CN210419644U - Contain clean system of salt organic waste water - Google Patents
Contain clean system of salt organic waste water Download PDFInfo
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- CN210419644U CN210419644U CN201921134740.9U CN201921134740U CN210419644U CN 210419644 U CN210419644 U CN 210419644U CN 201921134740 U CN201921134740 U CN 201921134740U CN 210419644 U CN210419644 U CN 210419644U
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- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The utility model relates to a purification system for organic wastewater containing salt, which comprises a chemical softening and hardness removing device, an ion exchange device, a membrane separation and concentration device, an organic matter separation device, a Fenton oxidation device and a biochemical oxidation device which are sequentially communicated, wherein a discharge port of the biochemical oxidation device is communicated with a feeding port of the chemical softening and hardness removing device; the ion exchange device is provided with a discharge hole, an acid waste liquid outlet and an alkali waste liquid outlet, the discharge hole of the ion exchange device is communicated with the feeding hole of the membrane separation and concentration device, the acid waste liquid outlet is communicated with the feeding hole of the Fenton oxidation device, and the alkali waste liquid outlet is communicated with the feeding hole of the biochemical oxidation device. In the organic matter removing process, the purification system utilizes regenerated acid, alkali waste liquid, sludge produced by preoxidation, sodium chloride crystal salt produced by evaporative crystallization and the like of ion exchange to the maximum extent, so that the investment is saved, and the resource waste and the secondary pollution to the environment are avoided.
Description
Technical Field
The utility model relates to a waste water treatment technical field especially relates to a contain organic waste water's of salt clean system.
Background
The high-salt water mainly comes from industries such as coal chemical industry, printing and dyeing, electric power, electronics and the like, and comprises concentrated water after reclaimed water is recycled, sewage water of a cooling circulating water system, drainage of a chemical water station and the like. High-salinity water contains a large amount of organic matter in addition to inorganic salts. In recent years, environmental protection departments in many areas are concerned about not only the standard discharge of wastewater, but also the maximum recycling of high-salinity water by enterprises, and particularly in environmentally sensitive areas, the wastewater is not discharged, so that the zero discharge of the high-salinity wastewater is realized. In the zero-emission treatment process, the existence of organic matters not only influences the use effect and the service life of the membrane element, but also influences the evaporation crystallization process at the rear end and the quality of crystallized salt. Therefore, in the zero discharge treatment process of the high-salt wastewater, the removal of organic matters is imperative.
At present, the technologies for removing organic matters in high-salt water mainly comprise activated carbon adsorption, incineration, deep oxidation, high-salt biochemical treatment and the like. The activated carbon adsorption is to adsorb and remove organic matters in the high-salinity wastewater by utilizing the porous adsorption of granular activated carbon or powdered activated carbon. The activated carbon is difficult to regenerate after being adsorbed and saturated, the secondary utilization is difficult, and the solid waste yield is high. The incineration method is to incinerate the organic matters in the wastewater at 800-1000 ℃. The incineration method is suitable for waste water with high organic matter content, has the defects of high equipment investment and high operation cost, and seriously corrodes incineration equipment due to the high content of chloride ions in high-salt water. The deep oxidation method is to utilize hydroxyl radicals generated by the reaction of ozone or other oxidants to react with organic matters in the wastewater, and the organic matters are mineralized to generate carbon dioxide and water which are removed from the system. The deep oxidation technology is an organic matter removal technology commonly used for water treatment at present, but the deep oxidation technology still has the problems of large oxidant consumption, high operation cost, low treatment efficiency and large influence by water quality fluctuation, and the removal rate is generally between 30 and 60 percent. The high salt biochemical method is to culture salt-tolerant microbes and degrade the microbes to eliminate organic matters in water in high salt condition. Because the biochemical property of organic matters in high-salt water is generally poor, the water quality fluctuation is large, and the halotolerant bacteria are difficult to culture, the high-salt biochemical method is still in a research stage at present and is not applied practically. The above processes have a certain removal effect on organic matters in the high-salt-content wastewater, but the problems of high equipment investment, high operation cost, low treatment efficiency and large influence of water quality fluctuation generally exist, and meanwhile, the processes such as incineration, activated carbon adsorption and the like also generate waste gas, solid waste and hazardous waste in the treatment process, so that secondary pollution is caused.
SUMMERY OF THE UTILITY MODEL
Therefore, the purification system for the salt-containing organic wastewater, which has the advantages of high organic matter removal efficiency, low operation cost and no generation of solid waste and hazardous waste, is needed to be provided.
A purification system for salt-containing organic wastewater comprises a chemical softening and hardness-removing device, an ion exchange device, a membrane separation and concentration device, an organic matter separation device, a Fenton oxidation device and a biochemical oxidation device which are sequentially communicated, wherein a discharge port of the biochemical oxidation device is communicated with a feed port of the chemical softening and hardness-removing device; the ion exchange device is provided with a discharge hole, an acid waste liquid outlet and an alkali waste liquid outlet, the discharge hole of the ion exchange device is communicated with the feeding hole of the membrane separation and concentration device, the acid waste liquid outlet is communicated with the feeding hole of the Fenton oxidation device, and the alkali waste liquid outlet is communicated with the feeding hole of the biochemical oxidation device.
The utility model discloses a clean system removes hard device and ion exchange unit etc. at first through chemical softening, makes hardness, basicity, silica, suspended solid etc. in the high salt waste water obtain getting rid of more thoroughly. Then the inorganic salt and organic matter in the high-salinity water are synchronously concentrated by a membrane separation and concentration device, the TDS of the concentrated produced water can reach more than 10000mg/L, and the concentration of the organic matter can reach more than 150 mg/L. The concentrated produced water enters an organic matter separation device, the separated wastewater enters a Fenton oxidation device and then enters a biochemical oxidation device, and a large amount of organic matters are removed in the biochemical oxidation device. The utility model discloses a clean system has following beneficial effect: the COD (chemical oxygen demand) is removed by adopting the processes of pretreatment, membrane concentration, organic matter separation, Fenton oxidation and biochemical oxidation, the total removal rate of the COD can reach more than 60 percent, the organic matter is prevented from being directly mineralized by adopting an advanced oxidation device, and the investment and the operation cost are greatly reduced; the adoption of the Fenton oxidation device for pre-oxidation effectively improves the B/C ratio (biodegradability, BOD/COD), and utilizes the regenerated acid waste liquid and the regenerated alkali waste liquid obtained by the ion exchange device to respectively adjust the pH values of the system before and after Fenton oxidation, thereby reducing the acid-base consumption of oxidation treatment and simultaneously avoiding the additional treatment operation on the regenerated acid waste liquid and the regenerated alkali waste liquid.
In one embodiment, the device further comprises a sludge dewatering device, wherein the chemical softening hardness removing device and the biochemical oxidation device are provided with sewage outlets, and the sewage outlet of the chemical softening hardness removing device and the sewage outlet of the biochemical oxidation device are communicated with the sludge dewatering device.
In one embodiment, the chemical softening and hardness removing device further comprises a pre-oxidation sludge acidification pool and a hydrochloric acid tank, wherein the Fenton oxidation device is provided with a drain outlet, the drain outlet of the Fenton oxidation device and the hydrochloric acid tank are both communicated with a feeding inlet of the pre-oxidation sludge acidification pool, and a discharge outlet of the pre-oxidation sludge acidification pool is communicated with a feeding inlet of the chemical softening and hardness removing device.
In one embodiment, the system further comprises an evaporation salt separation device, wherein the organic matter separation device is provided with a water production port and a sewage port, the sewage port of the organic matter separation device is communicated with the feed port of the Fenton oxidation device, the water production port of the organic matter separation device is communicated with the feed port of the evaporation salt separation device, and the evaporation salt separation device is provided with a crystallized salt outlet which is communicated with the feed port of the organic matter separation device.
In one embodiment, the device further comprises a dilution tank arranged between the Fenton oxidation device and the biochemical oxidation device, and the alkaline waste liquid outlet is communicated with the feeding port of the biochemical oxidation device through the dilution tank.
In one embodiment, the evaporation salt separation device is further provided with a condensed water outlet which is communicated with the dilution pool.
In one embodiment, the system further comprises a miscellaneous salt evaporation device, the sewage port of the organic matter separation device is further communicated with the feeding port of the miscellaneous salt evaporation device, and a TDS detector and a water volume detector are arranged in the organic matter separation device and are respectively used for detecting TDS and water volume of the waste water separated in the organic matter separation device.
In one embodiment, the device further comprises a precise filtering device arranged between the chemical softening and hardness removing device and the ion exchange device, wherein the precise filtering device is one or more of a sand filtering device, a micro-filtering device and an ultrafiltration device.
In one embodiment, the system further comprises a homogenizing and homogenizing equalizing tank which is arranged upstream of the chemical softening and hardness removing device and communicated with the chemical softening and hardness removing device.
In one embodiment, the chemical softening and hardness removing device is one or more of a high-density sedimentation tank, a mechanical accelerated clarification tank, a V-shaped filter tank, a sand filter tank and a multi-media filter.
Drawings
Fig. 1 is a schematic structural diagram of a purification system for salt-containing organic wastewater according to an embodiment.
Detailed Description
In order to facilitate understanding of the present invention, the present invention will be described more fully below, and preferred embodiments of the present invention will be described. The invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The utility model relates to a purification method of salt-containing organic wastewater, which comprises the following steps S1-S6:
and S1, chemically softening and removing hardness of the salt-containing organic wastewater to obtain softened water.
And S2, performing ion exchange treatment on the softened water to obtain ion exchange water, acid waste liquid and alkali waste liquid. It can be understood that in the process of ion exchange treatment, the ion exchange resin is saturated in adsorption after being used for a period of time, and needs to be regenerated by acid and alkali, so that acid waste liquid and alkali waste liquid can be obtained.
And S3, carrying out membrane separation and concentration on the ion exchange produced water to obtain concentrated produced water and recyclable reuse water.
And S4, carrying out organic matter separation treatment on the concentrated produced water to obtain separated wastewater.
And S5, adding the acid waste liquid into the separation waste water, and then performing Fenton oxidation treatment to obtain preoxidation water.
And S6, adding the alkali waste liquid into the pre-oxidation produced water, then carrying out biochemical oxidation treatment to obtain biochemical produced water, and mixing the biochemical produced water with the salt-containing organic wastewater for recycling.
The purification method of the utility model firstly removes the hardness and the ion exchange treatment by chemical softening, and thoroughly removes the hardness, the alkalinity, the silicon dioxide, the suspended solids and the like in the high-salinity wastewater. Then, inorganic salt and organic matters in the high-salinity water are synchronously concentrated through membrane separation and concentration, the treated water amount is greatly reduced, the TDS of the concentrated produced water can reach more than 10000mg/L, and the concentration of the organic matters can reach more than 150 mg/L. And (4) carrying out organic matter separation treatment on the concentrated produced water, wherein the organic matter separation efficiency is more than 70%, and the separation wastewater amount produced by the organic matter separation treatment is less than 10%. And performing Fenton oxidation treatment on the separated wastewater, and performing biochemical oxidation treatment, wherein a large amount of organic matters are removed in the biochemical oxidation process. The utility model discloses a purification method has following beneficial effect: COD (chemical oxygen demand) is removed by adopting the modes of pretreatment, membrane concentration, organic matter separation, Fenton oxidation and biochemical oxidation, the total removal rate of the COD can reach more than 60 percent, the organic matter is prevented from being directly mineralized by adopting an advanced oxidation system, and the investment and the operation cost are greatly reduced; the Fenton pre-oxidation is adopted, the B/C ratio (biodegradability, BOD/COD) is effectively improved, the pH values of reaction systems before and after Fenton oxidation treatment are respectively adjusted by using the regenerated acid waste liquid and the regenerated alkali waste liquid obtained by ion exchange treatment, the acid-base consumption of the oxidation treatment is reduced, and the additional treatment operation on the regenerated acid waste liquid and the regenerated alkali waste liquid is avoided.
In one specific example, the chemical softening and hardness removal comprises one or more of high-density precipitation treatment, mechanical accelerated clarification treatment, V-shaped filter tank filtration treatment, sand filter tank treatment and multi-medium filtration treatment, and during the chemical softening and hardness removal, lime, sodium carbonate, sodium hydroxide, a coagulant, a flocculant and the like are added to treat the high-salinity wastewater within a preset time. After the chemical softening and hardness removal treatment, most of calcium, magnesium, heavy metals, total alkalinity, suspended matters, partial organic matters, silicon dioxide, fluorine ions and the like in the high-salt wastewater are effectively removed, and the stable operation of a subsequent system is guaranteed. It is understood that the salt-containing organic wastewater may also be subjected to a homogeneous homogenization treatment before being subjected to chemical softening and hardness removal.
In one specific example, the purification method further comprises the steps of: the softened product water is subjected to microfiltration selected from one or more of sand filtration, microfiltration and ultrafiltration prior to the ion exchange treatment. Through the microfiltration, colloid, particulate matter, macromolecular organic matters, microorganisms and the like in water can be further removed, the SDI (sludge density index) of effluent is less than 3, and the turbidity is less than 0.5 NTU. And (3) carrying out ion exchange treatment on the softened water produced after the microfiltration to further remove hardness, wherein the total hardness of the ion exchange water produced is less than 10mg/L (calculated by calcium carbonate).
In one particular example, the membrane separation concentration includes one or more of reverse osmosis, nanofiltration, electrodialysis, and forward osmosis. After membrane separation and concentration treatment, the product water can be directly recycled, the TDS of the concentrated produced water reaches more than 10000mg/L, organic matters are also enriched, and the concentration of the organic matters is more than 150 mg/L.
In a specific example, the organic matter separation treatment is one or more selected from roll-to-roll ultrafiltration treatment, nanofiltration treatment, reverse osmosis treatment and resin adsorption treatment, and the separated wastewater obtained from the organic matter separation treatment is subjected to fenton pre-oxidation treatment. Further, the step of organic matter separation treatment also obtains separation produced water, the separation produced water is evaporated to separate salt to obtain crystal salt, the crystal salt such as sodium chloride is used for regenerating the adsorption resin used in the organic matter separation treatment, and the regenerated waste liquid is waste water rich in organic matters and is subjected to Fenton pre-oxidation treatment. Optionally, the crystalline salt comprises one or more of sodium chloride, sodium sulfate, and sodium nitrate. The adsorption resin in the organic matter separation treatment uses sodium chloride and the like generated by evaporating and separating salt as a regeneration medicament, so that the introduction of external chemical medicaments is avoided, and the system load and the operation cost can be further reduced. Preferably, when the TDS of the separated wastewater is more than or equal to 80000mg/L and the water quantity is less than or equal to 2m3During the reaction, the separated waste water can also directly enter mixed salt evaporation equipmentEvaporating and crystallizing, and discharging in mixed salt form when the TDS of the separated wastewater is less than 80000mg/L or the water amount is more than 2m3During the/h, then get into fenton oxidation unit and handle, select different processing routes according to the quality of water of separation waste water so, can make the purifying process more reasonable and high-efficient.
In one specific example, the pH value of the separated wastewater is controlled to be less than 3.5 by adding the acid waste liquid, and then H is added2O2And Fe2+Performing Fenton oxidation treatment, oxidizing the organic matters in the separated wastewater, opening a ring and breaking a chain, and improving B/C to obtain preoxidation water. Further, adding alkali waste liquid into the pre-oxidation water, adjusting the pH value to 6.5-8.5, and then carrying out subsequent treatment.
In one embodiment, the step of separating the evaporated produced water to separate the salt may further comprise evaporating condensed water, and the evaporating condensed water is used to dilute the pre-oxidation produced water to a TDS of less than 5000mg/L and a temperature of 25 ℃ to 30 ℃ before the biochemical oxidation treatment. The evaporation condensate water obtained by evaporation salt separation is used as a water source to dilute the pre-oxidation product water after Fenton pre-oxidation, the TDS of the inlet water of the biochemical oxidation device is ensured to be less than 5000mg/L, the inhibition and toxicity of salt to the growth of microorganisms can be prevented, meanwhile, the temperature of the condensate water is high, the inlet water temperature entering the biochemical oxidation device can be flexibly adjusted after being mixed with the pre-oxidation product water, the efficient propagation of the microorganisms is facilitated, and the biochemical effect is enhanced.
In a specific example, the fenton oxidation treatment step can also obtain pre-oxidized sludge which is mainly iron salt, and the ferric chloride solution is prepared by adding hydrochloric acid and can be used as a coagulant for chemical softening and hardness removal. The main component of the sludge obtained by Fenton oxidation reaction is iron salt generated in situ, the flocculation effect is good, the iron salt coagulant is prepared by adding hydrochloric acid and is used for chemical softening and hardness removal, the using amount of the chemical softening and coagulation flocculant can be effectively reduced, and the operation cost is reduced.
In one specific example, the biochemical oxidation treatment comprises one or more of multi-stage a/O (anaerobic-aerobic activated sludge process), SBR (sequencing batch activated sludge process), MBR (membrane bioreactor process) and biological aerated filter process, and the biochemical produced water COD is less than 100mg/L after the biochemical oxidation treatment. Further, softened sludge can be obtained in the chemical softening hardness removing step, biochemical sludge can be obtained in the biochemical oxidation treatment step, and the softened sludge and the biochemical sludge are mixed and then dehydrated and then discharged for outward transportation and disposal. The softened sludge is mixed with the biochemical sludge, so that the biochemical sludge is favorably digested, the filter-pressing dehydration is convenient, and the water content of the dehydrated sludge can reach below 60 percent.
The utility model discloses a technical problem that purification method mainly solved lies in: firstly, the problems of difficult degradation of organic matters in the salt-containing organic wastewater and high investment and operation cost are effectively solved; secondly, the ion exchange regeneration acid and alkali waste liquid is used for a pH regulating medicament of a Fenton system, so that the consumption of acid and alkali medicaments is reduced, and the treatment process of the acid and alkali waste liquid is omitted; thirdly, the iron-containing sludge produced by the Fenton system is prepared into a coagulant and applied to chemical softening and hardness removal, so that the consumption of the coagulant in the chemical softening and hardness removal is reduced, and the problem of sludge disposal is effectively solved; finally, the produced water after the pre-oxidation is diluted by utilizing the distilled water of the evaporation and salt separation, so that the water temperature is effectively controlled, and the stable and efficient operation of biochemistry is facilitated.
The utility model discloses a contain organic waste water's of salt clean system 100, as shown in FIG. 1, including the chemical softening that communicates in proper order except that hard device 10, ion exchange device 20, membrane separation enrichment facility 30, organic matter separator 40, fenton oxidation unit 50 and biochemical oxidation unit 60, biochemical oxidation unit 60's discharge gate and chemical softening except that the pan feeding mouth intercommunication of hard device 10. The ion exchange device 20 is provided with a discharge port, an acid waste liquid outlet and an alkali waste liquid outlet, the discharge port of the ion exchange device 20 is communicated with the feeding port of the membrane separation and concentration device 30, the acid waste liquid outlet is communicated with the feeding port of the Fenton oxidation device 50, and the alkali waste liquid outlet is communicated with the feeding port of the biochemical oxidation device 60.
The utility model discloses a clean system 100 at first removes hard device 10 and ion exchange device 20 etc. through chemical softening, makes hardness, basicity, silica, suspended solid etc. in the high salt waste water get rid of more thoroughly. Then the inorganic salt and organic matter in the high-salinity water are synchronously concentrated by the membrane separation and concentration device 30, the TDS of the concentrated produced water can reach more than 10000mg/L, and the concentration of the organic matter can reach more than 150 mg/L. The concentrated produced water enters the organic matter separation device 40, the separated wastewater enters the Fenton oxidation device 50 and then enters the biochemical oxidation device 60, and a large amount of organic matters are removed in the biochemical oxidation device 60. The utility model discloses a clean system 100 has following beneficial effect: the COD (chemical oxygen demand) is removed by adopting the processes of pretreatment, membrane concentration, organic matter separation, Fenton oxidation and biochemical oxidation, the total removal rate of the COD can reach more than 60 percent, the organic matter is prevented from being directly mineralized by adopting an advanced oxidation device, and the investment and the operation cost are greatly reduced; the adoption of the Fenton oxidation device for pre-oxidation effectively improves the B/C ratio (biodegradability, BOD/COD), and utilizes the regenerated acid waste liquid and the regenerated alkali waste liquid obtained by the ion exchange device to respectively adjust the pH values of the system before and after Fenton oxidation, thereby reducing the acid-base consumption of oxidation treatment and simultaneously avoiding the additional treatment operation on the regenerated acid waste liquid and the regenerated alkali waste liquid.
In one specific example, the purification system 100 further comprises a sludge dewatering device 71, the chemical softening and hardness removing device 10 and the biochemical oxidation device 60 are provided with sewage outlets, and the sewage outlet of the chemical softening and hardness removing device 10 and the sewage outlet of the biochemical oxidation device 60 are communicated with the sludge dewatering device 71. Therefore, softened sludge discharged by the chemical softening and hardness removing device 10 and biochemical sludge discharged by the biochemical oxidation device 60 are mixed and then enter the sludge dewatering device 71 for dewatering, the softened sludge and the biochemical sludge are mixed to be beneficial to digestion of the biochemical sludge, filter pressing and dewatering are facilitated, and the water content of the dewatered sludge can reach below 60%.
In one specific example, the purification system 100 further comprises a pre-oxidation sludge acidification tank 72 and a hydrochloric acid tank 73, the fenton oxidation device 50 has a sewage outlet, the sewage outlet of the fenton oxidation device 50 and the hydrochloric acid tank 73 are both communicated with the feeding port of the pre-oxidation sludge acidification tank 72, and the discharging port of the pre-oxidation sludge acidification tank 72 is communicated with the feeding port of the chemical softening and hardness removing device 10. The main component of the sludge discharged from the Fenton oxidation device 50 is iron salt generated in situ, so that the flocculation effect is good, hydrochloric acid is added into the hydrochloric acid tank 73 to prepare an iron salt coagulant, and the iron salt coagulant flows back to the chemical softening and hardness removing device 10, so that the dosage of the coagulation flocculant in chemical softening can be effectively reduced, and the operation cost is reduced.
In one specific example, the purification system 100 further comprises an evaporation salt separation device 74, the organic matter separation device 40 has a water production port and a sewage port, the sewage port of the organic matter separation device 40 is communicated with the feed port of the fenton oxidation device 50, the water production port of the organic matter separation device 40 is communicated with the feed port of the evaporation salt separation device 74, and the evaporation salt separation device 74 has a crystallized salt outlet which is communicated with the feed port of the organic matter separation device 40. Thus, the separated water from the organic matter separator 40 enters the evaporation salt separator 74 to evaporate and separate salt to obtain crystal salt, the crystal salt, such as sodium chloride solution, enters the organic matter separator 40 again to regenerate the adsorbent resin therein, and the regenerated waste water, i.e., waste water rich in organic matters, enters the fenton oxidation apparatus 50. The adsorbent resin in the organic substance separation device 40 uses sodium chloride and the like generated by the evaporation salt separation device 74 as a regeneration agent, so that the introduction of external chemical agents is avoided, and the system load and the operation cost can be further reduced.
In one specific example, the purification system 100 further includes a dilution tank 75 disposed between the fenton oxidation device 50 and the biochemical oxidation device 60, and the alkaline waste liquid outlet is communicated with the feed inlet of the biochemical oxidation device 60 through the dilution tank 75. The dilution tank 75 is used to dilute the pre-oxidation product water discharged from the fenton oxidation device 50, to ensure that the TDS of the inlet water of the biochemical oxidation device 60 is less than 5000mg/L, to prevent the inhibition and toxicity of the salt to the growth of the microorganisms. Further, the evaporation salt separation device 74 also has a condensed water outlet, and the condensed water outlet is communicated with the dilution pool 75. Therefore, the evaporation condensate water of the evaporation salt separation device 74 is used as a water source to dilute the pre-oxidation produced water, the system load and the operation cost are further reduced, and meanwhile, the temperature of the condensate water is higher, so that the inlet water temperature entering the biochemical oxidation device 60 can be flexibly adjusted after the condensate water is mixed with the pre-oxidation produced water, the efficient propagation of microorganisms is facilitated, and the biochemical effect is enhanced.
In one particular example, the purification system 100 further includes a microfiltration device 76 disposed between the chemical softening and hardness removal device 10 and the ion exchange device 20, the microfiltration device 76 may be one or more of a sand filtration device, a microfiltration device, and an ultrafiltration device. It will be appreciated that when a plurality of devices are included, they may be connected in series as desired. Through the precise filtering device 76, colloid, particulate matters, macromolecular organic matters, microorganisms and the like in water can be further removed, the effluent SDI (sludge density index) is less than 3, and the turbidity is less than 0.5 NTU.
In a specific example, the purification system 100 further includes a miscellaneous salt evaporation device 77, the sewage port of the organic matter separation device 40 is further communicated with the feeding port of the miscellaneous salt evaporation device 77, and a TDS detector and a water volume detector are disposed in the organic matter separation device 40 and are respectively used for detecting TDS and water volume of the sewage in the organic matter separation device 40. When the TDS of the sewage, namely the separation waste water, is more than or equal to 80000mg/L and the water quantity is less than or equal to 2m3When the water flow path is switched by the control mechanism, the separated wastewater enters the mixed salt evaporation device 77 for evaporation and crystallization, and is finally discharged out of the system in the form of mixed salt, when the TDS of the separated wastewater is less than 80000mg/L or the water quantity is more than 2m3At/h, the effluent enters the Fenton oxidation device 50, so that the purification process is more reasonable and efficient.
Optionally, the purification system 100 further comprises a homogenizing and homogenizing equalizing basin (not shown) disposed upstream of the chemical softening and hardness removing device 10, and the salt-containing organic wastewater enters the homogenizing and equalizing basin for water quality and quantity adjustment and then enters the chemical softening and hardness removing device 10.
In one particular example, the chemical softening and hardness removal apparatus 10 may be one or more of a high density settling tank, a mechanically accelerated clarifier, a V-bank filter, a sand filter tank, a multimedia filter.
In one particular example, the membrane separation concentration device 30 may be one or more of a reverse osmosis device, a nanofiltration device, an electrodialysis device, and a forward osmosis device.
In one particular example, the organic matter separation device 40 may be one or more of a roll-to-roll ultrafiltration device, a nanofiltration device, a reverse osmosis device, and a resin adsorption device.
In one particular example, the biochemical oxidation unit may be one or more of a multi-stage a/O unit, an SBR unit, an MBR unit, and a biological aerated filter.
The following are specific examples.
Example 1
The flow Q of the organic wastewater with high salt content discharged from a certain chemical industry park is 180m3/h，COD≤60mg/L，TDS≤6000mg/L，Cl-＝3200mg/L，SO4 2-200mg/L, the total hardness is less than or equal to 700mg/L, the silicon dioxide is less than or equal to 50mg/L, and the pH value is 8-9.
The high-salt-content wastewater firstly enters a chemical softening and hardness removing device 10, lime, sodium carbonate, polyferric, PAM, hydrochloric acid, a silicon removing agent and the like are added into the chemical softening and hardness removing device 10, suspended matters, colloids, hardness, alkalinity, silicon dioxide and the like in the wastewater are removed in a coagulating sedimentation mode, and the treatment effect of the chemical softening and hardness removing device 10 is shown in the following table.
| Index of water quality | Total hardness (mg/L) | Silicon dioxide (mg/L) | pH | Suspended matter concentration SS (mg/L) |
| Softened produced water | 150 | 20 | 7.5 | 20 |
The softened produced water is sequentially subjected to precise filtration by a sand filtration device and an ultrafiltration/microfiltration device to remove fine particles, colloid and the like, and after being filtered by the precise filtration device 76, the turbidity of the produced water is less than 0.5NTU, and the SDI is less than 3.
The water produced by the secondary filter 76 enters the ion exchange device 20 for further hardness removal treatment, and Ca remained in the softened water is softened by the exchange action of cation exchange resin2+、Mg2+Further, the ion exchange produced water is substantially free of hardness. The acid waste liquid and the alkali waste liquid generated from the ion exchange device 20 are used for pH adjustment of the reaction system of the subsequent fenton oxidation device 50, and the treatment effect of the ion exchange device 20 is shown in the following table.
The ion exchange produced water enters the membrane separation and concentration device 30 for separation and concentration, the membrane separation and concentration device 30 comprises a reverse osmosis device and a high-pressure reverse osmosis membrane device which are sequentially connected, after being treated by the membrane separation and concentration device 30, the TDS of the high-salt-content wastewater is concentrated to 16 times of the original TDS, the water quantity of the wastewater is reduced to 1/16 of the original TDS, the concentration of organic matters reaches 960mg/L, and the specific treatment result is shown in the following table.
| Index of water quality | Flow rate (m)3/h) | COD(mg/L) | TDS(mg/L) | pH |
| Concentrated water production | 11.3 | 960 | 99000 | 7.5 |
The concentrated produced water enters an organic matter separation device 40 to separate organic matters, and the organic matters are extracted from the concentrated brine by interception in the combined form of a roll type ultrafiltration device and a nanofiltration device. The separated water enters an evaporation salt separation device 74 to be evaporated and separated into salt, the evaporation salt separation device 74 adopts an MVR (mechanical vapor recompression) device to produce sodium chloride crystallized salt with the purity of more than 98.5 percent, the sodium chloride crystallized salt is used as an industrial raw material, and the separated wastewater enters a Fenton oxidation device 50 to be treated. The treatment effect of the organic matter separation device 40 is shown in the following table.
| Index of water quality | Flow rate (m)3/h) | COD(mg/L) | TDS(mg/L) | pH |
| Separating produced water | 10.7 | 200 | 98000 | 7.5 |
| Separating waste water | 0.6 | 14513 | 116833 | 7.5 |
The separated wastewater (rich in organic matters) enters a Fenton oxidation device 50 for Fenton pre-oxidation treatment, the pH value of the concentrated produced water is adjusted to 3.0-3.5 by using the regenerated acid waste liquid produced by the ion exchange device 20, and H is added2O2And Fe2+So as to oxidize the organic substances therein, open the ring and break the chain and improve the B/C. After pre-oxidation, the COD of the produced water is 13061mg/L, and the B/C ratio is 0.4. Adding the regenerated alkali waste liquid generated by the ion exchange device 20 into the pre-oxidation produced water, adjusting the pH value of the produced water to 7.5, and then entering a dilution tank 75 for dilution treatment.
Dehydrating sludge generated by pre-oxidation, adding 31% hydrochloric acid, controlling the mass ratio to be (0.3-0.5): 1, controlling the reaction temperature to be 40-50 ℃, reacting for 1-1.5 h to prepare a ferric trichloride coagulant, and returning the prepared coagulant to the chemical softening and hardness removing device 10 to be used as the coagulant.
And (4) the water produced by the pre-oxidation enters a diluting pool, and the evaporation condensate water produced by the evaporation salt separating device 74 and the reuse water produced by the membrane separation and concentration device 30 are used as a fresh water source to dilute the pre-oxidized wastewater with high salt content and high organic matter content. In the embodiment, the water is diluted by 25 times, and the water amount after dilution reaches 15m3And/h, the TDS of the effluent is 4673mg/L, the COD is 522mg/L, and the water temperature is 28 ℃.
The diluted pre-oxidation produced water enters a biochemical oxidation device 60 for biochemical oxidation treatment, and the biochemical oxidation device 60 adopts a combination form of an A/O treatment device and an MBR device. In the embodiment, the total retention time of the biochemical oxidation device 60 is 20h, and the COD of the produced water is 80mg/L after the treatment of the biochemical oxidation device 60. Mixing biochemical sludge and softened sludge, dewatering, and transporting outside.
Example 2
The flow Q of the organic wastewater with high salt content discharged from a certain chemical industry park is 30m3/h，COD≤400mg/L，TDS≤65000mg/L，Cl-＝26000mg/L，SO4 2-11000mg/L, the total hardness is less than or equal to 600mg/L, the silicon dioxide is less than or equal to 40mg/L, and the pH value is 7.5-8.8.
The high-salt-content wastewater firstly enters a chemical softening and hardness removing device 10, lime, sodium carbonate, polyferric, PAM, hydrochloric acid, a silicon removing agent and the like are added into the chemical softening and hardness removing device 10, suspended matters, colloids, hardness, alkalinity, silicon dioxide and the like in the wastewater are removed in a coagulating sedimentation mode, and the treatment effect of the chemical softening and hardness removing device 10 is shown in the following table.
| Index of water quality | Total hardness (mg/L) | Silicon dioxide (mg/L) | pH | Suspended matter concentration SS (mg/L) |
| Softened produced water | 150 | 20 | 7.5 | 20 |
The softened produced water is sequentially subjected to precise filtration by a sand filtration device and an ultrafiltration/microfiltration device to remove fine particles, colloid and the like, and after being filtered by the precise filtration device 76, the turbidity of the produced water is less than 0.5NTU, and the SDI is less than 3.
The water produced by the secondary filter 76 enters the ion exchange device 20 for further hardness removal treatment, and Ca remained in the softened water is softened by the exchange action of cation exchange resin2+、Mg2+Further, the ion exchange produced water is substantially free of hardness. The acid waste liquid and the alkali waste liquid generated by the ion exchange device 20 are used for the reaction system of the subsequent Fenton oxidation device 50The treatment effect of the ion exchanger 20 is shown in the following table.
The ion exchange produced water enters the membrane separation and concentration device 30 for separation and concentration, the membrane separation and concentration device 30 comprises a reverse osmosis device and a high-pressure reverse osmosis membrane device which are sequentially connected, after being treated by the membrane separation and concentration device 30, the high-salt-content wastewater TDS is concentrated to 2 times of the original TDS, the wastewater water volume is reduced to 1/2 of the original TDS, the organic matter concentration reaches 800mg/L, and the specific treatment result is shown in the following table.
| Index of water quality | Flow rate (m)3/h) | COD(mg/L) | TDS(mg/L) | pH |
| Concentrated water production | 15 | 800 | 12740 | 7.5 |
The concentrated produced water enters an organic matter separation device 40 to separate organic matters, and the embodiment adopts a roll-type ultrafiltration device to extract the organic matters from the concentrated brine by interception. The separated water enters an evaporation salt separation device 74 for evaporation salt separation, the evaporation salt separation device 74 adopts an MVR (mechanical vapor recompression) device to produce sodium chloride crystallized salt with the purity of more than 98.5 percent, the sodium chloride crystallized salt is used as an industrial raw material, and the separated wastewater enters a mixed salt evaporation device 77 for treatment. The treatment effect of the organic matter separation device 40 is shown in the following table.
| Index of water quality | Flow rate (m)3/h) | COD(mg/L) | TDS(mg/L) | pH |
| Separating produced water | 14.1 | 190 | 126850 | 7.5 |
| Separating waste water | 0.9 | 10356.7 | 136010 | 7.5 |
The TDS of the separated wastewater is 136010mg/L, and the water quantity is 0.9m3Therefore, the mixed salt can directly enter a mixed salt evaporation device 77 for evaporation and crystallization, and 21.56kg/h of mixed salt is produced.
If the treatment is carried out according to the process route of example 1, the separated wastewater (rich in organic substances) enters the Fenton oxidation device 50 for treatmentPerforming Fenton pre-oxidation treatment, adjusting the pH value of the concentrated produced water to 3.0-3.5 by using the regenerated acid waste liquid produced by the ion exchange device 20, and adding H2O2And Fe2+So as to oxidize the organic substances therein, open the ring and break the chain and improve the B/C. After pre-oxidation, the COD of the produced water is 9321mg/L, and the B/C ratio is 0.37. Adding the regenerated alkali waste liquid generated by the ion exchange device 20 into the pre-oxidation produced water, adjusting the pH value of the produced water to 7.5, and then entering a dilution tank 75 for dilution treatment.
Dehydrating sludge generated by pre-oxidation, adding 31% hydrochloric acid, controlling the mass ratio to be (0.3-0.5): 1, controlling the reaction temperature to be 40-50 ℃, reacting for 1-1.5 h to prepare a ferric trichloride coagulant, and returning the prepared coagulant to the chemical softening and hardness removing device 10 to be used as the coagulant.
And (4) the water produced by the pre-oxidation enters a diluting pool, and the evaporation condensate water produced by the evaporation salt separating device 74 and the reuse water produced by the membrane separation and concentration device 30 are used as a fresh water source to dilute the pre-oxidized wastewater with high salt content and high organic matter content. In the embodiment, the water is diluted by 30 times, and the water amount after dilution reaches 27m3And/h, outlet water TDS is 4534mg/L, COD is 310.7mg/L, and water temperature is 25 ℃.
The diluted pre-oxidation produced water enters a biochemical oxidation device 60 for biochemical oxidation treatment, and the biochemical oxidation device 60 adopts a combination form of an A/O treatment device and an MBR device. In the embodiment, the total retention time of the biochemical oxidation device 60 is 20h, and the COD of the produced water is 85mg/L after the treatment of the biochemical oxidation device 60. Mixing biochemical sludge and softened sludge, dewatering, and transporting outside.
The technical-economic comparison of the two process routes is shown in the following table
| Item | Investment cost (Wanyuan) | Running cost (Yuan/ton) | Floor area (m)2) |
| Miscellaneous salt evaporation plant | 110 | 60 | 50 |
| Fenton preoxidation + biochemistry | 260 | 68 | 600 |
As can be seen from the above table, for small flows (typically < 2 m)3The waste water of the separation of the/h) adopts a direct miscellaneous salt evaporation mode, and has obvious economic advantages.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only represent some embodiments of the present invention, and the description thereof is specific and detailed, but not to be construed as limiting the scope of the present invention. It should be noted that, for those skilled in the art, without departing from the spirit of the present invention, several variations and modifications can be made, which are within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the appended claims.
Claims (10)
1. A purification system for salt-containing organic wastewater is characterized by comprising a chemical softening and hardness-removing device, an ion exchange device, a membrane separation and concentration device, an organic matter separation device, a Fenton oxidation device and a biochemical oxidation device which are sequentially communicated, wherein a discharge port of the biochemical oxidation device is communicated with a feed port of the chemical softening and hardness-removing device; the ion exchange device is provided with a discharge hole, an acid waste liquid outlet and an alkali waste liquid outlet, the discharge hole of the ion exchange device is communicated with the feeding hole of the membrane separation and concentration device, the acid waste liquid outlet is communicated with the feeding hole of the Fenton oxidation device, and the alkali waste liquid outlet is communicated with the feeding hole of the biochemical oxidation device.
2. The purification system of claim 1, further comprising a sludge dewatering device, wherein the chemical softening and hardness removing device and the biochemical oxidation device are provided with sewage outlets, and the sewage outlet of the chemical softening and hardness removing device and the sewage outlet of the biochemical oxidation device are communicated with the sludge dewatering device.
3. The purification system of claim 1, further comprising a pre-oxidation sludge acidification tank and a hydrochloric acid tank, wherein the Fenton oxidation device is provided with a drain outlet, the drain outlet of the Fenton oxidation device and the hydrochloric acid tank are both communicated with a feed inlet of the pre-oxidation sludge acidification tank, and a discharge outlet of the pre-oxidation sludge acidification tank is communicated with a feed inlet of the chemical softening hardness removal device.
4. The purification system of claim 1, further comprising an evaporative salt separation device having a water production port and a waste port, the waste port of the organic separation device being in communication with the feed port of the Fenton oxidation device, the water production port of the organic separation device being in communication with the feed port of the evaporative salt separation device, the evaporative salt separation device having a crystallized salt outlet in communication with the feed port of the organic separation device.
5. The purification system of claim 4, further comprising a dilution tank disposed between the Fenton oxidation device and the biochemical oxidation device, wherein the alkaline waste liquid outlet is communicated with the feed inlet of the biochemical oxidation device through the dilution tank.
6. The purification system of claim 5, wherein the evaporative salt separation device further has a condensate outlet in communication with the dilution tank.
7. The purification system of claim 4, further comprising a miscellaneous salt evaporation device, wherein the sewage port of the organic matter separation device is further communicated with the feed port of the miscellaneous salt evaporation device, and the organic matter separation device is provided with a TDS detector and a water volume detector for respectively detecting TDS and water volume of the wastewater separated in the organic matter separation device.
8. The purification system of claim 1, further comprising a microfiltration device disposed between the chemical softening and hardness removal device and the ion exchange device, the microfiltration device being one or more of a sand filtration device, a microfiltration device, and an ultrafiltration device.
9. The purification system of claim 1, further comprising a homogenizing and homogenizing conditioning tank disposed upstream of and in communication with the chemical de-hardening device.
10. The purification system of any one of claims 1 to 9, wherein the chemical softening and hardness removal device is one or more of a high-density sedimentation tank, a mechanical accelerated clarification tank, a V-shaped filter tank, a sand filter tank and a multi-media filter.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110342740A (en) * | 2019-07-19 | 2019-10-18 | 内蒙古久科康瑞环保科技有限公司 | The purification method and purification system of salt-containing organic wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110342740A (en) * | 2019-07-19 | 2019-10-18 | 内蒙古久科康瑞环保科技有限公司 | The purification method and purification system of salt-containing organic wastewater |
| CN110342740B (en) * | 2019-07-19 | 2024-01-19 | 内蒙古久科康瑞环保科技有限公司 | Method and system for purifying organic wastewater containing salt |
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