WO2018088727A1 - Method for purifying waste hydrochloric acid - Google Patents
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- WO2018088727A1 WO2018088727A1 PCT/KR2017/011869 KR2017011869W WO2018088727A1 WO 2018088727 A1 WO2018088727 A1 WO 2018088727A1 KR 2017011869 W KR2017011869 W KR 2017011869W WO 2018088727 A1 WO2018088727 A1 WO 2018088727A1
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- hydrochloric acid
- organic solvent
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- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
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- the present invention relates to a method for purifying waste hydrochloric acid.
- Ethylene dichloride (1,2-dichloroethane, EDC) is a substance produced during the reaction of vinyl chloride monomer synthesis (see Scheme 1 below), which is a direct chlorine method through the reaction of ethylene and chlorine, ethylene, hydrogen chloride and air (oxygen). It can be prepared by the chlorine oxide method by the reaction of).
- waste hydrochloric acids are recycled into hydrochloric acid in the chlor-alkali electrolyzer anolyte, or recycled as oxy-chlorination raw materials
- the plant can reduce the emissions of hazardous substances and reduce the cost of purchasing hydrogen chloride. Red and economic benefits can occur. Therefore, various methods for purifying and recycling waste hydrochloric acid have been studied in order to reduce manufacturing costs.
- the free residual chlorine present in the spent hydrochloric acid causes severe deactivation of the active site of the ion exchange resin, the free residual chlorine must be removed before the Fe refining process is performed.
- the free residual chlorine is removed by vacuum dechlorination, steam / air stripping, sulfite addition, active carbon, and UV method. Etc. can be used.
- the vacuum (decompression) desalting method is a method of removing Cl 2 through pressure control, and can be combined with the existing anolyte desalting method.
- the steam / air stripping method has a disadvantage in that energy consumption is large and additional investment costs are generated by stripping through steam or air.
- the sulfite addition method is a method of reducing Cl 2 through an oxidation reaction of sulfite, such as Na 2 SO 3 , NaHSO 3 , to sulfate, as in Scheme 2 below, and this method also removes free residual chlorine efficiency.
- This low, existing SRS system Sulfate Removal System
- the method of using activated carbon is a method of adsorbing Cl 2 using activated carbon, and it is troublesome to consider efficiency in a strong acid atmosphere and to consider a gas target and a liquid target.
- the UV method is a process of selectively removing free residual chlorine using UV energy as shown in Scheme 3, and it is reported that HOCl is well absorbed at a wavelength of 238 nm.
- this method also has the disadvantage of increased process cost and low free chlorine removal efficiency.
- the conventional method of removing Fe from waste hydrochloric acid has a problem of not only high energy and cost consumption because of complicated process steps, but also low free chlorine removal efficiency from waste hydrochloric acid.
- Patent Document 1 US Patent No. 2,787,525
- Patent Document 2 Japanese Patent Publication No. 3511244
- a first object of the present invention is to provide a waste hydrochloric acid purification method using a solvent extraction method.
- the amount of the extractant is 40 mol or more based on 1 mol of iron (Fe) ions among the metal components contained in the waste hydrochloric acid,
- the waste hydrochloric acid: extract solution is 1: 1 to 1: 1 to provide a waste hydrochloric acid purification method to be mixed.
- the organic solvent used to prepare the extraction solution may include at least one solvent selected from the group consisting of an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, and an alcohol.
- the aromatic hydrocarbon solvent may include at least one selected from the group consisting of toluene and xylene.
- the aliphatic hydrocarbon solvent is at least one cycloaliphatic hydrocarbon solvent selected from the group consisting of methyl cyclohexane and cyclohexane, or a linear hydrocarbon solvent having 6 to 20 carbon atoms, such as kerosene (kerosene, kerosene), normal hexane, heptane, octane, And one or more selected from the group consisting of nonane, decane, and dodetan.
- kerosene kerosene, kerosene
- normal hexane normal hexane
- heptane heptane
- octane octane
- the alcohol may include a monohydric alcohol having 6 to 20 carbon atoms.
- the extracting agent may be at least one or more selected from the group consisting of trioctylamine, methyl isobutyl ketone, trialkylphosphine oxide and tributyl phosphate, specifically selected from the group consisting of trioctylamine and methyl isobutyl ketone It may be at least one, more specifically trioctylamine.
- the amount of the extractant may be 40 mol to 60 mol based on 1 mol of the iron (Fe) ion component among the metal components contained in the waste hydrochloric acid.
- the metal component, especially the iron (Fe) ion component can be effectively removed to 1 ppm or less from the waste hydrochloric acid, the recycling efficiency of hydrochloric acid Can improve.
- waste hydrochloric acid purification method using the solvent extraction method of the present invention can be repeated several times through the regeneration of the solvent used, resulting in a simplification of the process compared to the existing process, thereby reducing energy and manufacturing costs have.
- FIG. 1 is a flowchart illustrating a waste hydrochloric acid purification method using the solvent extraction method of the present invention.
- FIG. 2 is a process schematic diagram of a method for purifying waste hydrochloric acid using the solvent extraction method of the present invention.
- Figure 3 is a photograph comparing the color change of hydrochloric acid before and after purification of the purified hydrochloric acid using the solvent extraction method of the present invention.
- the metal component particularly the iron (Fe) ion component
- the metal component can be effectively removed to 1 ppm or less, specifically 0.1 ppm or less. It is possible to reduce the energy consumption and cost, and at the same time provide a method for purifying waste hydrochloric acid with high purity.
- the amount of the extractant is 40 mol or more based on 1 mol of iron (Fe) ions among the metal components contained in the waste hydrochloric acid,
- the waste hydrochloric acid: extract solution is 1: 1 to 1: 1 to provide a waste hydrochloric acid purification method to be mixed.
- FIG. 1 is a flowchart illustrating a waste hydrochloric acid purification method using the solvent extraction method of the present invention according to exemplary embodiments.
- 2 is a process schematic diagram of a method for purifying waste hydrochloric acid using the solvent extraction method of the present invention.
- the method for purifying hydrochloric acid of the present invention may further include a step (S0) of measuring the concentration of iron (Fe) ion component among the metal components included in the waste hydrochloric acid before the step (S1) of preparing the extraction solution. have.
- the concentration of iron (Fe) ions of the metal components contained in the waste hydrochloric acid can be measured by an inductively coupled plasma mass spectrometry (Inductively coupled plasma mass spectrometry). Specifically, the method measured about 5g of the sample in a corning tube (corning tube) was added as an internal standard, diluted with 25 mL of ultrapure water and analyzed using an ICP-OES (Optima 7300 DV) apparatus.
- ICP-OES Optima 7300 DV
- the hydrochloric acid purification method of the present invention may include the step of preparing an extraction solution by dissolving the extractant in an organic solvent (S1).
- the organic solvent is a (dilution) solvent used to improve the physical properties such as viscosity, specific gravity, etc. of the organic phase, and to control the concentration of the extractant, and representative examples thereof include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and alcohols. It may include at least one solvent selected from the group consisting of.
- the aromatic hydrocarbon solvent may include at least one selected from the group consisting of toluene and xylene.
- the aliphatic hydrocarbon solvent is at least one cycloaliphatic hydrocarbon solvent selected from the group consisting of methyl cyclohexane and cyclohexane, or a linear hydrocarbon solvent having 6 to 20 carbon atoms, specifically kerosene (kerosene, kerosene), normal hexane, heptane, octane And nonane, decane, and dodetan.
- the alcohol may include a monohydric alcohol having 6 to 20 carbon atoms, and representative examples thereof include 2-ethyl hexanol, 2-dodecanol, and the like.
- the organic solvent may be affected by the extraction equilibrium and the extraction rate according to the hydrocarbon content, specifically, the organic solvent is a phase separation with water smoothly, selectivity to the metal (selectivity) ) Is higher than water, and it is preferable to use toluene which shows the lowest value of TOC (total organic carbon) after the extraction process.
- the TOC value is a value that can know how much the extractant or diluent is contained by checking the concentration of organic impurities contained in the purified high purity hydrochloric acid after the extraction process.
- the extractant may be used as a compound for ion exchange reaction, at least one selected from the group consisting of trioctylamine, methyl isobutyl ketone, trialkylphosphine oxide and tributyl phosphate as a representative example, Among them, the phase separation effect is higher than that of the trialkylphosphine oxide or tributyl phosphate, which is a phosphorus-based extractant, and it is easy to remove metal components, particularly iron (Fe) ions, from waste hydrochloric acid, and reuse the organic solvent used in the purification process And it is more preferable to use trioctylamine and methyl isobutyl ketone which can implement a cost-saving effect and the like, more preferably trioctylamine.
- Alamine 336 or Aliquat 336 which is a nitrogen-based extractant (containing trioctylamine), or Cyanex 923, which is a phosphorus-based extractant (containing trialkylphosphine oxide), may be used alone or in addition. have.
- the amount of the extractant is 40 moles or more, specifically 40 moles to 60 moles, more specifically 40 moles to 50 moles, and more specifically 40 moles based on 1 mole of iron (Fe) ions in the metal components included in the spent hydrochloric acid Moles to 45 moles.
- the effect of removing metal components, particularly iron (Fe) ions may be insignificant.
- the amount of the extractant exceeds 60 moles, the effect of removing the metal components, particularly iron (Fe) ions component is not significantly different, but the manufacturing cost may increase because a large amount of the extractant is used. Therefore, considering the proper manufacturing cost and the efficiency of iron (Fe) ion component removal, it can be used in less than 60 moles.
- the waste hydrochloric acid is added to a reaction vessel, and then, an extraction solution is added and the metal component contained in the waste hydrochloric acid is extracted with an organic solvent while stirring. It can be carried out (S2).
- the metal component included in the spent hydrochloric acid mainly contains iron ions, and in addition to the metal components, such as Al 3+ , Ca 2+ , K + , Mg 2+ , Ni 2+ may be further included. .
- the hydrochloric acid the extraction solution may be mixed in a 1: 0.1 to 1: 1 volume ratio, specifically 1: 1 volume ratio. If the extraction solution is added in less than 0.1 volume ratio (1/10) with respect to the waste hydrochloric acid, there is a disadvantage in that an emulsion occurs in the waste hydrochloric acid layer and thus phase separation is impossible. In addition, when the extraction solution is added in more than 1 volume ratio, there is a disadvantage that the process cost increases.
- the extraction step (S2) may be carried out for 10 seconds to 60 seconds, specifically 20 seconds to 60 seconds while stirring the mixed solution of the hydrochloric acid and the extraction solution at a speed of 200 rpm to 600 rpm at an atmospheric temperature.
- the room temperature is the average temperature or the temperature in the atmosphere throughout the year, specifically, means a temperature of 20 ⁇ 5 °C range.
- the stirring speed is less than 200 rpm, the mixing is not smooth, there is a disadvantage in that the extraction efficiency of the metal component or the iron ion component is reduced.
- the stirring speed exceeds 600 rpm, the metal component extraction effect is insignificant while the energy consumption may increase.
- stirring step may be performed using a magnetic bar stirring plate or a static mixer.
- the mixing step for the phase separation may be carried out within 20 seconds.
- purified hydrochloric acid may be obtained by recovering the waste hydrochloric acid layer which is an phase separated from the phase separation step (S3) and is located at the bottom (S4). ).
- the purified hydrochloric acid may effectively remove the metal component, particularly the iron (Fe) ion component, the iron (Fe) ion component may remain at a concentration of 1 ppm or less, specifically 0.1 ppm or less.
- the waste hydrochloric acid purification method of the present invention may further comprise the step of purifying the organic solvent used in the waste hydrochloric acid, in order to increase the regeneration efficiency of the organic solvent used in the waste hydrochloric acid purification.
- Recovering the phase-separated organic solvent and the water layer, respectively (S7); may further include.
- the organic solvent recovered by phase separation after waste hydrochloric acid purification may be added to the reactor once again, and then distilled water may be added to remove metal components remaining in the organic solvent (S5).
- the residual metal component in the organic solvent can be extracted with water.
- the organic solvent: distilled water may be mixed in a volume ratio of 1: 0.1 to 1: 1, specifically 1: 1 volume ratio. If the distilled water is less than 0.1, the extraction effect of the metal component is reduced, and when the distilled water is added in more than 1 volume ratio (1/1), the emulsion may occur and phase separation may not occur.
- the stripping step (S5) may be performed for 10 seconds to 60 seconds, specifically 20 seconds to 60 seconds while stirring the mixed solution of the separated organic solvent and distilled water at a speed of 200 rpm to 600 rpm at room temperature.
- the room temperature is the average temperature or the temperature in the atmosphere throughout the year, specifically, means a temperature of 20 ⁇ 5 °C range.
- the stirring speed is less than 200 rpm, the mixing is not smooth, there is a disadvantage in that the extraction efficiency of the metal component is reduced.
- the stirring speed exceeds 600 rpm, the metal component extraction effect is insignificant while the energy consumption may be increased.
- the stirring time for the stripping is less than 20 seconds, there is a disadvantage in that sufficient time for extracting the metal is not secured, thereby reducing the extraction efficiency of the metal component.
- the stirring time exceeds 60 seconds, the amount of the extracted metal component does not show a big difference, but the process time and cost increases because the amount of waste organic solvent that can be processed in the process is limited.
- the stripping step (S5) may be used a variety of mixing device, as a representative example may use a magnetic bar stirring plate or a static mixer.
- the phase separation step may be carried out within 20 seconds.
- the distilled water layer which is the phase separated and the extracted phase located at the bottom, is removed, and the organic layer located at the top is recovered (S7), thereby effectively regenerating the organic phase used for waste hydrochloric acid purification.
- the method of the present invention further comprises the step of regenerating the organic solvent used in the waste hydrochloric acid purification method, it is possible to repeat the use of the organic solvent several times, significantly reducing the process operating costs and the like compared to the existing process can do.
- the concentration of iron (Fe) ions contained in 100 ml of waste hydrochloric acid was measured by an inductively coupled plasma mass spectrometry (S0).
- the extraction solution was added to 100 ml of waste hydrochloric acid, and metal components contained in the waste hydrochloric acid were extracted with an organic solvent while stirring at room temperature for 60 seconds at a speed of 200 rpm (S2).
- the residual metal concentration was measured using Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-OES), and the total organic carbon (TOC) component was analyzed by a TOC analyzer (analyzer).
- ICP-OES Inductively Coupled Plasma Atomic Emission Spectroscopy
- TOC total organic carbon
- the residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 1 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that cyclohexane was used instead of toluene in Example 1.
- the residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
- Example 3 The hydrochloric acid purified in the same manner as in Example 3 was obtained except that the waste hydrochloric acid layer separated in Example 3 was extracted once more using cyclohexane in which 40 moles of the extractant was dissolved (S2). The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that xylene was used instead of toluene in Example 1.
- the residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
- Example 2 The hydrochloric acid purified in the same manner as in Example 1 was obtained except that the waste hydrochloric acid layer separated in Example 5 was extracted once more using xylene in which 40 moles of the extractant was dissolved (S2). The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that in Example 1, a mixed solution of octane and 2-ethyl hexanol (1: 1 volume ratio) was used instead of toluene.
- the residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that in Example 1, a mixed solution of decane and 2-ethyl hexanol (1: 1 volume ratio) was used instead of toluene.
- the residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that a mixed solution (1: 1 volume ratio) of dodecane and 2-ethyl hexanol was used instead of toluene in Example 1.
- the residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that a mixed solution of kerosene and 2-ethyl hexanol (1: 1 volume ratio) was used instead of toluene in Example 1.
- the residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that in Example 1, a mixed solution of kerosene and 2-dodecanol (1: 1 by volume) was used instead of toluene.
- the residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that in the step (S1) of Example 1, an extraction solution was prepared by dissolving trialkylphosphine oxide instead of trioctylamine as an extractant.
- the residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 3, except that in the step (S1) of Example 3, an extraction solution was prepared by dissolving trialkylphosphine oxide instead of trioctylamine as an extractant.
- the residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that methyl cyclohexane was used instead of toluene when preparing the extraction solution in the step (S1) of Example 1.
- the residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
- Purified hydrochloric acid was obtained in the same manner as in Comparative Example 1 except for using the ion exchange resin (IRA-910) instead of the ion exchange resin (IRA-900) in Comparative Example 1.
- the residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 1 below.
- the reaction was then filtered to remove the ion exchange resin and to obtain purified hydrochloric acid.
- the residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 1 below.
- reaction was then filtered to remove the ion exchange resin and to obtain purified hydrochloric acid.
- Example 3 Trioctylamine Cyclohexane 5 16 ⁇ 0.1 5 5
- Example 4 Trioctylamine Cyclohexane (twice) 5 16 ⁇ 0.1 5 5
- Example 5 Trioctylamine xylene 6 16 ⁇ 0.1 5
- Example 6 Trioctylamine Xylene (2 times) 6 17 ⁇ 0.1 5 5
- Example 7 Trioctylamine Octane + 2-ethyl hexanol 7 17 ⁇ 0.1 5 5
- Example 8 Trioctylamine Decane + 2-ethyl hexanol 7 16 ⁇ 0.1 5 5
- Example 9 Trioctylamine Dodecane + 2-ethyl hexanol 7 16 ⁇ 0.1 5
- the concentration of the residual iron (Fe) ion component is 1 ppm or less (95% or more removed) regardless of the type of the organic solvent. You can see that.
- Comparative Examples 1 to 3 using ion exchange resins to remove iron (Fe) ions in the waste hydrochloric acid the concentration of residual iron (Fe) ions is 1 ppm or more (about 80%). You can see that. In particular, in the case of Comparative Example 3 in which NaSO 3 was added to remove free residual chlorine, it was confirmed that the Fe removal efficiency is not affected.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that 50 ml of the organic solvent was used instead of 100 ml in Example 1. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 3 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that 30 ml of the organic solvent was used instead of 100 ml in Example 1. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 3 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that 10 ml of the organic solvent was used instead of 100 ml in Example 1. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 3 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that the extraction time by stirring the organic solvent and the spent hydrochloric acid in Example 1 was performed at 50 seconds. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 4 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that the extraction time by stirring the organic solvent and the spent hydrochloric acid in Example 1 was performed for 30 seconds.
- the concentration of iron (Fe) ions in the purified hydrochloric acid was measured, and the results are shown in Table 4 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that the extraction time by stirring the organic solvent and the spent hydrochloric acid in Example 1 was performed for 20 seconds.
- the concentration of iron (Fe) ions in the purified hydrochloric acid was measured, and the results are shown in Table 4 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that the extraction time by stirring the organic solvent and the spent hydrochloric acid in Example 1 was performed for 10 seconds.
- the concentration of iron (Fe) ions in the purified hydrochloric acid was measured, and the results are shown in Table 4 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that the stirring speed of the organic solvent and the hydrochloric acid for extraction in Example 1 was performed at 600 rpm instead of 200 rpm. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 5 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that the stirring speed of the organic solvent and the hydrochloric acid for extraction in Example 1 was performed at 300 rpm instead of 200 rpm.
- the residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 5 below.
- Purified hydrochloric acid was obtained in the same manner as in Example 1, except that the stirring speed of the organic solvent and the hydrochloric acid for extraction in Example 1 was performed at 100 rpm instead of 200 rpm. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 5 below.
- the extraction solution was added to 100 ml of hydrochloric acid, and the metal components contained in the hydrochloric acid were extracted with an organic solvent while stirring at room temperature for 60 seconds at a speed of 200 rpm (S2).
- the mixed solution of the organic solvent (1) and the water layer removed in the separator was phase-separated for about 20 seconds, to separate the organic solvent and the water layer (S6).
- the separated water layer 1 was recovered (S7).
- the organic solvent (1) recovered by phase separation from the waste hydrochloric acid layer of Example 25 was re-injected into 100 ml of waste hydrochloric acid, and the organic solvent was mixed with the metal components contained in the waste hydrochloric acid while stirring at room temperature for 1 hour at a speed of 200 rpm. Extracted with (S2-2).
- the organic solvent (2) recovered by phase separation from the waste hydrochloric acid layer of Example 26 was recycled to 100 ml of waste hydrochloric acid, and the metal components contained in the waste hydrochloric acid were stirred at room temperature for 1 hour at 200 rpm. Extracted with (S2-3).
- the mixed solution of the organic solvent (3) and the water layer removed in the separator was phase-separated for about 20 seconds, to separate the organic solvent and the water layer (S6-3).
- the separated water layer 3 was recovered (S7-3).
- the organic solvent (3) recovered by phase separation from the waste hydrochloric acid layer of Example 27 was re-injected into 100 ml of waste hydrochloric acid, and the metal components contained in the waste hydrochloric acid were stirred at room temperature for 1 hour at 200 rpm. Extracted with (S2-4).
- the extraction solution was added to 100 ml of waste hydrochloric acid, and metal components contained in the waste hydrochloric acid were extracted with an organic solvent while stirring at room temperature for 60 seconds at a speed of 200 rpm (S'2).
- the extraction solution was added to 100 ml of waste hydrochloric acid, and metal components contained in the waste hydrochloric acid were extracted with an organic solvent while stirring at room temperature for 60 seconds at a speed of 200 rpm (S'2).
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Abstract
The present invention relates to a method for purifying waste hydrochloric acid and, specifically, to a method for purifying waste hydrochloric acid, comprising the steps of: (S1) preparing an extraction solution by dissolving an extractant in an organic solvent; (S2) extracting a metal component with an organic solvent by injecting the extraction solution into waste hydrochloric acid; (S3) phase separating a water hydrochloric acid layer and the organic solvent containing the metal component; and (S4) obtaining purified hydrochloric acid by recovering the phase separated (fractionated) water hydrochloric acid layer, wherein at least 40 mol of the extractant is used on the basis of 1 mol of Fe contained in the waste hydrochloric acid, and the waste hydrochloric acid and the extraction solution are mixed in a volume ratio of waste hydrochloric acid : extraction solution of 1 to 0.1-1.
Description
관련 출원들과의 상호 인용Cross Citation with Related Applications
본 출원은 2016년 11월 09일자 한국 특허 출원 제10-2016-0148633호 및 2017년 10월 24일자 한국 특허 출원 제10-2017-0138499호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0148633 dated November 09, 2016 and Korean Patent Application No. 10-2017-0138499 dated October 24, 2017. All content disclosed in the literature is included as part of this specification.
기술분야Technical Field
본 발명은 폐염산 정제 방법에 관한 것이다. The present invention relates to a method for purifying waste hydrochloric acid.
에틸렌 디클로라이드 (1,2-디클로로에탄, EDC)는 비닐 클로라이드 단량체 합성 반응시에 생성되는 물질로서 (하기 반응식 1 참조), 에틸렌과 염소의 반응에 의한 직접염소방법과 에틸렌과 염화수소 및 공기(산소)의 반응에 의한 산화염소방법으로 제조할 수 있다. Ethylene dichloride (1,2-dichloroethane, EDC) is a substance produced during the reaction of vinyl chloride monomer synthesis (see Scheme 1 below), which is a direct chlorine method through the reaction of ethylene and chlorine, ethylene, hydrogen chloride and air (oxygen). It can be prepared by the chlorine oxide method by the reaction of).
[반응식 1]Scheme 1
C2H4 + Cl2(또는 HCl) → CH2=CHCl + CH2ClCH2ClC 2 H 4 + Cl 2 (or HCl) → CH 2 = CHCl + CH 2 ClCH 2 Cl
CH2ClCH2Cl → CH2=CHCl + HClCH 2 ClCH 2 Cl → CH 2 = CHCl + HCl
한편, 상기 에틸렌 디클로라이드 생산 시에 일정량의 폐염산 (또는 희염산)과 같은 부산물이 지속적으로 발생한다. On the other hand, a constant amount of by-products such as spent hydrochloric acid (or dilute hydrochloric acid) are continuously generated in the production of the ethylene dichloride.
이러한 폐염산을 염소 알칼리 (Chlor-Alkali) 전해조 양극액에 들어가는 염산으로 재활용하거나, 또는 산소첨가염소화 (oxy-chlorination) 원료로 재활용하는 경우, 공장의 유해 물질 배출량 감소 및 염화수소 구입 비용 감소로 인하여 환경적 및 경제적 이득이 발생할 수 있다. 따라서, 제조 비용 절감 등을 위하여, 폐염산을 정제하여 재활용하는 방법이 다양하게 연구되고 있다.When these waste hydrochloric acids are recycled into hydrochloric acid in the chlor-alkali electrolyzer anolyte, or recycled as oxy-chlorination raw materials, the plant can reduce the emissions of hazardous substances and reduce the cost of purchasing hydrogen chloride. Red and economic benefits can occur. Therefore, various methods for purifying and recycling waste hydrochloric acid have been studied in order to reduce manufacturing costs.
폐염산을 재활용하기 위해서는 폐염산 내에 잔류하는 Fe, Al, Ca, K, Mg, 및 Ni 등과 같은 다양한 금속 성분들을 제거해야 한다. 만약, 상기와 같은 금속의 양이온이 양극액 (anolyte) 내에 존재하는 경우, 전해조 내의 멤브레인 표면이나 내부에서 OH- 이온과 반응하여 수산화물을 야기하기 때문에, 전압 상승 및 전류 효율을 감소시키는 원인이 되고 있다.In order to recycle the waste hydrochloric acid, various metal components such as Fe, Al, Ca, K, Mg, and Ni remaining in the waste hydrochloric acid need to be removed. If the cations of such metals are present in the anolyte, they react with OH - ions on the surface or inside of the membrane in the electrolytic cell, causing hydroxides, which leads to a decrease in voltage rise and current efficiency. .
특히, 상기 Fe를 제외한 대부분의 금속 성분은 에틸렌 디클로라이드 공정에 사용되는 물이 데미 워터 (de-minerals water)로 교체될 때 제거되는 반면, Fe는 물을 교체해도 여전히 잔류하기 때문에, 폐염산 내에서 Fe를 제거하기 위해서는 추가적인 정제 공정이 필요하다.In particular, most of the metal components, except for Fe, are removed when the water used in the ethylene dichloride process is replaced with de-minerals water, while Fe remains in waste hydrochloric acid because An additional purification process is required to remove Fe from.
현재, Fe를 제거하기 위한 가장 일반적인 방법은 폐염산에 존재하는 유리 잔류염소 (free residual chlorine) 성분을 제거한 다음, 이온교환수지를 이용하여 FeCl3를 분리하는 방법이다.Currently, the most common method for removing Fe is to remove free residual chlorine in waste hydrochloric acid, and then separate FeCl 3 using an ion exchange resin.
상기 폐염산에 존재하는 유리 잔류염소는 이온교환수지의 활성점의 심각한 비활성화를 야기하기 때문에, Fe 정제 공정을 수행하기 전에 반드시 유리 잔류염소를 먼저 제거하는 공정을 실시해야 한다.Since the free residual chlorine present in the spent hydrochloric acid causes severe deactivation of the active site of the ion exchange resin, the free residual chlorine must be removed before the Fe refining process is performed.
상기 유리 잔류염소를 제거하는 방법은 진공(감압) 탈염법 (vacuum dechlorination), 증기/공기 탈거법 (steam/air stripping), 설파이트 투입법 (sulfite addition), 활성탄 (active carbon) 이용법 및 UV 방법 등을 이용할 수 있다. The free residual chlorine is removed by vacuum dechlorination, steam / air stripping, sulfite addition, active carbon, and UV method. Etc. can be used.
상기 진공(감압) 탈염법은 압력 조절을 통하여 Cl2를 제거하는 방법으로, 기존 양극액 탈염법과 병합 가능하다. 하지만, 공정 과정이 복잡하고, 높은 공정 비용 및 제거 효율이 낮다는 단점이 있다. 상기 증기/공기 탈거법은 증기 혹은 공기를 통한 탈거법으로 에너지 소모가 크고, 추기 투자 비용이 발생한다는 단점이 있다. 또한, 상기 설파이트 투입법은 하기 반응식 2와 같이 Na2SO3, NaHSO3 등의 설파이트로부터 설페이트로의 산화 반응을 통해, Cl2를 환원하는 공정 방법으로, 이 방법 역시 유리 잔류염소 제거 효율이 낮고, 기존 SRS system (Sulfate Removal System)에서 설페이트 처리에 과부하를 줄 수 있다.The vacuum (decompression) desalting method is a method of removing Cl 2 through pressure control, and can be combined with the existing anolyte desalting method. However, there are disadvantages in that the process is complicated, high process cost and low removal efficiency. The steam / air stripping method has a disadvantage in that energy consumption is large and additional investment costs are generated by stripping through steam or air. In addition, the sulfite addition method is a method of reducing Cl 2 through an oxidation reaction of sulfite, such as Na 2 SO 3 , NaHSO 3 , to sulfate, as in Scheme 2 below, and this method also removes free residual chlorine efficiency. This low, existing SRS system (Sulfate Removal System) can overload the sulfate treatment.
[반응식 2] Scheme 2
NaHSO3
+ HOCl → NaHSO4 +HClNaHSO 3 + HOCl → NaHSO 4 + HCl
상기 활성탄 이용법은 활성탄을 이용하여 Cl2를 흡착하는 방법으로, 강산 분위기에서의 효율을 고려해야 하며 기체 대상, 액체 대상 여부 등을 고려해야 하는 번거로움이 있다.The method of using activated carbon is a method of adsorbing Cl 2 using activated carbon, and it is troublesome to consider efficiency in a strong acid atmosphere and to consider a gas target and a liquid target.
상기 UV 방법은 하기 반응식 3과 같이 UV 에너지를 이용하여 유리 잔류염소를 선택적으로 제거하는 공정으로 HOCl은 238nm 파장에서 잘 흡수된다고 보고되고 있다. 하지만, 이 방법 역시 공정 비용의 증가와 유리 잔류염소 제거 효율이 낮다는 단점이 있다.The UV method is a process of selectively removing free residual chlorine using UV energy as shown in Scheme 3, and it is reported that HOCl is well absorbed at a wavelength of 238 nm. However, this method also has the disadvantage of increased process cost and low free chlorine removal efficiency.
[반응식 3]Scheme 3
Cl2 + H2O → HOCl + HClCl 2 + H 2 O → HOCl + HCl
2HOCl → O2 + 2HCl2HOCl → O 2 + 2HCl
전술한 바와 같이, Fe 제거 전에 유리 잔류염소를 제거하기 위한 다양한 방법이 제안되고 있으나, 폐염산과 같이 pH가 0.8 이하로 매우 낮은 경우에는 5 ppm 미만으로 유리 잔류염소를 제거하기가 쉽지 않다는 문제가 있다. As described above, various methods for removing free residual chlorine before Fe removal have been proposed, but when the pH is very low, such as waste hydrochloric acid, below 0.8, there is a problem that it is not easy to remove free residual chlorine below 5 ppm. .
또한, 상기 이온교환수지를 이용하여 FeCl3를 분리하는 일반적인 방법의 경우, 상기 유리 잔류염소가 제거된 물을 흔들어(swing) 재생하여 사용하고 있기 때문에, 2 단계의 정제 공정이 요구되고 있다. 따라서, 공정 설비 및 유지 비용이 증가하여, 실제 공정에 적용하기 어려움이 있다.In addition, in the general method of separating FeCl 3 using the ion exchange resin, since the free residual chlorine removed water is regenerated and used, a two-stage purification process is required. Therefore, the process equipment and maintenance costs are increased, it is difficult to apply to the actual process.
이와 같이, 종래 폐염산으로부터 Fe를 제거하는 방법은 공정 단계가 복잡하기 때문에 에너지 및 비용 소비가 많을 뿐만 아니라, 폐염산으로부터 유리 잔류염소 제거 효율 또한 낮다는 문제가 있다.As such, the conventional method of removing Fe from waste hydrochloric acid has a problem of not only high energy and cost consumption because of complicated process steps, but also low free chlorine removal efficiency from waste hydrochloric acid.
따라서, 에너지 소비량 및 비용을 절감함과 동시에, 고순도의 폐염산 정제 방법에 대한 개발이 필요한 실정이다.Therefore, while reducing energy consumption and cost, it is necessary to develop a high purity waste hydrochloric acid purification method.
선행기술문헌Prior art literature
(특허문헌 1) 미국 특허등록공보 제2,787,525호(Patent Document 1) US Patent No. 2,787,525
(특허문헌 2) 일본 등록특허공보 제3511244호(Patent Document 2) Japanese Patent Publication No. 3511244
상기와 같은 문제점을 해결하기 위하여, 본 발명의 제1 기술적 과제는 용매 추출법을 이용한 폐염산 정제 방법을 제공하는 것을 목적으로 한다.In order to solve the above problems, a first object of the present invention is to provide a waste hydrochloric acid purification method using a solvent extraction method.
구체적으로, 본 발명의 일 실시예에서는Specifically, in one embodiment of the present invention
추출제를 유기용매에 용해시켜 추출 용액을 제조하는 단계(S1);Dissolving the extractant in an organic solvent to prepare an extraction solution (S1);
폐염산에 상기 추출 용액을 투입하여 폐염산 내의 금속 성분을 유기용매로 추출(extraction)하는 단계(S2);Injecting the extraction solution into the waste hydrochloric acid to extract metal components in the waste hydrochloric acid with an organic solvent (S2);
금속 성분을 함유한 유기용매와 폐염산층을 상분리(separation)하는 단계(S3); 및Phase separation of the organic solvent containing the metal component and the waste hydrochloric acid layer (S3); And
상분리(분획)된 폐염산층을 회수하여 정제된 염산을 수득하는 단계(S4);를 포함하며,Recovering the phase separation (fractionated) hydrochloric acid layer to obtain purified hydrochloric acid (S4); and
상기 추출제의 사용량은 폐염산에 함유된 금속 성분 중 철(Fe) 이온 성분 1 몰을 기준으로 40 몰 이상이고, The amount of the extractant is 40 mol or more based on 1 mol of iron (Fe) ions among the metal components contained in the waste hydrochloric acid,
상기 폐염산 : 추출 용액은 1:0.1 내지 1:1 부피비로 혼합하는 것인 폐염산 정제 방법을 제공한다.The waste hydrochloric acid: extract solution is 1: 1 to 1: 1 to provide a waste hydrochloric acid purification method to be mixed.
상기 본 발명의 폐염산 정제 방법에 있어서, 상기 추출 용액을 제조하기 위하여 사용되는 유기용매는 방향족 탄화수소 용매, 지방족 탄화수소 용매, 및 알코올로 이루어진 군으로부터 선택된 적어도 하나 이상의 용매를 포함할 수 있다.In the hydrochloric acid purification method of the present invention, the organic solvent used to prepare the extraction solution may include at least one solvent selected from the group consisting of an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, and an alcohol.
구체적으로, 상기 방향족 탄화수소 용매는 톨루엔 및 크실렌으로 이루어진 군으로부터 선택된 적어도 하나 이상을 포함할 수 있다.Specifically, the aromatic hydrocarbon solvent may include at least one selected from the group consisting of toluene and xylene.
상기 지방족 탄화수소 용매는 메틸 시클로헥산 및 시클로헥산으로 이루어진 군으로부터 선택된 적어도 하나 이상의 지환족 탄화수소 용매, 또는 탄소수 6 내지 20의 선형 탄화수소 용매, 예컨대 케로센 (kerosene, 등유), 노르말헥산, 헵탄, 옥탄, 노난, 데칸, 및 도데탄으로 이루어진 군으로부터 선택된 하나 이상을 포함할 수 있다.The aliphatic hydrocarbon solvent is at least one cycloaliphatic hydrocarbon solvent selected from the group consisting of methyl cyclohexane and cyclohexane, or a linear hydrocarbon solvent having 6 to 20 carbon atoms, such as kerosene (kerosene, kerosene), normal hexane, heptane, octane, And one or more selected from the group consisting of nonane, decane, and dodetan.
상기 알코올은 탄소수 6 내지 20의 1가 알코올을 포함할 수 있다.The alcohol may include a monohydric alcohol having 6 to 20 carbon atoms.
또한, 상기 추출제는 트리옥틸아민, 메틸 이소부틸케톤, 트리알킬포스핀 옥사이드 및 트리부틸 포스페이트로 이루어진 군으로부터 선택된 적어도 하나 이상일 수 있으며, 구체적으로 트리옥틸아민 및 메틸 이소부틸케톤으로 이루어진 군으로부터 선택된 적어도 하나 이상일 수 있으며, 보다 구체적으로 트리옥틸아민 일 수 있다.In addition, the extracting agent may be at least one or more selected from the group consisting of trioctylamine, methyl isobutyl ketone, trialkylphosphine oxide and tributyl phosphate, specifically selected from the group consisting of trioctylamine and methyl isobutyl ketone It may be at least one, more specifically trioctylamine.
상기 추출제의 사용량은 폐염산에 함유된 금속 성분 중 철(Fe) 이온 성분 1 몰을 기준으로 40 몰 내지 60 몰일 수 있다.The amount of the extractant may be 40 mol to 60 mol based on 1 mol of the iron (Fe) ion component among the metal components contained in the waste hydrochloric acid.
이상에서 설명한 바와 같이, 본 발명에 따른 용매 추출법을 이용한 폐염산 정제 방법의 경우, 폐염산으로부터 금속 성분, 특히 철(Fe) 이온 성분을 1 ppm 이하로 효과적으로 제거할 수 있기 때문에, 염산의 재활용 효율을 향상시킬 수 있다.As described above, in the case of the waste hydrochloric acid purification method using the solvent extraction method according to the present invention, since the metal component, especially the iron (Fe) ion component can be effectively removed to 1 ppm or less from the waste hydrochloric acid, the recycling efficiency of hydrochloric acid Can improve.
또한, 본 발명의 용매 추출 방법을 이용한 폐염산 정제 방법은 사용 용매의 재생을 통해 수회의 반복 사용이 가능함에 따라, 기존 공정에 비해 공정의 단순화와, 이에 따른 에너지 및 제조 비용 절감 효과를 가져올 수 있다. In addition, the waste hydrochloric acid purification method using the solvent extraction method of the present invention can be repeated several times through the regeneration of the solvent used, resulting in a simplification of the process compared to the existing process, thereby reducing energy and manufacturing costs have.
본 명세서에 첨부되는 다음의 도면은 본 발명의 바람직한 실시예를 예시하는 것이며, 전술한 발명의 내용과 함께 본 발명의 기술 사상을 더욱 이해시키는 역할을 하는 것이므로, 본 발명은 그러한 도면에 기재된 사항에만 한정되어 해석되어서는 아니다.The following drawings, which are attached to this specification, illustrate exemplary embodiments of the present invention, and together with the contents of the present invention serve to further understand the technical idea of the present invention, the present invention is limited to the matters described in such drawings. It is not to be construed as limited.
도 1은 본 발명의 용매 추출 방법을 이용한 폐염산 정제 방법을 설명하기 위한 흐름도이다.1 is a flowchart illustrating a waste hydrochloric acid purification method using the solvent extraction method of the present invention.
도 2는 본 발명의 용매 추출 방법을 이용한 폐염산 정제 방법에 대한 공정 개략도이다.2 is a process schematic diagram of a method for purifying waste hydrochloric acid using the solvent extraction method of the present invention.
도 3은 본 발명의 용매 추출 방법을 이용하여 정제된 폐염산의 정제 전,후의 염산의 색 변화를 비교한 사진이다.Figure 3 is a photograph comparing the color change of hydrochloric acid before and after purification of the purified hydrochloric acid using the solvent extraction method of the present invention.
이하, 본 발명을 더욱 상세하게 설명한다. Hereinafter, the present invention will be described in more detail.
본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.
종래 폐염산으로부터 금속 성분, 특히 철(Fe) 이온 성분을 제거하는 방법은 유리 잔류염소 제거 단계를 포함하는 등 공정 단계가 복잡하기 때문에 에너지 및 비용 소비가 많을 뿐만 아니라, 폐염산으로부터 유리 잔류염소 및 철(Fe) 이온 성분의 제거 효율 또한 낮다는 단점이 있다. Conventional methods for removing metal components, particularly iron (Fe) ions, from spent hydrochloric acid are not only costly and energy consuming because of the complex process steps, including free residual chlorine removal, but also free residual chlorine and There is a disadvantage in that the removal efficiency of the iron (Fe) ion component is also low.
이에, 본 발명에서는 용매 추출법을 이용하여 폐염산으로부터 유기 잔류염소 성분 제거 단계를 추가로 수행하지 않아도, 금속 성분, 특히 철(Fe) 이온 성분을 1 ppm 이하, 구체적으로 0.1 ppm 이하로 효과적으로 제거할 수 있어, 에너지 소비량 및 비용을 절감함과 동시에, 폐염산을 고순도로 정제할 수 있는 방법을 제공하고자 한다.Therefore, in the present invention, even if the organic residual chlorine component removal step from the waste hydrochloric acid is not additionally performed using the solvent extraction method, the metal component, particularly the iron (Fe) ion component, can be effectively removed to 1 ppm or less, specifically 0.1 ppm or less. It is possible to reduce the energy consumption and cost, and at the same time provide a method for purifying waste hydrochloric acid with high purity.
구체적으로, 본 발명의 일 실시예에서는Specifically, in one embodiment of the present invention
추출제를 유기용매에 용해시켜 추출 용액을 제조하는 단계(S1);Dissolving the extractant in an organic solvent to prepare an extraction solution (S1);
폐염산에 상기 추출 용액을 투입하여 폐염산 내의 금속 성분을 유기용매로 추출(extraction)하는 단계(S2);Injecting the extraction solution into the waste hydrochloric acid to extract metal components in the waste hydrochloric acid with an organic solvent (S2);
금속 성분을 함유한 유기용매와 폐염산층을 상분리(separation)하는 단계(S3); 및Phase separation of the organic solvent containing the metal component and the waste hydrochloric acid layer (S3); And
상분리(분획)된 폐염산층을 회수하여 정제된 염산을 수득하는 단계(S4);를 포함하며,Recovering the phase separation (fractionated) hydrochloric acid layer to obtain purified hydrochloric acid (S4); and
상기 추출제의 사용량은 폐염산에 함유된 금속 성분 중 철(Fe) 이온 성분 1 몰을 기준으로 40 몰 이상이고, The amount of the extractant is 40 mol or more based on 1 mol of iron (Fe) ions among the metal components contained in the waste hydrochloric acid,
상기 폐염산 : 추출 용액은 1:0.1 내지 1:1 부피비로 혼합하는 것인 폐염산 정제 방법을 제공한다.The waste hydrochloric acid: extract solution is 1: 1 to 1: 1 to provide a waste hydrochloric acid purification method to be mixed.
구체적으로, 도 1은 예시적인 실시예들에 따른 본 발명의 용매 추출 방법을 이용한 폐염산 정제 방법을 설명하기 위한 흐름도이다. 도 2는 본 발명의 용매 추출 방법을 이용한 폐염산 정제 방법에 대한 공정 개략도이다.Specifically, FIG. 1 is a flowchart illustrating a waste hydrochloric acid purification method using the solvent extraction method of the present invention according to exemplary embodiments. 2 is a process schematic diagram of a method for purifying waste hydrochloric acid using the solvent extraction method of the present invention.
먼저, 본 발명의 페염산 정제 방법은 상기 추출 용액을 제조하는 단계(S1) 전에, 폐염산에 포함된 금속 성분 중 철(Fe) 이온 성분의 농도를 측정하는 단계(S0)를 더 포함할 수 있다. First, the method for purifying hydrochloric acid of the present invention may further include a step (S0) of measuring the concentration of iron (Fe) ion component among the metal components included in the waste hydrochloric acid before the step (S1) of preparing the extraction solution. have.
이때, 폐염산에 포함된 금속 성분 중 철(Fe) 이온 성분의 농도는 유도 결합플라즈마 질량분석기 방법 (Inductively coupled plasma mass spectrometry)으로 측정할 수 있다. 구체적으로, 상기 방법은 시료 약 5g을 코닝 튜브 (corning tube)에 측정하여 내부 표준물로 투입하고, 초순수 25 mL로 희석한 다음 ICP-OES (Optima 7300 DV) 장치를 사용하여 분석을 실시하였다. At this time, the concentration of iron (Fe) ions of the metal components contained in the waste hydrochloric acid can be measured by an inductively coupled plasma mass spectrometry (Inductively coupled plasma mass spectrometry). Specifically, the method measured about 5g of the sample in a corning tube (corning tube) was added as an internal standard, diluted with 25 mL of ultrapure water and analyzed using an ICP-OES (Optima 7300 DV) apparatus.
또한, 도 1을 참조하면, 본 발명의 폐염산 정제 방법에서는 유기용매에 추출제를 용해시켜 추출 용액을 제조하는 단계를 포함할 수 있다(S1).In addition, referring to Figure 1, the hydrochloric acid purification method of the present invention may include the step of preparing an extraction solution by dissolving the extractant in an organic solvent (S1).
이때, 상기 유기용매는 유기상의 점도, 비중 등의 물리적 성질을 개선하고, 일정량의 추출제 농도를 조절하기 위하여 사용되는 (희석) 용매로서, 그 대표적인 예로 방향족 탄화수소 용매, 지방족 탄화수소 용매, 및 알코올로 이루어진 군으로부터 선택된 적어도 하나 이상의 용매를 포함할 수 있다.At this time, the organic solvent is a (dilution) solvent used to improve the physical properties such as viscosity, specific gravity, etc. of the organic phase, and to control the concentration of the extractant, and representative examples thereof include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and alcohols. It may include at least one solvent selected from the group consisting of.
구체적으로, 상기 방향족 탄화수소 용매는 톨루엔, 및 크실렌으로 이루어진 군으로부터 선택된 적어도 하나 이상을 포함할 수 있다.Specifically, the aromatic hydrocarbon solvent may include at least one selected from the group consisting of toluene and xylene.
상기 지방족 탄화수소 용매는 메틸 시클로헥산 및 시클로헥산으로 이루어진 군으로부터 선택된 적어도 하나 이상의 지환족 탄화수소 용매, 또는 탄소수 6 내지 20의 선형 탄화수소 용매, 구체적으로 케로센 (kerosene, 등유), 노르말헥산, 헵탄, 옥탄, 노난, 데칸, 및 도데탄으로 이루어진 군으로부터 선택된 적어도 하나 이상을 포함할 수 있다.The aliphatic hydrocarbon solvent is at least one cycloaliphatic hydrocarbon solvent selected from the group consisting of methyl cyclohexane and cyclohexane, or a linear hydrocarbon solvent having 6 to 20 carbon atoms, specifically kerosene (kerosene, kerosene), normal hexane, heptane, octane And nonane, decane, and dodetan.
또한, 상기 알코올은 탄소수 6 내지 20의 1가 알코올을 포함할 수 있으며, 그 대표적인 예로 2-에틸 헥산올, 또는 2-도데칸올 등을 들 수 있다.In addition, the alcohol may include a monohydric alcohol having 6 to 20 carbon atoms, and representative examples thereof include 2-ethyl hexanol, 2-dodecanol, and the like.
상기 유기용매는 탄화 수소의 함유 율에 따라 추출 평형 및 추출 속도의 영향을 받을 수 있는데, 구체적으로 상기 유기용매는 물과의 상분리(phase separation)가 원활하게 이루어지며, 금속에 대한 선택도(selectivity)가 물에 비해 높아, 추출 공정 후 TOC (total organic carbon) 수치가 가장 낮은 값을 나타내는 톨루엔을 사용하는 것이 바람직하다. The organic solvent may be affected by the extraction equilibrium and the extraction rate according to the hydrocarbon content, specifically, the organic solvent is a phase separation with water smoothly, selectivity to the metal (selectivity) ) Is higher than water, and it is preferable to use toluene which shows the lowest value of TOC (total organic carbon) after the extraction process.
이때, TOC 수치란 추출 공정 후 정제된 고순도 염산에 포함되어 있는 유기 불순물의 농도를 확인함으로써 추출제 또는 희석제가 얼마나 포함되어 있는지를 알 수 있는 수치이다.At this time, the TOC value is a value that can know how much the extractant or diluent is contained by checking the concentration of organic impurities contained in the purified high purity hydrochloric acid after the extraction process.
또한, 상기 추출제는 이온 교환 반응을 위한 화합물로서, 그 대표적인 예로서 트리옥틸아민, 메틸 이소부틸케톤, 트리알킬포스핀 옥사이드 및 트리부틸 포스페이트로 이루어진 군으로부터 선택된 적어도 하나 이상을 사용할 수 있으며, 이 중에서도 인계 추출제인 트리알킬포스핀 옥사이드 또는 트리부틸 포스페이트보다 상 분리 효과가 높을 뿐만 아니라, 폐염산 내에서 금속 성분, 특히 철(Fe) 이온 성분 제거가 용이하고, 정제 과정에 사용된 유기용매의 재사용과 이에 따른 비용 절감 효과 등을 구현할 수 있는 트리옥틸아민 및 메틸 이소부틸케톤을 사용하는 것이 보다 바람직하며, 트리옥틸아민이 더욱 바람직하다.In addition, the extractant may be used as a compound for ion exchange reaction, at least one selected from the group consisting of trioctylamine, methyl isobutyl ketone, trialkylphosphine oxide and tributyl phosphate as a representative example, Among them, the phase separation effect is higher than that of the trialkylphosphine oxide or tributyl phosphate, which is a phosphorus-based extractant, and it is easy to remove metal components, particularly iron (Fe) ions, from waste hydrochloric acid, and reuse the organic solvent used in the purification process And it is more preferable to use trioctylamine and methyl isobutyl ketone which can implement a cost-saving effect and the like, more preferably trioctylamine.
현재 시판되고 있는 추출제로는 질소계 추출제 (트리옥틸아민 함유)인 알라민 (Alamine) 336 또는 Aliquat 336, 또는 인계 추출제 (트리알킬포스핀 옥사이드 함유)인 Cyanex 923 등을 들 수 있으며, 이들을 단독으로 또는 추가하여 사용할 수도 있다. Commercially available extractants Alamine 336 or Aliquat 336, which is a nitrogen-based extractant (containing trioctylamine), or Cyanex 923, which is a phosphorus-based extractant (containing trialkylphosphine oxide), may be used alone or in addition. have.
상기 추출제의 사용량은 폐염산에 포함된 금속 성분 중 철(Fe) 이온 성분 1 몰을 기준으로 40 몰 이상, 구체적으로 40 몰 내지 60 몰, 보다 구체적으로 40 몰 내지 50 몰, 더욱 구체적으로 40 몰 내지 45 몰일 수 있다.The amount of the extractant is 40 moles or more, specifically 40 moles to 60 moles, more specifically 40 moles to 50 moles, and more specifically 40 moles based on 1 mole of iron (Fe) ions in the metal components included in the spent hydrochloric acid Moles to 45 moles.
상기 추출제의 사용량이 40 몰 미만인 경우, 금속 성분 특히 철(Fe) 이온 성분 제거 효과가 미미할 수 있다. 또한, 추출제 사용량이 60 몰을 초과하는 경우, 금속 성분 특히, 철(Fe) 이온 성분 제거 효과는 크게 차이가 없으나, 추출제를 다량 사용해야 하기 때문에 제조 비용이 증가할 수 있다. 따라서, 적절한 제조 비용과 철(Fe) 이온 성분 제거 효율을 고려할 때, 60 몰 이하로 사용될 수 있다.When the amount of the extractant is less than 40 moles, the effect of removing metal components, particularly iron (Fe) ions, may be insignificant. In addition, when the amount of the extractant exceeds 60 moles, the effect of removing the metal components, particularly iron (Fe) ions component is not significantly different, but the manufacturing cost may increase because a large amount of the extractant is used. Therefore, considering the proper manufacturing cost and the efficiency of iron (Fe) ion component removal, it can be used in less than 60 moles.
이어서, 도 1 및 2를 참조하면, 본 발명의 폐염산 정제 방법에서는 폐염산을 반응 용기에 투입한 다음, 추출 용액을 투입하고, 교반하면서 폐염산에 함유된 금속 성분을 유기용매로 추출하는 단계를 실시할 수 있다(S2). 1 and 2, in the hydrochloric acid purification method of the present invention, the waste hydrochloric acid is added to a reaction vessel, and then, an extraction solution is added and the metal component contained in the waste hydrochloric acid is extracted with an organic solvent while stirring. It can be carried out (S2).
이때, 상기 폐염산 내에는 포함된 금속 성분은 주로 철 이온 성분이 포함되어 있고, 이 외에 Al3+, Ca2+, K+, Mg2+, Ni2+ 등의 금속 성분이 더 포함될 수 있다.In this case, the metal component included in the spent hydrochloric acid mainly contains iron ions, and in addition to the metal components, such as Al 3+ , Ca 2+ , K + , Mg 2+ , Ni 2+ may be further included. .
또한, 상기 폐염산 : 추출 용액은 1:0.1 내지 1:1 부피비, 구체적으로 1:1 부피비로 혼합될 수 있다. 만약, 상기 추출 용액이 폐염산에 대하여 0.1 부피비(1/10) 미만으로 투입되는 경우, 폐염산 층에서 에멀젼이 발생하여 상분리가 불가능하다는 단점이 있다. 또한, 상기 추출 용액이 1 부피비를 초과하여 투입되는 경우, 공정 비용이 증가하는 단점이 있다. In addition, the hydrochloric acid: the extraction solution may be mixed in a 1: 0.1 to 1: 1 volume ratio, specifically 1: 1 volume ratio. If the extraction solution is added in less than 0.1 volume ratio (1/10) with respect to the waste hydrochloric acid, there is a disadvantage in that an emulsion occurs in the waste hydrochloric acid layer and thus phase separation is impossible. In addition, when the extraction solution is added in more than 1 volume ratio, there is a disadvantage that the process cost increases.
상기 추출 단계(S2)는 폐염산과 추출 용액의 혼합 용액을 상온(atmospheric temperature)에서 200 rpm 내지 600 rpm의 속도로 교반하면서 10초 내지 60초, 구체적으로 20초 내지 60초동안 실시할 수 있다.The extraction step (S2) may be carried out for 10 seconds to 60 seconds, specifically 20 seconds to 60 seconds while stirring the mixed solution of the hydrochloric acid and the extraction solution at a speed of 200 rpm to 600 rpm at an atmospheric temperature.
이때 상온이란 연간을 통한 평상의 평균 온도 또는 대기 중의 온도로서, 구체적으로 20±5℃의 범위의 온도를 의미한다.At this time, the room temperature is the average temperature or the temperature in the atmosphere throughout the year, specifically, means a temperature of 20 ± 5 ℃ range.
상기 교반 속도가 200 rpm 미만인 경우, 혼합이 원활하지 않아 금속 성분이나, 철 이온 성분의 추출 효율이 감소하는 단점이 있다. 또한, 상기 교반 속도가 600 rpm을 초과하는 경우, 금속 성분 추출 효과는 미미한 반면에 에너지 소비가 증가할 수 있다.When the stirring speed is less than 200 rpm, the mixing is not smooth, there is a disadvantage in that the extraction efficiency of the metal component or the iron ion component is reduced. In addition, when the stirring speed exceeds 600 rpm, the metal component extraction effect is insignificant while the energy consumption may increase.
또한, 상기 교반 시간이 10초 미만인 경우, 금속을 추출하기 위한 충분한 시간을 확보하기 못하여, 금속 성분 추출 효율이 감소하는 단점이 있다. 한편, 교반 시간이 60초를 초과하여도 추출되는 금속 성분의 양은 큰 차이를 보이지 않는 반면, 공정상 처리 가능 폐염산의 양이 제한되기 때문에 공정 시간 및 비용이 증가하는 단점이 있다.In addition, when the stirring time is less than 10 seconds, there is a disadvantage that the sufficient time for extracting the metal is not secured, and the metal component extraction efficiency is reduced. On the other hand, even if the stirring time exceeds 60 seconds, the amount of the extracted metal component does not show a big difference, but the process time and cost increases because the amount of waste hydrochloric acid that can be processed in the process is limited.
상기 교반 단계는 여러 가지 혼합장치가 이용될 수 있는데, 그 대표적인 예로서 마그네틱바 교반식 플레이트 또는 스태틱 믹서를 이용하여 실시할 수 있다.Various stirring apparatuses may be used for the stirring step, and as a representative example, the stirring step may be performed using a magnetic bar stirring plate or a static mixer.
한편, 본 발명의 방법 중 추출 단계(S2)에서는 폐염산 내에 함유되어 있는 금속 성분, 구체적으로 철(Fe) 이온 성분뿐만 아니라, 노란색을 나타내는 성분인 FeCl4
- 및 FeCl3도 함께 제거되므로(하기 반응식 4 참조), 정제 후 수득된 고순도의 염산은 색이 투명하게 변화한 것을 확인할 수 있다 (도 3 참조) On the other hand, in the extraction step (S2) of the method of the present invention, not only the metal component contained in the waste hydrochloric acid, specifically the iron (Fe) ion component, but also the yellow component FeCl 4 - and FeCl 3 are removed together (below) See Scheme 4), the high purity hydrochloric acid obtained after purification can be seen that the color is transparent (see Figure 3)
[반응식 4]Scheme 4
R3N (유기상) + HCl (폐염산) → R3NHCl (유기상)R 3 N (organic phase) + HCl (waste hydrochloric acid) → R 3 NHCl (organic phase)
FeCl4
- (물층) + R3NHCl (유기상) → FeCl3R3NHCl (유기상) + Cl- (물층)FeCl 4 - (aqueous) + R 3 NHCl (organic phase) → FeCl 3 R 3 NHCl (organic phase) + Cl - (aqueous)
FeCl3 (물층) + R3NHCl (유기상) → FeCl3R3NHCl (유기상)FeCl 3 (water layer) + R 3 NHCl (organic phase) → FeCl 3 R 3 NHCl (organic phase)
그 다음으로, 도 1 및 도 2를 참조하면, 본 발명의 폐염산 정제 방법에서는 교반이 평형에 도달한 후, 상기 유기용매와 폐염산의 혼합 용액을 세퍼레이터에 넣고 흔든 후 정치시켜 잔류하는 상인 금속 성분을 함유한 유기용매와, 추출상(extract)인 폐염산층으로 상분리(분획)시켰다(S3).Next, referring to FIGS. 1 and 2, in the method for purifying waste hydrochloric acid of the present invention, after stirring reaches an equilibrium, the mixed solution of the organic solvent and waste hydrochloric acid is placed in a separator, shaken, and left to stand. Phase separation (fractionation) of the organic solvent containing the component and the waste hydrochloric acid layer as an extract phase (S3).
이때, 상기 상분리를 위한 혼합 단계는 20초 이내로 실시할 수 있다. At this time, the mixing step for the phase separation may be carried out within 20 seconds.
이어서, 도 1 및 도 2를 참조하면, 본 발명의 폐염산 정제 방법에서는 상기 상분리 단계(S3)에서 상분리되어 하단에 위치하는 추출상인 폐염산층을 회수하여 정제된 염산을 수득할 수 있다(S4).Subsequently, referring to FIGS. 1 and 2, in the hydrochloric acid purification method of the present invention, purified hydrochloric acid may be obtained by recovering the waste hydrochloric acid layer which is an phase separated from the phase separation step (S3) and is located at the bottom (S4). ).
이때, 상기 정제된 염산 중에는 금속 성분, 특히 철(Fe) 이온 성분이 효과적으로 제거되어, 철(Fe) 이온 성분이 1 ppm 이하, 구체적으로 0.1 ppm 이하의 농도로 잔류할 수 있다. In this case, the purified hydrochloric acid may effectively remove the metal component, particularly the iron (Fe) ion component, the iron (Fe) ion component may remain at a concentration of 1 ppm or less, specifically 0.1 ppm or less.
또한, 도 2를 참조하면, 본 발명의 폐염산 정제 방법은 상기 폐염산 정제에 사용되는 유기용매의 재생 효율을 높이기 위하여, 폐염산에 사용된 유기용매를 정제하는 단계를 추가로 포함할 수 있다.In addition, referring to Figure 2, the waste hydrochloric acid purification method of the present invention may further comprise the step of purifying the organic solvent used in the waste hydrochloric acid, in order to increase the regeneration efficiency of the organic solvent used in the waste hydrochloric acid purification. .
즉, 본 발명의 폐염산 정제 방법은 상기 정제된 염산 수득단계(S4) 후에, That is, the waste hydrochloric acid purification method of the present invention after the purified hydrochloric acid obtaining step (S4),
상기 상분리 단계(S3)에서 분리된 금속 성분을 함유한 유기용매에 증류수를 첨가하여 유기용매 중의 잔류 금속 성분을 탈거하는 단계(S5);Removing residual metal components in the organic solvent by adding distilled water to the organic solvent containing the metal components separated in the phase separation step (S3) (S5);
탈거된 유기용매와 물층을 상분리(분획)하는 단계(S6); 및Phase separating (fractionating) the stripped organic solvent and the water layer (S6); And
상분리된 유기용매 및 물층을 각각 회수하는 단계(S7);를 추가로 포함할 수 있다.Recovering the phase-separated organic solvent and the water layer, respectively (S7); may further include.
즉, 본 발명의 방법에서는 폐염산 정제 후 상분리되어 회수된 유기용매를 다시 한번 반응기에 투입한 다음, 증류수를 첨가하여 유기용매 중에 잔류하는 금속 성분을 탈거하는 단계를 실시할 수 있다(S5).That is, in the method of the present invention, the organic solvent recovered by phase separation after waste hydrochloric acid purification may be added to the reactor once again, and then distilled water may be added to remove metal components remaining in the organic solvent (S5).
상기 탈거 단계에 의해 유기용매 중의 잔류 금속 성분을 물로 추출해 낼 수 있다.By the stripping step, the residual metal component in the organic solvent can be extracted with water.
이때, 상기 유기용매 : 증류수는 1: 0.1 내지 1:1의 부피비, 구체적으로 1:1 부피비로 혼합될 수 있다. 만약, 상기 증류수가 0.1 미만으로 투입되는 경우, 금속 성분 추출 효과가 감소하고, 상기 증류수가 1 부피비 (1/1)를 초과하여 투입되는 경우, 에멀젼이 일어나 상분리가 일어나지 않을 수 있다. At this time, the organic solvent: distilled water may be mixed in a volume ratio of 1: 0.1 to 1: 1, specifically 1: 1 volume ratio. If the distilled water is less than 0.1, the extraction effect of the metal component is reduced, and when the distilled water is added in more than 1 volume ratio (1/1), the emulsion may occur and phase separation may not occur.
상기 탈거 단계(S5)는 분리된 유기용매와 증류수의 혼합 용액을 상온에서 200 rpm 내지 600 rpm의 속도로 교반하면서 10초 내지 60초, 구체적으로 20초 내지 60초 동안 실시할 수 있다.The stripping step (S5) may be performed for 10 seconds to 60 seconds, specifically 20 seconds to 60 seconds while stirring the mixed solution of the separated organic solvent and distilled water at a speed of 200 rpm to 600 rpm at room temperature.
이때 상온이란 연간을 통한 평상의 평균 온도 또는 대기 중의 온도로서, 구체적으로 20±5℃의 범위의 온도를 의미한다.At this time, the room temperature is the average temperature or the temperature in the atmosphere throughout the year, specifically, means a temperature of 20 ± 5 ℃ range.
상기 교반 속도가 200 rpm 미만인 경우, 혼합이 원활하지 않아 금속 성분의 추출 효율이 감소하는 단점이 있다. 또한, 상기 교반 속도가 600 rpm을 초과하는 경우, 금속 성분 추출 효과는 미미한 반면에 에너지 소비가 증가될 수 있다.If the stirring speed is less than 200 rpm, the mixing is not smooth, there is a disadvantage in that the extraction efficiency of the metal component is reduced. In addition, when the stirring speed exceeds 600 rpm, the metal component extraction effect is insignificant while the energy consumption may be increased.
상기 탈거를 위한 교반 시간이 20초 미만인 경우, 금속을 추출하기 위한 충분한 시간을 확보하기 못하여, 금속 성분 추출 효율이 감소하는 단점이 있다. 한편, 교반 시간이 60초를 초과하여도 추출되는 금속 성분의 양은 큰 차이를 보이지 않는 반면, 공정상 처리 가능한 폐 유기용매의 양이 제한되기 때문에 공정 시간 및 비용이 증가하는 단점이 있다.If the stirring time for the stripping is less than 20 seconds, there is a disadvantage in that sufficient time for extracting the metal is not secured, thereby reducing the extraction efficiency of the metal component. On the other hand, even if the stirring time exceeds 60 seconds, the amount of the extracted metal component does not show a big difference, but the process time and cost increases because the amount of waste organic solvent that can be processed in the process is limited.
상기 탈거 단계(S5)는 여러 가지 혼합장치가 이용될 수 있는데, 그 대표적인 예로서 마그네틱바 교반식 플레이트 또는 스태틱 믹서를 이용할 수 있다.The stripping step (S5) may be used a variety of mixing device, as a representative example may use a magnetic bar stirring plate or a static mixer.
그 다음으로, 도 2를 참조하면, 본 발명의 방법에서는 교반이 평형에 도달한 후, 상기 유기용매와 증류수층의 혼합 용액을 세퍼레이터에 넣고 흔든 후 정치시켜 금속 성분이 탈거된 유기용매와, 철(Fe) 이온 성분 등이 함유된 증류수층으로 상분리(분획)시켰다(S6).Next, referring to FIG. 2, in the method of the present invention, after stirring reaches an equilibrium, the organic solvent and the organic solvent in which the metal component is removed by stirring by stirring the mixed solution of the organic solvent and the distilled water layer in a separator, and iron, Phase separation (fractionation) was carried out with a distilled water layer containing the (Fe) ion component and the like (S6).
이때, 상기 상분리 단계는 20초 이내로 실시할 수 있다. At this time, the phase separation step may be carried out within 20 seconds.
이어서, 본 발명의 방법에서는 상분리되어 하단에 위치하는 추출상인 증류수층을 제거하고, 상단에 위치하는 유기층을 회수하여(S7) 폐염산 정제에 사용되는 유기상을 효과적으로 재생할 수 있다.Subsequently, in the method of the present invention, the distilled water layer, which is the phase separated and the extracted phase located at the bottom, is removed, and the organic layer located at the top is recovered (S7), thereby effectively regenerating the organic phase used for waste hydrochloric acid purification.
이때, 회수된 유기용매 및 물층에 포함된 잔여 금속의 농도를 측정하여, 본 발명이 방법에 따른 유기용매의 재생 효율 정도를 확인할 수 있다.At this time, by measuring the concentration of the residual metal contained in the recovered organic solvent and the water layer, it is possible to determine the degree of regeneration efficiency of the organic solvent according to the present invention.
전술한 바와 같이, 본 발명의 방법에 따른 용매 추출법을 이용한 폐염산 정제 방법의 경우, 폐염산으로부터 철(Fe) 이온 성분을 효과적으로 제거할 수 있기 때문에, 공정의 단순화에 이에 따른 에너지 및 비용 절감 효과를 가져올 수 있다. 더욱이, 본 발명의 방법에서는 추가로 폐염산 정제 방법에 사용된 유기용매를 재생하는 단계를 포함함으로써, 상기 유기용매를 수회 반복 사용이 가능해짐에 따라, 기존 공정에 비해 공정 운용 비용 등을 크게 절감할 수 있다.As described above, in the case of the waste hydrochloric acid purification method using the solvent extraction method according to the method of the present invention, since iron (Fe) ion component can be effectively removed from the waste hydrochloric acid, the energy and cost saving effect according to the process simplification Can be imported. In addition, the method of the present invention further comprises the step of regenerating the organic solvent used in the waste hydrochloric acid purification method, it is possible to repeat the use of the organic solvent several times, significantly reducing the process operating costs and the like compared to the existing process can do.
실시예Example
이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명한다. 그러나, 본 발명에 따른 실시예는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예에 한정되는 것으로 해석되어서는 안 된다. 본 발명의 실시예는 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되는 것이다.Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
실시예 1.Example 1.
유도 결합플라즈마 질량분석기(Inductively coupled plasma mass spectrometry)로 폐염산 100 ml에 포함된 철(Fe) 이온 성분의 농도를 측정하였다(S0).The concentration of iron (Fe) ions contained in 100 ml of waste hydrochloric acid was measured by an inductively coupled plasma mass spectrometry (S0).
이어서, 유기용매인 톨루엔 100ml에 추출제인 트리옥틸아민 (폐염산에 포함된 철(Fe) 이온 성분 : 추출제 = 1몰 : 40몰)를 용해시켜 추출 용액을 제조하였다(S1).Subsequently, an extraction solution was prepared by dissolving trioctylamine (an iron (Fe) ion component included in waste hydrochloric acid: extractant = 1 mol: 40 mol) in 100 ml of an organic solvent toluene (S1).
그 다음으로, 폐염산 100 ml에 상기 추출 용액을 투입하고, 200 rpm의 속도로 60초 동안 상온에서 교반하면서 폐염산에 포함된 금속 성분들을 유기용매로 추출하였다(S2).Next, the extraction solution was added to 100 ml of waste hydrochloric acid, and metal components contained in the waste hydrochloric acid were extracted with an organic solvent while stirring at room temperature for 60 seconds at a speed of 200 rpm (S2).
교반이 평형에 도달한 후, 상기 유기용매와 폐염산의 혼합 용액을 세퍼레이터에 넣고 약 20초간 흔든 후 정치시켜 금속 성분을 함유한 유기용매와, 폐염산층으로 상분리(분획)시켰다(S3).After stirring reached equilibrium, the mixed solution of organic solvent and waste hydrochloric acid was placed in a separator, shaken for about 20 seconds, and allowed to stand for phase separation (fractionation) into an organic solvent containing a metal component and a waste hydrochloric acid layer (S3).
이어서, 분리된 폐염산층을 회수하여 정제된 염산을 수득하였다(S4) (도 3 참조).Subsequently, the separated hydrochloric acid layer was recovered to obtain purified hydrochloric acid (S4) (see FIG. 3).
상기 정제된 염산 내의 잔여 금속 농도와, TOC를 측정하고, 그 결과를 하기 표 1 및 2에 나타내었다.The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
이때, 잔여 금속 농도는 Inductively coupled plasma atomic emission spectroscopy (ICP-OES)를 이용하여 측정하였으며, TOC (total organic carbon) 성분은 TOC 분석기 (analyzer)를 통하여 분석하였다. At this time, the residual metal concentration was measured using Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-OES), and the total organic carbon (TOC) component was analyzed by a TOC analyzer (analyzer).
실시예 2.Example 2.
상기 실시예 1의 (S1) 단계에서 폐염산에 포함된 Fe : 추출제 = 1 : 60몰비로 추출제를 사용하는 것을 제외하고는 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 1에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1 except for using the extracting agent in a Fe: extractant = 1: 60 molar ratio included in the waste hydrochloric acid in the step (S1) of Example 1. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 1 below.
실시예 3.Example 3.
상기 실시예 1에서 톨루엔 대신 시클로헥산을 사용하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도와 TOC를 측정하고, 그 결과를 하기 표 1 및 2에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that cyclohexane was used instead of toluene in Example 1. The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
실시예 4.Example 4.
상기 실시예 3에서 분리된 폐염산층을 추출제 40 몰이 용해된 시클로헥산을 이용하여 한번 더 추출(S2)하는 것을 제외하고는, 상기 실시예 3과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도와 TOC를 측정하고, 그 결과를 하기 표 1 및 2에 나타내었다.The hydrochloric acid purified in the same manner as in Example 3 was obtained except that the waste hydrochloric acid layer separated in Example 3 was extracted once more using cyclohexane in which 40 moles of the extractant was dissolved (S2). The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
실시예 5.Example 5.
상기 실시예 1에서 톨루엔 대신 크실렌을 사용하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도와 TOC를 측정하고, 그 결과를 하기 표 1 및 2에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that xylene was used instead of toluene in Example 1. The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
실시예 6.Example 6.
상기 실시예 5에서 분리된 폐염산층을 추출제 40 몰이 용해된 크실렌을 이용하여 한번 더 추출(S2)하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도와 TOC를 측정하고, 그 결과를 하기 표 1 및 2에 나타내었다.The hydrochloric acid purified in the same manner as in Example 1 was obtained except that the waste hydrochloric acid layer separated in Example 5 was extracted once more using xylene in which 40 moles of the extractant was dissolved (S2). The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
실시예 7.Example 7.
상기 실시예 1에서 톨루엔 대신 옥탄과 2-에틸 헥산올의 혼합 용액 (1:1 부피비)을 사용하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도와 TOC를 측정하고, 그 결과를 하기 표 1 및 2에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that in Example 1, a mixed solution of octane and 2-ethyl hexanol (1: 1 volume ratio) was used instead of toluene. The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
실시예 8.Example 8.
상기 실시예 1에서 톨루엔 대신 데칸과 2-에틸 헥산올의 혼합 용액 (1:1 부피비)을 사용하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도와 TOC를 측정하고, 그 결과를 하기 표 1 및 2에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that in Example 1, a mixed solution of decane and 2-ethyl hexanol (1: 1 volume ratio) was used instead of toluene. The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
실시예 9.Example 9.
상기 실시예 1에서 톨루엔 대신 도데칸과 2-에틸 헥산올의 혼합 용액 (1:1 부피비)을 사용하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도와 TOC를 측정하고, 그 결과를 하기 표 1 및 2에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that a mixed solution (1: 1 volume ratio) of dodecane and 2-ethyl hexanol was used instead of toluene in Example 1. The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
실시예 10.Example 10.
상기 실시예 1에서 톨루엔 대신 케로센과 2-에틸 헥산올의 혼합 용액 (1:1 부피비)을 사용하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도와 TOC를 측정하고, 그 결과를 하기 표 1 및 2에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that a mixed solution of kerosene and 2-ethyl hexanol (1: 1 volume ratio) was used instead of toluene in Example 1. The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
실시예 11.Example 11.
상기 실시예 1에서 톨루엔 대신 케로센과 2-도데칸올의 혼합 용액 (1:1 부피비)을 사용하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도와 TOC를 측정하고, 그 결과를 하기 표 1 및 2에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that in Example 1, a mixed solution of kerosene and 2-dodecanol (1: 1 by volume) was used instead of toluene. The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
실시예Example
12. 12.
상기 실시예 1의 (S1) 단계에서 추출제로 트리옥틸아민 대신 트리알킬포스핀 옥사이드를 용해시켜 추출 용액을 제조하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도와 TOC를 측정하고, 그 결과를 하기 표 1 및 2에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that in the step (S1) of Example 1, an extraction solution was prepared by dissolving trialkylphosphine oxide instead of trioctylamine as an extractant. The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
실시예Example
13. 13.
상기 실시예 3의 (S1) 단계에서 추출제로 트리옥틸아민 대신 트리알킬포스핀 옥사이드를 용해시켜 추출 용액을 제조하는 것을 제외하고는, 상기 실시예 3과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도와 TOC를 측정하고, 그 결과를 하기 표 1 및 2에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 3, except that in the step (S1) of Example 3, an extraction solution was prepared by dissolving trialkylphosphine oxide instead of trioctylamine as an extractant. The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
실시예Example
14. 14.
상기 실시예 1의 (S1) 단계에서 추출 용액 제조 시에 톨루엔 대신 메틸 사이클로헥산을 사용하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도와 TOC를 측정하고, 그 결과를 하기 표 1 및 2에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that methyl cyclohexane was used instead of toluene when preparing the extraction solution in the step (S1) of Example 1. The residual metal concentration and TOC in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
비교예 1.Comparative Example 1.
폐염산 100ml에 이온 교환수지(IRA-900) 10 중량%를 주입하고, 200 rpm의 속도로 1시간 동안 상온에서 교반하였다. 이어서, 상기 반응물을 여과하여 이온 교환 수지를 제거하고, 정제된 염산을 수득하였다.10 wt% of an ion exchange resin (IRA-900) was injected into 100 ml of waste hydrochloric acid, and stirred at room temperature for 1 hour at a speed of 200 rpm. The reaction was then filtered to remove the ion exchange resin and to obtain purified hydrochloric acid.
상기 정제된 염산 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 1에 나타내었다.The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 1 below.
비교예 2.Comparative Example 2.
상기 비교예 1에서 이온교환수지(IRA-900) 대신 이온교환수지(IRA-910)을 사용하는 것을 제외하고는, 상기 비교예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 1에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Comparative Example 1 except for using the ion exchange resin (IRA-910) instead of the ion exchange resin (IRA-900) in Comparative Example 1. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 1 below.
비교예 3.Comparative Example 3.
폐염산 100ml에 유리 잔류염산을 제거하기 위하여 NaSO3를 투입하고 200 rpm의 속도로 1시간 동안 상온에서 교반한 다음, 상기 혼합물에 이온 교환수지(IRA-910) 10 중량%를 주입하고, 200 rpm의 속도로 1시간 동안 상온에서 교반하였다.To remove free residual hydrochloric acid in 100 ml of waste hydrochloric acid, NaSO 3 was added, stirred at room temperature for 1 hour at a speed of 200 rpm, and then 10% by weight of an ion exchange resin (IRA-910) was injected into the mixture, and 200 rpm. Stirred at room temperature for 1 hour at a rate of.
이어서, 상기 반응물을 여과하여 이온 교환 수지를 제거하고, 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 1에 나타내었다.The reaction was then filtered to remove the ion exchange resin and to obtain purified hydrochloric acid. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 1 below.
비교예 4.Comparative Example 4.
폐염산 100ml에 활성탄 20 중량%를 투입하고 200 rpm의 속도로 1시간 동안 상온에서 교반한 다음, 상기 반응물을 여과하여 활성탄을 제거하였다.20% by weight of activated carbon was added to 100 ml of waste hydrochloric acid and stirred at room temperature for 1 hour at a speed of 200 rpm, and then the reaction product was filtered to remove activated carbon.
상기 여과 공정에 의해 얻어진 폐염산 100 ml에 이온 교환수지(IRA-910) 10 중량%를 주입하고, 200 rpm의 속도로 1시간 동안 상온에서 교반하였다. 10 wt% of an ion exchange resin (IRA-910) was injected into 100 ml of waste hydrochloric acid obtained by the filtration process, and stirred at room temperature for 1 hour at a speed of 200 rpm.
이어서, 상기 반응물을 여과하여 이온 교환 수지를 제거하고, 정제된 염산을 수득하였다. The reaction was then filtered to remove the ion exchange resin and to obtain purified hydrochloric acid.
상기 정제된 염산 내의 잔여 수득된 염산 내의 잔여 금속 농도와 TOC를 측정하고, 그 결과를 하기 표 1 및 2 에 나타내었다.The residual metal concentration and TOC in the obtained hydrochloric acid in the purified hydrochloric acid were measured, and the results are shown in Tables 1 and 2 below.
추출 용액Extraction solution | AlAl | CaCa | FeFe | KK | MgMg | ||
추출제Extractant | 유기용매Organic solvent | ||||||
폐염산Waste hydrochloric acid | -- | -- | 55 | 1515 | 2020 | 55 | 55 |
실시예 1Example 1 | 트리옥틸아민Trioctylamine | 톨루엔toluene | 66 | 1616 | <0.1<0.1 | 55 | 55 |
실시예 2Example 2 | 트리옥틸아민Trioctylamine | 톨루엔toluene | 66 | 1717 | <0.1<0.1 | 55 | 55 |
실시예 3Example 3 | 트리옥틸아민Trioctylamine | 시클로헥산Cyclohexane | 55 | 1616 | <0.1<0.1 | 55 | 55 |
실시예 4Example 4 | 트리옥틸아민Trioctylamine | 시클로헥산 (2회)Cyclohexane (twice) | 55 | 1616 | <0.1<0.1 | 55 | 55 |
실시예 5Example 5 | 트리옥틸아민Trioctylamine | 크실렌xylene | 66 | 1616 | <0.1<0.1 | 55 | 55 |
실시예 6Example 6 | 트리옥틸아민Trioctylamine | 크실렌 (2회)Xylene (2 times) | 66 | 1717 | <0.1<0.1 | 55 | 55 |
실시예 7Example 7 | 트리옥틸아민Trioctylamine | 옥탄+2-에틸 헥산올Octane + 2-ethyl hexanol | 77 | 1717 | <0.1<0.1 | 55 | 55 |
실시예 8Example 8 | 트리옥틸아민Trioctylamine | 데칸+ 2-에틸 헥산올Decane + 2-ethyl hexanol | 77 | 1616 | <0.1<0.1 | 55 | 55 |
실시예 9Example 9 | 트리옥틸아민Trioctylamine | 도데칸+2-에틸 헥산올Dodecane + 2-ethyl hexanol | 77 | 1616 | <0.1<0.1 | 55 | 55 |
실시예 10Example 10 | 트리옥틸아민Trioctylamine | 케로센+ 2-에틸 헥산올Kerosene + 2-ethyl hexanol | 77 | 1717 | <0.1<0.1 | 66 | 55 |
실시예 11Example 11 | 트리옥틸아민Trioctylamine | 케로센+ 2-도데칸올Kerosene + 2-dodecanol | 66 | 1616 | 1One | 55 | 55 |
실시예 12Example 12 | 트리알킬포스핀 옥사이드Trialkylphosphine oxide | 톨루엔toluene | 33 | 1616 | <0.1<0.1 | 33 | 44 |
실시예 13Example 13 | 트리알킬포스핀 옥사이드Trialkylphosphine oxide | 시클로헥산Cyclohexane | 44 | 1616 | <0.1<0.1 | 44 | 55 |
실시예 14Example 14 | 트리옥틸아민Trioctylamine | 메틸 사이클로헥산Methyl cyclohexane | 22 | 88 | <0.1<0.1 | 33 | 22 |
비교예1Comparative Example 1 | -- | -- | 44 | 1616 | 44 | 44 | 55 |
비교예2Comparative Example 2 | -- | -- | 44 | 1616 | 44 | 44 | 55 |
비교예3Comparative Example 3 | -- | -- | 44 | 1818 | 44 | 44 | 66 |
비교예4Comparative Example 4 | -- | -- | N.DN.D | N.DN.D | 2121 | N.DN.D | N.DN.D |
* 금속 성분 농도 단위 (ppm)* Metal concentration unit (ppm)
상기 표 1에 나타낸 바와 같이, 본 발명이 용매 추출법을 이용한 실시예 1 내지 14의 경우, 유기용매의 종류에 상관 없이 잔류 철(Fe) 이온 성분의 농도가 1 ppm 이하 (95% 이상 제거)인 것을 확인할 수 있다. As shown in Table 1, in Examples 1 to 14 using the solvent extraction method of the present invention, the concentration of the residual iron (Fe) ion component is 1 ppm or less (95% or more removed) regardless of the type of the organic solvent. You can see that.
더욱이, 정제 공정 중에 폐염산의 노란색을 나타내는 성분인 FeCl4
- 및 FeCl3가 함께 제거되어, 정제 후 폐염산 색이 투명하게 변화한 것을 확인할 수 있다 (도 3 참조), Furthermore, during the purification process, FeCl 4 − and FeCl 3 , which are yellow components of the spent hydrochloric acid, were removed together to confirm that the color of the spent hydrochloric acid became transparent after purification (see FIG. 3).
반면에, 폐염산 내의 철(Fe) 이온 성분을 제거하기 위하여 이온교환수지를 이용한 비교예 1 내지 3의 경우, 잔류 철(Fe) 이온 성분의 농도가 1 ppm 이상 (약 80% 정도 제거) 인 것을 확인할 수 있다. 특히, 유리 잔류염소를 제거하기 위하여 NaSO3를 첨가한 비교예 3의 경우, Fe 제거 효율에 영향이 없는 것을 확인하였다.On the other hand, in Comparative Examples 1 to 3 using ion exchange resins to remove iron (Fe) ions in the waste hydrochloric acid, the concentration of residual iron (Fe) ions is 1 ppm or more (about 80%). You can see that. In particular, in the case of Comparative Example 3 in which NaSO 3 was added to remove free residual chlorine, it was confirmed that the Fe removal efficiency is not affected.
또한, 활성탄 처리한 이후 이온 교환수지를 사용한 비교예 4의 방법의 경우, 비교예 1 및 2과 비교하여 오히려 Fe 의 농도가 증가한 것을 확인하였다. 이러한 결과는 활성 탄소에서 과량의 금속 불순물이 포함되어 배출된 것으로 예측할 수 있다.In addition, in the case of the method of Comparative Example 4 using the ion exchange resin after the activated carbon treatment, it was confirmed that the concentration of Fe increased rather than Comparative Examples 1 and 2. These results can be predicted to include excess metal impurities from activated carbon emissions.
추출 용액Extraction solution | TOC(total organic carbon)TOC (total organic carbon) | TIC(total inorganic carbon)TIC (total inorganic carbon) | TC(total carbon)TC (total carbon) | ||
추출제Extractant | 유기용매Organic solvent | ||||
폐염산Waste hydrochloric acid | -- | -- | 67.6567.65 | 54.6454.64 | 122.29122.29 |
실시예 1Example 1 | 트리옥틸아민 Trioctylamine | 톨루엔toluene | 5.225.22 | 64.1864.18 | 69.469.4 |
실시예 3Example 3 | 트리옥틸아민Trioctylamine | 시클로헥산Cyclohexane | 37.137.1 | 54.1754.17 | 91.2791.27 |
실시예 4Example 4 | 트리옥틸아민Trioctylamine | 시클로헥산 (2회)Cyclohexane (twice) | 14.2714.27 | 53.8553.85 | 68.1268.12 |
실시예 5Example 5 | 트리옥틸아민Trioctylamine | 크실렌xylene | 40.740.7 | 54.454.4 | 95.195.1 |
실시예 6Example 6 | 트리옥틸아민Trioctylamine | 크실렌 (2회)Xylene (2 times) | 6.286.28 | 63.763.7 | 69.9869.98 |
실시예 7Example 7 | 트리옥틸아민Trioctylamine | 옥탄 + 2-에틸 헥산올Octane + 2-ethyl hexanol | 45.9345.93 | 54.8454.84 | 100.77100.77 |
실시예 8Example 8 | 트리옥틸아민Trioctylamine | 데칸 + 2-에틸 헥산올Decane + 2-ethyl hexanol | 65.4865.48 | 140.56140.56 | 206.04206.04 |
실시예 9Example 9 | 트리옥틸아민Trioctylamine | 도데칸 + 2-에틸 헥산올Dodecane + 2-ethyl hexanol | 66.1566.15 | 145.06145.06 | 211.21211.21 |
실시예 10Example 10 | 트리옥틸아민Trioctylamine | 케로센 + 2-에틸 헥산올Kerosene + 2-ethyl hexanol | 59.5159.51 | 144.24144.24 | 203.85203.85 |
실시예 11Example 11 | 케로센 + 2-도데칸올Kerosene + 2-dodecanol | 53.5153.51 | 55.0555.05 | 108.56108.56 | |
실시예 14Example 14 | 트리옥틸아민Trioctylamine | 메틸 사이클로헥산Methyl cyclohexane | 53.5853.58 | 151.7151.7 | 205.28205.28 |
비교예4Comparative Example 4 | -- | -- | 18.7918.79 | 54.7854.78 | 73.5773.57 |
또한, 상기 표 2에 나타낸 바와 같이, 추출 후 회수된 정제된 염산의 TOC 값을 비교해 보면, 톨루엔을 추출 용액에 사용했을 때의 수치가 5.22로, 가장 낮은 TOC 함량을 나타내었다. 이러한 결과로부터, 톨루엔을 사용하는 경우 상분리가 가장 효과적으로 이루어져 상분리 이후 유기 불순물이 폐염산에 포함되지 않는 것을 알 수 있다.In addition, as shown in Table 2, when comparing the TOC value of the purified hydrochloric acid recovered after extraction, the value when using toluene in the extraction solution was 5.22, showing the lowest TOC content. From these results, it can be seen that when toluene is used, phase separation is most effective, and organic impurities are not included in the waste hydrochloric acid after phase separation.
실시예 15.Example 15.
상기 실시예 1에서 유기용매를 100ml를 사용하는 대신 50 ml를 사용하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 3에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that 50 ml of the organic solvent was used instead of 100 ml in Example 1. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 3 below.
실시예 16.Example 16.
상기 실시예 1에서 유기용매를 100ml를 사용하는 대신 30 ml를 사용하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 3에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that 30 ml of the organic solvent was used instead of 100 ml in Example 1. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 3 below.
실시예 17.Example 17.
상기 실시예 1에서 유기용매를 100ml를 사용하는 대신 10 ml를 사용하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 3에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that 10 ml of the organic solvent was used instead of 100 ml in Example 1. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 3 below.
비교예Comparative example
5. 5.
상기 실시예 1에서 유기용매를 100 ml를 사용하는 대신 9 ml를 사용하는 경우, 폐염산층에서 에멀젼(emulsion) 현상이 발생하면서, 상분리가 쉽지 않았다.When using 9 ml instead of 100 ml of the organic solvent in Example 1, while the emulsion (emulsion) occurs in the waste hydrochloric acid layer, phase separation was not easy.
유기용매 함량 (ml)Organic Solvent Content (ml) | AlAl | CaCa | FeFe | KK | MgMg | |
폐염산Waste hydrochloric acid | -- | 55 | 1515 | 2020 | 55 | 55 |
실시예 15Example 15 | 5050 | 44 | 1616 | <0.1<0.1 | 44 | 55 |
실시예 16Example 16 | 3030 | 44 | 1616 | <0.1<0.1 | 44 | 55 |
실시예 17Example 17 | 1010 | 44 | 1616 | <0.1<0.1 | 44 | 55 |
비교예 5Comparative Example 5 | 99 | -- | -- | -- | -- | -- |
상기 표 3으로부터 알 수 있는 바와 같이, 추출 용액과 및 폐염산의 혼합 비율을 변화해 가며 철(Fe) 이온 성분의 농도 변화를 측정한 결과, 추출 용액 중의 유기용매의 사용량이 감소하여도 Fe 제거 효율이 감소하지 않는 것을 알 수 있다. As can be seen from Table 3, as a result of measuring the concentration change of the iron (Fe) ions while changing the mixing ratio of the extraction solution and the waste hydrochloric acid, Fe removal even if the amount of the organic solvent in the extraction solution decreases It can be seen that the efficiency does not decrease.
한편, 상기 비교예 5와 같이 유기용매/폐염산의 혼합비가 1/10 이하인 경우 에멀젼 현상이 발생하여, 상분리 자체가 어려워 순수한 염산 정제가 어려운 것을 확인하였다.On the other hand, when the mixing ratio of the organic solvent / waste hydrochloric acid is less than 1/10 as in Comparative Example 5, an emulsion phenomenon occurs, it was confirmed that it is difficult to purify pure hydrochloric acid because the phase separation itself is difficult.
실시예 18.Example 18.
상기 실시예 1에서 유기용매와 폐염산을 교반하여 추출하는 시간을 50초로 실시하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 4에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that the extraction time by stirring the organic solvent and the spent hydrochloric acid in Example 1 was performed at 50 seconds. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 4 below.
실시예 19.Example 19.
상기 실시예 1에서 유기용매와 폐염산을 교반하여 추출하는 시간을 30초로 실시하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 철(Fe) 이온 성분의 농도를 측정하고, 그 결과를 하기 표 4에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that the extraction time by stirring the organic solvent and the spent hydrochloric acid in Example 1 was performed for 30 seconds. The concentration of iron (Fe) ions in the purified hydrochloric acid was measured, and the results are shown in Table 4 below.
실시예 20.Example 20.
상기 실시예 1에서 유기용매와 폐염산을 교반하여 추출하는 시간을 20초로 실시하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 철(Fe) 이온 성분의 농도를 측정하고, 그 결과를 하기 표 4에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that the extraction time by stirring the organic solvent and the spent hydrochloric acid in Example 1 was performed for 20 seconds. The concentration of iron (Fe) ions in the purified hydrochloric acid was measured, and the results are shown in Table 4 below.
실시예 21.Example 21.
상기 실시예 1에서 유기용매와 폐염산을 교반하여 추출하는 시간을 10초로 실시하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 철(Fe) 이온 성분의 농도를 측정하고, 그 결과를 하기 표 4에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that the extraction time by stirring the organic solvent and the spent hydrochloric acid in Example 1 was performed for 10 seconds. The concentration of iron (Fe) ions in the purified hydrochloric acid was measured, and the results are shown in Table 4 below.
교반 시간 (초)Agitation time (seconds) | FeFe | |
폐염산Waste hydrochloric acid | -- | 2020 |
실시예 18Example 18 | 5050 | <0.1<0.1 |
실시예 19Example 19 | 3030 | <0.1<0.1 |
실시예 20Example 20 | 2020 | <0.1<0.1 |
실시예 21Example 21 | 1010 | 0.10.1 |
상기 표 4로부터 알 수 있는 바와 같이, 유기용매와 폐염산의 혼합 시간을 변화해 가며 철(Fe) 이온 성분의 농도 변화를 측정한 결과, 추출 시간을 20초까지 감소시켜도 폐염산 내 Fe 제거 효율이 우수 것을 알 수 있다. As can be seen from Table 4, as a result of measuring the concentration change of the iron (Fe) ions while changing the mixing time of the organic solvent and waste hydrochloric acid, Fe removal efficiency in the waste hydrochloric acid even if the extraction time is reduced to 20 seconds It can be seen that this is excellent.
하지만, 추출 시간을 10초로 하는 경우, Fe 제거 효율이 감소하여 1 ppm 이하의 Fe가 검출되는 것을 알 수 있다.However, when the extraction time is 10 seconds, the Fe removal efficiency is reduced, it can be seen that less than 1 ppm of Fe is detected.
실시예 22.Example 22.
상기 실시예 1에서 추출을 위한 유기용매와 폐염산의 교반 속도를 200 rpm 대신 600 rpm으로 실시하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 5에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that the stirring speed of the organic solvent and the hydrochloric acid for extraction in Example 1 was performed at 600 rpm instead of 200 rpm. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 5 below.
실시예 23.Example 23.
상기 실시예 1에서 추출을 위한 유기용매와 폐염산의 교반 속도를 200 rpm 대신 300 rpm으로 실시하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 5에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that the stirring speed of the organic solvent and the hydrochloric acid for extraction in Example 1 was performed at 300 rpm instead of 200 rpm. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 5 below.
실시예 24.Example 24.
상기 실시예 1에서 추출을 위한 유기용매와 폐염산의 교반 속도를 200 rpm 대신 100 rpm으로 실시하는 것을 제외하고는, 상기 실시예 1과 마찬가지의 방법으로 정제된 염산을 수득하였다. 상기 정제된 염산 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 5에 나타내었다.Purified hydrochloric acid was obtained in the same manner as in Example 1, except that the stirring speed of the organic solvent and the hydrochloric acid for extraction in Example 1 was performed at 100 rpm instead of 200 rpm. The residual metal concentration in the purified hydrochloric acid was measured and the results are shown in Table 5 below.
교반 속도 (rpm)Stirring Speed (rpm) | AlAl | CaCa | FeFe | KK | MgMg | |
폐염산Waste hydrochloric acid | -- | 55 | 1515 | 2020 | 55 | 55 |
실시예 22Example 22 | 600600 | 1One | 77 | <0.1<0.1 | 22 | 22 |
실시예 23Example 23 | 300300 | 1One | 77 | <0.1<0.1 | 22 | 22 |
실시예 24Example 24 | 100100 | 1One | 77 | 0.70.7 | 22 | 22 |
상기 표 5로부터 알 수 있는 바와 같이, 추출을 위한 교반 과정에서 교반 속도를 낮춰가며 실험한 결과, 200rpm 보다 낮은 100 rpm 속도로 교반하는 경우 층간 혼합이 원활하지 않아, ICP 측정 결과 약 0.7 ppm의 Fe가 검출되는 것을 알 수 있다.As can be seen from Table 5, as a result of experiments while lowering the stirring speed in the stirring process for extraction, intermixing is not smooth when stirring at a speed of 100 rpm lower than 200rpm, ICP measurement results of about 0.7 ppm of Fe It can be seen that is detected.
실시예 25.Example 25.
폐염산 100 ml에 포함된 철(Fe) 이온 성분의 농도를 측정한 후, 유기용매인 톨루엔 100ml에 추출제인 트리옥틸아민 (폐염산에 포함된 Fe : 추출제 = 1 : 40몰)를 용해시켜 추출 용액을 제조하였다(S1).After measuring the concentration of iron (Fe) ions contained in 100 ml of waste hydrochloric acid, trioctylamine (Fe: extractant in waste hydrochloric acid = 1: 40 mol) was extracted in 100 ml of toluene, an organic solvent. An extraction solution was prepared (S1).
이어서, 폐염산 100 ml에 상기 추출 용액을 투입하고, 200 rpm의 속도로 60초 동안 상온에서 교반하면서 폐염산에 포함된 금속 성분들을 유기용매로 추출하였다(S2).Subsequently, the extraction solution was added to 100 ml of hydrochloric acid, and the metal components contained in the hydrochloric acid were extracted with an organic solvent while stirring at room temperature for 60 seconds at a speed of 200 rpm (S2).
교반이 평형에 도달한 후, 상기 유기용매와 폐염산의 혼합 용액을 세퍼레이터에 넣고 약 20초간 흔든 후 정치시켜 금속 성분을 함유한 유기용매와, 폐염산층으로 상분리(분획)시켰다(S3).After stirring reached equilibrium, the mixed solution of organic solvent and waste hydrochloric acid was placed in a separator, shaken for about 20 seconds, and allowed to stand for phase separation (fractionation) into an organic solvent containing a metal component and a waste hydrochloric acid layer (S3).
이어서, 분리된 폐염산층을 회수하여 정제된 염산(1)을 수득하였다(S4).Subsequently, the separated hydrochloric acid layer was recovered to obtain purified hydrochloric acid (1) (S4).
이어서, 분리된 유기용매에 증류수 100 ml를 첨가하고, 200 rpm의 속도로 1시간 동안 상온에서 교반하면서 유기용매 중 잔류 금속 성분을 탈거하였다(S5).Subsequently, 100 ml of distilled water was added to the separated organic solvent, and the remaining metal component was removed from the organic solvent while stirring at room temperature for 1 hour at a speed of 200 rpm (S5).
교반 완료 후, 상기 탈거된 유기용매(1)와 물층의 혼합 용액을 세퍼레이터에 넣고 약 20초간 상분리하여, 유기용매와 물층을 분획하였다(S6). 분리된 물층(1)을 회수하였다(S7).After completion of the stirring, the mixed solution of the organic solvent (1) and the water layer removed in the separator was phase-separated for about 20 seconds, to separate the organic solvent and the water layer (S6). The separated water layer 1 was recovered (S7).
상기 정제된 염산(1)과 물층(1) 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 6에 나타내었다.The residual metal concentration in the purified hydrochloric acid (1) and the water layer (1) was measured, and the results are shown in Table 6 below.
실시예 26.Example 26.
폐염산 100 ml에 상기 실시예 25의 폐염산층으로부터 상분리되어 회수된 유기용매(1)를 재투입하고, 200 rpm의 속도로 1시간 동안 상온에서 교반하면서 폐염산에 포함된 금속 성분들을 유기용매로 추출하였다(S2-2).The organic solvent (1) recovered by phase separation from the waste hydrochloric acid layer of Example 25 was re-injected into 100 ml of waste hydrochloric acid, and the organic solvent was mixed with the metal components contained in the waste hydrochloric acid while stirring at room temperature for 1 hour at a speed of 200 rpm. Extracted with (S2-2).
교반이 평형에 도달한 후, 상기 재투입된 유기용매(1)와 폐염산의 혼합 용액을 세퍼레이터에 넣고 약 20초간 흔든 후 정치시켜 금속 성분을 함유한 유기용매와 폐염산층으로 상분리(분획)시켰다(S3-2).After stirring reached equilibrium, the mixed solution of the re-injected organic solvent (1) and waste hydrochloric acid was placed in a separator, shaken for about 20 seconds, and allowed to stand for phase separation (fractionation) into an organic solvent containing a metal component and a waste hydrochloric acid layer. (S3-2).
이어서, 분리된 폐염산층을 회수하여 정제된 염산(2)을 수득하였다(S4-2).Subsequently, the separated hydrochloric acid layer was recovered to obtain purified hydrochloric acid (2) (S4-2).
이어서, 상분리된 유기용매에 증류수 100 ml를 첨가하고, 200 rpm의 속도로 1시간 동안 상온에서 교반하면서 유기용매 중 잔류 금속 성분을 재탈거하였다(S5-2).Subsequently, 100 ml of distilled water was added to the phase-separated organic solvent, and the remaining metal component in the organic solvent was removed again while stirring at room temperature for 1 hour at a speed of 200 rpm (S5-2).
교반 완료 후, 상기 탈거된 유기용매(2)와 물층의 혼합 용액을 세퍼레이터에 넣고 약 20초간 상분리하여, 유기용매와 물층을 상분리하였다(S6-2). 상분리된 물층(2)을 회수하였다(S7-2).After completion of the stirring, the mixed solution of the organic solvent (2) and the water layer removed in the separator was phase-separated for about 20 seconds, the organic solvent and the water layer was phase-separated (S6-2). The phase separated water layer 2 was recovered (S7-2).
상기 정제된 염산(2)과 물층(2) 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 6에 나타내었다.The residual metal concentration in the purified hydrochloric acid (2) and the water layer (2) was measured, and the results are shown in Table 6 below.
실시예 27.Example 27.
폐염산 100 ml에 상기 실시예 26의 폐염산층으로부터 상분리되어 회수된 유기용매(2)를 재투입하고, 200 rpm의 속도로 1시간 동안 상온에서 교반하면서 폐염산에 포함된 금속 성분들을 유기용매로 추출하였다(S2-3).The organic solvent (2) recovered by phase separation from the waste hydrochloric acid layer of Example 26 was recycled to 100 ml of waste hydrochloric acid, and the metal components contained in the waste hydrochloric acid were stirred at room temperature for 1 hour at 200 rpm. Extracted with (S2-3).
교반이 평형에 도달한 후, 상기 재투입된 유기용매와 폐염산의 혼합 용액을 세퍼레이터에 넣고 약 20초간 흔든 후 정치시켜 금속 성분을 함유한 유기용매와 폐염산층으로 상분리(분획)시켰다(S3-3)After stirring reached equilibrium, the mixed solution of the re-injected organic solvent and waste hydrochloric acid was placed in a separator, shaken for about 20 seconds, and allowed to stand for phase separation (fractionation) into an organic solvent containing a metal component and a waste hydrochloric acid layer (S3-). 3)
이어서, 분리된 폐염산층을 회수하여 정제된 염산(3)을 수득하였다(S4-3).Subsequently, the separated hydrochloric acid layer was recovered to obtain purified hydrochloric acid (3) (S4-3).
이어서, 상분리된 유기용매에 증류수 100 ml를 첨가하고, 200 rpm의 속도로 1시간 동안 상온에서 교반하면서 유기용매 중 잔류 금속 성분을 탈거하였다(S5-3).Subsequently, 100 ml of distilled water was added to the phase-separated organic solvent, and the remaining metal component was removed from the organic solvent while stirring at room temperature for 1 hour at a speed of 200 rpm (S5-3).
교반 완료 후, 상기 탈거된 유기용매(3)와 물층의 혼합 용액을 세퍼레이터에 넣고 약 20초간 상분리하여, 유기용매와 물층을 분획하였다(S6-3). 분리된 물층(3)을 회수하였다(S7-3).After completion of the stirring, the mixed solution of the organic solvent (3) and the water layer removed in the separator was phase-separated for about 20 seconds, to separate the organic solvent and the water layer (S6-3). The separated water layer 3 was recovered (S7-3).
상기 정제된 염산(3)과 물층(3) 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 6에 나타내었다.The residual metal concentration in the purified hydrochloric acid (3) and the water layer (3) was measured, and the results are shown in Table 6 below.
실시예 28.Example 28.
폐염산 100 ml에 상기 실시예 27의 폐염산층으로부터 상분리되어 회수된 유기용매(3)를 재투입하고, 200 rpm의 속도로 1시간 동안 상온에서 교반하면서 폐염산에 포함된 금속 성분들을 유기용매로 추출하였다(S2-4).The organic solvent (3) recovered by phase separation from the waste hydrochloric acid layer of Example 27 was re-injected into 100 ml of waste hydrochloric acid, and the metal components contained in the waste hydrochloric acid were stirred at room temperature for 1 hour at 200 rpm. Extracted with (S2-4).
교반이 평형에 도달한 후, 상기 재투입된 유기용매와 폐염산의 혼합 용액을 세퍼레이터에 넣고 약 20초간 흔든 후 정치시켜 금속 성분을 함유한 유기용매와 폐염산인층으로 상분리(분획)시켰다(S3-4).After stirring reached equilibrium, the mixed solution of the re-injected organic solvent and waste hydrochloric acid was placed in a separator, shaken for about 20 seconds, and allowed to stand for phase separation (fractionation) into an organic solvent containing a metal component and a phosphorus hydrochloric acid (S3-). 4).
이어서, 분리된 폐염산층을 회수하여 정제된 염산(4)을 수득하였다(S4-4).Subsequently, the separated hydrochloric acid layer was recovered to obtain purified hydrochloric acid (4) (S4-4).
이어서, 상분리된 유기용매에 증류수 100 ml를 첨가하고, 200 rpm의 속도로 1시간 동안 상온에서 교반하면서 유기용매 중 잔류 금속 성분을 탈거하였다(S5-4).Subsequently, 100 ml of distilled water was added to the phase-separated organic solvent, and the residual metal component of the organic solvent was removed while stirring at room temperature for 1 hour at a speed of 200 rpm (S5-4).
교반 완료 후, 상기 탈거된 유기용매(4)와 물층의 혼합 용액을 세퍼레이터에 넣고 약 20초간 상분리하여, 유기용매와 물층을 분획하였다(S6-4). 분리된 물층(4)을 회수하였다(S7-4).After completion of the stirring, the mixed solution of the stripped organic solvent 4 and the water layer was put in a separator and phase separated for about 20 seconds to separate the organic solvent and the water layer (S6-4). The separated water layer 4 was recovered (S7-4).
상기 정제된 염산(4)과 물층(4) 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 6에 나타내었다.The residual metal concentration in the purified hydrochloric acid (4) and the water layer (4) was measured, and the results are shown in Table 6 below.
추출 횟수Extraction count | AlAl | CaCa | FeFe | KK | MgMg | |
폐염산Waste hydrochloric acid | -- | 55 | 1515 | 2020 | 55 | 55 |
실시예 25Example 25 | 정제된 염산 (1)Purified hydrochloric acid (1) | 44 | 1616 | <0.1<0.1 | 44 | 55 |
물층 (1)Water Layers (1) | 0.60.6 | 0.20.2 | 2020 | 0.30.3 | <0.1<0.1 | |
실시예 26Example 26 | 정제된 염산 (2)Purified hydrochloric acid (2) | 44 | 1616 | <0.1<0.1 | 44 | 55 |
물층 (2)Water Layers (2) | 0.50.5 | 0.20.2 | 2121 | 0.20.2 | <0.1<0.1 | |
실시예 27Example 27 | 정제된 염산 (3)Purified hydrochloric acid (3) | 44 | 1616 | <0.1<0.1 | 44 | 55 |
물층 (3)Water Layers (3) | 0.50.5 | 0.20.2 | 2121 | 0.20.2 | <0.1<0.1 | |
실시예 28Example 28 | 정제된 염산 (4)Purified hydrochloric acid (4) | 44 | 1616 | <0.1<0.1 | 44 | 55 |
물층 (4)Water Layers (4) | 0.50.5 | 0.20.2 | 2121 | 0.20.2 | <0.1<0.1 |
상기 표 6에 나타낸 바와 같이, 탈거된 유기용매를 이용하여 폐염산 정제 과정을 수 회 반복한 결과, 폐염산 내 철(Fe) 이온 성분은 0.1 ppm 이하로 일정하게 제거되는 것을 알 수 있다.As shown in Table 6, as a result of repeating the waste hydrochloric acid purification process several times using the removed organic solvent, it can be seen that the iron (Fe) ion component in the waste hydrochloric acid is constantly removed to 0.1 ppm or less.
즉, 유기용매를 정제하여 실시예 26 내지 28와 같이 여러 차례 폐염산 정제 단계 (금속 성분 추출 단계)에 이용하여도, 실시예 25의 폐염산 정제 효과와 크게 차이가 없는 것을 알 수 있다. 따라서, 본 발명의 폐염산 정제 방법의 경우 유기용매를 효과적으로 재생하여 사용할 수 있음을 확인할 수 있다.That is, even when the organic solvent was purified and used in the hydrochloric acid purification step (metal component extraction step) as many times as in Examples 26 to 28, it can be seen that there is no significant difference from the waste hydrochloric acid purification effect of Example 25. Therefore, in the case of the waste hydrochloric acid purification method of the present invention it can be confirmed that the organic solvent can be effectively recycled.
실시예 29.Example 29.
폐염산 100 ml에 포함된 철(Fe) 이온 성분의 농도를 측정한 후, 유기용매인 톨루엔 100ml에 추출제인 트리알킬포스핀 옥사이드 (폐염산에 포함된 Fe : 추출제 = 1 : 40몰)를 용해시켜 추출 용액을 제조하였다(S'1).After measuring the concentration of iron (Fe) ions contained in 100 ml of waste hydrochloric acid, trialkylphosphine oxide (Fe: extractant in waste hydrochloric acid = 1: 40 mol) was extracted in 100 ml of toluene, an organic solvent. It was dissolved to prepare an extraction solution (S'1).
이어서, 폐염산 100 ml에 상기 추출 용액을 투입하고, 200 rpm의 속도로 60초 동안 상온에서 교반하면서 폐염산에 포함된 금속 성분들을 유기용매로 추출하였다(S'2).Subsequently, the extraction solution was added to 100 ml of waste hydrochloric acid, and metal components contained in the waste hydrochloric acid were extracted with an organic solvent while stirring at room temperature for 60 seconds at a speed of 200 rpm (S'2).
교반이 평형에 도달한 후, 상기 유기용매와 폐염산의 혼합 용액을 세퍼레이터에 넣고 약 20초간 흔든 후 정치시켜 금속 성분을 함유한 유기용매와, 폐염산층으로 상분리(분획)시켰다(S'3).After stirring reached equilibrium, the mixed solution of organic solvent and waste hydrochloric acid was placed in a separator, shaken for about 20 seconds, and allowed to stand for phase separation (fractionation) into an organic solvent containing a metal component and a waste hydrochloric acid layer (S'3). ).
이어서, 분리된 폐염산층을 회수하여 정제된 염산(1)을 수득하였다(S'4).Subsequently, the separated hydrochloric acid layer was recovered to obtain purified hydrochloric acid (1) (S'4).
이어서, 분리된 유기용매에 증류수 100 ml를 첨가하고, 200 rpm의 속도로 1시간 동안 상온에서 교반하면서 유기용매 중 잔류 금속 성분을 탈거하였다(S'5).Subsequently, 100 ml of distilled water was added to the separated organic solvent, and the remaining metal component was removed from the organic solvent while stirring at room temperature for 1 hour at a speed of 200 rpm (S'5).
교반 완료 후, 상기 유기용매와 물층의 혼합 용액을 세퍼레이터에 넣고 약 20초간 상분리하여, 유기용매와 물층을 분획하였다(S'6). 분리된 물층(1)을 회수하였다(S'7).After the stirring was completed, the mixed solution of the organic solvent and the water layer was put in a separator and phase separated for about 20 seconds, and the organic solvent and the water layer were fractionated (S'6). The separated water layer 1 was recovered (S'7).
상기 정제된 유기용매와 물층(1) 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 7에 나타내었다.The residual metal concentration in the purified organic solvent and the water layer 1 was measured, and the results are shown in Table 7 below.
실시예 30.Example 30.
폐염산 100 ml에 포함된 철(Fe) 이온 성분의 농도를 측정한 후, 유기용매인 시클로헥산 100ml에 추출제인 트리알킬포스핀 옥사이드 (폐염산에 포함된 Fe : 추출제 = 1 : 40몰)를 용해시켜 추출 용액을 제조하였다(S'1).After measuring the concentration of iron (Fe) ions contained in 100 ml of waste hydrochloric acid, trialkylphosphine oxide as an extractant in 100 ml of organic solvent cyclohexane (Fe: extractant in waste hydrochloric acid = 1: 40 mol) Was dissolved to prepare an extraction solution (S'1).
이어서, 폐염산 100 ml에 상기 추출 용액을 투입하고, 200 rpm의 속도로 60초 동안 상온에서 교반하면서 폐염산에 포함된 금속 성분들을 유기용매로 추출하였다(S'2).Subsequently, the extraction solution was added to 100 ml of waste hydrochloric acid, and metal components contained in the waste hydrochloric acid were extracted with an organic solvent while stirring at room temperature for 60 seconds at a speed of 200 rpm (S'2).
교반이 평형에 도달한 후, 상기 유기용매와 폐염산의 혼합 용액을 세퍼레이터에 넣고 약 20초간 흔든 후 정치시켜 금속 성분을 함유한 유기용매와, 폐염산층으로 상분리(분획)시켰다(S'3).After stirring reached equilibrium, the mixed solution of organic solvent and waste hydrochloric acid was placed in a separator, shaken for about 20 seconds, and allowed to stand for phase separation (fractionation) into an organic solvent containing a metal component and a waste hydrochloric acid layer (S'3). ).
이어서, 분리된 폐염산층을 회수하여 정제된 염산(1)을 수득하였다(S'4).Subsequently, the separated hydrochloric acid layer was recovered to obtain purified hydrochloric acid (1) (S'4).
이어서, 분리된 유기용매에 증류수 100 ml를 첨가하고, 200 rpm의 속도로 1시간 동안 상온에서 교반하면서 유기용매 중 잔류 금속 성분을 탈거하였다(S'5).Subsequently, 100 ml of distilled water was added to the separated organic solvent, and the remaining metal component was removed from the organic solvent while stirring at room temperature for 1 hour at a speed of 200 rpm (S'5).
교반 완료 후, 상기 유기용매와 물층의 혼합 용액을 세퍼레이터에 넣고 약 20초간 상분리하여, 유기용매와 물층을 분획하였다(S'6). 분리된 물층(1)을 회수하였다(S'7).After the stirring was completed, the mixed solution of the organic solvent and the water layer was put in a separator and phase separated for about 20 seconds, and the organic solvent and the water layer were fractionated (S'6). The separated water layer 1 was recovered (S'7).
상기 정제된 유기용매와 물층(1) 내의 잔여 금속 농도를 측정하고, 그 결과를 하기 표 7에 나타내었다.The residual metal concentration in the purified organic solvent and the water layer 1 was measured, and the results are shown in Table 7 below.
추출 횟수Extraction count | AlAl | CaCa | FeFe | KK | MgMg | |
폐염산Waste hydrochloric acid | -- | 55 | 1515 | 2020 | 55 | 55 |
실시예 29Example 29 | 유기용매층Organic solvent layer | 1One | <0.1<0.1 | 99 | 1One | 1One |
물층 (1)Water Layers (1) | 0.40.4 | 0.20.2 | 1111 | 0.30.3 | <0.1<0.1 | |
실시예 30Example 30 | 유기용매층Organic solvent layer | <0.1<0.1 | <0.1<0.1 | 1212 | <0.1<0.1 | <0.1<0.1 |
물층 (1)Water Layers (1) | 0.40.4 | 0.10.1 | 88 | 0.20.2 | <0.1<0.1 |
상기 표 7에 나타낸 바와 같이, 추출제로 트리알킬포스핀 옥사이드를 이용하여 폐염산 정제 및 유기용매에 대한 탈거 과정을 실시한 결과, 상기 표 1에 나타낸 바와 같이 폐염산 내 금속 성분, 특히 철(Fe) 이온 성분은 1 ppm 이하로 제거된 반면에, 유기용매층 내에서 탈거가 효과적으로 이루어지지 않기 때문에, 유기용매를 재사용하는 것이 제약이 있음을 알 수 있다. As shown in Table 7, as a result of performing the hydrochloric acid purification and the organic solvent stripping process using trialkylphosphine oxide as an extractant, as shown in Table 1, the metal components in the waste hydrochloric acid, in particular iron (Fe) While the ionic component is removed to 1 ppm or less, it can be seen that there is a limitation in reusing the organic solvent because stripping is not effectively performed in the organic solvent layer.
Claims (15)
- 추출제를 유기용매에 용해시켜 추출 용액을 제조하는 단계(S1);Dissolving the extractant in an organic solvent to prepare an extraction solution (S1);폐염산에 상기 추출 용액을 투입하여 폐염산 내의 금속 성분을 유기용매로 추출하는 단계(S2);Injecting the extraction solution into the waste hydrochloric acid to extract the metal component in the waste hydrochloric acid with an organic solvent (S2);금속 성분을 함유한 유기용매와 폐염산층을 상분리하는 단계(S3); 및Phase-separating the organic solvent containing the metal component and the waste hydrochloric acid layer (S3); And상분리(분획)된 폐염산층을 회수하여 정제된 염산을 수득하는 단계(S4);를 포함하며,Recovering the phase separation (fractionated) hydrochloric acid layer to obtain purified hydrochloric acid (S4); and상기 추출제의 사용량은 폐염산에 함유된 금속 성분 중 철(Fe) 이온 성분 1 몰을 기준으로 40 몰 이상이고,The amount of the extractant is 40 mol or more based on 1 mol of iron (Fe) ions among the metal components contained in the waste hydrochloric acid,상기 폐염산 : 추출 용액은 1:0.1 내지 1:1 부피비로 혼합하는 것인 폐염산 정제 방법.The waste hydrochloric acid: extraction solution is a waste hydrochloric acid purification method that is mixed in a 1: 0.1 to 1: 1 volume ratio.
- 청구항 1에 있어서,The method according to claim 1,상기 폐염산 정제 방법은 추출 용액을 제조하기 전에 폐염산에 포함된 금속 성분 중 철(Fe) 이온 성분의 농도를 측정하는 단계(S0)를 더 포함하는 것인 폐염산 정제 방법.The waste hydrochloric acid purification method further comprises the step (S0) of measuring the concentration of the iron (Fe) ion component in the metal component contained in the waste hydrochloric acid before preparing the extraction solution.
- 청구항 1에 있어서,The method according to claim 1,상기 유기용매는 방향족 탄화수소 용매, 지방족 탄화수소 용매 및 알코올로 이루어진 군으로부터 선택된 적어도 하나 이상의 용매를 포함하는 것인 폐염산 정제 방법.The organic solvent is a hydrochloric acid purification method comprising at least one solvent selected from the group consisting of an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent and an alcohol.
- 청구항 3에 있어서,The method according to claim 3,상기 방향족 탄화수소 용매는 톨루엔, 및 크실렌으로 이루어진 군으로부터 선택된 적어도 하나 이상을 포함하고, The aromatic hydrocarbon solvent comprises at least one selected from the group consisting of toluene, and xylene,상기 지방족 탄화수소 용매는 메틸 시클로헥산 및 시클로헥산으로 이루어진 군으로부터 선택된 적어도 하나 이상의 지환족 탄화수소 용매, 또는 탄소수 6 내지 20의 선형 탄화수소 용매를 포함하며,The aliphatic hydrocarbon solvent includes at least one alicyclic hydrocarbon solvent selected from the group consisting of methyl cyclohexane and cyclohexane, or a linear hydrocarbon solvent having 6 to 20 carbon atoms,상기 알코올은 탄소수 6 내지 20의 1가 알코올을 포함하는 것인 폐염산 정제 방법.The alcohol is a hydrochloric acid purification method comprising a monohydric alcohol having 6 to 20 carbon atoms.
- 청구항 1에 있어서,The method according to claim 1,상기 추출제는 트리옥틸아민, 메틸 이소부틸케톤, 트리알킬포스핀 옥사이드 및 트리부틸 포스페이트로 이루어진 군으로부터 선택된 적어도 하나 이상인 것인 폐염산 정제 방법.Wherein said extracting agent is at least one selected from the group consisting of trioctylamine, methyl isobutyl ketone, trialkylphosphine oxide and tributyl phosphate.
- 청구항 5에 있어서,The method according to claim 5,상기 추출제는 트리옥틸아민 및 메틸 이소부틸케톤으로 이루어진 군으로부터 선택된 적어도 하나 이상인 것인 폐염산 정제 방법.The extracting agent is at least one selected from the group consisting of trioctylamine and methyl isobutyl ketone waste hydrochloric acid purification method.
- 청구항 6에 있어서,The method according to claim 6,상기 추출제는 트리옥틸아민인 것인 폐염산 정제 방법.The extracting agent is trioctylamine waste hydrochloric acid purification method.
- 청구항 1에 있어서,The method according to claim 1,상기 추출제의 사용량은 철(Fe) 이온 성분 1 몰을 기준으로 40 몰 내지 60 몰인 것인 폐염산 정제 방법.The amount of the extractant is 40 to 60 moles based on 1 mole of iron (Fe) ionic component will waste hydrochloric acid purification method.
- 청구항 8에 있어서,The method according to claim 8,상기 추출제의 사용량은 철(Fe) 이온 성분 1 몰을 기준으로 40 몰 내지 50 몰인 것인 폐염산 정제 방법.The amount of the extractant is 40 to 50 moles based on 1 mole of iron (Fe) ionic component will waste hydrochloric acid purification method.
- 청구항 1에 있어서,The method according to claim 1,상기 추출 단계(S2)는 폐염산과 추출 용액의 혼합 용액을 200 rpm 내지 600 rpm의 속도로 교반하면서 상온에서 20초 내지 60초 동안 실시하는 것인 폐염산 정제 방법.The extraction step (S2) is a waste hydrochloric acid purification method that is carried out at room temperature for 20 seconds to 60 seconds while stirring the mixed solution of waste hydrochloric acid and the extraction solution at a speed of 200 rpm to 600 rpm.
- 청구항 1에 있어서,The method according to claim 1,상기 상분리 단계(S3)는 20초 이내로 실시하는 것인 폐염산 정제 방법.The phase separation step (S3) is a hydrochloric acid purification method that is carried out within 20 seconds.
- 청구항 1에 있어서,The method according to claim 1,상기 방법은 정제된 염산 수득단계(S4) 후에, The method after the purified hydrochloric acid step (S4),상기 분리된 금속 성분을 함유한 유기용매에 증류수를 첨가하여 유기용매 중의 잔류 금속 성분을 탈거하는 단계(S5);Removing distilled water from the organic solvent containing the separated metal component to remove residual metal components from the organic solvent (S5);탈거된 유기용매와 물층을 상분리하는 단계(S6); 및Phase separating the stripped organic solvent and the water layer (S6); And상분리된 유기용매 및 물층을 각각 회수하는 단계(S7);를 추가로 포함하는 것인 폐염산 정제 방법.Recovering the phase separated organic solvent and the water layer, respectively (S7); Waste hydrochloric acid purification method further comprising.
- 청구항 12에 있어서,The method according to claim 12,상기 유기용매:증류수는 1:1의 부피비로 혼합하는 것인 폐염산 정제 방법.The organic solvent: distilled water is a waste hydrochloric acid purification method of mixing in a volume ratio of 1: 1.
- 청구항 12에 있어서,The method according to claim 12,상기 탈거 단계(S5)는 분리된 유기용매와 증류수의 혼합 용액을 200 rpm 내지 600 rpm의 속도로 교반하면서 상온에서 20초 내지 60초 동안 실시하는 것인 폐염산 정제 방법.The stripping step (S5) is a waste hydrochloric acid purification method that is carried out at room temperature for 20 seconds to 60 seconds while stirring the mixed solution of the separated organic solvent and distilled water at a speed of 200 rpm to 600 rpm.
- 청구항 12에 있어서,The method according to claim 12,상기 상분리 단계(S6)는 20초 이내로 실시하는 것인 폐염산 정제 방법.The phase separation step (S6) is a hydrochloric acid purification method that is carried out within 20 seconds.
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CN201780004237.9A CN108290083B (en) | 2016-11-09 | 2017-10-25 | Method for purifying waste hydrochloric acid |
US15/774,915 US11472702B2 (en) | 2016-11-09 | 2017-10-25 | Method of purifying waste hydrochloric acid |
EP17863300.4A EP3539636A4 (en) | 2016-11-09 | 2017-10-25 | Method for purifying waste hydrochloric acid |
JP2018538688A JP6660476B2 (en) | 2016-11-09 | 2017-10-25 | Purification method of waste hydrochloric acid |
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