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    • 专利摘要:
    method of monitoring colloidal macroparticles (macrostickies) in the process of recycling and manufacturing paper or fabric involving recycled pulp. a challenge in the use of recycled material in the papermaking process is the presence of hydrophobic organic materials with adhesive properties, commonly known as stickies. hydrophobic agglomerates can result in stains or defects in the final paper product or deposits on papermaking equipment, resulting in poor production capacity and downtime. technologies exist for the monitoring and control of colloidal microparticles (microstickies). however, there is a need for a technique in order to quickly determine the size and content of colloidal macroparticles (macrostickies) (diameter above 100 microns) in the recycled pulp process flows. the present invention deals with a device and method for carrying out the analysis of macrostickies in real time and / or any hydrophobic particles visible in an aqueous medium. when using the present invention, the quality offered can be monitored and the performance of the treatment can be monitored and controlled. the technique is based on the analysis of a fluorescence image in order to identify and count sticky particles, as well as to measure their size.
    公开号:BR112013025767B1
    申请号:R112013025767-9
    申请日:2012-04-04
    公开日:2021-02-23
    发明作者:William A. Von Drasek；Brett Brotherson；Sergey M. Shevchenko；Michael J. Murcia
    申请人:Nalco Company；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    The present invention relates to a method that measures the concentration and size of visible hydrophobic particles ("macrostickies") in flowing pulp slurries. In more specific terms, the present invention refers to a device and method that performs the analysis of these colloidal macroparticles (“macrostickies”) in real time in a current pulp flow. The method uses fluorescence image analysis to identify and count macrostickies, as well as to measure their size. BACKGROUND OF THE INVENTION
    The characterization of visible hydrophobic particles, more particularly of visible hydrophobic particles in an aqueous medium is a major general problem, with a specific application in the paper and cellulose industry, especially when dealing with a secondary fiber. The deposition of colloidal (“stickies”) and sticky (“tackies”) residues and the formation of large clusters of hydrophobic materials are the main obstacles in the manufacture of paper or fabric using recycled fiber. In order to obtain paper qualities, these non-polar, sticky contaminants, particularly when released during pulping, can become undesirable components in papermaking as well as problematic deposits in the milling equipment, for example, in the paper machine wires or fabric.
    Stickies (colloidal residues) and tackies (sticky residues) are organic materials that do not have a precise definition. Stickies and tackies are sticky substances contained in the process water system and in the pulp that are deposited on the lining of the paper and fabric machine, in cylinders or rolls. The synthetic materials that make up stickies or tackies (also known as white tar) include adhesives and coating binders, such as styrene butadiene rubber, ethylene vinyl acetate, vinyl polyacetate, vinyl polyacrylate, polyvinyl butyral, polybutadiene, etc., and components of the printing ink, such as wax, alkyd resins, polyol acrylates, etc. The natural wood pitch normally found in virgin pulp consists of fatty acids, fatty esters and pitch acids. Natural wood pitch is more polar than stickies, however, in general, it also belongs to the class of hydrophobic additives and is similar, in its relevant properties, to monitoring contaminants.
    The most common classification system for stickies used by the pulp and paper industry is based on size in order to categorize stickies into three classes: macro, micro and colloidal. Macrostickies are considered to be the particles that result from the preliminary disintegration of the recycled material during a pulp reprocessing. For classification purposes, macrostickies typically have a particle size greater than 0.1 mm. Macrostickies can be removed to a large extent through a thick and fine sieve.
    Macrostickies are also those stickies that remain as sieving residues after laboratory sieving with a gap width of 0.10 to 0.15 mm. The main sources of these materials are hot melts and pressure sensitive adhesives. Macrostickies can include adhesives and coating binders, such as styrene and butadiene rubber, ethylene vinyl acetate, vinyl polyacetate, vinyl polyacrylate, polyvinyl butyral, polybutadiene, and / or components of printing ink, such as waxes, alkyd resins, polyol acrylates, and other similar substances. The methods of quantifying macrostickies that are currently practiced are laborious, and there is no continuous monitoring technique.
    Microstickies (visible hydrophobic microparticles) (from 0.1 to 0.001 mm) and colloidal (<0.001 mm) are those that can pass through the sieve slits. The micro-tickies that pass through the sieves may later agglomerate and result in deposits on the paper / tissue machine or pass to the product as newly formed secondary macrostickies.
    This differentiation, based on size, is arbitrary and cannot be strictly applied to different monitoring methods. Therefore, the size limitation of the proposed method is not the same as the size limitations that define macrostickies, although those skilled in the art recognize the method as a method for monitoring macrostickies. In fact, in paper and cellulose applications, the size of the measured stickies can be less than 0.1 mm, as long as the particles are detectable by means of an image generation system, which can include an optically differentiated digital microscopic camera. with respect to the surrounding environment. Colloidal stickies do not fit this definition, although a fraction of 0.05 to 0.10 mm of macrostickies does. The size limits are generally defined by the capabilities of the image generation system used and the signal-to-noise ratio of the captured image, the noise being electronic, as well as the background of the surrounding environment.
    Nalco has developed a proprietary technology for monitoring microstickies based on a quartz crystal micro scale (QCM) (see, for example, Duggirala & Shevchenko, United States Patent Application Publication No. 2006/0281191; Shevchenko et al., United States Patent No. 7,842,165). The technology based on the QCM micro scale is suitable for monitoring microstickies, but not macrostickies, since macrostickies are not expected to adhere to the surface of the QCM micro scale in the pulp slurry flow.
    Fluorescent dye molecules that are emitted from an intramolecular charge transfer state are known to be sensitive to the polarity of the medium. The fluorescence of the dye molecules (both their wavelength and their intensity) is affected by polarity, as well as in the case of non-homogeneous systems, such as suspensions of non-water-soluble organic liquids. These dyes can bind directly to hydrophobic particles or droplets that have a similar effect on the optical properties of the dyes. Based on these properties, methods have been developed to visualize protein stains based on dyes that clump non-covalently to protein complexes. These techniques were also coupled with electrophoresis procedures.
    Perfect et al. (Patent Application Publication WIPO No. WO2010007390) describes a method for evaluating multiphase fluid compositions (aqueous / organic) that, in specific terms, monitor oil in water in the wastewater treatment area. Perfect et al. identified Nile Red as a preferable molecule used to perform the method. Nile Red is ideal for the evaluation of the organic phase of a multiphase sample, since it emits a more intense signal in contact with the organic phase than in contact with the aqueous phase, the change in wavelength being significant. Nile Red has strong photochemical stability, a peak of intense fluorescent emission, and relatively low cost. Perfect et al. it also reveals that the method can be used to determine the size distribution of the droplets both in the organic and in the aqueous phase in the multiphase sample based on image analysis. Perfect et al. it also anticipates on-line and on-line applications.
    Gerli et al. (United States Patent Application Publication No. 2009/0260767) describes a method of monitoring and controlling one or more types of hydrophobic contaminants in a papermaking process. The method uses measurement with dyes that are able to fluoresce and interact with hydrophobic contaminants. Gerli et al. it does not allow the measurement of macrostickies or monitoring on the line. Gerli et al. provides the mass characterization of a summary of microstickies in a sample of filtered material.
    Sakai (Japanese Patent Application Publication No. 2007/332467) proposed the processing of microscopic images of the particles in a non-ink pulp fluid for the quantification of the particles. However, the process described in Sakai does not refer to continuous monitoring with an injection of dye.
    Therefore, there is a need to complement the technology of measuring microstickies with a similar in-line method for monitoring macrostickies. Such a measurement method would allow a paper producer / recycler to use less quality material and more recycled pulp than one is able to use today. Undoubtedly, the two measurement methods would allow for continuous in-line process adjustments in order to maximize the efficiency of the process. SUMMARY OF THE INVENTION
    The present invention relates to a method for monitoring a variable in an aqueous pulp slurry. The aqueous slurry is composed of contaminants. The method comprises the steps of providing an aqueous paste flow; illuminate the aqueous pulp slurry with light; adding a hydrophobic dye to the aqueous pulp slurry, the addition being made under conditions that cause the hydrophobic dye to interact with the contaminants, this interaction causing a change in the fluorescent emission; capture an image of the change in fluorescent emission; alter the image in order to isolate the change in fluorescent emission caused by the interaction of the hydrophobic dye with at least one contaminant among the contaminants; and measuring the aqueous pulp slurry variable based on the altered image.
    The present invention also relates to an apparatus for monitoring a variable of a watery slurry slurry, the watery slurry slurry being composed of contaminants. The apparatus comprises a container equipped with a mixer, a temperature control device, a sample cell, an aqueous pulp fluid circulation device, a light source, an imaging device, and a processing device . The temperature control device is operationally attached to the apparatus in order to control the temperature of the aqueous pulp slurry. The container is operationally attached to the sample cell and the aqueous pulp slurry circulation device, so that the aqueous pulp slurry circulates through the sample cell. The light source is operationally positioned to provide light for the aqueous pulp slurry as the slurry passes through the sample cell. The imaging device is operationally positioned to capture an image of a change in fluorescent emission. The sample cell is equipped to operationally recycle the aqueous pulp slurry into the container.
    All methods are preferably used for the characterization of macrostiques in an aqueous medium. These and other features and advantages of the present invention will be apparent from the detailed description below, together with the appended claims. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
    The benefits and advantages of the present invention will become more readily apparent to those with simple knowledge of the technique in question after reviewing the following detailed description and the accompanying drawings, in which:
    Figure 1A is a perspective view of a first embodiment of the present invention;
    Figure 1B is a flow chart of several of the steps used to determine the particle size of a macrosticky in multiphase flow;
    Figure 1C is a perspective view of a second embodiment of the present invention;
    Figure 1D is a perspective view of a third embodiment of the present invention;
    Figure 1E is a perspective view of a fourth embodiment of the present invention;
    Figure 1F is a perspective view of a fifth embodiment of the present invention, which includes an aerodynamic body;
    Figure 1G is a side view of a fifth embodiment of the present invention, which also includes an aerodynamic body; and
    Figure 2 is a schematic representation of a modality of the hydrophobic batch analysis apparatus. DETAILED DESCRIPTION OF THE INVENTION
    Although the present invention is susceptible of modality in various forms, it is shown in the drawings and a presently preferred modality will be described hereinafter with the understanding that this description should be considered an exemplification of the present invention and is not intended to limit the present invention to the specific modality illustrated.
    It should also be understood that the title of this section of this specification, namely, "Detailed Description of the Invention", refers to a requirement of the United States Patent Office, and does not imply, nor should it be inferred to limit the described in this document. DEFINITIONS:
    For the purposes of this patent application, the following terms have the definitions set out below: "Aqueous pulp slurry" means any aqueous medium that may or may not contain some level of pulp. "Aqueous pulp slurry circulation device" means a device that circulates an aqueous slurry slurry through a conduit. A typical aqueous pulp slurry circulation device is a pump. "Capture" means to record an image.
    "Concentration" means any measurement of a subset of a set by the whole. The concentration in relation to this application can be measured as the mass of the subset per unit volume of the ensemble, the volume of the subset per volume unit of the ensemble, the amount of the subset by mass of the ensemble, the amount of the subset per unit volume of the set, the quantity of the subset per quantity of the set, and so on. For the purposes of the present patent application, particle counting is a type of concentration measurement.
    "Contaminant" means any organic material found in an aqueous slurry, other than pulp, water, or a material that is intentionally added to the aqueous slurry. Typical contaminants are stickies, tar, and similar substances.
    "Digital microscopic camera" means a camera that is capable of capturing microscopic images in a digital storage format.
    "Cell through flow" means a device that has at least one non-opaque space that allows the flow of a fluid, slurry, or the like, through the device, allowing external observation of the flow through the device.
    "Fluid" includes any aqueous, homogeneous or heterogeneous medium, and in particular liquids used in the paper and cellulose industry, such as an aqueous suspension for the manufacture of paper from a papermaking process (for example, a fluid containing fibers in a pulping stage), a fine raw material, a thick raw material, aqueous suspensions removed from the papermaking process (for example, several locations on a papermaking machine or a pulp process). tion), an aqueous fluid in a Uhle box, a section of dehydration under pressure and / or any part of the papermaking process that a person with simple knowledge in the art would need to monitor hydrophobic contaminants. For the purposes of the present patent application, a slurry is a fluid.
    "Hydrophobic dye" means any dye capable of emitting a fluorescent emission when interacting with a contaminant, as defined above.
    "Macroscopic contaminant" means any contaminant having a particle size greater than or equal to 0.10 mm, as typically used by the pulp and paper industry. A visible hydrophobic particle is an example of a type of macroscopic contaminant, although it may not be the only type of macroscopic contaminant.
    "Non-macroscopic contaminant" means any contaminant that is not a macroscopic contaminant
    "Papermaking process" means a method of making any type of paper product (for example, paper, fabric, board, etc.) from pulp comprising the formation of an aqueous cellulosic papermaking material, the draining the material to form a sheet, and drying the sheet. The steps of forming the papermaking material, draining, and drying can be carried out in any manner generally known to those skilled in the art. The papermaking process can include a pulping stage (for example, the production of cellulose from raw material of wood or secondary fibers) and a bleaching stage (for example, the chemical treatment of the pulp to increase the pulp). shine). The materials may contain fillers and / or other contaminants.
    "Temperature control device" means any device or combination of devices that provide heating, cooling, or heating and cooling, manually or automatically, so that the temperature can be controlled.
    "Variable" means a measurable or quantifiable value. While not wishing to be restricted, examples of variables typically measured in the context of the present invention include particle size distribution, concentration, particle count, the effectiveness of an additive, etc.
    "Visible contaminant" means any contaminant that is detectable by a microscope or microscopic camera. A visible contaminant is a form of macroscopic contaminant.
    The present invention relates to an online method for evaluating visible, or more specifically, macroscopic contaminants in an aqueous slurry, particularly an aqueous pulp slurry containing a recycled material. These contaminants can be broadly divided into two categories: hydrophilic dirt particles and hydrophobic colloidal particles (“stickies”). Hard hydrophobic particles, such as plastic parts, may also be present in such a slurry, but these particles are typically removed in a pulp preparation stage of a papermaking process. The method allows the quantification of said contaminants in a flow of diluted pulp slurry. In specific terms, medium sized stickies and macrostickies can be selected and characterized on the line. In its preferred embodiment, the method involves treating the pulp slurry with a fluorescent dye. Both the concentration and the size distribution of these particles can be evaluated through the injection of fluorescent dye dependent on combined hydrophobicity, excitation and optical image generation, and image analysis. In addition, visible dirt particles can be characterized using conventional optical means. In this way, a complete picture of the macroscopic contamination of the recycled pulp can be obtained using the same optical flow configuration that can be carried out in the form of a batch, closed-circuit, pump-driven configuration or in a continuous lateral flow device. in a factory.
    It is important that this characterization can be done in a flow of current cellulose, with material present, without any filtration or sample preparation. In addition, the pulp can be characterized in the same experiment for the level of hydrophobic microparticles deposited on its surface. As a whole, the method allows a person to characterize the efficiency of the screening at the factory, the quality of the material supplied, and the degree of hydrophobic coating of the pulp.
    As a first aspect of the present invention, a method and apparatus are described for detecting stickies visible in a multiphase fluid consisting of water having a chemical composition typically found in a paper mill, fibrous pulp, and in the mixture of hydrophilic and hydrophobic particles. . Detection of the visible hydrophobic particle by fluorescence requires at least four steps.
    First, a fluorophore dye is added to a multiphase flow, at a fixed concentration, mixing rate, and sample temperature. In a closed circuit system, the dye is dosed into a container containing the mass of the pulp slurry and which is equipped with a mixer. The pulp is circulated through the circuit, the residence time is determined experimentally (until the readings are stable), and measurements are made several times in order to assess the margin of error. In a side flow system, the mixture is provided by means of devices, potentially including a stationary mixer or coiled hose and sufficient residence time. The control of the residence time, the concentration and the temperature of the sample affect the absorption rate of the fluorophore dye on the surface of the hydrophobic particles, which affects the measurement time.
    Second, an excitation light source illuminates the hydrophobic particle having a fluorophore dye sorbed on the surface.
    Third, an imaging device is used to measure the fluorescence emitted from the hydrophobic particle resulting from the energy transfer process of the fluorophore absorbing photons from the excitation source.
    Fourth, an image processing algorithm is used to distinguish a hydrophobic particle from the bottom and determine the particle size. Through the collection and processing of a series of images in a flow system, the number and particle size distribution for the macrostickies are determined. Details for the different steps are described later.
    An apparatus for detecting and measuring the size and distribution of macrostickies is illustrated in Figure 1A. The apparatus consists of a flow cell 102 with an optical access 103 and an imaging device 101. The multiphase fluid composed of a fibrous material 104 and particles 105 that can be hydrophilic or hydrophobic flows through the cell through the image window. optical access 103. A light source 100 that operates at the excitation wavelength for the hydrophobic dye (Nile Red) is oriented towards the optical access window 103. The detection of the hydrophobic particle (s) is done with an imaging device 101 by monitoring the emission of fluorescent light 106. The light emitted is of a lower energy (longer wavelength) compared to that of the excitation source, thus allowing the hydrophobic particles are distinguished from the excitation source wavelength and the emission wavelengths using narrowband or bandpass filters.
    The excitation source 100 used can be pulsed or continuous. Examples of light sources that can be used include sources of specific wavelengths, such as an LED, a laser (diode, Nd: YAG, Argon-ion, etc.), or a combination of any white light source ( LED, incandescent, arc lamp, etc.) and an optical filter in order to reach the appropriate excitation wavelength (s). The preferred method is to collimate the light source in order to uniformly illuminate the area to be worked. Multiple sources or a single light source could / could be used with an incident angle (θ) ranging from slightly above zero degrees to perpendicular. For the configuration shown in Figure 1A, the excitation light is detected and positioned on the same side of the optical access window 103. In this configuration, excitation light losses from dispersion and extinction in the multiphase fluid are minimized , since the length of light propagation through the medium is minimized. Alternative configurations for the introduction of the excitation light are shown in Figure 1C and 1D.
    A preferred embodiment of the imaging device 101 is a matrix detector camera with a lens and filter assembly in combination. The camera detector can be of a CMOS or CCD type, as long as the quantum efficiency (or low lux) is high enough with short exposure times in order to detect fluorescence. The combination of high quantum efficiency and a short exposure time is necessary in order to detect the weak fluorescence of the particles in a fluent medium without bias or uncertainty. The typical quantum efficiency for commercially available CCD cameras is high enough for fluorescence detection for this application. In addition, typical CCD cameras use a global shutter that helps reduce image distortion or blurring.
    CMOS cameras can also be used, but greater care in camera selection is necessary, as these cameras typically have poorer quantum efficiency and use rolling shutter technology. CMOS image intensification cameras or specialized high-gain CMOS cameras can be used, but these devices are generally more expensive. For the lens filter combination, the choice of a lens will depend on the desired magnification and the filter to be used will depend on the wavelength of fluorescent emission.
    The image processing steps used to identify and determine the size of a hydrophobic particle are described in the flow diagram shown in Figure 1B. Image processing can be done in real time, by capturing an image and processing the image with a computer or a processor that is integrated into or embedded in the camera. Alternatively, images can be obtained by using a storage medium (for example, a magnetic tape, a hard disk, etc.) for post-processing at a later time.
    The flowchart in Figure 1B lists the processing steps and the sample image to illustrate the effect of each processing step. In the first step, a raw image is captured for analysis. The sample image is shown from the laboratory measurements of a sample flowing in the factory using a configuration similar to that illustrated in Figure 1A. In this example, a hydrophobic particle is clearly identified by the bright spot in the image. However, the raw image also shows smaller particles, along with the fibrous material with a general image background that appears gray. Through the application of a background correction, in this case, an energy transformation is applied in order to decrease the brightness and contrast in the dark regions, while increasing the contrast in the bright regions. As can be seen in the sample image, the transformation essentially eliminates the gray background, along with a large portion of the background emission features. Alternative background correction methods may include subtracting a collected image without any change in fluorescence caused by hydrophobic contaminants or subtracting an average from the previous images. For the average image, a run average can be used with an algorithm to identify and remove images from the average that contain fluorescent hydrophobic contaminants. Particle identification is done in the next step by converting the image to a binary with a limit in order to further remove the weak emission resources in the image. In this example, some small residual particles remain in the binary image for a fixed limit configuration, as shown in the image. Additional filtering based on a size parameter (for example, particles smaller than a specified size) removes images of the small residual particles, resulting in a clear binary image with a single particle. In the final step, the particles are characterized by measurements related to their attributes, such as the particle area, hydraulic radius, Waddel spheric diameter, location, vertical height, horizontal length, etc., recorded in terms number of pixels. The conversion of pixel values into physical units (for example, mm per pixel) is performed by a person skilled in the art when calibrating the camera using a known standard. The results of the single frame analysis are then stored and the process is repeated for the next captured image. By collecting the results of the analysis for n images, it will be possible to develop the frequency distributions and descriptive statistics for the different particle attributes. The historical trend of particle attributes (for example, the average particle size) can be performed in order to monitor the characteristics of the fluid and the impact of operational changes and chemical treatment of the process.
    A second aspect of the present invention uses a combination of cameras in order to monitor both the fluorescence of the hydrophobic particles coated with a fluorophore dye as well as the transmittance properties through the multiphase fluid in order to identify the hydrophilic particles, the fibers, and the flocculants. An illustration of the dual camera system is shown in Figure 1E with camera 101 monitoring the fluorescence of hydrophobic particles and camera 102 monitoring general transmission characteristics through multiphase fluid. The source of illumination and excitation is directed through the fluid and then divided using a dichroic element 111 that allows the transmission of the emission light and reflects the excitation light. The camera 110 monitors the excitation light that will be attenuated by the density of the fiber, flake and particle in the fluid. By simultaneously collecting and processing images from cameras 101 and 110, it becomes possible to identify hydrophilic and hydrophobic particles, as well as fibers with or without the hydrophobic material absorbed on the surface. A combination that uses reflectance for the detection of hydrophobic particles and transmission through the fluid to the fiber as a whole and particle monitoring is an alternative configuration. In this case, the dichroic element 111 is still used as a filter and a reflection element. A variation of the configuration shown in Figure 1E involves the use of a beam splitting prism (not shown) with both cameras. Simultaneous monitoring of different fluid characteristics can be done with the appropriate filtration known in the art. In addition, a multiple camera system can also be used for monitoring at different optical depths in the fluid.
    A third aspect of the present invention is a method for concentrating multiphase fluid in the measurement area, using an aerodynamic body 200, as shown in Figures 1F and 1G. When inserting the aerodynamic body 200 into the flow, the area close to the measurement zone is reduced, thereby concentrating the solid material closest to the focal plane of the imaging system. The geometry of the aerodynamic body 200 provides a smooth transition as the fluid approaches and flows around the body, as long as the Reynolds number for the flow remains below the turbulent transition level (ReD <4000). The use of the aerodynamic body will improve detection by increasing the number of particles that flow through the focal plane of the imaging system. In addition, the design minimizes pressure drop across the flow cell, as well as reducing the risk of clogging.
    A fourth aspect of the present invention is based on the capture of adherent particles (micro and macro) in an optical window coated with a transparent semi-hydrophobic material similar to that described by Shevchenko et al. (United States Patent Application Publication No. 2009/0056897) and its continuation in part (United States Patent Application Serial No. 12/907 478, filed on October 19, 2010), both applications being incorporated into the this document as a reference. However, instead of using a quartz crystal micro-scale to detect the accumulation of sticky particles that adhere to a coated substrate, in this case the method is based on monitoring the change in fluorescence over time. The configuration is similar to that of Figure 1A, but the optical access window 103 is coated with a hydrophobic material. The particles that adhere to the window are detected by fluorescence using the excitation source 100. In this case, the flow dynamics are removed from the measurement, thus reducing the image generation requirements (exposure time, quantum efficiency, rate of capture, etc.) As a number of particles accumulate on the surface, the intensity and / or the covered area will change over time. The trend of this data over time will show the rate of accumulation of stickies on the coated window. The change in the rate of accumulation may be related to the effect and concentration of chemical additives, to the composition of the material, or to operational changes in the process.
    Finally, all the configurations shown in Figures 1A, 1C, 1D and 1E can be used with the aerodynamic body 200. In the case that the light is transmitted in the opposite direction to that of the camera (through the bottom of the cell, as shown in Figure 1D and 1E), the aerodynamic body 200 can become optically transparent. If designed correctly, an optically transparent aerodynamic body can act as collimated lines of light introduced through the bottom of the cell.
    One embodiment of the present invention is a method for monitoring the size of at least one macroscopic contaminant, or the concentration of macroscopic contaminants, in an aqueous medium, such as an aqueous pulp slurry, and more particularly the water slurry slurry. water pulp recycled. The aqueous medium consists of contaminants, both macroscopic and microscopic. The method comprises the steps of providing a flow of the aqueous pulp slurry; injecting a hydrophobic dye in the flow of the aqueous pulp slurry, the injection being made so that the hydrophobic dye interacts with the contaminants, the interaction causing a change in the fluorescent emission; capture an image of the change in fluorescent emission, the image having a background; correct the background of the image; filter from the image the change captured in the fluorescent emission caused by the non-macroscopic contaminant; and quantifying the particle size of at least one macroscopic contaminant, or the concentration of macroscopic contaminants, using the captured unfiltered change in the fluorescent emission. The method is carried out with an apparatus comprising a flow cell, a light source, and at least one digital microscopic camera. The background correction reinforces the change in the fluorescent emission generated by the interaction of the hydrophobic dye and the macroscopic contaminant (s), while weakening the change in the fluorescent emission of the contaminant (s) ) non-macroscopic (s) and fibers coated with a hydrophobic layer. Emission from fibers is much less intense than from visible / macroscopic hydrophobic contaminants.
    In another embodiment, the present invention is a method for measuring the effectiveness of an additive. The additive is added to an aqueous slurry in order to decrease the deposition of macroscopic contaminants in a papermaking process. The aqueous slurry is composed of contaminants, both macroscopic and microscopic. The method comprises the steps of providing a flow of aqueous slurry; injecting a hydrophobic dye in the flow of the aqueous slurry, the injection being made so that the hydrophobic dye interacts with the contaminants, the interaction causing a first change in the fluorescent emission; capture an image of the first change in fluorescent emission, the image having a background; correct the background of the image; filter from the image the first change captured in the fluorescent emission generated by the non-macroscopic contaminant; add an additive to the aqueous slurry; repeat the steps of injecting, capturing, correcting, and filtering in order to create a second, unfiltered captured change in the fluorescent emission; and comparing the second captured, unfiltered change in the fluorescent emission with the first captured, unfiltered change in the fluorescent emission. The method is carried out with an apparatus comprising a flow cell, a light source, and at least one digital microscopic camera. The background correction reinforces the changes captured in the fluorescent emission caused by the interaction of the hydrophobic dye and macroscopic contaminants, while weakening the changes captured in the fluorescent emission of non-macroscopic contaminants.
    In yet another embodiment, the present invention is a method for measuring the effectiveness of a microstickie fixing additive that decreases the concentration of non-visible (colloidal) microstickies in an aqueous slurry. The fixative additive is uniformly attached to the surface of a fiber. As a result, the fluorescence of the hydrophobically coated fiber increases. The magnification can be used to quantify the effect of the fixative. Typically, the fiber fluorescence is filtered as the background of the captured image. In this modality, the filter is configured in such a way that the fluorescence of the coated fiber is measured and the fluorescence corresponding to both visible and colloidal contaminants is filtered from the captured image.
    The additive is added to the aqueous slurry in order to reduce the deposition of macroscopic hydrophobic contaminants in a papermaking process. The aqueous slurry is usually composed of hydrophobic contaminants, both macroscopic and microscopic. The method comprises the steps of providing a flow of aqueous slurry; injecting a hydrophobic dye in the flow of the aqueous slurry, the injection being made so that the hydrophobic dye interacts with the contaminants, the interaction causing a change in the fluorescent emission; capture an image of the change in fluorescent emission, the image having a background; correct the background of the image; filter from the image the change captured in the fluorescent emission generated by floating macroscopic and microscopic contaminants; and determining the effectiveness of the additive using the captured, unfiltered change in the fluorescent emission generated by the fiber. The step of determining can be done by comparing the measured change in the fluorescent emission generated by the fiber with average values or by any other means available to a person skilled in the art. The method is carried out with an apparatus comprising a flow cell, a light source, and at least one digital microscopic camera. The background correction reinforces the change captured in the fluorescent emission caused by the interaction of the hydrophobic dye and the hydrophobic layer on the surface of the fibers, at the same time that it weakens the change captured in the fluorescent emission of the floating contaminants.
    In an attempt to prevent the deposition of contaminants on the papermaking equipment, a chemical can be added to an aqueous slurry. The effectiveness of the additive can be measured by means of the present invention by determining whether the concentration of macroscopic contaminants has increased, decreased, remained unchanged, dropped to a selected range, or whether the particle size of the contaminants has become larger, smaller or has remained equal. The effectiveness of a particular class of additives that may include fixative additives can also be measured based on the change in the fluorescence of the hydrophobically coated fibers that increases when more contaminants are fixed on the fibers. This measurement may allow the comparison of the effectiveness of one additive with another (or several others), or the measurement may allow the optimization of the amount or concentration of the additive to the aqueous pulp slurry. Similar calculations or comparisons can be made for the pulp sources, the process variables, or anywhere that a person skilled in the art can understand as appropriate.
    The light source can be in the form of an LED, which is a preferred modality. The hydrophobic dye can be a solvatochromatic dye, such as a chemical that comprises a phenoxazone dye, a carbocyanine, a pyridinium dye, a polysulfonated pyrene, a rhodamine, a fluorescein, or some combination of one or more among these substances. A particularly preferred embodiment of the hydrophobic dye is composed of Nile Red.
    The hydrophobic dye can be dissolved in a water-miscible organic solvent, such as methanol, ethanol, propanol, isopropanol, butanol, or a combination of one or more of these solvents.
    Figure 2 illustrates a modality of a hydrophobic batch analysis system. For carrying out an analysis, a slurry of pulp 304 is kept in a container 302. A heating element 303 is wrapped around the container 302 for heating the sample and for maintaining the temperature. A mixer 301 is used to ensure that the pulp is evenly distributed in the aqueous solution, as well as to provide a rapid mixture between the slurry and the added dye solution. As illustrated, the flow from the mixer (pulp slurry and dye) circulates clockwise through the outlet of container 302 through tube 305 and is pumped through sample cell 102, as previously described, using pump 306 The analysis of the current slurry is made using the imaging system 300, which consists of an imaging device and an excitation source, as previously described. After the sample cell, the slurry is returned to container 302.
    In one embodiment, the variable is a particle size distribution. In one embodiment, the variable is a concentration. In one embodiment, the variable is a particle count. In one embodiment, the variable is an additive's effectiveness.
    The flow of the aqueous slurry can be provided from a processing stage of a papermaking process. This stage can be a repopping stage, a deinking stage, a water cycle stage, a wet section stock preparation stage, a papermaking stage, and a fabric manufacturing stage. A person skilled in the art can easily identify these stages and each of the corresponding unit operations. The flow of the aqueous slurry can be done from a closed-loop circulation system, in which the flow is supported by a pump, or from a side flow device in a factory. EXAMPLES:
    A portable batch analyzer as illustrated in Figure 2, using a flow cell and an optical imaging system, was tested in a continuous pulp flow in a closed-loop circulation system. The analyzer includes a bucket mixer that mixes at 400 rpm, with a flow rate of 1.2 gpm, a pulp preheater, when necessary, and the temperature maintained by means of a heated outer sheet and a thermocouple. The optical system can be used as a bench instrument or reconfigured for continuous in-line monitoring. For these examples, a bench configuration was used. A fresh pulp was sampled from a first source. The fresh pulp was made from recycled fibers and then diluted 1: 4 with water to 15 L. A Nile Red dye was added to the diluted slurry, 30 ml of 0.1% dye solution by weight in isopropanol under mixing and the registration started immediately (with the exception of the experiment documented in Table II). The obtained data were electronically stored. Using the appropriate camera and the imaging processing settings listed in Table I below, fluorescent stickies can be detected in the diluted pulp flow without any interference from the cellulose fibers. Fluorescence from the fibers became present, as expected, but much weaker than the emission from the particles. Considering that each test took 11 minutes, the timing was set in the middle of the test for the experiments documented in Tables IV to VI.

    In order to have comparable data, the dilution and consistency of each pulp needs to be invoiced in the data. The number of particles adjusted for consistency, indicated as No adjusted for consistency / 100 in the tables below represents the comparable values between the two pulps. Values were calculated by dividing the number of particles by the dilution ratio (20%), then dividing by consistency. The "No adjusted for consistency" particles were then arbitrarily divided by 100, and the values are shown in the tables below.
    For the first experiment, a pulp with a low sticky content was used. The pulp had a consistency of 1.68%. In this experiment, data were collected seven times starting after 45 min. since the dye was added in order to provide full saturation beyond an induction period. The data show good reproducibility both in number of particles and in particle size distribution.
    Table II illustrates the results of the first experiment.
    For the second experiment, a more contaminated pulp was characterized in the same way. The pulp had a consistency of 4.15%. In this experiment, data were collected continuously after the dye was added. This test provided a dynamic image and demonstrated the length of the induction period before complete saturation (40 minutes at room temperature; the time for complete saturation was drastically reduced by adjusting the temperature to standard 40 ° repopping conditions Ç). The data show good reproducibility both in number of particles and in particle size distribution after obtaining saturation. Table III illustrates the results of the second experiment. The comparison of the two experiments showed consistent data for the two samples, offered an example of an induction period before the dye balance, and allowed for a comparative contamination of the two pulps that corresponded to expectations. The ratio of the stickies content was approximately 1: 6.5, which was an expected ratio.
    In this third experiment, the test temperature was varied in order to assess its effect on the saturation time. According to the chosen conditions, the stable readings at room temperature (saturation) are obtained in about 1 hour. Increasing the temperature to 40 ° C reduces this time to about 30 minutes and further increases the temperature to 55 ° C (at the time of adding the dye) in approximately 15 min.


    All patents referred to in this document are incorporated by reference into this document, whether this incorporation has been made or not within the text of the present invention.
    In the present description, the words "one" or "one" are to be understood both in the singular and in the plural. On the other hand, any reference to items in the plural, if applicable, includes the singular.
    From what has been presented above, it should be noted that countless modifications and variations can be made without departing from the true spirit and scope of the new concepts of the present invention. It should be understood that any limitation with respect to the specific modalities illustrated or the examples shown is intentional or should not be inferred. The present invention is intended to cover, by means of the appended claims, all such modifications as they fall within the scope of the claims.
    权利要求:
    Claims (12)
    [0001]
    1. Method to monitor a variable of an aqueous pulp slurry, the aqueous pulp slurry being composed of contaminants, the method being CHARACTERIZED by the fact that it comprises: providing a flow of the aqueous pulp slurry; illuminating the aqueous pulp slurry with light having visible contaminants flowing through an aerodynamic body; adding a hydrophobic dye to the aqueous pulp slurry in such a way that a change in fluorescent emission occurs and is captured in the fluid through the aerodynamic body; capture, through a digital camera, a digital image of the change in fluorescent emission in the aqueous pulp slurry flowing through an aerodynamic body; alter the digital image in order to isolate the fluorescent emission caused by the interaction of the hydrophobic dye with at least one visible contaminant among the visible contaminants; and measuring the aqueous pulp slurry variable based on the altered digital image; wherein the aerodynamic body restricts the flow of the aqueous pulp slurry in the measurement area; where the variable is selected from a concentration of visible contaminants, an average particle size of visible contaminants, an efficacy of an additive added to the aqueous pulp slurry, and combinations thereof.
    [0002]
    2. Method, according to claim 1, CHARACTERIZED by the fact that the hydrophobic dye is a solvatochromic dye composed of a chemical selected from a phenoxazone dye, a carbocyanine, a betaine pyridinium dye, a polysulfonated pyrene, a rhodamine , a fluorescein, and their combinations.
    [0003]
    3. Method, according to claim 1, CHARACTERIZED by the fact that the hydrophobic dye is a Nile Red.
    [0004]
    4. Method, according to claim 1, CHARACTERIZED by the fact that the change comprises correcting the digital image, the correction strengthening the change in the captured fluorescent emission that is caused by the interaction of the hydrophobic dye with the visible contaminant, and weakening the change in the captured fluorescent emission that is caused by the interaction of the hydrophobic dye with anything other than the visible contaminant.
    [0005]
    5. Method according to claim 1, CHARACTERIZED by the fact that one or more of the macroscopic contaminants has a particle size of 100 micrometers or more.
    [0006]
    6. Method according to claim 1, CHARACTERIZED by the fact that the aqueous pulp slurry originates from a processing stage selected from a group consisting of a repulping stage, a de-inking stage, a de-inking stage water cycle, a wet section stock preparation stage, a papermaking stage and a fabric manufacturing stage.
    [0007]
    7. Method, according to claim 1, CHARACTERIZED by the fact that at least the capture, the alteration and the measurement are repeated.
    [0008]
    8. Method, according to claim 1, CHARACTERIZED by the fact that the variable is the concentration of visible contaminants.
    [0009]
    9. Method, according to claim 1, CHARACTERIZED by the fact that the light is from an LED light source.
    [0010]
    10. Apparatus for monitoring a variable of a watery pulp slurry, the watery pulp slurry being composed of contaminants, a hydrophobic dye added to the aqueous pulp slurry, the apparatus FEATURED by the fact that it comprises: a container , the container being equipped with a mixer (301); a temperature control device (303); a flow sample cell (102); an aqueous pulp slurry circulation device (306); a light source (100); a digital microscopic camera as an imaging device (101); and a processing device, and an aerodynamic body (200) in a flow sample cell; wherein the temperature control device operationally controls the temperature of the aqueous pulp slurry; wherein the container is operatively attached to the flow sample cell and the aqueous pulp slurry circulation device, the aqueous pulp slurry being circulated through the flow sample cell; wherein the light source is operatively positioned to provide light for the aqueous pulp slurry as the aqueous pulp slurry passes through the flow sample cell; wherein the imaging device is operatively positioned to capture an image of a change in fluorescent emission; wherein the processing device is configured to receive the captured image of the change in fluorescent emission, to process the captured image, and to emit the effectiveness of the additive added to the aqueous pulp slurry; and wherein the sample cell is equipped so as to operationally recycle the aqueous pulp slurry into the container.
    [0011]
    11. Apparatus according to claim 10, CHARACTERIZED by the fact that the light source, the imaging device and the processing device 5 are units of less than three individual devices.
    [0012]
    12. Apparatus according to claim 10, CHARACTERIZED by the fact that the light source is an LED light source.
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    同族专利:
    公开号 | 公开日
    US20120258547A1|2012-10-11|
    CN103608515A|2014-02-26|
    WO2012138704A2|2012-10-11|
    BR112013025767A2|2017-07-04|
    CN103608515B|2016-05-04|
    TWI565939B|2017-01-11|
    MX349559B|2017-08-03|
    EP2694729B1|2017-11-22|
    RU2602158C2|2016-11-10|
    US9562861B2|2017-02-07|
    CA2831874C|2020-11-03|
    CA2831874A1|2012-10-11|
    AR085930A1|2013-11-06|
    TW201303280A|2013-01-16|
    JP6059201B2|2017-01-11|
    KR101911848B1|2018-10-25|
    EP2694729A4|2014-09-17|
    EP2694729A2|2014-02-12|
    CL2013002860A1|2014-01-24|
    AU2012240348A1|2013-10-17|
    WO2012138704A3|2013-01-17|
    AU2012240348B2|2016-12-22|
    KR20140025441A|2014-03-04|
    RU2013143534A|2015-05-10|
    MX2013011467A|2013-10-17|
    JP2014510201A|2014-04-24|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-16| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-08-25| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-12-22| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-12| B09X| Republication of the decision to grant [chapter 9.1.3 patent gazette]|
    2021-02-23| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/04/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/079,891|2011-04-05|
    US13/079,891|US9562861B2|2011-04-05|2011-04-05|Method of monitoring macrostickies in a recycling and paper or tissue making process involving recycled pulp|
    PCT/US2012/032087|WO2012138704A2|2011-04-05|2012-04-04|Method of monitoring macrostickies in a recycling and paper or tissue making process involving recycled pulp|
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