CN114538471A - Method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt - Google Patents
Method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt Download PDFInfo
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Abstract
The invention discloses a method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt, which uses the sodium sulfate-sodium chloride mixed salt and solution thereof as raw materials, uses ammonium bicarbonate as a resolving agent, and skillfully utilizes HCO3 ‑Ions and NH4 +The ion-generated homoionic effect forces Na in the solution+Ions and Cl‑The ions are crystallized and separated out in the form of sodium bicarbonate and ammonium chloride, and sodium, sulfate radical and chlorine in the mixed salt are fully and effectively separated and utilized by utilizing the equilibrium relationship of heterogeneous crystallization-dissolution of the sodium bicarbonate, the ammonium sulfate, the ammonium chloride, the ammonium sulfate and the sodium chloride under different conditions through gradient crystallization and reverse refiningThe method can directly produce three qualified products of sodium carbonate, ammonium sulfate and ammonium chloride, has the advantages of simple process, high comprehensive utilization rate, good economic benefit, convenient operation and the like, and is suitable for industrial production of comprehensively utilizing the sodium sulfate-sodium chloride mixed salt and the solution thereof.
Description
Technical Field
The invention belongs to the fields of chemical industry and environmental protection, and particularly relates to a method for comprehensively utilizing a sodium sulfate-sodium chloride mixed salt.
Background
The mixed salt of sodium sulfate and sodium chloride is solid waste obtained by purifying, removing impurities, evaporating and concentrating waste water containing sodium sulfate and sodium chloride discharged from the treatment of reaction materials by using sulfuric acid or hydrochloric acid or sodium chloride. The sodium sulfate-sodium chloride mixed salt is colorless or earthy yellow or earthy gray powder, and the earthy yellow or earthy gray powder contains impurities such as iron, aluminum, silicon, lead, arsenic and silt besides sulfur, sodium and chlorine. Waste salt produced in chemical and metallurgical processes has been listed in the book of national hazardous wastes, which was passed through in 2016. It is known that sodium sulfate and sodium chloride are cheap sodium salts, and the separation and recovery of sodium sulfate and sodium chloride from a sodium sulfate-sodium chloride mixed salt is not economical. Therefore, many metallurgical and chemical enterprises face an embarrassing situation at present, wastewater generated in the production process cannot be purified, and purified sodium sulfate-sodium chloride mixed salt cannot find a market. Therefore, the sodium sulfate-sodium chloride mixed salt obtained by purifying the waste water can only be built and stockpiled, the stock pressure is increased along with the lapse of time, and the sodium sulfate and the sodium chloride are both materials which are easy to dissolve in water, and secondary pollution can be caused once the management is not good.
Disclosure of Invention
The invention aims to develop a method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt, which has the advantages of simple process, high comprehensive utilization rate, good economic benefit and convenient operation.
A method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt comprises the following steps:
the method comprises the following steps: removing sodium and precipitating chlorine
Using a slurry or solution of a mixed salt of sodium sulfate and sodium chloride as a raw material, and using ammonium bicarbonate, or CO2/NH3The mixed gas of (A) is used as a resolving agent, and ammonium bicarbonate or CO is used as2/NH3Adding the mixed gas into the slurry or solution of the sodium sulfate-sodium chloride mixed salt, stirring, and using HCO3 -Ions and NH4 +The ion generates a homoionic effect to force Na in the solution+And Cl-Crystallizing out in the form of sodium bicarbonate and ammonium chloride respectively to obtain slurry, and then treating by adopting any one of the following two ways:
(1) filtering the obtained slurry to obtain a primary crystal and a primary crystallization mother liquor, freezing the primary crystallization mother liquor, further crystallizing, and filtering to obtain a secondary crystal and a secondary crystallization mother liquor;
(2) freezing the obtained slurry, further crystallizing, and filtering to obtain a mixture of a primary crystal and a secondary crystallization mother liquor;
step two: separating and recovering ammonium sulfate
Evaporating and concentrating the secondary crystallization mother liquor obtained in the first step to crystallize and separate out 45% -85% of ammonium sulfate, filtering to obtain a tertiary crystal and a tertiary crystallization mother liquor, returning the tertiary crystallization mother liquor to the first step to be combined with a mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning a dissolving solution for preparing a sodium sulfate-sodium chloride mixed salt, drying the obtained tertiary crystal and directly using the dried tertiary crystal as an agricultural ammonium sulfate fertilizer, or using a saturated ammonium sulfate solution as a first refined solution, adding the tertiary crystal into the tertiary crystal, heating, stirring, washing, cooling, and filtering to obtain a washed solution and a refined ammonium sulfate product;
step three: separating and recovering sodium carbonate and ammonium chloride
Adding the primary crystal obtained in the step one or the mixture of the primary crystal and the secondary crystal into a saturated sodium bicarbonate solution serving as a second refined solution, heating, stirring and refining to dissolve ammonium chloride, ammonium sulfate, sodium chloride and sodium sulfate into the solution, filtering while hot to obtain a sodium bicarbonate filter cake and an ammonium chloride dissolved solution, washing the sodium bicarbonate filter cake again, then thermally decomposing to obtain a refined sodium carbonate product, cooling the obtained ammonium chloride dissolved solution, crystallizing, and filtering to obtain an ammonium chloride filter cake and an ammonium chloride crystallization mother solution; returning the obtained ammonium chloride crystallization mother liquor to be continuously used as a second refined solution, performing closed cycle until any one of ammonium sulfate, sodium chloride and sodium sulfate is enriched to be close to saturation, performing open circuit, returning to the step I, combining with the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning to a dissolving solution for preparing sodium sulfate-sodium chloride mixed salt; drying the obtained ammonium chloride filter cake and then directly using the dried ammonium chloride filter cake as a product, or using a saturated ammonium chloride solution as a third refined solution, adding the ammonium chloride filter cake into the third refined solution, heating, stirring, refining, cooling, filtering to obtain a refined solution and a refined ammonium chloride product, returning the refined solution to be continuously used as the third refined solution, performing closed cycle until any one of ammonium sulfate, sodium bicarbonate, sodium chloride and sodium sulfate is enriched to be close to saturation, opening the circuit, returning to the step I, mixing with a mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning to a dissolved solution for preparing a sodium sulfate-sodium chloride mixed salt.
Further, the method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt comprises the following technical processes and technical conditions:
in the first step of the method,
the raw material is SO4 2-/Cl-The sodium sulfate-sodium chloride mixed salt slurry or solution with the molar ratio of 0.1-50 is used as a raw material, and the sodium sulfate-sodium chloride mixed salt is added into water to prepare Na+A solution with an ion concentration of 90-162 g/L, or Na+Mixing sodium sulfate-sodium chloride mixed salt with water to prepare slurry or directly taking solution containing sodium sulfate and sodium chloride as raw materials, purifying and concentrating to obtain Na+The ion concentration reaches 90-162 g/L;
NH control with ammonium bicarbonate as resolving agent4 +/Na+Stirring and adding ammonium bicarbonate into slurry or solution of sodium sulfate-sodium chloride mixed salt, wherein the molar ratio is 1.05-1.25: 1;
with CO2/NH3The mixed gas of (A) is used as a resolving agent, wherein CO2/NH3The molar ratio is 1-1.1: 1, and NH is controlled3/Na+Blowing mixed gas into the slurry or solution of the sodium sulfate-sodium chloride mixed salt or blowing NH into the slurry or solution of the sodium sulfate-sodium chloride mixed salt at a molar ratio of 1.05-1.25: 13Then according to CO2/NH3Blowing CO at the molar ratio of 1-1.1: 12；
Adding a resolving agent, stirring for 0.5-2.5 h at the temperature of 1-40 ℃, and using HCO3 -Ions and NH4 +The ion generates a homoionic effect to force Na in the solution+And Cl-Respectively crystallizing and separating out in the forms of sodium bicarbonate and ammonium chloride,filtering to obtain a primary crystal and a primary crystallization mother liquor, then placing the primary crystallization mother liquor at the temperature of-18-0 ℃ for freezing and crystallizing for 2-6 h, filtering to obtain a secondary crystal and a secondary crystallization mother liquor, or directly placing the split slurry containing crystals at the temperature of-18-0 ℃ for freezing, continuing crystallizing for 2-6 h, and filtering to obtain a mixture of the primary crystal and the secondary crystallization mother liquor;
in the second step, the first step is carried out,
taking saturated ammonium sulfate solution at room temperature as first refined liquid, adding three-time crystals according to a solid-to-liquid ratio of 1: 0.3-3 g/mL, stirring and washing at 25-95 ℃ for 0.5-1 h, cooling to room temperature, filtering to obtain washed liquid and a refined ammonium sulfate product, returning the obtained washed liquid to be continuously used as the first refined liquid, performing closed cycle until any one of ammonium chloride, sodium carbonate and sodium sulfate is enriched to be close to saturation, opening the circuit, returning to the step I, combining with a mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning to a dissolved solution for preparing a sodium sulfate-sodium chloride mixed salt;
in the third step, the first step is that,
adding a primary crystal or a mixture of the primary crystal and a secondary crystal into a secondary refined solution by using a saturated sodium bicarbonate solution at the temperature of-5-25 ℃ as the second refined solution according to a solid-to-liquid ratio of 1: 0.5-5 g/mL, stirring for 0.5-1 h at the temperature of 40-64 ℃ to dissolve ammonium chloride, ammonium sulfate, sodium chloride and sodium sulfate in the solution, filtering while hot to obtain a sodium bicarbonate filter cake and a solution containing ammonium chloride, washing the sodium bicarbonate filter cake, then thermally decomposing to obtain a qualified sodium carbonate product, cooling the obtained solution, crystallizing for 0.5-2.5 h at the temperature of-5-25 ℃, and filtering to obtain an ammonium chloride filter cake and an ammonium chloride crystal mother solution; returning the obtained ammonium chloride crystallization mother liquor to be continuously used as a second refined solution, performing closed cycle until any one of ammonium sulfate, sodium chloride and sodium sulfate is enriched to be close to saturation, opening the circuit, returning to the step I, combining with the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning to a dissolving solution for preparing sodium sulfate-sodium chloride mixed salt; drying the obtained ammonium chloride filter cake and then directly using the ammonium chloride filter cake as a product, or using a saturated ammonium chloride solution at room temperature as a third refined liquid, adding the ammonium chloride filter cake into the third refined liquid according to a solid-to-liquid ratio of 1: 0.5-2.5 g/mL, stirring and refining for 0.5-2.5 h at 25-105 ℃, cooling to room temperature, filtering to obtain a refined liquid and a refined ammonium chloride product, returning the obtained refined liquid to be continuously used as the third refined liquid, performing closed cycle until any one of ammonium sulfate, sodium bicarbonate, sodium chloride and sodium sulfate is enriched to be close to saturation, opening a circuit, returning to the step I, combining with sodium sulfate and sodium chloride for comprehensive utilization, or returning a mixed solution for preparing a sodium sulfate-sodium chloride mixed salt.
The invention relates to a method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt, which comprises the step two of evaporating and concentrating CO released in the process of secondary crystallization mother liquor2And NH3Collecting the slurry or solution of the sodium sulfate-sodium chloride mixed salt used for synthesizing the ammonium bicarbonate or directly leading the mixed salt into the step I to be used as a resolving agent so as to improve the utilization rate of the ammonium bicarbonate.
The invention relates to a method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt, which comprises the following three steps,
in the ammonium chloride dissolving process, the ammonium bicarbonate included in the primary crystal and the mixture of the primary crystal and the secondary crystal is decomposed and volatilized NH in a saturated sodium bicarbonate solution at the temperature of 30-60 DEG C3And the ammonia is absorbed by dilute sulfuric acid or ammonium bisulfate solution to prevent the escape of the ammonia.
The invention relates to a method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt, which comprises the third step of adding a sodium bicarbonate filter cake into water or saturated sodium bicarbonate water solution according to a solid-to-liquid ratio of 1: 0.5-3.5 g/mL, stirring and washing for 0.5-2.5 h at 25-60 ℃, filtering to obtain washing sodium bicarbonate and washing liquid thereof, returning the obtained washing liquid to be continuously used as a washing liquid of the sodium bicarbonate filter cake, performing closed-loop circulation until any one of ammonium sulfate, ammonium chloride, sodium chloride and sodium sulfate is enriched to be close to saturation, performing open-loop circulation, and combining with the sodium sulfate and sodium chloride mixed solution in the first step for comprehensive utilization or preparing a dissolving solution of the sodium sulfate-sodium chloride mixed salt.
The invention relates to a method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt, which comprises the following steps that in the third step, pyrolysis is selected from dry pyrolysis or wet pyrolysis, and gas released in the pyrolysis process is directly introduced into slurry or solution of the sodium sulfate-sodium chloride mixed salt in the first step, so that the comprehensive utilization rate of raw and auxiliary materials is improved;
the dry pyrolysis refers to calcining the washed sodium bicarbonate filter cake at 150-300 ℃ for 0.25-1.25 h to convert sodium bicarbonate in the sodium bicarbonate filter cake into sodium carbonate;
the wet pyrolysis is to use a saturated sodium carbonate solution at a temperature of 25-60 ℃ as a wet pyrolysis agent, stir and add a washed sodium bicarbonate filter cake into the wet pyrolysis agent according to a solid-to-liquid ratio of 1: 0.5-5 g/mL, carry out heating decomposition, stir at a temperature of 65-250 ℃ for 0.5-2.5 h to convert the sodium bicarbonate filter cake into sodium carbonate, cool the sodium carbonate filter cake and the pyrolyzed solution to 25-60 ℃, filter the sodium carbonate filter cake and the pyrolyzed solution to obtain the pyrolyzed solution, return the pyrolyzed solution to be continuously used as the pyrolysis agent of the sodium bicarbonate, carry out closed cycle until sodium chloride or sodium sulfate in the pyrolyzed solution is enriched to be nearly saturated, open circuit, introduce CO2And (3) converting sodium carbonate into sodium bicarbonate, crystallizing, separating out, filtering, directly using a filter cake as a sodium bicarbonate product, or returning to pyrolysis to produce a sodium carbonate product, and returning the filtrate to the step I to be combined with a mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or to be used for preparing a dissolved solution of a mixed salt of sodium sulfate and sodium chloride.
In the comprehensive utilization process of the sodium sulfate-sodium chloride mixed salt and the solution thereof, the effective utilization rates of the sodium sulfate and the sodium chloride are both more than or equal to 97 percent.
The invention relates to a method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt, wherein the purity of a refined sodium carbonate product obtained in the technical process reaches 98-99.2%, the purity of a refined ammonium sulfate product reaches 98.5-99.6%, and the purity of a refined ammonium chloride product reaches 99.0-99.8%.
The invention relates to a method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt, which has the following basic principle:
NH3+H2O+CO2＝NH4HCO3 (1)
Na2SO4+2NH4HCO3＝2NaHCO3↓+(NH4)2SO4(2)
NaCl+NH4HCO3＝NaHCO3↓+NH4Cl↓(3)
compared with the prior art, the invention has the following advantages and effects:
the present invention uses sodium sulfate-sodium chloride mixed salt and its solution as raw material, uses ammonium hydrogen carbonate as resolving agent, and skillfully utilizes HCO as resolving agent3 -Ions and NH4 +The ion generates a homoionic effect to force Na in the solution+Ions and Cl-The ions are crystallized and separated out in the form of sodium bicarbonate and ammonium chloride, and by utilizing the multiphase crystallization-dissolution equilibrium relationship of the sodium bicarbonate, the ammonium sulfate, the ammonium chloride, the ammonium sulfate and the sodium chloride under different conditions, through gradient crystallization and reverse refining, sodium, sulfate radical and chlorine in the mixed salt are fully and effectively separated and utilized, three qualified products of sodium carbonate, ammonium sulfate and ammonium chloride are directly produced, wherein sodium carbonate (soda) is an important basic chemical raw material, ammonium sulfate is a popular agricultural fertilizer, the method solves the problem of overstocking and expanding the storehouse of the sodium sulfate-sodium chloride mixed salt in the metallurgy and chemical industry, has the advantages of simple process, high comprehensive utilization rate, good economic benefit, convenient operation and the like, and is suitable for industrial production of comprehensive utilization of the sodium sulfate-sodium chloride mixed salt and the solution thereof.
Detailed Description
The invention will now be further described with reference to the following examples, which are intended to illustrate the invention but not to limit it further.
Example 1
Sodium carbonate, ammonium sulfate and ammonium chloride are prepared by using sodium chloride and sodium sulfate as raw materials and using ammonium bicarbonate as a resolving agent. 210.01g of sodium chloride and 420.03g of anhydrous sodium sulfate are weighed, 700mL of water is added for mixing, stirring and heating are carried out until the temperature reaches 25 ℃, 827.32g of ammonium bicarbonate is added into the slurry in batches slowly, the reaction is continued for 1h at room temperature after the addition is finished, and then the mixture containing a large amount of sodium chloride is addedFreezing the reaction slurry of sodium bicarbonate and ammonium chloride crystals at-11 deg.C for 6h, further crystallizing, filtering to obtain 1001.6g of a mixture of primary crystals and secondary crystals and 643mL of secondary crystallization mother liquor containing Na+18.21g/L、Cl-16.17 g/L. The obtained secondary crystallization mother liquor is evaporated and concentrated to 250mL, cooled to room temperature and filtered to obtain 264.83g of tertiary crystals and 143mL of tertiary crystallization mother liquor. And returning the mother liquor of the third crystallization to a dissolving solution for preparing a mixed salt of sodium chloride and sodium sulfate, adding a saturated ammonium sulfate solution serving as a refined solution of the obtained third crystallization into the refined solution according to the solid-to-liquid ratio of 1:1g/mL, stirring and washing at 65 ℃ for 0.5h, cooling to room temperature, and centrifuging and drying to obtain 256.42g of a refined ammonium sulfate product with the purity of 99.5% and a washed solution thereof. And returning the obtained washing liquid to be continuously used as a refined liquid of the third-time crystal until any one of ammonium chloride, sodium carbonate and sodium sulfate in the washing liquid is enriched to be close to saturation, stopping recycling, opening a circuit, and combining the washing liquid and the purified waste water liquid for comprehensive utilization. And taking the obtained mixture of the primary crystal and the secondary crystal as a solution of ammonium chloride in a saturated sodium bicarbonate solution, adding the saturated sodium bicarbonate solution into the solution according to the solid-to-liquid ratio of 1:4g/mL, stirring at 55 ℃ for 1h to dissolve the ammonium chloride in the solution, and filtering while the solution is hot to obtain a sodium bicarbonate filter cake and an ammonium chloride solution. Leaching the obtained sodium bicarbonate filter cake with saturated sodium bicarbonate solution, drying, and pyrolyzing at 215 ℃ to obtain 508.9g of sodium carbonate product with the purity of 98.3 percent; cooling the obtained ammonium chloride solution, crystallizing at 5 ℃ for 2h, filtering to obtain ammonium chloride crystals and a crystallization mother liquor thereof, returning the crystallization mother liquor to be continuously used as the ammonium chloride solution until any one of ammonium sulfate, sodium chloride and sodium sulfate is enriched to be close to saturation, opening a circuit, and returning the solution for preparing sodium chloride and sodium sulfate; and adding the obtained ammonium chloride crystal into a saturated ammonium chloride solution according to the solid-to-liquid ratio of 1:1.5g/mL for refining, stirring at 85 ℃ for 0.5h, cooling to room temperature, and centrifuging and drying to obtain a refined ammonium chloride product with the purity of 99.6%. Returning the refined liquid to be used as the refined liquid of the ammonium chloride filter cake until any one of ammonium sulfate, sodium bicarbonate, sodium chloride and sodium sulfate is enriched to be close to saturation, stopping recycling, opening the circuit, and returningAnd recycling the solution for preparing a solution of sodium chloride and sodium sulfate. After the solution is recycled in the process, the effective utilization rates of the sodium sulfate and the sodium chloride are both high>98％。
Example 2
Using waste water produced in the course of catalyst production, purified and concentrated solution containing sodium sulfate and sodium chloride as raw material, in which the Na content is+142.08g/L、Cl-82.81g/L、SO4 2-184.42g/L, 2m3Purifying the concentrated solution, stirring at room temperature, slowly adding 1142.17kg ammonium bicarbonate, heating to 30 deg.C after adding ammonium bicarbonate, stirring for 1 hr, filtering to obtain primary crystal and primary crystallization mother liquor, freezing and crystallizing the primary crystallization mother liquor at-12.5 deg.C for 5 hr to force Na therein+And Cl-Further crystallizing and separating out in the form of sodium bicarbonate and ammonium chloride, and filtering to obtain a secondary crystal and a secondary crystallization mother liquor. The secondary crystallization mother liquor is evaporated and concentrated to 0.5m3Cooling, filtering to obtain a third crystal and a third crystal mother liquor, returning the third crystal mother liquor to be combined with the purified wastewater liquor for comprehensive utilization, using a saturated ammonium sulfate solution as a refined solution of the third crystal, adding the third crystal according to the solid-to-liquid ratio of 1:2g/mL, stirring and washing at 35 ℃ for 0.5h, filtering to obtain a washed solution and an agricultural ammonium sulfate fertilizer with the purity of 98.9%, returning the obtained washed solution to be continuously used as the refined solution of the third crystal until any one of ammonium chloride, sodium carbonate and sodium sulfate in the solution is enriched to be nearly saturated, stopping recycling, opening a circuit, returning the step to be combined with the purified wastewater concentrated solution for comprehensive utilization. Mixing the obtained primary crystal and secondary crystal, using saturated sodium bicarbonate solution as a dissolving solution of ammonium chloride, adding the mixture according to a solid-to-liquid ratio of 1:4g/mL, stirring at 59 ℃ for 1h, and filtering while hot to obtain a sodium bicarbonate filter cake and an ammonium chloride dissolving solution; stirring and washing the obtained sodium bicarbonate filter cake by using a saturated sodium bicarbonate solution, then using the saturated sodium bicarbonate solution as a wet pyrolysis agent, slowly adding the wet pyrolysis agent into the wet pyrolysis agent in batches according to the solid-to-liquid ratio of 1:1.5g/mL, stirring for 1.5h at 110 ℃ to carry out wet pyrolysis, filtering and drying the filter cake at 250 ℃ to obtain an anhydrous sodium carbonate product with the purity of 99.6 percentThe filtrate is returned to be continuously used as a pyrolysis agent of the sodium bicarbonate; cooling the obtained ammonium chloride solution, crystallizing at 3 ℃ for 1.5h, and filtering to obtain ammonium chloride crystals and crystallization mother liquor thereof; the obtained crystallization mother liquor is returned to be continuously used as a dissolving solution of ammonium chloride until any one of ammonium sulfate, sodium chloride and sodium sulfate is enriched to be close to saturation, and the crystallization mother liquor is opened and returned to be combined with the wastewater purification concentrated solution for comprehensive utilization; and (3) taking a saturated ammonium chloride solution as a refined solution of the ammonium chloride crystal, adding the ammonium chloride crystal into the solution according to a solid-to-liquid ratio of 1:1g/mL, stirring and refining the solution at 65 ℃ for 0.5h, cooling the solution to room temperature, filtering the solution to obtain a refined solution and a refined ammonium chloride product with the purity of 99.3%, returning the refined solution to be continuously used as the refined solution of an ammonium chloride filter cake until any one of ammonium sulfate, sodium bicarbonate, sodium chloride and sodium sulfate is enriched to be close to saturation, stopping the cyclic use, opening a circuit, returning the mixture to be combined with the wastewater purification concentrated solution for comprehensive utilization. After the solution in the technical process is recycled, Na in the purified wastewater+Ions, SO4 2-Ions and Cl-The effective utilization rates of the ions are 97.5%, 98.2% and 98.8% respectively.
Example 3
The method is characterized in that a mixed sodium salt of earthy yellow sodium sulfate and sodium chloride with peculiar smell obtained by purifying zinc smelting wastewater is used as a raw material, wherein Na is2SO4And NaCl content was 78.62% and 12.08%, respectively. Firstly, heating the mixed sodium salt in the air to 350 ℃ to carbonize the organic matters in the mixed sodium salt, cooling to 60 ℃, stirring, adding the mixture into water to dissolve the mixture to obtain Na+And (3) adding sodium carbonate into the dissolved solution with the ion concentration of 151.16g/L to adjust the pH value to 8.6, and filtering to remove solid suspended substances to obtain clear purified liquid. Taking 3L of purified liquid, and adding CO2/NH3Using mixed gas with the molar ratio of 1.03:1 as a resolving agent, stirring and slowly blowing the resolving agent into purified liquid at 15 ℃ until NH is obtained3/Na+The molar ratio is increased to 1.06:1, the blowing of the mixed gas is stopped, the stirring is continued for 1h, the slurry is split and filtered to obtain a primary crystal and a primary crystallization mother liquor, and then the primary crystallization mother liquor is frozen and crystallized for 4h at the temperature of-14.5 ℃, so that Na in the primary crystallization mother liquor is forced to be dissolved+And Cl-Further crystallizing and separating out in the form of sodium bicarbonate and ammonium chloride, and filtering to obtain a secondary crystal and a secondary crystallization mother liquor. Evaporating and concentrating the secondary crystallization mother liquor to 600mL, cooling, filtering to obtain a tertiary crystal and a tertiary crystallization mother liquor, returning the tertiary crystallization mother liquor to a dissolving solution for preparing mixed sodium salt, taking a saturated ammonium sulfate solution as a refined solution of the tertiary crystal, adding the tertiary crystal according to the solid-to-liquid ratio of 1:1.5g/mL, stirring and washing at 85 ℃ for 1h, cooling to room temperature, filtering to obtain a washed solution and a refined ammonium sulfate product with the purity of 99.3%, returning the obtained washed solution to be continuously used as the refined solution of an ammonium sulfate filter cake until any one of ammonium chloride, sodium carbonate and sodium sulfate is enriched to be nearly saturated, stopping recycling, opening a path, returning and combining with the purified solution for comprehensive utilization. Returning the obtained secondary crystal to be stirred and added into the next batch of split slurry for comprehensive recovery, taking a saturated sodium bicarbonate solution as a dissolving solution of ammonium chloride in the obtained primary crystal, adding the primary crystal into the saturated sodium bicarbonate solution according to the solid-to-liquid ratio of 1:5g/mL, stirring for 1h at 50 ℃, and filtering while hot to obtain a sodium bicarbonate filter cake and an ammonium chloride dissolving solution; stirring and washing the obtained sodium bicarbonate filter cake by using a saturated sodium bicarbonate solution, carrying out dry pyrolysis at 185 ℃ to obtain a sodium carbonate product with the purity of 99.1%, cooling the obtained ammonium chloride solution, crystallizing for 2.5h at 1 ℃, and filtering to obtain an ammonium chloride filter cake and an ammonium chloride crystallization mother liquor; drying the obtained ammonium chloride filter cake to obtain the agricultural ammonium chloride fertilizer containing 25.5 percent of N, returning the obtained ammonium chloride crystallization mother liquor to be continuously used as a dissolving solution of ammonium chloride until any one of ammonium sulfate, sodium chloride and sodium sulfate is enriched to be close to saturation, opening a circuit, returning and combining with the purified liquor for comprehensive utilization. After the solution is recycled in the process, the effective utilization rates of sodium sulfate and sodium chloride in the mixed sodium salt are respectively 98.5 percent and 97.6 percent.
Claims (8)
1. A method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt is characterized by comprising the following steps:
the method comprises the following steps: removing sodium and precipitating chlorine
Using slurries or solutions of mixed salts of sodium sulphate-sodium chlorideUsing ammonium bicarbonate, or CO, as a raw material2/NH3The mixed gas of (A) is used as a resolving agent, and ammonium bicarbonate or CO is used as2/NH3Adding the mixed gas into the slurry or solution of the sodium sulfate-sodium chloride mixed salt, stirring, and using HCO3 -Ions and NH4 +The ion generates a homoionic effect to force Na in the solution+And Cl-Crystallizing out in the form of sodium bicarbonate and ammonium chloride respectively to obtain slurry, and then treating by adopting any one of the following two modes:
(1) filtering the obtained slurry to obtain a primary crystal and a primary crystallization mother liquor, freezing the primary crystallization mother liquor, further crystallizing, and filtering to obtain a secondary crystal and a secondary crystallization mother liquor;
(2) freezing the obtained slurry, further crystallizing, and filtering to obtain a mixture of primary crystals and secondary crystals and a secondary crystallization mother liquor;
step two: separating and recovering ammonium sulfate
Evaporating and concentrating the secondary crystallization mother liquor obtained in the first step to crystallize and separate 45% -85% of ammonium sulfate, filtering to obtain a tertiary crystal and a tertiary crystallization mother liquor, returning the tertiary crystallization mother liquor to the first step to be combined with a mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning a dissolving solution for preparing a sodium sulfate-sodium chloride mixed salt, drying the obtained tertiary crystal and then directly using the dried tertiary crystal as an agricultural ammonium sulfate fertilizer, or using a saturated ammonium sulfate solution as a first refined solution, adding the tertiary crystal into the tertiary crystal, heating, stirring, washing, cooling, and filtering to obtain a washed solution and a refined ammonium sulfate product;
step three: separating and recovering sodium carbonate and ammonium chloride
Adding the primary crystal obtained in the step one or the mixture of the primary crystal and the secondary crystal into a saturated sodium bicarbonate solution serving as a second refined solution, heating, stirring and refining to dissolve ammonium chloride, ammonium sulfate, sodium chloride and sodium sulfate into the solution, filtering while hot to obtain a sodium bicarbonate filter cake and an ammonium chloride dissolved solution, washing the sodium bicarbonate filter cake again, then thermally decomposing to obtain a refined sodium carbonate product, cooling the obtained ammonium chloride dissolved solution, crystallizing, and filtering to obtain an ammonium chloride filter cake and an ammonium chloride crystallization mother solution; returning the obtained ammonium chloride crystallization mother liquor to be continuously used as a second refined solution, performing closed cycle until any one of ammonium sulfate, sodium chloride and sodium sulfate is enriched to be close to saturation, opening a circuit, returning to the step I, combining with the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning to a dissolving solution for preparing sodium sulfate-sodium chloride mixed salt; drying the obtained ammonium chloride filter cake and then directly using the dried ammonium chloride filter cake as a product, or using a saturated ammonium chloride solution as a third refined solution, adding the ammonium chloride filter cake into the third refined solution, heating, stirring, refining, cooling, filtering to obtain a refined solution and a refined ammonium chloride product, returning the refined solution to be continuously used as the third refined solution, performing closed cycle until any one of ammonium sulfate, sodium bicarbonate, sodium chloride and sodium sulfate is enriched to be close to saturation, opening the circuit, returning to the step I, mixing the solution with a mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning to a dissolved solution for preparing a sodium sulfate-sodium chloride mixed salt.
2. The method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt according to claim 1, characterized in that the technological process and technological conditions are as follows:
in the first step of the method,
the raw material is SO4 2-/Cl-The sodium sulfate-sodium chloride mixed salt slurry or solution with the molar ratio of 0.1-50 is used as a raw material, and the sodium sulfate-sodium chloride mixed salt is added into water to prepare Na+A solution with an ion concentration of 90-162 g/L, or Na+Mixing sodium sulfate-sodium chloride mixed salt with water to prepare slurry or directly taking solution containing sodium sulfate and sodium chloride as raw materials, purifying and concentrating to obtain Na+The ion concentration reaches 90-162 g/L;
NH control with ammonium bicarbonate as resolving agent4 +/Na+Stirring ammonium bicarbonate into slurry or solution of sodium sulfate-sodium chloride mixed salt, wherein the molar ratio is 1.05-1.25: 1;
with CO2/NH3As a resolving agent, wherein CO2/NH3Molar ratio of1 to 1.1:1, control of NH3/Na+Blowing mixed gas into the slurry or solution of the sodium sulfate-sodium chloride mixed salt or blowing NH into the slurry or solution of the sodium sulfate-sodium chloride mixed salt at a molar ratio of 1.05-1.25: 13Then according to CO2/NH3Blowing CO at the molar ratio of 1-1.1: 12；
Adding a resolving agent, stirring for 0.5-2.5 h at the temperature of 1-40 ℃, and using HCO3 -Ions and NH4 +The ion generates a homoionic effect to force Na in the solution+And Cl-Crystallizing and separating out in the form of sodium bicarbonate and ammonium chloride respectively, filtering to obtain a primary crystal and a primary crystallization mother liquor, then placing the primary crystallization mother liquor at the temperature of-18-0 ℃ for freezing and crystallizing for 2-6 h, filtering to obtain a secondary crystal and a secondary crystallization mother liquor, or directly placing the slurry containing crystals obtained after the separation at the temperature of-18-0 ℃ for freezing, continuing crystallizing for 2-6 h, and filtering to obtain a mixture of the primary crystal and the secondary crystallization mother liquor;
in the second step, the first step is carried out,
taking saturated ammonium sulfate solution at room temperature as first refined liquid, adding three-time crystals according to a solid-to-liquid ratio of 1: 0.3-3 g/mL, stirring and washing at 25-95 ℃ for 0.5-1 h, cooling to room temperature, filtering to obtain washed liquid and a refined ammonium sulfate product, returning the washed liquid to be continuously used as the first refined liquid, performing closed cycle until any one of ammonium chloride, sodium carbonate and sodium sulfate is enriched to be close to saturation, opening the circuit, returning to the step I, combining with mixed liquid of sodium sulfate and sodium chloride for comprehensive utilization, or returning to dissolved liquid for preparing sodium sulfate-sodium chloride mixed salt;
in the third step, the first step is that,
adding a primary crystal or a mixture of the primary crystal and a secondary crystal into a second refined solution by using a saturated sodium bicarbonate solution at the temperature of-5-25 ℃ as the second refined solution according to a solid-to-liquid ratio of 1: 0.5-5 g/mL, stirring for 0.5-1 h at the temperature of 40-64 ℃ to dissolve ammonium chloride, ammonium sulfate, sodium chloride and sodium sulfate in the solution, filtering while hot to obtain a sodium bicarbonate filter cake and a solution containing ammonium chloride, washing the sodium bicarbonate filter cake, then performing pyrolysis to obtain a qualified sodium carbonate product, cooling the obtained solution, crystallizing for 0.5-2.5 h at the temperature of-5-25 ℃, and filtering to obtain an ammonium chloride filter cake and an ammonium chloride crystal mother solution; returning the obtained ammonium chloride crystallization mother liquor to be continuously used as a second refined solution, performing closed cycle until any one of ammonium sulfate, sodium chloride and sodium sulfate is enriched to be close to saturation, opening the circuit, returning to the step I, mixing with the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning to a dissolving solution for preparing sodium sulfate-sodium chloride mixed salt; drying the obtained ammonium chloride filter cake and then directly using the ammonium chloride filter cake as a product, or using a saturated ammonium chloride solution at room temperature as a third refined liquid, adding the ammonium chloride filter cake into the third refined liquid according to a solid-to-liquid ratio of 1: 0.5-2.5 g/mL, stirring and refining for 0.5-2.5 h at 25-105 ℃, cooling to room temperature, filtering to obtain a refined liquid and a refined ammonium chloride product, returning the obtained refined liquid to be continuously used as the third refined liquid, performing closed cycle until any one of ammonium sulfate, sodium bicarbonate, sodium chloride and sodium sulfate is enriched to be close to saturation, opening a circuit, returning to the step I, combining the refined liquid with a mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning to a dissolved solution for preparing a mixed salt of sodium sulfate and sodium chloride.
3. The method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt according to claim 1 or 2, characterized in that: in the second step, CO released in the evaporation concentration process of the secondary crystallization mother liquor2And NH3Collecting the slurry or solution used for synthesizing the ammonium bicarbonate or directly introducing the sodium sulfate-sodium chloride mixed salt in the step one as a resolving agent so as to improve the utilization rate of the ammonium bicarbonate.
4. The method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt according to claim 1 or 2, characterized in that: in the third step, in the ammonium chloride dissolving process, the ammonium bicarbonate included in the primary crystal and the mixture of the primary crystal and the secondary crystal is decomposed and volatilized NH in a saturated sodium bicarbonate solution at the temperature of 30-60 DEG C3And the ammonia is absorbed by dilute sulfuric acid or ammonium bisulfate solution to prevent the escape of the ammonia.
5. The method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt according to claim 1 or 2, characterized in that: and in the third step, the washing is to add the sodium bicarbonate filter cake into water or a saturated sodium bicarbonate water solution according to a solid-to-liquid ratio of 1: 0.5-3.5 g/mL, stir and wash the sodium bicarbonate filter cake for 0.5-2.5 h at 25-60 ℃, filter the sodium bicarbonate and a washed liquid thereof to obtain a washed liquid, return the washed liquid to be continuously used as a washing liquid of the sodium bicarbonate filter cake, circulate the washed liquid in a closed loop until any one of ammonium sulfate, ammonium chloride, sodium chloride and sodium sulfate is enriched to be close to saturation, open the loop, combine the washed liquid with the sodium sulfate and sodium chloride mixed liquid in the first step for comprehensive utilization, or prepare a solution of sodium sulfate-sodium chloride mixed salt.
6. The method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt according to claim 1 or 2, characterized in that: in the third step, the pyrolysis is selected from dry pyrolysis or wet pyrolysis, and gas released in the pyrolysis process is directly introduced into the slurry or the solution of the sodium sulfate-sodium chloride mixed salt in the first step, so that the comprehensive utilization rate of the raw and auxiliary materials is improved;
the dry pyrolysis refers to calcining the washed sodium bicarbonate filter cake at 150-300 ℃ for 0.25-1.25 h to convert sodium bicarbonate in the sodium bicarbonate filter cake into sodium carbonate;
the wet pyrolysis is to use a saturated sodium carbonate solution at a temperature of 25-60 ℃ as a wet pyrolysis agent, stir and add a washed sodium bicarbonate filter cake into the wet pyrolysis agent according to a solid-to-liquid ratio of 1: 0.5-5 g/mL, carry out heating decomposition, stir at a temperature of 65-250 ℃ for 0.5-2.5 h, convert the sodium bicarbonate filter cake into sodium carbonate, cool the sodium carbonate filter cake and the pyrolyzed solution to 25-60 ℃, filter the sodium carbonate filter cake and the pyrolyzed solution to obtain the pyrolyzed solution, return the pyrolyzed solution to be continuously used as the pyrolysis agent of the sodium bicarbonate, carry out closed cycle until sodium chloride or sodium sulfate in the pyrolyzed solution is enriched to be close to saturation, open circuit, introduce CO2Converting sodium carbonate into sodium bicarbonate crystals, separating out the sodium bicarbonate crystals, filtering, directly using filter cakes as sodium bicarbonate products, or returning to pyrolysis to produce sodium carbonate products, and returning filtrate to the first step to be combined with sodium sulfate and sodium chloride mixed solution for comprehensive utilization, or being used for preparing sodium sulfate-sodium chloride mixed salt dissolving solution.
7. The method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt according to claim 1 or 2, characterized in that: in the process of comprehensively utilizing the sodium sulfate-sodium chloride mixed salt and the solution thereof, the effective utilization rates of the sodium sulfate and the sodium chloride are both more than or equal to 97 percent.
8. The method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt as claimed in claims 1 to 7, which is characterized in that: the purity of the refined sodium carbonate product obtained in the process reaches 98-99.2%, the purity of the refined ammonium sulfate product reaches 98.5-99.6%, and the purity of the refined ammonium chloride product reaches 99.0-99.8%.
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