WO2005049873A1 - Method for recovering catalyst metal from waste of terephthalic acid production - Google Patents
Method for recovering catalyst metal from waste of terephthalic acid production Download PDFInfo
- Publication number
- WO2005049873A1 WO2005049873A1 PCT/KR2004/002978 KR2004002978W WO2005049873A1 WO 2005049873 A1 WO2005049873 A1 WO 2005049873A1 KR 2004002978 W KR2004002978 W KR 2004002978W WO 2005049873 A1 WO2005049873 A1 WO 2005049873A1
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- WIPO (PCT)
- Prior art keywords
- waste
- terephthalic acid
- acid production
- nahco
- catalyst metal
- Prior art date
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 52
- 239000002184 metal Substances 0.000 title claims abstract description 52
- 239000002699 waste material Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000011541 reaction mixture Substances 0.000 claims abstract description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract 3
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract 3
- 238000006243 chemical reaction Methods 0.000 description 37
- 239000000243 solution Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000011084 recovery Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 150000005323 carbonate salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- -1 aliphatic monocarboxylic acid Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/026—Obtaining nickel or cobalt by dry processes from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
- C22B47/0009—Obtaining manganese from spent catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- This invention relates to a method for recovering catalyst metal from waste of terephthalic acid production, and more specifically to a method for rapidly and environmentally-friendly recovering valuable catalyst metal such as Co, Mn or so on from waste of terephthalic acid production.
- Terephthalic acid the raw material used in the polymerization of polyester, is produced by oxidizing para-xylene with oxygen or oxygen-containing gas in the presence of lower aliphatic monocarboxylic acid solvent such as acetic acid and catalyst including metal such as Co, Mn or so on, and by filtering or centrifugally separating the oxidized product.
- Acetic acid in the mother liquor, from which te rephthalic acid is filtered off, can be easily recovered by the method such as distillation.
- the valuable metal catalyst exists in mixed state with the byproducts and organic impurities such as alkylbenzene, para-xylene, 4-carboxylbenzaldehjde, benzoic acid and so on.
- the present invention provides a method for recovering catalyst metal from waste of terephthalic acid production, which comprises the steps of: adjusting pH of the waste of terephthalic acid production to 2.5 to 7; adding NaHCO slurry, which is prepared by mixing NaHCO and water, into a pre- 3 3 cipitation reactor, into which the waste of terephthalic acid production is added; heating a mixture of the waste of terephthalic acid production and NaHCO slurry; and 3 separating a metal precipitate from the reaction mixture.
- FIG. 1 is a diagram for illustrating the method for recovering catalyst metals according to an embodiment of the present invention.
- pH of the waste of terephthalic acid production which contains catalyst metal such as Co, Mn or so on, other metals such as Fe, and various organic impurities, is adjusted to 2.5 to 7, and preferably 4 to 6.
- R-eferable waste of terephthalic acid production is a waste sludge obtained by extracting acetic acid and terephthalic acid from the reaction solution of terephthalic acid production, and then adding water into the reaction solution.
- the pH- adjusting step is to facilitate the transfer of the waste into a precipitation reactor 10 by pump and pipe line.
- the pH-adjusting step can be carried out by adding basic aqueous solution such as NaOH aqueous solution into the waste.
- pH of the waste can be adjusted to 4 to 5 by adding 48 weight% NaOH aqueous solution into the waste, and then pH of the waste is adjusted to 5 to 6 by adding 5 weight% NaOH aqueous solution into the waste, successively.
- the pH-adjusted terephthalic acid production waste is transferred into the precipitation reactor 10.
- NaHCO slurry which is prepared by mixing NaHCO and water, is added 3 3 into the precipitation reactor 10, into which the pH-adjusted terephthalic acid production waste is also added.
- the amount of water mixed with NaHCO is 3 preferably 1 to 3 times by weight with respect to that of NaHCO , and more preferably 3 1.5 to 2.5 times.
- the solubility of NaHCO in water is generally 7 to 8 at room 3 temperature, and increases to 13 as the temperature increases. However, in the present invention, excess NaHCO is used considering the amount of NaHCO consumed in 3 3 the following chemical reaction and precipitation step.
- the amount of water is less than 1 time with respect to the amount of NaHCO , NaHCO can not be adequately 3 3 dissolved or dispersed in water, and if the amount of water is more than 3 times with respect to the amount of NaHCO , there is a problem in that the productivity can be de- 3 teriorated due to the excess water.
- the amount of NaHCO is preferably 2 3 to 2.2 times with respect to the amount of Co and Mn in the terephthalic acid production waste.
- the mixture of NaHCO slurry and the waste of terephthalic acid production is heated to the temperature of preferably 40 to 90°C, more preferably 60 to 85°C, and most preferably about 80°C. If the temperature of the mixture is less than 40°C, the excess NaHCO can not be dissolved sufficiently and carbonate group does not suf- 3 ficiently activated, and if the temperature is more than 90°C, there is a problem in that NaHCO can be evaporated without reacting with Co and Mn.
- the heating step can be 3 carried out after mixing the waste and the slurry. Alternatively, the waste and the slurry are heated separately, and the heated waste and the heated slurry can be mixed.
- the present invention directly utilizes 2- CO /HCO , which is produced by heating the NaHCO slurry, for the above- 3 3 3 mentioned chemical reaction and precipitation, rather than using carbonic acid gas of scrubber for the chemical reaction of organic impurities.
- the organic impurities in terephthalic acid production waste are converted to organic 2- carboxylic acid due to CO /HCO produced by decompsition of NaHCO , and the 3 3 3 produced organic carboxylic acid reacts with sodium(Na) in the precipitation reactor 10 to be dissolved in the reaction solution.
- the valuable catalyst metal such as Co, Mn or so on is precipitated by the reaction with the carbonate group.
- the organic impurities dissolve in the reaction solution, and exist in a liquid phase, and catalyst metal is precipitated in the form of more stable salt.
- the produced metal precipitate exists in the form of very stable salt, and can be stably stayed in the precipitation reactor 10 for a long time. Therefore, the large quantity of waste can be reacted in the precipitation reactor 10.
- the reaction solution is generally neutral, and specifically pH thereof is 6 to 8, for example pH thereof is 7.5. Accordingly, the reaction conditions are mild, and the disposal of the reaction solution, from which the metal precipitate is recovered, is easy and environmentally favorable.
- the pure metal precipitate such as Co or Mn precipitate is separated from the reaction solution by means of, for example, filter 20 (See Fig. 1) or centrifugal separator.
- filter 20 See Fig. 1
- centrifugal separator In the method for recovering catalyst metal according to the present 2- invention, CO /HCO has higher activity than the carbonate salt used in the con- 3 3 ventional metal recovery method. Therefore, the metal precipitate can be recovered more easily.
- the method of the present invention is applicable not only for the recovery of Co or Mn, but also for the recovery of other metal which can react with carbonate ion.
- Example 1 [22] 48 weight% aqueous NaOH solution was added to waste of terephthalic acid production to adjust pH of the waste to 4, and 500g of the pH-adjusted waste was transferred into a precipitation reactor.
- NaHCO slurry which was prepared by mixing 3 75g of NaHCO and 150g of water, was added into the precipitation reactor, and the 3 mixture was reacted and remained for 45 minutes. The temperature of NaHCO slurry, 3 and the temperature of the precipitation reactor were maintained at 75°C. After completion of the reaction, the reaction solution was filtered to recover the pure metal precipitate.
- Example 2 Except for adjusting pH of the waste to 6, and using 70g of NaHCO and 140g of water, the metal precipitate was recovered in the same manner as described in Example 1.
- Example 1 As shown in Table 1, the amount of alkalinizing agent used in Example 1 was more than that used in Example 2. This is due to the fact that the amount of alkalinizing agent, which is required in the precipitation reaction, increases when pH of the waste is low.
- pH of the reaction solution after coirnietion of reaction is the result of actual reaction and was not artificially controlled.
- the amount of the alkalinizing agent was twice by weight as much as the amount required in the precipitation reaction, which is resulted from the fact that the alkalinizing agent was used to remove the organic impurities with the increase of pH.
- Rom Table 1 it is clear that the reaction solution of Exarrnies is neutral, pH of which is about 7.5, and has good filterability, while those of Comparative examrles is strongly alkaline, and doesn't have good filterability.
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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
A method for rapidly and environmentally-friendly recovering valuable catalyst metal such as Co, Mn or so on from waste of terephthalic acid production is disclosed. The method comprises the steps of: adjusting pH of the waste of terephthalic acid production to 2.5 to 7; adding NaHCO3 slurry, which is prepared by mixing NaHCO3 and water, into a precipitation reactor, into which the waste of terephthalic acid production is added; heating a mixture of the waste of terephthalic acid production and NaHCO3 slurry; and separating a metal precipitate from the reaction mixture.
Description
Description METHOD FOR RECOVERING CATALYST METAL FROM WASTE OF TEREPHTHALIC ACID PRODUCTION Technical Field
[1] This invention relates to a method for recovering catalyst metal from waste of terephthalic acid production, and more specifically to a method for rapidly and environmentally-friendly recovering valuable catalyst metal such as Co, Mn or so on from waste of terephthalic acid production.
[2] Background Art
[3] Terephthalic acid, the raw material used in the polymerization of polyester, is produced by oxidizing para-xylene with oxygen or oxygen-containing gas in the presence of lower aliphatic monocarboxylic acid solvent such as acetic acid and catalyst including metal such as Co, Mn or so on, and by filtering or centrifugally separating the oxidized product. Acetic acid in the mother liquor, from which te rephthalic acid is filtered off, can be easily recovered by the method such as distillation. However, the valuable metal catalyst exists in mixed state with the byproducts and organic impurities such as alkylbenzene, para-xylene, 4-carboxylbenzaldehjde, benzoic acid and so on. In order to recover the catalyst metals, the methods of using sodium hjdroxide(NaOH), sodium carbonate(Na CO ), 2 3 carbonate salt or bicarbonate salt are generally used. However, these conventional methods of recovering catalyst metal have drawbacks in that the equipments are complicated, the recovery conditions are severe, and the recovery efficiency of catalyst metals by filtration is low. Especially, in case of using NaOH, the reaction solution of the recovery reaction is strongly alkaline, and pH thereof is 12 to 14. Even in case of using Na CO , pH of the reaction solution is 8 to 10. Therefore, it is not easy to 2 3 dispse the reaction solution after the metal recovery, and the reaction solution may induce the environmental contamination. In order to overcome the drawbacks, the method for recovering catalyst metal with carbonic acid gas, carbonate salt or bicarbonate salt scavenged from a scrubber is used. However, the method has a drawback in that the equipments become more complicated. [4]
Disclosure of Invention Technical Problem
[5] Therefore, it is an object of the present invention to provide a method for rapidly and environmentally-favorably recovering catalyst metal from waste of terephthalic acid production. It is other object of the present invention to provide a method for recovering catalyst metal from waste of terephthalic acid production, in which the equipments are simple, and the disposal of the reaction solution is easy.
[6] Technical Solution
[7] To accomplish these objects, the present invention provides a method for recovering catalyst metal from waste of terephthalic acid production, which comprises the steps of: adjusting pH of the waste of terephthalic acid production to 2.5 to 7; adding NaHCO slurry, which is prepared by mixing NaHCO and water, into a pre- 3 3 cipitation reactor, into which the waste of terephthalic acid production is added; heating a mixture of the waste of terephthalic acid production and NaHCO slurry; and 3 separating a metal precipitate from the reaction mixture. [8] Brief Description of the Drawings
[9] A more complete appreciation of the invention, and many of the attendant advantages thereof, will be readily apparent by reference to the following detailed description when considered in conjunction with the accompanying drawing, wherein Fig. 1 is a diagram for illustrating the method for recovering catalyst metals according to an embodiment of the present invention.
[10] Mode for the Invention
[11] As shown in Fig. 1, in order to recover catalyst metal from the waste of terephthalic acid production according to an embodiment of the present invention, pH of the waste of terephthalic acid production, which contains catalyst metal such as Co, Mn or so on, other metals such as Fe, and various organic impurities, is adjusted to 2.5 to 7, and preferably 4 to 6. R-eferable waste of terephthalic acid production is a waste sludge obtained by extracting acetic acid and terephthalic acid from the reaction solution of terephthalic acid production, and then adding water into the reaction solution. The pH- adjusting step is to facilitate the transfer of the waste into a precipitation reactor 10 by pump and pipe line. When pH of the waste is less than 2.5, there is a problem in that
organic impurities in the waste are not properly dissolved or dispersed, and when pH of the waste is more than 7, there is a problem in that Co or Mn is liable to be reacted to form Co or Mn precipitate. The pH-adjusting step can be carried out by adding basic aqueous solution such as NaOH aqueous solution into the waste. I r example, pH of the waste can be adjusted to 4 to 5 by adding 48 weight% NaOH aqueous solution into the waste, and then pH of the waste is adjusted to 5 to 6 by adding 5 weight% NaOH aqueous solution into the waste, successively. The pH-adjusted terephthalic acid production waste is transferred into the precipitation reactor 10.
[12]
[13] Then, NaHCO slurry, which is prepared by mixing NaHCO and water, is added 3 3 into the precipitation reactor 10, into which the pH-adjusted terephthalic acid production waste is also added. The amount of water mixed with NaHCO is 3 preferably 1 to 3 times by weight with respect to that of NaHCO , and more preferably 3 1.5 to 2.5 times. The solubility of NaHCO in water is generally 7 to 8 at room 3 temperature, and increases to 13 as the temperature increases. However, in the present invention, excess NaHCO is used considering the amount of NaHCO consumed in 3 3 the following chemical reaction and precipitation step. If the amount of water is less than 1 time with respect to the amount of NaHCO , NaHCO can not be adequately 3 3 dissolved or dispersed in water, and if the amount of water is more than 3 times with respect to the amount of NaHCO , there is a problem in that the productivity can be de- 3 teriorated due to the excess water. In addition, the amount of NaHCO is preferably 2 3 to 2.2 times with respect to the amount of Co and Mn in the terephthalic acid production waste. If the amount of NaHCO is less than 2 times, there is a problem in 3 that the unreacted Co and Mn can be remained in the reaction solution, and if the amount of NaHCO is more than 2.2 times, there is a problem in that excess NaHCO 3 3 is not reacted and remained in the reaction solution, and Na concentration can be undesirably increased in the reaction solution.
[14]
[15] Then, the mixture of NaHCO slurry and the waste of terephthalic acid production is heated to the temperature of preferably 40 to 90°C, more preferably 60 to 85°C, and most preferably about 80°C. If the temperature of the mixture is less than 40°C, the excess NaHCO can not be dissolved sufficiently and carbonate group does not suf- 3 ficiently activated, and if the temperature is more than 90°C, there is a problem in that NaHCO can be evaporated without reacting with Co and Mn. The heating step can be 3 carried out after mixing the waste and the slurry. Alternatively, the waste and the
slurry are heated separately, and the heated waste and the heated slurry can be mixed. By maintaining the mixture of NaHCO slurry and the waste at the temperature of 40 3 to 90°C, the chemical reaction of organic impurities and the precipitation of catalyst metal is carried out simultaneously. Therefore, the present invention directly utilizes 2- CO /HCO , which is produced by heating the NaHCO slurry, for the above- 3 3 3 mentioned chemical reaction and precipitation, rather than using carbonic acid gas of scrubber for the chemical reaction of organic impurities. In the chemical reaction, the organic impurities in terephthalic acid production waste are converted to organic 2- carboxylic acid due to CO /HCO produced by decompsition of NaHCO , and the 3 3 3 produced organic carboxylic acid reacts with sodium(Na) in the precipitation reactor 10 to be dissolved in the reaction solution. Meanwhile, the valuable catalyst metal such as Co, Mn or so on is precipitated by the reaction with the carbonate group. Thus, when the reaction is complete, the organic impurities dissolve in the reaction solution, and exist in a liquid phase, and catalyst metal is precipitated in the form of more stable salt. The produced metal precipitate exists in the form of very stable salt, and can be stably stayed in the precipitation reactor 10 for a long time. Therefore, the large quantity of waste can be reacted in the precipitation reactor 10. The reaction solution is generally neutral, and specifically pH thereof is 6 to 8, for example pH thereof is 7.5. Accordingly, the reaction conditions are mild, and the disposal of the reaction solution, from which the metal precipitate is recovered, is easy and environmentally favorable.
[16]
[17] Then, the pure metal precipitate such as Co or Mn precipitate is separated from the reaction solution by means of, for example, filter 20 (See Fig. 1) or centrifugal separator. In the method for recovering catalyst metal according to the present 2- invention, CO /HCO has higher activity than the carbonate salt used in the con- 3 3 ventional metal recovery method. Therefore, the metal precipitate can be recovered more easily. The method of the present invention is applicable not only for the recovery of Co or Mn, but also for the recovery of other metal which can react with carbonate ion.
[18]
[19] Hereinafter, the preferable examples are provided for better understanding of the present invention. However, the present invention is not limited to the following examples.
[20]
[21] [Example 1]
[22] 48 weight% aqueous NaOH solution was added to waste of terephthalic acid production to adjust pH of the waste to 4, and 500g of the pH-adjusted waste was transferred into a precipitation reactor. NaHCO slurry, which was prepared by mixing 3 75g of NaHCO and 150g of water, was added into the precipitation reactor, and the 3 mixture was reacted and remained for 45 minutes. The temperature of NaHCO slurry, 3 and the temperature of the precipitation reactor were maintained at 75°C. After completion of the reaction, the reaction solution was filtered to recover the pure metal precipitate.
[23] [24] [Example 2] [25] Except for adjusting pH of the waste to 6, and using 70g of NaHCO and 140g of water, the metal precipitate was recovered in the same manner as described in Example 1.
[26] [27] [Comparative Example 1] [28] Except for using 70g of Na CO and 300g of water instead of 75g of NaHCO and 2 3 3 150g of water, the metal precipitate was recovered in the same manner as described in Example 1.
[29] [30] [Comparative Example 2] [31] Except for using 40g of NaOH and 80g of water instead of 75g of NaHCO and 3 150g of water, the metal precipitate was recovered in the same manner as described in Example 1,
[32] [33] The reaction conditions of Examples 1-2 and Comparative Examples 1-2, pH of the reaction solution and filterability of the reaction solution are set forth in the following Table 1.
[34] Table 1
[35] As shown in Table 1, the amount of alkalinizing agent used in Example 1 was more than that used in Example 2. This is due to the fact that the amount of alkalinizing agent, which is required in the precipitation reaction, increases when pH of the waste is low. In Table 1, pH of the reaction solution after coirnietion of reaction is the result of actual reaction and was not artificially controlled. In the above Examrles and Comparative examrles, the amount of the alkalinizing agent was twice by weight as much as the amount required in the precipitation reaction, which is resulted from the fact that the alkalinizing agent was used to remove the organic impurities with the increase of pH. Rom Table 1, it is clear that the reaction solution of Exarrnies is neutral, pH of which is about 7.5, and has good filterability, while those of Comparative examrles is strongly alkaline, and doesn't have good filterability.
[36]
[37] The amounts of Co, Mn, Fe and Na in the metal precipitate, the amount of the organic impurities in the metal precipitate, Co recovery efficiency, and Mn recovery efficiency are measured using chelatometry and elemental analyzer, and the results are set forth in the following Table 2. [38] Table 2
[39] From Table 2, it is clear that the recovery efficiency of catalyst metal is desirable, an dd ppuurree c catalyst metals can be obtained in Examries utilizing NaHCO for metal pre- 3 cipitation.
[40] [41] The metal salt, filterability thereof, pH of the reaction solution and metal oxidation state during the reaction are set forth in the following Table 3.
[42] Table 3
[43] From Table 3, it is clear that the more favorable metal salt can be obtained in mild conditions when NaHCO is used for the metal precipitation. 3
[44] [45] While the present invention has been described with respect to certain preferred em bodiments and examples only, other modifications and variations may be made without departing from the spirit and scope of the present invention as set forth in the following claims.
Claims
[1] A method for recovering catalyst metal from waste of terephthalic acid production, comprising the steps of: adjusting pH of the waste of terephthalic acid production to 2.5 to 7; adding NaHCO slurry, which is prepared by mixing NaHCO and water, into a 3 3 precipitation reactor, into which the waste of terephthalic acid production is added; heating a mixture of the waste of terephthalic acid production and NaHCO 3 slurry; and separating a metal precipitate from the reaction mixture.
[2] The method for recovering catalyst metal according to claim 1, wherein pH of the waste of terephthalic acid production is adjusted to 4 to 6. [3] The method for recovering catalyst metal according to claim 1, wherein the amount of water mixed with NaHCO is 1 to 3 times by weight with respect to that of NaHCO .
3
[4] The method for recovering catalyst metal according to claim 1, wherein the amount of NaHCO is 2 to 2.2 times with respect to the amount of Co and Mn in 3 the waste of terephthalic acid production. [5] The method for recovering catalyst metal according to claim 1, wherein the mixture of NaHCO slurry and the waste of terephthalic acid production is 3 heated to the temperature of 40 to 90°C. [6] The method for recovering catalyst metal according to claim 1, wherein the metal precipitate is Co and/or Mn precipitate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2003-0083208 | 2003-11-19 | ||
| KR20030083208A KR100575192B1 (en) | 2003-11-19 | 2003-11-19 | Method for recovering cobalt and manganese from waste catalyst of terephthalic acid production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2005049873A1 true WO2005049873A1 (en) | 2005-06-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/KR2004/002978 WO2005049873A1 (en) | 2003-11-19 | 2004-11-17 | Method for recovering catalyst metal from waste of terephthalic acid production |
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| Country | Link |
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| KR (1) | KR100575192B1 (en) |
| WO (1) | WO2005049873A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7326808B2 (en) | 2006-03-01 | 2008-02-05 | Eastman Chemical Company | Polycarboxylic acid production system employing cooled mother liquor from oxidative digestion as feed to impurity purge system |
| US7326807B2 (en) | 2006-03-01 | 2008-02-05 | Eastman Chemical Company | Polycarboxylic acid production system with enhanced heating for oxidative digestion |
| US7420082B2 (en) | 2006-03-01 | 2008-09-02 | Eastman Chemical Company | Polycarboxylic acid production system employing hot liquor removal downstream of oxidative digestion |
| US7772424B2 (en) | 2006-03-01 | 2010-08-10 | Eastman Chemical Company | Polycarboxylic acid production system employing enhanced evaporative concentration downstream of oxidative digestion |
| US7816556B2 (en) | 2006-03-01 | 2010-10-19 | Eastman Chemical Company | Polycarboxylic acid production system employing enhanced multistage oxidative digestion |
| US7829037B2 (en) | 2006-03-01 | 2010-11-09 | Eastman Chemical Company | Oxidation system with sidedraw secondary reactor |
| CN101963785A (en) * | 2010-09-17 | 2011-02-02 | 南京工业大学 | On-line control method for oxidation mother liquor filter process in purified terephthalic acid production |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200061616A (en) | 2018-11-26 | 2020-06-03 | 롯데케미칼 주식회사 | Method for Recovering Metal Catalysts Comprising Cobalt and Manganese |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53122694A (en) * | 1977-04-01 | 1978-10-26 | Matsuyama Sekyu Kagaku Kk | Method of collecting liquid phase oxidation heavy metal catalyst |
| US4311521A (en) * | 1980-10-01 | 1982-01-19 | Standard Oil Company (Indiana) | Membrane separation of catalyst metals from trimellitic acid production and separation of cobalt from manganese |
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2003
- 2003-11-19 KR KR20030083208A patent/KR100575192B1/en active IP Right Grant
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2004
- 2004-11-17 WO PCT/KR2004/002978 patent/WO2005049873A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53122694A (en) * | 1977-04-01 | 1978-10-26 | Matsuyama Sekyu Kagaku Kk | Method of collecting liquid phase oxidation heavy metal catalyst |
| US4311521A (en) * | 1980-10-01 | 1982-01-19 | Standard Oil Company (Indiana) | Membrane separation of catalyst metals from trimellitic acid production and separation of cobalt from manganese |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7326808B2 (en) | 2006-03-01 | 2008-02-05 | Eastman Chemical Company | Polycarboxylic acid production system employing cooled mother liquor from oxidative digestion as feed to impurity purge system |
| US7326807B2 (en) | 2006-03-01 | 2008-02-05 | Eastman Chemical Company | Polycarboxylic acid production system with enhanced heating for oxidative digestion |
| US7420082B2 (en) | 2006-03-01 | 2008-09-02 | Eastman Chemical Company | Polycarboxylic acid production system employing hot liquor removal downstream of oxidative digestion |
| US7772424B2 (en) | 2006-03-01 | 2010-08-10 | Eastman Chemical Company | Polycarboxylic acid production system employing enhanced evaporative concentration downstream of oxidative digestion |
| US7816556B2 (en) | 2006-03-01 | 2010-10-19 | Eastman Chemical Company | Polycarboxylic acid production system employing enhanced multistage oxidative digestion |
| US7829037B2 (en) | 2006-03-01 | 2010-11-09 | Eastman Chemical Company | Oxidation system with sidedraw secondary reactor |
| US8153840B2 (en) | 2006-03-01 | 2012-04-10 | Grupo Petrotemex, S.A. De C.V. | Oxidation system with sidedraw secondary reactor |
| EP2574606A1 (en) | 2006-03-01 | 2013-04-03 | Grupo Petrotemex, S.A. De C.V. | Polycarboxylic acid production system employing cooled mother liquor from oxidative digestion as feed to impurity purge system |
| CN101963785A (en) * | 2010-09-17 | 2011-02-02 | 南京工业大学 | On-line control method for oxidation mother liquor filter process in purified terephthalic acid production |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100575192B1 (en) | 2006-04-28 |
| KR20050049279A (en) | 2005-05-25 |
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