CN107540134B - Strong brine standard-reaching discharge treatment system and method for cold rolling wastewater ion exchange - Google Patents

Strong brine standard-reaching discharge treatment system and method for cold rolling wastewater ion exchange Download PDF

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CN107540134B
CN107540134B CN201610497265.6A CN201610497265A CN107540134B CN 107540134 B CN107540134 B CN 107540134B CN 201610497265 A CN201610497265 A CN 201610497265A CN 107540134 B CN107540134 B CN 107540134B
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heavy metal
low
temperature plasma
metal adsorption
resin
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CN107540134A (en
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吴昊
殷玫婕
秦志浩
陈砚秋
倪建春
宋艳丽
施杰
胡义纯
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Baowu Water Technology Co., Ltd
Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
Baosteel Engineering and Technology Group Co Ltd
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Abstract

The invention discloses a strong brine standard-reaching discharge treatment system and method for cold rolling wastewater ion exchange. The treatment effect is stable, the production running cost is low, the operation is simple and convenient, and the effluent quality reaches the standard.

Description

Strong brine standard-reaching discharge treatment system and method for cold rolling wastewater ion exchange
Technical Field
The invention relates to the technical field of water treatment, in particular to a standard-reaching discharge treatment system and a treatment method for strong brine generated by ion exchange of cold rolling wastewater in the steel industry.
Background
The latest emission standard of wastewater in the steel industry, namely the emission standard of water pollutants in the steel industry, is issued by the national environmental protection ministry in 2012 in 6 months (GB 13456-2012). The new standard sets stricter emission limits for main pollutants, for example, in the emission Standard of Water pollutants for iron and Steel industry (GB13456 1992), the first-class standard requires that CODcr is less than or equal to 100mg/L, oil is less than or equal to 8mg/L, and SS is less than or equal to 70mg/L, and the new standard table 3 cold rolling wastewater emission regulations, CODcr is less than or equal to 30mg/L, oil is less than or equal to 1mg/L, and SS is less than or equal to 20 mg/L. In addition, the new standard adds part of pollutant emission control items, such as total iron, total copper, total arsenic, total chromium, total lead, total nickel, total cadmium, total mercury and the like. Standards require that from 1/2015, existing enterprises must perform as required in table 2, which has been of higher density for homeland development. The water pollutant emission limit specified in table 3 is implemented in areas where the environmental bearing capacity begins to weaken, or the environmental capacity is small, the ecological environment is fragile, and serious environmental pollution problems easily occur, and special protective measures are required. Therefore, most iron and steel enterprises in China face upgrading and transformation, so that the finally discharged wastewater meets the requirements of new standards.
The cold rolling waste water is various in types and mainly comprises emulsion waste water, concentrated oil strong alkali waste water, leveling liquid waste water, thin oil weak alkali waste water, acid waste water, chromium-containing waste water and the like. The final discharged wastewater refers to the wastewater treated by the traditional procedures of oil removal, pH adjustment, oxidation, reduction, coagulating sedimentation, biochemistry and the like, and the water quality of the part of the wastewater is better than that of other cold rolling wastewater, so that the advanced treatment and the recycling are easier to carry out.
The strong brine is a well-known problem due to high ion content and complex components in the water, and at present, many enterprises often abandon the energy-saving and environment-friendly measure of wastewater recycling because of worry that the problem of strong brine treatment in the recycling process cannot be solved, and select direct discharge to increase the burden on the ecological environment. With the aim of energy conservation and emission reduction, the finally discharged wastewater can be deeply recycled by using an ion exchange method, so that the effluent meets the water replenishing requirement of a circulating cooling water system. However, the strong brine produced by the ion exchange method also needs to be treated, so that the effluent water of the ion exchange method also needs to meet the requirements of the emission standard of pollutants for water in the steel industry (GB13456-2012) in Table 3 to be discharged. The strong brine generated after the deep recycling of the ion exchange method mainly exceeds the standard water quality condition CODCr: 100-150mg/L, SS: 80-120mg/L, total nitrogen: 25-45mg/L, total lead: 0.16-0.24mg/L, total nickel: 0.082-0.11mg/L, total chromium: 0.12-0.22mg/L, total iron: 2.5-3 mg/L.
The standard discharge treatment processes of the concentrated brine adopted in the prior art are different, and the treatment processes are as follows, for example, the invention name with the publication number of CN 105084602A: the method for degrading COD in strong brine comprises the following steps: softening the strong brine, and reducing the hardness of the strong brine by a chemical method so as to remove part of COD in the strong brine; then the catalytic oxidation treatment and the flocculation sedimentation treatment are carried out to strengthen the flocculation effect, thereby achieving the purpose of degrading COD. The combination of catalytic oxidation technology and flocculation sedimentation technology can effectively degrade COD in the strong brine. The COD removal rate can be improved by 10-15%, and the chroma can be reduced by 5-10 times. However, besides the excessive COD, the excessive COD of the concentrated brine is accompanied by the excessive total nitrogen and other ions such as heavy metal ions. Meanwhile, a large amount of medicament needs to be added in the process of reducing the hardness of the concentrated brine by a chemical method, the operation cost is high, and the alkalinity of the concentrated brine can be improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a standard-reaching discharge treatment system for ion exchange strong brine aiming at high-conductivity cold rolling wastewater in a saturated state.
The technical problem to be solved can be implemented by the following technical scheme.
A strong brine standard-reaching discharge treatment system for cold rolling wastewater ion exchange sequentially comprises a neutralization tank, a lifting pump, a low-temperature plasma air floatation device, an electro-oxidation device, an intermediate water tank, a filter water inlet pump, a security filter and a heavy metal adsorption filter according to a wastewater flow sequence, wherein an outlet of the neutralization tank is connected with the lifting pump and then connected with the low-temperature plasma air floatation device;
the low-temperature plasma air floatation device comprises a low-temperature plasma generator, a multiphase flow water pump, a dissolved air tank and a release head which are sequentially connected, and a slag scraper positioned at the upper part of the device; the upper inlet of the low-temperature plasma air floatation device is connected with the water outlet pipeline of the lift pump, and the outlet of the low-temperature plasma air floatation device is connected with the electrooxidation device;
the low-temperature plasma air floatation device adopts a pulse power supply system, the pulse power supply system is a bipolar pulse power supply, the power supply adopts low-voltage alternating current (voltage 220V, frequency 50Hz), the pulse width is less than 600ns, the output working voltage is 30-40KV, the working pulse is more than 80Hz, and the discharge electrode system consists of a plurality of groups of electrodes; the electrode spacing is 10mm-20mm, and the surface is covered with an insulating medium; the device shell is made of organic glass material;
an electrooxidation air-floating electrode plate is arranged in the electrooxidation device and is divided into a positive electrode and a negative electrode, and the positive electrode and the negative electrode are overlapped into an electrode group in a cross arrangement and combination mode;
the thickness of an electrode plate of the electrooxidation device is 1-3 mm, the distance between adjacent electrode plates is 1-5 mm, and an insulating medium covers between an anode and a cathode of the electrode; the working voltage of the power supply is 0-30V, the output current is 0-400A, the medium flow rate is 0.5-2.5 m/s, and the output power of the rectifier cabinet is less than 12 kw.
As a further improvement of the technical scheme, the plasma in the low-temperature plasma air-floating device is composed of particles such as electrons, positive and negative ions, excited atoms, molecules and free radicals; the gas with hydroxyl radicals and ozone generated by the excitation of the air with humidity in the low-temperature plasma reaction bin by the low-temperature plasma generator is conveyed to the flowing wastewater by the release head, so that the hydroxyl radicals and the ozone are fully contacted with pollutants to generate an oxidation reaction, and the pollutants are directly oxidized into CO2Water or salt, and no secondary pollution.
The low-temperature plasma air floatation device sucks mixed gas of hydroxyl free radicals and ozone and water into a dissolved air tank through a multiphase flow water pump and releases the mixed gas and water through a release head. The release head rotates under the driving force of high-pressure water flow, large bubbles are cut into micro-nano bubbles, the bubbles are provided with negative charges, and the adsorption effect on pollutants or suspended matters in water is remarkable. The bubbles have slow rising speed, self-pressurization effect, very large specific surface area and supernormal gas dissolving capacity.
The electrode of the electro-oxidation device is in the heart position in the electro-catalytic oxidation technology, can conduct electricity, can activate reactants and improve the transfer rate of electrons. The electrode plate takes a titanium substrate as a base material, and has good conductivity, stable chemical property, corrosion resistance and loss resistance. The electrode is solidified with composite materials (such as Ti, SnO2, Pt, PbO2 and other noble metal materials) with good catalytic action as surface materials, and has the advantages of long operation period, consumption resistance of the electrode, no loss of the catalyst and no secondary pollution.
The electrooxidation device is internally provided with an electrooxidation air flotation electrode plate and an electrooxidation air flotation slag scraping machine. Alternating current passes through the electrode plate after being converted into direct current through rectification equipment, and the electrode plate produces the microbubble, through producing effects such as electrolytic coagulation, and the impurity of aquatic is carried to the surface of water by the microbubble and is scraped the sediment machine to the scum groove.
As a further improvement of the technical scheme, the neutralization tank is connected with a compressed air pipeline and is also connected with a sodium hydroxide medicament feeding pipe; the upper part of the electrooxidation device is provided with a slag scraper and a scum collecting tank, the bottom of the electrooxidation device is provided with a sediment collecting tank, and the outlet of the electrooxidation device is connected with the intermediate water tank; the outlet of the middle water tank is connected with a security filter through a filter water inlet pump, and the filter water inlet pump is also connected with the low-temperature plasma air floatation device; the outlet of the security filter is connected with the heavy metal adsorption filter; and the outlet of the heavy metal adsorption filter is connected to a discharge port.
In addition, the heavy metal adsorption filter is connected with a resin acid-base regeneration device, the inlet of the heavy metal adsorption filter is also connected with a pure water pipeline, and the outlet of the heavy metal adsorption filter is connected with a waste liquid tank; the inlet of the resin acid-base regeneration device is respectively connected with pure water, hydrochloric acid medicament and sodium hydroxide medicament, and the outlet of the resin acid-base regeneration device is respectively connected with the heavy metal adsorption filter through an acid and alkali liquor delivery pump.
Further, the pH value of the wastewater flowing through the neutralization tank after being neutralized by the sodium hydroxide is 6.5-8.5; aerating with compressed air, and stirring uniformly.
Similarly, the heavy metal adsorption filter can be internally provided with special chromium-removing resin, has better adsorption performance on other types of heavy metals and can adsorb common heavy metal ions. The main components of the resin are acrylic acid and acrylamide. The volume of the heavy metal adsorption filter is 40-100L, the volume of the built-in resin is 20-50L, and the resin volume accounts for 50-60%. The flow rate of the medium allowed by the heavy metal adsorption filter is 0.5-1.5 m/s.
The invention aims to solve another technical problem of providing a treatment method of a strong brine standard-reaching discharge treatment system adopting the above cold rolling wastewater ion exchange, which comprises the following steps:
(1) the air with humidity in the low-temperature plasma reaction bin in the low-temperature plasma air floatation device is excited by the low-temperature plasma generator to generate gas with hydroxyl radicals and ozone, the gas is conveyed to flowing wastewater through the release head, the hydroxyl radicals and the ozone are fully contacted with pollutants to generate oxidation reaction, and the gas is directly oxidized into CO2Water or salt;
(2) the electrooxidation device breaks bonds of organic molecules through direct electrocatalysis so as to degrade soluble organic matters and organic matters which are difficult to biodegrade in the wastewater; by anodic reaction to produce intermediate products with strong oxidation or by intermediate reactions other than anodic reaction to produce OH and O2Or HO2The free radical intermediate matters oxidize and degrade the treated pollutants.
As a further improvement of the method, the heavy metal adsorption filter is connected with a resin acid-base regeneration device, the inlet of the heavy metal adsorption filter is also connected with a pure water pipeline, and the outlet of the heavy metal adsorption filter is connected with a waste liquid tank; the inlet of the resin acid-base regeneration device is respectively connected with pure water, hydrochloric acid medicament and sodium hydroxide medicament, and the outlet of the resin acid-base regeneration device is respectively connected with the heavy metal adsorption filter through an acid and alkali liquor delivery pump.
And (3) regenerating a heavy metal adsorption filter: after the operation is carried out for a certain time, the resin layer of the heavy metal adsorption filter intercepts and adsorbs a certain amount of pollutants, and the quality of effluent water is deteriorated when the pressure difference between an inlet and an outlet is more than 0.5-0.8 Pa. Performing acid-base combined countercurrent regeneration by a resin regeneration device, firstly using a medicament, namely hydrochloric acid with the content of 5-10% in percentage by weight, and a regenerant with the dosage of 2 times of the volume of the resin, performing countercurrent regeneration, and then rinsing the resin to be nearly neutral by pure water; then using a medicament which is sodium hydroxide with the mass percent content of 4-8% and a regenerant with the dosage of 1 time of the volume of the resin, carrying out countercurrent regeneration, and rinsing the resin to be nearly neutral by using pure water after the countercurrent regeneration is finished.
The electrooxidation device in the method can remove impurities in water through the air flotation effect, and can degrade soluble organic matters in the wastewater, particularly organic matters which are difficult to biodegrade. The organic matter degradation principle is as follows:
1) direct oxidation, namely oxidation is carried out when the pollutants lose electrons directly at the anode, and direct electrocatalytic conversion of organic matters is carried out in two types: one is electrochemical conversion, i.e. converting toxic substances into non-toxic substances, or converting non-biocompatible organic substances into biocompatible substances (e.g. aromatic ring oxidation to fatty acids) for further biodegradation; and secondly, electrochemical combustion, namely, the organic matters are directly and deeply oxidized into carbon dioxide.
2) Indirect oxidation, i.e. by anodic reaction, to form intermediates (e.g. OH, O) with strong oxidation2、·HO2And the like) to finally achieve the purpose of oxidizing and degrading pollutants. Organic matter is degraded under the action of oxygen-containing free radicals, so that the current efficiency is improved, and the electric energy consumption is saved.
The electro-oxidation air floatation oxidizes the Fe in the wastewater2+Oxidation to Fe3+The flocculant can improve the air flotation effect and the filtration effect of the wastewater and remove Fe in the wastewater3+. Therefore, the electro-oxidation air floatation achieves the effects of degrading organic matters, removing suspended matters, sterilizing and killing algae under the condition of not adding any chemical agent.
After the strong brine subjected to the ion exchange of the cold rolling wastewater and treated by the standard-reaching discharge treatment system and the treatment method sequentially flows through the devices, the quality of the effluent of the system meets the standard in table 3 of the discharge standard of pollutants for water in the iron and steel industry (GB13456-2012), and the indexes of main pollutants can reach the following data:
pH:7.0-9.0,CODCr: less than or equal to 30mg/L, SS: less than or equal to 20mg/L, total nitrogen: less than or equal to 15mg/L, total lead: less than or equal to 1mg/L, total nickel: less than or equal to 0.5mg/L, total chromium: less than or equal to 1mg/L, total iron: less than or equal to 2 mg/L.
The process for treating the cold rolling wastewater by ion exchange strong brine to reach the standard has the advantages of stable treatment effect, low production and operation cost and simple and convenient operation, and the quality of effluent can reach the standard of Table 3 in the discharge Standard of pollutants for Water in the iron and Steel industry (GB 13456-2012); by adopting the process system, only two medicaments, namely hydrochloric acid and sodium hydroxide are used, so that the effects of pollutants such as COD (chemical oxygen demand), SS (suspended solid), total nitrogen, heavy metals and the like are achieved, and the operation cost of wastewater treatment is reduced.
Drawings
FIG. 1 is a process flow diagram of the standard-reaching treatment of cold-rolled ion-exchange concentrated brine provided by the invention;
FIG. 2 is a schematic diagram of an application of the acid tank of the present invention;
FIG. 3 is a schematic diagram of an application flow of the lye tank of the present invention;
FIG. 4 is a schematic view of an application of the waste liquid tank according to the present invention;
FIG. 5 is a schematic view of an electrooxidation apparatus;
FIG. 6 is a schematic diagram of an electrode structure of an electrooxidation apparatus.
In the figure: 1-neutralization tank 2-lift pump 3-low temperature plasma air flotation 4-low temperature plasma generator 5-multiphase flow water pump 6-dissolved air tank 7-slag scraper 8-rectifier cabinet 9-electrooxidation device 10-electrode plate 11-intermediate water tank 12-filter water inlet pump 13-safety filter 14-heavy metal adsorption filter 15-sodium hydroxide 16-aeration head 17-release head 18-waste residue collection tank 19-hydrochloric acid 20-heavy metal removal resin 21-waste liquid tank 22-pure water 23-acid liquid tank 24-acid liquid delivery pump 25-alkali liquid tank 26-alkali liquid delivery pump 27-waste liquid delivery pump 28-positive electric stage 29-negative electrode 30-insulating net
Detailed Description
The following description will explain embodiments of the present invention in further detail with reference to the accompanying drawings.
Example 1
Example 1 the concentrated brine generated when the final discharge wastewater of the cold rolling wastewater station is deeply recycled by the ion exchange method is used as raw water, the quality of the raw water is shown in the following table 1, the treatment capacity is 0.1m3/h, and the treatment flow of example 1 is shown in the treatment flow of fig. 1.
Table 1: water quality meter
The wastewater sequentially passes through a neutralization tank 1, a lifting pump 2, a low-temperature plasma air float 3, an electro-oxidation device 9, an intermediate water tank 11, a filter water inlet pump 12, a cartridge filter 13 and a heavy metal adsorption filter 14. The neutralization tank 1 neutralizes the wastewater to pH 7.5 by means of an agent of sodium hydroxide 15, and aerates by means of compressed air, stirring uniformly (i.e. by means of an aeration head 16 in fig. 1).
The low-temperature plasma air floatation device comprises a low-temperature plasma generator 4, a multiphase flow water pump 5, a dissolved air tank 6 and a release head 17 which are connected in sequence. The plasma in the low-temperature plasma device is composed of particles such as electrons, positive and negative ions, excited atoms, molecules, radicals and the like. The low-temperature plasma device is used for exciting air with humidity in the low-temperature plasma reaction bin to generate gas with hydroxyl radicals and ozone, and then the gas is conveyed to sewage through the release head, so that the hydroxyl radicals and the ozone are fully contacted with pollutants to generate oxidation reaction, and the gas is directly oxidized into CO2Water or salt, and no secondary pollution.
The low-temperature plasma device is characterized in that a pulse power supply system adopts a bipolar pulse power supply, the power supply adopts low-voltage alternating current (voltage 220v, frequency 50Hz), the pulse width is 500ns, the output working voltage is 30kv, the working pulse is 100Hz, and a discharge electrode system consists of a plurality of groups of electrodes. The electrode spacing is 15mm, and the surface is covered with an insulating medium. The device shell is made of organic glass materials.
The electrode plate 10 of the electric oxidation device 9 is connected with an external rectifying cabinet 8, the electrode is divided into a positive electrode 28 and a negative electrode 29, the positive electrode 28 and the negative electrode 29 are overlapped into an electrode group shown in figure 6 in a cross arrangement combination mode, and an insulating net 30 is arranged between the positive electrode 28 and the negative electrode 29. The electrooxidation device breaks bonds of organic molecules through direct electrocatalysis, and can degrade soluble organic matters in the wastewater, particularly organic matters which are difficult to biodegrade. Intermediate products having strong oxidation effect produced by the anodic reaction or intermediate substances (. OH,. O) produced by intermediate reactions other than the anodic reaction2、·HO2Equal free radical), oxidizing the treated pollutant, and finally achieving the purpose of oxidizing and degrading the pollutantThe purpose is.
The electrode of the electro-oxidation device is in the heart position in the electro-catalytic oxidation technology, can conduct electricity, can activate reactants and improve the transfer rate of electrons. The electrode takes a titanium substrate as a base material, and has good conductivity, stable chemical property, corrosion resistance and loss resistance). The electrode is solidified into a composite material (Ru noble metal material) with good catalytic action as a surface material, and has the advantages of long running period, consumption resistance of the electrode, no loss of the catalyst and no secondary pollution.
The thickness of an electrode plate of the electrooxidation device is 1mm, the distance between adjacent electrode plates is 3mm, and an insulating medium covers between the anode and the cathode of the electrode. The working voltage of the power supply is 10v, the output current is 350A, and the medium flow velocity is 1 m/s. The output power of the rectifier cabinet is 3.5 kw.
The upper surface of the electro-oxidation device 9 is provided with a slag scraper 7 and a scum collecting tank 18, and the bottom of the electro-oxidation device is provided with a sediment collecting tank.
The heavy metal adsorption filter 14 is internally provided with chromium-removing special resin (see heavy metal-removing resin 20 in the figure), and has better adsorption performance on other types of heavy metals, and can adsorb common heavy metal ions. The main components of the resin are acrylic acid and acrylamide. The volume of the heavy metal adsorption filter 14 is 40L, the volume of the built-in resin is 20L, and the volume percentage of the resin is 50%. The heavy metal adsorption filter allows a medium flow rate of 1 m/s.
And (3) regenerating a heavy metal adsorption filter: after the operation is carried out for a certain time, the resin layer of the heavy metal adsorption filter intercepts and adsorbs a certain amount of pollutants, and the effluent quality is deteriorated when the pressure difference between an inlet and an outlet is more than 0.5. Through a resin regeneration device, acid-base combined countercurrent regeneration is adopted, hydrochloric acid (the joint is shown as the position 19 in the figure) with the medicament content of 5 percent is firstly used, the dosage of the regenerant is 2 times of the volume of the resin, countercurrent regeneration is carried out, and then pure water (the joint is shown as the position 22 in the figure) is used for rinsing to be close to neutrality; then using a medicament which is sodium hydroxide (the interface is referred to as the right side of the reference number 15 in the figure 1) with the mass percent of 4 percent, using the regenerant with the volume 1 time of the resin volume, carrying out countercurrent regeneration, and rinsing the resin to be nearly neutral by using pure water after the regeneration is finished.
As shown in fig. 2, the acid solution tank 23, which is a regeneration link of the heavy metal adsorption filter 14, is connected schematically, one end of the acid solution tank 23 is a water inlet for hydrochloric acid and pure water, and the other end is led to the heavy metal adsorption resin through an acid solution delivery pump 24. Similarly, as shown in FIG. 3, one end of the lye tank 25 is connected with the inlets for sodium hydroxide and pure water, and the other end is connected to the heavy metal adsorption resin via a lye pump 26. In the acid-base combined countercurrent regeneration process of the resin regeneration device, the waste liquid passes through the waste liquid tank 21 in fig. 4 and is sent to the professional heavy metal recovery through the waste liquid conveying pump 27.
The effluent quality of the system of example 1 is shown in table 2 below:
table 2: water quality condition of effluent
Example 2
Example 2 the final discharge wastewater from the cold rolling wastewater station was used and the concentrated brine produced during the deep recycling by the ion exchange method was used as the raw water, the quality of which is shown in table 3 below, and the treatment amount was 0.2m3Example 2 the process flow is as shown in FIG. 1.
Table 3: water quality meter
The wastewater sequentially passes through a neutralization tank 1, a lifting pump 2, a low-temperature plasma air float 3, an electro-oxidation device 9, an intermediate water tank 11, a filter water inlet pump 12, a cartridge filter 13 and a heavy metal adsorption filter 14.
The neutralization tank neutralizes the wastewater to pH 7.8 with sodium hydroxide agent, and aerates with compressed air and stirs uniformly.
The plasma in the low-temperature plasma device is composed of particles such as electrons, positive and negative ions, excited atoms, molecules, radicals and the like. The low-temperature plasma device excites air with humidity in the low-temperature plasma reaction bin to generate gas with hydroxyl radicals and ozone, and the gas is conveyed to sewage through the release head to ensure that the hydroxyl radicals and the ozone are fully contacted with pollutants to generate oxidation reaction until the oxidation reaction is carried outThen oxidizing it to CO2Water or salt, and no secondary pollution.
The low-temperature plasma device is characterized in that a pulse power supply system adopts a bipolar pulse power supply, the power supply adopts low-voltage alternating current (voltage 220V, frequency 50Hz), the pulse width is 500ns, the output working voltage is 30kv, the working pulse is 100Hz, and a discharge electrode system consists of a plurality of groups of electrodes. The electrode spacing is 15mm, and the surface is covered with an insulating medium. The device shell is made of organic glass materials.
The electrode of the electrooxidation device is divided into a positive electrode and a negative electrode, and the positive electrode and the negative electrode are overlapped into an electrode group in a cross arrangement combination mode. The electrooxidation device breaks bonds of organic molecules through direct electrocatalysis, and can degrade soluble organic matters in the wastewater, particularly organic matters which are difficult to biodegrade. Intermediate products having strong oxidation effect produced by the anodic reaction or intermediate substances (. OH,. O) produced by intermediate reactions other than the anodic reaction2、·HO2And the like) to oxidize the treated pollutants, and finally, the purpose of oxidizing and degrading the pollutants is achieved.
The electrode of the electro-oxidation device is in the heart position in the electro-catalytic oxidation technology, can conduct electricity, can activate reactants and improve the transfer rate of electrons. The electrode takes a titanium substrate as a base material, and has good conductivity, stable chemical property, corrosion resistance and loss resistance). The electrode is solidified with a composite material (PbO2 precious metal material) with good catalytic action as a surface material, and has the advantages of long running period, consumption resistance of the electrode, no loss of catalyst and no secondary pollution.
The electrooxidation device is characterized in that the thickness of the electrode plate is 1mm, the distance between adjacent electrode plates is 2mm, and insulating media cover between the anode and the cathode of the electrode. The power supply working voltage is 10v, the output current is 330A, and the medium flow rate is 0.9 m/s. The output power of the rectifier cabinet is 3.3 kw.
The upper surface of the electrooxidation device is provided with a slag scraping machine and a scum collecting tank, and the bottom of the electrooxidation device is provided with a sediment collecting tank.
The heavy metal adsorption filter is internally provided with special chromium-removing resin, has better adsorption performance on other types of heavy metals and can adsorb common heavy metal ions. The main components of the resin are acrylic acid and acrylamide. The volume of the heavy metal adsorption filter is 40L, the volume of the built-in resin is 20L, and the resin volume accounts for 50%. The heavy metal adsorption filter allows a medium flow rate of 0.9 m/s.
And (3) regenerating a heavy metal adsorption filter: after the operation is carried out for a certain time, the resin layer of the heavy metal adsorption filter intercepts and adsorbs a certain amount of pollutants, and the effluent quality is deteriorated when the pressure difference between an inlet and an outlet is more than 0.5. Performing acid-base combined countercurrent regeneration by a resin regeneration device, firstly using a medicament, namely hydrochloric acid with the content of 5 percent in percentage by weight, using 2 times of resin volume of a regenerant, performing countercurrent regeneration, and then rinsing the resin to be nearly neutral by using pure water; then the sodium hydroxide with the mass percentage content of 4 percent is used as a medicament, the dosage of a regenerant is 1 time of the volume of the resin, the resin is regenerated in a countercurrent mode, and the resin is rinsed to be nearly neutral by pure water after the regeneration is finished.
The effluent quality of the system of example 2 is shown in table 4 below:
table 4: water quality condition of effluent
The standard-reaching discharge treatment process and the standard-reaching discharge treatment system for the strong brine of the cold rolling wastewater ion exchange provided by the invention are specially used for the characteristic of the saturated high-conductivity sewage of the strong brine of the cold rolling wastewater ion exchange, adopt a specific sequence, mainly utilize technical means such as low-temperature plasma air flotation, an electro-oxidation device, heavy metal adsorption and the like, achieve a better treatment effect, have the advantages of stable treatment system, good effect, low treatment cost and convenience in operation, and the quality of the effluent can reach the quality of the effluent which basically meets the requirements of the discharge standard of pollutants in the steel industry (GB13456-2012) in Table 3. Also can be used as a strong brine standard-reaching discharge treatment process flow for cold rolling and silicon steel wastewater standard improvement and reconstruction.

Claims (9)

1. A strong brine standard-reaching discharge treatment system for cold rolling wastewater ion exchange is characterized by sequentially comprising a neutralization tank, a lifting pump, a low-temperature plasma air floatation device, an electro-oxidation device, an intermediate water tank, a filter water inlet pump, a security filter and a heavy metal adsorption filter according to a wastewater flow sequence, wherein an outlet of the neutralization tank is connected with the lifting pump and then connected with the low-temperature plasma air floatation device; a chromium-removing special resin is arranged in the heavy metal adsorption filter;
the low-temperature plasma air floatation device comprises a low-temperature plasma generator, a multiphase flow water pump, a dissolved air tank and a release head which are sequentially connected, and a slag scraper positioned at the upper part of the device; the upper inlet of the low-temperature plasma air floatation device is connected with the water outlet pipeline of the lift pump, and the outlet of the low-temperature plasma air floatation device is connected with the electrooxidation device;
the low-temperature plasma air floatation device adopts a pulse power supply system, the pulse power supply system comprises a bipolar pulse power supply, the voltage of the bipolar pulse power supply is 220V, the frequency is 50Hz, the pulse width is less than 600ns, the output working voltage is 30-40KV, the working pulse is more than 80Hz, a discharge electrode system consists of a plurality of groups of electrodes, and the electrode spacing is 10mm-20 mm;
an electrooxidation air-floating electrode plate is arranged in the electrooxidation device and is divided into a positive electrode and a negative electrode, and the positive electrode and the negative electrode are overlapped into an electrode group in a cross arrangement and combination mode;
the thickness of an electrode plate of the electrooxidation device is 1-3 mm, the distance between adjacent electrode plates is 1-5 mm, and an insulating medium covers between an anode and a cathode of the electrode; the working voltage of the power supply is 0-30V, the output current is 0-400A, the medium flow rate is 0.5-2.5 m/s, and the output power of the rectifier cabinet is less than 12 kw.
2. The ion-exchanged strong brine discharge-reaching treatment system for cold rolling wastewater according to claim 1, wherein plasmas in the low-temperature plasma air flotation device comprise electrons, positive and negative ions, excited atoms, molecules and free radicals; and the gas with hydroxyl radicals and ozone generated by the excitation of the air with humidity in the low-temperature plasma reaction bin by the low-temperature plasma generator is conveyed to the wastewater flowing through the release head.
3. The ion-exchanged concentrated brine reaching the standard discharging treatment system for the cold rolling wastewater according to claim 1, wherein the electrode plate takes a titanium substrate as a base material, and one or more metal composite materials selected from Ti, SnO2, Pt or PbO2 are solidified on the surface of the electrode plate.
4. The ion-exchanged strong brine discharge standard treatment system for cold rolling wastewater according to claim 1, wherein the neutralization tank is connected with a compressed air pipeline and is further connected with a sodium hydroxide medicament feeding pipe; the upper part of the electrooxidation device is provided with a slag scraper and a scum collecting tank, the bottom of the electrooxidation device is provided with a sediment collecting tank, and the outlet of the electrooxidation device is connected with the intermediate water tank; the outlet of the middle water tank is connected with a security filter through a filter water inlet pump, and the filter water inlet pump is also connected with the low-temperature plasma air floatation device; the outlet of the security filter is connected with the heavy metal adsorption filter; and the outlet of the heavy metal adsorption filter is connected to a discharge port.
5. The strong brine standard-reaching discharge treatment system for the cold-rolling wastewater ion exchange according to claim 1 or 4, wherein the heavy metal adsorption filter is connected with a resin acid-base regeneration device, a pure water pipeline is further connected to an inlet of the heavy metal adsorption filter, and an outlet of the heavy metal adsorption filter is connected with a waste liquid tank; the inlet of the resin acid-base regeneration device is respectively connected with pure water, hydrochloric acid medicament and sodium hydroxide medicament, and the outlet of the resin acid-base regeneration device is respectively connected with the heavy metal adsorption filter through an acid and alkali liquor delivery pump.
6. The system of claim 4, wherein the pH value of the waste water from the neutralization tank after being neutralized by the sodium hydroxide is 6.5-8.5.
7. The ion-exchanged strong brine discharge-reaching system of cold rolling wastewater according to claim 1, wherein the main components of the chromium-removing special resin are acrylic acid and acrylamide; the volume of the heavy metal adsorption filter is 40-100L, the volume of the built-in resin is 20-50L, and the resin volume accounts for 50-60%; the flow velocity of the medium allowed by the heavy metal adsorption filter is 0.5-1.5 m/s.
8. A strong brine standard-reaching discharge treatment method adopting the strong brine standard-reaching discharge treatment system for the ion exchange of the cold rolling wastewater in any one of claims 1, 2, 3, 4, 6 and 7 is characterized by comprising the following steps of:
(1) the air with humidity in the low-temperature plasma reaction bin in the low-temperature plasma air floatation device is excited by the low-temperature plasma generator to generate gas with hydroxyl radicals and ozone, the gas is conveyed to flowing wastewater through the release head, the hydroxyl radicals and the ozone are fully contacted with pollutants to generate oxidation reaction, and the gas is directly oxidized into CO2Water or salt;
(2) the electrooxidation device breaks bonds of organic molecules through direct electrocatalysis so as to degrade soluble organic matters and organic matters which are difficult to biodegrade in the wastewater; by anodic reaction to produce intermediate products with strong oxidation or by intermediate reactions other than anodic reaction to produce OH and O2Or HO2The free radical intermediate matters oxidize and degrade the treated pollutants.
9. The method for treating the standard-reaching discharge of the concentrated brine according to claim 8, wherein the heavy metal adsorption filter is connected with a resin acid-base regeneration device, a pure water pipeline is further connected to an inlet of the heavy metal adsorption filter, and an outlet of the heavy metal adsorption filter is connected with a waste liquid tank; the inlet of the resin acid-base regeneration device is respectively connected with pure water, hydrochloric acid medicament and sodium hydroxide medicament, and the outlet of the resin acid-base regeneration device is respectively connected with the heavy metal adsorption filter through an acid and alkali liquor delivery pump; when the pressure difference between an inlet and an outlet of the heavy metal adsorption filter is larger than 0.5-0.8 Pa, starting a resin acid-base regeneration device, performing acid-base combined countercurrent regeneration, firstly, using a medicament which is hydrochloric acid with the mass percentage content of 5% -10% and a regenerant with the dosage of 2 times of the resin volume, performing countercurrent regeneration, and then rinsing the obtained product with pure water to be close to neutral; then using a medicament which is sodium hydroxide with the mass percent content of 4-8% and a regenerant with the dosage of 1 time of the volume of the resin, carrying out countercurrent regeneration, and rinsing the resin to be nearly neutral by using pure water after the countercurrent regeneration is finished.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101306896A (en) * 2008-07-14 2008-11-19 中国矿业大学(北京) Process and system for treating high-ammonia-nitrogen-containing waste water
CN105217846A (en) * 2014-05-29 2016-01-06 宝山钢铁股份有限公司 Cold rolling alkaline waste discharge advanced treatment system and treatment process
CN105217826A (en) * 2014-05-29 2016-01-06 宝山钢铁股份有限公司 A kind of cold rolling wastewater advanced treatment system and treatment process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101306896A (en) * 2008-07-14 2008-11-19 中国矿业大学(北京) Process and system for treating high-ammonia-nitrogen-containing waste water
CN105217846A (en) * 2014-05-29 2016-01-06 宝山钢铁股份有限公司 Cold rolling alkaline waste discharge advanced treatment system and treatment process
CN105217826A (en) * 2014-05-29 2016-01-06 宝山钢铁股份有限公司 A kind of cold rolling wastewater advanced treatment system and treatment process

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