WO2023121346A1 - Appareil de production de bicarbonate de sodium à partir de sous-produits industriels contenant du sulfate de sodium - Google Patents

Appareil de production de bicarbonate de sodium à partir de sous-produits industriels contenant du sulfate de sodium Download PDF

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WO2023121346A1
WO2023121346A1 PCT/KR2022/021075 KR2022021075W WO2023121346A1 WO 2023121346 A1 WO2023121346 A1 WO 2023121346A1 KR 2022021075 W KR2022021075 W KR 2022021075W WO 2023121346 A1 WO2023121346 A1 WO 2023121346A1
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generating unit
calcium
sulfate
solid precipitate
sodium bicarbonate
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PCT/KR2022/021075
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English (en)
Korean (ko)
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안치규
문정기
이창훈
김국희
이만수
박해웅
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재단법인 포항산업과학연구원
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Publication of WO2023121346A1 publication Critical patent/WO2023121346A1/fr

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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
    • 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
    • C01D7/35—Varying the content of water of crystallisation or the specific gravity
    • C01D7/37—Densifying sodium carbonate
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing

Definitions

  • the present invention relates to an apparatus for producing sodium bicarbonate from an industrial by-product containing sodium sulfate. More specifically, the present invention relates to an apparatus for producing sodium bicarbonate and other valuable resources from industrial by-products containing sodium sulfate.
  • Na-based sodium bicarbonate NaHCO 3 , sodium bicarbonate
  • Na-based sodium bicarbonate has higher desulfurization efficiency than Ca-based desulfurization agents, but is more expensive than Ca-based desulfurization agents, and Na 2 SO 4 is finally produced.
  • Waste Ca-based desulfurization agent is CaSO 4 , which can be reused as a raw material for gypsum.
  • Na 2 SO 4 produced by Na-based desulfurization agent has no large amount of use, contains impurities, etc., and has high water solubility, so it is difficult to landfill. It is difficult, so the waste disposal costs are high. Therefore, it is required to develop a technology for recycling waste desulfurization agent containing Na 2 SO 4 to reduce the cost of waste treatment and to improve the economic feasibility of recovering sodium bicarbonate through regeneration of sodium sulfate.
  • U.S. Patent No. 5,830,422 discloses the preparation of sodium bicarbonate, sodium carbonate and ammonium sulfate from sodium sulfate.
  • the US patent uses ammonia to produce NaHCO 3 from desulfurization waste.
  • the process itself is complicated because ammonia is used to dissolve CO 2 or an additional process for recovering ammonia is included, and Ca(OH) 2 is used to treat the waste liquid of NaHCO 3 produced from Na 2 SO 4 . It is different from the process in the manufacturing apparatus of the present invention in that it is used for the purpose.
  • Patent Document 1 US Patent No. 5,830,422
  • the present invention relates to an apparatus capable of effectively producing sodium bicarbonate and other valuable resources from industrial by-products containing sodium sulfate.
  • an apparatus for producing sodium hydrogen carbonate from industrial by-products containing sodium sulfate including a dissolution unit, a first solid precipitate generation unit and a sodium hydrogen carbonate generation unit,
  • an aqueous solution of sodium sulfate in which industrial by-products containing sodium sulfate are dissolved in water is prepared;
  • calcium sulfate is generated and recovered by reacting sulfate ions in the sodium sulfate aqueous solution with calcium ions provided by a calcium source;
  • a production device in which sodium bicarbonate is produced and recovered by dissolving carbon dioxide in the filtrate remaining after recovering calcium sulfate in the first solid precipitate generating unit.
  • an apparatus for producing sodium hydrogen carbonate from industrial by-products containing sodium sulfate including a dissolution unit, a first solid precipitate generation unit, and a sodium hydrogen carbonate generation unit,
  • the treatment in the manufacturing apparatus includes a first cycle in which industrial by-products containing sodium sulfate are sequentially processed in the dissolving unit, the first solid precipitate generating unit, and the sodium bicarbonate generating unit; And after the filtrate remaining after the recovery of sodium bicarbonate in the sodium bicarbonate generating unit of the first circulation is recycled to the dissolving unit, it is sequentially processed in the dissolving unit, the first solid precipitate generating unit, and the sodium bicarbonate generating unit. Including a second cycle that becomes,
  • an aqueous solution of sodium sulfate in which industrial by-products containing sodium sulfate are dissolved in water is prepared;
  • calcium sulfate is generated and recovered by reacting sulfate ions in the sodium sulfate aqueous solution with calcium ions provided by a calcium source;
  • an industrial by-product containing sodium sulfate is dissolved in the filtrate remaining after the recovery of sodium hydrogen carbonate in the sodium hydrogen carbonate generating part of the first cycle to prepare a sodium sulfate aqueous solution saturated with sodium hydrogen carbonate;
  • sulfate ions and bicarbonate ions in an aqueous solution of sodium sulfate saturated with sodium bicarbonate react with calcium ions provided by a calcium source to produce and recover calcium sulfate and calcium carbonate;
  • a production device in which sodium bicarbonate is generated and recovered by dissolving carbon dioxide in the filtrate remaining after the recovery of calcium sulfate and calcium carbonate in the first solid precipitate generating unit.
  • an apparatus for producing sodium bicarbonate from industrial by-products containing sodium sulfate including a dissolution unit, a first solid precipitate generating unit, a second solid precipitate generating unit and a sodium hydrogen carbonate generating unit,
  • an aqueous solution of sodium sulfate in which industrial by-products containing sodium sulfate are dissolved in water is prepared;
  • calcium sulfate is generated and recovered by reacting sulfate ions in the sodium sulfate aqueous solution with calcium ions provided by a calcium source;
  • the sodium bicarbonate generating unit After the recovery of calcium carbonate in the second solid precipitate generating unit, carbon dioxide is dissolved in the remaining filtrate to produce and recover sodium bicarbonate, a manufacturing apparatus is provided.
  • an apparatus for producing sodium bicarbonate from industrial by-products containing sodium sulfate including a dissolution unit, a first solid precipitate generating unit, a second solid precipitate generating unit and sodium bicarbonate generating unit,
  • the treatment in the manufacturing apparatus includes a first cycle in which industrial by-products containing sodium sulfate are sequentially processed in the dissolving unit, the first solid precipitate generating unit, and the sodium bicarbonate generating unit; And after the filtrate remaining after the recovery of sodium bicarbonate in the sodium bicarbonate generating unit of the first circulation is recycled to the dissolving unit, the dissolving unit, the first solid precipitate generating unit, and the second solid precipitate generating unit and hydrogen carbonate Including a second circulation sequentially processed in the sodium generating unit,
  • an aqueous solution of sodium sulfate in which industrial by-products containing sodium sulfate are dissolved in water is prepared;
  • calcium sulfate is generated and recovered by reacting sulfate ions in the sodium sulfate aqueous solution with calcium ions provided by a calcium source;
  • an industrial by-product containing sodium sulfate is dissolved in the filtrate remaining after the recovery of sodium hydrogen carbonate in the sodium hydrogen carbonate generating part of the first cycle to prepare a sodium sulfate aqueous solution saturated with sodium hydrogen carbonate;
  • calcium carbonate is produced and recovered by reacting bicarbonate ions in an aqueous solution of sodium sulfate saturated with sodium bicarbonate and calcium ions provided by a calcium source;
  • a production device in which sodium bicarbonate is produced and recovered by dissolving carbon dioxide in the filtrate remaining after the recovery of calcium sulfate in the second solid precipitate generating unit.
  • an apparatus for producing sodium bicarbonate from industrial by-products containing sodium sulfate including a dissolution unit, a first solid precipitate generating unit, a second solid precipitate generating unit and sodium hydrogen carbonate generating unit,
  • the treatment in the manufacturing apparatus includes a first cycle in which industrial by-products containing sodium sulfate are sequentially processed in the dissolving unit, the first solid precipitate generating unit, the second solid precipitate generating unit, and the sodium bicarbonate generating unit; And after the filtrate remaining after the recovery of sodium bicarbonate in the sodium bicarbonate generating unit of the first circulation is recycled to the dissolving unit, it is sequentially processed in the dissolving unit, the first solid precipitate generating unit, and the sodium bicarbonate generating unit. Including a second cycle that becomes,
  • an aqueous solution of sodium sulfate in which industrial by-products containing sodium sulfate are dissolved in water is prepared;
  • calcium sulfate is generated and recovered by reacting sulfate ions in the sodium sulfate aqueous solution with calcium ions provided by a calcium source;
  • an industrial by-product containing sodium sulfate is dissolved in the filtrate remaining after the recovery of sodium hydrogen carbonate in the sodium hydrogen carbonate generating part of the first cycle to prepare a sodium sulfate aqueous solution saturated with sodium hydrogen carbonate;
  • calcium sulfate and calcium carbonate are generated and recovered by reacting calcium ions provided by a calcium supply source with sulfate ions and bicarbonate ions in an aqueous solution of sodium sulfate saturated with sodium bicarbonate;
  • a production device in which sodium bicarbonate is produced and recovered by dissolving carbon dioxide in the filtrate remaining after the recovery of calcium sulfate and calcium carbonate in the first solid precipitate generating unit.
  • An apparatus for producing sodium bicarbonate from industrial by-products containing sodium sulfate including a dissolution unit, a first solid precipitate generating unit, a second solid precipitate generating unit, and a sodium hydrogen carbonate generating unit,
  • the treatment in the manufacturing apparatus includes a first cycle in which industrial by-products containing sodium sulfate are sequentially processed in the dissolving unit, the first solid precipitate generating unit, the second solid precipitate generating unit, and the sodium bicarbonate generating unit; And after the filtrate remaining after the recovery of sodium bicarbonate in the sodium bicarbonate generating unit of the first circulation is recycled to the dissolving unit, the dissolving unit, the first solid precipitate generating unit, the second solid precipitate generating unit and sodium bicarbonate It includes a second cycle that is sequentially processed in the generating unit,
  • an aqueous solution of sodium sulfate in which industrial by-products containing sodium sulfate are dissolved in water is prepared;
  • calcium sulfate is generated and recovered by reacting sulfate ions in the sodium sulfate aqueous solution with calcium ions provided by a calcium source;
  • an industrial by-product containing sodium sulfate is dissolved in the filtrate remaining after the recovery of sodium hydrogen carbonate in the sodium hydrogen carbonate generating part of the first cycle to prepare a sodium sulfate aqueous solution saturated with sodium hydrogen carbonate;
  • calcium carbonate is produced and recovered by reacting bicarbonate ions in an aqueous solution of sodium sulfate saturated with sodium bicarbonate and calcium ions provided by a calcium source;
  • a production device in which sodium bicarbonate is generated and recovered by dissolving carbon dioxide in the filtrate remaining after recovering calcium sulfate in the second solid precipitate generating unit.
  • the calcium source is at least one selected from the group consisting of Ca 2+ -containing waste, calcium oxide and calcium hydroxide, and a manufacturing apparatus according to any one of the first to sixth aspects is provided.
  • a manufacturing apparatus according to any one of the first to sixth aspects is provided in which industrial by-products containing sodium sulfate are dissolved in water or a filtrate at a temperature of 10 ° C to 50 ° C in the dissolution unit. .
  • the production of calcium sulfate, calcium sulfate and calcium carbonate or calcium carbonate in the first solid precipitate generating unit is carried out at a temperature of 25 °C to 45 °C, a manufacturing apparatus is provided.
  • the production of calcium carbonate or calcium sulfate in the second solid precipitate generating unit is carried out at a temperature of 25 °C to 45 °C, the manufacturing apparatus according to any one of the third to sixth aspects is provided do.
  • the production of sodium hydrogen carbonate in the sodium hydrogen carbonate generating unit is performed at a temperature of 25 ° C to 45 ° C, the manufacturing apparatus according to any one of the first to sixth aspects is provided.
  • the manufacturing apparatus according to any one of the first to sixth aspects, wherein the industrial by-product containing sodium sulfate is a waste desulfurization agent or a sulfuric acid neutralized waste liquid, is provided.
  • industrial by-products containing sodium sulfate are stably treated, and sodium bicarbonate (NaHCO 3 ) as well as calcium sulphate (CaSO 4 , gypsum) and calcium carbonate (CaCO 3 ) are recovered.
  • NaHCO 3 sodium bicarbonate
  • CaSO 4 calcium sulphate
  • CaCO 3 calcium carbonate
  • CO 2 is fixed according to the formation of calcium carbonate (CaCO 3 ), contributing to CO 2 reduction.
  • Regenerated sodium bicarbonate (NaHCO 3 ) can be used as a desulfurization agent in the desulfurization process, and calcium sulfate (CaSO 4 ) and/or calcium carbonate (CaCO 3 ) can be used as a building material.
  • the manufacturing apparatus of the present invention produces less wastewater.
  • the manufacturing apparatus of the present invention does not use a substance (eg, ammonia) for dissolving CO 2 , sodium bicarbonate, calcium sulfate, and calcium carbonate are efficiently recovered from industrial by-products containing sodium sulfate through a simple process.
  • industrial by-products containing sodium sulfate can be treated at a low cost and expensive sodium bicarbonate is recovered, which is economical.
  • FIG. 1 is a view schematically showing a manufacturing apparatus and a process in the manufacturing apparatus according to the present invention.
  • FIG. 2 is a view showing the manufacturing apparatus according to the present invention in more detail.
  • FIG 3 is a graph showing the solubility of sodium sulfate (Na 2 SO 4 ) in water according to temperature.
  • the present invention relates to an apparatus for producing sodium bicarbonate (bacteria, NaHCO 3 ) from industrial by-products containing sodium sulfate.
  • Industrial by-products containing sodium sulfate (hereinafter also referred to as 'industrial by-products') may be solid or liquid industrial by-products.
  • the industrial by-products are, but are not limited to, for example, waste desulfurization agent generated after using sodium bicarbonate as a desulfurization agent in a desulfurization process for removing sulfur oxides (SOx) in exhaust gas, sulfuric acid neutralization generated after neutralizing sulfuric acid Waste liquid etc. are mentioned.
  • sodium bicarbonate used as a desulfurization agent reacts with SO 2 in exhaust gas as shown in the following Reaction Formula [A] to convert NaHCO 3 into Na 2 SO 4 .
  • most of the components of the waste desulfurization agent are Na 2 SO 4 , and major impurities include K, Ca, Fe, and the like.
  • Components of the waste desulfurization agent were analyzed by XRF (X-Ray Fluorescence) and are shown in Table 1 below.
  • the waste desulfurization agent may include, for example, components as shown in Table 1 below in the component contents of Table 1, but is not limited thereto.
  • the content of sodium sulfate in the waste desulfurization agent depends on the amount of sodium bicarbonate (NaHCO 3 ) used in the desulfurization process. Although not limited thereto, the content of sodium sulfate in the waste desulfurization agent may be approximately 70% to 100% by weight. .
  • the manufacturing apparatus of the present invention includes a dissolving unit 10, a first solid precipitate generating unit 20, an optional second solid precipitate generating unit 20 ', and a sodium bicarbonate generating unit ( 30) included.
  • the first solid precipitate generating unit 20 in the manufacturing apparatus 100 includes a first solid precipitate generating tank 21 and a filter 22, an optional second solid precipitate
  • the generation unit 20' includes a second solid precipitate generation tank 21' and a filter 22'
  • the sodium bicarbonate generation unit 30 includes a sodium bicarbonate generation tank 31 and a filter 32.
  • Apparatus 100 for producing sodium bicarbonate from industrial by-products containing sodium sulfate includes a dissolving unit 10, a first solid precipitate generating unit 20, and an optional second solid precipitate generating unit. (20 '), and a sodium hydrogen carbonate generating unit 30, wherein the treatment of sodium hydrogen carbonate from industrial by-products containing sodium sulfate in the manufacturing apparatus includes the dissolving unit 10, the first solid precipitate generating unit 20 , Optional second solid precipitate generating unit 20 ', and may include only the first cycle sequentially processed in the sodium bicarbonate generating unit 30.
  • the apparatus 100 for producing sodium bicarbonate from industrial by-products containing sodium sulfate includes a dissolving unit 10, a first solid precipitate generating unit 20, an optional second solid precipitate It includes a generating unit 20 ', and a sodium hydrogen carbonate generating unit 30, and the treatment of sodium bicarbonate from industrial by-products containing sodium sulfate in the manufacturing apparatus includes the dissolving unit 10, the first solid precipitate generating unit ( 20), the optional second solid precipitate generating section 20', and the first cycle sequentially processed in the sodium bicarbonate generating section 30; And after the filtrate remaining after the recovery of sodium bicarbonate in the sodium bicarbonate generating unit 30 of the first circulation is recycled to the dissolving unit 10, the dissolving unit 10, the first solid precipitate generating unit ( 20), an optional second solid precipitate generating unit 20', and a second cycle sequentially processed in the sodium bicarbonate generating unit 30.
  • 'first circulation' refers to the introduction of sodium sulfate-containing industrial by-products into the dissolving unit 10 for the first time in the manufacturing apparatus of the present application, the dissolving unit 10, the first solid precipitate generating unit 20, and the optional second Refers to a cycle that first passes through the solid precipitate generating unit 20 'and the sodium bicarbonate generating unit 30, and 'second circulation' refers to hydrogen carbonate in the sodium bicarbonate generating unit 30 in the first cycle.
  • the filtrate remaining after sodium recovery is recycled to the dissolving unit 10, and the dissolving unit 10, the first solid precipitate generating unit 20, the optional second solid precipitate generating unit 20 ', and the sodium bicarbonate generating unit Refers to a cycle that is processed by going through (30) again.
  • the filtrate remaining after recovering sodium bicarbonate in the sodium bicarbonate generating unit 30 of the second circulation is recycled back to the dissolving unit 10 (eg, the third circulation, the fourth circulation, etc.) It may be repeated, and herein it is also referred to as 'after the second cycle' or 'above the second cycle'.
  • Reactions in the dissolution section and the production section in the first and second cycles of the manufacturing apparatus are as follows.
  • 1st solid precipitate generating unit 20 2Na + + SO 4 2- + 2Ca(OH) 2 ⁇ 2Na + + CaSO 4(s) ⁇ + Ca 2+ + 4OH - ----(2)
  • Optional second solid phase precipitate generating section 20' 2Na + + Ca 2+ + 4OH - + CO 2 ⁇ 2Na + + CaCO 3(s) ⁇ + H 2 O + 2OH - --- (2')
  • the first solid phase precipitate generating unit 20 3Na + + SO 4 2- + HCO 3 - + 2Ca(OH) 2 ⁇ 3Na + + CaSO 4(s) + CaCO 3(s) + 3OH - + H 2 O - ---(5)
  • reaction formula (5) in the first solid precipitate generating unit 20, or the following reaction formula in the first solid precipitate generating unit 20 and the second solid precipitate generating unit 20' It proceeds as in (5') and (5").
  • the first solid phase precipitate generation unit 20 3Na + + SO 4 2- + HCO 3 - + Ca(OH) 2 ⁇ 3Na + + SO4 2- + CaCO 3(s) + OH - + H 2 O --- (5')
  • the dissolving unit 10, the first solid precipitate generating unit 20 (including the first solid precipitate generating tank 21 and the filter 22), the optional second solid precipitate generating unit 20' (the second 2 manufacturing apparatus 100 including a solid precipitate generating tank 21' and a filter 22'), and a sodium bicarbonate generating unit 30 (including a sodium bicarbonate generating tank 31 and a filter 32) )
  • the dissolving unit 10 the first solid precipitate generating unit 20, the optional second solid precipitate generating unit 20 ', and Treatment of sodium hydrogen carbonate from industrial by-products containing sodium sulfate in the process in the sodium hydrogen carbonate production section 30 describes the process.
  • the industrial by-product containing sodium sulfate is dissolved in water to prepare an aqueous solution of sodium sulfate.
  • the industrial by-product contains sodium sulfate (Na 2 SO 4 ), and therefore, the sodium sulfate aqueous solution dissolved in water contains sodium ions and sulfate ions as shown in the reaction formula (1) above.
  • the amount of industrial by-products dissolved in water in the dissolving unit 10 is an amount in which sodium sulfate in industrial by-products is dissolved in water at 100 g/L to 400 g/L. That is, in the sodium sulfate aqueous solution, an amount of industrial by-products corresponding to 100 g to 400 g of sodium sulfate dissolved in 1 L of water is dissolved in water.
  • the amount of sodium sulfate among industrial by-products can be found by XRF (X-Ray Fluorescence), IC (Ion Chromatography), etc. These methods are generally known methods for analyzing the components of chemical substances. , which will not be described in detail here.
  • Industrial by-products include, but are not limited to, as described above, for example, waste desulfurization agent generated after using sodium bicarbonate as a desulfurization agent in a desulfurization process for removing sulfur oxides (SOx) from exhaust gas, and/or sulfuric acid. and sulfuric acid neutralization waste liquid generated after neutralization.
  • SOx sulfur oxides
  • Fresh water or tap water may be used as the water.
  • solubility of Na 2 SO 4 increases as the temperature rises in a certain range, but decreases at a temperature of 40° C. or higher while maintaining a certain level.
  • 3 shows a graph of solubility of sodium sulfate (Na 2 SO 4 ) in water according to temperature.
  • the industrial by-products are dissolved in water in the dissolution unit 10 of the manufacturing apparatus at a temperature of 10 ° C to 50 ° C, preferably 25 ° C to 45 ° C. Dissolution is preferred.
  • Na 2 SO 4 in industrial by-products is It is preferable to dissolve industrial by-products in water in an amount dissolved in 100 to 400 g (100 to 400 g/L) per 1 L of water. If it is less than 100 g/L, the production of NaHCO 3 is low, and the process cycle must be repeatedly operated several times in the manufacturing apparatus of the present invention to produce NaHCO 3 , so excessive operating energy may be consumed. If it exceeds 400 g/L, the solubility of Na 2 SO 4 is exceeded, and Na 2 SO 4 is undissolved, and the undissolved Na 2 SO 4 is removed in the filtration process, and the utilization rate of Na 2 SO 4 may be lowered.
  • the sodium sulfate aqueous solution in the dissolving unit 10 may be adjusted so that the concentration of Na 2 SO 4 in the solution-phase industrial by-product is 100 to 400 g/L.
  • the first solid precipitate generating unit 20 calcium sulfate is generated by reacting sulfate ions in the sodium sulfate aqueous solution prepared in the dissolving unit 10 with calcium ions provided by a calcium source.
  • the reaction in the first solid precipitate generating unit 20 is as shown in the above reaction formula (2).
  • the first solid precipitate generating unit 20 includes a first solid precipitate generating tank 21 and a filter 22 for filtering and recovering the generated calcium sulfate solids to generate the first solid precipitate. It can be included at the rear end of the jaw 21.
  • sodium ions (Na + ) and sulfate ions (SO 4 2- ) generated by dissolving industrial by-products containing sodium sulfate in water in the sodium sulfate aqueous solution in the dissolving unit 10 exist.
  • a calcium source is supplied to the sodium sulfate aqueous solution in the first solid precipitate generating unit 20, Ca 2+ supplied by the calcium source reacts with SO 4 2- to form CaSO 4 .
  • the calcium source is not limited thereto, but for example, at least one selected from the group consisting of Ca-containing waste, Ca(OH) 2 and CaO may be used.
  • the calcium source (calcium source).
  • the description of the calcium source is equally applied to the content of the calcium source of the present application.
  • the addition amount of the calcium source is determined according to the concentration of SO 4 2- present in the aqueous solution of sodium sulfate in the dissolving unit 10, which is proportional to the amount of Na 2 SO 4 dissolved in water in the dissolving unit 10.
  • the calcium source has a molar concentration of Ca 2+ that is 0.9 to 1.1 times greater than the molar concentration of SO 4 2- (ie, the molar concentration of Na 2 SO 4 dissolved in water) (ie, SO 4 2- or Na When the concentration of 2 SO 4 is 1 M, 0.9 to 1.1 mol of calcium source (ie, the molar concentration of Ca 2+ ) is added so that the same applies below).
  • the added amount of the calcium source is less than 0.9 times the molarity of Ca 2+ molarity, SO 4 2- is excessively remaining, and if it exceeds 1.1 times the molarity, the second solid precipitate generation unit described below ( 20') is required.
  • a calcium source is supplied to an aqueous solution of sodium sulfate at 25° C. to 45° C. to produce calcium sulfate.
  • the temperature is less than 25° C. or more than 45° C., the solubility of sodium sulfate is lowered and sodium sulfate may precipitate, which is not preferable.
  • CaSO 4 Due to the low solubility of CaSO 4 , CaSO 4 is formed as a solid precipitate, which is removed and recovered as a solid content by filtration, and unreacted Ca 2+ and Na + remain as main components in the filtrate. Specifically, calcium sulfate may be filtered and recovered by the filter 22 at the rear of the first solid precipitate generating tank 21 shown in FIG. 2 .
  • the second solid precipitate generating unit 20 ' may optionally be included in the manufacturing apparatus 100 of the present invention as needed.
  • Ca 2+ may remain in the filtrate remaining after recovering calcium sulfate in the first solid precipitate generating unit 20 due to the solubility of CaSO 4 , and CO 2 may be present in the filtrate in the sodium bicarbonate generating unit 30 When added, residual Ca 2+ can precipitate as CaCO 3 and affect the purity of the final product, NaHCO 3 . Therefore, in order to precipitate and remove Ca 2+ in the filtrate as calcium carbonate solids, a second solid precipitate generating unit 20 ′ may be additionally included as needed.
  • reaction in the second solid precipitate generating unit 20' is as shown in the reaction formula (2').
  • CO 2 is added to the residual filtrate after calcium sulfate recovery in the first solid precipitate generating unit 20' to precipitate and remove Ca 2+ as calcium carbonate solid content.
  • CO 2 is added to the molar concentration, which is the molar solubility of calcium sulfate in the filtrate (ie, the molar concentration in the saturated solution).
  • the second solid precipitate generating unit 20' may not operate when the concentration of Ca 2+ remaining in the filtrate is lower than the solubility of CaCO 3 . That is, when the concentration of Ca 2+ remaining in the filtrate is greater than the solubility of CaCO 3 , the second solid precipitate generating unit 20 ′ may be additionally provided to the removal device 100 . The second solid precipitate generating unit 20' may further improve the purity of the finally produced sodium bicarbonate by precipitating and removing Ca 2+ remaining in the filtrate in the form of CaCO 3 .
  • the supply of CO 2 to the filtrate in the second solid precipitate generating unit 20' and the production of calcium carbonate are performed at 25°C to 45°C.
  • the temperature is lower than 25°C or higher than 45°C, the solubility of Na 2 SO 4 is lowered and Na 2 SO 4 may precipitate, which is not preferable.
  • the filtrate remaining after filtration of calcium sulfate in the filter 22 of the first solid precipitate generating unit 20 (or the second solid precipitate generating unit 20 ') is included In this case, sodium bicarbonate is generated and recovered by dissolving carbon dioxide in the filtrate after calcium carbonate is recovered in the second solid precipitate generating unit 20'.
  • the reaction in the sodium hydrogen carbonate generating unit 30 is as shown in the above Reaction Formula (3).
  • the sodium bicarbonate producing unit 30 includes a sodium bicarbonate producing tank 31 and a filter 32 for filtering and recovering the generated sodium bicarbonate solids in the sodium bicarbonate producing tank 31 ) can be included at the end of
  • CO 2 is added so that the molar concentration of CO 2 is 1.0 to 2.2 times the molar concentration of sodium sulfate in the sodium sulfate aqueous solution of the dissolving unit 10. do. If the molar concentration of CO 2 is less than 1.0 times, NaHCO 3 is not formed as much as the solubility of NaHCO 3 , so the production of NaHCO 3 is lowered.
  • the filtrate remaining after the recovery of sodium bicarbonate in the sodium bicarbonate generating unit 30 may be recycled (after the second circulation) to the dissolving unit 10 there is.
  • the filtrate remaining after recovering sodium bicarbonate in the sodium bicarbonate generating unit 30 of the first cycle is introduced into the dissolving unit 10, and the filtrate is introduced as a sodium bicarbonate saturated solution. This is dissolved
  • sodium bicarbonate, calcium sulfate and calcium carbonate are additionally recovered by recycling the filtrate in which sodium bicarbonate is dissolved to the dissolving unit 10 and operating the manufacturing apparatus 100.
  • the filtrate (sodium hydrogen carbonate saturated solution) from which sodium bicarbonate is removed from the sodium bicarbonate generating unit 30 is supplied to the dissolution unit 10 after the second circulation, and industrial by-products containing sodium sulfate are dissolved in the filtrate to obtain carbonic acid.
  • An aqueous solution of sodium sulfate saturated with sodium hydrogen is obtained.
  • Industrial by-products containing sodium sulfate are applied in the same manner as described in the dissolution section 10 of the first cycle.
  • the reaction in the dissolving unit 10 after the second circulation is as shown in the above reaction equation (4).
  • industrial by-products are added to the filtrate (filtrate from which sodium bicarbonate is removed from the sodium bicarbonate generating unit 30 of the first cycle, sodium bicarbonate saturated solution), and the content of sodium sulfate in the filtrate is reduced.
  • an aqueous solution of sodium sulfate saturated with sodium bicarbonate is obtained.
  • the sodium sulfate content is less than 100 g/L, the production of NaHCO 3 is low and excessive operating energy may be consumed because NaHCO 3 is produced only when the process cycle is repeatedly operated several times in the manufacturing apparatus of the present invention. If it exceeds 400 g/L, the solubility of Na 2 SO 4 is exceeded, and Na 2 SO 4 is undissolved, and the undissolved Na 2 SO 4 is removed in the filtration process, and the utilization rate of Na 2 SO 4 may be lowered.
  • the aqueous solution of sodium sulfate in which sodium bicarbonate is saturated in the dissolving unit 10 is dissolved in the aqueous solution by using the solution-type industrial by-product and/or water (eg, fresh water or tap water).
  • the concentration of Na 2 SO 4 may be adjusted to be 100 to 400 g/L.
  • the industrial by-products in the filtrate at 10 ° C to 50 ° C, preferably at 25 ° C to 45 ° C in the dissolution unit 10 after the second circulation.
  • the temperature exceeds 50 °C, there is a problem in that only energy is excessively input without inducing solubility improvement, and there is a problem in that the dissolution rate and amount of CO 2 are reduced due to the high temperature when CO 2 is supplied in the subsequent step.
  • the solubility of sodium sulfate (Na 2 SO 4 ) in industrial by-products is low, and sodium sulfate may not be dissolved or it may take a long time to dissolve.
  • the aqueous solution of sodium sulfate saturated with sodium bicarbonate in the dissolving unit 10 after the second circulation contains 3Na + , SO 4 2- and HCO 3 - .
  • the production and recovery of calcium sulfate and calcium carbonate in the solid precipitate production unit after the second cycle may be performed sequentially in a single step or in two steps.
  • Ca 2+ is supplied by a calcium source to the sodium sulfate aqueous solution saturated with sodium bicarbonate in the first solid precipitate generating unit 20, specifically, the first solid precipitate generating tank 21,
  • sulfate ion (SO 4 2- ) and bicarbonate ion (HCO 3 - ) in sodium sulfate aqueous solution saturated with sodium hydrogen carbonate It reacts with Ca 2+ to form calcium sulfate and calcium carbonate, and is recovered in the filter 22 by a method such as filtration. In this case, after the second cycle, the second solid precipitate generating unit 20' is unnecessary.
  • the calcium source may include at least one selected from the group consisting of Ca 2+ -containing waste, calcium oxide and calcium hydroxide, preferably at least one selected from the group consisting of calcium oxide and calcium hydroxide. At this time, impurities such as heavy metals and particulate matter contained in industrial by-products may be filtered and removed together.
  • the amount of the calcium source added to the sodium bicarbonate-saturated aqueous solution of sodium sulfate is such that the molar concentration of Ca 2+ is 0.9 relative to the sum of the molar concentrations of Na 2 SO 4 and the molar concentrations of NaHCO 3 in the aqueous sodium sulfate solution saturated with sodium bicarbonate. to 1.1 times the molar concentration. If the amount of Ca 2+ is less than 0.9 times the molar concentration, SO 4 2- and HCO 3 - are not completely removed, and if it exceeds 1.1 times the molar concentration, the undissolved calcium source is removed together with calcium sulfate and calcium carbonate precipitates. This is undesirable because the drug cost increases accordingly.
  • the first solid precipitate generating unit 20 after the second circulation addition of a calcium source and thus production of calcium sulfate and calcium carbonate are performed at 25°C to 45°C.
  • the temperature is lower than 25°C or higher than 45°C, the solubility of Na 2 SO 4 is lowered and Na 2 SO 4 may precipitate, which is not preferable.
  • the production and recovery of calcium sulfate and calcium carbonate after the second circulation may be performed sequentially in two steps, in which case, calcium carbonate and calcium sulfate are generated in the first solid precipitate generating unit 20 And in the second solid precipitate generating unit 20 ', respectively, they are generated and recovered sequentially.
  • a calcium source is added to an aqueous solution of sodium sulfate saturated with sodium bicarbonate prepared in the dissolving unit 10, and the sodium bicarbonate is saturated.
  • the generation and recovery of calcium carbonate in the first solid precipitate generating unit 20 is performed at 25 °C to 45 °C. When the temperature is lower than 25°C or higher than 45°C, the solubility of Na 2 SO 4 is lowered and Na 2 SO 4 may precipitate, which is not preferable.
  • the calcium supply source is added to the remaining filtrate.
  • Calcium sulfate precipitate is produced by dissolving sodium hydrogen so that the molar concentration of Ca 2+ is 0.9 to 1.1 times the molar concentration of Na 2 SO 4 in a saturated aqueous solution of sodium sulfate, and calcium sulfate is formed in the filter 22'. This is recovered by filtration or the like.
  • the generation and recovery of the calcium sulfate precipitate in the second solid precipitate generating unit 20' is performed at 25 °C to 45 °C.
  • the temperature is lower than 25°C or higher than 45°C, the solubility of Na 2 SO 4 is lowered and Na 2 SO 4 may precipitate, which is not preferable.
  • the process in the sodium bicarbonate generating unit 30 after the second cycle is the same as the process in the sodium bicarbonate generating unit 30 in the first cycle.
  • the reaction in the sodium bicarbonate generating unit 30 after the second circulation is as shown in the above reaction formula (6).
  • Sodium bicarbonate is formed by the addition of CO 2 in the sodium bicarbonate generating unit 30 after the second cycle, specifically, in the sodium bicarbonate generating tank 31, which is recovered by filtration in the filter 32 and the remaining The filtrate to be recycled is recycled back to the dissolving unit 10 (specifically, the dissolving unit 10, the first solid precipitate generating unit 20 and the sodium bicarbonate generating unit 30 are repeated, or the dissolving unit 10, the second 1 solid precipitate generating unit 20, the second solid precipitate generating unit 20 'and sodium bicarbonate generating unit 30 may be repeated).
  • the filtrate (after the second circulation, when the production and recovery of calcium sulfate and calcium carbonate are performed in a single step in the solid precipitate generating unit) , The filtrate after calcium carbonate and calcium sulfate are recovered in the first solid precipitate generating unit 20; After the second cycle, the production and recovery of calcium sulfate and calcium carbonate in the solid precipitate generating unit are sequentially performed in two steps.
  • CO 2 is dissolved at a molar concentration of 1.0 to 2.2 times the sum of the molar concentrations of Na 2 SO 4 and NaHCO 3 in the filtrate after calcium sulfate is recovered in the second solid precipitate generating unit 20).
  • a molar concentration less than 1.0 times NaHCO 3 is not formed as much as the solubility of NaHCO 3 , which is undesirable in that the production of NaHCO 3 is lowered, and when CO 2 exceeds 2.2 times the molar concentration, excess CO It is not preferable in that CO 2 is lost as 2 is added.
  • the filtrate remaining after recovering sodium bicarbonate in the sodium bicarbonate generating unit 30 of the second circulation is recycled back to the dissolving unit 10 (eg, the third circulation, the fourth circulation, etc.)
  • This may be referred to as 'after the second cycle' or 'second cycle abnormality'.
  • the process 'after the second cycle' or 'above the second cycle' is the same as the process of the 'second cycle', and therefore, the 'second cycle' is also referred to as 'after the second cycle'.
  • each circulation step of the manufacturing apparatus of the present invention described above, and each process in the dissolution section and the production section has been generally described.
  • the manufacturing apparatus of the present invention is configured as in the following 1 to 6, and each process may be performed.
  • the information described herein is equally applicable to all of the embodiments 1 to 6 below.
  • the first embodiment as an apparatus for producing sodium hydrogen carbonate from industrial by-products containing sodium sulfate, including a dissolution unit, a first solid precipitate generation unit and a sodium hydrogen carbonate generation unit,
  • an aqueous solution of sodium sulfate in which industrial by-products containing sodium sulfate are dissolved in water is prepared;
  • calcium sulfate is generated and recovered by reacting sulfate ions in the sodium sulfate aqueous solution with calcium ions provided by a calcium source;
  • a production device in which sodium bicarbonate is generated and recovered by dissolving carbon dioxide in the filtrate remaining after recovering calcium sulfate in the first solid precipitate generating unit.
  • an apparatus for producing sodium hydrogen carbonate from industrial by-products containing sodium sulfate including a dissolution unit, a first solid precipitate generation unit, and a sodium hydrogen carbonate generation unit,
  • the treatment in the manufacturing apparatus includes a first cycle in which industrial by-products containing sodium sulfate are sequentially processed in the dissolving unit, the first solid precipitate generating unit, and the sodium bicarbonate generating unit; And after the filtrate remaining after the recovery of sodium bicarbonate in the sodium bicarbonate generating unit of the first circulation is recycled to the dissolving unit, it is sequentially processed in the dissolving unit, the first solid precipitate generating unit, and the sodium bicarbonate generating unit. Including a second cycle that becomes,
  • an aqueous solution of sodium sulfate in which industrial by-products containing sodium sulfate are dissolved in water is prepared;
  • calcium sulfate is generated and recovered by reacting sulfate ions in the sodium sulfate aqueous solution with calcium ions provided by a calcium source;
  • an industrial by-product containing sodium sulfate is dissolved in the filtrate remaining after the recovery of sodium hydrogen carbonate in the sodium hydrogen carbonate generating part of the first cycle to prepare a sodium sulfate aqueous solution saturated with sodium hydrogen carbonate;
  • sulfate ions and bicarbonate ions in an aqueous solution of sodium sulfate saturated with sodium bicarbonate react with calcium ions provided by a calcium source to produce and recover calcium sulfate and calcium carbonate;
  • a production device in which sodium bicarbonate is generated and recovered by dissolving carbon dioxide in the filtrate remaining after recovering calcium sulfate and calcium carbonate in the first solid precipitate generating unit.
  • an apparatus for producing sodium bicarbonate from industrial by-products containing sodium sulfate including a dissolution unit, a first solid precipitate generating unit, a second solid precipitate generating unit and sodium bicarbonate generating unit,
  • an aqueous solution of sodium sulfate in which industrial by-products containing sodium sulfate are dissolved in water is prepared;
  • calcium sulfate is generated and recovered by reacting sulfate ions in the sodium sulfate aqueous solution with calcium ions provided by a calcium source;
  • a production device in which sodium bicarbonate is generated and recovered by dissolving carbon dioxide in the filtrate remaining after recovering the calcium carbonate in the second solid precipitate generating unit.
  • an apparatus for producing sodium bicarbonate from industrial by-products containing sodium sulfate including a dissolution unit, a first solid precipitate generating unit, a second solid precipitate generating unit and sodium bicarbonate generating unit,
  • the treatment in the manufacturing apparatus includes a first cycle in which industrial by-products containing sodium sulfate are sequentially processed in the dissolving unit, the first solid precipitate generating unit, and the sodium bicarbonate generating unit; And after the filtrate remaining after the recovery of sodium bicarbonate in the sodium bicarbonate generating unit of the first circulation is recycled to the dissolving unit, the dissolving unit, the first solid precipitate generating unit, and the second solid precipitate generating unit and hydrogen carbonate Including a second circulation sequentially processed in the sodium generating unit,
  • an aqueous solution of sodium sulfate in which industrial by-products containing sodium sulfate are dissolved in water is prepared;
  • calcium sulfate is generated and recovered by reacting sulfate ions in the sodium sulfate aqueous solution with calcium ions provided by a calcium source;
  • an industrial by-product containing sodium sulfate is dissolved in the filtrate remaining after recovering sodium hydrogen carbonate in the sodium hydrogen carbonate generating part of the first cycle to prepare an aqueous solution of sodium sulfate saturated with sodium hydrogen carbonate;
  • calcium carbonate is produced and recovered by reacting bicarbonate ions in an aqueous solution of sodium sulfate saturated with sodium bicarbonate and calcium ions provided by a calcium source;
  • a production device in which sodium bicarbonate is generated and recovered by dissolving carbon dioxide in the filtrate remaining after the recovery of calcium sulfate in the second solid precipitate generating unit.
  • an apparatus for producing sodium bicarbonate from industrial by-products containing sodium sulfate including a dissolution unit, a first solid precipitate generating unit, a second solid precipitate generating unit and sodium bicarbonate generating unit,
  • the treatment in the manufacturing apparatus includes a first cycle in which industrial by-products containing sodium sulfate are sequentially processed in the dissolving unit, the first solid precipitate generating unit, the second solid precipitate generating unit, and the sodium bicarbonate generating unit; And after the filtrate remaining after the recovery of sodium bicarbonate in the sodium bicarbonate generating unit of the first circulation is recycled to the dissolving unit, it is sequentially processed in the dissolving unit, the first solid precipitate generating unit, and the sodium bicarbonate generating unit. Including a second cycle that becomes,
  • an aqueous solution of sodium sulfate in which industrial by-products containing sodium sulfate are dissolved in water is prepared;
  • calcium sulfate is generated and recovered by reacting sulfate ions in the sodium sulfate aqueous solution with calcium ions provided by a calcium source;
  • an industrial by-product containing sodium sulfate is dissolved in the filtrate remaining after the recovery of sodium hydrogen carbonate in the sodium hydrogen carbonate generating part of the first cycle to prepare a sodium sulfate aqueous solution saturated with sodium hydrogen carbonate;
  • calcium sulfate and calcium carbonate are generated and recovered by reacting calcium ions provided by a calcium supply source with sulfate ions and bicarbonate ions in an aqueous solution of sodium sulfate saturated with sodium bicarbonate;
  • a production device in which sodium bicarbonate is generated and recovered by dissolving carbon dioxide in the filtrate remaining after the recovery of calcium sulfate and calcium carbonate in the first solid precipitate generating unit.
  • an apparatus for producing sodium bicarbonate from industrial by-products containing sodium sulfate including a dissolution unit, a first solid precipitate generating unit, a second solid precipitate generating unit and sodium hydrogen carbonate generating unit,
  • the treatment in the manufacturing apparatus includes a first cycle in which industrial by-products containing sodium sulfate are sequentially processed in the dissolving unit, the first solid precipitate generating unit, the second solid precipitate generating unit, and the sodium bicarbonate generating unit; And after the filtrate remaining after the recovery of sodium bicarbonate in the sodium bicarbonate generating unit of the first circulation is recycled to the dissolving unit, the dissolving unit, the first solid precipitate generating unit, the second solid precipitate generating unit and sodium bicarbonate It includes a second cycle that is sequentially processed in the generating unit,
  • an aqueous solution of sodium sulfate in which industrial by-products containing sodium sulfate are dissolved in water is prepared;
  • calcium sulfate is generated and recovered by reacting sulfate ions in the sodium sulfate aqueous solution with calcium ions provided by a calcium source;
  • an industrial by-product containing sodium sulfate is dissolved in the filtrate remaining after the recovery of sodium hydrogen carbonate in the sodium hydrogen carbonate generating part of the first cycle to prepare a sodium sulfate aqueous solution saturated with sodium hydrogen carbonate;
  • calcium carbonate is produced and recovered by reacting bicarbonate ions in an aqueous solution of sodium sulfate saturated with sodium bicarbonate and calcium ions provided by a calcium source;
  • a production device in which sodium bicarbonate is generated and recovered by dissolving carbon dioxide in the filtrate remaining after recovering calcium sulfate in the second solid precipitate generating unit.
  • the filtrate remaining after recovery of sodium bicarbonate in the sodium bicarbonate generating unit of the second cycle may be recycled back to the dissolving unit, and the number of times of recirculation is not particularly limited, and may be appropriately repeated, for example, by those skilled in the art in consideration of treatment of industrial by-products and/or recovery of sodium bicarbonate, calcium sulfate, and/or calcium carbonate.
  • Calcium sulfate, calcium carbonate and/or sodium bicarbonate are efficiently recovered with high purity by the production apparatus 100 of the present invention as described above.
  • a sodium sulfate aqueous solution was prepared by dissolving the waste desulfurization agent having the composition shown in Table 1 in fresh water at 30° C. to 40° C. in the dissolving unit 10. At this time, the waste desulfurization agent was dissolved in water so that the amount of sodium sulfate dissolved in 1 L of water was 400 g (400 g/L) in the sodium sulfate aqueous solution.
  • a sodium sulfate aqueous solution was prepared by dissolving the waste desulfurization agent having the composition shown in Table 1 in fresh water at 30° C. to 40° C. in the dissolving unit 10. At this time, the waste desulfurization agent was dissolved in water so that the amount of sodium sulfate dissolved in 1 L of water was 400 g in the sodium sulfate aqueous solution.
  • the waste desulfurization agent having the composition shown in Table 1 was dissolved in 1 L of the filtrate (2) at 40° C. in the dissolving unit 10 so that the amount of sodium sulfate was 400 g (400 g/L), thereby obtaining an aqueous solution of sodium sulfate saturated with sodium bicarbonate. .
  • a sodium sulfate aqueous solution was prepared by dissolving the waste desulfurization agent having the composition shown in Table 1 in fresh water at 30° C. to 40° C. in the dissolving unit 10. At this time, the waste desulfurization agent was dissolved in water so that the amount of sodium sulfate dissolved in 1 L of water was 400 g in the sodium sulfate aqueous solution.
  • a sodium sulfate aqueous solution was prepared by dissolving the waste desulfurization agent having the composition shown in Table 1 in fresh water at 30° C. to 40° C. in the dissolving unit 10. At this time, the waste desulfurization agent was dissolved in water so that the amount of sodium sulfate dissolved in 1 L of water was 400 g in the sodium sulfate aqueous solution.
  • the waste desulfurization agent having the composition of Table 1 is dissolved in 1 L of the filtrate (2) at 40° C. so that the amount of sodium sulfate is 400 g (i.e., 400 g/L) to obtain an aqueous solution of sodium sulfate saturated with sodium bicarbonate. got it
  • a sodium sulfate aqueous solution was prepared by dissolving the waste desulfurization agent having the composition shown in Table 1 in fresh water at 30° C. to 40° C. in the dissolving unit 10. At this time, the waste desulfurization agent was dissolved in water so that the amount of sodium sulfate dissolved in 1 L of water was 400 g in the sodium sulfate aqueous solution.
  • the waste desulfurization agent having the composition of Table 1 is dissolved in 1 L of the filtrate (3) at 40° C. so that the amount of sodium sulfate is 400 g (i.e., 400 g/L) to obtain an aqueous solution of sodium sulfate saturated with sodium bicarbonate. got it
  • a sodium sulfate aqueous solution was prepared by dissolving the waste desulfurization agent having the composition shown in Table 1 in fresh water at 30° C. to 40° C. in the dissolving unit 10. At this time, the waste desulfurization agent was dissolved in water so that the amount of sodium sulfate dissolved in 1 L of water was 400 g in the sodium sulfate aqueous solution.
  • the waste desulfurization agent having the composition of Table 1 is dissolved in 1 L of the filtrate (3) at 40° C. so that the amount of sodium sulfate is 400 g (i.e., 400 g/L) to obtain an aqueous solution of sodium sulfate saturated with sodium bicarbonate. got it
  • industrial by-products containing sodium sulfate are stably treated, and sodium bicarbonate (NaHCO 3 ) as well as calcium sulphate (CaSO 4 , gypsum) and calcium carbonate (CaCO 3 ) are recovered.

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Abstract

La présente invention concerne un appareil de production de bicarbonate de sodium à partir de sous-produits industriels contenant du sulfate de sodium. L'invention concerne l'appareil de production de bicarbonate de sodium à partir de sous-produits industriels contenant du sulfate de sodium, comprenant une unité de dissolution, une première unité de production de précipité en phase solide, et une unité de production de bicarbonate de sodium, dans l'unité de dissolution, une solution aqueuse de sulfate de sodium dans laquelle des sous-produits industriels contenant du sulfate de sodium sont dissous dans de l'eau étant préparée ; dans la première unité de production de précipité en phase solide, du sulfate de calcium est produit et récupéré par une réaction entre des ions sulfate dans la solution aqueuse de sulfate de sodium et des ions calcium fournis par une source de calcium ; et dans l'unité de production de bicarbonate de sodium, du bicarbonate de sodium est produit et récupéré par dissolution de dioxyde de carbone dans le filtrat restant après la récupération de sulfate de calcium dans la première unité de production de précipité en phase solide. Par l'appareil de production de la présente invention, les sous-produits industriels contenant du sulfate de sodium peuvent être traités à faible coût, et le bicarbonate de sodium coûteux peut être efficacement récupéré.
PCT/KR2022/021075 2021-12-22 2022-12-22 Appareil de production de bicarbonate de sodium à partir de sous-produits industriels contenant du sulfate de sodium WO2023121346A1 (fr)

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JP2002126448A (ja) * 2000-07-31 2002-05-08 Showa Denko Kk 燃焼排ガスの処理方法及び処理装置
JP2002523330A (ja) * 1998-08-26 2002-07-30 ソルヴェイ 塩化ナトリウム結晶の製造方法
KR20160000480A (ko) * 2014-06-24 2016-01-05 순천대학교 산학협력단 탈황폐액으로부터 소듐바이카보네이트(NaHCO3)를 합성하는 방법 및 장치
KR20200061649A (ko) * 2018-11-26 2020-06-03 현대제철 주식회사 탈황부산물을 이용한 중조 재생 방법

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Publication number Priority date Publication date Assignee Title
JP2803863B2 (ja) * 1988-10-26 1998-09-24 ソルヴェイ 硫酸ナトリウムを含有する残渣を除去する方法
JP2002523330A (ja) * 1998-08-26 2002-07-30 ソルヴェイ 塩化ナトリウム結晶の製造方法
JP2002126448A (ja) * 2000-07-31 2002-05-08 Showa Denko Kk 燃焼排ガスの処理方法及び処理装置
KR20160000480A (ko) * 2014-06-24 2016-01-05 순천대학교 산학협력단 탈황폐액으로부터 소듐바이카보네이트(NaHCO3)를 합성하는 방법 및 장치
KR20200061649A (ko) * 2018-11-26 2020-06-03 현대제철 주식회사 탈황부산물을 이용한 중조 재생 방법

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117902610A (zh) * 2024-01-19 2024-04-19 天津大学 一种硫酸钠高盐废水资源化回收利用的方法

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