Method for determination of system parameters for reducing crude unit corrosion

• US 9,134,238 B2
• Filed: 12/01/2010
• Issued: 09/15/2015
• Est. Priority Date: 12/01/2010
• Status: Active Grant

• Current Assignee: Ecolab USA Incorporated (Ecolab, Inc.)
• Original Assignee: Nalco Company (Ecolab, Inc.)
• Inventors: Banks, Rodney H., Ciota, Steven R., Welz, Sascha J.
• Primary Examiner(s): Gakh, Yelena G
• Assistant Examiner(s): Adams, Michelle
• Application Number:
  US12/957,854
• Publication Number:
  US 20120142113A1
• Time in Patent Office: 1,749 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: G01N 2021/6421 Measuring at two or more wavelengths
• CPC Class Codes: G01N 2021/6491 Measuring fluorescence and transmission; Correcting inner filter effect
• CPC Class Codes: G01N 2021/7786 Fluorescence
• CPC Class Codes: G01N 21/05 Flow-through cuvettes G01N21/09 takes precedence; handling fluid samples G01N1/10
• CPC Class Codes: G01N 21/6428 Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" in vivo A61B5/00; immunoassay G01N33/53
• CPC Class Codes: G01N 21/643 non-biological material
• CPC Class Codes: G01N 21/77 by observing the effect on a chemical indicator
• CPC Class Codes: G01N 21/7703 using reagent-clad optical fibres or optical waveguides using measurement of total internal reflection or attenuated total reflection G01N21/552; optical fibres or waveguides per se G02B
• CPC Class Codes: G01N 21/80 Indicating pH value
• CPC Class Codes: G01N 21/82 producing a precipitate or turbidity
• CPC Class Codes: G01N 31/22 using chemical indicators G01N31/02 takes precedence
• CPC Class Codes: G01N 31/221 for investigating pH value
• CPC Class Codes: G01N 33/1813 specific cations in water, e.g. heavy metals electrochemical analysis G01N27/26; detection of ions by colorimetry G01N31/22
• CPC Class Codes: G01N 35/08 using a stream of discrete samples flowing along a tube system, e.g. flow injection analysis
• CPC Class Codes: Y10T 436/11 Automated chemical analysis
• CPC Class Codes: Y10T 436/193333 In aqueous solution
• CPC Class Codes: Y10T 436/25125 Digestion or removing interfering materials

Abstract

The invention provides a method and apparatus for determining the amount of various materials in a liquid sample. Because the apparatus is particularly resilient it can be used repeatedly with very harsh liquid samples such as boot water from an oil refinery. The apparatus uses at least one volume and/or concentration independent optical analysis method to determine at least one of: the pH, amount of chloride, and/or amount of iron in the sample. The optical property can be colorimetric, fluorescent or both and result from adding dyes, complexing agents, turbidity inducing compounds, and other optically effecting reagents to the sample. Because the measurements are concentration and volume independent they can be done continuously, quickly, and avoid the inconvenient start and stop procedures in prior art measurement regimens. The method further includes using a BDD cell to oxidize materials (such as sulfoxy compounds) that would otherwise interfere with the optical analysis and/or to sparge the sample with gas.

Claims

1. A method of measuring at least one property of a predominantly liquid sample, the method comprising the steps of:

positioning the sample within an apparatus, the apparatus comprising a boron doped diamond (BDD) cell, a chamber, and at least one reagent source constructed and arranged to feed at least one chemical reagent into the chamber,

pre-conditioning the sample by performing one or more pre-conditioning steps which include passing the sample through the BDD cell thereby oxidizing sulfoxy compounds within the sample via the BDD cell,

after pre-conditioning, adding the at least one chemical reagent to the sample in the chamber, the at least one chemical reagent capable of inducing a measurable optical effect when added to the sample that is directly related to the at least one property,

mixing the at least one chemical reagent with the sample in the chamber to form a mixture,

moving the mixture past an optical sensor,

measuring at least two optical properties of the mixture to determine a measured optical effect of the sample, and

deducing the value of the at least one property by comparing the measured optical effect to predetermined values associated with the at least one property,

wherein the measured optical effect is independent of the volume of the sample and independent of the volume of the at least one chemical reagent added to the sample.

2. The method of claim 1 wherein the at least one property is one item selected from the list consisting of:

pH, iron concentration, chloride concentration, and any combination thereof.

3. The method of claim 1 wherein the at least two optical properties comprise at least one of a colorimetric effect, a turbidity effect, or a fluorescent effect.

4. The method of claim 1 wherein the measuring and analyzing the at least two optical properties of the predominantly liquid sample to determine the measured optical effect comprises (i) determining an absorbance level at a particular wavelength that is an isosbestic point for all values of the at least one property, and (ii) determining at least one other absorbance level for one other wavelength, and wherein the step of deducing the value of the at least one property comprises comparing the two absorbance levels with pre-determined data, and correlating the two absorbance levels to known absorbance levels of a particular value of the at least one property.

5. The method of claim 4, wherein determining the measured optical effect further comprises ratioing the absorbance levels determined at the isosbestic point and the one other wavelength, such that the measured optical effect comprises a ratio of the two absorbance levels.

6. The method of claim 1 wherein the measuring and analyzing the at least two optical properties of the sample to determine the measured optical effect comprises (i) determining a fluorescence level at a particular wavelength that is an isosbestic point for all values of the at least one property, and (ii) determining at least one other fluorescence level for one other wavelength, and wherein the step of deducing the value of the at least one property comprises correlating a ratio of the two fluorescence levels to a known ratio of fluorescence levels of a particular value of the at least one property.

7. The method of claim 1 wherein the measuring and analyzing the at least two optical properties of the sample to determine the measured optical effect comprises (i) determining an absorbance level at a particular wavelength that is an isosbestic point for all values of the at least one property, and (ii) determining a fluorescence level for one other wavelength, and wherein the step of deducing the value of the at least one property comprises correlating a ratio of the absorbance level and the fluorescence level to a control ratio of a known value of the at least one property.

8. The method of claim 1, wherein the apparatus further comprises a light source.

9. The method of claim 1, wherein the apparatus further comprises a light source positioned in line or perpendicular to the optical sensor.

10. The method of claim 9 in which the apparatus comprises at least two light sources and corresponding optical sensors in line with the light sources, a path between the light sources and corresponding optical sensors being substantially perpendicular to a flow path of the mixture, each of the optical sensors being constructed and arranged to measure an optical property of the same volume of the mixture in the same region of the flow path as the other optical sensors, and wherein the method further comprises:

turning on the at least two light sources, and

taking readings from the corresponding optical sensors.

11. The method in claim 10 wherein the turning on the at least two light sources and the taking readings from the corresponding optical sensors are performed simultaneously.

12. The method of claim 1, wherein the apparatus further comprises a vertically angled sensor flow path through which the mixture flows, and wherein the measuring of the at least two optical properties comprises light passing to the optical sensor passing horizontally through the mixture.

13. The method of claim 12, wherein the apparatus further comprises a tube downstream from the sensor, at least a portion of the tube is higher than the sensor and extends at an more horizontal angle than the vertically angled sensor flow path, the tube is constructed and arranged to facilitate the migration of gas bubbles away from the sensor, wherein the tube is in one shape selected from the list consisting of:

inverted U-shaped, bent, curved, and angled.

14. The method of claim 1 where temperature measurements are taken to correct for temperature effects.

15. The method of claim 1,

wherein the apparatus further comprises a gas source,

the step of pre-conditioning the sample further comprises adding a pre-sparge material to the sample and then sparging the sample at the gas source upstream from the sensor, wherein the adding a pre-sparge material to the sample comprises adding at least one item selected from the list consisting of:

acid, hydrogen peroxide, and any combination thereof, such that the pre-sparge material increases the rate of expulsion of undesired materials from the sample.

16. The method of claim 1, in which the apparatus is interfaced with a control system governing at least some of the operations of a chemical process stream from which the sample was taken, the deduced value of the at least one property resulting in the control system implementing a counter-measure in response to the at least one property.

17. The method of claim 1 wherein the at least one chemical reagent is selected from the list consisting of:

bromcresol purple, fluorescein, pyrenetetrasulfonic acid (PTSA), 5,10,15,20-tetraphenyl-21H,23H-porphine-tetrasulfonic acid, tetrasodium hydrate (TPPTSA), calcein blue, Ferrozine, silver nitrate, thioglycolic acid, ammonia, pH buffer, ferric iron reductant, fluorescent dye, lucigenin, and any combination thereof.

18. The method of claim 1 further comprising the step of adding a foulant removing cleaner to at least one item used to measure a property of the sample, the cleaner being one item selected from the list consisting of:

ethanolamine, methoxy propylamine, ammonium hydroxide, hypochlorite, hydrogen peroxide, nitric acid, and any combination thereof.