TW201309387A - Method for producing cobalt-manganese-acetic acid (CMA) catalyst from waste cobalt-manganese-bromine (CMB) catalyst - Google Patents

Abstract

The present invention relates to a method for producing cobalt-manganese-acetic acid (CMA) liquid catalyst from waste cobalt-manganese-bromine (CMB) catalyst, which comprises (a) a step of adding sulfuric acid in sample of waste CMB catalyst for soaking and dissolving, (b) a step of filtering the soaking and dissolving solution of step (a) to obtain a first-stage soaking and dissolving solution, (c) a step of adding a fresh sample of waste CMB catalyst in the first-stage soaking and dissolving solution for soaking and dissolving, (d) a step of filtering the soaking and dissolving solution of step (c) to obtain a second-stage soaking and dissolving solution, (e)a step of adding a solvent in the second-stage soaking and dissolving solution of step (d) for extraction, and (f) a step of adding CH3COOH solution to the extraction liquid obtained in step (e) and applying back extraction to obtain a Co-Mn-CH3COOH removed solution. According to the present invention, a method of recovering cobalt and manganese from waste CMB catalyst, improving the removal rate of impurity and the recovery rate for recovery of high purity cobalt and manganese, and producing CMA liquid catalyst by using cobalt and manganese so recovered as raw materials is provided.

Description

Method for producing cobalt acetate manganese liquid catalyst from waste cobalt manganese bromine catalyst

The invention relates to a method for producing a cobalt-containing manganese (CMA:Co-Mn-CH ₃ COOH) liquid catalyst from a waste cobalt manganese bromine (CMB) catalyst, and more specifically relates to a waste CMB catalyst in sequence. The process for producing a Co-Mn-CH ₃ COOH liquid catalyst is removed by a reverse leaching solution of sulfuric acid, a solid-liquid separation, a solvent extraction, and a water washing process by back-extracting a solution of cobalt and manganese recovered using an acetic acid solution.

Cobalt-manganese bromine (CMB) and cobalt-manganese acetate (CMA) liquid catalysts are used in the production of terephthalic acid (TPA) by oxidation of a para-Xylene in petrochemicals. Catalyst use. In addition, terephthalic acid (TPA) is a raw material for polyester fiber, PET (polyethylene terephthalate), film, paint, tire cord, which is closely related to people's life. The main producer of formic acid, the domestic production of terephthalic acid in 2006 was 5.5 million tons, accounting for about 21% of the world's total output (26 million tons), so these catalyst markets are also very large. Therefore, a CMA catalyst can be economically produced by producing a CMA catalyst by recovering cobalt and manganese from a waste CMB catalyst.

In order to develop a method for efficiently recovering cobalt and manganese from waste CMB catalyst, the inventors of the present invention confirmed that sequential multi-stage continuous soak dissolution, solid-liquid separation, solvent extraction, and water were sequentially applied to the above samples. In the case of the cleaning process, high-purity cobalt and manganese from which impurities are removed are recovered, and the CMA liquid catalyst can be produced by using the cobalt and manganese, and the present invention has been completed.

[The subject to be solved by the invention]

The present invention has been made in order to solve the above problems, and an object thereof is to provide a method for producing a Co-Mn-CH ₃ COOH (CMA) liquid catalyst by using an extract obtained by selectively recovering cobalt and manganese from a waste CMB catalyst. .

[Means to solve the problem]

In order to achieve the above object, the present invention provides a method for producing a cobalt-manganese-cobalt (CMA) liquid catalyst from a waste cobalt manganese bromine (CMB) catalyst, comprising: (a) adding sulfuric acid to a waste CMB catalyst sample a step of soaking and eluting, (b) filtering the soaking solution of the above step (a) to obtain a step of soaking the leachate in the first stage, and (c) adding a new sample of the waste CMB catalyst to the soaking solution of the first stage, soaking and dissolving a step of (d) filtering the soaked eluate of the above step (c) to obtain a second stage soaking solution, and (e) a step of soaking the eluate to the solvent for extraction in the second stage of the above step (d), and (f) a step of adding a CH ₃ COOH solution to the extract obtained in the above step (e), and performing a Co-Mn-CH ₃ COOH removal solution by back extraction.

In addition, the method for producing a cobalt-cobalt-manganese liquid-like catalyst from a waste cobalt-manganese bromine catalyst as described above, further comprising: adding a cobalt salt and a manganese salt to the removal solution of the above step (f) to match an appropriate concentration Step (g).

Further, as described above, the method for producing a cobalt cobalt oxide liquid catalyst from a waste cobalt manganese bromine catalyst, wherein the pH of the step (a) is in the range of 0 to 1.5.

Further, as in the above method for producing a cobalt acetate manganese liquid catalyst from a waste cobalt manganese bromine catalyst, the pH of the step (c) is in the range of 4.5 to 6.5.

In addition, the above method for producing a cobalt cobalt manganese liquid catalyst from a waste cobalt manganese bromine catalyst, comprising: removing free Fe, Pb, Cu by continuous soaking dissolution in the above steps (a) to (d) And impurities of the group consisting of these mixtures.

Further, as described above, the method for producing a cobalt-manganese-cobalt liquid catalyst from a spent cobalt-manganese bromine catalyst, wherein the solvent used in the solvent extraction in the above step (e) is selected from the group consisting of free di(2-ethylhexyl)phosphoric acid ( di - 2 - ethyl hexyl phosphoric acid ) based solvent, (2-ethylhexyl) phosphonic acid (2 - ethyl hexyl phosphonic acid) based solvent, mono (2-ethylhexyl) phosphate (mono-2-ethyl hexyl ester ) Solvent, di(2,4,4-trimethylpentyl)phosphinic acid (di-2,4,4-trimethyl pentyl phosphinic acid) solvent, di(2-ethylhexyl)phosphinic acid ( di - 2 - ethyl hexyl phosphonic acid ) solvent, di-2,4,4-trimethyl pentyl dithiophosphinic acid, di(2,4-trimethyl pentyl dithiophosphinic acid) A solvent of 2,4,4-trimethylpentyl) pentylmonodithiophosphinic acid and a mixture of these mixtures.

Further, as described above, a method for producing a cobalt cobalt oxide liquid catalyst from a waste cobalt manganese bromine catalyst, wherein the solvent is alkalized by an alkaline solution.

Further, as described above, the method for producing a cobalt cobalt oxide liquid catalyst from a waste cobalt manganese bromine catalyst, wherein the alkaline solution is NaOH or NH ₄ OH.

Further, the above method for producing a cobalt cobalt oxide liquid catalyst from a waste cobalt manganese bromine catalyst, wherein the solvent is a 30 to 50% alkalized solvent.

Further, as described above, the method for producing a cobalt cobalt oxide liquid catalyst from a waste cobalt manganese bromine catalyst, wherein the concentration of the solvent is in the range of 0.8 to 1.5 M.

Further, the above method for producing a cobalt cobalt oxide liquid catalyst from a waste cobalt manganese bromine catalyst, wherein the extract obtained in the above step (f) is obtained through the above step (e).

[effect of the invention]

According to the present invention, cobalt and manganese can be recovered from waste cobalt manganese bromide (CMB) catalyst, and high purity cobalt and manganese can be recovered by increasing impurity removal rate and recovery rate, and cobalt and manganese are used as raw materials to produce cobalt acetate. Manganese (CMA) liquid catalyst method.

[Formation for carrying out the invention]
The invention relates to a method for producing a cobalt-manganese acetate (CMA) liquid catalyst from a waste cobalt manganese bromide (CMB) catalyst, comprising: (a) adding a sulfuric acid to a waste CMB catalyst sample to soak and dissolve the solution, (b) Filtering the soaking solution of the above step (a) to obtain the first stage soaking solution, (c) adding a new waste CMB catalyst sample to the first stage soaking solution, soaking and dissolving, and (d) filtering The step of soaking the eluate of the above step (c) to obtain the second stage soaking of the eluate, (e) the step of soaking the eluate in the second stage of the above step (d), adding a solvent for extraction, and (f) the above (e) The extract obtained in the step is added with a CH ₃ COOH solution, and subjected to back extraction to obtain a Co-Mn-CH ₃ COOH removal solution.
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
In the waste CMB catalyst (SO), a large amount of impurities are contained in addition to the valuable metals such as cobalt and lithium. Therefore, the present invention suppresses impurities such as Fe, Pb, Cu, Zn, etc. in a small amount (S10 to S40) via a continuous multi-stage soaking dissolution process using sulfuric acid.
In the present invention, the above step (a) is a process in which a sulfuric acid solution is used as a soaking solution to dissolve and elute a valuable metal in a spent CMB catalyst. At this time, the pH value at the time of immersion elution is in the range of 0 to 1.5 (S10).
In the present invention, the step (b) is a step of filtering the solution of the step (a) to obtain the first-stage soaking solution, and preparing the next step (S20).
In the present invention, the step (c) is a step of soaking and eluting using the first-stage soaking solution obtained in the above step (a). In this step, instead of using the waste CMB catalyst of the above step (a), the new waste CMB catalyst is used as a sample to dissolve the metal, but since the pH of the first stage soaking solution is in the range of 0 to 1.5, Therefore, it can fully serve as a function of immersing the eluting agent, and the pH of the soaking eluate of the second stage obtained by such soaking and elution is in the range of 4.5 to 6.5 (S30).
In the present invention, the above step (d) is also a step of filtering the solution of the above step (c) to obtain the second-stage soaking solution, in the same manner as the above step (b), in order to prepare the next step. (S40).
In the present invention, the above steps (b) and (d) may be filtered using a filter press or filter paper to separate into a solution and a residue, and the above filtration means can be easily selected by the manufacturer.
The solvent extraction described below has the advantage that the selective organic phase extracts each metal ion to the organic phase. In particular, such selectivity depends on the equilibrium pH, that is, the tendency to extract each metal ion by balancing the pH range. For example, in the case of using Cyanex 272 of the present process as a solvent extraction, the equilibrium pH for extracting cobalt and manganese ranges from pH 4.5 to 6.5. In the case of producing a supply solution for solvent extraction, a sample was dissolved with metal ions using a 1 M H ₂ SO ₄ solution. At this time, the pH of the soaking solution is approximately PH0 to PH1.5. As mentioned above, the equilibrium pH for extracting cobalt and manganese is pH 4.5 to 6.5, but for the initial pH 0 to pH 1.5, the equilibrium pH is raised to 4.5 to 6.5 and the extraction of cobalt and manganese by Cyanex 272 is equivalent. unfavorable. However, with multi-stage soaking, the pH can be adjusted to pH 4.5 to 6.5. Further, Cr, Fe, Pb, and the like which are discriminated as impurities by multi-stage soaking and elution also have an effect of automatically precipitating and removing impurities while increasing the pH.
The multi-stage soaking dissolution system dissolves the metal in the sample with metal ions in the first stage reaction tank with an acid. The soaked eluate is filtered using a filter press or a filtration device. At this time, the acid in the sample was not dissolved, and the residual residue was approximately 2%, and the residue was at most 5%. It can be judged that the metal ions in the sample are approximately 100% soaked and dissolved. Since the soaked solution has a pH of 0 to 1.5, it has a H ⁺ ion which can sufficiently dissolve the sample with metal ions. Therefore, in the second-stage reaction tank, the soaked eluate obtained in the first-stage reaction tank is used as a soaking eluent to put in a new sample to be soaked and dissolved, but the sample is immersed in the second-stage reaction tank, and the pH is raised to PH 4.5 to 6.5. Through this process, Fe, Cr, Pb, etc., which are discriminated as impurities, are precipitated, and the desired components, that is, Co and Mn, are only immersed and dissolved by a common ion effect. The resulting soaked eluate obtained by two-stage multi-stage soaking dissolution produces 80 to 90% of the residue after filtration. The 80 to 90% residue is re-introduced into the first-stage reaction tank to reduce the generation of waste water, thereby minimizing the disappearance of the raw material, and obtaining a soaking solution capable of selectively extracting PH and 5 to 6 and 6 of Co and manganese.
In the present invention, the solvent used in the above step (e) (S50) is characterized in that a free di(2-ethylhexyl)phosphoric acid (di-2-ethylhexylphosphoric acid) solvent and (2-ethylhexyl) are selected. 2-ethyl hexylphosphonic acid solvent, mono-2-ethyl hexyl ester solvent, bis(2,4,4-trimethylpentyl)phosphinic acid (di-2,4,4-trimethyl pentyl phosphinic acid) solvent, di-2-ethyl hexylphosphinic acid solvent, di(2,4,4-trimethyl) Di-, 4,4-trimethyl pentyl dithiophosphinic acid, and bis(2,4,4-trimethylpentyl)monothiophosphinic acid solvent A group consisting of a solvent of (di-2,4,4-trimethyl pentylmonodithiophosphinic acid) is preferably a solvent of di-2-ethyl hexylphosphoric acid.
The above solvent is preferably alkalized by an alkaline solution, in which case 30 to 60% of an alkalized solvent can be used, preferably by using 40 to 50% of an alkalized solvent to increase the recovery of cobalt and manganese. Minimize the generation of impurities.
Further, when the solvent used for the solvent extraction described above is alkalized, the solvent can be prevented from being changed to improve the efficiency of solvent extraction.
For example, in solvent extraction, di-2,4,4-trimethyl pentyl phosphinic acid (Cyanex 272, Cytec Inc., USA) is used as a solvent. The extraction reaction of cobalt and manganese used is:
X ²⁺ + 2HR↔XR ₂ + 2H ⁺ (1)
As the reaction formula (1) is carried out, the pH of the solution after the solid-liquid separation in the step (b) is decreased, and the solvent is extracted by using an alkaline solution such as NaOH or NH ₄ OH to suppress the decrease in the pH. After the solvent is alkalized (reaction formula (2)), it is used for solvent extraction (reaction formula (3)).
HR + NaOH (or NH ₄ OH) ↔ NaR (or NH ₄ R) + H ₂ O (2)
X ²⁺ + 2NaR (or 2NH ₄ R)↔XR ₂ + 2Na ⁺ (or 2NH ₄ ⁺ ) (3)
The reaction formula (2) is a reaction formula showing the alkalization process of the solvent, and the H ⁺ ion of the solvent is replaced with Na ⁺ or NH ₄ ⁺ ions, so that when the cobalt or manganese ion is extracted by the solvent in the reaction formula (3), The Na ⁺ or NH ₄ ⁺ ions displaced by the reaction formula (2) are discharged as a solution, so that the pH of the solution can be prevented from changing.
After the completion of the step (e) of the present invention, a water washing step (not shown) may be added, which is a ratio of the extract obtained by the solvent to O/A (Organic/Aqueous) of 10:1 to 1 The distilled water of 50 ° C to 70 ° C can be washed in 1 minute under conditions of 10, preferably at 60 ° C distilled water under 2:1 O/A (Organic/Aqueous) conditions.
The step (f) of the present invention (S60) is a step of adding a CH ₃ COOH solution to the extract obtained in the above step (e), and obtaining a Co-Mn-CH ₃ COOH removing solution by back extraction, the above-mentioned "extract solution" It can be mixed with "extraction solvent extracted by Cyanex 272" or "extraction solvent", and the above extraction solvent used in the above-mentioned Co-Mn-CH ₃ COOH liquid catalyst production method can be used for cobalt and manganese recovery methods (e The extract obtained in the step is used as a starting solvent.
Other aspects of the present invention may further include a step of adding a cobalt salt and a manganese salt to the appropriate solubility in the Co-Mn-CH ₃ COOH removal solution subjected to the above (f) step (step (g)). This step is to use the Co-Mn-CH ₃ COOH removal solution obtained by the above-described back extraction (removal) step (step (f)) as a Co-Mn-CH ₃ COOH liquid catalyst, and the content of each constituent component is used. When the amount is not reached, the removal solution is obtained in a CH ₃ COOH solution, and the appropriate concentration of the cobalt salt and the manganese salt is additionally mixed in the removal solution to form a suitable composition ratio of the liquid catalyst of CH ₃ COOH. The step of concentration.
In the above step (g), in the case where the cobalt salt and the manganese salt are CoBr ₂ (Cobalt bromide), MnBr (Maganese Bromide), and Mn (OAc) ₂ (maganese acetate), in order to manufacture Co-Mn-CH ₃ COOH The amount of the liquid catalyst added to the removal solution depends on the contents of cobalt, manganese and acetic acid in the Co-Mn-CH ₃ COOH removal solution which is initially obtained.
Hereinafter, the present invention will be described in more detail by way of specific examples. The embodiments are intended to describe the present invention in more detail, and the scope of the present invention is not limited to the specific embodiments of the invention in accordance with the spirit of the present invention.
(Example of implementation)
1. Produced by the first stage soaking dissolution and the second stage continuous soaking solvent extraction supply solution. Spent CMB according to the temperature of sulfuric acid 0.5M, 1M, 1.5M, normal temperature 40 ° C, 50 ° C, Soaking and dissolving was carried out at 60 ° C and 70 ° C. Thereafter, the second stage continuous immersion elution was carried out under the conditions of setting the solution eluted by 1 M sulfuric acid immersion at 60 ° C, and the solid-liquid ratio was 1:10 for 120 minutes. Through the second stage of continuous soaking and dissolution, the pH value is adjusted to become PH1.17 to PH6.15. Simultaneously with the PH-regulated wastewater reduction type process, impurities such as Fe, Pb, Cu, Zn, etc. are suppressed in a small amount, and are manufactured. Solvent extraction supply solution.
The composition of the waste CMB catalyst sample is shown in Table 1 below.

The composition (mg/L) of the solution controlled by the pH adjustment of the soaking solution was as shown in Table 2.

2. Solvent extraction In order to extract the solvent for recovering and separating Co and Mn for the above-mentioned supply solution, Na-Cyanex 272 was used as a solvent.
In the state of the commercial extractant, bis(2,4,4-trimetyl pentyl)phosphinic acid (trade name Cyanex 272, Cytec Inc.) It can be used without refining. Cyanex 272 has a molecular weight of 290, a viscosity of 142 cp (25 ° C), a specific gravity of 0.92 gm/cc (24 ° C), and a purity of 85%. The molecular formula is C ₁₆ H ₃₄ PO ₂ H, and its structure is as follows:

The diluent used kerosene (bp 180-270 ° C) (Junsei Chemicals, Japan).
Solvent extraction conditions for the production of liquid Co-Mn-CH ₃ COOH catalyst based on a supply solution in which the impurities are slightly controlled are solvent concentrations of 0.88 M Cyanex 272, O/A = 4, 1.17 M Cyanex 272, O/A = 3. The entire solvent extraction experiment was carried out under the conditions of 25 ° C and shaking time for 5 minutes, and the first stage extraction (1 step extraction) was carried out. In order to increase the extraction rate, an alkaline solution, that is, a NaOH solution, was used for 30%, 40%, and 50% alkalization. The chemical formula according to the alkalized Cyanex 272 is shown below. After extracting (re-extracting) with CH ₃ COOH solution, an organic load was obtained to prepare a liquid CMA.

2.1 Solvent extraction of 0.88 M Cyanex 27230%, 40%, 50% alkalized solvent using waste CMB catalyst Stage 2 sulfuric acid soaking solution. Use 0.88M Cyanex 272 solvent to soak the waste CMB catalyst in continuous sulfuric acid. The eluate was subjected to selective extraction experiments of Co and Mn. At this time, the solvent was alkalized using a NaOH solution, and solvent extraction experiments were carried out under conditions of alkalinity of 30%, 40%, and 50%. The entire solvent extraction experiment was carried out at 25 ° C, and the solvent extraction conditions were carried out with O/A = 4 (40 ml: 10 ml), shaking time 5 min, and 1 step extraction.
Table 3 shows the composition (mg/L) of the raffinate produced after solvent extraction, and Table 4 shows the extraction rate (%) of the valuable metal according to the degree of alkalization.

According to the 0.88 M Cyanex 272, the alkalinity of Co and Mn extraction rates were 55.1% and 41.2%, respectively, under conditions of 30% alkalization, and 74.8% and 72.6%, respectively, under 40% alkalization conditions. Under 50% alkalization conditions, they were 89.8% and 75.2%, respectively. Fig. 2 is a graph showing the extraction ratio (O/A = 4, 25 ° C, 1 ^st step, 5 min) of a metal according to a degree of alkalinity of 0.88 M Cyanex 272.
2.2 Using waste CMB catalyst Stage 2 sulfuric acid soaking solution 1.17M Cyanex 27230%, 40%, 50% alkalized solvent solvent extraction using 1.17M Cyanex 272 solvent to waste CMB catalyst stage 2 sulfuric acid soaking solution Selective extraction experiments of Co and Mn were carried out. At this time, the solvent was alkalized using a NaOH solution, and solvent extraction experiments were carried out under conditions of alkalinity of 30%, 40%, and 50%. The entire solvent extraction experiment was carried out at 25 ° C, and the solvent extraction conditions were carried out with O/A = 3 (30 ml: 10 ml), shaking time of 5 min, and first stage extraction (1 step extraction).
The composition of the supply solution (mg/L) is shown in Table 5.

Table 6 shows the composition (mg/L) of the raffinate produced after solvent extraction, and Table 7 shows the extraction rate (%) of the valuable metal according to the degree of alkalization.

According to the 1.17M Cyanex 272 alkalinity, the extraction rates of Co and Mn were 42.3% and 70.8% under 30% alkalization conditions, respectively, and 62.9% and 86.0% under 40% alkalization conditions. Under 50% alkalization conditions, they were 81.6% and 94.8%, respectively. It is shown that the extraction ratio of Co and Mn tends to increase as the degree of alkalization increases. Figure 3 is a graph showing the extraction ratio (O/A =, 25 ° C, 1 ^st step, 5 min) of a metal according to 1.17 M Cyanex 272 alkalinity.
2.3 2-stage countercurrent multi-stage simulated extraction of 0.88 M Cyanex 27230%, 40% alkalized solvent using waste CMB catalyst stage 2 sulfuric acid soaking solution. Using 0.88 M Cyanex 272 solvent for waste CMB catalyst continuous The sulfuric acid soaked solution was used for the selective extraction of Co and Mn. A solvent extraction experiment of 2-stage countercurrent multi-stage simulated extraction was carried out under two conditions of alkalization degree of 30% and 40%. The whole solvent extraction experiment was carried out at 25 ° C, and the solvent extraction conditions were carried out with O/A = 4 (40 ml: 10 ml) and shaking time of 5 min.
The extraction results (mg/L) and extraction ratio (%) of the 2-stage countercurrent multi-stage simulated extraction using a 30% alkalized solvent are shown in Tables 8 and 9 below, respectively.

The extraction results and extraction rates of the two-stage countercurrent multi-stage simulated extraction using a 40% alkalized solvent are shown in Tables 10 and 11 below, respectively.

As shown in Table 10 and Table 11, using the extraction results of the two-stage countercurrent multi-stage simulated extraction, the extraction ratio of Co was 99.9 and the Mn was also extracted by 99.9%. In the case of 40% alkalized solvent, in the first stage extraction, Co was 10.8%, Mn was 71.7%, and the amount of Co and Mn extracted from the final raffinate was 0.174 mg/L, 0.176 mg/ L. Figures 6 and 7 show the results of a 2-stage countercurrent multi-stage simulated extraction according to the elements, respectively.
Figure 6 is a 2-step count-current simulation extraction using Co of 0.88 M Cyanex 27240% alkalizing solvent.
Figure 7 is a 2-step count-current simulation extraction using Mn of 0.88 M Cyanex 27240% alkalizing solvent.
2.4 2-stage countercurrent multi-stage simulated extraction of 1.17M Cyanex 27240% alkalized solvent using waste CMB catalyst continuous sulfuric acid soaking solution. Using 1.17M Cyanex 272 solvent for waste CMB catalyst continuous sulfuric acid soaking solution Selective extraction experiments of Co and Mn. A solvent extraction experiment of 2-stage countercurrent multi-stage simulated extraction was carried out under conditions of 40% alkalization. The whole solvent extraction experiment was carried out at 25 ° C, and the solvent extraction conditions were carried out with O/A = 3 (30 ml: 10 ml) and shaking time of 5 min.

Tables 12 and 13 show the extraction results and extraction rates of Co and Mn, respectively, when subjected to 2-stage countercurrent multi-stage simulated extraction using a 1.17 M Cyanex 27240% alkalized solvent. As a result, the extraction ratio of Co was 99.9% and the extraction of Mn was 99.9%. In the case of the first stage extraction, Co was 89.5% and Mn was 95%. Fig. 8 and Fig. 9 show the extraction results of the 2-stage countercurrent multi-stage simulated extraction according to the elements, respectively.

2.5 3-stage countercurrent multi-stage simulated extraction of 1.17M Cyanex 27230% alkalized solvent using waste CMB catalyst continuous sulfuric acid soaking solution

A 2-stage countercurrent multi-stage simulated extraction experiment of 30% alkalized solvent, a 3-stage countercurrent multi-stage simulated extraction experiment was carried out because no complete extraction was formed.
Tables 14 and 15 show the extraction results (mg/L) and the extraction ratio (%) of the 3-stage countercurrent multi-stage simulated extraction using a 30% alkalized solvent, respectively.

As shown in Table 14 and Table 15, the results of 3-stage countercurrent multi-stage simulated extraction using 1.17 M Cyanex 27230% alkalized solvent showed an extraction ratio of Co of 99.9 and Mn extraction of 99.9%. In the first stage extraction, Co was 1.9%, Mn was 41.2%, and the amounts of Co and Mn released from the final raffinate were 0.28 mg/L and 0.21 mg/L, respectively. Fig. 10 and Fig. 11 show the extraction results of the three-stage countercurrent multi-stage simulated extraction according to Co and Mn, respectively.
Figures 10 and 11 are the results of 3-step counter-current simulation extraction using Co of 1.17M Cyanex 27230% alkalization solution of Co and Mn, respectively.
3. Preparation of liquid CMA3.1 from the removal solution for the selective use of alkalized 40% 0.88M Cyanex 272 solvent for the selective recovery of Co, Mn in the organic loaded organic phase produced by 2-stage countercurrent multi-stage simulated extraction. The removal liquid was used to make CMA alkalized 40% of 0.88 M Cyanex 272 solvent, and the organic load produced by the 2-stage countercurrent multi-stage simulated extraction was at a concentration of 10 to 90% (V/V%) of acetic acid. The 1-stage removal experiment was repeated. The entire removal conditions were carried out at O/A = 1 (10 ml: 10 ml) at 25 ° C for 5 min.
Tables 16 and 17 show the removal concentration and removal rate of Co according to the removal conditions of the acetic acid concentration (V/V%), respectively.

[Table 17]

Fig. 12a is a graph showing the Co removal rate in accordance with the acetic acid concentration and the number of removals, and Fig. 12b is a graph showing the Co cumulative removal rate in accordance with the number of removals.
When the cobalt removal rate is 50% acetic acid (V/V%), it is the highest at 94.9% for the first time and 50% (V/V%) for the first time. The removal rate of Co is 99.2% when the concentration is 50% (V/V%), and the rest is about 97% to 98%, and the concentration of acetic acid is 20 to 80% (V/V%). In the third time, the entire Co was removed. Therefore, it is appropriate to carry out a 3-stage countercurrent multi-stage simulated extraction experiment using the removal of Co by 50% (V/V%) acetic acid concentration through this experiment.
Tables 18 and 19 show the removal concentration and removal rate of Mn, respectively, according to the removal times of the acetic acid concentration (V/V%).

The 13th is a graph of the Mn removal rate according to the acetic acid concentration and the number of removals, and the 13th is a graph showing the Mn cumulative removal rate according to the number of removals.
The removal rate of manganese was the highest at 60.4% in the first time when 50% (V/V%) was used, but the removal rate was not improved compared with the expected value of Co. Then, based on 50% (V/V%), if it is increased, it will decrease. The removal rate of the entire Mn according to the first time was mostly between 17.6% and 60%, and Mn was not completely removed even in the repeated removal experiments of the number of passes. The highest removal was still the same as the removal of Co. When 50% (V/V%) acetic acid concentration was used, the cumulative removal rate was 93% maximum. Therefore, it is considered that the number of stages must be increased to more than 5 stages in order to completely remove Mn.
3.2 Use of alkalized 40% 1.17M Cyanex 272 solvent for the production of CMA in the organically loaded (organic-loaded organic) produced by two-stage countercurrent multi-stage simulated extraction using acetic acid removal solution
The organic load produced by the two-stage countercurrent multi-stage simulated extraction using alkalized 40% 1.17M Cyanex 272 solvent was repeated at a concentration of 10 to 90% (V/V%) of acetic acid. Stage removal experiments. The entire removal conditions were carried out at O/A = 1 (10 ml/10 ml), 25 ° C, and 5 min.
Table 20 and Table 21 show the removal concentration (mg/L) and the removal rate (%) of Co, respectively, in accordance with the removal times of the acetic acid concentration (V/V%).

Fig. 14a is a graph showing the removal rate of Co according to the concentration of acetic acid and the number of removals, and Fig. 14b is a graph showing the cumulative removal rate of Co according to the number of removals.
The removal rate of cobalt is 50% (V/V%), which is the highest at 71.4% for the first time and decreases at 50% (V/V%). According to the removal rate of Co for the whole number of times, when using the concentration of 30% (V/V%), 97.5% is removed, and the rest is 93% to 97%. The removal time is other than the removal experiment, when the concentration of acetic acid is 30 to 60%. At (V/V%), all Co was removed in the third time, and the rest was mostly removed in the fourth time. Therefore, it is appropriate to perform a 3-stage countercurrent multi-stage simulation removal experiment using 50% (V/V%) acetic acid concentration as a result of the removal of Co through this experiment.
Table 22 and Table 23 show the removal concentration (mg/L) and the removal rate (%) of Mn according to the removal times of the acetic acid concentration (V/V%), respectively.

Fig. 15a is a graph showing the removal rate of Mn according to the concentration of acetic acid and the number of removals, and Fig. 15b is a graph showing the cumulative removal rate of Mn according to the number of removals.
When the manganese removal rate was 40% (V/V%) of acetic acid, it was the highest at 38.7% for the first time and 30% (V/V%) for the second time at 69.4%. Even if the number of passes was repeated, the experimental Mn was completely removed. The highest removal was still the same as the removal of Co. When 50% (V/V%) acetic acid concentration was used, the cumulative removal rate was 93.5% maximum. Therefore, it is considered that the number of stages must be increased to more than four stages in order to completely remove Mn.
4. 3-stage countercurrent multi-stage simulated removal. Using an alkalized 40% 0.88 M Cyanex 272 solvent, the extracted organic load solution was subjected to a three-stage reaction with 50% acetic acid (V/V%). Countercurrent multi-stage simulation removal.
Figure 16 is a three-stage countercurrent multistage of 50% (V/V%) acetic acid removal solution in organically loaded (loaded organic) prepared by two-stage countercurrent multi-stage simulated extraction using Co-0.88M Cyanex 272 solvent. Simulate the removal results.
Figure 17 is a three-stage countercurrent multistage of 50% (V/V%) acetic acid removal solution in organically loaded (loaded organic) prepared by two-stage countercurrent multi-stage simulated extraction using Mn-0.88M Cyanex 272 solvent. Simulate the removal results.
Through the 3-stage countercurrent multi-stage simulation removal experiment, the removal rate of Co was 100.74% and the manganese was 103.8%. The remaining major impurities are 6 ppm for Ca, 0.2 ppm for Mg, and 1.9 ppm for Na to remove impurities.
Figure 18 is a three-stage countercurrent multistage of 50% (V/V%) acetic acid removal solution in an organic loaded organic phase prepared by two-stage countercurrent multi-stage simulated extraction using Co-1.17M Cyanex 272 solvent. Simulate the removal results.
Figure 19 is a three-stage countercurrent multistage of 50% (V/V%) acetic acid removal solution in organically loaded (loaded organic) prepared by two-stage countercurrent multi-stage simulated extraction using Mn-1.17M Cyanex 272 solvent. Simulate the removal results.
Through the 3-stage countercurrent multi-stage simulation removal experiment, the removal rate of Co was 109.1% and the manganese was 100.3%. The remaining major impurities are 8.9 ppm for Ca, 0.7 ppm for Mg, and 2.28 ppm for Na to remove impurities.
Table 24 shows the results of component analysis (g/L) showing the removed solution to be produced.

Through the 3-stage countercurrent multi-stage simulation removal experiment, as shown in Table 24, 50% (V/V) CH ₃ COOH can be used as the removal liquid, and 6.1 g/L in 0.88 M organic load (loaded organic) can be recovered. Co, 3.7g / L Mn; 1.17M organic loaded (loaded organic) solution of 10.5g / L Co, 4.2g / L of Mn, from both solutions can produce impurities, namely Ca, Mg, Zn Cu, Fe, and Pb are Co-Mn-CH ₃ COOH of 10 ppm or less.

S0. . . Waste cobalt manganese bromide (CMB)

S10. . . Stage 1 sulfuric acid soaking and dissolution

S20. . . filter

S30. . . Stage 2 continuous soak dissolution

S40. . . filter

S50. . . Solvent extraction

S60. . . Back extraction

S70. . . Production of cobalt acetate manganese (CMA) liquid catalyst

Fig. 1 is a process diagram for producing a Co-Mn-CH ₃ COOH liquid catalyst.

Fig. 2 is a graph showing the extraction ratio (O/A = 4, 25 ° C, 1 ^st step, 5 min) of a metal according to a degree of alkalinity of 0.88 M Cyanex 272.

Figure 3 is a graph showing the extraction ratio (O/A =, 25 ° C, 1 ^st step, 5 min) of a metal according to 1.17 M Cyanex 272 alkalinity.

Figure 4 is a 2-step count-current simulation extraction using Co of 0.88 M Cyanex 272 30% alkalizing solvent.

Figure 5 is a 2-step count-current simulation extraction using Mn of 0.88 M Cyanex 272 30% alkalizing solvent.

Figure 6 is a 2-step count-current simulation extraction of Co using 0.88 M Cyanex 272 40% alkalizing solvent.

Figure 7 is a 2-step count-current simulation extraction using Mn of 0.88 M Cyanex 272 40% alkalizing solvent.

Figure 8 is a 2-step count-current simulation extraction of Co using 1.17M Cyanex 272 40% alkalization solvent.

Figure 9 is a 2-step count-current simulation extraction using Mn of 1.17M Cyanex 272 40% alkalizing solvent.

Figure 10 is a 3-step count-current simulation extraction of Co using 1.17M Cyanex 272 30% alkalization solvent.

Figure 11 is a 3-step count-current simulation extraction using Mn of 1.17M Cyanex 272 30% alkalizing solvent.

Figure 12a shows the Co removal rate based on the concentration of acetic acid and the number of removals.

Figure 12b is a graph showing the cumulative removal rate of Co according to the number of removals.

Figure 13a shows the Mn removal rate based on the concentration of acetic acid and the number of removals.

Figure 13b is a graph showing the cumulative removal rate of Mn according to the number of removals.

Figure 14a shows the Co removal rate based on the concentration of acetic acid and the number of removals.

Figure 14b is a graph showing the cumulative removal rate of Co according to the number of removals.

Figure 15a shows the Mn removal rate based on the concentration of acetic acid and the number of removals.

Figure 15b is a graph showing the cumulative removal rate of Mn according to the number of removals.

Figure 16 is a three-stage countercurrent multi-stage simulation showing the use of 50% (v/v) acetic acid removal in organic loaded organics prepared by two-stage countercurrent multi-stage simulated extraction with Co-0.88M Cyanex 272 solvent. The result of (3 step count-current simulation stripping) is removed.

Figure 17 is a three-stage countercurrent multi-stage simulation showing the use of 50% (v/v) acetic acid removal in organic loaded organics prepared by two-stage countercurrent multi-stage simulated extraction with Mn-0.88M Cyanex 272 solvent. Remove the result.

Figure 18 is a three-stage countercurrent multi-stage simulation showing the use of 50% (v/v) acetic acid removal solution in organically loaded organic phase prepared by two-stage countercurrent multi-stage simulated extraction with Co-1.17M Cyanex 272 solvent. Remove the result.

Figure 19 is a three-stage countercurrent multi-stage simulation showing the use of 50% (v/v) acetic acid removal solution in organically loaded organic phase prepared by two-stage countercurrent multi-stage simulated extraction with Mn-1.17M Cyanex 272 solvent. Remove the result.

S0. . . Waste cobalt manganese bromide (CMB)

S10. . . Stage 1 sulfuric acid soaking and dissolution

S20. . . filter

S30. . . Stage 2 continuous soak dissolution

S40. . . filter

S50. . . Solvent extraction

S60. . . Back extraction

S70. . . Production of cobalt acetate manganese (CMA) liquid catalyst

Claims (11)

A method for producing cobalt cobalt manganese liquid catalyst from waste cobalt manganese bromine catalyst, comprising:
(a) a step of adding sulfuric acid to the waste CMB catalyst sample to dissolve and dissolve;
(b) filtering the soaking solution of the above step (a) to obtain the first stage of soaking the eluate;
(c) a step of adding a new waste CMB catalyst sample to the first stage soaking solution to soak and dissolve;
(d) filtering the soaking solution of the above step (c) to obtain the second stage of soaking the eluate;
(e) a step of extracting the solvent by adding the solvent to the second stage of the above step (d) to extract; and (f) adding a CH ₃ COOH solution to the extract obtained in the above step (e), and obtaining a Co by back extraction - Mn-CH ₃ COOH removal of the solution. The method for producing a cobalt cobalt manganese liquid catalyst from a waste cobalt manganese bromine catalyst according to claim 1, wherein the method further comprises: adding a cobalt salt and a manganese salt to the removal solution of the above step (f); And step (g) with the appropriate concentration. A method for producing a cobalt cobalt oxide liquid catalyst from a waste cobalt manganese bromine catalyst according to the first aspect of the invention, wherein the pH of the step (a) is in the range of 0 to 1.5. A method for producing a cobalt acetate manganese liquid catalyst from a waste cobalt manganese bromine catalyst according to the first aspect of the invention, wherein the pH of the step (c) is in the range of 4.5 to 6.5. A method for producing a cobalt cobalt manganese liquid catalyst from a waste cobalt manganese bromine catalyst according to claim 4, wherein the method comprises: removing the selective freedom by continuous soaking dissolution by the above steps (a) to (d) Fe, Pb, Cu, and impurities of the group consisting of these mixtures. The method for producing a cobalt-cobalt-manganese liquid-like catalyst from a waste cobalt-manganese bromine catalyst according to the first aspect of the patent application, wherein the solvent used in the solvent extraction of the above step (e) is selected as a free two (2-B) ethylhexyl) phosphoric acid (di - 2 - ethyl hexyl phosphoric acid) based solvent, (2-ethylhexyl) phosphonic acid (2 - ethyl hexyl phosphonic acid) based solvent, mono (2-ethylhexyl) phosphate (mono-2 -ethyl hexyl ester) solvent, di(2,4,4-trimethylpentyl)phosphinic acid (di-2,4,4-trimethyl pentyl phosphinic acid) solvent, di(2-ethylhexyl) Di-2-ethyl hexyl phosphinic acid solvent, di(2,4,4-trimethylpentyl)dithiophosphinic acid solvent (di-2,4,4-trimethyl pentyl dithiophosphinic) Acid), a solvent of di-2,4,4-trimethyl pentylmonodithiophosphinic acid, and a mixture of these mixtures. A method for producing a cobalt acetate manganese liquid catalyst from a spent cobalt-manganese bromine catalyst according to claim 6, wherein the solvent is alkalized by an alkaline solution. The method for producing a cobalt acetate manganese liquid catalyst from a waste cobalt manganese bromine catalyst according to claim 7, wherein the alkaline solution is NaOH or NH ₄ OH. The method for producing a cobalt acetate manganese liquid catalyst from a waste cobalt manganese bromine catalyst according to claim 7, wherein the solvent is a solvent of 30 to 50% alkalization. A method for producing a cobalt acetate manganese liquid catalyst from a spent cobalt-manganese bromine catalyst according to claim 7, wherein the concentration of the solvent is in the range of 0.8 to 1.5M. The method for producing a cobalt acetate manganese liquid catalyst from a waste cobalt manganese bromine catalyst according to the first aspect of the invention, wherein the extract obtained in the step (f) is obtained through the above step (e).