DE878350C - Process for the preparation of oxidation products of saturated cyclic hydrocarbons - Google Patents
Process for the preparation of oxidation products of saturated cyclic hydrocarbonsInfo
- Publication number
- DE878350C DE878350C DEF2312D DEF0002312D DE878350C DE 878350 C DE878350 C DE 878350C DE F2312 D DEF2312 D DE F2312D DE F0002312 D DEF0002312 D DE F0002312D DE 878350 C DE878350 C DE 878350C
- Authority
- DE
- Germany
- Prior art keywords
- oxidation
- saturated cyclic
- cyclic hydrocarbons
- oxidation products
- preparation
- 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
Links
- 230000003647 oxidation Effects 0.000 title claims description 21
- 238000007254 oxidation reaction Methods 0.000 title claims description 21
- 125000000753 cycloalkyl group Chemical group 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Oxydationsprodukten gesättigter cyclischer Kohlenwasserstoffe Es ist schon vorgeschlagen worden, aus gesättigten cyclischen Kohlenwasserstoffen in flüssiger Phase durch Oxydation mit Sauerstoff oder sauerstoffhaltigen Gasen, gegebenenfalls in Gegenwart von Katalysatoren, wertvolle Oxydationsprodukte herzustellen. So entsteht z. B. aus Cyclohexan bei der Oxydation Cyclohexanol, Cyclohexanon, Adipinsäure und ein aus Säuren, Estern u. dgl. bestehendes Gemisch, dessen Zusammensetzung nicht eindeutig feststeht. Aus diesem Stoffgemisch kann durch Verseifung eine beträchtliche Menge Cyclohexanol und aus dieser Verseifungslauge eine entsprechende Menge Säuren, z. B. Adipinsäure, gewonnen werden.Process for the preparation of oxidation products of saturated cyclic Hydrocarbons It has already been suggested from saturated cyclic Hydrocarbons in the liquid phase by oxidation with oxygen or those containing oxygen Gases, if appropriate in the presence of catalysts, valuable oxidation products to manufacture. So z. B. from cyclohexane in the oxidation of cyclohexanol, cyclohexanone, Adipic acid and a mixture consisting of acids, esters and the like, its composition is not clearly established. From this mixture of substances, a considerable amount can be obtained by saponification Amount of cyclohexanol and, from this saponification liquor, a corresponding amount of acids, z. B. adipic acid can be obtained.
Es wurde nun gefunden, daß die obenerwähnte Oxydation cyclischer Kohlenwasserstoffe auch in Gegenwart von wäßrigen Alkalien durchgeführt werden kann. Die entstandenen neutralen Oxydationsprodukte (Ketone und Alkohole) bleiben hierbei in dem nicht umgesetzten Kohlenwasserstoff gelöst, woraus sie z. B. durch Abdestillieren gewonnen oder mit Salpetersäure zu der entsprechenden Säure weiteroxydiert werden können. Aus der sich vom Öl abtrennenden wäßrigen Schicht fallen beim Ansäuern die sauren Oxydationsprodukte zum Teil aus, zum Teil können sie aus der Mutterlauge durch Extrahieren oder Destillieren gewonnen werden. Eine Esterbildung tritt unter diesen Reaktionsbedingungen praktisch nicht mehr ein.It has now been found that the above-mentioned oxidation of cyclic hydrocarbons can also be carried out in the presence of aqueous alkalis. The resulting neutral oxidation products (ketones and alcohols) do not remain in this reacted hydrocarbon dissolved, from which it z. B. obtained by distillation or can be further oxidized with nitric acid to give the corresponding acid. On acidification, the acidic layers fall from the aqueous layer which separates from the oil Oxidation products partly from, partly they can be extracted from the mother liquor or distilling. Ester formation occurs under these reaction conditions practically no longer one.
Die Oxydation des Cyclohexans in flüssiger Phase mit Luft in Gegenwart der wäßrigen Alkalien kann z. B. bei Temperaturen über ioo" und unter erhöhtem Druck in Gegenwart oder Abwesenheit von Schwermetallkatalysatoren oder von oxydationsbeschleunigenden Stoffen, wie Ketonen, Aldehyden u. dgl., durchgeführt werden. Die Menge des zugesetzten Alkalis kann verschieden bemessen werden; vorzugsweise fügt man dem Ansatz so viel Alkali zu, daß alle während der Oxydation gebildeten Säuren neutralisiert werden. Der Zusatz der Alkalien kann so erfolgen, daß man die gesamte Menge schon vor Beginn der Oxydation zufügt, oder derart, daß man sie, um ein schnelles Anspringen der Oxydation zu gewährleisten, erst nach Beginn der Oxydation kontinuierlich in dem Maße zuführt, in welchem Säuren sich bilden. Beispiel i In ein elektrisch beheiztes Druckrohr werden 111 Cyclohexan und eine Lösung von 350 g Ätznatron in 1,5 1 Wasser eingefüllt. Bei einer Temperatur von Z55° und einem Druck von 35 at wird durch das Substanzgemisch ein Luftstrom von 500 1 je Stunde geleitet. 3 Stunden nach Beginn der Oxydation wird der Versuch abgebrochen und das Rohr entleert. Der Rohrinhalt scheidet sich in eine wäßrige und eine Cyclohexanschicht. Aus dieser werden nach dem Abdestillieren des Cyclohexans 8oo g eines Öls gewonnen, welches die Säurezahl 2o und die Verseifungszahl 42 besitzt. Dieses Öl enthält 48 °/o Cyclohexanol und 51 °/o Cyclohexanon, bei der Oxydation mit Salpetersäure liefert es =2o °/o des Eigengewichtes an Adipinsäure.The oxidation of cyclohexane in the liquid phase with air in the presence of the aqueous alkalis can, for. B. at temperatures above 100 "and under increased pressure in the presence or absence of heavy metal catalysts or oxidation-accelerating substances such as ketones, aldehydes and the like. The amount of alkali added can be measured differently; add a lot of alkali so that all acids formed during the oxidation are neutralized. The addition of the alkalis can be done in such a way that the entire amount is added before the start of the oxidation, or in such a way that they are added in order to ensure a quick start of the oxidation, supplying only after the start of the oxidation continuously at the rate in which acids are formed. example I in an electrically heated pressure tube are charged 11 1 of cyclohexane and a solution of 350 g sodium hydroxide in 1.5 1 of water. at a temperature of Z55 ° and At a pressure of 35 atm, an air stream of 500 liters per hour is passed through the substance mixture, 3 hours after the start of the oxidation The attempt was terminated and the pipe was emptied. The pipe contents are separated into an aqueous and a cyclohexane layer. From this, after the cyclohexane has been distilled off, 800 g of an oil which has an acid number of 20 and a saponification number of 42 are obtained. This oil contains 48% cyclohexanol and 51% cyclohexanone; when oxidized with nitric acid it yields 20% of its own weight in adipic acid.
Aus der alkalischen Schicht kann man durch Erhitzen noch 2o g Cyclohexanol-Cyclohexanon-Gemisch austreiben. Die Lösung wird dann kongosauer gemacht. Durch sofortiges Abheben gewinnt man 298 g (trockene) Säuren, aus der Mutterlauge fallen 59 g rohe Adipinsäure aus, und durch Extraktion der Mutterlauge gewinnt man weitere 164 g Säuren, insgesamt somit 521 g. qoo g dieser Säuren werden mit Butanol verestert und liefern qio g Butylester vom Kp. = 7o bis 2q0°.20 g of a cyclohexanol / cyclohexanone mixture can be expelled from the alkaline layer by heating. The solution is then made Congo acidic. Immediately lifting off, 298 g of (dry) acids are obtained, 59 g of crude adipic acid precipitate from the mother liquor, and a further 164 g of acids are obtained by extraction of the mother liquor, a total of 521 g. qoo g of these acids are esterified with butanol and yield qio g of butyl ester with a boiling point of 70 to 2q0 °.
Beispiel 2 In ein Schachtrohr werden =i 1 Cyclohexan gefüllt, in dem =o g Kobaltnaphthenat gelöst sind. Dann wird bei einem Druck von 2o at und einer Temperatur von =6o' ein Luftstrom von iooo 1 je Stunde durch die Flüssigkeit geblasen. Nach Beginn der Oxydation läßt man während i Stunde eine Lösung von 350 g Ätznatron in 1,5 1 Wasser in das Rohr laufen.Example 2 A shaft pipe is filled with 1 liter of cyclohexane in which the above-mentioned cobalt naphthenate is dissolved. Then, at a pressure of 20 atm and a temperature of 60 ', an air current of 100 liters per hour is blown through the liquid. After the start of the oxidation, a solution of 350 g of caustic soda in 1.5 l of water is allowed to run into the tube for 1 hour.
Nach i Stunde Versuchsdauer wird das Rohr entleert und die Cyclohexanschicht von der wäßrigen Schicht getrennt. Nach dem Abdestillieren des Cyclohexans gewinnt man 8=o g eines Öls mit der Säurezahl 12 und der Verseifungszahl 25, das bei der Oxydation mit Salpetersäure iig g Adipinsäure liefert.After one hour of testing, the tube and the cyclohexane layer are emptied separated from the aqueous layer. After distilling off the cyclohexane wins one 8 = o g of an oil with the acid number 12 and the saponification number 25, which in the Oxidation with nitric acid yields some g of adipic acid.
Man kann die Reaktion dadurch kontinuierlich gestalten, daß man während der Oxydation ständig einen Teil der Natronlauge aus dem Rohr entfernt und dafür eine entsprechende Menge frische zuführt. Ebenso verfährt man mit dem Cyclohexan.You can make the reaction continuous that you during the oxidation constantly removes part of the caustic soda from the pipe and for this supplies a corresponding amount of fresh. The same applies to cyclohexane.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF2312D DE878350C (en) | 1941-12-11 | 1941-12-11 | Process for the preparation of oxidation products of saturated cyclic hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF2312D DE878350C (en) | 1941-12-11 | 1941-12-11 | Process for the preparation of oxidation products of saturated cyclic hydrocarbons |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE878350C true DE878350C (en) | 1953-06-01 |
Family
ID=7083229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF2312D Expired DE878350C (en) | 1941-12-11 | 1941-12-11 | Process for the preparation of oxidation products of saturated cyclic hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE878350C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE969501C (en) * | 1951-12-13 | 1958-06-12 | Huels Chemische Werke Ag | Process for removing disruptive impurities from cyclohexanol-cyclohexanone mixtures |
| DE1082255B (en) * | 1958-06-28 | 1960-05-25 | Bergwerksgesellschaft Hibernia | Process for the production of hydroperoxides of the terpene hydrocarbons |
-
1941
- 1941-12-11 DE DEF2312D patent/DE878350C/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE969501C (en) * | 1951-12-13 | 1958-06-12 | Huels Chemische Werke Ag | Process for removing disruptive impurities from cyclohexanol-cyclohexanone mixtures |
| DE1082255B (en) * | 1958-06-28 | 1960-05-25 | Bergwerksgesellschaft Hibernia | Process for the production of hydroperoxides of the terpene hydrocarbons |
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