CN101952039A - Process for the recovery of oxidation catalyst using ion exchange resins - Google Patents
Process for the recovery of oxidation catalyst using ion exchange resins Download PDFInfo
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- CN101952039A CN101952039A CN2008800178562A CN200880017856A CN101952039A CN 101952039 A CN101952039 A CN 101952039A CN 2008800178562 A CN2008800178562 A CN 2008800178562A CN 200880017856 A CN200880017856 A CN 200880017856A CN 101952039 A CN101952039 A CN 101952039A
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- 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
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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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
- 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
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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
- 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
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- 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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- 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
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- 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
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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
- B01J49/50—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
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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- 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
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- 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
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Abstract
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 is disclosed. The process comprises the steps of contacting the liquid stream with a strong base anion exchange resin; and contacting a discharge stream from the first step 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. Optimally, 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.
Description
The cross reference of related application
The application requires in the rights and interests of the U.S. Provisional Application sequence number 60/932,400 of submission on May 31st, 2007.
Invention field
The present invention relates to a kind of method that is used to use a series of ion-exchanges and chelating resin recovery heavy metal and halogen.
Background of invention
Aromatic carboxylic acid's preparation is undertaken by the direct oxidation of aromatic hydrocarbon usually.Wherein, terephthalic acid (TPA) is a kind of such carboxylic acid that uses in the preparation of the many different polymer that comprise ethylene glycol terephthalate (PET).Terephthalic acid (TPA) prepares by the direct oxidation with the paraxylene of heavy metal such as Co and Mn and radical initiator such as bromine catalysis.Oxidation product subsequent crystallisation and carry out Separation of Solid and Liquid, thereby produce i) comprise the efflux of solids of product, ii) to partly be recycled to mother liquor stream and iii) liquid stream in the oxidation technology.Liquid stream is processed reclaiming solvent, and in this solvent recovery operation, be present in the catalyst in the liquid stream and radical initiator is lost or chemistry and/or physical method by poor efficiency only are partially recovered.In addition, when the low-purity raw material was used for aromatic carboxylic acid's preparation, liquid stream must increase with respect to other stream, thereby has increased by the catalyst of liquid flowing loss and the value of initator.
Recently carried out attempting to solve the catalyst loss in aromatic carboxylic acid's preparation process.For example, US 2002/0016500A1, US 3,959,449, US 4,202,797, US 4,162,991 and JP10015390A have all described and have been used to reclaim the component of catalyst such as the whole bag of tricks of heavy metal and/or halogen.Yet, above-mentioned prior art list of references has been described and need carry out pretreated method to one or more in the stream that relates in the technology that reclaims heavy metal or halogen, and/or needs to require to use the method for the additional processing step of expensive capital equipment.
Other trial that is used for heavy metal and halogen recovery of having described comprises the use of ion exchange resin.For example, US 4,238, and 294, US 5,880,313 and US 5,955,394 described and be used for by making spent ion exchange resin reclaim the method for heavy metal and/or halogen.Yet these lists of references need widely pre-treatment step or other to require the procedure of processing of expensive capital equipment.
Not needing the more efficient method that additional processing step or preliminary treatment contain the stream of heavy metal and halogen to reclaim and relatively large heavy metal and the halogen of purifying, will be an advantage in the technology of recovery heavy metal and halogen.The optimized mode of the recovery of heavy metal and halogen is utilized ion exchange resin, will be another advantage that reclaims in the technology of heavy metal and halogen.
Summary of the invention
In first aspect, the present invention is the method that is used for shifting out and reclaiming from the liquid stream of chemical technology at least a heavy metal and at least a halogen, said method comprising the steps of: liquid stream is contacted with strong basic type anion-exchange resin; With b) discharge currents from step (a) is contacted with the chelating cationic ion-exchange resin.Recovery method randomly comprises by making anion exchange resin and anion exchange resin actified solution contact the anion regenerant exchanger resin with the heavy metal of formation recovery and the step of halogen.Optimally, recovery method of the present invention comprises that also regeneration chelating cationic ion-exchange resin is to form the heavy metal that reclaims and the step of halogen.
In second aspect, the present invention is the method that is used for shifting out and reclaiming from the liquid stream of chemical technology the following: i) be selected from least a heavy metal the group of being made up of Co, Mn and their combination, ii) bromine, the described method that is used to shift out and reclaim may further comprise the steps: liquid stream is contacted with the strong basic type anion-exchange resin of halide mode; B) discharge currents from step (a) is contacted with the chelating cationic ion-exchange resin; C) by making anion exchange resin and the anion exchange resin actified solution that comprises water and acetate contact anion exchange resin among the regeneration step a, to form heavy metal and the bromine that reclaims; D) by the chelating cationic ion-exchange resin is contacted with the regeneration substrate (primer) that comprises HBr, make the chelating cationic ion-exchange resin contact the chelating cationic ion-exchange resin of regenerating then, thereby form heavy metal and the bromine that reclaims with the actified solution that comprises water; E) contact the heavy metal and the bromine of purifying recovery by the heavy metal that makes recovery with the bromine and the strong basic type anion-exchange resin of hydroxide form, thereby form the heavy metal and the bromine of purifying; And f) heavy metal and the bromine of use purifying in chemical technology.
The invention provides the preliminary treatment that do not need liquid stream or the method that is used to reclaim metal and halogen of additional processing step.
The accompanying drawing summary
Fig. 1 is the schematic diagram of an embodiment of recovery system of the present invention.
Fig. 2 is the schematic diagram of another embodiment of recovery system of the present invention.
Detailed Description Of The Invention
The present invention is the method that is used for being recovered in the catalyst that chemical technology uses.On the one hand, described chemical technology is the liquid phase oxidation technique that produces the Alkylaromatics of one or more liquid that contains catalyst streams, and described Alkylaromatics includes but not limited to dimethylbenzene and trimethylbenzene.In one embodiment, one or more liquid streams are extracted from oxidation technology, separate then, thereby produce product stream, mother liquor stream and the liquid stream that contains solid, wherein said liquid stream comprises catalyst, reaction dissolvent, reaction intermediate, byproduct of reaction and corrosion product.The example of liquid phase oxidation technique comprises the preparation of terephthalic acid (TPA), M-phthalic acid and trimellitic acid.For example, the preparation of terephthalic acid (TPA) comprises that p xylene oxidation is to form terephthalic acid (TPA).Catalyst in liquid stream that use in liquid phase oxidation and final comprises heavy metal and/or halogen.In many embodiments, for example, in terephthalic acid (TPA), M-phthalic acid and the trimellitic acid technology, heavy metal comprises one or more in cobalt, manganese, cerium, zirconium and the hafnium; And halogen comprises bromine.
Fig. 1 shows an embodiment that can be used for recovery system 10 of the present invention.As shown, recovery system 10 comprise storage tank 11, contain the post 13 of ion exchange resin and contain chelating resin the bed 17.
As shown in fig. 1, extract stream 12 from storage tank 11.The structure of storage tank 11 is not crucial for the present invention, and the same with most of chemical processing systems, and the person's character of chemical technology will be stipulated the structure and the building material of storage tank 11 and other auxiliary equipment.
Heavy metal and the halogen concentration in liquid stream 12 is not crucial for the present invention, and the present invention is all effective for the heavy metal and/or the halogen of any concentration almost.Heavy metal and the halogen typical concentration scope in liquid stream can for, for example, bromine concentration is between 200 and 1,000 hundred ten thousand/a (ppm); Cobalt concentration is between 100ppm and 800ppm; And manganese concentration is between 200ppm and 1000ppm.
Liquid stream is fed to ion exchange resin bed 13 from storage tank 11, there liquid stream when passing ion exchange resin bed 13 and at least a ion exchange resin come in contact.Optimally, the temperature when liquid flows 12 contact ions exchanger resins is at 20-150 ℃, more preferably 40-100 ℃, and most preferably in 65-100 ℃ the scope.
Ion exchange resin is to select to be used for to absorb the heavy metal of at least a portion and the strong basic type anion-exchange resin of halogen from liquid stream.Preferably, strong basic type anion-exchange resin is the strong basic type anion-exchange resin of halide mode, and is more preferably the anion exchange resin of chlorination or bromination.Preferably, strong base anion exchange functions group is an amido.Most preferably, strong basic type anion-exchange resin is the strong base quaternary amine anion exchange resin of bromide form.Anion exchange resin for the bromination form, as known in the art, strong basic type anion-exchange resin can obtain by the following method to the transformation of bromide form: in any form with the strong base solution of 10-50 times of resin bed volume (being defined as the volume of ion exchange resin bed herein), then with the preferred bromide concentration of 5-20 times of resin bed volume the solution washing resin bed that contains bromide at least 3 weight %.
Strong basic type anion-exchange resin can load on any matrix.Preferably, strong basic type anion-exchange resin loads on the styryl matrix, and more preferably styrene-divinylbenzene matrix.
Liquid stream is not crucial by the flow direction of resin bed 13.Yet as shown in fig. 1, liquid stream typically is fed to the top of resin bed 13, makes it flow downward by resin bed 13.
Chelating resin in the bed 17 is to select to be used for to absorb heavy metal and/or halogen, the more specifically resin of cobalt, manganese, cerium, zirconium, hafnium, bromine from liquid stream.Preferably, the chelation group of chelating resin is the carboxylic acid chelation group, more preferably the dicarboxyl acidic group.Most preferably, chelating resin is imido-acetic acid (imidodiacetic acid) resin.Chelating resin can be any form, for example, and sodium type or Hydrogen, and more preferably Hydrogen.
Chelating resin can load on any matrix.Preferably, chelating resin loads on the styryl matrix, and more preferably styrene-divinylbenzene matrix.
After a period of time, the same with most of ion exchange resin and chelating resin, the chelating resin in anion exchange resin in the post 13 and the bed 17 will become by heavy metal and/or the complete load of halogen, thereby must be reproduced.The capacity (size) with resin bed of those skilled in the art will recognize that typically is decided to be needs regeneration after continuing the specific time, thereby or the concentration level that flows out heavy metal in the logistics 18 and/or halogen change and send the signal that needs regeneration.In the process of regeneration step, heavy metal and/or halogen are reclaimed, and optimally can be used for aromatic carboxylic acid's preparation technology.
For the anion regenerant exchanger resin, anion exchange resin is contacted with the anion exchange resin actified solution.Preferably, the anion exchange resin actified solution comprises the combination of water or water and acetate.Preferably, the concentration of water in the anion exchange resin actified solution is 10 to 100 weight %, and more preferably 30 to 70 weight %.Preferably, the concentration of acetate in the anion exchange resin actified solution is 90 to 0 weight %, and more preferably 70 to 30 weight %.
For the chelating resin of regenerating, chelating resin is at first contacted with the regeneration substrate, contact with chelating cationic ion-exchange resin actified solution then.
The regeneration substrate comprises acid, such as hydrochloric acid or hydrobromic acid, and can comprise acetate.Preferably, hydrobromic acid or hydrochloric acid are 1-20 weight % in the concentration of regeneration in the substrate, more preferably 2-10 weight %, and more preferably 3-6 weight %.Preferably, acetate is 0 to 98 weight % in the concentration of regeneration in the substrate, more preferably 10-95 weight %, and more preferably 85-90 weight %.Randomly, can with 1.5-100 weight %, more preferably 3-50 weight % and more preferably the preferred concentration of 4-35 weight % add entry to regeneration in the substrate.Select the volume of employed regeneration substrate, with for the absorption metal of per 1 gram to the bromide of resin feeding 3-10g.In the process of this step, by resin adsorption, the heavy metal of a part is recovered together with bromide.For example, when cobalt and manganese are described heavy metal, can be in the process of this step reclaim 10% the cobalt at the most that loads on the chelating resin and 50% manganese from chelating resin.
Preferably, chelating cationic ion-exchange resin actified solution comprises the combination of water or water and acetate.Preferably, the concentration of water in chelating cationic ion-exchange resin actified solution is 30 to 100 weight %, more preferably 50 to 100 weight %, and more preferably 80 to 100 weight %, and the concentration of acetate in chelating cationic ion-exchange resin actified solution is 0 to 30%.Resulting stream contains the heavy metal and the halogen of recovery, and wherein the ratio of halide and heavy metal is about 3 to about 10.For example, in PTA technology, Br-: ratio (Co+Mn) is about 2 to about 10, more preferably 2 to 8, and more preferably 2 to 5.As described below then this is contained the heavy metal of recovery and the stream purifying of halogen.
Referring now to Fig. 2, the another kind of feasible alternative embodiment of recovery system 20.Recovery system 20 among Fig. 2 comprises storage tank 21 and chelating resin bed 23.As shown, selecting chelating resin to make only needs chelating resin to reclaim heavy metal and halogen, and does not need anion exchange resin.In addition, bed 23 with bed 17 embodiment shown in Figure 1 in identical mode turn round.The character of outflow logistics 24 and the character of the outflow logistics 18 in the embodiment shown in Fig. 1 are similar.
Optimally, heavy metal and/or the halogen that reclaims carried out purifying, be used for aromatic carboxylic acid's technology afterwards.Such purification step relates to the heavy metal that makes recovery and contacts with strong basic type anion-exchange resin with halogen.Preferably, the strong basic type anion-exchange resin that is used for purifying is the form of hydroxide or acetate, and the form of hydroxide preferably.
As shown in fig. 1, incoming flow 19 contains the heavy metal and the halogen of recovery to be purified.In the embodiment shown in Fig. 2, incoming flow 25 contains the heavy metal and the halogen of recovery to be purified.Incoming flow 19 or incoming flow 25 are fed in the bed 40 that contains the strong basic type anion-exchange resin that is useful on purifying.Incoming flow 19 or incoming flow 25 can be fed to the bed 40 of connecting with strong base resin anion (R.A.) bed and chelating cation exchange resin bed 17/23, or be fed to bed 40 by the buffer container 30 that disposes pump.Incoming flow 19 or incoming flow 25 optimally also comprise at least 35% water, so that with the efficiency optimizationization of the operation of the strong basic type anion-exchange resin 40 of purification step and OH-form as shown in Figure 2.After purification step, can get back in the oxidation technology containing the heavy metal of purifying and stream 41 chargings of halogen.
When the strong basic type anion-exchange resin in the bed 40 during by the complete load of bromide, it must be reproduced.The capacity with resin bed of those skilled in the art will recognize that typically is decided to be needs regeneration after continuing the specific time, thereby or the concentration level of heavy metal in the outlet stream and/or halogen will change to send and need the signal that regenerate.As shown in Figure 2, the regeneration of this strong basic type anion-exchange resin in the bed 40 is by being used as the hot strong base solution 42 of regenerative agent, and for example NaOH solution or KOH solution washing are finished.Resulting solution from outlet 43 is sent to suitably processing or recirculation.
Embodiment
Definition term among the embodiment:
The strong basic type anion-exchange resin of " DOWEX 21K-XLT " expression chloride form is produced by Dow Chemical.
The chelating cationic ion-exchange resin that " DOWEX IDA-1 " expression is produced by Dow Chemical.
" post A " expression is filled with the jacketed glass post of the DOWEX 21K-XLT of 250ml.
" post B " expression is filled with the jacketed glass post of the DOWEX 21K-XLT of 250ml.
" post C " expression is filled with the jacketed glass post of the DOWEX IDA-1 of 390ml.
The liquid stream that " charging " indicates to handle according to the present invention from PTA technology.
" effluent " expression is from the discharge currents of post A, B or C.
" wash-out catalyst " represented according to the present invention from the catalyst of post A, B or C regeneration.
The program of Shi Yonging in an embodiment:
Anion exchange resin is transformed into the program of bromide form:
As described below DOWEX 21K-XLT is transformed into the bromide form: the 4 weight %NaOH aqueous solution that make 12 liters are by the resin bed among the post A, the water of 70 ℃ of circulations in the post chuck.Make water pass through resin bed then,, use the 4 weight %HBr solution washing resin beds of 1000ml then until the pH neutrality of discharging side.
Anion exchange resin is transformed into the program of OH-form:
As described below the DOWEX 21K-XLT among the post B is transformed into the OH-form: the 4 weight %NaOH aqueous solution that make 12 liters are by the resin bed among the post B, the water of 70 ℃ of circulations in the post chuck.Make water pass through resin bed then, until the pH neutrality of discharging side.
The program that is used for the concentration of definite metal ion:
Use the concentration of atomic absorption spectrophotometer analyzer 300 definite metal ions of Perkin Elmer.The samples with water that will analyze is suitably diluted, and adopts following service condition to measure absorbance:
| Ion | Wavelength (nm) | C 2H 2Flow (ml/min) | Flow (ml/min) | Slit (nm) |
| Cobalt | 240.7 | 1.5 | Air 10 | 0.2 |
| Iron | 248.3 | 1.5 | Air 8 | 0.7 |
| Manganese | 279.5 | 1.5 | Air 10 | 0.2 |
The absorbance of the sample absorbance with the reference material that is used for atomic absorption spectrophotometer in the Normex bottle that contains the solution that concentration guarantees by the manufacturer is compared.Control software by instrument calculates the concentration of each single metal in mg/l automatically.
Be used to measure the program of bromide concentration:
Pass through with silver nitrate (AgNO according to following program
3) the titration determination bromide:
The sample of the about 30g of weighing.
The ammonium sulfate ferrous solution of 5ml and 1: 1 nitric acid of 5ml are joined in the flask.The final color of solution is a yellow green.
Add the 0.02N ammonium sulfocyanate (NH that 2-3 drips
4CNS) solution.Solution will become orange red.
Add excessive 0.02NAgNO
3Point to orange red disappearance.
Use NH
4The AgNO of CNS overtitration
3Orange red until reappearing.
Use formula: Br=(A-B) * N*79.9*100/P*1000 to carry out the calculating of bromide concentration, wherein:
The AgNO that A=consumes
3Ml;
The NH that B=consumes
4The ml of CNS;
N=is used for the equivalent concentration (0.02N) of the solution of titration; With
The P=example weight.
Embodiment 1
With post A and C series connection, be similar to the structure that shows among Fig. 1, wherein resin bed 13 is post A, and resin bed 17 is post C.Incoming flow to post A comprises heavy metal and halogen, reaction dissolvent, oxidation reaction by-products and oxidation reaction intermediate and corrosion product, and concrete concentration is reported in the table 1.Incoming flow is heated to 70C.Two resin beds are passed through in the glacial acetic acid pumping of 500ml, and the stream that will test is fed in the resin bed then, and reclaims in the discharge side of last bed.In test process, keep the post jacket temperature constant.After absorption, by two beds, will test stream and shift out from post by the pumping glacial acetic acid.By using 100% water as the regenerative agent that is used for post A, regenerate as the actified solution that the substrate that is used for post C and the conduct of 100% aqueous solution are used for post C by solution that acetate/HBr/ water=90/4/6 weight % forms.In the ending of test, with two resin beds of glacial acetic acid washing.Relevant data report is in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| The post of test | A C | C | B | B |
| Resinous type | DOWEX 21K-XLT (in post A, at first contact) DOWEX IDA-1 (in post C, second contact) | DOWEX IDA-1 | DOWEX 21K-XLT | DOWEX 21K-XLT |
| Flow (ml/min) | 58 | 70 | 50 | 50 |
| The volume of the solution of charging (ml) | 36800 | 23800 | 2550 | 2550 |
| Jacket temperature (℃) | 60 | 60 | 35 | 35 |
| Feed composition: Br (ppm) Co (ppm) Mn (ppm) Fe (ppm) H 2O | 390 200 422 2.5 | 416 295 520 3.3 | 32000 (77% absorption) 1800 (74% absorption), 2980 (44% absorption) 20% | 23200 (49% absorption) 1400 (3% absorption), 2310 (4% absorption) 35% |
| The effluent group | ||||
| Become: Br (ppm) Co (ppm) Mn (ppm) Fe (ppm) | 30 13 125 1.3 | 80 63 161 2.6 | ||
| The wash-out catalyst is formed: Br (ppm) Co (ppm) Mn (ppm) Fe (ppm) | 23924 2350 5188 6 | 19118 2199 3561 8 |
Embodiment 2
Except test pole C only, make structure be similar to shown in Fig. 2, its center pillar C is beyond the resin bed 23, repeats the program of using in embodiment 1.Regenerate as the actified solution that is used for post C as the substrate that is used for post C and 100% aqueous solution by using by the solution that acetate/HBr/ water=90/4/6 weight % forms.Related data is reported in the table 1.
Embodiment 3
Test pole B makes structure be similar to shown in Fig. 1 and Fig. 2, and its center pillar B is a resin bed 40.Representing the incoming flow of stream 19 among Fig. 1 and 2 and 25 composition to form respectively is reported in the table 1.Resin bed is passed through in the glacial acetic acid pumping of 500ml, and the stream that will test is fed in the resin bed then, and reclaims in the discharge side of bed self.In the process of test, keep the post jacket temperature constant.After absorption, by bed, the stream of testing is shifted out from post by pumps water.Related data is reported in the table 1.
Embodiment 4
Except the water concentration with incoming flow is increased to 35 weight %, repeat the same program that in embodiment 3, carries out.Correlated results is reported in the table 1.
Claims (21)
1. one kind is used for flowing the method that shifts out and reclaim at least a heavy metal and at least a halogen from the liquid of chemical technology, said method comprising the steps of:
A) described liquid stream is contacted with strong basic type anion-exchange resin; With
B) discharge currents from step (a) is contacted with the chelating cationic ion-exchange resin.
2. method according to claim 1, described method is further comprising the steps of:
C), thereby form heavy metal and the halogen that reclaims by making described anion exchange resin contact the described anion exchange resin of regenerating with the anion exchange resin actified solution.
3. method according to claim 2, wherein said anion exchange resin actified solution comprises water and acetate.
4. according to each described method in the claim 1 to 3, described method is further comprising the steps of:
D) the described chelating cationic ion-exchange resin of regeneration is to form heavy metal and the halogen that reclaims.
5. method according to claim 4, wherein step (d) comprising: described chelating cationic ion-exchange resin is contacted with the regeneration substrate, and described chelating cationic ion-exchange resin is contacted with chelating cationic ion-exchange resin actified solution.
6. method according to claim 5, wherein said regeneration substrate comprises hydrogen bromide or hydrogen chloride.
7. according to claim 5 or 6 described methods, wherein said chelating cationic ion-exchange resin actified solution is a water.
8. according to each described method among the claim 1-7, described method is further comprising the steps of:
E) heavy metal of the described recovery of purifying and halogen.
9. method according to claim 8, wherein step (e) comprises that the heavy metal that makes described recovery contacts with the strong basic type anion-exchange resin of halogen with hydroxide or acetate form, to form the heavy metal and the halogen of purifying.
10. method according to claim 9, described method is further comprising the steps of:
F) heavy metal and the halogen of the described purifying of use in described chemical technology.
11. according to each described method among the claim 1-10, wherein said heavy metal is Co, Mn, Ce, Zr, Hf or their combination.
12. according to each described method among the claim 1-11, wherein said chemical technology is terephthalic acid (TPA) preparation technology, M-phthalic acid technology or trimellitic acid technology.
13. according to each described method among the claim 1-12, wherein said halogen is Br.
14. according to each described method among the claim 1-13, wherein the described anion exchange resin among the step a is halogenation anion exchange resin.
15. method according to claim 14, wherein said anion exchange resin are the brominated anionic exchanger resins.
16. according to each described method among the claim 1-15, wherein the described chelate exchange resin in the step (b) is the imido-acetic acid resin.
17. one kind is used for flowing the method that shifts out and reclaim the following from the liquid of chemical technology: i) be selected from least a heavy metal the group of being made up of Co, Mn, Ce, Zr, Hf and their combination, ii) bromine, the described method that is used to shift out and reclaim may further comprise the steps:
A) described liquid stream is contacted with the strong basic type anion-exchange resin of halide mode;
B) discharge currents from step (a) is contacted with the chelating cationic ion-exchange resin;
C), thereby form heavy metal and the bromine that reclaims by making described anion exchange resin and the anion exchange resin actified solution that comprises water and acetate contact described anion exchange resin in the regeneration step (a);
D) by described chelating cationic ion-exchange resin is contacted with the regeneration substrate that comprises HBr, make described chelating cationic ion-exchange resin contact the described chelating cationic ion-exchange resin of regenerating with the actified solution that comprises water then, thereby form heavy metal and the bromine that reclaims;
E) contact the heavy metal and the bromine of the described recovery of purifying by the heavy metal that makes described recovery with the bromine and the strong basic type anion-exchange resin of hydroxide form, thereby form the heavy metal and the bromine of purifying; With
F) heavy metal and the bromine of the described purifying of use in described chemical technology.
18. method according to claim 6, wherein the described strong basic type anion-exchange resin among the step a is the brominated anionic exchanger resin.
19. according to claim 16 or 17 described methods, wherein said chelating cationic ion-exchange resin is the imido-acetic acid resin.
20. method that is used for shifting out and reclaiming from the liquid of PTA technology stream the following: i) be selected from least a heavy metal and ii) bromine the group of being made up of Co, Mn and their combination, the described method that is used to shift out and reclaim may further comprise the steps:
A) described liquid stream is contacted with the chelating cationic ion-exchange resin;
B) by described chelating cationic ion-exchange resin is contacted with the regeneration substrate that comprises HBr, make described chelating cationic ion-exchange resin contact the described chelating cationic ion-exchange resin of regenerating with the actified solution that comprises water then, thereby form heavy metal and the bromine that reclaims;
C) contact the heavy metal and the bromine of the described recovery of purifying by the heavy metal that makes described recovery with the bromine and the strong basic type anion-exchange resin of hydroxide form, thereby form the heavy metal and the bromine of purifying; With
D) heavy metal and the bromine of the described purifying of use in described PTA technology.
21. method according to claim 20, wherein said chelating cationic ion-exchange resin is the imido-acetic acid resin.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US93240007P | 2007-05-31 | 2007-05-31 | |
| US60/932,400 | 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 (2)
| Publication Number | Publication Date |
|---|---|
| CN101952039A true CN101952039A (en) | 2011-01-19 |
| CN101952039B CN101952039B (en) | 2015-05-20 |
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|---|---|---|---|
| CN200880017856.2A Active CN101952039B (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 (en) |
| JP (1) | JP5296781B2 (en) |
| KR (1) | KR101467603B1 (en) |
| CN (1) | CN101952039B (en) |
| BR (1) | BRPI0811377A2 (en) |
| RU (1) | RU2009149338A (en) |
| WO (1) | WO2009022237A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107555654A (en) * | 2017-09-25 | 2018-01-09 | 浙江绿维环境科技有限公司 | A kind of Treated sewage reusing technique for metal industry cooling system |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011102479A1 (en) * | 2010-02-19 | 2011-08-25 | 三菱瓦斯化学株式会社 | Pretreatment method for chelate resin having pyridine ring used for collecting catalyst in aromatic carboxylic acid production process |
| JP5655055B2 (en) * | 2010-02-19 | 2015-01-14 | 三菱瓦斯化学株式会社 | Pretreatment method of pyridine ring-containing chelate resin for catalyst recovery in terephthalic acid production process |
| DE102013001972A1 (en) * | 2013-02-05 | 2014-08-07 | Thyssenkrupp Industrial Solutions Ag | Process for the selective removal of catalyst components from effluents of oxidation reactions of aromatic compounds, suitable plant and use |
| EP2774490B1 (en) | 2013-03-06 | 2018-04-25 | Cargill, Incorporated | Syrup purification by capacitive deionization |
| KR102067687B1 (en) | 2016-03-11 | 2020-02-11 | 주식회사 엘지화학 | Economic manufacturing method of polyalkylenecarbonate with improved thermal stability and processability |
Family Cites Families (15)
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| JPS557300B2 (en) * | 1973-03-30 | 1980-02-23 | ||
| JPS5419399B2 (en) * | 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 (en) * | 1992-02-15 | 1993-08-31 | Mitsubishi Heavy Ind Ltd | Recovery of iron chloride in aqueous hydrochloric acid |
| GB9305902D0 (en) * | 1993-03-22 | 1993-05-12 | Bp Chem Int Ltd | Process |
| KR100321476B1 (en) * | 1995-01-07 | 2002-07-31 | 에스케이 주식회사 | Method for regenerating oxidizing catalyst for use in fabrication of trimellitic acid |
| 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 (en) * | 1996-12-16 | 1998-06-30 | Sanshin Seisakusho:Kk | Regenerating method for engine cooling liquid |
| US5880313A (en) * | 1997-09-09 | 1999-03-09 | Mitsubishi Gas Chemical Company, Inc. | Process for producing aromatic carboxylic acid |
| MXPA02001652A (en) * | 1999-08-17 | 2002-08-06 | Mobile Process Technology Co | Recovery process for oxidation catalyst in the manufacture of aromatic carboxylic acids. |
| 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 (en) * | 2000-06-27 | 2011-10-05 | 三菱瓦斯化学株式会社 | Method for recovering catalyst components from liquid phase oxidation reaction mother liquor |
| 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 |
-
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/en active Active
- 2008-05-16 KR KR1020097024810A patent/KR101467603B1/en active IP Right Grant
- 2008-05-16 BR BRPI0811377-7A2A patent/BRPI0811377A2/en not_active Application Discontinuation
- 2008-05-16 JP JP2010509919A patent/JP5296781B2/en not_active Expired - Fee Related
- 2008-05-16 RU RU2009149338/04A patent/RU2009149338A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107555654A (en) * | 2017-09-25 | 2018-01-09 | 浙江绿维环境科技有限公司 | A kind of Treated sewage reusing technique for metal industry cooling system |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009022237A2 (en) | 2009-02-19 |
| WO2009022237A3 (en) | 2009-10-01 |
| KR20100017447A (en) | 2010-02-16 |
| JP2010527785A (en) | 2010-08-19 |
| KR101467603B1 (en) | 2014-12-01 |
| EP2158039A2 (en) | 2010-03-03 |
| BRPI0811377A2 (en) | 2014-12-09 |
| CN101952039B (en) | 2015-05-20 |
| WO2009022237A9 (en) | 2009-08-13 |
| JP5296781B2 (en) | 2013-09-25 |
| RU2009149338A (en) | 2011-07-10 |
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