CN113562924A - Treatment system and method for resource utilization of high-salinity wastewater in ferrous metallurgy - Google Patents
Treatment system and method for resource utilization of high-salinity wastewater in ferrous metallurgy Download PDFInfo
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- C02F5/02—Softening water by precipitation of the hardness
Abstract
The invention relates to a treatment system and a method for recycling high-salt wastewater in ferrous metallurgy, wherein impurities such as fluoride, silicon scale, heavy metal, suspended matters and the like in the high-salt wastewater are removed through a regulating tank, a softening reaction tank, a concentration sedimentation tank and a tubular microfiltration device, clear water treated by a primary RO device and a secondary RO device is recycled, concentrated water generated by the primary RO device sequentially passes through an ozone catalytic oxidation device, an active carbon adsorption device and a resin softening device to sequentially reduce the hardness and COD (chemical oxygen demand) in the concentrated water, water discharged from the resin softening device enters a nanofiltration device, and the concentrated water of the nanofiltration device enters a freezing crystallization device and an evaporation crystallization device to precipitate sodium sulfate for sale. The water produced by the nanofiltration device respectively enters the high-pressure reverse osmosis device, the defluorination device, the electrodialysis device and the bipolar membrane electrodialysis device to generate dilute hydrochloric acid and dilute alkali liquor, and the invention has the advantages that: low-cost treatment, removal of various harmful substances in the high-salinity wastewater step by step, and realization of reasonable utilization of wastewater and waste resources.
Description
Technical Field
The invention belongs to the technical field of industrial wastewater treatment, and particularly relates to a treatment system and method for resource utilization of high-salinity wastewater in ferrous metallurgy.
Background
The water treatment process of iron and steel enterprises inevitably generates a large amount of high-salinity wastewater in the desalting process, and the high-salinity wastewater mainly contains inorganic salt and heavy metal and also contains a small amount of organic agents used in the desalting process. For the treatment of high-salinity wastewater, steel enterprises generally utilize the high-salinity wastewater to hot-pour slag. However, the high-salinity wastewater has large water volume and extremely high salt content, and is easy to corrode and scale slag splashing equipment, pipelines and nozzles.
In recent years, a series of laws and regulations, industrial specifications and standards are issued by the nation for solving the problems of energy conservation, environmental protection, and the like, and the requirements on water use and pollution control of steel enterprises are gradually increased. Various iron and steel enterprises also actively carry out the improvement of strong brine treatment, but the bottleneck problems that the requirement on water use indexes of users is high, the treatment cost of per ton water of high-salt wastewater treatment is high, the crystallized salt of the high-salt wastewater is difficult to go out and the like are encountered in the strong brine treatment at present. Therefore, the technical problems of saving water and realizing the resource recycling of low-cost high-salinity wastewater of iron and steel enterprises are urgently solved.
Disclosure of Invention
The invention aims to provide a treatment system and a treatment method for recycling high-salinity wastewater in ferrous metallurgy, which can recycle the high-salinity wastewater in the steel industry, obtain sodium chloride, sodium sulfate and other products, have low operation cost and good effect, and have practical significance for realizing water conservation, consumption reduction and income increase of steel enterprises.
The purpose of the invention is realized by the following technical scheme:
the invention relates to a treatment system for resource utilization of high-salinity wastewater in ferrous metallurgy, which is characterized by comprising the following components:
the high-salinity wastewater regulating tank is communicated with an inlet pipeline of the high-salinity wastewater regulating tank and is used for regulating and buffering the water quantity and the water quality of the high-salinity wastewater;
the softening reaction tank is communicated with the outlet of the high-salinity wastewater adjusting tank and is used for reducing the hardness and alkalinity of the high-salinity wastewater and removing silica scale and heavy metals;
the concentration sedimentation tank is communicated with the outlet of the softening reaction tank and is used for reducing suspended matters of the high-salinity wastewater;
the sludge dewatering device is communicated with a sludge discharge port of the concentration sedimentation tank, a water outlet of the sludge dewatering device is communicated with an inlet of the high-salinity wastewater regulating tank, and the effluent of the sludge dewatering device returns to the high-salinity wastewater regulating tank to form a closed circuit for sludge waste treatment;
the tubular microfiltration device is communicated with the water outlet of the concentration sedimentation tank and is used for further reducing suspended matters of the high-salinity wastewater, and the outlet of the tubular microfiltration device is also communicated with the water inlet of the concentration sedimentation tank;
the first-stage RO device is communicated with the outlet of the tubular microfiltration device and is used for reducing the salt content in the high-salinity wastewater;
the second-stage RO device is communicated with the first-stage RO device clear water outlet and is used for further reducing the salt content in the clear water produced by the first-stage RO device, the concentrated water outlet of the second-stage RO device is communicated with the first-stage RO device inlet, the concentrated water returns to the first-stage RO device to form a closed circuit, and the clear water produced by the clear water outlet of the second-stage RO device is a clear water resource and is recycled;
the ozone catalytic oxidation device is communicated with the concentrated water outlet of the primary RO device and is used for reducing COD in the high-salinity concentrated water of the primary RO device;
the activated carbon adsorption device is communicated with the outlet of the ozone catalytic oxidation device and is used for further reducing COD in the high-salinity concentrated water;
the resin softening device is communicated with the outlet of the activated carbon adsorption device and is used for reducing the hardness of the high-salinity concentrated water and removing residual total metal ions;
the nanofiltration device is communicated with the outlet of the resin softening device and is used for separating monovalent anions and cations and divalent and polyvalent anions and cations in the effluent of the resin softening device;
the freezing and crystallizing device is communicated with a concentrated water outlet of the nanofiltration device and is used for separating a sodium chloride component and a sodium sulfate component in the nanofiltration concentrated water, and mother liquor mainly containing the sodium chloride component is subjected to slag flushing treatment after separation to obtain a sodium chloride product for recycling;
the evaporative crystallization device is communicated with the outlet of the freezing crystallization device and is used for evaporating and crystallizing sodium sulfate components in the freezing crystallization device into sodium sulfate so as to obtain a sodium sulfate product for recycling;
the high-pressure reverse osmosis device is communicated with the water outlet of the nanofiltration device and is used for further concentrating the water produced by the nanofiltration device; the clean water port of the high-pressure reverse osmosis device is connected with the water inlet of the secondary RO device, and the produced water of the high-pressure reverse osmosis device returns to the secondary RO device to form a closed circuit;
the fluorine removal device is communicated with the concentrated water outlet of the high-pressure reverse osmosis device and is used for removing fluorine ions in the concentrated water of the high-pressure reverse osmosis device;
the electrodialysis device is communicated with the water outlet of the defluorination device and is used for further concentrating the water produced by the defluorination device; a water production port of the electrodialysis device is connected with the high-salinity wastewater regulating reservoir, and water produced by the electrodialysis device returns to the high-salinity wastewater regulating reservoir to form a closed circuit;
the ion exchange device is communicated with the concentrated water outlet of the electrodialysis device and is used for removing heavy metals in the concentrated water of the electrodialysis device;
the bipolar membrane electrodialysis device is communicated with the outlet of the ion exchange device and is used for further separating the outlet water of the ion exchange device to generate a dilute hydrochloric acid product and a dilute alkali liquor product for recycling;
a dilute brine outlet of the bipolar membrane electrodialysis device is connected with a water inlet of the defluorination device, and the dilute brine of the bipolar membrane electrodialysis device returns to the defluorination device to form a closed circuit;
and bipolar membrane electrodialysis, which is communicated with the concentrated water outlet of the electrodialysis device and is used for further separating the electrodialysis concentrated water to generate a dilute hydrochloric acid product and a dilute alkali liquor product for recycling.
Preferably, the softening reaction tank is of an open square structure, a stirring device is arranged in the softening reaction tank, and the stirring device is guide cylinder type mechanical stirring equipment;
the concentrating and precipitating tank is in a closed square or round lower cone structure, a sludge concentrating device is arranged in the concentrating and precipitating tank, and the sludge concentrating device is slow scraper equipment.
Preferably, the tubular microfiltration device is made of PVDF, PES or PTFE; the second-stage RO device of the first-stage RO device is a low-pressure pollution-resistant reverse osmosis device; the ozone catalytic oxidation device adopts an ozone catalytic oxidation tower, and a catalyst is filled in the ozone catalytic oxidation tower.
Preferably, the activated carbon adsorption device selects 10-28 mm fruit shell-filled activated carbon for adsorbing organic matters in water; the resin softening device is a weak acid cation resin exchange device with the working exchange capacity of more than or equal to 2000mmol/l-R (H).
Preferably, the nanofiltration device is a low-pressure anti-pollution organic composite nanofiltration membrane device.
Preferably, the freezing crystallization device is a freezing crystallization separation device, and the evaporative crystallization device is a triple effect evaporative crystallization device or an MVR evaporative crystallization device.
Preferably, the high-pressure reverse osmosis device is a high-pressure-resistant anti-pollution seawater reverse osmosis device, a disc tube type reverse osmosis device or a disc type reverse osmosis device; the defluorination device adopts a F860 defluorination resin exchange device with a macroporous structure.
Preferably, the electrodialysis device is a homogeneous membrane or an alloy membrane; the ion exchange device adopts a chelating cation resin device D851.
Preferably, the sludge dewatering device is preferably a mechanical concentration + plate-and-frame filter pressing or centrifugal dewatering or spiral dewatering device, and the bipolar membrane electrodialysis device is a three-compartment bipolar membrane electrodialysis device.
The invention discloses a treatment method for recycling high-salinity wastewater in ferrous metallurgy, which adopts a treatment system and is characterized by comprising the following steps of:
s1: introducing high-salt wastewater into a high-salt wastewater adjusting tank for homogenizing and uniform treatment, introducing the high-salt wastewater into a softening reaction tank, adding alkali liquor with the concentration of 5% -30% and sodium carbonate solution with the concentration of 5% -15% into the softening reaction tank for chemical reaction precipitation, stirring, introducing the high-salt wastewater into a concentration precipitation tank for precipitation and clarification, conveying the produced water of the concentration precipitation tank into a tubular microfiltration device, conveying the chemical reaction precipitate generated by the concentration precipitation tank into a sludge dewatering device, returning the wastewater generated by the sludge dewatering device into the high-salt wastewater adjusting tank, adding 30% dilute hydrochloric acid at the outlet of the tubular microfiltration device for neutralization until the pH value is 7-8, and obtaining first neutral high-salt clear water;
the content of suspended matters in the first neutral high-salt clear water is less than 1mg/L, and the hardness content is less than 25 mg/L;
s2: introducing the first neutral high-salt clear water into a primary RO device for desalting treatment, introducing the water produced by the primary RO device into a secondary RO device, further desalting the water produced by the primary RO device to obtain qualified produced water for recycling, returning the concentrated water produced by the secondary RO device to the inlet of the primary RO device to form a closed circuit, introducing the concentrated water produced by the primary RO device into an ozone catalytic oxidation device and an active carbon adsorption device, further removing COD (chemical oxygen demand) in the concentrated water, and obtaining second neutral high-salt clear water;
the COD content in the second neutral high-salt clear water is less than 15 mg/L;
s3: introducing the second neutral high-salt clear water into a resin softening device for hardness and heavy metal removal treatment to obtain third neutral high-salt clear water;
the hardness content of the third neutral high-salt clear water is less than 5 mg/L;
s4: introducing the third neutral high-salinity clear water into a nanofiltration device, introducing the water produced by the nanofiltration device into a high-pressure reverse osmosis device, introducing the concentrated water produced by the nanofiltration device into a freezing crystallization device and an evaporative crystallization device, and separating out sodium sulfate salt, wherein mother liquor which is mainly sodium chloride salt and is generated by the freezing crystallization device is subjected to slag flushing and utilization, clear water produced by the high-pressure reverse osmosis device enters a secondary RO device, and the concentrated water produced by the high-pressure reverse osmosis device enters a defluorination device and is treated by the defluorination device to obtain fourth neutral high-salinity clear water;
the fluoride content in the fourth neutral high-salt clear water is less than 5 mg/L;
s5: and introducing the fourth neutral high-salt clear water into an electrodialysis device for concentration and purification, returning the water produced by the electrodialysis device to a high-salt wastewater regulating reservoir for homogenizing and uniform treatment, introducing the concentrated water of the electrodialysis device into an ion exchange device for removing divalent and above heavy metal cations, introducing the effluent of the ion exchange device into a bipolar membrane electrodialysis device to obtain 5-8% dilute hydrochloric acid and 5-8% dilute sodium hydroxide solution, and introducing the dilute brine generated by the bipolar membrane electrodialysis into a defluorinating resin exchange bed for recovery treatment.
Compared with the prior art, the invention has the advantages that:
1) the treatment system has the characteristics of wide concentration range of treated inlet water salt, high concentration of concentrated solution, strong corrosion resistance of equipment, COD resistance, strong antimicrobial pollution, low operation cost, low maintenance cost and the like;
2) the invention realizes the recycling of valuable components in the high-salinity wastewater
In the invention, the electrodialysis concentrated water enters the ion exchange device to remove divalent and above cations, and the treated high-salinity concentrated water enters the bipolar membrane electrodialysis to generate dilute hydrochloric acid and dilute alkali liquor, thereby realizing the recycling of valuable components in the high-salinity wastewater.
3) The invention realizes the recycling and zero discharge of all high-salinity wastewater.
In the treatment process, the sludge discharged from the concentration sedimentation tank device is removed to the sludge dewatering device for sludge dewatering, the sewage after sludge dewatering returns to the high-salinity wastewater regulating tank, the concentrated water of the second-level RO device enters the first-level RO device for recycling, the produced water of the high-pressure RO reverse osmosis device enters the second-level RO device for recycling, the produced water of the electrodialysis device enters the high-salinity wastewater regulating tank for recycling, and the dilute brine of the bipolar membrane electrodialysis device is recycled to the defluorination device, so that the recycling of all the wastewater is realized without discharging, and the real zero discharge of the high-salinity wastewater is realized.
The method can effectively treat the high-salinity wastewater in the steel industry, realizes the purpose of removing various harmful substances in the wastewater step by step, has simple operation and low energy consumption level, can recycle the treated effluent as industrial new water, realizes zero discharge of the wastewater, generates byproducts with certain economic recycling value, realizes resource utilization, and has practical significance for realizing water conservation, consumption reduction and income increase of steel enterprises.
Drawings
FIG. 1 is a diagram of a treatment system for resource utilization of high-salinity wastewater in ferrous metallurgy.
In the figure: 1. high salt waste water equalizing basin, 2, softening reaction tank, 3, concentrated sedimentation tank, 4, tubular microfiltration device, 5, one-level RO device, 6, second grade RO device, 7, ozone catalytic oxidation device, 8, activated carbon adsorption device, 9, resin softening device, 10, nanofiltration device, 11, freezing crystallization device, 12, evaporation crystallization device, 13, high-pressure reverse osmosis device, 14, defluorination device, 15, electrodialysis, 16, ion exchange device, 17, bipolar membrane electrodialysis device, 18, sludge dewatering device.
Detailed Description
The invention is further illustrated by the following figures and examples.
In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of one or more embodiments; it may be evident, however, that such embodiment(s) may be practiced without these specific details.
Examples
As shown in fig. 1, in this embodiment, a treatment system for recycling high-salinity wastewater in ferrous metallurgy is provided, and is used for treating and recycling high-salinity wastewater in the steel industry.
The processing system comprises:
the high-salinity wastewater adjusting tank 1 is communicated with an inlet pipeline of the high-salinity wastewater adjusting tank and is used for adjusting and buffering the water quantity and the water quality of the high-salinity wastewater;
the softening reaction tank 2 is communicated with the outlet of the high-salinity wastewater adjusting tank 1 and is used for reducing the hardness and alkalinity of the high-salinity wastewater and removing silica scale and heavy metals;
the concentration sedimentation tank 3 is communicated with the outlet of the softening reaction tank 2 and is used for reducing suspended matters of the high-salinity wastewater;
the sludge dewatering device 18 is communicated with a sludge discharge port of the concentration sedimentation tank 3, a water outlet of the sludge dewatering device 18 is communicated with an inlet of the high-salinity wastewater adjusting tank 1, and the water outlet of the sludge dewatering device 18 returns to the high-salinity wastewater adjusting tank 1 to form a closed circuit for sludge waste treatment;
the tubular microfiltration device 4 is communicated with the water outlet of the concentration sedimentation tank 3 and is used for further reducing suspended matters of the high-salinity wastewater, and the outlet of the tubular microfiltration device 4 is also communicated with the water inlet of the concentration sedimentation tank 3;
the primary RO device 5 is communicated with the outlet of the tubular microfiltration device 4 and is used for reducing the salt content in the high-salinity wastewater;
the secondary RO device 6 is communicated with the clear water outlet of the primary RO device 5 and is used for further reducing the salt content in the clear water produced by the primary RO device 5, the concentrated water outlet of the secondary RO device 6 is communicated with the inlet of the primary RO device 5, the concentrated water of the secondary RO device 6 returns to the primary RO device 5 to form a closed circuit, and the clear water produced by the clear water outlet of the secondary RO device 6 is a clear water resource and is recycled;
the ozone catalytic oxidation device 7 is communicated with the concentrated water outlet of the primary RO device 5 and is used for reducing COD in the concentrated water of the primary RO device 5;
the activated carbon adsorption device 8 is communicated with the outlet of the ozone catalytic oxidation device 7 and is used for further reducing COD in the concentrated water;
the resin softening device 9 is communicated with the outlet of the activated carbon adsorption device 8 and is used for reducing the hardness of the concentrated water and removing residual total metal ions;
a nanofiltration device 10 which is communicated with the outlet of the resin softening device 9 and is used for separating univalent anions and cations and bivalent and multivalent anions and cations in the outlet water of the resin softening device 9;
the freezing and crystallizing device 11 is communicated with a concentrated water outlet of the nanofiltration device 10 and is used for separating a sodium chloride component and a sodium sulfate component in the concentrated water of the nanofiltration device 10, and mother liquor mainly containing the sodium chloride component is subjected to slag flushing treatment after separation to obtain a sodium chloride product for recycling;
the evaporative crystallization device 12 is communicated with the outlet of the freezing crystallization device 11 and is used for evaporating and crystallizing sodium sulfate components in the freezing crystallization device 11 into sodium sulfate, and obtaining a sodium sulfate product for recycling;
the high-pressure reverse osmosis device 13 is communicated with a water outlet of the nanofiltration device 10 and is used for further concentrating the water produced by the nanofiltration device 10; the water outlet of the high-pressure reverse osmosis device 13 is connected with the water inlet of the secondary RO device 6, and the clean water of the high-pressure reverse osmosis device 13 returns to the secondary RO device 6 to form a closed circuit;
the fluorine removal device 14 is communicated with the concentrated water outlet of the high-pressure reverse osmosis device 13 and is used for removing fluorine ions in the concentrated water of the high-pressure reverse osmosis device 13;
the electrodialysis device 15 is communicated with the water outlet of the defluorination device 14 and is used for further concentrating the water produced by the defluorination device 14; a water production port of the electrodialysis device 15 is connected with the high-salinity wastewater regulating reservoir 1, and water produced by the electrodialysis device 15 returns to the high-salinity wastewater regulating reservoir 1 to form a closed circuit;
the ion exchange device 16 is communicated with the concentrated water outlet of the electrodialysis device 15 and is used for removing heavy metals in the concentrated water of the electrodialysis device;
the bipolar membrane electrodialysis device 17 is communicated with the outlet of the ion exchange device 16 and is used for further separating the water discharged from the ion exchange device 16 to generate a dilute hydrochloric acid product and a dilute alkali liquor product for recycling;
the dilute brine outlet of the bipolar membrane electrodialysis device 17 is connected with the water inlet of the fluorine removal device 14, and the dilute brine of the bipolar membrane electrodialysis device returns to the fluorine removal device 14 to form a closed circuit.
Wherein the softening reaction tank 2 is preferably of an open square structure and the stirring device in the softening reaction tank 2 is preferably provided with a guide cylinder type mechanical stirring device.
The thickening and settling tank 3 is preferably in a closed square or round lower cone structure, and the sludge thickening device in the thickening and settling tank 3 is preferably provided with a mechanical slow scraper device.
The material of the tubular microfiltration device 4 is preferably PVDF, PES or PTFE.
The primary RO unit 5 and the secondary RO unit 6 are preferably low pressure fouling resistant reverse osmosis units.
The catalytic ozonation unit 7 is preferably a catalytic ozonation tower filled with a catalyst.
The active carbon adsorption device 8 preferably selects 10-28 mm fruit shell active carbon for adsorbing organic matters in water.
The resin softening device 9 is preferably a weak acid cation resin exchange device with the working exchange capacity of more than or equal to 2000mmol/l-R (H).
The nanofiltration device 10 is preferably a low-pressure anti-pollution organic composite nanofiltration membrane device.
The freezing and crystallizing device 11 is a freezing and crystallizing separation device, and preferably adopts a two-stage precooling and freezing process.
The evaporative crystallization device 12 may be a three-way evaporative crystallization device, or an MVR evaporative crystallization device.
The high-pressure reverse osmosis device 13 is preferably a high-pressure resistant anti-pollution seawater reverse osmosis device, a disc tube type reverse osmosis device or a disc type reverse osmosis device.
The fluorine removal device 14 is preferably a large pore structured F860 fluorine removal resin exchange device.
The electrodialysis device 15 is preferably a homogeneous membrane or alloy membrane electrodialysis device.
The ion exchange means 16 is preferably a chelating cationic resin means of D851.
The sludge dewatering device 18 is preferably a mechanical thickening + plate and frame filter pressing or centrifugal dewatering or screw dewatering device.
The bipolar membrane electrodialysis device 17 is preferably a three-compartment bipolar membrane electrodialysis device.
The membrane concentration device and the bipolar membrane electrodialysis device adopted in the embodiment can realize automatic and stable operation, and the generated dilute hydrochloric acid product and dilute alkali liquor product can be reused in the wastewater treatment system and can also be used in sections of steel making, steel rolling and the like.
In the embodiment, the introduction of a coagulation aid agent and a coagulation agent is avoided, the purity of byproducts such as acid, alkali and salt generated is ensured, and the resource utilization of wastewater is realized.
The invention also provides a treatment method for recycling the ferrous metallurgy high-salinity wastewater, which utilizes the treatment system for recycling the ferrous metallurgy high-salinity wastewater and can further explain the structure and the function of each device in the treatment system by the treatment method. The treatment method comprises the following specific steps:
step S1: the high-salinity wastewater is introduced into a high-salinity wastewater adjusting tank 1 for homogeneous and uniform treatment, and then introduced into a softening reaction tank 2, alkali liquor and sodium carbonate solution are added into the softening reaction tank 2 for chemical reaction precipitation, the softened high-salinity wastewater enters a concentration sedimentation tank 3 for precipitation and clarification through stirring, the produced water of the concentration sedimentation tank 3 is delivered into a tubular microfiltration device 4, the chemical reaction precipitate generated by the concentration sedimentation tank 3 is delivered into a sludge dewatering device 18, and the wastewater generated by the sludge dewatering device 18 returns into the high-salinity wastewater adjusting tank 1. And adding dilute hydrochloric acid at the outlet of the tubular microfiltration device 4 for neutralization to obtain first neutral high-salt clear water.
The softening reaction tank 2 adopts alkali liquor and sodium carbonate solution, the concentration of the alkali liquor is within the range of 5-30%, and the concentration of the sodium carbonate solution is within the range of 5-15%. The hardness removal principle in the step is that carbonate ions are introduced into the wastewater and then combined with calcium ions to generate calcium carbonate precipitates, and the chemical reaction formula is as follows: ca2++CO3 2-→CaCO3And ↓andcarbonate radical ions and magnesium ions are gathered to generate magnesium carbonate precipitate, and the chemical reaction formula is as follows: mg (magnesium)2++CO3 2-→MgCO3↓. When the pH value of most heavy metals in the wastewater is adjusted to be more than 11, metal hydroxide precipitates can be generated, and the precipitates in the chemical reaction in the step are mainly calcium-magnesium sludge and partial heavy metals and silica scale particles. Considering that the waste water contains more magnesium ions, the magnesium ions are used as a silicon removal agent, and redundant magnesium ions are not required to be introduced.
After the steps are carried out, the content of suspended matters in the first neutral high-salt clear water is less than 1mg/L, and the hardness content is less than 25 mg/L.
Step S2: will first neutral high salt clear water lets in one-level RO device 5, carries out the desalination to first neutral high salt clear water and handles, and one-level RO device 5 produces water and gets into second grade RO device 6, produces water further desalination to one-level RO device 5 and handles, obtains qualified product water, and the dense water that second grade RO device 6 produced returns 5 imports of one-level RO device, to dense water recovery processing, and the dense water that one-level RO device 5 produced lets in ozone catalytic oxidation device 7 and active carbon adsorption device 8, further gets rid of the COD in the dense water, and then obtains the neutral high salt clear water of second.
Concentrated water generated by the second-level RO device 6 is introduced into the first-level RO device 5 to form a closed circuit, and then is introduced into the ozone catalytic oxidation device 7 and the activated carbon adsorption device 8 to remove and separate COD in the wastewater, and no medicament is introduced, so that the medicament adding cost of the COD of the system is reduced.
After the steps are carried out, the COD content in the second neutral high-salt clear water is less than 15 mg/L.
Step S3: and introducing the second neutral high-salt clear water into a resin softening device 9, and performing hardness and heavy metal removal treatment on the second neutral high-salt concentrated water to obtain third neutral high-salt clear water.
After the steps are carried out, the hardness content of the third neutral high-salt clear water is less than 5 mg/L.
Step S4: and (3) introducing the third neutral high-salt clear water into a nanofiltration device 10, introducing water produced by the nanofiltration device 10 into a high-pressure reverse osmosis device 13, introducing concentrated water produced by the nanofiltration device 10 into a freezing crystallization device 11 and an evaporation crystallization device 12, and separating out sodium sulfate, wherein mother liquor mainly containing sodium chloride generated by the freezing crystallization device 11 is subjected to slag flushing and utilization, clear water produced by the high-pressure reverse osmosis device 11 enters a secondary RO device 6, concentrated water produced by the high-pressure reverse osmosis device 13 enters a defluorination device 14, and after being treated by the defluorination device 14, fourth neutral high-salt clear water is obtained.
The nanofiltration device 10 can effectively intercept bivalent and high-valent ions and organic small molecules with the molecular weight higher than 200, so that most of monovalent inorganic salt permeates to realize the separation of monovalent salt and high-valent ions, and high-salt clear water containing high-concentration monovalent salt is subjected to high-pressure reverse osmosis desalination and concentration and then subjected to defluorination treatment.
After the steps, the fluoride content in the fourth neutral high-salt clear water is less than 5 mg/L.
Step S5: and (3) introducing the fourth neutral high-salt clear water into an electrodialysis device 15 to concentrate and purify the fourth neutral high-salt clear water, returning water produced by the electrodialysis device 15 to a high-salt wastewater regulating reservoir 1 to carry out homogeneous and uniform treatment, introducing the concentrated water of the electrodialysis device 15 into an ion exchange device 16, removing bivalent and above heavy metal cations in the ion exchange device 16, wherein the content of heavy metals in the effluent is less than 1mg/L, and introducing the effluent into a bipolar membrane electrodialysis device 17 to obtain dilute hydrochloric acid and dilute alkali liquor.
The method can effectively treat the high-salinity wastewater in the steel industry, and achieves the purpose of removing various harmful substances in the wastewater step by step.
The treatment method is further explained by using high-salinity wastewater with known initial water quality in the steel industry.
The initial water quality of the high salinity wastewater of the steel industry is shown in table 1.
Table 1:
the specific treatment method comprises the following steps:
s1, after introducing the high-salinity wastewater in the steel industry into a high-salinity wastewater adjusting tank, introducing into a softening reaction tank with a flow guide cylinder type mechanical stirring device, introducing a sodium carbonate solution with the concentration of 10% and a sodium hydroxide solution with the concentration of 30%, stirring and adjusting the pH value of the wastewater to 11.5, sequentially introducing into a concentration sedimentation tank and a tubular microfiltration device, conveying the precipitate generated by the concentration sedimentation tank into a high-pressure diaphragm automatic flushing plate-and-frame filter pressing device, obtaining a first chemical reaction precipitate, and returning the wastewater generated by the high-pressure diaphragm automatic flushing plate-and-frame filter pressing device into the high-salinity wastewater adjusting tank. And adding 30% dilute hydrochloric acid at the outlet of the tubular microfiltration device to neutralize until the pH value is 7-8, and then obtaining first neutral high-salt clear water.
S2, introducing the first neutral high-salt clear water obtained in the S1 into a first-level pollution-resistant RO device, allowing the water produced by the first-level pollution-resistant RO device to enter a second-level pollution-resistant brackish water RO device to obtain qualified produced water, returning the concentrated water generated by the second-level pollution-resistant brackish water RO device to an inlet of the first-level pollution-resistant RO device, recycling the concentrated water generated by the second-level pollution-resistant brackish water RO device, and introducing the concentrated water generated by the first-level pollution-resistant RO device into an ozone catalytic oxidation tower and an active carbon adsorption filter to obtain second neutral high-salt clear water.
And S3, introducing the second neutral high-salt clear water obtained in the step S2 into a countercurrent regenerated weak-acidic resin softening bed to obtain third neutral high-salt clear water.
S4, introducing third neutral high-salt clear water obtained in S3 into a NF8040F nanofiltration membrane device, introducing water produced by the NF8040F nanofiltration membrane device into a high-pressure pollution-resistant XC70 reverse osmosis device, introducing concentrated water produced by the NF8040F nanofiltration membrane device into a freeze crystallization device and an MVR to separate out sodium sulfate salt, flushing slag by mother liquor mainly containing sodium chloride salt generated by the freeze crystallization device, introducing clear water produced by the high-pressure pollution-resistant XC70 reverse osmosis device into a secondary pollution-resistant brackish water RO device, introducing concentrated water produced by the high-pressure pollution-resistant XC70 reverse osmosis device into a defluorination resin exchange bed, and treating by the defluorination resin exchange bed to obtain fourth neutral high-salt clear water.
And S5, introducing the fourth neutral high-salt clear water obtained in the step S4 into an electrodialysis device, returning the water produced by the electrodialysis device to a high-salt wastewater adjusting tank, introducing the concentrated water of the electrodialysis device into a chelating resin ion exchange bed, introducing the effluent into a bipolar membrane electrodialysis device in the chelating resin ion exchange bed to obtain 5-8% of dilute hydrochloric acid and 5-8% of dilute sodium hydroxide solution, and introducing the dilute brine produced by the bipolar membrane electrodialysis into a defluorination resin exchange bed for recovery treatment.
The invention can effectively treat and recycle the high-salinity wastewater in ferrous metallurgy, and realizes zero discharge of the high-salinity wastewater in the steel industry; and meanwhile, products such as sodium chloride, sodium sulfate and the like are obtained, the operation cost is low, the effect is good, and the method has practical significance for realizing water conservation, consumption reduction and income increase of iron and steel enterprises.
The above embodiments of the present invention are described in detail, and the principle and the implementation of the present invention are explained by applying specific embodiments, and the above description of the embodiments is only used to help understanding the method of the present invention and the core idea thereof; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (10)
1. A processing system for resource utilization of high-salinity wastewater in ferrous metallurgy is characterized by comprising:
the high-salinity wastewater regulating tank is communicated with an inlet pipeline of the high-salinity wastewater regulating tank and is used for regulating and buffering the water quantity and the water quality of the high-salinity wastewater;
the softening reaction tank is communicated with the outlet of the high-salinity wastewater adjusting tank and is used for reducing the hardness and alkalinity of the high-salinity wastewater and removing silica scale and heavy metals;
the concentration sedimentation tank is communicated with the outlet of the softening reaction tank and is used for reducing suspended matters of the high-salinity wastewater;
the sludge dewatering device is communicated with a sludge discharge port of the concentration sedimentation tank, a water outlet of the sludge dewatering device is communicated with an inlet of the high-salinity wastewater regulating tank, and the effluent of the sludge dewatering device returns to the high-salinity wastewater regulating tank to form a closed circuit for sludge waste treatment;
the tubular microfiltration device is communicated with the water outlet of the concentration sedimentation tank and is used for further reducing suspended matters of the high-salinity wastewater, and the outlet of the tubular microfiltration device is also communicated with the water inlet of the concentration sedimentation tank;
the first-stage RO device is communicated with the outlet of the tubular microfiltration device and is used for reducing the salt content in the high-salinity wastewater;
the second-stage RO device is communicated with the first-stage RO device clear water outlet and is used for further reducing the salt content in the clear water produced by the first-stage RO device, the concentrated water outlet of the second-stage RO device is communicated with the first-stage RO device inlet, the concentrated water returns to the first-stage RO device to form a closed circuit, and the clear water produced by the clear water outlet of the second-stage RO device is a clear water resource and is recycled;
the ozone catalytic oxidation device is communicated with the concentrated water outlet of the primary RO device and is used for reducing COD in the high-salinity concentrated water of the primary RO device;
the activated carbon adsorption device is communicated with the outlet of the ozone catalytic oxidation device and is used for further reducing COD in the high-salinity concentrated water;
the resin softening device is communicated with the outlet of the activated carbon adsorption device and is used for reducing the hardness of the high-salinity concentrated water and removing residual total metal ions;
the nanofiltration device is communicated with the outlet of the resin softening device and is used for separating monovalent anions and cations and divalent and polyvalent anions and cations in the effluent of the resin softening device;
the freezing and crystallizing device is communicated with a concentrated water outlet of the nanofiltration device and is used for separating a sodium chloride component and a sodium sulfate component in the nanofiltration concentrated water, and mother liquor mainly containing the sodium chloride component is subjected to slag flushing treatment after separation to obtain a sodium chloride product for recycling;
the evaporative crystallization device is communicated with the outlet of the freezing crystallization device and is used for evaporating and crystallizing sodium sulfate components in the freezing crystallization device into sodium sulfate so as to obtain a sodium sulfate product for recycling;
the high-pressure reverse osmosis device is communicated with the water outlet of the nanofiltration device and is used for further concentrating the water produced by the nanofiltration device; the clean water port of the high-pressure reverse osmosis device is connected with the water inlet of the secondary RO device, and the produced water of the high-pressure reverse osmosis device returns to the secondary RO device to form a closed circuit;
the fluorine removal device is communicated with the concentrated water outlet of the high-pressure reverse osmosis device and is used for removing fluorine ions in the concentrated water of the high-pressure reverse osmosis device;
the electrodialysis device is communicated with the water outlet of the defluorination device and is used for further concentrating the water produced by the defluorination device; a water production port of the electrodialysis device is connected with the high-salinity wastewater regulating reservoir, and water produced by the electrodialysis device returns to the high-salinity wastewater regulating reservoir to form a closed circuit;
the ion exchange device is communicated with the concentrated water outlet of the electrodialysis device and is used for removing heavy metals in the concentrated water of the electrodialysis device;
the bipolar membrane electrodialysis device is communicated with the outlet of the ion exchange device and is used for further separating the outlet water of the ion exchange device to generate a dilute hydrochloric acid product and a dilute alkali liquor product for recycling;
a dilute brine outlet of the bipolar membrane electrodialysis device is connected with a water inlet of the defluorination device, and the dilute brine of the bipolar membrane electrodialysis device returns to the defluorination device to form a closed circuit;
and bipolar membrane electrodialysis, which is communicated with the concentrated water outlet of the electrodialysis device and is used for further separating the electrodialysis concentrated water to generate a dilute hydrochloric acid product and a dilute alkali liquor product for recycling.
2. The treatment system for recycling high-salinity wastewater from ferrous metallurgy according to claim 1, characterized in that the softening reaction tank is of an open-type square structure, a stirring device is arranged in the softening reaction tank, and the stirring device is a guide cylinder type mechanical stirring device;
the concentrating and precipitating tank is in a closed square or round lower cone structure, a sludge concentrating device is arranged in the concentrating and precipitating tank, and the sludge concentrating device is slow scraper equipment.
3. The treatment system for recycling high-salinity wastewater from ferrous metallurgy according to claim 1, wherein the tubular microfiltration device is made of PVDF, PES or PTFE; the second-stage RO device of the first-stage RO device is a low-pressure pollution-resistant reverse osmosis device; the ozone catalytic oxidation device adopts an ozone catalytic oxidation tower, and a catalyst is filled in the ozone catalytic oxidation tower.
4. The treatment system for recycling high-salinity wastewater from ferrous metallurgy according to claim 1, characterized in that the activated carbon adsorption device is 10-28 mm pieces of shelled activated carbon for adsorbing organic matters in water; the resin softening device is a weak acid cation resin exchange device with the working exchange capacity of more than or equal to 2000mmol/l-R (H).
5. The treatment system for recycling high-salinity wastewater from ferrous metallurgy according to claim 1, characterized in that the nanofiltration device is a low-pressure anti-pollution organic composite nanofiltration membrane device.
6. The treatment system for recycling high-salinity wastewater from ferrous metallurgy according to claim 1, characterized in that the freezing and crystallizing device is a freezing and crystallizing separation device, and the evaporative crystallizing device is a triple effect evaporative crystallizing device or an MVR evaporative crystallizing device.
7. The treatment system for recycling high-salinity wastewater from ferrous metallurgy according to claim 1, characterized in that the high-pressure reverse osmosis device is a high-pressure resistant and anti-pollution seawater reverse osmosis device, a disc tube type reverse osmosis device or a disc type reverse osmosis device; the defluorination device adopts a F860 defluorination resin exchange device with a macroporous structure.
8. The treatment system for recycling high-salinity wastewater from ferrous metallurgy according to claim 1, wherein the electrodialysis device is a homogeneous membrane or an alloy membrane; the ion exchange device adopts a chelating cation resin device D851.
9. The treatment system for recycling of high-salinity wastewater from ferrous metallurgy according to claim 1, characterized in that the sludge dewatering device is preferably a mechanical concentration + plate-and-frame filter press or centrifugal dewatering or spiral dewatering device, and the bipolar membrane electrodialysis device is a three-compartment bipolar membrane electrodialysis device.
10. A treatment method for recycling high-salinity wastewater in ferrous metallurgy, which adopts the treatment system of claim 1, and is characterized by comprising the following steps:
s1: introducing high-salt wastewater into a high-salt wastewater adjusting tank for homogenizing and uniform treatment, introducing the high-salt wastewater into a softening reaction tank, adding alkali liquor with the concentration of 5% -30% and sodium carbonate solution with the concentration of 5% -15% into the softening reaction tank for chemical reaction precipitation, stirring, introducing the high-salt wastewater into a concentration precipitation tank for precipitation and clarification, conveying the produced water of the concentration precipitation tank into a tubular microfiltration device, conveying the chemical reaction precipitate generated by the concentration precipitation tank into a sludge dewatering device, returning the wastewater generated by the sludge dewatering device into the high-salt wastewater adjusting tank, adding 30% dilute hydrochloric acid at the outlet of the tubular microfiltration device for neutralization until the pH value is 7-8, and obtaining first neutral high-salt clear water;
the content of suspended matters in the first neutral high-salt clear water is less than 1mg/L, and the hardness content is less than 25 mg/L;
s2: introducing the first neutral high-salt clear water into a primary RO device for desalting treatment, introducing the water produced by the primary RO device into a secondary RO device, further desalting the water produced by the primary RO device to obtain qualified produced water for recycling, returning the concentrated water produced by the secondary RO device to the inlet of the primary RO device to form a closed circuit, introducing the concentrated water produced by the primary RO device into an ozone catalytic oxidation device and an active carbon adsorption device, further removing COD (chemical oxygen demand) in the concentrated water, and obtaining second neutral high-salt clear water;
the COD content in the second neutral high-salt clear water is less than 15 mg/L;
s3: introducing the second neutral high-salt clear water into a resin softening device for hardness and heavy metal removal treatment to obtain third neutral high-salt clear water;
the hardness content of the third neutral high-salt clear water is less than 5 mg/L;
s4: introducing the third neutral high-salinity clear water into a nanofiltration device, introducing the water produced by the nanofiltration device into a high-pressure reverse osmosis device, introducing the concentrated water produced by the nanofiltration device into a freezing crystallization device and an evaporative crystallization device, and separating out sodium sulfate salt, wherein mother liquor which is mainly sodium chloride salt and is generated by the freezing crystallization device is subjected to slag flushing and utilization, clear water produced by the high-pressure reverse osmosis device enters a secondary RO device, and the concentrated water produced by the high-pressure reverse osmosis device enters a defluorination device and is treated by the defluorination device to obtain fourth neutral high-salinity clear water;
the fluoride content in the fourth neutral high-salt clear water is less than 5 mg/L;
s5: and introducing the fourth neutral high-salt clear water into an electrodialysis device for concentration and purification, returning the water produced by the electrodialysis device to a high-salt wastewater regulating reservoir for homogenizing and uniform treatment, introducing the concentrated water of the electrodialysis device into an ion exchange device for removing divalent and above heavy metal cations, introducing the effluent of the ion exchange device into a bipolar membrane electrodialysis device to obtain 5-8% dilute hydrochloric acid and 5-8% dilute sodium hydroxide solution, and introducing the dilute brine generated by the bipolar membrane electrodialysis into a defluorinating resin exchange bed for recovery treatment.
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| CN114163054A (en) * | 2021-12-02 | 2022-03-11 | 苏州金渠环保科技有限公司 | Near-zero emission treatment process for steel pickling wastewater |
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| CN114163054A (en) * | 2021-12-02 | 2022-03-11 | 苏州金渠环保科技有限公司 | Near-zero emission treatment process for steel pickling wastewater |
| CN114180756A (en) * | 2021-12-14 | 2022-03-15 | 莱特莱德(上海)技术有限公司 | Treatment device and method for softening and desalting high-salinity high-hardness wastewater |
| CN114716053A (en) * | 2022-03-02 | 2022-07-08 | 华电水务工程有限公司 | Softening pretreatment method for high-COD high-salinity wastewater |
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