CN112850747B - Method and device for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate - Google Patents
Method and device for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate Download PDFInfo
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- CN112850747B CN112850747B CN202110148228.5A CN202110148228A CN112850747B CN 112850747 B CN112850747 B CN 112850747B CN 202110148228 A CN202110148228 A CN 202110148228A CN 112850747 B CN112850747 B CN 112850747B
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- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/244—Preparation by double decomposition of ammonium salts with sulfates
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/02—Preparation by double decomposition
Abstract
The invention relates to a method and a device for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate. According to the invention, the sodium sulfate stock solution and the ammonium bicarbonate stock solution are subjected to ion pairing again through the arranged electrodialysis module to form the concentrated solution, and the concentrated solution is evaporated and crystallized to prepare the high-purity sodium bicarbonate crystal and the high-purity ammonium sulfate crystal.
Description
Technical Field
The invention relates to the field of chemical processes, in particular to a method and a device for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate.
Background
Soda ash, sodium carbonate (Na) by scientific name2CO3) The shape of the powder is usually white powder, the powder is not easy to decompose under high temperature, the powder is easy to dissolve in water, and the aqueous solution is alkaline. The sodium carbonate is one of important basic chemical raw materials and two bases in 'three acids and two bases', has the reputation of 'the mother of chemical engineering', is widely applied to various fields of national economy such as building materials, chemical engineering, metallurgy, textile, food, national defense, medicine and the like, and plays an important role in the national economy. The soda ash industry is a resource-dependent low-threshold industry, and as an important basic industrial raw material, no matter soda ash or glass, no competitive substitute exists under the current technical conditions. Ammonium sulfate ((NH)4)2SO4) It is an excellent nitrogen fertilizer (commonly called "fertilizer field powder"), suitable for general soil and crops, and can make branches and leaves grow vigorously, raise fruit quality and yield, and raise the resistance of crops to calamities, and can be used as base fertilizer, top dressing and seed fertilizer. Can produce ammonium chloride by double decomposition reaction with salt and react with aluminum sulfate to produceAmmonium alum is used together with boric acid to produce a refractory. The addition of the plating solution can increase the conductivity. Also a catalyst for food dark brown, a nitrogen source for culturing yeast in the production of fresh yeast, an acid dye dyeing auxiliary agent and a leather deliming agent. In addition, the method is also used for brewing beer, producing chemical reagents and storage batteries and the like. The mining method also has an important function of mining the rare earth, wherein the mining uses ammonium sulfate as a raw material, the rare earth elements in the ore soil are exchanged in an ion exchange mode, and then the rare earth raw ore is obtained after the leachate is collected for impurity removal, precipitation, squeezing and firing, and about 5 tons of ammonium sulfate is needed for each 1 ton of the rare earth raw ore produced by mining.
According to the report of market research and investment strategy planning of the Chinese soda industry in 2014-2019 published by the Chinese industry information network, the method comprises the following steps: the soda ash manufacturing process is mainly divided into an ammonia-soda process, a combined soda process and a natural soda process. The ammonia-soda process, also called as the solvay process, was developed in 1863 by the Belgium engineer from the comprehensive previous experience of solvay, and the main production processes include limestone calcination, brine refining, ammonia absorption, carbonation, sodium bicarbonate filtration, calcination, mother liquor distillation, etc. The ammonia-soda process has the advantages of suitability for large-scale production and high product quality and purity; the defects are low salt utilization rate and large amount of waste liquid generated in the production of soda ash. The combined alkali method is mainly characterized by that on the basis of ammonia-alkali method, the processes of alkali preparation and ammonia preparation are combined, and the mother liquor after alkali preparation is deep-processed, at the same time the ammonium chloride is obtained. With the continuous innovation of the traditional process technology, the new alkali combination methods such as 'the Cannon method', 'the Xinxu method', 'the AC method', 'the NA method' and the like are continuously available, and the technical requirements of enterprises with different resources or production conditions for alkali preparation are met. The combined alkali method has the advantages of high salt utilization efficiency and small environmental protection pressure; the disadvantages are large investment of the device for synthesizing ammonia and large influence of the ammonium chloride on the market. The natural alkali method, the alkali-making process, mainly uses manpower or machinery (dredger or salt-mining ship) to mine solid ore, or directly extracts lake water, and obtains alkali product by 'solarization in alkali field'. The trona resource mainly refers to soda lake or solid deposit. The natural alkali method has the advantages of low cost, high quality, energy conservation, environmental protection and high economic benefit; the disadvantage is due to the trona resource.
Soda ash can also be prepared in practice from sodium bicarbonate plus sodium hydroxide. The Chinese invention with publication number CN102198953A discloses a method for preparing sodium bicarbonate and co-producing ammonium sulfate by a double decomposition method, which uses sodium sulfate and ammonium bicarbonate as raw materials, obtains sodium bicarbonate by double decomposition reaction, obtains sodium sulfate crystals by separating the obtained mother liquor through high-temperature deamination and evaporation concentration at 130 ℃, obtains double salts of sodium sulfate and ammonium sulfate by separating the mother liquor through cooling crystallization, and obtains ammonium sulfate products by evaporating crystallization of the mother liquor.
Chinese invention publication No. CN111039304A discloses a method for preparing sodium bicarbonate and co-producing ammonium sulfate by double decomposition, which comprises reacting one or a mixture of at least two of diammonium hydrogen phosphate, ammonium formate or ammonium nitrate with sodium sulfate to generate a first target product ammonium sulfate and sodium salt, then crystallizing by evaporation to obtain ammonium sulfate crystals and a sodium salt solution, and further adding ammonium bicarbonate (or carbon dioxide + ammonia gas) into the sodium salt solution to react to generate a second target product sodium bicarbonate. The method has the advantages of large medicament consumption, large equipment floor area and high production cost.
In summary, it is urgently needed to solve the problems of how to shorten the whole process flow, reduce the floor area, reduce the medicament consumption cost, concentrate and purify the sodium bicarbonate and ammonium sulfate solution, improve the utilization rate of the raw material medicament, avoid secondary pollution to the environment and reduce the whole cost of the system in the process of preparing the sodium bicarbonate and ammonium sulfate from the sodium sulfate and the ammonium bicarbonate.
Disclosure of Invention
The present invention aims to overcome the defects in the prior art, and provides a method and a device for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate comprises the following steps:
s1, pretreating the sodium sulfate stock solution and the ammonium bicarbonate stock solution to enable the particle size of particles in the sodium sulfate stock solution and the ammonium bicarbonate stock solution to be less than 5 microns;
s2, arranging a plurality of groups of electrodialysis units which are sequentially connected in an electric field, wherein each electrodialysis unit is sequentially provided with an A channel, a B channel, a C channel and a D channel from one end of the positive pole of the electric field to one end of the negative pole of the electric field, the D channel of the previous electrodialysis unit is connected with the A channel of the next electrodialysis unit, cation exchange membranes are arranged between the adjacent A channels and the B channels and between the adjacent C channels and the D channels, and anion exchange membranes are arranged between the adjacent D channels and the A channels and between the adjacent B channels and the C channels;
s3, introducing a sodium sulfate stock solution into the channel A, introducing an ammonium bicarbonate stock solution into the channel C, wherein under the action of an electric field, sodium ions in the sodium sulfate stock solution in the channel A penetrate through a cation exchange membrane to enter the channel B, sulfate ions in the sodium sulfate stock solution in the channel A penetrate through an anion exchange membrane to enter the channel D, ammonium ions in the ammonium bicarbonate stock solution in the channel C penetrate through the cation exchange membrane to enter the channel D to form an ammonium sulfate solution with the sulfate ions, and bicarbonate ions in the ammonium bicarbonate stock solution in the channel C penetrate through the anion exchange membrane to enter the channel B to form a sodium bicarbonate solution with the sodium ions;
s4, leading the ammonium sulfate solution in the channel D out to an ammonium sulfate liquid tank, and when the concentration of the ammonium sulfate solution in the ammonium sulfate liquid tank reaches a preset overflow standard, overflowing to an evaporative crystallization unit to obtain ammonium sulfate crystals; and (3) guiding the sodium bicarbonate solution in the channel B into a sodium bicarbonate solution tank, and overflowing to an evaporation crystallization unit to obtain sodium bicarbonate crystals after the concentration of the sodium bicarbonate solution in the sodium bicarbonate solution tank reaches a preset overflow standard.
Further, in S1, the method for pretreating the sodium sulfate stock solution and the ammonium bicarbonate stock solution includes passing the sodium sulfate stock solution and the ammonium bicarbonate stock solution through a cartridge filter by a lift pump to remove impurities.
Further, sodium sulfate stock solution led out from the passage A in the S3 is led back to the sodium sulfate solution tank and then led out from the sodium sulfate solution tank to the passage A, and when the concentration of the sodium sulfate stock solution in the sodium sulfate solution tank is lower than a preset overflow standard, sodium sulfate concentration supplement is carried out; and in the step S3, the ammonium bicarbonate stock solution led out from the channel C is led back to the ammonium bicarbonate liquid tank and then led out to the channel C by the ammonium bicarbonate liquid tank, and when the concentration of the ammonium bicarbonate stock solution in the ammonium bicarbonate liquid tank is lower than a preset overflow standard, ammonium bicarbonate concentration supplement is carried out.
Further, the sodium sulfate concentration supplementing method comprises the following steps:
s311, arranging a sodium sulfate dissolving tank connected with a sodium sulfate liquid tank, and guiding sodium sulfate stock solution into the sodium sulfate dissolving tank from the sodium sulfate liquid tank after the concentration of the sodium sulfate stock solution in the sodium sulfate liquid tank is lower than a preset overflow standard;
s312, supplementing solid sodium sulfate into the sodium sulfate dissolving tank until the concentration of a sodium sulfate stock solution in the sodium sulfate dissolving tank reaches 10-20%;
s313, pretreating the sodium sulfate stock solution in the sodium sulfate dissolving pool and then returning the sodium sulfate stock solution to the sodium sulfate solution tank.
Further, the ammonium bicarbonate concentration supplementing method comprises the following steps:
s321, arranging an ammonium bicarbonate dissolving tank connected with an ammonium bicarbonate liquid tank, and leading the ammonium bicarbonate stock solution into the ammonium bicarbonate dissolving tank from the ammonium bicarbonate liquid tank after the concentration of the ammonium bicarbonate stock solution in the ammonium bicarbonate liquid tank is lower than a preset overflow standard;
s322, supplementing solid ammonium bicarbonate to the ammonium bicarbonate dissolving tank until the concentration of an ammonium bicarbonate stock solution in the ammonium bicarbonate dissolving tank reaches 10-20%;
s323, pretreating the ammonium bicarbonate stock solution in the ammonium bicarbonate dissolving tank and then returning the ammonium bicarbonate stock solution to the ammonium bicarbonate solution tank.
Further, the overflow standard stated in S3 is a TDS range of 100000mg/L or less.
Further, the overflow standard of the ammonium sulfate solution in S4 is that TDS is more than or equal to 200000 mg/L; the overflow standard of the sodium bicarbonate solution in S4 is TDS more than or equal to 200000 mg/L.
A device for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate comprises a sodium sulfate dissolving tank, a sodium sulfate liquid tank, an ammonium bicarbonate dissolving tank, an ammonium bicarbonate liquid tank, an electrodialysis module, an ammonium sulfate liquid tank, a sodium bicarbonate liquid tank, an ammonium sulfate evaporation crystallization unit and a sodium bicarbonate evaporation crystallization unit, wherein the sodium sulfate liquid tank is connected with the sodium sulfate dissolving tank through an overflow pipe, the sodium sulfate dissolving tank is connected with a first cartridge filter provided with a lift pump, and the other end of the first cartridge filter is connected with the sodium sulfate liquid tank; the ammonium bicarbonate liquid tank is connected with the ammonium bicarbonate dissolving tank through an overflow pipe, the ammonium bicarbonate dissolving tank is connected with a second security filter provided with a lifting pump, and the other end of the second security filter is connected with the ammonium bicarbonate liquid tank; the ammonium sulfate liquid tank is connected with the ammonium sulfate evaporative crystallization unit through an overflow pipe, and the sodium bicarbonate liquid tank is connected with the sodium bicarbonate evaporative crystallization unit through an overflow pipe; the electrodialysis module comprises an electric field module provided with a positive electrode and a negative electrode and a plurality of connected electrodialysis units arranged in the electric field module and between the positive electrode and the negative electrode, each electrodialysis unit comprises an A channel, a B channel, a C channel and a D channel which are sequentially arranged from the positive electrode to the negative electrode, the D channel is connected with the A channel between every two adjacent electrodialysis units, cation exchange membranes are arranged between every two adjacent A channels and B channels and between every two adjacent C channels and D channels, and anion exchange membranes are arranged between every two adjacent D channels and A channels and between every two adjacent B channels and C channels; an inlet pipe I and an outlet pipe I are connected between the sodium sulfate liquid tank and the channel A, an inlet pipe II and an outlet pipe II are connected between the sodium bicarbonate liquid tank and the channel B, an inlet pipe III and an outlet pipe III are connected between the ammonium bicarbonate liquid tank and the channel C, and an inlet pipe IV and an outlet pipe IV are connected between the ammonium sulfate liquid tank and the channel D.
Preferably, the inlet pipe I, the inlet pipe II, the inlet pipe III and the inlet pipe IV are all provided with circulating pumps.
Compared with the prior art, the invention has the following advantages and effects: through the arranged electrodialysis module, ions of the sodium sulfate stock solution and the ammonium bicarbonate stock solution are recombined to finally form two concentrated solutions, high-purity sodium bicarbonate crystals and ammonium sulfate crystals can be directly prepared through the two concentrated solutions in subsequent evaporation crystallization units which are respectively connected, the high-concentration solution is more beneficial to salt preparation of the evaporation crystallization units, and the energy consumption of the evaporation crystallization units is reduced; the whole process basically has no additional medicament except the raw material medicament, so that the medicament adding cost is greatly saved; the whole process flow is shorter, the occupied area of required equipment is smaller, and the utilization rate of raw material medicaments is higher.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for preparing ammonium sulfate and sodium bicarbonate from sodium sulfate and ammonium bicarbonate according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of an electrodialysis module part in an embodiment of the invention.
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
In the following description, references to "a," "B," "C," "D," "one," "two," "three," and "four" are intended only to distinguish between similar objects and not to imply a particular order to the objects, but it is to be understood that "a," "B," "C," "D," "one," "two," "three," and "four" are, where permissible, interchangeable in any particular order or sequence to enable embodiments of the invention described herein to be practiced in other than as specifically illustrated or described herein.
The invention provides a method for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate, which comprises the following steps:
s1, pretreating the sodium sulfate stock solution and the ammonium bicarbonate stock solution to enable the particle size of particles in the sodium sulfate stock solution and the ammonium bicarbonate stock solution to be less than 5 microns.
In some embodiments, the sodium sulfate and ammonium bicarbonate stock solutions are pretreated in S1 by passing the sodium sulfate and ammonium bicarbonate stock solutions through a cartridge filter to remove impurities before use by using the lift pump 12, so that the particle size of the particles in the sodium sulfate and ammonium bicarbonate stock solutions is less than 5 μm.
The sodium sulfate stock solution and the ammonium bicarbonate stock solution are respectively stored in a sodium sulfate solution tank 1 and an ammonium bicarbonate solution tank 2.
S2, arranging a plurality of groups of electrodialysis units which are connected in sequence in an electric field, wherein each electrodialysis unit is provided with an A channel 32, a B channel 33, a C channel 34 and a D channel 35 in sequence from one end of the positive pole of the electric field to one end of the negative pole of the electric field, the D channel 35 of the previous electrodialysis unit is connected with the A channel 32 of the next electrodialysis unit, cation exchange membranes 36 are arranged between the adjacent A channels 32 and the B channels 33 and between the adjacent C channels 34 and the D channel 35, and anion exchange membranes 37 are arranged between the adjacent D channels 35 and the A channels 32 and between the adjacent B channels 33 and the C channels 34. Under the action of the electric field, the cations in the a channel 32 and the C channel 34 move toward the negative electrode while passing through the cation exchange membrane 36, and the negative ions in the a channel 32 and the C channel 34 move toward the positive electrode while passing through the anion exchange membrane 37.
S3, introducing a sodium sulfate stock solution into the A channel 32, introducing an ammonium bicarbonate stock solution into the C channel 34, wherein under the action of an electric field, sodium ions in the sodium sulfate stock solution in the A channel 32 penetrate through the cation exchange membrane 36 to enter the B channel 33, sulfate ions in the sodium sulfate stock solution in the A channel 32 penetrate through the anion exchange membrane 37 to enter the D channel 35, ammonium ions in the ammonium bicarbonate stock solution in the C channel 34 penetrate through the cation exchange membrane 36 to enter the D channel 35 to form an ammonium sulfate solution with the sulfate ions, and bicarbonate ions in the ammonium bicarbonate stock solution in the C channel 34 penetrate through the anion exchange membrane 37 to enter the B channel 33 to form a sodium bicarbonate solution with the sodium ions.
Specifically, the sodium sulfate stock solution led out from the passage a 32 in S3 is led back to the sodium sulfate solution tank 1 and then led out from the sodium sulfate solution tank 1 to the passage a 32, and when the concentration of the sodium sulfate stock solution in the sodium sulfate solution tank 1 is lower than a preset overflow standard, sodium sulfate concentration replenishment is performed.
The sodium sulfate concentration supplementing method comprises the following steps:
s311, arranging a sodium sulfate dissolving tank 11 connected with a sodium sulfate liquid tank 1, and introducing sodium sulfate stock solution into the sodium sulfate dissolving tank 11 from the sodium sulfate liquid tank 1 when the concentration of the sodium sulfate stock solution in the sodium sulfate liquid tank 1 is lower than a preset overflow standard;
s312, supplementing solid sodium sulfate to the sodium sulfate dissolving tank 11 until the concentration of the sodium sulfate stock solution in the sodium sulfate dissolving tank 11 reaches 10-20%;
s313, pretreating the sodium sulfate stock solution in the sodium sulfate dissolving tank 11 and then returning the sodium sulfate stock solution to the sodium sulfate solution tank 1.
Specifically, in S3, the ammonium bicarbonate raw solution led out from the C channel 34 is led back to the ammonium bicarbonate tank 2 and then led out from the ammonium bicarbonate tank 2 to the C channel 34, and when the ammonium bicarbonate raw solution concentration in the ammonium bicarbonate tank 2 is lower than a preset overflow standard, ammonium bicarbonate concentration supplementation is performed.
The ammonium bicarbonate concentration supplementing method comprises the following steps:
s321, arranging an ammonium bicarbonate dissolving tank 21 connected with the ammonium bicarbonate liquid tank 2, and leading the ammonium bicarbonate stock solution into the ammonium bicarbonate dissolving tank 21 from the ammonium bicarbonate liquid tank 2 when the concentration of the ammonium bicarbonate stock solution in the ammonium bicarbonate liquid tank 2 is lower than a preset overflow standard;
s322, supplementing solid ammonium bicarbonate to the ammonium bicarbonate dissolving tank 21 until the concentration of the ammonium bicarbonate stock solution in the ammonium bicarbonate dissolving tank 21 reaches 10-20%;
s323, the ammonium bicarbonate stock solution in the ammonium bicarbonate dissolving tank 21 is guided back to the ammonium bicarbonate solution tank 2 after being pretreated.
Specifically, the overflow standard of the sodium sulfate stock solution and the ammonium bicarbonate stock solution in S3 is that the TDS range is smaller than or equal to 100000 mg/L.
S4, leading the ammonium sulfate solution in the channel D35 out to an ammonium sulfate liquid tank 5, and when the concentration of the ammonium sulfate solution in the ammonium sulfate liquid tank 5 reaches a preset overflow standard, overflowing to an evaporative crystallization unit to obtain ammonium sulfate crystals; and (3) guiding the sodium bicarbonate solution in the channel B33 into the sodium bicarbonate solution tank 4, and overflowing to an evaporation crystallization unit to obtain sodium bicarbonate crystals when the concentration of the sodium bicarbonate solution in the sodium bicarbonate solution tank 4 reaches a preset overflow standard.
Specifically, the overflow standard of the ammonium sulfate solution in S4 is that TDS is more than or equal to 200000 mg/L; the overflow standard of the sodium bicarbonate solution in S4 is TDS more than or equal to 200000 mg/L.
In the method for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate, sodium sulfate (Na) is treated by an electrodialysis module with a four-channel structure2SO4) Mixing the stock solution with ammonium hydrogen carbonate ((NH)4)2CO3) Ion in the stock solution is subjected to re-pairing to finally form two concentrated solutions, namely sodium carbonate (Na)2CO3) Solution and ammonium sulfate ((NH)4)2SO4) The solution can be directly prepared into high-purity sodium carbonate (Na) in respective subsequent evaporation and crystallization units2CO3) And ammonium sulfate ((NH)4)2SO4) The product and the high-concentration solution are more beneficial to salt preparation of the evaporative crystallization unit, and the energy consumption of the evaporative crystallization unit is reduced. The whole process basically has no additional medicament except the raw material medicament, thereby greatly saving the medicament adding cost. The whole process flow is short, the occupied area is reduced, and the utilization rate of raw material medicaments is improved. The sodium bicarbonate and the sodium hydroxide are matched to prepare the soda ash.
The method for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate can also be used for preparing ammonium sulfate and sodium carbonate by using sodium sulfate and ammonium carbonate, or other similar products.
Based on the above concept, an embodiment of the present invention provides an apparatus for preparing ammonium sulfate and sodium bicarbonate from sodium sulfate and ammonium bicarbonate, as shown in fig. 1, including
And a sodium sulfate liquid tank 1 for accumulating a sodium sulfate stock solution and outputting the sodium sulfate stock solution.
And the ammonium bicarbonate liquid tank 2 is used for accumulating the ammonium bicarbonate stock solution and outputting the ammonium bicarbonate stock solution.
The sodium sulfate dissolution tank 11 is used for charging solid sodium sulfate to increase the concentration of the sodium sulfate stock solution therein.
The sodium sulfate dissolving tank 11 is connected with the sodium sulfate solution tank 1 through an overflow pipe 9, and when the concentration of the sodium sulfate stock solution in the sodium sulfate solution tank 1 is lower than a preset overflow standard, the sodium sulfate stock solution in the sodium sulfate solution tank 1 overflows to the sodium sulfate dissolving tank 11. The sodium sulfate dissolving tank 11 is further connected with a cartridge filter 13 provided with a lift pump 12, the other end of the cartridge filter 13 is connected with the sodium sulfate liquid tank 1, and when the concentration of sodium sulfate stock solution in the sodium sulfate dissolving tank 11 is increased to a certain degree after solid sodium sulfate is added, the sodium sulfate stock solution flows back to the sodium sulfate liquid tank 1 after passing through the cartridge filter 13 under the action of the lift pump 12.
And an ammonium bicarbonate dissolving tank 21 for adding solid ammonium bicarbonate to increase the concentration of the ammonium bicarbonate stock solution therein.
The ammonium bicarbonate dissolving tank 21 is connected with the ammonium bicarbonate liquid tank 2 through an overflow pipe 9, and when the concentration of the ammonium bicarbonate stock solution in the ammonium bicarbonate liquid tank 2 is lower than a preset overflow standard, the ammonium bicarbonate stock solution in the ammonium bicarbonate liquid tank 2 overflows to the ammonium bicarbonate dissolving tank 21. The ammonium bicarbonate dissolving tank 21 is also connected with a security filter II 22 provided with a lifting pump 12, the other end of the security filter II 22 is connected with the ammonium bicarbonate liquid tank 2, when the ammonium bicarbonate raw liquid in the ammonium bicarbonate dissolving tank 21 is added with solid ammonium bicarbonate and the concentration rises to a certain degree, the ammonium bicarbonate raw liquid flows back to the ammonium bicarbonate liquid tank 2 after passing through the security filter II 22 under the action of the lifting pump 12.
The electrodialysis module, as shown in fig. 2, includes an electric field module 31 having a positive electrode and a negative electrode, and a plurality of electrodialysis units connected to each other between the positive electrode and the negative electrode are disposed in the electric field module 31. Each electrodialysis unit comprises an A channel 32, a B channel 33, a C channel 34 and a D channel 35 which are sequentially arranged from the positive pole to the negative pole, and the D channel 35 of the previous electrodialysis unit is connected with the A channel 32 of the next electrodialysis unit between the two adjacent electrodialysis units. In the electrodialysis module, cation exchange membranes 36 are arranged between adjacent channels A32 and B33 and between adjacent channels C34 and D35, and anion exchange membranes 37 are arranged between adjacent channels D35 and A32 and between adjacent channels B33 and C34.
An inlet pipe I81 and an outlet pipe I82 are connected between the sodium sulfate liquid tank 1 and the channel A32, specifically, the sodium sulfate liquid tank 1 outputs sodium sulfate stock solution to each channel A32 through the inlet pipe I81, sodium ions in the sodium sulfate stock solution pass through the cation exchange membrane 36 and enter the channel B33 after entering the channel A32 under the action of an electric field, sulfate ions in the sodium sulfate stock solution pass through the anion exchange membrane 37 and enter the channel D35, and the sodium sulfate stock solution passing through the channel A32 flows back to the sodium sulfate liquid tank 1 through the outlet pipe I82.
An inlet pipe III 85 and an outlet pipe III 86 are connected between the ammonium bicarbonate liquid tank 2 and the C channel 34, specifically, the ammonium bicarbonate liquid tank 2 outputs ammonium bicarbonate stock solution to each C channel 34 through the inlet pipe III 85, ammonium ions in the ammonium bicarbonate stock solution pass through the cation exchange membrane 36 and enter the D channel 35 after entering the C channel 34 under the action of an electric field, bicarbonate ions in the ammonium bicarbonate stock solution pass through the anion exchange membrane 37 and enter the B channel 33, and the ammonium bicarbonate stock solution passing through the C channel 34 flows back to the ammonium bicarbonate liquid tank 2 through the outlet pipe III 86.
And a sodium bicarbonate solution tank 4 for accumulating the sodium bicarbonate solution and outputting the sodium bicarbonate solution.
A second inlet pipe 83 and a second outlet pipe 84 are connected between the sodium bicarbonate liquid tank 4 and the channel B33, specifically, a low-concentration sodium bicarbonate solution in the sodium bicarbonate liquid tank 4 is output to the channel B33 through the second inlet pipe 83, sodium carbonate formed by sodium ions and bicarbonate ions which pass through the cation exchange membrane 36 and the anion exchange membrane 37 and enter the channel B33 is taken away in the channel B33, and the sodium carbonate flows back into the sodium bicarbonate liquid tank 4 through the second outlet pipe 84.
And the sodium bicarbonate evaporation and crystallization unit 41 is used for evaporating and crystallizing a sodium bicarbonate solution with qualified concentration to obtain sodium bicarbonate crystals.
The sodium bicarbonate evaporative crystallization unit 41 is connected with the sodium bicarbonate liquid tank 4 through an overflow pipe 9, specifically, the concentration of the sodium bicarbonate solution gradually increases along with the circulation of the sodium bicarbonate solution in the B channel 33, and when the concentration of the sodium bicarbonate solution is higher than a preset overflow standard, the sodium bicarbonate solution in the sodium bicarbonate liquid tank 4 is output to the sodium bicarbonate evaporative crystallization unit 41 through the overflow pipe 9 to perform evaporative crystallization, so as to obtain sodium bicarbonate crystals. After this process, the concentration of the sodium bicarbonate solution will decrease.
And an ammonium sulfate solution tank 5 for accumulating the ammonium sulfate solution and outputting the ammonium sulfate solution.
Be connected with between ammonium sulfate liquid case 5 and the D passageway 35 and advance a tub four 87 and go out a tub four 88, specifically, low concentration ammonium sulfate solution in ammonium sulfate liquid case 5 exports to D passageway 35 through advancing tub four 87, takes away the ammonium sulfate that gets into the ammonium ion and the sulfate radical ion formation of D passageway 35 because of passing cation exchange membrane 36 and anion exchange membrane 37 in D passageway 35, flows back to in ammonium sulfate liquid case 5 through an exit pipe four 88.
And the ammonium sulfate evaporation crystallization unit 51 is used for evaporating and crystallizing an ammonium sulfate solution with qualified concentration to obtain ammonium sulfate crystals.
The ammonium sulfate liquid tank 5 is connected with the ammonium sulfate evaporative crystallization unit 51 through the overflow pipe 9, specifically, the concentration of the ammonium sulfate solution gradually increases along with the circulation of the ammonium sulfate solution in the B channel 33, and when the concentration of the ammonium sulfate solution is higher than a preset overflow standard, the ammonium sulfate solution in the ammonium sulfate liquid tank 5 is output to the ammonium sulfate evaporative crystallization unit 51 along the overflow pipe 9 to be evaporated and crystallized, so as to obtain ammonium sulfate crystals. After this process, the concentration of the ammonium sulfate solution will decrease.
In some embodiments, the first inlet pipe 81, the second inlet pipe 83, the third inlet pipe 85 and the fourth inlet pipe 87 are all provided with a circulating pump 89, and the circulating pumps 89 can help the circulating speed of various solutions in the whole device, so that the efficiency of the preparation process is improved.
The device for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate can also be used for preparing ammonium sulfate and sodium carbonate by using sodium sulfate and ammonium carbonate.
The above description of the present invention is intended to be illustrative. Various modifications, additions and substitutions for the specific embodiments described may be made by those skilled in the art without departing from the scope of the invention as defined in the accompanying claims.
Claims (9)
1. A method for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate is characterized by comprising the following steps:
s1, pretreating the sodium sulfate stock solution and the ammonium bicarbonate stock solution to enable the particle size of particles in the sodium sulfate stock solution and the ammonium bicarbonate stock solution to be less than 5 microns;
s2, arranging a plurality of groups of electrodialysis units which are sequentially connected in an electric field, wherein each electrodialysis unit is sequentially provided with an A channel, a B channel, a C channel and a D channel from one end of the positive pole of the electric field to one end of the negative pole of the electric field, the D channel of the previous electrodialysis unit is connected with the A channel of the next electrodialysis unit, cation exchange membranes are arranged between the adjacent A channels and the B channels and between the adjacent C channels and the D channels, and anion exchange membranes are arranged between the adjacent D channels and the A channels and between the adjacent B channels and the C channels;
s3, introducing a sodium sulfate stock solution into the channel A, introducing an ammonium bicarbonate stock solution into the channel C, wherein under the action of an electric field, sodium ions in the sodium sulfate stock solution in the channel A penetrate through a cation exchange membrane to enter the channel B, sulfate ions in the sodium sulfate stock solution in the channel A penetrate through an anion exchange membrane to enter the channel D, ammonium ions in the ammonium bicarbonate stock solution in the channel C penetrate through the cation exchange membrane to enter the channel D to form an ammonium sulfate solution with the sulfate ions, and bicarbonate ions in the ammonium bicarbonate stock solution in the channel C penetrate through the anion exchange membrane to enter the channel B to form a sodium bicarbonate solution with the sodium ions;
s4, leading the ammonium sulfate solution in the channel D out to an ammonium sulfate liquid tank, and when the concentration of the ammonium sulfate solution in the ammonium sulfate liquid tank reaches a preset overflow standard, overflowing to an evaporative crystallization unit to obtain ammonium sulfate crystals;
and (3) guiding the sodium bicarbonate solution in the channel B into a sodium bicarbonate solution tank, and overflowing to an evaporation crystallization unit to obtain sodium bicarbonate crystals after the concentration of the sodium bicarbonate solution in the sodium bicarbonate solution tank reaches a preset overflow standard.
2. The method for preparing ammonium sulfate and sodium bicarbonate from sodium sulfate and ammonium bicarbonate of claim 1, wherein the sodium sulfate stock solution and the ammonium bicarbonate stock solution are pretreated by a lift pump to remove impurities from the sodium sulfate stock solution and the ammonium bicarbonate stock solution respectively through a cartridge filter in S1.
3. The method for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate as claimed in claim 1, wherein the sodium sulfate stock solution led out from the passage A in S3 is led back to the sodium sulfate solution tank and then led out from the sodium sulfate solution tank to the passage A, and when the concentration of the sodium sulfate stock solution in the sodium sulfate solution tank is lower than a preset overflow standard, sodium sulfate concentration supplement is carried out;
and in the step S3, the ammonium bicarbonate stock solution led out from the channel C is led back to the ammonium bicarbonate liquid tank and then led out to the channel C by the ammonium bicarbonate liquid tank, and when the concentration of the ammonium bicarbonate stock solution in the ammonium bicarbonate liquid tank is lower than a preset overflow standard, ammonium bicarbonate concentration supplement is carried out.
4. The method for preparing ammonium sulfate and sodium bicarbonate from sodium sulfate and ammonium bicarbonate as claimed in claim 3, wherein the sodium sulfate concentration supplementing method comprises:
s311, arranging a sodium sulfate dissolving tank connected with a sodium sulfate liquid tank, and guiding sodium sulfate stock solution into the sodium sulfate dissolving tank from the sodium sulfate liquid tank after the concentration of the sodium sulfate stock solution in the sodium sulfate liquid tank is lower than a preset overflow standard;
s312, supplementing solid sodium sulfate into the sodium sulfate dissolving tank until the concentration of a sodium sulfate stock solution in the sodium sulfate dissolving tank reaches 10-20%;
s313, pretreating the sodium sulfate stock solution in the sodium sulfate dissolving pool and then returning the sodium sulfate stock solution to the sodium sulfate solution tank.
5. The method for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate according to claim 3, wherein the ammonium bicarbonate concentration supplementing method comprises the following steps:
s321, arranging an ammonium bicarbonate dissolving tank connected with an ammonium bicarbonate liquid tank, and leading the ammonium bicarbonate stock solution into the ammonium bicarbonate dissolving tank from the ammonium bicarbonate liquid tank after the concentration of the ammonium bicarbonate stock solution in the ammonium bicarbonate liquid tank is lower than a preset overflow standard;
s322, supplementing solid ammonium bicarbonate to the ammonium bicarbonate dissolving tank until the concentration of an ammonium bicarbonate stock solution in the ammonium bicarbonate dissolving tank reaches 10-20%;
s323, pretreating the ammonium bicarbonate stock solution in the ammonium bicarbonate dissolving tank and then returning the ammonium bicarbonate stock solution to the ammonium bicarbonate solution tank.
6. The method for preparing ammonium sulfate and sodium bicarbonate from sodium sulfate and ammonium bicarbonate as claimed in any one of claims 3-5, wherein the overflow standard in S3 is TDS range of 100000mg/L or less.
7. The method for preparing ammonium sulfate and sodium bicarbonate from sodium sulfate and ammonium bicarbonate of claim 1, wherein the overflow standard of the ammonium sulfate solution in S4 is TDS greater than or equal to 200000 mg/L;
the overflow standard of the sodium bicarbonate solution in S4 is TDS more than or equal to 200000 mg/L.
8. The utility model provides a device with ammonium sulfate and bicarbonate of sodium sulfate preparation ammonium sulfate and sodium bicarbonate which characterized in that: the device comprises a sodium sulfate dissolving tank, a sodium sulfate liquid tank, an ammonium bicarbonate dissolving tank, an ammonium bicarbonate liquid tank, an electrodialysis module, an ammonium sulfate liquid tank, a sodium bicarbonate liquid tank, an ammonium sulfate evaporative crystallization unit and a sodium bicarbonate evaporative crystallization unit, wherein the sodium sulfate liquid tank is connected with the sodium sulfate dissolving tank through an overflow pipe, the sodium sulfate dissolving tank is connected with a first security filter with a lifting pump, and the other end of the first security filter is connected with the sodium sulfate liquid tank; the ammonium bicarbonate liquid tank is connected with the ammonium bicarbonate dissolving tank through an overflow pipe, the ammonium bicarbonate dissolving tank is connected with a second security filter provided with a lifting pump, and the other end of the second security filter is connected with the ammonium bicarbonate liquid tank; the ammonium sulfate liquid tank is connected with the ammonium sulfate evaporative crystallization unit through an overflow pipe, and the sodium bicarbonate liquid tank is connected with the sodium bicarbonate evaporative crystallization unit through an overflow pipe;
the electrodialysis module comprises an electric field module provided with a positive electrode and a negative electrode and a plurality of connected electrodialysis units arranged in the electric field module and between the positive electrode and the negative electrode, each electrodialysis unit comprises an A channel, a B channel, a C channel and a D channel which are sequentially arranged from the positive electrode to the negative electrode, the D channel is connected with the A channel between every two adjacent electrodialysis units, cation exchange membranes are arranged between every two adjacent A channels and B channels and between every two adjacent C channels and D channels, and anion exchange membranes are arranged between every two adjacent D channels and A channels and between every two adjacent B channels and C channels;
an inlet pipe I and an outlet pipe I are connected between the sodium sulfate liquid tank and the channel A, an inlet pipe II and an outlet pipe II are connected between the sodium bicarbonate liquid tank and the channel B, an inlet pipe III and an outlet pipe III are connected between the ammonium bicarbonate liquid tank and the channel C, and an inlet pipe IV and an outlet pipe IV are connected between the ammonium sulfate liquid tank and the channel D.
9. The apparatus for preparing ammonium sulfate and sodium bicarbonate from sodium sulfate and ammonium bicarbonate as claimed in claim 8, wherein: and circulating pumps are arranged on the inlet pipe I, the inlet pipe II, the inlet pipe III and the inlet pipe IV.
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| US4592817A (en) * | 1984-12-03 | 1986-06-03 | Allied Corporation | Electrodialytic water splitting process for gaseous products |
| CN1089235A (en) * | 1993-12-29 | 1994-07-13 | 张祥林 | The method of the single-phase decomposition system sodium bicarbonate of sodium sulfate and bicarbonate of ammonia |
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| CN110917882B (en) * | 2019-11-04 | 2020-11-17 | 杭州匠容道环境科技有限公司 | Four-channel electrodialysis device for extracting lithium from salt lake and method for extracting lithium from salt lake |
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