CA1058637A - Liquid phase oxidation of propane - Google Patents
Liquid phase oxidation of propaneInfo
- Publication number
- CA1058637A CA1058637A CA210,617A CA210617A CA1058637A CA 1058637 A CA1058637 A CA 1058637A CA 210617 A CA210617 A CA 210617A CA 1058637 A CA1058637 A CA 1058637A
- Authority
- CA
- Canada
- Prior art keywords
- propane
- oxygen
- reaction
- range
- liquid
- 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for the oxidation of propane is disclosed. The process comprises contracting oxygen with a liquid reaction medium comprising propane and a liquid organic material that is a solvent for propane and which is non-reactive with oxygen under the con-ditions of the process. The process is carried out under superatmospheric pressure, at an elevated temperature, and for a period of time sufficient to produce oxygenated products, including one or more of acetone and isopropyl alcohol.
1.
A process for the oxidation of propane is disclosed. The process comprises contracting oxygen with a liquid reaction medium comprising propane and a liquid organic material that is a solvent for propane and which is non-reactive with oxygen under the con-ditions of the process. The process is carried out under superatmospheric pressure, at an elevated temperature, and for a period of time sufficient to produce oxygenated products, including one or more of acetone and isopropyl alcohol.
1.
Description
~058637 The invention relates to a method for the oxidation of propane to produce valuable oxygenated products. The method is a liquid phase process for the oxidation of propane to useful oxygenated products, which comprises contacting oxygen with a liquid reaction medium comprising propane and a liquid organic material that is a solvent for propane and which is non-reactive with oxygen under the conditions of the process, wherein the process is carried out in an enclosed reaction zone that is maintained under superatmospheric pressure, and at an elevated temperature and for a period of time sufficient to produce oxygenated products. The principal products of the reaction are acetone and isopropyl alcohol.
Any organic liquid that-does not react readily with oxygen under the conditions used for the oxidation process can be employed as a solvent in the process of the invention. Of course, the liquid must also be a solvent for propane. Such organic liquids include aromatic materials such as benzene, nitrobenzene, and chlorobenzene, and aliphatic materials such as acetonitrile.
The organic liquid must also remain liquid under the con-ditions of the reaction.
The exact proportion of organic liquid to propane that is employed in the process is not narrowly critical. For example, the solvent: propane ratio can be in the range of from about 1:5 to 1:1. Higher ratios than 1:1 can be employed, although the productivity of 105863q the reaction tends to decrease as the dilution of the propane becomes greater. At weight ratios of solvent to propane of less than 1:5, the amount of solvent tends to become insufficient to dissolve st of the propane present in the reaction zone.
The reaction is carried out at an elevated temperature sufficient to oxidize the propane to valuable oxygenated products, including acetone and/or isopropyl alcohol. For example, a temperature within the range of from about 160 to about 220C. can be employed. Preferred temperatures are found within the range of from about 180 to about 200C. Below 160C., the reaction rate tends to become impracticably slow, and at temperatures above 220C., the incidence of undesired side reactions tends to become greater.
The reaction is carried out under superatmospheric pressure. Because the temperatures employed in the reaction are above the critical temperature of propane, the auto-geneous pressure of the reaction is high. Thus, the normal minimum pressure of the reaction will be about 700 p.s.i.
The reaction can be carried out at pressures of up to 2000 p.s.i. or higher, if desired.
The reaction time is not narrowly critical. If the process is carried out as a batch operation, there will usually be an induction period before the oxidation begins.
In such a case, the residence time of the reactants in the reaction zone may vary from about 1 to about 8 hours, and preferably from about 2 to about 5 hours. If the reaction is carried out as a continuous reaction, with reaction mixture being constantly withdrawn as fresh reactants are added to the reaction zone, the residence time in the reaction zone may be as short as 5 minutes to as long as 1 hour or more. Preferred residence times in such a case would be from about 10 to about 30 minutes.
With reaction times longer than those indicated above, the incidence of undesired side reactions tends to become greater, with the result that the efficiency of the reaction to the desired acetone and isopropyl alcohol pro-ducts is reduced. With very short reaction times, the amount of propane oxidized tends to become so low that the operation becomes economically unattractive.
Oxygen is employed in the reaction, either as pure oxygen or as an oxygen-containing gas such as air.
The oxygen concentration in the gas phase of the reaction zone is controlled so that it is below the explosive range of the organic material-oxygen mixture present. If the reaction is carried out in a continuous manner, the desired amount of oxygen and propane, along with the liquid solvent for the propane, are continuQusly fed to the reaction zone.
At the same time, reaction mixture is continuously drawn off in order to maintain a constant amount of material in the reaction zone. If the reaction is carried out as a batch process, an initial quantity of oxygen, propane, and solvent are charged to the reaction zone, and after the induction period when oxygen begins to be consumed (as i6 evidenced by a drop in pressure), additional oxygen can be fed to the reaction zone as needed.
The total amount of oxygen employed is preferably an excess of stoichiometric. (The stoichio-metric proportion is i mole of 2 per mole of propane.) In order to avoid an explosive mixture in the gas phase of the reaction zone, the amount of oxygen at all times in said gas phase should be not more than about 11 per-cent, by volume.
The process may be carried out in a vessel such as an autoclave, equipped with means for heating, cooling, pressure regulation, agitation, and the like.
The material of construction can be stainless steel, Hastelloy C, titanium, tantalum, or other material that is inert to the reactants and is capable of withstanding the elevated pressures attained in the process.
The products of the reaction can be recovered by conventional procedures. For example, the products can be separated by fractional distillation, and un-reacted propane as well as the organic solvent can be recycled to the reaction.
The following example illustrates the practice of the invention:
8s33 EXAMPLE
Liquid-Phase Oxidation of Propane in Benzene Solvent The reaction vessel was a stainless steel autoclave equipped with a stirrer, temperature indicator, gas inlet line, and safety device for accommodating sudden pressure increases. The autoclave contained an internal coil through which steam could be passed for heating or water for cooling. To the vessel were charged 780 grams of benzene (10 moles) and 900 grams of propane (20.5 moles). The mixture was heated to 182C. At that temperature, the autogeneous pressure was 720 p.s.i. Oxygen was then added to raise the total pressure to 810 p.s.i., and the reaction mixture was stirred. After an hour, the pressure on the system began to drop slowly, indicating that the consumption of oxygen had started. Periodically, additionaly oxygen was added to maintain the total pressure at 810 p.s.i.
At the end of 3 hours, no re oxygen was consumed. The reaction mixture was cooled, and the gas and liquid por-tions of the product were analyzed by gas chromatograph.
The conversion of the propane charged was 3.7 percent.
Of the propane that reacted, 55.3 percent formed acetone, 10.7 percent formed isopropyl alcohol, and 3.6 percent formed normal propanol.
A complete analysis of the products is displayed in the table below.
TABLE I
LIQUID-PHASE OXIDATION OF PROPANE
BENZENE SOLVENT
Reaction Conditions 180C.
810 psi max pressure 4 hours reaction time
Any organic liquid that-does not react readily with oxygen under the conditions used for the oxidation process can be employed as a solvent in the process of the invention. Of course, the liquid must also be a solvent for propane. Such organic liquids include aromatic materials such as benzene, nitrobenzene, and chlorobenzene, and aliphatic materials such as acetonitrile.
The organic liquid must also remain liquid under the con-ditions of the reaction.
The exact proportion of organic liquid to propane that is employed in the process is not narrowly critical. For example, the solvent: propane ratio can be in the range of from about 1:5 to 1:1. Higher ratios than 1:1 can be employed, although the productivity of 105863q the reaction tends to decrease as the dilution of the propane becomes greater. At weight ratios of solvent to propane of less than 1:5, the amount of solvent tends to become insufficient to dissolve st of the propane present in the reaction zone.
The reaction is carried out at an elevated temperature sufficient to oxidize the propane to valuable oxygenated products, including acetone and/or isopropyl alcohol. For example, a temperature within the range of from about 160 to about 220C. can be employed. Preferred temperatures are found within the range of from about 180 to about 200C. Below 160C., the reaction rate tends to become impracticably slow, and at temperatures above 220C., the incidence of undesired side reactions tends to become greater.
The reaction is carried out under superatmospheric pressure. Because the temperatures employed in the reaction are above the critical temperature of propane, the auto-geneous pressure of the reaction is high. Thus, the normal minimum pressure of the reaction will be about 700 p.s.i.
The reaction can be carried out at pressures of up to 2000 p.s.i. or higher, if desired.
The reaction time is not narrowly critical. If the process is carried out as a batch operation, there will usually be an induction period before the oxidation begins.
In such a case, the residence time of the reactants in the reaction zone may vary from about 1 to about 8 hours, and preferably from about 2 to about 5 hours. If the reaction is carried out as a continuous reaction, with reaction mixture being constantly withdrawn as fresh reactants are added to the reaction zone, the residence time in the reaction zone may be as short as 5 minutes to as long as 1 hour or more. Preferred residence times in such a case would be from about 10 to about 30 minutes.
With reaction times longer than those indicated above, the incidence of undesired side reactions tends to become greater, with the result that the efficiency of the reaction to the desired acetone and isopropyl alcohol pro-ducts is reduced. With very short reaction times, the amount of propane oxidized tends to become so low that the operation becomes economically unattractive.
Oxygen is employed in the reaction, either as pure oxygen or as an oxygen-containing gas such as air.
The oxygen concentration in the gas phase of the reaction zone is controlled so that it is below the explosive range of the organic material-oxygen mixture present. If the reaction is carried out in a continuous manner, the desired amount of oxygen and propane, along with the liquid solvent for the propane, are continuQusly fed to the reaction zone.
At the same time, reaction mixture is continuously drawn off in order to maintain a constant amount of material in the reaction zone. If the reaction is carried out as a batch process, an initial quantity of oxygen, propane, and solvent are charged to the reaction zone, and after the induction period when oxygen begins to be consumed (as i6 evidenced by a drop in pressure), additional oxygen can be fed to the reaction zone as needed.
The total amount of oxygen employed is preferably an excess of stoichiometric. (The stoichio-metric proportion is i mole of 2 per mole of propane.) In order to avoid an explosive mixture in the gas phase of the reaction zone, the amount of oxygen at all times in said gas phase should be not more than about 11 per-cent, by volume.
The process may be carried out in a vessel such as an autoclave, equipped with means for heating, cooling, pressure regulation, agitation, and the like.
The material of construction can be stainless steel, Hastelloy C, titanium, tantalum, or other material that is inert to the reactants and is capable of withstanding the elevated pressures attained in the process.
The products of the reaction can be recovered by conventional procedures. For example, the products can be separated by fractional distillation, and un-reacted propane as well as the organic solvent can be recycled to the reaction.
The following example illustrates the practice of the invention:
8s33 EXAMPLE
Liquid-Phase Oxidation of Propane in Benzene Solvent The reaction vessel was a stainless steel autoclave equipped with a stirrer, temperature indicator, gas inlet line, and safety device for accommodating sudden pressure increases. The autoclave contained an internal coil through which steam could be passed for heating or water for cooling. To the vessel were charged 780 grams of benzene (10 moles) and 900 grams of propane (20.5 moles). The mixture was heated to 182C. At that temperature, the autogeneous pressure was 720 p.s.i. Oxygen was then added to raise the total pressure to 810 p.s.i., and the reaction mixture was stirred. After an hour, the pressure on the system began to drop slowly, indicating that the consumption of oxygen had started. Periodically, additionaly oxygen was added to maintain the total pressure at 810 p.s.i.
At the end of 3 hours, no re oxygen was consumed. The reaction mixture was cooled, and the gas and liquid por-tions of the product were analyzed by gas chromatograph.
The conversion of the propane charged was 3.7 percent.
Of the propane that reacted, 55.3 percent formed acetone, 10.7 percent formed isopropyl alcohol, and 3.6 percent formed normal propanol.
A complete analysis of the products is displayed in the table below.
TABLE I
LIQUID-PHASE OXIDATION OF PROPANE
BENZENE SOLVENT
Reaction Conditions 180C.
810 psi max pressure 4 hours reaction time
2-gallon stainless steel autoclave Product Composition Liquid Component Weight Percent Propane 4.13 Acetaldehyde 0.02 Propylene Oxide 0-04 Acetone 2.26 Methanol 0.23 Isopropanol 9l 2l n-Propanol 0.16 Water 0.27 Unknown 0.41 Acetic Acid 0.07 Propylene Glycol (tentative) 0.60 Gas Component Weight Percent Carbon Dioxide 0.9 Oxygen 6.8 Nitrogen 7.36 Carbon Monoxide 1.05 Propane 808 4321 Propane Impurities o 49 Benzene 1.35 Charge Benzene 780 g Propane 900 g
Claims (4)
1. A liquid phase process for the oxidation of pro-pane to useful oxygenated products including isopropanol and acetone, which comprises reacting at least a stoichiometric amount of oxygen with propane in a liquid reaction medium consisting essentially of propane and a liquid organic material that is a solvent for propane and which is non-reactive with oxygen under the conditions of said process, said liquid organic material being selected from the group consisting of benzene, nitrobenzene, chlorobenzene, or acetonitrile, in an enclosed reaction zone that is maintained under superatmospheric pressure of at least autogeneous pres-sure within the range of from about 700 psi to about 2000 psi, at an elevated temperature within the range of from about 160°C.
to about 220°C., and for a period of time sufficient to produce oxygenated products, wherein the weight ratio of said liquid organic material to propane is within the range of from about 1:5 to about 1:1.
to about 220°C., and for a period of time sufficient to produce oxygenated products, wherein the weight ratio of said liquid organic material to propane is within the range of from about 1:5 to about 1:1.
2. The process of claim 1 wherein said process is carried out as a batch process, and wherein said period of time is within the range of from about 1 hour to about 8 hours.
3. The process of claim 1 wherein said process is carried out as a continuous process, and wherein the residence time of the reactants in said reaction zone is within the range of from about 5 minutes to about 1 hour.
4. The process of claim l wherein said liquid organic material is benzene.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40688673A | 1973-10-16 | 1973-10-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1058637A true CA1058637A (en) | 1979-07-17 |
Family
ID=23609775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA210,617A Expired CA1058637A (en) | 1973-10-16 | 1974-10-02 | Liquid phase oxidation of propane |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1058637A (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 |
-
1974
- 1974-10-02 CA CA210,617A patent/CA1058637A/en not_active Expired
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 |
|---|---|---|
| US2723994A (en) | Oxidation of xylene and toluic acid mixtures to phthalic acids | |
| US4950786A (en) | Method for making 2,6-naphthalene dicarboxylic acid | |
| US4366325A (en) | Process for the preparation of 3-phenoxy-benzaldehydes | |
| US4131742A (en) | Cobalt-catalyzed oxidation of hydrocarbons | |
| CA1058637A (en) | Liquid phase oxidation of propane | |
| US3184506A (en) | Preparation of carboxylic acid chlorides | |
| US5359134A (en) | Process for preparing phenylterephthalic acid | |
| US4185024A (en) | Nitric acid process for the manufacture of anthraquinone from o-benzyl-toluene | |
| US4124633A (en) | Tellurium catalyzed decomposition of peroxide intermediates resulting from the autoxidation of unsaturated aldehydes | |
| US4354037A (en) | Process for preparing benzenecarboxylic acids | |
| US2966513A (en) | Production of naphthalene dicarboxylic acids | |
| US3196182A (en) | Oxidation of hydrocarbons | |
| CA1091692A (en) | Preparation of oxalate esters from carbon monoxide and an alkoxycycloalkene | |
| US5436364A (en) | Process for producing dimethyl 2,6-naphthalene-dicarboxylate | |
| US4131741A (en) | Cobalt-catalyzed oxidation of C3 to C7 saturated aliphatic hydrocarbons to oxygenated products | |
| EP1085006B1 (en) | Process for producing fluoroalkylcarboxylic acid | |
| US4086267A (en) | Cobalt-catalyzed oxidation of C3 to C7 saturated aliphatic hydrocarbons to oxygenated products including acetic acid | |
| US20060167310A1 (en) | Preparation method of naphthalene dicarboxylic acid | |
| US4423245A (en) | Process for preparing 2,5-dichloro-3-nitrobenzoic acid from 2,5-dichloro-3-nitro-p-xylene | |
| NO157415B (en) | PROCEDURE FOR THE PREPARATION OF AN ALKYL OXALATE. . | |
| CA2140027A1 (en) | Process for 2,5-diphenylterephthalic acid | |
| GB1577544A (en) | Process for the preparation of iso- or terephthalic acid | |
| US3030414A (en) | Process of preparing meta- and para-nitrobenzoic acids | |
| KR820002063B1 (en) | Process for preparation of chloro benzoic acid | |
| EP0329273B1 (en) | Process for producing 2,6-naphthalene dicarboxylic acid |