CA2403008A1 - Determination of the properties of a solution or solid using raman ratios - Google Patents
Determination of the properties of a solution or solid using raman ratios Download PDFInfo
- Publication number
- CA2403008A1 CA2403008A1 CA002403008A CA2403008A CA2403008A1 CA 2403008 A1 CA2403008 A1 CA 2403008A1 CA 002403008 A CA002403008 A CA 002403008A CA 2403008 A CA2403008 A CA 2403008A CA 2403008 A1 CA2403008 A1 CA 2403008A1
- Authority
- CA
- Canada
- Prior art keywords
- measurement
- sample
- property
- raman
- amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract 27
- 239000007787 solid Substances 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract 38
- -1 hemicellulose Chemical class 0.000 claims abstract 15
- 230000002829 reductive effect Effects 0.000 claims abstract 8
- 230000001590 oxidative effect Effects 0.000 claims abstract 7
- 239000000126 substance Substances 0.000 claims abstract 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract 2
- 238000005259 measurement Methods 0.000 claims 100
- 150000002978 peroxides Chemical class 0.000 claims 14
- 229940097156 peroxyl Drugs 0.000 claims 14
- 230000001678 irradiating effect Effects 0.000 claims 4
- 238000006243 chemical reaction Methods 0.000 claims 3
- 238000012545 processing Methods 0.000 claims 3
- 229920001131 Pulp (paper) Polymers 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 238000004061 bleaching Methods 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- 238000004076 pulp bleaching Methods 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 238000004458 analytical method Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000012993 chemical processing Methods 0.000 claims 1
- 230000002860 competitive effect Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 230000001052 transient effect Effects 0.000 claims 1
- 229920002488 Hemicellulose Polymers 0.000 abstract 1
- 238000001237 Raman spectrum Methods 0.000 abstract 1
- 230000000536 complexating effect Effects 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 150000002605 large molecules Chemical class 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 229920001277 pectin Polymers 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/34—Paper
- G01N33/343—Paper pulp
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C7/00—Digesters
- D21C7/12—Devices for regulating or controlling
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to the use of ratios of Raman peak intensities to predict the properties of a solution or a solid such as pulp that is processed with the solution. The intensity of the Raman shifted light is used to create Raman peak intensity ratios. These Raman intensities are related to the concentration of species dissolved in the liquid. The Raman spectra are baseline corrected and the scattering from a water reference is subtracted before extraction of intensities for Raman peak intensity ratios. The Raman scattering intensities provide a good measure of the concentration of small, oxygenated molecules. The potential of an oxidative reductive process is conveniently determined using Raman peak intensity ratios. The method may also be used to determine a property related to the relative size, degree of polymerization, branching or network formation of complexing or polymerized species, or to measure large molecules such as hemicellulose, extractives and pectic substances.
Claims (27)
1. A method for controlling a property of a sample in a reductive oxidative process comprising the steps of:
(a) irradiating at least a portion of the sample with a laser light for generating a Raman emitted light from the sample;
(b) obtaining at least two measurements of the Raman emitted light between 200 cm-1 and 4000 cm-1, a first measurement at a first wavenumber and a second measurement at a second wavenumber; and (c) varying the property in the reductive oxidative process using feedback control for adjusting at least one feed input component in accordance with a determined ratio between the two measurements for adjusting the process toward a predetermined ratio of the two measurements in a subsequent iteration.
(a) irradiating at least a portion of the sample with a laser light for generating a Raman emitted light from the sample;
(b) obtaining at least two measurements of the Raman emitted light between 200 cm-1 and 4000 cm-1, a first measurement at a first wavenumber and a second measurement at a second wavenumber; and (c) varying the property in the reductive oxidative process using feedback control for adjusting at least one feed input component in accordance with a determined ratio between the two measurements for adjusting the process toward a predetermined ratio of the two measurements in a subsequent iteration.
2, An apparatus for determining a property of a sample in a reductive axidative process comprising:
a laser light source for irradiating at least a portion of the sample for generating a Raman emitted light from the sample;
a detector for detecting the Raman emitted light from the sample, said detector for iteratively obtaining at least two measurements of the Raman emitted light, a first measurement at a first wavenumher and a second measurement at a second wavenumber; and a member for controlling the property in the reductive oxidative process using feedback control for adjusting at least one feed input component in accordance with a determined ratio between the two measurements for adjusting the process toward a predetermined ratio of the two measurements in a subsequent iteration.
a laser light source for irradiating at least a portion of the sample for generating a Raman emitted light from the sample;
a detector for detecting the Raman emitted light from the sample, said detector for iteratively obtaining at least two measurements of the Raman emitted light, a first measurement at a first wavenumher and a second measurement at a second wavenumber; and a member for controlling the property in the reductive oxidative process using feedback control for adjusting at least one feed input component in accordance with a determined ratio between the two measurements for adjusting the process toward a predetermined ratio of the two measurements in a subsequent iteration.
3. A method as defined in claim 1 wherein a defining relationship between the ratio of the two measurements and the property controlled in the reductive oxidative is a non-linear relationship between one of a function of the first measurement and a ratio including the first measurement and the second measurement, and function of the first measurement and a product including the first measurement and the second measurement, a function of the first measurement and a sum including the first measurement and the second measurement, a function of the ratio including the first measurement and the second measurement and a product including the first measurement and the second measurement, and a function of two different ratios, each of the two different ratios including at least one of the first measurement and the second measurement.
4. A method as defined in claim 3 wherein the non-linear relationship is determined by regression methods.
5. A method as defined in claim 4 wherein the non-linear relationship is expressed as at least one of the following functions between the property of the sample and the first and second measurement:
property of sample = f (first measurement, first measurement / second measurement);
property of sample = f (first measurement, first measurement * second measurement);
property of sample = f (first measurement, first measurement + second measurement);
property of sample - f (first measurement, first measurement / (first measurement +
second measurement));
property of sample = f (first measurement, (first measurement + second measurement) /
first measurement);
property of sample = f (first measurement / second measurement, (first measurement +
second measurement) / first measurement);
property of sample = f (first measurement / second measurement, (first measurement +
second measurement) / second measurement);
property of sample = f (first measurement / second measurement, first measurement: /
(first measurement + second measurement));
properly of sample = f (first measurement / second measurement, second measurement /
(first measurement + second measurement)); and property of sample = f (first measurement / second measurement, first measurement *
second measurement).
property of sample = f (first measurement, first measurement / second measurement);
property of sample = f (first measurement, first measurement * second measurement);
property of sample = f (first measurement, first measurement + second measurement);
property of sample - f (first measurement, first measurement / (first measurement +
second measurement));
property of sample = f (first measurement, (first measurement + second measurement) /
first measurement);
property of sample = f (first measurement / second measurement, (first measurement +
second measurement) / first measurement);
property of sample = f (first measurement / second measurement, (first measurement +
second measurement) / second measurement);
property of sample = f (first measurement / second measurement, first measurement: /
(first measurement + second measurement));
properly of sample = f (first measurement / second measurement, second measurement /
(first measurement + second measurement)); and property of sample = f (first measurement / second measurement, first measurement *
second measurement).
6, A method as defined in claim 5 wherein the property of the sample is one of an amount of a peroxide contained in the sample and an amount of a peroxyl ion contained in the sample.
7. A method as defined in claim 6 wherein the first measurement is for determining a Raman intensity relating to one of the amount of a peroxide and the amount of a peroxyl ion, and the second measurement is for determining a Raman intensity relating to the other one of the amount of a peroxide and the amount of a peroxyl ion.
8. A method as defined in claim 7 wherein the Raman intensity relating to the amount of a peroxide is obtained at approximately 877 cm-1 and the Raman intensity relating to the amount of a peroxyl ion is obtained at approximately 850 cm-1.
9. A method as defined in claim 5 wherein the property is a potential of a reductive oxidative process occurring within the sample.
10. A method as defined in claim 4 further comprising the steps of obtaining at least a third measurement of the Raman emitted light between 200 cm-1 and 4000 cm-1 and determining a non-linear relationship between the at least three measurements and the property of the sample.
11. A method as defined in claim 10 wherein the non-linear relationship is expressed as the function of two different ratios, each of the two different ratios including at least one of the first measurement and the second measurement and at least one of the two different ratios including the at least a third measurement.
12. A method as defined in claim 1 wherein the sample is produced by one of a wood pulp bleaching process and a wood pulp delignification process.
13. A method as defined in claim 1 wherein the property is one of an equilibrium property, a property that occurs due to competitive processes where relative rate constants are important, and a property that signifies an extent of a reaction.
14, A method as defined in any of claims 1,5, and 11 wherein the property is one of an amount of a pulp bleaching chemical and an amount of a pulp delignification chemical.
15. A method as defined in claim 1 wherein a characteristic relating to an extent of bleaching of a pulp or pulp effluent contained in the sample is determined using the property, the characteristic being one of pulp brightness, pulp yellowness, and bleaching efficiency.
16. A method as defined in claim 13 wherein the property that signifies the extent of the reaction is a degree of polymerisation.
17. A method as defined in claim 13 wherein the property is one of a degree of polymerisation, ionisation, and network formation of a silicate solution.
18. A method as defined in any of claims 1 and 5 wherein the property is related to an amount of organic substances in the sample, said properly being one of chemical oxygen demand, biological oxygen demand, and total organic carbon.
19. A method as defined in claim 1 wherein the property is one of an amount of ionised species and a charge density.
20. A method as defined in claim 13 wherein the property is related to a propensity to form scale.
21. A method as defined in claim 13 wherein the property is a reduction-oxidation potential of the sample or another measure of the reductive or oxidative capacity of the sample.
22. A method as defined in claim 11 wherein the property of the sample is one of an amount of a peroxide contained in the sample and an amount of a peroxyl ion contained in the sample.
23. A method as defined in claim 22 wherein the first measurement is for determining a Raman intensity relating to the amount of a peroxide or the amount of a peroxyl ion, and the second measurement is for determining a Raman intensity relating;
to the other one of the amount of a peroxide and the amount of a peroxyl ion.
to the other one of the amount of a peroxide and the amount of a peroxyl ion.
24. A method defined in claim 13 wherein the property is a relative amount of a transient species with inspect to either a reactant or a product during a chemical reaction or processing step.
25. A method for determining a property of a sample comprising the steps of:
(a) irradiating at least a portion of the sample with a laser light for generating a Raman emitted light from the sample;
(b) obtaining at least two measurements of the Raman emitted light between 200 cm-1 and 4000 cm-1, a first measurement at a first wavenumber and a second measurement at a second wavenumber; and (c) formulating a non-linear relationship between the at least two measurements and the property, of the sample, the non-linear relationship expressed as one of a function of the first measurement and a ratio including the first measurement.
and the second measurement, a function of the first measurement and a product including the first measurement and the second measurement, a function of the first measurement and a the including the first measurement and the second measurement, a function of the ratio including the first measurement and the second measurement and a.
product including the first measurement and the second measurement, and a function of two different ratios, each of the two different ratios including at toast one of the first measurement and the second measurement.
(a) irradiating at least a portion of the sample with a laser light for generating a Raman emitted light from the sample;
(b) obtaining at least two measurements of the Raman emitted light between 200 cm-1 and 4000 cm-1, a first measurement at a first wavenumber and a second measurement at a second wavenumber; and (c) formulating a non-linear relationship between the at least two measurements and the property, of the sample, the non-linear relationship expressed as one of a function of the first measurement and a ratio including the first measurement.
and the second measurement, a function of the first measurement and a product including the first measurement and the second measurement, a function of the first measurement and a the including the first measurement and the second measurement, a function of the ratio including the first measurement and the second measurement and a.
product including the first measurement and the second measurement, and a function of two different ratios, each of the two different ratios including at toast one of the first measurement and the second measurement.
26. In apparatus for determining a property of a sample comprising;
a laser light source foe irradiating at least a portion of the sample for generating a Raman emitted light from the sample;
a detector for detecting the Raman emitted light from the sample, said detector for obtaining at least two measurements of the Raman emitted light, a first measurement at a first wavenumber and a second measurement at a second wavenumber;
a processor for receiving and processing data from the detector for determining a non-linear relationship between the at least two measurements and the property of the sample, and a member for controlling the property in a process using feedback control for adjusting at least one feed input component in accordance with a determined value of the property for obtaining a predetermined valve of the property.
a laser light source foe irradiating at least a portion of the sample for generating a Raman emitted light from the sample;
a detector for detecting the Raman emitted light from the sample, said detector for obtaining at least two measurements of the Raman emitted light, a first measurement at a first wavenumber and a second measurement at a second wavenumber;
a processor for receiving and processing data from the detector for determining a non-linear relationship between the at least two measurements and the property of the sample, and a member for controlling the property in a process using feedback control for adjusting at least one feed input component in accordance with a determined value of the property for obtaining a predetermined valve of the property.
27. A system for determining an amount of at least one of a peroxide and a peroxyl ion in a solution, comprising:
means for receiving information containing data related to at least one of a Raman intensity peak corresponding to the peroxide and a Raman intensity peak corresponding to the peroxyl ion; and, means for processing the information to determine indicia of a concentration of at least one of the peroxide and the peroxyl ion, the processing including an analysis of at least one of data related to the intensity peak corresponding to the peroxide, data related the intensity peak corresponding to the peroxyl ion, a sum of data related to the intensity peaks of the peroxide and the peroxyl ion, a product of data related io the intensity peaks of the peroxide and the peroxyl ion; and a ratio of data related to the intensity peaks of the peroxide and the peroxyl ion.
means for receiving information containing data related to at least one of a Raman intensity peak corresponding to the peroxide and a Raman intensity peak corresponding to the peroxyl ion; and, means for processing the information to determine indicia of a concentration of at least one of the peroxide and the peroxyl ion, the processing including an analysis of at least one of data related to the intensity peak corresponding to the peroxide, data related the intensity peak corresponding to the peroxyl ion, a sum of data related to the intensity peaks of the peroxide and the peroxyl ion, a product of data related io the intensity peaks of the peroxide and the peroxyl ion; and a ratio of data related to the intensity peaks of the peroxide and the peroxyl ion.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/499,450 | 2000-02-07 | ||
| US09/499,450 US6774992B1 (en) | 1997-03-10 | 2000-02-07 | Determination of the property of a solution or solid using raman ratios |
| PCT/CA2001/000123 WO2001059437A1 (en) | 2000-02-07 | 2001-02-05 | Determination of the properties of a solution or solid using raman ratios |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2403008A1 true CA2403008A1 (en) | 2001-02-05 |
| CA2403008C CA2403008C (en) | 2011-11-01 |
Family
ID=23985290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2403008A Expired - Fee Related CA2403008C (en) | 2000-02-07 | 2001-02-05 | Determination of the properties of a solution or solid using raman ratios |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1254363A1 (en) |
| BR (1) | BR0108300A (en) |
| CA (1) | CA2403008C (en) |
| NO (1) | NO20023720L (en) |
| WO (1) | WO2001059437A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009117823A1 (en) * | 2008-03-25 | 2009-10-01 | Alberta Research Council Inc. | Continuous measurement of amine loading in gas processing plants using raman spectroscopy |
| WO2016090455A1 (en) * | 2014-12-12 | 2016-06-16 | Canfor Pulp Ltd | Method and apparatus for controlling a cellulosic pulp process |
| CN111751510A (en) * | 2020-08-13 | 2020-10-09 | 北京雪域飞虹环保科技有限公司 | TOC detection method of multi-channel induction noise reduction compensation reduction algorithm |
| CN115290562A (en) * | 2022-08-09 | 2022-11-04 | 江苏经贸职业技术学院 | SERS detection method of 5-hydroxymethylfurfural |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7521254B2 (en) | 2004-04-12 | 2009-04-21 | Transform Pharmaceuticals, Inc. | Quantitative measurements of concentration and solubility using Raman spectroscopy |
| FI122238B (en) * | 2006-02-09 | 2011-10-31 | Metso Automation Oy | Method and apparatus for determining the total peroxide content of a pulp suspension |
| US8009277B2 (en) | 2007-10-26 | 2011-08-30 | International Paper Company | Sensor technique for black liquor oxidation control |
| CN112362636A (en) * | 2020-11-04 | 2021-02-12 | 西安建筑科技大学 | Chlorite mineral species identification method based on Raman spectrum |
| CN116785967B (en) * | 2023-04-28 | 2024-03-08 | 福建省龙德新能源有限公司 | Automatic batching system for electronic grade lithium hexafluorophosphate preparation |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5139334A (en) * | 1990-09-17 | 1992-08-18 | Boston Advanced Technologies, Inc. | Hydrocarbon analysis based on low resolution raman spectral analysis |
| EP0714025A1 (en) * | 1994-11-25 | 1996-05-29 | Kyoto Dai-ichi Kagaku Co., Ltd. | Method of and apparatus for determining hydrogen peroxide by Raman scattering |
| US5999255A (en) * | 1997-10-09 | 1999-12-07 | Solutia Inc. | Method and apparatus for measuring Raman spectra and physical properties in-situ |
| DE19814385C1 (en) * | 1998-03-31 | 1999-10-07 | Siemens Ag | Process and device for process control and process optimization of chemical recovery in the manufacture of pulp |
-
2001
- 2001-02-05 CA CA2403008A patent/CA2403008C/en not_active Expired - Fee Related
- 2001-02-05 BR BR0108300-7A patent/BR0108300A/en not_active Application Discontinuation
- 2001-02-05 WO PCT/CA2001/000123 patent/WO2001059437A1/en not_active Application Discontinuation
- 2001-02-05 EP EP01903539A patent/EP1254363A1/en not_active Withdrawn
-
2002
- 2002-08-06 NO NO20023720A patent/NO20023720L/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009117823A1 (en) * | 2008-03-25 | 2009-10-01 | Alberta Research Council Inc. | Continuous measurement of amine loading in gas processing plants using raman spectroscopy |
| WO2016090455A1 (en) * | 2014-12-12 | 2016-06-16 | Canfor Pulp Ltd | Method and apparatus for controlling a cellulosic pulp process |
| US10450700B2 (en) | 2014-12-12 | 2019-10-22 | Canfor Pulp Ltd. | Method and apparatus for controlling a cellulosic pulp process |
| CN111751510A (en) * | 2020-08-13 | 2020-10-09 | 北京雪域飞虹环保科技有限公司 | TOC detection method of multi-channel induction noise reduction compensation reduction algorithm |
| CN115290562A (en) * | 2022-08-09 | 2022-11-04 | 江苏经贸职业技术学院 | SERS detection method of 5-hydroxymethylfurfural |
Also Published As
| Publication number | Publication date |
|---|---|
| BR0108300A (en) | 2003-03-11 |
| EP1254363A1 (en) | 2002-11-06 |
| CA2403008C (en) | 2011-11-01 |
| NO20023720D0 (en) | 2002-08-06 |
| WO2001059437A1 (en) | 2001-08-16 |
| NO20023720L (en) | 2002-10-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20170206 |