Process for separating relatively pure fractions of methane and carbon dioxide from gas mixtures

• US 4,370,156 A
• Filed: 05/29/1981
• Issued: 01/25/1983
• Est. Priority Date: 05/29/1981
• Status: Expired due to Term

• Current Assignee: Amoco Corporation (BP PLC)
• Original Assignee: Standard Oil Company (BP PLC)
• Inventors: McGalliard, Russell L., Goddin, Clifton S. Jr.
• Primary Examiner(s): Sever, Frank
• Application Number:
  US06/268,832
• Time in Patent Office: 606 Days
• Field of Search: 208/189, 208/207, 208/208 R, 208/236, 208/347, 208/350, 208/351, 208/354, 208/355, 55/68, 55/73, 62/9, 62/11, 62/12, 62/17, 62/20, 62/23, 62/24, 62/27, 62/28
• US Class Current: 62/625
• CPC Class Codes: F25J 2205/50 using absorption, i.e. with selective solvents or lean oil, heavier CnHm and including generally a regeneration step for the solvent or lean oil
• CPC Class Codes: F25J 2220/66 Separating acid gases, e.g. CO2, SO2, H2S or RSH
• CPC Class Codes: F25J 3/0209 Natural gas or substitute natural gas
• CPC Class Codes: F25J 3/0233 separation of CnHm with 1 carbon atom or more
• CPC Class Codes: F25J 3/0238 separation of CnHm with 2 carbon atoms or more
• CPC Class Codes: F25J 3/0266 separation of carbon dioxide production of carbon dioxide in general C01B32/00
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y10S 62/929 From natural gas

Abstract

A cryogenic process for separating relatively pure fractions of methane and carbon dioxide from mixtures thereof which also contain other components. The process utilizes a lean oil as an absorbent which performs the additional functions of preventing the formation of solid carbon dioxide within the apparatus and preventing formation of an azeotrope of carbon dioxide with ethane and enhancing the separation of hydrogen sulfide from carbon dioxide.

Claims

1. A cryogenic process for separating relatively pure fractions of methane and carbon dioxide from a mixture thereof containing at least about twenty mol percent (20%) carbon dioxide and at least about five mol percent (5%) methane and which also contains other components including ethane and higher hydrocarbons and hydrogen sulfide, said process comprising:

(a) Cooling said mixture to a temperature of between about zero°

F. and minus 40°

F. and introducing said mixture into a demethanizer distillation column maintained at a pressure of between about 450 and about 650 psia;

(b) taking an overhead distillate stream from said column comprising methane and at least about ten mol percent carbon dioxide and absorbing said carbon dioxide from said overhead stream by contacting it with a lean oil absorbent to produce sweet product methane containing less than two mol percent carbon dioxide;

(c) withdrawing a bottoms stream comprising carbon dioxide, ethane and higher hydrocarbons and hydrogen sulfide from said column and introducing said bottoms stream into a carbon dioxide separation column maintained at a pressure of between about 400 and about 500 psia;

(d) also introducing into said carbon dioxide column a stream of lean oil in sufficient amount to enhance the volatility of carbon dioxide relative to hydrogen sulfide and thereby produce a sweet high purity product carbon dioxide overhead stream;

(e) withdrawing from the bottom of said carbon dioxide column a bottoms stream comprising hydrogen sulfide, ethane and higher hydrocarbons;

(f) separating said lean oil from said bottoms stream to provide the lean oil requirements for the carbon dioxide absorption step set forth in (b) above and for introduction into said carbon dioxide column as is set forth in (d) above.

2. The process as set forth in claim 1 wherein the quantity of lean oil utilized to absorb carbon dioxide from the overhead stream in step (b) is between about 0.40 and about 0.95 mols of lean oil per mol of overhead stream and the temperatures within the absorption step are greater than minus 70°

F.

3. The process set forth in claim 2 wherein the quantity of lean oil added to the carbon dioxide column is between about 0.40 and about 2.0 mols of lean oil per mol of overhead CO₂.

4. The process of claim 3 wherein the quantity of lean oil components in the feed to the process exceeds process losses of lean oil so that a net gain in natural gas liquids results.

5. A cryogenic process for separating relatively pure fractions of methane and carbon dioxide from mixtures thereof which also contain other components, including ethane and higher hydrocarbons and hydrogen sulfide, said process comprising:

(a) cooling said methane carbon dioxide mixture comprising at least about twenty mol percent (20%) carbon dioxide and at least about five mol percent (5%) methane to a temperature of between about minus 10°

F. and minus 40°

F. and introducing the mixture at an intermediate level into a demethanizer distillation column maintained at a pressure of between about 450 and 650 psia;

(b) maintaining the top of said column at a temperature of between about minus 20°

F. and minus 60°

F. by refluxing of condensed vapors withdrawn from the top of said column, the bottom of said column being maintained at a temperature of between about 50°

F. to 120°

F. by a reboiler which provides a stripping vapor for the column;

(c) introducing the bottoms stream into a carbon dioxide column at an intermediate level, the carbon dioxide column being provided with external reflux means at its upper end and reboiler means at its lower end whereby purified carbon dioxide product is withdrawn from the top of said carbon dioxide column and a bottoms stream comprising ethane and higher hydrocarbons and hydrogen sulfide is withdrawn at the bottom;

(d) depropanizing the withdrawn bottoms stream from the carbon dioxide column by fractionation to separate hydrogen sulfide and C₃ '"'"'s from lean oil; and

(e) recycling the lean oil fraction to an upper region of either or both of the columns to permit operating at temperatures high enough to prevent the formation of solid carbon dioxide in the methane separation step and to increase the volatility of carbon dioxide relative to hydrogen sulfide in the case of the carbon dioxide column.