WO2012021960A1 - Procédé de floculation - Google Patents

Procédé de floculation Download PDF

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Publication number
WO2012021960A1
WO2012021960A1 PCT/CA2010/001256 CA2010001256W WO2012021960A1 WO 2012021960 A1 WO2012021960 A1 WO 2012021960A1 CA 2010001256 W CA2010001256 W CA 2010001256W WO 2012021960 A1 WO2012021960 A1 WO 2012021960A1
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Prior art keywords
flocculant
suspension
metal
concentration
sediment
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PCT/CA2010/001256
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English (en)
Inventor
Haihong Li
Zhiang Zhou
Ross Sam Chow
Pablo Contreras
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Alberta Innovates - Technology Futures
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Priority to PCT/CA2010/001256 priority Critical patent/WO2012021960A1/fr
Publication of WO2012021960A1 publication Critical patent/WO2012021960A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5209—Regulation methods for flocculation or precipitation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)

Definitions

  • This invention relates to a group of hybrid polymeric flocculants for use in solid-liquid separation processes.
  • Flocculation is a unit operation widely used for enhancing the separation of solids from liquid in aqueous suspensions.
  • An organic polymeric flocculant alone or in combination with inorganic coagulants, is normally added in the flocculation process.
  • the most widely used flocculants are synthetic polyacrylamide (PAM)-based flocculants and derivatives thereof. Since its first use in the 1950s, PAM has found application in industries including mining and mineral processing, coal mining, pulp and paper, particularly de-inking, wastewater treatment, soil cleaning, waste oil recovery in oil and gas processing and treatment of tailings and wastewater in the oil and gas industry.
  • PAM polyacrylamide
  • oilsands tailings Treatment of oilsands tailings is a particularly troublesome environmental concern for the oil and gas industry, as the industry comes under increasing pressure to improve its environmental performance.
  • oilsands tailings have been discharged directly from extraction to enormous tailings ponds where they are allowed to naturally settle.
  • the fundamental drawback of this approach is the very large amount of time needed for fine tailings to settle.
  • tailings mature into Matured Fine Tailings (MFT), having a solid loading of about content 30% by weight. MFT tend to resist further consolidation due to the high surface charges on the fine solids and residual bitumen droplets and their interactions.
  • Tailings ponds currently in operation in the Alberta oilsands occupy a total area of more than 130 km 2 . Given their scale, these open ponds pose significant risk of contamination to adjacent surface water resources.
  • the fine tailings paste may be discharged to a tailings pond to allow time for further gradual dewatering and consolidation.
  • the fine tailings paste may be subjected to further rapid dewatering as, for example, by centrifugation.
  • the fine tailings paste which comprises flocculated fine solids and associated water, achieves high solids content when formed and is amenable to subsequent further dewatering and consolidation.
  • the ultimate objective is that the paste be converted into compacted fine solids having at least a minimum solids content that corresponds to the minimum load bearing capacity to support construction traffic and enable final deposition in a reclamation operation.
  • linear PAM having a high molecular mass
  • PAM can only operate within a relatively narrow concentration range, outside of which its flocculating performance deteriorates, resulting in process control difficulties in large scale industrial operations. Over-dosing can result in curling of PAM molecules and associated loss of effectiveness, or results in dispersing rather than flocculating the suspended solid particles.
  • hybrid polymer flocculants is greatly needed to achieve an effective and cost effective means of separation of fine solids from liquids suspensions at an industrial scale, including oilsands tailings suspensions.
  • a method for producing freely draining flocculated sediment from a suspension comprising finely divided solids in water comprises dispersing, at increasing concentrations, a charged particle hybrid polymer (CPHP) flocculant into the suspension to determine a minimum concentration of CPHP flocculant above which a freely draining flocculated sediment is produced that has a minimum permeability of 1 Darcy. Then, the concentration of dispersed CPHP flocculant in the suspension is maintained at or above the minimum concentration.
  • CPHP charged particle hybrid polymer
  • a method for separating fine solids and water from a suspension comprising finely divided solids in water involves dispersing, at increasing concentrations, a charged particle hybrid polymer (CPHP) flocculant into the suspension to determine a minimum concentration of CPHP flocculant above which a freely draining flocculated sediment is produced that has a minimum permeability of 1 Darcy. Then, the concentration of dispersed CPHP flocculant in the suspension is maintained at or above the minimum concentration. The dispersion of CPHP flocculant in the suspension is agitated and the solid floccules are then separated from the supernatant liquid.
  • CPHP charged particle hybrid polymer
  • FIG. 1 shows the form of the floccules produced as a result of increasing metal-hydroxide hybrid polymer (M HP) flocculant dosing concentration
  • Figure 2 shows the results of flocculation of oilsands tailings with Fe(OH) 3 -PAM;
  • Figure 3 shows the floccules produced from flocculation of oilsands tailings with AI(OH) 3 -PAM
  • Figure 4 shows solids loading in the flocculated sediment as a function of flocculant concentration
  • Figure 5 is a graph showing settling time results of two flocculants: PAM and AI(OH) 3 -PAM tested on an oilsands tailings suspension;
  • Figure 6 is a graph showing settling time results of two flocculants: PAM and AI(OH) 3 -PAM tested on a kaolinite suspension.
  • the present invention relates to the applicability of charged particle hybrid polymer (CPHP) flocculants to the separation of finely dispersed solids from aqueous suspensions. More preferably, the present invention explores metal-hydroxide hybrid polymer (MHP) flocculants, a subset of CPHP flocculants, for the treatment of oilsands tailings. The inventors have further investigated the impact of increasing dosing concentrations of the present MHP flocculants. The present flocculants were tested on kaolinite and oilsands clay and fine tailings suspensions, at a variety of dosing concentrations.
  • MHP metal-hydroxide hybrid polymer
  • Dosing concentration for the purposes of the present invention is described in parts per million (ppm), which is defined as milligrams of flocculant per litre of suspension.
  • the inventors have surprisingly found that dosing concentrations of the present CPHP flocculants can be increased beyond the concentration ranges where conventional flocculated sediment is formed and still produce good flocculation results. If dosing is increased further, the present CPHP flocculants were found to significantly increase the solids content and robustness of individual floccules, which settle quickly and produce a flocculated sediment having high permeability and showing excellent dewatering ability.
  • the minimum permeability of the flocculated sediment resulting from the present methods is 1 Darcy. More preferably, a minimum permeability of 10 Darcy is achieved and even further preferably a minimum permeability of 100 Darcy is achieved. No ill-effects previously associated with overdosing were found for the present group of flocculants.
  • the present CPHP flocculants comprise sub-micron size charged particles and a polymer which has been polymerized in the presence of the charged particles.
  • solid particles When solid particles are dispersed in water, they acquire electrical charges, due to either dissolution of the solid surfaces, ionization of surface groups, adsorption of ions from the water on the surfaces, or substitution of ions in the lattice of the solids, etc.
  • the whole suspension system is in electroneutrality, a difference in charge exist between the stationary layer (or plane of shear) of water attached to the dispersed particle and the bulk water. The extent of this difference is normally called zeta-potential.
  • the polarity of zeta potential can be evaluated based on the determination of the iso-electric point (IEP) or point of zero change (PZC), where the net surface charge is zero at a given solution pH, pH pzc , which varies with different types of dispersed solids. Therefore, by changing solution pH, the solids can be positively charged at solution pH less than pH pzc , or negatively charged at solution pH greater than pH pzc . Most mineral particles, for example clays, are negatively charged under natural conditions. For AI(OH)3 the PZC occurs at pH between 9 and 10 .
  • the sub-micron sized particles can be metal oxides or metal hydroxides.
  • the sub-micron sized charged particles are positively charged metal-hydroxide particles and the resulting polymer formed is a metal-hydroxide hybrid polymer (M HP) flocculant. Further preferably, but not necessarily, the polymer can be
  • polyacrylamide or other commercially available polymers that are known in the art to be useful as flocculants. It is understood by the inventors that ionic bonding links PAM to the surface of the positively charged metal-hydroxide particles.
  • An exemplary MHP flocculant is illustrated below using AI(OH) 3 or Fe(OH) 3 _ and showing them to have a positive charge.
  • the metal is preferably, but not necessarily, a transition metal or a multivalent metal when ionized. More preferably, the metal can be aluminum or iron and the metal-hydroxides are most preferably aluminum hydroxide (AI(OH) 3 ) or iron hydroxide (Fe(OH) 3 ). Alternatively, the hydroxides may be mixed metal hydroxides.
  • the flocculant can be a synthesized organic-inorganic hybrid AI(OH) 3 -PAM or Fe(OH) 3 -PAM flocculant.
  • the present group of CPHP flocculants and, more preferably M HP flocculants have shown good flocculating results and excellent dewatering results for a number of types of suspensions. It is hypothesized that these positive results are due to the synergistic effects of both hydrogen bonding between polymer chains bonded on the charged particles and fine solids, and electrostatic attraction between the charged particle core and the oppositely charged fine solids. In the case of M H P flocculants, electrostatic attraction commonly, but not always, exists between the positively charged metal-hydroxide core and the negatively charged fine solids.
  • the dispersion of CPHP flocculant in the suspension is accomplished by one or more methods including stirring, mixing, mechanical agitation and injection mixing.
  • flocculant dosage concentrations can be maintained at this minimum level, or increased further.
  • dosage concentrations are increased by from 1.2 to 3 times the minimum concentration level.
  • the m inimum concentration of CPH P flocculant to achieve high solids loading floccules depends on the concentration and size of the suspended solid particles. It also depends on the degree of agitation applied during flocculation, wherein, up to a certain point, increased agitation results in a reduction in the minimum concentration.
  • Very small scale testing in graduated cylinders with mild agitation provided by shaking, often produced a single large high solids floccule.
  • Beaker scale testing with an impeller type stirrer in some cases inserted to the bottom and imbedded in the flocculated sediment, resulted in sediment comprising largely discrete high solids floccules. In both cases, the supernatant was readily separated from the sediment, either by decanting or by allowing the water to drain away through the flocculated sediment.
  • the residence time for flocculation with the present group of flocculants and flocculant dosage regime is very fast, measured in seconds.
  • the settling rate for the high solids floccules produced is very fast ranging from 12 mm/s to 25 mm/s on clay and mineral suspensions.
  • the turbidity of the supernatant is very low, indicating that the residual solids content of the supernatant is very low, which will contribute to reduced treatment costs and greater flexibility for reuse or disposal of the recovered water.
  • the method was found to produce compacted floccules having high solids content. This is positively correlated with the mechanical robustness of the floccules and, in turn, with the formation of high permeability flocculated sediment that can be readily dewatered. Preliminary results from drained consolidation tests of the flocculated sediments of the present invention indicate that these flocculated sediments are amenable to further compaction and dewatering.
  • the resulting dense and highly dewatered floccules produce a high permeability sediment that is readily amenable to further dewatering by commonly known means including, but not limited to screening, filtering or simply by letting the supernatant liquid drain away through the sediment.
  • the present CPHP flocculants showed good results on oilsands tailings and kaolinite suspension, but can also be used in a number of separation applications including, but not limited to mining and mineral processing, coal mining, pulp and paper, particularly de-inking, water treatment, wastewater treatment, soil cleaning, waste oil recovery in oil and gas processing and treatment of tailings and wastewater in oil and gas production and processing. Examples
  • AI(OH) 3 -PAM Two MHPs were synthesized with different particulates: AI(OH) 3 -PAM and Fe(OH) 3 -PAM.
  • AI(OH) 3 - PAM was made by following a published procedure (Yang et al., 2004).
  • Fe(OH) 3 -PAM was made following a procedure similar to that used for AI(OH) 3 -PAM.
  • MHP synthesis consists of three steps: a. Preparation of a metal-hydroxide colloidal solution comprising sub-micron particles of metal- hydroxide. AI(OH) 3 and Fe(OH) 3 colloid solutions were prepared by a slow and dropwise addition of an ammonium carbonate solution into a metal chloride solution under agitation at room
  • the suspensions used for testing M H P were prepared by mixing fine solid samples with deionised (Dl) or process water at specific solids concentrations. Two solids samples were used for the M HP testing:
  • the suspension was prepared by mixing oil sands clay with process water, containing about 13.1 ppm Ca ++ and 9.2 ppm Mg ++ and allowing 10 minutes for the coarser particles to settle to obtain, as the supernatant, a suspension at pH 8.3 containg 1 wt% suspended solids with a particle size less than 10 microns.
  • the fine solid suspension and the M HP flocculant at the desired dosing concentration were mixed in a 50 ml cylinder for the settling test.
  • the cylinder was sealed with a paraffin wax film and then shaken upside down several times to mix the suspension and M HP flocculant and then placed on a solid plate to begin the settling test.
  • a Canon G10 camera mounted on a tripod was used to take pictures at predetermined time intervals to record the descent of the solids/liquid interface, also called the mudline, in the cylinder.
  • the image data was analysed and transferred to a settling plot of supernatant layer height vs. settling time, which was used to determine the initial settling rate (mm/second) from the slope of the initial linear portion of the plot. All tests were conducted at room temperature of 22°C. 4.
  • Estimation of solid content in sediment was made by dividing the mass of dry solid by the mass of wet, free-drained sediment, and converting to a volume percent.
  • the wet, free-drained sediment is removed from the suspension and weighed to obtain the mass of free-drained, wet sediment and then is heated in an oven (110°C) to dry.
  • the dry solid sediment is weighed to obtain the mass of dry solid.
  • the weight percent is converted to a volume percent by dividing by the known densities of the sediment and of water.
  • FIGS 2 and 3 illustrate the sediments produced by using Fe(OH) 3 -PAM and AI(OH) 3 -PAM flocculants respectively at varying concentrations into the sample suspensions. From Figures 2 and 3 it is evident that a flocculant concentration of 60 ppm in the case of Fe(OH) 3 -PAM and 100 ppm in the case of AI(OH) 3 -PAM is sufficient to produce solid floccules with a clear supernatant liquid.
  • FIG 4 shows the solids loading in the drained sediment resulting from flocculation of the sample suspension with Fe(OH) 3 -PAM.
  • the solids loading in the drained sediment produced at this flocculant concentration is only 21.5 % by weight or 8.6 % by volume.
  • the solid loading in the drained flocculated sediments is 53% by weight or 21.2 % by volume.
  • the minimum concentration lies at a value between 80 ppm and 100 ppm for the present sample suspension and hybrid flocculant tested. Sediment with exactly the same solids loading is produced at a flocculant concentration of 200 ppm, which is at least 200 % of the minimum concentration.
  • Figure 5 compares settling rates of flocculated sediment resulting from flocculation of the present oilsands sample suspensions with PAM and AI(OH) 3 -PAM. With reference to Figure 5, a clear difference is seen in the use of, for example AI(OH) 3 -PAM, versus PAM as a flocculant for oilsands tailings. In the particular example of Figure 5, the settling rate is nearly doubled, leading to faster, cleaner separation of solids and liquid.
  • Figure 6 compares settling rates for a kaolinite suspension treated with AI(OH) 3 -PAM and PAM respectively. Again, the hybrid metal-polymer flocculant performs much better than PAM, in which settling rate actually reduces as dosage increases.
  • Example 2
  • PAM denotes the commercial product designated as Magnafloc 1011, which is a high-molecular-weight medium-charge-density anionic flocculant, supplied by Ciba Specialty Chemicals Ltd. Magnafloc 1011 is reported to be a particularly good flocculant for use with oilsands fine tailings. (Cymerman, G.; Kwong, T.; Lord, E.; Hamza, H.; Xu, Y. In Polymers in Mineral Processing; J. S. Laskowski, Ed.; 38th Annual Conference of Metallurgists of CIM: Quebec, 1999; pp 605-619.) a. The suspensions were conditioned with the added metal hybrid or PAM flocculant in a 1000ml beaker and agitated at 300-450 rpm;
  • the conditioned slurry was then poured into a transparent tube with ID6.35 cm, a screen with an average pore size of _0.6 mm to retain flocculated sediment, a conical tapered section below the screen, and a valve below the tapered section to shut off or allow flow through the sediment layer.
  • This apparatus was first tested with clean water and no sediment layer to determine the extent of the maximum flow rate for the apparatus itself. This was measured to be 166.3 ml/sec;
  • Permeability of the sediment layer was determined in the same apparatus as used for the drainage tests referred to above.
  • the volume of water flowing through the sediment layer was measured while maintaining a constant head of (potable Edmonton) water above the sediment layer.
  • the measured fow rate stabilized withinlO seconds and the stabilized flow rate was used to calculate permeability.
  • the hydrostatic head provided by the experimental apparatus was about 47 cm, which was assessed to be representative of the upper limits of what might be expected in industrial screening or filtration practice. This is an important consideration since above some threshold hydrostatic pressure the sediment bed may undergo accelerated consolidation and consequently a rapid reduction in its permeability. It was determined by observation that when a sediment layer was present, the conical section and tubing downstream from the screen were at all times flowing only partially full.
  • the measured flow rates through the apparatus when a sediment layer was present were, even for the most permeable sediments, only a fraction of those for the apparatus with no sediment layer. Therefore, for the purpose of determining the pressure drop across the sediment layer it was assumed that the pressure at the upstream side of the screen was atmospheric. Consequently the pressure drop across the sediment layer was equal to the hydrostatic pressure of the constant column of water maintained above the sediment layer.
  • k is the permeability of the sediment (m 2 );
  • ⁇ is the dynamic viscosity of the fluid (Pa.s);
  • L is the measured thickness of the sediment layer (m);
  • Q is the measured flow rate through the sediment layer (m 3 /sec).
  • p is the density of the fluid (Kg/m 3 )
  • h is the measured height of water above the sediment layer (m)
  • A is the cross sectional area of the sediment layer (m 2 )
  • the value used for the viscosity of the potable water was 0.00089 Pa ' s.
  • the filtrate was analysed for dissolved calcium, magnesium and iron and compared to concentrations of these metals in the starting process water.
  • Permeability of the flocculated sediment was greatly improved by use of the present M HP flocculants provided the treated suspension contained an adequate fraction of fine (less than 2 micron) particles. It was not possible to determine permeability for tests 1, 2, 3 and 5 because there was insufficient drainage through the flocculated sediment. Increased permeability enables faster and more complete separation of supernatant from the flocculated sediment with less energy input. d. Compressibility of flocculated sediment

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

L'invention porte sur un procédé pour produire, à partir d'une suspension comprenant des solides finement divisés dans l'eau, un sédiment floculé s'évacuant librement. Le procédé comprend la dispersion, à des concentrations croissantes, d'un floculant polymère hybride à particules chargées (CPHP) dans la suspension de façon à déterminer une concentration minimale de floculant CPHP au-dessus de laquelle un sédiment floculé s'évacuant librement est produit, ledit sédiment ayant une perméabilité minimale de 1 Darcy. Ensuite, la concentration du floculant CPHP dispersé dans la suspension est maintenue à la concentration minimale ou au-dessus de celle-ci. L'invention porte également sur un procédé pour séparer des solides fins et de l'eau à partir d'une suspension comprenant des solides finement divisés dans l'eau. Le procédé met en jeu la dispersion, à des concentrations croissantes, d'un floculant polymère hybride à particules chargées (CPHP) dans la suspension de façon à déterminer une concentration minimale de floculant CPHP au-dessus de laquelle un sédiment floculé s'évacuant librement est produit, ledit sédiment ayant une perméabilité minimale de 1 Darcy. Ensuite, la concentration de floculant CPHP dispersé dans la suspension est maintenue à la concentration minimale ou au-dessus de celle-ci. La dispersion de floculant CPHP dans la suspension est agitée et les flocons solides sont ensuite séparés du liquide surnageant.
PCT/CA2010/001256 2010-08-18 2010-08-18 Procédé de floculation WO2012021960A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7439865B2 (ja) 2022-07-28 2024-02-28 栗田工業株式会社 監視システム、学習装置、監視方法、学習方法およびプログラム

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GRAY, GEORGE R. ET AL.: "Composition and Properties of Oil Well Drilling Fluids (4th Edition)", 1980, pages: 286 - 293 *
GREEN, DON W. ET AL.: "Perry's Chemical Engineers' Handbook (8th Edition).", MCGRAW-HILL. *
YANG, W.Y.: "A novel flocculant of A1(OH)3- polyacrylamide ionic hybrid", JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 273, no. IS.2, 2004, pages 400 - 405 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7439865B2 (ja) 2022-07-28 2024-02-28 栗田工業株式会社 監視システム、学習装置、監視方法、学習方法およびプログラム

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