CN114715921B - High-value conversion method for mixed sodium salt - Google Patents
High-value conversion method for mixed sodium salt Download PDFInfo
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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
- C01D7/12—Preparation of carbonates from bicarbonates or bicarbonate-containing product
- C01D7/123—Preparation of carbonates from bicarbonates or bicarbonate-containing product by thermal decomposition of solids in the absence of a liquid medium
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- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
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- C01C1/24—Sulfates of ammonium
- C01C1/244—Preparation by double decomposition of ammonium salts with sulfates
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- C01D7/02—Preparation by double decomposition
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Abstract
The invention provides a high-value conversion method of mixed sodium salt, which comprises the following steps: (1) mixing the mixed sodium salt with the second mother liquor, and performing primary sodium dissolution to obtain dechlorinated solid and primary sodium dissolution liquid; (2) mixing ammonium bicarbonate solid or mixed gas with sodium primary solution, and performing a first double decomposition reaction to obtain first sodium bicarbonate and first mother liquor; (3) cooling and crystallizing the first mother liquor to obtain ammonium chloride and cooled mother liquor; (4) mixing the deammoniated solid, the dechlorinated solid and the cooled mother liquor, and performing secondary sodium dissolution to obtain ammonium-sodium composite salt and secondary sodium dissolution liquid; (5) mixing the ammonium bicarbonate solid or the mixed gas with a sodium secondary dissolved solution, and performing a second double decomposition reaction to obtain second sodium bicarbonate and a second mother solution; (6) mixing the evaporation mother liquor and ammonium-sodium composite salt, and enriching by ammonium sulfate to obtain a rich ammonium sulfate solution and a deammoniated solid; (7) and evaporating and crystallizing the rich ammonium sulfate solution to obtain ammonium sulfate and an evaporated mother liquor. The method converts the mixed sodium salt into a product with high added value, and does not generate three wastes.
Description
Technical Field
The invention belongs to the technical field of solid waste treatment, relates to a high-value conversion method of industrial waste salt, and particularly relates to a high-value conversion method of mixed sodium salt.
Background
The industrial waste salt is mainly generated in the high-salinity wastewater treatment process in the chemical industry, such as the industries of pesticide, medicine, fine chemical industry, printing and dyeing, coal chemical industry, wet metallurgy and the like. About 2000 million tons of industrial waste salt is generated in China every year, and the main components of the industrial waste salt are sodium sulfate and sodium chloride, and in addition, the industrial waste salt also contains potassium, magnesium, calcium, heavy metal ions and organic matters. At present, the treatment technology of domestic industrial waste salt mainly comprises methods such as landfill, high-temperature oxidation, salt washing and the like, and large-scale popularization and application cannot be realized due to the treatment cost, environmental pollution and the like. In recent years, industrial salt separation technology is mature, sodium sulfate and sodium chloride in waste salt can be separated, but sodium sulfate and sodium chloride have low additional value and low price and are difficult to digest by the market.
CN102320625A discloses a method for treating sodium chloride solution containing sodium sulfate, which comprises concentrating the solution containing sodium sulfate and sodium chloride mixed salt through nanofiltration membrane, adding soft water into the concentrated salt solution, performing constant dissolution desalination with nanofiltration membrane, directly discharging the obtained concentrated solution, and desalting the dilute solution. However, this method cannot completely separate sodium sulfate from sodium chloride, and a part of the high-concentration sodium sulfate solution is discharged, resulting in waste of resources.
CN111634925A discloses a separation method after carbonization of a mixed salt containing sodium chloride and sodium sulfate, which comprises the steps of firstly preparing the mixed salt into a solution, freezing and crystallizing at-3 to-5 ℃ to separate out sodium sulfate crystals, and then washing and purifying the sodium sulfate crystals to obtain a sodium sulfate product; and then evaporating and concentrating the refrigerating fluid at high temperature to 1/4 of the original volume, cooling and crystallizing to separate out sodium chloride crystals, and washing to obtain a sodium chloride product. Although this method can separate sodium sulfate and sodium chloride from the mixed salt, these two products are inexpensive and not easily sold, and it has not been possible to achieve high-value utilization of the mixed salt of sodium sulfate and sodium chloride.
CN102153113A discloses a process for coproducing sodium carbonate, sodium chloride, sodium sulfate and ammonium chloride from mirabilite type brine, which comprises the following steps: preparing sodium bicarbonate and heavy alkali mother liquor from mirabilite type brine through ammoniation and carbonization, calcining the sodium bicarbonate at high temperature to obtain sodium carbonate, deaminating the heavy alkali mother liquor at high temperature to obtain deaminated mother liquor, separating the deaminated mother liquor through a sodium filter membrane to obtain denitrated exudation clear liquor and rich nitrate concentrated liquor, evaporating the rich nitrate concentrated liquor at high temperature to obtain sodium sulfate, evaporating the denitrated exudation clear liquor and circulating ammonium preparation mother liquor at high temperature to obtain sodium chloride and salt preparation mother liquor, and evaporating the ammonium preparation mother liquor at low temperature to obtain ammonium chloride and ammonium preparation mother liquor. The method converts part of sodium into sodium carbonate and part of chlorine into ammonium chloride, realizes resource recovery to a certain extent, but is not thorough, sodium sulfate and sodium chloride products are still generated, the cost of a sodium filter membrane is high, the evaporation and concentration steps are complicated, and the operation cost is greatly increased.
It follows that most technicians currently invest a great deal of research in the separation technology of mixed salts of sodium sulfate and sodium chloride, but few research into high-value conversion technology of mixed sodium salts. How to convert the mixed salt of sodium sulfate and sodium chloride into a product with high added value without generating three wastes becomes a problem which needs to be solved urgently by technical personnel in the field at present.
Disclosure of Invention
The invention aims to provide a method for converting mixed sodium salt, in particular to a method for converting the mixed sodium salt into high-value sodium carbonate, ammonium sulfate and ammonium chloride products, which can convert the mixed salt of sodium sulfate and sodium chloride into the high-value sodium carbonate, ammonium sulfate and ammonium chloride products, realizes the high-value conversion of the mixed sodium salt, simultaneously considers simplicity and economy, and does not generate three wastes.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a high-value conversion method of mixed sodium salt, which comprises the following steps:
(1) mixing the mixed sodium salt with the second mother liquor, carrying out primary sodium dissolution, and carrying out solid-liquid separation to obtain dechlorinated solid and primary sodium dissolution liquid;
(2) mixing ammonium bicarbonate solid or mixed gas of ammonia gas and carbon dioxide with the primary sodium solution obtained in the step (1), carrying out a first double decomposition reaction at the temperature of 20-50 ℃, and carrying out solid-liquid separation to obtain first sodium bicarbonate and first mother liquor;
(3) cooling and crystallizing the first mother liquor obtained in the step (2), and performing solid-liquid separation to obtain ammonium chloride and cooled mother liquor;
(4) mixing the deammoniated solid, the dechlorinated solid obtained in the step (1) and the cooling mother liquor obtained in the step (3), performing sodium secondary dissolution, and performing solid-liquid separation to obtain ammonium-sodium composite salt and sodium secondary dissolution liquid;
(5) mixing ammonium bicarbonate solid or mixed gas of ammonia gas and carbon dioxide with the sodium secondary dissolved solution obtained in the step (4), carrying out a second double decomposition reaction at the temperature of 20-50 ℃, and carrying out solid-liquid separation to obtain second sodium bicarbonate and second mother liquor; recycling the obtained second mother liquor to the step (1);
(6) mixing the evaporation mother liquor with the ammonium-sodium compound salt obtained in the step (4), carrying out ammonium sulfate enrichment, and carrying out solid-liquid separation to obtain an ammonium sulfate-rich solution and a deammoniated solid; recycling the obtained deammoniated solid in the step (4);
(7) evaporating and crystallizing the rich ammonium sulfate solution obtained in the step (6), and performing solid-liquid separation to obtain ammonium sulfate and evaporation mother liquor; the resulting evaporation mother liquor was reused in step (6).
Wherein the mixed sodium salt in the step (1) comprises sodium sulfate and sodium chloride; calcining the first sodium bicarbonate obtained in the step (2) and the second sodium bicarbonate obtained in the step (5) respectively and independently to prepare sodium carbonate; the step (5) and the step (6) are not in sequence.
According to the method provided by the invention, according to the change rule of a phase diagram of a water-salt system at different temperatures, the high-value conversion of the mixed salt of sodium sulfate and sodium chloride is realized by adopting the modes of dissolution, double decomposition reaction, cooling crystallization, salting out and evaporative crystallization; the whole process is simple to operate, high in conversion rate and low in cost, the required equipment is conventional equipment in the chemical field, and the industrial process is easy to realize; the process is clean, no waste water, waste gas and waste residue are discharged, and the economic and environmental benefits are obvious.
The product obtained by the method provided by the invention has high purity, the purity of the sodium carbonate product meets the requirement of a class II qualified product light sodium carbonate in GB/T210.1-2004, the purity of the ammonium sulfate product meets the requirement of a type I product in GB/T535-2020, and the purity of the ammonium chloride product meets the requirement of agricultural ammonium chloride in GB/T2946-2018.
In the present invention, the temperature of the first metathesis reaction in step (2) is 20 to 50 ℃ and may be, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ or 50 ℃, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
In the present invention, the temperature of the second metathesis reaction in the step (5) is 20 to 50 ℃ and may be, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ or 50 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the mass ratio of sodium sulfate to sodium chloride in the mixed sodium salt in step (1) is (0.35-5):1, and may be, for example, 0.35:1, 0.4:1, 0.6:1, 0.8:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature for primary dissolution of sodium in step (1) is 20 to 60 ℃, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, and more preferably 30 to 50 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the molar ratio of total bicarbonate to total sodium in the first metathesis reaction of step (2) is (1-1.5):1, and may be, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1 or 1.5:1, and more preferably (1-1.2):1, but is not limited to the recited values, and other values not recited within this range are equally applicable.
Preferably, the reaction time of the first metathesis reaction in step (2) is 20 to 180min, for example, 20min, 40min, 60min, 80min, 100min, 120min, 140min, 160min or 180min, and more preferably 30 to 120min, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the cooling crystallization temperature in step (3) is 5-35 ℃, for example, 5 ℃, 6 ℃, 8 ℃, 10 ℃, 12 ℃, 14 ℃, 16 ℃, 18 ℃, 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃ or 35 ℃, more preferably 10-20 ℃, but not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
Preferably, the temperature for the secondary dissolution of sodium in step (4) is 20 to 60 ℃, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, and more preferably 30 to 50 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the molar ratio of total bicarbonate to total sodium in the second metathesis reaction of step (5) is (1-1.5):1, and may be, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1 or 1.5:1, and more preferably (1-1.2):1, but is not limited to the recited values, and other values not recited within this range are equally applicable.
Preferably, the reaction time of the second metathesis reaction in step (5) is 20 to 180min, for example, 20min, 40min, 60min, 80min, 100min, 120min, 140min, 160min or 180min, and more preferably 30 to 120min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the ammonium sulfate enrichment in step (6) is carried out at a temperature of 80-100 ℃, for example 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃ or 100 ℃, more preferably 80-90 ℃, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the temperature of the evaporative crystallization in step (7) is 80 to 110 ℃, for example 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃ or 110 ℃, and more preferably 90 to 100 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the solid-liquid separation manner in steps (1) to (7) includes any one or a combination of at least two of hydrocyclone, centrifugal, filtration or sedimentation, and typical but non-limiting combinations include hydrocyclone and centrifugal, centrifugation and filtration, filtration and sedimentation, hydrocyclone, centrifugation and filtration, or centrifugation, filtration and sedimentation, respectively.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) mixing the mixed sodium salt with the second mother liquor, carrying out primary sodium dissolution at 20-60 ℃, and carrying out solid-liquid separation to obtain dechlorinated solid and primary sodium dissolution liquid;
(2) mixing ammonium bicarbonate solid or mixed gas of ammonia gas and carbon dioxide with the primary sodium solution obtained in the step (1), controlling the molar ratio of total bicarbonate radicals to total sodium in a reaction system to be (1-1.5):1, carrying out a first double decomposition reaction at 20-50 ℃ for 20-180min, and carrying out solid-liquid separation to obtain first sodium bicarbonate and first mother liquor;
(3) cooling and crystallizing the first mother liquor obtained in the step (2) at 5-35 ℃, and performing solid-liquid separation to obtain ammonium chloride and cooled mother liquor;
(4) mixing the deammoniated solid, the dechlorinated solid obtained in the step (1) and the cooling mother liquor obtained in the step (3), performing sodium secondary dissolution at the temperature of 20-60 ℃, and performing solid-liquid separation to obtain ammonium-sodium composite salt and sodium secondary dissolution liquid;
(5) mixing ammonium bicarbonate solid or mixed gas of ammonia gas and carbon dioxide with the sodium secondary dissolving solution obtained in the step (4), controlling the molar ratio of total bicarbonate radicals to total sodium in the reaction system to be (1-1.5):1, carrying out a second double decomposition reaction at 20-50 ℃ for 20-180min, and carrying out solid-liquid separation to obtain second sodium bicarbonate and a second mother solution; recycling the obtained second mother liquor to the step (1);
(6) mixing the evaporation mother liquor with the ammonium-sodium compound salt obtained in the step (4), carrying out ammonium sulfate enrichment at the temperature of 80-100 ℃, and carrying out solid-liquid separation to obtain a rich ammonium sulfate solution and a deammoniated solid; recycling the obtained deammoniated solid in the step (4);
(7) evaporating and crystallizing the rich ammonium sulfate solution obtained in the step (6) at the temperature of 80-110 ℃, and performing solid-liquid separation to obtain ammonium sulfate and evaporation mother liquor; the resulting evaporation mother liquor is reused in step (6).
Wherein the mixed sodium salt in the step (1) comprises sodium sulfate and sodium chloride, and the mass ratio of the sodium sulfate to the sodium chloride is (0.35-5) to 1; calcining the first sodium bicarbonate obtained in the step (2) and the second sodium bicarbonate obtained in the step (5) respectively and independently to prepare sodium carbonate; the step (5) and the step (6) are not in sequence; the solid-liquid separation modes in the steps (1) to (7) respectively and independently comprise any one or combination of at least two of hydrocyclone separation, centrifugal separation, filtering separation or sedimentation separation.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method provided by the invention, according to the change rule of a phase diagram of a water-salt system at different temperatures, the high-value conversion of the mixed salt of sodium sulfate and sodium chloride is realized by adopting the modes of dissolution, double decomposition reaction, cooling crystallization, salting out and evaporative crystallization; the whole process is simple to operate, high in conversion rate and low in cost, the required equipment is conventional equipment in the chemical field, and the industrial process is easy to realize; the process is clean, no waste water, waste gas and waste residue are discharged, and the economic and environmental benefits are remarkable;
(2) the product obtained by the method provided by the invention has high purity, the purity of the sodium carbonate product meets the requirement of II-class qualified light sodium carbonate in GB/T210.1-2004, the purity of the ammonium sulfate product meets the requirement of I-type product in GB/T535-2012020, and the purity of the ammonium chloride product meets the requirement of agricultural ammonium chloride in GB/T2946-2018.
Drawings
FIG. 1 is a flow chart of the high value conversion method of mixed sodium salt provided by the invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The invention provides a high-value conversion method of mixed sodium salt, which comprises the following steps of before a recycling system of intermediate materials is established:
(1) mixing the mixed sodium salt with clear water, carrying out primary sodium dissolution at the temperature of 20-60 ℃, and carrying out solid-liquid separation to obtain dechlorinated solid and primary sodium dissolution liquid;
(2) mixing ammonium bicarbonate solid or mixed gas of ammonia gas and carbon dioxide with the primary sodium solution obtained in the step (1), controlling the molar ratio of total bicarbonate radicals to total sodium in a reaction system to be (1-1.5):1, carrying out a first double decomposition reaction at 20-50 ℃ for 20-180min, and carrying out solid-liquid separation to obtain first sodium bicarbonate and first mother liquor;
(3) cooling and crystallizing the first mother liquor obtained in the step (2) at 5-35 ℃, and performing solid-liquid separation to obtain ammonium chloride and cooled mother liquor;
(4) mixing the dechlorinated solid obtained in the step (1) and the cooling mother liquor obtained in the step (3), performing sodium secondary dissolution at the temperature of 20-60 ℃, and performing solid-liquid separation to obtain ammonium-sodium composite salt and sodium secondary dissolution liquid;
(5) mixing ammonium bicarbonate solid or mixed gas of ammonia gas and carbon dioxide with the sodium secondary dissolving solution obtained in the step (4), controlling the molar ratio of total bicarbonate radicals to total sodium in the reaction system to be (1-1.5):1, carrying out a second double decomposition reaction at 20-50 ℃ for 20-180min, and carrying out solid-liquid separation to obtain second sodium bicarbonate and a second mother solution; recycling the obtained second mother liquor to the step (1);
(6) mixing the ammonium-sodium compound salt obtained in the step (4) with clean water, carrying out ammonium sulfate enrichment at the temperature of 80-100 ℃, and carrying out solid-liquid separation to obtain a rich ammonium sulfate solution and a deammoniated solid; recycling the obtained deammoniated solid in the step (4);
(7) evaporating and crystallizing the rich ammonium sulfate solution obtained in the step (6) at the temperature of 80-110 ℃, and performing solid-liquid separation to obtain ammonium sulfate and evaporation mother liquor; the resulting evaporation mother liquor is reused in step (6).
Wherein the mixed sodium salt in the step (1) comprises sodium sulfate and sodium chloride, and the mass ratio of the sodium sulfate to the sodium chloride is (0.35-5) to 1; calcining the first sodium bicarbonate obtained in the step (2) and the second sodium bicarbonate obtained in the step (5) respectively and independently to prepare sodium carbonate; the step (5) and the step (6) are not in sequence; the solid-liquid separation modes of the steps (1) to (7) respectively and independently comprise any one or combination of at least two of hydrocyclone separation, centrifugal separation, filtering separation and sedimentation separation.
Example 1
This example provides a process for high value conversion of mixed sodium salts, as shown in figure 1, comprising the steps of:
(1) mixing the mixed sodium salt with the second mother liquor, carrying out primary sodium dissolution at 40 ℃, and carrying out settling separation to obtain dechlorinated solid and primary sodium dissolution liquid;
(2) mixing ammonium bicarbonate solid and the sodium primary solution obtained in the step (1), controlling the molar ratio of total bicarbonate radicals to total sodium in a reaction system to be 1.1:1, carrying out a first double decomposition reaction at 35 ℃ for 60min, carrying out hydraulic cyclone separation, and then filtering and separating to obtain first sodium bicarbonate and first mother liquor;
(3) cooling and crystallizing the first mother liquor obtained in the step (2) at 15 ℃, and filtering and separating to obtain ammonium chloride and cooling mother liquor;
(4) mixing the de-ammonified solid, the de-chlorinated solid obtained in the step (1) and the cooling mother liquor obtained in the step (3), performing sodium secondary dissolution at 40 ℃, and performing sedimentation separation to obtain an ammonium-sodium composite salt and a sodium secondary dissolution liquid;
(5) mixing a mixed gas of ammonia gas and carbon dioxide with the sodium secondary dissolved solution obtained in the step (4), controlling the molar ratio of total bicarbonate radicals to total sodium in the reaction system to be 1.1:1, carrying out a second double decomposition reaction at 40 ℃, wherein the reaction time is 100min, and carrying out hydrocyclone separation and then filtering separation to obtain second sodium bicarbonate and a second mother solution; recycling the obtained second mother liquor to the step (1);
(6) mixing the evaporation mother liquor with the ammonium-sodium composite salt obtained in the step (4), carrying out ammonium sulfate enrichment at 85 ℃, and carrying out centrifugal separation to obtain an ammonium sulfate-rich solution and a deammoniated solid; the obtained deammoniated solid is reused in the step (4);
(7) evaporating and crystallizing the rich ammonium sulfate solution obtained in the step (6) at 95 ℃, and performing hydrocyclone separation and then centrifugal separation to obtain ammonium sulfate and evaporation mother liquor; the resulting evaporation mother liquor was reused in step (6).
Wherein the mixed sodium salt in the step (1) comprises sodium sulfate and sodium chloride, and the mass ratio of the sodium sulfate to the sodium chloride is 2.3: 1; and (3) independently calcining the first sodium bicarbonate obtained in the step (2) and the second sodium bicarbonate obtained in the step (5) to prepare sodium carbonate.
Through detection, the utilization rate of sodium (the ratio of sodium to sodium carbonate, the same applies below) in this example is 96%; the total alkali content of the obtained sodium carbonate product is 99.12 percent, and the requirement of II-class qualified product light sodium carbonate in GB/T210.1-2004 is met; the nitrogen content of the obtained ammonium sulfate product is 21.03 percent, and the requirement of I type products in GB/T535-2020; the nitrogen content of the obtained ammonium chloride product is 24.94 percent, and the requirement of first-class products of the ammonium chloride for the agriculture in GB/T2946-2018 is met.
Example 2
This example provides a process for high value conversion of mixed sodium salts, as shown in figure 1, comprising the steps of:
(1) mixing the mixed sodium salt with the second mother liquor, carrying out primary sodium dissolution at 20 ℃, and carrying out settling separation to obtain dechlorinated solid and primary sodium dissolution liquid;
(2) mixing a mixed gas of ammonia gas and carbon dioxide with the primary sodium solution obtained in the step (1), controlling the molar ratio of total bicarbonate radicals to total sodium in a reaction system to be 1.5:1, carrying out a first double decomposition reaction at 50 ℃, wherein the reaction time is 20min, and carrying out hydrocyclone separation and then filtering separation to obtain first sodium bicarbonate and first mother liquor;
(3) cooling and crystallizing the first mother liquor obtained in the step (2) at 5 ℃, and filtering and separating to obtain ammonium chloride and cooling mother liquor;
(4) mixing the de-ammonified solid, the de-chlorinated solid obtained in the step (1) and the cooling mother liquor obtained in the step (3), performing sodium secondary dissolution at the temperature of 20 ℃, and performing sedimentation separation to obtain ammonium-sodium composite salt and sodium secondary dissolution liquid;
(5) mixing the ammonium bicarbonate solid and the sodium secondary solution obtained in the step (4), controlling the molar ratio of total bicarbonate radicals to total sodium in the reaction system to be 1:1, carrying out a second double decomposition reaction at 20 ℃, wherein the reaction time is 180min, and carrying out hydrocyclone separation and then filtering separation to obtain second sodium bicarbonate and second mother liquor; recycling the obtained second mother liquor to the step (1);
(6) mixing the evaporation mother liquor and the ammonium-sodium compound salt obtained in the step (4), carrying out ammonium sulfate enrichment at the temperature of 80 ℃, and carrying out centrifugal separation to obtain a rich ammonium sulfate solution and a deammoniated solid; recycling the obtained deammoniated solid in the step (4);
(7) evaporating and crystallizing the rich ammonium sulfate solution obtained in the step (6) at 110 ℃, and performing hydrocyclone separation and centrifugal separation to obtain ammonium sulfate and evaporation mother liquor; the resulting evaporation mother liquor is reused in step (6).
Wherein the mixed sodium salt in the step (1) comprises sodium sulfate and sodium chloride, and the mass ratio of the sodium sulfate to the sodium chloride is 5: 1; and (3) independently calcining the first sodium bicarbonate obtained in the step (2) and the second sodium bicarbonate obtained in the step (5) to prepare sodium carbonate.
Through detection, the utilization rate of sodium in the embodiment is 95%; the total alkali content of the obtained sodium carbonate product is 98.56 percent, and the requirement of II-class qualified product light sodium carbonate in GB/T210.1-2004 is met; the nitrogen content of the obtained ammonium sulfate product is 20.68 percent, and the requirement of the I-type product in GB/T535-2020; the nitrogen content of the obtained ammonium chloride product is 24.51 percent, and the requirement of first-class products of agricultural ammonium chloride in GB/T2946-2018 is met.
Example 3
This example provides a process for high value conversion of mixed sodium salts, as shown in figure 1, comprising the steps of:
(1) mixing the mixed sodium salt with the second mother liquor, carrying out primary sodium dissolution at 40 ℃, and carrying out settling separation to obtain dechlorinated solid and primary sodium dissolution liquid;
(2) mixing ammonium bicarbonate solid and the sodium primary solution obtained in the step (1), controlling the molar ratio of total bicarbonate radicals to total sodium in a reaction system to be 1:1, carrying out a first double decomposition reaction at 20 ℃ for 180min, carrying out hydrocyclone separation, and then filtering separation to obtain first sodium bicarbonate and first mother liquor;
(3) cooling and crystallizing the first mother liquor obtained in the step (2) at 35 ℃, and filtering and separating to obtain ammonium chloride and cooling mother liquor;
(4) mixing the de-ammonified solid, the de-chlorinated solid obtained in the step (1) and the cooled mother liquor obtained in the step (3), performing sodium secondary dissolution at 60 ℃, and performing sedimentation separation to obtain ammonium-sodium composite salt and sodium secondary dissolution liquid;
(5) mixing a mixed gas of ammonia gas and carbon dioxide with the sodium secondary dissolved solution obtained in the step (4), controlling the molar ratio of total bicarbonate radicals to total sodium in the reaction system to be 1.5:1, carrying out a second double decomposition reaction at 50 ℃ for 20min, carrying out hydrocyclone separation firstly, and then filtering and separating to obtain second sodium bicarbonate and second mother liquor; recycling the obtained second mother liquor to the step (1);
(6) mixing the evaporation mother liquor and the ammonium-sodium compound salt obtained in the step (4), carrying out ammonium sulfate enrichment at 100 ℃, and carrying out centrifugal separation to obtain a rich ammonium sulfate solution and a deammoniated solid; recycling the obtained deammoniated solid in the step (4);
(7) evaporating and crystallizing the rich ammonium sulfate solution obtained in the step (6) at 80 ℃, and performing hydrocyclone separation and centrifugal separation to obtain ammonium sulfate and evaporation mother liquor; the resulting evaporation mother liquor is reused in step (6).
Wherein the mixed sodium salt in the step (1) comprises sodium sulfate and sodium chloride, and the mass ratio of the sodium sulfate to the sodium chloride is 0.35: 1; and (3) independently calcining the first sodium bicarbonate obtained in the step (2) and the second sodium bicarbonate obtained in the step (5) to prepare sodium carbonate.
Through detection, the utilization rate of sodium in the embodiment is 95%; the total alkali content of the obtained sodium carbonate product is 98.63 percent, and the requirement of II-class qualified product light sodium carbonate in GB/T210.1-2004 is met; the nitrogen content of the obtained ammonium sulfate product is 20.56 percent, and the requirement of I type products in GB/T535-2020; the nitrogen content of the obtained ammonium chloride product is 24.26 percent, and the requirement of first-class products of agricultural ammonium chloride in GB/T2946-2018 is met.
Example 4
This example provides a method for high-value conversion of mixed sodium salt, which is the same as example 1 except that the molar ratio of total bicarbonate to total sodium in the reaction system in step (2) is changed to 0.8:1, and thus the details are not repeated herein.
Through detection, the utilization rate of sodium in the embodiment is 93%; the total alkali content of the obtained sodium carbonate product is 98.5 percent, and the requirement of II-class qualified product light sodium carbonate in GB/T210.1-2004 is met; the nitrogen content of the obtained ammonium sulfate product is 20.51 percent, and the requirement of I type products in GB/T535-2020; the nitrogen content of the obtained ammonium chloride product is 23.64 percent, and the requirement of qualified products of the ammonium chloride for the agricultural industry in GB/T2946-2018 is met.
Example 5
This example provides a method for high-value conversion of mixed sodium salt, which is the same as example 1 except that the molar ratio of total bicarbonate to total sodium in the reaction system in step (2) is changed to 1.8:1, and thus the details are not repeated herein.
Through detection, the utilization rate of sodium in the embodiment is 96%; the total alkali content of the obtained sodium carbonate product is 99.1 percent, and the requirement of II-class qualified product light sodium carbonate in GB/T210.1-2004 is met; the nitrogen content of the obtained ammonium sulfate product is 20.60 percent, and the requirement of I type products in GB/T535-2020 is met; the nitrogen content of the obtained ammonium chloride product is 24.51 percent, and the requirement of first-class products of agricultural ammonium chloride in GB/T2946-2018 is met.
However, compared to example 1, since the bicarbonate in step (2) of this example is too much, a large amount of bicarbonate remains and enters the sodium bicarbonate in solid phase, and is converted into gas during the calcination process, although the purity of sodium carbonate is not affected, the energy consumption and the utilization rate of ammonium bicarbonate are affected, that is, the economic efficiency is adversely affected.
Example 6
This example provides a method for high-value conversion of mixed sodium salt, which is the same as example 1 except that the molar ratio of total bicarbonate to total sodium in the reaction system in step (5) is changed to 0.8:1, and thus the details are not repeated herein.
Through detection, the utilization rate of sodium in the embodiment is 81%; the total alkali content of the obtained sodium carbonate product is 98.7 percent, and the requirement of II-class qualified product light sodium carbonate in GB/T210.1-2004 is met; the nitrogen content of the obtained ammonium sulfate product is 20.54 percent, and the requirement of the I-type product in GB/T535-2020; the nitrogen content of the obtained ammonium chloride product is 23.60 percent, and the requirement of qualified products of the ammonium chloride for the agricultural industry in GB/T2946-2018 is met.
Example 7
This example provides a method for high-value conversion of mixed sodium salt, which is the same as example 1 except that the molar ratio of total bicarbonate to total sodium in the reaction system in step (5) is changed to 1.8:1, and thus the details are not repeated herein.
Through detection, the utilization rate of sodium in the embodiment is 96%; the total alkali content of the obtained sodium carbonate product is 98.6 percent, and the requirement of II-class qualified product light sodium carbonate in GB/T210.1-2004 is met; the nitrogen content of the obtained ammonium sulfate product is 20.7 percent, and the requirement of I type products in GB/T535-2020; the nitrogen content of the obtained ammonium chloride product is 24.9 percent, and the requirement of first-class products of the ammonium chloride for the agricultural industry in GB/T2946-2018 is met.
However, compared to example 1, in step (5) of this example, since too many hydrogen carbonates are present, a large amount of bicarbonate remains and enters the sodium bicarbonate in solid phase, and is converted into gas during the calcination process, although the purity of sodium carbonate is not affected, the energy consumption and the utilization rate of ammonium bicarbonate are affected, that is, the economic efficiency is adversely affected.
Comparative example 1
This comparative example provides a high value conversion method of mixed sodium salt, which is the same as example 1 except that the temperature of the first metathesis reaction in step (2) is changed to 15 ℃, and the other steps and conditions are not repeated herein.
Through detection, the utilization rate of sodium in the comparative example is 75%; the total alkali content of the obtained sodium carbonate product is 82 percent, and the requirement of II-class qualified product light sodium carbonate in GB/T210.1-2004 is not met; the nitrogen content of the obtained ammonium sulfate product is 20.62 percent, and the requirement of I type products in GB/T535-2020 is met; the nitrogen content of the obtained ammonium chloride product is 24.5 percent, and the requirement of first-class products of the ammonium chloride for the agricultural industry in GB/T2946-2018 is met.
Comparative example 2
This comparative example provides a high value conversion method of mixed sodium salt, which is the same as example 1 except that the temperature of the first metathesis reaction in step (2) is changed to 60 ℃, and the rest of the steps and conditions are not repeated herein.
Through detection, the utilization rate of sodium in the comparative example is 96%; the total alkali content of the obtained sodium carbonate product is 98.5 percent, and the requirement of II-class qualified product light sodium carbonate in GB/T210.1-2004 is met; the nitrogen content of the obtained ammonium sulfate product is 20.55 percent, and the requirement of I type products in GB/T535-2020; the nitrogen content of the obtained ammonium chloride product is 17.3 percent, which does not meet the requirements of first-class products of ammonium chloride for the agricultural industry in GB/T2946-2018.
In addition, compared with example 1, the single-pass recovery rate of sodium carbonate and ammonium chloride in the comparative example is obviously reduced, and particularly, ammonium chloride is difficult to precipitate.
Comparative example 3
This comparative example provides a high value conversion method of mixed sodium salt, which is the same as example 1 except that the temperature of the second metathesis reaction in step (5) is changed to 15 ℃, and the remaining steps and conditions are not repeated herein.
Through detection, the utilization rate of sodium in the comparative example is 65%; the total alkali content of the obtained sodium carbonate product is 78 percent, and the requirement of II-class qualified product light sodium carbonate in GB/T210.1-2004 is not met; the nitrogen content of the obtained ammonium sulfate product is 15.6 percent, which does not meet the requirement of I type products in GB/T535-2020; the nitrogen content of the obtained ammonium chloride product is 24.80 percent, and the requirement of first-class products of ammonium chloride for the agricultural industry in GB/T2946-2018 is met.
Compared with example 1, the solubility of sodium sulfate is obviously reduced due to the low temperature of the second double decomposition reaction of the comparative example, the reaction is converted into solid-solid reaction, the conversion rate is low, the purity of sodium carbonate is reduced, and the sodium sulfate is difficult to react completely; meanwhile, because the conversion rate is low, the ammonium sulfate is difficult to crystallize, and the crystal is a mixture of the ammonium sulfate and the sodium sulfate.
Comparative example 4
This comparative example provides a high value conversion method of mixed sodium salt, which is the same as example 1 except that the temperature of the second metathesis reaction in step (5) is changed to 60 ℃, and the rest of the steps and conditions are not repeated herein.
Through detection, the utilization rate of sodium in the comparative example is 82%; the total alkali content of the obtained sodium carbonate product is 98.7 percent, and the requirement of II-class qualified product light sodium carbonate in GB/T210.1-2004 is met; the nitrogen content of the obtained ammonium sulfate product is 17.1 percent, which does not meet the requirement of I type products in GB/T535-2020; the nitrogen content of the obtained ammonium chloride product is 24.8 percent, and the requirement of first-class products of the ammonium chloride for the agricultural industry in GB/T2946-2018 is met.
Compared to example 1, due to the excessively high temperature of the second metathesis reaction of this comparative example, the solubility of ammonia and carbon dioxide is significantly reduced, resulting in a reduced single pass recovery, but without affecting the quality of the sodium carbonate. Because the single-pass recovery rate is low, the content of sodium sulfate in the ammonium sulfate hot solution is too high, and the ammonium sulfate with higher purity is difficult to obtain.
Therefore, according to the change rule of the phase diagram of the water-salt system at different temperatures, the method provided by the invention adopts the modes of dissolution, double decomposition reaction, cooling crystallization, salting out and evaporative crystallization to realize high-value conversion of the mixed salt of sodium sulfate and sodium chloride; the whole process is simple to operate, high in conversion rate and low in cost, required equipment is conventional equipment in the chemical field, and the industrial process is easy to realize; the process is clean, no waste water, waste gas and waste residue are discharged, and the economic and environmental benefits are remarkable; in addition, the product obtained by the method provided by the invention has high purity, the purity of the sodium carbonate product meets the requirement of II-class qualified light sodium carbonate in GB/T210.1-2004, the purity of the ammonium sulfate product meets the requirement of I-type product in GB/T535-2018, and the purity of the ammonium chloride product meets the requirement of agricultural ammonium chloride in GB/T2946-2018.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein fall within the scope and disclosure of the present invention.
Claims (7)
1. A method for high value conversion of mixed sodium salts, comprising the steps of:
(1) mixing the mixed sodium salt with the second mother liquor, carrying out primary sodium dissolution at 20-60 ℃, and carrying out solid-liquid separation to obtain dechlorinated solid and primary sodium dissolution liquid;
(2) mixing ammonium bicarbonate solid or mixed gas of ammonia gas and carbon dioxide with the sodium primary solution obtained in the step (1), controlling the molar ratio of total bicarbonate radicals to total sodium in a reaction system to be (1-1.5):1, carrying out a first double decomposition reaction at 20-50 ℃, wherein the reaction time is 20-180min, and carrying out solid-liquid separation to obtain first sodium bicarbonate and first mother liquor;
(3) cooling and crystallizing the first mother liquor obtained in the step (2), and performing solid-liquid separation to obtain ammonium chloride and cooled mother liquor;
(4) mixing the deammoniated solid, the dechlorinated solid obtained in the step (1) and the cooling mother liquor obtained in the step (3), performing sodium secondary dissolution, and performing solid-liquid separation to obtain ammonium-sodium composite salt and sodium secondary dissolution liquid;
(5) mixing ammonium bicarbonate solid or mixed gas of ammonia gas and carbon dioxide with the sodium secondary dissolving solution obtained in the step (4), controlling the molar ratio of total bicarbonate radicals to total sodium in the reaction system to be (1-1.5):1, carrying out a second double decomposition reaction at 20-50 ℃ for 20-180min, and carrying out solid-liquid separation to obtain second sodium bicarbonate and a second mother solution; recycling the obtained second mother liquor to the step (1);
(6) mixing the evaporation mother liquor with the ammonium-sodium compound salt obtained in the step (4), carrying out ammonium sulfate enrichment, and carrying out solid-liquid separation to obtain an ammonium sulfate-rich solution and a deammoniated solid; recycling the obtained deammoniated solid in the step (4);
(7) evaporating and crystallizing the rich ammonium sulfate solution obtained in the step (6), and performing solid-liquid separation to obtain ammonium sulfate and evaporation mother liquor; recycling the obtained evaporation mother liquor to the step (6);
wherein the mixed sodium salt in the step (1) comprises sodium sulfate and sodium chloride, and the mass ratio of the sodium sulfate to the sodium chloride is (0.35-5): 1; calcining the first sodium bicarbonate obtained in the step (2) and the second sodium bicarbonate obtained in the step (5) respectively and independently to prepare sodium carbonate; the step (5) and the step (6) are not in sequence.
2. The method according to claim 1, wherein the temperature of the cooling crystallization in the step (3) is 5-35 ℃.
3. The method according to claim 1, wherein the temperature for the secondary dissolution of sodium in step (4) is 20-60 ℃.
4. The method of claim 1, wherein the ammonium sulfate enrichment of step (6) is at a temperature of 80-100 ℃.
5. The method according to claim 1, wherein the temperature of the evaporative crystallization in step (7) is 80-110 ℃.
6. The method according to claim 1, wherein the solid-liquid separation in steps (1) to (7) comprises any one or a combination of at least two of hydrocyclone separation, centrifugal separation, filtration separation and sedimentation separation.
7. Method according to any of claims 1-6, characterized in that the method comprises the steps of:
(1) mixing the mixed sodium salt with the second mother liquor, carrying out primary sodium dissolution at 20-60 ℃, and carrying out solid-liquid separation to obtain dechlorinated solid and primary sodium dissolution liquid;
(2) mixing ammonium bicarbonate solid or mixed gas of ammonia gas and carbon dioxide with the primary sodium solution obtained in the step (1), controlling the molar ratio of total bicarbonate radicals to total sodium in a reaction system to be (1-1.5):1, carrying out a first double decomposition reaction at 20-50 ℃ for 20-180min, and carrying out solid-liquid separation to obtain first sodium bicarbonate and first mother liquor;
(3) cooling and crystallizing the first mother liquor obtained in the step (2) at 5-35 ℃, and performing solid-liquid separation to obtain ammonium chloride and cooled mother liquor;
(4) mixing the deammoniated solid, the dechlorinated solid obtained in the step (1) and the cooling mother liquor obtained in the step (3), performing sodium secondary dissolution at the temperature of 20-60 ℃, and performing solid-liquid separation to obtain ammonium-sodium composite salt and sodium secondary dissolution liquid;
(5) mixing ammonium bicarbonate solid or mixed gas of ammonia gas and carbon dioxide with the sodium secondary dissolving solution obtained in the step (4), controlling the molar ratio of total bicarbonate radicals to total sodium in a reaction system to be (1-1.5):1, carrying out a second double decomposition reaction at 20-50 ℃, wherein the reaction time is 20-180min, and carrying out solid-liquid separation to obtain second sodium bicarbonate and a second mother solution; the second mother liquor is recycled in the step (1);
(6) mixing the evaporation mother liquor with the ammonium-sodium compound salt obtained in the step (4), carrying out ammonium sulfate enrichment at the temperature of 80-100 ℃, and carrying out solid-liquid separation to obtain a rich ammonium sulfate solution and a deammoniated solid; recycling the obtained deammoniated solid in the step (4);
(7) evaporating and crystallizing the rich ammonium sulfate solution obtained in the step (6) at the temperature of 80-110 ℃, and performing solid-liquid separation to obtain ammonium sulfate and evaporation mother liquor; recycling the obtained evaporation mother liquor to the step (6);
wherein the mixed sodium salt in the step (1) comprises sodium sulfate and sodium chloride, and the mass ratio of the sodium sulfate to the sodium chloride is (0.35-5): 1; calcining the first sodium bicarbonate obtained in the step (2) and the second sodium bicarbonate obtained in the step (5) respectively and independently to prepare sodium carbonate; the step (5) and the step (6) are not in sequence; the solid-liquid separation modes of the steps (1) to (7) respectively and independently comprise any one or combination of at least two of hydrocyclone separation, centrifugal separation, filtering separation and sedimentation separation.
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