CN214571331U - Zero release and resourceful treatment system of industry high salt waste water - Google Patents
Zero release and resourceful treatment system of industry high salt waste water Download PDFInfo
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- CN214571331U CN214571331U CN202120520251.8U CN202120520251U CN214571331U CN 214571331 U CN214571331 U CN 214571331U CN 202120520251 U CN202120520251 U CN 202120520251U CN 214571331 U CN214571331 U CN 214571331U
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Abstract
The utility model belongs to the technical field of industrial waste water treatment, especially, relate to a zero release and resourceful treatment system of industry high salt waste water, its characterized in that includes that second grade chemistry removes hard device, remove the sheet frame filter pressing device that hard device is connected with second grade chemistry, the softening that the export of entry and sheet frame filter pressing device is connected deposits the device, the tubular micro-filtration device that the export of entry and softening deposit the device is connected, the sodium ion softening installation that the export of entry and tubular micro-filtration device is connected, the nanofiltration device that the export of entry and sodium ion softening installation is connected, the entry is with the bipolar membrane electrodialysis device that the product water gap of nanofiltration device is connected, the freezing crystallization device that the dense mouth of a river that the entry is connected with the nanofiltration device, the metathesis reaction device that the export of entry and freezing crystallization device is connected. The utility model provides a system can the high salt waste water of effective treatment industry, when multiple harmful substance in the waste water is got rid of to the substep, realizes resource recovery, has better development application prospect.
Description
Technical Field
The utility model belongs to the technical field of industrial waste water treatment, especially, relate to a zero release and resourceful treatment system of industry high salt waste water.
Background
With the continuous development of wastewater zero discharge technology in the industries of metallurgy, coal-fired power plants, petrochemical industry and the like, the treatment process of high-salinity wastewater gradually becomes a research hotspot. The industrial high-salinity wastewater is mainly characterized by complex chemical components and high salinity, which causes great treatment difficulty, and simultaneously has the problems of low yield, high treatment cost, easy generation of waste byproducts and the like in the resource process. If the waste water is not treated and discharged, the waste water can permeate into a soil system to destroy the structure of the soil, so that the activity of the soil is difficult to recover.
The traditional high-salinity wastewater zero-discharge technology mainly comprises membrane concentration and evaporative crystallization, most of the salt obtained by the method is mixed salt (namely sodium chloride and sodium sulfate), but the sodium chloride and the sodium sulfate have lower recovery value, the product still needs to be treated by solid waste or dangerous waste after the evaporative crystallization, and the zero discharge in the true sense is not realized.
Bipolar Membrane Electrodialysis (BMED) is a new type of ion exchange technology, and Bipolar membranes are generally formed by combining an anion exchange layer, a cation exchange layer and an interfacial hydrophilic layer. The bipolar membrane electrodialysis can dissociate water under the action of an electric field to obtain H on two sides of the membrane respectively+And OH, the salt in the solution is converted into corresponding acid and alkali, and the corresponding acid and alkali can be reused for pH adjustment or recovery in the system, so that the method has a good application prospect in the aspect of resource utilization of inorganic salt.
The double decomposition reaction of mirabilite and potassium chloride can prepare potassium sulfate, which is a high-quality potash fertilizer, especially suitable for avoiding chlorine crops and is a chemical fertilizer in short supply in the current market of China. The method has the advantages of simple process, low requirement on raw material quality, low investment, low energy consumption, no pollution and easy large-scale device, and is commonly used for the production of chemical enterprises.
Aiming at the defects in the zero-discharge treatment technology of the high-salinity wastewater at present, the bipolar membrane electrodialysis technology and the double decomposition reaction technology for preparing the chlorine-free potash fertilizer are combined, so that the real zero discharge can be realized effectively and practically, and the product is recycled as the resource, and the method is a new idea for treating the industrial high-salinity wastewater.
Disclosure of Invention
The utility model aims at providing a zero release and resource processing system of industry high salt waste water can carry out the zero release effectively to industry high salt waste water and handle and resource recycle product.
The purpose of the utility model is realized by the following technical scheme:
the utility model discloses a zero release and resourceful treatment system of industry high salt waste water, its characterized in that includes that second grade chemistry removes hard device, the frame filter pressing device that the export of entry and this second grade chemistry removes hard device is connected, the softening precipitation device that the export of entry and this frame filter pressing device is connected, the tubular micro-filtration device that the export of entry and this softening precipitation device is connected, the sodium ion softening installation that the export of entry and this tubular micro-filtration device is connected, the nanofiltration device that the export of entry and this sodium ion softening installation is connected, the bipolar membrane electrodialysis device that the product water mouth of entry and this nanofiltration device is connected, the entry with the freezing crystallization device that the dense mouth of nanofiltration device is connected, the inlet is with the metathesis reaction device that this freezing crystallization device's export is connected,
the second-stage chemical hardness removal device comprises a neutralization tank, a reaction tank with an inlet connected with an outlet of the neutralization tank, a plate-frame filter pressing device with an inlet connected with an outlet of the reaction tank,
the softening and precipitating device comprises a softening device and a precipitating device, the inlet of the precipitating device is connected with the outlet of the softening device, the outlet of the plate frame filter pressing device is connected with the inlet of the softening device, the outlet of the precipitating device is connected with the inlet of the tubular microfiltration device, the outlet of the tubular microfiltration device is connected with the inlet of the precipitating device,
and introducing industrial high-salinity wastewater into a neutralization tank of the secondary chemical hardness removal device.
And the outlet of the bipolar membrane electrodialysis device is respectively connected with the inlet of the sodium ion softening device and the inlet of the nanofiltration device.
The outlet of the bipolar membrane electrodialysis device is connected with the reaction tank of the secondary chemical hardness removal device.
And the sewage discharge port of the precipitation device is connected with the plate frame filter pressing device.
And a byproduct outlet of the freezing crystallization device is connected with an inlet of the nanofiltration device.
And a byproduct outlet of the double decomposition reaction device is connected with an inlet of the nano-filtration device.
The utility model has the advantages that:
(1) the utility model discloses a zero release and resourceful processing system of industry high salt waste water utilizes the second grade chemistry to remove hard device at first, successively adds lime cream and sodium hydroxide solution (bipolar membrane electrodialysis product part retrieval and utilization) respectively in neutralization groove and reaction tank, carries out the chemical reaction with hardness, fluoride, silica scale, heavy metal and basicity in the waste water and deposits and get rid of, then carries out the filter-pressing by sheet frame filter-pressing device and handles, has both reduced the medicine volume of subsequent processing suspended solid in the waste water, alleviates the operation burden of rear end equipment to the suspended solid index again; the supernatant fluid after filter pressing is sent to a softening and precipitating device, and after a hardness removing agent is added, permanent calcium and magnesium hardness is effectively removed under an alkaline condition; the effluent is connected to a tubular microfiltration device to further remove suspended matters and slightly soluble hardness in the wastewater.
(2) The utility model discloses a zero release and resource treatment system of industrial high-salinity wastewater, which adopts the bipolar membrane electrodialysis technology, and can realize the desalination and acid-base preparation of the high-salinity wastewater simultaneously under the condition of not introducing other components; compared with the evaporative crystallization technology, the treatment product of the bipolar membrane electrodialysis can be reused in a high-salt wastewater treatment system, and has more advantages in the aspects of product utilization value and the like;
(3) the utility model discloses a zero release and resourceful treatment system of industry high salt waste water has adopted freezing crystallization and metathesis reaction to handle and has received the divalent salt sodium sulfate of branch salt concentrated water, has not only solved the difficult problem that the solid waste of result was handled to the potassium sulphate that makes can carry out resourceful recycle as chlorine-free potash fertilizer, reaches real zero release and handles.
Drawings
Fig. 1 is a schematic structural diagram of the present invention.
Detailed Description
The following further describes the embodiments of the present invention with reference to the drawings.
As shown in figure 1, the utility model discloses a zero release and resource treatment system of industrial high-salinity wastewater, which is characterized in that comprises a second-level chemical hardness removal device 1, a plate-frame filter pressing device 2 with an inlet connected with an outlet of the second-level chemical hardness removal device 1, a softening and precipitating device 3 with an inlet connected with an outlet of the plate-frame filter pressing device 2, a tubular microfiltration device 4 with an inlet connected with an outlet of the softening and precipitating device 3, a sodium ion softening device 5 with an inlet connected with an outlet of the tubular microfiltration device 4, a nanofiltration device 6 with an inlet connected with an outlet of the sodium ion softening device 5, a bipolar membrane electrodialysis device 7 with an inlet connected with a water producing port of the nanofiltration device 6, a freezing and crystallization device 8 with an inlet connected with a dense water port of the nanofiltration device 6, a double decomposition reaction device 9 with an inlet connected with an outlet of the freezing and crystallization device 8,
the secondary chemical hardness removal device 1 comprises a neutralization tank 1-1, a reaction tank 1-2 with an inlet connected with an outlet of the neutralization tank 1-1, an inlet of the plate-frame filter pressing device 2 is connected with an outlet of the reaction tank 1-2,
the softening and precipitating device 3 comprises a softening device 3-1 and a precipitating device 3-2, the inlet of the precipitating device is connected with the outlet of the softening device 3-1, the outlet of the plate frame filter pressing device 2 is connected with the inlet of the softening device 3-1, the outlet of the precipitating device 3-2 is connected with the inlet of the tubular microfiltration device 4, the outlet of the tubular microfiltration device 4 is connected with the inlet of the precipitating device 3-2,
and introducing industrial high-salinity wastewater into a neutralization tank 1-1 of the secondary chemical hardness removal device 1.
The outlet of the bipolar membrane electrodialysis device 7 is respectively connected with the inlet of the sodium ion softening device 5 and the inlet of the nanofiltration device 6.
The outlet of the bipolar membrane electrodialysis device 7 is connected with the reaction tank 1-2 of the secondary chemical hardness removal device 1.
And the sewage discharge port of the precipitation device 3-2 is connected with the plate frame filter pressing device 2.
The byproduct outlet of the freezing and crystallizing device 8 is connected with the inlet of the nanofiltration device 6.
The by-product outlet of the double decomposition reaction device 9 is connected with the inlet of the nano-filtration device 6.
The utility model discloses a zero release and resourceful treatment system of industry high salt waste water, include:
the secondary chemical hardness removal device 1 comprises a neutralization tank 1-1 and a reaction tank 1-2, and is used for reducing the hardness, fluoride, silicon scale, heavy metal and alkalinity of the desulfurization wastewater; the plate frame filter pressing device 2 is communicated with the secondary chemical hardness removal device 1 and is used for reducing suspended matters of the high-salinity wastewater; the softening and precipitating device 3 is communicated with the plate-frame filter pressing device 2 and is used for reducing the hardness of the high-salinity wastewater; the tubular microfiltration device 4 is communicated with the softening and precipitating device 3 and is used for removing suspended matters in the high-salinity wastewater and reducing the hardness and silica scale in the high-salinity wastewater; the sodium ion softening device 5 is communicated with the tubular microfiltration device 4 and is used for removing the hardness in the high-salinity wastewater; the nanofiltration device 6 is communicated with the sodium ion softening device 5 and is used for separating salt from the high-salinity wastewater; the bipolar membrane electrodialysis device 7 is communicated with a water outlet of the nanofiltration device 6 and is used for desalting the high-salinity wastewater (the products are hydrochloric acid solution and sodium hydroxide solution); the freezing and crystallizing device 8 is communicated with a concentrated water outlet of the nanofiltration device 6 and is used for extracting mirabilite from concentrated water of the bipolar membrane electrodialysis device 7; and the double decomposition reaction device 9 is communicated with the outlet of the freezing and crystallizing device 8 and is used for converting the mirabilite into chlorine-free potassium fertilizer (potassium sulfate).
Preferably, 1-3 mol/L hydrochloric acid solution of the bipolar membrane electrodialysis product is recycled to the inlet of the sodium ion softening device and the inlet of the nanofiltration device 5 for adjusting the pH value;
preferably, the bipolar membrane electrodialysis product 1-3 mol/L sodium hydroxide solution is recycled to the inlet of the reaction tank 1-2 of the second-stage hardness removal device 1 for adjusting the pH value;
preferably, the sewage discharge port of the softening and precipitating device 3 is connected with a plate-and-frame filter pressing device 2;
preferably, the by-product outlet of the freezing and crystallizing device 8 is connected to the inlet of the nanofiltration device 6;
preferably, the by-product outlet of the metathesis reaction unit 9 is connected to the inlet of the nanofiltration unit 6;
the utility model discloses at first utilize second grade chemistry to remove hard device 1, successively add lime milk and sodium hydroxide solution (bipolar membrane electrodialysis result part retrieval and utilization) respectively in neutralization groove 1-1 and reaction tank 1-2, carry out the chemical reaction with hardness, fluoride, silica scale, heavy metal and basicity in the waste water and deposit and get rid of, then carry out the filter-pressing by sheet frame filter-pressing device 2 and handle, both reduced the charge volume of suspended solid in the follow-up treatment waste water, alleviateed the operation burden of rear end equipment to the suspended solid index again. And (3) delivering the filter-pressed supernatant into a softening and precipitating device 3, and adding a hardness removing agent to effectively remove the permanent calcium and magnesium hardness under an alkaline condition. The effluent is connected to a tubular microfiltration device 4 to further remove suspended matters and slightly-dissolved hardness in the wastewater. Furthermore, the utility model discloses a bipolar membrane electrodialysis technique can realize high salt waste water desalination and acid-base preparation simultaneously under the condition of not introducing other components. Compared with the evaporative crystallization technology, the treatment product of the bipolar membrane electrodialysis can be reused in a high-salt wastewater treatment system, and has more advantages in the aspects of product utilization value and the like. On the other hand, the utility model discloses a freezing crystallization and double decomposition reaction are handled and are received divalent salt sodium sulfate in the branch salt dense water, have not only solved the difficult problem that the product was useless admittedly and handled to the potassium sulfate that makes can regard as chlorine-free potash fertilizer to carry out resource recycle, reach real zero release and handle.
Fig. 1 is a schematic structural diagram of an industrial high-salinity wastewater zero-discharge and recycling treatment system according to an embodiment of the present invention.
Referring to fig. 1, in this embodiment, a zero discharge treatment and recycling treatment system for industrial high-salinity wastewater is provided, which is used for treating industrial high-salinity wastewater. The processing system comprises: the device comprises a neutralization tank 1-1 of a secondary chemical hardness removal device 1, a reaction tank 1-2 of the secondary chemical hardness removal device 1, a plate frame filter pressing device 2, a softening device 3-1, a precipitation device 3-2, a tubular microfiltration device 4, a sodium ion softening device 5, a nanofiltration device 6, a bipolar membrane electrodialysis device 7, a freezing crystallization device 8 and a double decomposition reaction device 9 which are connected in sequence.
As the sedimentation device 3-2 can generate sludge when in use, the plate-and-frame filter pressing device 2 is also connected with the sewage discharge outlet of the sedimentation device 3-2 and is used for collecting the sludge. Meanwhile, a hydrochloric acid solution product outlet of the bipolar membrane electrodialysis device 7 is connected with inlets of the sodium ion softening device 5 and the nanofiltration device 6 and is used for adjusting the pH value; the sodium hydroxide solution product outlet of the bipolar membrane electrodialysis device 7 is connected with the inlet of the reaction tank 1-2 of the second-stage hardness removal device 1 and is used for adjusting the pH value. In addition, a byproduct outlet of the freezing and crystallizing device 8 and a byproduct outlet of the metathesis reaction device 9 are connected to an inlet of the nanofiltration device 6.
Wherein, the stirring devices in the secondary chemical hardness removal device 1 and the softening device 3-1 are preferably provided with a guide cylinder type mechanical stirring device. The secondary chemical de-hardening means 1 and the softening means 3-1 are preferably closed square structures. The transmission device of the settling device 3-2 is preferably a mechanical slow scraper device with a guide cylinder, and the settling device 3-2 is preferably in a closed square or round lower cone structure form. The tubular microfiltration device 4 uses a tubular microfiltration membrane, and the material is preferably PP, PVDF, PES or PTFE. The sodium ion softening device 5 is preferably a counter-current regeneration sodium ion softening device or a co-current regeneration sodium ion softening device. The nanofiltration device 6 uses nanofiltration membrane, and the material is preferably CA, SPS, SPES or PVA. The bipolar membrane electrodialysis device 7 is preferably a three-chamber bipolar membrane electrodialysis device. The freezing and crystallizing device 8 is preferably an automatic operation device, is easy to overhaul and maintain on line, and can avoid certain potential safety hazards.
The metathesis reaction device 9 needs to add reactants of potassium chloride and water, the mass concentration of potassium element in the system is controlled to be 9.5 wt% -11.5 wt% (preferably 10 wt% -11 wt%), the reaction is completed by two steps, the operation temperature of the first step reaction is ensured to be 20-25 ℃, and the operation temperature of the second step reaction is ensured to be 60-100 ℃. The product of the double decomposition reaction is potassium sulfate which can be used as chlorine-free potash fertilizer in agriculture, and the byproduct (mainly sodium chloride) flows back to the inlet of the nano-filtration device 6 for continuous circulation treatment.
In addition, in the embodiment, acid (1 mol/L-3 mol/L hydrochloric acid solution) and alkali (1 mol/L-3 mol/L sodium hydroxide solution) generated by the bipolar membrane electrodialysis device 7 are partially recycled in a front-end device for adjusting pH, so that the utilization rate of the product is improved, and the running cost of zero emission of high-salinity wastewater is reduced.
In this embodiment, a treatment method for zero discharge and recycling of industrial high-salinity wastewater is also provided, the treatment system for industrial high-salinity wastewater is utilized, and the structure and the function of each device in the treatment system can be further explained by the treatment method. The treatment method comprises the following specific steps:
step S1: and (3) introducing the high-salinity wastewater into a secondary chemical hardness removal device 1, adding a calcium hydroxide solution and recycled alkali liquor to perform chemical reaction precipitation, and stirring to obtain a first chemical reaction precipitate and alkaline high-salinity wastewater.
The secondary chemical hardness removal device 1 adopts calcium ions and fluorine ions to form calcium fluoride precipitates, calcium agents are introduced to reduce the hardness and COD content of water, the calcium ions and the fluorine ions are used as calcium hydroxide solution with the preferred concentration of 5% -10%, recycled alkali liquor is added at the same time, the pH value of the wastewater is adjusted to 10-11, the alkali liquor is used as sodium hydroxide solution with the preferred concentration of 1-3 mol/L, and magnesium ions and hydroxide ions are enabled to generate magnesium hydroxide precipitates. The chemical reaction formula is as follows: ca2++2F-→CaF2↓，Mg2++2OH-→Mg(OH)2↓. When the pH value of most heavy metals in the wastewater is adjusted to 10-11, metal hydroxide precipitates can be generated. Considering that the waste water contains more magnesium ions and can be used as a silicon removing agent, the excessive magnesium ions are not required to be introduced.
Step S2: and (3) conveying the chemical reaction precipitate and the alkaline high-salt wastewater to a plate-and-frame filter pressing device 2 for filter pressing treatment, so that the sludge is separated from the alkaline high-salt wastewater.
As the wastewater contains more suspended matters, calcium, magnesium, heavy metals, fluoride and silicon scale precipitates and is extremely easy to precipitate in the wastewater, the plate-and-frame filter pressing device 2 is adopted for solid-liquid separation, the burden of a subsequent treatment system is reduced, and the plate-and-frame filter pressing device is used as a preferred high-pressure diaphragm for automatically flushing the plate-and-frame filter pressing device.
Step S3: and (3) sequentially introducing the alkaline high-salt wastewater into a softening device 3-1 (adding a hardness removing agent), a precipitation device 3-2 and a tubular microfiltration device 4 to obtain a second chemical reaction precipitate and alkaline high-salt clear water.
The hardness-removing agent can be sodium carbonate solution, and the concentration of the solution is 10-30%, preferably 15-20%. The hardness in the wastewater is primarily non-carbonate hardness, i.e., permanent hardness. 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↓. The second chemical reaction precipitate in the step is mainly calcium-magnesium sludge, and simultaneously has partial heavy metals and silica scale particles.
The settling device 3-2 is preferably in the form of a closed square or round lower cone structure, and the settling device 3-2 is also internally provided with a transmission device, such as a mechanical slow scraper device with a guide cylinder. Firstly, the wastewater after the reaction of the softening device 3-1 is introduced into a closed precipitation device 3-2, so that suspended matters and calcium-magnesium reaction precipitates in the wastewater are gathered and concentrated to form precipitates. And simultaneously, delivering the precipitate generated by the precipitation device 3-2 to the plate-and-frame filter pressing device 2 to generate sludge and alkaline high-salinity wastewater.
The wastewater is introduced into the tubular microfiltration device 4, suspended matters and calcium and magnesium ions in the wastewater are separated, and a coagulation agent and a coagulation aid agent are not introduced, so that the adding cost of the system agent is reduced.
After the above steps, the content of suspended substances in the alkaline high-salt clear water is less than 5mg/L, preferably less than 3 mg/L. The hardness content is less than 50mg/L, preferably less than 20 mg/L.
Step S4: adjusting the pH value of the alkaline high-salt clear water to be neutral, sequentially introducing a sodium ion softening device 5, a nanofiltration device 6 and a bipolar membrane electrodialysis device 7, further thoroughly removing the hardness of calcium and magnesium in the wastewater, performing salt separation and resource treatment, and obtaining a hydrochloric acid solution and a sodium hydroxide solution at an outlet of the bipolar membrane electrodialysis device 7, wherein part of the hydrochloric acid solution and the sodium hydroxide solution can be recycled to a front-end device for adjusting the pH value.
Preferably, a bipolar membrane electrodialysis product 1-3 mol/L hydrochloric acid solution is partially recycled to adjust the pH value of the wastewater to 7-8, bipolar membrane electrodialysis is developed based on a bipolar membrane water dissociation process and an electrodialysis technology, acid and alkali can be regenerated in situ and partially recycled, and other components are not required to be added. Because of its environmental protection, it is considered as a high-efficiency membrane separation technology in the treatment of saline-alkali wastewater. The bipolar membrane electrodialysis device 7 is preferably a three-chamber bipolar membrane electrodialysis device.
Step S5: the concentrated water produced by the nanofiltration device 6 passes through a freezing crystallization device 8 and a double decomposition reaction device 9 in sequence, and after the concentrated water produced by salt separation through nanofiltration is nitrified in the freezing crystallization device 8, the obtained product (mirabilite) reacts with potassium chloride to generate a chlorine-free potassium fertilizer, namely potassium sulfate. The byproducts generated by the freezing and crystallizing device 8 and the double decomposition reaction device 9 are connected to the inlet of the nano-filtration device for recycling treatment.
Preferably, the process of preparing the chlorine-free potash fertilizer from the mirabilite and the potassium chloride is completed by adopting two-step double decomposition reaction, the operating temperature of the first step of reaction is ensured to be 10-30 ℃, the preferred temperature is 20-25 ℃, the operating temperature of the second step of reaction is 60-100 ℃, and the preferred temperature is 70-90 ℃. Meanwhile, the mass concentration of the potassium element in the system is controlled to be 9.5 wt% -11.5 wt%, and the preferred concentration is 10 wt% -11 wt%.
The utility model discloses a zero release and resourceful processing's of industry high salt waste water method utilizes bipolar membrane electroosmosis system technique and glauber's salt law to make potassium sulphate technique coupled, has realized not having newly-increased pollutant, product resource recovery and saving cost, has advantages such as economic nature and suitability.
The above treatment process is further illustrated below with respect to industrial high-salinity wastewater of known initial water quality.
The initial water quality of the industrial high-salinity wastewater is shown in table 1.
Table 1:
the specific treatment method comprises the following steps:
1) introducing the high-salinity wastewater into a secondary chemical hardness removal device 1 (a neutralization tank 1-1 and a reaction tank 1-2) with a guide flow cylinder type mechanical stirring device, introducing a 5% calcium hydroxide solution and a 1-3 mol/L sodium hydroxide solution (part of bipolar membrane electrodialysis products are recycled), stirring and adjusting the pH value of the wastewater to 11.5, and obtaining a first chemical reaction precipitate and alkaline high-salinity wastewater.
2) And (3) introducing the first chemical reaction precipitate and the alkaline high-salt wastewater into a high-pressure diaphragm automatic flushing plate-and-frame filter pressing device 2 for solid-liquid separation to obtain sludge and the alkaline high-salt wastewater.
3) And (2) sequentially introducing the alkaline high-salt wastewater into a softening device 3-1 with a guide flow cylinder type mechanical stirring device, a precipitation device 3-2 with a guide flow cylinder type mechanical slow scraper device and a tubular microfiltration device 4, introducing a drain outlet of the precipitation device 3-2 into a high-pressure diaphragm automatic flushing plate-frame filter pressing device 2, adding a 10% sodium carbonate solution into the softening device 3-1, and synchronously removing permanent hardness, heavy metal ions and silica scale in the wastewater to obtain a second chemical reaction precipitate and slightly alkaline high-salt clear water.
4) And adding 1-3 mol/L hydrochloric acid solution (part of bipolar membrane electrodialysis products is recycled) into the alkaline high-salt clear water obtained in the last step to adjust the pH value of the wastewater to 7.5, sequentially introducing a countercurrent regeneration sodium ion softening device 5, a nanofiltration device 6 and a three-chamber bipolar membrane electrodialysis device 7, and ensuring that the hardness of the wastewater at the outlet of the countercurrent regeneration sodium ion softening device 5 is approximately equal to 0 mmol/L. After the treatment by the device, 1-3 mol/L hydrochloric acid solution and sodium hydroxide solution are obtained at the bipolar membrane electrodialysis outlet and can be partially reused in a front-end device for adjusting the pH value, wherein the hydrochloric acid solution can be reused at the inlet of a reaction tank 1-2 of the secondary hardness removal device 1, and the sodium hydroxide solution can be reused at the inlets of a sodium ion softening device 5 and a nanofiltration device 6.
5) And (2) sequentially introducing the concentrated water of the nanofiltration device 6 obtained in the last step into a freezing crystallization device 8 and a double decomposition reaction device 9, and after nitrate is taken out from the concentrated water generated by salt separation through nanofiltration in the freezing crystallization device 8, reacting the obtained product (mirabilite) with potassium chloride (the mass concentration of potassium element is 9.5 wt% -11.5 wt%) to generate potassium sulfate. The byproducts generated by the freezing and crystallizing device 8 and the double decomposition reaction device 9 are connected to the inlet of the nano-filtration device for recycling treatment.
The utility model provides a zero release and resourceful treatment system of industry high salt waste water removes impurity such as hardness, fluoride, silica scale, heavy metal, suspended solid in the industry high salt waste water through second grade chemistry except that hard device 1, sheet frame filter pressing device 2, softening precipitation device 3, tubular micro-filtration device 4 are got rid of to utilize sodium ion softening installation 5 to further get rid of dissolving Ca in the water2+、Mg2+And the ion is treated by the nanofiltration device 6 and the bipolar membrane electrodialysis device 7 to obtain 1-3 mol/L hydrochloric acid solution and sodium hydroxide solution which can be partially reused for adjusting the pH of the reaction tank 1-2, the sodium ion softening device 5 and the nanofiltration device 6, concentrated water generated by the nanofiltration device 6 passes through the freezing crystallization device 8 to generate mirabilite, the mirabilite and potassium chloride are subjected to double decomposition reaction to prepare chlorine-free potassium fertilizer, resource recycling is achieved, and reaction byproducts (mainly sodium chloride) flow back to the nanofiltration device 6, so that zero discharge treatment of industrial high-salinity wastewater is realized. The utility model provides a system can the high salt waste water of effective treatment industry, when multiple harmful substance in the waste water is got rid of to the substep, realizes resource recovery, has better development application prospect.
Claims (6)
1. A zero-emission and recycling treatment system for industrial high-salinity wastewater is characterized by comprising a secondary chemical hardness removal device, a plate-frame filter pressing device with an inlet connected with an outlet of the secondary chemical hardness removal device, a softening and precipitating device with an inlet connected with an outlet of the plate-frame filter pressing device, a tubular microfiltration device with an inlet connected with an outlet of the softening and precipitating device, a sodium ion softening device with an inlet connected with an outlet of the tubular microfiltration device, a nanofiltration device with an inlet connected with an outlet of the sodium ion softening device, a bipolar membrane electrodialysis device with an inlet connected with a water production port of the nanofiltration device, a freezing and crystallizing device with an inlet connected with a thick water port of the nanofiltration device, and a metathesis reaction device with an inlet connected with an outlet of the freezing and crystallizing device,
the second-stage chemical hardness removal device comprises a neutralization tank, a reaction tank with an inlet connected with an outlet of the neutralization tank, a plate-frame filter pressing device with an inlet connected with an outlet of the reaction tank,
the softening and precipitating device comprises a softening device and a precipitating device, the inlet of the precipitating device is connected with the outlet of the softening device, the outlet of the plate frame filter pressing device is connected with the inlet of the softening device, the outlet of the precipitating device is connected with the inlet of the tubular microfiltration device, the outlet of the tubular microfiltration device is connected with the inlet of the precipitating device,
and introducing industrial high-salinity wastewater into a neutralization tank of the secondary chemical hardness removal device.
2. The system for zero discharge and recycling of industrial high-salinity wastewater according to claim 1, characterized in that the outlet of the bipolar membrane electrodialysis device is connected to the inlet of the sodium ion softening device and the inlet of the nanofiltration device respectively.
3. The system for zero discharge and recycling of industrial high-salinity wastewater according to claim 1, characterized in that the outlet of the bipolar membrane electrodialysis device is connected with the reaction tank of the secondary chemical hardness removal device.
4. The system for zero discharge and resource treatment of industrial high-salinity wastewater according to claim 1, characterized in that the sewage discharge outlet of the settling device is connected with the plate-and-frame filter pressing device.
5. The system for zero discharge and recycling of industrial high-salinity wastewater according to claim 1, characterized in that the byproduct outlet of the freezing and crystallizing device is connected with the inlet of the nanofiltration device.
6. The system for zero emission and recycling of industrial high-salinity wastewater according to claim 1, characterized in that the by-product outlet of the metathesis reaction device is connected with the inlet of the nanofiltration device.
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