DE1191355B - Process for the production of aqueous glyoxal solution stabilized against discoloration - Google Patents
Process for the production of aqueous glyoxal solution stabilized against discolorationInfo
- Publication number
- DE1191355B DE1191355B DEN22512A DEN0022512A DE1191355B DE 1191355 B DE1191355 B DE 1191355B DE N22512 A DEN22512 A DE N22512A DE N0022512 A DEN0022512 A DE N0022512A DE 1191355 B DE1191355 B DE 1191355B
- Authority
- DE
- Germany
- Prior art keywords
- solution
- aqueous glyoxal
- aqueous
- glyoxal
- glyoxal solution
- 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.)
- Pending
Links
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 title claims description 58
- 229940015043 glyoxal Drugs 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 15
- 238000002845 discoloration Methods 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title description 4
- 150000001768 cations Chemical class 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 26
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 5
- 235000005985 organic acids Nutrition 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/79—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/86—Use of additives, e.g. for stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. α.:Int. α .:
C07cC07c
Deutsche Kl.: 12 ο-7/03German class: 12 ο-7/03
Nummer: 1191355Number: 1191355
Aktenzeichen: N 22512IV b/12 οFile number: N 22512IV b / 12 ο
Anmeldetag: 21. Dezember 1962Filing date: December 21, 1962
Auslegetag: 22. April 1965Opening day: April 22, 1965
Die Erfindung betrifft ein Verfahren zur Herstellung von gegen Verfärbung stabilisierter wäßriger Glyoxallösung.The invention relates to a process for the production of aqueous stabilized against discoloration Glyoxal solution.
Es ist bekannt, daß Glyoxal durch Oxydation von organischen Verbindungen, wie Acetylen, Äthylen, Acetaldehyd, Paraldehyd oder Äthylenglykol, mit einem Oxydationsmittel, wie Sauerstoff, Salpetersäure, Selendioxyd usw., hergestellt werden kann.It is known that glyoxal is produced by the oxidation of organic compounds such as acetylene, ethylene, Acetaldehyde, paraldehyde or ethylene glycol, with an oxidizing agent such as oxygen, nitric acid, Selenium dioxide, etc., can be produced.
Da reines, monomerisches Glyoxal für die industrielle Herstellung und Verwendung zu unstabil ist, wird es fast immer in Form einer wäßrigen Lösung hergestellt und für verschiedene Zwecke verwendet.Because pure, monomeric glyoxal is too unstable for industrial production and use it is almost always made in the form of an aqueous solution and used for various purposes used.
In vielen Fällen jedoch ist eine industriell hergestellte wäßrige Glyoxallösung gegen Alterang nicht völlig stabil und zeigt nach längerem Stehen bei Zimmertemperatur und insbesondere beim Erwärmen eine Neigung zu gelblicher oder bräunlicher Verfärbung. In many cases, however, an industrially produced aqueous glyoxal solution is not effective against Alterang completely stable and shows after prolonged standing at room temperature and especially when heated a tendency to yellowish or brownish discoloration.
Es ist ein Verfahren zur Verbesserung der Stabilität von ungesättigten Aldehyden, z. B. Acrolein oder Methacrolein bekannt. Die Polymerisation von «,^-ungesättigten Aldehyden, wie z. B. Glyoxal, tritt nur in der Gegenwart von Peroxyd und Metallionen ein. Es ist nicht die Stabilisierung von gesättigten Dialdehyden, z. B. Glyoxal, und insbesondere nicht die Hemmung der Verfärbung der wäßrigen Glyoxallösung vergesehen.It is a method of improving the stability of unsaturated aldehydes, e.g. B. acrolein or Known as methacrolein. The polymerization of «, ^ - unsaturated aldehydes, such as. B. glyoxal occurs only in the presence of peroxide and metal ions. It's not the stabilization of saturated Dialdehydes, e.g. B. glyoxal, and in particular not the inhibition of the discoloration of the aqueous glyoxal solution disregarded.
Es ist weiter bekannt, Glyoxal zu stabilisieren, das im industriellen Bereich hergestellt wird. Eine solche Glyoxallösung ist im allgemeinen nicht notwendigerweise rein und enthält verschiedene Unreinheiten in annehmbarer Menge. Daher ist es nahezu unmöglich, daß die Wirkung von Sauerstoff und Licht oder die Berührung mit einer Metalloberfläche oder einer Glasoberfläche völlig vermieden werden kann. Ferner enthält die Glyoxallösung normalerweise mehr oder weniger organische Säuren, und so ist es nicht möglich, letztere aus ersterer völlig zu entfernen, selbst wenn eine Behandlung mit einem Anionenaustauschharz durchgeführt wird. Daher ist der Ausschluß aller Ionen praktisch nahezu unmöglich.It is also known to stabilize glyoxal which is produced in the industrial sector. Such Glyoxal solution is generally not necessarily pure and contains various impurities in acceptable amount. Therefore, it is almost impossible to have the effect of oxygen and light or the Contact with a metal surface or a glass surface can be completely avoided. Further the glyoxal solution usually contains more or less organic acids, so it is not possible to completely removing the latter from the former even when subjected to an anion exchange resin treatment is carried out. Therefore, the exclusion of all ions is practically almost impossible.
Zwar lassen sich mit einem Kationenaustauschharz geringe Mengen eines Metalls entfernen, jedoch war es bisher unbekannt, daß Metallionen die Ursache für die Verfärbung des Glyoxals sind.Small amounts of a metal can be removed with a cation exchange resin, however it was previously unknown that metal ions are the cause of the discoloration of the glyoxal.
Schließlich ist es bekannt, ein Anionenaustauschharz als Mittel zur Entfernung von Säuren zu verwenden. Finally, it is known to use an anion exchange resin as an acid removing agent.
Es ist die Aufgabe der Erfindung, ein Verfahren zur Herstellung von gegen Verfärbung stabilisierter
wäßriger Glyoxallösung ohne aufwendige und Verfahren zur Herstellung von gegen
Verfärbung stabilisierter wäßriger GlyoxallösungIt is the object of the invention to provide a process for the production of anti-discoloration-stabilized aqueous glyoxal solution without expensive and process for the production of against
Discoloration of stabilized aqueous glyoxal solution
Anmelder:Applicant:
Nippon Gosei Kagaku Kogyo Kabushiki Kaisha, Osaka City (Japan)Nippon Gosei Kagaku Kogyo Kabushiki Kaisha, Osaka City (Japan)
Vertreter:Representative:
Dr. H. Haalck, Rechtsanwalt,Dr. H. Haalck, lawyer,
Hamburg 20, Goernestr. 12Hamburg 20, Goernestr. 12th
Als Erfinder benannt:Named as inventor:
Kaname Tsunemitsu, Nishinomiya City;Kaname Tsunemitsu, Nishinomiya City;
Yoshiaki Tsujino, Ogaki City (Japan)Yoshiaki Tsujino, Ogaki City (Japan)
schwierige Arbeitsgänge zum Abtrennen von gereinigtem Glyoxal aus seiner Lösung zu schaffen.create difficult operations to separate purified glyoxal from its solution.
Diese Äitfgabe läßt sich erfindungsgemäß dadurch lösen, daß eine wäßrige Glyoxallösung mit einem Kationenaustauscher behandelt wird.According to the invention, this output can thereby be achieved solve that an aqueous glyoxal solution is treated with a cation exchanger.
Der genaue Mechanismus, mit dem sich ein Kationenaustauscher wirksam zur Herstellung einer gegen Verfärbung stabilisierten wäßrigen Glyoxallösung bei dem erfindungsgemäßen Verfahren verwenden läßt, ist noch nicht ganz erkennbar. Im Hinblick auf die oben gemachten Feststellungen wird jedoch angenommen, daß die unerwünschte Verfärbung der Lösung durch einige in der Glyoxallösung enthaltene Unreinigkeiten, wahrscheinlich durch Metallkationen, hervorgerufen oder gefördert wird, obgleich eine derartige Hypothese niemals in der Literatur vorgeschlagen wurde. Es kann daher zur Verbesserung der Stabilität einer wäßrigen Glyoxallösung ebenfalls wünschenswert sein, von Metallkationen befreite Rohstoffe zur Herstellung der Lösung zu verwenden.The exact mechanism by which a cation exchanger is effective in producing a Use aqueous glyoxal solution stabilized against discoloration in the process according to the invention leaves is not yet fully recognizable. In view of the above observations, however, it was believed that the undesirable discoloration of the solution was caused by some in the glyoxal solution contained impurities, probably caused or promoted by metal cations, although such a hypothesis has never been proposed in the literature. It can therefore be used for Improving the stability of an aqueous glyoxal solution may also be desirable of metal cations to use freed raw materials to produce the solution.
Bei der Durchführung des erfindungsgemäßen Verfahrens wird eine nach einem bekannten Verfahren hergestellte wäßrige Glyoxallösung durch eine Schicht des Kationenaustauschers hindurchgeleitet. Gegebenenfalls kann die wäßrige Lösung, bevor sie mit dem Kationenaustauscher behandelt wird, nach einem bekannten Verfahren unter Verwendung eines Anionenaustauschers konzentriert -and/oder behandelt werden, um einige als Nebenprodukt gewonnene organische Säuren und den Rückstand des verwendeten Oxydationsmittels, z. B. Salpetersäure, zu ent-When carrying out the method according to the invention is an aqueous glyoxal solution prepared by a known method by a Passed through layer of the cation exchanger. Optionally, the aqueous solution before it is treated with the cation exchanger, according to a known method using a Anion exchanger concentrated and / or treated be to some by-produced organic acids and the residue of the used Oxidizing agent, e.g. B. nitric acid, to
509 540/410509 540/410
fernen. Als Kationenaustaucher kann vorzugsweise einer von den handelsüblichen Kationenaustauschern verwendet werden, die unter den Handelsbezeichnungen »Dowes« (Dow Chemical Co.), »Amberlite« (Röhm & Haas Co.), »Diaion« (Mitsubishi Chemical Industries Ltd.) usw. verkauft werden.distant. One of the commercially available cation exchangers can preferably be used as the cation exchanger used under the trade names "Dowes" (Dow Chemical Co.), "Amberlite" (Röhm & Haas Co.), "Diaion" (Mitsubishi Chemical Industries Ltd.) and so on.
Das erfindungsgemäße Verfahren läßt sich mit Erfolg bei allen nach bekannten Verfahren hergestellten wäßrigen Glyoxallösungen anwenden, um ihre Stabilität gegen Verfärbung zu verbessern. The process according to the invention can be used successfully with all aqueous glyoxal solutions prepared by known processes in order to improve their stability against discoloration .
Durch das erfindungsgemäße Verfahren können wäßrige Glyoxallösungen hergestellt werden, die wegen ihrer verbesserten Stabilität gegen Verfärbung einen großen Handelswert besitzen, denn es werden alle Unzuträglichkeiten vermieden, die durch die Verfärbung der wäßrigen Glyoxallösungen während der Lagerung oder des Versands und auch bei Erwärmung bisher auftraten. The process according to the invention can be used to produce aqueous glyoxal solutions which are of great commercial value because of their improved stability against discoloration, since all inconveniences are avoided which have previously occurred due to the discoloration of the aqueous glyoxal solutions during storage or shipping and also when heated.
Die Erfindung wird durch das folgende Beispiel näher erläutert, in dem eine durch Oxydation von Acetaldehyd mit Salpetersäure hergestellte wäßrige Glyoxallösung als Versuchsprobe verwendet v/urde. Die Mengen sind in Gewichtsteilen und Gewichtsprozenten angegeben. The invention is illustrated in more detail by the following example, in which an aqueous glyoxal solution prepared by the oxidation of acetaldehyde with nitric acid was used as the test sample. The amounts are given in parts by weight and percentages by weight.
Beispiel Herstellung einer wäßrigen Glyoxallösung Example Preparation of an aqueous glyoxal solution
Die in dem Beispiel zu Versuchszwecken verwendete wäßrige Glyoxallösung wurde in nicht beanspruchter Weise nach folgendem Verfahren hergestellt:The aqueous glyoxal solution used in the example for experimental purposes was prepared in a manner not claimed by the following process:
50%iges verdünntes Acetaldehyd und 4O°/oige verdünnte Salpetersäure wurden unter Verrühren in einem Molverhältnis von etwa 2,5:1 in ein Reaktionsgefäß eingebracht, das mit einem Rückflußkühler und einem Rührwerk versehen war und auf einer Temperatur von 38 bis 39° C gehalten wurde. Aus einer Füllung von 11,1 Teilen Acetaldehyd und 6,74 Teilen Salpetersäure wurden 39,2 Teile einer wäßrigen Lösung gewonnen, die 9,1% Glyoxal, 6,3% organische Säuren als Nebenprodukt, 1,4% unveränderte Salpetersäure und 16,5% unveränder tes Acetaldehyd enthielt. Die Lösung wurde bei einem unter dem atmosphärischen Druck liegenden Druck konzentriert, bis die Salpetersäurekonzentration etwa 5% erreichte, und bei etwa 500C mit einer geringen Acetaldehydmenge behandelt, um die verbliebene Salpetersäure zu verbrauchen. Dann wurde die Lösung zwecks Entfernung der organischen Säuren durch eine mit einem Anionenaustauscher gefüllte Säule geleitet, nachdem flüchtige Substanzen, wie z. B. Acetaldehyd, abdestilliert worden waren. Man erhielt 8,9 Teile einer wäßrigen Glyoxallösung, die etwa 40% Glyoxal und weniger als etwa 0,8% organische Säuren enthielt. 50% dilute acetaldehyde and 40% dilute nitric acid were introduced into a reaction vessel, which was provided with a reflux condenser and a stirrer and kept at a temperature of 38 to 39 ° C. , with stirring in a molar ratio of about 2.5: 1 became. From a filling of 11.1 parts of acetaldehyde and 6.74 parts of nitric acid, 39.2 parts of an aqueous solution were obtained which contained 9.1% glyoxal, 6.3% organic acids as a by-product, 1.4% unchanged nitric acid and 16, Contained 5% unchanged acetaldehyde. The solution was concentrated at a pressure below atmospheric pressure until the nitric acid concentration reached about 5% and treated with a small amount of acetaldehyde at about 50 ° C. to consume the remaining nitric acid. The solution was then passed through a column filled with an anion exchanger for the purpose of removing the organic acids, after volatile substances such as. B. acetaldehyde, had been distilled off. 8.9 parts of an aqueous glyoxal solution were obtained which contained about 40% glyoxal and less than about 0.8% organic acids.
Behandlung mit einem KationenaustauscherTreatment with a cation exchanger
Die auf diese Weise gewonnene wäßrige Glyoxailösung wurde erfindungsgemäß behandelt, indem sie durch eine Säule geleitet wurde, die mit 0,6 Teilen eines aus sulfonierten! Folystyrolharz bestehenden Kationenaustauschers vom freien Säuretyp gefüllt war, und wurde dann lange Zeit bei einer Temperatur von 35 bis 40° C auf einem Regal stehengelassen. Selbst nach 2 Monaten konnte keine Verfärbung der Lösung festgestellt werden.The aqueous glyoxylic solution obtained in this way was treated according to the invention by was passed through a column containing 0.6 parts of a sulfonated! Existing folystyrene resin Free acid type cation exchanger was filled, and then it was kept at one temperature for a long time left on a shelf at a temperature of 35 to 40 ° C. There was no discoloration even after 2 months the solution can be determined.
Als die in gleicher Weise wie oben beschrieben hergestellte wäßrige Glyoxallösung dagegen ohne Behandlung mit einem Kationenaustauscher auf dem Regal stehengelassen wurde, wurde festgestellt, daß die Lösung schon nach 2 Wochen eine starke gelblich braune Färbung zeigte.In contrast, as the aqueous glyoxal solution prepared in the same manner as described above without Treatment with a cation exchanger was left standing on the shelf, it was found that the solution showed a strong yellowish brown color after just 2 weeks.
Claims (1)
Deutsche Auslegeschrift Nr. 1 034 634;
USA.-Patentschriften Nr. 2379 555, 2 463 030, 2 874100;Considered publications:
German Auslegeschrift No. 1 034 634;
U.S. Patent Nos. 2,379,555, 2,463,030, 2,874,100;
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEN22512A DE1191355B (en) | 1962-12-21 | 1962-12-21 | Process for the production of aqueous glyoxal solution stabilized against discoloration |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEN22512A DE1191355B (en) | 1962-12-21 | 1962-12-21 | Process for the production of aqueous glyoxal solution stabilized against discoloration |
| US248887A US3290378A (en) | 1963-01-02 | 1963-01-02 | Stabilization of glyoxal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1191355B true DE1191355B (en) | 1965-04-22 |
Family
ID=25988838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEN22512A Pending DE1191355B (en) | 1962-12-21 | 1962-12-21 | Process for the production of aqueous glyoxal solution stabilized against discoloration |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1191355B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4054555A (en) * | 1973-01-04 | 1977-10-18 | Societa' Italiana Resine S.I.R. S.P.A. | Process for the purification of halo-aldehydes |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2379555A (en) * | 1942-01-19 | 1945-07-03 | Du Pont | Polyglyoxal hydrate |
| US2463030A (en) * | 1947-01-31 | 1949-03-01 | Carbide & Carbon Chem Corp | Process of purifying glyoxal |
| DE1034634B (en) * | 1953-05-12 | 1958-07-24 | Dow Chemical Co | Process for the separation of a strong acid from the aqueous solution of a dissolved organic substance |
| US2874100A (en) * | 1956-12-31 | 1959-02-17 | Shell Dev | Stabilization of unsaturated aldehydes |
-
1962
- 1962-12-21 DE DEN22512A patent/DE1191355B/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2379555A (en) * | 1942-01-19 | 1945-07-03 | Du Pont | Polyglyoxal hydrate |
| US2463030A (en) * | 1947-01-31 | 1949-03-01 | Carbide & Carbon Chem Corp | Process of purifying glyoxal |
| DE1034634B (en) * | 1953-05-12 | 1958-07-24 | Dow Chemical Co | Process for the separation of a strong acid from the aqueous solution of a dissolved organic substance |
| US2874100A (en) * | 1956-12-31 | 1959-02-17 | Shell Dev | Stabilization of unsaturated aldehydes |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4054555A (en) * | 1973-01-04 | 1977-10-18 | Societa' Italiana Resine S.I.R. S.P.A. | Process for the purification of halo-aldehydes |
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