CN114538471B - Comprehensive utilization method of sodium sulfate-sodium chloride mixed salt - Google Patents
Comprehensive utilization method of sodium sulfate-sodium chloride mixed salt Download PDFInfo
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- CN114538471B CN114538471B CN202210034244.6A CN202210034244A CN114538471B CN 114538471 B CN114538471 B CN 114538471B CN 202210034244 A CN202210034244 A CN 202210034244A CN 114538471 B CN114538471 B CN 114538471B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/244—Preparation by double decomposition of ammonium salts with sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/12—Preparation of carbonates from bicarbonates or bicarbonate-containing product
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
Abstract
The invention discloses a method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt, which takes sodium sulfate-sodium chloride mixed salt and solution thereof as raw materials, ammonium bicarbonate as resolving agent and skillfully utilizes HCO 3 ‑ Ions and NH 4 + The homoionic effect of the ions 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 gradient crystallization and reverse refining by utilizing the multiphase crystallization-dissolution balance relation of sodium bicarbonate, ammonium sulfate, ammonium chloride, ammonium sulfate and sodium chloride under different conditions, so that three qualified products of sodium carbonate, ammonium sulfate and ammonium chloride are directly produced.
Description
Technical Field
The invention belongs to the fields of chemical industry and environmental protection, and particularly relates to a method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt.
Background
The mixed salt of sodium sulfate and sodium chloride is solid waste obtained by treating chlorine-containing materials with sulfuric acid or sulfate-containing materials with hydrochloric acid, and treating waste water containing sodium sulfate and sodium chloride discharged from reaction materials with sulfuric acid and hydrochloric acid or sodium chloride, purifying, removing impurities, evaporating and concentrating. 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 the like, sediment and the like besides sulfur, sodium and chlorine. Waste salts generated in the chemical and metallurgical production process have been listed in the national hazardous waste directory passed in 2016. It is known that sodium sulfate and sodium chloride are both inexpensive sodium salts, and there is no economic benefit in separating and recovering sodium sulfate and sodium chloride from a sodium sulfate-sodium chloride mixed salt. Therefore, many metallurgical and chemical enterprises face an extremely embarrassing situation at present, the waste water generated in the production process is not purified and the purified sodium sulfate-sodium chloride mixed salt cannot find a market. Therefore, the sodium sulfate-sodium chloride mixed salt obtained by wastewater purification can only be built up and piled up, the stock pressure is increased along with the time, and sodium sulfate and sodium chloride are materials which are easy to dissolve in water, so that secondary pollution is 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:
step one: sodium removal and chlorine precipitation
Using slurry or solution of sodium sulfate-sodium chloride mixed salt as raw material, using ammonium bicarbonate or CO 2 /NH 3 The mixed gas of ammonium bicarbonate or CO is used as a resolving agent 2 /NH 3 Adding the mixed gas of sodium sulfate and sodium chloride into slurry or solution of mixed salt, stirring, and utilizing HCO 3 - Ions and NH 4 + The homoionic effect of the ions forces Na therein + And Cl - Crystallizing and separating out the slurry in the forms of sodium bicarbonate and ammonium chloride respectively to obtain slurry, and then treating the slurry in any one of the following two modes:
(1) Filtering the obtained slurry to obtain primary crystals and primary crystallization mother liquor, freezing the primary crystallization mother liquor, further crystallizing, and filtering to obtain secondary crystals and secondary crystallization mother liquor;
(2) Freezing the obtained slurry, crystallizing, and filtering to obtain a mixture of primary crystals and secondary crystallization mother liquor;
step two: separating and recovering ammonium sulfate
Evaporating and concentrating the secondary crystallization mother liquor obtained in the step one to separate out 45% -85% of ammonium sulfate crystals, filtering to obtain a tertiary crystal and a tertiary crystallization mother liquor, returning the tertiary crystallization mother liquor to the step one to be combined with the mixed liquor of sodium sulfate and sodium chloride for comprehensive utilization, or returning the solution for preparing the mixed salt of sodium sulfate and sodium chloride, drying the obtained tertiary crystal and directly using the dried tertiary crystal as an agricultural ammonium sulfate fertilizer, or using saturated ammonium sulfate solution as a first refined solution, adding the tertiary crystal into the solution, 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 or the mixture of the primary crystal and the secondary crystal obtained in the step one into a saturated sodium bicarbonate solution serving as a second refined solution, heating and stirring for refining to dissolve ammonium chloride, ammonium sulfate, sodium chloride and sodium sulfate into the solution, filtering while the solution is hot to obtain a sodium bicarbonate filter cake and ammonium chloride solution, washing the sodium bicarbonate filter cake again, pyrolyzing the sodium bicarbonate filter cake to obtain a refined sodium carbonate product, cooling the obtained ammonium chloride solution, crystallizing, and filtering to obtain an ammonium chloride filter cake and an ammonium chloride crystallization mother solution; the obtained ammonium chloride crystallization mother liquor is returned to be continuously used as a second refined solution, and is circulated in a closed circuit until any one of ammonium sulfate, sodium chloride and sodium sulfate is enriched to be close to saturation, and is opened, and the ammonium chloride crystallization mother liquor is returned to be combined with the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization in the step one or is returned to be used for preparing the solution of the sodium sulfate-sodium chloride mixed salt; the obtained ammonium chloride filter cake is directly used as a product after being dried, or a saturated ammonium chloride solution is used as a third refined solution, the ammonium chloride filter cake is added into the product, heating, stirring and refining are carried out, cooling is carried out, the refined solution and the refined ammonium chloride product are obtained after filtering, the obtained refined solution is returned to be continuously used as the third refined solution, the circulation is closed until any one of ammonium sulfate, sodium bicarbonate, sodium chloride and sodium sulfate is enriched to be close to saturation, the circulation is opened, and the first step is returned to be combined with the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or the solution for preparing sodium sulfate-sodium chloride mixed salt is returned.
Further, the method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt comprises the following technical processes and conditions:
in the first step, the first step is to perform,
the raw material is SO 4 2- /Cl - The slurry or solution of sodium sulfate-sodium chloride mixed salt with the molar ratio of 0.1-50 is used as raw material, and the sodium sulfate-sodium chloride mixed salt is added into water to prepare Na + Ion concentrationSolutions with a degree of 90-162 g/L, or Na + Mixing sodium sulfate-sodium chloride mixed salt with water to obtain slurry or directly using sodium sulfate-sodium chloride-containing solution as raw material, purifying and concentrating to obtain Na + The ion concentration reaches 90-162 g/L;
ammonium bicarbonate is used as resolving agent to control NH 4 + /Na + The molar ratio is 1.05-1.25:1, and ammonium bicarbonate is added into slurry or solution of sodium sulfate-sodium chloride mixed salt by stirring;
by CO 2 /NH 3 Wherein CO is used as a resolving agent 2 /NH 3 The molar ratio is 1-1.1:1, and NH is controlled 3 /Na + The mixed gas is blown into the slurry or the solution of the mixed salt of sodium sulfate and sodium chloride with the molar ratio of 1.05-1.25:1, or NH is blown into the slurry or the solution first 3 Then according to CO 2 /NH 3 CO is blown in according to the mol ratio of 1-1.1:1 2 ；
Adding resolving agent, stirring at 1-40deg.C for 0.5-2.5 hr, and using HCO 3 - Ions and NH 4 + The homoionic effect of the ions forces Na therein + And Cl - Crystallizing and separating out the primary crystallization and primary crystallization mother liquor in the form of sodium bicarbonate and ammonium chloride respectively, filtering to obtain primary crystallization and primary crystallization mother liquor, then placing the primary crystallization mother liquor at the temperature of-18-0 ℃ for freezing and crystallizing for 2-6 hours, filtering to obtain secondary crystallization and secondary crystallization mother liquor, or directly placing the slurry containing crystals obtained after resolution at the temperature of-18-0 ℃ for freezing, continuing to crystallize for 2-6 hours, filtering to obtain a mixture of the primary crystallization and the secondary crystallization and secondary crystallization mother liquor;
in the second step, the second step is to carry out the process,
adding the tertiary crystal into the saturated ammonium sulfate solution at room temperature according to the solid-to-liquid ratio of 1:0.3-3 g/mL, stirring and washing for 0.5-1 h at 25-95 ℃, cooling to room temperature, filtering to obtain a washed solution and a refined ammonium sulfate product, returning the obtained washed solution to be continuously used as the first refined solution, carrying out closed circulation until any one of ammonium chloride, sodium carbonate and sodium sulfate is enriched to be close to saturation, carrying out open circuit, returning to the step I, combining the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning to the solution for preparing sodium sulfate-sodium chloride mixed salt;
in the third step, the first step is performed,
adding primary crystals or a mixture of the primary crystals and the secondary crystals into saturated sodium bicarbonate solution with the solid-to-liquid ratio of 1:0.5-5 g/mL serving as second refined solution, stirring for 0.5-1 h at the temperature of 40-64 ℃ to dissolve ammonium chloride, ammonium sulfate, sodium chloride and sodium sulfate into the solution, filtering while the solution is hot to obtain a sodium bicarbonate filter cake and a solution containing ammonium chloride, washing and pyrolyzing the sodium bicarbonate filter cake to obtain qualified sodium carbonate products, cooling the 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 crystallization mother solution; the obtained ammonium chloride crystallization mother liquor is returned to be continuously used as a second refined solution, and is circulated in a closed circuit until any one of ammonium sulfate, sodium chloride and sodium sulfate is enriched to be close to saturation, and is opened, and the ammonium chloride crystallization mother liquor is returned to be combined with the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization in the step one or is returned to be used for preparing the solution of the sodium sulfate-sodium chloride mixed salt; the obtained ammonium chloride filter cake is directly used as a product after being dried, or saturated ammonium chloride solution is used as a third refined solution, the ammonium chloride filter cake is added into the third refined solution according to the solid-to-liquid ratio of 1:0.5-2.5 g/mL, the mixture is stirred and refined for 0.5-2.5 h at the temperature of 25-105 ℃, the mixture is cooled to the room temperature, the refined solution and the refined ammonium chloride product are obtained after filtration, the refined solution is returned to be continuously used as the third refined solution, the circulation is closed until any one of ammonium sulfate, sodium bicarbonate, sodium chloride and sodium sulfate is enriched to be close to saturation, the circulation is opened, and the first step is returned to be combined with the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or the solution for preparing sodium sulfate-sodium chloride mixed salt is returned.
The invention relates to a method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt, which comprises the following steps of evaporating and concentrating secondary crystallization mother liquor to release CO 2 And NH 3 Collecting the slurry or solution of sodium sulfate-sodium chloride mixed salt used for synthesizing ammonium bicarbonate or directly introducing the slurry or solution into the step one 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, in the step three,
ammonium chloride dissolving process, in which ammonium bicarbonate mixed in primary crystal and mixture of primary crystal and secondary crystal is decomposed and volatilized into NH in 30-60 deg.C saturated sodium bicarbonate solution 3 Absorbing with dilute sulfuric acid or ammonium bisulfate solution to prevent ammonia from escaping.
The invention relates to a method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt, which comprises the following steps of adding sodium bicarbonate filter cakes into water or saturated sodium bicarbonate aqueous 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 washed sodium bicarbonate and washing liquid thereof, returning the obtained washing liquid to be continuously used as washing liquid of the sodium bicarbonate filter cakes, and carrying out closed cycle until any one of ammonium sulfate, ammonium chloride, sodium chloride and sodium sulfate is enriched to be close to saturation, carrying out open circuit, and combining with the sodium sulfate and sodium chloride mixed liquid in the step one for comprehensive utilization, or preparing solution of the sodium sulfate-sodium chloride mixed salt.
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 slurry or solution of the sodium sulfate-sodium chloride mixed salt in the first step so as to improve the comprehensive utilization rate of raw materials and auxiliary materials;
the dry pyrolysis is that the washed sodium bicarbonate filter cake is calcined for 0.25 to 1.25 hours at the temperature of between 150 and 300 ℃ so that sodium bicarbonate in the filter cake is converted into sodium carbonate;
the wet pyrolysis is to use a saturated sodium carbonate solution at 25-60 ℃ as a wet pyrolysis agent, stir and add the washed sodium bicarbonate filter cake into the solution according to a solid-to-liquid ratio of 1:0.5-5 g/mL, heat and decompose the sodium bicarbonate filter cake, stir the solution for 0.5-2.5 h at 65-250 ℃ to convert the sodium bicarbonate filter cake into sodium carbonate, cool the sodium carbonate filter cake to 25-60 ℃, filter the sodium carbonate filter cake to obtain a sodium carbonate filter cake and a pyrolyzed solution, and return the pyrolyzed solution to be continuously used as the pyrolyzing agent of sodium bicarbonate until the sodium chloride or sodium sulfate in the pyrolyzed solution is enriched to be close to saturation, open-circuit and introduce CO 2 Converting sodium carbonate into sodium bicarbonate for crystallization, filteringThe cake is directly used as sodium bicarbonate product, or returned to pyrolysis to produce sodium carbonate product, and the filtrate is returned to the first step to be combined with the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or used for preparing the solution of the mixed salt of sodium sulfate and sodium chloride.
The invention relates to a method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt, wherein the effective utilization rate of sodium sulfate and sodium chloride is more than or equal to 97 percent in the technical process of comprehensively utilizing the sodium sulfate-sodium chloride mixed salt and solution thereof.
The method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt has the technical process that the purity of the refined sodium carbonate product is 98-99.2 percent, the purity of the refined ammonium sulfate product is 98.5-99.6 percent, and the purity of the refined ammonium chloride product is 99.0-99.8 percent.
The invention relates to a method for comprehensively utilizing sodium sulfate-sodium chloride mixed salt, which comprises the following basic principles:
NH 3 +H 2 O+CO 2 ＝NH 4 HCO 3 (1)
Na 2 SO 4 +2NH 4 HCO 3 ＝2NaHCO 3 ↓+(NH 4 ) 2 SO 4 (2)
NaCl+NH 4 HCO 3 ＝NaHCO 3 ↓+NH 4 Cl↓(3)
compared with the prior art, the invention has the following advantages and effects:
the existing technology is to separate sodium sulfate from sodium chloride, then to produce sodium carbonate with sodium sulfate or sodium chloride as material, and the present invention uses sodium sulfate-sodium chloride mixed salt and its solution as material, ammonium bicarbonate as resolving agent and HCO as well as other materials 3 - Ions and NH 4 + The homoionic effect of the ions forces Na therein + Ions and Cl - The ions are crystallized and separated out in the form of sodium bicarbonate and ammonium chloride, and are reversely refined by gradient crystallization by utilizing the multiphase crystallization-dissolution equilibrium relationship of sodium bicarbonate, ammonium sulfate, ammonium chloride, ammonium sulfate and sodium chloride under different conditionsThe method has the advantages of fully and effectively separating and utilizing sodium, sulfate radical and chlorine in the mixed salt, directly producing three qualified products of sodium carbonate, ammonium sulfate and ammonium chloride, wherein sodium carbonate (sodium carbonate) is an important basic chemical raw material, and ammonium sulfate is a popular agricultural fertilizer, solving the problem of the accumulation and expansion of the sodium sulfate-sodium chloride mixed salt in the metallurgical and chemical industries, along with simple process, high comprehensive utilization rate, good economic benefit, convenient operation and the like, and being suitable for industrial production of the sodium sulfate-sodium chloride mixed salt and solution thereof.
Detailed Description
The invention is further described in connection with the following examples which are intended to illustrate the invention and are not intended to be limiting.
Example 1
Sodium chloride and sodium sulfate are used as raw materials, and ammonium bicarbonate is used as a resolving agent to prepare sodium carbonate, ammonium sulfate and ammonium chloride. 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 to 25 ℃, 827.32g of ammonium bicarbonate is slowly added into the slurry in batches, reaction is continued for 1h at room temperature after the addition is finished, then the reaction slurry containing a large amount of sodium bicarbonate and ammonium chloride crystals is frozen for 6h at-11 ℃, further crystallization is carried out, 1001.6g of a mixture of primary crystals and secondary crystals and 643mL of secondary crystallization mother liquor are obtained through filtration, and Na is contained in the secondary crystallization mother liquor + 18.21g/L、Cl - 16.17g/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 crystal and 143mL of tertiary crystallization mother liquor. And returning the tertiary crystallization mother liquor to a solution for preparing mixed salt of sodium chloride and sodium sulfate, adding the tertiary crystallization mother liquor into the refined solution by using saturated ammonium sulfate solution as the refined solution according to the solid-to-liquid ratio of 1:1g/mL, stirring and washing for 0.5h at 65 ℃, cooling to room temperature, and performing centrifugal drying to obtain 256.42g of refined ammonium sulfate product with the purity of 99.5% and washing liquid thereof. The obtained washed liquid is returned to be continuously used as the refined liquid of the tertiary crystal until any one of ammonium chloride, sodium carbonate and sodium sulfate is enriched to be close to saturation, the cyclic use is stopped, the circuit is opened, and the return step is combined with the purified liquid of the wastewaterAnd comprehensively utilizing the materials together. The obtained mixture of the primary crystal and the secondary crystal is taken as a solution of ammonium chloride, and is added into the solution according to the solid-to-liquid ratio of 1:4g/mL, and is stirred for 1h at 55 ℃ to dissolve the ammonium chloride therein, and the sodium bicarbonate filter cake and the ammonium chloride solution are obtained by filtering while the mixture is hot. Leaching and spin-drying the obtained sodium bicarbonate filter cake by using a saturated sodium bicarbonate solution, and pyrolyzing at 215 ℃ to obtain 508.9g of sodium carbonate product with the purity of 98.3%; cooling the obtained ammonium chloride solution, crystallizing for 2 hours at 5 ℃, 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, and returning the ammonium chloride crystal and the crystallization mother liquor to be used for preparing the sodium chloride and the sodium sulfate solution; and adding the obtained ammonium chloride crystal into 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%. The refined solution is returned to be continuously used as refined solution of ammonium chloride filter cake until any one of ammonium sulfate, sodium bicarbonate, sodium chloride and sodium sulfate is enriched to be close to saturation, the cyclic use is stopped, and the solution is returned to be used for preparing sodium chloride and sodium sulfate. After the solution is recycled in the process, the effective utilization rate of sodium sulfate and sodium chloride is both>98％。
Example 2
Purifying and concentrating the waste water generated in the catalyst production process to obtain sodium sulfate-and sodium chloride-containing solution as raw material, wherein the solution contains Na + 142.08g/L、Cl - 82.81g/L、SO 4 2- 184.42g/L, 2m 3 Purifying the concentrated solution, stirring at room temperature, slowly adding ammonium bicarbonate 1142.17kg in batches, heating to 30deg.C after adding ammonium bicarbonate, stirring for 1 hr, filtering to obtain primary crystal and primary crystallization mother liquor, and freeze crystallizing at-12.5deg.C for 5 hr to force Na therein + And Cl - Further crystallizing and separating out sodium bicarbonate and ammonium chloride, and filtering to obtain secondary crystal and secondary crystallization mother liquor. Evaporating and concentrating the secondary crystallization mother liquor to 0.5m 3 Cooling, filtering to obtain three crystals and threeAnd (3) returning the secondary crystallization mother liquor, merging the secondary crystallization mother liquor with the purified wastewater liquid for comprehensive utilization, adding the secondary crystallization into the secondary crystallization mother liquor by using a saturated ammonium sulfate solution as a refined solution according to the solid-to-liquid ratio of 1:2g/mL, stirring and washing for 0.5h at 35 ℃, filtering to obtain a washed liquid and an agricultural ammonium sulfate fertilizer with the purity of 98.9%, returning the obtained washed liquid to be continuously used as the refined solution of the secondary crystallization until any one of ammonium chloride, sodium carbonate and sodium sulfate is enriched to be close to saturation, stopping recycling, opening a circuit, and merging the return step with the purified wastewater concentrated solution for comprehensive utilization. Mixing the obtained primary crystal and the secondary crystal, using saturated sodium bicarbonate solution as a solution of ammonium chloride, adding the mixture into the solution according to a solid-to-liquid ratio of 1:4g/mL, stirring for 1h at 59 ℃, and filtering while the mixture is hot to obtain a sodium bicarbonate filter cake and an ammonium chloride solution; stirring and washing the obtained sodium bicarbonate filter cake with saturated sodium bicarbonate solution, using the saturated sodium carbonate solution as a wet pyrolysis agent, slowly adding the saturated sodium carbonate solution into the wet pyrolysis agent in batches according to the solid-to-liquid ratio of 1:1.5g/mL, stirring at 110 ℃ for 1.5h to carry out wet pyrolysis, filtering and spin-drying, drying the filter cake at 250 ℃ to obtain an anhydrous sodium carbonate product with the purity of 99.6%, and returning the filtrate to be continuously used as the pyrolysis agent of the sodium bicarbonate; cooling the obtained ammonium chloride solution, crystallizing for 1.5 hours at 3 ℃, and filtering to obtain ammonium chloride crystals and crystallization mother liquor thereof; the obtained crystallization mother liquor returns to be continuously used as the dissolution liquid of ammonium chloride until any one of ammonium sulfate, sodium chloride and sodium sulfate is enriched to be close to saturation, is opened, and returns to be combined with the wastewater purification concentrated solution for comprehensive utilization; the obtained ammonium chloride crystal is prepared by using saturated ammonium chloride solution as refined solution, adding the ammonium chloride crystal into the solution according to the solid-to-liquid ratio of 1:1g/mL, stirring and refining for 0.5h at 65 ℃, cooling to room temperature, filtering to obtain refined solution and refined ammonium chloride product with the purity of 99.3%, returning the obtained refined solution to be continuously used as refined solution of ammonium chloride filter cakes until any one of ammonium sulfate, sodium bicarbonate, sodium chloride and sodium sulfate is enriched to be close to saturation, stopping recycling, opening a circuit, and returning to be combined with the wastewater purification concentrated solution for comprehensive utilization. After the technical process solution is recycled, na in the solution after wastewater purification + Ions, SO 4 2- Ions and Cl - The effective utilization rate of the ions is 97.5%, 98.2% and 98.8% respectively.
Example 3
The mixed sodium salt of turkish sodium sulfate and sodium chloride with peculiar smell obtained by purifying zinc smelting wastewater is used as raw material, wherein Na 2 SO 4 And NaCl content was 78.62% and 12.08%, respectively. Firstly, heating the mixed sodium salt to the temperature of 350 ℃ in the air to carbonize organic matters in the mixed sodium salt, cooling to the temperature of 60 ℃ and stirring the mixed sodium salt to be added into water to dissolve the mixed sodium salt to obtain Na + And 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 matters in the solution to obtain clear purified solution. Taking 3L of purified liquid, using CO 2 /NH 3 The mixed gas with the molar ratio of 1.03:1 is taken as a resolving agent, stirred and slowly blown into the purified liquid at 15 ℃ until NH 3 /Na + The molar ratio is increased to 1.06:1, the bubbling of mixed gas is stopped, stirring is continued for 1h, the split slurry is filtered to obtain primary crystal and primary crystallization mother liquor, and then the primary crystallization mother liquor is placed at the temperature of minus 14.5 ℃ for freezing and crystallizing for 4h, so that Na in the primary crystallization mother liquor is forced + And Cl - Further crystallizing and separating out sodium bicarbonate and ammonium chloride, and filtering to obtain secondary crystal and 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 be used for preparing a solution of mixed sodium salt, adding the tertiary crystal into the solution of the tertiary crystal by using a saturated ammonium sulfate solution as a refined solution 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 in the solution is enriched to be close to saturation, stopping recycling, opening a circuit, and returning the solution to be combined with the purified solution for comprehensive utilization. The obtained secondary crystallization is returned to be stirred and added into the next batch of resolution slurry for comprehensive recovery, the obtained primary crystallization uses saturated sodium bicarbonate solution as the solution of ammonium chloride, the primary crystallization is added into the solution according to the solid-to-liquid ratio of 1:5g/mL,stirring for 1h at 50 ℃, and filtering while the mixture is hot to obtain a sodium bicarbonate filter cake and ammonium chloride solution; stirring and washing the obtained sodium bicarbonate filter cake with saturated sodium bicarbonate solution, performing dry pyrolysis at 185 ℃ to obtain a sodium carbonate product with the purity of 99.1%, cooling the obtained ammonium chloride solution, crystallizing at 1 ℃ for 2.5h, and filtering to obtain an ammonium chloride filter cake and an ammonium chloride crystallization mother solution; and (3) drying the obtained ammonium chloride filter cake to obtain the agricultural ammonium chloride fertilizer with the N of 25.5%, returning the obtained ammonium chloride 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, and opening a circuit, and returning the ammonium chloride crystallization mother liquor to be combined with the purified solution for comprehensive utilization. After the technical process solution is recycled, the effective utilization rates of sodium sulfate and sodium chloride in the mixed sodium salt are 98.5 percent and 97.6 percent respectively.
Claims (8)
1. The method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt is characterized by comprising the following steps of:
step one: sodium removal and chlorine precipitation
Using slurry or solution of sodium sulfate-sodium chloride mixed salt as raw material, using ammonium bicarbonate or CO 2 /NH 3 The mixed gas of ammonium bicarbonate or CO is used as a resolving agent 2 /NH 3 Adding the mixed gas of sodium sulfate and sodium chloride into slurry or solution of mixed salt, stirring, and utilizing HCO 3 - Ions and NH 4 + The homoionic effect of the ions forces Na therein + And Cl - Crystallizing and separating out the slurry in the forms of sodium bicarbonate and ammonium chloride respectively to obtain slurry, and then treating the slurry in any one of the following two modes:
(1) Filtering the obtained slurry to obtain primary crystals and primary crystallization mother liquor, freezing the primary crystallization mother liquor, further crystallizing, and filtering to obtain secondary crystals and secondary crystallization mother liquor;
(2) Freezing the obtained slurry, crystallizing, and filtering to obtain a mixture of primary crystals and secondary crystallization mother liquor;
step two: separating and recovering ammonium sulfate
Evaporating and concentrating the secondary crystallization mother liquor obtained in the step one to separate out 45% -85% of ammonium sulfate crystals, filtering to obtain a tertiary crystal and a tertiary crystallization mother liquor, returning the tertiary crystallization mother liquor to the step one to be combined with the mixed liquor of sodium sulfate and sodium chloride for comprehensive utilization, or returning the solution for preparing sodium sulfate-sodium chloride mixed salt, adding the obtained tertiary crystal into a saturated ammonium sulfate solution, heating, stirring, washing, cooling, and filtering to obtain a washed liquid and a refined ammonium sulfate product;
step three: separating and recovering sodium carbonate and ammonium chloride
Adding the primary crystal or the mixture of the primary crystal and the secondary crystal obtained in the step one into a saturated sodium bicarbonate solution serving as a second refined solution, heating and stirring for refining to dissolve ammonium chloride, ammonium sulfate, sodium chloride and sodium sulfate into the solution, filtering while the solution is hot to obtain a sodium bicarbonate filter cake and ammonium chloride solution, washing the sodium bicarbonate filter cake again, pyrolyzing the sodium bicarbonate filter cake to obtain a refined sodium carbonate product, cooling the obtained ammonium chloride solution, crystallizing, and filtering to obtain an ammonium chloride filter cake and an ammonium chloride crystallization mother solution; the obtained ammonium chloride crystallization mother liquor is returned to be continuously used as a second refined solution, and is circulated in a closed circuit until any one of ammonium sulfate, sodium chloride and sodium sulfate is enriched to be close to saturation, and is opened, and the ammonium chloride crystallization mother liquor is returned to be combined with the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization in the step one or is returned to be used for preparing the solution of the sodium sulfate-sodium chloride mixed salt; adding the obtained ammonium chloride filter cake into saturated ammonium chloride solution, heating, stirring, refining, cooling, filtering to obtain refined solution and refined ammonium chloride product, returning the refined solution to be continuously used as third refined solution, performing closed circulation until any one of ammonium sulfate, sodium bicarbonate, sodium chloride and sodium sulfate is enriched to be close to saturation, performing open circuit, returning to the step one, combining with the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning to the solution for preparing sodium sulfate-sodium chloride mixed salt;
in the first step, the first step is to perform,
the raw material is SO 4 2- /Cl - The slurry or solution of sodium sulfate-sodium chloride mixed salt with the molar ratio of 0.1-50 is used as raw material, and the sodium sulfate-sodium chloride mixed salt is added withAdding into water to prepare Na + The ion concentration is 90-162 g/L, or according to Na + Mixing sodium sulfate-sodium chloride mixed salt with water to prepare slurry, or directly using sodium sulfate-sodium chloride-containing solution as raw material, purifying and concentrating to obtain Na + The ion concentration reaches 90-162 g/L;
ammonium bicarbonate is used as resolving agent to control NH 4 + /Na + The molar ratio is 1.05-1.25:1, and ammonium bicarbonate is stirred and added into slurry or solution of sodium sulfate-sodium chloride mixed salt;
by CO 2 /NH 3 Wherein CO is used as a resolving agent 2 /NH 3 The molar ratio is 1-1.1:1, and NH is controlled 3 /Na + The molar ratio of 1.05-1.25:1, mixed gas is blown into the slurry or solution of the sodium sulfate-sodium chloride mixed salt, or NH is blown first 3 Then according to CO 2 /NH 3 CO is blown in a molar ratio of 1-1.1:1 2 ；
In the second step, the second step is to carry out the process,
saturated ammonium sulfate solution is used as a first refined solution at room temperature, and the tertiary crystal is added into the first refined solution according to the solid-to-liquid ratio of 1:0.3-3 g/mL;
in the third step, the first step is performed,
adding primary crystals or a mixture of the primary crystals and the secondary crystals into saturated sodium bicarbonate solution serving as second refined solution according to a solid-to-liquid ratio of 1:0.5-5 g/mL, stirring to dissolve ammonium chloride, ammonium sulfate, sodium chloride and sodium sulfate into the solution, filtering to obtain a sodium bicarbonate filter cake and a solution containing ammonium chloride, washing the sodium bicarbonate filter cake, pyrolyzing the sodium bicarbonate filter cake to obtain a qualified sodium carbonate product, cooling the solution, crystallizing, and filtering to obtain an ammonium chloride filter cake and an ammonium chloride crystallization mother solution; the obtained ammonium chloride crystallization mother liquor is returned to be continuously used as a second refined solution, and is circulated in a closed circuit until any one of ammonium sulfate, sodium chloride and sodium sulfate is enriched to be close to saturation, and is opened, and the ammonium chloride crystallization mother liquor is returned to be combined with the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization in the step one or is returned to be used for preparing the solution of the sodium sulfate-sodium chloride mixed salt; and (3) directly taking the obtained ammonium chloride filter cake as a product after drying, or taking saturated ammonium chloride solution as a third refined solution, adding the ammonium chloride filter cake into the solution according to the solid-to-liquid ratio of 1:0.5-2.5 g/mL, stirring, cooling to room temperature, filtering to obtain refined solution and refined ammonium chloride product, returning the refined solution to be continuously used as the third refined solution, carrying out closed circulation until any one of ammonium sulfate, sodium bicarbonate, sodium chloride and sodium sulfate is enriched to be close to saturation, carrying out open circuit, and returning to the step I to be combined with the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning to the solution for preparing the sodium sulfate-sodium chloride mixed salt.
2. The method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt according to claim 1, which is characterized in that the technical process and the technical conditions are as follows:
in the first step, the first step is to perform,
the raw material is SO 4 2- /Cl - The slurry or solution of sodium sulfate-sodium chloride mixed salt with the molar ratio of 0.1-50 is used as raw material, and the sodium sulfate-sodium chloride mixed salt is added into water to prepare Na + The ion concentration is 90-162 g/L, or according to Na + Mixing sodium sulfate-sodium chloride mixed salt with water to prepare slurry, or directly using sodium sulfate-sodium chloride-containing solution as raw material, purifying and concentrating to obtain Na + The ion concentration reaches 90-162 g/L;
ammonium bicarbonate is used as resolving agent to control NH 4 + /Na + The molar ratio is 1.05-1.25:1, and ammonium bicarbonate is stirred and added into slurry or solution of sodium sulfate-sodium chloride mixed salt;
by CO 2 /NH 3 Wherein CO is used as a resolving agent 2 /NH 3 The molar ratio is 1-1.1:1, and NH is controlled 3 /Na + The molar ratio of 1.05-1.25:1, mixed gas is blown into the slurry or solution of the sodium sulfate-sodium chloride mixed salt, or NH is blown first 3 Then according to CO 2 /NH 3 CO is blown in a molar ratio of 1-1.1:1 2 ；
After the resolving agent is added, stirring is carried out for 0.5 to 2.5 hours at the temperature of 1 to 40 ℃, and HCO is utilized 3 - Ions and NH 4 + Generated by ionsThe homoionic effect forces Na therein + And Cl - Crystallizing and separating out the primary crystallization and primary crystallization mother liquor in the form of sodium bicarbonate and ammonium chloride respectively, filtering to obtain primary crystallization and primary crystallization mother liquor, then placing the primary crystallization mother liquor at the temperature of-18-0 ℃ for freezing and crystallizing for 2-6 hours, filtering to obtain secondary crystallization and secondary crystallization mother liquor, or directly placing the slurry containing crystals obtained after resolution at the temperature of-18-0 ℃ for freezing, continuing to crystallize for 2-6 hours, filtering to obtain a mixture of the primary crystallization and the secondary crystallization and secondary crystallization mother liquor;
in the second step, the second step is to carry out the process,
adding the tertiary crystal into the saturated ammonium sulfate solution at room temperature according to the solid-to-liquid ratio of 1:0.3-3 g/mL, stirring and washing for 0.5-1 h at 25-95 ℃, cooling to room temperature, filtering to obtain a washed solution and a refined ammonium sulfate product, returning the obtained washed solution to be continuously used as the first refined solution, carrying out closed circulation until any one of ammonium chloride, sodium carbonate and sodium sulfate is enriched to be close to saturation, carrying out open circuit, returning to the step I, combining the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning to the solution for preparing sodium sulfate-sodium chloride mixed salt;
in the third step, the first step is performed,
adding primary crystals or a mixture of the primary crystals and the secondary crystals into saturated sodium bicarbonate solution with the solid-to-liquid ratio of 1:0.5-5 g/mL serving as second refined solution, stirring for 0.5-1 h at the temperature of 40-64 ℃ to dissolve ammonium chloride, ammonium sulfate, sodium chloride and sodium sulfate into the solution, filtering while the solution is hot to obtain a sodium bicarbonate filter cake and ammonium chloride-containing solution, washing the sodium bicarbonate filter cake, pyrolyzing the sodium bicarbonate filter cake to obtain qualified sodium carbonate products, 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 ammonium chloride crystallization mother solution; the obtained ammonium chloride crystallization mother liquor is returned to be continuously used as a second refined solution, and is circulated in a closed circuit until any one of ammonium sulfate, sodium chloride and sodium sulfate is enriched to be close to saturation, and is opened, and the ammonium chloride crystallization mother liquor is returned to be combined with the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization in the step one or is returned to be used for preparing the solution of the sodium sulfate-sodium chloride mixed salt; and (3) directly taking the obtained ammonium chloride filter cake as a product after drying, or taking saturated ammonium chloride solution as a third refined solution at room temperature, adding the ammonium chloride filter cake into the saturated ammonium chloride solution according to the 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 refined solution and refined ammonium chloride product, returning the refined solution to be continuously used as the third refined solution, carrying out closed circulation until any one of ammonium sulfate, sodium bicarbonate, sodium chloride and sodium sulfate is enriched to be close to saturation, carrying out open circuit, returning to the step one, combining the mixed solution of sodium sulfate and sodium chloride for comprehensive utilization, or returning to the solution for preparing sodium sulfate-sodium chloride mixed salt.
3. The method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt according to claim 1 or 2, which is characterized in that: in the second step, CO released in the evaporation and concentration process of the secondary crystallization mother solution 2 And NH 3 Collecting the slurry or solution of sodium sulfate-sodium chloride mixed salt used for synthesizing ammonium bicarbonate or directly introducing the slurry or solution into 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, which is characterized in that: in the third step, ammonium chloride is dissolved, and ammonium bicarbonate mixed in the primary crystal and the mixture of the primary crystal and the secondary crystal is decomposed and volatilized into NH in a saturated sodium bicarbonate solution at 30-60 DEG C 3 Absorbing with dilute sulfuric acid or ammonium bisulfate solution to prevent ammonia from escaping.
5. The method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt according to claim 1 or 2, which is characterized in that: and thirdly, adding the sodium bicarbonate filter cake into water or saturated sodium bicarbonate aqueous 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 washed sodium bicarbonate and washing liquid thereof, returning the obtained washing liquid to be continuously used as washing liquid of the sodium bicarbonate filter cake, carrying out closed circulation until any one of ammonium sulfate, ammonium chloride, sodium chloride and sodium sulfate is enriched to be close to saturation, carrying out open circuit, combining with the sodium sulfate and sodium chloride mixed liquid in the first step for comprehensive utilization, or preparing 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, which is characterized in that: in the third step, the pyrolysis is selected from dry pyrolysis or wet pyrolysis, and the gas released in the pyrolysis process is directly introduced into the slurry or solution of the sodium sulfate-sodium chloride mixed salt in the first step so as to improve the comprehensive utilization rate of the raw materials and the auxiliary materials;
the dry pyrolysis is that the washed sodium bicarbonate filter cake is calcined for 0.25-1.25 hours at the temperature of 150-300 ℃ to convert sodium bicarbonate into sodium carbonate;
the wet pyrolysis is to use a saturated sodium carbonate solution at 25-60 ℃ as a wet pyrolysis agent, stir and add the washed sodium bicarbonate filter cake into the solution according to a solid-to-liquid ratio of 1:0.5-5 g/mL, heat and decompose the sodium bicarbonate filter cake, stir for 0.5-2.5 h at 65-250 ℃ to convert the sodium bicarbonate filter cake into sodium carbonate, cool the sodium carbonate filter cake to 25-60 ℃, filter the sodium carbonate filter cake to obtain a sodium carbonate filter cake and a pyrolyzed solution, and return the pyrolyzed solution to be continuously used as the pyrolyzing agent of sodium bicarbonate, and perform closed cycle until sodium chloride or sodium sulfate in the pyrolyzed solution is enriched to be close to saturation, open circuit and introduce CO 2 The sodium carbonate is converted into sodium bicarbonate to be crystallized and separated out, the sodium bicarbonate is filtered, a filter cake is directly used as sodium bicarbonate product, or the sodium carbonate product is produced by pyrolysis, and the filtrate is returned to the step one to be combined with sodium sulfate and sodium chloride mixed solution for comprehensive utilization, or used for preparing the solution of sodium sulfate-sodium chloride mixed salt.
7. The method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt according to claim 1 or 2, which is characterized in that: in the technological process of comprehensive utilization of sodium sulfate-sodium chloride mixed salt and its solution, the effective utilization rate of sodium sulfate and sodium chloride is no less than 97%.
8. The method for comprehensively utilizing the sodium sulfate-sodium chloride mixed salt according to claim 1 or 2, which is characterized in that: the purity of the refined sodium carbonate product obtained in the process is 98.3-99.2%, the purity of the refined ammonium sulfate product is 99.3-99.5%, and the purity of the refined ammonium chloride product is 99.3-99.6%.
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