CN111039305B - Method for preparing sodium bicarbonate and ammonium sulfate by sodium sulfate in short process - Google Patents
Method for preparing sodium bicarbonate and ammonium sulfate by sodium sulfate in short process Download PDFInfo
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- CN111039305B CN111039305B CN201811458108.XA CN201811458108A CN111039305B CN 111039305 B CN111039305 B CN 111039305B CN 201811458108 A CN201811458108 A CN 201811458108A CN 111039305 B CN111039305 B CN 111039305B
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
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Abstract
The invention provides a method for preparing sodium bicarbonate and ammonium sulfate by sodium sulfate in a short process, which takes sodium sulfate as a raw material to perform double decomposition reaction with ammonium bicarbonate, and prepares the sodium bicarbonate and the ammonium sulfate by phase region reinforcement; the method has simple flow and low cost, the utilization rate of the sodium sulfate is more than 85 percent, the purity of the sodium bicarbonate is more than 90 percent, and the purity of the ammonium sulfate product meets the requirement of GB 535-1995.
Description
Technical Field
The invention belongs to the field of alkali preparation and secondary resource recovery, and particularly relates to a method for preparing sodium bicarbonate and ammonium sulfate by using sodium sulfate as a raw material in a short process.
Background
Sodium sulfate, called anhydrous sodium sulphate, contains crystal water which is mirabilite, is an industrial byproduct with huge storage quantity and is mainly generated in the processes of flue gas desulfurization, wastewater treatment and the like. However, the product has small market demand, no very effective resource utilization way exists, and most of the products are mainly stockpiled; and sodium sulfate is easy to dissolve in water, and sodium sulfate produced by some enterprises contains a large amount of heavy metals such as vanadium, chromium, zinc and the like, so that the stockpiling is easy to cause environmental problems. With the increasingly strict environmental protection requirements of the state on the chemical industry, an effective sodium sulfate resource utilization technology is urgently needed, and a great deal of research is carried out in China and abroad.
CN105000579A, CN105712382A disclose a precipitation method, in which sodium bicarbonate is prepared by double decomposition reaction of ammonium bicarbonate and sodium sulfate, and then lime is added into the mother solution of sodium bicarbonate to recover ammonia therein, but the recovery rate of ammonia in the process is only about 50%, which results in resource waste and increases the operation cost, and the production amount of calcium sulfate is large, the value is low, the quality is poor, the sale is difficult, and secondary pollution is easily caused.
CN103754898A discloses a method for preparing sodium chloride by using sodium sulfate and calcium chloride and producing sodium carbonate by combining a combined soda production method, wherein sodium sulfate and calcium chloride are used as raw materials, a sodium chloride solution and calcium sulfate solids are obtained through double decomposition reaction, and then the sodium carbonate is produced by the combined soda production method.
CN101544385A discloses a method for preparing sodium carbonate and calcium sulfate by using sodium sulfate as a raw material and organic amine as an auxiliary material, wherein the method refers to the process route of the former Soviet Union, and the sodium conversion rate can reach more than 90%; but the organic amine has high boiling point, large viscosity and high energy consumption for evaporation and recovery; the organic amine in the sodium bicarbonate and the calcium sulfate has more entrainment, difficult recovery, more loss and high production cost.
CN104355326A, CN102198953A, CN202016881U disclose a method for preparing sodium bicarbonate and ammonium sulfate by a double decomposition method, wherein sodium sulfate and ammonium bicarbonate are used as raw materials, sodium bicarbonate is obtained by double decomposition reaction, separated mother liquor is deaminated at high temperature and evaporated and concentrated at 130 ℃ to obtain sodium sulfate crystals, the separated mother liquor is cooled and crystallized to obtain double salts of sodium sulfate and ammonium sulfate, and the mother liquor is evaporated and crystallized to obtain an ammonium sulfate product. The method has the advantages of complex flow, high energy consumption through multiple working procedures of high temperature, cooling and the like, low utilization rate of sodium ions and sulfate radicals, large evaporation depth, large material circulation amount and high production cost, and does not have an industrial precedent at present.
CN87104642A, CN1046142A, US5830442, CN1761617A disclose a process, in which sodium bicarbonate mother liquor is deeply cooled to obtain sodium sulfate crystals, so that the ratio of ammonium sulfate to sodium sulfate in the mother liquor is close to 2:1, and ammonium sulfate is obtained by evaporation crystallization. The method requires a low cooling temperature, the optimal cooling temperature is-5 ℃ to-2 ℃, the energy consumption is high, the overall yield is low, the utilization rate of sulfate radicals is only about 25%, the material circulation amount is large, the production and operation cost is high, and no industrialization precedent exists so far.
Therefore, how to provide a method for preparing sodium bicarbonate and ammonium sulfate from sodium sulfate, which has the advantages of simple flow, low cost, high utilization rate of sodium sulfate and high purity of sodium bicarbonate, has become a problem to be solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a technical route which is short in flow, high in sodium sulfate conversion rate and low in cost. The invention realizes higher utilization rate of sodium sulfate, and the purity of the obtained sodium bicarbonate product is more than 90 percent; the phase region strengthening effect of the accelerator is utilized to enlarge the crystallization region of the ammonium sulfate, the generation of double salt or mixed salt is effectively avoided, and the purity of the obtained ammonium sulfate product meets the requirement of GB 535-1995.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing sodium bicarbonate and ammonium sulfate by sodium sulfate in a short process.
The method adopts sodium sulfate and ammonium bicarbonate as raw materials, sodium bicarbonate and ammonium sulfate can be obtained through one-step double decomposition reaction, then the utilization rate of the sodium sulfate and the purity of the ammonium sulfate are further improved through a phase region strengthening method, the product purity of the ammonium sulfate prepared by the method meets GB535-1995, and the utilization rate of the sodium sulfate is more than 85%.
The phase region strengthening in the invention is realized by using the accelerator, the phase region strengthening effect of the accelerator expands the crystallization region of the ammonium sulfate, thereby effectively avoiding the generation of double salt or mixed salt, and the purity of the obtained ammonium sulfate product meets the requirement of GB 535-1995.
Preferably, the phase zone strengthening method comprises adding a promoter to the sodium bicarbonate mother liquor obtained by the liquid-solid separation of the products of the metathesis reaction.
The promoter provided by the invention has the effect of increasing the crystallization area of ammonium sulfate in the evaporation crystallization process of flash evaporation mother liquor, so that the precipitation rate of the ammonium sulfate is increased by 20-30% (including 20%, 23%, 25%, 27% or 30% for example), and the generation of double salt and mixed salt of sodium sulfate and ammonium sulfate is inhibited, thereby achieving the purpose of increasing the purity of the ammonium sulfate.
Preferably, the accelerator comprises any one of, or a mixture of at least two of, diammonium phosphate, disodium phosphate, ammonium nitrate, sodium nitrate, ammonium formate, or sodium formate, and the mixture illustratively comprises a mixture of diammonium phosphate and disodium phosphate, a mixture of ammonium nitrate and sodium nitrate, a mixture of ammonium formate and sodium formate, a mixture of disodium phosphate and ammonium nitrate, or a mixture of sodium nitrate and ammonium formate, and the like.
The accelerator provided by the invention adopts any one or a mixture of at least two of diammonium hydrogen phosphate, disodium hydrogen phosphate, ammonium nitrate, sodium nitrate, ammonium formate or sodium formate, the flash evaporation mother liquor contains ammonium sulfate generated by double decomposition reaction, a crystallization area of the ammonium sulfate in the evaporation crystallization process is enlarged under the condition that the accelerator added before flash evaporation coexists with the ammonium sulfate, and the generation of double salt and mixed salt is inhibited by the existence of the accelerator, so that the purity of the ammonium sulfate product is improved.
Preferably, the promoter is recycled in the manufacturing process.
The components of the ammonium sulfate mother liquor obtained by evaporating and crystallizing the flash evaporation mother liquor comprise unseparated sulfate and an accelerant, and in the subsequent cooling process, the sulfate is separated out from the ammonium sulfate mother liquor and returns to the double decomposition reaction, so that the utilization rate of sodium sulfate is improved; meanwhile, the cooling mother liquor formed in the cooling process is rich in the accelerant, and the cooling mother liquor and the sodium bicarbonate mother liquor are mixed for flash evaporation, so that the recycling of the accelerant is realized, and the production cost is saved.
Preferably, the sodium sulfate short-process preparation method of sodium bicarbonate and ammonium sulfate comprises the following steps:
(1) carrying out double decomposition reaction on sodium sulfate and ammonium bicarbonate, and carrying out solid-liquid separation and washing on reaction slurry to obtain a sodium bicarbonate product and a sodium bicarbonate crude product washing solution;
(2) mixing and flashing mother solution of sodium bicarbonate obtained by solid-liquid separation after the double decomposition reaction with a crude washing solution of sodium bicarbonate and an accelerator to obtain ammonium bicarbonate, and returning the ammonium bicarbonate to the double decomposition reaction in the step (1);
(3) evaporating and crystallizing the flash evaporation mother liquor obtained by flash evaporation in the step (2) to obtain ammonium sulfate;
(4) and (3) cooling the ammonium sulfate mother liquor obtained by evaporation and crystallization in the step (3), cooling the crystals, returning the cooled crystals to the double decomposition reaction in the step (1), and returning the cooled mother liquor to the step (2) to be mixed with the liquid which is not flashed.
The method adopts sodium sulfate and ammonium bicarbonate (or carbon dioxide and ammonia gas) to react to generate sodium bicarbonate and ammonium sulfate, the solubility of the sodium bicarbonate is low, after the sodium bicarbonate is separated from liquid and solid, the sodium bicarbonate mother liquor is added with an accelerant to carry out flash evaporation to obtain the ammonium bicarbonate and flash evaporation mother liquor, the flash evaporation mother liquor contains the ammonium sulfate generated by double decomposition reaction, the crystallization interval of the ammonium sulfate is expanded under the action of the accelerant, 80 percent of the ammonium sulfate in the solution can be separated out after further evaporation and crystallization, the obtained ammonium sulfate mother liquor contains sulfate and the accelerant, the cooling mother liquor is cooled to 15-30 ℃ to obtain cooling crystal and cooling mother liquor, the cooling crystal is rich in sulfate and returns to the double decomposition reaction, thereby the utilization rate of the sodium sulfate is increased, the obtained cooling mother liquor is rich in the accelerant and returns to the step (2) to be mixed with the sodium bicarbonate mother liquor which is not flashed to carry out flash evaporation, thereby realizing the recycling of the accelerant.
Preferably, the solid-liquid separation method of step (1) comprises filtration.
Preferably, the temperature of the double decomposition reaction is 15 to 45 ℃, for example, 15 ℃, 17 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ or 45 ℃, preferably 20 to 40 ℃, and more preferably 30 to 35 ℃.
Preferably, the pH of the metathesis reaction is 7.0 to 9.0, for example, 7.0, 7.2, 7.5, 7.7, 8.0, 8.2, 8.5, or 9.0, etc., preferably 7.5 to 8.5, and more preferably 8.0 to 8.5.
Preferably, the liquid-solid volume mass ratio of the crude sodium bicarbonate obtained by solid-liquid separation to be washed is 0.3-0.5L/kg, such as 0.3L/kg, 0.35L/kg, 0.4L/kg, 0.45L/kg or 0.5L/kg.
Preferably, the ammonium bicarbonate in the metathesis reaction is added in an amount such that the molar ratio of ammonium ions to sodium ions in the solution is greater than or equal to 1, e.g., 1, 2, 2.5, 3.5, or 4.
Preferably, the molar weight ratio of the promoter to the sulfate ions in the mixed solution before the flash evaporation in the step (2) is (0.7-2): 1, e.g. 0.7: 1. 0.9: 1. 1: 1. 1.3: 1. 1.5: 1 or 2:1, etc.
Preferably, the temperature of the flash evaporation is 60 to 100 ℃, for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, preferably 70 to 90 ℃, and more preferably 80 to 85 ℃.
Preferably, the temperature of the evaporative crystallization in step (3) is 50 to 90 ℃, such as 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, preferably 60 to 80 ℃.
Preferably, the condensed water of the evaporative crystallization is returned to step (1) for dissolving sodium sulfate.
The method of the invention uses the condensed water obtained by evaporation and crystallization to dissolve the sodium sulfate, thus realizing the recycling of water.
Preferably, the ammonium sulfate mother liquor in the step (4) is cooled to 15-30 ℃, such as 15 ℃, 17 ℃, 20 ℃, 22 ℃, 25 ℃, 28 ℃ or 30 ℃.
As a preferred technical scheme of the invention, the method for preparing the sodium bicarbonate and the ammonium sulfate by the sodium sulfate short-flow process comprises the following steps:
(1) mixing sodium sulfate and condensed water to prepare a mixed solution, slowly adding ammonium bicarbonate or a mixture of carbon dioxide and ammonia gas into the mixed solution to perform double decomposition reaction at the temperature of 15-45 ℃ and the pH of 7.0-9.0, filtering and washing reaction slurry to obtain a sodium bicarbonate product and a sodium bicarbonate crude product washing solution, wherein the liquid-solid volume mass ratio of washing is 0.3-0.5L/kg;
(2) mixing the sodium bicarbonate mother liquor obtained by filtering in the step (1), sodium bicarbonate crude product washing liquid and an accelerator, flashing and recovering ammonium bicarbonate at the temperature of 60-100 ℃, returning the obtained ammonium bicarbonate to the double decomposition reaction in the step (1), wherein the molar weight ratio of the accelerator to sulfate ions in the mixed solution before flashing is (0.7-2): 1;
(3) evaporating and crystallizing the flash evaporation mother liquor obtained in the step (2) at 50-90 ℃ to obtain ammonium sulfate and ammonium sulfate mother liquor;
(4) and (3) cooling the ammonium sulfate mother liquor in the step (3) to 15-30 ℃, cooling the crystal, returning to the double decomposition reaction in the step (1), returning the cooled mother liquor to the step (2), and mixing with the sodium bicarbonate mother liquor.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the method adopts sodium sulfate and ammonium bicarbonate as raw materials, sodium bicarbonate and ammonium sulfate can be obtained through one-step double decomposition reaction, and then the utilization rate of the sodium sulfate and the purity of the ammonium sulfate are further improved through a phase region strengthening method, wherein the product purity of the ammonium sulfate prepared by the method meets GB535-1995, and the utilization rate of the sodium sulfate is more than 85%;
(2) the method for strengthening the phase zone adopted by the method comprises the steps of adding an accelerant into the sodium bicarbonate mother liquor obtained by the liquid-solid separation of the product of the double decomposition reaction, wherein the accelerant can be recycled in a reaction system, so that the production cost is reduced;
(3) the method of the invention has simple operation process and low cost.
Drawings
FIG. 1 is a process flow diagram of a short-flow sodium sulfate process for preparing sodium bicarbonate and ammonium sulfate according to the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
The invention provides a method for preparing sodium bicarbonate and ammonium sulfate by sodium sulfate in a short process, which has a process flow as shown in figure 1, and comprises the following steps:
(1) mixing sodium sulfate, optional cooled crystals and condensed water in the step (4) to prepare a mixed solution, slowly adding ammonium bicarbonate (or carbon dioxide and ammonia gas) into the mixed solution to perform double decomposition reaction, and filtering and washing reaction slurry to obtain a sodium bicarbonate product and a sodium bicarbonate crude product washing solution;
(2) mixing the sodium bicarbonate mother liquor obtained by filtering in the step (1) and a sodium bicarbonate crude product washing solution, the cooling mother liquor obtained in the step (4) and an accelerator, flashing and recovering ammonium bicarbonate, and returning the obtained ammonium bicarbonate to the step (1);
(3) evaporating and crystallizing the flash evaporation mother liquor obtained by flash evaporation in the step (2) to obtain ammonium sulfate and ammonium sulfate mother liquor, and condensing the evaporated and crystallized water vapor and returning the condensed water vapor to the step (1);
(4) and (3) cooling the ammonium sulfate mother liquor in the step (3), cooling crystals, returning to the step (1), and returning the cooled mother liquor to the step (2) to be mixed with the sodium bicarbonate mother liquor which is not flashed.
Detailed description of the inventionwhat is meant by "optional" in the description of the embodiments is that the cooling crystals, condensed water, and cooling mother liquor are not produced at the beginning of the production, and therefore the above-mentioned substances are not added at the beginning of the production, and after the cooling crystals are produced, the main component of the cooling crystals is sulfate, which can replace part of the sodium sulfate, and before the condensed water is produced, the dissolution of the sodium sulfate requires the addition of water, and after the condensed water is produced, which can replace part of the addition of water; the cooled mother liquor is rich in the accelerant and can replace part of the accelerant after the cooled mother liquor is generated.
Example 1
A method for preparing sodium bicarbonate and ammonium sulfate by sodium sulfate in a short process comprises the following steps:
(1) mixing sodium sulfate, optional cooled crystals in the step (4) and condensate water to prepare a mixed solution, and slowly adding ammonium bicarbonate at 35 ℃ while ensuring that the molar weight of ammonium ions and the molar weight of sodium ions in the solution are not less than 1; after the double decomposition reaction is finished, carrying out liquid-solid separation to obtain a sodium bicarbonate crude product, and washing to obtain a sodium bicarbonate product;
(2) mixing the sodium bicarbonate mother liquor obtained by liquid-solid separation in the step (1), a sodium bicarbonate crude washing liquid and ammonium nitrate with optional cooling mother liquor obtained in the step (4), flashing at 80 ℃ to recover ammonium bicarbonate, and returning the ammonium bicarbonate to the step (1), wherein the adding amount of the ammonium nitrate is such that the molar weight ratio of the ammonium nitrate to sulfate ions in the mixed solution is 1.5: 1;
(3) evaporating and crystallizing the flash evaporation mother liquor in the step (2) at 80 ℃ to obtain an ammonium sulfate product, and condensing the water vapor and returning to the step (1) for dissolving sodium sulfate;
(4) and (3) cooling the amine sulfate mother liquor obtained by evaporation and crystallization in the step (3) to 25 ℃, returning the cooled crystals to the step (1), returning the cooled mother liquor to the step (2), and mixing with the sodium bicarbonate mother liquor which is not flashed.
In the product prepared by the embodiment, the ammonia nitrogen content of the ammonium sulfate is 20.8%, the free acid content is less than 0.1%, the requirement of GB535-1995 is met, the purity of the sodium bicarbonate is 93%, and the utilization rate of the sodium sulfate is 92%.
Example 2
A method for preparing sodium bicarbonate and ammonium sulfate by sodium sulfate in a short process comprises the following steps:
(1) mixing sodium sulfate, optional cooled crystals in the step (4) and condensed water to prepare a mixed solution, and further slowly adding ammonium bicarbonate at 35 ℃ while ensuring that the ratio of the molar weight of ammonium ions to the molar weight of sodium ions in the solution is not less than 1; after the double decomposition reaction is finished, carrying out liquid-solid separation to obtain a sodium bicarbonate crude product, and washing to obtain a sodium bicarbonate product and a sodium bicarbonate mother liquor;
(2) mixing the sodium bicarbonate mother liquor obtained by the liquid-solid separation in the step (1) with a sodium bicarbonate crude washing solution, ammonium formate and an optional cooling crystallization mother liquor in the step (4), flashing at 80 ℃ to recover ammonium bicarbonate, and returning the obtained ammonium bicarbonate to the step (1) at the point that the addition amount of the ammonium formate meets the condition that the molar weight ratio of the ammonium formate to sulfate ions in the mixed solution is 0.7: 1;
(3) evaporating and crystallizing the flash mother liquor obtained by flash evaporation in the step (2) at 80 ℃ to obtain an ammonium sulfate product, and condensing the water vapor and returning to the step (1) for dissolving sodium sulfate;
(4) cooling the ammonium sulfate mother liquor obtained by evaporation and crystallization in the step (3) to 15 ℃, returning the cooled crystals to the step (1), returning the cooled mother liquor to the step (2), and mixing the cooled mother liquor with the sodium bicarbonate mother liquor which is not flashed.
In the product prepared by the embodiment, the ammonia nitrogen content in the ammonium sulfate is 21.01 percent, and the free acid content is less than 0.1 percent, so that the requirement of GB535-1995 is met; the purity of sodium bicarbonate is 92.5%, and the utilization rate of sodium sulfate is 91%.
Example 3
A method for preparing sodium bicarbonate and ammonium sulfate by sodium sulfate in a short process comprises the following steps:
(1) mixing sodium sulfate, optional cooled crystals in the step (4) and condensed water to prepare a mixed solution, and further slowly adding ammonium bicarbonate at 35 ℃ while ensuring that the ratio of the molar weight of ammonium ions to the molar weight of sodium ions in the solution is not less than 1; after the double decomposition reaction is finished, carrying out liquid-solid separation to obtain a sodium bicarbonate crude product, and washing to obtain a sodium bicarbonate product and a sodium bicarbonate mother liquor;
(2) mixing the sodium bicarbonate mother liquor obtained by the liquid-solid separation in the step (1) with a sodium bicarbonate crude washing solution, ammonium formate and an optional cooling crystallization mother liquor in the step (4), recovering ammonium bicarbonate by flash evaporation at 100 ℃, and returning the obtained ammonium bicarbonate to the step (1), wherein the ammonium formate is added in an amount which satisfies a molar ratio of ammonium formate to sulfate ion in the mixed solution of 2: 1;
(3) evaporating and crystallizing the flash mother liquor obtained by flash evaporation in the step (2) at 60 ℃ to obtain an ammonium sulfate product, and condensing the water vapor and returning the condensed water vapor to the step (1) for solution of sodium sulfate;
(4) cooling the ammonium sulfate mother liquor obtained by evaporation and crystallization in the step (3) to 30 ℃, returning the cooled crystals to the step (1), returning the cooled mother liquor to the step (2), and mixing with the sodium bicarbonate mother liquor which is not flashed.
In the product prepared by the embodiment, the ammonia nitrogen content of the ammonium sulfate is 20.89%, and the free acid content is less than 0.2%, so that the requirement of GB535-1995 is met; the purity of sodium bicarbonate is 94%, and the utilization rate of sodium sulfate is 93.5%.
Example 4
This example differs from example 1 in that ammonium nitrate was replaced with sodium nitrate equimolar to the other conditions being exactly the same as in example 1.
In the product prepared by the embodiment, the ammonia nitrogen content of the ammonium sulfate is 20.71%, and the free acid content is less than 0.1%, so that the requirement of GB535-1995 is met; the purity of sodium bicarbonate is 90.7%, and the utilization rate of sodium sulfate is 88.2%.
Example 5
This example differs from example 1 in that ammonium nitrate was replaced with sodium formate equimolar and the other conditions were exactly the same as in example 1.
In the product prepared by the embodiment, the ammonia nitrogen content of the ammonium sulfate is 20.51 percent, and the free acid content is less than 0.1 percent, so that the requirement of GB535-1995 is met; the purity of sodium bicarbonate was 91%, and the utilization rate of sodium sulfate was 87%.
Example 6
This example differs from example 1 in that ammonium nitrate was replaced with ammonium phosphate dibasic containing ammonium ions in equimolar amounts, and the other conditions were exactly the same as in example 1.
In the product prepared by the embodiment, the ammonia nitrogen content of the ammonium sulfate is 20.47%, and the free acid content is less than 0.1%, so that the requirement of GB535-1995 is met; the purity of sodium bicarbonate is 90.4%, and the utilization rate of sodium sulfate is 88%.
Example 7
This example differs from example 6 in that the equimolar amount of diammonium phosphate was replaced with disodium phosphate, and the other conditions were exactly the same as in example 6.
In the product prepared by the embodiment, the ammonia nitrogen content of the ammonium sulfate is 20.57%, and the free acid content is less than 0.1%, so that the requirement of GB535-1995 is met; the purity of sodium bicarbonate was 91.7%, and the utilization rate of sodium sulfate was 86%.
Example 8
This example differs from example 1 in that ammonium nitrate was replaced equimolar with a mixture of ammonium nitrate and sodium formate in a molar ratio of 1:1, the other conditions being exactly the same as in example 1.
In the product prepared by the embodiment, the ammonia nitrogen content of the ammonium sulfate is 20.2%, and the free acid content is less than 0.1%, so that the requirement of GB535-1995 is met; the purity of sodium bicarbonate was 91.5%, and the utilization rate of sodium sulfate was 87.5%.
Example 9
This example differs from example 1 in that the equimolar substitution of ammonium nitrate with a molar ratio of 1: 2 diammonium phosphate and sodium formate, otherwise identical to example 1.
In the product prepared by the embodiment, the ammonia nitrogen content of the ammonium sulfate is 20.4%, and the free acid content is less than 0.1%, so that the requirement of GB535-1995 is met; the purity of sodium bicarbonate is 92.4%, and the utilization rate of sodium sulfate is 89.6%.
Comparative example 1
This comparative example differs from example 1 in that no ammonium nitrate was added and the other conditions were exactly the same as in example 1.
In the product prepared by the comparative example, the ammonia nitrogen content in the ammonium sulfate is 11 percent, and the requirement of GB535-1995 cannot be met; the purity of sodium bicarbonate was 91%, and the utilization rate of sodium sulfate was 60%.
Comparing examples 1-9 with comparative example 1, it can be seen that the method of the present invention makes the ammonia nitrogen content of the ammonium sulfate prepared by the method of the present invention 20.2-21.01% and the free acid content < 0.1% by phase region strengthening method, which meets the requirement of GB535-1995, and the purity of the obtained sodium bicarbonate > 90%, whereas in comparative example 1, the ammonia nitrogen content of the ammonium sulfate is 11% without adding promoter, which does not meet the requirement of GB535-1995, the purity of the obtained sodium bicarbonate is 91%, and the utilization rate of sodium sulfate is only 60%, so the method of the present invention is feasible to perform phase region strengthening on the product of double decomposition reaction of sodium sulfate and ammonium bicarbonate to improve the product purity and the utilization rate of raw materials.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (14)
1. The method for preparing the sodium bicarbonate and the ammonium sulfate through the sodium sulfate short flow is characterized in that the sodium sulfate is used as a raw material and is subjected to double decomposition reaction with the ammonium bicarbonate, and the sodium bicarbonate and the ammonium sulfate are prepared through phase region strengthening;
the method for strengthening the phase zone comprises the steps of adding a promoter into sodium bicarbonate mother liquor obtained by liquid-solid separation of products of the double decomposition reaction;
the accelerant comprises any one or a mixture of at least two of ammonium nitrate, sodium nitrate, ammonium formate or sodium formate;
the method for preparing sodium bicarbonate and ammonium sulfate by using sodium sulfate in a short flow comprises the following steps:
(1) carrying out double decomposition reaction on sodium sulfate and ammonium bicarbonate, and carrying out solid-liquid separation and washing on reaction slurry to obtain a sodium bicarbonate product and a sodium bicarbonate crude product washing solution;
(2) mixing and flashing mother solution of sodium bicarbonate obtained by solid-liquid separation after the double decomposition reaction with a crude washing solution of sodium bicarbonate and an accelerator to obtain ammonium bicarbonate, and returning the ammonium bicarbonate to the double decomposition reaction in the step (1);
(3) evaporating and crystallizing the flash evaporation mother liquor obtained by flash evaporation in the step (2) to obtain ammonium sulfate;
(4) cooling ammonium sulfate mother liquor obtained by evaporation crystallization in the step (3), cooling crystals, returning to the double decomposition reaction in the step (1), and returning the cooled mother liquor to the step (2) to be mixed with liquid which is not flashed;
the solid-liquid separation method in the step (1) comprises filtration;
the temperature of the double decomposition reaction is 15-45 ℃;
the pH value of the double decomposition reaction is 7.0-9.0;
the adding amount of ammonium bicarbonate in the double decomposition reaction ensures that the molar ratio of ammonium ions to sodium ions in the solution is more than or equal to 1;
the molar weight ratio of the accelerator to sulfate ions in the mixed solution before flash evaporation in the step (2) is (0.7-2): 1;
the temperature of the flash evaporation in the step (2) is 60-100 ℃.
2. The short run sodium bicarbonate and ammonium sulfate process of claim 1 wherein the promoter is recycled during the process.
3. The method for preparing sodium bicarbonate and ammonium sulfate by using sodium sulfate in a short process according to claim 1, wherein the temperature of the double decomposition reaction is 20-40 ℃.
4. The method for preparing sodium bicarbonate and ammonium sulfate by using sodium sulfate in a short process according to claim 3, wherein the temperature of the double decomposition reaction is 30-35 ℃.
5. The method for preparing sodium bicarbonate and ammonium sulfate by sodium sulfate in a short flow according to claim 1, wherein the pH value of the double decomposition reaction is 7.5-8.5.
6. The method for preparing sodium bicarbonate and ammonium sulfate with the sodium sulfate in a short flow according to claim 5, wherein the pH value of the double decomposition reaction is 8.0-8.5.
7. The method for preparing sodium bicarbonate and ammonium sulfate by using sodium sulfate in a short process as claimed in claim 1, wherein the liquid-solid volume mass ratio of the crude sodium bicarbonate obtained by solid-liquid separation to be washed is 0.3-0.5L/kg.
8. The short-run preparation method of sodium bicarbonate and ammonium sulfate by sodium sulfate according to claim 1, wherein the flash evaporation temperature in the step (2) is 70-90 ℃.
9. The short-run preparation method of sodium bicarbonate and ammonium sulfate with sodium sulfate according to claim 8, wherein the flash evaporation temperature in the step (2) is 80-85 ℃.
10. The short-run preparation method of sodium bicarbonate and ammonium sulfate with sodium sulfate according to claim 1, wherein the temperature of evaporative crystallization in the step (3) is 50-90 ℃.
11. The short-run preparation method of sodium bicarbonate and ammonium sulfate with sodium sulfate according to claim 10, wherein the temperature of evaporative crystallization in the step (3) is 60-80 ℃.
12. The short-run sodium sulfate process for the preparation of sodium bicarbonate and ammonium sulfate as claimed in claim 1, wherein the condensed water of the evaporative crystallization in step (3) is returned to step (1) for the dissolution of sodium sulfate.
13. The method for preparing sodium bicarbonate and ammonium sulfate by using sodium sulfate in a short flow as claimed in claim 1, wherein the ammonium sulfate mother liquor in the step (4) is cooled to 15-30 ℃.
14. The sodium sulfate short run method for preparing sodium bicarbonate and ammonium sulfate of claim 1, wherein the sodium sulfate short run method for preparing sodium bicarbonate and ammonium sulfate comprises the following steps:
(1) mixing sodium sulfate and condensed water to prepare a mixed solution, slowly adding ammonium bicarbonate or a mixture of carbon dioxide and ammonia gas into the mixed solution to perform a double decomposition reaction under the conditions that the temperature is 15-45 ℃ and the pH is 7.0-9.0, filtering and washing reaction slurry to obtain a sodium bicarbonate product and a sodium bicarbonate crude product washing solution, wherein the liquid-solid volume mass ratio of washing is 0.3-0.5L/kg, and the adding amount of ammonium bicarbonate in the double decomposition reaction ensures that the molar ratio of ammonium ions to sodium ions in the solution is more than or equal to 1;
(2) mixing the sodium bicarbonate mother liquor obtained by filtering in the step (1), sodium bicarbonate crude product washing liquid and an accelerator, flashing and recovering ammonium bicarbonate at the temperature of 60-100 ℃, returning the obtained ammonium bicarbonate to the double decomposition reaction in the step (1), wherein the molar weight ratio of the accelerator to sulfate ions in the mixed solution before flashing is (0.7-2): 1;
(3) evaporating and crystallizing the flash evaporation mother liquor obtained in the step (2) at 50-90 ℃ to obtain ammonium sulfate and ammonium sulfate mother liquor;
(4) and (3) cooling the ammonium sulfate mother liquor in the step (3) to 15-30 ℃, cooling the crystal, returning to the double decomposition reaction in the step (1), returning the cooled mother liquor to the step (2), and mixing with the sodium bicarbonate mother liquor.
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| CN115159760A (en) * | 2022-08-02 | 2022-10-11 | 攀钢集团钒钛资源股份有限公司 | Method for precipitating deamination nitrogen and byproducts of sodium sulfate and ammonium sulfate in vanadium precipitation wastewater |
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