US2501088A - Catalytic oxidation of aromatic hydrocarbons in presence of nitroalkanes - Google Patents
Catalytic oxidation of aromatic hydrocarbons in presence of nitroalkanes Download PDFInfo
- Publication number
- US2501088A US2501088A US679574A US67957446A US2501088A US 2501088 A US2501088 A US 2501088A US 679574 A US679574 A US 679574A US 67957446 A US67957446 A US 67957446A US 2501088 A US2501088 A US 2501088A
- Authority
- US
- United States
- Prior art keywords
- hydrocarbon
- oxygen
- aromatic hydrocarbons
- oxidation
- aromatic hydrocarbon
- 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 - Lifetime
Links
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
- C07C45/27—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
- C07C45/36—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 in compounds containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
Definitions
- This invention relates to a process for oxidizing aromatic hydrocarbons and particularly b enzene hydrocarbons.
- An object of this invention is to produce aromatic alcohols and aromaticcarbonyl compounds.
- Another object of this invention is to oxidize an aromatic hydrocarbon in the presence of a nitrated aliphatic hydrocarbon.
- Still another object of this invention is to oxidize an aromatic hydrocarbon by means of an oxygen-containing gas in the presence of a nitroalkane.
- a further object of this invention is to oxidize an alkyl benzene hydrocarbon in the presence of a catalytic amount of a nitroalkane.
- a still further object of this invention is to oxidize an aromatic hydrocarbon in the presence of a catalyst comprising a metal selected from the group consisting of the metals having atomic numbers of from 23 to 30, inclusive, and in the presence of a nitroalkane.
- One specific embodiment of the present invention relates to a process for oxidizing an aromatic hydrocarbon which comprises reacting said arematic hydrocarbon and an oxygen-containing gas in the presence of a nitroalkane.
- a further embodiment of this invention relates to a process for oxidizing an aromatic hydrocarbon which comprises reacting said aromatic hydrocarbons and an oxygen-containing gas in the presence of a nitroalkane in a reaction zone containing a metal selected from the group consisting of the metals having atomic numbers of from 23 to 30, inclusive.
- Still further embodiment of this invention relates to a process for oxidizing an alkyl benzene hydrocarbon which comprises reacting said benzene hydrocarbon, a nitroalkane, and an oxygen-containing gas in a reaction zone containing a refractory packing material composited with a metal selected from the group of metals having atomicnumbers of 23 to 30, inclusive.”
- aromatic hydrocarbons and particularly aromatic hydrocarbons of the benzene series are oxidized readily by an oxygencontaining gas in a reaction zone containing a refractory packing material upon which a small amount of a metal or a metal oxide is deposited.
- the oxidation process is also catalyzed by 2. nitroparafdn which may be mixed with the aromatic hydrocarbon charged to the process or it may be introduced to the reaction zone by other means.
- Aromatic l'lydrocarbons such as toluene, xylene, ethyl benzene, cumene, cymene, a butyl benzene,
- allrylated benzenes, naphthalene, an 55 alkylated naphthalene, and other polynuclear and alkylated polynuclear aromatic hydrocarbons which are oxidized by our process have at least 7 carbon atoms per molecule and include alkyl benzene hydrocarbons and polycyclic aromatic hydrocarbons.
- Our process is carried out in the presence of a liquid catalyst, a solid catalyst, and preferably in the presence of both a liquid catalyst and a solid catalyst, the latter employed as a reactor packing material.
- Liquid catalysts which we employ comprise nitroaliphatic hydrocarbons and particularly the nitroalkanes which are also referred to as the nitroparafiins.
- the following table gives the boiling points and specific gravity of some of the nitroparaflins used in our process, although other nitroparafiins containing more than four carbon atoms per molecule, and particularly the nitropentanes are also useful as oxidation catalysts.
- the solid catalysts which we use in our process as packing material in the oxidation reactor comprise metals with atomic numbers of 23 to 30, inelusive, thus including the metals vanadium, chromium, manganese, iron, cobalt, copper, and zinc, supported by a refractory packing material such as crushed firebrick, granular pumice, quartz chips, crushed porcelain. silica, or other refractory granular materials which do not have a harmful influence upon the oxidation reaction.
- Such composites of a refractory packing material and a metal are produced preferably by dissolving a metal salt of an organic acid and particularly a metal salt of a long chain fatty acid, such as a metal stearate, in a normally liquid aromatic hydrocarbon which is oxidized by our process.
- a metal salt of an organic acid and particularly a metal salt of a long chain fatty acid, such as a metal stearate in a normally liquid aromatic hydrocarbon which is oxidized by our process.
- a metal salt of an organic acid and particularly a metal salt of a long chain fatty acid, such as a metal stearate in oxidized by our process.
- the metal salt of the organic acid which is dissolved in the aromatic hydrocarbon and charged to the reaction zone is decomposed therein and the resultant metal oxide is deposited upon the refractory packing material to form a highly active oxidation catalyst.
- the metal salt which is sometimes referred to as a metal soap, is thus introduced either continuously or intermittently as clesiredin order to maintain in the reaction zone an amount of metal oxide suflicient to catalyze the oxidation of the aromatic hydrocarbon charged thereto together with the aforementioned liquid catalyst comprising a nitropar afi'iln or a mixture of nitroparaflin.
- Our oxidation process may be carried out in either a batch operation or a continuous type of operation, although the latter is generally preierred.
- the oxidation treatment is efiected at a temperature of from about 50 to about 200 C. and at a pressure of from substantially atmospheric to about 100 atmospheres.
- the oxidizing medium employed comprises air, oxygen, a mixture of air and oxygen, or either air or oxygen diluted with an inert gas.
- nitroalkanes which are the liquid catalysts preferred in our process may be substituted or partially substituted by an oxide of nitrogen, particularly nitrogen dioxide, nitrogen trioxide, and nitrogen tetraoxide.
- Example I Cumene containing 0.5 mole per cent of a nitropentane and air were charged simultaneously to a steel reactor, containing granular pumice supporting 0.9% by weight of manganese oxide and maintained at a temperature of 150 C. and operating at a pressure of 35 atmospheres.
- the mixture of cumene and nitropentane was charged at a rate corresponding to an hourly liquid space velocity of 1.6 and the amount of air introduced to the reaction zone was such that the molar ratio of oxygen to hydrocarbon in the. reaction mixture was 3.
- 39 mole per cent of the cumene was oxidized per pass and on a recycle basis yielded 56 mole per cent of acetophenone and 21 per cent of dimethylphenylcarbinol.
- Example I! In another run, cumene was mixed with 2 mole per cent of nitromethane and the iesultant solution was subjected to the oxidation treatment as described in Example I. Twenty-nine per cent of the cumene was converted per pass with the formation on a recycle basis 01' 45 per cent of acetophenone and 30 per cent of dimethylphenylcarbinol.
- a process foroxidizing an aromatic hydrocarbon of at least '7 carbon atoms per molecule which comprises reacting said hydrocarbon with an oxygen-containing gas in the presence of a nitroalkane.
- a process tor oxidizing an aromatic hydrocarbon of at least 7 carbon atoms per molecule which comprises reacting said hydrocarbon with an oxygen-containing gas in the presence of a nitroalkane and an oxide of a metal having an atomic number of from 23 to 30, inclusive.
- a process for oxidizing an aromatic hydrocarbon of at least '7 carbon atoms per molecule which comprises reacting said hydrocarbon with an oxygen-containing gas in the presence 01! a nitroalkane at 'a temperature of from about 50 C. to about 200 C.
- a process for oxidizing an aromatic hydrocarbon of at least 7 carbon atoms per molecule which comprises reacting said hydrocarbon with an oxygen-containing gas at a temperature of from about 50 C. to about 200 C. in the presence of a nitroalkane and an oxide of a metal having an atomic number of from 23 to 30, inclusive.
- a process for producing dimethylphenylcarbinol and acetophenone which comprises reacting cumene and air in the presence of nitromethane at a temperature of from about 50 to about 200 C. and at a pressure of from about 1 to about atmospheres in a reaction zone containing a granular composite of manganese oxide and pumice.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Mar. 21, 1950 CATALYTIC OXIDATION OF AROMATIC HY- DROCARBONS IN PRESENCE OF NITRO- ALKANES Herman Pines and Bruno to Universal Oil Products Comllls assignors Kvetlnskas, Chicago,
pan'y, Chicago, 111., a corporation of Delaware no Drawing. Application June 26, 1946,
= Serial No. 679,574
9 Claims. ll
This invention relates to a process for oxidizing aromatic hydrocarbons and particularly b enzene hydrocarbons.
An object of this invention is to produce aromatic alcohols and aromaticcarbonyl compounds.
Another object of this invention is to oxidize an aromatic hydrocarbon in the presence of a nitrated aliphatic hydrocarbon.
Still another object of this invention is to oxidize an aromatic hydrocarbon by means of an oxygen-containing gas in the presence of a nitroalkane.
A further object of this invention is to oxidize an alkyl benzene hydrocarbon in the presence of a catalytic amount of a nitroalkane.
A still further object of this invention is to oxidize an aromatic hydrocarbon in the presence of a catalyst comprising a metal selected from the group consisting of the metals having atomic numbers of from 23 to 30, inclusive, and in the presence of a nitroalkane.
One specific embodiment of the present invention relates to a process for oxidizing an aromatic hydrocarbon which comprises reacting said arematic hydrocarbon and an oxygen-containing gas in the presence of a nitroalkane.
A further embodiment of this invention relates to a process for oxidizing an aromatic hydrocarbon which comprises reacting said aromatic hydrocarbons and an oxygen-containing gas in the presence of a nitroalkane in a reaction zone containing a metal selected from the group consisting of the metals having atomic numbers of from 23 to 30, inclusive.
still further embodiment of this invention relates to a process for oxidizing an alkyl benzene hydrocarbon which comprises reacting said benzene hydrocarbon, a nitroalkane, and an oxygen-containing gas in a reaction zone containing a refractory packing material composited with a metal selected from the group of metals having atomicnumbers of 23 to 30, inclusive."
We have found that aromatic hydrocarbons and particularly aromatic hydrocarbons of the benzene series are oxidized readily by an oxygencontaining gas in a reaction zone containing a refractory packing material upon which a small amount of a metal or a metal oxide is deposited. The oxidation process is also catalyzed by 2. nitroparafdn which may be mixed with the aromatic hydrocarbon charged to the process or it may be introduced to the reaction zone by other means.
Aromatic l'lydrocarbons such as toluene, xylene, ethyl benzene, cumene, cymene, a butyl benzene,
Lil
and other allrylated benzenes, naphthalene, an 55 alkylated naphthalene, and other polynuclear and alkylated polynuclear aromatic hydrocarbons which are oxidized by our process have at least 7 carbon atoms per molecule and include alkyl benzene hydrocarbons and polycyclic aromatic hydrocarbons.
Our process is carried out in the presence of a liquid catalyst, a solid catalyst, and preferably in the presence of both a liquid catalyst and a solid catalyst, the latter employed as a reactor packing material.
Liquid catalysts which we employ comprise nitroaliphatic hydrocarbons and particularly the nitroalkanes which are also referred to as the nitroparafiins. The following table gives the boiling points and specific gravity of some of the nitroparaflins used in our process, although other nitroparafiins containing more than four carbon atoms per molecule, and particularly the nitropentanes are also useful as oxidation catalysts.
- Specific Compound fg fla giiogig Nitromethane 101 1.139 Nitroethane 114 1. 052 l-Nitropropane 132 l. 003 2-Nitropropane 120 0.992 l-Nitrobutane 151 0. 975
The solid catalysts which we use in our process as packing material in the oxidation reactor comprise metals with atomic numbers of 23 to 30, inelusive, thus including the metals vanadium, chromium, manganese, iron, cobalt, copper, and zinc, supported by a refractory packing material such as crushed firebrick, granular pumice, quartz chips, crushed porcelain. silica, or other refractory granular materials which do not have a harmful influence upon the oxidation reaction.
Such composites of a refractory packing material and a metal are produced preferably by dissolving a metal salt of an organic acid and particularly a metal salt of a long chain fatty acid, such as a metal stearate, in a normally liquid aromatic hydrocarbon which is oxidized by our process. Thus from about 0.1 to about 0.5% by weight of metal salt is dissolved in a normally liquid aromatic hydrocarbon and the resultant solution is then conducted to a heated reaction zone containing a refractory packing material in granular form or small particles. Oxygen, air, or another oxygen-containing gas is charged simul taneously to the reaction zone containing the packing material in order to efiect oxidation of the aromatic hydrocarbon. During this oxidation 3 treatment, the metal salt of the organic acid which is dissolved in the aromatic hydrocarbon and charged to the reaction zone is decomposed therein and the resultant metal oxide is deposited upon the refractory packing material to form a highly active oxidation catalyst. The metal salt, which is sometimes referred to as a metal soap, is thus introduced either continuously or intermittently as clesiredin order to maintain in the reaction zone an amount of metal oxide suflicient to catalyze the oxidation of the aromatic hydrocarbon charged thereto together with the aforementioned liquid catalyst comprising a nitropar afi'iln or a mixture of nitroparaflin.
Our oxidation process may be carried out in either a batch operation or a continuous type of operation, although the latter is generally preierred. The oxidation treatment is efiected at a temperature of from about 50 to about 200 C. and at a pressure of from substantially atmospheric to about 100 atmospheres. The oxidizing medium employed comprises air, oxygen, a mixture of air and oxygen, or either air or oxygen diluted with an inert gas.
The nitroalkanes which are the liquid catalysts preferred in our process may be substituted or partially substituted by an oxide of nitrogen, particularly nitrogen dioxide, nitrogen trioxide, and nitrogen tetraoxide.
The following examples are given to illustrate the results obtained in this process, although the data presented are not introduced with the intention of restricting unduly the broad scope of the invention.
Example I Cumene containing 0.5 mole per cent of a nitropentane and air were charged simultaneously to a steel reactor, containing granular pumice supporting 0.9% by weight of manganese oxide and maintained at a temperature of 150 C. and operating at a pressure of 35 atmospheres. The mixture of cumene and nitropentane was charged at a rate corresponding to an hourly liquid space velocity of 1.6 and the amount of air introduced to the reaction zone was such that the molar ratio of oxygen to hydrocarbon in the. reaction mixture was 3. By this treatment, 39 mole per cent of the cumene was oxidized per pass and on a recycle basis yielded 56 mole per cent of acetophenone and 21 per cent of dimethylphenylcarbinol.
Example I! In another run, cumene was mixed with 2 mole per cent of nitromethane and the iesultant solution was subjected to the oxidation treatment as described in Example I. Twenty-nine per cent of the cumene was converted per pass with the formation on a recycle basis 01' 45 per cent of acetophenone and 30 per cent of dimethylphenylcarbinol.
The nature of the present invention and its utility are evident from the specification and examples, although neither section is introduced to limit unduly the generally broad scope of the invention.
We claim as our invention:
1. A process foroxidizing an aromatic hydrocarbon of at least '7 carbon atoms per molecule which comprises reacting said hydrocarbon with an oxygen-containing gas in the presence of a nitroalkane.
2. A process tor oxidizing an aromatic hydrocarbon of at least 7 carbon atoms per molecule which comprises reacting said hydrocarbon with an oxygen-containing gas in the presence of a nitroalkane and an oxide of a metal having an atomic number of from 23 to 30, inclusive.
3. A process for oxidizing an aromatic hydrocarbon of at least '7 carbon atoms per molecule which comprises reacting said hydrocarbon with an oxygen-containing gas in the presence 01! a nitroalkane at 'a temperature of from about 50 C. to about 200 C.
4. A process for oxidizing an aromatic hydrocarbon of at least 7 carbon atoms per molecule which comprises reacting said hydrocarbon with an oxygen-containing gas at a temperature of from about 50 C. to about 200 C. in the presence of a nitroalkane and an oxide of a metal having an atomic number of from 23 to 30, inclusive.
5. The process as defined in claim 1 further characterized in that said hydrocarbon is an alkyl benzene.
6. The process as defined in claim 2 further characterized in that said hydrocarbon is an alkyl benzene.
'1. The process as defined in claim 1 further characterized in that said hydrocarbon comprises cumene.
8. The process as defined in claim 2 further characterized in that said hydrocarbon comprises cumene.
9. A process for producing dimethylphenylcarbinol and acetophenone which comprises reacting cumene and air in the presence of nitromethane at a temperature of from about 50 to about 200 C. and at a pressure of from about 1 to about atmospheres in a reaction zone containing a granular composite of manganese oxide and pumice.
BRUNO KVETINSKAS.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,813,606 Binapfl et al July 7, 1931 2,245,528 Loder June 10, 1941 2,376,674 Emerson et a1. May 22, 1945 OTHER REFERENCES Gimmelman et al., Acta Physicochim. URSS., vol. 7, pages 221-246 (1937).
Gimmelman et al., Chemical Abstracts, vol. 31, column 8287 (1937).
Ajello et al., Chemical Abstracts, vol. 33, 4581- 4582 (1939).
Berezovskaya et al., Chemical Abstracts, vol. 39. 2024 (1945).
Claims (1)
1. A PROCESS FOR OXIDIZING AN AROMATIC HYDROCARBON OF AT LEAST 7 CARBON ATOMS PER MOLECULE WHICH COMPRISES REACTING SAID HYDROCARBON WITH AN OXYGEN-CONTAINING GAS IN THE PRESENCE OF A NITROALKANE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US679574A US2501088A (en) | 1946-06-26 | 1946-06-26 | Catalytic oxidation of aromatic hydrocarbons in presence of nitroalkanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US679574A US2501088A (en) | 1946-06-26 | 1946-06-26 | Catalytic oxidation of aromatic hydrocarbons in presence of nitroalkanes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2501088A true US2501088A (en) | 1950-03-21 |
Family
ID=24727463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US679574A Expired - Lifetime US2501088A (en) | 1946-06-26 | 1946-06-26 | Catalytic oxidation of aromatic hydrocarbons in presence of nitroalkanes |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2501088A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0308896A1 (en) * | 1987-09-24 | 1989-03-29 | Mitsubishi Kasei Corporation | Method for producing a cycloalkanol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1813606A (en) * | 1926-12-23 | 1931-07-07 | Ig Farbenindustrie Ag | Process of obtaining oxygenated compounds from alkyl benzenes |
| US2245528A (en) * | 1938-10-18 | 1941-06-10 | Du Pont | Catalytic oxidation of alkyl substituted aromatic compounds |
| US2376674A (en) * | 1943-07-24 | 1945-05-22 | Monsanto Chemicals | Method for oxidation of aromatic hydrocarbons |
-
1946
- 1946-06-26 US US679574A patent/US2501088A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1813606A (en) * | 1926-12-23 | 1931-07-07 | Ig Farbenindustrie Ag | Process of obtaining oxygenated compounds from alkyl benzenes |
| US2245528A (en) * | 1938-10-18 | 1941-06-10 | Du Pont | Catalytic oxidation of alkyl substituted aromatic compounds |
| US2376674A (en) * | 1943-07-24 | 1945-05-22 | Monsanto Chemicals | Method for oxidation of aromatic hydrocarbons |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0308896A1 (en) * | 1987-09-24 | 1989-03-29 | Mitsubishi Kasei Corporation | Method for producing a cycloalkanol |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| GB944773A (en) | Improved process for the oxidation of organic compounds | |
| US20060281629A1 (en) | Catalyst comprising N-substituted cyclic imide compound and process for producing organic compound using the catalyst | |
| US1815985A (en) | Process for the manufacture of oxygenated organic compounds | |
| Gao et al. | The efficient liquid‐phase oxidation of aromatic hydrocarbons by molecular oxygen in the presence of MnCO3 | |
| US7084090B2 (en) | Catalyst comprised of n-substituted cyclic imides and processes for preparing organic compounds with the catalyst | |
| US2859247A (en) | Process for the preparation of bicyclic ketones | |
| US2838558A (en) | Catalytic production of aromatic nitriles and imides | |
| US1678627A (en) | Method of regenerating catalysts | |
| US2552278A (en) | Liquid phase oxidation | |
| US2501088A (en) | Catalytic oxidation of aromatic hydrocarbons in presence of nitroalkanes | |
| US3390174A (en) | Process for the preparation of adipic acid | |
| EP1238704B1 (en) | Catalyst comprising a cyclic imide compound and process for producing organic compounds using the catalyst | |
| US2495904A (en) | Production of aromatic keto alcohols | |
| Peng et al. | Facile access to nitroalkanes: Nitration of alkanes by selective CH nitration using metal nitrate, catalyzed by in-situ generated metal oxide | |
| US2928879A (en) | Oxidation of hydrocarbons with sulfur dioxides | |
| US2614130A (en) | Oxidative condensation of alkyl aromatic hydrocarbons and of nuclearly chlorinated alkyl aromatic hydrocarbons | |
| US3428700A (en) | Preparation of polycyclic hydrocarbons | |
| US2443832A (en) | Oxidation of aromatic compounds | |
| US2377025A (en) | Conversion of a mixture of acetaldehyde and ethylene to butadiene | |
| US2792430A (en) | Production of phenolic compounds | |
| US2913492A (en) | Selective formic acid removal | |
| US3161693A (en) | Aromatic polycarboxylic acids | |
| JPS61158940A (en) | Oxidation dehydrogenation of para-ethyltoluene to para-methyltoluene | |
| US3398199A (en) | Process and catalyst for the oxidation of olefins | |
| US3042722A (en) | Oxidation of cyclic olefins |