osmosis filtration treatment of the circulating water of the power plant by adopting a precipitation method;
the separation membrane device is used for filtering and removing the precipitate obtained in the cation impurity removing device;
the ion exchange resin column is used for carrying out ion exchange impurity cation removal treatment on the filtrate obtained by the separation membrane device;
the organic membrane is used for filtering the produced water obtained by the ion exchange resin column;
and the ionic membrane electrolytic cell is connected to the permeation side of the organic membrane and is used for carrying out ionic membrane electrolytic treatment on the purified brine obtained by the organic membrane.
In one embodiment, the device for removing cationic impurities comprises a precipitation reaction tank, a NaOH feeding tank and Na2CO3Adding tank, sedimentation reaction tank and separation membraneThe device is connected, NaOH is added into the tank and Na2CO3The adding tank is respectively used for adding NaOH and Na into the precipitation reaction tank2CO3。
In one embodiment, the separation membrane device refers to a microfiltration or ultrafiltration membrane; the average pore diameter of a separation membrane in the separation membrane device is 0.002-1 mu m, or the cut-off molecular weight is 10000-5000000 Da.
In one embodiment, the device further comprises a plate and frame filter for concentrating the trapped fluid of the separation membrane device, wherein the permeation side of the plate and frame filter is connected with the water inlet of the separation membrane device.
In one embodiment, the resin type packed in the ion exchange resin column is LSC-100 or S-930 or D463.
In one embodiment, the material of the organic membrane is one or a combination of several of PVC, PEEK, PES, PS, PP, PET, PVDF, etc., and the cut-off molecular weight of the organic membrane is 200-.
In one embodiment, the device further comprises a Fenton reactor, an adsorption column and an electric flocculator which are connected in sequence; the water production end of the electric flocculator is connected with the water inlet end of the cationic impurity removing device;
the Fenton reactor is used for carrying out Fenton oxidation treatment on concentrated water obtained after reverse osmosis filtration treatment on the circulating water of the power plant; the adsorption column is filled with active carbon and is used for carrying out adsorption treatment on the produced water of the Fenton reactor; the electric flocculator is used for carrying out electric flocculation treatment on the produced water of the adsorption column;
the utility model also provides an application of foretell device in ionic membrane electrolysis process.
Advantageous effects
The utility model provides a method can be to the concentrated solution recycle once more after reverse osmosis membrane concentration of power plant's circulating water, can get rid of the impurity in the RO concentrated solution effectively to can reuse NaCl wherein in the ionic membrane electrolysis process.
Drawings
FIG. 1 is a schematic diagram of a RO strong brine treatment device according to the present invention.
FIG. 2 is a structural view of another RO strong brine treatment device provided by the present invention. Figure 3 is a graph of the run of the nanofiltration membrane. Fig. 4 is a comparison of the steady flux for ceramic ultrafiltration membrane operation. FIG. 5 is a comparison of flux recovery rates for ceramic ultrafiltration membranes.
Wherein, 1, a device for removing cationic impurities; 2. a separation membrane device; 3. ion exchange resin column; 4. a plate frame filter; 5. an organic film; 6. an ionic membrane electrolytic cell; 7. adding NaOH into a tank; 8. adding Na2CO3 into a tank; 9. a precipitation reaction tank; 10. a Fenton reactor; 11. an adsorption column; 12. an electric flocculator.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as "about," is not to be limited to the precise value specified. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Unless context or language indicates otherwise, range limitations may be combined and/or interchanged, and such ranges are identified and include all the sub-ranges included herein. Other than in the operating examples, or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the word "about".
The recitation of values by ranges is to be understood in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a concentration range of "about 0.1% to about 5%" should be interpreted to include not only the explicitly recited concentration of about 0.1% to about 5%, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and sub-ranges (e.g., 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%) within the indicated range.
The term "removal" in the present specification includes not only a case where a target substance is completely removed but also a case where the target substance is partially removed (the amount of the substance is reduced). "purification" in this specification includes the removal of any or specific impurities.
The words "include," "have," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. It will be understood that when an element is referred to as being "connected" to another element, it can be directly connected to the other element or be indirectly connected to the other element with the element interposed therebetween. The percentages in the present invention refer to mass percentages without specific reference.
The utility model discloses the waste water that will handle is the circulating water of power plant, and power plant's circulating water system mainly regards as the cooling water of condenser, also regards as the cooling water of auxiliary equipment such as some power plant's hydrogen coolers, oil coolers simultaneously. The system with more water consumption in the thermal power plant is a cooling water system, and the pollution discharge loss of circulating cooling water accounts for a great proportion. The main technical approach for reducing the loss is to increase the concentration ratio of the circulating cooling water system. Along with the increase of the concentration ratio, the concentration degree of impurities in water is higher and higher, and some salts with low solubility are supersaturated and tend to be separated out in a circulating water system; the mass propagation of microorganisms in the water system will produce biological deposits on the heat exchange surfaces. If water treatment is not carried out, serious scaling problems are generated, and the safe and economic operation of a power plant is influenced. In the treatable RO strong brine of the power plant, the RO strong brine is brine mainly containing NaCl; the COD range in the saline water is 1-500 ppm; the TOC range of the brine is 1-150 ppm; the ammonia nitrogen content in the brine is 1-1000 ppm; the sulfate radical content in the brine is 1-5000 ppm.
In the treatment method of the present invention, firstly, the circulating water is treated with cation for removing impurities, and the cation impurities in the brine can be removed by various methods known in the art, such as: ion exchange, adsorption, precipitation, etc., as long as it is possible to achieve removal of the impurity cations from the NaCl salt, and in a preferred embodiment, the precipitation method is very suitable for industrial use, and the main steps of the precipitation method are: first, CO is added to the crude brine3 2-And OH-Ions, after reaction, CO3 2-And OH-The ions can make Ca2+、Mg2+Conversion to CaCO respectively3And Mg (OH)2When the crude brine also contains Cs+、Ni+When ionic, CO3 2-And OH-The ions may also convert them to Cs2CO3And Ni (OH)2Then sent into a separation membrane for filtration, and CaCO generated by the reaction can be removed3、Mg(OH)2、Cs2CO3And Ni (OH)2And obtaining the purified separation membrane clear solution.
Ca as an impurity cation2+、Mg2+、Cs+、Ni+The concentration range of the ion is not particularly limited, and may be in the range of 0.01 to 50g/L, as long as an appropriate precipitant CO is selected according to the concentration of the impurity cation3 2-And OH-The addition of ions converts the impurity cations into precipitate, CO3 2-And OH-The amount of ions added can be calculated by one skilled in the art from the stoichiometric balance. In order to completely convert the impurity cations into precipitates, a precipitating agent selected from NaOH and Na is added2CO3KOH or K2CO3The addition amount of each precipitator is equal to or slightly larger than that of the completely precipitated impurityIon required amount, for example: adding NaOH and Na2CO3KOH or K2CO3The addition amount of the cationic surfactant is equal to or more than 0.01-0.3 g/L than the amount required for completely precipitating the impurity cations. The "complete precipitation" in the present invention refers to the required precipitation amount calculated according to the chemical reaction balance, and those skilled in the art can calculate the required precipitation amount according to the chemical reaction molar ratio, and it is not understood that the impurity ions are completely precipitated in the actual reaction.
The content of cationic impurities in the obtained separation membrane permeate is further reduced by resin adsorption; then feeding the purified RO strong brine obtained by the resin into an organic membrane system for purification treatment to obtain a purified sodium chloride solution; the resin type is LSC-100 or S-930 or D463, the membrane component adopted by the organic membrane is a spiral-wound membrane component, and the membrane material is selected from one or a combination of more of PVC, PEEK, PES, PS, PP, PET, PVDF and the like.
In one embodiment, the RO strong brine is sequentially subjected to Fenton oxidation, activated carbon adsorption and electric flocculation treatment, and then the electric flocculation effluent is fed into a reactor added with NaOH and Na2CO3The step (2). In the Fenton oxidation process, COD (chemical oxygen demand) substances in RO (reverse osmosis) strong brine can be effectively reduced, subsequent microfiltration/ultrafiltration membrane pollution is avoided, the inhibition of organic matters on the filtration efficiency of an organic membrane system can be reduced, and Fe is introduced into wastewater in the Fenton oxidation process2+By oxidation to form Fe3+Adding NaOH and Na2CO3In the precipitation reaction of (3), Fe (OH) is produced3Colloids, CaCO formed3And Mg (OH)2The precipitation crystallization is increased, small particles are prevented from precipitating on the surface of the microfiltration/ultrafiltration membrane to block pores, the irreversible pollution of the separation membrane is reduced, and the separation membrane can have higher flux after the reversible pollution on the surface of the membrane is removed after the membrane is washed by water; at the same time, Fe2+、Fe3+The flocculation effect can be exerted to improve the removal rate of the electro-flocculation on the ammonia nitrogen in the concentrated brine, and the ionic strength in the subsequent organic membrane filtration process is reduced. In the Fenton oxidation treatment, Fe2+And H2O2The concentration is 50-300 mg/L and200-700 mg/L, the pH value of the system is 3-5, the reaction temperature is 20-40 ℃, and the reaction time is 60-180 min. In the electric flocculation process, the electrode plate is an aluminum plate, and the current density is 200-300A/m2The retention time is 30-120 min.
In one embodiment, after the electric flocculation treatment, magnetic nano zirconium hydroxide particles with sulfate radical adsorption are added into produced water, and because the circulating water contains sulfate radical ions with certain concentration, the sulfate radical ions and residual calcium ions can generate calcium sulfate scale on the surface of the reverse osmosis membrane in the concentration process of adopting the reverse osmosis membrane, and the long-term operation can cause irreversible scale pollution on the surface of the reverse osmosis membrane, thereby influencing the service life of the reverse osmosis membrane. Therefore, the magnetic nano zirconium hydroxide particles are added into the electric flocculation product water, on one hand, the zirconium hydroxide particles can selectively adsorb sulfate radicals in circulating water, on the other hand, the zirconium hydroxide particles can play a role of a filter aid in the filtering process of microfiltration/nanofiltration, the blockage of small particles and colloids on membrane pores is prevented, the membrane flux is improved, and the irreversible pollution is reduced. The flocculate-containing magnetic nano zirconium hydroxide particles are easily concentrated and separated by a subsequent plate-frame filter, and the magnetic zirconium hydroxide particles can be recycled from a plate-frame filter cake under the action of a magnetic field due to the magnetism of the magnetic zirconium hydroxide. The preparation of the magnetic nano zirconium hydroxide can adopt the prior art, such as: li Miss, Bao Jian Guo, Hongyan et al, research on sulfate radical adsorption characteristics of magnetic nano zirconium hydroxide [ J ]. environmental science and technology, v.36(06): 47-52. The application of the magnetic nano zirconium hydroxide in RO strong brine can improve the filtration flux and the flux recovery rate of the separation membrane, improve the operation stability of the nanofiltration membrane and reduce scaling.
Based on above method, the utility model provides a device can be as shown in figure 1, a device of recycling of RO strong brine, include:
the device for removing cationic impurities 1 is used for removing cationic impurities from concentrated water obtained by reverse osmosis filtration treatment of power plant circulating water by a precipitation method;
the separation membrane device 2 is used for filtering and removing the precipitate obtained in the cation impurity removing device 1;
the ion exchange resin column 3 is used for carrying out ion exchange impurity cation removal treatment on the filtrate obtained by the separation membrane device 2;
the organic membrane 5 is used for filtering the produced water obtained by the ion exchange resin column 3;
and an ion membrane electrolyzer 6 connected to the permeation side of the organic membrane 5 for performing ion membrane electrolysis treatment on the purified brine of the organic membrane 5.
In one embodiment, the device 1 for removing cationic impurities comprises a precipitation reaction tank 9, a NaOH feeding tank 7 and Na2CO3A feeding tank, a precipitation reaction tank 9 is connected with the separation membrane device 2, and a NaOH feeding tank 7 and Na2CO3The adding tanks are respectively used for adding NaOH and Na into the precipitation reaction tank 92CO3。
In one embodiment, separation membrane device 2 refers to a microfiltration or ultrafiltration membrane; the average pore diameter of the separation membrane in the separation membrane device 2 is 0.002-1 μm, or the cut-off molecular weight is 10000-5000000 Da.
In one embodiment, the device further comprises a plate and frame filter 4 for concentrating the retentate of the separation membrane device 2, and the permeate side of the plate and frame filter 4 is connected to the water inlet of the separation membrane device 2.
In one embodiment, the resin type packed in the ion exchange resin column 3 is LSC-100 or S-930 or D463.
In one embodiment, the material of the organic membrane is one or a combination of several of PVC, PEEK, PES, PS, PP, PET, PVDF, etc., and the cut-off molecular weight of the organic membrane is 200-.
As shown in fig. 2, in one embodiment, the device further comprises a fenton reactor 10, an adsorption column 11 and an electric flocculator 12 which are connected in sequence; the water production end of the electric flocculator 12 is connected with the water inlet end of the cationic impurity removing device 1;
the Fenton reactor 10 is used for carrying out Fenton oxidation treatment on concentrated water obtained after reverse osmosis filtration treatment on the circulating water of the power plant; the adsorption column 11 is filled with active carbon and is used for carrying out adsorption treatment on the produced water of the Fenton reactor 10; the electric flocculator 12 is used for performing electric flocculation treatment on the produced water of the adsorption column 11.
In the following examples, concentrated brine obtained by concentrating circulating sewage of a power plant by RO by 16 times is treated, wherein the concentrated brine mainly contains sodium chloride, and the main components of NaCl 1g/L and Mg in the concentrated brine2+0.03g/L，Ca2+0.4g/L, COD 220mg/L, TOC 98mg/L and ammonia nitrogen 10mg/L, SO4 2-0.7 g/L. The brine filtered by the deionization device and adsorbed by the resin is sent to an organic membrane for purification, and the water recovery rate is more than 98%.
Example 1
Adding NaOH0.1g/L and Na into RO strong brine of a power plant2CO31.06g/L, reacting in a reactor sufficiently, and then adding Ca2 +、Mg2+Conversion to CaCO respectively3And Mg (OH)2Then the mixture enters a microfiltration membrane for filtration, the microfiltration membrane with the average pore diameter of 800nm is adopted, the operation pressure is 0.3MPa, the concentration is 50 times, and the stable flux is 333.3L/m after the operation is carried out for 2 hours2H, CaCO can be removed3Precipitation and Mg (OH)2Colloid, and the ion content in the obtained microfiltration membrane penetrating fluid is as follows: mg (magnesium)2+Content 2.3mg/L, Ca2+The content is 5.1mg/L, the microfiltration membrane penetrating fluid COD is 101mg/L, the TOC is 78mg/L, and the ammonia nitrogen is 7.5 mg/L; after the microfiltration membrane runs for 8h, the membrane surface is washed by water for 30min, and the membrane flux is measured again to be 628.7L/m2H. And (3) feeding the microfiltration membrane penetrating fluid into S-930 type resin for deep hardness removal treatment to remove impurity cations in the microfiltration membrane penetrating fluid. Purifying the resin effluent in an organic membrane system, filtering by adopting a nanofiltration membrane with the molecular weight cutoff of 800Da, obtaining a clean sodium chloride solution with TOC2mg/L by using the operating pressure of 3.5MPa and the concentration multiple of 80 times, and feeding the sodium chloride solution into an ionic membrane electrolytic cell to carry out an electrolytic method for preparing NaOH and Cl2Treating at 80 deg.C with current density of 2.5kA/m2The current efficiency is 94.1%.
Example 2
Adding NaOH0.1g/L and Na into RO strong brine of a power plant2CO31.06g/L, reacting in a reactor sufficiently, and then adding Ca2 +、Mg2+Conversion to CaCO respectively3And Mg (OH)2Then the mixture enters an ultrafiltration membrane for filtration, the ultrafiltration membrane with the average pore diameter of 50nm is adopted, the operating pressure is 0.3MPa, the concentration is 80 times, and the flux reaching the stable operation after 2 hours of operation is 298.3L/m2H, CaCO can be removed3Precipitation and Mg (OH)2And (3) colloid, wherein the obtained ultrafiltration membrane penetrating fluid contains the following ions: mg (magnesium)2+Content 1.8mg/L, Ca2+The content is 4.5mg/L, the ultrafiltration membrane penetrating fluid COD is 97mg/L, the TOC is 65mg/L, and the ammonia nitrogen is 7.0 mg/L; after the ultrafiltration membrane runs for 8h, the permeation side is closed, the surface of the membrane is washed by water for 30min, and the membrane flux is measured again to be 441.3L/m2H, feeding the ultrafiltration membrane penetrating fluid into an LSC-100 type resin for deep hardness removal treatment to remove impurity cations in the microfiltration membrane penetrating fluid. Purifying the resin effluent in an organic membrane system, filtering by adopting a nanofiltration membrane with the molecular weight cutoff of 800Da, obtaining a clean sodium chloride solution with TOC3mg/L by using the operating pressure of 3MPa and the concentration multiple of 50 times, and feeding the sodium chloride solution into an ion membrane electrolytic cell to perform an electrolytic method for preparing NaOH and Cl2The treatment is carried out at a bath temperature of 85 ℃ and an operating current density of 2.6kA/m2The current efficiency is 94.5%.
Example 3
Performing electric flocculation reaction on RO strong brine of a power plant, wherein the plate electrode is an aluminum plate and the current density is 250A/m2The retention time is 90 min; COD of RO concentrated brine after the electrocoagulation treatment is reduced from 220mg/L to 165mg/L, and then NaOH0.1g/L and Na are added into the brine after the electrocoagulation reaction2CO31.06g/L, reacting in a reactor sufficiently, and then adding Ca2+、Mg2+Conversion to CaCO respectively3And Mg (OH)2Then the mixture enters an ultrafiltration membrane for filtration, the ultrafiltration membrane with the average pore diameter of 50nm is adopted, the operating pressure is 0.3MPa, the concentration is 80 times, and the flux reaching the stable operation of 355.8L/m after the operation for 2 hours2H, CaCO can be removed3Precipitation and Mg (OH)2And (3) colloid, wherein the obtained ultrafiltration membrane penetrating fluid contains the following ions: mg (magnesium)2+Content 1.2mg/L, Ca2+The content is 3.0mg/L, the ceramic membrane penetrating fluid COD is 71mg/L, the TOC is 42mg/L, and the ammonia nitrogen is 3.1 mg/L; after running the ultrafiltration membrane for 8h, closing the permeation side, washing the membrane surface with water for 30min, and measuring againThe membrane flux is 467.8L/m2H, feeding the ultrafiltration membrane penetrating fluid into D463 type resin for deep hardness removal treatment to remove impurity cations in the microfiltration membrane penetrating fluid. Purifying the resin effluent by an organic membrane system, filtering by a nanofiltration membrane with the molecular weight cutoff of 800Da under the operating pressure of 3.5MPa and the concentration multiple of 60 times to obtain a clean sodium chloride solution with TOC2.4mg/L, and feeding the sodium chloride solution into an ionic membrane electrolytic cell to perform an electrolytic method for preparing NaOH and Cl2The treatment is carried out at a bath temperature of 85 ℃ and an operating current density of 2.6kA/m2The current efficiency was 95.2%.
Example 4
The RO strong brine of the power plant is oxidized in a Fenton reactor, and Fe2+And H2O2The concentration is 120mg/L and 440mg/L respectively, the pH value of the system is 3-4, the reaction temperature is 30 ℃, and the reaction time is 90 min; the brine after the reaction is subjected to electric flocculation reaction, the electrode plate is an aluminum plate, and the current density is 250A/m2The retention time is 90 min; after the electric flocculation treatment, the COD of the RO concentrated brine is reduced from 220mg/L to 113mg/L, and then NaOH0.1g/L and Na are added into the produced water of the electric flocculation2CO31.06g/L, reacting in a reactor sufficiently, and then adding Ca2+、Mg2+Conversion to CaCO respectively3And Mg (OH)2Then the mixture enters an ultrafiltration membrane for filtration, the ultrafiltration membrane with the average pore diameter of 50nm is adopted, the operating pressure is 0.3MPa, the concentration is 80 times, and the stable flux of the operation is 371L/m after the operation for 2 hours2H, CaCO can be removed3Precipitation and Mg (OH)2And (3) colloid, wherein the obtained ultrafiltration membrane penetrating fluid contains the following ions: mg (magnesium)2+Content 0.8mg/L, Ca2+The content is 2.4mg/L, the ultrafiltration membrane penetrating fluid COD is 53mg/L, the TOC is 31mg/L, and the ammonia nitrogen is 1 mg/L; after the ultrafiltration membrane runs for 8h, the permeation side is closed, the surface of the membrane is washed by water for 30min, and the membrane flux is measured again to be 558.4L/m2H, feeding the ultrafiltration membrane penetrating fluid into the D463 type resin. Purifying the resin effluent in an organic membrane system, filtering by adopting a nanofiltration membrane with the molecular weight cutoff of 800Da, obtaining a clean sodium chloride solution with TOC1.2mg/L by using the operating pressure of 3.5MPa and the concentration multiple of 60 times, and feeding the sodium chloride solution into an ionic membrane electrolytic cell for preparing NaOH and Cl by an electrolytic method2Treatment, bath temperatureAt 85 ℃ and an operating current density of 2.6kA/m2And the current efficiency is 95.7%.
Example 5
The RO strong brine of the power plant is oxidized in a Fenton reactor, and Fe2+And H2O2The concentration is 120mg/L and 440mg/L respectively, the pH value of the system is 3-4, the reaction temperature is 30 ℃, and the reaction time is 90 min; the brine after the reaction is subjected to electric flocculation reaction, the electrode plate is an aluminum plate, and the current density is 250A/m2The retention time is 90 min; after the electrocoagulation treatment, the COD of the RO concentrated brine is reduced from 220mg/L to 113mg/L, then 5g/L of magnetic nano zirconium hydroxide particles are added into the electrocoagulation produced water, and NaOH0.1g/L and Na are added2CO31.06g/L, reacting in a reactor sufficiently, and then adding Ca2+、Mg2+Conversion to CaCO respectively3And Mg (OH)2Then the mixture enters an ultrafiltration membrane for filtration, the ultrafiltration membrane with the average pore diameter of 50nm is adopted, the operating pressure is 0.3MPa, the concentration is 80 times, and the stable flux of operation is 404L/m after the operation is carried out for 2 hours2H, CaCO can be removed3Precipitation and Mg (OH)2And (3) colloid, wherein the obtained ultrafiltration membrane penetrating fluid contains the following ions: mg (magnesium)2+Content 0.8mg/L, Ca2+Content 2.4mg/L, SO4 2-The content of the active carbon is reduced to 0.53g/L from 0.7g/L in raw water, the ultrafiltration membrane penetrating fluid COD is 51mg/L, the TOC is 27mg/L, and the ammonia nitrogen is 1 mg/L; after the ultrafiltration membrane runs for 8h, the permeation side is closed, the surface of the membrane is washed by water for 30min, and the membrane flux is measured again to be 614.3L/m2H, feeding the ultrafiltration membrane penetrating fluid into the D463 type resin. Purifying the resin effluent in an organic membrane system, filtering by adopting a nanofiltration membrane with the molecular weight cutoff of 800Da, obtaining a clean sodium chloride solution with TOC1.2mg/L by using the operating pressure of 3.5MPa and the concentration multiple of 60 times, and feeding the sodium chloride solution into an ionic membrane electrolytic cell for preparing NaOH and Cl by an electrolytic method2The treatment is carried out at a bath temperature of 85 ℃ and an operating current density of 2.6kA/m2And the current efficiency is 96.3 percent. The operation curve diagram of the nanofiltration membrane in the above embodiment is shown in fig. 3, and it can be seen from the diagram that the electrocoagulation liquid treated by the magnetic nano zirconium hydroxide particles can effectively keep the nanofiltration membrane operating under a better flux condition; at the same time, the magnetic nano hydrogen hydroxideThe zirconium particles can play a role of a filter aid, so that the ceramic ultrafiltration membrane is not easy to be polluted and blocked by the floccule, and has better operation stable flux and flux recovery rate, as shown in figures 4 and 5.
Claims (7)
1. A device for recycling RO strong brine is characterized by comprising:
the device (1) for removing the cationic impurities is used for removing the cationic impurities from the concentrated water obtained by the reverse osmosis filtration treatment of the circulating water of the power plant by adopting a precipitation method;
the separation membrane device (2) is used for filtering and removing the precipitate obtained in the cationic impurity removing device (1);
the ion exchange resin column (3) is used for carrying out ion exchange impurity cation removal treatment on the filtrate obtained by the separation membrane device (2);
the organic membrane (5) is used for filtering the produced water obtained by the ion exchange resin column (3);
and an ion membrane electrolyzer (6) connected to the permeation side of the organic membrane (5) and used for performing ion membrane electrolysis treatment on the purified brine of the organic membrane (5).
2. The RO strong brine recycling device according to claim 1, wherein the cation impurity removing device (1) comprises a precipitation reaction tank (9), an NaOH feeding tank (7) and Na2CO3A deposition reaction tank (9) is connected with the separation membrane device (2), and a NaOH deposition tank (7) and a Na2CO3 deposition tank are respectively used for depositing NaOH and Na into the deposition reaction tank (9)2CO3。
3. A RO brine re-use plant according to claim 1, characterized in that the separation membrane device (2) is a micro-or ultra-filtration membrane; the separation membrane in the separation membrane device (2) has an average pore diameter of 0.002-1 μm or a molecular weight cutoff of 10000-5000000 Da.
4. A re-use unit of RO brine according to claim 1 further comprising a plate and frame filter (4) for concentrating the retentate of the separation membrane unit (2), the permeate side of the plate and frame filter (4) being connected to the water inlet of the separation membrane unit (2).
5. An RO brine reuse apparatus according to claim 1, wherein the type of resin packed in the ion exchange resin column (3) is LSC-100 or S-930 or D463.
6. The apparatus of claim 1, wherein the organic membrane is made of one or more of PVC, PEEK, PES, PS, PP, PET, PVDF, etc., and has a molecular weight cut-off of 200-500000 Da.
7. The RO strong brine recycling apparatus according to claim 1, further comprising a Fenton reactor (10), an adsorption column (11) and an electric flocculator (12) connected in this order; the water production end of the electric flocculator (12) is connected with the water inlet end of the cationic impurity removing device (1); the Fenton reactor (10) is used for carrying out Fenton oxidation treatment on concentrated water obtained after reverse osmosis filtration treatment on the circulating water of the power plant; the adsorption column (11) is filled with active carbon and is used for carrying out adsorption treatment on the produced water of the Fenton reactor (10); the electric flocculator (12) is used for carrying out electric flocculation treatment on the produced water of the adsorption column (11).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526439A (en) * | 2019-04-02 | 2019-12-03 | 江苏久吾高科技股份有限公司 | A kind of reuse method and device of RO strong brine |
| CN111892224A (en) * | 2020-08-07 | 2020-11-06 | 重庆大学 | Ammonia nitrogen wastewater treatment system and method based on south of road dialysis and osmotic distillation coupling |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526439A (en) * | 2019-04-02 | 2019-12-03 | 江苏久吾高科技股份有限公司 | A kind of reuse method and device of RO strong brine |
| CN111892224A (en) * | 2020-08-07 | 2020-11-06 | 重庆大学 | Ammonia nitrogen wastewater treatment system and method based on south of road dialysis and osmotic distillation coupling |
| CN111892224B (en) * | 2020-08-07 | 2023-02-07 | 重庆大学 | Ammonia-nitrogen wastewater treatment system and method based on south crossing dialysis and osmotic distillation coupling |
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