EP0241685B1 - Procédé de déhalogénation des acides chloro- et bromoacétiques - Google Patents

Procédé de déhalogénation des acides chloro- et bromoacétiques Download PDF

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Publication number
EP0241685B1
EP0241685B1 EP87102846A EP87102846A EP0241685B1 EP 0241685 B1 EP0241685 B1 EP 0241685B1 EP 87102846 A EP87102846 A EP 87102846A EP 87102846 A EP87102846 A EP 87102846A EP 0241685 B1 EP0241685 B1 EP 0241685B1
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EP
European Patent Office
Prior art keywords
electrolysis
cells
salts
acid
divided
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.)
Expired
Application number
EP87102846A
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German (de)
English (en)
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EP0241685A1 (fr
Inventor
Steffen Dr. Dapperheld
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
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Hoechst AG
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Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT87102846T priority Critical patent/ATE48657T1/de
Publication of EP0241685A1 publication Critical patent/EP0241685A1/fr
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Publication of EP0241685B1 publication Critical patent/EP0241685B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction

Definitions

  • Chloro and bromoacetic acids are the mono-, di- and tri-haloacetic acids of the formulas
  • the partial dehalogenation of the triple and the double halogenated acetic acids is desirable or necessary, for example, if the intention is to obtain the monohalogenated acetic acids by chlorination or bromination of acetic acid in the highest possible yields.
  • a current density of about 500 to 700 A / m 2 is used.
  • the electrolysis temperature is below 100 ° C.
  • the yields of the desired partially or completely dehalogenated products should be between 95 and 100% of theory lie.
  • Example 4 the electrolysis is continued until complete dehalogenation - i.e. to halogen-free acetic acid - continued.
  • the catholyte is an aqueous solution of dichloroacetic acid + HCl and / or H 2 S0 4 with a conductivity of more than 0.01 Ohm -1 ⁇ cm-1.
  • this object could be achieved by using such aqueous solutions of chloro- or bromoacetic acids as starting electrolysis solutions which still contain one or more salts of metals with a hydrogen overvoltage of at least 0.4 V (at a current density of 4000 A / m 2 ) included dissolved.
  • the subject of the invention is therefore a process for the dehalogenation of chloroacids and bromoacetic acids by electrolysis of aqueous solutions of these acids using carbon cathodes and anodes also made of carbon or from other conventional electrode materials in undivided or divided (electrolysis) cells, which is characterized in that that the aqueous electrolysis solutions in the undivided cells and in the cathode compartment of the divided cells still contain one or more salts of metals with a hydrogen overvoltage of at least 0.4 V (at a current density of 4000 A / m 2 ) dissolved.
  • salts of metals with a hydrogen overvoltage of at least 0.4 V come mainly the soluble salts of Cu, Ag, Au, Zn, Cd, Hg, Sn, Pb, Ti, Zr, Bi, V, Ta, Cr and / or Ni, preferably only the soluble Cu and Pb salts, in question.
  • the most common anions of these salts are mainly CI-, Br, S0 4 2- , NO s - and CH 3 0CO-.
  • these anions cannot be combined in the same way with all of the above-mentioned metals, because in some cases this results in salts which are difficult to dissolve (such as AgCI and AgBr; AgNOs are primarily possible as soluble salts).
  • the salts can be added directly to the electrolysis solution or, e.g. by adding oxides, carbonates etc. - in some cases also the metals themselves (if soluble) - in the solution.
  • the salt concentration in the electrolyte of the undivided cell and in the catholyte of the divided cell is expediently set to about 0.1 to 5000 ppm, preferably to about 10 to 1000 ppm.
  • This modification of the known methods ensures an extraordinary corrosion resistance of the electrodes, combined with the possibility of working with current densities that are about 10 times higher (up to about 8000 A / m 2 ), without deposits forming on the electrodes even during prolonged continuous operation ; the process is therefore extremely economical and progressive.
  • Trichloric and dichloroacetic acid and tribromoic and dibromoacetic acid are preferably used as starting compounds for the process; the electrolysis here is preferably carried out only up to the monohalogen stage (monochloro or monobromoacetic acid).
  • aqueous solutions of the starting haloacetic acids of all possible concentrations can be used as the electrolyte (in the undivided cell) or catholyte (in the divided cell).
  • the solutions can also contain mineral acids (for example HCl, H 2 S0 4 etc.) and must contain the content of certain metal salts according to the invention.
  • the anolyte (in the divided cell) is preferably an aqueous mineral acid, in particular aqueous hydrochloric acid and sulfuric acid.
  • carbon cathodes e.g. Electrode graphites, impregnated graphite materials and also glassy carbon.
  • the metal on which the metal salt added according to the invention is based is deposited on the cathode, which leads to a change in the properties of the cathode.
  • the cathodic current density can be increased to values of up to about 8000 A / m 2 , preferably up to about 6000 A / m 2 , without excessive hydrogen evolution and a progress of the dehalogenation reaction beyond the desired stage occurring as side reactions.
  • the metal deposited on the cathode is repeatedly partially dissolved by the acidic solution surrounding the cathode and then deposited again, etc. There is no disruptive deposit formation on the cathode.
  • the same material as for the cathode can be used as the anode material.
  • other conventional electrode materials which, however, must be inert under the electrolysis conditions.
  • a preferred such other common electrode material is titanium, coated with Ti0 2 and doped with a noble metal oxide such as platinum oxide.
  • Preferred anolyte liquids are aqueous mineral acids such as e.g. aqueous hydrochloric acid or aqueous sulfuric acid, the use of aqueous hydrochloric acid is preferable when working in divided cells and other uses exist for the anodically formed chlorine; otherwise the use of aqueous sulfuric acid is cheaper.
  • aqueous mineral acids such as e.g. aqueous hydrochloric acid or aqueous sulfuric acid
  • the implementation in the divided cells is preferred.
  • the same ion exchange membranes as those described in the aforementioned JP-A-54 (1979) -76521 are suitable for dividing the cells into the anode and cathode compartments; d.s. thus those made from perfluorinated polymers with carboxyl and / or sulfonic acid groups, preferably also with the ion exchange capacities specified in JP-A.
  • diaphragms made of other perfluorinated polymers or inorganic materials that are stable in the electrolyte.
  • the electrolysis temperature should be below 100 ° C; it is preferably between about 5 and 95 ° C., in particular between about 40 and 80 ° C.
  • a method of operation in divided electrolysis cells with discontinuous execution of the cathode reaction and continuous operation of the anode reaction is particularly expedient. If the anolyte contains HCI, the anodic chlorine evolution constantly consumes CI, which can be compensated for by the continuous addition of gaseous HCI or aqueous hydrochloric acid.
  • the electrolysis product is worked up in a known manner, for example by distillation.
  • the Metal salts remain behind here and can be returned to the process.
  • the electrolytic cell used in all (invention and comparative) examples was a split (plate and frame) circulation cell.

Claims (6)

1. Procédé pour déshalogéner des acides chloracétiques et des acides bromacétiques par électrolyse de solutions aqueuses de ces acides à l'aide de cathodes en carbone et d'anodes en carbone ou en d'autre matériaux usuels pour électrodes, dans des cellules (d'électrolyse) non compartimentées ou compartimentées, procédé caractérisé en ce que les solutions aqueuses d'électrolyse, dans les cellules non compartimentées ainsi que dans le compartiment cathodique des cellules compartimentées, contiennent en outre, en solution, un ou plusieurs sels de métaux présentant une surtension d'hydrogène d'au moins 0,4 V (pour une densité de courant de 4000 A/m2).
2. Procédé selon la revendication 1 caractérisé en ce qu'on utilise, comme sels de métaux ayant une surtension d'hydrogène d'au moins 0,4 V (pour une densité de courant de 4000 A/m2), les sels solubles de Cu, Ag, Au, Zn, Cd, Hg, Sn, Pb, Ti, Zr, Bi, V, Ta, Cr et/ou Ni, de préférence seulement les sels solubles de Cu et de Pb.
3. Procédé selon l'une des revendications 1 et 2, caractérisé en ce que la concentration de la solution d'électrolyse en sels de métaux ayant une surtension d'hydrogène d'au moins 0,4 V (pour une densité de courant de 4000 A/m2) est comprise entre environ 0,1 et 5000 ppm, de préférence entre environ 10 et 1000 ppm.
4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'on utilise, comme acides chloracétiques et bromacétiques, l'acide trichloracétique et l'acide dichloracétique ainsi que l'acide tribromacétique et l'acide dibromacétique, de préférence l'acide tri- et/ou di-chloracétique, et en ce qu'on ne poursuit l'électrolyse que jusqu'au stade du composé monohalogéné.
5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'on effectue l'électrolyse dans des cellules d'électrolyse compartimentées.
6. Procédé selon la revendication 5 caractérisé en ce qu'on utilise, comme membranes dans les cellules d'électrolyse compartimentées, des membranes en échangeurs de cations qui sont constituées de polymères perfluorés portant des radicaux carboxy et/ou sulfo.
EP87102846A 1986-03-07 1987-02-27 Procédé de déhalogénation des acides chloro- et bromoacétiques Expired EP0241685B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87102846T ATE48657T1 (de) 1986-03-07 1987-02-27 Verfahren zur enthalogenierung von chlor- und von bromessigsaeuren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3607446 1986-03-07
DE19863607446 DE3607446A1 (de) 1986-03-07 1986-03-07 Verfahren zur enthalogenierung von chlor- und von bromessigsaeuren

Publications (2)

Publication Number Publication Date
EP0241685A1 EP0241685A1 (fr) 1987-10-21
EP0241685B1 true EP0241685B1 (fr) 1989-12-13

Family

ID=6295698

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87102846A Expired EP0241685B1 (fr) 1986-03-07 1987-02-27 Procédé de déhalogénation des acides chloro- et bromoacétiques

Country Status (13)

Country Link
US (1) US4707226A (fr)
EP (1) EP0241685B1 (fr)
JP (1) JPS62214189A (fr)
AT (1) ATE48657T1 (fr)
AU (1) AU583980B2 (fr)
BR (1) BR8701046A (fr)
CA (1) CA1313362C (fr)
DD (1) DD258424A5 (fr)
DE (2) DE3607446A1 (fr)
FI (1) FI79863C (fr)
HU (1) HUT43023A (fr)
IL (1) IL81785A (fr)
MX (1) MX168882B (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3731914A1 (de) * 1987-09-23 1989-04-06 Hoechst Ag Verfahren zur herstellung von fluorierten acrylsaeuren und ihren derivaten
DE3802745A1 (de) * 1988-01-30 1989-08-03 Hoechst Ag Verfahren zur herstellung von fluormalonsaeure und ihren derivaten
EP0334796B1 (fr) * 1988-03-19 1993-05-12 Hoechst Aktiengesellschaft Procédé de préparation d'hydrocarbures halogénés insaturés
US5348629A (en) * 1989-11-17 1994-09-20 Khudenko Boris M Method and apparatus for electrolytic processing of materials
DE4016063A1 (de) * 1990-05-18 1991-11-21 Hoechst Ag Verfahren zur teilweisen elektrolytischen enthalogenierung von di- und trichloressigsaeure sowie elektrolyseloesung
BR9305923A (pt) * 1992-02-22 1997-08-26 Hoechst Ag Processo eletroquimico para a preparação de ácido glioxálico
DE4217338C2 (de) * 1992-05-26 1994-09-01 Hoechst Ag Elektrochemisches Verfahren zur Reduktion von Oxalsäure zu Glyoxylsäure
JP2003205221A (ja) * 2001-11-12 2003-07-22 Canon Inc 有機塩素化合物の処理方法及びそれに用いる装置、土壌の修復方法及びそれに用いる装置
JP5413836B2 (ja) * 2006-05-26 2014-02-12 ディーエイチ テクノロジーズ デベロップメント プライベート リミテッド ヒドロキシル化化合物のためのタグ付け試薬およびその方法
CN114409025A (zh) * 2021-12-17 2022-04-29 浙江工业大学 一种维生素b12修饰电极催化电解三溴乙酸脱溴的方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL63449C (fr) * 1942-03-12
FR1471108A (fr) * 1965-03-13 1967-02-24 Ajinomoto Kk Méthode électrolytique de conversion des groupes polychlorométhyle de composés organiques en groupe monochlorométhyle
JPS5476521A (en) * 1977-11-30 1979-06-19 Chlorine Eng Corp Ltd Preparation of monochloroacetic acid
US4588484A (en) * 1985-02-28 1986-05-13 Eli Lilly And Company Electrochemical reduction of 3-chlorobenzo[b]thiophenes
US4585533A (en) * 1985-04-19 1986-04-29 Exxon Research And Engineering Co. Removal of halogen from polyhalogenated compounds by electrolysis

Also Published As

Publication number Publication date
AU583980B2 (en) 1989-05-11
FI79863B (fi) 1989-11-30
ATE48657T1 (de) 1989-12-15
DE3607446A1 (de) 1987-09-10
EP0241685A1 (fr) 1987-10-21
JPS62214189A (ja) 1987-09-19
AU6977887A (en) 1987-09-10
IL81785A (en) 1990-03-19
FI79863C (fi) 1990-03-12
HUT43023A (en) 1987-09-28
BR8701046A (pt) 1988-01-05
DE3607446C2 (fr) 1987-12-03
MX168882B (es) 1993-06-14
DD258424A5 (de) 1988-07-20
US4707226A (en) 1987-11-17
CA1313362C (fr) 1993-02-02
FI870972A (fi) 1987-09-08
FI870972A0 (fi) 1987-03-05
DE3761151D1 (de) 1990-01-18
IL81785A0 (en) 1987-10-20

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