Apparatus and method for delivering supercritical fluid

• US 5,237,824 A
• Filed: 10/12/1990
• Issued: 08/24/1993
• Est. Priority Date: 02/16/1989
• Status: Expired due to Fees

• Current Assignee: University of Waikato
• Original Assignee: University of Waikato
• Inventors: Pawliszyn, Janusz B.
• Primary Examiner(s): Bennet, Henry A.
• Assistant Examiner(s): Kilner, Christopher B.
• Application Number:
  US07/613,784
• Time in Patent Office: 1,047 Days
• Field of Search: 62/45.1, 62/46.1, 62/47.1, 62/50.1, 62/50.4, 62/48.1, 62/51.1, 62/50.2
• US Class Current: 62/51.1
• CPC Class Codes: B01D 11/0203 with a supercritical fluid
• CPC Class Codes: B01D 11/0407 the supercritical fluid acting as solvent for the solute
• CPC Class Codes: B01D 15/40 using supercritical fluid as mobile phase or eluent
• CPC Class Codes: B01J 3/008 Processes carried out under supercritical conditions
• CPC Class Codes: B01J 3/042 in the form of a tube
• CPC Class Codes: F17C 2205/0332 Safety valves or pressure relief valves
• CPC Class Codes: F17C 2205/0335 Check-valves or non-return valves
• CPC Class Codes: F17C 2221/013 Carbone dioxide
• CPC Class Codes: F17C 2223/0153 Liquefied gas, e.g. LPG, GPL
• CPC Class Codes: F17C 2225/0115 dense or supercritical, i.e. at high pressure and high density
• CPC Class Codes: F17C 2227/0302 by heating
• CPC Class Codes: F17C 2227/0337 by cooling
• CPC Class Codes: F17C 2250/032 using computers
• CPC Class Codes: F17C 2250/043 Pressure
• CPC Class Codes: F17C 2250/0439 Temperature
• CPC Class Codes: F17C 2250/0626 Pressure
• CPC Class Codes: F17C 2250/0631 Temperature
• CPC Class Codes: F17C 7/00 Methods or apparatus for discharging liquefied, solidified, or compressed gases from pressure vessels, not covered by another subclass
• CPC Class Codes: G01N 2030/326 pumps
• CPC Class Codes: G01N 30/02 Column chromatography
• CPC Class Codes: G01N 30/32 : of pressure or speed G01N30/36 takes precedence
• CPC Class Codes: Y02P 20/54 : using solvents, e.g. supercritical solvents or ionic liquids

Abstract

A method and apparatus for delivering supercritical fluids uses one or two high pressure vessels. Each vessel is cooled below the critical temperature of the fluid while the vessel is being filled. The inlet is then closed and the vessel is heated to attain a predetermined pressure. The outlet of the vessel is then opened and supercritical fluid flows from the vessel for use in various processes such as extraction or chromatography. As the fluid flows from the high pressure vessel, the pressure is controlled by adjusting the temperature of the high pressure vessel. Usually, the temperature of the vessel will be increased as the supercritical fluid exits from the vessel. When two high pressure vessels are used, the vessels can be refilled on an alternating basis so that a continuous supply of supercritical fluid can be made available as long as it is required. The high pressure vessels can be two pieces of stainless steel tubing. The system is essentially maintenance free as there are virtually no moving parts. With previous delivery systems for high pressure fluids, high pressure pumps are used. These pumps are relatively expensive and can be subject to problems such as noise and leakage.

Claims

1. A process for delivering supercritical fluid for various uses has a first high pressure vessel with means to cool and means to heat said vessel, said vessel having an inlet and outlet with control means to control the flow of fluid through said inlet and through said outlet, said inlet being connected to a pressurized fluid source, said process being characterized by lowering the temperature of said vessel below the critical temperature of the fluid while opening the inlet to fill the vessel with the fluid, closing the inlet, heating the vessel while monitoring the temperature and pressure to greatly increase the pressure until a desired pressure is attained, opening the outlet to deliver supercritical fluid from the vessel while continuously adjusting the temperature during delivery of the fluid to control the pressure as desired.

2. A process as claimed in claim 1 wherein, while the vessel is delivering supercritical fluid, controlling the temperature by increasing it to maintain a substantially constant pressure.

3. A process as claimed in claim 1 wherein while the vessel is delivering supercritical fluid controlling the temperature by increasing it rapidly to cause the pressure to increase at a predetermined rate.

4. A process as claimed in claim 1 wherein there is a second high pressure vessel connected in parallel to said first vessel with means to cool and means to heat said second vessel, said second vessel having an inlet and an outlet, said control means being adapted to control the flow of fluid through said inlet and through said outlet of said second vessel, the inlet of said second outlet being connected to a pressurized fluid source, said control means controlling the cooling, heating, inlet and outlet of each vessel independently, said process being characterized by, while said first vessel is delivering supercritical fluid, lowering the temperature of the second vessel below the critical temperature of the fluid while opening the inlet to the second vessel to fill the second vessel with fluid, closing the inlet to the second vessel, heating the second vessel while monitoring the temperature and pressure to greatly increase the pressure to the desired level, waiting for the vessel, immediately closing the outlet of the first vessel when said first vessel is substantially empty and opening the outlet of the second vessel to deliver supercritical fluid from the second vessel while continuously adjusting the temperature of the second vessel during delivery of the fluid to control the pressure as desired until the second vessel is substantially empty of fluid, repeating the process to recharge the first vessel with supercritical fluid and ultimately the second vessel, as desired.

5. A process as claimed in claim 4 wherein while the vessels are delivering supercritical fluid, adjusting the temperature by increasing it to maintain a substantially constant pressure.

6. A process as claimed in claim 4 wherein while the vessels are delivering supercritical fluid, adjusting the temperature by increasing it rapidly to cause the pressure to increase at a predetermined rate.

7. A process as claimed in claim 1 wherein there is a second high pressure vessel connected in parallel to said first vessel with means to cool and means to heat said second vessel, said second vessel having an inlet and an outlet, said control means being adapted to control the flow of fluid through said inlet and through said outlet of said second vessel, the inlet of said second vessel being connected to a pressurized fluid source, said control means controlling the cooling, heating, inlet and outlet of each vessel independently, there being a restrictor connected in the outlet of the second vessel, said second vessel containing a modifier, said process being characterized by adding a modifier to said second vessel, lowering the temperature of the second vessel below the critical temperature of the fluid while opening the inlet to the second vessel to fill the second vessel with fluid and modifier, closing the inlet to the second vessel, heating the second vessel while monitoring the temperature and pressure to greatly increase the pressure to the desired level, having both the first vessel and second vessel charged with supercritical fluid and opening the outlets of said first vessel and said second vessel independently as required to deliver supercritical fluid from the first vessel or supercritical fluid and modifier from the second vessel while continuously adjusting temperature of the first and second vessel during delivery of the fluid to control the pressure as desired until each vessel is substantially empty of fluid.

8. An apparatus for continuously delivering supercritical fluid, said apparatus being characterized by two high pressure vessels, each vessel having an inlet and an outlet, said vessels being connected in parallel, said inlets of each vessel being connected to a pressurized fluid source, there being means to cool and means to heat each vessel, with control means to cool, heat, fill and empty the two vessels independently.

9. An apparatus as claimed in claim 8 wherein the outlets on each vessel are check valves that are connected so that a first check valve will close and a second check valve will open as soon as the pressure on the second check valve exceeds the pressure on the first check valve and subsequently the second check valve will close and the first check valve will open as soon as the pressure on the first check valve exceeds the pressure on the second check valve.

10. An apparatus as claimed in any one of claims 8 or 9 wherein the vessels are constructed from stainless steel tubing.

11. An apparatus as claimed in any one of claims 8, 9 or 10 wherein the supercritical fluid is selected from the group of carbon dioxide and nitrous oxide.

12. An apparatus as claimed in any one of claims 8, 9 or 10 wherein said means to cool is capable of cooling each high pressure vessel well below the critical temperature of the fluid so that, when the inlet to that vessel is closed and the vessel is heated until a predetermined pressure is attained, the temperature of the fluid at that point in time is much less than its supercritical temperature.

13. An apparatus as claimed in any one of claims 8 or 9 wherein one of the vessels contains a modifier along with the fluid and a restrictor is connected to an outlet of said vessel that contains the modifier.