Method for analyzing impurities in carbon dioxide

• US 7,064,834 B2
• Filed: 01/22/2003
• Issued: 06/20/2006
• Est. Priority Date: 01/22/2002
• Status: Expired due to Term

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Billingham, John Fredric, Johnson, Michael Clinton, Heim, Carl Joseph, Malczewski, Mark Leonard
• Primary Examiner(s): Lauchman, Layla G.
• Assistant Examiner(s): VALENTIN, JUAN D
• Application Number:
  US10/350,307
• Publication Number:
  US 20030197852A1
• Time in Patent Office: 1,245 Days
• Field of Search: 356/437, 356/336, 356/337, 356/338, 356/339, 356/340, 356/341, 356/342, 356/343, 356/37, 73/10.1, 73/10.2, 73/10.6, 73/232, 73/232.1, 73 2322- 2342, 73 2401- 2406, 73 2501- 2505, 73 2801- 2806, 73 2901- 2902, 7333501-33514, 73 2903- 2905, 73 3001- 3004, 73 3101- 3107
• US Class Current: 356/437
• CPC Class Codes: B01D 15/40 using supercritical fluid as mobile phase or eluent
• CPC Class Codes: C01B 32/50 Carbon dioxide
• CPC Class Codes: F25J 2290/50 Arrangement of multiple equipments fulfilling the same process step in parallel
• CPC Class Codes: G01N 1/2202 involving separation of sample components during sampling
• CPC Class Codes: G01N 1/40 Concentrating samples
• CPC Class Codes: G01N 1/42 Low-temperature sample treatment, e.g. cryofixation
• CPC Class Codes: G01N 15/04 Investigating sedimentation of particle suspensions
• CPC Class Codes: G01N 15/06 Investigating concentration of particle suspensions by weighing G01N5/00; investigating sedimentation of particle suspensions G01N15/04; investigating individual particles G01N15/10
• CPC Class Codes: G01N 15/075 by optical means
• CPC Class Codes: G01N 2001/2238 the gas being compressed or pressurized
• CPC Class Codes: G01N 2001/2282 with cooling means
• CPC Class Codes: G01N 33/0016 by regulating a physical variable, e.g. pressure, temperature

Abstract

This invention relates to methods and systems for detecting contaminants that can precipitate and deposit on a workpiece during a carbon dioxide application, especially contaminants that are already present and dissolved in the fresh carbon dioxide fed to the application. One aspect of this invention includes a method of detecting contaminants dissolved in a carbon dioxide stream, including the steps of sampling at least a portion of the carbon dioxide stream to form a carbon dioxide sample; modifying at least one physical condition of the carbon dioxide sample to form an aerosol that includes gaseous carbon dioxide and at least one suspended contaminant; and detecting the number of particles of suspended contaminant in at least a portion of the carbon dioxide sample with at least one particle counter. A system for continuously detecting contaminants dissolved in a carbon dioxide stream is also described.

Claims

1. A method of detecting contaminants dissolved in a carbon dioxide stream, comprising the steps of:

a) sampling at least a portion of the carbon dioxide stream in liquid or supercritical phase to form a carbon dioxide sample;

b) modifying at least one physical condition of the carbon dioxide sample to form an aerosol that includes gaseous carbon dioxide and at least one suspended contaminant; and

c) detecting the number of particles of suspended contaminant, wherein the suspended contaminant is in the form of aerosol droplets, in at least a portion of the carbon dioxide sample with at least one particle counter.

2. The method of claim 1, wherein the step of modifying at least one physical condition includes increasing the temperature of the carbon dioxide sample to above the sublimation point of carbon dioxide at the pressure at which the suspended contaminant is detected.

3. The method of claim 2, wherein the step of modifying at least one physical condition includes increasing the temperature of the carbon dioxide sample to above the boiling point of carbon dioxide at the pressure at which the suspended contaminant is detected.

4. The method of claim 1, wherein the particle counter is at least one device selected from the group consisting of a white-light particle counter, a laser diode particle counter, a gas-powered laser particle counter, and a condensation nucleus counter.

5. The method of claim 4, wherein the suspended contaminant are detected by at least two of the devices selected from the group consisting of a white-light particle counter, a laser diode particle counter, a gas-powered laser particle counter, and a condensation nucleus counter.

6. The method of claim 4, wherein at least a portion of the suspended contaminant is detected by a piezoelectric device.

7. The method of claim 6, wherein the piezoelectric device is at least one device selected from the group consisting of a surface wave resonator and a microcantilever.

8. The method of claim 1, further including the step of directing the carbon dioxide sample through a filter prior to modifying at least one physical condition of the carbon dioxide sample to form an aerosol that includes gaseous carbon dioxide and at least one suspended contaminant.

9. The method of claim 1, further including the step of directing the carbon dioxide sample through a filter after modifying at least one physical condition of the carbon dioxide sample to form an aerosol that includes gaseous carbon dioxide and at least one suspended contaminant.

10. The method of claim 1, wherein the number of particles of suspended contaminant is detected at a pressure less than about 3,000 psia.

11. The method of claim 10, wherein the number of particles of suspended contaminant is detected at a pressure less than about 1,065 psia.

12. The method of claim 11, wherein the number of particles of suspended contaminant is detected at a pressure of about 14.7 psia.

13. The method of claim 1, wherein the carbon dioxide stream contains less than 1×

10<sup>−

6</sup>% by weight dissolved contaminant.

14. The method of claim 13, wherein the carbon dioxide stream contains less than 1×

10<sup>−

7</sup>% by weight dissolved contaminant.

15. A method for monitoring contaminants in a carbon dioxide stream that is directed to a workpiece, comprising the steps of:

a) identifying a reference value, wherein said reference value indicates that the dissolved contaminants will precipitate and deposit onto the workpiece in acceptably low levels, by detecting the number of particles of at least a portion of the dissolved contaminants in a calibration process which includes the steps of;

i) sampling at least a potion of an acceptable carbon dioxide stream to form an acceptable carbon dioxide sample;

ii) modifying the conditions of the acceptable carbon dioxide sample to form an aerosol of gaseous carbon dioxide and precipitated contaminants, whereby at least a portion of the contaminants are in the form of suspended droplets; and

iii) detecting the number of particles of at least a portion of the acceptable carbon dioxide sample with at least one particle counter;

thereby identifying said reference value;

b) subsequently directing a carbon dioxide stream to the workpiece;

c) sampling said carbon dioxide stream to identify at least one measured value, wherein said measured value indicates whether contaminants will precipitate from the carbon dioxide stream and deposit onto the workpiece in an acceptably low level, by detecting the number of particles of an essentially equal portion of the dissolved contaminants as employed to determine the reference value in a monitoring process which includes the steps of;

i) sampling at least a portion of said carbon dioxide stream to form a carbon dioxide sample;

ii) modifying the conditions of the carbon dioxide sample to form an aerosol of gaseous carbon dioxide and precipitated contaminants; and

iii) detecting the number of particles in the portion of the carbon dioxide sample with at least one particle counter;

thereby identifying said measured values; and

d) comparing the measured values with the reference value to determine the number of dissolved particles that will precipitate from the subsequently directed carbon dioxide and deposit onto the workpiece is an acceptably low level, thereby monitoring contaminants of the carbon dioxide stream.

16. The method of claim 15, wherein the reference value indicates that the carbon dioxide stream contains less than 1×

10<sup>−

6</sup>% by weight dissolved contaminant.

17. The method of claim 16, wherein the reference value indicates that the carbon dioxide stream contains less than 1×

10<sup>−

7</sup>%by weight dissolved contaminant.

18. A system for continuously detecting contaminants dissolved in a carbon dioxide stream flowing through a solvent feed line, comprising:

a) a sampling means for removing a sample stream, wherein said sample stream is at least a portion of the carbon dioxide stream flowing through the solvent feed line;

b) a modification means in fluid communication with the sampling means, wherein said modification means modifies the conditions of the sample stream to form an aerosol of gaseous carbon dioxide and suspended contaminants;

c) at least one contaminant measurement zone in fluid communication with the modification means; and

d) at least one particle counting means, wherein said particle counting means can detect at least a portion of the suspended contaminants in the contaminant measurement zone with at least one particle counter.

19. The system of claim 18, further including a solids-removal means in fluid communication with the modification means, wherein said solids-removal means filters solid particles from the sample stream before the sample stream reaches at least one contaminant measurement zone.

20. The system of claim 18, further including a particle detecting means which can detect at least a portion of the suspended contaminants in at least one contaminant measurement zone with at least one turbidmetry-based particle detector.

21. The system of claim 18, further including a particle detecting means which can detect at least a portion of the suspended contaminants in at least one contaminant measurement zone with at least one nephelometry-based particle detector.