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US2800506A - Production of aliphatic acids - Google Patents

Production of aliphatic acids Download PDF

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Publication number
US2800506A
US2800506A US422932A US42293254A US2800506A US 2800506 A US2800506 A US 2800506A US 422932 A US422932 A US 422932A US 42293254 A US42293254 A US 42293254A US 2800506 A US2800506 A US 2800506A
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US
United States
Prior art keywords
residues
oxidation
aliphatic acids
carbon atoms
boiling
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
US422932A
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English (en)
Inventor
Millidge Alfred Frank
Robson Ian Kenneth Miles
Elce Alec
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.)
Distillers Co Yeast Ltd
Distillers Co Ltd
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Distillers Co Yeast Ltd
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 Distillers Co Yeast Ltd filed Critical Distillers Co Yeast Ltd
Application granted granted Critical
Publication of US2800506A publication Critical patent/US2800506A/en
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    • 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
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups

Definitions

  • residues comprise compounds containing acid, ketone, hydroxyl and ester groups, and are for the most part composed of poly functional compounds.
  • the residues may also contain certain proportions of the lower aliphatic acids in the form of esters, or these may be present in minor amounts as the free acids owing to the difliculty of removing them completely by distillation.
  • the invention accordingly comprises the novel processes and steps of processes, specific embodiments of which are described hereinafter by way of example and in accordance with which we now prefer to practice the invention.
  • the present invention is for a process for the production of aliphatic acids which comprises oxidising in the liquid phase a paraflin hydrocarbon of at least four carbon atoms with a gas consisting of or comprising molecular oxygen to produce lower aliphatic acids, distilling the oxidation product toseparate the volatile materials from the high boiling residues and thereafter oxidising in the liquid phase said residues with molecular oxygen to produce lower aliphatic acids.
  • volatile materials is meant the materials boiling below 170 C. at atmospheric pressure or its equivalent at other pressures, and by the term high boiling residues the ma terials boiling above this temperature.
  • the residues obtained by distillation of the product are fluid and easy to handle, and that on allowing these residues to cool succinic acid separates in crystalline form and may be recovered by simple filtration in a purity sufiicient for many purposes, and which by a single recrystallisation from a solvent, for example water, is obtained in a high state of purity.
  • the said high boiling residues are recycled with the paraffins charged or fed to the oxidation, the residues from the distillation of the product being cooled to permit the separation of succinic acid prior to recycle to the oxidation.
  • the distillation of the oxidation product may be carried out in two or more columns as desired.
  • the non? acidic volatile materials for example boiling below 99 C. in the presence of water, are removed in a first column and the aqueous aliphatic acids in a second column.
  • any gas containing molecular oxygen whether in the form of air or of mixtures poorer or richer in oxygen than is air, part of the molecular oxygen may, if desired, be in the form of ozone.
  • the pressure used in the oxidation should be such as may be necessary to maintain the reactants substantially in the liquid phase, while the temperature should be sllfiiciently high to obtain an economically attractive rate of oxidation, suitably in the range ISO-250 C.
  • the oxidation of the residues may, if desired, be carried out in the presence of an oxidation catalyst. Where catalysts such as compounds of heavy metals have been used In the primary oxidation, the addition of oxidation catalysts to the residues is generally unnecessary, since these catalytic materials will be found in the distillation residues.
  • the oxidation of the residues may be carried out batchwise or continuously and may be effected in any of the known type of apparatus in which the oxidising gas is intimately contacted with the liquid oxidation mixture.
  • reaction conditions When the residues are mixed with fresh paratfin feed and charged or fed to the primary oxidation the reaction conditions may be such as described in the said copending applications Serial Nos. 385,272 and 385,182, each filed October 9, 1953.
  • the hydrocarbon employed in the process of the present invention is preferably a parafiinic hydrocarbon fraction containing hydrocarbons of 4-8 carbon atoms, at least 40% by Weight of said fraction consisting of hydrocarbons of 6-8 carbon atoms, wherein at least 40% by weight of the parafiins of 6-8 carbon atoms of said fraction consists of paraflins having one or more methyl branch chains and wherein said fraction boils at a temperature not exceeding 100 C. Desirably the fraction boils Within the range about 15 to about C.
  • methyl branch chain used above is meant a p'arafiin bearing a methyl group in a non-terminal posi tion in a chain.
  • Suitable feedstocks which may be used are straight run petroleum fractions containing a high proportion of branched molecules; the products from isomerisation of predominantly straight chain paraffins by aluminium chlo- Example 1 V
  • Benzene Methylcyclopentane 2: 2-D imethylpentane. 2: 4Dimethylpentane. Cyclohexane 2:3Dimethy1pentane. Z-Methylhexane 1 3-D imethylcyclopentane (cis n-Heptane Methyl cyclohexane Toluene Unidentified material was oxidised and the product obtained was separated by distillation to yield as successive fractions volatile nonacidic products, lower aliphatic acids and water, and distillation residues.
  • 1,356 grams of the residues were charged to a stainless steel reactor fitted with a stirrer, a bottom air inlet, a line for removing waste gas and means for measuring and controlling the temperature.
  • the temperature of the reactor was raised to 160 C. and air introduced at a rate of about 3 litres/minute over a period of 15 hours during which the temperature was increased to 190 (3., and at the end of which time no further oxygen was absorbed.
  • the products were subjected to distillation and there were recovered, for each 100 grams, residues charged, 2.3 grams formic acid, 9.2 grams acetic acid, 2.4 grams propionic acid and 0.59 gram butyric acid, as well as 38.1 grams of high boiling material, the remainder being water and gaseous products.
  • Example 2 The apparatus is shown diagrammatically in the accompanying figure and consists of a vertical tower 1 of 2.7 inches internal diameter and 6 litres capacity, having air feed points 2 at the base and about the midpoint.
  • the tower is provided with oil jackets for controlling the temperature.
  • Fresh hydrocarbon is introduced continuously by line 3 through a preheater 13.
  • Both gaseous and liquid products are removed from the reactor by line 4 and after cooling in cooler 5 to a temperature below 80 C. are fed to a gas liquid separator 6 from which the waste gases are withdrawn by line 7.
  • Small amounts of hydrocarbon in the waste gas may be recovered in part by suitable means, for example oil scrubbing, and recycled to the oxidation.
  • the cooled liquid products are passed to a liquid-liquid separator 8 where the product separates into two liquid phases.
  • the lower layer comprising the aqueous acid product is withdrawn at least in part through line 9.
  • the upper layer comprising hydrocarbon, together with part of the lower layer, is returned to the reactor through the preheater 10.
  • the withdrawn aqueous product is fed by line 9 through a preheater 15 to the mid-point of a packed distillation column 11 which has the equivalent of 5 theoretical plates above and below the feed point.
  • the column is operated with a reflux ratio of 4:1, the temperature being about 66 C. at the head, approximately 82 C. at the feed point and 104105 C. in the reboiler.
  • the distillate comprising the volatile non-acidic oxidation products are returned by line 12 for admixture with the feed to the reactor 1.
  • the base product from this column is withdrawn by line 14 and fed to the mid-point of a second packed distillation column 15A which has the equivalent of 5 theoretical plates above and below the feed point.
  • the column is operated with a reflux ratio of 3:1, the temperature being approximately 102-105" C. at the head, approximately C. at the feed point, and C. in the reboiler.
  • the distillate withdrawn by line 16 comprises the aqueous aliphatic acid product.
  • the base product from this still comprising the high boiling residues is withdrawn by line 17, cooled in the cooler 18, filtered in the filter 19 to separate the precipitated succinic acid which is removed, and the filtrate returned for admixture with the feed to the reactor 1.
  • a continuous process for the production of aliphatic acids which comprises oxidising in the liquid phase a paraffin hydrocarbon of four to eight carbon atoms with molecular oxygen to produce lower aliphatic acids, separating at least part of the oxidation product containing aliphatic acids of one to four carbon atoms and a high-boiling residue having a boiling point of at least 170 C., distilling said separated oxidation product to separate and recover said acids from the high-boiling residues, returning substantially all of the resulting residues and admixing same with the supply of parafiin hydro carbon to the oxidation zone, and oxidising said residues in the liquid phase to produce further aliphatic acids of one to four carbon atoms.
  • a continuous process for the production of aliphatic acids as claimed in claim 1 wherein the separated oxidation product is cooled to a temperature below 80 and allowed to separate into two layers, the upper layer returned to the oxidation zone and at least part of the lower layer subjected to the said distillation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US422932A 1953-04-25 1954-04-13 Production of aliphatic acids Expired - Lifetime US2800506A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB11469/53A GB767290A (en) 1953-04-25 1953-04-25 Production of aliphatic carboxylic acids

Publications (1)

Publication Number Publication Date
US2800506A true US2800506A (en) 1957-07-23

Family

ID=9986831

Family Applications (1)

Application Number Title Priority Date Filing Date
US422932A Expired - Lifetime US2800506A (en) 1953-04-25 1954-04-13 Production of aliphatic acids

Country Status (5)

Country Link
US (1) US2800506A (fr)
DE (1) DE1019289B (fr)
FR (1) FR1099323A (fr)
GB (1) GB767290A (fr)
NL (1) NL95035C (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3335160A (en) * 1961-04-19 1967-08-08 Knapsack Ag Process for the continuous manufacture of substantially acetic acidcontaining mixtures of low molecular weight fatty acids by paraffin oxidation
US3347756A (en) * 1962-11-08 1967-10-17 Distillers Co Yeast Ltd Production of pure acetic acid from methyl vinyl ketone by distillation
US3388157A (en) * 1965-02-10 1968-06-11 Ethyl Corp Process for the production of dicarboxylic acids
US3493609A (en) * 1966-05-10 1970-02-03 Bayer Ag Production of acetic acid with partial recycling
US3505400A (en) * 1966-06-01 1970-04-07 Bayer Ag Process for the production of acetic acid
US3923882A (en) * 1974-04-17 1975-12-02 Union Carbide Corp Production of acetic acid
EP0546677A1 (fr) * 1991-12-09 1993-06-16 The Standard Oil Company Procédé pour oxyder l'éthane en acide acétique dans un lit fluidisé
US5710318A (en) * 1994-06-02 1998-01-20 The Standard Oil Company Fluid bed process for the acetoxylation of ethylene in the production of vinyl acetate

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4337356A (en) * 1980-03-20 1982-06-29 Union Carbide Corporation Catalytic liquid-phase oxidation of butane

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2241487A (en) * 1939-02-18 1941-05-13 Standard Oil Dev Co Catalytic oxidation of ketones
US2265948A (en) * 1939-08-02 1941-12-09 Du Pont Catalytic oxidation of lower aliphatic hydrocarbons
US2530512A (en) * 1947-06-13 1950-11-21 Celanese Corp Oxidation of aliphatic esters
US2578306A (en) * 1950-01-19 1951-12-11 Eastman Kodak Co Process for direct oxidation of aldehydes and alcohol to acid

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE570732C (de) * 1927-12-02 1933-02-22 I G Farbenindustrie Akt Ges Verfahren zur Herstellung wertvoller organischer Produkte durch Behandlung von fluessigen Kohlenwasserstoffen mit oxydierenden Gasen
US2287125A (en) * 1938-10-12 1942-06-23 Standard Oil Dev Co Oxidation of low molecular weight hydrocarbons in liquid phase and catalyst therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2241487A (en) * 1939-02-18 1941-05-13 Standard Oil Dev Co Catalytic oxidation of ketones
US2265948A (en) * 1939-08-02 1941-12-09 Du Pont Catalytic oxidation of lower aliphatic hydrocarbons
US2530512A (en) * 1947-06-13 1950-11-21 Celanese Corp Oxidation of aliphatic esters
US2578306A (en) * 1950-01-19 1951-12-11 Eastman Kodak Co Process for direct oxidation of aldehydes and alcohol to acid

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3335160A (en) * 1961-04-19 1967-08-08 Knapsack Ag Process for the continuous manufacture of substantially acetic acidcontaining mixtures of low molecular weight fatty acids by paraffin oxidation
US3347756A (en) * 1962-11-08 1967-10-17 Distillers Co Yeast Ltd Production of pure acetic acid from methyl vinyl ketone by distillation
US3388157A (en) * 1965-02-10 1968-06-11 Ethyl Corp Process for the production of dicarboxylic acids
US3493609A (en) * 1966-05-10 1970-02-03 Bayer Ag Production of acetic acid with partial recycling
US3505400A (en) * 1966-06-01 1970-04-07 Bayer Ag Process for the production of acetic acid
US3923882A (en) * 1974-04-17 1975-12-02 Union Carbide Corp Production of acetic acid
EP0546677A1 (fr) * 1991-12-09 1993-06-16 The Standard Oil Company Procédé pour oxyder l'éthane en acide acétique dans un lit fluidisé
US5710318A (en) * 1994-06-02 1998-01-20 The Standard Oil Company Fluid bed process for the acetoxylation of ethylene in the production of vinyl acetate

Also Published As

Publication number Publication date
GB767290A (en) 1957-01-30
FR1099323A (fr) 1955-09-02
DE1019289B (de) 1957-11-14
NL95035C (fr) 1960-07-16

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