CN215102628U - Processing system of concentrated water resourceization of high salt - Google Patents
Processing system of concentrated water resourceization of high salt Download PDFInfo
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- CN215102628U CN215102628U CN202121116919.9U CN202121116919U CN215102628U CN 215102628 U CN215102628 U CN 215102628U CN 202121116919 U CN202121116919 U CN 202121116919U CN 215102628 U CN215102628 U CN 215102628U
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Abstract
The utility model discloses a high-salinity concentrated water recycling treatment system, which comprises a buffer tank, a nanofiltration device and a reverse osmosis device which are connected in sequence, wherein the reverse osmosis device is connected with a water production outlet of the nanofiltration device, and the water production outlet of the reverse osmosis device is connected with a recycling water tank; a concentrated water outlet of the reverse osmosis device is connected with a sodium chloride evaporative crystallizer and a sodium chloride brine tank; the sodium chloride brine tank is also connected with the BPED unit, a brine outlet and an acid-base outlet are arranged on the BPED unit, and the brine outlet of the BPED unit is connected with a pipeline between the reverse osmosis device and the nanofiltration device; a concentrated water outlet of the nanofiltration device is connected with a sodium sulfate treatment unit; the sodium chloride evaporative crystallizer and the sodium sulfate processing unit are both connected with the miscellaneous salt processing unit. The utility model provides a processing system can convert salt into acid-base product, has reduced the outsourcing volume of acid-base, has realized the resource cyclic utilization of salt.
Description
Technical Field
The utility model belongs to the technical field of the water treatment, concretely relates to processing system of dense water resourceization of high salt.
Background
The wastewater generated in the energy chemical production process generally has the characteristics of high salt, high organic matter, high hardness, high silicon content and the like, the industrial wastewater treatment realizes the standard discharge and partial reuse of the wastewater through the wastewater treatment at first, and then the zero discharge of the wastewater is realized according to the further requirements of the environmental protection policy, thereby forming the necessary premise of the construction and operation of energy chemical projects. The separation of water and salt in the waste water can be effectively realized through long series connection combined process units by a general zero discharge system, wherein most suspended matters, scaling ions and organic pollutants in high-concentration brine in chemical production are removed by a front-end main process unit, water and salt are separated by a tail end salt separating technology, and produced water is recycled, so that the resource recycling of the water is basically realized. With the realization of zero discharge of wastewater, the environmental protection department requires to band the salt solarization pool, definitely the miscellaneous salt is solid dangerous waste and to gradually cancel the piling of the miscellaneous salt, and requires the resource utilization of the waste salt slag dissolved in water at the tail end of zero discharge, thereby greatly promoting the innovation and development of technical researchers to develop the waste salt resource utilization process.
Nanofiltration (NF) salt separation, hot salt separation and cold-hot salt separation are common salt separation technologies of zero emission systems in the existing coal chemical industry, wherein a 'NF + evaporation' coupling process is a feasible design of concentrated salt water and salt at the present stage, but in the operation of an actual system, because the front-end treatment is incomplete, the difficulty of nanofiltration salt separation is increased, salt deposition and blockage of an evaporation unit are serious, and the long-period stable operation capacity of the zero emission system is weakened. The generated mixed salt mainly comprises NaCl and Na2SO4The mixed salt is further treated to remove organic impurities and can be used as industrial raw materials, the secondary application and operation cost is relatively high, and the added value of the product is relatively low. Conventional disposal technical bag for waste saltThe treatment is inconsistent with the waste salt reduction, harmless and resource utilization principles, so that the upstream and downstream industries are disconnected, the comprehensive utilization cannot be realized, and the resource waste is caused. On the other hand, 50-70% of mixed salt obtained by separating the energy chemical wastewater is a product of adding medicament acid and alkali in the industrial production process. Therefore, if the strong brine can be converted into the acid and alkali which can be used by the system, the generated acid and alkali can be used as a main device for adjusting pH, chemically cleaning, regenerating a resin bed and the like, and solid waste and secondary pollution are not generated, the recycling economy of waste salt recycling and energy chemical industry can be fully realized, and the significance is great.
SUMMERY OF THE UTILITY MODEL
To prior art's defect, the utility model provides a processing system of dense water resourceization of high salt can realize waste salt recycle, has reduced the pollution of waste salt and has piled up, has reduced zero release running cost.
A treatment system for recycling high-salinity concentrated water comprises a buffer tank, a nanofiltration device and a reverse osmosis device which are sequentially connected, wherein a produced water outlet and a concentrated water outlet are formed in the nanofiltration device and the reverse osmosis device respectively, the reverse osmosis device is connected with the produced water outlet of the nanofiltration device, and the produced water outlet of the reverse osmosis device is connected with a reuse water tank;
a concentrated water outlet of the reverse osmosis device is connected with a sodium chloride evaporative crystallizer and a sodium chloride brine tank; the sodium chloride brine tank is also connected with the BPED unit, the BPED unit is provided with a brine outlet and an acid-base outlet, the acid-base outlet of the BPED unit is respectively connected with the acid tank and the base tank through pipelines, and the brine outlet of the BPED unit is connected with a pipeline between the reverse osmosis device and the nanofiltration device;
a concentrated water outlet of the nanofiltration device is connected with a sodium sulfate treatment unit;
the sodium chloride evaporative crystallizer and the sodium sulfate processing unit are both connected with the miscellaneous salt processing unit.
Preferably, the sodium sulfate treatment unit comprises a freezing crystallizer, an ozone catalytic oxidation device and a filter are sequentially connected to the freezing crystallizer, and the filter is also connected with a buffer tank; the freezing crystallizer is also sequentially connected with a hot melting tank and a sodium sulfate evaporation crystallizer; the freezing crystallizer is connected with a concentrated water outlet of the nanofiltration device.
Preferably, the mixed salt treatment unit comprises a mixed salt evaporative crystallizer and a mother liquor drying system which are connected in sequence, and the mixed salt evaporative crystallizer is respectively connected with the sodium chloride evaporative crystallizer and the sodium sulfate evaporative crystallizer.
Preferably, the BPED unit is provided with a pH meter on a pipeline connected with the acid tank and the alkali tank respectively.
Preferably, the filter is a multimedia filter, a V-bank filter or a fiber filter.
Preferably, the miscellaneous salt evaporative crystallizer is a forced circulation evaporative crystallizer.
Preferably, the mother liquor drying system is a vacuum drum dryer or a spray dryer.
A treatment method for recycling high-salinity concentrated water adopts the treatment system for recycling high-salinity concentrated water to treat, and comprises the following steps:
(1) the wastewater enters a nanofiltration device from a buffer tank and is filtered by the nanofiltration device to be subjected to salt separation treatment; the operating pressure of the nanofiltration device is 3.5-30bar, the TDS of the inlet water is 30000-40000mg/L, the recovery rate is 90%, and the sulfate radical rejection rate is more than or equal to 97%;
(2) the produced water filtered by the nanofiltration device enters a reverse osmosis device for concentration, and the reverse osmosis produced water flows into a reuse water tank; part of reverse osmosis concentrated water is decompressed and then enters a BPED unit through a sodium chloride brine tank, generated acid and alkali respectively enter an acid tank and an alkali tank after being detected by a pH meter to meet the acidity requirement under the action of an electric field of the BPED unit, and generated brine flows back to a reverse osmosis device; the other part of the reverse osmosis concentrated water is decompressed and then enters a sodium chloride evaporation crystallizer to generate a sodium chloride product;
(3) the concentrated water filtered by the nanofiltration device enters a sodium sulfide treatment unit, passes through a freezing crystallizer, and the separated crystals enter a hot melting tank and then enter a sodium sulfate evaporation crystallizer to obtain a sodium sulfate product; oxidizing the frozen clear liquid generated by the freezing crystallizer by an ozone catalyst oxidizer to remove COD, filtering by a filter, and refluxing the filtered water to a buffer tank;
(4) mother liquor generated by the sodium chloride evaporation crystallizer and the sodium sulfate evaporation crystallizer enter the mixed salt evaporation crystallizer, and the mother liquor generated by the mixed salt evaporation crystallizer is dried by a mother liquor drying system to obtain the mixed salt.
Preferably, the TDS of the mother liquor generated by the miscellaneous salt evaporative crystallizer is less than or equal to 1000mg/L, COD and less than or equal to 500 mg/L.
Preferably, the mother liquor drying system is a vacuum drum dryer or a spray dryer; the temperature of the vacuum drum dryer is 60-90 ℃, the pressure is 55kPa-70kPa, and the clearance between the scraper and the drum is not less than 0.6 mm.
The BPED of the utility model is bipolar membrane electrodialysis.
The utility model has the advantages that:
1. the treatment system provided by the utility model converts salt into acid-base products, and the generated acid-base can be used for sewage acid-base regulation, ion exchange resin regeneration, chemical cleaning and the like in a garden, so that the outsourcing amount of acid-base is reduced, and the resource recycling of salt is realized;
2. the salt is separated by nanofiltration and is electrolyzed by the BPED membrane stack, so that the resource utilization rate of the salt is improved, the generation of the amount of miscellaneous salt is reduced, and the disposal cost of solid waste is reduced.
Drawings
FIG. 1 is a schematic view of a high-salinity concentrated water recycling treatment system of the present invention;
the device comprises a buffer tank 1, a nanofiltration device 2, a reverse osmosis device 3, a sodium chloride brine tank 4, a BPED 5, an acid tank 6, an alkali tank 7, a sodium chloride evaporative crystallizer 8, a miscellaneous salt evaporative crystallizer 9, a mother liquor drying system 10, a freezing crystallizer 11, an ozone catalytic oxidizer 12, a filter 13, a hot melting tank 14, a sodium sulfate evaporative crystallizer 15 and a recycling water tank 16.
Detailed Description
Example 1
A treatment system for recycling high-salinity concentrated water comprises a buffer tank 1, a nanofiltration device 2 and a reverse osmosis device 3 which are sequentially connected, wherein both the nanofiltration device 2 and the reverse osmosis device 3 are provided with a produced water outlet and a concentrated water outlet, the reverse osmosis device 3 is connected with the produced water outlet of the nanofiltration device 2, and the produced water outlet of the reverse osmosis device 3 is connected with a reuse water tank 16;
a concentrated water outlet of the reverse osmosis device 3 is connected with a sodium chloride evaporative crystallizer 8 and a sodium chloride brine tank 4; the sodium chloride brine tank 4 is also connected with a BPED unit 5, a brine outlet and an acid-base outlet are formed in the BPED unit 5, the acid-base outlet of the BPED unit 5 is respectively connected with an acid tank 6 and an alkali tank 7 through pipelines, the brine outlet of the BPED unit 5 is connected with a pipeline between the reverse osmosis device 3 and the nanofiltration device 2, and brine generated by the BPED unit 5 flows back to the reverse osmosis device 3;
a concentrated water outlet of the nanofiltration device 2 is connected with a sodium sulfate treatment unit, and the sodium sulfate treatment unit is used for treating concentrated water generated by nanofiltration to obtain sodium sulfate;
the sodium chloride evaporative crystallizer 8 and the sodium sulfate processing unit are both connected with the mixed salt processing unit, and the mixed salt processing unit further processes the liquid discharged by the sodium chloride evaporative crystallizer 8 and the sodium sulfate processing unit to recover the salt in the liquid.
In the embodiment, the high-salinity wastewater is separated from monovalent salt and divalent salt through a nanofiltration device 2, divalent ions are mainly used in nanofiltration concentrated water, salt components mainly comprise sodium sulfate and a small amount of sodium chloride; the main salt component in the nanofiltration product water is monovalent salt sodium chloride, after further concentration by reverse osmosis, the reverse osmosis product water enters a reuse water tank 16, and the reverse osmosis concentrated water enters a BPED unit, so that the sodium chloride solution entering the BPED is ensured to be in a reasonable concentration range; after the reverse osmosis concentrated water is decompressed, one part of the reverse osmosis concentrated water enters the BPED through the sodium chloride brine tank 4, and the sodium chloride brine tank 4 can ensure the stable water coming from the BPED; the other part enters a sodium chloride evaporative crystallizer 8, and sodium chloride products are separated after evaporative crystallization;
under the action of a direct current electric field, chloride ions migrate to an acid chamber through a negative membrane in BPED, and when encountering a positive membrane surface of the bipolar membrane, the chloride ions cannot continuously migrate due to the negative charge of the positive membrane surface, remain in the acid chamber and combine with hydrogen ions decomposed from the positive membrane surface of the bipolar membrane to generate hydrochloric acid; similarly, sodium ions migrate to the alkaline chamber through the positive membrane and meet the negative membrane surface of the bipolar membrane, and because the positive electricity is generated on the positive membrane surface, the sodium ions cannot continuously migrate and are left in the alkaline chamber to be combined with hydroxide ions continuously decomposed from the negative membrane surface of the bipolar membrane under the action of the direct-current electric field to generate sodium hydroxide; thus, acid radical ions in the salt chamber continuously enter the acid chamber, so that the concentration of the acid liquor is continuously improved; sodium ions continuously enter the alkali chamber to receive hydroxide ions decomposed by the bipolar membrane, and the concentration of the alkali solution is continuously improved. Finally, sodium chloride is converted into hydrochloric acid and sodium hydroxide solution through bipolar membrane electrodialysis.
Example 2
On the basis of embodiment 1, the sodium sulfate treatment unit comprises a freezing crystallizer 11, an ozone catalytic oxidation device 12 and a filter 13 are sequentially connected to the freezing crystallizer 11, and the filter 13 is also connected to the buffer tank 1; the freezing crystallizer 11 is also sequentially connected with a hot melting tank 14 and a sodium sulfate evaporation crystallizer 15; the freezing crystallizer 11 is connected with a concentrated water outlet of the nanofiltration device 2.
In the embodiment, nanofiltration concentrated water passes through a freezing crystallizer 11, the solubility of sodium sulfate is rapidly reduced along with the reduction of the temperature at 0-100 ℃ by utilizing the principle of the solubility difference of sodium sulfate and sodium chloride in a low-temperature medium, and the sodium chloride is basically kept unchanged, so that sodium sulfate decahydrate crystals are crystallized and separated out in a cooling and freezing mode; the frozen clear liquid generated by freezing crystallization is subjected to ozone oxidation to remove COD in the frozen clear liquid, is further filtered by a filter 13 and returns to the buffer tank 1; sodium sulfate decahydrate crystals separated by freezing crystallization are subjected to hot melting in a hot melting tank 14, and then are subjected to evaporation crystallization to obtain sodium sulfate salt.
Example 3
On the basis of embodiment 2, the mixed salt treatment unit comprises a mixed salt evaporative crystallizer 9 and a mother liquor drying system 10 which are sequentially connected, wherein the mixed salt evaporative crystallizer 9 is respectively connected with a sodium chloride evaporative crystallizer 8 and a sodium sulfate evaporative crystallizer 15.
Mother liquor discharged from the sodium chloride evaporation crystallizer 8 and the sodium sulfate evaporation crystallizer 15 enters the mixed salt evaporation crystallizer 9 to separate out mixed salt, and the mother liquor discharged from the mixed salt evaporation crystallizer 9 is dried to further recover the mixed salt.
Example 4
On the basis of embodiment 3, the pipelines of the BPED unit 5 connected with the acid tank 6 and the alkali tank 7 are respectively provided with a pH meter, and when the generated acid and alkali reach the required concentration, the generated acid and alkali are respectively conveyed to the acid tank 6 and the alkali tank 7.
Example 5
On the basis of the embodiment 4, the filter 13 is a multi-media filter, a V-shaped filter pool or a fiber filter; the miscellaneous salt evaporative crystallizer 9 is a forced circulation evaporative crystallizer; the mother liquor drying system 10 is a vacuum drum dryer or a spray dryer.
Example 6
A treatment method for recycling high-salinity concentrated water adopts the treatment system for recycling high-salinity concentrated water to treat, and comprises the following steps:
(1) the wastewater enters a nanofiltration device 2 from a buffer tank 1 and is filtered by the nanofiltration device 2 to be subjected to salt separation treatment; the operating pressure of the nanofiltration device 2 is 3.5-30bar, the TDS of the inlet water is 30000-40000mg/L, the recovery rate is 90%, and the sulfate radical rejection rate is more than or equal to 97%;
(2) the produced water filtered by the nanofiltration device 2 enters a reverse osmosis device 3 for concentration, and the reverse osmosis produced water flows into a reuse water tank 16; part of reverse osmosis concentrated water is decompressed and then enters a BPED unit 5 through a sodium chloride brine tank 4, under the action of an electric field of the BPED unit 5, generated acid and alkali reach acidity requirements through pH meter detection and then respectively enter an acid tank 6 and an alkali tank 7, and generated brine flows back to a reverse osmosis device 3; the other part of the reverse osmosis concentrated water enters a sodium chloride evaporation crystallizer 8 after being decompressed to generate a sodium chloride product, wherein the quality of the sodium chloride product is not lower than the index requirement of a first-grade industrial wet salt in the GBT5462-2015 standard of Industrial salt;
(3) the concentrated water filtered by the nanofiltration device 2 enters a sodium sulfide treatment unit, passes through a freezing crystallizer 11, and the separated crystals enter a hot melting tank 14 and then enter a sodium sulfate evaporation crystallizer 15 to obtain a sodium sulfate product; the frozen clear liquid generated by the freezing crystallizer 11 is oxidized by an ozone catalyst oxidizer to remove COD, and then is filtered by a filter 13, the filtered water flows back to a buffer tank 1, and the quality of the product sodium sulfate is not lower than the standard requirement of second-class qualified products in the standard of GBT 6009-;
(4) mother liquor generated by the sodium chloride evaporation crystallizer 8 and the sodium sulfate evaporation crystallizer 15 enters the mixed salt evaporation crystallizer 9, and the mother liquor generated by the mixed salt evaporation crystallizer 9 is dried by the mother liquor drying system 10 to obtain the mixed salt.
Example 7
Taking a zero emission project of a sewage plant in a certain petrochemical industry base as an example, the method of the embodiment 6 is adopted, the adopted mother liquor drying system 10 is a vacuum drum dryer, the temperature of the vacuum drum dryer is 60-90 ℃, the pressure is 55kPa-70kPa, and the clearance between a scraper and a drum is not less than 0.6 mm; nanofiltration influent TDS 35500mg/L and water amount 241m3The recovery rate is 90%, the TDS of the BPED inlet water is 10.9 ten thousand mg/L, and the quality of other inlet water is shown in Table 1.
The mixture enters a BPED unit to separate 8 percent of sodium hydroxide product and 7.3 percent of hydrochloric acid product, and 22.5 tons of 7.3 percent hydrochloric acid is produced per hour, and 22.5 tons of 8.0 percent sodium hydroxide is produced per hour;
TDS of mother liquor generated by the miscellaneous salt evaporation crystallizer is less than or equal to 1000mg/L, COD and less than or equal to 500 mg/L;
the water inflow of the sodium chloride evaporative crystallizer is 23.7m3The TDS of the inlet water is 10.9 ten thousand mg/L, and 2.2 tons of sodium chloride are produced per hour; the water inflow of the freezing crystallizer is 24.1m3The TDS is 7.6 ten thousand mg/L, and 1.46 tons of sodium sulfate is produced per hour; 0.64 ton of miscellaneous salt;
the final acid and alkali yield after treatment and the garden requirement are shown in the following table 2, the acid yield is higher than the acid yield required by the garden, the alkali yield is lower than the alkali yield required by the garden, and the medicament cost and the solid waste treatment cost are fully reduced.
The implementation effect is as follows: the BPED process is adopted to prepare acid and alkali from sodium chloride, the acid and alkali can be reused in sewage plants in chemical industrial parks or industrial parks, in the aspect of operation, the saved acid and alkali amount is 3-4 yuan/ton of water, so that partial energy consumption of the BPED can be offset, the salt content is greatly reduced, and the produced acid and alkali products can be completely applied to the sewage plants in the parks, so that the acid and alkali consumption in the parks is reduced, and the problem of unsmooth sale of a large amount of product salt (sodium chloride) can be avoided.
Claims (7)
1. The utility model provides a processing system of concentrated water resourceization of high salt which characterized in that: the device comprises a buffer tank (1), a nanofiltration device (2) and a reverse osmosis device (3) which are connected in sequence, wherein a produced water outlet and a concentrated water outlet are respectively arranged on the nanofiltration device (2) and the reverse osmosis device (3), the reverse osmosis device (3) is connected with the produced water outlet of the nanofiltration device (2), and the produced water outlet of the reverse osmosis device (3) is connected with a reuse water tank (16); a concentrated water outlet of the reverse osmosis device (3) is connected with a sodium chloride evaporative crystallizer (8) and a sodium chloride brine tank (4); the sodium chloride brine tank (4) is also connected with a BPED unit (5), a brine outlet and an acid-base outlet are formed in the BPED unit (5), the acid-base outlet of the BPED unit (5) is respectively connected with an acid tank (6) and an alkali tank (7) through pipelines, and the brine outlet of the BPED unit (5) is connected with a pipeline between the reverse osmosis device (3) and the nanofiltration device (2); a concentrated water outlet of the nanofiltration device (2) is connected with a sodium sulfate treatment unit; the sodium chloride evaporative crystallizer (8) and the sodium sulfate processing unit are both connected with the mixed salt processing unit.
2. The high-salinity concentrated water recycling treatment system according to claim 1, characterized in that: the sodium sulfate treatment unit comprises a freezing crystallizer (11), an ozone catalytic oxidation device (12) and a filter (13) are sequentially connected to the freezing crystallizer (11), and the filter (13) is also connected with the buffer tank (1); the freezing crystallizer (11) is also sequentially connected with a hot melting tank (14) and a sodium sulfate evaporation crystallizer (15); the freezing crystallizer (11) is connected with a concentrated water outlet of the nanofiltration device (2).
3. The high-salinity concentrated water recycling treatment system according to claim 2, characterized in that: the mixed salt treatment unit comprises a mixed salt evaporation crystallizer (9) and a mother liquor drying system (10) which are sequentially connected, wherein the mixed salt evaporation crystallizer (9) is respectively connected with a sodium chloride evaporation crystallizer (8) and a sodium sulfate evaporation crystallizer (15).
4. The high-salinity concentrated water recycling treatment system according to claim 3, characterized in that: and the BPED unit (5) is respectively provided with a pH meter on a pipeline connected with the acid tank (6) and the alkali tank (7).
5. The high-salinity concentrated water recycling treatment system according to claim 2, characterized in that: the filter (13) is a multi-media filter, a V-shaped filter or a fiber filter.
6. The high-salinity concentrated water recycling treatment system according to claim 3, characterized in that: the miscellaneous salt evaporative crystallizer (9) is a forced circulation evaporative crystallizer.
7. The high-salinity concentrated water recycling treatment system according to claim 3, characterized in that: the mother liquor drying system (10) is a vacuum drum dryer or a spray dryer.
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| CN113173674A (en) * | 2021-05-24 | 2021-07-27 | 陕西省石油化工研究设计院 | High-salinity concentrated water recycling treatment system and method |
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Address after: No.61 Xiyan Road, Yanta District, Xi'an City, Shaanxi Province, 710054 Patentee after: Shaanxi Chemical Research Institute Co.,Ltd. Address before: No.61 Xiyan Road, Yanta District, Xi'an City, Shaanxi Province, 710054 Patentee before: SHAANXI RESEARCH DESIGN INSTITUTE OF PETROLEUM CHEMICAL INDUSTRY |
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