EP2158039A2 - Process for the recovery of oxidation catalyst using ion exchange resins - Google Patents
Process for the recovery of oxidation catalyst using ion exchange resinsInfo
- Publication number
- EP2158039A2 EP2158039A2 EP08827459A EP08827459A EP2158039A2 EP 2158039 A2 EP2158039 A2 EP 2158039A2 EP 08827459 A EP08827459 A EP 08827459A EP 08827459 A EP08827459 A EP 08827459A EP 2158039 A2 EP2158039 A2 EP 2158039A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- exchange resin
- heavy metals
- anion exchange
- contacting
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/74—Regeneration or reactivation of catalysts, in general utilising ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/403—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
- B01J41/05—Processes using organic exchangers in the strongly basic form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/05—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds
- B01J49/08—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds containing cationic and anionic exchangers in separate beds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
- B01J49/53—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for cationic exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
- B01J49/57—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for anionic exchangers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to a process for recovery of heavy metals and halogens using a series of ion exchange and chelating resins.
- Terephthalic acid is one such carboxylic acid that is used in the production of many different polymers, including polyethylene terephthalate (PET).
- PET polyethylene terephthalate
- Terephthalic Acid is produced by direct oxidation of p-xylene, catalyzed by heavy metals, such as Co and Mn, and a radical initiator, such as bromine.
- the oxidized product is subsequently crystallized and subjected to solid liquid separation, producing i) a solid stream comprising the product, ii) a mother liquor stream to be partially recycled to the oxidation process, and iii) a liquid stream.
- the liquid stream is processed for solvent recovery, and in this solvent recovery operation, the catalysts and radical initiators present in the liquid stream are either lost or only partially recovered by means of low-efficient chemical and/or physical methods. Moreover when low purity feed stocks are used for the production of aromatic carboxylic acids, the liquid stream has to be increased relative to the other streams, increasing the value of the catalysts and initiator lost through the liquid stream.
- the present invention is a process for the removal and recovery of at least one heavy metal and at least one halogen from a liquid stream in a chemical process comprising the steps of: a) contacting the liquid stream with a strong base anion exchange resin; and b) contacting a discharge stream from step (a) with a chelating cation exchange resin.
- the recovery process optionally includes a step regenerating the anion exchange resin by contacting the anion exchange resin with an anion exchange resin regeneration solution to form recovered heavy metals and halogens.
- the recovery process of the present invention also includes a step of regenerating the chelating cation exchange resin to form recovered heavy metals and halogens.
- the present invention is a process for the removal and recovery of i) at least one heavy metal selected from the group consisting of Co, Mn, and a combination thereof, and ii) bromine, from a liquid stream in a chemical process, the process for the removal and recovery comprising the steps of: a) contacting the liquid stream with a strong base anion exchange resin in halogenide form; b) contacting a discharge stream from step (a) with a chelating cation exchange resin; c) regenerating the anion exchange resin in step a by contacting the anion exchange resin with an anion exchange resin regeneration solution comprising water and acetic acid to form recovered heavy metals and bromine; d) regenerating the chelating cation exchange resin by contacting the chelating cation exchange resin with a regeneration primer comprising HBr and thereafter contacting the chelating cation exchange resin with a regeneration solution comprising water to form recovered heavy metals and bromine; e) purifying the recovered heavy metals and
- the present invention provides a method for the recovery of metals and halogens without the need for pretreatment of the liquid stream or extra processing steps.
- Figure 1 is a schematic diagram of one embodiment of a recovery system of the present invention.
- Figure 2 is a schematic diagram of another embodiment of a recovery system of the present invention.
- the present invention is a method for the recovery of catalyst used in a chemical process.
- the chemical process is a liquid phase oxidation process of alkyl aromatics, including but not limited to di- and tri methylbenzene that produces one or more liquid streams containing the catalyst.
- the liquid stream(s) is withdrawn from the oxidation process, then separated to produce a solid-containing product stream, a mother liquor stream, and a liquid stream, wherein the liquid stream comprises catalysts, reaction solvent, reaction intermediates, reaction byproducts and corrosion products.
- liquid phase oxidation processes include the production of terephthalic acid, isophthalic acid and trimellitic acid.
- terephthalic acid for example, comprises the oxidation of p-xylene to form terephthalic acid.
- the catalysts used in the liquid phase oxidation and ending up in the liquid stream comprise heavy metals and/or halogens.
- the heavy metals comprise one or more of cobalt, manganese, cerium, zirconium and hafnium; and the halogen comprises bromine.
- Figure 1 shows one embodiment of a recovery system 10 that can be used for the present invention. As shown, recovery system 10 comprises a reservoir 11, a column 13 containing an ion exchange resin, and a bed 17 containing a chelating resin.
- a liquid stream 12 is withdrawn from reservoir 11.
- the configuration of reservoir 11 is not critical to the present invention, and as with most chemical processing systems, the nature of the chemical process will dictate the configuration and materials of construction of the reservoir 11 and other auxiliary equipment.
- the concentration of heavy metals and halogens in the liquid stream 12 is not critical to the present invention, and the present invention is effective with nearly any concentration of heavy metals and/or halogens.
- Typical concentration ranges of heavy metals and halogens in a liquid stream can be, for example, a bromide concentration of between 200 and 1000 parts per million (ppm); a cobalt concentration of between 100 ppm and 800 ppm; and a manganese concentration of between 200 ppm and 1000 ppm.
- the liquid stream is fed from reservoir 11 to ion exchange resin bed 13, where the liquid stream comes into contact with at least one ion exchange resin as it passes through ion exchange resin bed 13.
- the temperature of the liquid stream 12 when contacting the ion exchange resin is in the range of from 20 - 150 0 C, more preferably from 40-100 0 C, and most preferably from 65-100 0 C.
- the ion exchange resin is a strong base anion exchange resin selected to absorb at least a portion of heavy metals and halogens from the liquid stream.
- the strong base anion exchange resin is a strong base anion exchange resin in the halide form, and more preferably a chlorinated or brominated anion exchange resin.
- the strong base anion exchange functional group is an amine group.
- the strong base anion exchange resin is a strong base quaternary amine anion exchange resin in the bromide form.
- the conversion of a strong base anion exchange resin to the bromide form can be obtained by washing the bed of the resin, in any form, with 10-50 times the resin bed volume (defined herein as the volume of the ion exchange resin bed) of a strong base solution and then with 5- 20 resin bed volume of a solution containing bromide, preferably at a concentration of at least 3 wt % bromide.
- the strong base anion exchange resin can be supported on any matrix.
- the strong base anion exchange resin is supported on a styrene-based matrix, and more preferably a styrene-divinylbenzene matrix.
- the direction of flow of the liquid stream through resin bed 13 is not critical. However, as shown in Figure 1 , typically the liquid stream will be fed to the top of resin bed 13 such that it flows downward through resin bed 13.
- Discharge stream 16 from column 13 comprises the reaction solvent, residual catalysts not absorbed by the strong base anion exchange resin, reaction byproducts, reaction intermediates and corrosion products.
- Discharge stream 16 is fed to bed 17 where it comes into contact with a chelating resin.
- the chelating resin absorbs remaining heavy metals and/or halogens such that the resulting effluent stream 18 is substantially free of heavy metal catalysts and/or halogens.
- Effluent stream 18 thus consists essentially of reaction byproducts, reaction intermediates, most of the corrosion products.
- the chelating resin in bed 17 is a resin selected to absorb heavy metals and/or halogens, and more particularly, cobalt, manganese, cerium, zirconium, hafnium bromine, from the liquid stream.
- the chelating group of the chelating resin is a carboxylic acid chelating group, more preferably a dicarboxylic acid group.
- the chelating resin is an imido diacetic acid resin.
- the chelating resin can be in any form such as, for example, the sodium or hydrogen form, and more preferably the hydrogen form.
- the chelating resin can be supported on any matrix.
- the chelating resin is supported on a styrene-based matrix, and more preferably a styrene-divinylbenzene matrix.
- the direction of flow of discharge stream 16 through chelating resin bed 17 is not critical. However, as shown in Figure 1, typically the discharge stream 16 will be fed to the top of bed 17 such that it flows downward through bed 17.
- the anion exchange resin in column 13 and the chelating resin in bed 17 will become fully loaded with heavy metals and/or halogens and therefore must be regenerated.
- a resin bed is typically sized to last for a specified period of time before regeneration is required, or that the concentration levels of heavy metals and/or halogens in effluent stream 18 will change, signaling a need for regeneration.
- the heavy metals and/or halogens are recovered and optimally may be used in the production process for the aromatic carboxylic acids.
- the anion exchange resin is contacted with an anion exchange resin regeneration solution.
- the anion exchange resin regeneration solution comprises water or a combination of water and acetic acid.
- the concentration of water in the anion exchange resin regeneration solution is from 10 to 100% by weight, and more preferably from 30 to 70 % by weight.
- the concentration of acetic acid in the anion exchange resin regeneration solution is from 90 to 0% by weight, and more preferably from 70 to 30 % by weight.
- the chelating resin is first contacted with a regeneration primer and then contacted with a chelating cation exchange resin regeneration solution.
- the regeneration primer comprises an acid such as hydrochloric acid or hydrobromic acid and may also include acetic acid.
- the concentration of hydrobromic acid or hydrochloric acid in the regeneration primer is from 1-20% by weight, more preferably from 2-10% by weight, and even more preferably from 3-6% by weight.
- the concentration of acetic acid in the regeneration primer is from 0 to 98% by weight, more preferably from 10-95% by weight, and even more preferably from 85-90% by weight.
- water can be added to the regeneration primer in a preferred concentration of from 1.5-100% by weight, more preferably from 3-50% by weight, and even more preferably from 4-35% by weight.
- the volume of the regeneration primer used is selected in order to feed to the resin 3-10 g of bromide for every 1 gram of absorbed metal.
- a portion of the heavy metals are recovered. For example, when cobalt and manganese are the heavy metals, up to 10% of the cobalt and 50% of the manganese loaded on the chelating resin may be recovered from the chelating resin during this step.
- the chelating cation exchange resin regeneration solution comprises water or a combination of water and acetic acid.
- concentration of water in the chelating cation exchange resin regeneration solution is from 30 to 100 weight %, more preferably from 50 to 100 wt %, and even more preferably from 80 to 100 wt%.
- concentration of acetic acid in the chelating cation exchange resin regeneration solution is from 0 to 30%.
- the resulting stream contains the recovered heavy metals and halogens in a ratio of halide to heavy metals of from about 3 to about 10.
- the ratio of Br- : (Co + Mn) is from about 2 to about 10, more preferably from 2 to 8, and even more preferably from 2 to 5.
- the recovery system 20 in Figure 2 comprises reservoir 21 , and chelating resin bed 23.
- the chelating resin is selected such that only the chelating resin is needed to recover the heavy metals and halogens, and an anion exchange resin is not needed. Otherwise, bed 23 operates in the same manner as bed 17 in the embodiment depicted in Figure 1.
- Effluent stream 24 has similar properties to those of effluent stream 18 in the embodiment depicted in Figure 1.
- the recovered heavy metals and/or halogens are purified before being used in the aromatic carboxylic acid process.
- Such purification step involves contacting the recovered heavy metals and halogens with a strong base anion exchange resin.
- the strong base anion exchange resin used for purification is in hydroxide or acetate form, and more preferably in the hydroxide form.
- feed stream 19 contains the recovered heavy metals and halogens to be purified.
- feed stream 25 contains the recovered heavy metals and halogens to be purified.
- Feed stream 19 or feed stream 25 is fed to a bed 40 containing the strong base anion exchange resin used for purification.
- Feed stream 19 or feed stream 25 can be fed to bed 40 either in series with the strong base anion resin bed and chelating cation exchange resin beds 17/23, or by means of a buffer vessel 30 equipped with a pump.
- Feed stream 19 or feed stream 25 optimally also comprises at least 35% water so as to optimize the efficiency of the purification step and of the operation of the strong base anion exchange resin in the OH- form, 40, as illustrated in Fig. 2.
- stream 41, containing purified heavy metals and halogens may be fed back to the oxidation process.
- the strong base anion exchange resin in bed 40 When the strong base anion exchange resin in bed 40 is fully loaded with bromide, it must be regenerated. Those skilled in the art understand that a resin bed is typically sized to last for a specified period of time before regeneration is required, or that the concentration levels of heavy metals and/or halogens in the outlet stream will change, signaling a need for regeneration. As illustrated in Fig. 2, the regeneration of this strong base anion exchange resin in bed 40 is carried out by washing with a regeneration agent that is a hot strong base solution, 42, such as, for example, NaOH solution or a KOH solution. The resulting solution from the outlet 43 is either sent for appropriate disposal or recycled.
- a regeneration agent that is a hot strong base solution, 42, such as, for example, NaOH solution or a KOH solution.
- DOWEX 2 IK-XLT means a strong base anion exchange resin in chloride form, manufactured by The Dow Chemical Company.
- DOWEX IDA-I means a chelating cation exchange resin manufactured by The Dow Chemical Company.
- Column A means a jacketed glass column packed with 250 ml of DOWEX 2 IK-XLT.
- Cold B means a jacketed glass column packed with 250 ml of DOWEX 2 IK-XLT.
- Column C means a jacketed glass column packed with 390 ml of DOWEX IDA-I.
- eed means a liquid stream from a PTA process to be treated according to the present invention.
- Effective means the discharge stream from Column A, B, or C.
- Eluted catalyst means the catalyst regenerated from column A, B, or C according to the present invention.
- DOWEX 2 IK-XLT was converted in bromide form as follows: 12 liters of NaOH 4% by weight aqueous solution were passed through the resin bed in column A, recirculating water at 70 0 C in the column jacket. Water was then passed through the resin bed up to neutral pH on the discharge side and then the resin bed was washed with 1000ml aqueous solution of HBr 4% by weight.
- DOWEX 2 IK-XLT in column B was converted in OH- form as follows: 12 liters of NaOH 4% by weight aqueous solution were passed through the resin bed in Column B, recirculating water at 70 °C in the column jacket. Water was then passed through the resin bed, up to neutral pH on the discharge side.
- Bromide was measured by titration with silver nitrate (AgNO 3 ) according to the following procedure: Weigh about 30g of the sample.
- Columns A and C are put in series, similar to the configuration shown in Fig. 1 , where resin bed 13 is Column A and resin bed 17 is Column C.
- the feed stream to column A comprises heavy metals and halogens, reaction solvent, oxidation reaction byproducts and oxidation reaction intermediates and corrosion product, with specific concentrations reported in Table 1.
- the feed stream is heated to 70 C. 500 ml of glacial acetic acid are pumped through the two resin beds, and then the stream to be tested is fed to the resin beds and recovered on the discharge side of the last bed.
- the column jacket temperatures are kept constant during the test. After absorption the tested stream is removed from the columns by pumping through the two beds glacial acetic acid.
- Example 3 The same procedures performed in Example 3 are repeated except that the water concentration of the feed stream is increased to 35% by weight. Relevant results are reported in Table 1.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US93240007P | 2007-05-31 | 2007-05-31 | |
PCT/IB2008/003112 WO2009022237A2 (en) | 2007-05-31 | 2008-05-16 | Process for the recovery of oxidation catalyst using ion exchange resins |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2158039A2 true EP2158039A2 (en) | 2010-03-03 |
Family
ID=40351232
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08827459A Withdrawn EP2158039A2 (en) | 2007-05-31 | 2008-05-16 | Process for the recovery of oxidation catalyst using ion exchange resins |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP2158039A2 (zh) |
JP (1) | JP5296781B2 (zh) |
KR (1) | KR101467603B1 (zh) |
CN (1) | CN101952039B (zh) |
BR (1) | BRPI0811377A2 (zh) |
RU (1) | RU2009149338A (zh) |
WO (1) | WO2009022237A2 (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011102479A1 (ja) * | 2010-02-19 | 2011-08-25 | 三菱瓦斯化学株式会社 | 芳香族カルボン酸類製造プロセスの触媒回収に用いるピリジン環含有キレート樹脂の前処理方法 |
JP5655055B2 (ja) * | 2010-02-19 | 2015-01-14 | 三菱瓦斯化学株式会社 | テレフタル酸製造プロセスの触媒回収に用いるピリジン環含有キレート樹脂の前処理方法 |
DE102013001972A1 (de) * | 2013-02-05 | 2014-08-07 | Thyssenkrupp Industrial Solutions Ag | Verfahren zur selektiven Entfernung von Katalysatorbestandteilen aus Abströmen von Oxidationsreaktionen aromatischer Verbindungen, dafür geeignete Anlage und Verwendung |
EP2774490B1 (en) | 2013-03-06 | 2018-04-25 | Cargill, Incorporated | Syrup purification by capacitive deionization |
KR102067687B1 (ko) | 2016-03-11 | 2020-02-11 | 주식회사 엘지화학 | 열안정성 및 가공성이 향상된 폴리알킬렌 카보네이트를 포함하는 수지 조성물의 경제적 제조방법 |
CN107555654A (zh) * | 2017-09-25 | 2018-01-09 | 浙江绿维环境科技有限公司 | 一种用于金属工业冷却***的中水回用工艺 |
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JPS557300B2 (zh) * | 1973-03-30 | 1980-02-23 | ||
JPS5419399B2 (zh) * | 1973-04-26 | 1979-07-14 | ||
JPS53104590A (en) * | 1977-02-24 | 1978-09-11 | Asahi Chem Ind Co Ltd | Recovery method for liquid-phase oxidation catalyst and solvent |
GB1595904A (en) * | 1977-04-25 | 1981-08-19 | Ici Ltd | Recovery catalyst values |
JPH05221655A (ja) * | 1992-02-15 | 1993-08-31 | Mitsubishi Heavy Ind Ltd | 塩酸水溶液中の塩化鉄の回収方法 |
GB9305902D0 (en) * | 1993-03-22 | 1993-05-12 | Bp Chem Int Ltd | Process |
KR100321476B1 (ko) * | 1995-01-07 | 2002-07-31 | 에스케이 주식회사 | 트리멜리트산(trimellitic acid)제조용 산화촉매의 분리방법 |
US5955394A (en) * | 1996-08-16 | 1999-09-21 | Mobile Process Technology, Co. | Recovery process for oxidation catalyst in the manufacture of aromatic carboxylic acids |
JPH10176532A (ja) * | 1996-12-16 | 1998-06-30 | Sanshin Seisakusho:Kk | エンジン冷却液の再生方法 |
US5880313A (en) * | 1997-09-09 | 1999-03-09 | Mitsubishi Gas Chemical Company, Inc. | Process for producing aromatic carboxylic acid |
MXPA02001652A (es) * | 1999-08-17 | 2002-08-06 | Mobile Process Technology Co | Proceso de recuperacion del catalizador de oxidacion en la elaboracion de acidos carboxilicos aromaticos. |
AU5490799A (en) * | 1999-08-17 | 2001-03-13 | Mobile Process Technology, Co. | Process for the purification of wash water from the production of aromatic acids |
JP4788023B2 (ja) * | 2000-06-27 | 2011-10-05 | 三菱瓦斯化学株式会社 | 液相酸化反応母液からの触媒成分の回収方法 |
US6825387B2 (en) * | 2002-10-15 | 2004-11-30 | Kellogg Brown & Root, Inc. | Low sodium cleavage product |
US7527733B2 (en) * | 2004-09-30 | 2009-05-05 | The University Of Southern California | Chelating agents for heavy metal removal |
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2008
- 2008-05-16 EP EP08827459A patent/EP2158039A2/en not_active Withdrawn
- 2008-05-16 WO PCT/IB2008/003112 patent/WO2009022237A2/en active Application Filing
- 2008-05-16 CN CN200880017856.2A patent/CN101952039B/zh active Active
- 2008-05-16 KR KR1020097024810A patent/KR101467603B1/ko active IP Right Grant
- 2008-05-16 BR BRPI0811377-7A2A patent/BRPI0811377A2/pt not_active Application Discontinuation
- 2008-05-16 JP JP2010509919A patent/JP5296781B2/ja not_active Expired - Fee Related
- 2008-05-16 RU RU2009149338/04A patent/RU2009149338A/ru unknown
Non-Patent Citations (1)
Title |
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Also Published As
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WO2009022237A2 (en) | 2009-02-19 |
WO2009022237A3 (en) | 2009-10-01 |
KR20100017447A (ko) | 2010-02-16 |
JP2010527785A (ja) | 2010-08-19 |
KR101467603B1 (ko) | 2014-12-01 |
CN101952039A (zh) | 2011-01-19 |
BRPI0811377A2 (pt) | 2014-12-09 |
CN101952039B (zh) | 2015-05-20 |
WO2009022237A9 (en) | 2009-08-13 |
JP5296781B2 (ja) | 2013-09-25 |
RU2009149338A (ru) | 2011-07-10 |
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