CN213060531U - Ammonium sulfate effluent disposal system - Google Patents
Ammonium sulfate effluent disposal system Download PDFInfo
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- CN213060531U CN213060531U CN202021557160.3U CN202021557160U CN213060531U CN 213060531 U CN213060531 U CN 213060531U CN 202021557160 U CN202021557160 U CN 202021557160U CN 213060531 U CN213060531 U CN 213060531U
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Abstract
The utility model discloses an ammonium sulfate effluent disposal system, including the membrane processing apparatus, pH equalizing basin, blow and take off device and the MVR evaporative concentration system that connect gradually. The utility model discloses with the high concentration ammonium sulfate waste water that metatitanic acid production process produced, comprehensive utilization blows take-off device, membrane processing apparatus and MVR evaporative concentration system, but with high-efficient quick decomposition of ammonium sulfate for cyclic utilization's sodium sulfate and aqueous ammonia, whole processing procedure realizes the closed loop, closely combines with titanium white powder production, and does not use plus the treating agent, also does not have any discarded object of outer row, has good economic benefits and environmental benefit.
Description
[ technical field ] A method for producing a semiconductor device
The utility model belongs to the technical field of useless pair is recycled, concretely relates to ammonium sulfate effluent disposal system.
[ background of the invention ]
In recent years, with the rapid development of industry and the increasing severity of environmental problems, the emission standards of chemical enterprises are more strict, and low emission of ammonia nitrogen is frequently required. Ammonia nitrogen means swimming in waterAmmonia (NH) present in the free state3) And ammonium ion (NH)4 +) Excessive ammonia nitrogen is discharged into a water body, and water body eutrophication can be caused, so that aquatic plants and animals die. The traditional treatment method of ammonia nitrogen in water body includes stripping method, zeolite deamination method and breakpoint chlorination method. Wherein, the stripping method (including air or water vapor) has simple process, stable effect and large energy consumption, especially the stripping process (adopting water vapor stripping) and the effluent ammonia nitrogen is still higher; the zeolite deamination needs to consider the regeneration problem of the zeolite; the breakpoint chlorination process is costly and produces harmful gases.
Titanium dioxide has the characteristics of excellent whiteness, covering power, weather resistance, chemical stability and the like, and is widely applied to the fields of coatings, plastics, papermaking, printing ink and the like.
The traditional sulfuric acid method titanium dioxide production process comprises the following steps:
(1) acid hydrolysis: carrying out acidolysis reaction on the titanium concentrate or the acid-soluble waste residue and sulfuric acid to obtain titanyl sulfate;
(2) hydrolysis: hydrolyzing titanyl sulfate to obtain metatitanic acid slurry;
(3) first washing: washing the hydrolyzed metatitanic acid slurry with water;
(4) bleaching and secondary washing: bleaching and washing the metatitanic acid after washing with calcined crystal seeds to obtain metatitanic acid slurry qualified in washing;
(5) salt treatment: performing salt treatment on the metatitanic acid qualified by washing, and performing filter pressing to obtain a filter cake before the kiln;
(6) and (3) calcining: feeding the filter cake in front of the kiln into a rotary kiln for calcining to obtain a kiln product;
(7) and (3) post-treatment: and carrying out organic/inorganic coating and other processes on the kiln product to obtain a finished titanium dioxide product.
The calcination process in the step (5) is divided into four stages of dehydration, desulfurization, crystal form conversion and particle growth, and in production practice, it is found that about 7% of chemisorption sulfuric acid (including a part of bound acid) is still contained in the metatitanic acid qualified by bleaching and washing in the step (4), the part of sulfuric acid cannot be removed in the washing process, and can be removed only at high temperature in the calcination kiln, and simultaneously, the rutile conversion and particle growth can be inhibited, so that the cost of tail gas treatment is increased, the calcination energy consumption is increased, material sintering is easily caused at high temperature, and the post-grinding is difficult.
A method of wet desulfurization by neutralization with aqueous ammonia is mentioned in patent publication No. CN 108408770A. In the method, the metatitanic acid is neutralized by ammonia water, so that the sulfur content in the titanium dioxide is reduced. In the process, although the content of sulfur oxides generated in the calcining process is reduced and the pressure for treating calcining tail gas is reduced, a large amount of high-concentration ammonium sulfate wastewater is generated, so that the pressure for treating the ammonium sulfate wastewater is brought. At present, a plurality of treatment methods are adopted as membrane treatment methods, although the ammonium sulfate wastewater can be treated by the membrane treatment method, the method is simple and convenient to operate and has no secondary pollution, but because a filtering membrane has the requirement of the upper limit of the ammonia nitrogen of inlet water in the membrane treatment process, the treatment concentration is limited, and the yield is not high.
[ Utility model ] content
The utility model aims at providing an ammonium sulfate effluent disposal system for solving prior art's is not enough, the device has combined the advantage of prior art air stripping method and membrane processing method, has realized the high efficiency processing of high concentration ammonium sulfate waste water.
The purpose of the utility model is realized by the following technical scheme:
an ammonium sulfate wastewater treatment system comprises a membrane treatment device, a pH adjusting tank, a stripping device and an MVR evaporation concentration system which are sequentially connected;
the membrane treatment device is provided with an ammonium sulfate wastewater inlet and an ammonium sulfate wastewater outlet and is used for carrying out membrane treatment on the ammonium sulfate wastewater to obtain ammonium sulfate concentrated water, and then discharging and conveying the ammonium sulfate concentrated water to the pH adjusting tank;
the pH adjusting tank is provided with a sodium hydroxide inlet and is used for adjusting the pH of the ammonium sulfate concentrated water to be alkaline to obtain ammonium sulfate concentrated water containing ammonia gas, and then the ammonium sulfate concentrated water is discharged and conveyed to the stripping device;
the stripping device is provided with an ammonium sulfate concentrated water inlet, an ammonia gas outlet and a solution outlet and is used for stripping the ammonium sulfate concentrated water and separating ammonia gas in the solution, the ammonia gas is discharged through the ammonia gas outlet, and the solution after the ammonia gas is separated is discharged and conveyed to the MVR evaporation and concentration system;
and the MVR evaporation concentration system is used for treating the solution after the ammonia gas is separated and separating to obtain sodium sulfate.
Preferably, the membrane treatment device is a reverse osmosis membrane treatment system.
Preferably, the air stripping device is an air stripping device.
Preferably, the device also comprises an ammonia gas absorption device which is connected with the ammonia gas outlet of the stripping device.
Preferably, the system also comprises a sodium sulfate storage tank and an evaporation condensed water storage tank which are connected with the MVR evaporation concentration system.
The utility model discloses with the high concentration ammonium sulfate waste water that metatitanic acid production process produced, comprehensive utilization blows take-off device, membrane processing apparatus and MVR evaporative concentration system, but with high-efficient quick decomposition of ammonium sulfate for cyclic utilization's sodium sulfate and aqueous ammonia, whole processing procedure realizes the closed loop, closely combines with titanium white powder production, and does not use plus the treating agent, also does not have any discarded object of outer row, has good economic benefits and environmental benefit.
[ description of the drawings ]
FIG. 1 is a schematic structural diagram of an ammonium sulfate wastewater treatment system provided by the present invention.
[ detailed description ] embodiments
The utility model provides an ammonium sulfate wastewater treatment system, as shown in figure 1, which comprises a membrane treatment device 2, a pH adjusting tank 3, a blow-off device 4 and an MVR evaporation concentration system 5 which are connected in sequence;
the membrane treatment device 2 is provided with an ammonium sulfate wastewater inlet and an ammonium sulfate wastewater outlet, the ammonium sulfate wastewater inlet is connected with an ammonium sulfate wastewater conveying system 1, metatitanic acid is neutralized by adding ammonia water, ammonium sulfate wastewater generated in the wet desulphurization process is conveyed to the membrane treatment device 2 through the ammonium sulfate wastewater conveying system 1, the ammonium sulfate wastewater is treated by the membrane treatment device 2, the concentration of ammonium sulfate is improved, ammonium sulfate concentrated water is obtained, and the ammonium sulfate concentrated water is discharged to a pH adjusting tank 3 through the outlet;
the pH adjusting tank 3 is provided with a sodium hydroxide adding port 31, the pH of the ammonium sulfate concentrated water is adjusted to about alkaline pH 11 by adding sodium hydroxide to generate ammonia gas, the ammonium sulfate concentrated water containing the ammonia gas is obtained, and then the ammonia gas is discharged and conveyed to the stripping device 4;
the stripping device 4 is provided with an ammonium sulfate concentrated water inlet, an ammonia gas outlet and a solution outlet, the ammonium sulfate concentrated water containing ammonia gas is stripped through air or steam, ammonia gas continuously escapes from the solution in the stripping process and is discharged from the ammonia gas outlet, most of ammonia nitrogen in the solution after stripping is removed, a small amount of ammonia nitrogen and a large amount of sulfate radicals and sodium ions are also contained, and the ammonia nitrogen and the large amount of sulfate radicals and sodium ions are discharged from the solution outlet and are conveyed to the MVR evaporation concentration system 5;
MVR evaporative concentration system 5, after the air stripping device blows off, the solution that contains a small amount of ammonia nitrogen and a large amount of sulfate radicals, sodium ion is handled through MVR evaporative concentration system 5, ammonia nitrogen and sulfate radicals, sodium ion separation, ammonia nitrogen gets into evaporative condensation water system, and sodium sulfate is appeared with the solid salt form, can obtain the sodium sulfate solid and contain the mother liquor of sodium sulfate after the centrifugation, sodium sulfate mother liquor, sodium sulfate solid can be collected respectively and utilized, the sodium sulfate mother liquor also can circulate again to MVR evaporative concentration system and continue to handle. The MVR evaporation concentration system generally comprises a preheater, an evaporator, a gas-liquid separator, a crystallizer, a centrifuge, a compressor, a pump set and other components, secondary steam which is compressed, heated and boosted is recycled, ammonia nitrogen can be evaporated to enter an evaporation condensation water system under the alkaline high-temperature condition, and further separation of the ammonia nitrogen and a sodium sulfate solution is realized. Separating the sodium sulfate solution after ammonia nitrogen to obtain a concentrated solution, and when the concentrated solution reaches a certain saturated state, allowing the concentrated solution to flow into a crystallizer for crystallization, and further separating the crystallized solution by a centrifuge to obtain sodium sulfate solid and sodium sulfate mother liquor; the MVR evaporation concentration system fully utilizes the latent heat of the steam, so that the heat exchange efficiency is high, and the energy consumption and the operation cost are low; the ammonia gas generated by the stripping device can be absorbed by water to obtain ammonia water which can be recycled to be neutralized by adding metatitanic acid and ammonia water, in the wet desulphurization process, the sodium sulfate solid separated out by the MVR evaporation concentration system and the sodium sulfate mother liquor basically do not contain ammonia nitrogen, the purity is high, the sodium sulfate solid and the sodium sulfate mother liquor can be used for preparing high-salt water (refer to a CN108675499A method), then sodium hydroxide (chlor-alkali process) is prepared from the high-salt water, and the sodium hydroxide is introduced into the pH adjusting tank for recycling. Of course, the high-purity sodium sulfate and the ammonia water can also be used for other purposes, so that the cyclic utilization of sulfate ions and ammonia nitrogen is realized.
The utility model discloses an ammonium sulfate waste water can select for use the ammonium sulfate waste water that the publication is CN108408770A patent discloses add the aqueous ammonia neutralization with metatitanic acid ground paste, carries out the ammonium sulfate waste water that wet flue gas desulfurization produced.
The utility model discloses the high concentration ammonium sulfate waste water that produces among the metatitanic acid wet flue gas desulfurization process at first adopts membrane processing apparatus to carry out the membrane treatment concentration, obtains behind the higher ammonium sulfate dense water of concentration, sends to pH adjusting tank again and adjusts pH with sodium hydroxide, then sends to and blows off the device and blow off ammonia in the separation liquid. Firstly, the concentration of ammonium sulfate in the high-concentration ammonium sulfate wastewater is further improved by adopting membrane treatment, so that the reaction efficiency with sodium hydroxide can be improved, the alkali consumption is saved, the stripping efficiency can be improved, the energy consumption is reduced, and the ammonia gas with higher concentration is obtained. The ammonia gas after stripping separation can be recycled to the wet desulphurization process of metatitanic acid after being absorbed by water or ammonia water. The solution after blowing off still contains the ammonia nitrogen of higher concentration, consequently, the utility model discloses the solution after will blowing off is handled through MVR evaporative concentration system again, and the separation concentration obtains the sodium sulfate. The obtained sodium sulfate does not contain ammonia nitrogen basically, has high purity, and can be used for preparing high-salinity water, further preparing sodium hydroxide from the high-salinity water for recycling, or being used for other purposes such as chemical industry, fertilizers and the like. The ammonia water can be circularly used in the wet desulphurization process of the metatitanic acid.
Therefore, the utility model provides an ammonium sulfate effluent disposal system, membrane treatment has been combined, blow off, and MVR evaporation concentration system effluent treatment plant, only adopt with prior art and blow off the device and compare, adopt membrane treatment before blowing off, make ammonium sulfate concentration concentrated, follow-up blowing off can high efficiency's separation obtain the ammonia of high concentration, the ammonia nitrogen clearance has been improved, thereby make the ammonia nitrogen content in the liquid after blowing off lower, still adopt MVR to handle the ammonia nitrogen in the separation sodium sulfate solution after blowing off in addition, can reduce the later stage and blow off the time (along with the reduction of ammonia nitrogen concentration, it is also more and more low to blow off efficiency). And if only adopt MVR evaporation concentration system, to high concentration ammonia nitrogen desorption efficiency be less than the air stripping device, consequently with membrane treatment, air stripping device and MVR evaporation concentration system combined use, can synthesize the air stripping device and get rid of the higher advantage of high concentration ammonia nitrogen desorption efficiency, and MVR processing system energy consumption is lower, and can solve prior art and only adopt membrane treatment, have the requirement to the ammonia nitrogen upper limit of intaking, the problem that concentration of handling is limited, the yield is not high.
According to the above analysis, the utility model discloses with the high concentration ammonium sulfate waste water that metatitanic acid production process produced, comprehensive utilization blows off device, membrane processing apparatus and MVR evaporative concentration system, but with high-efficient quick decomposition of ammonium sulfate for cyclic utilization's sodium sulfate and aqueous ammonia, whole processing procedure realizes the closed loop, closely combines with titanium white powder production, and does not use plus processing agent, also does not have any discarded object of outer row, has good economic benefits and environmental benefit.
Preferably, the membrane treatment apparatus is a reverse osmosis membrane treatment apparatus. Reverse osmosis is a process of separating a solvent from a solution by taking pressure difference as a driving force, and has the advantages of low energy consumption, no pollution, simple use and wide application; the reverse osmosis membrane can be a polyamide composite reverse osmosis membrane, a cellulose acetate membrane and the like, and the aperture is 0.5-10 nm.
Preferably, the air stripping device is an air stripping device, and compared with the steam stripping device, the energy consumption is saved. An aeration tank or a stripping tower can be adopted.
Preferably, the utility model provides a processing system still includes ammonia absorbing device 6, with the ammonia exit linkage who blows off device 4, but the ammonia that can adopt water or aqueous ammonia absorption to blow off the device production obtains the aqueous ammonia to convenient cyclic utilization prevents that the ammonia from discharging the polluted environment in the atmosphere.
Preferably, the utility model provides a processing system still includes sodium sulfate storage tank 7 and evaporation condensate water storage tank 8, all is connected with MVR evaporation concentration system 5, and sodium sulfate storage tank 7 can be used to store sodium sulfate solid or mother liquor, can set up a plurality of sodium sulfate storage tanks, is used for storing sodium sulfate solid and sodium sulfate mother liquor respectively, and evaporation condensate water storage tank 8 is used for storing the evaporation condensate water, contains a small amount of ammonia nitrogen in the evaporation condensate water, can carry to ammonia absorbing device for absorb the ammonia of air stripping device separation.
Example 1
According to the method disclosed in the patent with the publication number of CN108408770A, the metatitanic acid slurry is subjected to wet desulphurization, and the ammonium sulfate concentration in the obtained ammonium sulfate wastewater is 9.26g/L, and the ammonia nitrogen content is 2500 mg/L.
Conveying the ammonium sulfate wastewater to a membrane treatment device shown in figure 1, performing reverse osmosis membrane treatment to obtain ammonium sulfate concentrated water, and after the ammonium sulfate concentrated water is subjected to reverse osmosis membrane treatment, increasing the concentration of ammonium sulfate in the ammonium sulfate concentrated water to 25.9g/L, wherein the content of ammonia nitrogen is 7000 mg/L.
Conveying the ammonium sulfate concentrated water to a pH adjusting tank, adding a NaOH solution with the mass fraction of 30%, and adjusting the pH to 10.8.
Conveying the ammonium sulfate concentrated water after pH adjustment to a stripping device, stripping by air, allowing the generated ammonia gas to escape to an ammonia gas absorption device 6, and absorbing by water to obtain ammonia water, wherein the ammonia water is to be used in wet desulfurization in step S1 of metatitanic acid desulfurization; the ammonia nitrogen content of the solution obtained after ammonia gas separation is 1050mg/L, and the ammonia nitrogen removal rate is 85%.
And conveying the solution subjected to stripping and ammonia gas removal to an MVR evaporation concentration system for treatment, further evaporating the residual ammonia nitrogen to enter an evaporation condensation water system, separating out sodium sulfate, centrifuging to obtain sodium sulfate solid and sodium sulfate mother liquor, preparing high-salt water according to the method disclosed in the publication No. CN108675499A, further reacting the high-salt water to obtain sodium hydroxide, and recycling the sodium hydroxide to a pH adjusting tank to react with ammonium sulfate concentrated water. The sodium sulfate mother liquor can be circulated to an evaporation concentration system for further evaporation concentration treatment.
While the preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the appended claims be interpreted as including the preferred embodiment and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (5)
1. An ammonium sulfate wastewater treatment system is characterized by comprising a membrane treatment device, a pH adjusting tank, a stripping device and an MVR evaporation concentration system which are sequentially connected;
the membrane treatment device is provided with an ammonium sulfate wastewater inlet and an ammonium sulfate wastewater outlet and is used for carrying out membrane treatment on the ammonium sulfate wastewater to obtain ammonium sulfate concentrated water, and then discharging and conveying the ammonium sulfate concentrated water to the pH adjusting tank;
the pH adjusting tank is provided with a sodium hydroxide inlet and is used for adjusting the pH of the ammonium sulfate concentrated water to be alkaline to obtain ammonium sulfate concentrated water containing ammonia gas, and then the ammonium sulfate concentrated water is discharged and conveyed to the stripping device;
the stripping device is provided with an ammonium sulfate concentrated water inlet, an ammonia gas outlet and a solution outlet and is used for stripping the ammonium sulfate concentrated water and separating ammonia gas in the solution, the ammonia gas is discharged through the ammonia gas outlet, and the solution after the ammonia gas is separated is discharged and conveyed to the MVR evaporation and concentration system;
and the MVR evaporation concentration system is used for treating the solution after the ammonia gas is separated and separating to obtain sodium sulfate.
2. The ammonium sulfate wastewater treatment system as set forth in claim 1,
the membrane treatment device is a reverse osmosis membrane treatment device.
3. The ammonium sulfate wastewater treatment system as set forth in claim 1,
the air stripping device is an air stripping device.
4. The ammonium sulfate wastewater treatment system as set forth in claim 1,
the ammonia absorption device is connected with the ammonia outlet of the stripping device.
5. The ammonium sulfate wastewater treatment system as set forth in claim 1,
still include sodium sulfate storage tank and evaporation condensate water storage tank, all with MVR evaporation concentration system connects.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202021557160.3U CN213060531U (en) | 2020-07-31 | 2020-07-31 | Ammonium sulfate effluent disposal system |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202021557160.3U CN213060531U (en) | 2020-07-31 | 2020-07-31 | Ammonium sulfate effluent disposal system |
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| CN213060531U true CN213060531U (en) | 2021-04-27 |
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| CN202021557160.3U Active CN213060531U (en) | 2020-07-31 | 2020-07-31 | Ammonium sulfate effluent disposal system |
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Address after: No.1669, Zhongjiao Road, jiaokezuo District, Henan Province Patentee after: Longbai Group Co.,Ltd. Address before: No.1669, Zhongjiao Road, jiaokezuo District, Henan Province Patentee before: LOMON BILLIONS GROUP Co.,Ltd. |