Cryogenic separation of gaseous mixtures

• US 4,900,347 A
• Filed: 04/05/1989
• Issued: 02/13/1990
• Est. Priority Date: 04/05/1989
• Status: Expired due to Term

• Current Assignee: Mobil Oil Corporation (Exxon Mobil Corporation), Stone & Webster Process Technology, Inc. (Technip Energies NV)
• Original Assignee: Mobil Corporation (Exxon Mobil Corporation)
• Inventors: Pickering, John L. Jr., McCue, Richard H. Jr.
• Primary Examiner(s): Capossela, Ronald C.
• Application Number:
  US07/333,214
• Time in Patent Office: 314 Days
• Field of Search: 62/24, 62/28, 62/29, 62/31, 62/32
• US Class Current: 62/627
• CPC Class Codes: F25J 2200/80 using integrated mass and heat exchange, i.e. non-adiabatic rectification in a reflux exchanger or dephlegmator
• CPC Class Codes: F25J 2210/12 Refinery or petrochemical off-gas
• CPC Class Codes: F25J 2270/04 Internal refrigeration with work-producing gas expansion loop
• CPC Class Codes: F25J 2270/60 Closed external refrigeration cycle with single component refrigerant [SCR], e.g. C1-, C2- or C3-hydrocarbons
• CPC Class Codes: F25J 2290/80 Retrofitting, revamping or debottlenecking of existing plant
• CPC Class Codes: F25J 3/0219 Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
• 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 3/0242 separation of CnHm with 3 carbon atoms or more
• CPC Class Codes: F25J 3/0252 separation of hydrogen production of hydrogen containing gas in general C01B3/00, e.g. separation of hydrogen or hydrogen containing gases form gaseous mixtures at low temperatures C01B3/506

Abstract

A cyrogenic technique for recovering ethene from a gaseous mixture containing methane, ethane, etc. Operating methods and apparatus are provided for passing the gas feed through a chilling train having a series of dephlegmator-type exchange units to condense liquid rich in ethene and ethane, while separating a major portion of methane and lighter gas. A multizone demethanizer removes condensed methane from the C₂ fraction to provide a pure product economically.

Claims

1. A cryogenic separation method for recovering C₁⁺ hydrocarbons from cracked hydrocarbon feed gas comprising methane, ethene and ethane, wherein cold pressurized gaseous streams are separated in a plurality of dephlegmator units, each of said dephlegmator units being operatively connected to accumulate condensed liquid in a lower dephlegmator drum vessel by gravity flow from an upper dephlegmator heat exchanger comprising a plurality of vertically disposed indirect heat exchange passages through which gas from the lower drum vessel passes in an upward direction for cooling with refrigerant fluid by indirect heat exchange within said heat exchange passages, whereby gas flowing upwardly is partially condensed on vertical surfaces of said passages to form a reflux liquid in direct contact with the upward flowing gas stream to provide a condensed stream of cooler liquid flowing downwardly and thereby enriching condensed dephlegmator liquid gradually with C₂⁺ hydrocarbon components;

comprising the steps of;

introducing dry feed gas into a primary dephlegmation zone having a plurality of serially connected, sequentially colder dephlegmator units for separation of feed gas into a primary methane-rich gas stream recovered at low temperature and at least one primary liquid condensate stream rich in C₂⁺ hydrocarbon components and containing a minor amount of methane;

passing at least one primary liquid condensate stream from the primary dephlegmation zone to serially connected demethanizer fractionators, wherein a moderately low cryogenic temperature is employed in a first demethanizer fractionator unit to recover substantially all of the methane from the primary liquid condensate stream in a first demethanizer overhead vapor stream and to recover a first C₂⁺ liquid demethanizer bottoms stream substantially free of methane, wherein said demethanizer overhead vapor stream is cooled with moderately low temperature coolant to provide liquid reflux for recycled to a top portion of the first demethanizer fractionator;

further separating at least a portion of the first demethanizer overhead vapor stream in an ultra-low temperature final demethanizer fractionator unit to recover a liquid ethene-rich predominantly C₂ hydrocarbon crude product stream and a final demethanizer ultra-low temperature overhead vapor stream substantially free of C₂⁺ hydrocarbons, wherein a major amount of total demethanization heat exchange duty is provided by moderately low temperature refrigerant and overall energy requirements for refrigeration utilized in separating C₂⁺ hydrocarbons from methane and lighter components are decreased; and

fractionating said second crude ethene stream and said first ethene-rich C₂ hydrocarbon crude product stream to obtain a pure ethene product.

2. The process of claim 1 including the further step of fractionating the C2⁺ liquid bottoms stream from the first demethanizer fractionator to remove ethane and heavier hydrocarbons therefrom and provide a second crude ethene stream.

3. The process of claim 1 wherein liquid condensate is recovered from at least three serially connected dephlegmation zones, including the steps of contacting at least a portion of said first demethanizer overhead vapor stream in heat exchange relationship with an intermediate liquid stream from an intermediate dephlegmator zone, thereby reducing ultra low temperature cooling requirements for the second reflux condenser means.

4. The process of claim 3 wherein a countercurrent direct stream contact unit is operatively connected between the primary and secondary demethanizer zones, with liquid from said countercurrent contact zone being directed to a lower stage of the secondary demethanizer zone and vapor from said countercurrent contact zone being directed to a higher stage of the secondary demethanizer zone.

5. An improved cryogenic technique for separating and recovering C₂⁺ hydrocarbons from a feed gas containing hydrogen, methane, ethene and ethane, comprising the steps of:

separating cold pressurized gaseous feed gas in a series of at least three dephlegmator rectification units wherein liquid condensate is recovered from at least three serially connected dephlegmation zones, each of said dephlegmator units being operatively connected to accumulate condensed C₂⁺ -rich liquid in a lower dephlegmator drum vessel by gravity flow from an upper dephlegmator heat exchanger comprising a plurality of vertically disposed indirect heat exchange passages through which gas from the lower drum vessel passes in an upward direction for cooling by indirect heat exchange within said heat exchange passages, whereby gas flowing upwardly is partially condensed on vertical surfaces of said passages to form a reflux liquid in direct contact with the upward flowing gas stream to provide a condensed stream of cooler liquid flowing downwardly and thereby enriching condensed dephlegmator liquid gradually with C₂⁺ hydrocarbon components;

introducing dry feed gas into a primary dephlegmation zone in said series of dephlegmation units for separation of feed gas into a primary methane-rich gas stream recovered and at least one primary liquid condensate stream rich in C₂ hydrocarbon components and containing a minor amount of methane;

passing at least one primary liquid condensate stream from the dephlegmation units to serially connected demethanizer fractionators, wherein a moderately low cryogenic temperature is employed in a first demethanizer fractionator unit to recover a substantially all of the methane from the primary liquid condensate stream in a first demethanizer overhead vapor stream and to recover a first C₂⁺ liquid demethanizer bottoms stream substantially free of methane;

further separating at least a portion of the first demethanizer overhead vapor stream in an ultra-low temperature final demethanizer fractionator unit to recover ethene-rich C₂ hydrocarbon liquid product and a final demethanizer ultra-low temperature overhead vapor stream;

contacting at least a portion of said first demethanizer overhead vapor stream in direct heat exchange relationship with an intermediate liquid stream from an intermediate dephlegmation zone in a countercurrent contact unit operatively connected between primary and secondary demethanizer fractionator zones, with liquid from said countercurrent contact zone being directed to a lower stage of the secondary demethanizer fractionator zone and vapor from said countercurrent contact zone being directed to a higher stage of the secondary demethanizer fractionator zone; and

passing the final demethanizer overhead vapor stream to a final dephlegmator unit to obtain a final liquid reflux stream for recycle to a top portion of the final demethanizer fractionator and a methane-rich final dephlegmator overhead vapor stream substantially free of C₂⁺ hydrocarbons, whereby energy requirements for refrigeration utilized in separating the C₂⁺ hydrocarbons from methane and lighter components are low.

6. In a cryogenic separation method for recovering purified ethene from hydrocarbon feedstock gas consisting mainly of methane, ethene and ethane, wherein cold pressurized gaseous streams are separated in a plurality of sequentially arranged rectification units, each of said rectification units being operatively connected to accumulate condensed liquid in a lower liquid accumulator portion by gravity flow from an upper vertical rectifier portion through which gas from the lower accumulator portion passes in an upward direction for direct gas-liquid contact exchange within said reactifier portion, whereby methane-rich gas flowing upwardly is partially condensed in said rectifier portion with cold refluxed liquid in direct contact with the upward flowing gas stream to provide a condensed stream of cold liquid flowing downwardly and thereby enriching condensed liquid gradually with ethene and ethane components;

the improvement comprising;

introducing dry feed gas into a primary rectification zone having a plurality of serially connected, sequentially colder rectification units for separation of feed gas into a primary methane-rich gas stream recovered at low temperature and at least one primary liquid condensate stream rich in C₂ hydrocarbon components and containing a minor amount of methane;

passing at least one primary liquid condensate stream from the primary rectification zone to a fractionation system having serially connected demethanizer zones, wherein a moderately low cryogenic temperature is employed in a first demethanizer fractionation zone to recover a major amount of methane from the primary liquid condensate stream in a first demethanizer overhead vapor stream and to recover a first liquid demethanized bottoms stream rich in ethane and ethene and substantially free of methane, wherein said demethanizer overhead vapor stream is cooled with moderately low temperature coolant to provide liquid reflux for recycle to a top portion of the first demethanizer zone;

further separating at least a portion of the first demethanizer overhead vapor stream in an ultra-low temperature final demethanizer zone to recover a first liquid ethene-rich C₂ hydrocarbon crude product stream and a final demethanizer ultra-low temperature overhead vapor stream substantially free C₂⁺ hydrocarbons, wherein a major amount of total demethanization heat exchange duty is provided by moderately low temperature coolant and overall energy requirements for refrigeration utilized in separating C₂⁺ hydrocarbons from methane and lighter components are decreased;

further fractionating the C₂⁺ liquid bottoms stream from the first demethanizer zone to remove ethane and heavier hydrocarbons therefrom and provide a second crude ethene stream; and

fractionating said second crude ethene stream and said first ethene-rich hydrocarbon crude product stream to obtain a purified ethene product.

7. The process of claim 6 wherein said serially connected rectification units include at least one intermediate rectification unit for partially condensing an intermediate liquid stream from primary rectification overhead vapor prior to final serial rectification unit;

and

contacting at least a portion of said first demethanizer overhead vapor stream with said intermediate liquid stream directly in a countercurrent contact zone operatively connected between the primary and secondary demethanizer zones, with methane-depleted liquid from said countercurrent contact zone being directed to a lower portion of the secondary demethanizer zone and methane-enriched vapor from said countercurrent contact zone being directed to an upper portion of the secondary demethanizer zone.

8. The process of claim 6 including the step of passing the final demethanizer overhead vapor stream to a final rectification unit to obtain a final ultra-low temperature liquid reflux stream for recycle to a top portion of the final demethanizer fractionator and a methane-rich final rectification overhead vapor stream.

9. The process of claim 8 wherein a final serial dephlegmator-type rectification unit is operatively connected as the final demethanizer rectification unit to obtain a final ultra-low temperature liquid reflux stream substantially free of ethane for recycle to a top portion of the final demethanizer fractionator.

10. The process of claim 6 wherein said serially connected rectification units include two intermediate rectification units for partially condensing first and second progressively colder intermediate liquid streams respectively from primary rectification overhead vapor prior to a final serial rectification unit;

fractionating the first intermediate liquid stream in the primary demethanizer zone; and

fractionating the second intermediate liquid stream in the secondary demethanizer zone.

11. The process of claim 10 including the step of contacting at least a portion of said first demethanizer overhead vapor stream with said second intermediate liquid stream substantially free of ethane in a countercurrent contact zone operatively connected between the primary and secondary demethanizer zones, with ethene-rich liquid from said countercurrent contact zone being directed to a lower portion of the secondary demethanizer zone and methane-enriched vapor from said countercurrent contact zone being directed to an upper portion of the secondary demethanizer zone.

12. The process of claim 6 wherein said moderately low temperature coolant is maintained at a temperature of about 235°

K. to 290°

K. and the ultra low temperature coolant is maintained below 235°

K.

13. The process of claim 6 wherein pressurized moderately low temperature refrigerant is condensed in a refrigerant cycle in heat exchange relationship with a primary demethanizer reboiler unit to heat liquid methanized bottoms therein.

14. The process of claim 6 wherein said feedstock gas comprises cracking gas containing about 10 to 50 mole percent ethene, 5 to 20% ethane, 10 to 40% methane, 10 to 40% hydrogen, and up to 10% C₃ hydrocarbons.

15. The process of claim 6 wherein a major amount of ethane present in the feedstock gas is recovered in the first liquid demethanized bottoms stream;

wherein said ethene-rich hydrocarbon crude product stream from the secondary demethanizer zone contains at least 7 moles of ethene per mole of ethane; and

wherein at least 25% of feedstock ethene is passed to the ultra-low temperature final demethanizer zone along with less than 5 mole % C₃ components.

16. The process of claim 6 wherein said second crude ethene stream has substantially greater ethane content than said ethene-rich hydrocarbon crude product stream, and wherein said ethene-rich crude product stream is introduced separately to a final ethene product fractionation tower at a higher fractionation stage than said second crude ethene stream, thereby conserving refrigeration energy in said final ethene product fractionation tower.

17. The process of claim 6 including a closed loop moderately low temperature source of primary refrigerant consisting essentially of propylene and a separate closed loop ultra low temperature refrigerant source of secondary refrigerant consisting essentially of ethylene;

and wherein overhead gas recovered from a final serial rectification unit contains a major portion of feedstock methane content and substantially all hydrogen in the feedstock.

18. The process of claim 6 wherein at least one of said rectification units comprises a dephlegmator, a packed column or tray contact unit.

19. An improved cryogenic separation system for recovering a higher-boiling first gaseous component from a lower-boiling second gaseous component in a feedstock mixture thereof comprising:

a source of primary refrigerant, moderately low temperature refrigerant and ultra low temperature refrigerant;

sequential chilling train means including a primary dephlegmator unit operatively connected in serial flow relationship with intermediate and final dephlegmator units, wherein a cold pressurized gaseous stream is separated in the series of dephlegmator units, each of said dephlegmator units having means for accumulating condensed liquid rich in higher-boiling component in a lower dephlegmator drum from an upper dephlegmator heat exchanger wherein gas flowing upwardly is partially condensed to form a reflux liquid in direct contact with upward flowing gas to provide a condensed stream of cooler liquid flowing downwardly and thereby enriching condensed dephlegmator liquid gradually with higher-boiling component;

means for feeding dry pressurized feedstock to the primary dephlegmator unit for sequential chilling to separate the feedstock mixture into a primary gas stream rich in lower boiling component recovered at about primary refrigerant temperature temperature and a primary liquid condensate stream rich in higher boiling component and containing a minor amount of lower boiling component;

fluid handling means for passing the primary liquid condensate stream from the primary dephlegmator unit to a low temperature fractionation system for recovering condensed lower-boiling components from condensed liquid, said fractionation system having a first fractionation zone including first reflux condenser means operatively connected to the source of moderately low temperature refrigerant to recover a major amount of lower-boiling component from the primary liquid condensate stream in a first fractionator overhead vapor stream and to recover a first liquid fractionator bottoms stream substantially free of lower-boiling component;

said fractionation system having a second fractionation zone including second reflux condenser means operatively connected to the source of ultra low temperature refrigerant to recover a liquid product stream consisting essentially of higher boiling component and a second fractionator ultra-low temperature overhead vapor stream; and

means for passing an intermediate liquid stream condensed from at least one intermediate dephlengmator unit to to a middle stage of the second fractionation zone.

20. The system of claim 19 including means for contacting at least a portion of said first fractionator overhead vapor stream in heat exchange relationship with said intermediate liquid stream, thereby reducing ultra low temperature refrigeration requirements for the second reflux condenser means.

21. The system of claim 20 including a countercurrent direct stream contact unit operatively connected between the primary and secondary fractionator zones, with liquid from said countercurrent contact zone being directed to a lower stage of the secondary fractionator zone and vapor from said countercurrent contact zone being directed to a higher stage of the secondary fractionator zone.

22. The system of claim 19 including a closed loop moderately low temperature source of primary refrigerant consisting essentially of propylene and a separate closed loop ultra low temperature refrigerant source of secondary refrigerant consisting essentially of ethylene.

23. The system of claim 19 including a final dephlegmator unit connected to receive the second fractionator overhead vapor stream, including ultra low temperature refrigerant heat exchange means for obtaining a final liquid reflux stream for recycle to an upper stage of the second fractionation zone and a final dephlegmator overhead vapor stream substantially free of higher-boiling components.