Plural stage purification of propylene oxide

• US 5,262,017 A
• Filed: 04/19/1993
• Issued: 11/16/1993
• Est. Priority Date: 04/19/1993
• Status: Expired due to Term

• Current Assignee: Huntsman International LLC (Huntsman Corporation)
• Original Assignee: Texaco Chemical Company (Huntsman Corporation)
• Inventors: Meyer, Robert A., Demoll, Gregory B., Smith, William A., Mueller, Mark A.
• Primary Examiner(s): Bascomb, Jr., Wilbur
• Application Number:
  US08/047,910
• Time in Patent Office: 211 Days
• Field of Search: 203/14, 203/64, 203/68, 203/70, 203/56, 203/74, 203/77, 549/541, 549/542
• US Class Current: 203/64
• CPC Class Codes: B01D 3/40 Extractive distillation
• CPC Class Codes: C07D 301/32 Separation; Purification

Abstract

Impure propylene oxide is purified by a distillation process wherein it is (a) extractively distilled in a first column using a C₂ to C₆ alkylene glycol extractive distillation agent to form a first overhead fraction comprising propylene oxide, C₅ -C₇ hydrocarbons methanol, water and oxygen-containing impurities, (b) wherein the first overhead fraction is separated in a second column into a second overhead fraction comprising most of the pentanes, pentenes and oxygen-containing impurities and a partially purified propylene oxide bottoms fraction comprising propylene oxide, hexenes, hexanes, and only residual quantities of pentenes and pentanes, (c) wherein the partially purified bottoms fraction is extracting distilled in a third column using a C₇ -C₁₀ alkane hydrocarbon extractive distillation agent to provide a further purified bottoms fraction containing substantially all of the propylene oxide, hexenes, hexanes charged to the third distillation column, and (d) the further purified bottoms fraction is extractively distilled in a fourth column using a C₇ to C₁₀ alkane hydrocarbon extractive distillation agent to provide a purified propylene oxide overhead fraction consisting essentially of propylene oxide.

Claims

1. A process for separating contaminating quantities of hexenes, hexanes, pentenes, pentanes, water and oxygen-containing impurities from impure propylene oxide which comprises:

extractively distilling the impure propylene oxide in a first distillation column using a C₂ to C₆ alkylene glycol extractive distillation agent to form a first overhead fraction comprising propylene oxide, hexenes, hexanes, pentenes, pentanes, water, methanol and oxygen-containing impurities boiling above propylene oxide;

fractionating the first overhead fraction in a second distillation column to obtain a second overhead fraction comprising essentially all of the pentanes and pentenes and most of the oxygen-containing impurities boiling above propylene oxide and a partially purified propylene oxide bottoms fraction comprising propylene oxide, hexenes, hexanes, and only residual quantities of pentenes and pentanes;

extractively distilling the partially purified bottoms fraction in a third distillation column using a C₇ to C₁₀ alkane hydrocarbon extractive distillation agent to provide a further purified bottoms fraction comprising substantially all of the propylene oxide, hexenes and hexanes charged to the third distillation column; and

extractively distilling the further purified bottoms fraction in a fourth distillation column using a C₇ to C₁₀ alkane hydrocarbon extractive distillation agent to provide a purified propylene oxide overhead fraction consisting essentially of propylene oxide free of said contaminants.

2. A distillation process for the purification of an impure propylene oxide contaminated feedstock with hexenes, hexanes, pentanes, pentenes, water and oxygen-containing impurities which comprises the steps of:

separately charging said impure propylene oxide feedstock and a C₂ to C₆ alkylene glycol extractive distillation agent to a first extractive distillation column at ascending charge points, and separating said impure propylene oxide therein into a first lighter distillation fraction containing residual methanol and water and all of the propylene oxide, hexenes, hexanes, pentenes and pentanes and oxygen-containing impurities boiling with and above propylene oxide and a first heavier distillation fraction containing oxygen-containing impurities boiling below propylene oxide and all of the extractive distillation agent,

charging a second feedstock comprising said first lighter distillation fraction to a second distillation column and separating it therein into a second lighter distillation fraction containing most of the pentanes and pentenes, oxygen-containing impurities boiling above propylene oxide, and a second heavier distillation fraction containing substantially all of the propylene oxide, methanol, water, hexenes, hexanes, and only residual quantities of pentenes and pentanes,

separately charging a third feedstock comprising said second heavier distillation fraction and a C₇ to C₁₀ alkane hydrocarbon extractive distillation agent to a third extractive distillation column at ascending charge points and fractionating them therein into a third lighter distillation fraction containing methanol, water and oxygen-containing impurities boiling above propylene oxide, and a third heavier distillation fraction containing substantially all of the propylene oxide, hexenes and hexanes, and extractive distillation agent charged to said third distillation column,

separately charging a fourth feedstock comprising said third heavier distillation fraction and a C₇ to C₁₀ alkane hydrocarbon extractive distillation agent to a fourth extractive distillation column at ascending charge points and fractionating it therein into a fourth lighter distillation fraction consisting essentially of propylene oxide and a fourth heavier distillation fraction containing substantially all of the extractive distillation agent, all of the hexenes and hexanes charged to said third distillation column, and also residual quantities of propylene oxide.

3. A distillation process for the purification of an impure propylene oxide contaminated feedstock with impurities including water, propylene, propane, acetaldehyde, methyl formate, propionaldehyde, hexenes, acetone, hexanes, methanol, t-butyl alcohol, pentane, isopentane, pentenes, isopropyl alcohol and t-butyl formate which comprises the steps of:

charging said impure propylene oxide feedstock to a first extractive distillation column,

charging a C₂ to C₆ alkylene glycol extractive distillation agent to said first extractive distillation column at a feed point above the point of introduction of said impure propylene oxide,

fractionating said impure propylene oxide in said first extractive distillation column under distillation conditions selected to provide a first lighter distillation fraction containing all of the propylene oxide, propylene, propane, acetaldehyde, methyl formate, hexenes, hexanes, pentenes and pentanes, and a portion of the methanol and water and a first heavier distillation fraction containing all of the propionaldehyde, acetone, t-butyl alcohol, t-butyl formate, isopropyl alcohol, the remainder of the methanol and water and all of the extractive distillation agent,

charging a second feedstock comprising said first lighter distillation fraction to a second distillation column,

fractionating said second feedstock in said second distillation column under distillation conditions selected to provide a second lighter distillation fraction containing all of the propylene, propane, acetaldehyde, pentanes and pentenes, and a residual amount of propylene oxide, and a second heavier distillation fraction containing substantially all of the propylene oxide, hexenes, hexanes, and only residual quantities of pentenes and pentanes,

charging a third feedstock comprising said second heavier distillation fraction to a third extractive distillation column,

charging a C₇ to C₁₀ alkane hydrocarbon extractive distillation agent to said third extractive distillation column at a feed point above the point of introduction of said third feedstock,

fractionating said third feedstock in said third extractive distillation column under distillation conditions selected to provide a third lighter distillation fraction containing all of the acetaldehyde, methyl formate, methanol and water and residual quantities of propylene oxide and octane, and a third heavier distillation fraction containing substantially all of the propylene oxide and extractive distillation agent charged to said third distillation column and all of the hexenes and hexanes charged to said third distillation column,

charging a fourth feedstock comprising said third heavier distillation fraction to a fourth extractive distillation column,

charging a C₇ to C₁₀ alkane hydrocarbon extractive distillation agent to said fourth extractive distillation column at a feed point above the point of introduction of said third feedstock,

fractionating said fourth feedstock in said fourth extractive distillation column under distillation conditions selected to provide a fourth lighter distillation fraction consisting essentially of propylene oxide and a fourth heavier distillation fraction containing substantially all of the extractive distillation agent, all of the hexenes and hexanes charged to said third distillation column, and also residual quantities of propylene oxide.

4. A method as in claim 3 wherein the pressure maintained at the top of the first distillation column is about 10-30 psia, wherein the temperature maintained at the top of the first distillation column is about 90°

130°

F., wherein the pressure maintained at the bottom of the first distillation column is about 20-50 psia, and wherein the temperature maintained at the bottom of the first distillation column is about 300°

-380°

F.

5. A method as in claim 3 wherein the pressure maintained at the top of the second distillation column is about 35-45 psia, wherein the temperature maintained at the top of the second distillation column is about 110°

-130°

F., wherein the pressure maintained at the bottom of the second distillation column is about 40-50 psia, and wherein the temperature maintained at the bottom of the second distillation column is about 150°

-160°

F.

6. A method as in claim 3 wherein the pressure maintained at the top of the third distillation column is about 20-40 psia, wherein the temperature maintained at the top of the third distillation column is about 130°

-160°

F., wherein the pressure maintained at the bottom of the third distillation column is about 30-50 psia, and wherein the temperature maintained at the bottom of the third distillation column is about 180°

-220°

F.

7. A method as in claim 3 wherein the pressure maintained at the top of the fourth distillation column is about 10-30 psia, wherein the temperature maintained at the top of the fourth distillation column is about 100°

-130°

F., wherein the pressure maintained at the bottom of the fourth distillation column is about 25-45 psia, and wherein the temperature maintained at the bottom of the fourth distillation column is about 250°

-290°

F.

8. A method as in claim 3 wherein the first distillation column contains about 40 to about 80 theoretical trays, wherein the first feedstock is introduced at least about 10 trays from the bottom of the column, wherein the first extractive distillation agent is introduced at least about 30 theoretical trays above the tray at which the first feedstock is introduced, and wherein the weight ratio of first feedstock to the first extractive distillation agent is about 2 to about 7.

9. A method as in claim 3 wherein the second distillation column contains about 20 to about 40 theoretical trays, and wherein the second feedstock is introduced at least about 8 trays from the bottom of the column.

10. A method as in claim 3 wherein the third distillation column contains about 50 to about 80 theoretical trays, wherein the third feedstock is introduced at least about 30 trays from the bottom of the column, wherein the third extractive distillation agent is introduced at least about 10 theoretical trays above the tray at which the third feedstock is introduced, and wherein the ratio of third feedstock to the third extractive distillation agent is about 0.1 to about 0.3.

11. A method as in claim 3 wherein the fourth distillation column contains about 40 to about 80 theoretical trays, wherein the fourth feedstock is introduced at least about 3 trays from the bottom of the column, wherein the fourth extractive distillation agent is introduced at least about 15 theoretical trays above the tray at which the fourth feedstock is introduced, and wherein the ratio of fourth feedstock to the fourth extractive distillation agent is about 1.3 to about 2.2.

12. A method as in claim 3 wherein a fifth feedstock comprising said first heavier distillation fraction is charged to a fifth distillation column wherein:

said fifth feedstock is fractionated in said fifth distillation column under distillation conditions selected to provide a fifth lighter distillation fraction containing substantially all of the water, acetone, t-butyl alcohol, methanol and isopropyl alcohol charged to the fifth distillation column and a fifth heavier distillation fraction containing substantially all of the alkylene glycol extractive distillation agent charged to the fifth distillation column, and wherein said fifth heavier distillation fraction is recycled to said first distillation column as said first extractive distillation agent.

13. A method as in claim 12 wherein the pressure maintained at the top of the fifth distillation column is about 0.1-1.0 psia, wherein the temperature maintained at the top of the fifth distillation column is about 90°

-130°

F., wherein the pressure maintained at the bottom of the fifth distillation column is about 0.1-1.1 psia, and wherein the temperature maintained at the bottom of the fifth distillation column is about 300°

-360°

F.

14. A method as in claim 13 wherein the fifth distillation column contains about 10 to about 30 theoretical trays, and wherein the sixth feedstock is introduced at least about 10 trays from the bottom of the column.

15. A method as in claim 3 wherein a sixth feedstock comprising said third lighter distillation fraction and said fourth heavier distillation fraction is charged to sixth distillation column, and wherein

said sixth feedstock is fractionated in said sixth distillation column under distillation conditions selected to provide a sixth lighter distillation fraction containing substantially all of the acetaldehyde, methyl formate, propylene oxide, hexenes, methanol, water and a minor portion of the octane charged to the sixth distillation column and a sixth heavier distillation fraction containing substantially all of the C₇ to C₈ alkane extractive distillation agent charged to the third and fourth distillation columns, and wherein said sixth heavier distillation fraction is recycled to said third and fourth distillation columns as said third and fourth extractive distillation agents.

16. A method as in claim 15 wherein the pressure maintained at the top of the sixth distillation column is about 15-30 psia, wherein the temperature maintained at the top of the sixth distillation column is about 110°

-140°

F., wherein the pressure maintained at the bottom of the sixth distillation column is about 20-40 psia, wherein the temperature maintained at the bottom of the sixth distillation column is about 200°

-300°

F.

17. A method as in claim 15 wherein the sixth distillation column contains about 30 to about 50 theoretical trays, and wherein the sixth feedstock is introduced at least about 20 trays from the bottom of the column.