CA2304201C - Analyzer for temperature sensitive colloidal mixtures - Google Patents
Analyzer for temperature sensitive colloidal mixtures Download PDFInfo
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- CA2304201C CA2304201C CA2304201A CA2304201A CA2304201C CA 2304201 C CA2304201 C CA 2304201C CA 2304201 A CA2304201 A CA 2304201A CA 2304201 A CA2304201 A CA 2304201A CA 2304201 C CA2304201 C CA 2304201C
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- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/47—Scattering, i.e. diffuse reflection
- G01N21/4738—Diffuse reflection, e.g. also for testing fluids, fibrous materials
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- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
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- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/47—Scattering, i.e. diffuse reflection
- G01N21/49—Scattering, i.e. diffuse reflection within a body or fluid
- G01N21/53—Scattering, i.e. diffuse reflection within a body or fluid within a flowing fluid, e.g. smoke
- G01N21/534—Scattering, i.e. diffuse reflection within a body or fluid within a flowing fluid, e.g. smoke by measuring transmission alone, i.e. determining opacity
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- 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
- G01N33/18—Water
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- 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
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
A method and apparatus for characterizing colloids by suc-cessive measurements of light attenuation or emission of a colloidal mixture at two or more temperatures and at one or more wavelengths. The difference or ratio of the measurements at two or more temper-atures provides a measure of the colloidal stability with respect to temperature. The amount of certain organic colloids that are unsta-ble to temperature variation may be determined from the magnitude of the measurement change. In appropriate mixtures, this method provides a means to distinguish components of colloidal substances based. This method may be specifically applied to determine the sta-bility and concentration of colloidal pitch or wood resin in a pulp or paper process water. In this context it may be used to distinguish colloidal pitch or wood resin from talc, clay, carbon black or other fillers.
Description
WO 99/14577= PCT/CA98/00871 ANALYZER FOR TEMPERATURE SENSITIVE COLLOIDAL MIXTURES
Field of the Invention This invention relates to the application of ultraviolet-visible light measurements for the determination of colloidal substances in a liquid sample. More particularly, the invention relates to the application of light absorption and/or scattering measurements for determining a property of colloidal substances that undergo a temperature dependent phase transition.
Background of the Invention Papermaker's demands for high speed and efficiency, flexible manufacturing, stringent quality standards, and environmental compatibility coupled with new developments in on-line process control are driving the development of new sensor technology for the paper machine wet-end. The need for better means for providing wet-end chemistry control is emphasized by recent reports that only 10% of the world's 150 newsprint paper machines operate at above 88% efficiency and over 60 % operate under in the low efficiency range of below 82.5%. (Mardon, J., Chinn, G. P., O'Blenes, G., Robertson, G., Tkacz, A. Pulp and Paper Canada, Vol. 99 No. 5 pp. 43-46. (1998).
William E. Scott addressed problems related to wet-end chemistry control.
Principles of Wet End Chemistry. Tappi Press, Atlanta, 1996. p 3. "Deposits and scale usually arise from out-of-control wet end chemistry. Typical examples include chemical additive overdosing, charge imbalances, chemical incompatibility and the shifting of chemical equilibria. All of these phenomena can lead to the formation of precipitates or colloidal aggregates that produce deposits and scale. While there are numerous approaches to treating the symptoms of deposits the best approach is to determine what is out of control and fix it."
Although variations in the composition and quantity of dissolved solids can lead to problems throughout the paper mill it is particularly important at the wet-end of the paper I
SUBSTITUTE SHEET (RULE 26) WO 99/14577 PCT/CA98l00871 machine where the colloidal chemistry must be tuned for optimal machine performance.
It is important to gain knowledge and understanding of the relationship between measurements at both the point of origin (pulp mills, bleaching points) and the point of impact (headbox, press-section of the paper machine).
The measurement and characterization of colloidal particles distributed in a liquid stream is an important function in the control of industrial processes involving heterogeneous mixtures. Examples of such processes include pulping and papermaking, water treatment, brewing and food processing, chemical synthesis and manufacturing. Although numerous methods are available to characterize colloid size and concentration, methods to measure the amount of different colloids components mixed together or to rapidly evaluate the temperature stability of the colloid suspension are not readily available.
Measurements relating the intensity and angular dependence of scattered or absorbed light to the total concentration or size distribution of colloids are available in numerous forms. Instruments for characterizing the amount of colloidal particles that rely on scattering (nepholometry) and attenuation (turbidimetry) are commercially available in laboratory, hand-held and on-line instruments. On line turbidimeters relate a ratio of light detected in line and at an angle to a source to a turbidity value in Jackson or NTU units.
Silveston, U.S. Patent No. 4,999,514 taught methods for controlling the intensity of the light source to provide a turbidimeter that operates over a broad range of particle concentrations. Kubisiak and Wilson (U.S. Patent No. 5,331,177) describe a analog to digital turbitimeter apparatus that provides a measure of the change in turbidity over time.
Other, more sophisticated, methods involving the analysis of the time and spatial dependence of light attenuation and scattering may provide information on particle size distributions as taught by Strickland et (U.S. Patent No. 5,576,827 and the patents referenced therein). Instrumentation specifically designed for measuring particle and fiber size distributions in low consistency (<%) pulp suspensions by analysis of the time and spatial variation of scattered or absorbed light includes the BTG (British Technology Group) RET-5300 Retention Monitoring System. This instrument employs methods taught by Lundqvist; Pettersson and Fladda U.S. Patent No. 4,318,180. The available SUBSTITUTE SHEET (RULE 26) instruments do not have a means to differentiate concentrations of similarly sized colloidal pitch particles from colloidal clay particles.
In the area of pulp and paper manufacture the maintenance of a level of stability and removal of colloidal pitch is an important objective in the wet-end chemistry programs.
Deposition leading to poor paper machine efficiency is a costly problem that is addressed through numerous strategies involving pulp processing or chemical addition.
Polymer, clay and talc additives are used to prevent pitch accumulation that may lead to deposition and fouling of pulp processing and papermaking equipment. For example, Cutts taught one method for controlling pitch using micro-particle bentonite addition with cationic polymer flocculation, U.S. Patent No. 5,676,796. Another combination of using kaolin as inorganic colloid and poly(diallyldimethyl-ammonium chloride) cationic polymer has been taught by Lamar; Pratt; Weber and Roeder (U.S. Patent No. 4,964,955).
Alternatively, Dreisbach and Barton taught (U.S. Patent No. 5,266,166) a method of preventing pitch deposits by the addition of nonionic polymeric dispersing agent. A
physical process for reducing wood resin pitch from wood process water employing a centrifuge has been taught by Allen and Lapointe (U.S. Patent No. 5,468,396).
The teachings of this invention review the sources and problems associated with wood resin in paper mills and provide further information on physical methods of reducing pitch in pulp and paper process waters.
Chemical and physical methods of controlling pitch may be monitored by turbidity or Zeta or streaming potential or charge measurements. Although surface charge or total charge are important measures of the colloidal stability these measurements do not distinguish colloidal pitch from other, less problematic colloids such as added clay.
Furthermore, turbidity may provide a means of evaluating the total amount of colloidal substance, but pitch colloids are not normally distinguished from other colloids in a turbidity measurement. Typically no instrumental means are employed to supervise chemical methods of controlling pitch. Despite the high cost of chemical treatment programs and the potential downtime caused by over or under dosing, chemical methods of controlling pitch are often invariant over time and substantial swings in wet-end chemistry.
Field of the Invention This invention relates to the application of ultraviolet-visible light measurements for the determination of colloidal substances in a liquid sample. More particularly, the invention relates to the application of light absorption and/or scattering measurements for determining a property of colloidal substances that undergo a temperature dependent phase transition.
Background of the Invention Papermaker's demands for high speed and efficiency, flexible manufacturing, stringent quality standards, and environmental compatibility coupled with new developments in on-line process control are driving the development of new sensor technology for the paper machine wet-end. The need for better means for providing wet-end chemistry control is emphasized by recent reports that only 10% of the world's 150 newsprint paper machines operate at above 88% efficiency and over 60 % operate under in the low efficiency range of below 82.5%. (Mardon, J., Chinn, G. P., O'Blenes, G., Robertson, G., Tkacz, A. Pulp and Paper Canada, Vol. 99 No. 5 pp. 43-46. (1998).
William E. Scott addressed problems related to wet-end chemistry control.
Principles of Wet End Chemistry. Tappi Press, Atlanta, 1996. p 3. "Deposits and scale usually arise from out-of-control wet end chemistry. Typical examples include chemical additive overdosing, charge imbalances, chemical incompatibility and the shifting of chemical equilibria. All of these phenomena can lead to the formation of precipitates or colloidal aggregates that produce deposits and scale. While there are numerous approaches to treating the symptoms of deposits the best approach is to determine what is out of control and fix it."
Although variations in the composition and quantity of dissolved solids can lead to problems throughout the paper mill it is particularly important at the wet-end of the paper I
SUBSTITUTE SHEET (RULE 26) WO 99/14577 PCT/CA98l00871 machine where the colloidal chemistry must be tuned for optimal machine performance.
It is important to gain knowledge and understanding of the relationship between measurements at both the point of origin (pulp mills, bleaching points) and the point of impact (headbox, press-section of the paper machine).
The measurement and characterization of colloidal particles distributed in a liquid stream is an important function in the control of industrial processes involving heterogeneous mixtures. Examples of such processes include pulping and papermaking, water treatment, brewing and food processing, chemical synthesis and manufacturing. Although numerous methods are available to characterize colloid size and concentration, methods to measure the amount of different colloids components mixed together or to rapidly evaluate the temperature stability of the colloid suspension are not readily available.
Measurements relating the intensity and angular dependence of scattered or absorbed light to the total concentration or size distribution of colloids are available in numerous forms. Instruments for characterizing the amount of colloidal particles that rely on scattering (nepholometry) and attenuation (turbidimetry) are commercially available in laboratory, hand-held and on-line instruments. On line turbidimeters relate a ratio of light detected in line and at an angle to a source to a turbidity value in Jackson or NTU units.
Silveston, U.S. Patent No. 4,999,514 taught methods for controlling the intensity of the light source to provide a turbidimeter that operates over a broad range of particle concentrations. Kubisiak and Wilson (U.S. Patent No. 5,331,177) describe a analog to digital turbitimeter apparatus that provides a measure of the change in turbidity over time.
Other, more sophisticated, methods involving the analysis of the time and spatial dependence of light attenuation and scattering may provide information on particle size distributions as taught by Strickland et (U.S. Patent No. 5,576,827 and the patents referenced therein). Instrumentation specifically designed for measuring particle and fiber size distributions in low consistency (<%) pulp suspensions by analysis of the time and spatial variation of scattered or absorbed light includes the BTG (British Technology Group) RET-5300 Retention Monitoring System. This instrument employs methods taught by Lundqvist; Pettersson and Fladda U.S. Patent No. 4,318,180. The available SUBSTITUTE SHEET (RULE 26) instruments do not have a means to differentiate concentrations of similarly sized colloidal pitch particles from colloidal clay particles.
In the area of pulp and paper manufacture the maintenance of a level of stability and removal of colloidal pitch is an important objective in the wet-end chemistry programs.
Deposition leading to poor paper machine efficiency is a costly problem that is addressed through numerous strategies involving pulp processing or chemical addition.
Polymer, clay and talc additives are used to prevent pitch accumulation that may lead to deposition and fouling of pulp processing and papermaking equipment. For example, Cutts taught one method for controlling pitch using micro-particle bentonite addition with cationic polymer flocculation, U.S. Patent No. 5,676,796. Another combination of using kaolin as inorganic colloid and poly(diallyldimethyl-ammonium chloride) cationic polymer has been taught by Lamar; Pratt; Weber and Roeder (U.S. Patent No. 4,964,955).
Alternatively, Dreisbach and Barton taught (U.S. Patent No. 5,266,166) a method of preventing pitch deposits by the addition of nonionic polymeric dispersing agent. A
physical process for reducing wood resin pitch from wood process water employing a centrifuge has been taught by Allen and Lapointe (U.S. Patent No. 5,468,396).
The teachings of this invention review the sources and problems associated with wood resin in paper mills and provide further information on physical methods of reducing pitch in pulp and paper process waters.
Chemical and physical methods of controlling pitch may be monitored by turbidity or Zeta or streaming potential or charge measurements. Although surface charge or total charge are important measures of the colloidal stability these measurements do not distinguish colloidal pitch from other, less problematic colloids such as added clay.
Furthermore, turbidity may provide a means of evaluating the total amount of colloidal substance, but pitch colloids are not normally distinguished from other colloids in a turbidity measurement. Typically no instrumental means are employed to supervise chemical methods of controlling pitch. Despite the high cost of chemical treatment programs and the potential downtime caused by over or under dosing, chemical methods of controlling pitch are often invariant over time and substantial swings in wet-end chemistry.
SUBSTITUTE SHEET (RULE 26) There is no colloidal pitch measurement available on-line. The accepted laboratory method of pitch analysis using microscopy was taught by Allen (Allen, L. H., Trans. Tech Sect. CPPA 3(2):32 (1977)). This procedure is time consuming, as it has not yet been successfully automated by computerized image analysis techniques. An instrumental method employing a laser beam to count particles flowing through a capillary has been described by Eisenlauer; Hom; Ditter; Eipel; (U.S. Patent No. 4,752,131). The laser method, known as a pitch counter, requires expensive and specialized instrumentation that is not easily adopted to analysis in an industrial setting.
It is an object of the invention to provide a method of identifying and measuring a characteristic of a colloidal mixture.
It is a further object of this invention to provide a method and means for the rapid determination of an amount of colloidal pitch.
Polychromatic light passed through a colloid sample and detected at an array of wavelengths is a complicated function of the light absorption of the liquid, the light absorption of the particles, the light emission by fluorescence from dissolved or colloidal components and the scattering that may deflect light away from or towards the detector.
The scattering of particles in the range of 0.1-10 times the wavelength of light (Mie scattering) is a complicated function of wavelength, particle size, concentration, and refractive index of the particles and of the medium. Hence when the absorption of the colloidal particles is examined we are looking at both scattering and the UV
absorbance of the particles. The wavelength dependence will be a function of the color of the particles, and also the size of the particles. Mie-scattering theory may be solved to back out the particle size distribution from the wavelength dependence of absorption or scattering for a pure or well-characterized substance. But the theory and the calculations are complex and they are certainly can not be directly applied to analyzing heterogeneous industrial or pulp and paper colloids. The measurements described in this invention provide a means to empirically identify and measure a property related to the particle size, composition, and concentration of a colloidal mixture.
It is an object of the invention to provide a method of identifying and measuring a characteristic of a colloidal mixture.
It is a further object of this invention to provide a method and means for the rapid determination of an amount of colloidal pitch.
Polychromatic light passed through a colloid sample and detected at an array of wavelengths is a complicated function of the light absorption of the liquid, the light absorption of the particles, the light emission by fluorescence from dissolved or colloidal components and the scattering that may deflect light away from or towards the detector.
The scattering of particles in the range of 0.1-10 times the wavelength of light (Mie scattering) is a complicated function of wavelength, particle size, concentration, and refractive index of the particles and of the medium. Hence when the absorption of the colloidal particles is examined we are looking at both scattering and the UV
absorbance of the particles. The wavelength dependence will be a function of the color of the particles, and also the size of the particles. Mie-scattering theory may be solved to back out the particle size distribution from the wavelength dependence of absorption or scattering for a pure or well-characterized substance. But the theory and the calculations are complex and they are certainly can not be directly applied to analyzing heterogeneous industrial or pulp and paper colloids. The measurements described in this invention provide a means to empirically identify and measure a property related to the particle size, composition, and concentration of a colloidal mixture.
SUBSTITUTE SHEET (RULE 26) Summary of the Invention In accordance with the invention there is provided a method for identifying and measuring a characteristic of a colloidal mixture comprising the steps of:
irradiating at-least a first portion of the colloidal mixture with light in an ultraviolet-visible region at a first temperature and obtaining a first measurement of a first wavelength within the ultraviolet-visible region, said first measurement for obtaining a measure of one of an absorption, emission and scattering of the first wavelength when said colloidal mixture is irradiated with the light;
waiting for the temperature of the colloidal mixture to change;
irradiating at least a second portion of the colloidal mixture with light in an ultraviolet-visible region at a second different temperature and obtaining a second measurement of the first wavelength within the ultraviolet-visible region;
said second measurement for obtaining a measure of one of an absorption, emission and scattering of the first wavelength when said colloidal mixture is irradiated with the light;
and determining the characteristic of the colloidal mixture from a relationship including the first measurement and the second measurement.
In accordance with the invention there is further provided a method for identifying and measuring a characteristic of a colloidal mixture comprising the steps of irradiating at least a first portion of the colloidal mixture with light in an ultraviolet-visible region at a first temperature and obtaining at least a first measurement of a first and a second wavelength within the ultraviolet-visible region, said first measurement for obtaining one of an absorption, emission and scattering of the first wavelength when said colloidal mixture is irradiated with the light;
waiting for the temperature of the colloidal mixture to change;
irradiating at least a second portion of the colloidal mixture with light in an ultraviolet-visible region at a second different temperature and obtaining at least a second measurement of the first and the second wavelength within the ultraviolet-visible region, SUBSTITUTE SHEET (RULE 26) said second measurement for obtaining one of an absorption, emission and scattering of the second wavelength when said colloidal mixture is irradiated with the light; and determining the characteristic of the colloidal mixture from a relationship including a ratio of the at least first and second measurement.
In accordance with another aspect of the invention there is provided, an apparatus for identifying and measuring a characteristic of a colloidal mixture comprising:
filtration means for substantially removing fiber from the colloidal mixture;
detecting means for obtaining a first measurement and a second measurement of light in an ultraviolet-visible region, said first measurement for obtaining a measure of one of an absorption, emission and scattering of at least a first wavelength of the light at a first temperature when the colloidal mixture is irradiated with the light, and said second measurement for obtaining a measure of one of an absorption, emission and scattering of the first wavelength of the light at a second different temperature when the colloidal mixture is irradiated with the light; and a suitably programmed processor for determining the characteristic of the colloidal mixture from a relationship including the first and second measurement, said characteristic is a function of a first or second derivative of the at least first and second measurement.
Brief Description of the Drawings Exemplary embodiments of the invention will now be described in accordance with the drawings in which:
Figure 1 presents a block diagram of an on-line sensor/apparatus for colloidal substances as in accordance with the invention;
Figure 2 shows a detailed schematic diagram of the filtration and backflushing unit, a currbackflushing apparatus for the Mott Filtration system;
irradiating at-least a first portion of the colloidal mixture with light in an ultraviolet-visible region at a first temperature and obtaining a first measurement of a first wavelength within the ultraviolet-visible region, said first measurement for obtaining a measure of one of an absorption, emission and scattering of the first wavelength when said colloidal mixture is irradiated with the light;
waiting for the temperature of the colloidal mixture to change;
irradiating at least a second portion of the colloidal mixture with light in an ultraviolet-visible region at a second different temperature and obtaining a second measurement of the first wavelength within the ultraviolet-visible region;
said second measurement for obtaining a measure of one of an absorption, emission and scattering of the first wavelength when said colloidal mixture is irradiated with the light;
and determining the characteristic of the colloidal mixture from a relationship including the first measurement and the second measurement.
In accordance with the invention there is further provided a method for identifying and measuring a characteristic of a colloidal mixture comprising the steps of irradiating at least a first portion of the colloidal mixture with light in an ultraviolet-visible region at a first temperature and obtaining at least a first measurement of a first and a second wavelength within the ultraviolet-visible region, said first measurement for obtaining one of an absorption, emission and scattering of the first wavelength when said colloidal mixture is irradiated with the light;
waiting for the temperature of the colloidal mixture to change;
irradiating at least a second portion of the colloidal mixture with light in an ultraviolet-visible region at a second different temperature and obtaining at least a second measurement of the first and the second wavelength within the ultraviolet-visible region, SUBSTITUTE SHEET (RULE 26) said second measurement for obtaining one of an absorption, emission and scattering of the second wavelength when said colloidal mixture is irradiated with the light; and determining the characteristic of the colloidal mixture from a relationship including a ratio of the at least first and second measurement.
In accordance with another aspect of the invention there is provided, an apparatus for identifying and measuring a characteristic of a colloidal mixture comprising:
filtration means for substantially removing fiber from the colloidal mixture;
detecting means for obtaining a first measurement and a second measurement of light in an ultraviolet-visible region, said first measurement for obtaining a measure of one of an absorption, emission and scattering of at least a first wavelength of the light at a first temperature when the colloidal mixture is irradiated with the light, and said second measurement for obtaining a measure of one of an absorption, emission and scattering of the first wavelength of the light at a second different temperature when the colloidal mixture is irradiated with the light; and a suitably programmed processor for determining the characteristic of the colloidal mixture from a relationship including the first and second measurement, said characteristic is a function of a first or second derivative of the at least first and second measurement.
Brief Description of the Drawings Exemplary embodiments of the invention will now be described in accordance with the drawings in which:
Figure 1 presents a block diagram of an on-line sensor/apparatus for colloidal substances as in accordance with the invention;
Figure 2 shows a detailed schematic diagram of the filtration and backflushing unit, a currbackflushing apparatus for the Mott Filtration system;
SUBSTITUTE SHEET (RULE 26) Figure 3 is a timing diagram depicting the valve sequence of the filtration and backflushing unit;
Figure 4 presents the UV-visible spectra of dissolved sprucelpine extractives obtained by filtration of a colloidal mixture at 0.45 microns;
Figure 5 presents the UV-visible spectrum of dissolved and colloidal spruce/pine extractives at pH 5.4;
Figure 6 shows the UV-visible difference spectrum isolating the absorbance of the colloidal pitch;
Figure 7 shows the UV-visible spectra of dissolved and colloidal pitch at pH
5.4 and different temperatures;
Figure 8 shows the UV-visible difference spectrum showing the difference between the absorbance at 20 C and 80 C ;
Figure 9 shows a comparison of UV absorbance at different temperatures compared as ratios;
Figure IOa presents a plot showing the temperature dependence of the UV-visible absorbance at two wavelengths;
Figure I Ob presents a matrix plot showing the temperature dependence of the UV-visible absorbance of a mixture of wood-resin dissolved and colloidal substances at pH
11;
Figure I Oc presents a plot showing the UV absorbance at 280 nm versus temperature showing the first derivative absorbance-temperature relationship;
SUBSTITUTE SHEET (RULE 26) Figure 11 shows a plot depicting the concentration dependence of the slope (dA/dT) and intercept from a linear regression of the absorbance of a wood-resin suspension obtained at 500 nm and the temperature;
Figure 12 shows a UV-visible difference spectrum from TMP (thermomechanical pulp) white water;
Figure 13 shows a plot depicting the temperature dependence of the absorbance of a TMP
white water at 500 nm;
Figure 14 shows UV-visible spectra of a colloidal mixture of wood-resin with different amounts of added clay;
Figure 15 presents a plot showing the relationship between clay concentration in a pitch/clay mixture and absorbance at 500 nm at two temperatures;
Figure 16 shows a 3-D plot of the UV ratio A35o/A2so versus temperature and concentration;
Figure 17 shows a 3-D plot of UV ratios A274/A280 versus temperature and concentration (TDS);
Figure 18 shows a 3-D plot of UV ratios A230/A500 versus temperature and concentration (MS); and Figure 19 shows a 3-D plot of UV ratios A250/A280 versus temperature and concentration (TDS).
Detailed Description of the Invention SUBSTITUTE SHEET (RULE 26) Figure 17 shows a 3-D plot of UV ratios A274/A230 versus temperature and concentration (TDS);
Figure 18 shows a 3-D plot of UV ratios A230/A500 versus temperature and concentration (TDS); and Figure 19 shows a-" )-D plot of UV ratios A250/A280 versus temperature and concentration (TDS).
Detailed Description of the Invention The method and the apparatus in accordance with the invention provides for on-line measurements of colloidal substances in a liquid sample. This invention is particularly useful for determining or estimating the amount of colloidal substances in pulp or paper mill process water or effluents.
Referring now to Figure 1, a block diagram of such an on-line sensor/apparatus for colloidal substances is depicted. In a preferred embodiment, the apparatus in agreement with the invention is controlled by a computer/processor 10 for sampling, filtration, data acquisition, cleaning, and temperature control.
In a preferred embodiment of the invention the processor 10 has the following characteristics.
The processor is a Computer-Micro-AllianceTM Industrial Computer with 14 slot chassis, 300W/ fans, 14" Industrial Rackmount monitor, and software such as LabviewTM
for WindowsTM Development System, LabviewTM PID Control Toolkit, and PC-DIO and NI-DAQ Software. The input/output hardware used are National InstrumentsTM AT-MIO-50 Multifunction IO board (ISA card), National InstrumentsTM AT-A0-6; 6 channel analog output (ISA card) (this is for the 4-20 mA output to the temperature controller and the Distributed Control system), NationaIInsfrumentsTM NI DIO-24; 24 channel digital input/output (ISA card). This has all the output for the valves and input for the proximity sensors, and an Ocean OpticsTM ADC-500 A/D board with 500 kHz sampling frequency.
This is for communication with the MQ-2000 spectrophotometer.
The sample tubing is shown as thick solid lines, the optical fibre is shown as thick dashed lines, the sequence control is shown as thin dashed lines, and the water flow is shown as thin solid lines. The processor 10 is connected to the sample manifold 12 for controlling the operation of a valve or a plurality of valves (not shown). In a preferred embodiment, six ball valves are actuated in sequence by the processor 10. The sample manifold 12 allows a plurality of water or pulp slurry samples to be sampled on-line from a process. The liquid sample is then delivered from the sample manifold 12 to the filtration and backflushing unit (FBU) 14. The FBU 14 filters the liquid sample to provide a fibre-free liquid sample and returns the remaining sample back into the process. The operation of this FBU
14 is also controlled by the processor 10 and is explained in more detail below, see Figure 2.
The usefulness of the invention could be extended by extraction of liquid samples from a high consistency pulp slurry before final removal of the fiber in the FBU 14.
The FBU 14 delivers the fibre-free liquid sample to a sample manager and cleaning unit (SMCU) 16. The operation of the SMCU 16 is controlled by the processor 12. In one mode of operation the SMCU 16 delivers the liquid sample to a temperature controlled dual UV
cell holder (DUVCH) 18 for obtaining a UV measurement and in another mode of operation it delivers a cleaning fluid to the temperature controlled DUVCH 18 for cleaning said DUVCH. Both, the liquid sample and the cleaning fluid are delivered to the DUVCH 18 by means of a pump, such as a Cole PalmerTM variable speed peristaltic pump P-77962-10.
In a preferred embodiment, the DUVCH 18 has a SciencetechTM custom-built cell holder and a temperature control unit with a Peltier Effect thermoelectric heat pump.
This means that the DUVCH allows for UV measurements to be taken at a plurality of temperatures.
Figure 4 presents the UV-visible spectra of dissolved sprucelpine extractives obtained by filtration of a colloidal mixture at 0.45 microns;
Figure 5 presents the UV-visible spectrum of dissolved and colloidal spruce/pine extractives at pH 5.4;
Figure 6 shows the UV-visible difference spectrum isolating the absorbance of the colloidal pitch;
Figure 7 shows the UV-visible spectra of dissolved and colloidal pitch at pH
5.4 and different temperatures;
Figure 8 shows the UV-visible difference spectrum showing the difference between the absorbance at 20 C and 80 C ;
Figure 9 shows a comparison of UV absorbance at different temperatures compared as ratios;
Figure IOa presents a plot showing the temperature dependence of the UV-visible absorbance at two wavelengths;
Figure I Ob presents a matrix plot showing the temperature dependence of the UV-visible absorbance of a mixture of wood-resin dissolved and colloidal substances at pH
11;
Figure I Oc presents a plot showing the UV absorbance at 280 nm versus temperature showing the first derivative absorbance-temperature relationship;
SUBSTITUTE SHEET (RULE 26) Figure 11 shows a plot depicting the concentration dependence of the slope (dA/dT) and intercept from a linear regression of the absorbance of a wood-resin suspension obtained at 500 nm and the temperature;
Figure 12 shows a UV-visible difference spectrum from TMP (thermomechanical pulp) white water;
Figure 13 shows a plot depicting the temperature dependence of the absorbance of a TMP
white water at 500 nm;
Figure 14 shows UV-visible spectra of a colloidal mixture of wood-resin with different amounts of added clay;
Figure 15 presents a plot showing the relationship between clay concentration in a pitch/clay mixture and absorbance at 500 nm at two temperatures;
Figure 16 shows a 3-D plot of the UV ratio A35o/A2so versus temperature and concentration;
Figure 17 shows a 3-D plot of UV ratios A274/A280 versus temperature and concentration (TDS);
Figure 18 shows a 3-D plot of UV ratios A230/A500 versus temperature and concentration (MS); and Figure 19 shows a 3-D plot of UV ratios A250/A280 versus temperature and concentration (TDS).
Detailed Description of the Invention SUBSTITUTE SHEET (RULE 26) Figure 17 shows a 3-D plot of UV ratios A274/A230 versus temperature and concentration (TDS);
Figure 18 shows a 3-D plot of UV ratios A230/A500 versus temperature and concentration (TDS); and Figure 19 shows a-" )-D plot of UV ratios A250/A280 versus temperature and concentration (TDS).
Detailed Description of the Invention The method and the apparatus in accordance with the invention provides for on-line measurements of colloidal substances in a liquid sample. This invention is particularly useful for determining or estimating the amount of colloidal substances in pulp or paper mill process water or effluents.
Referring now to Figure 1, a block diagram of such an on-line sensor/apparatus for colloidal substances is depicted. In a preferred embodiment, the apparatus in agreement with the invention is controlled by a computer/processor 10 for sampling, filtration, data acquisition, cleaning, and temperature control.
In a preferred embodiment of the invention the processor 10 has the following characteristics.
The processor is a Computer-Micro-AllianceTM Industrial Computer with 14 slot chassis, 300W/ fans, 14" Industrial Rackmount monitor, and software such as LabviewTM
for WindowsTM Development System, LabviewTM PID Control Toolkit, and PC-DIO and NI-DAQ Software. The input/output hardware used are National InstrumentsTM AT-MIO-50 Multifunction IO board (ISA card), National InstrumentsTM AT-A0-6; 6 channel analog output (ISA card) (this is for the 4-20 mA output to the temperature controller and the Distributed Control system), NationaIInsfrumentsTM NI DIO-24; 24 channel digital input/output (ISA card). This has all the output for the valves and input for the proximity sensors, and an Ocean OpticsTM ADC-500 A/D board with 500 kHz sampling frequency.
This is for communication with the MQ-2000 spectrophotometer.
The sample tubing is shown as thick solid lines, the optical fibre is shown as thick dashed lines, the sequence control is shown as thin dashed lines, and the water flow is shown as thin solid lines. The processor 10 is connected to the sample manifold 12 for controlling the operation of a valve or a plurality of valves (not shown). In a preferred embodiment, six ball valves are actuated in sequence by the processor 10. The sample manifold 12 allows a plurality of water or pulp slurry samples to be sampled on-line from a process. The liquid sample is then delivered from the sample manifold 12 to the filtration and backflushing unit (FBU) 14. The FBU 14 filters the liquid sample to provide a fibre-free liquid sample and returns the remaining sample back into the process. The operation of this FBU
14 is also controlled by the processor 10 and is explained in more detail below, see Figure 2.
The usefulness of the invention could be extended by extraction of liquid samples from a high consistency pulp slurry before final removal of the fiber in the FBU 14.
The FBU 14 delivers the fibre-free liquid sample to a sample manager and cleaning unit (SMCU) 16. The operation of the SMCU 16 is controlled by the processor 12. In one mode of operation the SMCU 16 delivers the liquid sample to a temperature controlled dual UV
cell holder (DUVCH) 18 for obtaining a UV measurement and in another mode of operation it delivers a cleaning fluid to the temperature controlled DUVCH 18 for cleaning said DUVCH. Both, the liquid sample and the cleaning fluid are delivered to the DUVCH 18 by means of a pump, such as a Cole PalmerTM variable speed peristaltic pump P-77962-10.
In a preferred embodiment, the DUVCH 18 has a SciencetechTM custom-built cell holder and a temperature control unit with a Peltier Effect thermoelectric heat pump.
This means that the DUVCH allows for UV measurements to be taken at a plurality of temperatures.
Alternatively, the temperature in the DUVCH 18 is controlled by a water flow system as shown in Figure 1. The DUVCH has 2 UV cells, one 1.0 mm flow-through quartz UV
cell (UV region, short wavelength)and another 10.0 mm flow-through quartz UV cell (visible region, long wavelength). This is desired since the absorbance in the visible region is very low and requires a cell having a longer path length and vice versa, the absorbance in the UV
region is very intense and a cell having a shorter path length is more desirable. The processor 10 controls the operation of a temperature controller 20. This temperature controller 20 is connected to the DUVCH 18 for controlling the temperature therein as. One possible temperature controller for use with this invention is a Wavelength ElectronicsTM
Model LFI-3526 Temperature Controller.
The DUVCH 18 is connected to a UV-visible light source (UV-vis LS) 22, such as a Deuterium-Tungsten combination light source, and a spectrophotometer 24, such as a Rack Mount Ocean OpticsTM spectrometer, through optical fibre cables suitable for good transmission of light at 230 nm. The UV-vis LS 22 irradiates the DUVCH 18 for obtaining a UV measurement of the liquid sample. The spectrophotometer 24 measures the UV
light upon passing the liquid sample. The optical system, i.e. the UV-vis LS 22 and the spectrophotometer 24 are controlled by a LabviewTM VI software.
The processor 10, the DUVCH 18, the temperature controller 20, the UV-vis LS
22, and the spectrophotometer 24 are placed within a constant temperature enclosure (CTE) 26, a Hoffmann EnclosureTM with air conditioning for temperature control. The CTE 26 prevents the apparatus from being effected by unwanted fluctuations in the temperature.
This is done to prevent a possible damage to the processor 10 from excessive heat or humidity in industrial applications, such as in pulp and paper processing, and to obtain reproducible results. The CTE 26 is needed as in accordance with an embodiment of the invention because the response of spectrophotometer detector elements varies with temperature.
cell (UV region, short wavelength)and another 10.0 mm flow-through quartz UV cell (visible region, long wavelength). This is desired since the absorbance in the visible region is very low and requires a cell having a longer path length and vice versa, the absorbance in the UV
region is very intense and a cell having a shorter path length is more desirable. The processor 10 controls the operation of a temperature controller 20. This temperature controller 20 is connected to the DUVCH 18 for controlling the temperature therein as. One possible temperature controller for use with this invention is a Wavelength ElectronicsTM
Model LFI-3526 Temperature Controller.
The DUVCH 18 is connected to a UV-visible light source (UV-vis LS) 22, such as a Deuterium-Tungsten combination light source, and a spectrophotometer 24, such as a Rack Mount Ocean OpticsTM spectrometer, through optical fibre cables suitable for good transmission of light at 230 nm. The UV-vis LS 22 irradiates the DUVCH 18 for obtaining a UV measurement of the liquid sample. The spectrophotometer 24 measures the UV
light upon passing the liquid sample. The optical system, i.e. the UV-vis LS 22 and the spectrophotometer 24 are controlled by a LabviewTM VI software.
The processor 10, the DUVCH 18, the temperature controller 20, the UV-vis LS
22, and the spectrophotometer 24 are placed within a constant temperature enclosure (CTE) 26, a Hoffmann EnclosureTM with air conditioning for temperature control. The CTE 26 prevents the apparatus from being effected by unwanted fluctuations in the temperature.
This is done to prevent a possible damage to the processor 10 from excessive heat or humidity in industrial applications, such as in pulp and paper processing, and to obtain reproducible results. The CTE 26 is needed as in accordance with an embodiment of the invention because the response of spectrophotometer detector elements varies with temperature.
11 AME14DFD SHtt-;-Exemplary Detector Specifications:
Detector: 2048-element linear silicon CCD array CCD elements: 2048 elements @ 12.5 mm x 200 mm per element Well depth (@600 run): 160,000 photons Sensitivity (estimated):86 photons/count; 2.9 x 10-17 joule/count;
2.9 x 10-17 watts/count (for 1-second integration) Effective range: 200-1100 nm Integration time: 4 milliseconds to 60 seconds (with 500 kHz A/D card) 20 milliseconds to 60 seconds (with 100 kHz PCMCIA A/D card) (shorter integration times available with custom electronic interface) Exemplary Optics Specifications:
Gratings: multiple grating choices, optimized for UV, VIS or Shortwave NIR
Slits: 10, 25, 50, 100, 200 mm widths (slit height is 1000 mm); alternative option is no slit (optical fiber is entrance aperture) Order-sorting: single-piece, multi-bandpass detector coating for applications from - 200-850 nm (available only with 600-line gratings) or Schott glass longpass filters (installed or loose) Resolution: -0.3 nm-10.0 nm FWHM (depends on groove density of grating and diameter of fiber or width of slit) Stray light: < 0.05% at 600 nm; < 0.10% at 435 nm Fiber optic connector: SMA 905 to single-strand optical fiber (0.22 NA) Exemplary Rack-mount Housing Specifications:
Width: 17-5/8"
Depth: 10-1/6"
Weight: -12 lb.
* With 8 spectrometer channels installed.
Detector: 2048-element linear silicon CCD array CCD elements: 2048 elements @ 12.5 mm x 200 mm per element Well depth (@600 run): 160,000 photons Sensitivity (estimated):86 photons/count; 2.9 x 10-17 joule/count;
2.9 x 10-17 watts/count (for 1-second integration) Effective range: 200-1100 nm Integration time: 4 milliseconds to 60 seconds (with 500 kHz A/D card) 20 milliseconds to 60 seconds (with 100 kHz PCMCIA A/D card) (shorter integration times available with custom electronic interface) Exemplary Optics Specifications:
Gratings: multiple grating choices, optimized for UV, VIS or Shortwave NIR
Slits: 10, 25, 50, 100, 200 mm widths (slit height is 1000 mm); alternative option is no slit (optical fiber is entrance aperture) Order-sorting: single-piece, multi-bandpass detector coating for applications from - 200-850 nm (available only with 600-line gratings) or Schott glass longpass filters (installed or loose) Resolution: -0.3 nm-10.0 nm FWHM (depends on groove density of grating and diameter of fiber or width of slit) Stray light: < 0.05% at 600 nm; < 0.10% at 435 nm Fiber optic connector: SMA 905 to single-strand optical fiber (0.22 NA) Exemplary Rack-mount Housing Specifications:
Width: 17-5/8"
Depth: 10-1/6"
Weight: -12 lb.
* With 8 spectrometer channels installed.
AME Fn _, Exemplary Computer and Data Acquisition:
a) Computer-Micro-AllianceTM Industrial Computer with 14 slot chassis, 300W/
fans, b) Monitor. 14" Industrial Rackmount monitor.
c) software i) LabviewTM for Windows Development System ii) LabviewTM PID Control Toolkit iii) PC-DIO and NI-DAQ Software d) input/output hardware i) National InstrumentsTM AT-MIO-16XE-50 Multifunction IO board (ISA card) ii) National InstrumentsTM AT-A0-6; 6 channel analog output (ISA card) (this is for the 4-20 mA output to the temperature controller and the Distributed Control system) iii) National InstrumentsTM NI DIO-24; 24 channel digital input/output (ISA
card).
(This has all the output for valves and input for the proximity sensors.) iv) Ocean OpticsTM ADC-500. A/D board with 500 kHz sampling frequency. This is for communication with the MQ-2000 spectrophotometer.
Now turning to Figure 2, the FBU 14 is presented in a more detailed manner.
The FBU in Figure 2 is a backflushing apparatus for the MottTM Filtration system. The Filtration and backflushing unit provides a fiber-free liquid sample. The colloidal liquid is separated from the fiber by cross-flow filtration using a 5 or 10 micron MottTM sintered metal filter 109.
Tangential flow through the filter 109 is greater than 20 liters/minute and preferably >40 liters/min. The flow across the filter 109 is 10-200 ml/minute. The backflushing unit allows a reservoir 112 to fill with filtrate. Then the sample valve 104 is opened for 2 seconds to deliver 1-20 ml of colloidal sample to the DUVCH 18. The sampling period is followed by a delay period during which the filter 109 is closed and temperature dependent UV
measurements are made by the spectrophotometer 24 using the recently obtained sample.
After the measuring delay the reservoir 112 is purged by opening an air valve 102 (labeled purge air in) and backpulsing the filtrate backwards through the filter 109 for a specified . .
-= .
period of at least 1 second but no longer than until the filtrate reaches the bottom proximity sensor 106. Backpulse pressure at pressure transmitter 107 is preferably greater than normal pressure measured at pressure transmitter 108. The bottom proximity sensor 106 relays a signal to the system controller/processor 10 to close the purge air valve 102 and open the reservoir vent valve 101. At this point the filter valve 103 is opened and the reservoir 112 fills until the top proximity sensor 105 detects the filtrate. The full sample valve 104 immediately opens to obtain another sample of the colloid material.
The valve sequence is shown in Figure 3 which is a detailed sketch of the operation of valves 101-104, the top proximity sensor 105, the bottom proximity sensor106, the filtrate pressure sensor, and the inlet pressure sensor for the various steps in a filtration and measurement, cycle, such as filling, sampling, measurement, and purge.
There are a number of methods of obtaining a fiber-free colloidal sample. In a preferred methods a sample is obtained without filtering the liquid through a pulp mat or filter cake. It has been found that a pulp mat will significantly change the sample.
Centrifugal methods are ideal, but continuous solids ejecting centrifuges are expensive. A sand filter will remove fiber, but the backwashing cycle would have to be frequent to prevent filtration through a fiber mat at the top of the sand. Backwashing would have to be done with the filtrate.
The characteristics of the FBU are as follows:
a) filters: MottTM 7000-1/2-24-5.0 or MottTM 7000-1/2-24-10.0 (10 micron) b) valves (stainless steel):
i) 4 '/2" NPT, 24 volt solenoid, normally closed, TelktronTM
ii) 3 3/8 tubing, ball valve, pressure actuated WhiteyTM 131 SR, normally closed, stainless steel iii) 1 3/8 tubing, ball valve, pressure actuated WhiteyTM 131 SR, normally open, stainless steel AMENDED SHEET
c) sensors: i) pressure sensor 107 and 108, 0-60 psi Cole ParmerTM Instrument Co.
Model 68001, 4-20 mA output ii) proximity sensor 105 and 106, DwyerTM capacitive proximity switch model Colloidal components are normally measured by turbidity or light-scattering techniques to give an overall composition or amount of colloidal components. However, colloidal substances include inorganic colloids, such as clays, insoluble salts (CaSO4), or fillers, and organic colloids, such as pitch. Prior art techniques cannot readily distinguish between these two classes of colloidal matter. Various forms of turbidity measurements, light scattering, and electrokinetic separation are used to measure a quantity of colloidal particles. Using hydrodynamic, electrokinetic separation or advanced light scattering techniques some information can be obtained about the particle size distribution. These methods are not suitable to distinguish chemically between the different types of particles.
The method and the apparatus in accordance with the invention allow to empirically identify and measure a property related to the size, composition, and concentration of a colloidal mixture.
It should be recognized that pitch is a generic term and the composition of an individual pitch particle may vary from relatively pure mixtures of fresh resin and fatty acids to heterogeneous agglomerations of wood extractives, wood-derived lignin and hemicellulose, salt, cationic polymer and filler particle. The degree that temperature will alter the equilibria between colloidal pitch and dissolved substances is a complicated function of solution conditions and the composition of the pitch particle. For example, our laboratory tests have shown that temperature changes on the same mixture at different pH values produce a different Dabsorbanc relationship. Furthermore, it has been reported that Otemperature hemicellulose components may stabilize wood colloidal resin (Sundberg, K;
Thornton, J.;
Holmbom, B.; and Ekman, R. Journal of Pulp and Paper Science Vol. 22 Number 7, 1996, Pp J226-J230. Effects of wood polysaccharides on the stability of colloidal wood resin). We have found, however,.- that variatiows-of-pH, and-ionic strength that typically occur in a pulp 4. Defining an relative amount of colloidal pitch as a function of a concentration determined by the dA/dT method and the concentration determined by the total absorbance or turbidity at a given temperature; and 5. A.system that has been characterized is simply analyzed following steps 2, 3 and 4.
And, in accordance with an embodiment of the invention, the steps in the identification of a transition temperature or a metastable mixture include:
1. Identification of a suitable wavelengths for the analysis by identifying a region with maximum and minimum change in absorbance with respect to temperature;
2. Measurement of the dA/dT, and d2A/dT2 to determine the point of the minimum rate of change in the slope. The point at which d2A/dT2 is zero is the temperature that is characteristic of the phase change;
3. Plot of the ratio of the absorbance at two wavelengths representing maximum and minimum values in the difference or ratio spectra obtained comparison of the absorbance at one temperature from the absorbance at another temperature. This plot provides a means to emphasize the change in the optical properties of the colloid relative to the composition of the mixture as a whole. A change in the slope of this plot indicates the initiation or termination of a phase transition.
For example, a t-butyl ether extract of wood resin is obtained by successive extraction of a sample of white water obtained from a spruce/pine thermomechanical pulp mill. The extract is concentrated and then the resin is redispersed in pH 4.85 acetic acid aqueous buffer by sonication. A stock mixture of the dissolved and colloidal wood resin is diluted with buffer to six different concentrations. The UV-visible absorbance spectra of the colloidal mixture are obtained directly from these mixtures at room temperature and are presented in Figure 5. The colloidal mixtures of different concentrations are filtered with a 0.45 micron syringe filter to obtain solutions of dissolved wood resin and their UV-visible spectra are shown in Figure 4. The signal from dissolved and colloidal matter followed the expected linear relationship with concentration. The attenuation of the signal due to the colloidal substance alone is obtained by subtraction of the signal from the filtered and unfiltered samples. An example for this is presented in Figure 6. In this example, the signal above 350 rim is taken to primarily represent turbidity or attenuation SUBSTITUTE SHEET (RULE 26) of the light due to the Mie scattering of the particles. The peaks at 230 and 280 nm indicate that the chromophore containing wood extractives in the colloidal particles adsorbs light.
The temperature dependence of wood resin colloidal mixtures were characterized at different pH values, ionic strengths values, and with different amounts of clay relative to pitch. An example of the temperature dependence of the UV-visible spectrum of wood resin colloid mixtures is shown in Figure 7. The wavelength dependence of the temperature variation of the UV-visible spectrum can be examined as a difference or a ratio of the spectra taken at two wavelengths as shown in Figure 8 or Figure 9. Both methods show a similar pattern. In the UV region the changes due to a decrease in scattering are compensated by an increase in the UV absorbance. This is likely due to the greater absorbance of the dissolved materials compared to the colloidal materials.
The temperature dependence of the UV absorbance of the extracted pitch is plotted for two wavelengths in Figure I Oa. The variation at the 242 nm minimum in the difference spectrum shown in Figure 8 and 9 amounts to less than 3% of the total absorbance at that wavelength. On the other hand, the variation at 500 nm is approximately 25% of the absorbance at that wavelength. The variation of the absorbance at 500 nm is substantially linear with changes in temperature ranges between 40 C and 80 C. It is within this linear region that two measurements provide a slope (dA/dT) that is proportional to the concentration of colloidal pitch. The slope (dA500 /dT) and intercept lim Abss are temperature--O
calculated from the temperature dependence of multiple concentrations of colloidal pitch.
The slope (dA/dT) and the intercept plotted against the relative concentration are shown in Figure 11. These original results demonstrate, for the first time, that the temperature variation of the absorbance or turbidity of colloidal pitch is proportional to the amount of pitch in the mixture. The results showing the variation of the intercept with concentration confirm the expected result that the turbidity is a function of the colloid concentration.
There, is a small non-linearity of the dA/dT with respect to concentration at unusually SUBSTITUTE SHEET (RULE 26) high concentrations. Measurements are normally made in the concentration region that produces dA/dT values between 0.0 and -0.0025.
Multiple regressions fit to temperature and concentration for absorbance measurements made for UV data at eight representative wavelengths. Exemplary regressions are presented below:
A500 =0.033499 +.152465*c -.0011 80*T-.00465 1 *c2 A450=0=04060 + =195378*c -.001387*T-.004470*c2 A350=0.084676 + .674637*c -.002693*T-.006859*c2 A300=0.073323 + 1.584808*c -.002703*T-.013407*c2 A280=0.26034 + 3.054065*c -.005966*T
A274=0.22676 + 3.007551 *c -.006236*T-.019463*c2 A250=0.05867+ 2.893070*c-.003785*T-.039531*c2 A230=0.60932 + 7.328961 *c-.019106*T-.141523*c2 Multiple regression for UV absorbance at selected wavelengths for TMP white water pitch. The equations are a function of concentration, temperature and the square of the concentration. Regression correlation coefficients of >0.99 were found. The coefficient for the concentration squared indicates interaction between components similar to a second virial coefficient.
In order to make a colloid concentration measurement using this technique a temperature change must significantly perturb an equilibrium between dissolved and colloidal components. The dissolved and colloidal components must have measurably different properties. The material, solution conditions determine if such a change occurs and the temperature range and wavelength must be selected to best measure the phase change.
The optimal wavelength is selected by choosing a maximum or minimum from the ratio or difference of two spectra obtained at two temperatures as shown in figures 8 and 9.
The optimal temperature range is chosen by identification of a temperature region around SUBSTITUTE SHEET (RULE 26) a zero point in the second derivative of the absorbance with respect to temperature. An example of the method of selection of a temperature region follows.
Figure I Ob shows a matrix plot of the temperature variation of the UV
absorbance at pH
11Ø Plots A-D show a variation in the shape of the curves of the absorbance at different wavelengths with respect to temperature (abscissa). At this mixture there is a relatively complete transition between the dissolved and colloidal components. In particular, the slope falls off significantly at the temperature extremes for the absorbance values at 280 nm. Plot D in figure l Ob is examined in more detail in Figure I Oc.
Inspection of the graph indicates that two measurements made in the region between 20 C and 40 C
would give different results than measurements made between 40 C and 60 C. The best region to measure the transition between the colloidal and liquid state is selected from the region where the slope is most constant. This occurs around the central point in the transition that is defined by the minimum in the first derivative function plotted in figure 10c. This minimum in the first derivative is the zero point in the second derivative function that occurs, for the data shown in figure l Oc at 50 C. Secondary zero points in the second derivative occur around 23 C and 74 C but these are small regions with very small changes in the absorbance.
The matrix plot presented in Figure I Ob provides further means for the identification of phase changes in colloidal mixtures. In six plots (F, G, H, J, K, M) the absorbance at one wavelength is plotted against another. The linear relationship in plot G shows-that the component which provides the dominant temperature variation contributes to both of these wavelengths at all temperatures. Plot H, on the other hand shows that the relative change absorbance is linear in two regions, but the relationship appears to change in an intermediate region. The relative absorbance at two wavelengths may be captured in a ratio as is plotted against temperature in plot E. At the simplest level the ratio of absorbance values provides a means to inspect the relative change in one component with respect to the change in another component. The linear region with little slope in the central portion of the plot corresponds to a temperature region where changes in the absorbance at 500 nm directly correspond with a change in the absorbance at 280 nm.
a) Computer-Micro-AllianceTM Industrial Computer with 14 slot chassis, 300W/
fans, b) Monitor. 14" Industrial Rackmount monitor.
c) software i) LabviewTM for Windows Development System ii) LabviewTM PID Control Toolkit iii) PC-DIO and NI-DAQ Software d) input/output hardware i) National InstrumentsTM AT-MIO-16XE-50 Multifunction IO board (ISA card) ii) National InstrumentsTM AT-A0-6; 6 channel analog output (ISA card) (this is for the 4-20 mA output to the temperature controller and the Distributed Control system) iii) National InstrumentsTM NI DIO-24; 24 channel digital input/output (ISA
card).
(This has all the output for valves and input for the proximity sensors.) iv) Ocean OpticsTM ADC-500. A/D board with 500 kHz sampling frequency. This is for communication with the MQ-2000 spectrophotometer.
Now turning to Figure 2, the FBU 14 is presented in a more detailed manner.
The FBU in Figure 2 is a backflushing apparatus for the MottTM Filtration system. The Filtration and backflushing unit provides a fiber-free liquid sample. The colloidal liquid is separated from the fiber by cross-flow filtration using a 5 or 10 micron MottTM sintered metal filter 109.
Tangential flow through the filter 109 is greater than 20 liters/minute and preferably >40 liters/min. The flow across the filter 109 is 10-200 ml/minute. The backflushing unit allows a reservoir 112 to fill with filtrate. Then the sample valve 104 is opened for 2 seconds to deliver 1-20 ml of colloidal sample to the DUVCH 18. The sampling period is followed by a delay period during which the filter 109 is closed and temperature dependent UV
measurements are made by the spectrophotometer 24 using the recently obtained sample.
After the measuring delay the reservoir 112 is purged by opening an air valve 102 (labeled purge air in) and backpulsing the filtrate backwards through the filter 109 for a specified . .
-= .
period of at least 1 second but no longer than until the filtrate reaches the bottom proximity sensor 106. Backpulse pressure at pressure transmitter 107 is preferably greater than normal pressure measured at pressure transmitter 108. The bottom proximity sensor 106 relays a signal to the system controller/processor 10 to close the purge air valve 102 and open the reservoir vent valve 101. At this point the filter valve 103 is opened and the reservoir 112 fills until the top proximity sensor 105 detects the filtrate. The full sample valve 104 immediately opens to obtain another sample of the colloid material.
The valve sequence is shown in Figure 3 which is a detailed sketch of the operation of valves 101-104, the top proximity sensor 105, the bottom proximity sensor106, the filtrate pressure sensor, and the inlet pressure sensor for the various steps in a filtration and measurement, cycle, such as filling, sampling, measurement, and purge.
There are a number of methods of obtaining a fiber-free colloidal sample. In a preferred methods a sample is obtained without filtering the liquid through a pulp mat or filter cake. It has been found that a pulp mat will significantly change the sample.
Centrifugal methods are ideal, but continuous solids ejecting centrifuges are expensive. A sand filter will remove fiber, but the backwashing cycle would have to be frequent to prevent filtration through a fiber mat at the top of the sand. Backwashing would have to be done with the filtrate.
The characteristics of the FBU are as follows:
a) filters: MottTM 7000-1/2-24-5.0 or MottTM 7000-1/2-24-10.0 (10 micron) b) valves (stainless steel):
i) 4 '/2" NPT, 24 volt solenoid, normally closed, TelktronTM
ii) 3 3/8 tubing, ball valve, pressure actuated WhiteyTM 131 SR, normally closed, stainless steel iii) 1 3/8 tubing, ball valve, pressure actuated WhiteyTM 131 SR, normally open, stainless steel AMENDED SHEET
c) sensors: i) pressure sensor 107 and 108, 0-60 psi Cole ParmerTM Instrument Co.
Model 68001, 4-20 mA output ii) proximity sensor 105 and 106, DwyerTM capacitive proximity switch model Colloidal components are normally measured by turbidity or light-scattering techniques to give an overall composition or amount of colloidal components. However, colloidal substances include inorganic colloids, such as clays, insoluble salts (CaSO4), or fillers, and organic colloids, such as pitch. Prior art techniques cannot readily distinguish between these two classes of colloidal matter. Various forms of turbidity measurements, light scattering, and electrokinetic separation are used to measure a quantity of colloidal particles. Using hydrodynamic, electrokinetic separation or advanced light scattering techniques some information can be obtained about the particle size distribution. These methods are not suitable to distinguish chemically between the different types of particles.
The method and the apparatus in accordance with the invention allow to empirically identify and measure a property related to the size, composition, and concentration of a colloidal mixture.
It should be recognized that pitch is a generic term and the composition of an individual pitch particle may vary from relatively pure mixtures of fresh resin and fatty acids to heterogeneous agglomerations of wood extractives, wood-derived lignin and hemicellulose, salt, cationic polymer and filler particle. The degree that temperature will alter the equilibria between colloidal pitch and dissolved substances is a complicated function of solution conditions and the composition of the pitch particle. For example, our laboratory tests have shown that temperature changes on the same mixture at different pH values produce a different Dabsorbanc relationship. Furthermore, it has been reported that Otemperature hemicellulose components may stabilize wood colloidal resin (Sundberg, K;
Thornton, J.;
Holmbom, B.; and Ekman, R. Journal of Pulp and Paper Science Vol. 22 Number 7, 1996, Pp J226-J230. Effects of wood polysaccharides on the stability of colloidal wood resin). We have found, however,.- that variatiows-of-pH, and-ionic strength that typically occur in a pulp 4. Defining an relative amount of colloidal pitch as a function of a concentration determined by the dA/dT method and the concentration determined by the total absorbance or turbidity at a given temperature; and 5. A.system that has been characterized is simply analyzed following steps 2, 3 and 4.
And, in accordance with an embodiment of the invention, the steps in the identification of a transition temperature or a metastable mixture include:
1. Identification of a suitable wavelengths for the analysis by identifying a region with maximum and minimum change in absorbance with respect to temperature;
2. Measurement of the dA/dT, and d2A/dT2 to determine the point of the minimum rate of change in the slope. The point at which d2A/dT2 is zero is the temperature that is characteristic of the phase change;
3. Plot of the ratio of the absorbance at two wavelengths representing maximum and minimum values in the difference or ratio spectra obtained comparison of the absorbance at one temperature from the absorbance at another temperature. This plot provides a means to emphasize the change in the optical properties of the colloid relative to the composition of the mixture as a whole. A change in the slope of this plot indicates the initiation or termination of a phase transition.
For example, a t-butyl ether extract of wood resin is obtained by successive extraction of a sample of white water obtained from a spruce/pine thermomechanical pulp mill. The extract is concentrated and then the resin is redispersed in pH 4.85 acetic acid aqueous buffer by sonication. A stock mixture of the dissolved and colloidal wood resin is diluted with buffer to six different concentrations. The UV-visible absorbance spectra of the colloidal mixture are obtained directly from these mixtures at room temperature and are presented in Figure 5. The colloidal mixtures of different concentrations are filtered with a 0.45 micron syringe filter to obtain solutions of dissolved wood resin and their UV-visible spectra are shown in Figure 4. The signal from dissolved and colloidal matter followed the expected linear relationship with concentration. The attenuation of the signal due to the colloidal substance alone is obtained by subtraction of the signal from the filtered and unfiltered samples. An example for this is presented in Figure 6. In this example, the signal above 350 rim is taken to primarily represent turbidity or attenuation SUBSTITUTE SHEET (RULE 26) of the light due to the Mie scattering of the particles. The peaks at 230 and 280 nm indicate that the chromophore containing wood extractives in the colloidal particles adsorbs light.
The temperature dependence of wood resin colloidal mixtures were characterized at different pH values, ionic strengths values, and with different amounts of clay relative to pitch. An example of the temperature dependence of the UV-visible spectrum of wood resin colloid mixtures is shown in Figure 7. The wavelength dependence of the temperature variation of the UV-visible spectrum can be examined as a difference or a ratio of the spectra taken at two wavelengths as shown in Figure 8 or Figure 9. Both methods show a similar pattern. In the UV region the changes due to a decrease in scattering are compensated by an increase in the UV absorbance. This is likely due to the greater absorbance of the dissolved materials compared to the colloidal materials.
The temperature dependence of the UV absorbance of the extracted pitch is plotted for two wavelengths in Figure I Oa. The variation at the 242 nm minimum in the difference spectrum shown in Figure 8 and 9 amounts to less than 3% of the total absorbance at that wavelength. On the other hand, the variation at 500 nm is approximately 25% of the absorbance at that wavelength. The variation of the absorbance at 500 nm is substantially linear with changes in temperature ranges between 40 C and 80 C. It is within this linear region that two measurements provide a slope (dA/dT) that is proportional to the concentration of colloidal pitch. The slope (dA500 /dT) and intercept lim Abss are temperature--O
calculated from the temperature dependence of multiple concentrations of colloidal pitch.
The slope (dA/dT) and the intercept plotted against the relative concentration are shown in Figure 11. These original results demonstrate, for the first time, that the temperature variation of the absorbance or turbidity of colloidal pitch is proportional to the amount of pitch in the mixture. The results showing the variation of the intercept with concentration confirm the expected result that the turbidity is a function of the colloid concentration.
There, is a small non-linearity of the dA/dT with respect to concentration at unusually SUBSTITUTE SHEET (RULE 26) high concentrations. Measurements are normally made in the concentration region that produces dA/dT values between 0.0 and -0.0025.
Multiple regressions fit to temperature and concentration for absorbance measurements made for UV data at eight representative wavelengths. Exemplary regressions are presented below:
A500 =0.033499 +.152465*c -.0011 80*T-.00465 1 *c2 A450=0=04060 + =195378*c -.001387*T-.004470*c2 A350=0.084676 + .674637*c -.002693*T-.006859*c2 A300=0.073323 + 1.584808*c -.002703*T-.013407*c2 A280=0.26034 + 3.054065*c -.005966*T
A274=0.22676 + 3.007551 *c -.006236*T-.019463*c2 A250=0.05867+ 2.893070*c-.003785*T-.039531*c2 A230=0.60932 + 7.328961 *c-.019106*T-.141523*c2 Multiple regression for UV absorbance at selected wavelengths for TMP white water pitch. The equations are a function of concentration, temperature and the square of the concentration. Regression correlation coefficients of >0.99 were found. The coefficient for the concentration squared indicates interaction between components similar to a second virial coefficient.
In order to make a colloid concentration measurement using this technique a temperature change must significantly perturb an equilibrium between dissolved and colloidal components. The dissolved and colloidal components must have measurably different properties. The material, solution conditions determine if such a change occurs and the temperature range and wavelength must be selected to best measure the phase change.
The optimal wavelength is selected by choosing a maximum or minimum from the ratio or difference of two spectra obtained at two temperatures as shown in figures 8 and 9.
The optimal temperature range is chosen by identification of a temperature region around SUBSTITUTE SHEET (RULE 26) a zero point in the second derivative of the absorbance with respect to temperature. An example of the method of selection of a temperature region follows.
Figure I Ob shows a matrix plot of the temperature variation of the UV
absorbance at pH
11Ø Plots A-D show a variation in the shape of the curves of the absorbance at different wavelengths with respect to temperature (abscissa). At this mixture there is a relatively complete transition between the dissolved and colloidal components. In particular, the slope falls off significantly at the temperature extremes for the absorbance values at 280 nm. Plot D in figure l Ob is examined in more detail in Figure I Oc.
Inspection of the graph indicates that two measurements made in the region between 20 C and 40 C
would give different results than measurements made between 40 C and 60 C. The best region to measure the transition between the colloidal and liquid state is selected from the region where the slope is most constant. This occurs around the central point in the transition that is defined by the minimum in the first derivative function plotted in figure 10c. This minimum in the first derivative is the zero point in the second derivative function that occurs, for the data shown in figure l Oc at 50 C. Secondary zero points in the second derivative occur around 23 C and 74 C but these are small regions with very small changes in the absorbance.
The matrix plot presented in Figure I Ob provides further means for the identification of phase changes in colloidal mixtures. In six plots (F, G, H, J, K, M) the absorbance at one wavelength is plotted against another. The linear relationship in plot G shows-that the component which provides the dominant temperature variation contributes to both of these wavelengths at all temperatures. Plot H, on the other hand shows that the relative change absorbance is linear in two regions, but the relationship appears to change in an intermediate region. The relative absorbance at two wavelengths may be captured in a ratio as is plotted against temperature in plot E. At the simplest level the ratio of absorbance values provides a means to inspect the relative change in one component with respect to the change in another component. The linear region with little slope in the central portion of the plot corresponds to a temperature region where changes in the absorbance at 500 nm directly correspond with a change in the absorbance at 280 nm.
SUBSTITUTE SHEET (RULE 26) Additional techniques to obtain accurate and reproducible measurements are learned through experience of applying these measurement techniques at a paper mill.
Trial experiments were conducted at a paper mill using white water manually filtered on a Whatman 41 filter paper. This filter paper has a nominal size cut-off of approximately 20 microns. The results are exemplified by the difference spectrum in Figure 12.
This spectrum was obtained with a 1 mm UV cell on a Cary 1 spectrophotometer. This spectrum shows the same minimum points as the difference spectrum in Figures 8 and 9.
However, in this case the relative absorbance at long wavelengths is much lower. The difference spectrum demonstrates that the temperature change necessary to get accurate measurements must be at least 30 degrees C. Furthermore, a long path UV cell (10 or 20 mm) is used to increase the accuracy of the measurements made at long wavelengths.
Scatter in the mill data required to obtain dA/dT is shown in the Figure 13.
Figure 14 shows the spectral effects of adding multiples of a clay concentration to a colloidal pitch solution. The absorbance changes are nearly linear with clay concentration and relatively monotonic with wavelength. Clay and fillers scatter light well and absorb little light compared to colloidal pitch.
Figure 15 shows absorbance at 500 nm for different concentrations of clay in a colloidal pitch mixture. The total absorbance is linear with clay concentration. The temperature variation, representing the constant amount of pitch, is shown by the gap between the absorbance at 20 C and 80 C. Although the size of the gap appears to increase slightly at higher clay concentrations, it is relatively constant given the dramatic range in clay concentrations. Normal variation in clay or filler concentration in a paper mill is usually no more than a factor of two. The data in Figures 14 and 15 may be used with a measure of the temperature dependence to first calculate the total amount of the colloids and then calculate the amount of colloidal pitch and finally calculate the difference that constitutes colloidal clay and other components that are insensitive to transitions between the colloidal and dissolved phases in the measured temperature range.
.30 In a paper mill situation, it is advantageous to make maximum use of carrying capacity of water resources and still minimize the risk of sudden or catastrophic wet-end chemistry SUBSTITUTE SHEET (RULE 25) events that lead to deposits and machine fouling associated with poor efficiency and runability. A measurement that provides the paper-maker a better means of predicting the sensitivity of the white water system upsets may be applied to circumvent expensive episodes of deposition on the paper machine. Among diverse causes of wet-end.
chemistry upsets the sudden variation in white water temperature leading to a wet-end upset is known among papermakers as temperature shock. A sudden change in white water temperature may occur when unusual quantities of fresh water are brought into the water system. In an embodiment, this invention provides a measure of the susceptibility of the water system to a temperature shock. UV ratios track critical behavior better than UV absorbance.
In another embodiment in agreement with the invention concentrations of dissolved and colloidal substances that may lead to deposition events are identified. The intention of the papermaker is thus to avoid a metastable state where dissolved components may suddenly come out with a minor fluctuation in operating conditions.
Figures 8, 9, 1Ob, and 12 all show that spectral changes occurring pitch phase transitions are rich sources of information about the transitions occurring. Comparing absorbance values at different wavelengths provides a means of comparing the amount of one component to another component. Examples of three-dimensional plots of temperature, relative dissolved and colloidal substances are provided in Figures 16 to 19.
Although for the most part UV-visible absorbance shows linear or nearly linear relationships with concentration (TDS) and temperature, the use of UV ratios provides insight into discrete changes in the state of the dissolved and colloidal substances. Figure 16 shows the ratio A350A2so versus temperature and concentration. The most pronounced change exhibited in this plot is below I mg/ml. The relative absence of slope in this graph at high temperatures suggests a change of state that is more discrete than the gradual change at low temperature. The UV ratio A330/A28o appears to be a comparison of the contributions of turbidity and UV absorbance. Figure 17 shows UV ratios of A274/A280 versus temperature and concentration (TDS). At high concentrations this ratio is essentially constant. At low concentrations the ratio decreases. This is interpreted as a red shift due SUBSTITUTE SHEET (RULE 28) to the comparative effects of solvation in water versus solvation in pitch.
Figure 18 shows UV ratios of A230/A500 versus temperature and concentration (TDS). At high concentrations this ratio is essentially constant. Scattering adds proportionately to both long and short wavelengths. At low concentrations the ratio increases as more extractives are UV absorbing in the dissolved state but not colloidal. Figure 19 shows UV
ratios of A250/A280 versus temperature and concentration (TDS). At high concentrations this ratio is essentially constant indicating no substantial change in the ionization. At low concentrations the ratio increases as more extractives become ionized as they dissolve.
At concentrations above a critical concentration the UV ratio is essentially constant.
Ratios that are important include ratios that emphasize ionization (A250/A280, A300/A280); solvent shifts (A300/A292) and a comparison between scattered and UV
absorbed light (A500/A230). The absorbance at 292 nm is essentially constant as a function of colloidal or dissolved state.
A scan of selected wavelength ratios versus temperature and identification of points at which the slope changes will identify temperatures that correspond to a transition between dissolved and colloidal components. These temperatures may be used as guides of the system stability at a different temperature.
The above-described embodiments of the invention are intended to be examples of the present invention and numerous modifications, variations, and adaptations may be made to the particular embodiments of the invention without departing from the scope and spirit of the invention, which is defined in the claims.
SUBSTITUTE SHEET (RULE 26)
Trial experiments were conducted at a paper mill using white water manually filtered on a Whatman 41 filter paper. This filter paper has a nominal size cut-off of approximately 20 microns. The results are exemplified by the difference spectrum in Figure 12.
This spectrum was obtained with a 1 mm UV cell on a Cary 1 spectrophotometer. This spectrum shows the same minimum points as the difference spectrum in Figures 8 and 9.
However, in this case the relative absorbance at long wavelengths is much lower. The difference spectrum demonstrates that the temperature change necessary to get accurate measurements must be at least 30 degrees C. Furthermore, a long path UV cell (10 or 20 mm) is used to increase the accuracy of the measurements made at long wavelengths.
Scatter in the mill data required to obtain dA/dT is shown in the Figure 13.
Figure 14 shows the spectral effects of adding multiples of a clay concentration to a colloidal pitch solution. The absorbance changes are nearly linear with clay concentration and relatively monotonic with wavelength. Clay and fillers scatter light well and absorb little light compared to colloidal pitch.
Figure 15 shows absorbance at 500 nm for different concentrations of clay in a colloidal pitch mixture. The total absorbance is linear with clay concentration. The temperature variation, representing the constant amount of pitch, is shown by the gap between the absorbance at 20 C and 80 C. Although the size of the gap appears to increase slightly at higher clay concentrations, it is relatively constant given the dramatic range in clay concentrations. Normal variation in clay or filler concentration in a paper mill is usually no more than a factor of two. The data in Figures 14 and 15 may be used with a measure of the temperature dependence to first calculate the total amount of the colloids and then calculate the amount of colloidal pitch and finally calculate the difference that constitutes colloidal clay and other components that are insensitive to transitions between the colloidal and dissolved phases in the measured temperature range.
.30 In a paper mill situation, it is advantageous to make maximum use of carrying capacity of water resources and still minimize the risk of sudden or catastrophic wet-end chemistry SUBSTITUTE SHEET (RULE 25) events that lead to deposits and machine fouling associated with poor efficiency and runability. A measurement that provides the paper-maker a better means of predicting the sensitivity of the white water system upsets may be applied to circumvent expensive episodes of deposition on the paper machine. Among diverse causes of wet-end.
chemistry upsets the sudden variation in white water temperature leading to a wet-end upset is known among papermakers as temperature shock. A sudden change in white water temperature may occur when unusual quantities of fresh water are brought into the water system. In an embodiment, this invention provides a measure of the susceptibility of the water system to a temperature shock. UV ratios track critical behavior better than UV absorbance.
In another embodiment in agreement with the invention concentrations of dissolved and colloidal substances that may lead to deposition events are identified. The intention of the papermaker is thus to avoid a metastable state where dissolved components may suddenly come out with a minor fluctuation in operating conditions.
Figures 8, 9, 1Ob, and 12 all show that spectral changes occurring pitch phase transitions are rich sources of information about the transitions occurring. Comparing absorbance values at different wavelengths provides a means of comparing the amount of one component to another component. Examples of three-dimensional plots of temperature, relative dissolved and colloidal substances are provided in Figures 16 to 19.
Although for the most part UV-visible absorbance shows linear or nearly linear relationships with concentration (TDS) and temperature, the use of UV ratios provides insight into discrete changes in the state of the dissolved and colloidal substances. Figure 16 shows the ratio A350A2so versus temperature and concentration. The most pronounced change exhibited in this plot is below I mg/ml. The relative absence of slope in this graph at high temperatures suggests a change of state that is more discrete than the gradual change at low temperature. The UV ratio A330/A28o appears to be a comparison of the contributions of turbidity and UV absorbance. Figure 17 shows UV ratios of A274/A280 versus temperature and concentration (TDS). At high concentrations this ratio is essentially constant. At low concentrations the ratio decreases. This is interpreted as a red shift due SUBSTITUTE SHEET (RULE 28) to the comparative effects of solvation in water versus solvation in pitch.
Figure 18 shows UV ratios of A230/A500 versus temperature and concentration (TDS). At high concentrations this ratio is essentially constant. Scattering adds proportionately to both long and short wavelengths. At low concentrations the ratio increases as more extractives are UV absorbing in the dissolved state but not colloidal. Figure 19 shows UV
ratios of A250/A280 versus temperature and concentration (TDS). At high concentrations this ratio is essentially constant indicating no substantial change in the ionization. At low concentrations the ratio increases as more extractives become ionized as they dissolve.
At concentrations above a critical concentration the UV ratio is essentially constant.
Ratios that are important include ratios that emphasize ionization (A250/A280, A300/A280); solvent shifts (A300/A292) and a comparison between scattered and UV
absorbed light (A500/A230). The absorbance at 292 nm is essentially constant as a function of colloidal or dissolved state.
A scan of selected wavelength ratios versus temperature and identification of points at which the slope changes will identify temperatures that correspond to a transition between dissolved and colloidal components. These temperatures may be used as guides of the system stability at a different temperature.
The above-described embodiments of the invention are intended to be examples of the present invention and numerous modifications, variations, and adaptations may be made to the particular embodiments of the invention without departing from the scope and spirit of the invention, which is defined in the claims.
SUBSTITUTE SHEET (RULE 26)
Claims (22)
1. A method for identifying and measuring a characteristic of a colloidal mixture comprising the steps of:
(a) irradiating at least a first portion of the colloidal mixture at a first temperature with light in an ultraviolet-visible region and obtaining a first measurement of a first wavelength within the ultraviolet-visible region, said first measurement for obtaining a measure of one of an absorption, emission and scattering of the first wavelength when said colloidal mixture is irradiated with the light;
(b) waiting for the temperature of the colloidal mixture to change;
(c) irradiating at least a second portion of the colloidal mixture at a second different temperature with light in the ultraviolet-visible region and obtaining a second measurement of the first wavelength within the ultraviolet-visible region, said second measurement for obtaining a measure of the same one of an absorption, emission and scattering of the at least a first wavelength when said colloidal mixture is irradiated with the light; and (d) determining the characteristic of the colloidal mixture from a relationship including the first measurement and the second measurement.
(a) irradiating at least a first portion of the colloidal mixture at a first temperature with light in an ultraviolet-visible region and obtaining a first measurement of a first wavelength within the ultraviolet-visible region, said first measurement for obtaining a measure of one of an absorption, emission and scattering of the first wavelength when said colloidal mixture is irradiated with the light;
(b) waiting for the temperature of the colloidal mixture to change;
(c) irradiating at least a second portion of the colloidal mixture at a second different temperature with light in the ultraviolet-visible region and obtaining a second measurement of the first wavelength within the ultraviolet-visible region, said second measurement for obtaining a measure of the same one of an absorption, emission and scattering of the at least a first wavelength when said colloidal mixture is irradiated with the light; and (d) determining the characteristic of the colloidal mixture from a relationship including the first measurement and the second measurement.
2. A method as defined in claim 1, wherein the first portion and the second portion is substantially a same portion.
3. A method as defined in claim 1, wherein the first measurement and the second measurement are each obtained at the first wavelength and at a second wavelength.
4. A method as defined in claim 3, wherein the first measurement and the second measurement each comprise a same one of:
(a) an absorbance ratio between the absorbance of the light at the first wavelength and at the second wavelength, (b) a scattering ratio between the scattering of the light at the first wavelength and at the second wavelength, and (c) an emission ratio between the emission of the light at the first wavelength and at the second wavelength.
(a) an absorbance ratio between the absorbance of the light at the first wavelength and at the second wavelength, (b) a scattering ratio between the scattering of the light at the first wavelength and at the second wavelength, and (c) an emission ratio between the emission of the light at the first wavelength and at the second wavelength.
5. A method as defined in any of claims 1 to 4, wherein the characteristic is a first or second derivative of a function expressing a temperature dependence of absorption, emission, or scattering derived from the relationship including the first measurement and the second measurement.
6. A method as defined in any of claims 1 to 5, wherein the characteristic of the colloidal mixture is a measure of an amount of a substance within the colloidal mixture determined in dependence upon the variation of the measurements in response to the change in temperature.
7. A method as defined in claim 6, wherein the method is for measuring the characteristic in both inorganic colloidal substances and organic colloidal substances.
8. A method as defined in claim 7, wherein the organic colloidal substance is at least one of a colloidal pitch and a colloidal wood extractive.
9. A method as defined in claim 7, wherein the inorganic colloidal substance is at least one of a clay, a TiO2, carbon black, and a talc.
10. A method as defined in claim 6, further including the step of determining a stability of the colloidal mixture based on the measure of the amount of the substance.
11. A method as defined in claim 10, further including the step of determining a temperature stability of the colloidal mixture based on the measure of the amount of the substance.
12. A method as defined in claim 11, further including the step of determining an amount of colloidal pitch in the colloidal mixture based on a temperature dependency of the absorption, emission, or scattering.
13. A method as defined in claim 6, further including the step of identifying a change in a state of the substance based on the measure of the amount of the substance, said change including a dissolved state and a colloidal state.
14. A method as defined in claim 1, wherein an initial step comprises the step of filtering the colloidal mixture for substantially removing fiber therefrom.
15. A method as defined in any of claims 1 to 14, wherein a difference between the first temperature and the second temperature is at least 30°C.
16. A method as defined in claim 3 or 4 wherein the characteristic is a measure for one of a critical concentration and a critical temperature for a transition between a dissolved state and a colloidal state determined in dependence upon the variation of the measurements in response to the change in temperature.
17. A method as defined in any of claims 1, 2, 3, 4, 5, 6, or 16, wherein the characteristic is a measure of a stability of the colloidal mixture determined in dependence upon the variation of the measurements in response to the change in temperature.
18. A method as defined in any of claims 1, 2, 3, 4, 5, 6, or 16, wherein the characteristic is a measure of a composition of the colloidal mixture determined in dependence upon the variation of the measurements in response to the change in temperature.
19. A method as defined in claim 18, wherein the colloidal mixture includes a component that is temperature sensitive when measuring the absorption, emission, or scattering of the light, and a component that is temperature insensitive when measuring the absorption emission, or scattering of the light.
20. An apparatus for identifying and measuring a characteristic of a colloidal mixture, comprising:
filtration means arranged to substantially remove fiber from the colloidal mixture;
detecting means for obtaining a first measurement and a second measurement of light in an ultraviolet-visible region, said first measurement for obtaining a measure of one of an absorption, emission, and scattering of at least a first wavelength of the light at a first temperature when the colloidal mixture is irradiated with the light, and said second measurement for obtaining a measure of the same one of an absorption, emission and scattering of the at least a first wavelength of light at a second different temperature when the colloidal mixture is irradiated with the light; and a suitably programmed processor for determining the characteristic of the colloidal mixture from a relationship including the first and second measurement.
filtration means arranged to substantially remove fiber from the colloidal mixture;
detecting means for obtaining a first measurement and a second measurement of light in an ultraviolet-visible region, said first measurement for obtaining a measure of one of an absorption, emission, and scattering of at least a first wavelength of the light at a first temperature when the colloidal mixture is irradiated with the light, and said second measurement for obtaining a measure of the same one of an absorption, emission and scattering of the at least a first wavelength of light at a second different temperature when the colloidal mixture is irradiated with the light; and a suitably programmed processor for determining the characteristic of the colloidal mixture from a relationship including the first and second measurement.
21. An apparatus as defined in claim 20 further comprising control means arranged to control the detecting means such that first and second measurements are made when the colloidal mixture is at the first temperature and the second temperature, respectively.
22. An apparatus as defined in claim 21, wherein said characteristic is a first or second derivative of a function expressing the temperature dependence of the absorption, emission, or scattering derived from a relationship including the first measurement and the second measurement.
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| CA2304201A CA2304201C (en) | 1997-09-18 | 1998-09-18 | Analyzer for temperature sensitive colloidal mixtures |
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| Application Number | Priority Date | Filing Date | Title |
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| CA002216046A CA2216046A1 (en) | 1997-09-18 | 1997-09-18 | In-line sensor for colloidal and dissolved substances |
| CA2,216,046 | 1997-09-18 | ||
| PCT/CA1998/000871 WO1999014577A1 (en) | 1997-09-18 | 1998-09-18 | Analyzer for temperature sensitive colloidal mixtures |
| CA2304201A CA2304201C (en) | 1997-09-18 | 1998-09-18 | Analyzer for temperature sensitive colloidal mixtures |
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