US2443832A - Oxidation of aromatic compounds - Google Patents

Oxidation of aromatic compounds Download PDF

Info

Publication number
US2443832A
US2443832A US658576A US65857646A US2443832A US 2443832 A US2443832 A US 2443832A US 658576 A US658576 A US 658576A US 65857646 A US65857646 A US 65857646A US 2443832 A US2443832 A US 2443832A
Authority
US
United States
Prior art keywords
oxidation
catalyst
oxidized
partially oxidized
vapor phase
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
Application number
US658576A
Inventor
Charles E Morrell
Leland K Beach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Standard Oil Development Co
Original Assignee
Standard Oil Development Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Standard Oil Development Co filed Critical Standard Oil Development Co
Priority to US658576A priority Critical patent/US2443832A/en
Application granted granted Critical
Publication of US2443832A publication Critical patent/US2443832A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups

Definitions

  • This invention relates to catalytic vapor phase oxidation of a partially oxidized alkylated benzene and more particularly to the production of polyba-sic aromaticacids and acid anhydrides.
  • An object of this invention is to provide a more selective reaction for producing the desired dicarboxy acids than is obtained in previous practice with the aromatic hydrocarbon feeds.
  • Another object is to derive further advantages from the use of a partially oxidized alkylated benzene feed, as will become apparent from the following description.
  • the desired aromatic acids are preferably produced by vapor phase oxidation of an alkyl substituted benzenoid compound having another side chain substituent which contains oxygen linked to carbon adjacent the benzenoid ring.
  • the partially oxidized compounds to be used as starting material for the vapor phase oxidation may be obtained by alkylation, liquid phase oxidation or other suitable methods.
  • a dialkyl benzene may be partially oxidized in pure form or in mixtures with other hydrocarbons under relatively less vigorous catalyst conditions than those employed in the vapor phase oxidation of the dialkyl benzene to form a dicarboxy acid anhydride.
  • the oxidized side chain groups in the alkyl benzene compounds to be employed as starting materials for vapor phase oxidation to dicarboxy acids may contain a carbinol, carbonyl, or carboxy function. such as occurs in alkyl-aryl alcohols, aldehydes. ketones, acids, esters, ethers, etc.
  • Alkylated benzenes with more than one side chain partially oxidized, e. g., o-hydroxymethyl benzyl alcohol, may be used also.
  • Example 1 Ortho-xylene, 1 mol, was oxidized with 100 mols of air at 4,000 v./v./hr. and about 450 0.
  • Example 2 Naphthalene under conditions similar to Example 1 was oxidized 76 mol per cent to phthalic anhydrideand 8 mol per cent to maleic anhydride.
  • Example 3 Ortho-toluic acid under conditions similar to Examples 1 and 2 was oxidized over 85 mol per cent to phthalic anhydride containing no toluic acid and only traces of maleic anhydride.
  • the partially oxidized alkyl aromatic feed material is more selectively oxidized to the aromatic acid anhydride than are the aromatic hydrocarbon feeds under comparable vapor phase conditions with the same proportions of air and with the same conventional type oxidation catalyst
  • the partially oxidized feed material may be more advantageously oxidized in higher concentrations with respect to air or oxygen-containing gas.
  • the concentration of the hydrocarbon reactant in air must be limited to about 1 to 4 mol per cent, whereas, in accordance with the present invention, the concentration of the partially oxidized aromatic compound present in the air feed may be 6 to 10 mol .per cent.
  • Various methods of operation and kinds of apparatus may be used in the vapor phase oxidation of the partially oxidized starting material.
  • the fixed bed, fluid catalyst, or other types of operations applicable in the vapor phase oxida- .3 tion oi the aromatic hydrocarbons may be used, and since such operations are known in the art and are not part oi this invention, they will not be described in detail.
  • one of the best catalytic materials to be used is corundum coated with a metal oxide catalyst such as vanadium oxides.
  • the catalytic material in finely divided or powdered form is suspended in a moving stream oi gaseous reactants, usually passed upwardly through a reaction zone.
  • the suspended particles of catalytic material are put into a turbulent, or fluidized, state within the reaction zone to make eflective contact with the.
  • Catalytic materials which are particularly adapted for. use with the fluid catalyst technique and in countercurrent motion are hydrous oxide gels, such as silica gel or alumina gel impregnated with a metal oxide catalyst, preferably to 40% by weight of vanadium pentoxide and heat treated at a temperature between 700 C. and 1200 C. These heat-treated, impregnated gels are rugged so that they resist disintegration, have a homogeneous composition, and avoid excessive oxidation or combustion.
  • the optimum contact time of the reactants with the catalyst is short, only about 0.05 to 0.9 second, and the optimum contact temperatures are generally within the range of 400 C. to 550 C. With less efllcient catalysts, longer contact times, such as 1 to 8 seconds, are used, generally with optimum reaction temperatures within the range of 275 C. to 400 C.
  • the catalyst may comprise one or more oxides of metals in groups V, VI, and VIII of the 4 periodic system, unsupported or supported by an inert carrier.
  • the method of producing a dicarboxy acid which comprises feeding 0.5 to 10 mol per cent ortho-tol-uic acid vapor into air to form a reaction mixture, and contacting the mixture with an oxidation catalyst at a temperature in the range of 275 C. to 550 C.
  • the method of producing phthalic anhydride which comprises reacting vapors of orthotoluic acid with oxygen at a temperature in the range of 400 C. to 550 C. for less than one second in contact with a' fluid catalyst material of silica gel impregnated with vanadium P ntoxide and heat treated at a temperature in the range of 700 C. to 1200 C.

Description

Patented June 22, 1948 OXIDATION OF AROMA' HC COMPOUNDS Charles E. Morrell, Westiield, and Leland K.
Beach, Mountainside, N. J., assignors to Standard Oil Development Company, a corporation of Delaware No Drawing This invention relates to catalytic vapor phase oxidation of a partially oxidized alkylated benzene and more particularly to the production of polyba-sic aromaticacids and acid anhydrides.
Hitherto, the practice has been to use specific aromatic hydrocarbons for vapor phase oxidation to certain dicarboxy acids, tor example, to use benzene to form maleic anhydride andto use naphthalene or o-xylene to form phthalic anhydride. These dicarboxy acids are formed from the specific aromatic hydrocarbons with difllculty in preventing combustion and undesired side reactions which lower the yields of the desired acids.
An object of this invention is to provide a more selective reaction for producing the desired dicarboxy acids than is obtained in previous practice with the aromatic hydrocarbon feeds. 3
Another object is to derive further advantages from the use of a partially oxidized alkylated benzene feed, as will become apparent from the following description.
With the present invention, the desired aromatic acids are preferably produced by vapor phase oxidation of an alkyl substituted benzenoid compound having another side chain substituent which contains oxygen linked to carbon adjacent the benzenoid ring.
The partially oxidized compounds to be used as starting material for the vapor phase oxidation may be obtained by alkylation, liquid phase oxidation or other suitable methods. For example, a dialkyl benzene may be partially oxidized in pure form or in mixtures with other hydrocarbons under relatively less vigorous catalyst conditions than those employed in the vapor phase oxidation of the dialkyl benzene to form a dicarboxy acid anhydride.
In general, the oxidized side chain groups in the alkyl benzene compounds to be employed as starting materials for vapor phase oxidation to dicarboxy acids may contain a carbinol, carbonyl, or carboxy function. such as occurs in alkyl-aryl alcohols, aldehydes. ketones, acids, esters, ethers, etc. Alkylated benzenes with more than one side chain partially oxidized, e. g., o-hydroxymethyl benzyl alcohol, may be used also.
For the purpose of illustrating the greater yield emciency in production of an aromatic dicarboxy acid anhydride from a partially oxidized reactant teed, comparative data are presented in the following examples.
Example 1 Ortho-xylene, 1 mol, was oxidized with 100 mols of air at 4,000 v./v./hr. and about 450 0.
Application March 80, 1946, erial No. 658,575
2 Claims. (Cl. 260-342) 2 over a V205 catalyst to phthalic anhydride in 6''! mol per cent yield and to maleic anhydride in 7 mol per cent yield.
Example 2 Naphthalene under conditions similar to Example 1 was oxidized 76 mol per cent to phthalic anhydrideand 8 mol per cent to maleic anhydride.
Example 3 Ortho-toluic acid under conditions similar to Examples 1 and 2 was oxidized over 85 mol per cent to phthalic anhydride containing no toluic acid and only traces of maleic anhydride.
In the operation described by Example 3, it is clear that a considerably better yield of phthalic dized compounds.
Although it is demonstrated that the partially oxidized alkyl aromatic feed material is more selectively oxidized to the aromatic acid anhydride than are the aromatic hydrocarbon feeds under comparable vapor phase conditions with the same proportions of air and with the same conventional type oxidation catalyst, further investigations indicate that the partially oxidized feed material may be more advantageously oxidized in higher concentrations with respect to air or oxygen-containing gas. For example, in oxidizing naphthalene or o-xylene, the concentration of the hydrocarbon reactant in air must be limited to about 1 to 4 mol per cent, whereas, in accordance with the present invention, the concentration of the partially oxidized aromatic compound present in the air feed may be 6 to 10 mol .per cent.
With the higher concentration of the organic reactant in the oxygen containing gas, the capacity oi the reactor is considerably increased; also, the problem of product recovery is greatly simplified. Furthermore, temperature and heat control is more easily obtained when using the partially oxidized starting material.
Various methods of operation and kinds of apparatus may be used in the vapor phase oxidation of the partially oxidized starting material. The fixed bed, fluid catalyst, or other types of operations applicable in the vapor phase oxida- .3 tion oi the aromatic hydrocarbons may be used, and since such operations are known in the art and are not part oi this invention, they will not be described in detail. In the conventional fixed bed operation one of the best catalytic materials to be used is corundum coated with a metal oxide catalyst such as vanadium oxides. In fluid catalyst operations, the catalytic material in finely divided or powdered form is suspended in a moving stream oi gaseous reactants, usually passed upwardly through a reaction zone. The suspended particles of catalytic material are put into a turbulent, or fluidized, state within the reaction zone to make eflective contact with the.
reactants. Instead of having the particles carried by the moving stream of gaseous reactants, they may be put in motion countercurrent to the ilow of the gaseous reactants. Catalytic materials which are particularly adapted for. use with the fluid catalyst technique and in countercurrent motion are hydrous oxide gels, such as silica gel or alumina gel impregnated with a metal oxide catalyst, preferably to 40% by weight of vanadium pentoxide and heat treated at a temperature between 700 C. and 1200 C. These heat-treated, impregnated gels are rugged so that they resist disintegration, have a homogeneous composition, and avoid excessive oxidation or combustion.
With an eilicient catalyst, the optimum contact time of the reactants with the catalyst is short, only about 0.05 to 0.9 second, and the optimum contact temperatures are generally within the range of 400 C. to 550 C. With less efllcient catalysts, longer contact times, such as 1 to 8 seconds, are used, generally with optimum reaction temperatures within the range of 275 C. to 400 C. The catalyst may comprise one or more oxides of metals in groups V, VI, and VIII of the 4 periodic system, unsupported or supported by an inert carrier.
It is to be understood that the foregoing examples and described conditions serve as illustrations.
The present invention may be appliedmore generally and with variations which come within the scope of the appended claims.
We claim:
1. The method of producing a dicarboxy acid, which comprises feeding 0.5 to 10 mol per cent ortho-tol-uic acid vapor into air to form a reaction mixture, and contacting the mixture with an oxidation catalyst at a temperature in the range of 275 C. to 550 C.
2. The method of producing phthalic anhydride, which comprises reacting vapors of orthotoluic acid with oxygen at a temperature in the range of 400 C. to 550 C. for less than one second in contact with a' fluid catalyst material of silica gel impregnated with vanadium P ntoxide and heat treated at a temperature in the range of 700 C. to 1200 C.
' CHARLES E. MORRELL.
LELAND K. BEACH.
7 REFERENCES CITED The following references are of record in the file of this patent:
OTHER REFERENCES Whitmore: Org. Chem, page 826, 3rd print, D. Van Nostrand.
US658576A 1946-03-30 1946-03-30 Oxidation of aromatic compounds Expired - Lifetime US2443832A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US658576A US2443832A (en) 1946-03-30 1946-03-30 Oxidation of aromatic compounds

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US658576A US2443832A (en) 1946-03-30 1946-03-30 Oxidation of aromatic compounds

Publications (1)

Publication Number Publication Date
US2443832A true US2443832A (en) 1948-06-22

Family

ID=24641808

Family Applications (1)

Application Number Title Priority Date Filing Date
US658576A Expired - Lifetime US2443832A (en) 1946-03-30 1946-03-30 Oxidation of aromatic compounds

Country Status (1)

Country Link
US (1) US2443832A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2925425A (en) * 1957-05-21 1960-02-16 Celanese Corp Oxidation of phthalide and mixtures thereof to phthalic anhydride

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2142678A (en) * 1934-12-31 1939-01-03 Solvay Process Co Preparation of phthalic anhydride
US2245528A (en) * 1938-10-18 1941-06-10 Du Pont Catalytic oxidation of alkyl substituted aromatic compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2142678A (en) * 1934-12-31 1939-01-03 Solvay Process Co Preparation of phthalic anhydride
US2245528A (en) * 1938-10-18 1941-06-10 Du Pont Catalytic oxidation of alkyl substituted aromatic compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2925425A (en) * 1957-05-21 1960-02-16 Celanese Corp Oxidation of phthalide and mixtures thereof to phthalic anhydride

Similar Documents

Publication Publication Date Title
US2941007A (en) Process for the oxidation of olefins
CA1050523A (en) One step process for preparation of vanadium-phosphorus complex oxidation catalysts
US3293268A (en) Production of maleic anhydride by oxidation of n-butane
US3156705A (en) Production of dicarboxylic acid anhydrides by the catalytic oxidation of olefins
US3226421A (en) Catalytic process for the preparation of nitriles
GB944773A (en) Improved process for the oxidation of organic compounds
US3192259A (en) Production of alpha, beta-unsaturated oxygen-containing compounds
US2404438A (en) Process for the manufacture of olefin oxides
US5928983A (en) Process for the preparation of high activity carbon monoxide hydrogenation catalysts and the catalyst compositions
US4182907A (en) Process for the oxidation of olefins to aldehydes and acids
US3173957A (en) Process for the preparation of acrolein
CA3119825A1 (en) Alkane oxidative dehydrogenation and/or alkene oxidation
US4171316A (en) Preparation of maleic anhydride using a crystalline vanadium(IV)bis(metaphosphate) catalyst
US2985668A (en) Preparation of olefin oxides
US4176234A (en) Process for the oxidation of olefins to aldehydes and acids
US4323703A (en) Process for the oxidation of olefins to aldehydes and acids
US2443832A (en) Oxidation of aromatic compounds
US3162683A (en) Liquid phase oxidation of alkyl-substituted aromatics
US2398612A (en) Oxidation of organic compounds
US3012043A (en) Oxidation of aromatic hydrocarbons
US2990427A (en) Processes for the oxidation of organic compounds
US3325504A (en) Manufacture of aromatic nitriles and aldehydes
US3770812A (en) Catalytic formation of double bonds
US2504034A (en) Production of maleic acid from branched-chain dienes
US2995528A (en) Oxidation processes