Process and system for selective abatement of reactive gases and recovery of perfluorocompound gases

• US 5,759,237 A
• Filed: 06/14/1996
• Issued: 06/02/1998
• Est. Priority Date: 06/14/1996
• Status: Expired due to Fees

• Current Assignee: American Air Liquide Incorporated (L'Air Liquide SA), L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Original Assignee: American Air Liquide Incorporated (L'Air Liquide SA), L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Inventors: Li, Yao-En, Duchateau, Eric L.
• Primary Examiner(s): SPITZER, ROBERT H
• Application Number:
  US08/663,884
• Time in Patent Office: 718 Days
• Field of Search: 95/45, 95/47, 95/52-55, 95/39, 95/41, 95/42, 95/128, 95/131, 95/142, 95/149, 96/4, 96/7, 96/8, 96/10
• US Class Current: 95/41
• CPC Class Codes: B01D 53/228 characterised by specific membranes

Abstract

Processes and systems to recover at least one perfluorocompound gas from a gas mixture are provided. In one embodiment the inventive process comprises the steps of a) providing a gas mixture comprising at least one perfluorocompound gas and at least one carrier gas, the gas mixture being at a predetermined pressure; b) providing at least one glassy polymer membrane having a feed side and a permeate side; c) contacting the feed side of the at least one membrane with the gas mixture; d) withdrawing from the feed side of the membrane as a non-permeate stream at a pressure which is substantially equal to the predetermined pressure a concentrated gas mixture comprising essentially the at least one perfluorocompound gas; and e) withdrawing from the permeate side of the membrane as a permeate stream a depleted gas mixture comprising essentially the at least one carrier gas.

Claims

1. A process to recover at least one perfluorocompound gas from a gas mixture comprising reactive gases, perfluorocompound gases, and carrier gases, the process comprising the steps of:

a) providing a gas mixture comprising at least one perfluorocompound gas, at least one carrier gas, and at least one reactive gas;

b) directing the gas mixture to an abatement unit, wherein a major portion of the reactive gases are converted into substantially inert species, and thereby forming an intermediate gas mixture consisting essentially of the perfluorocompound gases and the carrier gases;

c) providing at least one membrane unit having a plurality of hollow fiber glassy polymer membranes, the membrane unit having a feed side and a permeate side, the hollow fibers of the membrane unit being permeable to the at least one carrier gas and being non-permeable to the at least one perfluorocompound gases;

d) contacting the feed side of the at least one membrane unit with the intermediate gas mixture, the intermediate gas mixture being at a predetermined pressure;

e) withdrawing from the feed side of the membrane unit as a first non-permeate stream at a pressure which is substantially equal to the predetermined pressure, a concentrated gas mixture comprising essentially the at least one perfluorocompound gas; and

f) withdrawing from the permeate side of the at least one membrane unit as a permeate stream a depleted gas mixture consisting essentially of the at least one carrier gas.

2. Process in accordance with claim 1 wherein said predetermined pressure is supplied by compressing said gas mixture with a sealed, oil-free compressor.

3. Process in accordance with claim 1 wherein said feed side of the membrane unit comprises a bore side of each of said plurality of hollow fiber and glassy polymer membranes, while the permeate side is an outside of each hollow fiber glassy polymer membrane.

4. Process in accordance with claim 1 wherein said gas mixture comprises an effluent stream from a process selected from the group consisting of etching processes including oxide, metal and dielectric;

deposition processes including silicon CVD, tungsten backetching, and dry chamber cleaning.

5. A process according to claim 1, wherein the at least one perfluorocompound gas is selected from the group consisting of CF₄, CHF₃, C₂ F₆, NF₃, SF₆, C₃ F₈ and mixtures thereof.

6. A process according to claim 1, wherein the carrier gas is selected from the group consisting of Ar, N₂, Kr, Xe, Ne, O₂, He, H₂, Air and mixtures thereof.

7. A process according to claim 1, wherein the glassy polymer membrane is made of at least one polymer selected from the group consisting of polyimides, polyamides, polyamides-mides, polyesters, polycarbonates, polysulfones, polyethersulfone, polyetherketone, alkyl substituted aromatic polyesters, blends of polyethersulfone, fluorinated aromatic polyimides, polyamides and polyamide-imides, copolymers thereof, substituted polymers thereof.

8. A process according to claim 1 wherein the membranes each comprise a core and a skin which are made of different polymers, the permeability of the polymer of the skin being lower for perfluorocompound than for nitrogen.

9. A process according to claim 1 wherein the intermediate gas mixture which is contacted with the membrane comprises less than 1% vol. of said reactive gases.

10. A process according to claim 1 wherein the intermediate gas mixture which is contacted with the membrane comprises less than 10 ppm of said reactive gases.

11. A process according to claim 1 wherein the intermediate gas mixture which is contacted with the membrane comprises less than 1 ppm of said reactive gases.

12. A process according to claim 1 wherein the intermediate gas mixture prior to being fed to the membrane, is brought to a pressure which is effective for carrying out the separation of the perfluorocompound gas or gas mixture in order to recover said first non-permeate stream which is concentrated in perfluorocompound species compared to the gas mixture.

13. A process according to claim 1 wherein the pressure of the intermediate gas mixture ranges from about 10⁵ Pascal to about 10⁶ Pascal.

14. A process according to claim 1, wherein the first non-permeate stream is compressed and/or cooled, and stored in storage means for further processing.

15. A process according to claim 1, wherein at least a portion of the first non-permeate stream is recycled.

16. Process in accordance with claim 15 wherein the portion of the first non-permeate stream which is recycled is routed to a surge tank prior to re-entering the process, or prior to being routed to storage.

17. A process according to claim 1, wherein the gas mixture comprising essentially the at least one perfluorocompound gas comprises gases selected from the group consisting of SF₆, C₂ F₆, CHF₃, CF₄ and NF₃.

18. A process according to claim 1, wherein at least one of the perfluorocompound gases of the first non-permeate stream is further separated from other perfluorocompounds in said first non-permeate stream via a separation step.

19. A process according to claim 18 wherein said separation step employs a heat exchanger using a cooling fluid at an effective temperature and flowrate.

20. A process according to claim 18 wherein at least a portion of the first non-permeate stream consists essentially of NF₃ and CF₄ and said separation step is an adsorption step wherein NF₃ is adsorbed and CF₄ is not.

21. A process according to claim 18 wherein at least a portion of the first non-permeate stream consists essentially of CHF₃ and C₂ F₆, and said separation step is an adsorption system wherein CHF₃ is adsorbed and C₂ F₆ is not.

22. A process according to claim 1 wherein the intermediate gas has a temperature ranging from about 20°

C. to 120°

C.

23. Process in accordance with claim 1 wherein at least a portion of the first non-permeate stream is used as a sweep gas on feed side of the membrane.

24. Process in accordance with claim 1 wherein said gas mixture is emitted from a plurality of like or unlike semiconductor manufacturing tools.

25. Process in accordance with claim 1 wherein said abatement unit is selected from the group consisting of plasma decomposition, thermal decomposition, catalytic decomposition, scrubbing, and adsorption.

26. A process to recover at least one perfluorocompound gas from a gas mixture flowing from a semiconductor manufacturing tool, the gas mixture comprising at least one carrier gas and at least one reactive gas, the process comprising the steps of:

a) directing the gas mixture to an abatement unit, wherein a major portion of the reactive gases are converted into substantially inert species, and thereby forming an intermediate gas mixture consisting essentially of the perfluorocompound gases and the carrier gases;

b) directing the intermediate gas mixture into a feed side of at least one membrane unit having a plurality of hollow fiber glassy polymer membranes, the membrane unit having a permeate side, each hollow fiber glassy polymer membrane of the membrane unit being permeable to the at least one carrier gas and being non-permeable to the at least one perfluorocompound gases;

c) withdrawing from the feed side of the membrane unit as a non-permeate stream at a pressure which is substantially equal to the predetermined pressure, a concentrated gas mixture comprising essentially the at least one perfluorocompound gas; and

d) withdrawing from the permeate side of the at least one membrane as a permeate stream a depleted gas mixture consisting essentially of the at least one carrier gas.

27. A system combining abatement and recovery units for treating gas mixtures comprising a perfluorocompound gas, a reactive gas, and a carrier gas, the system comprising:

a) an abatement unit adapted to receive the gas mixture, the abatement unit selected from the group consisting of combustion, thermal-chemical, plasma decomposers, pulsed corona reactors, and combinations thereof, the abatement unit adapted to produce an intermediate gas mixture consisting essentially of the perfluorocompound gas and the carrier gas; and

b) at least one membrane separation unit having a feed side and a permeate side, and comprising a plurality of glassy polymer hollow fibers, the glassy polymer hollow fibers being permeable to the carrier gas and being substantially non-permeable to at least one perfluorocompound gas, the membrane unit connected to the abatement unit via an abatement unit effluent conduit, the membrane unit having a permeate vent conduit and a non-permeate conduit.

28. System in accordance with claim 27 wherein the non-permeate conduit is adapted to be removably connected to a processing tool, the processing tool adapted to use the perfluorocompound gases.

29. System in accordance with claim 28 wherein the processing tool is a semiconductor manufacturing tool.

30. System in accordance with claim 29 wherein the semiconductor manufacturing tool is selected from the group consisting of etching tools, deposition tools, tungsten backetching tools, and dry chambers.

31. System in accordance with claim 27 including the provision of a compressor, heat exchanger, cryogenic pump or vacuum pump in the non-permeate conduit.

32. A system combining abatement and recovery units for treating gas mixtures comprising a perfluorocompound gas, a reactive gas, and a carrier gas, the system comprising:

a) an abatement unit adapted to receive the gas mixture, the abatement unit selected from the group consisting of combustion, thermal-chemical, plasma decomposers, pulsed corona reactors, and combinations thereof, the abatement unit adapted to produce an intermediate gas mixture consisting essentially of the perfluorocompound gas and the carrier gas;

b) a compressor connected to the abatement unit through an abatement unit discharge conduit, the compressor adapted to provide a compressed intermediate gas mixture through a compressor discharge conduit;

c) optional heating or cooling means in the compressor discharge conduit adapted to provide a desired compressed intermediate gas temperature; and

d) at least one membrane separation unit having a feed side and a permeate side, and comprising a plurality of glassy polymer hollow fibers, the glassy polymer hollow fibers being permeable to the carrier gas and being substantially non-permeable to at least one perfluorocompound gas, the membrane unit connected to the compressor via the compressor discharge conduit, the membrane unit having a permeate vent conduit and a non-permeate conduit.

33. System in accordance with claim 32 adapted to receive a plurality of gas mixtures in a parallel operating mode, wherein at least two of the gas mixtures have differing gas compositions requiring differing abatement units.