US3652430A - Electrolytic condensation of carboxylic acids - Google Patents

Electrolytic condensation of carboxylic acids Download PDF

Info

Publication number
US3652430A
US3652430A US774415A US3652430DA US3652430A US 3652430 A US3652430 A US 3652430A US 774415 A US774415 A US 774415A US 3652430D A US3652430D A US 3652430DA US 3652430 A US3652430 A US 3652430A
Authority
US
United States
Prior art keywords
percent
electrolysis
electrodes
acids
carboxylic acids
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 - Lifetime
Application number
US774415A
Other languages
English (en)
Inventor
Fritz Beck
Walter Himmele
Juergen Haufe
Andreas Brunold
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.)
BASF SE
Original Assignee
BASF SE
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
Priority claimed from DE19671643693 external-priority patent/DE1643693C3/de
Application filed by BASF SE filed Critical BASF SE
Application granted granted Critical
Publication of US3652430A publication Critical patent/US3652430A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C25B3/29—Coupling reactions

Definitions

  • the invention relates to the electrolytic condensation of carboxylic acids which is known under the name Kolbe synthesis.
  • Electrolytic condensation of carboxylic acids is a method for reacting substituted or unsubstituted carboxylic acids with elimination of carbon dioxide according to the equation:
  • R denotes an alkyl radical which may bear carboxyalkyl groups or acylated amino groups as substituents.
  • a high current density may be used in which case a high degree of neutralization is required to achieve adequate cell voltages, i.e., a considerable proportion of the acid has to be neutralized prior to electrolysis so that the solution has adequate conductance. It is also possible to be content with a low degree of neutralization but then high current densities cannot be used. In the former case it is comparatively difficult to process the reaction mixture because a small amount of reaction product has to be separated from a large amount of salt. In the second case long reaction periods have to be accepted.
  • Degree of neutralization is defined as the molar proportion of the organic carboxylic acid which is neutralized with a base prior to electrolysis in order to achieve the necessary conductance in the electrolysis system.
  • the process is particularly important for the production of diesters of sebacic acid from hemiesters of adipic acid, particularly the methyl or ethyl esters, and for the synthesis of N,N'- diacetyl-decamethylenediamine from epsilonacetylaminocaproic acid, of 1,10-dibromodecane from omega-bromocaproic acid and of octane-2,7-dione from lawlinic acid.
  • Electrochemical condensation is carried out using solvents, for example water, but preferably using nonaqueous solvents such as lower alcohols, for example those having one to four carbon atoms such as methanol, ethanol, ethylene glycol and isopropanol, or N,N-dialkylamides of lower alkanedicarboxylic acids, for example those having one to five carbon atoms whose alkyl radicals contain not more than three carbon atoms, particularly dimethylformamide, diethylformamide, dimethylacetamide or diethylacetamide, or using N-methylpyrrolidone, or a mixture of solvents with or without water. Generally 10 to 20 percent by weight solutions of the carboxylic acids to be electrolyzed are used.
  • the degree of neutralization is adjusted by adding bases prior to electrolysis. It is kept at less than 10 percent and preferably at only 2 to 5 percent.
  • the bases used may be aqueous alkalies such as caustic soda solution, caustic potash solution, sodium or potassium carethylate, sodium carbonate or potassium carbonate; in all cases, ammonia or bases having adequate basicity such as dimethylamine, trimethylamine, triethylamine or alkanolamines such as dimethylethanolamine or morpholine, may also be used.
  • the process is advantageously carried out in electrolytic cells having pairs of vibrating electrodes such as are described in detail for example in British Pat. application No. 30712/66.
  • Electrodes are liquid-permeable, for example in the form of netting, expanded metal or screens and are arranged opposite to each other at a very small distance of less than 1 mm,, preferably of from 0.1 to 0.3 mm.
  • a layer of woven or non-woven glass fiber cloth, paper, polyamide cloth, polyester cloth, polyvinyl chloride cloth, polypropylene cloth or polytetrafluoroethylene cloth, which is permeable to liquid is provided between the electrodes as a spacer and insulator.
  • the electrodes are held in position by suitable mechanical means made of alloy steel, titanium, aluminum (particularly anodized aluminum), polyvinyl chloride, polypropylene, polyethylene or glass.
  • the pair of horizontal electrodes is preferably vibrated perpendicularly to their planes with a frequency of from 1 to 1,000 cycles per second and an amplitude of 0.3 to 2 mm.
  • Platinum, alloys of platinum and rhodium or of platinum and iridium, gold, alloys of gold and platinum, for example Au:Pt :10, platinized titanium or tantalum, or titanium or tantalum which'have been gilded, are suitable as the material for the anodes.
  • the material for the cathodes is not critical; all that is necessary is that it should not corrode in the weakly acid electrolytes when no current is passing.
  • Platinum, alloy steel, nickel or titanium are suitable. Platinum and nickel have the advantage of low hydrogen overvoltage.
  • FIG. 1 is a sectional elevation of an electrolytic cell
  • FIGS. 2 and 3 illustrate embodiments of pairs of electrodes.
  • the electrolytic cell shown diagrammatically in FIG. 1 is a convenient embodiment given by way of example. It consists of an electrolysis vessel 1 provided with a cover 2.
  • the electrolysis vessel contains a horizontal pair of electrodes consisting of a cathode netting 3 and an anode netting 4 which are kept apart from each other by a coarsely porous insulating material 5.
  • the two nettings are pressed together by two wheel-shaped members 6 and 7 of suitable plastics which are secured at the lower end of the axis 8 of a vibrator. Contact is made with the nettings by contacts 9 and 10 which in turn are connected with the vibrator axis 8 (sewing as an electric lead) and with a flexible lead 11.
  • the vibrator axis 8 is carried by a vibrator 12 and is passed into the cell through a rubber membrane 13 which gives a gastight seal.
  • the apparatus is also provided with a glass electrode 14, a thermometer 15, a dropping funnel l6 and an offgas pipe through a brine-cooled reflux condenser 17.
  • the cell stands in a waterbath (not shown) through which tap water fiows for the purpose of cooling.
  • liquid-permeable cathode of the said type with a liquid-permeable anode. It is very difficult to prepare liquidpermeable anodes having good resistance to corrosion if it is not desired to use anodes made wholly of precious metal which are too expensive for large scale manufacture. It is preferable to use composite electrodes, i.e., those consisting of a base metal, for example aluminum or an alloy thereof for example with l to 3 percent of magnesium, having a coating of precious metal, particularly of platinum. The layer of precious metal then need only be from about 3 to 70 microns in thickness. It is essential that the coating of precious metal is continuous. Parts which are not covered with precious metal may be covered with a plastics resin or paint which is insoluble in the reaction medium.
  • the pair of electrodes formed by anode, insulating layer and cathode may be disposed horizontally or vertically in the electrolytic cell and then in the reaction mixture.
  • the pair of electrodes may be vibrated perpendicular or parallel to the macroscopic surface of the electrodes.
  • FIGS. 2 and 3 Two possibilities are shown in FIGS. 2 and 3 which have proved to be particularly suitable.
  • FIG. 2 illustrates a pair of electrodes which vibrates perpendicularly to the planes of the electrodes while
  • FIG. 3 illustrates a pair of electrodes which vibrates parallel to the planes of the electrodes.
  • the anode is a circular or square plate consisting of a base metal 18 covered on one side with a thin layer 19 of platinum.
  • a liquid-permeable insulating layer and the liquidpermeable cathode 3 are placed on top of the anode.
  • the sides of the base metal of the anode which are not covered by platinum are coated with plastics 20 to protect them from corrosion.
  • the pair of electrodes is submerged in the reaction mixture contained in the electrode vessel 1.
  • the axis 8 of the vibrator passes through the cover 2 of the electrolysic cell and is driven by the vibrator 12.
  • the output of the apparatus may easily be increased by arranging two or more pairs of electrodes in series one above the other in an analogous manner as bipolar units.
  • the vibrator axis may serve at the same time for clamping together and as electric return lead.
  • the electrodes vibrate parallel to the surface (as in FIG. 3) separate bolts have to be passed through for clamping.
  • the current density may be set at a high figure in spite ofthe low degree of neutralization. Current densities of 25 to 50 amperes per square decimeter are immediately possible industri ally. Cell voltages of from 5 to 18, particularly from 8 to 12, volts are generally used.
  • the reaction temperature is usually kept at from 30 to 65 C. It has been found that in methanol solutions a flat minimum of the cell voltage occurs at 40 to 55 C.
  • Conversion of carboxylic acids may be very high, for example more than 90 percent, by reason of the low degree of neutralization, and this has an advantageous effect on the processing of the reaction mixture.
  • the cell voltage declines during electrolysis although a relatively nonpolar product accumulates, whereas in conventional methods the cell voltage increases during electrolysis and the increase may exceed 100 percent ofthe original value.
  • the process may be carried out continuously at a high concentration of the electrolysis products and a low concentration of the acid to be electrolyzed without impairment of the yield.
  • the anodic oxidation of the product thus plays no part, i.e., in spite of the low concentration of the starting materials these are preferentially reacted at the electrodes.
  • reaction mixture (illustrated later by way of example with reference to the synthesis of sebacic esters) is very simple.
  • Countercurrent extraction with organic solvents for example octane or cyclohexane, such as is necessary in the prior art methods, can be dispensed with.
  • the solvent is advantageously distilled off from the reaction mixture in a falling film evaporator.
  • the bottom contains a mixture of sebacic esters, unreacted hemiesters of adipic acid, precipitated salt of the hemiester and low boiling C monocarboxylic esters formed as byproducts (these are particularly methyl valerate, methyl allylacetate, methylw-alkoxyvalerates and methylw-hydroxyvalerate) and the salts and unreacted hemiesters may be separated therefrom by extraction with water.
  • the sebacic esters and the byproducts remaining in the organic phase may be separated by distillation or by freezing out the sebacic ester and filtering it off.
  • the mixture remaining after distilling off the residue may also be separated into its components by filtering off precipitated salts, freezing out the sebacic esters from the filtrate and separating by distillation the unreacted hemiesters of adipic acid and the byproducts.
  • a horizontal pair of electrodes is mounted in a glass electrolytic cell 1 as shown diagrammatically in FIG. 1 which is provided with a polyethylene cover 2 .
  • This consists of a circular cathode netting 3 (nickel, 400 meshes per cm?) and an anode netting 4 of the same size made of an alloy of platinum and rhodium and having 1,024 meshes per cm. which are insulated from each other by a coarsely porous non-woven glass fiber fabric 5 having a thickness of 0.15 mm.
  • the two nettings are pressed together by two wheel-shaped members 6 and 7 of polypropylene and are secured at the lower end of a vibrator axis 8.
  • contacts 9 and 10 which are connected with the electrical supply through the vibrator shaft 8 serving as an electrical conductor and a flexible lead 11.
  • the vibrator shaft 8 is secured to a vibrator 12 (40 watts, 50 cycles per second) and passes into the cell 1 through a rubber membrane 13 which gives a gastight seal.
  • the apparatus is also provided with a glass electrode 14, a thermometer 15, a dropping funnel 16 and an offgas outlet through a brine cooled reflux condenser 17.
  • the cell stands in a bath (not shown) of flowing tap water to keep it cool.
  • Electrolysis is carried out at 10.0 amperes, i.e., a current density of 25 amperes per dm. with reference to the exposed area of netting of40 cm*.
  • the temperature is kept at 42 C.
  • the cell voltage at the beginning of the electrolysis is l4.8 volts, after 1 hour it is 14.3 volts, after 2 hours 13.9 volts, after 3 hours 12.7 volts and after 4 hours and 12 minutes (the end) 10.5 volts. During this period the pH value is raised from 5.1 to 7.0. The amount of current passed through corresponds to a conversion of 132 percent, with reference to the free hemiester.
  • EXAMPLE 6 333 g. of a mixture of 400 g. of monomethyl adipate, 587.4 g. of methanol and 12.6 g. of triethylamine is introduced into the electrolytic cell described in Example 1 at the beginning of electrolysis. 2 hours and 44 minutes later (i.e., after reaching a theoretical current conversion of 132 percent at 10 amperes and a current density of 25 amperes per cm?) further mixture is dripped in continuously at the rate of 2 grams per minute and an equivalent amount of reaction mixture is withdrawn. During this continuous period the cell voltage remains constant at 18.5 volts and the pH value at 6.8. Working up three fractions, each of 290 g., gives the following results:
  • EXAMPLE 7 A mixture of 14 g. of monomethyl adipate, 73.5 g. of sebacic ester, 8.05 g. of 29.5 percent sodium methylate solution and 254.4 g. of methanol is introduced at the beginning of electrolysis in the electrolytic cell described in Example 1. This mixture corresponds to the mixture described in Example 1 after 95 percent conversion of the free hemiester with an 80 percent yield.
  • the cell voltage at the beginning of electrolysis is 16.8 volts, after 1 hour it is 15.0 volts, after 2 hours 14.0 volts, after 3 hours 12.5 volts and after 4 hours 12 minutes (the end) it is 11.0 volts.
  • the pH value rises from 5.1 to 7.2.
  • the yield of sebacic ester is 82.2 percent and the current efficiency is 60.6 percent.
  • EXAMPLE 9 A vertical glass tube having an internal diameter of 100 mm. and a height of 1,000 mm. is used as the electrolytic cell.
  • a Liebig condenser is arranged parallel to the tube and is connected with the tube by horizontal pipes at the top and bottom.
  • Six pairs of electrodes (diameter 88 mm., spacing 100 mm.) are mounted on a vibrator shaft in the cell; the pairs of electrodes have the composition as described in Example 1.
  • the pairs of electrodes are connected electrically in series by shaft sections of anodized aluminum coated with condensation lacquer.
  • the pair of electrodes is as shown in FIG. 2 and consists of a horizontal circular base plate of aluminum 18 onto which is bonded a smooth platinum foil 19 having a thickness of 40 microns by means of a conducting synthetic resin adhesive.
  • the sides of the base plate which are not covered with platinum are coated at 20 with a polyether containing chlorine such as is sold under the registered trade mark PENTON.
  • the interlayer is a polyester cloth having 50 meshes per cm.
  • the cathode 3 is an alloy steel netting having 100 meshes per cm. The interlayer and the cathode are pressed against the platinum anode by means of a propylene member shaped like a spoked wheel (not shown).
  • the pair of electrodes is placed in an electrolytic vessel 1 of glass and is vibratedwith an electromagnetic vibrator 12; the vibrations are perpendicular to the surface of the electrodes and have an amplitude of 1 mm. and a frequency of 50 cp.
  • electrolysis 400 g. of a solution of l60 g. of monomethyl adipate in methanol, which has been neutralized to the extent of 5 percent with sodium methylate, is placed in the cell.
  • Electrolysis is carried on at amperes corresponding to a current density of 25 amperes per dm. and at a temperature of 42 C. 3 hours and 32 minutes later (corresponding to a theoretical current conversion of 132 percent) electrolysis is stopped.
  • the cell voltage falls continually from 15.5 volts at the beginning to l 1.0 volts at the end.
  • the reaction mixture is worked up to give a yield of dimethyl sebacate of 81.5 percent and a current efficiency of 60 percent. These voltages and yields substantially correspond to the values obtained under the same conditions with a double netting arrangement.
  • EXAMPLE 11 400 g. of a solution of 120 g. of mono-2-ethylhexyl adipate in methanol which has been neutralized to the extent of 10 percent with sodium methylate is placed in the electrolytic cell described in Example 10 at the beginning of electrolysis. Electrolysis is carried on at 8 amperes corresponding to a current density of amperes per dm. and at a temperature of 45 C. The vibrator operates at 50 cycles per second and an amplitude of 1.5 mm. After exactly 2 hours corresponding to a theoretical current conversion of 142 percent the electrolysis is stopped. During electrolysis the current is stopped for 10 seconds at intervals of 10 minutes. In this way the voltages vary within a fairly narrow range of from 15 to 17 volts.
  • the pair of electrodes consists of a vertical square base plate of aluminum 18 to which a smooth foil 19 of platinum having a thickness of 60 microns is bonded on one side.
  • the platinum foil is bent over the top edge of the base plate and at the upper narrow side contacts the vibrator shaft.
  • the surface of the aluminum plate which is not covered by platinum is coated with chlorinated polyether.
  • a polyester fabric having 50 meshes per cm. serves as interlayer 5 and a titanium netting with 13 meshes per cm. serves as cathode 3. Cathode and interlayer are pressed onto the anode by means of four bolts passing throughat the corners of the square.
  • the cell voltage drops during electrolysis from 15 to 12 volts.
  • Working up the reaction mixture gives a yield of 81 percent of dimethyl sebacate at a current efficiency of 60 percent.
  • a process for electrochemical condensation of an organic compound selected from the group consisting of alkanecarboxylic acids, hemiesters of alkanedicarboxylic acids and aminoalkanecarboxylic acids which comprises placing said organic compound in an electrolytic cell having vibrating pairs of electrodes and thereafter passing a current through said cell, said current having a density greater than 10 amperes per dmF, wherein the degree of neutralization of the organic com pound is less than 10 percent, and wherein the cell voltage is from 5 to 18.
  • anode is formed by a platinum foil or screen having a thickness of from 3 to 70 microns which is bonded by means of an electrically conducting adhesive to a flat base plate.

Landscapes

  • 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)
  • Polyamides (AREA)
US774415A 1967-11-11 1968-11-08 Electrolytic condensation of carboxylic acids Expired - Lifetime US3652430A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1967B0095375 DE1643693B2 (de) 1967-11-11 1967-11-11 Verfahren zur herstellung von sebacinsaeuredimethylester durch elektrolytische kondensation von adipinsaeuremonomethylester
DE19671643693 DE1643693C3 (de) 1967-11-11 1967-11-11 Verfahren zur Herstellung von Sebacinsäuredimethylester durch elektrolytische Kondensation von Adipinsäuremonomethylester
DE19681802865 DE1802865A1 (de) 1967-11-11 1968-10-12 Verfahren zur elektrolytischen Kondensation von Carbonsaeuren

Publications (1)

Publication Number Publication Date
US3652430A true US3652430A (en) 1972-03-28

Family

ID=27180970

Family Applications (1)

Application Number Title Priority Date Filing Date
US774415A Expired - Lifetime US3652430A (en) 1967-11-11 1968-11-08 Electrolytic condensation of carboxylic acids

Country Status (8)

Country Link
US (1) US3652430A (enrdf_load_stackoverflow)
AT (1) AT288346B (enrdf_load_stackoverflow)
BE (1) BE723694A (enrdf_load_stackoverflow)
CH (1) CH506451A (enrdf_load_stackoverflow)
DE (2) DE1643693B2 (enrdf_load_stackoverflow)
FR (1) FR1591366A (enrdf_load_stackoverflow)
GB (1) GB1250212A (enrdf_load_stackoverflow)
NL (1) NL6816045A (enrdf_load_stackoverflow)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3787299A (en) * 1970-03-28 1974-01-22 Basf Ag Electrolytic condensation of carboxylic acids
US3879271A (en) * 1972-10-04 1975-04-22 Basf Ag Production of diesters of dicarboxylic acids by electrochemical condensation of monoesters of dicarboxylic acids
US3941666A (en) * 1973-07-20 1976-03-02 Hoechst Aktiengesellschaft Process for the preparation of N-(α-alkoxyethyl)-carboxylic acid amides
US4011145A (en) * 1974-07-19 1977-03-08 Basf Aktiengesellschaft Electrochemical manufacture of aromatic esters
US4124453A (en) * 1975-09-29 1978-11-07 National Research Development Corporation Electrochemical processes
US5021131A (en) * 1990-05-17 1991-06-04 E. I. Du Pont De Nemours And Company Optically pure 1,4-diols
GB2392920A (en) * 2002-09-12 2004-03-17 Univ Hull Method of reacting carboxylic acids by electro-osmosis
WO2016170075A1 (de) * 2015-04-24 2016-10-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur elektrochemischen umwandlung von fettsäuren und anlage zur durchführung des verfahrens
US10143222B2 (en) * 2013-07-05 2018-12-04 Charles Adriano Duvoisin Compact device for electrolytic sterilization of food and utensils

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3576018D1 (de) * 1984-11-29 1990-03-15 Varta Batterie Galvanisches element mit einer polymerelektrode.
US5021132A (en) * 1990-08-07 1991-06-04 Sandoz Ltd. Electrochemical process for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and the salts thereof
DE102018201287A1 (de) 2018-01-29 2019-08-01 Siemens Aktiengesellschaft Poröse Elektrode zur elektrochemischen Umsetzung organischer Verbindungen in zwei nicht mischbaren Phasen in einem elektrochemischen Flussreaktor
US11512401B2 (en) 2019-01-14 2022-11-29 Gridthink Inc. Process for short chain alkane synthesis while maintaining faradaic efficiency
CN110016684B (zh) * 2019-04-08 2021-03-16 天津大学 一种由氨基酸电解制备烯胺的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE855403C (de) * 1944-07-27 1952-11-13 Basf Ag Verfahren zur Herstellung organischer Verbindungen durch Elektrolyse von Carbonsaeuren

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE855403C (de) * 1944-07-27 1952-11-13 Basf Ag Verfahren zur Herstellung organischer Verbindungen durch Elektrolyse von Carbonsaeuren

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3787299A (en) * 1970-03-28 1974-01-22 Basf Ag Electrolytic condensation of carboxylic acids
US3879271A (en) * 1972-10-04 1975-04-22 Basf Ag Production of diesters of dicarboxylic acids by electrochemical condensation of monoesters of dicarboxylic acids
US3941666A (en) * 1973-07-20 1976-03-02 Hoechst Aktiengesellschaft Process for the preparation of N-(α-alkoxyethyl)-carboxylic acid amides
US4011145A (en) * 1974-07-19 1977-03-08 Basf Aktiengesellschaft Electrochemical manufacture of aromatic esters
US4124453A (en) * 1975-09-29 1978-11-07 National Research Development Corporation Electrochemical processes
US5021131A (en) * 1990-05-17 1991-06-04 E. I. Du Pont De Nemours And Company Optically pure 1,4-diols
GB2392920A (en) * 2002-09-12 2004-03-17 Univ Hull Method of reacting carboxylic acids by electro-osmosis
US20040079630A1 (en) * 2002-09-12 2004-04-29 Paul Watts Method of reacting carboxylic acids
GB2392920B (en) * 2002-09-12 2006-03-08 Univ Hull Method of reacting carboxylic acids
US7279082B2 (en) 2002-09-12 2007-10-09 The University Of Hull Method of reacting carboxylic acids
US10143222B2 (en) * 2013-07-05 2018-12-04 Charles Adriano Duvoisin Compact device for electrolytic sterilization of food and utensils
WO2016170075A1 (de) * 2015-04-24 2016-10-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur elektrochemischen umwandlung von fettsäuren und anlage zur durchführung des verfahrens

Also Published As

Publication number Publication date
BE723694A (enrdf_load_stackoverflow) 1969-05-12
DE1802865A1 (de) 1970-09-17
NL6816045A (enrdf_load_stackoverflow) 1969-05-13
DE1643693A1 (de) 1970-07-09
AT288346B (de) 1971-02-25
DE1643693B2 (de) 1976-09-09
CH506451A (de) 1971-04-30
FR1591366A (enrdf_load_stackoverflow) 1970-04-27
GB1250212A (enrdf_load_stackoverflow) 1971-10-20

Similar Documents

Publication Publication Date Title
US3652430A (en) Electrolytic condensation of carboxylic acids
US3764492A (en) Electrolytic preparation of esters from organo halides
US3899401A (en) Electrochemical production of pinacols
US4062753A (en) Electrolysis method and apparatus
US4917781A (en) Process for preparing quaternary ammonium hydroxides
FI74945B (fi) Foerfarande foer framstaellning av hydroksifoereningar genom elektrokemisk reduktion.
US4256551A (en) Electrolytic process
US3896011A (en) Process for the preparation of sebacic acid
US3787299A (en) Electrolytic condensation of carboxylic acids
US3876514A (en) Electrolysis of allyl halides
US3511765A (en) Carrying out electrochemical reactions
US3779876A (en) Process for the preparation of glyoxylic acid
FI56557C (fi) Diafragmacell med ett flertal avdelningar foer framstaellning av klor och alkalimetallhydroxid
CN100585012C (zh) 制备2-炔-1-缩醛的方法
US3756928A (en) Ls process for the manufacture of sebacic acid diesters of higher alcoho
US4076601A (en) Electrolytic process for the preparation of ethane-1,1,2,2-tetracarboxylate esters and related cyclic tetracarboxylate esters
Baizer et al. Electrolytic Reductive Coupling: XV. Electroreductions of Aqueous Concentrated Solutions of Diethyl Maleate in the Presence of Sodium or Tetraethylammonium Cations
US3879271A (en) Production of diesters of dicarboxylic acids by electrochemical condensation of monoesters of dicarboxylic acids
US3871976A (en) Electrochemical adiponitrile process
US4647350A (en) Electrolytic preparation of perfluoroalkanoic acids, perfluoroalkanols and perfluoroalkyl esters
GB1443690A (en) Electrolytic cells
US3542656A (en) Production of cyclohexadiene dicarboxylic acids
US3477923A (en) Electrochemical hydrodimerization of acrylonitrile
US3630858A (en) A.c. electrolytic process
US2408036A (en) Electrolytic pinacol production