EP0012215B1 - 2-Hydroxybutanesulfonic acid choline and its use as conducting salt - Google Patents
2-Hydroxybutanesulfonic acid choline and its use as conducting salt Download PDFInfo
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- EP0012215B1 EP0012215B1 EP79104324A EP79104324A EP0012215B1 EP 0012215 B1 EP0012215 B1 EP 0012215B1 EP 79104324 A EP79104324 A EP 79104324A EP 79104324 A EP79104324 A EP 79104324A EP 0012215 B1 EP0012215 B1 EP 0012215B1
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- Prior art keywords
- salt
- electrolysis
- conducting salt
- salts
- acid choline
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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
Definitions
- the invention relates to 2-hydroxybutanesulfonic acid choline and its use as a conductive salt in organic liquids.
- organic liquids are used as solvents for the starting products or for the process product. especially alcohols needed.
- compounds In order to achieve the conductivity required for electrolysis, compounds must be added to the liquids which give the liquid the required conductivity.
- the compounds used for this purpose which are usually salts. must also be stable under the reaction conditions.
- Quaternary aryl-alkylammonium salts, quaternary tetraalkylammonium salts and ammonium salts of primary, secondary or tertiary amines are converted in the presence of alkaline compounds to ammonium bases or to the free amines and alkali metal salts, which can interfere with the electrochemical process, e.g. by side reactions of the free amines.
- Alkali metal or alkaline earth metal salts of arylsulfonic, aryicarboxylic acids, alkylsulfonic acids and alkylcarboxylic acids are often poorly soluble in the organic liquids used, so that adequate conductivity is not achieved.
- Alkali and alkaline earth metal salts of carboxylic acids can also be partially broken down by decarboxylation.
- Soluble sulfides, cyanides and rhodanides are not sufficiently stable during electrolysis because they are anodically oxidized (decomposition). Soluble chlorides such as lithium chloride etc. Corrosion problems occur and chlorination can occur at the anode in undivided cells. The chlorates and perchlorates, which are stable under the electrolysis conditions, represent a safety risk in organic media.
- the quaternary ammonium salt of formula is ideally suited as a conductive salt for electrolysis in organic liquids.
- the conductive salt to be used according to the invention is readily soluble in many solvents, in particular in C 1 -C 12 -alkanols, so that the solutions have high conductivity.
- the compound (I) is also stable under the electrolysis conditions and not hygroscopic, so that even those processes can be carried out without great effort, which would interfere with water.
- the quaternary ammonium salt of formula 1 according to the invention is excellent, for example, as the conducting salt in the process described in DE-A-2711005 for the production of metal-free phthalocyanine by electrolysis of o-phthalonitrile and in other electrochemical processes, for example in the synthesis of adiponitrile, in which Deposition of metals from organic electrolytes and the electrochemical reduction of C0 2 to oxalic acid.
- the quaternary ammonium salt according to the invention higher current yields with simultaneously low cell voltages are obtained than with conductive salts of the prior art.
- the compound I to be used as the conductive salt can be prepared by processes known per se. One way of producing it is to convert the carbonates of the compound with the stoichiometrically required amount of the corresponding acid.
- the salt of formula I is isolated by concentrating the solution obtained.
- Another way is e.g. in the reaction of the chloride or sulfate of the compound (II) with the alkali metal salts of the corresponding acid.
- the resulting alkali metal chloride is advantageously removed.
- the salt of the formula is obtained by concentration, crystallization and filtration or by extraction of the dry residues obtained by evaporation of the solutions with polar liquids, e.g. lower alkanols.
- the salt is generally obtained in a very pure form and can generally be used as the conducting salt without further purification.
- the mixture is stirred until a clear, colorless solution is obtained and the water is removed in a rotary evaporator at 80 to 100 ° C. in a water jet vacuum.
- reaction residue is extracted three times with 100 parts of ethanol each.
- the combined alcohol extracts are freed from the solvent in vacuo.
- the mixture is stirred at 90 to 100 ° C for 5 hours, the pH increasing to about 9. It is cooled to 15 to 20 ° C.
- the crystal slurry obtained is suction filtered and dried.
- the mass yield of phthalocyanine - based on the theoretically possible yield calculated from the current throughput - is 98.7% with a content of 99.8% of phthalocyanine.
- choline salt of p-toluenesulfonic acid is used instead of the above-mentioned conductive salt, phthalocyanine is obtained in a yield of 91% and a purity of 98.1%.
- 2.5% phosphoric acid is poured into the graphite tube (anolyte compartment) and a mixture of 40% by weight acrylonitrile as the catholyte on the side of the silver amalgam cathode. 34% by weight of water and 26% by weight of conductive salt of the formula
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
Die Erfindung betrifft 2-hydroxybutansulfonsaures Cholin und dessen Verwendung als Leitsalz in organischen Flüssigkeiten.The invention relates to 2-hydroxybutanesulfonic acid choline and its use as a conductive salt in organic liquids.
Für viele elektrochemisch durchgeführte Synthesen von organischen Verbindungen werden als Lösungsmittel für die Ausgangsprodukte oder für das Verfahrensprodukt organische Flüssigkeiten. insbesondere Alkohole benötigt. Um die für die Elektrolyse erforderliche Leitfähigkeit zu erreichen, müssen den Flüssigkeiten Verbindungen zugegeben werden, welche der Flüssigkeit die benötigte Leitfähigkeit geben. Die für diesen Zweck verwendeten Verbindungen, die in der Regel Salze sind. müssen außerdem unter den Reaktionsbedingungen stabil sein.For many electrochemical syntheses of organic compounds, organic liquids are used as solvents for the starting products or for the process product. especially alcohols needed. In order to achieve the conductivity required for electrolysis, compounds must be added to the liquids which give the liquid the required conductivity. The compounds used for this purpose, which are usually salts. must also be stable under the reaction conditions.
Quartäre Aryl-alkylammoniumsaize, quartäre Tetraalkylammoniumsalze sowie Ammoniumsalze von primären, sekundären oder tertiären Aminen werden in Gegenwart von alkalisch wirkenden Verbindungen zu Ammoniumbasen, bzw. zu den freien Aminen und Alkalimetallsalzen umgesetzt, wodurch der elektrochemische Prozeß gestört werden kann, z.B. durch Nebenreaktionen der freien Amine.Quaternary aryl-alkylammonium salts, quaternary tetraalkylammonium salts and ammonium salts of primary, secondary or tertiary amines are converted in the presence of alkaline compounds to ammonium bases or to the free amines and alkali metal salts, which can interfere with the electrochemical process, e.g. by side reactions of the free amines.
Alkalimetall- oder Erdalkalimetallsalze von Arylsulfon-, Aryicarbonsäuren, Alkylsulfonsäuren und Alkylcarbonsäuren sind in den verwendeten organischen Flüssigkeiten oft schlecht löslich, so daß keine ausreichende Leitfähigkeit erzielt wird. Alkali- und Erdalkalimetallsalze von Carbonsäuren können außerdem teilweise durch Decarboxylierung abgebaut werden.Alkali metal or alkaline earth metal salts of arylsulfonic, aryicarboxylic acids, alkylsulfonic acids and alkylcarboxylic acids are often poorly soluble in the organic liquids used, so that adequate conductivity is not achieved. Alkali and alkaline earth metal salts of carboxylic acids can also be partially broken down by decarboxylation.
Lösliche Sulfide, Cyanide und Rhodanide sind bei der Elektrolyse nicht genügend stabii, da diese anodisch oxidiert werden (Zersetzung). Durch lösliche Chloride, wie Lithiumchlorid u.a. treten Korrosionsprobleme auf und in ungeteilten Zellen können an der Anode Chlorierungen eintreten. Die unter den Elektrolysebedingungen stabilen Chlorate und Perchlorate stellen in organischen Medien ein Sicherheitsrisiko dar.Soluble sulfides, cyanides and rhodanides are not sufficiently stable during electrolysis because they are anodically oxidized (decomposition). Soluble chlorides such as lithium chloride etc. Corrosion problems occur and chlorination can occur at the anode in undivided cells. The chlorates and perchlorates, which are stable under the electrolysis conditions, represent a safety risk in organic media.
Aufgabe der vorliegenden Erfindung war es, Salze von Verbindungen aufzufinden, die für die Verwendung als Leitsalze bei elektrochemischen Prozessen in organischen Flüssigkeiten geeignet sind und weiche nicht die Nachteile der für diese Medien bekannten Leitsalze aufweisen.It was an object of the present invention to find salts of compounds which are suitable for use as conductive salts in electrochemical processes in organic liquids and which do not have the disadvantages of the conductive salts known for these media.
Es wurde gefunden, daß das quartäre Ammoniumsalz der Formel
Die Verbindung (I) ist außerdem unter den Elektrolysebedingungen stabil und nicht hygroskopisch, so daß auch solche Verfahren ohne großen Aufwand durchgeführt werden können, bei denen Wasser stören würde.The compound (I) is also stable under the electrolysis conditions and not hygroscopic, so that even those processes can be carried out without great effort, which would interfere with water.
Das erfindungsgemäße quartäre Ammoniumsalz der Formel 1 ist z.B. als Leitsalz ausgezeichnet bei dem in der DE-A-2711005 beschriebenen Verfahren zur Herstellung von metallfreiem Phthalocyanin durch Elektrolyse von o-Phthalodinitril und bei anderen elektrochemischen Verfahren geeignet, z.B. bei der Synthese von Adipinsäuredinitril, bei der Abscheidung von Metallen aus organischen Elektrolyten und der elektrochemischen Reduktion von C02 zu Oxalsäure. Mit dem erfindungsgemäßen quartären Ammoniumsalz erhält man höhere Stromausbeuten bei gleichzeitig niedrigen Zellspannungen als mit Leitsalzen des Standes der Technik.The quaternary ammonium salt of formula 1 according to the invention is excellent, for example, as the conducting salt in the process described in DE-A-2711005 for the production of metal-free phthalocyanine by electrolysis of o-phthalonitrile and in other electrochemical processes, for example in the synthesis of adiponitrile, in which Deposition of metals from organic electrolytes and the electrochemical reduction of C0 2 to oxalic acid. With the quaternary ammonium salt according to the invention, higher current yields with simultaneously low cell voltages are obtained than with conductive salts of the prior art.
So erhält man z.B. in Gegenwart des Salzes der Formel bei der technischen Durchführung der Elektrolyse von o-Phthalodinitril Phthalocyanin mit einem Reingehalt von 99,8 % und einer Ausbeute von 98,7 %, bezogen auf den Stromdurchsatz, wenn man die Elektrolyse nach 45 % des theoretisch erforderlichen Strombedarfs (bezogen auf eingesetztes o-Phthalodinitril) abbricht und das entstandene Phthalocyanin abtrennt.So you get e.g. in the presence of the salt of the formula in the technical implementation of the electrolysis of o-phthalonitrile phthalocyanine with a purity of 99.8% and a yield of 98.7%, based on the current throughput, if the electrolysis after 45% of the theoretically required electricity (based on the o-phthalonitrile used) breaks off and the phthalocyanine formed is separated off.
Verwendet man dagegen das in der US-A-3 440 154, Sp. 10, Z. 16/17 und in der GB-A-967 956, S. 7, Z. 44 genannte p-Toluolsulfonat des Cholins als Leitsalz, dann erhält man bei der ersten Elektrolyse unter sonst gleichen Bedingungen ein praktisch gleich gutes Phthalocyanin in einer Ausbeute von 91 %.On the other hand, if the p-toluenesulfonate of choline mentioned in US-A-3 440 154, column 10, line 16/17 and in GB-A-967 956, page 7, line 44 is used as the conductive salt, then a practically equally good phthalocyanine is obtained in a yield of 91% in the first electrolysis under otherwise identical conditions.
Die als Leitsalz zu verwendende Verbindung I kann nach an sich bekannten Verfahren hergestellt werden. Eine Herstellmöglichkeit besteht in der Umsetzung der Carbonate der Verbindung
Das Salz der Formel I wird durch Einengen der erhaltenen Lösung isoliert.The salt of formula I is isolated by concentrating the solution obtained.
Ein weiterer Weg besteht z.B. in der Umsetzung des Chlorids oder Sulfats der Verbindung (II) mit den Alkalimetallsalzen der entsprechenden Säure. Vorteilhafterweise wird das entstehende Alkalimetallchlorid entfernt. Das Salz der Formel wird durch Einengen, Kristallisieren und Filtrieren oder durch Extraktion der durch Eindampfen der Lösungen erhaltenen trockenen Rückstände mit polaren Flüssigkeiten, z.B. niederen Alkanolen, erhalten.Another way is e.g. in the reaction of the chloride or sulfate of the compound (II) with the alkali metal salts of the corresponding acid. The resulting alkali metal chloride is advantageously removed. The salt of the formula is obtained by concentration, crystallization and filtration or by extraction of the dry residues obtained by evaporation of the solutions with polar liquids, e.g. lower alkanols.
Das Salz wird bei diesem Verfahren im allgemeinen in sehr reiner Form erhalten und kann in der Regel ohne weitere Reinigung als Leitsalz verwendet werden.In this process, the salt is generally obtained in a very pure form and can generally be used as the conducting salt without further purification.
Die Erfindung soll durch die folgenden Beispiele weiter erläutert werden. Die angegebenen Teile.und Prozente beziehen sich auf das Gewicht.The invention is illustrated by the following examples. The parts and percentages given relate to the weight.
a) 35 Teile Natriumsalz der 2-Hydroxybutan-1-sulfonsäure und 36 Teile einer 78 %-igen wäßrigen Cholinchloridlösung werden in einem Rührgefäß mit 100 Teilen Wasser bei 60 °C gelöst. Es stellt sich dabei ein pH-Wert von 6,5 bis 7 ein.a) 35 parts of sodium salt of 2-hydroxybutane-1-sulfonic acid and 36 parts of a 78% aqueous choline chloride solution are dissolved in a stirred vessel with 100 parts of water at 60 ° C. A pH of 6.5 to 7 is established.
Man rührt bis eine klare farblose Lösung vorliegt und entfernt das Wasser im Rotationsverdampfer bei 80 bis 100°C im Wasserstrahlvakuum.The mixture is stirred until a clear, colorless solution is obtained and the water is removed in a rotary evaporator at 80 to 100 ° C. in a water jet vacuum.
Der Reaktionsrückstand wird drei Mal mit je 100 Teilen Äthanol extrahiert. Die vereinigten Alkoholextrakte werden im Vakuum vom Lösungsmittel befreit.The reaction residue is extracted three times with 100 parts of ethanol each. The combined alcohol extracts are freed from the solvent in vacuo.
Ausbeute : 47 Teile des Salzes der Formel
b) Das benötigte Natriumsalz der 2-Hydroxybutan-1-sulfonsäure wurde wie folgt hergestellt :
- In einem Rührkolben werden 800 Teile Wasser bei Raumtemperatur vorgelegt. Bei 75°C werden 840 Teile Natriumhydrogensulfit zugegeben, bis eine klare Lösung vorliegt. Es stellt sich ein pH-Wert von 4,3 ein. In etwa 45 Minuten läßt man 600 Teile 1,2-Butylenoxid zutropfen, wobei ein starker Rückfluß auftritt.
- 800 parts of water are placed in a stirred flask at room temperature. 840 parts of sodium hydrogen sulfite are added at 75 ° C. until a clear solution is obtained. A pH of 4.3 is established. 600 parts of 1,2-butylene oxide are added dropwise in about 45 minutes, with a strong reflux occurring.
Bei 90 bis 100°C wird 5 Stunden nachgerührt, wobei der pH-Wert bis etwa 9 ansteigt. Man kühlt auf 15 bis 20 °C ab. Der erhaltene Kristallbrei wird abgesaugt und getrocknet.The mixture is stirred at 90 to 100 ° C for 5 hours, the pH increasing to about 9. It is cooled to 15 to 20 ° C. The crystal slurry obtained is suction filtered and dried.
Ausbeute : 1 260 Teile (= 90 % der Theorie) Natriumsalz der 2-Hydroxybutan-1-sulfonsäure in Form eines farblosen schuppigen Salzes.Yield: 1 260 parts (= 90% of theory) of sodium salt of 2-hydroxybutane-1-sulfonic acid in the form of a colorless scaly salt.
Leitfähigkeit in organischen Lösungsmitteln bei 80 °C
Herstellung von Phthalocyanin durch Elektrolyse von o-Phthalodinitril.Production of phthalocyanine by electrolysis of o-phthalonitrile.
In 800 g n-Propanol, das 0,1 % Natrium als Natriumpropylat enthält, werden 70,6 g o-Phthalodinitril bei 88 °C gelöst. Zu dieser Lösung werden als Leitsalz 3 g des Cholinsalzes der 2-Hydroxybutansulfonsäure gegeben. AnschlieBend wird die Lösung bei 80 °C in einer ungeteilten Zelle mit Graphitanode und einer Kathode aus Chrom-Nickel-Stahl (18/8) unter Einleiten von Wasserstoff bei einer Stromdichte von 320 A/m2 elektrolysiert (Spannung : ca. 10 V). Nach - bezogen auf verwendeten o-Phthalodinitril ― 45 % des theoretisch erforderlichen Strombedarfs wird das gebildete Phthalocyanin abfiltriert. mit n-Propanol gewaschen, getrocknet und gewogen.70.6 g of o-phthalonitrile are dissolved at 800C in 800 g of n-propanol, which contains 0.1% sodium as sodium propylate. 3 g of the choline salt of 2-hydroxybutanesulfonic acid are added to this solution as the conductive salt. The solution is then electrolyzed at 80 ° C. in an undivided cell with graphite anode and a cathode made of chrome-nickel steel (18/8) while introducing hydrogen at a current density of 320 A / m 2 (voltage: approx. 10 V) . After - based on the o-phthalonitrile used - 45% of the theoretically required power requirement, the phthalocyanine formed is filtered off. washed with n-propanol, dried and weighed.
Die Massenausbeute an Phthalocyanin - bezogen auf die theoretisch mögliche Ausbeute errechnet aus dem Stromdurchsatz - beträgt 98,7 % bei einem Gehalt von 99,8 % an Phthalocyanin.The mass yield of phthalocyanine - based on the theoretically possible yield calculated from the current throughput - is 98.7% with a content of 99.8% of phthalocyanine.
Verwendet man anstelle des oben genannten Leitsalzes das Cholinsalz der p-Toluolsulfonsäure, so erhält man Phthalocyanin in einer Ausbeute von 91 % und einem Reingehalt von 98,1 %.If the choline salt of p-toluenesulfonic acid is used instead of the above-mentioned conductive salt, phthalocyanine is obtained in a yield of 91% and a purity of 98.1%.
Es wird eine Zelle aus einer porösen Graphitrohranode, die von einer amalgamierten Silbernetzkathode durch eine Kationenaustauschermembran aus einem Sulfonatgruppen enthaltenden Copolymerisat aus Styrol und Divinylbenzol getrennt ist, zur Dimerisierung von Acrylnitril verwendet. In das Graphitrohr (Anolytraum) wird 2,5%ige Phosphorsäure eingefüllt und als Katolyt auf der Seite der Silberamalgamkathode ein Gemisch aus 40 Gew.-% Acrylnitril. 34 Gew.% Wasser und 26 Gew.% Leitsalz der Formel
Bei einer Stromdichte von 100 Alm2, bezogen auf die Kathodenoberfläche, erhält man bei einer Strommenge von 40 % der theoretisch zur Umsetzung des Acrylnitrils erforderlichen eine Stromausbeute von 93% an Adipodinitril.With a current density of 100 Alm 2 , based on the cathode surface, a current yield of 93% of adiponitrile is obtained with a current amount of 40% of the theoretically required to convert the acrylonitrile.
Verwendet man an Stelle des oben genannten Leitsalzes Tetraäthylammonium-p-toluoisulfonat, so beträgt die Stromausbeute unter sonst gleichen Bedingungen nur 84 %.If tetraethylammonium p-toluoisulfonate is used instead of the above-mentioned conductive salt, the current yield is only 84% under otherwise identical conditions.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782849065 DE2849065A1 (en) | 1978-11-11 | 1978-11-11 | USE OF QUARTAINE AMMONIUM SALTS AS LEADING SALTS |
| DE2849065 | 1978-11-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0012215A1 EP0012215A1 (en) | 1980-06-25 |
| EP0012215B1 true EP0012215B1 (en) | 1982-06-30 |
Family
ID=6054472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP79104324A Expired EP0012215B1 (en) | 1978-11-11 | 1979-11-06 | 2-Hydroxybutanesulfonic acid choline and its use as conducting salt |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0012215B1 (en) |
| JP (1) | JPS5572147A (en) |
| DE (2) | DE2849065A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9790161B2 (en) | 2010-03-26 | 2017-10-17 | Dioxide Materials, Inc | Process for the sustainable production of acrylic acid |
| US9957624B2 (en) | 2010-03-26 | 2018-05-01 | Dioxide Materials, Inc. | Electrochemical devices comprising novel catalyst mixtures |
| US10173169B2 (en) | 2010-03-26 | 2019-01-08 | Dioxide Materials, Inc | Devices for electrocatalytic conversion of carbon dioxide |
| US10774431B2 (en) | 2014-10-21 | 2020-09-15 | Dioxide Materials, Inc. | Ion-conducting membranes |
| US10975480B2 (en) | 2015-02-03 | 2021-04-13 | Dioxide Materials, Inc. | Electrocatalytic process for carbon dioxide conversion |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58180463A (en) * | 1982-04-19 | 1983-10-21 | Toyama Chem Co Ltd | Preparation of bischolinedisulfonate |
| DE3501775A1 (en) * | 1985-01-21 | 1986-07-24 | Henkel KGaA, 4000 Düsseldorf | NEW QUARTAINE AMMONIUM COMPOUNDS AND THEIR USE IN CLEANING AGENTS |
| DE3620011A1 (en) * | 1986-06-13 | 1987-12-17 | Henkel Kgaa | NEW CATIONAL SIDE BASED ON QUARTA AMMONIUM COMPOUNDS AND THEIR USE IN CLEANING AGENTS |
| DE3811247A1 (en) * | 1988-04-02 | 1989-10-12 | Henkel Kgaa | QUARTER AMMONIUM COMPOUNDS |
| US4904825A (en) * | 1988-11-08 | 1990-02-27 | Ppg Industries, Inc. | Quaternary ammonium antistatic compounds |
| US5187214A (en) * | 1988-11-08 | 1993-02-16 | Ppg Industries, Inc. | Quaternary ammonium antistatic polymer compositions |
| US5053531A (en) * | 1988-11-08 | 1991-10-01 | Ppg Industries, Inc. | Quaternary ammonium antistatic compounds |
| DE59702678D1 (en) * | 1996-06-12 | 2001-01-04 | Akzo Nobel Nv | Carbonic acid ester betaines and their preparation and use |
| US9566574B2 (en) | 2010-07-04 | 2017-02-14 | Dioxide Materials, Inc. | Catalyst mixtures |
| US9012345B2 (en) | 2010-03-26 | 2015-04-21 | Dioxide Materials, Inc. | Electrocatalysts for carbon dioxide conversion |
| US9815021B2 (en) | 2010-03-26 | 2017-11-14 | Dioxide Materials, Inc. | Electrocatalytic process for carbon dioxide conversion |
| US20110237830A1 (en) | 2010-03-26 | 2011-09-29 | Dioxide Materials Inc | Novel catalyst mixtures |
| US9181625B2 (en) | 2010-03-26 | 2015-11-10 | Dioxide Materials, Inc. | Devices and processes for carbon dioxide conversion into useful fuels and chemicals |
| US8956990B2 (en) | 2010-03-26 | 2015-02-17 | Dioxide Materials, Inc. | Catalyst mixtures |
| US9193593B2 (en) | 2010-03-26 | 2015-11-24 | Dioxide Materials, Inc. | Hydrogenation of formic acid to formaldehyde |
| EP2588647A1 (en) * | 2010-07-04 | 2013-05-08 | Dioxide Materials Inc. | Novel catalyst mixtures |
| US10647652B2 (en) | 2013-02-24 | 2020-05-12 | Dioxide Materials, Inc. | Process for the sustainable production of acrylic acid |
| DE102016217730A1 (en) * | 2016-09-16 | 2018-03-22 | Siemens Aktiengesellschaft | CO2 electrolysis process |
| JP6761386B2 (en) * | 2016-09-29 | 2020-09-23 | 信越化学工業株式会社 | Adhesive composition, bioelectrode, method for producing bioelectrode, and salt |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB967956A (en) * | 1960-12-12 | 1964-08-26 | Monsanto Co | Manufacture of dimers |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3440154A (en) * | 1966-05-02 | 1969-04-22 | Monsanto Co | Electrolytic reductive coupling of olefinic compounds |
-
1978
- 1978-11-11 DE DE19782849065 patent/DE2849065A1/en not_active Withdrawn
-
1979
- 1979-11-06 EP EP79104324A patent/EP0012215B1/en not_active Expired
- 1979-11-06 DE DE7979104324T patent/DE2963267D1/en not_active Expired
- 1979-11-12 JP JP14559679A patent/JPS5572147A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB967956A (en) * | 1960-12-12 | 1964-08-26 | Monsanto Co | Manufacture of dimers |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9790161B2 (en) | 2010-03-26 | 2017-10-17 | Dioxide Materials, Inc | Process for the sustainable production of acrylic acid |
| US9957624B2 (en) | 2010-03-26 | 2018-05-01 | Dioxide Materials, Inc. | Electrochemical devices comprising novel catalyst mixtures |
| US10173169B2 (en) | 2010-03-26 | 2019-01-08 | Dioxide Materials, Inc | Devices for electrocatalytic conversion of carbon dioxide |
| US10774431B2 (en) | 2014-10-21 | 2020-09-15 | Dioxide Materials, Inc. | Ion-conducting membranes |
| US10975480B2 (en) | 2015-02-03 | 2021-04-13 | Dioxide Materials, Inc. | Electrocatalytic process for carbon dioxide conversion |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2963267D1 (en) | 1982-08-19 |
| DE2849065A1 (en) | 1980-05-22 |
| EP0012215A1 (en) | 1980-06-25 |
| JPS5572147A (en) | 1980-05-30 |
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