CN217627987U - Sodium sulfate-containing high-salinity wastewater resource utilization system - Google Patents
Sodium sulfate-containing high-salinity wastewater resource utilization system Download PDFInfo
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Abstract
The utility model discloses a recycling system for high-salinity wastewater containing sodium sulfate, which comprises a precipitation acidification extraction separation device, a concentration device, an ion exchange device and an acid-base preparation device; the precipitation acidification extraction separation device comprises a precipitation kettle, a precision filter, a pipeline mixer, a liquid membrane extraction separation tower, a first oil-water separator, a temporary storage tank for extracted brine, a rotational flow high-voltage pulse electrostatic emulsion breaker and a second oil-water separator; the concentration device comprises a homogeneous membrane electrodialyzer; the ion exchange device comprises a plurality of stages of ion exchange resin towers connected in series; the acid-base preparation device comprises a bipolar membrane electrodialyzer. The utility model discloses a harmful cation to the membrane except sodium ion, potassium ion, chloride ion, ammonium ion, lithium ion of sodium sulfate aqueous solution that the system was handled can fall to below 1 ppm.
Description
Technical Field
The utility model belongs to the technical field of waste water resource recycle, a contain sodium sulfate high salt waste water is related to, concretely relates to contain sodium sulfate high salt waste water resource utilization system.
Background
The high-salinity wastewater containing sodium sulfate is mainly produced in the industrial production fields of hydrometallurgy, materials, chemical industry and the like. In recent decades, with the development of rare earth and nonferrous metal industries, people have higher and higher requirements on the purity and the accurate proportion of materials, the separation technology of similar metals develops very rapidly, particularly, the extraction separation technology is utilized to ensure that the purity of the metals is higher, and the proportion of alloy materials is more accurate, so that more excellent new materials, such as corrosion-resistant and high-temperature-resistant alloys, power battery anode materials and the like, are produced. However, with the development of industries such as hydrometallurgy and material manufacturing, serious environmental protection problems are brought, and a large amount of wastewater containing sodium sulfate, high salt and high TOC is mainly generated, especially the wastewater generated by the production and recycling of large-capacity electric vehicle power batteries developed in the last two decades becomes a pain point in the industry. The nickel, cobalt and manganese in the ternary lithium anode material of the power battery are separated and purified from raw materials to produce a ternary precursor, at least 60 tons of sodium sulfate-containing high-salt wastewater containing 3-10% is produced per gold ton, and 320 ten thousand tons of high-salt, high-TOC and high ammonia nitrogen wastewater containing nickel, cobalt and manganese heavy metals can be produced every year in a 50000-ton-year economic scale ternary precursor production factory, wherein the contained sodium sulfate is 112000 tons. The high-salt wastewater has higher treatment cost, toxic and harmful organic matters in the high-salt wastewater are not treated by an economical method at present, ammonia nitrogen in the wastewater containing ammonia nitrogen needs to be stripped and deaminated before other methods are treated, the energy consumption is higher due to large amount of wastewater, the most economical biochemical treatment technology still has no breakthrough progress in the aspect of high-salt wastewater treatment, the current popular method is a mechanical vapor recompression (MVR-mechanical vapor recompression) high-temperature crystallization method, the method is distilled and crystallized after front-end chemical treatment to obtain anhydrous sodium sulphate, the method is widely applied to hydrometallurgy manufacturers due to simplicity and feasibility, the pressure of wastewater treatment in the industries is relieved, but a large amount of anhydrous sodium sulphate is generated, the byproducts have limited use, the good value is only 50-150 yuan, the product is usually sold at a price and is not excessive in transport cost, and the accumulated anhydrous sodium sulphate enterprises are more and more, and the water-soluble salts and heavy metals which can not be used as common solid waste landfill are generated, so that the problem of high-salt wastewater production cannot be normally treated by the enterprises is solved. On the other hand, the large amount of high-salinity wastewater generated by the enterprises is mainly the large amount of caustic soda, sulfuric acid and ammonia water used at the front end of the process, and along with the change of the national economic structure in the years, the most basic three acids and two bases in the chemical industry rise in price to different degrees, so that technical workers in the industry introduce the technology of preparing acid and alkali from inorganic salt into the recycling of the acid and alkali from waste salt, and the problem of comprehensive treatment and utilization of the high-salinity wastewater is expected to be fundamentally solved.
The method is divided into asbestos diaphragms and ionic membranes of different types according to different types of membranes adopted, the asbestos diaphragms are eliminated by the industry due to outdated process, low product quality and high energy consumption, only a small amount of asbestos diaphragms are used for wastewater treatment, and the ionic membrane method has very high requirements on the quality of electrolyzed brine and is rarely applied to the field of wastewater treatment due to large investment; the other technology for preparing acid and alkali from inorganic salt is a bipolar membrane electrodialysis method, the method is low in energy consumption, only generates acid and alkali corresponding to salt to be treated, and becomes a hotspot technology for industrial waste salt treatment, but similar to an ionic membrane, the membrane of the bipolar membrane electrodialysis has higher quality requirement on salt water and is only inferior to the ionic membrane, and the method is certainly the most important, even the only way for recycling high-salt wastewater in the future due to low energy consumption and no other byproducts. Then, the purification of high-salinity wastewater becomes the biggest technical obstacle to recycling. The main difficulty in purifying the high-salinity wastewater is to remove organic matters contained in the wastewater, particularly organic matters which are insoluble in water or soluble in water but have relatively large molecular weight, and on the other hand, to remove impurities harmful to the bipolar membrane, such as other cations, insoluble silicon substances and the like in the wastewater. The common removal of anions and cations has a relatively mature technology in the chlor-alkali industry, but the removal of organic matters and trace silicon substances has different treatment methods for different types of organic matters contained in different production links of waste water, but the methods for treating the waste water produced by the bipolar membrane electrodialysis, particularly the waste water produced by hydrometallurgy and power battery anode materials, are not many at present. The organic matters in the production wastewater mainly come from extracting agents and diluent kerosene of a hydrometallurgical extraction separation system, the extracting agents are mainly acidic phosphate esters or acidic phosphinic acid extracting agents (such as P204, P507 and C272), and the chemical properties of the extracting agents are stable, so that the bipolar membrane electrodialysis requirement can not be met by low-cost treatment of a conventional method.
Chinese patents with application numbers of CN201910255856.6, CN201910255859.X, CN201811419673.5, CN201810909767.4, CN201810408625.X, CN201510684466.2 and the like disclose a method for treating hydrometallurgy wastewater, and organic matters dissolved in high-salt wastewater are physically separated and then oxidized and decomposed by means of ultrasonic demulsification air flotation separation, ultrafiltration, electrocatalytic oxidation, ozone oxidation, hydrogen peroxide-fenton oxidation and the like, and are further treated by activated carbon adsorption after even oxidation, so that TOC in water is reduced to prepare for next desalting. The TOC of the wastewater treated by the methods is above 100mg/L in a cost acceptable range, the total TOC can be concentrated to above 1000mg/L according to the concentration (concentrated to 25-30%) of the inlet water of the bipolar membrane electrodialysis in China, and the stable operation of the bipolar membrane electrodialysis requires that harmful organic matters are less than 5mg/L for water quality, so that the treatment difficulty is large.
Chinese patents CN202210063607.9, CN202210063839.4, CN 20209107.7, etc. disclose that anhydrous sodium sulphate made from waste water by MVR can meet the requirements of bipolar membrane electrodialysis by high temperature treatment of molten salt, but this method is to concentrate waste salt water to make salt, then remove organic matter at high temperature, then dissolve it with pure water to make acid and alkali by bipolar membrane electrodialysis, and is complex in operation and high in energy consumption. Therefore, how to develop a new process to overcome the defects of the prior art and solve the problem of direct purification of sodium sulfate wastewater becomes the key of resource utilization of the sodium sulfate-containing high-salt wastewater.
Disclosure of Invention
Not enough to prior art exists, the utility model aims to provide a sodium sulfate-containing high salt waste water resource utilization system solves the technical problem that sodium sulfate waste water treatment can not satisfy bipolar membrane electrodialysis quality of intaking.
In order to solve the technical problem, the utility model discloses a following technical scheme realizes:
a resource utilization system for sodium sulfate-containing high-salinity wastewater comprises a precipitation acidification extraction separation device, a concentration device, an ion exchange device and an acid-base preparation device;
the precipitation acidification extraction separation device comprises a precipitation kettle, wherein one feed inlet of the precipitation kettle is connected with a high-salinity wastewater pipeline through a heat exchanger; the other feed inlet of the precipitation kettle is sequentially connected with a sodium sulfide and sodium carbonate aqueous solution high-level tank, a first feeding pump and a sodium sulfide and sodium carbonate mixing tank, and the sodium sulfide and sodium carbonate mixing tank is respectively connected with a softened water pipeline and a sodium sulfide and sodium carbonate conveying pipeline;
the device comprises a precipitation kettle, a compressed air buffer tank, a fine filter, a pipeline mixer, a dilute sulfuric acid solution high-level tank, a discharge port of supernatant of the precipitation kettle, a feed port of a supernatant low-level tank, a compressed air pipeline, a discharge port of the supernatant low-level tank, a discharge port of the fine filter, an input port of the pipeline mixer, a dilute sulfuric acid solution pipeline and an output port of the pipeline mixer, wherein the discharge port of the supernatant of the precipitation kettle is connected with the feed port of the supernatant low-level tank;
the acidified saline water storage tank is connected with an upper feeding port of the liquid membrane extraction separation tower through a second feeding pump, a lower feeding port of the liquid membrane extraction separation tower is connected with a bottom discharging port of the missible oil preparation kettle, and an external circulating pump is arranged on the missible oil preparation kettle; one feed inlet of the missible oil preparation kettle is connected with a discharge outlet of the dilute alkali preparation tank sequentially through the dilute alkali high-level tank and the third feeding pump, one feed inlet of the dilute alkali preparation tank is connected with a dilute alkali pipeline, and the other feed inlet of the dilute alkali preparation tank is connected with a softened water pipeline; the other feed inlet of the missible oil preparation kettle is connected with the discharge outlet of the liquid film oil preparation collecting tank through a liquid film oil high-level tank and a fourth feeding pump in sequence;
an upper discharge port of the liquid membrane extraction separation tower is connected with a feed inlet of a temporary storage tank for the extracted missible oil; a lower discharge port of the liquid membrane extraction separation tower is connected with a feed port of a first oil-water separator, an upper discharge port of the first oil-water separator is connected with a feed port of a temporary storage tank for extracted missible oil, and a lower discharge port of the first oil-water separator is connected with a temporary storage tank for extracted brine;
the discharge port of the temporary storage tank for the extracted missible oil is connected with the feed port of the cyclone high-voltage pulse electrostatic emulsion breaker through a fifth feeding pump, the cyclone high-voltage pulse electrostatic emulsion breaker is provided with a high-voltage pulse electrostatic power supply, the upper discharge port of the cyclone high-voltage pulse electrostatic emulsion breaker is connected with the feed port of the liquid film oil preparation and collection tank, the lower discharge port of the cyclone high-voltage pulse electrostatic emulsion breaker is connected with the feed port of the second oil-water separator, the upper discharge port of the second oil-water separator is connected with the feed port of the liquid film oil preparation and collection tank, and the lower discharge port of the second oil-water separator is connected with a wastewater biochemical treatment section.
The utility model discloses still have following technical characteristic:
the other discharge port of the precision filter is connected with a back washing liquid storage tank, and the back washing liquid storage tank is connected with a back washing port of the precision filter through a back washing pump; the bottom of precision filter go out the concentrate mouth and the bottom of reation kettle goes out the concentrate mouth and all links to each other with waiting to press filtrating temporary storage tank, waits to press filtrating temporary storage tank to link to each other through the feed inlet of sixth charge pump with the pressure filter, the filtrating export of pressure filter links to each other with pressure filter filtrating temporary storage tank, pressure filter filtrating temporary storage tank links to each other with high salt waste water pipeline through seventh charge pump.
The concentration device comprises a homogeneous membrane electrodialyzer, the homogeneous membrane electrodialyzer is provided with a light brine circulation tank and a first circulation pump for light brine circulation, and the homogeneous membrane electrodialyzer is also provided with a strong brine circulation tank and a second circulation pump for strong brine circulation;
a feed inlet of the light brine circulating tank is connected with the extracted brine temporary storage tank through an eighth feeding pump, and a discharge outlet of the light brine circulating tank is connected with a pipeline of a pure water preparation system through a light brine discharge pump;
the feed inlet of the strong brine circulating tank is connected with a dilute brine pipeline generated in the acid and alkali making process, and the discharge outlet of the strong brine circulating tank is connected with the feed inlet of an ion exchange resin tower in the ion exchange device through a strong brine discharge pump.
The ion exchange device comprises a plurality of stages of ion exchange resin towers which are connected in series, a discharge hole of the strong brine circulating tank is respectively and independently connected with a liquid inlet at the top of each ion exchange resin tower through a strong brine discharge pump, a feed inlet at the top of each ion exchange resin tower is also connected with a dilute sulfuric acid solution pipeline, and a gas inlet at the top of each ion exchange resin tower is also independently connected with a compressed air pipeline; and a liquid outlet at the bottom of each ion exchange resin tower is connected with a temporary storage tank of purified concentrated sodium sulfate solution.
The liquid outlet at the bottom of each ion exchange resin tower is also connected with a filter press filtrate temporary storage tank in the precipitation acidification extraction separation device through a regenerated wastewater pipeline.
The acid-base preparation device comprises a bipolar membrane electrodialyzer, the bipolar membrane electrodialyzer is provided with a brine circulation tank and a third circulation pump for brine circulation, the bipolar membrane electrodialyzer is also provided with a polar water circulation tank and a fourth circulation pump for polar water circulation, the bipolar membrane electrodialyzer is also provided with a dilute alkali solution circulation tank and a fifth circulation pump for dilute alkali solution circulation, and the bipolar membrane electrodialyzer is also provided with a dilute sulfuric acid solution circulation tank and a sixth circulation pump for dilute sulfuric acid solution circulation;
the brine circulating tank is connected with a temporary storage tank of purified concentrated sodium sulfate solution in the ion exchange device through a ninth feeding pump;
the feed inlets of the polar water circulating tank, the dilute alkali solution circulating tank and the dilute sulfuric acid solution circulating tank are all connected with a pure water pipeline;
the discharge port of the polar water circulation tank is connected with the brine circulation tank through a polar water discharge pump, and the discharge port of the brine circulation tank is connected with the feed port of the strong brine circulation tank through a brine discharge pump;
the dilute alkali solution circulating tank is connected with a dilute alkali concentration pipeline through a dilute alkali solution discharge pump and is also connected with a dilute alkali preparation tank in the precipitation acidification extraction separation device;
the dilute sulfuric acid solution circulating tank is connected with a dilute sulfuric acid solution concentration pipeline through a dilute sulfuric acid solution discharge pump and is also connected with a feed inlet of a dilute sulfuric acid solution high-level tank in the precipitation, acidification, extraction and separation device.
Compared with the prior art, the utility model, following technological effect has:
the system can reduce the harmful cations on the membrane except sodium ions, potassium ions, chloride ions, ammonium ions and lithium ions to below 1 ppm.
(II) the utility model discloses owing to adopted emulsion liquid membrane extraction separation technique, the super hydrophilic oleophobic membrane oil-water separation technique of permeation formula, make the organic matter in the waste water show and reduce, TOC is less than 1mg/L, and the removal rate is got to TOC among the high salt waste water is up to more than 99.5%.
(III) the utility model discloses owing to adopted super hydrophilic oleophobic homogeneous phase membrane electrodialysis concentration technique, further held back remaining organic matter in the salt solution through the ionic electricity impetus separation, finally make salt solution TOC be less than 0.1mg/L, silicon class rotary floater is less than 1mg/L in the salt solution.
(IV) the utility model discloses owing to adopted emulsion liquid membrane extraction separation technique, make the organic matter transfer concentration in the high salt waste water high TOC, low salt, low heavy metal ion waste water, high TOC waste water volume reduces to the tenth of raw water volume moreover, and accessible biochemistry, low-cost technologies such as reverse osmosis are further handled return system and are used mechanically.
(V) the utility model discloses owing to adopted bipolar membrane electrodialysis system acid, alkali, the desorption that makes ammonia nitrogen in the waste water can be in the concentrated process desorption of dilute alkali that generates and retrieve the ammonia reuse, avoids having faced the problem that current technology sodium sulfate, ammonium sulfate separation difficulty and strip deamination nitrogen energy consumption are high.
(IV) the whole process of the system of the utility model is basically to operate the liquid fluid, which is very easy to realize the automation of the whole process and can reduce the energy consumption and the cost.
Drawings
FIG. 1 is a schematic diagram of the overall structure of a resource utilization system for sodium sulfate-containing high-salinity wastewater,
FIG. 2 is a schematic diagram of a precipitation acidification extraction separation device.
Fig. 3 is a schematic view of the configuration of the concentration device.
FIG. 4 is a schematic view of the structure of an ion exchange apparatus.
Fig. 5 is a schematic structural view of the acid-base preparation apparatus.
FIG. 6 is a schematic diagram of the liquid membrane extraction separation mechanism.
The meaning of the individual reference symbols in the figures is: 1-a precipitation acidification extraction separation device, 2-a concentration device, 3-an ion exchange device, 4-an acid-base preparation device, 5-a precipitation kettle, 6-a heat exchanger, 7-a high-salinity wastewater pipeline, 8-a sodium sulfide and sodium carbonate aqueous solution high-level tank, 9-a first feeding pump, 10-a sodium sulfide and sodium carbonate dosing tank, 11-a softened water pipeline, 12-a sodium sulfide and sodium carbonate conveying pipeline, 13-a supernatant low-level tank, 14-a compressed air buffer tank, 15-a compressed air pipeline, 16-a precision filter, 17-a pipeline mixer, 18-a dilute sulfuric acid solution high-level tank, 19-a dilute sulfuric acid solution pipeline, 20-an acidified saline water storage tank, 21-a second feeding pump, 22-an extraction separation tower and 23-a missible oil preparation kettle, 24-an external circulating pump, 25-a dilute alkali high-level tank, 26-a third feeding pump, 27-a dilute alkali preparation tank, 28-a dilute alkali pipeline, 29-a liquid membrane oil high-level tank, 30-a fourth feeding pump, 31-a liquid membrane oil preparation collection tank, 32-a first oil-water separator, 33-a temporary extracted emulsion oil tank, 34-a temporary extracted brine tank, 35-a fifth feeding pump, 36-a cyclone high-voltage pulse electrostatic emulsion breaker, 37-a high-voltage pulse electrostatic power supply, 38-a second oil-water separator, 39-a biochemical wastewater treatment section, 40-a back-flushing liquid storage tank, 41-a back-flushing pump, 42-a temporary filtrate tank to be pressed, 43-a sixth feeding pump, 44-a filter press, 45-a temporary filtrate storage tank of the filter press, 46-a seventh feeding pump, 47-homogeneous membrane electrodialyzer, 48-dilute brine circulating tank, 49-first circulating pump, 50-concentrated brine circulating tank, 51-second circulating pump, 52-eighth feeding pump, 53-dilute brine discharging pump, 54-pure water preparation system pipeline, 55-dilute brine pipeline generated in acid and alkali making process, 56-concentrated brine discharging pump, 57-ion exchange resin tower, 58-purified concentrated sodium sulfate solution temporary storage tank, 59-regenerated wastewater pipeline, 60-bipolar membrane electrodialyzer, 61-brine circulating tank, 62-third circulating pump, 63-polar water circulating tank, 64-fourth circulating pump, 65-dilute alkali solution circulating tank, 66-fifth circulating pump, 67-dilute sulfuric acid solution circulating tank, 68-sixth circulating pump, 69-ninth feeding pump, 70-pure water pipeline, 71-polar water discharging pump, 72-brine discharging pump, 73-dilute alkali solution discharging pump, 74-alkaline solution concentrating pipeline, 75-sulfuric acid solution discharging pump, 76-sulfuric acid solution circulating tank, 76-high altitude valve, 77-78-high altitude gas flowmeter, 83-82-pH meter, and online water pressure meter.
The following examples are provided to explain the present invention in further detail.
Detailed Description
The process for purifying the sodium sulfate-containing high-salinity wastewater capable of meeting the feeding requirement of bipolar membrane electrodialysis mainly removes harmful organic matters, silicon insoluble substances, inorganic cations and other insoluble substances. The inorganic cation and other insoluble substances can meet the requirements of bipolar membrane electrodialysis by adopting the methods commonly used in the industries such as chemical precipitation, precise filtration, ion exchange resin exchange and the like, particularly the chlor-alkali industry. The removal of harmful organic substances and silicon insoluble substances is a difficult point for treatment, and from the analysis of the background technology, the organic substances in the high-salt wastewater generated in the production of hydrometallurgy and battery anode materials are mainly acidic phosphate esters or phosphinic acid extracting agents, diluent kerosene and extracting agents of an extraction separation system to degrade aging products isooctyl alcohol or isooctyl acid, because the pH value of the wastewater is generally close to neutral or even alkaline, the phosphate esters or phosphinic acid extracting agents are mainly dissolved in water in the form of sodium salt, the substances are relatively stable and difficult to completely degrade through oxidation, and the isooctyl alcohol which is relatively easy to oxidize is only oxidized into the isooctyl acid. The silicon insoluble matter is mainly the very fine insoluble silicic acid converted from soluble sodium silicate in the front-end process, and is difficult to remove by general filtration. The utility model discloses to the not enough that prior art and technology exist, especially to the higher requirement of cost, environmental protection, industrial automation under the present economic form, provided one kind and used techniques such as emulsion liquid membrane extraction separation to contain sodium sulfate high salt waste water treatment purification and resourceful system acid-base system as the core. The emulsion membrane extraction separation technology is adopted because the acid phosphate or acid phosphinic acid extractant and the sodium salt thereof have the following structural formula:
the structural formula of the phosphate extractant is M = H or Na.
The extractant is soluble in kerosene, the sodium salt generated by saponification of the extractant is soluble in water, the organic matters dissolved in water can be extracted and separated by an emulsion liquid membrane extraction and separation technology by utilizing the characteristic that acidic organic matters such as the extractant, isooctanoic acid and the like can form the sodium salt, and the organic matters such as the kerosene, isooctanol and the like dispersed in high-salt wastewater can be quickly absorbed by utilizing the super-strong stabilizing effect of the surfactant on the liquid membrane shape and the huge surface area of the emulsion particle membrane. The extraction principle of the emulsion liquid membrane extraction separation technology is that kerosene and surfactant are uniformly stirred and mixed according to a certain proportion to prepare liquid membrane oil, then the liquid membrane oil is mixed with dilute alkali according to a certain volume ratio, and stirred at a certain rotating speed to prepare water-in-oil type emulsion (called emulsifiable solution for short), and the emulsion and the waste water to be treated are dispersed and mixed according to a certain volume ratio so as to implement emulsion membrane extraction separation, and the liquid membrane is an emulsion particle membrane suspended in the continuous phase of the waste water to be treated, its thickness is 1-10 micrometers, and its structure is shown in figure 6. Kerosene constitutes a film-forming substrate, and the film shape is stabilized by a surfactant containing a hydrophilic group and a hydrophobic group which can be aligned to fix the oil-water interface. The water-in-oil type emulsifiable concentrate is also called oil film, namely, the inner phase and the outer phase are aqueous solutions, and the film is oily.
The utility model discloses a sodium sulfate high salt waste water resource utilization system's technological process as follows:
firstly, preheating the wastewater of the front-end production line, precipitating the wastewater by using a sodium sulfide and sodium carbonate aqueous solution with a certain concentration to enable divalent and trivalent cations in the wastewater to generate water-insoluble sulfides and carbonates, and then filtering to obtain primarily purified brine, wherein the cations in the water can reach the following indexes:
TABLE 1 concentration of harmful ions in the precipitated, acidified brine
| Name of harmful ion | Concentration of harmful ions |
| Ca 2+ +Mg 2+ | ≤3mg/L |
| Sr 2+ | ≤3mg/L |
| Ba 2+ | ≤0.1mg/L |
| Fe 2+ +Fe 3+ | ≤0.1mg/L |
| Si | ≤3mg/L |
| Al 3+ | ≤0.1mg/L |
| Ni 2+ +Co 2+ +Mn 2+ | ≤3mg/L |
| Sum of other cations | ≤3mg/L |
After the cation is primarily precipitated, the brine is acidified to pH =3 to 4, organic matters dissolved in the form of sodium salt in the brine are converted into free acid, and then emulsion membrane extraction is performed. In the process, a water phase wrapped by a liquid film is a sodium hydroxide solution, phosphate or phosphinic acid extracting agents and isooctanoic acid in acidic brine have high solubility in the oil film, the phosphate or phosphinic acid extracting agents and the isooctanoic acid selectively permeate through the film and react with inner phase sodium hydroxide wrapped by the film to generate sodium salt, the sodium salt is insoluble in the film phase and cannot return to the brine phase, the acidic phosphate or phosphinic acid extracting agents and the isooctanoic acid are gradually enriched in a sodium salt form from an outer phase to an inner phase of the liquid film depending on osmotic pressure difference between two sides of the film, and a small amount of oil-soluble organic matters such as kerosene and the like emulsified in original brine are absorbed by the oil film with a large surface area. The emulsifiable oil enriched with organic matters is demulsified and then recovered to be applied in a liquid film oil cycle, the internal phase of the emulsifiable oil can be returned to a system for applying mechanically or discharged after reaching the standard after further treatment by a biochemical method and the like due to low concentration and small amount of salt and heavy metal ions contained in the emulsifiable oil, the kerosene used by the liquid film oil is the same as the kerosene used by front-end hydrometallurgy, the kerosene and a surfactant are both high-boiling-point organic matters, other organic matters adsorbed by the liquid film oil are lower in boiling point such as isooctanol and the like, and the absorbed low-boiling-point organic matters can be removed by distillation after the liquid film oil is circulated for a period of time for regeneration.
The brine extracted by the emulsion liquid membrane is concentrated by homogeneous membrane electrodialysis, anions and cations in the brine pass through the membrane under the electric propulsion to be concentrated into pure water, silicon and organic matters which are insoluble in water and can not be ionized are trapped in the raw water, and the concentrated brine enters an ion exchange resin tower for ion exchange to further remove the concentrated divalent cations and trivalent cations, so that the following indexes can be achieved:
TABLE 2 brine index after extraction, concentration, ion exchange
| Class of matter | Index of concentration |
| Monovalent |
25～32％ |
| Ca 2+ +Mg 2+ | Less than or equal to 0.02g/L (calculated by Ca) |
| Sr 2+ | ≤0.02mg/L |
| Ba 2+ | ≤0.01mg/L |
| Fe 2+ +Fe 3+ | ≤0.05mg/L |
| Si | ≤0.02mg/L |
| Al 3+ | ≤0.1mg/L |
| Ni 2+ +Co 2+ +Mn 2+ | ≤0.02mg/L |
| Other harmful divalent and trivalent metal ions | ≤0.05mg/L |
| Organic TOC | ≤1.0mg/L |
Delivering the purified and concentrated sodium sulfate brine to a bipolar membrane electrodialysis brine circulation tank, and returning the discharged light brine to the homogeneous membrane electrodialysis for re-concentration after stable circulation. Dilute acid (about 98 g/L) discharged after the bipolar membrane electrodialysis acid water circulating tank is stable in circulation can be prepared into concentrated acid with the maximum concentration of 60% for returning to a system for application, dilute alkali (about 80 g/L) discharged after the bipolar membrane electrodialysis alkali water circulating tank is stable in circulation can be prepared into concentrated alkali with the concentration of 32% for returning to the system for application, and if the front-end wastewater contains ammonium sulfate, ammonia recovery is carried out during alkali concentration and the concentrated alkali returns to the front end for application.
As the whole process of the process mostly operates the liquid phase fluid and the solid phase is easy to realize automatic operation, the whole process is very easy to realize continuous automatic design, and the process lays a foundation for industrialization.
It is to be understood that all components and devices of the present invention, unless otherwise specified, are intended to be exemplary of those known in the art. The utility model provides an all be provided with various valves 77 on all pipelines as required, the utility model provides an all install flowmeter 78, manometer 79, level gauge 80, thermometer 81 and online pH meter 82 as required on each equipment.
The following embodiments of the present invention are given, and it should be noted that the present invention is not limited to the following embodiments, and all the equivalent transformations made on the basis of the technical solution of the present application all fall into the protection scope of the present invention.
Example 1:
the embodiment provides a resource utilization system for sodium sulfate-containing high-salinity wastewater, and as shown in fig. 1, the resource utilization system comprises a precipitation acidification extraction separation device 1, a concentration device 2, an ion exchange device 3 and an acid-base preparation device 4.
As shown in fig. 2, the precipitation acidification extraction separation device 1 comprises a precipitation kettle 5, wherein one feed inlet of the precipitation kettle 5 is connected with a high-salt wastewater pipeline 7 through a heat exchanger 6; the other feed inlet of the precipitation kettle 5 is sequentially connected with a sodium sulfide and sodium carbonate aqueous solution high-level tank 8, a first feeding pump 9 and a sodium sulfide and sodium carbonate batching tank 10, and the sodium sulfide and sodium carbonate batching tank 10 is respectively connected with a softened water pipeline 11 and a sodium sulfide and sodium carbonate conveying pipeline 12;
the discharge gate of the supernatant of the setting kettle 5 links to each other with the feed inlet of the supernatant low level jar 13, the supernatant low level jar 13 links to each other with compressed air pipeline 15 through compressed air buffer tank 14, the discharge gate of the supernatant low level jar 13 links to each other with the feed inlet of ultrafilter 16, a discharge gate of ultrafilter 16 links to each other with the input port of line mixer 17, the input port of line mixer 17 still links to each other with dilute sulphuric acid solution pipeline 19 through dilute sulphuric acid solution high level jar 18, the delivery outlet of line mixer 17 links to each other with salt solution storage tank 20 after the acidification.
The acidified saline water storage tank 20 is connected with an upper feeding port of a liquid membrane extraction separation tower 22 through a second feeding pump 21, a lower feeding port of the liquid membrane extraction separation tower 22 is connected with a bottom discharging port of a missible oil preparation kettle 23, and an external circulating pump 24 is arranged on the missible oil preparation kettle 23; one feed inlet of the missible oil preparation kettle 23 is connected with a discharge outlet of a dilute alkali preparation tank 27 sequentially through a dilute alkali high-level tank 25 and a third feeding pump 26, one feed inlet of the dilute alkali preparation tank 27 is connected with a dilute alkali pipeline 28, and the other feed inlet of the dilute alkali preparation tank 27 is connected with a softened water pipeline 11; the other inlet of the missible oil preparation kettle 23 is connected with the outlet of the liquid film oil preparation collecting tank 31 through a liquid film oil high-level tank 29 and a fourth feeding pump 30 in sequence.
The upper discharge hole of the liquid membrane extraction separation tower 22 is connected with the feed inlet of the temporary storage tank 33 of the emulsified oil after extraction; the lower discharge port of the liquid membrane extraction separation tower 22 is connected with the feed inlet of a first oil-water separator 32, the upper discharge port of the first oil-water separator 32 is connected with the feed inlet of a temporary storage tank 33 for extracted missible oil, and the lower discharge port of the first oil-water separator 32 is connected with a temporary storage tank 34 for extracted brine.
The discharge port of the temporary storage tank 33 for the extracted missible oil is connected with the feed port of a cyclone high-voltage pulse electrostatic emulsion breaker 36 through a fifth feeding pump 35, the cyclone high-voltage pulse electrostatic emulsion breaker 36 is provided with a high-voltage pulse electrostatic power supply 37, the upper discharge port of the cyclone high-voltage pulse electrostatic emulsion breaker 36 is connected with the feed port of a liquid film oil preparation collecting tank 31, the lower discharge port of the cyclone high-voltage pulse electrostatic emulsion breaker 36 is connected with the feed port of a second oil-water separator 38, the upper discharge port of the second oil-water separator 38 is connected with the feed port of the liquid film oil preparation collecting tank 31, and the lower discharge port of the second oil-water separator 38 is connected with a biochemical wastewater treatment section 39.
As a preferable scheme of the embodiment, the other discharge port of the precision filter 16 is connected with a backwashing liquid storage tank 40, and the backwashing liquid storage tank 40 is connected with a backwashing port of the precision filter 16 through a backwashing pump 41; the bottom concentrate outlet of the precision filter 16 and the bottom concentrate outlet of the precipitation kettle 5 are both connected with a temporary storage tank 42 for filtrate to be pressed, the temporary storage tank 42 for filtrate to be pressed is connected with the feed inlet of a filter press 44 through a sixth feeding pump 43, the filtrate outlet of the filter press 44 is connected with a temporary storage tank 45 for filtrate of the filter press, and the temporary storage tank 45 for filtrate of the filter press is connected with the high-salinity wastewater pipeline 7 through a seventh feeding pump 46.
In this embodiment, the filter residue discharged from the filter press 44 is waste salt containing heavy metals, and is returned to the front-end process for treatment.
In this embodiment, the liquid membrane oil preparation and collection tank 31 is connected to the kerosene and surfactant supply pipe and the separated and recovered liquid membrane oil pipe.
In this embodiment, both the first oil-water separator 32 and the second oil-water separator 38 employ a permeation oil-water separator provided with a super hydrophilic oleophobic permeation membrane.
As shown in fig. 3, the concentration apparatus 2 includes a homogeneous membrane electrodialyzer 47, the homogeneous membrane electrodialyzer 47 is provided with a dilute brine circulation tank 48 and a first circulation pump 49 for dilute brine circulation, and the homogeneous membrane electrodialyzer 47 is provided with a concentrated brine circulation tank 50 and a second circulation pump 51 for concentrated brine circulation.
The inlet of the weak brine circulating tank 48 is connected with the extracted brine temporary storage tank 34 through an eighth feeding pump 52, and the outlet of the weak brine circulating tank 48 is connected with a pure water preparation system pipeline 54 through a weak brine discharging pump 53.
The feed inlet of the concentrated brine circulating tank 50 is connected with a dilute brine pipeline 55 produced in the acid and alkali making process, and the discharge outlet of the concentrated brine circulating tank 50 is connected with the feed inlet of an ion exchange resin tower 57 in the ion exchange device 3 through a concentrated brine discharge pump 56.
As shown in fig. 4, the ion exchange device 3 includes a plurality of stages of ion exchange resin towers 57 connected in series, a discharge port of the concentrated brine circulation tank 50 is independently connected with a liquid inlet at the top of each ion exchange resin tower 57 through a concentrated brine discharge pump 56, a feed inlet at the top of each ion exchange resin tower 57 is further connected with a dilute sulfuric acid solution pipeline 19, and a gas inlet at the top of each ion exchange resin tower 57 is further independently connected with a compressed air pipeline 15; the liquid outlet at the bottom of each ion exchange resin tower 57 is connected to a temporary storage tank 58 for purified concentrated sodium sulfate solution.
In a preferred embodiment of this embodiment, the liquid outlet at the bottom of each ion exchange resin tower 57 is further connected to the filtrate temporary storage tank 45 of the filter press in the precipitation acidification extraction separation device 1 through a regenerated wastewater pipe 59.
As shown in fig. 5, the acid-base preparation apparatus 4 includes a bipolar membrane electrodialyzer 60, the bipolar membrane electrodialyzer 60 is provided with a brine circulation tank 61 and a third circulation pump 62 for circulating brine, the bipolar membrane electrodialyzer 60 is further provided with a brine circulation tank 63 and a fourth circulation pump 64 for circulating brine, the bipolar membrane electrodialyzer 60 is further provided with a dilute alkali solution circulation tank 65 and a fifth circulation pump 66 for circulating dilute alkali solution, and the bipolar membrane electrodialyzer 60 is further provided with a dilute sulfuric acid solution circulation tank 67 and a sixth circulation pump 68 for circulating dilute sulfuric acid solution.
The brine circulating tank 61 is connected to the temporary storage tank 58 of the purified concentrated sodium sulfate solution in the ion exchange device 3 through a ninth feeding pump 69.
The feed inlets of the polar water circulation tank 63, the dilute alkali solution circulation tank 65 and the dilute sulfuric acid solution circulation tank 67 are all connected with a pure water pipeline 70.
The discharge port of the polar water circulation tank 63 is connected with the brine circulation tank 61 through a polar water discharge pump 71, and the discharge port of the brine circulation tank 61 is connected with the feed port of the strong brine circulation tank 50 through a brine discharge pump 72.
The dilute alkali solution circulating tank 65 is connected with a dilute alkali concentration pipeline 74 through a dilute alkali solution discharging pump 73, and is also connected with the dilute alkali preparation tank 27 in the precipitation acidification extraction separation device 1.
The dilute sulfuric acid solution circulating tank 67 is connected with a dilute sulfuric acid solution concentration pipeline 76 through a dilute sulfuric acid solution discharge pump 75, and is also connected with a feed port of the dilute sulfuric acid solution high-level tank 18 in the precipitation acidification extraction separation device 1.
Example 2:
the embodiment provides a recycling process of sodium sulfate-containing high-salt wastewater, which adopts the recycling system of sodium sulfate-containing high-salt wastewater provided in embodiment 1.
The process comprises the following steps:
step S1, a process based on the precipitation acidification extraction separation device 1:
the step S1 specifically includes:
step S11, preheating the sodium sulfate-containing high-salinity wastewater to be treated, adding a sodium sulfide and sodium carbonate solution into the preheated sodium sulfate-containing high-salinity wastewater to precipitate in a precipitation kettle, and then filtering to obtain a filtrate.
And step S12, adding a dilute sulfuric acid solution into the filtrate obtained in the step S11 for acidification to obtain acidic high-salt water.
Step S13, performing liquid membrane extraction on the acidic high-salt water obtained in the step S12 by using water-in-oil type missible oil, and performing oil-water separation to obtain low-TOC (total organic carbon) high-salt wastewater; and demulsifying the extracted water-in-oil type missible oil, separating oil from water, recovering an oil phase after demulsification, returning the oil phase to a system to prepare new water-in-oil type missible oil, wherein a water phase after demulsification is low-salt high-TOC wastewater enriched with acidic organic matters in the original wastewater, and returning the wastewater to a production line for reuse after biochemical treatment.
As a preferable scheme of this embodiment, in step S1, in the precipitation step, the preparation concentrations of the sodium sulfide and the sodium carbonate solution are each 5wt.%, a calcium carbonate seed crystal of 0.1wt.% is added during preparation, the excess amount is controlled to be 0.2 to 0.5g/L when the sodium sulfide and the sodium carbonate solution are added, newly generated calcium carbonate, magnesium hydroxide and sulfide can be precipitated on the seed crystal to form larger particles, the precipitation temperature is 55 to 65 ℃, the precipitation time is 30 to 60min, and the final pH of the precipitation kettle is =11 to 12; the filtration adopts a full-tetrafluoro hollow filtration membrane with the filtration precision of 0.2 mu m, the filtration pressure is 0.2-0.4 Mpa, the sludge is discharged once every 8 times of filtration, and the back washing is performed once when the pressure exceeds 0.38 Mpa.
As a preferable scheme in this embodiment, in step S1, the pH of the acidified solution is =3 to 4, a sodium hydroxide solution with a dilute alkali concentration of 0.05 to 0.5wt.% is used for the emulsifiable solution during preparation, the solvent oil for the liquid film oil is kerosene, the surfactant is sodium polybutadiene sulfate, the amount of the surfactant added to the liquid film oil is 1 to 8wt.%, and the volume ratio of the liquid film oil to the dilute alkali (the oil-to-oil ratio R is) oi ) Is 1:1 to 1.2; volume ratio of emulsifiable concentrate (water-in-oil emulsion) to acidified aqueous sodium sulfate solution to be extracted (emulsion-water ratio R) ew ) Is 1:8 to 12; the residence time of the emulsion film extraction is 4-12 min; the high-voltage pulse electrostatic demulsification method has the demulsification voltage of 1-15 KV and the frequency of 20-80 Hz.
Step S2, a process based on the concentration device 2:
concentrating the low-TOC high-salinity wastewater obtained after the liquid membrane extraction in the step S13 through homogeneous membrane electrodialysis, and further removing residual organic matters and insoluble silicon suspended matters to obtain a sodium sulfate concentrated salt aqueous solution capable of meeting the requirements of preparing acid and alkali concentrations through bipolar membrane electrodialysis; the dilute brine with the organic matters and the insoluble silicon suspended matters intercepted by the homogeneous membrane returns to a pure water preparation working section, and is used for preparing pure water or used as softened water of other working sections through a reverse osmosis process;
in a preferred embodiment of this embodiment, in step S2, the electrodialysis concentration uses a homogeneous membrane and is treated with a superhydrophilic oleophobic surface.
Step S3, based on the process of the ion exchange device 3:
and (3) adding the sodium sulfate concentrated saline solution treated in the step (S2) into a resin exchange tower, carrying out ion exchange through the resin exchange tower to obtain a purified sodium sulfate solution, and returning the wastewater generated by resin regeneration to the step (S11) for treatment.
As a preferable mode of this embodiment, in step S3, the exchange resin in the resin exchange column is collectedBy chelating resins, exchanging the capacity Cu 2+ Not less than 0.6mmol/ml R-Na. A plurality of resin exchange towers which can be communicated with each other and are independently arranged adopt the operation mode that one part of the resin exchange towers works and the other part of the resin exchange towers is standby or regenerated,
further preferably, the number of the plurality of resin exchange columns which are communicated with each other and are independently arranged is three, and the operation mode that two resin exchange columns work in series and the other resin exchange column is standby or regenerated is adopted.
Step S4, based on the process of the acid-base preparation device 4:
and (2) performing electrodialysis on the sodium sulfate solution purified in the step (S3) through a bipolar membrane to prepare acid and alkali, concentrating the obtained diluted acid, returning the concentrated diluted acid to a front-end production line for application, concentrating (or performing stripping deamination concentration) the obtained diluted alkali, returning the diluted alkali to the front-end production line for application, and returning the generated light brine to homogeneous membrane electrodialysis for re-concentration.
As a preferred scheme of the embodiment, the high-level tank 18 of the dilute sulfuric acid solution uses acid to self-prepare dilute sulfuric acid from the system, and the dilute alkali preparation tank 27 uses alkali to self-prepare higher-concentration dilute alkali from the system.
Based on the sodium sulfate-containing high-salinity wastewater resource utilization system provided in the embodiment 1, the process specifically comprises the following steps:
firstly, preparing auxiliary materials:
preparing a precipitator:
the softened water pipe 11 is opened to feed water into the sodium sulfide and sodium carbonate proportioning tank 10 to a rated amount, and then the softened water pipe 11 is closed. Then the sodium sulfide + sodium carbonate batching tank 10 is started to stir, and rated amounts of sodium sulfide, sodium carbonate and calcium carbonate seed crystals are added through a solid feeder to prepare an aqueous solution containing 5wt.% of sodium sulfide, 5wt.% of sodium carbonate and 0.1wt.% of calcium carbonate seed crystals. And then the prepared sodium sulfide and sodium carbonate solution is conveyed to a sodium sulfide and sodium carbonate solution high-level tank 8 for standby through a first feeding pump 9.
Preparing dilute alkali:
starting a dilute alkali concentration pipeline 74 to add rated amount of alkaline water into the dilute alkali preparation tank 27, then closing the dilute alkali concentration pipeline 74, starting stirring, starting a softened water pipeline 11 to add rated amount of softened water into the dilute alkali preparation tank 27, then closing the softened water pipeline 11 to uniformly stir to obtain about 0.05-0.5% of dilute alkali, and then pumping the dilute alkali into a dilute alkali overhead tank 25 for later use through a third feeding pump 26.
Preparing liquid membrane oil:
adding a rated amount of kerosene into the liquid film oil preparation and collection tank 31, starting stirring, adding a rated amount of surfactant, uniformly stirring to obtain liquid film oil containing 0.5-8.0%, and pumping into a liquid film oil high-level tank 29 for later use through a fourth feeding pump 30. The recovered liquid film oil is circularly applied for a period of time and then supplemented with a small amount of surfactant according to the amount of the surfactant contained in the recovered liquid film oil for reuse, or removed by distillation according to the amount of other low-boiling-point organic matters absorbed by the recovered liquid film oil for reuse.
Preparation of water-in-oil emulsion:
adding a rated amount of the liquid membrane oil into an emulsifiable solution preparation kettle 23 through a liquid membrane oil high-level tank 29, starting a stirring and external circulating pump 24, then adding the rated amount of the prepared diluted alkali through a diluted alkali high-level tank 25, stirring and emulsifying at the rotating speed of 2500r/min to prepare an emulsifiable solution with the oil internal ratio Roi =1: 1-1.2 of milky white water-in-oil emulsion for later use.
Secondly, precipitation separation:
opening a high-salt wastewater pipeline 7 to add rated amount of high-salt wastewater into the precipitation kettle 5, simultaneously opening a heat exchanger 6 to preheat the high-salt wastewater to 55-65 ℃, starting the stirring of the precipitation kettle 5, opening a bottom valve of a sodium sulfide and sodium carbonate solution high-level tank 8 to add a sodium sulfide and sodium carbonate aqueous solution into the precipitation kettle 5 until the pH of the salt water in the precipitation kettle 5 is =11, and then closing the bottom valve of the sodium sulfide and sodium carbonate solution high-level tank 8. Stirring for 30-60 min, stopping stirring, standing for 10min, and putting the supernatant in the precipitation kettle 5 into a supernatant low-level tank 13. The actions are continuously repeated, and cations such as calcium, magnesium, nickel, cobalt, manganese and the like are precipitated by the precipitation kettle 5.
Opening a pressure air valve and a bottom valve at the upper end of the supernatant low-level tank 13, inputting the supernatant into a precision filter 16 under the pressure action of compressed air for filtering, then entering a pipeline mixer 17, simultaneously opening a bottom valve of a dilute sulfuric acid solution high-level tank 18 to enable the dilute sulfuric acid to enter the pipeline mixer 17, acidifying in the pipeline mixer 17, always keeping the pH = 3-4 of the acidified brine, and enabling the acidified brine to enter an acidified brine storage tank 20.
Thirdly, deslagging and backwashing:
after the supernatant liquid is discharged from the settling tank 5 each time, the bottom valve of the settling tank 5 is opened to discharge the residue liquid at the bottom, and the residue liquid is collected in the temporary storage tank 42 for filtrate to be pressed. The precision filter 16 discharges mud once every 8 times of filtration, a valve on the precision filter 16 is opened to discharge mud, and the mud is collected in a temporary storage tank 42 of filtrate to be pressed. And a certain amount of filtered brine is stored in the backwashing liquid storage tank 40 for later use through another discharge hole of the precision filter 16.
The back-flushing pump 41 is turned on to back flush the filter membrane of the precision filter 16 with filtered brine, and the residue liquid is collected in the temporary storage tank 42 of the filtrate to be pressed. And (3) opening a sixth feeding pump 43, carrying out pressure filtration on the slurry residue liquid in the to-be-pressed filtrate temporary storage tank 42 through a pressure filter 44, carrying out post-treatment on filter residues, collecting filtrate in a filtrate temporary storage tank 45 of the pressure filter, and returning the filtrate to the high-salinity wastewater pipeline 7 through a seventh feeding pump 46 for retreatment.
Fourthly, continuously extracting the emulsion membrane:
the second feeding pump 21 is started to feed acidified high-salt water into the continuous extraction tower through an upper feeding hole of the liquid film extraction separation tower 22, meanwhile, a bottom valve of the missible oil preparation kettle 23 is started to feed missible oil into the continuous extraction tower through a lower feeding hole of the liquid film extraction separation tower 22, an oil phase discharged from an upper discharging hole of the liquid film extraction separation tower 22 enters a missible oil temporary storage tank 33 after extraction, a water phase discharged from a lower discharging hole of the liquid film extraction separation tower 22 enters a first oil-water separator 32, a water phase discharged from a lower discharging hole of the first oil-water separator 32 enters a brine temporary storage tank 34 after extraction, and an oil phase discharged from an upper discharging hole of the first oil-water separator 32 enters the missible oil temporary storage tank 33 after extraction.
And the extracted missible oil enters a cyclone high-voltage pulse electrostatic emulsion breaker 36 through a fifth feeding pump 35, a high-voltage pulse electrostatic power supply 37 is started at the same time, an oil phase discharged from an upper discharge port of the cyclone high-voltage pulse electrostatic emulsion breaker 36 enters a liquid film oil preparation collecting tank 31, an aqueous phase discharged from a lower discharge port of the cyclone high-voltage pulse electrostatic emulsion breaker 36 enters a second oil-water separator 38, an oil phase discharged from an upper discharge port of the second oil-water separator 38 enters the liquid film oil preparation collecting tank 31, and an aqueous phase discharged from a lower discharge port of the second oil-water separator 38 enters a wastewater biochemical treatment section 39.
Fifth, brine concentration:
and starting an eighth feeding pump 52 to feed the extracted brine with the circulating amount to the dilute brine circulating tank 48, starting a brine discharging pump 72 to feed the dilute brine generated at the downstream of the circulating amount to the strong brine circulating tank 50, starting a homogeneous membrane electrodialyzer 47, a first circulating pump 49 and a second circulating pump 51, respectively and continuously feeding the circulating tanks after the concentration of the circulating tanks meets the requirement, and simultaneously and continuously discharging the brine through a dilute brine discharging pump 53 and a strong brine discharging pump 56.
Sixthly, re-purifying the strong brine ion exchange resin:
and the re-purification of the strong brine adopts a three-tower two-open one-standby mode to further purify the strong brine by using ion exchange resin. Opening the corresponding inlet and outlet valves of the first two ion exchange resin towers 57, feeding the two ion exchange resin towers 57 connected in series by the concentrated brine discharge pump 56, further purifying in the ion exchange resin towers 57, and allowing the qualified purified brine to enter the temporary storage tank 58 of the purified concentrated sodium sulfate solution.
After two ion exchange resin towers 57 connected in series are operated for a period of time, the former needs to be regenerated, and the latter is connected in series with the third ion exchange resin tower 57 to continue working. The compressed air pipeline 15 is opened to press out the residual saline water of the ion exchange resin tower 57 to be regenerated, dilute sulphuric acid is injected into the ion exchange resin tower 57 to be regenerated through a dilute sulphuric acid solution pipeline (19), and after the ion exchange resin tower is soaked for a period of time, the dilute sulphuric acid is pressed out by compressed air and is injected into strong brine for standby. The liquid pressed out from the ion exchange resin column 57 to be regenerated is returned to the front-end treatment.
Seventhly, preparing acid and alkali by bipolar membrane electrodialysis:
starting a ninth feeding pump 59 to inject circulation amount of strong brine into the brine circulating tank 61, starting a pure water pipeline 70 to inject circulation amount of pure water into the polar water circulating tank 63, the dilute alkali solution circulating tank 65 and the dilute sulfuric acid solution circulating tank 67, starting the bipolar membrane electrodialyzer 60, and simultaneously starting a third circulating pump 62, a fourth circulating pump 64, a fifth circulating pump 66 and a sixth circulating pump 68 to circulate. After the materials in each circulation tank reach a certain concentration, the polar water discharge pump 71, the brine discharge pump 72, the dilute alkali solution discharge pump 73 and the dilute sulfuric acid solution discharge pump 75 are started to continuously discharge, and simultaneously, strong brine is fed into the brine circulation tank 61, and pure water is fed into other circulation tanks. The generated dilute alkali enters a dilute alkali concentration pipeline 74 to be concentrated into 32wt.% of liquid alkali to be returned to the front end for sleeving, and the generated dilute acid enters a dilute sulfuric acid solution concentration pipeline 76 to be concentrated into 60wt.% of concentrated acid to be returned to the front end for sleeving.
Example 3:
the embodiment provides a resource utilization process of sodium sulfate-containing high-salinity wastewater based on the embodiment 2. In this embodiment, the sulfate wastewater to be treated is specifically sodium sulfate wastewater in a certain hydrometallurgy nickel and cobalt separation extraction line.
In this example, the pH of the acidified raffinate was adjusted to =3.5, the dilute alkali concentration was 0.4%, the surfactant content in the liquid film oil was 4% by weight of kerosene, and the volume ratio R of the liquid film oil to the dilute alkali was oi =1:1 volume ratio R of emulsifiable concentrate to acidified raffinate ew =1:8; the extraction residence time of the emulsion membrane is 12min, the demulsification voltage is 7.5KV, and the frequency is 40Hz.
The main component contents of the sodium sulfate aqueous solution before and after treatment by the process are shown in table 3.
Table 3 example 3 comparison of the content of main substances in an aqueous solution of sodium sulfate before and after treatment
As can be seen from Table 3, the amount of dilute alkaline water after extraction was one eighth of the amount of the original wastewater, the salt content was 0.7% as sodium sulfate, and the TOC was 6250mg/L. The concentration of dilute brine discharged by the homogeneous membrane electrodialysis is less than 1 percent. The concentration of acid discharged from the acid and alkali preparing device is 98g/L, the concentration of alkali is 80g/L, the concentration of acid is 60% and the concentration of alkali is 32% after concentration.
Example 4:
the embodiment provides a resource utilization process of sodium sulfate-containing high-salinity wastewater based on the embodiment 2. In this example, the wastewater to be treated was the same as in example 3.
In this example, the acidified raffinate was adjusted to pH =3.5, the dilute alkali concentration was 0.3%, and the liquid filmThe dosage of the surfactant in the oil is 6 percent of the weight of the kerosene, and the volume ratio R of the liquid membrane oil to the dilute alkali oi =1:1 volume ratio R of emulsifiable concentrate to acidified raffinate ew =1:10; the extraction residence time of the emulsion membrane is 12min, the demulsification voltage is 5.5KV, and the frequency is 60Hz.
The content of the main components of the sodium sulfate aqueous solution before and after the treatment by the process is shown in Table 4.
Table 4 example 4 control of the content of main substances in an aqueous solution of sodium sulfate before and after treatment
As is clear from Table 4, the amount of the dilute alkaline water after extraction was one tenth of the amount of the raw water, and the salt content was 0.53% in terms of sodium sulfate and the TOC was 7800mg/L. The concentration of the dilute brine discharged by the homogeneous membrane electrodialysis is less than 1 percent. The concentration of acid discharged by the acid and alkali preparation device is 98g/L, the concentration of alkali is 80g/L, and the concentration of acid is 60% and the concentration of alkali is 32% after concentration.
Example 5:
the embodiment provides a resource utilization process of sodium sulfate-containing high-salinity wastewater based on the embodiment 2. In this embodiment, the sodium sulfate high-salt wastewater to be treated is specifically wastewater discharged from a power battery ternary precursor NCM622 production line.
In this example, the pH of the acidified raffinate was adjusted to =3.2, the dilute alkali concentration was 0.1%, the surfactant content in the liquid film oil was 4% by weight of kerosene, and the volume ratio R of the liquid film oil to the dilute alkali was oi =1:1 volume ratio R of emulsifiable concentrate to acidified raffinate ew =1:10; the extraction residence time of the emulsion membrane is 12min, the demulsification voltage is 8.0KV, and the frequency is 30Hz.
The content of the main components of the sodium sulfate aqueous solution before and after the treatment by the process is shown in Table 5.
Table 5 example 5 comparison of the content of main substances in an aqueous solution of sodium sulfate before and after treatment
As is clear from Table 5, the amount of the dilute alkali water after extraction was one tenth of the amount of the raw water, and the salt content was 0.18% in terms of sodium sulfate and 390.20mg/L in TOC. The concentration of the dilute brine discharged by the homogeneous membrane electrodialysis is less than 1 percent. The concentration of acid discharged from the acid and alkali preparation device is 98g/L, the concentration of alkali is 80g/L, the concentration of acid is 60% and the concentration of alkali is 32% after concentration, and the concentration of recovered ammonia water is 10%.
Example 6:
the embodiment provides a resource utilization process of sodium sulfate-containing high-salinity wastewater based on the embodiment 2. In this embodiment, the sodium sulfate high-salinity wastewater to be treated is specifically sodium sulfate comprehensive wastewater discharged from a power battery ternary precursor NCM811 production line.
In this example, the pH of the acidified raffinate was adjusted to =3.6, the dilute alkali concentration was 0.05%, the surfactant amount in the liquid film oil was 5% by weight of kerosene, and the volume ratio R of the liquid film oil to the dilute alkali was oi =1:1 volume ratio R of emulsifiable concentrate to acidified raffinate ew =1:10; the extraction residence time of the emulsion membrane is 10min, the demulsification voltage is 9.0KV, and the frequency is 20Hz.
The content of the main components of the sodium sulfate aqueous solution before and after treatment by the process is shown in the table 6.
TABLE 6 EXAMPLE 6 comparison of the content of the main substances in the aqueous sodium sulfate solution before and after the treatment
As is clear from Table 6, the amount of the dilute alkali water after extraction was one tenth of the amount of the raw water, the salt content was 0.09% in terms of sodium sulfate, and the TOC was 390.10mg/L. The concentration of dilute brine discharged by the homogeneous membrane electrodialysis is less than 1 percent. The concentration of acid discharged from the acid and alkali preparation device is 98g/L, the concentration of alkali is 80g/L, the concentration of acid is 60%, the concentration of alkali is 32% and the concentration of recovered ammonia water is 10%.
Example 7:
the embodiment provides a resource utilization process of sodium sulfate-containing high-salinity wastewater based on the embodiment 2. In this embodiment, the sodium sulfate high-salinity wastewater to be treated is specifically sodium sulfate comprehensive wastewater discharged from a power battery ternary precursor NCA production line.
In this example, the acidified raffinate was adjusted to pH =3.5, the dilute alkali concentration was 0.2%, the surfactant amount in the liquid membrane oil was 5% of the kerosene weight, and the volume ratio R of the liquid membrane oil to the dilute alkali was oi =1:1 volume ratio R of emulsifiable concentrate to acidified raffinate ew =1:10; the extraction residence time of the emulsion membrane is 10min, the demulsification voltage is 9.0KV, and the frequency is 20Hz.
The content of the main components of the sodium sulfate aqueous solution before and after treatment by the process is shown in Table 7.
Table 7 example 7 comparison of the content of main substances in an aqueous solution of sodium sulfate before and after treatment
As is clear from Table 7, the amount of the dilute alkali water after extraction was one tenth of the amount of the raw water, the salt content was 0.35% in terms of sodium sulfate, and the TOC was 369.35mg/L. The concentration of dilute brine discharged by the homogeneous membrane electrodialysis is less than 1 percent. The concentration of acid discharged from the acid making device is 98g/L, the concentration of alkali is 80g/L, the concentration of acid is 60%, the concentration of alkali is 32% and the concentration of recovered ammonia water is 10%.
Claims (6)
1. A resource utilization system for sodium sulfate-containing high-salinity wastewater is characterized by comprising a precipitation acidification extraction separation device (1), a concentration device (2), an ion exchange device (3) and an acid-base preparation device (4);
the precipitation acidification extraction separation device (1) comprises a precipitation kettle (5), and a feed inlet of the precipitation kettle (5) is connected with a high-salinity wastewater pipeline (7) through a heat exchanger (6); the other feed inlet of the precipitation kettle (5) is sequentially connected with a sodium sulfide and sodium carbonate aqueous solution high-level tank (8), a first feeding pump (9) and a sodium sulfide and sodium carbonate batching tank (10), and the sodium sulfide and sodium carbonate batching tank (10) is respectively connected with a softened water pipeline (11) and a sodium sulfide and sodium carbonate conveying pipeline (12);
a discharge hole of supernatant of the precipitation kettle (5) is connected with a feed hole of a supernatant low-level tank (13), the supernatant low-level tank (13) is connected with a compressed air pipeline (15) through a compressed air buffer tank (14), a discharge hole of the supernatant low-level tank (13) is connected with a feed hole of a precision filter (16), a discharge hole of the precision filter (16) is connected with an input hole of a pipeline mixer (17), an input hole of the pipeline mixer (17) is also connected with a dilute sulfuric acid solution pipeline (19) through a dilute sulfuric acid solution high-level tank (18), and an output hole of the pipeline mixer (17) is connected with an acidified brine storage tank (20);
the acidified saline water storage tank (20) is connected with an upper feeding port of the liquid membrane extraction separation tower (22) through a second feeding pump (21), a lower feeding port of the liquid membrane extraction separation tower (22) is connected with a bottom discharging port of the missible oil preparation kettle (23), and an external circulating pump (24) is arranged on the missible oil preparation kettle (23); one feed inlet of the missible oil preparation kettle (23) is connected with a discharge outlet of a dilute alkali preparation tank (27) sequentially through a dilute alkali high-level tank (25) and a third feeding pump (26), one feed inlet of the dilute alkali preparation tank (27) is connected with a dilute alkali pipeline (28), and the other feed inlet of the dilute alkali preparation tank (27) is connected with a softened water pipeline (11); the other feed inlet of the missible oil preparation kettle (23) is connected with the discharge outlet of the liquid film oil preparation collecting tank (31) through a liquid film oil high-level tank (29) and a fourth feeding pump (30) in sequence;
the upper discharge hole of the liquid membrane extraction separation tower (22) is connected with the feed inlet of the temporary storage tank (33) of the extracted missible oil; a lower discharge port of the liquid membrane extraction separation tower (22) is connected with a feed inlet of a first oil-water separator (32), an upper discharge port of the first oil-water separator (32) is connected with a feed inlet of a temporary storage tank (33) for extracted missible oil, and a lower discharge port of the first oil-water separator (32) is connected with a temporary storage tank (34) for extracted brine;
the discharge port of the temporary storage tank (33) for the extracted missible oil is connected with the feed port of a cyclone high-voltage pulse electrostatic emulsion breaker (36) through a fifth feeding pump (35), the cyclone high-voltage pulse electrostatic emulsion breaker (36) is provided with a high-voltage pulse electrostatic power supply (37), the upper discharge port of the cyclone high-voltage pulse electrostatic emulsion breaker (36) is connected with the feed port of a liquid film oil preparation and collection tank (31), the lower discharge port of the cyclone high-voltage pulse electrostatic emulsion breaker (36) is connected with the feed port of a second oil-water separator (38), the upper discharge port of the second oil-water separator (38) is connected with the feed port of the liquid film oil preparation and collection tank (31), and the lower discharge port of the second oil-water separator (38) is connected with a biochemical wastewater treatment section (39).
2. The sodium sulfate-containing high-salt wastewater resource utilization system as claimed in claim 1, wherein another discharge port of the precision filter (16) is connected with the backwashing liquid storage tank (40), and the backwashing liquid storage tank (40) is connected with the backwashing port of the precision filter (16) through a backwashing pump (41); the bottom of precision filter (16) goes out the concentrate mouth and the bottom of setting kettle (5) goes out the concentrate mouth and all links to each other with waiting to press filtrating liquid temporary storage tank (42), waits to press filtrating liquid temporary storage tank (42) to link to each other through sixth feeding pump (43) and the feed inlet of pressure filter (44), the filtrating export of pressure filter (44) links to each other with pressure filter filtrating liquid temporary storage tank (45), pressure filter filtrating liquid temporary storage tank (45) links to each other with high salt waste water pipeline (7) through seventh feeding pump (46).
3. The system as claimed in claim 1, wherein the concentration device (2) comprises a homogeneous membrane electrodialyzer (47), the homogeneous membrane electrodialyzer (47) is provided with a weak brine circulation tank (48) and a first circulation pump (49) for weak brine circulation, and the homogeneous membrane electrodialyzer (47) is provided with a strong brine circulation tank (50) and a second circulation pump (51) for strong brine circulation;
a feed inlet of the light brine circulating tank (48) is connected with the extracted brine temporary storage tank (34) through an eighth feeding pump (52), and a discharge outlet of the light brine circulating tank (48) is connected with a pure water preparation system pipeline (54) through a light brine discharge pump (53);
the feed inlet of the strong brine circulating tank (50) is connected with a weak brine pipeline (55) generated in the acid and alkali making process, and the discharge outlet of the strong brine circulating tank (50) is connected with the feed inlet of an ion exchange resin tower (57) in the ion exchange device (3) through a strong brine discharge pump (56).
4. The sodium sulfate-containing high-salt wastewater resource utilization system as claimed in claim 1, wherein the ion exchange device (3) comprises a plurality of stages of ion exchange resin towers (57) connected in series, a discharge port of the concentrated brine circulating tank (50) is independently connected with a liquid inlet at the top of each ion exchange resin tower (57) through a concentrated brine discharge pump (56), a liquid inlet at the top of each ion exchange resin tower (57) is also connected with a dilute sulfuric acid solution pipeline (19), and a liquid inlet at the top of each ion exchange resin tower (57) is also independently connected with a compressed air pipeline (15); the liquid outlet at the bottom of each ion exchange resin tower (57) is connected with a temporary storage tank (58) of purified concentrated sodium sulfate solution.
5. The system for recycling the high-salinity wastewater containing sodium sulfate as claimed in claim 4, characterized in that the liquid outlet at the bottom of each ion exchange resin tower (57) is connected with the filtrate temporary storage tank (45) of the filter press in the precipitation acidification extraction separation device (1) through a regenerated wastewater pipeline (59).
6. The system for recycling the high-salinity wastewater containing sodium sulfate according to claim 1, wherein the acid-base preparation device (4) comprises a bipolar membrane electrodialyzer (60), the bipolar membrane electrodialyzer (60) is provided with a brine circulation tank (61) and a third circulation pump (62) for brine circulation, the bipolar membrane electrodialyzer (60) is further provided with a polar water circulation tank (63) and a fourth circulation pump (64) for polar water circulation, the bipolar membrane electrodialyzer (60) is further provided with a dilute alkaline solution circulation tank (65) and a fifth circulation pump (66) for dilute alkaline solution circulation, and the bipolar membrane electrodialyzer (60) is further provided with a dilute sulfuric acid solution circulation tank (67) and a sixth circulation pump (68) for dilute sulfuric acid solution circulation;
the brine circulating tank (61) is connected with a temporary storage tank (58) of purified concentrated sodium sulfate solution in the ion exchange device (3) through a ninth feeding pump (69);
the feed inlets of the polar water circulating tank (63), the dilute alkali solution circulating tank (65) and the dilute sulfuric acid solution circulating tank (67) are all connected with a pure water pipeline (70);
a discharge port of the polar water circulation tank (63) is connected with the brine circulation tank (61) through a polar water discharge pump (71), and a discharge port of the brine circulation tank (61) is connected with a feed port of the strong brine circulation tank (50) through a brine discharge pump (72);
the dilute alkali solution circulating tank (65) is connected with a dilute alkali concentration pipeline (74) through a dilute alkali solution discharge pump (73) and is also connected with a dilute alkali preparation tank (27) in the precipitation acidification extraction separation device (1);
the dilute sulfuric acid solution circulating tank (67) is connected with a dilute sulfuric acid solution concentration pipeline (76) through a dilute sulfuric acid solution discharge pump (75) and is also connected with a feed inlet of a dilute sulfuric acid solution high-level tank (18) in the precipitation acidification extraction separation device (1).
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