Plural stage drying and purification of propylene oxide

• US 5,354,431 A
• Filed: 09/23/1993
• Issued: 10/11/1994
• Est. Priority Date: 09/23/1993
• Status: Expired due to Term

• Current Assignee: Huntsman International LLC (Huntsman Corporation)
• Original Assignee: Texaco Chemical Company (Huntsman Corporation)
• Inventors: Taylor, Mark E.
• Primary Examiner(s): Bascomb, Jr, Wilbur
• Application Number:
  US08/125,276
• Time in Patent Office: 383 Days
• Field of Search: 203/64, 203/70, 203/51, 203/74, 203/75, 203/81, 203/82, 203/14, 203/5, 549/541, 549/542
• US Class Current: 203/64
• CPC Class Codes: B01D 3/146 Multiple effect distillation
• CPC Class Codes: B01D 3/40 Extractive distillation
• CPC Class Codes: C07D 301/32 Separation; Purification

Abstract

Crude 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 plurality of intermediate distillation columns to provide an intermediate propylene oxide overhead fraction consisting essentially of propylene oxide and water, and (c) the intermediate propylene oxide overhead fraction is charged to a final distillation column using a C₂ to C₆ alkylene glycol extractive distillation agent to form a final overhead fraction consisting essentially of propylene oxide.

Claims

1. A method for the purification of crude propylene oxide contaminated with minor amounts of water, C₅ and C₆ hydrocarbons and oxygen-containing impurities which comprises the steps of:

extractively distilling said crude propylene oxide in the presence of a C₂ to C₆ alkylene glycol extractive distillation agent in a first extractive distillation zone under extractive distillation conditions selected to provide a first lighter distillation fraction comprising propylene oxide, water and said hydrocarbon and said oxygen-containing impurities and a first heavier distillation fraction comprising said extractive distillation agent and a portion of the water present in the crude propylene oxide;

distilling said first lighter distillation fraction in a second distillation column, a third extractive distillation column and a fourth extractive distillation column in the presence of a C₈ to C₁₀ alkane hydrocarbon extractive distillation agent under distillation conditions selected to remove said hydrocarbon and oxygen-containing impurities and to provide a fourth distillation fraction consisting essentially of propylene oxide and a minor amount of water; and

extractively distilling said fourth fraction in a fifth distillation column in the presence of a C₂ to C₆ alkylene glycol extractive distillation agent under distillation conditions selected to provide a final fifth lighter distillation fraction consisting essentially of dehydrated propylene oxide and a final fifth heavier distillation fraction comprising said extractive distillation agent, water and a minor amount of propylene oxide.

2. A method as in claim 1 wherein the heavier final fifth distillation fraction is recycled to said first extractive distillation column.

3. A method as in claim 1 wherein the distillation conditions in the first extractive distillation column include a bottoms temperature of about 300°

to 400°

F., a bottoms pressure of about 20 to 50 psia, a temperature adjacent the top of the first extractive distillation column of about 80°

to about 120°

F., a pressure adjacent the top of the first extractive distillation column of about 15 to 25 psia and a ratio of crude propylene oxide to said C₂ to C₆ alkylene glycol extractive distillation agent of about 2 to 7, and wherein the distillation conditions in said fifth distillation column include a temperature adjacent the bottom of said fifth distillation column of about 200°

to 220°

F., a pressure adjacent the bottom of said fifth distillation column of about 20 to 50 psia, a temperature adjacent the top of said fifth distillation column of about 85°

to 120°

F., a pressure adjacent the top of said fifth distillation column of about 15 to 25 psia and a ratio of said second heavier distillation fraction to said C₂ to C₆ alkylene glycol extractive distillation agent of about 4 to 6.

4. 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 lighter fraction comprising propylene oxide, hexenes, hexanes, pentenes, pentanes, water, methanol and oxygen-containing impurities boiling above propylene oxide and a first heavier distillation fraction comprising said alkylene glycol extractive distillation agent and impurities;

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

extractively distilling the partially purified second heavier fraction in a third distillation column using a C₈ to C₁₀ alkane hydrocarbon extractive distillation agent to provide a third further purified heavier bottoms third fraction comprising substantially all of the propylene oxide, water, hexenes and hexanes charged to the third distillation column;

extractively distilling the further purified third heavier fraction in a fourth distillation column using a C₈ to C₁₀ alkane hydrocarbon extractive distillation agent to provide an additionally purified fourth propylene oxide lighter fraction consisting essentially of water and propylene oxide free of said contaminants; and

extractively distilling the fourth lighter propylene oxide fraction in a fifth terminal distillation column using a C₂ to C₆ alkylene glycol extractive distillation agent to form a fifth lighter fraction consisting essentially of propylene oxide.

5. A distillation process for the purification of impure propylene oxide feedstock contaminated with hexenes, hexanes, pentanes, pentenes, water, methanol 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 substantially 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 substantially 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 partially purified lighter distillation fraction containing pentanes, pentenes and oxygen-containing impurities boiling above propylene oxide, and a second heavier distillation fraction containing substantially all of the propylene oxide, methanol, water, hexenes and hexanes;

separately charging a third feedstock comprising said second heavier distillation fraction and a C₈ 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 further purified distillation fraction containing water and 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 C₈ 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 additionally purified distillation fraction consisting essentially of propylene oxide and water 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;

separately charging a fifth feedstock comprising said fourth lighter distillation fraction and a C₂ -C₆ alkylene glycol extractive distillation agent to a fifth distillation column at ascending charge points and fractionating it therein into a fifth lighter distillation fraction consisting essentially of propylene oxide and a fifth heavier distillation fraction comprising propylene oxide, water and substantially all of the extractive distillation agent.

6. A distillation process for the purification of a crude propylene oxide feedstock contaminated 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 crude propylene oxide feedstock to a first extractive distillation column;

charging an alkylene glycol extractive distillation agent selected from the group consisting of triethylene glycol and dipropylene glycol to said first extractive distillation column at a feed point above the point of introduction of said impure propylene oxide;

fractionating said crude propylene oxide feedstock in said first extractive distillation column under distillation conditions selected to provide a first lighter distillation fraction containing propylene oxide, propylene, propane, acetaldehyde, methyl formate, hexenes, hexanes, pentenes and pentanes, methanol and water and a first heavier distillation fraction containing substantially all of the propionaldehyde, acetone, t-butyl alcohol, t-butyl formate, isopropyl alcohol, the remainder of the methanol and water and substantially all of the said alkaline glycol 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 water, all of the propylene, propane, acetaldehyde, pentanes and pentenes, and a residual amount of propylene oxide, and a second heavier partially purified distillation fraction comprising propylene oxide, water, hexenes and hexanes;

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

charging an octane 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 further purified lighter distillation fraction containing water and substantially all of the acetaldehyde, methyl formate and methanol and residual quantities of propylene oxide and octane extractive distillation agent, and a third heavier distillation fraction containing water, substantially all of the propylene oxide and octane charged to said third distillation column and substantially 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 an octane extractive distillation agent to said fourth extractive distillation column at a feed point above the point of introduction of said fourth feedstock;

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

charging a fifth intermediate feedstock comprising said fourth lighter distillation fraction to a fifth extractive distillation column, charging an alkylene glycol extractive distillation agent selected from the group consisting of triethylene glycol and dipropylene glycol to said fifth extractive distillation column at a feed point above the point of introduction of said fifth feedstock;

fractionating said fifth feedstock in said fifth extractive distillation column under extractive distillation conditions selected to provide a fifth lighter distillation fraction consisting essentially of propylene oxide and a fifth heavier distillation fraction comprising water, alkylene glycol extractive distillation agents and residual quantities of propylene oxide, and recycling said fifth heavier distillation fraction to said first distillation column.

7. A method as in claim 6 wherein the pressure maintained at the top of the first distillation column is about 15-25 psia, wherein the temperature maintained at the top of the first distillation column is about 80°

-120°

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°

-400°

F.

8. A method as in claim 6 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.

9. A method as in claim 6 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.

10. A method as in claim 6 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.

11. A method as in claim 6 wherein the pressure maintained at the top of the fifth distillation column is about 15 to about 25 psia, wherein the temperature maintained at the top of the first distillation column is about 80°

to about 120°

F., wherein the pressure maintained at the bottom of the first distillation column is about 20 to about 50 psia and wherein the temperature maintained at the bottom of the fifth distillation column is about 180°

to about 220°

F.

12. A method as in claim 6 wherein the first distillation column contains about 50 to about 80 theoretical trays, wherein the crude propylene oxide feedstock is introduced at least about 10 trays from the bottom of the column, wherein the triethylene glycol or dipropylene glycol extractive distillation agent is introduced at least about 20 theoretical trays above the tray at which the crude propylene oxide feedstock is introduced, and wherein the weight ratio of crude propylene oxide feedstock to the said extractive distillation agent is about 2 to about 7.

13. A method as in claim 6 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.

14. A method as in claim 6 wherein the third distillation column contains about 50 to about 90 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.

15. A method as in claim 6 wherein the fourth distillation column contains about 50 to about 90 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.

16. A method as in claim 6 wherein the fifth distillation column contains about 10 to about 40 theoretical trays, wherein the fourth feedstock is introduced at least about 5 trays from the bottom of the column, wherein the extractive distillation agent is introduced at least about 20 theoretical trays above the tray at which the fourth feedstock is introduced and wherein the ratio of the fifth feedstock to the fifth extractive distillation agent is about 4 to about 6.

17. A method as in claim 6 wherein a sixth feedstock comprising said first heavier distillation fraction is charged to a sixth distillation column wherein:

said sixth feedstock is fractionated under distillation conditions selected to provide a sixth lighter distillation fraction containing substantially all of the propylene oxide, water, acetone, t-butyl alcohol, methanol and isopropyl alcohol charged to the sixth distillation column and a sixth heavier distillation fraction containing substantially all of the alkylene glycol extractive distillation agent charged to the sixth distillation column, and wherein said sixth heavier distillation fraction is recycled to said first and said fifth distillation columns as said alkylene glycol extractive distillation agents, said sixth distillation column containing about 10 to 30 theoretical trays, and the sixth feedstock being introduced at least about three theoretical trays from the bottom of the column.

18. A method as in claim 6 wherein the pressure maintained at the top of the sixth distillation column is about 0.1-1.0 psia, wherein the temperature maintained at the top of the sixth distillation column is about 90°

-130°

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

-400°

F.

19. A method as in claim 6 wherein a seventh feedstock comprising said third lighter distillation fraction and said fourth heavier distillation fraction is charged to a seventh distillation column, and wherein

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

20. A method as in claim 19 wherein the pressure maintained at the top of the seventh distillation column is about 15-30 psia, wherein the temperature maintained at the top of the seventh distillation column is about 110°

-140°

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

-300°

F.

21. A method as in claim 19 wherein the seventh distillation column contains about 30 to about 50 theoretical trays, and wherein the seventh feedstock is introduced at least about 20 trays from the bottom of the column.