TW201107036A - Method for regenerating Co-Mn alloy from mother liquor of purified terephthalic acid and the system thereof - Google Patents

Abstract

The present invention relates to a method for regenerating cobalt manganese alloy from mother liquor of purified terephthalic acid and the system thereof. Cobalt ions and manganese ions in mother liquor of purified terephthalic acid are first recovered and manufactured into acid liquid that containing cobalt ions and manganese ions. The acid liquid with cobalt ions and manganese ions is then processed for electrolysis to obtain cobalt manganese alloy. The obtained cobalt manganese alloy is used to prepare cobalt manganese bromide catalyst solution, which is then re-used in the process for producing purified terephthalic acid.

Description

201107036 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method and system for recovering and reclaiming a hard alloy from a pure terephthalic acid mother liquor, in particular, a purely stupid diterpene mother liquor and a catalyst oxidation unit. The catalyst in the residue is recovered and regenerated to recycle the method and system. [Prior Art]

Purified Terephthalic Acid is a compound raw material widely used in the chemical textile, light industry, electronics, and plastic industries. Since 2003, 'the annual global production has exceeded 30,000 tons, pure terephthalic acid is mainly used to manufacture polyester fiber upstream materials' and is used in the manufacture of polyester containers such as PET bottles, or other Engineering plastics and coatings. ^ Pure to the two T acid process can be divided into catalyst oxidation part and force〗 Hydrogen reduction part. In the oxidizing portion of the catalyst, the raw material is catalyzed by a catalyst to form a crude p-teric acid, and a product of 4-carboxybenzaldehyde is formed. Then the crude pair of 4-carboxybenzofural and diterpenic acid enter the hydrogenation reduction portion to obtain pure terephthalic acid, wherein 4, the reduction of the amyloid is hydrogenated to water-soluble high-purinylbenzene. Formic acid, and pure to the stupid dibasic acid mother liquor under the conditions of #, can be crystallized, separated from the separation, dried to obtain pure p-phenylene powder. e Acetate drill (four) two liquid (CMB, (10) group

Br〇mide S〇lutl0n) is pure phthalic acid lanthanum. The oxidized part must be added to the contact zone. The catalyst in the contact zone will provide a catalytic reaction with the suspension. Cheng tiv and part of the contact medium 'original p knife, and finally exist in the pure pair and 201107036 diacetic acid mother liquor together. Residues and strontium: The oxidized part of the oxidized part has a step-by-step; 'the catalyst of the 曱J mother liquor' cannot be arbitrarily discharged into the formic acid seed, for. Yahe, after the overall pure p-benzene is smoother than the pure p-benzene dependence, it will be helpful if the wastewater can be recovered in the later stage. [Inventive content]: The method of the second is to separate and recover the cobalt from the residue of the heavy knife. The manganese catalyst is reused in the pure terephthalic acid process to greatly reduce the production of floccules. The present invention is characterized in that the invention is a kind of pure cobalt-manganese alloy recovered from the mother liquor. The method comprises the steps of: controlling the water quality of the pure terephthalic acid mother liquor; performing the first-filtration step of the pure pure terephthalic acid mother liquor; and adding the liquid to adjust the enthalpy value to increase the organic cobalt and manganese m parent for the resin When the floating solid particles in the pure terephthalic acid mother liquor are coated, the organic matter and the other metals in the foregoing cobalt-containing manganese ion acid solution are removed without using 201107036, and the steps thereof include: an acid dissolution step in which a mineral acid and a catalyst are added, And increasing the temperature and adjusting the pH value, and performing a second filtering step to remove the iron and chromium ions in the cobalt-containing manganese ion acid solution; and the organic substance precipitation step, adjusting the pH value of the cobalt-containing manganese ion acid solution to precipitate the organic matter And filtering out by the third filtration step; and. 9 removing the pH of the cobalt-containing manganese ion acid solution in addition to the nickel and adsorbing organic matter step, and then adding the nickel precipitating agent and the adsorbent to selectively precipitate the nickel ion and adsorbing the organic The substance is further separated into a solid-liquid by a fifth filtration step; and an electrolysis step is performed, and the manganese-containing manganese acid solution purified by the foregoing steps is electrolyzed under appropriate conditions to obtain a drilling alloy. In a preferred embodiment, wherein the monitoring of the quality of the pure terephthalic acid mother liquor comprises measuring the pH and turbidity of the pure stearic acid mother liquor; and in a further embodiment, further comprising measuring In a preferred embodiment, if the concentration of zinc ions in the cobalt-containing manganese ion acid solution is too high, the step of extracting and removing zinc is performed, and the cobalt-containing manganese ion acid treated by the organic matter precipitation step is first adjusted. After the pH value of the liquid is further added to the extracting agent and the reaction is sufficiently carried out, the raffinate is subjected to a fourth filtration step to separate the solid and liquid. Another aspect of the present invention is a system for recovering a regenerated cobalt-manganese alloy from a pure terephthalic acid mother liquor according to the foregoing method, comprising: a water quality monitoring device; a pretreatment device comprising a first filter element; 201107036 column 43⁄4 An exchange unit comprising: a sub-exchange resin tube for purifying a device containing a sulphuric acid, comprising: an acid-soluble unit comprising a second filter element; an organic precipitation unit comprising a third filter element; extracting zinc removal Included in the fourth filter element; and in addition to recording and adsorbing organic matter, the t contains a fifth filter element; and an electrolysis device. In a preferred embodiment, the water quality monitoring device comprises a pH meter and a turbidimeter; and in a preferred embodiment, a differential pressure meter is included. In a preferred embodiment, the cation exchange resin will selectively produce wastewater from the selective adsorption of cobalt and manganese ions in the mother liquor of the dicarboxylic acid, and further pass through a wastewater treatment device to perform a wastewater treatment step to produce reclaimed water for circulation. use. Another aspect of the present invention is a self-containing cobalt-manganese acid solution. Manganese method ^The concentration of cobalt-containing manganese ion ΐ 任何 ΐ ΐ ΐ 前述 前述 前述 前述 前述 前述 前述 前述 前述 前述 前述 前述 ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ 任何 任何 任何 任何 任何 任何 任何 任何 任何 任何 任何 任何 任何The alloy, as described below: The organic metal in the cobalt-containing manganese ion acid solution is removed, the step comprising: a bismuth acid step, wherein 'the inorganic acid and the catalyst are added, and the temperature is adjusted and the pH is adjusted, and then the second filtration step is performed. The step of removing the iron and chromium ions in the cobalt-containing manganese ion acid solution and the organic matter precipitation step, adjusting the pH value of the cobalt-containing manganese ion acid solution to precipitate the organic matter, and removing it by the third filtration step 201107036; In addition to the pH of the nickel and the adsorbed organic acid, and then the above-mentioned cobalt-containing manganese separating agent to selectively precipitate nickel to remove the nickel precipitant and adsorb the fifth filtering step and adsorb the organic matter, and then electrolyze (4) The cobalt-containing manganese ion acid solution after the appropriate treatment, the electrolysis of the parts is purely in a preferred embodiment by the foregoing steps, if a cobalt alloy is obtained. If the concentration of the cation ion is too high, the method of introducing the cobalt-containing manganese ion acid solution comprises: first adjusting the above-mentioned reaction: c. This step contains the pH value of the cobalt-manganese acid solution; after the treatment step, the raffinate is subjected to the first step, the liquid = the anti-regeneration start, the alloy jm, the seed, the seed, the acid, the acid, the cobalt, the cobalt The square of manganese alloy: described from the device containing cobalt and manganese ions: The heart is lingering. The system comprises a device for purifying and containing the I-monic acid solution, which comprises: an acid-soluble unit comprising a second filter element i; 3· ί-mechanical precipitation unit comprising a third filter element; The fourth filter element is included; and the nickel and adsorbed organic matter unit comprises a fifth filter element; and an electrolysis device. In the embodiment of the rail, the electrolysis device is in the electrolysis step = the electrolysis waste liquid of the raw material, and further enters the electrolysis waste liquid treatment device into the electrolysis waste liquid treatment step. In a feasible embodiment, the filtering method of each of the foregoing filtration steps comprises: bag filtration, plate filtration, vane filtration, cross 8 201107036 filtration, centrifugation H, orbital filtration, hydrocyclone filtration or membrane bonding filter. < 纟= Above, the method for recovering and regenerating cobalt-manganese alloy from the pure p-terephthalic acid mother liquor cobalt 5 ion acid solution of the present invention is carried out by a plurality of precipitation and filtration steps, which are purely in the two mother liquors. Organic matter and metals other than cobalt and manganese

Quality;:; solution to obtain high-purity secret alloy, 匕 water ^ Wei set, (four) free of the water quality standard does not meet the water quality standards = the diterpene acid mother liquor into the system to destroy the device's effect, using the method and system of the present invention It can effectively recycle Ming 5 gold as a regenerative catalyst, which can effectively reduce the production cost of pure stearic acid. [Embodiment] The following embodiments are used to further understand the advantages of the present invention, and are not intended to limit the scope of the invention. ^ The first picture of Yinshen, purely used in the process of stearic acid, used for catalyst emulsification. The part of the sulphuric acid bromine solution (CMB, Cobalt Manganese Bromide Solution) is discharged with the residue of the oxidized part of the catalyst, and the rest follows the main enthalpy into the hydrogenation reduction part, and finally exists in pure benzene. The dicarboxylic acid mother liquor is discharged. — Referring to the first and second figures, the method of recovering the cobalt-manganese alloy from the pure terephthalic acid mother liquor of the present invention can be divided into the first stage and the second stage. The first stage comprises the steps of: monitoring the water quality of the pure terephthalic acid mother liquor, pre-treating the pure terephthalic acid mother liquor, and separating the cobalt and manganese ions from the pure para-dicarboxylic acid mother liquor with the cation exchange resin to obtain the cobalt-containing solution. Manganese ion acid solution. Please refer to the third diagram of the wheat, the second g section includes the steps of removing the organic matter and other metals and electrolysis steps in the above-mentioned 201107036 cobalt-manganese acid solution. The following is a detailed description of the first stage and the second stage: The first stage monitors the water quality of the pure stearic acid mother liquor. According to the method of the present invention, the water quality of the mother liquid is first monitored to avoid the pure para-phenylene which does not meet the processing requirements. The citrate mother liquor flows into the system, causing unfavorable results such as excessive water recovery, equipment damage, and system downtime. The monitoring of water quality includes:

Measure the pH value wisely, if the pH value of the pure terephthalic acid mother liquor introduced exceeds 5.0, discard it; measure the turbidity, if the turbidity of the imported pure terephthalic acid mother liquor exceeds 150 scattering water turbidity a unit (nephelometric turbidity unit, NTU) is disposed of; and in a preferred embodiment, the differential pressure is further measured, and if the differential pressure of the introduced pure terephthalic acid mother liquor exceeds 1. 〇 kg/cm 2 G, then Dispose of it. • Pre-treatment of pure stearic acid mother liquor to remove suspended solids and increase the solubility of organic matter in water. Since the mother liquor often contains a certain amount of organic matter, in subsequent processes, water-borne organic matter may precipitate due to temperature drop. , causing blockage of the overall system and affecting performance. The step comprises: a first filtration step of filtering suspended solid particles in the mother liquor; and adding an alkali solution to adjust the pH of the pure terephthalic acid mother liquor to increase the solubility of the organic matter, and ensuring that the amount of suspended solids in the mother liquor is kept to a minimum. . The test liquid includes, but is not limited to, hydrazine hydroxide, hydrogen 201107036, sodium oxide, ammonia, sodium carbonate or lithium carbonate, preferably from 3 to 4. The clumps are obtained according to the exchange resin, and the manganese ions are separated from the sputum. The separation of the cations containing the ionic acid-containing cation exchange resin column includes a strong acid-containing resin (SAC resin) and a weakly acidic cation exchange method. Type resin, preferably a strong acid cation exchange tree 9^. For example, its model may be Bayer spi2〇, ^2 PK228, Dower CM16 or Purolite cl6〇. The main reaction equation is as follows: R-Na + Co2+~>RC〇+ 2Na+ R-H+ Co2+^R-Co + 2H+ R-H+ Na+-> R-Na + 2H+ liquid exchange resin column adsorption pure p-phenylene When the ceric acid mother suspension solid particles are coated, the use of the Yiji: gas tree 匕2 exchange resin adsorption efficiency 1 is not = packet clock. Μ 卸 虱, 虱 虱 、 氨 氨 氨 氨 氨 氨 氨 氨 当 当 当 当 当 当 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子The inorganic acid is: J 3 (^, citric acid, hydrochloric acid or hydrochloric acid; more clearly ' ^ 4 〇 / 0 ^ „ Si. 5.2 〇〇 / 〇 first stored in the wrong tank; = to be found The words of the series of acid wastewater can be 嗲 ": ff 曰 曰 曰 曰 柱 尹 尹 产生 产生 产生 产生 产生 产生 产生 产生 产生 产生 产生 产生 产生 产生 产生 产生 产生 产生 产生 产生 产生 产生 / / / / / / / / / / / / / / / / The second stage, in addition to the aforementioned cobalt-containing manganese acid organic matter, other gold eyebrows, acid dissolution step, this step includes:

The inorganic acid is added to the cobalt-containing manganese ion acid solution to adjust the pH value, preferably 2.0 to 5.0 Å, preferably 3 〇 to 4.0. The inorganic acid includes, but is not limited to, sulfuric acid or hydrochloric acid; more specifically, 2 to 72% sulfuric acid or 20 to 32% hydrochloric acid. Further catalyst is added, including but not limited to: hydrogen peroxide, sodium thiosulfate, potassium thiosulfate, citric acid, sodium persulfate, persulfate or glucose. And then increase the temperature to fully dissolve the reaction. The temperature range is preferably 50 to 150 degrees Celsius, and most preferably 9 degrees Celsius. This temperature range allows precipitation of iron and chromium ions as hydroxides. A second filtration step is then performed to filter out the insoluble solids.

This step comprises the enthalpy of the material for 5 weeks of if H ionic acid to precipitate a phase. Further: ΐρ Λ is preferably from 0.5 to 3.5, most preferably (10) The third filtration step filters out the insoluble solids. The importance of extraction is: (4) avoiding the subsequent 'caused; phase (10) r agent forming the third... step, saving 1 〇 Q / per year, water phase waste water loss, organic matter in yin and yang 201107036 acid solution when performing the subsequent electrolysis step And the other metal-zinc step preparation 'containing more than 2 ppm of zinc ions in the cerium ion-containing acid solution', the extraction and zinc removal step, therefore, this step is carried out selectively. This step comprises: adjusting the pH of the cobalt-containing manganese ion acid solution to preferably 0.5 to 3.0, preferably 1.8 to 2.2. Further adding an extractant, including but not limited to: di(2-:S&S)^^^(di(2-ethylhexyl)phosphoricacid), 2·ethylhexylphosphoric acid-mono-2-ethylhexyl ester Mixture of di(2-ethylhexyl) phosphoric acid and acid 5 -dodecylsalicylaldoxime), methyl trioctyl ammonium chloride or bis(2,4,4-trimethylpentyl)-mono-thiophosphate (bis (2,4,4-trimethylpentyl) Monothiophosphinic acid); more precisely, the concentration of the aforementioned extractant is 0.1 to 25%. After the extractant is completely reacted with the cobalt-containing manganese acid solution, the raffinate is subjected to a fourth filtration step to filter out the insoluble solid. The extraction efficiency of this step can reach 95~99%. The step of removing the organic matter and other metals in the cobalt-containing manganese ion acid solution-extracting nickel and adsorbing organic matter comprises the steps of: adjusting the pH of the cobalt-containing manganese ion acid solution to be preferably 2.0 to 6.0, preferably 3.0 to 5.0. A nickel precipitant and an adsorbent are added to selectively precipitate the nickel 201107036 ion and adsorb the organic matter. The nickel precipitating agent includes, but is not limited to, phosphoric acid or dimercaptoacetaldehyde oxime. The adsorbent is, but not limited to, activated carbon, diatomaceous earth or anthracite. A fifth filtration step is then performed to filter out the insoluble solids. Electrolysis Step The electrolysis principle is based on the difference in oxidation-reduction potential of the metal, and the appropriate cation electrode is reacted at the control voltage and current intensity to cause the desired metal to precipitate on the electrode plate. • The electrolysis step is carried out as follows: The anode material includes, but is not limited to, platinum titanium mesh, titanium oxide mesh, titanium manganese alloy mesh, lead tin alloy plate or graphite; • cathode material includes, but is not limited to, stainless steel plate, plastic Electroplated cobalt plate or thin cobalt plate; Because the anode will produce acid during the electrolysis process, it is necessary to maintain the pH value of 2.0~4.0, preferably 2.5~3.0, to avoid re-dissolution of the precipitated metal drill; Good for 30 to 45 degrees Celsius, best for Celsius • 35 to 40 degrees; ❻ Electrolytic potential: 3 to 5V; • Anode current density · 100~200A/m2; and • Cathodic current density: 1〇〇~250A/ M2. The main reaction equations are as follows: • Anode main reaction: H20~>2H++l/202+2e_ • Anode side reaction·· 2H2〇+Mn2+_^4H++Mn〇2+2e • Cathode main reaction: Co2+ +2e3Co • Cathode side reaction: 2H++2e4H2 When the cobalt ion concentration in the cobalt-containing manganese acid solution is less than 1000 ppm, the electrolysis step is stopped and the obtained drill alloy is collected. 201107036 The recovery efficiency of cobalt-manganese alloy is preferably not less than 95%, and the best is not less than 99%. The resulting cobalt-manganese alloy can be used in the conventional catalyst manufacturing process in the field to re-manufacture the catalyst of CMB, Cobalt Manganese Bromide Solution for use in a pure terephthalic acid process. The electrolytic waste liquid can be added to the sinking agent in the prior art, and the pH of the electrolytic waste liquid is adjusted first, and then the solid matter is filtered by filtration. The precipitant includes, but is not limited to

In: sodium hydride, sodium carbonate or sodium hydrogencarbonate; the pH is preferably 7.5 to 9.5, preferably 8_5 to 9. 〇. The filtering methods of the foregoing listening steps include, but are not limited to, "clothing filtration, plate filtration", vane filtration, cross flow transition centrifugal hydrocyclone transition or film transition < liquid regenerative alloy gold. The formic acid mother liquor is recycled in accordance with the method of the present invention from the group of 3 == shipbuilding.糸, 光刀, part of the brother and the second part, please refer to the fourth and fifth figures, the goods. t ^ 1002 〇〇 where the water quality monitoring device 100 contains a few 300 c and the differential pressure gauge 130; ^^110, turbidity meter 12 (210; cation exchange unit 2 contains first filter element column 310 and storage tank 320. L 3 cation exchange resin tube, please refer to the fourth and sixth figures, a manganese ion acid solution The apparatus 400 and the collaterals comprise a purified kf f containing a condensed purified ion-containing acid solution, wherein the acid-soluble unit 41 〇, the gas containing the element 411 comprises a second filter 15 and a third filter element 42] 2 〇 〇 7 〇 36 extraction unit 420, a recording element 431 provided with a fourth filter element 431, and a nickel removal device with a fifth filter element 441 and an organic unit 440.

Acid solution °, two Ai map and the fourth figure, any concentration of cobalt-containing manganese ion slag contained in the pure oxidized part of the catalytic oxidation of the stearic acid process, έ & Meng catalyst also The cobalt-manganese alloy can be regenerated by slurrying with water to form a drill-containing short open text and then performing the subsequent steps from the second stage (ie, the second part of the apparatus) σ ^. Ion ^, ground 'the aforementioned waste diamond clock catalyst can be made of cobalt-containing manganese from the ^, +, i watering 'to form a high concentration of diamond-containing ionic acid liquid' re-rod second stage (ie the device's The second part) begins with the re-recording of the alloy after the order. Waste water enthalpy, the fourth figure, the cation exchange unit 300 generates the effluent treatment 600' to be treated in the prior art, such as RO. reverse osmosis treatment, to purify the waste water to produce waste water for recycling; The electric luxury liquid generated by the electrolysis device 500 can enter the electrolytic waste liquid processing device 7 and be processed.

Wan Wen. Embodiment 1

, θ Please refer to the second and fifth figures, and introduce the pure terephthalic acid solution into the system of the invention, firstly monitoring the water quality. The pH of the mother liquor obtained by the pH meter 110, the turbidity meter 120, and the differential metering ^30 is 2.6 to 4.2, the turbidity is a nephelometric turbidity unit (ΝΤ^), and the differential pressure is 0.1 to 0.8 kg. /cm2G, none of which exceeds the standard. In order to enter the pre-treatment of the pure terephthalic acid mother liquor, firstly filter the core solid particles in the mother liquor by a bag filter (not shown) in the second filter element 21〇, and then add 5 % Hydroxide 201107036 To adjust the pH of the pure terephthalic acid mother liquor to 3.5~4.3, to ensure that the amount of suspended solids in the mother liquor is kept to a minimum. Then, the cation exchange unit 300 is introduced, and a strong acid type 1% ion-replaced resin column 310 (Purolite) is introduced to adsorb the cobalt-manganese ions contained in the mother liquid. After the adsorption is saturated, ceric acid is added to desorb the cobalt-manganese ions adsorbed in the column (i.e., the cobalt-containing manganese ion acid)' and temporarily stored in the storage tank 320. If necessary, clean the column with 2% sodium hydroxide to maintain adsorption efficiency. 1 2nd stage / 2nd stage 厶 Refer to the third and sixth figures, the cobalt-containing manganese ion acid solution is then introduced into the device for purifying the cobalt-containing manganese ion acid solution. The acid dissolution step was first carried out, and sulfuric acid was added to the cobalt-containing manganese ion acid solution to adjust the pH to 2.7. Add hydrogen peroxide and adjust the temperature to 83 degrees Celsius. After the iron = chromium ion was precipitated as a hydroxide, it was filtered out in a second filter 兀 = 411 by a plate and frame filter press (not shown). Next, an organic matter precipitation step is carried out. First, the pH of the cobalt-containing manganese ion acid solution is adjusted to 1.8 to precipitate an organic substance, and then filtered in a second plate member 421 by a plate and frame filter press (not shown). After testing, the concentration of zinc ions in the cobalt-containing manganese ion acid solution was =Ppm, and the extraction and zinc removal step was carried out. First, the cobalt-containing manganese was adjusted to have a pH of 2. Further, bis(2-ethylhexyl)phosphoric acid is added as a solvent. After sufficient reaction, the insoluble solids are filtered off on the fourth filter element 431 by a bag filter (not shown). Final measurement = 2 The concentration of zinc ions in the cobalt-containing manganese ion acid solution is h3. Then, the steps of removing nickel and adsorbing organic matter are carried out, and the cobalt-containing: ionic acid solution is first adjusted to have a pH of 4.5. Then, a nickel-precipitating agent is added: monomethylglyoxime, and activated carbon as an adsorbent. Fully reverse 201107036 After that, the insoluble solids are filtered out in a fifth filter element 441 by a plate and frame filter press (not shown). The cobalt-containing manganese ion acid solution treated by the step of removing the organic matter and other metals is followed by electrolysis. The anode used is a cerium oxide titanium mesh and the cathode is a stainless steel plate. Other electrolysis parameters were as follows: pH was maintained at 3.5; temperature was 45 °C; electrolytic potential: 4.75 volts; _ anode current density: 120 A/m2; and cathode current density: 125 A/m2. After a period of time, the residual cobalt ion concentration in the cobalt-containing manganese ion acid solution was 860 ppm, that is, the electrolysis was stopped, and the obtained recording alloy was collected, and the recovery efficiency was 96%. All of the features disclosed in this specification may be combined with other methods, and each of the features disclosed in this specification may be selectively replaced with the same, equal or similar purpose features, and thus, in addition to the particularly salient features All of the present specification • The disclosed features are only one example of equal or similar features. While the invention has been described above in terms of the preferred embodiments thereof, it is not intended to limit the invention, and various modifications and improvements can be made without departing from the spirit and scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS The first figure is a flow chart of the method for recovering and regenerating cobalt-manganese alloy from the pure terephthalic acid mother liquor of the present invention in combination with the pure terephthalic acid process; the second figure is the self-purity pair of the present invention. The first stage of the method for recovering the cobalt-manganese alloy from the pure terephthalic acid mother liquor is the flow chart of the second stage of the method for recovering the cobalt-manganese alloy from the pure terephthalic acid mother liquor of the present invention; The fourth figure is a schematic diagram of the system for recovering the regenerated cobalt-manganese alloy from the pure terephthalic acid mother liquor of the present invention; the fifth figure is the system for recovering the regenerated cobalt-manganese alloy from the pure terephthalic acid mother liquor of the present invention. The first part is a schematic diagram; and the sixth figure is a schematic diagram of the second part of the system for recovering and regenerating the cobalt-manganese alloy from the pure terephthalic acid mother liquor. [Main component symbol description] 100-water quality monitoring device 110-pH meter 120-turbidity meter 130-differential pressure gauge 200-pretreatment device 210-first filter element•3〇0-cation exchange unit 310-cation exchange resin tube Column 320 - storage tank 400 - apparatus for purifying cobalt-containing manganese ion acid 410 - acid-soluble unit 411 - second filter element 420 - organic precipitation unit 421 - third filter element 430 - extraction zinc removal unit 431 - fourth filter element 440-Removing nickel and adsorbing organic matter unit 19 201107036

441-Fifth filter element 500-Electrolysis device 600-Wastewater treatment device 700-Electrolysis waste liquid treatment device 20

Claims (1)

201107036 VII, the scope of application for patents: 1. A self-purified pair of dimethicone method, the steps of which include: the secondary liquid recovery of the cobalt manganese alloy side a. f control pure water quality of the stupid acid mother liquor; b. two treatment pure For stupid dimethyl, add organic matter in water 'to remove suspended solids and increase c. With yang, the sub-exchange resin will be Ming: liquid, obtained with the name (four) of this -W d. remove the description of the cobalt-containing manganese, the steps The organic matter and other gold in the sputum liquid are used to remove the iron and chromium ions in the cobalt-containing manganese ion acid solution; and the II'H substance step is used to observe the pH value of the above-mentioned conjugated acid liquid to precipitate the organic substance; m · 3, η with organic steps, adjust the above-mentioned manganese ions containing ions: two p and then add nickel precipitant and adsorbent to selectively call the lion and absorb the material; e. conduct electrolysis step by step The cobalt-containing manganese ion acid solution after the purification in the foregoing step is used to obtain a cobalt-manganese alloy. U. The method described in item C, wherein the aforementioned monitoring pure infusion: formic acid mother liquor 3. = the method described above, wherein the aforementioned monitoring the pressure difference of the pure acid mother liquor to monitor the water turbidity. A. 4. The method of claim 2, wherein the aforementioned pH of the 2011 2011036 dicapric acid mother liquor exceeds 5.0, and is discharged without subsequent steps. 5. The method of claim 2, wherein the turbidity of the pure terephthalic acid mother liquor exceeds 150 nephelometric turbidity unit (NTU), and is discharged without subsequent steps. . 6. The method of claim 1, wherein the step of pre-treating the pure stearic acid mother liquor further comprises: a first filtration step and adjusting the pH with a lye to dissolve the organic matter. 7. The method of claim 6, wherein the liquid test comprises potassium hydroxide, sodium hydroxide, aqueous ammonia, sodium carbonate or lithium acid silicate. 8. The method of claim 6, wherein the pH is preferably from 2 to 5. 9. The method of claim 1, wherein the step c further comprises the following steps: I. selectively adsorbing cobalt and manganese ions in the pure terephthalic acid mother liquor to saturation with a cation exchange resin; ® II. The cobalt and manganese ions adsorbed by the above resin are desorbed by a mineral acid to obtain a diamond-containing acid solution. 10. The method of claim 9, wherein the inorganic cleaning is performed when the surface of the cation exchange resin is coated with suspended solid particles. 11. The method of claim 9, wherein the cation exchange resin comprises a strongly acidic cation exchange resin, a weakly acidic cation exchange resin or a chelating resin. 12. The method of claim 9, wherein the mineral acid 22 201107036 comprises sulfuric acid, nitric acid, hydrochloric acid or hydrobromic acid. 13. The method according to claim 10, wherein the inorganic base comprises potassium hydroxide, sodium hydroxide, aqueous ammonia, sodium carbonate or carbonic acid. 14. The method of claim 1, wherein the acid solubilizing step further comprises: I. adding a mineral acid and a catalyst; II. increasing the temperature between 50 degrees and 150 degrees Celsius; • III. adjusting the pH value. To 2.0 to 5.0; and IV. second filter step. 15. The method of claim 14, wherein the aforementioned temperature is 90 degrees Celsius. 16. The method of claim 14, wherein the aforementioned pH is from 3.0 to 4.0. 17. The method of claim 14, wherein the inorganic acid comprises sulfuric acid or hydrochloric acid. 18. The method of claim 14, wherein the catalytic catalyst comprises hydrogen peroxide, sodium thiosulfate, potassium thiosulfate, citric acid, sodium persulfate, persulfate or glucose. 19. The method of claim 1, wherein the pH of the organic matter precipitation step is preferably from 0.5 to 3.5. 20. The method of claim 1, wherein the organic precipitation step further comprises a third filtration step. 21. The method of claim 1, wherein the step of extracting the organic matter and the step of removing the nickel and adsorbing the organic matter further comprises an extracting and zinc removing step, the step comprising: 23 201107036 I. adjusting the aforementioned cobalt-containing manganese ion acid The pH of the liquid is in the range of 0.5 to 3.0; II. adding an extractant to the aforementioned cobalt-containing manganese ion acid solution; and III. performing a fourth filtration step. 22. The method of claim 21, wherein the aforementioned pH value ranges from 1.8 to 2.2. 23. The method of claim 21, wherein the extractant comprises di(2-ethylhexyl)phosphoric acid, 2-ethylhexyl squaric acid-single- Mixture of 2-ethylhexyl phosphoric acid -mono-2-ethylhexyl ester, bis(2-ethylhexyl) acid, and 5-tanning hydrazine Of di(2-ethylhexyl) phosphoric and acid 5-dodecylsalicylaldoxime), methyl trioctyl ammonium chloride or bis(2,4,4-tridecylpentyl)-mono-thio 24. The method of claim 1, wherein the pH of the step of removing nickel and adsorbing organic matter is preferably from 2.0 to 6.0. 25. The method of claim 1, wherein the step of removing nickel and adsorbing organic matter further comprises a fifth filtering step. 26. The method of claim 1, wherein the nickel removal precipitant for removing nickel and adsorbing organics comprises phosphoric acid or dimethylglyoxal. 27. The method of claim 1, wherein the adsorbent for the step of adsorbing organic matter is the activated carbon, diatomaceous earth or anthracite. 28. The method of claim 1, wherein the electrolysis conditions of the electrolysis step are in the range of pH 2.0 to 4.0; and the temperature is controlled between 30 and 45 degrees Celsius. 29. The method of claim 1, wherein the electrolysis step further comprises an electrolytic waste treatment step. 30. The method according to any one of the preceding claims, wherein the filtering method for each of the filtering is a bag filter, a plate filter, a blade filter, Cross flow filtration, centrifugal filtration, channel filtration, hydrocyclone filtration or membrane filtration. The method according to claim 9, wherein the cation exchange resin further removes waste water generated by selective adsorption of cobalt and sulphur ions in the pure terephthalic acid mother liquor, and further passes through a wastewater treatment step to produce reclaimed water. For recycling. 32. A system for recovering a regenerated cobalt-manganese alloy from a pure terephthalic acid mother liquor, comprising: a water quality monitoring device; a pretreatment device 'to remove suspended solids and increase the solubility of organic matter in water; j soup ion exchange unit' to select Separating the cobalt and manganese ions from the pure p-benzoic acid mother liquor to obtain the cobalt-containing ionic acid solution; + purifying the cobalt-containing manganese ion acid solution to remove the organic matter and other metals in the cobalt-containing manganese ion acid solution The method comprises: an acid-soluble unit for removing iron and chromium ions in the cobalt-containing manganese ion acid; 25 201107036 organic matter precipitation unit for adjusting the pH value of the aforementioned chlorinated acid solution to precipitate organic substances; and removing nickel and adsorbing The organic material unit, by adding a nickel precipitating agent and an adsorbent to selectively precipitate nickel ions and adsorbing the organic substance; and an electrolysis device, electrolyzing the purified ion-containing acid liquid after purification by the device for purifying the cobalt-containing manganese ion acid To obtain a manganese alloy. 33. The system of claim 32, wherein the aforementioned water quality monitoring device comprises a pH meter and a turbidimeter. 34. The system of claim 33, wherein the water quality monitoring device further comprises a differential pressure gauge for monitoring water turbidity. The system of claim 32, wherein the pre-processing device is provided with a first filter element. 36. The system of claim 32, wherein the aforementioned cation exchange unit is provided with a cation exchange resin column and a storage tank. 37. The system of claim 36, wherein the cation exchange resin column comprises a strongly acidic cation exchange resin tube column, a weakly acidic cation exchange resin column or a chelating resin column. 38. The system of claim 32, wherein the acid soluble unit comprises a second filter element. 39. The system of claim 32, wherein the organic precipitation unit comprises a third filter element. 40. The system of claim 32, further comprising a extraction unit. 41. The system of claim 40, wherein the extractive zinc removal unit comprises a fourth filter element. The system of claim 32, wherein the nickel removal and adsorbed organic unit comprises a fifth filter device. 43. The system of claim 32, further comprising an electrolytic waste treatment device. 44. The system of any one of claims 35, 38, 39, 41, and 42, wherein the filtering means of each of the filter elements comprises: a bag type, a plate type, a piece type Transition, parent fork flow filtration, centrifugation, channel filtration, hydrocyclone filtration or thin membrane filtration. 45. The system of claim 32, further comprising a wastewater treatment unit for regenerating waste water produced by the cation exchange unit for recycle. 46. A method for regenerating a cobalt-manganese alloy from a cobalt-containing manganese ion acid solution, the steps comprising: a. removing the organic matter and other metals in the cobalt-containing manganese ion acid solution, the steps comprising: I. an acid dissolution step, Removing the iron and chromium ions in the cobalt-containing manganese ion acid solution; II. the organic matter precipitation step, adjusting the pH value of the cobalt-containing manganese ion acid solution to precipitate the organic substance; and III. removing the nickel and adsorbing the organic matter, adjusting the foregoing The pH value of the cobalt-containing manganese ion acid solution is further added to remove the sinking agent and the adsorbent to selectively precipitate the nickel ions and adsorb the organic substances; b. performing an electrolysis step to electrolyze the manganese-containing manganese ions purified by the foregoing step a Acid solution to obtain a manganese alloy. 47. The method of claim 46, wherein the acid solubilization 27 201107036 step further comprises: I. adding a mineral acid and a catalyst; II. increasing the temperature between 50 degrees and 150 degrees Celsius; III. adjusting the pH Values to 2.0 to 5.0; and IV. Second filtration step. 48. The method of claim 47, wherein the inorganic acid comprises sulfuric acid or hydrochloric acid. 49. The method of claim 47, wherein the aforementioned temperature is 9 degrees Celsius. 50. The method of claim 47, wherein the aforementioned pH range is from 3.0 to 4.0. 51. The method of claim 46, wherein the pH of the organic precipitation step is preferably from 0.5 to 3.5. The method of claim 46, wherein the organic precipitation step further comprises a third filtration step. 53. The method of claim 46, wherein the step of extracting organic matter and the step of removing nickel and adsorbing organic matter further comprises extracting and removing zinc, the steps comprising: I. adjusting the aforementioned cobalt-containing manganese acid The pH of the liquid is from 0.5 to 3.0; II. adding an extractant to the aforementioned cobalt-containing manganese ion acid solution; and III. performing a fourth filtration step. 54. The method of claim 53, wherein the aforementioned pH range is from 1.8 to 2.2. 55. The method of claim 53, wherein the extractant comprises di(2-ethylhexyl)phosphoric acid, 2-ethylhexylphosphoric acid, and 2-ethylhexyl 28 201107036 Mixture of 2-ethylhexylphosphoric acid-mono-2-ethylhexyl ester, bis(2-ethylhexyl) acid and 5-d-methylhydrazine Of di(2-ethylhexyl) phosphoric and acid 5-dodecylsalicylaldoxime), methyl trioctyl ammonium chloride or bis(2,4 '4-tridecylpentyl)-mono-thio The method of claim 46, wherein the step of removing nickel and adsorbing organic matter further comprises a fifth filtration step. 57. The method of claim 46, wherein the nickel removal precipitant for removing nickel and adsorbing organics comprises phosphoric acid or dimercaptoethanedialdehyde oxime. 58. The method of claim 46, wherein the adsorbent for removing nickel and adsorbing organics comprises activated carbon, Shishizao or anthracite. 59. The method of claim 46, wherein the electrolysis condition of the electrolysis step is a pH in the range of 2.0 to 4.0; and the temperature is controlled to be between 30 and 45 degrees Celsius. 60. The method of claim 46, wherein the electrolysis step further comprises an electrolytic waste treatment step. The method of any one of claims 47, 52, 53, and 56, wherein the filtering method of each of the foregoing filtering steps comprises: 'over-type; filter, plate filter, vane filter, cross Flow filtration, centrifugal filtration, channel filtration, hydrocyclone filtration or membrane filtration. S S 1 29 201107036 62. A system for regenerating cobalt-manganese alloy from cobalt-containing manganese ion acid solution. The scoop contains: ', a device for purifying cobalt-containing manganese ion acid to remove organic matter and other metals in the acid solution. , which comprises a U-drilled chrome unit to remove the iron in the bottle-containing ionic acid solution, and to adjust the positive value of the above-mentioned salt-containing ion acid solution to precipitate organic substances; and to remove and adsorb organic matter early Yuan's addition of nickel sinking agent and adsorption sheet to selectively select nickel ions and adsorb organic matter; and set, to electrolyze the above-mentioned purified cobalt-containing manganese ion acid solution 1 from the toned cobalt-containing manganese ion Acid solution to obtain a cobalt-manganese alloy. The system of claim 62, wherein the acid solubilization comprises a second filter element. Wherein the aforementioned organic compound further comprises the third extraction element in which the foregoing extraction unit comprises the third filtration element as described in the sixth aspect of the invention. 5 · t apply for the system described in Section 62 of the patent extraction zinc removal unit. 6 6 · ^ The system described in claim 65: The zinc unit contains a fourth filter element. The system 7 68 described in claim 62, wherein the organic unit comprises a fifth filtering device. The system described in the electrolysis item further includes 6 9. As stated in any of the patents: Sections 63, 64, 66, and 67, ',,,, The filtering method of the filter element includes · 30 201107036 bag filter, plate type too far, blade type too far, parent fork flow over worry, centrifugal over 遽, road filter, hydrocyclone filter, or film over 遽. 31