DE721000C - Process for the oxidative degradation of essentially solid carbon-containing substances - Google Patents
Process for the oxidative degradation of essentially solid carbon-containing substancesInfo
- Publication number
- DE721000C DE721000C DEG101078D DEG0101078D DE721000C DE 721000 C DE721000 C DE 721000C DE G101078 D DEG101078 D DE G101078D DE G0101078 D DEG0101078 D DE G0101078D DE 721000 C DE721000 C DE 721000C
- Authority
- DE
- Germany
- Prior art keywords
- water
- carboxylic acids
- salts
- comma
- words
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 5
- 229910052799 carbon Inorganic materials 0.000 title claims description 5
- 239000000126 substance Substances 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 4
- 239000007787 solid Substances 0.000 title claims description 3
- 238000010525 oxidative degradation reaction Methods 0.000 title description 2
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 150000001735 carboxylic acids Chemical class 0.000 claims description 9
- 239000003245 coal Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003077 lignite Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 4
- 238000010438 heat treatment Methods 0.000 claims 2
- 239000003415 peat Substances 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000004021 humic acid Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 201000004384 Alopecia Diseases 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000003676 hair loss Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 241000238565 lobster Species 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 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
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Description
Verfahren zum oxydativen Abbau von im wesentlichen festen Kohlenstoff enthaltenden Stoffen Es ist bereits bekannt, Braunkohle in Gegenwart oder Abwesenheit vorn Alkalien der Druckoxydation zu unterwerfen (vgl. Franz Fischer, Ges. Abhdl. z. Kenntnis der Kohle, Bd. ii, S. 197 ff.). Hiernach geht (S. r98, Abs. i) die Braunkohle in alkalischem Medium bei hinreichend langer Behandlung völlig in Lösung unter Bildung von wasserunlöslichen Hummsäuren und wasserlöslichen Carbonsäuren. Außerdem entsteht infolge totaler Oxydation Kohlendioxyd. Auf S. zog a. a. O., Z. 3 von unten und ff., wird dann ein Versuch beschrieben, bei :der Druckoxydation in wäßrig-neutralem, Medium eine weitere Oxydation ider einmal gebildeten Säuren dadurch zu verhindern, daß plan die Oxydationslösung laufend aus dem Druckgefäß iabzieht und entsprechende Mengen Frischwasser einpreßt. Es handelt sich also hier -um ,einen einstufigen Oxydationsvorgang.Process for the oxidative degradation of essentially solid carbon containing substances It is already known to have lignite in the presence or absence to subject alkalis to pressure oxidation (cf. Franz Fischer, Ges. Abhdl. z. Knowledge of coal, vol. Ii, p. 197 ff.). After that goes (p. 98, Para. I) the lignite in an alkaline medium with sufficiently long treatment completely in solution with formation of water-insoluble lobster acids and water-soluble carboxylic acids. Also arises carbon dioxide as a result of total oxidation. On S. pulled a. a. O., line 3 from below and ff., an experiment is then described in: the pressure oxidation in aqueous-neutral, Medium to prevent further oxidation of the acids once formed by that plan the oxidation solution is continuously drawn off from the pressure vessel and corresponding Pressing in quantities of fresh water. So this is a one-step oxidation process.
Es wurde nun gefunden, daß, namentlich bei der Verarbeitung von Steinkohlen, z. B. Ruhrfettkohle, der oxydative Abbau zu Benzolcarbonsäuren durch Druckoxydation in Gegenwart eines Entsäüerungsimittels sich mit erheblich größerer Ausbeute durchführen läßt, wenn man in zwei Stufen arbeitet, derart, daß in der ersten Stufe hauptsächlich Huminsäuren gebildet werden, deren Umwandlung in wasserlösliche Carbonsäuren durch weitere Oxydation dann erst in der zweiten Stufe erfolgt. Es ist also nicht zweckmäßig,, in einer einzigen Stufe direkt auf die Bildung dieser Carbonsäuren hinzuarbeiten, sondern man erzeugt durch eine mildere Voroxydation zunächst Huminsäuren und oxydiert diese dann für sich in einer zweiten Stufe zu Carbon.-säuren.It has now been found that, especially in the processing of hard coal, z. B. Ruhr fat coal, the oxidative breakdown to benzene carboxylic acids by pressure oxidation in the presence of a deacidifying agent can be carried out with a considerably higher yield lets, if one works in two stages, in such a way that in the first stage mainly Humic acids are formed, their conversion into water-soluble carboxylic acids by further oxidation then only takes place in the second stage. So it is not practical, work directly towards the formation of these carboxylic acids in a single step, but humic acids are first produced by a milder pre-oxidation and then oxidized these then turn into carboxylic acids in a second stage.
Um also, in der ersten Stufe einte zu weit gehende Oxydation zu verhindern, zieht man, kontinuierlich oder absatzweise, aus dem Druckgefäß Anteile der Oxydätionslösumg unter Trennung von dem noch ungelöstem Ausgangsstoff ab und preßtentsprechende Mengen frischen Entsäuerungsmittels ein, z. B. Alkalilauge. Die abgezogenen Lösungsant@eilie enthalten im wesentlichen Huminsäuren als wasserlösliche Alkalisalze. Sie werden vereinigt und zwecks Bildung der eigentlichen Carbonsäuren in der zweiten Stufe einer energischeren Oxydation unterworfen, zweckmäßig in Gegenwart eines Katalysators. Als Kontakte eignen sich besonders Metallverbindungen verschiedener Wertigkeitsstufen, die auf Kieselgur oder ähnlich wirkenden Trägermassen niedergeschlagen sind, die von Sauerstoff unter den herrschenden Re.aktionsbedingungen nicht angegriffen werden. Ausführungsbeispiel 5oo Teile Ruhrfettkohle werden mit Zoo Teilen calcinierter Soda und 22oo Teilen Wasser vermischt und in einem Blasautoklaven unter etwa z 5o at bei 24o bis 25o° mit Luft im Kreisstrom behandelt. Hierbei wird stündlich ein Teil der Lösung durch ein Filter abgezogen und das noch Ungelöste mit der entsprechenden Menge frischer Sodalauge versetzt. Ein großer Teil der Kohle löst sich, der Rest wird einem späteren Ansatz zugefügt. Aus 202 Teilen Kohle entstehen 22z Teile an wasserunlöslichem Zwischenprodukt, ,außerdem noch 96 Teile an wasserlöslichen organischen Säuren. Die in dieser Oxydationsstufe gebildete Kohlensäuremenge entspricht 46 Gewichtsteilen Kohlenstoff. Der Luftverbrauch beträgt je Kilogramm Kahle 15 cbm. Der in der umgeführten Luft enthaltene Sauerstoff wird zu 48,2% ausgenutzt.So in order to prevent excessive oxidation in the first stage, one pulls, continuously or intermittently, portions of the Oxydätionslösumg from the pressure vessel with separation of the still undissolved starting material and presses appropriate amounts of fresh deacidifying agent, z. B. Alkali. The removed solvent components essentially contain humic acids as water-soluble alkali salts. They are combined and, for the purpose of forming the actual carboxylic acids, subjected to a more vigorous oxidation in the second stage, expediently in the presence of a catalyst. Metal compounds of various valency levels that are deposited on kieselguhr or similarly acting carrier materials that are not attacked by oxygen under the prevailing reaction conditions are particularly suitable as contacts. Embodiment 500 parts of Ruhr fat coal are mixed with zoo parts of calcined soda and 22oo parts of water and treated with air in a circulating current in a blown autoclave under about z 50 at at 24 ° to 25 °. Here, part of the solution is drawn off every hour through a filter and what is still undissolved is mixed with the appropriate amount of fresh soda lye. A large part of the coal dissolves, the rest is added to a later batch. 202 parts of coal produce 22z parts of water-insoluble intermediate product, and 96 parts of water-soluble organic acids. The amount of carbonic acid formed in this oxidation stage corresponds to 46 parts by weight of carbon. The air consumption is 1 5 cbm per kilogram of baldness. The oxygen contained in the circulated air is used up to 48.2%.
Die erhaltenen Lösungen werden vereinigt und nach Zusatz von auf Kieselgur niedergeschlagenem Eisenoxydhydrat in der zweiten Stufe bei 25o bis 26o'' weiteroxydiert. Man erhält 204 Teile tvasserlösliche organische Säuren neben einer Kohlensäuremenge entsprechend 29 Gewichtsteilen Kohlenstoff. Die Lösung wird vom Katalysator abfiltriert, der wieder verwendet werden kann.The solutions obtained are combined and, after the addition of kieselguhr precipitated iron oxide hydrate is further oxidized in the second stage at 25o to 26o ''. 204 parts of water-soluble organic acids are obtained in addition to an amount of carbonic acid corresponding to 29 parts by weight of carbon. The solution is filtered off from the catalyst, which can be used again.
Die Arbeitsweise kann in bezug auf die Menge der :angewandten Substanz, des Entsäuerungsimittels und des Wassers weitgehend abgeändert werden. Auch kann der Druck in weiten Grenzen schwanken, wenn man ihn auch am besten oberhalb etwa rooat hält. Das gleiche gilt von der Temperatur, welche in der ersten Stufe möglichst nicht unter 15o° sinken soll, während für die zweite Stufe vorteilhaft etwas höhere Temperaturen gewählt werden.The mode of operation can be related to the amount of: applied substance, the deacidifying agent and the water are largely changed. Also can the pressure fluctuate within wide limits, even if it is best above about rooat holds. The same applies to the temperature, which in the first stage is possible should not drop below 15o °, while for the second stage it is advantageous to have a little higher Temperatures can be chosen.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEG101078D DE721000C (en) | 1939-12-22 | 1939-12-22 | Process for the oxidative degradation of essentially solid carbon-containing substances |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEG101078D DE721000C (en) | 1939-12-22 | 1939-12-22 | Process for the oxidative degradation of essentially solid carbon-containing substances |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE721000C true DE721000C (en) | 1942-07-03 |
Family
ID=7141351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEG101078D Expired DE721000C (en) | 1939-12-22 | 1939-12-22 | Process for the oxidative degradation of essentially solid carbon-containing substances |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE721000C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2668099A (en) * | 1949-04-11 | 1954-02-02 | Stora Kopparbergs Bergslags Ab | Process of dewatering lignocellulosic materials in the production of fuel |
| US2704895A (en) * | 1950-02-18 | 1955-03-29 | Stora Kopparbergs Bergslags Ab | Drying peat and similar vegetable materials |
-
1939
- 1939-12-22 DE DEG101078D patent/DE721000C/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2668099A (en) * | 1949-04-11 | 1954-02-02 | Stora Kopparbergs Bergslags Ab | Process of dewatering lignocellulosic materials in the production of fuel |
| US2704895A (en) * | 1950-02-18 | 1955-03-29 | Stora Kopparbergs Bergslags Ab | Drying peat and similar vegetable materials |
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