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Hydrazinsulfat über den Hypochlorit-Ketazin Prozess
IllumiNobel-Gewinner 2012

Anmeldedatum: 08.05.2011
Beiträge: 672
Artikel: 4
Geschlecht: Geschlecht:Männlich
Vorbemerkung: Dies wurde auf VC schon von mir gepostet http://www.versuchschemie.de/topic,14851.html da ich bei VC nichts mehr schreibe, werde ich nach und nach die relevanten Threads zu Illumina migrieren.

Posting 1:
Das Video http://www.youtube.com/watch?v=UB7vwIFCnR0 wo aus Ammoniaklösung, Natriumhypochloritlösung und Ethylmethylketon über Ethylmethylketazin Hydrazinsulfat hergestellt wird, brachte mich auf die Idee mal etwas im Netz zu stöbern ob es da noch andere Möglichkeiten gibt.

Zum einen ist es ungünstig, wie im Video beschrieben, vom Aceton auszugehen, da das aus diesem gebildete Dimethylketazin (Acetonazin) nicht als leicht abtrennbare Phase abscheidet. Zum anderen stellt der Ethylmethylketon eine nach dem GÜG überwachte Chemikalie dar (ist zwar nur Kategorie 3 d.h. der Export in bestimmte Länder über eine bestimmte Menge ist meldepflichtig, allerdings wird von den Händlern auch bei kleinen Mengen z.B. 1 Liter eine EVE verlangt und wer weiß inwiefern sich da ein LKA in die Hose scheißt).

Eine Patentrecherche brachte nun folgendes Patent zum Vorschein:
Production of ketazines
http://www.freepatentsonline.com/3965097.pdf

Folgende Ketone können laut dem obigen Patent verwendet werden: Aceton, Ethylmethylketon, Diethylketon, Methylisopropylketon, Methylphenylketon, Cyclohexanon und Cycloheptanon.

Nach meiner Einschätzung sollten Diethylketon, Methylisopropylketon, Methylphenylketon, Cyclohexanon und Cycloheptanon ein 2 Phasensystem ähnlich dem im Video beschriebenen mit Ethylmethylketon bilden. Unter Umständen könnte man auch eine Mischung aus Aceton und z.B. Cyclohexanon verwenden und das gebildete unsymmetrische Ketazin abtrennen, was ebenfalls meine Einschätzung* ein 2 Phasensystem bilden sollte.

*= Begründung: "Lipophile Reihe aufsteigend": Aceton, Ethylmethylketon, Diethylketon usw.

Im Artikel "Versuche an einer neuen Caprolactamsynthese. I. Herstellung von 3,3-Pentamethylen-oxaziridin aus Cyclohexanon und Chloramin" http://onlinelibrary.wiley.com/doi/10.1002/prac.19773190204/abstract wird die Synthese von Pentamethylen-oxaziridin beschrieben u.U. findet sich da auch was über die Eigenschaften (komme da nicht ran).

Zusammenfassend wäre es so möglich das GÜG zu umgehen....und Hydrazinsalze herzustellen.....

Ein anderes Patent http://www.freepatentsonline.com/6818794.pdf beschreibt die Extraktion von Ketazinen mittels Isododecan was laut http://www.ineosoligomers.com/51-Isododecane.htm ein verzweigtes Isoparaffin darstellt.
[...]Example 1
250 g of an aqueous solution containing 6.80% by weight of ketazine, 14.9% by weight of NaCl, 13.7% by weight of ammonia and a molar excess of 50% free acetone, based on ketazine, were intensively stirred with 250 g of isododecane at a temperature of 60° C. over 30 min. The mixture was then left to settle for about 2 min and the phases were separated.
The aqueous phase contained 0.23% by weight of ketazine.
The organic phase contained 6.02% by weight of ketazine, 0.1% by weight of ammonia and 1.99% by weight of acetone.
[...]

Diese Extraktionsmethode könnte sich auch für für das Dimethylketazin eignen....


Bei der weiteren Recherche bin ich auf den Ugine Kuhkmann (Atochem) Process gestoßen vgl. http://books.google.com/books?id=NvRqIsu8YNAC&pg=PA187&lpg=PA187&dq=Ugine+Kuhkmann+Process+nitrile&source=bl&ots=ASjI7YJX4W&sig=lKbT2HQQGyjI5pe2dDTDdb-Dv4c&hl=en&ei=I1MYTfnkFMyUswbzuc3nDA&sa=X&oi=book_result&ct=result&resnum=1&ved=0CBMQ6AEwAA#v=onepage&q=Ugine%20Kuhkmann%20Process%20nitrile&f=false
und das führte zu folgendem Patent:
Method for manufacturing hydrazine
http://www.freepatentsonline.com/3869541.pdf

[...]A solution containing 20.5 gm (0.5 moles) acetonitrile, 58 gm (1.0 mole) acetone, 18 gm (1.0 mole) water, 1 gm of the disodium salt of ethylenediaminetetraacetic acid and 0.15 gm ammonium acetate in 160 gm (5 moles) of methanol was placed in a reactor equipped with a distillation column and gaseous ammonia was bubbled into this solution until 14.6 gm (0.86 moles) had become dissolved therein. The temperature of the reaction medium was raised to 50°C, and over a period of 5 minutes, 19.5 gm of an aqueous 70 percent by weight solution of H 2 O 2 (0.4 moles) was added. The medium was left to react for 7 hours at this temperature while gaseous ammonia was bubbled therein at a rate of 1.7 gm (0.1 mole) per hour. Then the pressure was progressively reduced to 200 mm Hg to drive off the excess ammonia and at this pressure, the distillation of unreacted methanol, acetone and acetonitrile was carried out while maintaining a boiling temperature at the base of the column of about 50°C. There were thus recovered 173 gm of a distillate boiling at 40°C of which the composition by weight was as follows: 88.7 percent methanol, 8.4 percent acetone, 1.2 percent acetonitrile and 0.1 percent acetoneazine. The pressure was then reduced to 50 mm Hg and 76 gm of a 44.3 percent aqueous solution of acetoneazine, boiling at 35°C was recovered. 29.6 gm of a residue consisting of 88 percent by weight acetamide as well as acetoneazine and hydrazine, at a level of 4.7 percent of the total expressed as acetoneazine were recovered. The total quantity of acetoneazine formed during the reaction was 35.2 gm (0.314 moles) which corresponded to a yield of 78.5 percent by comparison to the H 2 O 2 reacted.

20 gm water were added to 76 gm of the 44.3 percent aqueous solution of distilled acetoneazine (0.3 moles) and 57 gm of 66° Baume sulfuric acid (0.57 mole) were then progressively added. There resulted an immediate precipitation of hydrazine acid sulfate. The free acetone was distilled at atmospheric pressure and 32 gm (0.55 mole) of this ketone were recovered and recycled. The precipitated salt was filtered, washed with cold water and dried. 39 gm of hydrazine acid sulfate of 99.4 percent purity (0.3 mole) were recovered. The yield from hydrolysis was quantitative. The overall yield was 75 percent by comparison to the amount of H 2 O 2 reacted.
[...]

D.h. ich würde mal einen Ansatz von:

26 ml Acetonnitril (0.5 mol)
90 ml Ethylmethylketon (1 mol)
1 g EDTA * 2Na
0.15 g Ammoniumacetat
41 ml 30% Wasserstoffperoxid-Lösung (0.4 mol)
117 ml 25% Ammoniak-Lösung (1.56 mol)

zusammen mischen und das Ganze mal einige Stunden auf 50° C erwärmen.....und hoffen, dass sich da ein 2 Phasen Gemisch bildet.

Anderes Patent:
http://www.freepatentsonline.com/6562311.pdf

EXAMPLE 4
In Accordance with the Invention

180 g of water (10 mol), 77 g of ammonium acetate (1 mol), 177 g of acetamide (3 mol), 144 g of methyl ethyl ketone (2 mol) and 2 cm 3 of Dequest 2066 stabilizer (sodium salt of diethylenediaminepenta-(methylenephosphonic acid) as a 25% aqueous solution), sold by the Company Monsanto, are charged to a reactor. This mixture is brought to 50° C. and is then saturated with ammonia. 48.5 g of 70% hydrogen peroxide (1 mol) are then added over a period of 1 hour. Introduction of gaseous ammonia is continued, so as to keep the medium saturated. Reaction is allowed to take place for 7 hours at 50° C. After cooling to ambient temperature, the aqueous and organic phases are separated. Analysis is carried out and it is found that the H 2 O 2 conversion is 98% for an azine yield of 81%.

Bj68


Posting 2:


Kleines Update:


ChemDoc hat ein Patent gefunden http://www.freepatentsonline.com/3956282.pdf was die Verwendung von Carbonsäureestern als Ersatz für das ACN vorschlägt.....


Beim weiteren suchen fand ich folgendes:

[i][...]
EXAMPLE 7

A solution of peracetic acid was prepared by mixing 17.3 gm of glacial acetic acid (0.29 moles), 7.2 gm of a 68% by weight aqueous solution of hydrogen peroxide and 0.7 gm of concentrated sulfuric acid and reacting this mixture for several hours at ambient temperature. In this manner, a solution containing 0.10 moles of peracetic acid and 0.033 moles of unreacted hydrogen peroxide was obtained. This solution was added over a period of 30 minutes at 20°C to a solution of 8.5 gm ammonia (0.5 moles), 14.5 gm acetone (0.25 moles), 25 gm water and 0.25 gm of the disodium salt of ethylendiaminetetraacetic acid in 40 gm of methanol while at the same time passing a stream of gaseous ammonia, about 0.1 moles/hour, through the mixture. The mixture was left to react for fifteen minutes at this temperature and then titrated. 8.5 gm of acetoneazine (0.076 moles) corresponding to a yield of 76% by comparison to the total amount of peracid were found.

EXAMPLE 8

A 57% by weight aqueous solution of peracetic acid (0.10 moles) was added to a solution of 8.5 gm ammonia (0.5 moles) 14.5 gm of acetone (0.25 moles) and 0.25 gm of the disodium salt of ethylenediaminetetraacetic acid in 60 gm of water over a period of 30 minutes at 20°C. 8.1 gm of acetoneazine (0.072 moles) formed corresponding to a yield of 72% by comparison with the total amount of peracid.

EXAMPLE 9

A 24% by weight solution of peracetic acid (0.10 moles) in acetone (0.40 moles) was added to 57 gm of an aqueous solution of ammonia containing 15% ammonia by weight (0.5 moles) over 30 minutes at 20°C and left to react at this temperature for 30 minutes. 8.3 gm of acetoneazine (0.074 moles) formed corresponding to a yield of 74% by comparison with the total amount of peracid.
[...]


http://www.freepatentsonline.com/3959262.pdf

und Peressigsäure gibt es fertig als Lösung zu kaufen....


[...]EXAMPLE 1

A reactor is charged with 69.6 grams of acetone (1.2 mol), 118 grams of acetamide (2 mols), 10 grams of the disodium salt of ethylenediaminetetraacetic acid (EDTA), 198 grams of water, and 0.286 grams of dilithium phosphate. Into this mixture there are dissolved 13.6 grams of ammonia (0.8 mol). The mixture is heated to 56°C and over a period of 30 minutes there is added 29.6 grams of a 70% by weight aqueous solution of hydrogen peroxide (0.6 mol). The mixture is then maintained at 56°C for 6 hours while passing a light current of gaseous ammonia at a rate of about 0.3 mol per hour. The quantity of acetone-azine formed in the reaction mixture, as determined by chemical means and by gas chromatography, is found to be 44.8 grams (0.4 mol) corresponding to a yield of 66.6% based on the hydrogen peroxide used.

EXAMPLE 2

Proceeding in a manner similar to that of Example 1, a reactor of suitable volume is charged with 34.8 grams of acetone (0.6 mol), 59 grams of acetamide (1 mol), 3 grams of the disodium salt of ethylenediaminetetraacetic acid (EDTA), 58.9 grams of water and 0.442 grams of monosodium carbonate. In this medium there is dissolved 6.8 grams of gaseous ammonia (0.4 mol). This mixture is then heated to 56°C and 15 grams of a 68% by weight aqueous solution of hydrogen peroxide (0.3 mol) is introduced over a period of 30 minutes. The temperature of the mixture is maintained at 56°C over a period of 5 hours while a current of gaseous ammonia is continuously passed at the rate of about 0.3 mol per hour. Analysis then shows that 18.6 grams of acetoneazine (0.167 mols) has been formed, corresponding to a yield of 55.6% based on the hydrogen peroxide used.
[...]

http://www.freepatentsonline.com/3972878.pdf

Mit Backpulver, Acetamid geht es auch....

[...]
EXAMPLE I

A solution of 20 gm. of sodium hydroxide, 200 gm. of methanol and 10 cm3 of water were placed in a glass reactor equipped with a mechanical agitator. 73.5 gm. of cyclohexanone, 25 cm3 of 19% solution of ammonia and 0.5 gm. of the disodium salt of ethylenediaminetetraacetic acid were then added to the solution. Thereafter over a period of 30 minutes while maintaining a temperature of 20°C., 12.25 gm. of 70% hydrogen peroxide were added. After 24 hours, the reaction medium contained 8.6 gm. of cyclohexanoneazine.

EXAMPLE II

EXAMPLE I was substantially repeated replacing sodium hydroxide with an equal amount of lithium chloride. After the hydrogen peroxide was added, the reaction medium was heated for 2 hours at 50°C. after which the medium contained 15.4 gm. of cyclohexanoneazine.
[...]

http://www.freepatentsonline.com/3948902.pdf


und das ist noch besser....Lithiumchlorid tut es auch....

[...]
EXAMPLE 1

14.5 gm of acetone (0.25 moles), 5 gm of water, 65 gm of methanol, 5 gm of a 68% by weight solution of hydrogen peroxide (0.1 moles) and 0.25 gm of the disodium salt of ethylenediaminetetraacetic acid (EDTA) were placed in a reactor and thereafter 5.1 gm ammonia (0.3 moles) were dissolved in the reaction mixture. The reaction mixture was heated to 50°C and 4.5 gm of formamide (0.1 moles) were added to the mixture over 10 minutes. The temperature was maintained at 50°C for 31/2 hours during which a slight stream of ammonia, about 0.1 moles/hours, was introduced into the medium. The acetoneazine present in the reaction medium was measured chemically and by gas phase chromatography. 6.2 gm of acetoneazine (0.055 moles) had formed corresponding to a yield of 55% by comparison to the hydrogen peroxide.
After leaving the mixture for 24 hours at 20°C, the reaction was allowed to continue and the final yield of acetoneazine then attained 70%.

EXAMPLE 2

Example 1 was substantially repeated except that twice the amount of formamide (9.0 gm; 0.2 moles) was employed. After reacting for 31/2 hours at 50°C, the reaction medium contained 8.5 gm of acetoneazine (0.076 moles) corresponding to a yield of 76%; after 61/2 hours at 50°C, the reaction medium contained 9.0 gm of acetoneazine (0.08 moles) corresponding to a yield of 80% based on the amount of hydrogen peroxide used.

EXAMPLE 3

Example 1 was substantially repeated except that methanol was replaced with the same weight of water. After the reaction medium has reacted for 31/2 hours at 50°C, analysis indicated that 6.1 gm of acetoneazine (0.054 moles) had formed thus corresponding to a yield of 54% based on the amount of hydrogen peroxide used.

EXAMPLE 4

Example 1 was repeated except that the formamide was replaced with 14.7 gm of o-phthalimide (0.1 moles). After the reaction medium had reacted for 5 hours at 50°C, analysis indicated that 4.3 gm of acetoneazine (0.038 moles) had formed thus corresponding to a yield of 38% based on the amount of hydrogen peroxide used.
[....]

http://www.freepatentsonline.com/3943152.pdf

mit Formamid oder Phthalimid.....wobei das Letzte als nicht toxisch eingestuft ist.....


Further Reading:
http://www.freepatentsonline.com/5239119.pdf
http://www.freepatentsonline.com/3972876.pdf
http://www.freepatentsonline.com/4093656.pdf


Würde sagen, da gibt es jede Menge Möglichkeiten....die wahrscheinlich auch mit 10% Wasserstoffperoxid funktionieren dürften.....

BJ68


PS: Edit meint, dass das wieder ein perfektes Beispiel dafür ist, dass die Behörden sich ihren ganzen Überwachungsschwachsinn dahin stecken können, wo keine Sonne hinkommt....es bringt nichts....
[/i]


Posting 3:

Nachtrag:


Habe mir mal das Buch "Hydrazine and its derivatives" (ISBN 0-471-41553-7) http://www.amazon.com/Hydrazine-its-Derivatives-Preparation-Applications/dp/0471415537 vorgenommen und bin fündig geworden:


[...]Hydrazine form dilute Raschig process liquor can be recovered by reacting with a ketone (acetone or 2-butanone) in the presence of NaCl or CaCl2. The reaction product is insoluble in the brine, and the reaction mixture seperates in two phases. The organic phase can be decanted and hydrolyzed to free the hydrazine.
[...]

Hier das US-Patent dazu: http://www.freepatentsonline.com/3875231.pdf
und das deutsche: http://depatisnet.dpma.de/DepatisNet/depatisnet?action=pdf&docid=DE000002056357A


Zusätzlich noch das:
[...]Another of the patents in this area claims an improvement in hydrazine yield from 43 to 77% due the addition of acetone to the reacting mixture of ammonia and hypochlorite in aqueous solution. [...]

US-Patent: http://www.freepatentsonline.com/2993758.pdf
Deutsch: http://depatisnet.dpma.de/DepatisNet/depatisnet?action=pdf&docid=DE000001088939B

Beides zusammen dürfte den Einsatz von Aceton anstatt des MEK ermöglichen, da nun auch das Acetonazin als getrennte Phase abgezogen werden kann und somit die Destillation entfällt....und was gilt die Wette, dass dieses Aussalzen auch mit den diversen anderen Ansätzen funktioniert?

Bj68



Da ich ab Silvester Urlaub habe, wird u.U. (es ist da auch zugleich Winterlager von meinen Pfadfindern) wenn es zeitlich möglich ist Versuche geben....


Bj68
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