EP0241685A1 - 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
EP0241685A1
EP0241685A1 EP87102846A EP87102846A EP0241685A1 EP 0241685 A1 EP0241685 A1 EP 0241685A1 EP 87102846 A EP87102846 A EP 87102846A EP 87102846 A EP87102846 A EP 87102846A EP 0241685 A1 EP0241685 A1 EP 0241685A1
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EP
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Prior art keywords
electrolysis
cells
salts
acids
divided
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EP87102846A
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German (de)
English (en)
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EP0241685B1 (fr
Inventor
Steffen Dr. Dapperheld
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Hoechst AG
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Hoechst AG
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    • 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 CH2ClCOOH CH2BrCOOH CHCl2COOH CHBr2COOH CCl3COOH CBr3COOH
  • 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 / m2 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.
  • the following mixture is electrolyzed:
  • the electrolysis of the mixture was carried out according to the information in the example mentioned in the form of a 60% aqueous solution using magnetite cathodes and carbon anodes at an average voltage of 3.25 V and a current density of 500 to 600 A / m2 at 65 ° C up to the dehalogenation of the di- and trichloroacetic acids up to the monohalogen stage.
  • the yield of monochloroacetic acid is given as almost quantitative.
  • Example 4 the electrolysis is continued until complete dehalogenation - that is to say halogen-free acetic acid.
  • the dehalogenation essential for this process is a reduction reaction taking place at the cathode.
  • the following reaction equation can be given: CHCl2COOH + 2 H+ + 2 e ⁇ CH2ClCOOH + HCl
  • the reaction of the aggressive haloacetic acids at the cathode has a considerable corrosive effect on the cathode material, as was also shown by our own electrolysis experiments using magnetite and lead cathodes. Corrosion is hardly serious on carbon cathodes.
  • a disadvantage of all of the cathode materials mentioned here, however, is that increasing the current density leads to increasing hydrogen evolution at the cathode, and the electrodes are covered in a long-term test for 600 hours with a coating which makes cleaning the cathode necessary, which of course is economical the procedure significantly affected.
  • the halogen ions formed on the cathode are discharged at the anode; in the case of chlorine ions: 2 Cl ⁇ ⁇ Cl2 + 2 e
  • the anodically formed halogen can easily come into contact with the product dehalogenated at the cathode and "react" back to the starting product; e.g. CH2ClCOOH + Cl2 ⁇ CHCl2COOH + HCl This "back reaction” can be prevented by carrying out the electrolysis in divided electrolysis cells.
  • the catholyte is an aqueous solution of dichloroacetic acid + HCl and / or H2SO4 with a conductivity above 0.01 Ohm Oh1 ⁇ cm ⁇ 1.
  • Graphite, lead, lead alloys and titanium with a coating of oxides of platinum metals are mentioned as anode materials;
  • An aqueous mineral acid solution serves as the anolyte, with oxygen acids being preferred as mineral acids because here there is no chlorine but only oxygen evolution: H2O ⁇ 1/2 O2 + 2 H+ + 2 e
  • the ion exchange capacity in grams of dry weight of the exchanger is required for the membrane material resin indicated that are necessary to neutralize 1 gram equivalent of base.
  • the exchange capacity should be 500 to 1500, preferably 500 to 1000, for membrane material with SO3H groups 500 to 1800, preferably 1000 to 1500.
  • 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 / m2) 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 of carbon or of 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 / m2) dissolved.
  • the salts of metals with a hydrogen overvoltage of at least 0.4 V are 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 Cl ⁇ , Br ⁇ , SO42 ⁇ , NO3 ⁇ and CH3OCO ⁇ .
  • 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 AgCl and AgBr; here, the soluble salt is primarily AgNO3).
  • 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) - can be generated 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 at a current density that is about 10 times higher (up to about 8000 A / m2), 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 is preferably carried out only up to the monohalogen stage (monochloro or monobromoacetic acid).
  • aqueous solutions can be used as the electrolyte (in the undivided cell) or catholyte (in the divided cell) the starting haloacetic acids of all possible concentrations (approx. 1 to 95%) can be used.
  • the solutions can also contain mineral acids (eg HCl, H2SO4 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 / m2, preferably up to about 6000 A / m2, 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 TiO2 and doped with a noble metal oxide such as e.g. Platinum oxide.
  • Preferred anolyte liquids are aqueous mineral acids such as aqueous hydrochloric acid or aqueous sulfuric acid,
  • aqueous hydrochloric acid is preferable if one works in divided cells and there are other possible uses for the anodically formed chlorine; otherwise the use of aqueous sulfuric acid is cheaper.
  • 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 of 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 HCl, Cl ⁇ is constantly consumed by the anodic chlorine development, which can be compensated for by the continuous addition of gaseous HCl 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.
  • Electrodes Electrode graphite EH (from Sigri, Meitingen)
  • Cation exchange membrane (R) Nafion 315 (from DuPont); it is a 2-layer membrane made from copolymers of perfluorosulfonylethoxy vinyl ether + tetrafluoroethylene. There is a layer with the equivalent weight 1300 on the cathode side and one with the equivalent weight 1100 on the anode side.
  • Spacers polyethylene nets Flow: 500 l / h Temp.: 25 - 40 ° C Current density: 4000 A / m2 Terminal voltage: 8 - 4.8 V
  • Anolyte conc. HCl, continuously supplemented by gaseous HCl
  • the composition of the catholyte and the electrolysis result are shown in the following table:
  • Electrodes Electrode graphite EH (from Sigri, Meitingen)
  • Cation exchange membrane (R) Nafion 324 (from DuPont) it is a 2-layer membrane of the same composition as Nafion 315, only with slightly thinner layers.
  • Spacers polyethylene nets Flow: 1.6 m3 / h Temp .: 25-60 ° C
  • Anolyte conc.
  • Anode Electrode graphite EH (from Sigri, Meitingen)
  • Cathode completely and densely coated stainless steel with magnetite
  • Cation exchange membrane (R) Nafion 324 (from DuPont)
  • Spacers polyethylene nets Flow: 500 l / h Temp .: 39 ° C
  • Anolyte conc. HCl, continuously supplemented by gaseous HCl It became a catholyte with the composition 1.15 kg of monochloroacetic acid 1.28 kg dichloroacetic acid 0.24 kg acetic acid 1.43 kg water electrolyzed at a current density of 2000 A / m2.
  • the terminal voltage was 3.2 V.
  • the proportion of the current that was used for the development of hydrogen was 14.3%.
  • the hydrogen evolution decreased briefly, but then rose again.
  • 270 Ah 28% of the electricity was used for hydrogen development, after 350 Ah the value was 45% and then rose to approx. 80%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
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
DE19863607446 DE3607446A1 (de) 1986-03-07 1986-03-07 Verfahren zur enthalogenierung von chlor- und von bromessigsaeuren
DE3607446 1986-03-07

Publications (2)

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

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ID=6295698

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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)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0334796A1 (fr) * 1988-03-19 1989-09-27 Hoechst Aktiengesellschaft Procédé de préparation d'hydrocarbures halogénés insaturés
EP0457320A1 (fr) * 1990-05-18 1991-11-21 Hoechst Aktiengesellschaft Procédé de déshalogénation électrolytique partielle des acides dichloro-acétiques et solution d'électrolyse
WO1993017151A1 (fr) * 1992-02-22 1993-09-02 Hoechst Aktiengesellschaft Procede electrochimique de preparation d'acide glyoxylique

Families Citing this family (7)

* 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
US5348629A (en) * 1989-11-17 1994-09-20 Khudenko Boris M Method and apparatus for electrolytic processing of materials
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
CA2667854C (fr) * 2006-05-26 2015-04-07 Applied Biosystems, Llc Reactifs de marquage et procedes destines a determiner des composes hydroxyles
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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE848807C (de) * 1942-03-12 1952-09-08 Lech Chemie Gersthofen Verfahren zur elektrolytischen Reduktion von Chlor- oder Bromessigsaeuren

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE848807C (de) * 1942-03-12 1952-09-08 Lech Chemie Gersthofen Verfahren zur elektrolytischen Reduktion von Chlor- oder Bromessigsaeuren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 98, 1983, Seite 492, Zusammenfassung Nr. 24482h, Columbus, Ohio, US; G. HORANYI: "Electrocatalytic reduction of some halogenated derivatives of methane and acetic acid at a platinized platinum electrode in acid medium", & J. ELECTROANAL. CHEM. INTERFACIAL ELECTROCHEM. 1982, 140(2), 329-46 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0334796A1 (fr) * 1988-03-19 1989-09-27 Hoechst Aktiengesellschaft Procédé de préparation d'hydrocarbures halogénés insaturés
US5026460A (en) * 1988-03-19 1991-06-25 Hoechst Aktiengesellschaft Process for the preparation of unsaturated halogenated hydrocabons
EP0457320A1 (fr) * 1990-05-18 1991-11-21 Hoechst Aktiengesellschaft Procédé de déshalogénation électrolytique partielle des acides dichloro-acétiques et solution d'électrolyse
US5362367A (en) * 1990-05-18 1994-11-08 Hoechst Aktiengesellschaft Partial electrolytic dehalogenation of dichloroacetic and trichloroacetic acid and electrolysis solution
WO1993017151A1 (fr) * 1992-02-22 1993-09-02 Hoechst Aktiengesellschaft Procede electrochimique de preparation d'acide glyoxylique
US5474658A (en) * 1992-02-22 1995-12-12 Hoechst Ag Electrochemical process for preparing glyoxylic acid

Also Published As

Publication number Publication date
EP0241685B1 (fr) 1989-12-13
DE3761151D1 (de) 1990-01-18
BR8701046A (pt) 1988-01-05
DE3607446C2 (fr) 1987-12-03
IL81785A (en) 1990-03-19
ATE48657T1 (de) 1989-12-15
HUT43023A (en) 1987-09-28
JPS62214189A (ja) 1987-09-19
CA1313362C (fr) 1993-02-02
MX168882B (es) 1993-06-14
FI870972A0 (fi) 1987-03-05
US4707226A (en) 1987-11-17
FI870972L (fi) 1987-09-08
AU6977887A (en) 1987-09-10
AU583980B2 (en) 1989-05-11
DE3607446A1 (de) 1987-09-10
DD258424A5 (de) 1988-07-20
IL81785A0 (en) 1987-10-20
FI79863B (fi) 1989-11-30
FI79863C (fi) 1990-03-12

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