CN216662496U - Purification is handled with refining plant once to useless sodium sulfate - Google Patents
Purification is handled with refining plant once to useless sodium sulfate Download PDFInfo
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Abstract
The utility model provides a primary refining device for treating and purifying waste sodium sulfate, which comprises a U-shaped molten salt furnace and a first pipeline mixer, wherein the input end of the first pipeline mixer is also connected with a flocculant high-level tank; the feed end of the settling tank is also connected with a sodium carbonate solution high-level tank; and the input end of the second pipeline mixer is also connected with the dilute sulfuric acid solution high-level tank, and the output end of the second pipeline mixer is connected with the primary refined brine storage tank. The utility model adopts the design of the U-shaped molten salt furnace, the high-temperature part of the whole container can control the continuous feeding and discharging of materials and the starting and stopping of equipment even without any valve, and lays a foundation for automatic design. The utility model treats the organic matters in the waste sodium sulfate in a molten state, the organic matters are completely carbonized in an anoxic state, and the volatile organic matters can be collected by cooling the tail gas system without polluting the atmosphere.
Description
Technical Field
The utility model belongs to the technical field of chemical resource recycling, relates to waste sodium sulfate, and particularly relates to a primary refining device for treating and purifying waste sodium sulfate.
Background
In chemical industry, hydrometallurgy and other industrial industries, a large amount of sodium sulfate byproducts (including sodium sulfate decahydrate, commonly known as mirabilite, anhydrous sodium sulfate and commonly known as anhydrous sodium sulphate) are generated every year, the byproducts are different in source and contain impurities, particularly toxic and harmful organic matters and heavy metal ions, so that the application of the sodium sulfate as a product is greatly limited, and even with the increasingly strict national environmental protection standard, waste sodium sulfate generated in some industries is listed as dangerous waste. The waste sodium sulfate is mainly produced from high-salt wastewater, the high-salt wastewater has higher treatment cost, toxic and harmful organic matters are not treated in advance by an economic method at present, the most economic 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 economy of the method is obviously and widely applied to the fields of hydrometallurgy, chemical industry, pesticides and the like, the pressure of wastewater treatment in the industries is relieved, but simultaneously a large amount of anhydrous sodium sulphate is also generated, the quality and harmful byproducts have limited use, the good value is only 50-150 yuan coins, the price is usually not exceeded the product transportation cost, and the accumulated anhydrous sodium sulphate of enterprises is more and more, because the water-soluble salt cannot be used as common solid waste for landfill, great pressure is generated on enterprises, sodium sulfate needs to be found out, and the problem of high-salinity wastewater treatment in the industries can be really solved, so that the production is normally carried out. On the other hand, the large amount of high-salt wastewater generated in the industries, particularly the hydrometallurgy industry, is mainly characterized in that sulfuric acid and caustic soda are used in 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 alkalis in the chemical industry rise in price to different degrees, so that the technologists in the industry introduce the technology of preparing acid and alkali from inorganic salt into the waste salt for preparing acid and alkali for recycling, and the problem of comprehensive treatment and utilization of the high-salt wastewater is expected to be fundamentally solved.
The method is divided into asbestos diaphragms and different types of ionic membranes according to different types of membranes, the asbestos diaphragms are eliminated by the industry due to outdated process, low product quality and high energy consumption, only a small amount of the 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, which has low energy consumption, only generates acid and alkali corresponding to salt to be treated, and is a hot technology for treating industrial waste salt, but similar to an ionic membrane, the membrane of the bipolar membrane electrodialysis has higher quality requirement on salt, is inferior to the ionic membrane, but because the technology has low energy consumption and does not generate other byproducts, the industrial waste salt circulation is definitely the most important or even the only way to be used in the future. Then, the purification of the waste salt becomes the most technical obstacle for recycling the waste salt. The waste salt purification mainly removes organic matters contained in the waste salt, particularly organic matters which are insoluble in water or soluble in water but have larger molecular weight, and removes other impurities harmful to the bipolar membrane, such as other cations, anions, insoluble silicon substances and the like in the waste salt. The common removal of anions and cations has a relatively mature technology in the chlor-alkali industry, but the removal of organic matters has different treatment methods for different types of organic matters contained in different production links due to waste salt generation, but the methods which can meet the requirements of bipolar membrane electrodialysis and can adapt to waste salt from different sources are few in the prior art, the most common method is a pyrolysis method, the pyrolysis method is divided into an incineration method and a molten salt method according to the state of the waste salt during pyrolysis, and the adopted furnace kiln forms are different. The burning method is usually a rotary kiln method, the burning temperature of the method cannot be too high, otherwise, molten salt is easy to hang on the wall and form a ring to block a furnace body, but the temperature is low, so that the decomposition of organic matters cannot be thoroughly realized, and the pollution problems of burning dust, smoke and the like exist. The molten salt method has high temperature, and can achieve the purpose of thoroughly decomposing organic matters. The main problems are the design of a molten salt furnace, the discharge of molten salt and how to realize automation.
Chinese patent No. ZL201821209410.7 discloses a molten salt furnace for treating industrial waste salt slag, which adopts direct combustion to collect molten salt in a bottom molten salt pool, and how the molten salt is discharged is not clear, and harmful substances such as heavy metals contained in the waste salt cannot be removed by the method. Therefore, how to develop a new process to overcome the shortcomings of the prior art and solve the problem of purifying the waste sodium sulfate becomes the key of recycling the waste sodium sulfate at present.
Disclosure of Invention
Aiming at the defects in the prior art, the utility model aims to provide a primary refining device for treating and purifying waste sodium sulfate, and solve the technical problem that the purity of a product treated by the waste sodium sulfate is not enough in the prior art.
In order to solve the technical problems, the utility model adopts the following technical scheme:
a primary refining device for treating and purifying waste sodium sulfate comprises a U-shaped molten salt furnace, wherein a molten salt furnace kiln is arranged outside the U-shaped molten salt furnace, the feeding end of the U-shaped molten salt furnace conveys the waste sodium sulfate to be treated through an air flow drying conveyor, a high-level bin and a star-shaped feeder which are sequentially connected, and the discharging end of the U-shaped molten salt furnace is connected with a molten salt discharging pipeline;
the outlet of the molten salt discharging pipeline conveys molten salt to the molten salt inlet of the cooling water tank; a discharge port of the cooling water tank is connected with a crude brine storage tank through a first feeding pump to convey crude brine, and the crude brine storage tank is connected with a crude brine high-level tank through a second feeding pump and a heat exchanger which are sequentially connected to convey crude brine; the high-level tank of the crude brine is connected with the input end of a first pipeline mixer, the input end of the first pipeline mixer is also connected with the high-level tank of the flocculant, and the output end of the first pipeline mixer is connected with the feed end of a first precision filter;
the discharge end of the first precision filter is connected with the feed end of the precipitation tank, the feed end of the precipitation tank is also connected with the high-level tank of the sodium carbonate solution, and the supernatant discharge end of the precipitation tank is connected with the low-level tank of the supernatant after precipitation; the supernatant liquid low-level tank after precipitation is connected with the feed end of the second precision filter;
the discharge end of the second precision filter is connected with the input end of a second pipeline mixer, the input end of the second pipeline mixer is also connected with a dilute sulfuric acid solution high-level tank, and the output end of the second pipeline mixer is connected with a primary refined brine storage tank.
The utility model also has the following technical characteristics:
the bottom of first precision filter go out the concentrate end, the bottom of gunbarrel goes out the concentrate end and the bottom of second precision filter goes out the concentrate end 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 end of fourth charge pump with the pressure filter, the play filtrating end and the pressure filter filtrating temporary storage tank of pressure filter link to each other, pressure filter filtrating temporary storage tank links to each other with the crude salt water storage tank through the fifth charge pump, the useless salt impurity of play filter residue end output of pressure filter.
The primary refined brine storage tank is also connected with a back washing tank, and the back washing tank is respectively connected with the discharge ends of the first precise filter and the second precise filter through a back washing pump.
The device comprises an air flow drying conveyor, and is characterized by also comprising a waste sodium sulfate transfer device, wherein the waste sodium sulfate transfer device transfers waste sodium sulfate to be treated to a waste salt screw feeder arranged on the air flow drying conveyor, and the air flow drying conveyor is also provided with a hot air heater with a fan.
Still include the compressed air pipeline, the compressed air pipeline links to each other with the compressed air buffer tank, and the compressed air buffer tank links to each other with crude salt water high-order jar, flocculating agent high-order jar and deposit back supernatant low level jar respectively.
The flocculant high-level tank is also connected with the flocculant preparation kettle through a sixth feeding pump, the sodium carbonate solution high-level tank is also connected with the sodium carbonate solution preparation kettle through a seventh feeding pump, and the dilute sulfuric acid solution high-level tank is also connected with the dilute sulfuric acid solution preparation kettle through an eighth feeding pump; the system also comprises a softened water pipeline which is respectively connected with the cooling water tank, the flocculant preparation kettle, the sodium carbonate solution preparation kettle and the dilute sulfuric acid solution preparation kettle; the device also comprises a concentrated sulfuric acid pipeline, and the concentrated sulfuric acid pipeline is connected with the dilute sulfuric acid solution preparation kettle.
And the high-level stock bin is provided with an induced draft fan.
And the cooling water tank is also provided with a waste heat exchanger.
A first overflow pipe is also arranged between the crude brine high-level tank and the crude brine storage tank; and a second overflow pipe is arranged between the crude brine storage tank and the cooling water tank.
Compared with the prior art, the utility model has the following technical effects:
the primary refining device of the utility model adopts the design of the U-shaped molten salt furnace, and the high-temperature part of the whole container can control the continuous feeding and discharging of materials and the starting and stopping of equipment even without any valve, thereby laying a foundation for automatic design.
The device of the utility model treats the organic matters in the waste sodium sulfate in a molten state, the organic matters are completely carbonized in an anoxic state, and the volatile organic matters can be collected by cooling in an exhaust system without polluting the atmosphere.
Drawings
FIG. 1 is a schematic diagram of the overall structure of a waste sodium sulfate treatment and purification system.
FIG. 2 is a schematic view of the structure of a primary refining apparatus.
FIG. 3 is a schematic view of the structure of the secondary refining apparatus.
The meaning of the individual reference symbols in the figures is: 1-a primary refining device, 2-a secondary refining device, 3-U type molten salt furnace, 4-a molten salt furnace kiln, 5-an air flow drying conveyor, 6-a high-level bin, 7-a star-shaped feeder, 8-a molten salt discharging pipeline, 9-a cooling water tank, 10-a first feeding pump, 11-a crude brine storage tank, 12-a second feeding pump, 13-a heat exchanger, 14-a crude brine high-level tank, 15-a first pipeline mixer, 16-a flocculating agent high-level tank, 17-a first precision filter, 18-a precipitation tank, 19-a sodium carbonate solution high-level tank, 20-a supernatant low-level tank after precipitation, 21-a second precision filter, 22-a second pipeline mixer, 23-a dilute sulfuric acid solution high-level tank and 24-a primary refined brine storage tank, 25-resin exchange column, 26-third feeding pump; 27-a temporary storage tank for filtrate to be pressed, 28-a fourth feeding pump, 29-a filter press, 30-a temporary storage tank for filtrate in the filter press, 31-a fifth feeding pump, 32-a backwashing tank, 33-a backwashing pump, 34-a waste sodium sulfate transfer device, 35-a waste salt screw feeder, 36-a fan, 37-a hot air heater, 38-a compressed air pipeline, 39-a compressed air buffer tank, 40-a sixth feeding pump, 41-a flocculant preparation kettle, 42-a seventh feeding pump, 43-a sodium carbonate solution preparation kettle, 44-an eighth feeding pump, 45-a dilute sulfuric acid solution preparation kettle, 46-a softened water pipeline, 47-a concentrated sulfuric acid pipeline, 48-an induced draft fan, 49-a waste heat exchanger, 50-a first overflow pipe and 51-a second overflow pipe, 52-a pre-regeneration feeding pipeline, 53-a hydrochloric acid pipeline, 54-a sodium hydroxide pipeline, 55-a pure water pipeline, 56-a third pipeline mixer, 57-a waste water pipeline, 58-a sodium chloride water outlet pipeline, 59-a backwashing water outlet pipeline, 60-a purified sodium sulfate solution pipeline, 61-a thermometer, 62-a pressure gauge, 63-a flow meter, 64-an online pH meter and 65-a valve.
The present invention will be explained in further detail with reference to examples.
Detailed Description
The waste sodium sulfate is purified to prepare an aqueous solution which can meet the requirements of bipolar membrane electrodialysis, and harmful organic matters, cations, anions and other insoluble matters in the aqueous solution are mainly removed.
The system and the process of the utility model are adopted to treat the waste sodium sulfate to obtain the sodium sulfate aqueous solution which can meet the requirements of the two-stage membrane electrodialysis, and the main indexes of the sodium sulfate aqueous solution are shown in Table 1.
TABLE 1 Main indices of sodium sulfate aqueous solution that meet the two-stage Membrane electrodialysis requirements
| Serial number | Class of impurity | Index of |
| 1 | Ca2++Mg2+ | Less than or equal to 20 mu g/L (calculated by Ca) |
| 2 | Sr | 0.02mg/ |
| 3 | Ba | ≤0.02mg/ |
| 4 | Fe2+ | ≤0.02mg/ |
| 5 | SiO2 | ≤0.05mg/ |
| 6 | Al | ≤0.1mg/ |
| 7 | Ni | ≤0.01mg/ |
| 8 | Other metals | ≤0.2mg/ |
| 9 | Organic matter | Not detected out |
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 constructed as known in the art. The equipment of the utility model is provided with a thermometer 61, a pressure gauge 62, a flow meter 63 and an on-line pH meter 64 according to the requirement, and all pipelines of the utility model are provided with various valves 65 according to the requirement.
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1:
the embodiment provides a primary refining device for treating and purifying waste sodium sulfate, which comprises a U-shaped molten salt furnace 3, wherein a molten salt furnace kiln 4 is arranged outside the U-shaped molten salt furnace 3, the feeding end of the U-shaped molten salt furnace 3 conveys the waste sodium sulfate to be treated through an airflow drying conveyor 5, a high-level bin 6 and a star-shaped feeder 7 which are sequentially connected, and the discharging end of the U-shaped molten salt furnace 3 is connected with a molten salt discharging pipeline 8;
the outlet of the molten salt discharging pipeline 8 conveys molten salt to the molten salt inlet of the cooling water tank 9; a discharge port of the cooling water tank 9 is connected with a crude brine storage tank 11 through a first feeding pump 10 to convey crude brine, and the crude brine storage tank 11 is connected with a crude brine high-level tank 14 through a second feeding pump 12 and a heat exchanger 13 which are sequentially connected to convey crude brine; the crude brine high-level tank 14 is connected with the input end of a first pipeline mixer 15, the input end of the first pipeline mixer 15 is also connected with a flocculant high-level tank 16, and the output end of the first pipeline mixer 15 is connected with the feed end of a first precision filter 17;
the discharge end of the first precision filter 17 is connected with the feed end of the precipitation tank 18, the feed end of the precipitation tank 18 is also connected with the sodium carbonate solution high-level tank 19, and the supernatant discharge end of the precipitation tank 18 is connected with the supernatant low-level tank 20 after precipitation; the supernatant low-level tank 20 after precipitation is connected with the feed end of a second precision filter 21;
the discharge end of the second precision filter 21 is connected with the input end of a second pipeline mixer 22, the input end of the second pipeline mixer 22 is also connected with a dilute sulfuric acid solution high-level tank 23, and the output end of the second pipeline mixer 22 is connected with a primary refined brine storage tank 24;
as a preferable scheme of this embodiment, the bottom concentrate outlet end of the first precision filter 17, the bottom concentrate outlet end of the settling tank 18, and the bottom concentrate outlet end of the second precision filter 21 are all connected to a temporary storage tank 27 for filtrate to be pressed, the temporary storage tank 27 for filtrate to be pressed is connected to the feed end of the filter press 29 through a fourth feeding pump 28, the filtrate outlet end of the filter press 29 is connected to a temporary storage tank 30 for filtrate of the filter press, the temporary storage tank 30 for filtrate of the filter press is connected to the crude brine storage tank 11 through a fifth feeding pump 31, and the residue outlet end of the filter press 29 outputs waste salt impurities.
As a preferable scheme of the embodiment, the primary refined brine storage tank 24 is further connected with a back washing tank 32, and the back washing tank 32 is respectively connected with the discharge ends of the first precision filter 17 and the second precision filter 21 through a back washing pump 33.
As a preferable scheme of this embodiment, the system further comprises a waste sodium sulfate transfer device 34, the waste sodium sulfate transfer device 34 transfers the waste sodium sulfate to be treated to a waste salt screw feeder 35 arranged on the pneumatic drying conveyor 5, and the pneumatic drying conveyor 5 is further provided with a hot air heater 37 with a fan 36. The waste sodium sulfate transfer device 34 is a conventional device capable of transferring waste sodium sulfate.
As a preferable scheme of this embodiment, the system further comprises a compressed air pipeline 38, the compressed air pipeline 38 is connected to a compressed air buffer tank 39, and the compressed air buffer tank 39 is respectively connected to the crude brine high-level tank 14, the flocculant high-level tank 16 and the supernatant low-level tank 20 after precipitation.
As a preferable scheme of this embodiment, the flocculant high-level tank 16 is further connected to a flocculant preparation kettle 41 through a sixth feeding pump 40, the sodium carbonate solution high-level tank 19 is further connected to a sodium carbonate solution preparation kettle 43 through a seventh feeding pump 42, and the dilute sulfuric acid solution high-level tank 23 is further connected to a dilute sulfuric acid solution preparation kettle 45 through an eighth feeding pump 44; the system also comprises a softened water pipeline 46, wherein the softened water pipeline 46 is respectively connected with the cooling water tank 9, the flocculant preparation kettle 41, the sodium carbonate solution preparation kettle 43 and the dilute sulfuric acid solution preparation kettle 45; the device also comprises a concentrated sulfuric acid pipeline 47, wherein the concentrated sulfuric acid pipeline 47 is connected with the dilute sulfuric acid solution preparation kettle 45.
As a preferable scheme of this embodiment, an induced draft fan 48 is installed on the high-level bunker 6.
As a preferable scheme of this embodiment, the cooling water tank 9 is further provided with a waste heat exchanger 49.
As a preferable scheme of the present embodiment, a first overflow pipe 50 is further disposed between the crude brine high-level tank 14 and the crude brine storage tank 11; a second overflow pipe 51 is arranged between the crude brine storage tank 11 and the cooling water tank 9. Overflow pipes are arranged among the containers at the two ends corresponding to the sixth feeding pump 40, the seventh feeding pump 42 and the eighth feeding pump 44 according to requirements, so that excessive material conveying is avoided. A return pipe is arranged on the primary refined brine storage tank corresponding to the third feeding pump 26 and is used for matching with the third feeding pump 26 to avoid the third feeding pump 26 from stopping for many times.
Example 2:
this example provides a waste sodium sulfate treatment purification system, as shown in fig. 1 to fig. 3, comprising a primary refining device 1 and a secondary refining device 2;
the primary purification apparatus 1 used was the primary purification apparatus for treating and purifying sodium sulfate waste as described in example 1.
The secondary refining device 2 comprises a plurality of resin exchange towers 25 which can be communicated with each other and are arranged independently, a primary refined saline storage tank 24 is independently connected with the liquid inlet end of the top of each resin exchange tower 25 through a third feeding pump 26, and the liquid outlet end of the bottom of each resin exchange tower 25 is independently connected with a purified sodium sulfate solution pipeline 60.
As a preferable mode of the present embodiment, a plurality of resin exchange columns 25 which are communicable with each other and are independently provided are provided in an operation mode in which a part of the resin exchange columns 25 is operated and another part of the resin exchange columns 25 is used for standby or regeneration.
It is further preferable that three resin exchange columns 25 are provided so as to be communicable with each other and independently provided, and an operation mode is adopted in which two resin exchange columns 25 are operated and the other resin exchange column 25 is kept in standby or regenerated.
As a preferable scheme of the embodiment, the device further comprises a compressed air pipeline 38, the compressed air pipeline 38 is independently connected with the liquid inlet end at the top of each resin exchange tower 25, and the liquid outlet end at the bottom of each resin exchange tower 25 is also independently connected with the primary refined brine storage tank 24 through a feeding back pipeline 52 before regeneration.
As a preferable scheme of the embodiment, the system further comprises a hydrochloric acid pipeline 53, a sodium hydroxide pipeline 54 and a pure water pipeline 55, wherein the hydrochloric acid pipeline 53, the sodium hydroxide pipeline 54 and the pure water pipeline 55 are respectively and independently connected with an input end of a third pipeline mixer 56, an output end of the third pipeline mixer 56 is independently connected with a liquid inlet end at the top of each resin exchange tower 25, and a liquid outlet end at the bottom of each resin exchange tower 25 is also independently connected with a waste water pipeline 57 and a sodium chloride water outlet pipeline 58.
As a preferable scheme of the embodiment, the purified water pipeline 55 is also independently connected with the liquid outlet end at the bottom of each resin exchange tower 25 for back flushing, a back flushing water outlet pipeline 59 is arranged at the top of each resin exchange tower 25, and the back flushing pipeline 59 is connected with the sodium chloride water outlet pipeline 58.
The specific working process of the waste sodium sulfate treatment and purification system comprises the following steps:
firstly, preparing auxiliary materials:
the softened water pipe 46 is opened, water is respectively fed to the flocculant preparation kettle 41, the sodium carbonate solution preparation kettle 43 and the dilute sulfuric acid solution preparation kettle 45 to a rated amount, and then the softened water pipe 46 is closed. Then, a flocculant preparation kettle 41, a sodium carbonate solution preparation kettle 43 and a dilute sulfuric acid solution preparation kettle 45 are started to stir, and polyferric sulfate is added into the flocculant preparation kettle 41 to prepare 2 wt.% of water solution; adding sodium carbonate and seed crystals into a sodium carbonate solution preparation kettle 43 to prepare an aqueous solution containing 5 wt.% of sodium carbonate and 0.1 wt.% of seed crystals; 93 wt.% or 98 wt.% concentrated sulfuric acid is added to the dilute sulfuric acid solution preparation tank 45 to prepare a 5 wt.% aqueous solution. The prepared auxiliary materials are then conveyed to the flocculant high-level tank 16, the sodium carbonate solution high-level tank 19 and the dilute sulfuric acid solution high-level tank 23 by a sixth feeding pump 40, a seventh feeding pump 42 and an eighth feeding pump 44, respectively.
Secondly, the treatment of the waste sodium sulfate molten salt and the purification operation of the waste brine of the primary refining:
firstly, a fan 36 of the pneumatic dryer 5 is started, a hot air heater 37 generates hot air with the temperature of more than 80 ℃, then a waste salt spiral feeder 35 is started to feed materials into the high-level storage bin 6, and simultaneously a draught fan 48 is started to guide water vapor into a tail gas treatment system. Then, the molten salt furnace kiln 4 is started to raise the temperature to 950-1000 ℃, and the star-shaped feeder 7 is started to slowly feed materials into the U-shaped molten salt furnace 3. And meanwhile, the softened water pipeline 46 is started to supply water to the cooling water tank 9 to a rated amount, then the softened water pipeline 46 is closed, and meanwhile, the waste heat exchanger 49 is started to lead out and utilize the waste heat.
When the discharge hole of the U-shaped molten salt furnace 3 starts discharging and the concentration of salt in the cooling water tank 9 reaches 300-310 g/L, the first feeding pump 10 is started to pump the salt water in the cooling water tank 9 into the crude salt water storage tank 11. And opening a valve on the softened water pipe 46 and related to the cooling water tank 9, controlling the feeding speed of the star-shaped feeder 7, the softened water flow and the flow of the first feeding pump 10, and keeping the salt water in the cooling water tank 9 at a certain liquid level and the salt concentration at 300-310 g/L all the time.
And starting the second feeding pump 12 and the heat exchanger 13 to feed the crude brine high-level tank 14 to the first overflow pipe 50 for backflow, keeping the temperature of the materials in the crude brine high-level tank 14 at 65-75 ℃, and then closing the second feeding pump 12.
And simultaneously, opening a main valve and other related valves of a compressed air pipeline, controlling the flow, mixing the crude brine in the crude brine high-level tank 14 and the flocculant in the flocculant high-level tank 16 in proportion through a first pipeline mixer 15 under the pressure action of compressed air, filtering the mixture through a first precision filter 17, and then feeding the mixture into a settling tank 18 to a rated amount, so as to keep the concentration of the flocculant in the brine at 150-200 ppm. The stirring of the precipitation tank 18 is started, the bottom valve of the sodium carbonate solution high-level tank 19 is opened, the sodium carbonate aqueous solution is added into the precipitation tank 18 until the pH value of the brine in the precipitation tank 18 is 11, and then the bottom valve of the sodium carbonate solution high-level tank 19 is closed. Stirring for 30-60 min, stopping stirring, standing for 10min, and putting the supernatant in the precipitation tank 18 into the supernatant low-level tank 20 after precipitation. The above operations are repeated to precipitate cations such as calcium and magnesium in the precipitation tank 18.
And opening an upper end air pressure valve and a bottom valve of the precipitated supernatant low-level tank 20, inputting the supernatant into a second precision filter 21 under the pressure action of compressed air for filtering, then entering a second pipeline mixer 22, simultaneously opening a bottom valve of a dilute sulfuric acid solution high-level tank 23 to enable the dilute sulfuric acid to enter the second pipeline mixer 22, neutralizing in the second pipeline mixer 22, always keeping the pH value of the mixed brine to be 6-8, and enabling the neutralized brine to enter a primary refined brine storage tank 24.
Thirdly, primary refining deslagging and backwashing:
after the supernatant liquid is discharged from the settling tank 18, a bottom valve of the settling tank 18 is opened to discharge the residue liquid at the bottom, and the residue liquid is collected in the temporary storage tank 27 for filtrate to be pressed.
The primary precision filter 17 determines the frequency of sludge discharge according to the amount of impurities contained in the waste brine, the sludge discharge frequency is determined at most once every 10 times of filtering, a valve on the primary precision filter 17 is opened to discharge sludge, and the sludge is collected in a temporary storage tank 27 of the filtrate to be pressed.
The secondary precision filter 21 filters and discharges the sludge once every 8 times, a valve on the secondary precision filter 21 is opened to discharge the sludge, and the sludge is collected in a temporary storage tank 27 of the filtrate to be pressed.
The backwash tank 32 is stored with a certain amount of primary brine through a primary refined brine storage tank for standby.
And (3) turning on a back-flushing pump 33 to back flush the filtering membrane of the secondary precision filter 21 by using primary brine, and collecting the residue liquid in the temporary storage tank 27 of the filtrate to be pressed.
The back-flushing pump 33 is opened to back flush the filter element of the primary ultrafilter 17 with primary brine, and the residue liquid is collected in the temporary storage tank 27 for filtrate to be pressed.
And (3) opening a fourth feeding pump 28, carrying out pressure filtration on the slurry residue liquid in the temporary storage tank 27 of the filtrate to be pressed through a pressure filter 29, carrying out post-treatment on the filter residue, collecting the filtrate in a temporary storage tank 30 of the filtrate of the pressure filter, and returning the filtrate to the crude salt water storage tank 11 through a fifth feeding pump 31 for retreatment.
Fourthly, purification of secondary refining:
the purification of the secondary refining adopts a three-tower two-open one-standby mode to further purify primary brine by using ion exchange resin.
And opening corresponding feeding and discharging valves of the first two resin exchange towers 25, simultaneously opening a third feeding pump 26 to feed materials to the first two resin exchange towers 25, further purifying in the resin exchange towers 25, and allowing qualified secondary brine to enter the next working section through a purified sodium sulfate solution pipeline 60.
When the first resin exchange tower 25 exchanges a certain amount (by using time and detecting the concentration of calcium and magnesium ions in the brine discharged from the resin exchange tower, the former one is the former one), the first resin exchange tower 25 is switched to two groups, namely the latter two resin exchange towers 25, so that the resin in the first resin exchange tower 25 is regenerated.
Similarly, when the second resin exchange column 25 is exchanged to a certain amount, it is switched to three groups, i.e., the first and third resin exchange columns 25, so that the resin in the second resin exchange column 25 is regenerated.
Likewise, when the third resin exchange tower 25 is exchanged to a certain amount, it is switched to one group, i.e., the first two resin exchange towers 25, so that the resin in the third resin exchange tower 25 is regenerated.
Fifth, regeneration of the secondary refined resin:
taking the first resin exchange column 25 as an example: firstly, the residual sodium sulfate aqueous solution in the resin exchange tower 25 is pressed into a primary refined brine storage tank 24 through a feeding back pipeline 52 before regeneration by compressed air, then a valve corresponding to the compressed air and the feeding back pipeline 52 before regeneration is closed, pure water and 31 wt.% of HCl solution are input into a third pipeline mixer 56 through a pure water pipeline 55 and a hydrochloric acid pipeline 53, the third pipeline mixer 56 feeds 4 wt.% of HCl solution into the resin exchange tower 25 at a flow rate of 3-4 m/h for 2h according to the proportion, then the corresponding valve is closed, and after soaking for 20min, the residual diluted hydrochloric acid is pressed out to a waste water pipeline 57 by compressed air and then treated.
After the hydrochloric acid regeneration treatment is finished, pure water and 32 wt.% of sodium hydroxide solution are input into a third pipeline mixer 56 through a pure water pipeline 55 and a sodium hydroxide pipeline 54, the third pipeline mixer 56 proportionally feeds 5 wt.% of NaOH solution into the resin exchange tower 25 at the flow rate of 3-4 m/H for 2H to convert the resin from the H-type to the Na-type, then corresponding valves are closed, and after the resin is soaked for 20min, the residual diluted alkali is pressed out through compressed air. The pressed sodium chloride and dilute alkali aqueous solution are subjected to cross-linking post-treatment through a sodium chloride water outlet pipeline 58.
After the regeneration treatment of the sodium hydroxide is finished, feeding pure water into the resin exchange tower 25 through a pure water pipeline 55 at a speed of 5-8 m/h for countercurrent backwashing, washing the resin by the countercurrent washing of the pure water until the pH value of the effluent water in a backwashing effluent pipeline 59 is 7-8, collecting the sodium chloride-containing aqueous solution, and performing the after-treatment through a sodium chloride effluent pipeline 58.
Bubbling air from the bottom of the tower by compressed air can serve to agitate and disperse the regenerated tower resin.
The cations harmful to the membrane except sodium ions, potassium ions and chloride ions in the sodium sulfate aqueous solution treated by the device can be reduced to below 1ppm, the anions phosphate ions, silicate ions and other insoluble inorganic substances can be reduced to below 1ppm, and the organic substances in the treated brine are not detected.
The sodium sulfate treatment product obtained by the device has high purity, can meet the quality requirement of bipolar membrane electrodialysis on sodium sulfate, can realize full process automation in the follow-up process, and can reduce energy consumption and cost.
Example 3:
the embodiment provides a waste sodium sulfate treatment and purification process, which comprises a primary refining process and a secondary refining process, wherein the process adopts the waste sodium sulfate treatment and purification system provided in the embodiment 2, the system comprises a primary refining device 1 and a secondary refining device 2, the primary refining device 1 is used for realizing the primary refining process, and the secondary refining device 2 is used for realizing the secondary refining process.
The primary refining process comprises the following steps:
step S11, carrying out hot air drying on the waste sodium sulfate to be treated and then carrying out molten salt treatment;
in the step S11, the temperature of hot air drying is 80-100 ℃;
in the step S11, the temperature of molten salt treatment is 884-900 ℃;
step S12, adding the molten salt subjected to molten salt treatment in the step S11 into water, cooling to form crude brine, adding a flocculating agent into the crude brine, and performing primary filtration to obtain primary filtrate;
in the step S12, polyferric sulfate is used as a flocculating agent, the flocculation temperature is 60-75 ℃, the preparation concentration of the polyferric sulfate is 2 wt.%, and the addition mass part of the polyferric sulfate in the crude brine is 150-200 ppm;
in the step S12, a filter core made of stainless steel, ceramic or titanium material with the filtering precision of 0.5-15 μm is adopted for primary filtering, the filtering pressure is 0.2-0.4 Mpa, the sludge is discharged once every 10 times of filtering, and the backwashing is carried out once when the pressure exceeds 0.38 Mpa;
step S13, adding a sodium carbonate solution into the primary filtrate obtained in the step S12, precipitating in a precipitation tank to precipitate cations such as calcium, magnesium and the like, and then carrying out secondary filtration to obtain secondary filtrate;
in the step S13, in the precipitation process, the preparation concentration of a sodium carbonate solution is 5 wt.%, 0.1 wt.% of calcium carbonate seed crystal is added during preparation, the excessive amount is controlled to be 0.2-0.5 g/L during the addition of the sodium carbonate solution, newly generated calcium carbonate, magnesium carbonate and magnesium hydroxide can be precipitated on the seed crystal to form larger particles, the precipitation temperature is 55-65 ℃, the precipitation time is 30-60 min, and the final pH of a precipitation tank is 11-12;
in the step S13, the secondary 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.
Step S14, adding a dilute sulfuric acid solution into the secondary filtrate obtained in step S13 for neutralization to obtain a sodium sulfate aqueous solution after primary refining;
in step S14, the excess sodium carbonate is neutralized with dilute sulfuric acid, the concentration of the dilute sulfuric acid is 5 wt.%, and the pH of the sodium sulfate aqueous solution after primary purification is 6-8 after neutralization.
The secondary refining process comprises the following steps:
and adding the sodium sulfate aqueous solution after primary refining into a resin exchange tower, and performing ion exchange through the resin exchange tower to obtain the final purified sodium sulfate solution.
The exchange resin in the resin exchange tower 25 is chelate resin, exchange capacity Cu2+Not less than 0.6mmol/ml R-Na. The resin exchange tower of the utility model adopts a known resin exchange tower, and cation exchange resin is adopted in the resin exchange tower to further remove divalent and trivalent cations such as iron, calcium, magnesium, nickel, cobalt, manganese, aluminum and the like contained in the sodium sulfate aqueous solution, so that the requirement of bipolar membrane electrodialysis is met.
The process of the utility model has the advantages that the high-temperature organic matter is decomposed and carbonized thoroughly, and the generated carbon is filtered out during subsequent filtration.
The process of the utility model can completely carbonize and decompose the organic matters contained in the waste sodium sulfate at high temperature and in an anoxic state, completely convert the contained substances such as phosphorus, silicon and the like into phosphate and silicate at high temperature, and remove and purify other anions and cations through precipitation and ion exchange.
The whole process of the process can adopt automatic production control subsequently, not only can improve the production efficiency, but also can thoroughly purify industrial waste sodium sulfate into a sodium sulfate aqueous solution which can meet the requirements of bipolar membrane electrodialysis, and lays a foundation for recycling the waste sodium sulfate.
In this embodiment, the waste sodium sulfate to be treated is specifically waste sodium sulfate generated by waste water of a certain hydrometallurgy nickel and cobalt separation extraction line. The comparison table of the main impurity content of the sodium sulfate aqueous solution before and after the treatment of the waste sodium sulfate by adopting the process is shown in table 2.
TABLE 2 comparison of the main impurity levels of the aqueous sodium sulfate solutions before and after treatment in example 3
| Serial number | Class of impurities | Impurity content in waste sodium sulfate | Concentration of impurities in purified sodium sulfate aqueous solution of 300g/ |
| 1 | Ca2++Mg2+ | 850+400mg/ |
15 μ g/L (in Ca) |
| 2 | Sr | 110mg/L | 0.015mg/ |
| 3 | Ba | 200mg/L | 0.001mg/ |
| 4 | Fe2+ | 450mg/L | 0.018mg/ |
| 5 | SiO2 | 340mg/L | 0.04mg/ |
| 6 | Al | 430mg/L | 0.08mg/ |
| 7 | Ni | 2mg/L | 0.009mg/ |
| 8 | Total phosphorus | 140mg/L | 0.001mg/ |
| 9 | Other metals | 15mg/L | 0.18mg/ |
| 10 | Organic matter | 3528mg/L(COD) | Not detected out |
Example 4:
the embodiment provides a waste sodium sulfate treatment and purification process, which is basically the same as the waste sodium sulfate treatment and purification process in embodiment 3, except that in this embodiment, the waste sodium sulfate to be treated is specifically waste sodium sulfate generated in wastewater treatment of an acid leaching production line of an anode material of a waste power battery. The comparison table of the main impurity contents of the sodium sulfate aqueous solution before and after the treatment of the waste sodium sulfate by adopting the process is shown in table 3.
Table 3 pre and post treatment control of the main impurity content of aqueous sodium sulfate solution of example 4
Claims (9)
1. A primary refining device for treating and purifying waste sodium sulfate is characterized by comprising a U-shaped molten salt furnace (3), wherein a molten salt furnace kiln (4) is arranged outside the U-shaped molten salt furnace (3), the feeding end of the U-shaped molten salt furnace (3) conveys the waste sodium sulfate to be treated through an air flow drying conveyor (5), a high-level bin (6) and a star-shaped feeder (7) which are sequentially connected, and the discharging end of the U-shaped molten salt furnace (3) is connected with a molten salt discharging pipeline (8);
the outlet of the molten salt discharging pipeline (8) conveys molten salt to the molten salt inlet of the cooling water tank (9); a discharge hole of the cooling water tank (9) is connected with a crude brine storage tank (11) through a first feeding pump (10) to convey crude brine, and the crude brine storage tank (11) is connected with a crude brine high-level tank (14) through a second feeding pump (12) and a heat exchanger (13) which are sequentially connected to convey crude brine; the high-level tank (14) of the crude brine is connected with the input end of a first pipeline mixer (15), the input end of the first pipeline mixer (15) is also connected with a high-level tank (16) of a flocculating agent, and the output end of the first pipeline mixer (15) is connected with the feed end of a first precision filter (17);
the discharge end of the first precision filter (17) is connected with the feed end of a precipitation tank (18), the feed end of the precipitation tank (18) is also connected with a sodium carbonate solution high-level tank (19), and the supernatant discharge end of the precipitation tank (18) is connected with a precipitated supernatant low-level tank (20); the supernatant liquid low-level tank (20) after precipitation is connected with the feed end of a second precision filter (21);
the discharge end of the second precision filter (21) is connected with the input end of a second pipeline mixer (22), the input end of the second pipeline mixer (22) is also connected with a dilute sulfuric acid solution high-level tank (23), and the output end of the second pipeline mixer (22) is connected with a primary refined brine storage tank (24).
2. The primary refining device for the treatment and purification of waste sodium sulfate according to claim 1, wherein the bottom concentrate outlet end of the first ultrafilter (17), the bottom concentrate outlet end of the settling tank (18) and the bottom concentrate outlet end of the second ultrafilter (21) are connected with a temporary storage tank (27) of the filtrate to be pressed, the temporary storage tank (27) of the filtrate to be pressed is connected with the feed end of the filter press (29) through a fourth feeding pump (28), the filtrate outlet end of the filter press (29) is connected with a temporary storage tank (30) of the filter press filtrate, the temporary storage tank (30) of the filter press filtrate is connected with the crude brine storage tank (11) through a fifth temporary feeding pump (31), and the residue outlet end of the filter press (29) outputs waste salt impurities.
3. The primary refining device for treating and purifying waste sodium sulfate according to claim 1, wherein the primary refined brine storage tank (24) is further connected with a back washing tank (32), and the back washing tank (32) is respectively connected with the discharge ends of the first precision filter (17) and the second precision filter (21) through a back washing pump (33).
4. The primary refining device for the treatment and purification of the waste sodium sulfate according to claim 1, further comprising a waste sodium sulfate transfer device (34), wherein the waste sodium sulfate transfer device (34) transfers the waste sodium sulfate to be treated to a waste salt screw feeder (35) arranged on the pneumatic drying conveyor (5), and the pneumatic drying conveyor (5) is further provided with a hot air heater (37) with a fan (36).
5. The primary refining device for the treatment and purification of waste sodium sulfate according to claim 1, further comprising a compressed air pipeline (38), wherein the compressed air pipeline (38) is connected with a compressed air buffer tank (39), and the compressed air buffer tank (39) is respectively connected with the crude brine high-level tank (14), the flocculant high-level tank (16) and the supernatant low-level tank (20) after precipitation.
6. The primary refining device for the treatment and purification of waste sodium sulfate according to claim 1, wherein the flocculant elevated tank (16) is further connected with a flocculant preparation kettle (41) through a sixth feeding pump (40), the sodium carbonate solution elevated tank (19) is further connected with a sodium carbonate solution preparation kettle (43) through a seventh feeding pump (42), and the dilute sulfuric acid solution elevated tank (23) is further connected with a dilute sulfuric acid solution preparation kettle (45) through an eighth feeding pump (44); the device also comprises a softened water pipeline (46), wherein the softened water pipeline (46) is respectively connected with the cooling water tank (9), the flocculant preparation kettle (41), the sodium carbonate solution preparation kettle (43) and the dilute sulfuric acid solution preparation kettle (45); the device also comprises a concentrated sulfuric acid pipeline (47), wherein the concentrated sulfuric acid pipeline (47) is connected with the dilute sulfuric acid solution preparation kettle (45).
7. The primary refining device for the treatment and purification of the waste sodium sulfate according to claim 1, wherein the elevated bunker (6) is provided with an induced draft fan (48).
8. The primary refining device for the treatment and purification of the waste sodium sulfate according to claim 1, wherein the cooling water tank (9) is further provided with a waste heat exchanger (49).
9. The primary refining device for the treatment and purification of waste sodium sulfate according to claim 1, wherein a first overflow pipe (50) is further arranged between the crude brine high-level tank (14) and the crude brine storage tank (11); a second overflow pipe (51) is arranged between the crude brine storage tank (11) and the cooling water tank (9).
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