[go: up one dir, main page]

WO1985003530A1 - Procede de preparation de carboxylates metalliques - Google Patents

Procede de preparation de carboxylates metalliques Download PDF

Info

Publication number
WO1985003530A1
WO1985003530A1 PCT/GB1985/000054 GB8500054W WO8503530A1 WO 1985003530 A1 WO1985003530 A1 WO 1985003530A1 GB 8500054 W GB8500054 W GB 8500054W WO 8503530 A1 WO8503530 A1 WO 8503530A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
heavy metal
cathode
anode
carboxylic acid
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.)
Ceased
Application number
PCT/GB1985/000054
Other languages
English (en)
Inventor
Frank Stanley Holland
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.)
Manchem Ltd
Original Assignee
Manchem Ltd
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 Manchem Ltd filed Critical Manchem Ltd
Publication of WO1985003530A1 publication Critical patent/WO1985003530A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • 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

Definitions

  • This invention relates to an electrolytic method for the production of carboxylates of heavy metals.
  • Heavy metal carboxylates are usually manufactured by any of three established methods.
  • the first method involves the precipitation of the metal carboxylate by a double decomposition reaction between an aqueous solution of a water-soluble salt of the heavy metal, usually a halide such as the chloride or sulphate, and an alkali metal carboxylate, usually the sodium carboxylate.
  • the heavy metal carboxylate may then form an insoluble precipitate which can be washed free of soluble alkali metal salts, concentrated and dried by any of several well known methods.
  • the second method involves a fusion reaction between the heavy metal oxide, hydroxide or carbonate with the carboxylic acid in molten form or as a solution in an organic solvent.
  • This method is advantageous if sufficiently pure and soluble metal oxides, hydroxides or carbonates are available, but suffers from the disadvantage that there is practically no possibility of influencing the quality of the product, this being determined primarily by the purity of the starting materials.
  • the third method involves reaction of finely divided metal with the carboxylic acid in the presence of air.
  • a process for the production of heavy metal carboxylates which comprises passing an electric current between an anode comprising a heavy metal and a cathode through an aqueous electrolyte in the presence of at least one carboxylic acid whereby heavy metal ions generated at the anode combine with the products formed from the cathode product and the carboxylic acid giving the heavy metal carboxylate which is recovered from the electrolyte.
  • the process of the invention is carried out using an electrolysis cell which comprises a container manufactured of, or lined with, a non-conducting material that is resistant to the aqueous electrolyte contained therein.
  • the electrolyte is an aqueous electrolyte having dissolved therein an ionic compound that readily dissociates into anions and cations, preferably a water soluble salt of a strong inorganic acid with a strong inorganic base and, in particular, alkali metal halides such as sodium chloride.
  • the electrolyte can be, and preferably is, acidified by the incorporation therein of a mineral acid, preferably hydrochloric acid, to prevent or reduce the tendency of the heavy metal to plate out during electrolysis upon the cathode. Dipping into the electrolyte are at least two electrodes, a corrodible anode made of the desired heavy metal and a cathode.
  • the desired carboxylic acid is added to the cell. It may be present within the electrolyte, being incorporated directly therein in the case of water soluble carboxylic acids. If water insoluble carboxylic acids are to be employed, they may suitably be dissolved in a water miscible solvent and the solution of the carboxylic acid in the water miscible solvent can then be added to the aqueous electrolyte. When the carboxylic acid is itself water immiscible, it may be present as a liquid layer in which case it may be necessary to provide the cathode with an insulating sleeve to prevent the cathode from contacting the layer of carboxylic acid if it passes through that layer into the aqueous electrolyte.
  • the heavy metal anode is connected to the positive terminal of an electric power supply and the cathode is connected to the negative terminal. Current is passed to cause the heavy metal anode to corrode and, in essence, water to decompose at the cathode. It is a feature of the process of the invention that both the anode and cathode reaction products are used, that is the product of the anode is made to combine with the products formed from the cathode product and the carboxylic acid. The process can thus be very rapid and the desired heavy metal carboxylate can be prepared in high yields.
  • the process of the invention can be operated at any temperature between 0°and 100°C but temperatures between 40°and 80°C are preferred.
  • stannous octoate there is used an anode of tin, either in the massive form or in the form of finely divided particles associated with a feeder electrode of an inert conductor, such as of titanium, in the form of a cage or net containing the metal particles.
  • the cathode can be of any conductor material that is non-corrodible under the conditions of the electrolytic process, such as of stainless steel, titanium or graphite.
  • the electrolyte most conveniently is an aqueous solution of sodium chloride, optionally containing hydrochloric acid.
  • the reaction between the electrode products can De effected within the electrolysis cell or, when the products of the cathode and the anode reactions are kept apart, as by using an ion exchange membrane, the electrode products can be separately withdrawn from the electrolysis cell and reacted externally of the cell to provide the desired heavy metal carboxylate.
  • Heavy metals that can be used to provide the corrodible anode for use in the process of the present invention include the transition metals from titanium through to zinc (titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc) and from zirconium to antimony (zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin and antimony) and others such as lead.
  • titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc and from zirconium to antimony (zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin and antimony) and others such as lead.
  • zirconium to antimony zirconium, niobium, molybdenum, ruthen
  • carboxylic acids that may be used are acetic, octoic (2-ethyl hexoic) , neodecanoic, oxalic, tartaric and naphthenic.
  • carboxylic acids having up to 24 carbon atoms may be employed with octoic and naphthenic acids being particularly preferred.
  • the process of the invention can also be operated with acid mixtures such as a mixture of acetic acid and octoic acid, propionic and neodecanoic acids etc. in which case the mixture of the heavy metal carboxylates will be formed.
  • the process can be operated with heavy metal alloys in which case the product will be the carboxylates of the mixed metals.
  • suitable alloys include stainless steel, rass, co a -n c e a oys an ncone a oys.
  • the cathode to be employed in the process of the invention should be non-corrodible under the conditions of the electrolysis.
  • Suitable materials of which the cathode may be formed include stainless steel, titanium, copper and graphite.
  • the anode may, as previously mentioned, be the massive form of the heavy metal.
  • the heavy metal may be used in finely divided form when the current supply is carried to the finely divided heavy metal by a feeder electrode of a conductor material that is itself non-corrodible under the process conditions, for example titanium.
  • the feeder electrode in this case suitably is in the form of a cage or net of the non-corrodible conductor material enclosing the particulate, corrodible, heavy metal.
  • Suitable current densities at the anode and cathode are of the order of 1 milliamp to 10 amps per square centimetre.
  • the current density at the cathode is higher than at the anode. In this way it is possible to prevent or reduce the tendency of some heavy metals to plate out on the cathode during the course of the process, as for example when using tin, copper or lead as the anode metal.
  • the current density at a particular electrode can suitably be adjusted by varying the depth to which the electrode is immersed in the electrolyte during the electrolysis and its distance from the other electrode.
  • the desired heavy metal carboxylate is immiscible with the aqueous electrolyte and so separates therefrom during the course of the electrolysis.
  • the heavy metal carboxylate has a higher specific gravity than the aqueous electrolyte it collects at the bottom of the electrolyte cell and can readily be withdrawn therefrom, either batchwise or continuously as it is formed. This applies in the case of stannous octoate to the production of which the process of the present invention is particularly suited.
  • the cathode can be raised during the course of the reaction, or the product carboxylate can be removed from the cell.
  • the heavy metal carboxylate produced in accordance with the process of the invention can, if necessary, be extracted into an organic phase using a suitable solvent such as a hydrocarbon. The heavy metal carboxylate can then be separated from the organic phase by distilling the solvent and, if necessary, filtering the residual heavy metal carboxylate.
  • heavy metal carboxylates that are water immiscible and have a higher specific gravity than the electrolyte, such as stannous octoate.
  • an antioxidant or stabiliser can be added to the electrolysis cell before electrolysis.
  • Suitable antiox dants nclude 2,5-ditertiarybutyl hydroquinone and 4-tertiarybutyl catechol.
  • 0.1 weight per cent of the former and 0.02 per cent of the latter, based on the weight of the final product, have been found suitable amounts to employ in the production of stannous octoate.
  • the antioxidant can, for example, be dissolved in the carboxylic acid before it is added to the electrolysis cell.
  • stannous octoate that, because of the high specific gravity of stannous octoate, the product sinks through the electrolyte to collect below the cathode from where it can be removed, either when the reaction is complete or during the course of the reaction, and purified as more particularly described in the Examples below.
  • the specific gravity of the carboxylate is not high enough for the reaction product to sink through the electrolyte.
  • the reaction then is preferably carried out in the presence of a solvent, such as a hydrocarbon, for example white spirit, in a suitable amount, for example a weight ratio of about 1:1 with respect to the carboxylic acid.
  • nickel octoates using a nickel anode, stainless steel cathode and sodium chloride solution as electrolyte
  • a nickel octoate which dissolves in the hydrocarbon solvent.
  • the organic and aqueous layers can be separated and the nickel octoate product purified.
  • Heavy metal carboxylates produced in accordance with the process of the invention are useful in a variety of applications.
  • Heavy metal carboxylates, or metal soaps are well known for use as driers in the production of coatings, particularly air dried coatings.
  • heavy metal carboxylates, such as stannous octoate find use in the production of polyurethane foams and as curing agents for silicone rubbers.
  • a cell comprising a five litre glass beaker was charged with electrolyte comprising NaCl (637g) dissolved in water (2500g).
  • Octoic acid (293g) containing 2,5-di-t-butyl hydroquinone (0.4g) and 4-t-butyl catechol (O.Offg) was floated on the electrolyte.
  • the anode was connected to the positive terminal of a DC power supply and the cathode feeder to the negative terminal.
  • a current of 20A was passed through the cell for 3.75 hours. This gave a current density of 100mA.cm"2 at the anode and 2.1A.cm"2 t the cathode.
  • the temperature in the cell rose from 18°to 43°C and the cell voltage declined from 12V to 9V at the end.
  • a cell containing electrolyte, octoic acid and stabiliser as described in Example 1 was prepared.
  • a tin anode weighing 2083g was placed on the titanium sheet.
  • a current of 20A was passed through the cell until 53.51 Ampere hours had passed. During this time the temperature in the cell rose from 23°C to 60°C and the cell voltage declined from 10V to 7V.
  • Example 3 The product was allowed to settle and was purified as described in Example 1. The final product analysed at 97.5% stannous octoate.
  • Example 3 The product was allowed to settle and was purified as described in Example 1. The final product analysed at 97.5% stannous octoate.
  • a piece of titanium sheet (30cm x 10cm x 1mm) was folded into an L shape and placed into a 5 litre beaker.
  • Zircalloy (a commercial alloy of zirconium) turnings (77.6g) were placed on top of the titanium and a piece of perforated polypropylene pushed down onto the turnings so that they in turn were compressed and pushed against the titanium.
  • a nickel grid was placed about 10cm above the Zircalloy.
  • Sodium chloride solution (4 molar 2357g) was poured into the beaker covering the Zircalloy and nickel, and acetic acid (204g) was then added.
  • the titanium was connected to the positive terminal of a DC power supply, the nickel to the negative terminal. 12.85 Amp hours were passed through the cell resulting in the dissolution of llg of Zircalloy.
  • This process produced zirconium acetate solution. 2891g of zirconium acetate solution were produced at a zirconium concentration of 3.35% Zr.
  • a copper anode (7cm x 7cm x 6mm) and a copper cored titanium cathode (17mm diameter x 5.6cm Long) were immersed in a two phase system comprised of an aqueous sodium chloride electrolyte (10L water: 2230g NaCl) and a white spirit (1330g) - naphthenic acid (1993.6g) organic phase contained in a polypropylene tank (30cm x 30cm x 15cm) used as the cell. Approximately 100 Amp hours passed through the system. The copper anode was found to decrease in weight by 227g. The aqueous electrolyte was run off and the organic phase washed with water. The product was then dried to 140°C with oxygen bubbling. After filtration, the material was found to contain 3.3% copper.
  • a nickel anode (7cm x 15cm x 3mm) and a copper cored titanium cathode (17mm diameter x 5.6cm long) were immersed in a two phase system comprising of an aqueous sodium chloride electrolyte (10L water: 2230g NaCl) and a white spirit (861g) - octoic acid (1026g) organic phase contained in a polypropylene tank (30cm x 30cm x 15cm) used as the cell. 185.5 Amp hours were passed through the system. The nickel anode was found to have lost 192.2g.
  • Example 6 A cell was constructed from a plastic box (60cm x
  • a nickel cathode (37cm x 18cm x 3mm) was immersed in a 10% sodium hydroxide solution in the membrane compartment.
  • concentration of soluble tin in the anode compartment increased to 10%.
  • Concentration was maintained at 10% by overflowing the anode compartment by the monitored addition of sodium chloride solution.
  • concentration of sodium hydroxide was maintained at 10% in the membrane box by the addition of sodium chloride electrolyte and collecting the clear sodium hydroxide solution.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

Procédé de préparation de carboxylates de métal lourd, dans lequel un courant électrique traverse une anode comprenant un métal lourd et une cathode au travers d'un électrolyte aqueux en présence d'au moins un acide carboxylique. Les ions de métal lourd produits au niveau de l'anode se combinent avec les produits fermés à partir du produit de cathode et l'acide carboxylique, produisant le carboxylate de métal lourd qui est extrait de l'électrolyte.
PCT/GB1985/000054 1984-02-10 1985-02-11 Procede de preparation de carboxylates metalliques Ceased WO1985003530A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB848403538A GB8403538D0 (en) 1984-02-10 1984-02-10 Preparing metal carboxylates
GB8403538 1984-02-10

Publications (1)

Publication Number Publication Date
WO1985003530A1 true WO1985003530A1 (fr) 1985-08-15

Family

ID=10556392

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1985/000054 Ceased WO1985003530A1 (fr) 1984-02-10 1985-02-11 Procede de preparation de carboxylates metalliques

Country Status (2)

Country Link
GB (1) GB8403538D0 (fr)
WO (1) WO1985003530A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19516624A1 (de) * 1994-05-06 1995-11-09 Huls America Inc Elektrosynthese von Carbonsäure-Metallsalzen
EP0906970A1 (fr) * 1997-10-02 1999-04-07 Th. Goldschmidt AG Procédé de préparation de composés d'argent
US6790338B2 (en) 2002-12-06 2004-09-14 Om Group, Inc. Electrolytic process for preparing metal sulfonates
WO2016024285A3 (fr) * 2014-08-14 2016-07-07 Infinium Precious Resources Ltd. Procédé électrolytique de préparation de complexes métalliques de carboxylate
CN110923743A (zh) * 2019-12-27 2020-03-27 云南锡业研究院有限公司 一种辛酸亚锡电化学连续循环合成装置及其合成方法
CN110923745A (zh) * 2019-12-27 2020-03-27 昆明理工大学 采用射流搅拌电化学合成辛酸亚锡的装置及合成方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR760003A (fr) * 1932-11-17 1934-02-15 Procédé de production électrolytique de sels à acides organiques volatils et à métaux difficilement attaquables par ces acides
US4416743A (en) * 1982-01-07 1983-11-22 Manchem Limited Electrolysis using two electrolytically conducting phases

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR760003A (fr) * 1932-11-17 1934-02-15 Procédé de production électrolytique de sels à acides organiques volatils et à métaux difficilement attaquables par ces acides
US4416743A (en) * 1982-01-07 1983-11-22 Manchem Limited Electrolysis using two electrolytically conducting phases

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19516624A1 (de) * 1994-05-06 1995-11-09 Huls America Inc Elektrosynthese von Carbonsäure-Metallsalzen
US6197186B1 (en) 1997-02-10 2001-03-06 Th. Goldschmidt Ag Process for preparing silver compounds
EP0906970A1 (fr) * 1997-10-02 1999-04-07 Th. Goldschmidt AG Procédé de préparation de composés d'argent
US6790338B2 (en) 2002-12-06 2004-09-14 Om Group, Inc. Electrolytic process for preparing metal sulfonates
WO2016024285A3 (fr) * 2014-08-14 2016-07-07 Infinium Precious Resources Ltd. Procédé électrolytique de préparation de complexes métalliques de carboxylate
CN110923743A (zh) * 2019-12-27 2020-03-27 云南锡业研究院有限公司 一种辛酸亚锡电化学连续循环合成装置及其合成方法
CN110923745A (zh) * 2019-12-27 2020-03-27 昆明理工大学 采用射流搅拌电化学合成辛酸亚锡的装置及合成方法

Also Published As

Publication number Publication date
GB8403538D0 (en) 1984-03-14

Similar Documents

Publication Publication Date Title
US5389211A (en) Method for producing high purity hydroxides and alkoxides
EP0023077B1 (fr) Production électrolytique de certains acides trichloropicoliniques et/ou de l'acide 3,6-dichloropicolinique
CN102408134B (zh) 一种铱粉的电化学溶解方法
RU2107753C1 (ru) Способ получения металлического магния (варианты) и способ получения металлического магния из сплава магний - редкоземельный металл
EP0253783B1 (fr) Procédé et appareil pour la purification de l'or
JP4057056B2 (ja) 塩基性炭酸コバルト（ｉｉ）、塩基性炭酸シュウ酸コバルト（ｉｉ）、それらの製法及び使用法
WO1985003530A1 (fr) Procede de preparation de carboxylates metalliques
CA2027656C (fr) Dezingage galvanique d'acier galvanise
US4416743A (en) Electrolysis using two electrolytically conducting phases
EP0219213B1 (fr) Procédé de récupération de gallium à partir de déchets
US4437949A (en) Electrolysis of tin complexes
CA1272464A (fr) Methode d'extraction du gallium de rebuts qui le renferment
CA2081292C (fr) Procede de recuperation electrochimique du bismuth contenu dans des effluents de regenerations d'echangeurs d'ions
US6569310B2 (en) Electrochemical process for preparation of zinc powder
KR100522116B1 (ko) 비전도성 다공성 세라믹 용기를 이용한 리튬 전구체를포함하는 용융염에서의 리튬 회수장치 및 방법
EP0130250B1 (fr) Electrolyse utilisant deux phases électrolytiquement conductrices
RU2076865C1 (ru) Способ получения 2-(2'-гидрокси-5'-метилфенил)-бензотриазола
Sugino et al. Electrolytic Reduction of Nitrobenzene to Hydrazobenzene
JPS57134587A (en) Method for collecting of metallic as
SU825493A1 (en) Method of producing salts of aliphatic acids
SU1475985A1 (ru) Способ выделени свинца
Basha et al. Production of zinc from industrial byproduct zinc compounds
RU2123544C1 (ru) Способ получения кадмия
CN120649134A (zh) 一种废旧阴极炭块提纯的装置及高值化处理方法
JPS6021390A (ja) 電解質によつて導電する２相を用いる電解方法

Legal Events

Date Code Title Description
AK Designated states

Designated state(s): JP US

AL Designated countries for regional patents

Designated state(s): BE CH DE FR GB NL