DE1225645B - Process for the separation of hydrogen peroxide from such and sulfuric acid-containing crude tert-butyl hydroperoxide - Google Patents
Process for the separation of hydrogen peroxide from such and sulfuric acid-containing crude tert-butyl hydroperoxideInfo
- Publication number
- DE1225645B DE1225645B DEU9378A DEU0009378A DE1225645B DE 1225645 B DE1225645 B DE 1225645B DE U9378 A DEU9378 A DE U9378A DE U0009378 A DEU0009378 A DE U0009378A DE 1225645 B DE1225645 B DE 1225645B
- Authority
- DE
- Germany
- Prior art keywords
- hydrogen peroxide
- sulfuric acid
- butyl hydroperoxide
- tert
- separation
- 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims description 29
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 title claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 4
- 238000000926 separation method Methods 0.000 title claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Abtrennung von Wasserstoffperoxyd aus solches und Schwefelsäure enthaltendem rohem tert.-Butylhydroperoxyd Bei der Darstellung von höherprozentigem tert.-Butylhydroperoxyd aus tert.-Butanol und Wasserstoffperoxyd in Gegenwart von Schwefelsäure arbeitet man im allgemeinen mit Wasserstoffperoxydüberschuß. Das Reaktionsprodukt tert.-Butylhydroperoxyd ist in der Reaktionslösung nur mäßig löslich. Es scheidet sich daher bei entsprechenden Konzentrationen als obere Schicht ab und kann in dieser Form abgezogen werden. Dieses Hydroperoxyd enthält neben Di-tert.-Butylperoxyd geringe Mengen an Schwefelsäure, Wasser und tert.-Butanol sowie Wasserstoffperoxyd.Process for the separation of hydrogen peroxide from such and sulfuric acid containing crude tert-butyl hydroperoxide in the representation of higher percentage tert-Butyl hydroperoxide from tert-butanol and hydrogen peroxide in the presence of Sulfuric acid is generally used with an excess of hydrogen peroxide. The reaction product Tert-butyl hydroperoxide is only sparingly soluble in the reaction solution. It part therefore at the appropriate concentrations as the upper layer and can be in this Shape can be peeled off. This hydroperoxide contains small amounts of di-tert-butyl peroxide Amounts of sulfuric acid, water and tert-butanol and hydrogen peroxide.
So befinden sich in den bei der kontinuierlichen Herstellung von tert. -Butylhydroperoxyd aus tert. So are located in the continuous production of tert. -Butyl hydroperoxide from tert.
Butanol und 600/,igem Wasserstoffperoxyd anfallenden etwa 77- bis 800/0eigen Lösungen von tert.-Butylhydroperoxyd etwa 1 bis 2°/o Wasserstoffperoxyd. Bei einer Verwendung des tert.-Butylhydroperoxyds für weitere chemische Umsetzungen, wie z. B. zur Darstellung von 2,2-Bis-(tert.-butylperoxyd)-butan aus Methyläthylketon und tert.-Butylhydroperoxyd, ist aber die Anwesenheit derartiger Mengen ap Wasserstoffperoxyd wegen unerwünschter Nebenreaktionen zu vermeiden. Man hat daher das rohe tert.-Butylhydroperoxyd nach Neutralisation der geringen Mengen an gelösten Säuren destillativ oder über die Alkaliverbindungen gereinigt, wobei naturgemäß erhebliche Verluste an Hydroperoxyd auftreten.Butanol and 600% strength hydrogen peroxide produced about 77 to 800/0 own solutions of tert-butyl hydroperoxide about 1 to 2% hydrogen peroxide. When using the tert-butyl hydroperoxide for further chemical reactions, such as B. for the preparation of 2,2-bis (tert-butyl peroxide) butane from methyl ethyl ketone and tert-butyl hydroperoxide, but the presence of such amounts ap hydrogen peroxide to avoid because of undesirable side reactions. You therefore have the crude tert-butyl hydroperoxide after neutralization of the small amounts of dissolved acids by distillation or over the alkali compounds cleaned, with naturally considerable losses of hydroperoxide appear.
Es wurde nun überraschenderweise gefunden, daß das Wasserstoffperoxyd aus solches und Schwefelsäure enthaltendem rohem tert.-Butylhydroperoxyd in einfacher Weise praktisch restlos abgetrennt werden kann, wenn man dieses Rohprodukt nach der Neutralisation der Schwefelsäure mit Alkalilauge mit überschüssigem Erdalkalioxyd oder -hydroxyd behandelt und erforderlichenfalls mit einem Filterhilfsmittel klärt. It has now surprisingly been found that the hydrogen peroxide from such and sulfuric acid containing crude tert-butyl hydroperoxide in a simple Way can be separated practically completely, if this crude product after the neutralization of sulfuric acid with alkali with excess alkaline earth oxide or hydroxide treated and, if necessary, clarified with a filter aid.
Angesichts der bekannten Schwerlöslichkeit der Erdalkalisalze von Peroxyden in Wasser war nicht vorauszusehen, daß es auf diese Weise gelingt, Wasserstoffperoxyd als Erdalkalisalz selektiv aus Butylhydroperoxydlösung abzutrennen, da auch die Bildung von schwerlöslichen Erdalkalihydroperoxydsalzen zu erwarten war. Die Erdalkaliverbindungen werden z. B. in stückiger Form in einer Säule angeordnet und das rohe Butylhydroperoxyd darüber filtriert. Im Anschluß an die Behandlung mit den Erdalkaliverbindungen ist eine Filtration z. B. über Kieselgur, eventuell unter Druck, von Vorteil, um mitgerissene anorganische Verbindungen zu entfernen. Man kann die Erdalkalioxyde bzw. -hydroxyde auch in wäßriger Lösung oder Suspension anwenden, jedoch treten hierbei unter Umständen Verluste an tert.-Butylhydroperoxyd wegen seiner Wasserlöslichkeit auf. Von den Erdalkaliverbindungen werden am vorteilhaftesten stückiges Calciumoxyd oder -hydroxyd in einer Säule eingesetzt. Vor der Behandlung mit Erdalkalien ist es erforderlich, die von der Herstellung her vorhandene Schwefelsäure beispielsweise mit 400/,der Natronlauge zu neutralisieren und die wäßrige Schicht abzutrennen. Anderenfalls können Erdalkaliverbindungen gelöst bzw. suspendiert werden, die später auflocken bzw. nicht klar filtrierbar sind. In view of the known poor solubility of the alkaline earth salts of Peroxides in water could not be foreseen that hydrogen peroxide would succeed in this way to be separated selectively from butyl hydroperoxide solution as alkaline earth salt, since the Formation of poorly soluble alkaline earth hydroperoxide salts was to be expected. The alkaline earth compounds are z. B. arranged in lump form in a column and the crude butyl hydroperoxide filtered over it. Following the treatment with the alkaline earth compounds a filtration e.g. B. over kieselguhr, possibly under pressure, beneficial to entrained remove inorganic compounds. One can use the alkaline earth oxides or hydroxides also use in aqueous solution or suspension, however, this may occur Loss of tert-butyl hydroperoxide due to its water solubility. Of the Alkaline earth compounds are most advantageously lumpy calcium oxide or hydroxide used in a column. Before treatment with alkaline earths, it is necessary to the sulfuric acid present from the production, for example, with 400 /, the To neutralize sodium hydroxide solution and separate the aqueous layer. Otherwise alkaline earth compounds can be dissolved or suspended, which later loosen or are not clearly filterable.
Beispiel Ein schwefelsäurehaltiges Rohprodukt mit 79,2°/o tert.-Butylhydroperoxyd und 1,4 01o Wasserstoffperoxyd wurde in bekannter Weise mit Natronlauge neutralisiert. Dabei sank der Gehalt an Wasserstoffperoxyd auf 0,89 °/0. Das so erhaltene Produkt wurde 20 bzw. 40 Minuten mit stückigem Calciumoxyd behandelt und anschließend über Kieselgur filtriert. Example A crude product containing sulfuric acid with 79.2% tert-butyl hydroperoxide and 1.4 01o hydrogen peroxide was neutralized in a known manner with sodium hydroxide solution. The hydrogen peroxide content fell to 0.89 per cent. The product thus obtained was treated with lumpy calcium oxide for 20 or 40 minutes and then over Diatomaceous earth filtered.
Die sich hiernach ergebenden Wasserstoffperoxydgehalte waren 0,15 bzw. 0,05 O/o.The resulting hydrogen peroxide contents were 0.15 and 0.05 O / o, respectively.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEU9378A DE1225645B (en) | 1962-11-09 | 1962-11-09 | Process for the separation of hydrogen peroxide from such and sulfuric acid-containing crude tert-butyl hydroperoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEU9378A DE1225645B (en) | 1962-11-09 | 1962-11-09 | Process for the separation of hydrogen peroxide from such and sulfuric acid-containing crude tert-butyl hydroperoxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1225645B true DE1225645B (en) | 1966-09-29 |
Family
ID=7566770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEU9378A Pending DE1225645B (en) | 1962-11-09 | 1962-11-09 | Process for the separation of hydrogen peroxide from such and sulfuric acid-containing crude tert-butyl hydroperoxide |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1225645B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3449217A (en) * | 1968-01-05 | 1969-06-10 | Halcon International Inc | Process of buffering a neutralized t-butyl hydroperoxide during distillation |
| EP0135295A3 (en) * | 1983-09-14 | 1985-08-14 | Atlantic Richfield Company | Purification of tertiary butyl hydroperoxide containing primary and secondary alkyl hydroperoxide contaminants |
-
1962
- 1962-11-09 DE DEU9378A patent/DE1225645B/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3449217A (en) * | 1968-01-05 | 1969-06-10 | Halcon International Inc | Process of buffering a neutralized t-butyl hydroperoxide during distillation |
| EP0135295A3 (en) * | 1983-09-14 | 1985-08-14 | Atlantic Richfield Company | Purification of tertiary butyl hydroperoxide containing primary and secondary alkyl hydroperoxide contaminants |
| US4584413A (en) * | 1983-09-14 | 1986-04-22 | Atlantic Richfield Company | Purification of tertiary butyl hydroperoxide containing primary and secondary alkyl hydroperoxide contaminants |
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