CA2019355A1 - Removal of acidic impurities from tertiary butyl hydroperoxide containing feedstock - Google Patents
Removal of acidic impurities from tertiary butyl hydroperoxide containing feedstockInfo
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- CA2019355A1 CA2019355A1 CA 2019355 CA2019355A CA2019355A1 CA 2019355 A1 CA2019355 A1 CA 2019355A1 CA 2019355 CA2019355 CA 2019355 CA 2019355 A CA2019355 A CA 2019355A CA 2019355 A1 CA2019355 A1 CA 2019355A1
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- Prior art keywords
- tertiary butyl
- water
- isobutane
- butyl alcohol
- carboxylic acid
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Abstract
REMOVAL OF ACIDIC IMPURITIES FROM TERTIARY
BUTYL HYDROPEROXIDE CONTAINING FEEDSTOCK
(Docket No. 80,415-F) ABSTRACT OF THE DISCLOSURE
Isobutane is thermally and/or catalytically reacted with molecular oxygen to provide an initial reaction product composed of unreacted isobutane, tertiary butyl hydroperox-ide, tertiary butyl alcohol and acidic impurities, including acetic acid and formic acid and the initial reaction product is treated with water (preferably in a counter-current extraction zone) in order to preferentially remove a sig-nificant portion of the acidic impurities and to provide a final feedstock from which unreacted isobutane may be removed for recycle. The resultant mixture composed sub-stantially exclusively of tertiary butyl hydroperoxide dissolved in tertiary butyl alcohol may be further processed for thermal and/or catalytic conversion of the tertiary butyl hydroperoxide to tertiary butyl alcohol or may be used as a feedstock for the catalytic reaction of the tertiary butyl hydroperoxide with an olefin such as propylene to form an epoxide such as propylene oxide and additional tertiary butyl alcohol.
BUTYL HYDROPEROXIDE CONTAINING FEEDSTOCK
(Docket No. 80,415-F) ABSTRACT OF THE DISCLOSURE
Isobutane is thermally and/or catalytically reacted with molecular oxygen to provide an initial reaction product composed of unreacted isobutane, tertiary butyl hydroperox-ide, tertiary butyl alcohol and acidic impurities, including acetic acid and formic acid and the initial reaction product is treated with water (preferably in a counter-current extraction zone) in order to preferentially remove a sig-nificant portion of the acidic impurities and to provide a final feedstock from which unreacted isobutane may be removed for recycle. The resultant mixture composed sub-stantially exclusively of tertiary butyl hydroperoxide dissolved in tertiary butyl alcohol may be further processed for thermal and/or catalytic conversion of the tertiary butyl hydroperoxide to tertiary butyl alcohol or may be used as a feedstock for the catalytic reaction of the tertiary butyl hydroperoxide with an olefin such as propylene to form an epoxide such as propylene oxide and additional tertiary butyl alcohol.
Description
3 ~ 5 REMOVAL OF ACIDIC IMPURITIES ~ROM TERTIARY
BUTYL HYDROPEROXIDE CONTAINING FEEDSTOCR
(Docket No. 80,415-~) BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to the purification of a tertiary butyl hydroperoxide-containing feedstock. More particularly, this invention relates to a method for the preparation of an isobutane-tertiary butyl alcohol-tertiary butyl hydroperox-ide feedstock useful in the preparation of tertiary butylalcohol, propylene oxide, etc. Still more particularly, this invention relates to a method wherein an initial reac-tion product obtained by the oxidation of isobutane with oxygen and comprisin~ unreacted isobutane, tertiary butyl alcoholr tertiary butyl hydroperoxide and a minor amount of water soluble acidic by-products, including acetic acid~
formic acid, etc., is extracted with water to provide a - final feedstock comprising tertiary butyl alcohol, tertiary butyl hydroperoxide, ditertiary butyl peroxide, and unre-acted isobutane which is substantially free of water soluble acidic impurities.
Prior Art It is known to react oxygen with isobutane to form a peroxidation reaction product wherein the principal peroxide that is formed is tertiary butyl hydroperoxide. However, 2 ~
minor amounts of water-soluble and hydrocarbon-soluble impurities such as ditertiary butyl peroxide, acetic acid, formic acid, methyl formate, acetone, methanol, etc., are formed during the oxygenation reaction. These impurities, especially the carboxylic acids, adversely effect the quality of the tertiary butyl alcohol product. The carboxylic acids such as formic acid and acetic acid are corrosive to equip-ment and detrimental to subsequent operations.
A minor amount of other peroxides, including ditertiary butyl peroxide are also formed. Generally speaking, from about lQ to about 100 parts of tertiary butyl hydroperoxide are formed per part of ditertiary butyl peroxide.
The production of propylene oxide together with a coproduct, such as tertiary butyl alcohol, is described in Kollar U. S. Patents No. 3,350,422 and 3,351,635 which are directed to the catalytic epoxidation of an olefin by reac-tion with a hydroperoxide such as tertiary butyl hydroperox-ide in solution in a solvent such as tertiary butyl alcohol.
When the olefin is propylene and the hydroperoxide is ter-tiary butyl hydroperoxide, the principal reaction productsare propylene oxide and additional tertiary butyl alcohol.
Grane U. S. Patent No. 3,474,151 is also directed to the oxidation of isobutane with oxygen to provide tertiary butyl alcohol and discloses that the reaction mixture con-tains not only tertiary butyl hydroperoxide, but also diter-tiary butyl peroxide. In their U. S. Patent No. 4,239,926, _3_ 2~ ~3~
Grane et al. disclose a method for significantly purifying the tertiary butyl alcohol prepared by th~ oxidation of isohutane, the method involving extractive distillation of the tertiary butyl alcohol product using a specially propor-tioned ~lend of xylene, acetone and water as the extractant.
The product of the reaction of tertiary butyl hydro-peroxide with propylene i8 normally separated into useful components, usually by distillation, to form, for example, sequential distillate fractions composed of unreacted propylene, propylene oxide and tertiary butyl alcohol.
The contaminating impurities are normally soluble to at least a limited extent in tertiary butyl alcohol and are usually removed during the final stages of the process. For example, Grane et al. in U. S. Patent~ No. 3,474,151 and No.
15 3,239,926 and Worrell et al. in U. S. Patent No. 4,296,263 use a combination of thermal treating steps and fractiona tion steps in purifying the tertiary butyl alcohol.
Sanderson et al. utilize a combination of catalytic hydrogenation and distillation in purifying the tertiary 20 butyl alcohol. See U. S. Patent No. 4,704,482 dated Novem-ber 3, 1987, U. S. Patent No. 4,742,179 dated May 3, 1988 and U. S. Patent No. 4,705,903 dated November 10, 1987.
Harvey U. S. Patent No. 3,449,217 is directed to a method for the recovery of tertiary butyl hydroperoxide from a mixture of tertiary butyl hydroperoxide and tertiary butyl alcohol.
_4_ 2~3~
Tertiary butyl hydroperoxide is useful as a raw mate-rial for the manufacture of tertiary butyl alcohol either by the decomposition of the tertiary butyl hydroperoxide as such, or by the catalytic reaction of tertiary butyl hydro-peroxide with an olefin. When the tertiary butyl hydroper-oxide is reacted with propylene the principle reaction products are tertiary butyl alcohol and propylene oxide.
Carboxylic acids such as formic acid and acetic acid are detrimental in thse operations even when present in small amounts.
SUMMARY OF THE INVEN_ION
In accordance with the present invention, after isobu-tane has been thermally and/or catalytically reacted with molecular oxygen to provide a crude initial feedstock com-posed of unreacted isobutane, tertiary butyl hydroperoxide, tertiary butyl alcohol and oxygenated impurities including carboxylic acids such as formic acid and acetic acid, the crude initial feedstock is treated with water (preferably in a counter-current extraction zone) in order to preferentially remove a significant portion of the carboxylic acid impuri-ties and to provide a final feedstock from which unreacted isobutane may be removed (e.g., by distillation) for recycle.
The resultant mixture composed of tertiary butyl hydro-peroxide dissolved in tertiary butyl alcohol may be furtherprocessed for thermal and/or catalytic conversion of the _5_ 2 ~ ~35 ~
tertiary butyl hydroperoxide to tertiary butyl alcohol in the manner disclosed, for example, in Grane et al. U. S.
Patents No. 3,474,151 and No. 4,239,926 and Worrell et al.
U. S. Patent No. 4,296,263.
In the alternative, the solution of tertiary butyl hydroperoxide in tertiary butyl alcohol may be used as a charge stock for the coproduction of tertiary butyl alcohol and propylene oxide as disclosed for example, in Kollar U. S. Patents No. 3,350,422 and No. 3,351,635.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawing, Fig. 1 is a schematic flow sheet with conventional parts omitted showing the general reaction and recovery sequence that is used in the practice of a pre-ferred embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning now to Fig. 1, there is sh~wn a schematic flow sheet illustrating a preferred method of practicing the process of the present invention. In the drawing, conven-tional parts such as valves, pumps, temperature sensors, pressure sensors, heaters, coolers, control and flow regula-tion apparatus, reboilers, reflux condensers, etc., have been omitted.
In accordance with the present invention, an appropriate reactor 10 is charged with oxygen by way of a charge line 12 -6- 2~ ~3~
and with isobu~ane by way of a charge line 14 from appropri-ate sources (not shown) such as a storage tank. Within the reactor 10, and in accordance with known prior art proce-dures, the oxygen reacts with a portion of the isobutane to provide a reaction mixture which is discharged from the reactor 10 by way of a discharge line 16. The reaction mixture 16 comprises, for example, unreacted isobutane, ter-tiary butyl alcohol and minor quantities of other reaction components and by-products including acetic acid and formic acid. The liquid reaction product discharged from reactor 10 by line 16 constitutes a crude initial reaction product.
The initial reaction product discharged from the reactor 10 by discharge line 16 will normally have the composition shown in Table I.
TABLE I
COMPOSITION OF INITIAL REACTION PRODUCT
General Preferred ComponentRange, Wt.% Range, Wt.
Isobutane 25 - 90 50 - 80 t-butyl hydroperoxide70 - 0 25 - 55 t-butyl alcohol0 - 70 25 - 55 Others* 0.5 - 10 0.5 - 5 * Includes di-tertiary butyl peroxide, acetone, methanol, acetic acid, formic acid and other oxygenated impurities.
_7_ 2~ ~35~
The water may suitably be charged through the line 82 at the rate of about 10 to about 200 parts of water per 100 parts of initial reaction product charged by th~ line 16.
In accordance with the present invention, the initial reaction product 16 is charged to the bottom o~ a water extraction zone, such as a packed water extraction column 80. Water is charged to the column 80 by way of a water charge line 82 for countercurrent contact with the feed 16.
As a consequence of the countercurrent contact, a raffinate phase 84 is formed which is taken overhead and an extract phase 86 is formed, which is composed of water and extracted impurities. The extract is suitably discharged by line 86 for further processing.
By way of example, about 100 pounds per hour of a mixture of about 15 wt.~ of tertiary butyl alcohol, about 30 wt.~ isobutane, about 10 wt.% of tertiary butyl hydroperox-ide contaminated with from about 0.05 to about 2 wt.% of carboxylic acid impurities may be charged to the water extraction tower 80 by line 16 and about 50 pounds per hour of water may be charged to the water extraction tower 80 by line 82. The water-lean raffinate 84 from the water extrac-tion tower 80, in this instance may comprise, for example, substantially all of the isobutane, tertiary butyl alcohol and tertiary butyl hydroperoxide charged by line 16 and will contain only residual quantities (less than about 0.01 wt.%
-8- ~Q~3~
of carboxylic acid impurities. The water-ri~h extract solu-tion B6 discharged from water extraction zone 80 by line 86, in this instance, may comprise about 90 to about 95 wt.~ of a water and about 1 to about 5 wt.% of tertiary butyl alcohol and about 0.05 to about 2 wt.% of carboxylic acid impurities.
The raffinate phase 84 from water extraction zone 80 is suitably fed to a distillation zone 90 where it is separated into an overhead distillate fraction lS comprising isobutane which, if desired, may be recycled to isobutane charge line 14.
The higher boiling fraction 24 discharged from the zone 90 will be composed primarily of tertiary butyl hydroperox-ide in solution in tertiary butyl alcohol.
If the only primary product to be manufactured is tertiary butyl alcohol, the reaction conditions used in the reactor 10 will be selected so that the tertiary butyl hydroperoxide is converted directly to tertiary butyl alco-hol, as disclosed for example, in Worrell U. S. Patent No.
4,296,263 or, in the alternative, the decomposition of the tertiary butyl hydroperoxide is accomplished in a separate digestion zone (not shown), as described for example in Grane et al. U. S. Patent No. 4,294,999 or Grane et al.
U. S. Patent No. 4,296,262.
2~3!~
EXAMPLES
The invention will be further illustrated by the fol-lowing examplesr which are given by way of illustration and not as limitations on the scope of this invention.
The following laboratory examples were conducted under ambient conditions of temperature and pressure in a labora-tory. Since isobutane has a boiling point of about -11.7C., it will vaporize rapidly in an open vessel, such as a beaker, even when dissolved in a solvent such as tertiary butyl alcohol. Therefore, in the following experiments, isooctane, a related compound was used rather than isobutane, and was used to simulate the presence of isobutane in the pseudo reaction mixtures.
Example 1 Procedure - 5869-80 A pseudo reaction mixture was made up of approximately 70~ isooctane, approximately 29% text-butyl alcohol, and approximately 1% acetic acid. 100 ml of this solution was placed in a small separatory funnel and extracted three times with 5.0 ml of demineralized (DM) water. The results are shown in Table II.
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TABLE II
Notebook ml After Acid No.
No. Extracted 3x 5.0 ml H2O Extraction (mg/~) 5869-80-0 Reaction mixture - 11.27 5869-80-1 Reaction mixture after first extraction - 10.05 5869-80-2 Reaction mixture after second extraction - 8.66 5869-80-3 Reaction mixture after third extraction - 7.85 5869-80-4 Water layer 1st extraction4.3 18.97 5869-80-5 Water layer 2nd extraction6.6 17.09 5869-80-6 Water layer 3rd extraction6.8 15.05 - ~Q~9~i5 Example 2 (5898-18) The procedure was the same as Example 1. The results are shown in Table III.
TABLE III
Notebook Isooc*anea TBAa H2Oa Wt%b No. [Extracted 3xlO.0 ml H20] (Area%) (Area%) (Area%) Acid 5898-18-0 Reaction Mixture 67.20 31.79~0 1.30 -1 Rxn Mix after 1st extr. 68.8030.05 l,og 0.89 -2 H2O layer 1st extr. ~0 18.7481.14 1.77 -3 Rxn Mix after 2nd extr. 71.2626.65 2.04 0.66 -4 H20 layer 2nd extr. ~0 17.8782.05 1.41 -5 Rxn Mix after 3rd extr. 74.8523.26 1.86 0.46 -6 H20 layer 3rd extr. ~0 16.7483.15 1.05 a = Oktained frcm GC
b = Calculated from acid no.
2~ 3~5 Example 3 (5898-67) A pseudo reaction mixture was made up of isooctane, tert-butyl alcohol and formic acid. 100 ml of this solution was placed in a small separating funnel and extracted with 10.0 ml DM water. The results are shown in Table IV.
TABLE IV
Notebook Iso~nea TBAa H2Oa Wt%b No. [Extracted 3x10.0 ml H ~ (Area%) (Area%) (Area%) Acid 5898-67-0 ~eaction Mixture 66.45 33.42~0 1.30 -1 Rxn Mix after 1st extr. 67.4530.45 2.04 1.09 -2 ~2 layer 1st extr. ~0 18.4281.21 2.85 -3 Rxn Mix after 2nd extr. 71.4527.41 1.103 0.56 -4 H2O layer 2nd extr. ~0 16.5683.18 1.88 -5 Rxn Mix after 3rd extr. 75.4623.99 0.53 0.35 -6 H2O layer 3rd extr. ~0 15.2884.61 1.13 a = Ob~ned frcm GC
b - Calcul~ted from acid no.
Having thus described our invention, what is claimed is:
BUTYL HYDROPEROXIDE CONTAINING FEEDSTOCR
(Docket No. 80,415-~) BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to the purification of a tertiary butyl hydroperoxide-containing feedstock. More particularly, this invention relates to a method for the preparation of an isobutane-tertiary butyl alcohol-tertiary butyl hydroperox-ide feedstock useful in the preparation of tertiary butylalcohol, propylene oxide, etc. Still more particularly, this invention relates to a method wherein an initial reac-tion product obtained by the oxidation of isobutane with oxygen and comprisin~ unreacted isobutane, tertiary butyl alcoholr tertiary butyl hydroperoxide and a minor amount of water soluble acidic by-products, including acetic acid~
formic acid, etc., is extracted with water to provide a - final feedstock comprising tertiary butyl alcohol, tertiary butyl hydroperoxide, ditertiary butyl peroxide, and unre-acted isobutane which is substantially free of water soluble acidic impurities.
Prior Art It is known to react oxygen with isobutane to form a peroxidation reaction product wherein the principal peroxide that is formed is tertiary butyl hydroperoxide. However, 2 ~
minor amounts of water-soluble and hydrocarbon-soluble impurities such as ditertiary butyl peroxide, acetic acid, formic acid, methyl formate, acetone, methanol, etc., are formed during the oxygenation reaction. These impurities, especially the carboxylic acids, adversely effect the quality of the tertiary butyl alcohol product. The carboxylic acids such as formic acid and acetic acid are corrosive to equip-ment and detrimental to subsequent operations.
A minor amount of other peroxides, including ditertiary butyl peroxide are also formed. Generally speaking, from about lQ to about 100 parts of tertiary butyl hydroperoxide are formed per part of ditertiary butyl peroxide.
The production of propylene oxide together with a coproduct, such as tertiary butyl alcohol, is described in Kollar U. S. Patents No. 3,350,422 and 3,351,635 which are directed to the catalytic epoxidation of an olefin by reac-tion with a hydroperoxide such as tertiary butyl hydroperox-ide in solution in a solvent such as tertiary butyl alcohol.
When the olefin is propylene and the hydroperoxide is ter-tiary butyl hydroperoxide, the principal reaction productsare propylene oxide and additional tertiary butyl alcohol.
Grane U. S. Patent No. 3,474,151 is also directed to the oxidation of isobutane with oxygen to provide tertiary butyl alcohol and discloses that the reaction mixture con-tains not only tertiary butyl hydroperoxide, but also diter-tiary butyl peroxide. In their U. S. Patent No. 4,239,926, _3_ 2~ ~3~
Grane et al. disclose a method for significantly purifying the tertiary butyl alcohol prepared by th~ oxidation of isohutane, the method involving extractive distillation of the tertiary butyl alcohol product using a specially propor-tioned ~lend of xylene, acetone and water as the extractant.
The product of the reaction of tertiary butyl hydro-peroxide with propylene i8 normally separated into useful components, usually by distillation, to form, for example, sequential distillate fractions composed of unreacted propylene, propylene oxide and tertiary butyl alcohol.
The contaminating impurities are normally soluble to at least a limited extent in tertiary butyl alcohol and are usually removed during the final stages of the process. For example, Grane et al. in U. S. Patent~ No. 3,474,151 and No.
15 3,239,926 and Worrell et al. in U. S. Patent No. 4,296,263 use a combination of thermal treating steps and fractiona tion steps in purifying the tertiary butyl alcohol.
Sanderson et al. utilize a combination of catalytic hydrogenation and distillation in purifying the tertiary 20 butyl alcohol. See U. S. Patent No. 4,704,482 dated Novem-ber 3, 1987, U. S. Patent No. 4,742,179 dated May 3, 1988 and U. S. Patent No. 4,705,903 dated November 10, 1987.
Harvey U. S. Patent No. 3,449,217 is directed to a method for the recovery of tertiary butyl hydroperoxide from a mixture of tertiary butyl hydroperoxide and tertiary butyl alcohol.
_4_ 2~3~
Tertiary butyl hydroperoxide is useful as a raw mate-rial for the manufacture of tertiary butyl alcohol either by the decomposition of the tertiary butyl hydroperoxide as such, or by the catalytic reaction of tertiary butyl hydro-peroxide with an olefin. When the tertiary butyl hydroper-oxide is reacted with propylene the principle reaction products are tertiary butyl alcohol and propylene oxide.
Carboxylic acids such as formic acid and acetic acid are detrimental in thse operations even when present in small amounts.
SUMMARY OF THE INVEN_ION
In accordance with the present invention, after isobu-tane has been thermally and/or catalytically reacted with molecular oxygen to provide a crude initial feedstock com-posed of unreacted isobutane, tertiary butyl hydroperoxide, tertiary butyl alcohol and oxygenated impurities including carboxylic acids such as formic acid and acetic acid, the crude initial feedstock is treated with water (preferably in a counter-current extraction zone) in order to preferentially remove a significant portion of the carboxylic acid impuri-ties and to provide a final feedstock from which unreacted isobutane may be removed (e.g., by distillation) for recycle.
The resultant mixture composed of tertiary butyl hydro-peroxide dissolved in tertiary butyl alcohol may be furtherprocessed for thermal and/or catalytic conversion of the _5_ 2 ~ ~35 ~
tertiary butyl hydroperoxide to tertiary butyl alcohol in the manner disclosed, for example, in Grane et al. U. S.
Patents No. 3,474,151 and No. 4,239,926 and Worrell et al.
U. S. Patent No. 4,296,263.
In the alternative, the solution of tertiary butyl hydroperoxide in tertiary butyl alcohol may be used as a charge stock for the coproduction of tertiary butyl alcohol and propylene oxide as disclosed for example, in Kollar U. S. Patents No. 3,350,422 and No. 3,351,635.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawing, Fig. 1 is a schematic flow sheet with conventional parts omitted showing the general reaction and recovery sequence that is used in the practice of a pre-ferred embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning now to Fig. 1, there is sh~wn a schematic flow sheet illustrating a preferred method of practicing the process of the present invention. In the drawing, conven-tional parts such as valves, pumps, temperature sensors, pressure sensors, heaters, coolers, control and flow regula-tion apparatus, reboilers, reflux condensers, etc., have been omitted.
In accordance with the present invention, an appropriate reactor 10 is charged with oxygen by way of a charge line 12 -6- 2~ ~3~
and with isobu~ane by way of a charge line 14 from appropri-ate sources (not shown) such as a storage tank. Within the reactor 10, and in accordance with known prior art proce-dures, the oxygen reacts with a portion of the isobutane to provide a reaction mixture which is discharged from the reactor 10 by way of a discharge line 16. The reaction mixture 16 comprises, for example, unreacted isobutane, ter-tiary butyl alcohol and minor quantities of other reaction components and by-products including acetic acid and formic acid. The liquid reaction product discharged from reactor 10 by line 16 constitutes a crude initial reaction product.
The initial reaction product discharged from the reactor 10 by discharge line 16 will normally have the composition shown in Table I.
TABLE I
COMPOSITION OF INITIAL REACTION PRODUCT
General Preferred ComponentRange, Wt.% Range, Wt.
Isobutane 25 - 90 50 - 80 t-butyl hydroperoxide70 - 0 25 - 55 t-butyl alcohol0 - 70 25 - 55 Others* 0.5 - 10 0.5 - 5 * Includes di-tertiary butyl peroxide, acetone, methanol, acetic acid, formic acid and other oxygenated impurities.
_7_ 2~ ~35~
The water may suitably be charged through the line 82 at the rate of about 10 to about 200 parts of water per 100 parts of initial reaction product charged by th~ line 16.
In accordance with the present invention, the initial reaction product 16 is charged to the bottom o~ a water extraction zone, such as a packed water extraction column 80. Water is charged to the column 80 by way of a water charge line 82 for countercurrent contact with the feed 16.
As a consequence of the countercurrent contact, a raffinate phase 84 is formed which is taken overhead and an extract phase 86 is formed, which is composed of water and extracted impurities. The extract is suitably discharged by line 86 for further processing.
By way of example, about 100 pounds per hour of a mixture of about 15 wt.~ of tertiary butyl alcohol, about 30 wt.~ isobutane, about 10 wt.% of tertiary butyl hydroperox-ide contaminated with from about 0.05 to about 2 wt.% of carboxylic acid impurities may be charged to the water extraction tower 80 by line 16 and about 50 pounds per hour of water may be charged to the water extraction tower 80 by line 82. The water-lean raffinate 84 from the water extrac-tion tower 80, in this instance may comprise, for example, substantially all of the isobutane, tertiary butyl alcohol and tertiary butyl hydroperoxide charged by line 16 and will contain only residual quantities (less than about 0.01 wt.%
-8- ~Q~3~
of carboxylic acid impurities. The water-ri~h extract solu-tion B6 discharged from water extraction zone 80 by line 86, in this instance, may comprise about 90 to about 95 wt.~ of a water and about 1 to about 5 wt.% of tertiary butyl alcohol and about 0.05 to about 2 wt.% of carboxylic acid impurities.
The raffinate phase 84 from water extraction zone 80 is suitably fed to a distillation zone 90 where it is separated into an overhead distillate fraction lS comprising isobutane which, if desired, may be recycled to isobutane charge line 14.
The higher boiling fraction 24 discharged from the zone 90 will be composed primarily of tertiary butyl hydroperox-ide in solution in tertiary butyl alcohol.
If the only primary product to be manufactured is tertiary butyl alcohol, the reaction conditions used in the reactor 10 will be selected so that the tertiary butyl hydroperoxide is converted directly to tertiary butyl alco-hol, as disclosed for example, in Worrell U. S. Patent No.
4,296,263 or, in the alternative, the decomposition of the tertiary butyl hydroperoxide is accomplished in a separate digestion zone (not shown), as described for example in Grane et al. U. S. Patent No. 4,294,999 or Grane et al.
U. S. Patent No. 4,296,262.
2~3!~
EXAMPLES
The invention will be further illustrated by the fol-lowing examplesr which are given by way of illustration and not as limitations on the scope of this invention.
The following laboratory examples were conducted under ambient conditions of temperature and pressure in a labora-tory. Since isobutane has a boiling point of about -11.7C., it will vaporize rapidly in an open vessel, such as a beaker, even when dissolved in a solvent such as tertiary butyl alcohol. Therefore, in the following experiments, isooctane, a related compound was used rather than isobutane, and was used to simulate the presence of isobutane in the pseudo reaction mixtures.
Example 1 Procedure - 5869-80 A pseudo reaction mixture was made up of approximately 70~ isooctane, approximately 29% text-butyl alcohol, and approximately 1% acetic acid. 100 ml of this solution was placed in a small separatory funnel and extracted three times with 5.0 ml of demineralized (DM) water. The results are shown in Table II.
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TABLE II
Notebook ml After Acid No.
No. Extracted 3x 5.0 ml H2O Extraction (mg/~) 5869-80-0 Reaction mixture - 11.27 5869-80-1 Reaction mixture after first extraction - 10.05 5869-80-2 Reaction mixture after second extraction - 8.66 5869-80-3 Reaction mixture after third extraction - 7.85 5869-80-4 Water layer 1st extraction4.3 18.97 5869-80-5 Water layer 2nd extraction6.6 17.09 5869-80-6 Water layer 3rd extraction6.8 15.05 - ~Q~9~i5 Example 2 (5898-18) The procedure was the same as Example 1. The results are shown in Table III.
TABLE III
Notebook Isooc*anea TBAa H2Oa Wt%b No. [Extracted 3xlO.0 ml H20] (Area%) (Area%) (Area%) Acid 5898-18-0 Reaction Mixture 67.20 31.79~0 1.30 -1 Rxn Mix after 1st extr. 68.8030.05 l,og 0.89 -2 H2O layer 1st extr. ~0 18.7481.14 1.77 -3 Rxn Mix after 2nd extr. 71.2626.65 2.04 0.66 -4 H20 layer 2nd extr. ~0 17.8782.05 1.41 -5 Rxn Mix after 3rd extr. 74.8523.26 1.86 0.46 -6 H20 layer 3rd extr. ~0 16.7483.15 1.05 a = Oktained frcm GC
b = Calculated from acid no.
2~ 3~5 Example 3 (5898-67) A pseudo reaction mixture was made up of isooctane, tert-butyl alcohol and formic acid. 100 ml of this solution was placed in a small separating funnel and extracted with 10.0 ml DM water. The results are shown in Table IV.
TABLE IV
Notebook Iso~nea TBAa H2Oa Wt%b No. [Extracted 3x10.0 ml H ~ (Area%) (Area%) (Area%) Acid 5898-67-0 ~eaction Mixture 66.45 33.42~0 1.30 -1 Rxn Mix after 1st extr. 67.4530.45 2.04 1.09 -2 ~2 layer 1st extr. ~0 18.4281.21 2.85 -3 Rxn Mix after 2nd extr. 71.4527.41 1.103 0.56 -4 H2O layer 2nd extr. ~0 16.5683.18 1.88 -5 Rxn Mix after 3rd extr. 75.4623.99 0.53 0.35 -6 H2O layer 3rd extr. ~0 15.2884.61 1.13 a = Ob~ned frcm GC
b - Calcul~ted from acid no.
Having thus described our invention, what is claimed is:
Claims (9)
1. In a method wherein isobutane is reacted with oxygen to provide a crude initial feedstock comprising unreacted isobutane, tertiary butyl hydroperoxide, tertiary butyl alcohol and carboxylic acid impurities, including acetic acid and formic acid, the improvement for at least partially purifying said initial feedstock by substantially completely removing said carboxylic acid impurities there-from which comprises the steps of:
charging said crude initial feedstock and water to a water extraction zone in amounts and under extraction conditions sufficient to separate said charged crude initial feedstock and said charged water into an extract fraction comprising water, tertiary butyl alcohol and said carboxylic acid impurities and a raffinate final feedstock fraction comprising isobutane, tertiary butyl hydroperoxide and ter-tiary butyl alcohol, and recovering said final feedstock.
charging said crude initial feedstock and water to a water extraction zone in amounts and under extraction conditions sufficient to separate said charged crude initial feedstock and said charged water into an extract fraction comprising water, tertiary butyl alcohol and said carboxylic acid impurities and a raffinate final feedstock fraction comprising isobutane, tertiary butyl hydroperoxide and ter-tiary butyl alcohol, and recovering said final feedstock.
2. A method as in claim 1 wherein said water extrac-tion zone is a continuous countercurrent water extraction zone and wherein water is continuously charged to said countercurrent extraction zone at the rate of about 10 to about 200 parts of water per hour per 100 parts per hour of said initial feedstock.
3. A method as in claim 2 wherein said crude initial charge stock contains from about 50 to about 80 wt.% of isobutane, from about 25 to 55 wt.% of tertiary butyl hydro-peroxide, from about 25 to about 55 wt.% of tertiary butyl alcohol and about 0.05 to about 2 wt.% of said carboxylic acid impurities, wherein said raffinate contains from about 0.01 to about 0.05 wt.% of said carboxylic acid impurities and wherein said raffinate contains 0.5 to about 2 wt.% of said carboxylic acid impurities.
4. In a method wherein isobutane is reacted with oxygen in an oxidation reaction zone to provide a crude initial feedstock comprising unreacted isobutane, tertiary butyl hydroperoxide, tertiary butyl alcohol and carboxylic acid impurities, including acetic acid and formic acid, the improvement for at least partially purifying said initial feedstock by substantially completely removing said carboxy-lic acid impurities therefrom which comprises the steps of:
charging said crude initial feedstock and water to a water extraction zone in amounts and under extraction conditions sufficient to separate said charged initial feedstock and said charged water into an extract fraction comprising water, tertiary butyl alcohol and said carboxylic acid impurities and a raffinate final feedstock fraction comprising isobutane, tertiary butyl hydroperoxide and ter-tiary butyl alcohol, charging said final feedstock to a distillation zone and separating said final feedstock therein into an unreacted isobutane distillate fraction and a tertiary butyl hydroperoxide/tertiary butyl alcohol fraction.
charging said crude initial feedstock and water to a water extraction zone in amounts and under extraction conditions sufficient to separate said charged initial feedstock and said charged water into an extract fraction comprising water, tertiary butyl alcohol and said carboxylic acid impurities and a raffinate final feedstock fraction comprising isobutane, tertiary butyl hydroperoxide and ter-tiary butyl alcohol, charging said final feedstock to a distillation zone and separating said final feedstock therein into an unreacted isobutane distillate fraction and a tertiary butyl hydroperoxide/tertiary butyl alcohol fraction.
5. A method as in claim 4 wherein said water extrac-tion zone is a continuous countercurrent water extraction zone and wherein water is continuously charged to said countercurrent extraction zone at the rate of about 10 to about 200 parts of water per hour per 100 parts per hour of said initial feedstock.
6. A method as in claim 5 wherein said initial charge stock contains from about 50 to about 80 wt.% of isobutane, from about 25 to 55 wt.% of tertiary butyl hydroperoxide, from about 25 to about 55 wt.% of tertiary butyl alcohol and about 0.05 to about 2 wt.% of said carboxylic acid impuri-ties, wherein said raffinate contains from about 0.01 to about 0.05 wt.% of said carboxylic acid impurities and wherein said raffinate contains 0.5 to about 2 wt.% of said carboxylic acid impurities.
7. In a continuous method wherein isobutane is con-tinuously reacted with oxygen in an oxidation reaction zone to provide a crude initial feedstock comprising unreactaed isobutane, tertiary butyl hydroperoxide, tertiary butyl alcohol and carboxylic acid impurities, including acetic acid and formic acid, the improvement for at least partially purifying said initial feedstock by substantially completely removing said carboxylic acid impurities therefrom which comprises the steps of:
continuously withdrawing a stream of said crude initial charge stock from said oxidation reaction zone and continuously charging said stream of said initial feedstock to a continuous water extraction zone adjacent the bottom thereof, continuously charging a stream of water to said continuous reaction zone adjacent the top thereof under countercurrent extraction conditions sufficient to separate said charged initial feedstock and said charged water into an extract fraction comprising water, tertiary butyl alcohol and said carboxylic acid impurities and a raffinate final feedstock fraction comprising isobutane, tertiary butyl hydroperoxide and tertiary butyl alcohol, continuously removing a stream of said raffinate fraction from said water extraction zone, continuously removing a stream of said extract fraction from said water extraction zone, continuously charging said stream of said raffinate to a distillation zone and continuously separating said raf-finate stream therein into an unreacted isobutane distillate fraction and a heavier tertiary butyl hydroperoxide/tertiary butyl alcohol fraction.
continuously withdrawing a stream of said crude initial charge stock from said oxidation reaction zone and continuously charging said stream of said initial feedstock to a continuous water extraction zone adjacent the bottom thereof, continuously charging a stream of water to said continuous reaction zone adjacent the top thereof under countercurrent extraction conditions sufficient to separate said charged initial feedstock and said charged water into an extract fraction comprising water, tertiary butyl alcohol and said carboxylic acid impurities and a raffinate final feedstock fraction comprising isobutane, tertiary butyl hydroperoxide and tertiary butyl alcohol, continuously removing a stream of said raffinate fraction from said water extraction zone, continuously removing a stream of said extract fraction from said water extraction zone, continuously charging said stream of said raffinate to a distillation zone and continuously separating said raf-finate stream therein into an unreacted isobutane distillate fraction and a heavier tertiary butyl hydroperoxide/tertiary butyl alcohol fraction.
8. A method as in claim 7 wherein water is continu-ously charged to said countercurrent water extraction zone at the rate of about 10 to about 200 parts of water per hour per 100 parts per hour of said initial feedstock.
9. A method as in claim 8 wherein said initial charge stock contains from about 50 to about 80 wt.% of isobutane, from about 25 to 55 wt.% of tertiary butyl hydroperoxide, from about 25 to about 55 wt.% of tertiary butyl alcohol and about 0.05 to about 2 wt.% of said carboxylic acid impuri-ties, and wherein said raffinate contains from about 0.01 to about 0.05 wt.% of said carboxylic acid impurities and wherein said raffinate contains 0.5 to about 2 wt.% of said carboxylic acid impurities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2019355 CA2019355A1 (en) | 1990-06-20 | 1990-06-20 | Removal of acidic impurities from tertiary butyl hydroperoxide containing feedstock |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2019355 CA2019355A1 (en) | 1990-06-20 | 1990-06-20 | Removal of acidic impurities from tertiary butyl hydroperoxide containing feedstock |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2019355A1 true CA2019355A1 (en) | 1991-12-20 |
Family
ID=4145278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2019355 Abandoned CA2019355A1 (en) | 1990-06-20 | 1990-06-20 | Removal of acidic impurities from tertiary butyl hydroperoxide containing feedstock |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2019355A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102725267A (en) * | 2010-01-21 | 2012-10-10 | 罗地亚经营管理公司 | Method for producing alkyl hydroperoxide |
-
1990
- 1990-06-20 CA CA 2019355 patent/CA2019355A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102725267A (en) * | 2010-01-21 | 2012-10-10 | 罗地亚经营管理公司 | Method for producing alkyl hydroperoxide |
| CN102725267B (en) * | 2010-01-21 | 2014-10-08 | 罗地亚经营管理公司 | Method for producing alkyl hydroperoxide |
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