GB771992A - Recovery of aliphatic acids from the oxidation products of hydrocarbons - Google Patents

Recovery of aliphatic acids from the oxidation products of hydrocarbons

Info

Publication number
GB771992A
GB771992A GB1760053A GB1760053A GB771992A GB 771992 A GB771992 A GB 771992A GB 1760053 A GB1760053 A GB 1760053A GB 1760053 A GB1760053 A GB 1760053A GB 771992 A GB771992 A GB 771992A
Authority
GB
United Kingdom
Prior art keywords
water
acids
light ends
product
distillation
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
Application number
GB1760053A
Inventor
Alec Elce
Archibald Robert Graham
Alfred Frank Millidge
Ian Kenneth Miles Robson
Donald Peter Young
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
Original Assignee
Distillers Co Yeast Ltd
Distillers Co 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, Distillers Co Ltd filed Critical Distillers Co Yeast Ltd
Priority to GB1760053A priority Critical patent/GB771992A/en
Priority to NL188655A priority patent/NL113169C/xx
Publication of GB771992A publication Critical patent/GB771992A/en
Expired 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
    • C07C51/42Separation; Purification; Stabilisation; Use of additives
    • C07C51/43Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Formic and acetic acids are recovered from the product of the liquid phase oxidation of paraffinic hydrocarbons with a gas comprising molecular oxygen, said product containing (a) "light ends" which are defined as volatile non-acidic oxidation products of boiling point up to 99 DEG C. in the presence of water, (b) water, (c) aliphatic monocarboxylic acids of 1 to 4 carbon atoms, and (d) higher boiling residues, by distilling the product, desirably from which all or part of the light ends have been removed, to separate from the higher boiling residues a distillate mixture comprising water and the aliphatic monocarboxylic acids of 1 to 4 carbon atoms and then fractionally distilling this mixture, after removal of any remaining light <PICT:0771992/IV(b)/1> ends, to recover the formic and acetic acids. During the distillation of the oxidation product, small amounts of volatile, coloured, non-acidic materials boiling up to 99 DEG C. in the presence of water, e.g. ketones and esters, which are referred to as "subsidiary light ends" are formed and these co-distil with the mixture of water and C1-C4 acids and in a preferred embodiment of the invention the distillate mixture comprising water and the C1-C4 acids is subjected to fractional distillation to remove as distillate the subsidiary light ends prior to separating the formic acid-acetic acid fraction by fractional distillation of the residue. The separation of the mixture of water and C1-C4 acids may be carried out by flash distillation without fractionating, but a degree of fractionation by means of a fractionating column and reflux is preferred. The separation may be carried out under reduced pressure or at atmospheric pressure and the concentration of water in the base product should not be reduced to below about 8 per cent by weight. In examples: (1) a product obtained by liquid phase oxidation at 160 DEG C. and at 300 pounds per square inch gauge of a paraffinic fraction of boiling range 15-95 DEG C. prepared by the straight distillation of a Middle-East petroleum is fractionally distilled to remove completely the light ends boiling up to 99 DEG C. in the presence of water. The base product is then freed from the higher boiling compounds by distillation through a fractionating column to yield a crude mixture of water and C1-C4 acids which is then submitted to a further fractional distillation through a packed column up to a head temperature of 99 DEG C. at atmospheric pressure to remove subsidiary light ends. The residue is then fractionally distilled first in the presence of isopropyl ether to remove water and then to separate a formic acid-acetic acid fraction boiling at 100 DEG to 119 DEG C. at 760 mm. pressure; (2) as in (1) except that the initial oxidation product is prepared by oxidising the same feedstock at 170 DEG C. and 600 pounds per square inch gauge; (3) as in (2) except that only the more volatile light ends are removed in the first fractional distillation, the head temperature of the column being 60-65 DEG C., whilst the head temperature in the subsequent distillation to remove subsidiary light ends is about 95 DEG C.; (4) the same oxidation product as used in (2) is introduced by line (1) (see Figure) into a continuous still (2) operated at a head temperature of about 60-65 DEG C. The volatile light ends are removed by line (3) and the base product is passed to a continuous still (5) operated at a head temperature of about 100-110 DEG C. where it is fractionally distilled to separate the crude mixture of acids from the higher boiling material which is taken off at (6). The aqueous C1-C4 acids distillate is passed to a continuous distillation column (8), the reflux ratio being about 9 : 1 and the head temperature 90 DEG to 95 DEG C., to remove subsidiary light ends which are withdrawn through line (9) to a phase separator (10) where the distillate separates into two phases, all or part of the lower liquid phase and/or part of the upper liquid phase being returned to the still as reflux, the remainders being removed. The base product is passed by line (11) to a continuous dehydrating still 12 using isopropyl ether as entrainer and the still base product is passed to a still (15) in which toluene is used as entrainer. The overheads pass to phase separator (16), the lower layer comprising formic acid being taken off and the upper layer comprising toluene being returned to the column. The base product is passed to a continuous fractionation still (18) to separate acetic acid which is then finally distilled to remove traces of toluene and formic acid. The base product removed by line (20) comprises the C3 and C4 acids. Specifications 743,989, 743,990, 743,991, 767,290 and 771,991 are referred to.ALSO:Formic and acetic acids are recovered from the product of the liquid phase oxiation of paraffinic hydrocarbons with a gas comprising molecular oxygen, said product containing (a) "light ends" which are defined as volatile non-acidic oxidation products of boiling point up to 99 DEG C. in the presence of water, (b) water, (c) aliphatic monocarboxylic acids of 1 to 4 carbon atoms, and (d) higher boiling residues, by distilling the product, desirably from which all or part of the light ends have been removed, to separate from the higher boiling <PICT:0771992/III/1> residues a distillate mixture comprising water and the aliphatic monocarboxylic acids of 1 to 4 carbon atoms and then fractionally distilling this mixture after removal of any remaining light ends to recover the formic and acetic acids. During the distillation of the oxidation product small amounts of volatile, coloured, nonacidic materials boiling up to 99 DEG C. in the presence of water, e.g. ketones and esters, which are referred to as "subsidiary light ends" are formed and these co-distil with the mixture of water and C1 - C4 acids and in a preferred embodiment of the invention the distillate mixture comprising water and the C1 - C4 acids is subjected to fractional distillation to remove as distillate the subsidiary light ends prior to separating the formic acid-acetic acid fraction by fractional distillation of the residue. The separation of the mixture of water and C1 - C4 acids may be carried out by flash distillation without fractionating, but a degree of fractionation by means of a fractionating column and reflux is preferred. The separation may be carried out under reduced pressure or at atmospheric pressure and the concentration of water in the base product should not be reduced to below about 8 per cent by weight. In examples: (1) a product obtained by liquid phase oxidation at 160 DEG C. and at 300 pounds per square inch gauge of a paraffinic fraction of boiling range 15 DEG -95 DEG C. prepared by the straight distillation of a Middle-East petroleum is fractionally distilled to remove completely the light ends boiling up to 99 DEG C. in the presence of water. The base product is then freed from the higher boiling compounds by distillation through a fractionating column to yield a crude mixture of water and C1-C4 acids which is then submitted to a further fractional distillation through a packed column up to a head temperature of 99 DEG C. at atmospheric pressure to remove subsidiary light ends. The residue is then fractionally distilled first in the presence of isopropyl ether to remove water and then to separate a formic acid-acetic acid fraction boiling at 100 to 119 DEG C. at 760 mm pressure, (2) as in (1) except that the initial oxidation product is prepared by oxidizing the same feedstock at 170 DEG C. and 600 pounds per square inch gauge; (3) as in (2) except that only the more volatile light ends are removed in the first fractional distillation, the head temperature of the column being 60-65 DEG C., whilst the head temperature in the subsequent distillation to remove subsidiary light ends is about 95 DEG C.; (4) the same oxidation product as used in (2) is introduced by line (1) (see Figure) into a continuous still (2) operated at a head temperature of about 60-65 DEG C. The volatile light ends are removed by line (3) and the base product is passed to a continuous still (5) operated at a head temperature of about 100-110 DEG C. where it is fractionally distilled to separate the crude mixture of acids from the higher boiling material which is taken off at (6). The aqueous C1 - C4 acids distillate is passed to a continuous distillation column (8), the reflux ratio being about 9:1 and the head temperature 90 to 95 DEG C., to remove subsidiary light ends which are withdrawn through line (9) to a phase separator (10) where the distillate separates into two phases, all or part of the lower liquid phase and/or part of the upper liquid phase being returned to the still as reflux, the remainders being removed. The base product is passed by line (11) to a continuous dehydrating still 12 using isopropyl ether as entrainer and the still base product is passed to a still (15) in which toluene is used as entrainer. The overheads pass to phase separator (16), the lower layer comprising formic acid being taken off and the upper layer comprising toluene being returned to the column. The base product is passed to a continuous fractionation still (18) to separate acetic acid which is then finally distilled to remove traces of toluene and formic acid. The base product removed by line (20) comprises the C3 and C4 acids. Specificatio 743,989, 743,990, 743,991, 767,290 and 771,991 [all in Group IV(b)] are referred to.
GB1760053A 1953-06-25 1953-06-25 Recovery of aliphatic acids from the oxidation products of hydrocarbons Expired GB771992A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
GB1760053A GB771992A (en) 1953-06-25 1953-06-25 Recovery of aliphatic acids from the oxidation products of hydrocarbons
NL188655A NL113169C (en) 1953-06-25 1954-06-24

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB1760053A GB771992A (en) 1953-06-25 1953-06-25 Recovery of aliphatic acids from the oxidation products of hydrocarbons

Publications (1)

Publication Number Publication Date
GB771992A true GB771992A (en) 1957-04-10

Family

ID=10097996

Family Applications (1)

Application Number Title Priority Date Filing Date
GB1760053A Expired GB771992A (en) 1953-06-25 1953-06-25 Recovery of aliphatic acids from the oxidation products of hydrocarbons

Country Status (2)

Country Link
GB (1) GB771992A (en)
NL (1) NL113169C (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001007391A1 (en) * 1999-07-22 2001-02-01 Consortium für elektrochemische Industrie GmbH Method for separating and purifying an aqueous mixture that mainly consists of acetic acid and formic acid
RU2715698C1 (en) * 2019-11-28 2020-03-03 Акционерное Общество "Газпромнефть - Московский Нпз" (Ао "Газпромнефть - Мнпз") Method of producing acetic acid and methyl ethyl ketone
CN114133090A (en) * 2021-12-15 2022-03-04 江西吉煜新材料有限公司 Method and equipment for recycling propionic acid and butyric acid secondary mother liquor water

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001007391A1 (en) * 1999-07-22 2001-02-01 Consortium für elektrochemische Industrie GmbH Method for separating and purifying an aqueous mixture that mainly consists of acetic acid and formic acid
US6793777B1 (en) 1999-07-22 2004-09-21 Consortium für elektrochemische Industrie GmbH Method for separating and purifying an aqueous mixture that mainly consists of acetic acid and formic acid
RU2715698C1 (en) * 2019-11-28 2020-03-03 Акционерное Общество "Газпромнефть - Московский Нпз" (Ао "Газпромнефть - Мнпз") Method of producing acetic acid and methyl ethyl ketone
CN114133090A (en) * 2021-12-15 2022-03-04 江西吉煜新材料有限公司 Method and equipment for recycling propionic acid and butyric acid secondary mother liquor water
CN114133090B (en) * 2021-12-15 2022-12-13 江西吉煜新材料有限公司 Method and equipment for recycling propionic acid and butyric acid secondary mother liquor water

Also Published As

Publication number Publication date
NL113169C (en) 1966-08-16

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