WO2018052220A1 - Method and facility for preparing sodium bicarbonate and calcium carbonate - Google Patents

Method and facility for preparing sodium bicarbonate and calcium carbonate Download PDF

Info

Publication number
WO2018052220A1
WO2018052220A1 PCT/KR2017/009836 KR2017009836W WO2018052220A1 WO 2018052220 A1 WO2018052220 A1 WO 2018052220A1 KR 2017009836 W KR2017009836 W KR 2017009836W WO 2018052220 A1 WO2018052220 A1 WO 2018052220A1
Authority
WO
WIPO (PCT)
Prior art keywords
calcium carbonate
sodium bicarbonate
sodium
calcium
gas
Prior art date
Application number
PCT/KR2017/009836
Other languages
French (fr)
Korean (ko)
Inventor
한건우
안치규
이만수
이민우
김국희
손민아
박두영
김세훈
Original Assignee
재단법인 포항산업과학연구원
계명대학교 산학협력단
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 재단법인 포항산업과학연구원, 계명대학교 산학협력단 filed Critical 재단법인 포항산업과학연구원
Publication of WO2018052220A1 publication Critical patent/WO2018052220A1/en

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • 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
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/20—Waste processing or separation
    • 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
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies

Definitions

  • the present invention relates to a method and an apparatus for producing sodium bicarbonate and calcium carbonate from industrial by-products.
  • FIG. 1 is a view schematically showing a conventional process for producing sodium bicarbonate and calcium carbonate from industrial by-products.
  • Conventional sodium bicarbonate and calcium carbonate manufacturing processes are composed of carbon dioxide, industrial by-products containing calcium, and sodium hydroxide (NaOH), which are collected at power plants and steel mills, to form inorganic sodium carbonate (NaHCO 3 ) and calcium carbonate. (CaCO 3 ) relates to the technology of producing together.
  • the elution agent is used to elute calcium ions from the industrial by-product containing calcium, and to adjust the pH by supplying sodium hydroxide to the supernatant containing the eluted calcium ions. Thereafter, calcium carbonate is produced by supplying carbon dioxide. After recovering the calcium carbonate, the remaining filtrate is reacted with carbon dioxide in a heavy tank reactor to produce a heavy tank.
  • sodium hydroxide which is added to adjust pH, is recycled as a raw material of sodium bicarbonate to produce calcium carbonate and sodium bicarbonate together.
  • the high solubility of sodium bicarbonate i.e., recovery of the precipitated sodium bicarbonate due to the solubility of 96g / L at 20 °C and the remaining filtrate, the sodium ions (Na +) and bicarbonate ion (HCO 3 -) with the high Present in concentration.
  • the bicarbonate ions are converted to carbonate ions (CO 3 2 ⁇ ) due to the hydroxyl group (OH ⁇ ) eluted from industrial by-products.
  • the converted carbonate ions react with the calcium ions eluted from the industrial by-products to form calcium carbonates, and these calcium carbonates cover the surface of the industrial by-products such as slag, making it difficult to elute additional calcium ions.
  • FIG. 2 is a graph showing the elution amount of calcium ions eluted from industrial by-products according to the concentration of sodium bicarbonate dissolved in an eluent (2M aqueous ammonium chloride solution).
  • an eluent 2M aqueous ammonium chloride solution.
  • the concentration of the eluted calcium ions exceeds 6,000 mg / L, but the concentration of the eluted calcium ions decreases as the amount of sodium bicarbonate is increased.
  • the content of the sodium bicarbonate contained in the eluent is 0.7g / 100g-water, the dissolution rate is approximately 50% less than that without adding the sodium bicarbonate.
  • the amount of sodium bicarbonate is increased, the amount of calcium ions eluted rapidly decreases, and calcium ions are hardly eluted when the sodium bicarbonate is supplied to equilibrium solubility.
  • the carbon dioxide supplied solution provides a sodium bicarbonate and calcium carbonate manufacturing method further comprises a sodium salt having a higher solubility than the sodium bicarbonate.
  • the sodium salt may be supplied before the carbon dioxide containing gas is supplied to the sodium hydroxide solution.
  • the sodium salt may be supplied to the sodium hydroxide solution together with the carbon dioxide containing gas, or may be supplied after the carbon dioxide containing gas is supplied to the sodium hydroxide solution.
  • the sodium salt may be sodium nitrate (NaNO 3 ), sodium chloride (NaCl), or a mixture thereof.
  • the calcium ion-containing solution may be prepared by eluting calcium ion from an industrial by-product containing calcium using an eluent.
  • the eluent is an aqueous solution of ammonium chloride (NH 4 Cl), hydrogen chloride (HCl), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), acetic acid (CH 3 COOH), and ammonium nitrate (NH 4 NO 3 ). It may be selected from the group consisting of.
  • the industrial by-product may be at least one selected from the group consisting of steel slag, coal ash, bottom ash, fly ash, waste cement, waste concrete, and paper sludge.
  • Recovering the calcium carbonate may further comprise the step of reusing the remaining filtrate as the eluent.
  • the carbon dioxide-containing gas is FINEX off gas (FOG), FINEX tail gas (FTG, FINEX tail gas), blast furnace gas (BFG, Blast furnace gas), converter gas, coal power plant flue gas, gas power plant flue gas, incinerator flue gas It may be one or more selected from the group consisting of glass melting flue gas, thermal facility flue gas, petrochemical process flue gas, petrochemical process flue gas, pre-combustion flue gas and gasifier flue gas.
  • FINEX off gas FINEX tail gas
  • FFG FINEX tail gas
  • blast furnace gas BFG, Blast furnace gas
  • converter gas coal power plant flue gas
  • gas power plant flue gas gas power plant flue gas
  • incinerator flue gas It may be one or more selected from the group consisting of glass melting flue gas, thermal facility flue gas, petrochemical process flue gas, petrochemical process flue gas, pre-combustion flue gas and gasifier flue gas.
  • a sodium bicarbonate production unit including a sodium hydroxide solution supply unit, a carbon dioxide-containing gas supply unit, and a sodium salt supply unit for selectively supplying a sodium salt having a higher solubility than the sodium bicarbonate tank;
  • a first solid-liquid separator for recovering the heavy water precipitated in the heavy water producing unit and discharging the filtrate of the heavy water producing unit;
  • a calcium carbonate production unit including an inlet of the filtrate discharged from the sodium bicarbonate production unit and a calcium ion-containing solution supply unit;
  • a second solid-liquid separator for recovering the calcium carbonate obtained from the calcium carbonate producing unit and discharging the filtrate of the calcium carbonate producing unit.
  • a resupply unit configured to supply the filtrate discharged from the second solid-liquid separator to the heavy tank production unit.
  • the calcium ion-containing solution supply part may be in communication with the elution part in which the calcium ion-containing solution is produced.
  • the elution part may include an industrial by-product supply part and an eluent supply part containing calcium.
  • the eluent may be in communication so that the filtrate discharged from the second solid-liquid separator is supplied to the eluent.
  • 1 is a view schematically showing a conventional process for producing sodium bicarbonate and calcium carbonate from industrial by-products.
  • FIG. 2 is a graph showing the elution amount of calcium ions eluted from industrial by-products according to the concentration of sodium bicarbonate dissolved in an eluent (2M ammonium chloride).
  • 3 and 4 is a view schematically showing the sodium bicarbonate and calcium carbonate production equipment according to an embodiment of the present invention.
  • the present invention relates to a method and an apparatus for producing sodium bicarbonate and calcium carbonate from industrial byproducts, and specifically, an industrial sodium bicarbonate, an exhaust gas containing carbon dioxide, and sodium hydroxide, which is a high value-added substance using sodium hydroxide and A method and equipment for producing calcium carbonate.
  • a method for producing sodium bicarbonate and calcium carbonate is a) supplying a carbon dioxide-containing gas to a sodium hydroxide (NaOH) solution to produce a sodium bicarbonate (NaHCO 3 ) by the reaction of sodium hydroxide and carbon dioxide, b) recovering the sodium bicarbonate to the remaining filtrate Supplying a solution containing calcium ions to produce calcium carbonate (CaCO 3 ) by a reaction between calcium carbonate (CO 3 2- ) and calcium ions, and c) recovering the calcium carbonate, and the remaining filtrate is dissolved in the sodium hydroxide. Refeeding the solution.
  • the sodium bicarbonate is produced by the reaction of the sodium hydroxide and carbon dioxide. Since the solubility of the sodium bicarbonate is 96 g / L at 20 °C, the sodium bicarbonate is dissolved as much as solubility in the remaining filtrate after recovering the precipitated sodium bicarbonate. Accordingly, calcium carbonate is additionally produced by supplying calcium ions to the filtrate in which the sodium bicarbonate is dissolved. That is, by performing the steps a) and b) it is possible to produce a high value-added sodium bicarbonate and calcium carbonate together. On the other hand, since the remaining filtrate after recovering the calcium carbonate contains sodium ions, bicarbonate ions and the like, the filtrate is supplied to the solution in which sodium hydroxide is dissolved and reused in the production of sodium bicarbonate.
  • the sodium bicarbonate is produced by the reaction of the sodium hydroxide and carbon dioxide.
  • the reaction scheme of this sodium bicarbonate production reaction is shown in the following Equation 1.
  • Equation 1 NaOH + CO 2 ⁇ NaHCO 3
  • the sodium bicarbonate is dissolved as much as solubility in the remaining filtrate after recovering the precipitated sodium bicarbonate. That is, sodium ions (Na + ), bicarbonate ions (HCO 3 ⁇ ), carbonate ions (CO 3 2- ), and the like are dissolved in the filtrate.
  • the carbon dioxide-containing gas is a by-product generated in an industrial process such as an iron making process, and includes, for example, FINEX off gas (FOG), FINEX tail gas (FTG), and blast furnace gas (BFG, Blast furnace gas, converter gas, coal power plant flue gas, gas power plant flue gas, incinerator flue gas, glass melting flue gas, thermal facility flue gas, petrochemical process flue gas, petrochemical process gas, pre-combustion gas and gasifier flue gas There may be more than one.
  • FINEX off gas FINEX tail gas
  • BFG blast furnace gas
  • converter gas coal power plant flue gas
  • gas power plant flue gas gas power plant flue gas
  • incinerator flue gas incinerator flue gas
  • glass melting flue gas glass melting flue gas
  • thermal facility flue gas petrochemical process flue gas
  • petrochemical process gas petrochemical process gas
  • pre-combustion gas and gasifier flue gas There may be more than one.
  • the sodium hydroxide solution is further supplied with a sodium salt having a higher solubility than the sodium bicarbonate.
  • the sodium salt is to play a role of improving the precipitation amount of the sodium bicarbonate by the common ion effect.
  • the sodium bicarbonate having a solubility of 96 g / L at 20 ° C. is in equilibrium with sodium ions and bicarbonate ions as shown in Equation 2 below.
  • Equation 2 NaHCO 3 ⁇ Na + + HCO 3 -
  • sodium salt for example, sodium chloride
  • the sodium chloride is divided into sodium ions and chloride ions as shown in Equation 3 below.
  • Equation 3 NaCl ⁇ Na + + Cl -
  • Equation 2 Since sodium ions entering the equilibrium system of Equation 2 are the same ions as the sodium ions participating in the original equilibrium, it acts as a factor to increase the concentration of sodium ions in the equilibrium system. Thus, according to LeChatlier's principle, the equilibrium shifts to the left in Equation 2 to reduce the concentration of sodium ions to reach a new equilibrium. This equilibrium shift results in a decrease in the concentration of bicarbonate ions and precipitation of the sodium bicarbonate. That is, when sodium salt is supplied during the sodium bicarbonate reaction, the precipitation amount of the sodium bicarbonate is improved by the common ion effect of sodium ions that are dissolved by sodium chloride.
  • the sodium salt may be supplied to the sodium hydroxide solution before the carbon dioxide containing gas is supplied to the sodium hydroxide solution.
  • the solubility of carbon dioxide is increased as the precipitation amount of the sodium bicarbonate is improved, thereby reducing the content of carbon dioxide discharged into the air without being dissolved in the solution. There is this.
  • the sodium salt may be supplied to the sodium hydroxide solution together with the carbon dioxide-containing gas, or may be supplied after the carbon dioxide-containing gas is supplied to the sodium hydroxide solution.
  • the sodium salt is supplied to the sodium hydroxide solution together with the carbon dioxide-containing gas, or supplied after the carbon dioxide-containing gas is supplied, there is an advantage in that the sodium bicarbonate having a desired content can be obtained by controlling the amount of precipitated sodium bicarbonate.
  • the sodium salt is not particularly limited as long as it has a higher solubility than sodium bicarbonate and contains sodium ions, but is preferably sodium nitrate (NaNO 3 ), sodium chloride (NaCl), or a mixture thereof.
  • Equation 4 CO 3 2- + Ca 2+ ⁇ CaCO 3
  • calcium carbonate can be additionally prepared by recovering the sodium bicarbonate and supplying calcium ions to the remaining filtrate.
  • the manufacturing method according to an embodiment of the present invention using only calcium ion-containing material, sodium hydroxide and carbon dioxide-containing gas can be produced together with the sodium bicarbonate and calcium carbonate as a high value-added material.
  • the calcium ion-containing solution supplied to the filtrate may be prepared by eluting calcium ion from industrial by-products containing calcium.
  • the industrial by-products are not particularly limited as long as they contain calcium.
  • the industrial by-products may be at least one selected from the group consisting of steel slag, coal ash, bottom ash, fly ash, waste cement, waste concrete, and paper sludge. .
  • Calcium ions can be eluted from the industrial by-product using an eluent, and the type of the eluent is not particularly limited, for example, ammonium chloride (NH 4 Cl), hydrogen chloride (HCl), nitric acid (HNO 3 ). , At least one selected from the group consisting of sulfuric acid (H 2 SO 4 ), acetic acid (CH 3 COOH), and an aqueous solution of ammonium nitrate (NH 4 NO 3 ).
  • the concentration of calcium ions contained in the calcium ion-containing solution is preferably higher than the combined concentration of bicarbonate ions and carbonate ions contained in the filtrate.
  • the remaining filtrate after recovering the calcium carbonate prepared in the reaction of Equation 4 may be reused as an eluent.
  • the bicarbonate ions are eluted from the industrial by-products (OH ⁇ ).
  • This carbonate ion (CO 3 2- ) is converted.
  • the carbonate ions and the converted carbonate ions contained in the filtrate may react with the calcium ions eluted from the industrial by-products to form calcium carbonates.
  • These calcium carbonates cover the surface of the industrial by-products such as slag to prevent further elution of calcium ions. Problems may occur.
  • the concentration of calcium ions contained in the calcium ion-containing solution is controlled to be higher than the combined concentration of bicarbonate ions and carbonate ions contained in the filtrate, both bicarbonate ions and carbonate ions can be converted to calcium carbonate. Accordingly, the filtrate does not contain bicarbonate ions and carbonate ions, it is possible to prevent the problem of preventing elution of calcium ions from industrial by-products when reusing the filtrate remaining after the recovery of calcium carbonate as the eluent.
  • the filtrate since the remaining filtrate after recovering the calcium carbonate contains sodium ions, bicarbonate ions, etc., the filtrate is supplied to the solution in which sodium hydroxide is dissolved and reused in the production of sodium bicarbonate. In addition, as described above, the remaining filtrate after recovering the calcium carbonate can be reused as the eluent.
  • the present invention provides a plant for producing sodium bicarbonate and calcium carbonate.
  • 3 and 4 are diagrams schematically showing equipment for producing sodium bicarbonate and calcium carbonate according to an embodiment of the present invention.
  • a sodium bicarbonate production unit having a sodium hydroxide solution supply unit, a carbon dioxide-containing gas supply unit, and a sodium salt supply unit that can be selectively supplied with a higher solubility of sodium salt;
  • a first solid-liquid separator for recovering the heavy water precipitated in the heavy water producing unit and discharging the filtrate of the heavy water producing unit;
  • a calcium carbonate production unit including an inlet of the filtrate discharged from the first solid-liquid separator and a calcium ion-containing solution supply unit;
  • a second solid-liquid separator for recovering the calcium carbonate obtained from the calcium carbonate producing unit and discharging the filtrate of the calcium carbonate producing unit.
  • a resupply unit allowing the filtrate discharged from the second solid-liquid separator to be resupplyed to the heavy tank production unit.
  • the sodium bicarbonate production unit is supplied with sodium hydroxide solution, carbon dioxide-containing gas, and sodium salt having a higher solubility than sodium bicarbonate, and thus, sodium bicarbonate is produced by the reaction of sodium hydroxide and carbon dioxide, and the first and the second filtrate discharged from the sodium bicarbonate production unit.
  • the separated, specifically, precipitated sodium bicarbonate is recovered and the filtrate of the sodium bicarbonate production part is discharged.
  • the filtrate discharged from the sodium bicarbonate production unit flows into the calcium carbonate production unit through the inlet of the filtrate discharged from the first solid-liquid separation unit, and together with the calcium ion-containing solution through the calcium ion-containing solution supply unit, the calcium carbonate production unit In the reaction of calcium carbonate with calcium ions, calcium carbonate is produced. Thereafter, the calcium carbonate and the filtrate discharged from the calcium carbonate production unit are separated in the second solid-liquid separation unit, specifically, the calcium carbonate is recovered and the filtrate of the calcium carbonate production unit is discharged.
  • first solid-liquid separator and the second solid-liquid separator are not particularly limited as long as they can separate solid and liquid, and the same or different solid-liquid separator may be applied.
  • the first solid-liquid separator and the second solid-liquid separator may be independently selected from, for example, a filtration device, a filter press device, and the like, but is not limited thereto.
  • one or more pumps may be provided if necessary to smooth the flow including inflow and outflow between the respective regions constituting the sodium bicarbonate and calcium carbonate manufacturing facilities of the present invention.
  • a heavy tank is produced by the reaction of the supplied sodium hydroxide solution and carbon dioxide-containing gas.
  • the carbon dioxide-containing gas is not particularly limited as long as it is generated in an industrial process such as steelmaking industry and includes carbon dioxide.
  • FINEX off gas FINEX off gas
  • FINEX tail gas FINEX tail gas
  • BFG Blast furnace gas
  • converter gas coal power plant flue gas, gas power plant flue gas, incinerator flue gas, glass melting flue gas, heat facility flue gas, petrochemical process flue gas, petrochemical process gas, pre-combustion flue gas and gasifier flue gas It may be one or more selected from the group consisting of.
  • the sodium bicarbonate production unit may be supplied with sodium salt having a higher solubility than sodium bicarbonate, which serves to improve the amount of precipitation of the sodium bicarbonate as described above.
  • the sodium salt is not particularly limited as long as it has higher solubility than sodium bicarbonate and contains sodium ions.
  • the sodium salt may be sodium nitrate (NaNO 3 ), sodium chloride (NaCl), or a mixture thereof.
  • the sodium bicarbonate is precipitated in the sodium bicarbonate production unit, and the remaining filtrate after separating the precipitated sodium bicarbonate is supplied to the calcium carbonate producing unit.
  • the calcium carbonate production unit is supplied with the filtrate and the solution containing calcium ions, and calcium carbonate is produced by the reaction of the carbonate and calcium ions contained in the filtrate. Therefore, the production facility according to an embodiment of the present invention can produce calcium carbonate with sodium bicarbonate.
  • the manufacturing equipment may further include an elution part in which the calcium ion-containing solution is produced. That is, the calcium ion-containing solution supply part may be in communication with the elution part in which the calcium ion-containing solution is produced, wherein the elution part is supplied with industrial by-products and eluents containing calcium, and the elution agent receives calcium ions from the industrial by-products.
  • the elution unit may include an industrial by-product supply unit and an eluent supply unit containing calcium to elute to prepare the calcium ion-containing solution.
  • the industrial by-products are not particularly limited as long as they include calcium, but may be one or more selected from the group consisting of coal ash, bottom ash, fly ash, waste cement, waste concrete, and paper sludge.
  • the eluent may be an acid, a base, and the like, for example, ammonium chloride (NH 4 Cl), hydrogen chloride (HCl), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), acetic acid (CH 3 COOH), and at least one selected from the group consisting of an aqueous solution of ammonium nitrate (NH 4 NO 3 ).
  • the filtrate discharged from the second solid-liquid separator includes an eluent, sodium ions, bicarbonate ions, etc.
  • the filtrate may be re-supplied to the heavy tank production unit, or may be supplied to the elution unit and reused as an eluent.
  • a part of the filtrate may be re-supplied to the heavy tank production unit, and the remaining part may be supplied to the elution unit and reused as the eluent.
  • the eluent may be in communication with the second solid-liquid separator so that the filtrate discharged from the second solid-liquid separator is supplied to the eluent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

According to one embodiment of the present invention, provided is a method and a facility for preparing sodium bicarbonate and calcium carbonate, comprising the steps of: producing sodium bicarbonate (NaHCO3) through a reaction of sodium hydroxide and carbon dioxide by supplying a carbon dioxide-containing gas to a sodium hydroxide (NaOH) solution; producing calcium carbonate (CaCO3) through a reaction of a carbonate ion (CO3 2-) and a calcium ion by supplying a calcium ion-containing solution to the filtrate remaining after recovering the sodium bicarbonate; and resupplying the filtrate remaining after recovering the calcium carbonate to a solution in which the sodium hydroxide is dissolved, wherein a sodium salt having a solubility higher than that of the sodium bicarbonate is added to the sodium hydroxide solution. According to the present invention, there are effects enabling calcium carbonate and sodium bicarbonate, which are high-value-added materials, to be produced together from industrial by-products, which are to be disposed, and preventing the problem of a dissolution rate decrease of calcium ions when implementing a continuous process.

Description

중조 및 탄산칼슘 제조방법 및 제조설비Manufacturing method and equipment for sodium bicarbonate and calcium carbonate
본 발명은 산업부산물로부터 중조 및 탄산칼슘을 제조하는 방법 및 설비에 관한 것이다.The present invention relates to a method and an apparatus for producing sodium bicarbonate and calcium carbonate from industrial by-products.
도 1은 산업부산물로부터 중조 및 탄산칼슘을 제조하는 종래의 공정을 모식적으로 나타낸 도면이다. 종래의 중조 및 탄산칼슘 제조 공정은, 발전소/제철소 등에서 포집한 이산화탄소, 칼슘을 함유한 산업부산물, 및 수산화나트륨(NaOH)을 이용해 융합된 공정을 구성함으로써 무기탄산염인 중조(NaHCO3)와 탄산칼슘(CaCO3)을 함께 생산하는 기술에 관한 것이다.1 is a view schematically showing a conventional process for producing sodium bicarbonate and calcium carbonate from industrial by-products. Conventional sodium bicarbonate and calcium carbonate manufacturing processes are composed of carbon dioxide, industrial by-products containing calcium, and sodium hydroxide (NaOH), which are collected at power plants and steel mills, to form inorganic sodium carbonate (NaHCO 3 ) and calcium carbonate. (CaCO 3 ) relates to the technology of producing together.
구체적으로, 용출제를 이용해 칼슘을 함유한 산업부산물로부터 칼슘이온을 용출하고, 용출된 칼슘이온을 함유한 상등액에 수산화나트륨을 공급하여 pH를 조절한다. 이후, 이산화탄소를 공급함으로써 탄산칼슘이 생산된다. 상기 탄산칼슘을 회수한 후 남은 여액은 중조 반응기에서 이산화탄소와 반응하여 중조가 생산된다. 즉, pH 조절을 위해 투입되는 수산화나트륨은 중조의 원료로 재활용됨으로써 탄산칼슘과 중조가 함께 생산된다.Specifically, the elution agent is used to elute calcium ions from the industrial by-product containing calcium, and to adjust the pH by supplying sodium hydroxide to the supernatant containing the eluted calcium ions. Thereafter, calcium carbonate is produced by supplying carbon dioxide. After recovering the calcium carbonate, the remaining filtrate is reacted with carbon dioxide in a heavy tank reactor to produce a heavy tank. In other words, sodium hydroxide, which is added to adjust pH, is recycled as a raw material of sodium bicarbonate to produce calcium carbonate and sodium bicarbonate together.
한편, 중조 생성 공정에 있어서, 중조의 높은 용해도, 즉, 20℃에서 96g/L의 용해도로 인하여 침전된 중조를 회수하고 남은 여액에는 나트륨 이온(Na+)과 중탄산 이온(HCO3 -)이 높은 농도로 존재한다. 상기 중탄산 이온이 높은 농도로 포함된 여액을 용출제로 재사용하는 경우, 산업부산물에서 용출되는 수산화기(OH-)로 인해 상기 중탄산 이온이 탄산 이온(CO3 2-)으로 전환된다. 전환된 탄산 이온은 산업부산물로부터 용출된 칼슘이온과 반응하여 탄산칼슘을 형성하고, 이러한 탄산칼슘은 슬래그 등의 산업부산물 표면을 덮어 추가적인 칼슘이온의 용출을 어렵게 하는 문제점이 있다.On the other hand, in the sodium bicarbonate production process, the high solubility of sodium bicarbonate, i.e., recovery of the precipitated sodium bicarbonate due to the solubility of 96g / L at 20 ℃ and the remaining filtrate, the sodium ions (Na +) and bicarbonate ion (HCO 3 -) with the high Present in concentration. When the filtrate containing a high concentration of bicarbonate ions is reused as an eluent, the bicarbonate ions are converted to carbonate ions (CO 3 2− ) due to the hydroxyl group (OH − ) eluted from industrial by-products. The converted carbonate ions react with the calcium ions eluted from the industrial by-products to form calcium carbonates, and these calcium carbonates cover the surface of the industrial by-products such as slag, making it difficult to elute additional calcium ions.
도 2는 용출제(2M 염화암모늄 수용액)에 용해된 중조의 농도에 따른 산업부산물로부터 용출되는 칼슘이온의 용출량을 나타낸 그래프이다. 도 2에 따르면, 용출제에 중조가 포함되어 있지 않거나 미량으로 포함되어 있는 경우 용출된 칼슘이온의 농도는 6,000mg/L를 상회하나, 중조 투입량이 증가함에 따라 용출된 칼슘이온의 농도가 감소한다. 용출제에 포함된 중조의 함량이 0.7g/100g-water인 경우, 중조를 미투입한 경우 보다, 대략 50% 미만의 용출률을 보인다. 한편, 중조 투입량이 증가함에 따라 칼슘이온의 용출량은 급격히 감소하며, 평형 용해도까지 중조를 공급한 투입한 경우에는 칼슘이온이 거의 용출되지 않는다.FIG. 2 is a graph showing the elution amount of calcium ions eluted from industrial by-products according to the concentration of sodium bicarbonate dissolved in an eluent (2M aqueous ammonium chloride solution). According to FIG. 2, when the eluent does not contain heavy sodium or is present in a small amount, the concentration of the eluted calcium ions exceeds 6,000 mg / L, but the concentration of the eluted calcium ions decreases as the amount of sodium bicarbonate is increased. . When the content of the sodium bicarbonate contained in the eluent is 0.7g / 100g-water, the dissolution rate is approximately 50% less than that without adding the sodium bicarbonate. On the other hand, as the amount of sodium bicarbonate is increased, the amount of calcium ions eluted rapidly decreases, and calcium ions are hardly eluted when the sodium bicarbonate is supplied to equilibrium solubility.
본 발명의 일 실시예에 따르면, 버려지는 산업부산물로부터 고부가가치 물질인 탄산칼슘 및 중조를 생산하는 방법 및 설비를 제공하고자 한다.According to one embodiment of the present invention, there is provided a method and a facility for producing high value added calcium carbonate and sodium bicarbonate from discarded industrial by-products.
본 발명의 일 실시예에 따르면, 수산화나트륨(NaOH) 용액에 이산화탄소 함유 가스를 공급하여 이산화탄소가 공급된 용액을 제조하고, 상기 수산화나트륨과 이산화탄소의 반응으로 중조(NaHCO3)를 생산하는 단계, 상기 중조를 회수하고 남은 여액에 칼슘이온 함유 용액을 공급하여 탄산이온(CO3 2-)과 칼슘이온의 반응으로 탄산칼슘(CaCO3)을 생산하는 단계, 및 상기 탄산칼슘을 회수하고 남은 여액을 상기 수산화나트륨이 용해된 용액에 재공급하는 단계를 포함하며, 상기 이산화탄소가 공급된 용액은 상기 중조 보다 용해도가 높은 나트륨염을 더 포함하는 중조 및 탄산칼슘 제조방법을 제공한다.According to an embodiment of the present invention, by supplying a carbon dioxide-containing gas to a sodium hydroxide (NaOH) solution to prepare a solution in which carbon dioxide is supplied, producing a sodium bicarbonate (NaHCO 3 ) by the reaction of the sodium hydroxide and carbon dioxide, Recovering the sodium bicarbonate and supplying a solution containing calcium ions to the remaining filtrate to produce calcium carbonate (CaCO 3 ) by the reaction of carbonate (CO 3 2- ) and calcium ions, and recovering the calcium carbonate and the remaining filtrate Re-supply to a solution in which sodium hydroxide is dissolved, wherein the carbon dioxide supplied solution provides a sodium bicarbonate and calcium carbonate manufacturing method further comprises a sodium salt having a higher solubility than the sodium bicarbonate.
상기 나트륨염은 상기 이산화탄소 함유 가스를 상기 수산화나트륨 용액에 공급하기 전에 공급될 수 있다.The sodium salt may be supplied before the carbon dioxide containing gas is supplied to the sodium hydroxide solution.
상기 나트륨염은 상기 이산화탄소 함유 가스와 함께 상기 수산화나트륨 용액에 공급하거나, 또는 상기 이산화탄소 함유 가스를 상기 수산화나트륨 용액에 공급한 후에 공급될 수 있다.The sodium salt may be supplied to the sodium hydroxide solution together with the carbon dioxide containing gas, or may be supplied after the carbon dioxide containing gas is supplied to the sodium hydroxide solution.
상기 나트륨염은 질산나트륨(NaNO3), 염화나트륨(NaCl), 또는 이들의 혼합물일 수 있다.The sodium salt may be sodium nitrate (NaNO 3 ), sodium chloride (NaCl), or a mixture thereof.
상기 칼슘이온 함유 용액은 용출제를 이용해 칼슘을 함유하는 산업부산물로부터 칼슘이온을 용출하여 제조된 것일 수 있다.The calcium ion-containing solution may be prepared by eluting calcium ion from an industrial by-product containing calcium using an eluent.
상기 용출제는 염화암모늄(NH4Cl), 염화수소(HCl), 질산(HNO3), 황산(H2SO4), 아세트산(CH3COOH), 및 질산암모늄(NH4NO3)의 수용액으로 이루어진 군에서 선택될 수 있다.The eluent is an aqueous solution of ammonium chloride (NH 4 Cl), hydrogen chloride (HCl), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), acetic acid (CH 3 COOH), and ammonium nitrate (NH 4 NO 3 ). It may be selected from the group consisting of.
상기 산업부산물은 제철 슬래그, 석탄회, 바닥회, 비산회, 폐시멘트, 폐콘크리트, 및 제지 슬러지(Paper Sludge)로 이루어진 군에서 선택된 하나 이상일 수 있다.The industrial by-product may be at least one selected from the group consisting of steel slag, coal ash, bottom ash, fly ash, waste cement, waste concrete, and paper sludge.
상기 탄산칼슘을 회수하고 남은 여액을 상기 용출제로 재사용하는 단계를 더 포함할 수 있다.Recovering the calcium carbonate may further comprise the step of reusing the remaining filtrate as the eluent.
상기 이산화탄소 함유 가스는 파이넥스 오프 가스(FOG, FINEX off gas), 파이넥스 테일 가스(FTG, FINEX tail gas), 고로 가스(BFG, Blast furnace gas), 전로 가스, 석탄 발전소 배가스, 가스 발전소 배가스, 소각로 배가스, 유리용해 배가스, 열설비 배가스, 석유화학공정 배가스, 석유화학공정 공정가스, 연소전 배가스 및 가스화기 배가스로 이루어진 군에서 선택된 하나 이상일 수 있다.The carbon dioxide-containing gas is FINEX off gas (FOG), FINEX tail gas (FTG, FINEX tail gas), blast furnace gas (BFG, Blast furnace gas), converter gas, coal power plant flue gas, gas power plant flue gas, incinerator flue gas It may be one or more selected from the group consisting of glass melting flue gas, thermal facility flue gas, petrochemical process flue gas, petrochemical process flue gas, pre-combustion flue gas and gasifier flue gas.
본 발명의 다른 실시예에 따르면, 수산화나트륨 용액 공급부, 이산화탄소 함유 가스 공급부, 및 중조 보다 용해도가 높은 나트륨염이 선택적으로 공급될 수 있는 나트륨염 공급부를 구비하는 중조 생산부; 상기 중조 생산부에서 석출된 중조를 회수하고, 중조 생산부의 여액을 배출하는 제1 고액분리부; 상기 중조 생산부에서 배출된 여액의 유입부 및 칼슘이온 함유 용액 공급부를 구비하는 탄산칼슘 생산부; 및 상기 탄산칼슘 생산부에서 획득된 탄산칼슘을 회수하고, 탄산칼슘 생산부의 여액을 배출하는 제2 고액분리부; 및 상기 제2 고액분리부에서 배출된 여액이 상기 중조 생산부에 재공급되도록 하는 재공급부를 포함하는, 중조 및 탄산칼슘 제조설비를 제공한다.According to another embodiment of the present invention, a sodium bicarbonate production unit including a sodium hydroxide solution supply unit, a carbon dioxide-containing gas supply unit, and a sodium salt supply unit for selectively supplying a sodium salt having a higher solubility than the sodium bicarbonate tank; A first solid-liquid separator for recovering the heavy water precipitated in the heavy water producing unit and discharging the filtrate of the heavy water producing unit; A calcium carbonate production unit including an inlet of the filtrate discharged from the sodium bicarbonate production unit and a calcium ion-containing solution supply unit; And a second solid-liquid separator for recovering the calcium carbonate obtained from the calcium carbonate producing unit and discharging the filtrate of the calcium carbonate producing unit. And a resupply unit configured to supply the filtrate discharged from the second solid-liquid separator to the heavy tank production unit.
상기 칼슘이온 함유 용액 공급부는 칼슘이온 함유 용액이 생산되는 용출부와 연통되어 있을 수 있다.The calcium ion-containing solution supply part may be in communication with the elution part in which the calcium ion-containing solution is produced.
상기 용출부는 칼슘을 함유하는 산업부산물 공급부 및 용출제 공급부를 구비할 수 있다.The elution part may include an industrial by-product supply part and an eluent supply part containing calcium.
상기 용출부는 제2 고액분리부에서 배출되는 여액이 상기 용출부에 공급되도록 연통되어 있을 수 있다.The eluent may be in communication so that the filtrate discharged from the second solid-liquid separator is supplied to the eluent.
본 발명의 일 실시예에 따른 탄산칼슘 및 중조를 생산하는 방법 및 설비는, 버려지는 산업부산물로부터 고부가가치 물질인 탄산칼슘과 중조를 함께 생성할 수 있고, 연속 공정 구현 시 칼슘이온의 용출률이 하락하는 문제점을 방지하는 효과가 있다.Method and equipment for producing calcium carbonate and sodium bicarbonate according to an embodiment of the present invention, it is possible to produce a high value of calcium carbonate and sodium bicarbonate together from the industrial by-products discarded, the dissolution rate of calcium ions in the continuous process implementation is reduced There is an effect to prevent the problem.
도 1은 산업부산물로부터 중조 및 탄산칼슘을 제조하는 종래의 공정을 모식적으로 나타낸 도면이다. 1 is a view schematically showing a conventional process for producing sodium bicarbonate and calcium carbonate from industrial by-products.
도 2는 용출제(2M 염화암모늄)에 용해된 중조의 농도에 따른 산업부산물로부터 용출되는 칼슘이온의 용출량을 나타낸 그래프이다.FIG. 2 is a graph showing the elution amount of calcium ions eluted from industrial by-products according to the concentration of sodium bicarbonate dissolved in an eluent (2M ammonium chloride).
도 3 및 4는 본 발명의 일 실시예에 따른 중조 및 탄산칼슘 제조설비를 모식적으로 나타낸 도면이다.3 and 4 is a view schematically showing the sodium bicarbonate and calcium carbonate production equipment according to an embodiment of the present invention.
이하, 다양한 실시예를 참조하여 본 발명의 바람직한 실시 형태를 설명한다. 그러나 본 발명의 실시 형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described with reference to various examples. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.
본 발명은 산업부산물로부터 중조 및 탄산칼슘을 제조하는 방법 및 설비에 관한 것이며, 구체적으로, 칼슘을 함유하는 산업부산물과, 이산화탄소를 함유하는 배기가스, 및 수산화나트륨을 이용하여 고부가가치 물질인 중조 및 탄산칼슘을 제조하는 방법 및 설비에 관한 것이다.The present invention relates to a method and an apparatus for producing sodium bicarbonate and calcium carbonate from industrial byproducts, and specifically, an industrial sodium bicarbonate, an exhaust gas containing carbon dioxide, and sodium hydroxide, which is a high value-added substance using sodium hydroxide and A method and equipment for producing calcium carbonate.
본 발명의 일 실시예에 따르면 중조 및 탄산칼슘을 제조하는 방법을 제공한다. 이러한 중조 및 탄산칼슘 제조방법은 a)수산화나트륨(NaOH) 용액에 이산화탄소 함유 가스를 공급하여 수산화나트륨과 이산화탄소의 반응으로 중조(NaHCO3)를 생산하는 단계, b)상기 중조를 회수하고 남은 여액에 칼슘이온 함유 용액을 공급하여 탄산이온(CO3 2-)과 칼슘이온의 반응으로 탄산칼슘(CaCO3)을 생산하는 단계, 및 c)상기 탄산칼슘을 회수하고 남은 여액을 상기 수산화나트륨이 용해된 용액에 재공급하는 단계를 포함한다.According to one embodiment of the present invention there is provided a method for producing sodium bicarbonate and calcium carbonate. The manufacturing method of sodium bicarbonate and calcium carbonate is a) supplying a carbon dioxide-containing gas to a sodium hydroxide (NaOH) solution to produce a sodium bicarbonate (NaHCO 3 ) by the reaction of sodium hydroxide and carbon dioxide, b) recovering the sodium bicarbonate to the remaining filtrate Supplying a solution containing calcium ions to produce calcium carbonate (CaCO 3 ) by a reaction between calcium carbonate (CO 3 2- ) and calcium ions, and c) recovering the calcium carbonate, and the remaining filtrate is dissolved in the sodium hydroxide. Refeeding the solution.
먼저, a)수산화나트륨 용액에 이산화탄소 함유 가스를 공급하면 상기 수산화나트륨과 이산화탄소의 반응으로 중조가 생산된다. 상기 중조의 용해도는 20℃에서 96g/L이므로, 석출된 중조를 회수한 후 남은 여액에는 중조가 용해도만큼 용해되어 있다. 따라서, b)중조가 용해되어 있는 여액에 칼슘이온을 공급함으로써 탄산칼슘이 추가적으로 생산된다. 즉, a) 및 b) 단계를 수행함으로 인해 고부가가치 물질인 중조 및 탄산칼슘을 함께 제조할 수 있다. 한편, 상기 탄산칼슘을 회수하고 남은 여액은 나트륨이온, 중탄산이온 등을 포함하고 있으므로, 상기 여액을 상기 수산화나트륨이 용해된 용액에 공급하여 중조 생산에 재사용한다.First, a) by supplying a carbon dioxide-containing gas to the sodium hydroxide solution, the sodium bicarbonate is produced by the reaction of the sodium hydroxide and carbon dioxide. Since the solubility of the sodium bicarbonate is 96 g / L at 20 ℃, the sodium bicarbonate is dissolved as much as solubility in the remaining filtrate after recovering the precipitated sodium bicarbonate. Accordingly, calcium carbonate is additionally produced by supplying calcium ions to the filtrate in which the sodium bicarbonate is dissolved. That is, by performing the steps a) and b) it is possible to produce a high value-added sodium bicarbonate and calcium carbonate together. On the other hand, since the remaining filtrate after recovering the calcium carbonate contains sodium ions, bicarbonate ions and the like, the filtrate is supplied to the solution in which sodium hydroxide is dissolved and reused in the production of sodium bicarbonate.
이하에서는, 단계별로 자세히 설명한다.In the following, it will be described in detail step by step.
먼저, a)수산화나트륨 용액에 이산화탄소 함유 가스를 공급하면 상기 수산화나트륨과 이산화탄소의 반응으로 중조가 생산된다. 이러한 중조 생산 반응의 반응식은 하기 식 1과 같다.First, a) by supplying a carbon dioxide-containing gas to the sodium hydroxide solution, the sodium bicarbonate is produced by the reaction of the sodium hydroxide and carbon dioxide. The reaction scheme of this sodium bicarbonate production reaction is shown in the following Equation 1.
식 1: NaOH + CO2 → NaHCO3 Equation 1: NaOH + CO 2 → NaHCO 3
상기 중조의 용해도는 20℃에서 96g/L이므로, 석출된 중조를 회수한 후 남은 여액에는 중조가 용해도만큼 용해되어 있다. 즉, 상기 여액에는 나트륨 이온(Na+), 중탄산 이온(HCO3 -), 및 탄산 이온(CO3 2-) 등이 용해되어 있다. Since the solubility of the sodium bicarbonate is 96 g / L at 20 ℃, the sodium bicarbonate is dissolved as much as solubility in the remaining filtrate after recovering the precipitated sodium bicarbonate. That is, sodium ions (Na + ), bicarbonate ions (HCO 3 − ), carbonate ions (CO 3 2- ), and the like are dissolved in the filtrate.
한편, 상기 이산화탄소 함유 가스는 제철 공정 등의 산업 공정에서 발생되는 부산물으로, 예를 들어, 파이넥스 오프 가스(FOG, FINEX off gas), 파이넥스 테일 가스(FTG, FINEX tail gas), 고로 가스(BFG, Blast furnace gas), 전로 가스, 석탄 발전소 배가스, 가스 발전소 배가스, 소각로 배가스, 유리용해 배가스, 열설비 배가스, 석유화학공정 배가스, 석유화학공정 공정가스, 연소전 배가스 및 가스화기 배가스로 이루어진 군에서 선택된 하나 이상일 수 있다.Meanwhile, the carbon dioxide-containing gas is a by-product generated in an industrial process such as an iron making process, and includes, for example, FINEX off gas (FOG), FINEX tail gas (FTG), and blast furnace gas (BFG, Blast furnace gas, converter gas, coal power plant flue gas, gas power plant flue gas, incinerator flue gas, glass melting flue gas, thermal facility flue gas, petrochemical process flue gas, petrochemical process gas, pre-combustion gas and gasifier flue gas There may be more than one.
본 발명의 일 실시예에 따르면, 상기 수산화나트륨 용액에 상기 중조 보다 용해도가 높은 나트륨염을 더 공급한다. 상기 나트륨염은 공통이온효과로 중조의 석출량을 향상시키는 역할을 하는 것이다.According to an embodiment of the present invention, the sodium hydroxide solution is further supplied with a sodium salt having a higher solubility than the sodium bicarbonate. The sodium salt is to play a role of improving the precipitation amount of the sodium bicarbonate by the common ion effect.
구체적으로, 용해도가 20℃에서 96g/L인 중조는 하기 식 2와 같이 나트륨 이온과 중탄산 이온을 형성한 상태에서 평형을 이룬다.Specifically, the sodium bicarbonate having a solubility of 96 g / L at 20 ° C. is in equilibrium with sodium ions and bicarbonate ions as shown in Equation 2 below.
식 2: NaHCO3 ↔Na+ + HCO3 - Equation 2: NaHCO 3 ↔Na + + HCO 3 -
이러한 평형계에 나트륨염, 예를 들어, 염화나트륨을 넣으면 상기 염화나트륨은 하기 식 3과 같이 나트륨 이온과 염화 이온이 나뉘어 들어간다.When sodium salt, for example, sodium chloride, is added to the equilibrium system, the sodium chloride is divided into sodium ions and chloride ions as shown in Equation 3 below.
식 3: NaCl → Na+ + Cl- Equation 3: NaCl → Na + + Cl -
식 2의 평형계에 들어간 나트륨 이온은 본래의 평형에 참여하던 나트륨 이온과 같은 이온이므로 평형계에서 나트륨 이온의 농도를 증가시키는 요인으로 작용한다. 따라서, 르샤틀리에의 원리에 따라 평형은 나트륨 이온의 농도를 감소시키기 위해 식 2에서 왼쪽으로 이동하여 새로운 평형에 도달한다. 이렇게 평형이 이동하면 중조 평형계에서 중탄산 이온의 농도가 감소하고 중조가 석출되는 결과가 나타난다. 즉, 중조 생성 반응 시 나트륨염을 공급하는 경우 염화나트륨이 용해되어 나타나는 나트륨 이온의 공통이온효과에 의해 중조의 석출량이 향상되는 효과가 나타난다.Since sodium ions entering the equilibrium system of Equation 2 are the same ions as the sodium ions participating in the original equilibrium, it acts as a factor to increase the concentration of sodium ions in the equilibrium system. Thus, according to LeChatlier's principle, the equilibrium shifts to the left in Equation 2 to reduce the concentration of sodium ions to reach a new equilibrium. This equilibrium shift results in a decrease in the concentration of bicarbonate ions and precipitation of the sodium bicarbonate. That is, when sodium salt is supplied during the sodium bicarbonate reaction, the precipitation amount of the sodium bicarbonate is improved by the common ion effect of sodium ions that are dissolved by sodium chloride.
상기 나트륨염은 상기 이산화탄소 함유 가스를 상기 수산화나트륨 용액에 공급하기 전에 상기 수산화나트륨 용액에 공급될 수 있다. 상기 나트륨염을 이산화탄소 함유 가스를 공급하기 전에 수산화나트륨 용액에 공급하는 경우, 중조의 석출량이 향상됨에 따라 이산화탄소의 용해도가 증가되어 용액에 용해되지 않고 공기 중으로 배출되는 이산화탄소의 함량을 감소시킬 수 있는 장점이 있다.The sodium salt may be supplied to the sodium hydroxide solution before the carbon dioxide containing gas is supplied to the sodium hydroxide solution. When the sodium salt is supplied to the sodium hydroxide solution before supplying the carbon dioxide-containing gas, the solubility of carbon dioxide is increased as the precipitation amount of the sodium bicarbonate is improved, thereby reducing the content of carbon dioxide discharged into the air without being dissolved in the solution. There is this.
한편, 상기 나트륨염은 상기 이산화탄소 함유 가스와 함께 상기 수산화나트륨 용액에 공급하거나, 또는 상기 이산화탄소 함유 가스를 상기 수산화나트륨 용액에 공급한 후에 공급될 수 있다. 상기 나트륨염을 상기 이산화탄소 함유 가스와 함께 상기 수산화나트륨 용액에 공급하거나, 또는 이산화탄소 함유 가스를 공급한 후에 공급하는 경우, 석출되는 중조의 량을 제어하여 원하는 함량의 중조를 얻을 수 있는 장점이 있다.Meanwhile, the sodium salt may be supplied to the sodium hydroxide solution together with the carbon dioxide-containing gas, or may be supplied after the carbon dioxide-containing gas is supplied to the sodium hydroxide solution. When the sodium salt is supplied to the sodium hydroxide solution together with the carbon dioxide-containing gas, or supplied after the carbon dioxide-containing gas is supplied, there is an advantage in that the sodium bicarbonate having a desired content can be obtained by controlling the amount of precipitated sodium bicarbonate.
상기 나트륨염은 중조 보다 용해도가 높고 나트륨 이온을 포함하는 염이라면 특별히 한정하지 않으나, 질산나트륨(NaNO3), 염화나트륨(NaCl), 또는 이들의 혼합물인 것이 바람직하다.The sodium salt is not particularly limited as long as it has a higher solubility than sodium bicarbonate and contains sodium ions, but is preferably sodium nitrate (NaNO 3 ), sodium chloride (NaCl), or a mixture thereof.
한편, 석출된 중조가 회수되고 남은 여액에는 나트륨 이온(Na+), 중탄산 이온(HCO3 -), 및 탄산 이온(CO3 2-) 등이 용해되어 있다. 따라서, b) 상기 여액에 칼슘이온 함유 용액을 공급하면, 탄산이온(CO3 2-)과 칼슘이온의 반응으로 탄산칼슘(CaCO3)이 생산된다. 이러한 탄산칼슘 생산 반응의 반응식은 하기 식 4와 같다.On the other hand, sodium ions (Na + ), bicarbonate ions (HCO 3 − ), carbonates (CO 3 2- ), and the like are dissolved in the remaining filtrate after the precipitated sodium bicarbonate is recovered. Therefore, b) When the solution containing calcium ion is supplied to the filtrate, calcium carbonate (CaCO 3 ) is produced by the reaction of carbonate (CO 3 2- ) and calcium ions. The reaction formula of the calcium carbonate production reaction is shown in the following equation 4.
식 4: CO3 2- + Ca2+ → CaCO3 Equation 4: CO 3 2- + Ca 2+ → CaCO 3
따라서, 중조를 회수하고 남은 여액에 칼슘이온을 공급함으로써 탄산칼슘 추가적으로 제조 가능하다. 즉, 본 발명의 일 실시예에 따른 제조 방법은, 칼슘이온 함유 물질, 수산화나트륨 및 이산화탄소 함유 가스만을 이용하여 고부가가치 물질인 중조 및 탄산칼슘을 함께 제조할 수 있다.Therefore, calcium carbonate can be additionally prepared by recovering the sodium bicarbonate and supplying calcium ions to the remaining filtrate. In other words, the manufacturing method according to an embodiment of the present invention, using only calcium ion-containing material, sodium hydroxide and carbon dioxide-containing gas can be produced together with the sodium bicarbonate and calcium carbonate as a high value-added material.
상기 여액에 공급되는 칼슘이온 함유 용액은, 칼슘을 함유하는 산업부산물로부터 칼슘이온을 용출하여 제조될 수 있다. 상기 산업부산물은 칼슘을 함유하는 것이라면 특별히 한정하지 않으나, 예를 들어, 제철 슬래그, 석탄회, 바닥회, 비산회, 폐시멘트, 폐콘크리트, 및 제지 슬러지(Paper Sludge)로 이루어진 군에서 선택된 하나 이상일 수 있다.The calcium ion-containing solution supplied to the filtrate may be prepared by eluting calcium ion from industrial by-products containing calcium. The industrial by-products are not particularly limited as long as they contain calcium. For example, the industrial by-products may be at least one selected from the group consisting of steel slag, coal ash, bottom ash, fly ash, waste cement, waste concrete, and paper sludge. .
용출제를 이용하여 상기 산업부산물로부터 칼슘이온을 용출시킬 수 있으며, 이러한 용출제의 종류는 특별히 한정하지 않으나, 예를 들어, 염화암모늄(NH4Cl), 염화수소(HCl), 질산(HNO3), 황산(H2SO4), 아세트산(CH3COOH), 및 질산암모늄(NH4NO3)의 수용액으로 이루어진 군에서 선택된 하나 이상을 사용하는 것이 바람직하다.Calcium ions can be eluted from the industrial by-product using an eluent, and the type of the eluent is not particularly limited, for example, ammonium chloride (NH 4 Cl), hydrogen chloride (HCl), nitric acid (HNO 3 ). , At least one selected from the group consisting of sulfuric acid (H 2 SO 4 ), acetic acid (CH 3 COOH), and an aqueous solution of ammonium nitrate (NH 4 NO 3 ).
상기 칼슘이온 함유 용액에 포함된 칼슘이온의 농도는, 상기 여액에 포함된 중탄산 이온 및 탄산 이온을 합한 농도보다 높은 것이 바람직하다. 상기 식 4의 반응에서 제조된 탄산칼슘을 회수한 후 남은 여액은 용출제로 재사용될 수 있는데, 이때, 상기 여액에 중탄산이온이 포함되어 있으면 산업부산물에서 용출되는 수산화기(OH-)로 인해 상기 중탄산 이온이 탄산 이온(CO3 2-)으로 전환된다. 상기 여액에 포함된 탄산이온과 전환된 탄산이온은 산업부산물로부터 용출된 칼슘이온과 반응하여 탄산칼슘을 형성할 수 있고, 이러한 탄산칼슘은 슬래그 등의 산업부산물 표면을 덮어 추가적인 칼슘이온의 용출을 막는 문제점을 발생할 수 있다.The concentration of calcium ions contained in the calcium ion-containing solution is preferably higher than the combined concentration of bicarbonate ions and carbonate ions contained in the filtrate. The remaining filtrate after recovering the calcium carbonate prepared in the reaction of Equation 4 may be reused as an eluent. In this case, if the filtrate contains bicarbonate ions, the bicarbonate ions are eluted from the industrial by-products (OH − ). This carbonate ion (CO 3 2- ) is converted. The carbonate ions and the converted carbonate ions contained in the filtrate may react with the calcium ions eluted from the industrial by-products to form calcium carbonates. These calcium carbonates cover the surface of the industrial by-products such as slag to prevent further elution of calcium ions. Problems may occur.
그러나 상기 칼슘이온 함유 용액에 포함된 칼슘이온의 농도를 상기 여액에 포함된 중탄산이온 및 탄산 이온을 합한 농도보다 높게 제어하는 경우, 중탄산이온 및 탄산 이온을 모두 탄산칼슘으로 전환할 수 있다. 따라서, 상기 여액에는 중탄산이온 및 탄산 이온이 포함되어 있지 않아 탄산칼슘 회수 후 남은 여액을 용출제로 재사용 시 산업부산물로부터 칼슘이온의 용출을 막는 문제점을 방지할 수 있다.However, when the concentration of calcium ions contained in the calcium ion-containing solution is controlled to be higher than the combined concentration of bicarbonate ions and carbonate ions contained in the filtrate, both bicarbonate ions and carbonate ions can be converted to calcium carbonate. Accordingly, the filtrate does not contain bicarbonate ions and carbonate ions, it is possible to prevent the problem of preventing elution of calcium ions from industrial by-products when reusing the filtrate remaining after the recovery of calcium carbonate as the eluent.
한편, c)상기 탄산칼슘을 회수하고 남은 여액은 나트륨이온, 중탄산이온 등을 포함하고 있으므로, 상기 여액을 상기 수산화나트륨이 용해된 용액에 공급하여 중조 생산에 재사용한다. 또한, 상술한 바와 같이, 상기 탄산칼슘을 회수하고 남은 여액을 상기 용출제로 재사용할 수 있다. On the other hand, c) since the remaining filtrate after recovering the calcium carbonate contains sodium ions, bicarbonate ions, etc., the filtrate is supplied to the solution in which sodium hydroxide is dissolved and reused in the production of sodium bicarbonate. In addition, as described above, the remaining filtrate after recovering the calcium carbonate can be reused as the eluent.
본 발명은 중조 및 탄산칼슘을 제조하는 설비를 제공한다. 도 3 및 4는 본 발명의 일 실시예에 따른 중조 및 탄산칼슘을 제조하는 설비를 모식적으로 나타낸 도면이다.The present invention provides a plant for producing sodium bicarbonate and calcium carbonate. 3 and 4 are diagrams schematically showing equipment for producing sodium bicarbonate and calcium carbonate according to an embodiment of the present invention.
본 발명의 일 실시예에 따른 중조 및 탄산칼슘 제조 설비는, 수산화나트륨 용액 공급부, 이산화탄소 함유 가스 공급부, 및 중조 보다 용해도가 높은 나트륨염이 선택적으로 공급될 수 있는 나트륨염 공급부를 구비하는 중조 생산부; 상기 중조 생산부에서 석출된 중조를 회수하고, 중조 생산부의 여액을 배출하는 제1 고액분리부; 상기 제1 고액분리부에서 배출된 여액의 유입부 및 칼슘이온 함유 용액 공급부를 구비하는 탄산칼슘 생산부; 및 상기 탄산칼슘 생산부에서 획득된 탄산칼슘을 회수하고, 탄산칼슘 생산부의 여액을 배출하는 제2 고액분리부; 및 상기 제2 고액분리부에서 배출된 여액이 상기 중조 생산부에 재공급되도록 하는 재공급부를 포함하는 것이다.The sodium bicarbonate and calcium carbonate production equipment according to an embodiment of the present invention, a sodium bicarbonate production unit having a sodium hydroxide solution supply unit, a carbon dioxide-containing gas supply unit, and a sodium salt supply unit that can be selectively supplied with a higher solubility of sodium salt; A first solid-liquid separator for recovering the heavy water precipitated in the heavy water producing unit and discharging the filtrate of the heavy water producing unit; A calcium carbonate production unit including an inlet of the filtrate discharged from the first solid-liquid separator and a calcium ion-containing solution supply unit; And a second solid-liquid separator for recovering the calcium carbonate obtained from the calcium carbonate producing unit and discharging the filtrate of the calcium carbonate producing unit. And a resupply unit allowing the filtrate discharged from the second solid-liquid separator to be resupplyed to the heavy tank production unit.
상기 중조 생산부에서는 수산화나트륨 용액, 이산화탄소 함유 가스, 및 중조 보다 용해도가 높은 나트륨염이 공급되어 수산화나트륨과 이산화탄소의 반응으로 중조가 생산되며, 제1 고액분리부에서 상기 중조 생산부로부터 배출되는 중조 및 여액이 분리되고, 구체적으로는 석출된 중조가 회수되고, 중조 생산부의 여액을 배출하게 된다. The sodium bicarbonate production unit is supplied with sodium hydroxide solution, carbon dioxide-containing gas, and sodium salt having a higher solubility than sodium bicarbonate, and thus, sodium bicarbonate is produced by the reaction of sodium hydroxide and carbon dioxide, and the first and the second filtrate discharged from the sodium bicarbonate production unit. The separated, specifically, precipitated sodium bicarbonate is recovered and the filtrate of the sodium bicarbonate production part is discharged.
나아가, 상기 제1 고액분리부에서 배출된 여액의 유입부를 통해 상기 중조 생산부에서 배출된 여액이 탄산칼슘 생산부로 유입되고, 이와 함께칼슘이온 함유 용액 공급부를 통해 칼슘이온 함유 용액이 공급되어 탄산칼슘 생산부에서 탄산이온과 칼슘이온의 반응으로 탄산칼슘이 생산된다. 이후, 제2 고액분리부에서 상기 탄산칼슘 생산부로부터 배출되는 탄산칼슘 및 여액이 분리되고, 구체적으로는 탄산칼슘이 회수되고, 탄산칼슘 생산부의 여액을 배출하게 된다.Furthermore, the filtrate discharged from the sodium bicarbonate production unit flows into the calcium carbonate production unit through the inlet of the filtrate discharged from the first solid-liquid separation unit, and together with the calcium ion-containing solution through the calcium ion-containing solution supply unit, the calcium carbonate production unit In the reaction of calcium carbonate with calcium ions, calcium carbonate is produced. Thereafter, the calcium carbonate and the filtrate discharged from the calcium carbonate production unit are separated in the second solid-liquid separation unit, specifically, the calcium carbonate is recovered and the filtrate of the calcium carbonate production unit is discharged.
이때, 상기 제1 고액분리부 및 제2 고액분리부는 고체와 액체를 분리할 수 있는 구성이라면 특히 제한되지 않으며, 동일하거나 상이한 고액분리장치가 적용될 수 있다. 상기 제1 고액분리부 및 제2 고액분리부는 예를 들어, 여과 장치, 필터프레스 장치 등으로부터 독립적으로 선택될 수 있으며, 다만 이에 제한되는 것은 아니다.In this case, the first solid-liquid separator and the second solid-liquid separator are not particularly limited as long as they can separate solid and liquid, and the same or different solid-liquid separator may be applied. The first solid-liquid separator and the second solid-liquid separator may be independently selected from, for example, a filtration device, a filter press device, and the like, but is not limited thereto.
한편, 본 발명의 중조 및 탄산칼슘 제조설비를 구성하는 각각의 영역들 사이에서 유입 및 배출을 포함하는 흐름을 원활하게 하기 위해 필요한 경우 펌프가 1개 이상 추가로 구비될 수 있다.On the other hand, one or more pumps may be provided if necessary to smooth the flow including inflow and outflow between the respective regions constituting the sodium bicarbonate and calcium carbonate manufacturing facilities of the present invention.
상기 중조 생산부에서는 공급된 수산화나트륨 용액 및 이산화탄소 함유 가스의 반응으로 중조가 생성된다. 상기 이산화탄소 함유 가스는 제철 산업 등의 산업 공정에서 발생되며 이산화탄소를 포함하는 것이라면 특별히 한정하지 않으나, 예를 들어, 파이넥스 오프 가스(FOG, FINEX off gas), 파이넥스 테일 가스(FTG, FINEX tail gas), 고로 가스(BFG, Blast furnace gas), 전로 가스, 석탄 발전소 배가스, 가스 발전소 배가스, 소각로 배가스, 유리용해 배가스, 열설비 배가스, 석유화학공정 배가스, 석유화학공정 공정가스, 연소전 배가스 및 가스화기 배가스로 이루어진 군에서 선택된 하나 이상일 수 있다.In the heavy tank production unit, a heavy tank is produced by the reaction of the supplied sodium hydroxide solution and carbon dioxide-containing gas. The carbon dioxide-containing gas is not particularly limited as long as it is generated in an industrial process such as steelmaking industry and includes carbon dioxide. For example, FINEX off gas (FOG, FINEX off gas), FINEX tail gas (FTG, FINEX tail gas), Blast furnace gas (BFG), converter gas, coal power plant flue gas, gas power plant flue gas, incinerator flue gas, glass melting flue gas, heat facility flue gas, petrochemical process flue gas, petrochemical process gas, pre-combustion flue gas and gasifier flue gas It may be one or more selected from the group consisting of.
한편, 상기 중조 생산부에는 중조 보다 용해도가 높은 나트륨염이 공급될 수 있는데, 이는 상술한 바와 같이 중조의 석출량을 향상시키는 역할을 한다. 한편, 상기 나트륨염은 중조 보다 용해도가 높고 나트륨 이온을 포함한다면 특별히 한정하지 않으나, 예를 들어, 질산나트륨(NaNO3), 염화나트륨(NaCl), 또는 이들의 혼합물일 수 있다.On the other hand, the sodium bicarbonate production unit may be supplied with sodium salt having a higher solubility than sodium bicarbonate, which serves to improve the amount of precipitation of the sodium bicarbonate as described above. Meanwhile, the sodium salt is not particularly limited as long as it has higher solubility than sodium bicarbonate and contains sodium ions. For example, the sodium salt may be sodium nitrate (NaNO 3 ), sodium chloride (NaCl), or a mixture thereof.
상기 중조 생산부에서 중조가 석출되며, 석출된 중조를 분리하고 남은 여액은 상기 탄산칼슘 생산부로 공급된다. 상기 탄산칼슘 생산부에는 상기 여액과 칼슘이온 함유 용액이 공급되며, 상기 여액에 포함된 탄산 이온과 상기 칼슘이온의 반응에 의해 탄산칼슘이 생산된다. 따라서, 본 발명의 일 실시예에 따른 제조 설비는 중조와 함께 탄산칼슘을 생산할 수 있다. The sodium bicarbonate is precipitated in the sodium bicarbonate production unit, and the remaining filtrate after separating the precipitated sodium bicarbonate is supplied to the calcium carbonate producing unit. The calcium carbonate production unit is supplied with the filtrate and the solution containing calcium ions, and calcium carbonate is produced by the reaction of the carbonate and calcium ions contained in the filtrate. Therefore, the production facility according to an embodiment of the present invention can produce calcium carbonate with sodium bicarbonate.
본 발명의 일 실시예에 따른 제조설비는, 상기 칼슘이온 함유 용액이 생산되는 용출부를 더 포함할 수 있다. 즉, 상기 칼슘이온 함유 용액 공급부는 칼슘이온 함유 용액이 생산되는 용출부와 연통되어 있을 수 있으며, 이때 상기 용출부에는 칼슘을 함유하는 산업부산물 및 용출제가 공급되고, 용출제가 산업부산물로부터 칼슘이온을 용출하여 상기 칼슘이온 함유 용액을 제조할 수 있도록 상기 용출부는 칼슘을 함유하는 산업부산물 공급부 및 용출제 공급부를 구비할 수 있다.The manufacturing equipment according to an embodiment of the present invention may further include an elution part in which the calcium ion-containing solution is produced. That is, the calcium ion-containing solution supply part may be in communication with the elution part in which the calcium ion-containing solution is produced, wherein the elution part is supplied with industrial by-products and eluents containing calcium, and the elution agent receives calcium ions from the industrial by-products. The elution unit may include an industrial by-product supply unit and an eluent supply unit containing calcium to elute to prepare the calcium ion-containing solution.
상기 산업부산물은 칼슘을 포함하는 것이라면 특별히 한정하지 않으나, 석탄회, 바닥회, 비산회, 폐시멘트, 폐콘크리트, 및 제지 슬러지(Paper Sludge)로 이루어진 군에서 선택된 하나 이상일 수 있다. 한편, 상기 용출제는 산, 염기 등을 사용할 수 있으며, 예를 들어, 염화암모늄(NH4Cl), 염화수소(HCl), 질산(HNO3), 황산(H2SO4), 아세트산(CH3COOH), 및 질산암모늄(NH4NO3)의 수용액으로 이루어진 군에서 선택된 하나 이상인 것이 바람직하다.The industrial by-products are not particularly limited as long as they include calcium, but may be one or more selected from the group consisting of coal ash, bottom ash, fly ash, waste cement, waste concrete, and paper sludge. On the other hand, the eluent may be an acid, a base, and the like, for example, ammonium chloride (NH 4 Cl), hydrogen chloride (HCl), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), acetic acid (CH 3 COOH), and at least one selected from the group consisting of an aqueous solution of ammonium nitrate (NH 4 NO 3 ).
상기 제2 고액분리부에서 배출된 여액은 용출제, 나트륨이온, 중탄산이온 등을 포함하고 있으므로, 이를 상기 중조 생산부에 재공급하거나, 상기 용출부에 공급하여 용출제로 재사용할 수 있다. 또는, 상기 여액의 일부를 중조 생산부에 재공급하고, 나머지 일부를 용출부에 공급하여 용출제로 재사용할 수 있다.Since the filtrate discharged from the second solid-liquid separator includes an eluent, sodium ions, bicarbonate ions, etc., the filtrate may be re-supplied to the heavy tank production unit, or may be supplied to the elution unit and reused as an eluent. Alternatively, a part of the filtrate may be re-supplied to the heavy tank production unit, and the remaining part may be supplied to the elution unit and reused as the eluent.
이를 위해, 예를 들어 상기 용출부는 제2 고액분리부에서 배출되는 여액이 상기 용출부에 공급되도록 제2 고액분리부와 연통되어 있을 수 있다. To this end, for example, the eluent may be in communication with the second solid-liquid separator so that the filtrate discharged from the second solid-liquid separator is supplied to the eluent.
이상에서 본 발명의 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 수정 및 변형이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 자명할 것이다.Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and changes can be made without departing from the technical spirit of the present invention described in the claims. It will be obvious to those of ordinary skill in the field.

Claims (13)

  1. 수산화나트륨(NaOH) 용액에 이산화탄소 함유 가스를 공급하여 이산화탄소가 공급된 용액을 제조하고, 상기 수산화나트륨과 이산화탄소의 반응으로 중조(NaHCO3)를 생산하는 단계;Supplying a carbon dioxide-containing gas to a sodium hydroxide (NaOH) solution to prepare a solution supplied with carbon dioxide, and producing a sodium bicarbonate (NaHCO 3 ) by reacting the sodium hydroxide with carbon dioxide;
    상기 중조를 회수하고 남은 여액에 칼슘이온 함유 용액을 공급하여 탄산이온(CO3 2-)과 칼슘이온의 반응으로 탄산칼슘(CaCO3)을 생산하는 단계; 및Recovering the sodium bicarbonate and supplying a solution containing calcium ions to the remaining filtrate to produce calcium carbonate (CaCO 3 ) by the reaction of carbonate (CO 3 2- ) and calcium ions; And
    상기 탄산칼슘을 회수하고 남은 여액을 상기 수산화나트륨이 용해된 용액에 재공급하는 단계를 포함하며,Recovering the calcium carbonate and supplying the remaining filtrate to the solution in which sodium hydroxide is dissolved;
    상기 이산화탄소가 공급된 용액은 상기 중조 보다 용해도가 높은 나트륨염을 더 포함하는, 중조 및 탄산칼슘 제조방법.The solution supplied with carbon dioxide further comprises a sodium salt having a higher solubility than the sodium bicarbonate, sodium bicarbonate and calcium carbonate manufacturing method.
  2. 제1항에 있어서, 상기 나트륨염은 상기 이산화탄소 함유 가스를 상기 수산화나트륨 용액에 공급하기 전에 공급되는, 중조 및 탄산칼슘 제조방법.The method according to claim 1, wherein the sodium salt is supplied before the carbon dioxide containing gas is supplied to the sodium hydroxide solution.
  3. 제1항에 있어서, 상기 나트륨염은 상기 이산화탄소 함유 가스와 함께 상기 수산화나트륨 용액에 공급하거나, 또는 상기 이산화탄소 함유 가스를 상기 수산화나트륨 용액에 공급한 후에 공급되는, 중조 및 탄산칼슘 제조방법.The method of claim 1, wherein the sodium salt is supplied to the sodium hydroxide solution together with the carbon dioxide-containing gas, or is supplied after the carbon dioxide-containing gas is supplied to the sodium hydroxide solution.
  4. 제1항에 있어서, 상기 나트륨염은 질산나트륨(NaNO3), 염화나트륨(NaCl), 또는 이들의 혼합물인, 중조 및 탄산칼슘 제조방법.The method according to claim 1, wherein the sodium salt is sodium nitrate (NaNO 3 ), sodium chloride (NaCl), or a mixture thereof.
  5. 제1항에 있어서, 상기 칼슘이온 함유 용액은 용출제를 이용해 칼슘을 함유하는 산업부산물로부터 칼슘이온을 용출하여 제조된 것인, 중조 및 탄산칼슘 제조방법.The method of claim 1, wherein the calcium ion-containing solution is prepared by eluting calcium ion from an industrial by-product containing calcium using an eluent.
  6. 제5항에 있어서, 상기 용출제는 염화암모늄(NH4Cl), 염화수소(HCl), 질산(HNO3), 황산(H2SO4), 아세트산(CH3COOH), 및 질산암모늄(NH4NO3)의 수용액으로 이루어진 군에서 선택된 하나 이상인, 중조 및 탄산칼슘 제조방법.The method of claim 5, wherein the eluent is ammonium chloride (NH 4 Cl), hydrogen chloride (HCl), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), acetic acid (CH 3 COOH), and ammonium nitrate (NH 4 NO 3 ) is one or more selected from the group consisting of aqueous solution of sodium bicarbonate and calcium carbonate production method.
  7. 제5항에 있어서, 상기 산업부산물은 제철 슬래그, 석탄회, 바닥회, 비산회, 폐시멘트, 폐콘크리트, 및 제지 슬러지(Paper Sludge)로 이루어진 군에서 선택된 하나 이상인, 중조 및 탄산칼슘 제조방법.The method of claim 5, wherein the industrial by-product is at least one selected from the group consisting of steel slag, coal ash, bottom ash, fly ash, waste cement, waste concrete, and paper sludge.
  8. 제5항에 있어서, 상기 탄산칼슘을 회수하고 남은 여액을 상기 용출제로 재사용하는 단계를 더 포함하는, 중조 및 탄산칼슘 제조방법.The method of claim 5, further comprising recovering the calcium carbonate and reusing the remaining filtrate with the eluent.
  9. 제1항에 있어서, 상기 이산화탄소 함유 가스는 파이넥스 오프 가스(FOG, FINEX off gas), 파이넥스 테일 가스(FTG, FINEX tail gas), 고로 가스(BFG, Blast furnace gas), 전로 가스, 석탄 발전소 배가스, 가스 발전소 배가스, 소각로 배가스, 유리용해 배가스, 열설비 배가스, 석유화학공정 배가스, 석유화학공정 공정가스, 연소전 배가스 및 가스화기 배가스로 이루어진 군에서 선택된 하나 이상인, 중조 및 탄산칼슘 제조방법.The method of claim 1, wherein the carbon dioxide-containing gas is a FINEX off gas (FOG), a FINEX tail gas (FTG), a blast furnace gas (BFG), a converter gas, a coal power plant flue gas, Gas power plant flue gas, incinerator flue gas, glass melting flue gas, thermal equipment flue gas, petrochemical process flue gas, petrochemical process gas, pre-combustion flue gas and gasifier flue gas, at least one selected from the group consisting of sodium bicarbonate and calcium carbonate.
  10. 수산화나트륨 용액 공급부, 이산화탄소 함유 가스 공급부, 및 중조 보다 용해도가 높은 나트륨염이 선택적으로 공급될 수 있는 나트륨염 공급부를 구비하는 중조 생산부; A sodium bicarbonate production unit including a sodium hydroxide solution supply unit, a carbon dioxide-containing gas supply unit, and a sodium salt supply unit to selectively supply sodium salt having a higher solubility than that of the sodium bicarbonate tank;
    상기 중조 생산부에서 석출된 중조를 회수하고, 중조 생산부의 여액을 배출하는 제1 고액분리부; A first solid-liquid separator for recovering the heavy water precipitated in the heavy water producing unit and discharging the filtrate of the heavy water producing unit;
    상기 제1 고액분리부에서 배출된 여액의 유입부 및 칼슘이온 함유 용액 공급부를 구비하는 탄산칼슘 생산부; 및 A calcium carbonate production unit including an inlet of the filtrate discharged from the first solid-liquid separator and a calcium ion-containing solution supply unit; And
    상기 탄산칼슘 생산부에서 획득된 탄산칼슘을 회수하고, 탄산칼슘 생산부의 여액을 배출하는 제2 고액분리부; 및A second solid-liquid separator for recovering the calcium carbonate obtained from the calcium carbonate producing unit and discharging the filtrate of the calcium carbonate producing unit; And
    상기 제2 고액분리부에서 배출된 여액이 상기 중조 생산부에 재공급되도록 하는 재공급부A resupply unit for replenishing the filtrate discharged from the second solid-liquid separator to the heavy tank production unit
    를 포함하는, 중조 및 탄산칼슘 제조설비.Comprising, sodium bicarbonate and calcium carbonate manufacturing equipment.
  11. 제10항에 있어서, 상기 칼슘이온 함유 용액 공급부는 칼슘이온 함유 용액이 생산되는 용출부와 연통되어 있는, 중조 및 탄산칼슘 제조설비.11. The apparatus for manufacturing sodium bicarbonate and calcium carbonate according to claim 10, wherein the calcium ion-containing solution supply part is in communication with an elution part where a calcium ion-containing solution is produced.
  12. 제11항에 있어서, 상기 용출부는 칼슘을 함유하는 산업부산물 공급부 및 용출제 공급부를 구비하는, 중조 및 탄산칼슘 제조설비.12. The manufacturing apparatus for sodium bicarbonate and calcium carbonate according to claim 11, wherein the elution section includes an industrial by-product supply section and a eluent supply section containing calcium.
  13. 제11항에 있어서, 상기 용출부는 제2 고액분리부에서 배출되는 여액이 상기 용출부에 공급되도록 연통되어 있는, 중조 및 탄산칼슘 제조설비.12. The apparatus for manufacturing sodium bicarbonate and calcium carbonate according to claim 11, wherein the elution portion communicates with the filtrate discharged from the second solid-liquid separation portion to be supplied to the elution portion.
PCT/KR2017/009836 2016-09-13 2017-09-07 Method and facility for preparing sodium bicarbonate and calcium carbonate WO2018052220A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2016-0118332 2016-09-13
KR1020160118332A KR101856959B1 (en) 2016-09-13 2016-09-13 Manufacture method and equipment for sodium hydrogen carbonate and calcium carbonate

Publications (1)

Publication Number Publication Date
WO2018052220A1 true WO2018052220A1 (en) 2018-03-22

Family

ID=61618873

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/009836 WO2018052220A1 (en) 2016-09-13 2017-09-07 Method and facility for preparing sodium bicarbonate and calcium carbonate

Country Status (2)

Country Link
KR (1) KR101856959B1 (en)
WO (1) WO2018052220A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102002479B1 (en) 2018-11-20 2019-07-23 탑에코에너지주식회사 Manufacturing system of High-purity NaHCO3
KR102216206B1 (en) * 2018-11-29 2021-02-18 (주)평화엔지니어링 The all in one type system of carbon dioxide collecting and transforming into carbonated mineral at cement industry

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130032093A (en) * 2011-09-22 2013-04-01 현대자동차주식회사 Method for carbon dioxide solidification
KR20140087331A (en) * 2012-12-28 2014-07-09 재단법인 포항산업과학연구원 Method of manufacturing calcium carbonate from calcium silicate by-products
KR20150080687A (en) * 2014-01-02 2015-07-10 한국과학기술연구원 Manufacturing method carbonates of alkali metal ion or alkali earth metal ion using Electrolysis Unit
US20150291500A1 (en) * 2014-04-14 2015-10-15 Alstom Technology Ltd. Apparatus and method for production of formate from carbon dioxide
KR101571251B1 (en) * 2014-09-25 2015-11-23 한국전력공사 Apparatus for manufacturing for sodium bicarbonate and method for manufacturing the same
KR20170075252A (en) * 2015-12-23 2017-07-03 주식회사 포스코 Manufacture equipment and method for sodium hydrogen carbonate and calcium carbonate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130032093A (en) * 2011-09-22 2013-04-01 현대자동차주식회사 Method for carbon dioxide solidification
KR20140087331A (en) * 2012-12-28 2014-07-09 재단법인 포항산업과학연구원 Method of manufacturing calcium carbonate from calcium silicate by-products
KR20150080687A (en) * 2014-01-02 2015-07-10 한국과학기술연구원 Manufacturing method carbonates of alkali metal ion or alkali earth metal ion using Electrolysis Unit
US20150291500A1 (en) * 2014-04-14 2015-10-15 Alstom Technology Ltd. Apparatus and method for production of formate from carbon dioxide
KR101571251B1 (en) * 2014-09-25 2015-11-23 한국전력공사 Apparatus for manufacturing for sodium bicarbonate and method for manufacturing the same
KR20170075252A (en) * 2015-12-23 2017-07-03 주식회사 포스코 Manufacture equipment and method for sodium hydrogen carbonate and calcium carbonate

Also Published As

Publication number Publication date
KR101856959B1 (en) 2018-05-15
KR20180029783A (en) 2018-03-21

Similar Documents

Publication Publication Date Title
CN108118157B (en) Wiring board burns the recovery method of cigarette ash pretreatment and bromine
WO2018052220A1 (en) Method and facility for preparing sodium bicarbonate and calcium carbonate
KR101561637B1 (en) Recovery of Pottasium Chloride from Cl by pass Dust
WO2013165071A1 (en) Method for producing high-purity manganese sulfate monohydrate and high-purity manganese sulfate monohydrate produced by the method
WO2013094861A1 (en) Apparatus for reducing carbon dioxide by using molten slag
WO2023191414A1 (en) Method for preparing secondary battery material from black mass
WO2019022317A1 (en) High-purity recovery method of strontium in seawater
WO2019022319A1 (en) Sodium bicarbonate preparation apparatus using combustion exhaust gas and sodium bicarbonate preparation method using same
CN113428876A (en) System and process for harmless treatment and full-element recycling of secondary aluminum ash
WO2014098300A1 (en) Reduced-iron production method and production device
CN216155494U (en) System for harmless and full element resource of secondary aluminium ash
WO2023234462A1 (en) Method for manufacturing sodium bicarbonate and gypsum using sodium sulfate
WO2023234623A1 (en) Method for removing halides from waelz oxide
CN1321200C (en) Method for separating copper, arsenic and zinc from copper-smelting high-arsenic flue dust sulphuric acid leach liquor
WO2014030811A1 (en) Method and apparatus for fixing carbon dioxide
WO2022154250A1 (en) Method for collecting calcium and rare earth metal from slag
WO2018074638A1 (en) Method for producing high-purity calcium carbonate and reusing solvent using indirect carbonation of alkali industrial byproducts
WO2024122803A1 (en) Method for recovering lithium from waste crubicle of cathode material
WO2013042897A2 (en) Method for selectively separating calcium and magnesium from a solution containing calcium and magnesium, calcium oxalate and magnesium oxalate obtained by the method, and calcium oxide and magnesium oxide obtained from said oxalates
WO2023068587A1 (en) Method for preparing gypsum by using bio-sulfur, and use thereof
WO2022186647A1 (en) Method for preparing inorganic compound using desulfurization gypsum for reducing greenhouse gas emissions
WO2022045747A1 (en) Method for manufacturing lithium hydroxide from lithium-containing source
WO2018216886A1 (en) Method for preparing hydrogen gas
WO2021010577A1 (en) Method of recovering metals remaining in plating wastewater using wet treatment process
WO2016148446A1 (en) Method for manufacturing zinc compound from electric arc furnace dust

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17851094

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17851094

Country of ref document: EP

Kind code of ref document: A1