WO1994010083A1 - Procede pour la recuperation de l'iode contenu dans des composes organiques iodes - Google Patents

Procede pour la recuperation de l'iode contenu dans des composes organiques iodes Download PDF

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Publication number
WO1994010083A1
WO1994010083A1 PCT/EP1993/002822 EP9302822W WO9410083A1 WO 1994010083 A1 WO1994010083 A1 WO 1994010083A1 EP 9302822 W EP9302822 W EP 9302822W WO 9410083 A1 WO9410083 A1 WO 9410083A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
iodine
stage
organic
catalyst
Prior art date
Application number
PCT/EP1993/002822
Other languages
German (de)
English (en)
Inventor
Jürgen JACKE
Peter Blaszkiewicz
Original Assignee
Schering Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Schering Aktiengesellschaft filed Critical Schering Aktiengesellschaft
Priority to CA002147373A priority Critical patent/CA2147373A1/fr
Priority to EP93922560A priority patent/EP0666830A1/fr
Priority to JP6510620A priority patent/JPH08502469A/ja
Publication of WO1994010083A1 publication Critical patent/WO1994010083A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/13—Iodine; Hydrogen iodide
    • C01B7/14—Iodine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
    • C07B35/06—Decomposition, e.g. elimination of halogens, water or hydrogen halides
    • 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
    • C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification

Definitions

  • the invention relates to a process for the recovery of iodine from production residues which contain iodinated organic compounds.
  • iodine is bound so tightly that it is difficult to access even chemical degradation processes.
  • X-ray contrast media are predominantly derivatives of 2,4,6-triiodo-benzoic acid, 2,4,6-triiodo-isophthalic acid, 2,4,6-triiodo-3-amino-benzoic acid, 2,4,6-triiodo-5 -amino-isophthal- acid, 2,4,6-triiodo-3,5-diamino-benzoic acid, 2,4,6-triiodo-1,3,5-benzenetricarboxylic acid and corresponding di erer.
  • DE-OS 3 612 504 discloses a process for removing iodinated compounds from carbonylation products, in which the organically bound iodine is converted with oxidizing agents into iodine compounds which can be easily separated off by distillation.
  • EP 135 085 describes a process for the removal of iodinated compounds in which the carbonylation products are combined with phosphines or heterocyclic nitrogen compounds in the presence of at least one metal, such as, for. B. copper are treated and the reaction product is separated by distillation from the non-volatile iodine compounds.
  • EP-A-106 934 describes a process for the recovery of iodine from mother liquors and wastewater containing organically bound iodine, the technical further development being to consist in that the addition of catalytic amounts of copper (ions) in the alkaline medium the bound iodine is mineralized. This procedure gives satisfactory results when using dilute solutions (p. 6, line 11). In order to take into account the realities of modern operating processes on the one hand and to keep the amounts to be released to the environment as low as possible, there was still a demand for processes by means of which highly concentrated production residues can be easily, effectively and economically dehalogenated and both iodine and the de-iodinated organic ones Compounds can be recovered and reused for synthesis.
  • the present invention relates to a 3-stage process for the recovery of iodine from iodinated organic compounds, which is characterized in that in a first stage the substance to be de-iodinated is suspended or dissolved in water and with sufficient amounts of organic and / or inorganic bases are added and, after addition of a catalyst in the presence of hydrogen, if appropriate at elevated pressure, the deiodination is carried out at room or elevated temperature and after removal of the catalyst in
  • the solution is mixed with an organic and / or inorganic acid and then the precipitated, de-iodinated compound is filtered off and
  • the iodide present is oxidized to iodine with an oxidizing agent, which is separated from the aqueous reaction mixture using the customary processes.
  • the substance to be decoded in the first stage is hydrogenated in aqueous solution in the presence of bases and a catalyst.
  • the iodine-containing substrate is dissolved or suspended in at least the same amount by weight of water and mixed with an organic and / or inorganic base in an amount sufficient to keep the organic acid released after the hydrogenation in solution.
  • the amount is preferably selected so that the hydroiodic acid liberated and the acid groups bound to the organic molecule are neutralized and the pH after the hydrogenation is in particular in the range from 8 to 13.
  • all compounds with sufficient basicity which are stable under the given reaction conditions and do not act as a catalyst poison can be used as inorganic and / or organic bases.
  • inorganic bases such as alkali and / or alkaline earth metals as oxides, carbonates or hydroxides and NH3.
  • the bases are preferably used in solid form or as concentrated solutions such as, for example, solid sodium hydroxide, potassium hydroxide, calcium hydroxide.
  • Ni, Pd, Pt, Rh, if appropriate on support materials, have proven to be useful as catalysts according to the invention, usually in amounts of 0.01-10 % By weight, preferably 0.1-1% by weight, of the pure metal and based on the iodine-containing substrate.
  • the hydrogenation is carried out at room temperature up to approximately 150 ° C., preferably between 50 ° C. and 90 ° C., and a hydrogen pressure of approximately 1-50 bar. Higher pressures are possible if necessary, but pressures between 1-20, in particular 1-6 bar, are preferred according to the invention.
  • the catalyst is separated off, for example by filtration, and the filtrate containing the reaction products is acidified.
  • the acids used are one or more strong organic and / or inorganic acids such as, for example, oxalic acid, citric acid, acetic acid, sulfuric acid, hydrochloric acid, preferably those with pKa values ⁇ _3.5.
  • the amount of acid used must be sufficient for the neutralization of the bases contained in the reaction solution and for the protonation of the deiodinated carboxylic acids.
  • the iodide remaining in the reaction solution is oxidized with oxidizing agents to iodine, which is then separated off.
  • the oxidation is carried out using mild oxidizing agents known per se, such as preferably hydrogen peroxide in acidic solution or electrochemically.
  • mild oxidizing agents known per se such as preferably hydrogen peroxide in acidic solution or electrochemically.
  • the pH of the solution is adjusted to ⁇ 7 using one or more of the above-mentioned inorganic or organic acids.
  • pH values ⁇ 4, in particular ⁇ 2 are preferred.
  • the H 2 O 2 preferred according to the invention can be added continuously or in portions to the acidic solution at room temperature as a concentrated solution.
  • the reaction temperature is optionally kept at temperatures of preferably ⁇ 25 ° C. by cooling.
  • the progress of oxidation can by increasing the pH to track.
  • the pH is kept within the intended range by adding acid continuously or in portions.
  • the reaction is complete when the pH of the reaction mixture does not increase further by adding the oxidizing agent.
  • the iodine formed as a crystalline precipitate at reaction temperatures of preferably ⁇ 25 ° C. is filtered off. If necessary, the dissolved iodine remaining in the filtrate can be removed by extraction with solvents such as ethyl acetate or by water distillation / sublimation.
  • the remaining filtrate is largely free of iodine in the various oxidation states such as. B. iodide, iodate, iodine and iodinated and deiodinated organic compounds that after neutralization it can be easily added to biological wastewater treatment.
  • One of the advantages of the process according to the invention lies in the possibility of being able to process highly concentrated solutions, so that all reaction products are precipitated and can therefore be largely separated off in a simple manner.
  • the volume of the remaining solution is also comparatively small, so that, if necessary, the neutralized solution can be evaporated in whole or in part at low cost and the salts which precipitate out can be isolated.
  • Precipitation Ki precipitated and filtered off.
  • the mother liquor has a residual iodine content of 2 g / 1.
  • the residual iodine content of the mother liquor is reduced to 50 mg / l by extraction (2-stage) with the same volume of ethyl acetate.
  • iodamic acid (2, 6-triiod-5-amino-isophthalic acid) are suspended in 1.5 l of water and dissolved by adding 183 g (4.6 mol) of sodium hydroxide. After adding 20 g of palladium / carbon catalyst (5% Pd, 54% water), the mixture is hydrogenated at 60-70 ° C./5 bar hydrogen for 60 minutes. After 1 h After stirring at 60 ° C, the catalyst is filtered off. From the filtrate are concentrated by adding 120 ml (1.4 mol). Hydrochloric acid 191 g of white precipitate Ki precipitated and filtered off. The filtrate is concentrated with 210 ml.
  • the residual iodine content of the mother liquor is reduced to 45 mg / 1 by extraction (2-stage) with the same volume of ethyl acetate.
  • the temperature is kept at 25 ° C. by cooling.
  • the mother liquor has a residual iodine content of 4 g / 1.
  • the residual iodine content of the mother liquor is reduced to 100 mg / l by extraction (2-stage) with the same volume of ethyl acetate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Ce procédé pour la récupération de l'iode contenu dans des composés organiques iodés, est caractérisé par le fait que, dans une première phase, la substance à déioder est mise en suspension ou dissoute dans de l'eau, dans un reácteur, mélangée avec des quantités suffisantes de bases organiques et/ou inorganiques, et après addition d'un catalyseur en présence d'oxygène, le cas échéant sous une pression élevée, la déiodisation est effectuée à température ambiante ou élevée et que, dans une deuxième phase, après séparation du catalyseur, la solution est mélangée avec un acide organique et/ou inorganique, le composé déiodé précipité étant ensuite séparé par filtration, tandis que, dans une troisième phase, l'iodure présent dans le filtrat acide est oxydé au moyen d'un oxydant en iode qui est séparé du mélange de réaction aqueux selon les procédés habituels.
PCT/EP1993/002822 1992-10-30 1993-10-13 Procede pour la recuperation de l'iode contenu dans des composes organiques iodes WO1994010083A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002147373A CA2147373A1 (fr) 1992-10-30 1993-10-13 Methode pour recuperer l'iode a partir de composes organiques iodes
EP93922560A EP0666830A1 (fr) 1992-10-30 1993-10-13 Procede pour la recuperation de l'iode contenu dans des composes organiques iodes
JP6510620A JPH08502469A (ja) 1992-10-30 1993-10-13 ヨウ素化された有機化合物からヨウ素を回収する方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4236724.7 1992-10-30
DE19924236724 DE4236724A1 (de) 1992-10-30 1992-10-30 Verfahren zur Rückgewinnung von Jod aus jodierten organischen Verbindungen

Publications (1)

Publication Number Publication Date
WO1994010083A1 true WO1994010083A1 (fr) 1994-05-11

Family

ID=6471762

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/002822 WO1994010083A1 (fr) 1992-10-30 1993-10-13 Procede pour la recuperation de l'iode contenu dans des composes organiques iodes

Country Status (5)

Country Link
EP (1) EP0666830A1 (fr)
JP (1) JPH08502469A (fr)
CA (1) CA2147373A1 (fr)
DE (1) DE4236724A1 (fr)
WO (1) WO1994010083A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998007661A1 (fr) * 1996-08-20 1998-02-26 Schering Aktiengesellschaft Procede de decomposition de derives de triiodobenzene
CN112919678A (zh) * 2021-01-29 2021-06-08 江苏集萃托普索清洁能源研发有限公司 醋酸生产废水处理工艺
CN113265703A (zh) * 2021-04-28 2021-08-17 中南大学 一种金属砷晶体脱碘方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19806001A1 (de) * 1998-02-16 1999-08-19 Berger Johann Verfahren zur Dehalogenierung von in Wasser gelösten Halogenkohlenwasserstoffen (HKW) mit Hilfe von vernickeltem Zink
NZ757793A (en) 2017-06-07 2022-04-29 Bracco Imaging Spa A process for the recovery of iodine from aqueous solutions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0106934A1 (fr) * 1982-08-09 1984-05-02 BRACCO INDUSTRIA CHIMICA Società per Azioni Procédé pour la récupération de l'iode à partir d'eaux mères et d'eaux résiduelles contenant de l'iode en composés organiques
JPH01201002A (ja) * 1988-02-06 1989-08-14 Mitsui Toatsu Chem Inc 有機沃素化合物を含有する廃液からの沃素回収方法
JPH01224203A (ja) * 1988-03-03 1989-09-07 Mitsui Toatsu Chem Inc 有機沃素化合物を含有する廃液から沃素を回収する方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0106934A1 (fr) * 1982-08-09 1984-05-02 BRACCO INDUSTRIA CHIMICA Società per Azioni Procédé pour la récupération de l'iode à partir d'eaux mères et d'eaux résiduelles contenant de l'iode en composés organiques
JPH01201002A (ja) * 1988-02-06 1989-08-14 Mitsui Toatsu Chem Inc 有機沃素化合物を含有する廃液からの沃素回収方法
JPH01224203A (ja) * 1988-03-03 1989-09-07 Mitsui Toatsu Chem Inc 有機沃素化合物を含有する廃液から沃素を回収する方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8938, Derwent World Patents Index; AN 89-274993/38 *
DATABASE WPI Week 8942, Derwent World Patents Index; AN 89-304258/42 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998007661A1 (fr) * 1996-08-20 1998-02-26 Schering Aktiengesellschaft Procede de decomposition de derives de triiodobenzene
CN112919678A (zh) * 2021-01-29 2021-06-08 江苏集萃托普索清洁能源研发有限公司 醋酸生产废水处理工艺
CN113265703A (zh) * 2021-04-28 2021-08-17 中南大学 一种金属砷晶体脱碘方法

Also Published As

Publication number Publication date
EP0666830A1 (fr) 1995-08-16
CA2147373A1 (fr) 1994-05-11
JPH08502469A (ja) 1996-03-19
DE4236724A1 (de) 1994-05-05

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