Method for preventing adhesion of and clogging with mineral raw material

Abstract

A method for preventing adhesion of and clogging with a mineral raw material by performing at least any of transfer and treatment of a raw material mixture in which a mineral raw material has been brought into contact with a cationic w / o emulsion polymer in a transfer and treatment facility and preventing adhesion of and clogging with the mineral raw material in the transfer and treatment facility, wherein the cationic w / o emulsion polymer has an intrinsic viscosity of 10.0 dL / g or less.

Description

DESCRIPTIONTitle of Invention: METHOD FOR PREVENTING ADHESION OF AND CLOGGING WITH MINERAL RAW MATERIALTechnical Field

[0001] The present invention relates to a method for preventing adhesion of and clogging with a mineral raw material, and in particular to a method for preventing adhesion of and clogging with a mineral raw material that exhibits an excellent modification effect (reduction of adhesiveness) even when an excessive amount of w / o emulsion polymer is brought into contact with the mineral raw material.Background Art

[0002] Mineral raw materials, including coal, iron ore, and others, are mined at mines and conveyed to storage and preservation areas, treatment facilities, or other locations inside or outside the mining sites by means of transfer and treatment facilities such as conveyor belts, freight cars, cargo ships, and trucks, for storage, preservation, and treatment. After that, mineral raw materials are conveyed to the use facilities where the mineral raw materials are used (steel works, thermal power plants, factories, and other places) by means of transfer and treatment facilities.At such mining sites, storage and preservation areas, treatment facilities, use facilities, and other places, the mineral raw materials are usually stacked outdoors in raw material yards as inventory. The mineral raw materials stacked outdoors in raw material yards may contain water sprayed as a dust control measure or rainwater during storage and cleaning, and thus tend to have a high water content rate.

[0003] For example, when coal, a type of mineral raw material stacked outdoors in the raw material yard, is supplied to a boiler of a thermal power plant, generally, coal is conveyed to the boiler by a series of lines in which after the changing of conveyor belts, the coal passes through a coal grinding machine and a bucket type conveyor. At this time, if the coal conveyed to the boiler is wet, such wet coal is likely to adhere to the contact surfaces of treatment facilities such as pipings that supply coal to the boiler (coal supply pipe), conveyor belts, chutes, and hoppers, and is further fixed thereon, and the pipings and the like may be clogged.

[0004] When such adhesion and clogging occur, conventionally, it was required to stop the operation of the lines and remove the clogging coal or disassemble the transfer and treatmentfacilities to eliminate the adhesion and clogging. Therefore, the coal transfer efficiency is reduced, and furthermore, a situation in which power generation efficiency in the thermal power plant is decreased also occurs.

[0005] To address such a problem, there is a known method in which a modifying agent (such as a polymer (high molecular compound) with excellent water absorbency and water retainability) is brought into contact (sprayed, added, or otherwise) with the mineral raw material to modify the properties of the mineral raw material (such as reduction of adhesion and reduction of flowability).Examples of the method for bringing the modifying agent into contact with the mineral raw material include spraying the modifying agent on the mineral raw material stacked outdoors in the raw material yard, or spraying a fixed amount of the modifying agent from above the mineral raw material when the mineral raw material is being transferred by a transfer and treatment facility, such as a conveyor belt. However, with these methods, it is hardly possible to hope for a constant amount of modifying agent to be brought into contact with a constant amount of mineral raw material with constant quality (for example, water content or other properties) at any given time. That is, a portion of the mineral raw material may come in contact with an excessive amount of modifying agent compared to other portions, hi addition, in the case where a polymer (high molecular compound) is used as the modifying agent, when an excessive amount of the polymer (high molecular compound) is brought into contact with the mineral raw material, spinnability may occur due to the properties of the polymer (high molecular compound), which in turn may increase the adhesiveness of the mineral raw material. Therefore, for a method for preventing adhesion of and clogging with a mineral raw material by bringing a modifying agent into contact with the mineral raw material, it is desirable to exhibit an excellent modification effect (reduction of adhesiveness) even when an excessive amount of the modifying agent is brought into contact with the mineral raw material.

[0006] In Patent Literature 1, it is disclosed that by adding a water soluble high molecular compound (an anionic w / o emulsion polymer: modifying agent) to a coal and / or iron ore slurry and mixing them, the flowability of the coal and / or iron ore slurry can be reduced and the resulting modified product can be handled stably and easily.Citation ListPatent Literature

[0007] PTL1: JP 2012-214292 ASummary of InventionTechnical Problem

[0008] However, in the above Patent Literature 1 , there is a problem that when an excessive amount of water soluble high molecular compound (anionic w / o emulsion polymer: modifying agent) is brought into contact with the mineral raw material, it does not exhibit an excellent modification effect (reduction of adhesiveness).

[0009] The present invention has been made in view of such circumstances, and an object thereof is to provide a method for preventing adhesion of and clogging with a mineral raw material that exhibits an excellent modification effect (reduction of adhesiveness) even when an excessive amount of w / o emulsion polymer is brought into contact with the mineral raw material.Solution to Problem

[0010] The present invention is based on the finding that a cationic w / o emulsion polymer having a predetermined intrinsic viscosity exhibits an excellent modification effect (reduction of adhesiveness) even when it is brought into contact with the mineral raw material in an excessive amount.

[0011] That is, the present invention provides the following [1] to [8].

[0001] A method for preventing adhesion of and clogging with a mineral raw material by performing at least any of transfer and treatment of a raw material mixture in which a mineral raw material has been brought into contact with a cationic w / o emulsion polymer in a transfer and treatment facility and preventing adhesion of and clogging with the mineral raw material in the transfer and treatment facility, wherein the cationic w / o emulsion polymer has an intrinsic viscosity of 10.0 dL / g or less.Here, the intrinsic viscosity of the cationic w / o emulsion polymer is determined according to the following procedures (i) to (v).(i) Five Cannon-Fenske viscometers (manufactured by Kusano Kagaku K.K., No. 75) are immersed in neutral detergent for glassware for one day or longer, then thoroughly washed with water and dried.(ii) The cationic w / o emulsion polymer is diluted with water to prepare an aqueous solution with a polymer concentration of 0.2% by mass.(iii) To 50 mL of the aqueous solution with a polymer concentration of 0.2% by mass prepared in (ii), 50 mL of a 2 mol / L aqueous sodium nitrate solution is added, and the mixture is stirred with a magnetic stirrer at 500 rpm for 20 minutes to obtain a 1 mol / L aqueoussodium nitrate solution with a polymer concentration of 0.1% by mass. This is diluted with a 1 mol / L aqueous sodium nitrate solution to prepare polymer solution samples with five levels of polymer concentration: 0.02, 0.04, 0.06, 0.08, and 0.1% by mass. Note that a 1 mol / L aqueous sodium nitrate solution with no polymer added is used as the blank solution.(iv) In a thermostatic bath adjusted to a temperature of 30°C (within ±0.02°C), the five viscometers provided in (i) are attached vertically. After placing 10 mL of blank solution in each viscometer with a whole pipette, they are allowed to stand still for about 30 minutes in order to make the temperature constant. Thereafter, the solution is suctioned up by using a dropper plug, allowed to fall naturally, and the time it takes to pass through the marked line is measured to the nearest 1 / 100 second with a stopwatch. This measurement is repeated 5 times for each viscometer and the average value is taken as a blank value (to).(v) 10 mL of each of the polymer solution samples with five levels of polymer concentration prepared in (iii) is placed in the five viscometers by which the measurement of the blank solution has been carried out, and allowed to stand still for about 30 minutes in order to make the temperature constant. Thereafter, the same operation as in the measurement of the blank solution is repeated 3 times, and the average value of the passing times for each concentration is taken as a measurement value (t). From the blank value to, the measurement value t, and the concentration [mass / volume %] (= C [g / dL]) of the polymer solution sample, the relative viscosity prei, the specific viscosity psp, and the reduced viscosity T|SP / C [dL / g] are determined according to the relational expressions shown in the following expressions (II) and (III).From these values, the intrinsic viscosity [p] of each polymer is determined according to the method for determining intrinsic viscosity [p] based on the following Huggins equation. Note that the method for determining intrinsic viscosity [p] described above means a method in which multiple polymer solution samples with different polymer concentrations are prepared, the specific viscosity psp of the polymer solution sample with each concentration is determined and plotted on a graph with psp / C as the vertical axis and C as the horizontal axis, and the intercept (intrinsic viscosity [p]) is determined by extrapolating C to 0. Huggins equationk' = Huggins constant[2] The method for preventing adhesion of and clogging with a mineral raw material according to the above [1], wherein the cationic w / o emulsion polymer has a colloid equivalent value of 5.0 meq / g or less.Here, as for the colloid equivalent value of the cationic w / o emulsion polymer, the colloid equivalent value at pH 4 is determined according to the following procedures (1) to (8).(1) While stirring deionized water using a magnetic stirrer at 1500 rpm at room temperature 25°C, the cationic w / o emulsion polymer is quickly poured in along the inner surface of the vortex to a polymer concentration of 0.2% by mass, and the mixture is stirred for 1 hour. Note that, if dissolution is insufficient, the mixture is further stirred for 1 hour. Thereafter, the solution is allowed to stand still overnight at room temperature for dissolution.(2) 25 mL of the aqueous solution with a polymer concentration of 0.2% by mass prepared in (1) is measured out with a whole pipette, placed in a 200 mL measuring cylinder, diluted using deionized water, and stirred by inversion to prepare an aqueous solution (measurement sample) with a polymer concentration of 250 mg / L.(3) Four conical beakers are provided, 80 mL of deionized water is placed in each of the conical beakers, 20 mL of the measurement sample prepared in (2) is further added, and the mixture is thoroughly stirred with a magnetic stirrer and used as a sample to be titrated.(4) While checking with a pH meter, an aqueous hydrochloric acid solution or an aqueous sodium hydroxide solution is added to the sample to be titrated to reach a pH of 3, 5, 7, or 9, thereby adjusting the pH of the respective samples to be titrated.(5) To each of the samples to be titrated whose pH has been adjusted to 3, 5, 7, or 9, 1 to 2 drops of toluidine blue are immediately added as an indicator in advance, and the mixture is stirred for 10 seconds.(6) Next, the titration is immediately earned out using a 0.0025 mol / L (1 / 400 N) potassium polyvinyl sulfate standard solution as the titrant while stirring at a rate of 2 mL / min, and the titration volume, D mL, is determined at the endpoint where the color changes from blue to pink and the pink color is retained for 10 seconds or longer.(7) In the meantime, deionized water is also titrated by the same method as for the samples to be titrated described above to determine a blank titration volume, E mL. From the results of titration volume D mL and blank titration volume E mL, the colloid equivalent value of the samples to be titrated whose pH has been adjusted to 3, 5, 7, and 9 is calculated, respectively, according to the following expression: colloid equivalent value [meq / g] = (titrant concentration (0.0025 mol / L) x (D mL - E mL)) / amount of polymer in measurement sample (g).(8) For each of the samples to be titrated whose pH has been adjusted to pH 3, 5, 7, and 9, the pH value is measured after the titration is completed, and the measured pH value and the colloid equivalent value calculated according to the expression described above are plotted onthe X axis of a graph and on the Y axis of a graph, respectively. The colloid equivalent value at the value corresponding to pH 4 is read from the curve formed by connecting the four points plotted on the graph, and is taken as the colloid equivalent value (meq / g) at pH 4.[3] The method for preventing adhesion of and clogging with a mineral raw material according to the above [1] or [2], wherein the ratio of the colloid equivalent value to the intrinsic viscosity of the cationic w / o emulsion polymer (colloid equivalent value / intrinsic viscosity) is 0.5 meq / dL or more when the colloid equivalent value is 3.0 meq / g or more and the intrinsic viscosity is 4.0 to 10.0 dL / g.[4] The method for preventing adhesion of and clogging with a mineral raw material according to any of the above [1] to [3], wherein the transfer and treatment facility is at least one selected from the group consisting of a hold, an unloader, a stacker, a raw material yard, a reclaimer, a piping, a conveyor belt, a conveyor belt transfer portion, a conveyor chain, a chute, a hopper, a silo, a blending tank, a grinding machine, a coal moisture control facility, and a larry car.[5] The method for preventing adhesion of and clogging with a mineral raw material according to any of the above [1] to [4], wherein the mineral raw material is at least one selected from the group consisting of coal, ore, dust, coke, and limestone.[6] The method for preventing adhesion of and clogging with a mineral raw material according to any of the above [1] to [5], wherein the mineral raw material contains water, and the content of the water is 1.0% by mass or more in 100% by mass of the mineral raw material.[7] The method for preventing adhesion of and clogging with a mineral raw material according to any of the above [1] to [6], comprising a step of spraying the cationic w / o emulsion polymer on the mineral raw material at least either before transfer or during transfer in the transfer and treatment facility to obtain the raw material mixture.[8] The method for preventing adhesion of and clogging with a mineral raw material according to any of the above [1] to [7], comprising a step of adding the cationic w / o emulsion polymer into a container accommodating the mineral raw material, followed by stirring and mixing to obtain the raw material mixture.Advantageous Effects of Invention

[0012] According to the present invention, there can be provided a method for preventing adhesion of and clogging with a mineral raw material that exhibits an excellent modificationeffect (reduction of adhesiveness) even when an excessive amount of w / o emulsion polymer is brought into contact with the mineral raw material.The method of the present invention can contribute to efficient transfer or treatment of a mineral raw material.Description of Embodiments

[0013] Hereinafter, the present invention will be described in detail.In the present specification, the provisions regarded to be preferable can be adopted arbitrarily, and combinations of preferable ones can be said to be more preferable.In the present specification, the description of a numerical range "XX to YY" means "XX or more and YY or less".In the present specification, the lower limit values and upper limit values listed in stages for the preferable numerical ranges (for example, the range of content or the like) can be combined each independently. For example, from the description "preferably 10 to 90, more preferably 30 to 60", the "preferable lower limit value (10)" and the "more preferable upper limit value (60)" can be combined to form "10 to 60". Also, in the numerical ranges described in the present specification, the upper limit values or lower limit values of those numerical ranges may be replaced by the value shown in Examples.In the present specification, the expression "preventing adhesion of and clogging with" is used in the sense of including not only the case of neither adhesion nor clogging at all, but also the case where adhesion and clogging are sufficiently suppressed to the extent that the transfer of mineral raw material is not disturbed, even when adhesion of and clogging with the mineral raw material partially occur.In the present specification, the expression "excessive amount" in "when an excessive amount of w / o emulsion polymer is brought into contact with the mineral raw material" means the amount where spinnability can be confirmed (spinning is visible) when a modifying agent 4 (anionic w / o emulsion polymer) of Synthesis Example 4 disclosed herein is brought into contact with the mineral raw material.

[0014] [Method for preventing adhesion of and clogging with mineral raw material]A method for preventing adhesion of and clogging with a mineral raw material according to an embodiment of the present invention is a method for preventing adhesion of and clogging with a mineral raw material by performing at least any of transfer and treatment of a raw material mixture in which a mineral raw material, in particular, wet mineral raw material or slurry-like mineral raw material has been brought into contact with a cationic w / o emulsion polymer in a transfer and treatment facility and preventing adhesion of and cloggingwith the mineral raw material in the transfer and treatment facility, wherein the cationic w / o emulsion polymer has an intrinsic viscosity of 10.0 dL / g or less.The surface of the mineral raw material is modified by contact with the cationic w / o emulsion polymer described above. This suppresses the adhesiveness of the mineral raw material to the contact surfaces of the transfer and treatment facility, thereby enabling the adhesion of or clogging with the mineral raw material to be prevented in the transfer and treatment facility.

[0015] (Mineral raw material)There is no particular limitation on the type of mineral raw material, and examples thereof include coal, ore, dust, coke, limestone, oil coke, and semi-coke. These may be one type alone or a mixture of two or more types. Among these, coal, ore, dust, coke, and limestone are preferable; coal and ore are more preferable; coal and iron ore are still more preferable; and coal is particularly preferable.Note that there is no particular limitation on the ore described above, and examples thereof include gold ore, silver ore, copper ore, lead ore, iron ore, bismuth ore, tin ore, antimony ore, mercury ore, zinc ore, and chromium ore. These may be one type alone or a mixture of two or more types.

[0016] There is no particular limitation on the shape of the mineral raw material, and examples thereof include particle form and powder form.

[0017] There is no particular limitation on the particle diameter of the mineral raw material, but it is preferably 10.0 mm or less, more preferably 0.1 to 7.0 mm, and particularly preferably 1 .0 to 5.0 mm.Note that the particle diameter of the mineral atom can be determined by the measurement method described in Examples.

[0018] In the present specification, the expression "wet mineral raw material" means a mineral raw material in which moisture is present on the particle surface, and the expression "slurrylike mineral raw material" means a fluid mineral raw material in which particles are suspended in a liquid.The water content rate (contained moisture) of the wet mineral raw material and slurrylike mineral raw material depends on the type and properties of the mineral raw material and cannot be defined generally, but when the water content rate is 1 to 10% by mass in 100% by mass of the mineral raw material, it can be said to be in a wet state, and when the water content rate is more than 10% by mass, it can be said to be in a slurry state.In the case where the mineral raw material is coal, when the water content rate is 1 to 12% by mass in 100% by mass of the coal, it can be said to be in a wet state, and when the water content rate is more than 12% by mass, it can be said to be in a slurry state.In the case where the mineral raw material is iron ore out of ore, when the water content rate is 1 to 9% by mass in 100% by mass of the iron ore, it can be said to be in a wet state, and when the water content rate is more than 9% by mass, it can be said to be in a slurry state.There is no particular limitation on the origin of the water in the mineral raw material, and it may be derived from the mineral raw material itself, or it may be water such as rain or sprinkled water for dust prevention that has come in contact with the mineral raw material during conveyance or storage.

[0019] Although there is no particular limitation on the water content rate of the mineral raw material, from the viewpoint of fully demonstrating the effect of the present invention (to provide a method for preventing adhesion of and clogging with a mineral raw material that exhibits an excellent modification effect (reduction of adhesiveness) even when an excessive amount of w / o emulsion polymer is brought into contact with the mineral raw material), a condition requiring an excessive amount of w / o emulsion polymer, that is, a condition with a high water content rate, can be said to be suitable, and it is preferably 1% by mass or more, more preferably 7% by mass or more, still more preferably 10% by mass or more, and particularly preferably 15% by mass or more in 100% by mass of the mineral raw material.Also, in the case where the mineral raw material is coal, there is no particular limitation on the water content rate of the coal, but from the viewpoint of fully demonstrating the effect of the present invention (to provide a method for preventing adhesion of and clogging with a mineral raw material that exhibits an excellent modification effect (reduction of adhesiveness) even when an excessive amount of w / o emulsion polymer is brought into contact with the mineral raw material), a condition requiring an excessive amount of w / o emulsion polymer, that is, a condition with a high water content rate, can be said to be suitable, and it is preferably 10% by mass or more, more preferably 15% by mass or more, and particularly preferably 20% by mass or more in 100% by mass of the coal.Furthermore, in the case where the mineral raw material is iron ore out of ore, there is no particular limitation on the water content rate of the iron ore, but from the viewpoint of fully demonstrating the effect of the present invention (to provide a method for preventing adhesion of and clogging with a mineral raw material that exhibits an excellent modification effect (reduction of adhesiveness) even when an excessive amount of w / o emulsion polymer is brought into contact with the mineral raw material), a condition requiring an excessiveamount of w / o emulsion polymer, that is, a condition with a high water content rate, can be said to be suitable, and it is preferably 5% by mass or more and more preferably 8% by mass or more in 100% by mass of the iron ore.Note that the water content rate of the mineral raw material, coal, and other materials can be determined by the measurement method described in Examples.

[0020] (Cationic w / o emulsion polymer)There is no particular limitation on the cationic w / o emulsion polymer, and examples thereof include homopolymers and copolymers constituted by: (i) a nonionic monomer such as (meth)acrylic acid ester, (meth)acrylamide, and oxyalkylene; (ii) a cationic monomer such as alkyleneimine, (meth)acrylic acid N-alkylaminoalkyl ester, and (meth)acrylic acid N- alkylaminoalkyl ester quaternary salt; and others.Note that, in the present specification, the term "(meth)acryl" means "acryl" or "methacryl".

[0021] There is no particular limitation on the (meth)acrylic acid ester, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth) acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hydroxyethyl (meth)acrylate, and 2-ethylhexyl (meth) acrylate.There is no particular limitation on the oxyalkylene, and examples thereof include ethylene oxide and propylene oxide.There is no particular limitation on the (meth)acrylamide, and examples thereof include (meth)acrylamide and N-ethyl(meth)acrylamide. Among these, (meth)acrylamide is preferable, and acrylamide is more preferable.There is no particular limitation on the alkyleneimine, and examples thereof include ethylenimine and methylethylenimine.There is no particular limitation on the monomer constituting the (meth)acrylic acid N- alkylaminoalkyl ester, and examples thereof include 2-dimethylaminoethyl (meth)acrylate.There is no particular limitation on the monomer constituting the (meth)acrylic acid N- alkylaminoalkyl ester quaternary salt, and examples thereof include ethyl 2-(meth)acrylate trimethylammonium chloride and ethyl 2-(meth)acrylate dimethylethylammonium chloride. Among these, ethyl 2-(meth)acrylic acid trimethylammonium chloride is preferable.One type of the monomers described above may be used alone, or two or more types thereof may be used in combination.

[0022] There is no particular limitation on the cationic w / o emulsion polymer, but from the viewpoint of ease of availability, polymers constituted by (meth)acrylic acid N- alkylaminoalkyl ester quaternaiy salt and copolymers constituted by (meth)acrylamide and(meth)acrylic acid N-alkylaminoalkyl ester quaternary salt are preferable, polymers constituted by methacrylic acid N-alkylaminoalkyl ester quaternary salt and copolymers constituted by acrylamide and acrylic acid N-alkylaminoalkyl ester quaternary salt are more preferable, and polymers constituted by ethyl 2-methacrylate trimethylammonium chloride and copolymers constituted by ethyl 2-acrylate trimethylammonium chloride and acrylamide are particularly preferable.One type of the cationic w / o emulsion polymers may be used alone, or two or more types thereof may be used in combination.

[0023] The cationic w / o emulsion polymer may have or may not have a crosslinked structure. Such a crosslinked structure can be formed by using a crosslinking agent, if necessary, when producing the cationic w / o emulsion polymer.There is no particular limitation on the crosslinking agent, and examples thereof include N,N'-methylenebis(meth)acrylamide, triallylamine, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3 -butylene glycol di(meth)acrylate, triallylamine, and ethoxylated isocyanurate tri(meth)acrylate. One type of these may be used alone, or two or more types thereof may be used in combination.

[0024] The amount of the cationic w / o emulsion polymer brought into contact with the mineral raw material is adjusted as appropriate depending on the water content of the mineral raw material, the type of cationic w / o emulsion polymer, and other factors, and is not particularly limited, but it is preferably 0.005 to 0.500% by mass, more preferably 0.010 to 0.300% by mass, and particularly preferably 0.020 to 0.200% by mass with respect to 100% by mass of the mineral raw material.Also, in the case where the mineral raw material is coal, the amount of the cationic w / o emulsion polymer brought into contact with the coal is not particularly limited, but it is preferably 0.005 to 0.500% by mass, more preferably 0.010 to 0.300% by mass, and particularly preferably 0.020 to 0.200% by mass with respect to 100% by mass of the coal.Furthermore, in the case where the mineral raw material is iron ore out of ore, the amount of the cationic w / o emulsion polymer brought into contact with the iron ore is not particularly limited, but it is preferably 0.005 to 0.500% by mass, more preferably 0.010 to 0.300% by mass, and particularly preferably 0.020 to 0.200% by mass with respect to 100% by mass of the iron ore.When the amount is at or above the lower limit value of the range described above, it is easier to demonstrate the effect of reducing the adhesiveness of the mineral raw material. When the amount is at or below the upper limit value of the range described above, it is economically advantageous and adhesiveness tends to be low.

[0025] Although there is no particular limitation on the intrinsic viscosity of the cationic w / o emulsion polymer as long as it is 10.0 dL / g or less, it is preferably 1.0 to 10.0 dL / g, more preferably 2.0 to 9.0 dL / g, and particularly preferably 3.0 to 8.0 dL / g.When the intrinsic viscosity is at or above the lower limit value of the range described above, it is easier to demonstrate the effect of reducing the adhesiveness of the mineral raw material. When the intrinsic viscosity is at or below the upper limit value of the range described above, expression of spinnability due to the polymer is less likely to occur.Note that the intrinsic viscosity of the cationic w / o emulsion polymer can be determined by the measurement method described in Examples.

[0026] Although there is no particular limitation on the colloid equivalent value of the cationic w / o emulsion polymer, it is preferably 5.0 meq / g or less and more preferably 0.1 to 5.0 meq / g.When the colloid equivalent value is at or above the lower limit value of the range described above, it is easier to demonstrate the effect of reducing the adhesiveness of the mineral raw material.Note that the colloid equivalent value of the cationic w / o emulsion polymer can be determined by the measurement method described in Examples.

[0027] Although there is no particular limitation on the ratio of the colloid equivalent value to the intrinsic viscosity of the cationic w / o emulsion polymer (colloid equivalent value / intrinsic viscosity), it is preferably 0.5 meq / dL or more and more preferably 0.5 to 1.7 meq / dL when the colloid equivalent value is 3.0 meq / g or more and the intrinsic viscosity is 4.0 to 10.0 dL / g.

[0028] There is no particular limitation on the method for producing the cationic w / o emulsion polymer, and examples thereof include a reverse phase suspension polymerization method, an aqueous solution polymerization method, and an emulsion polymerization method.The reverse phase suspension polymerization method is a method in which a monomer mixture containing the monomer described above, a polymerization catalyst, and an aqueous solution containing a crosslinking agent and other materials are suspended with a dispersing agent in an organic solvent (hexane, toluene, or the like), and polymerized at a constant temperature (for example, 60 to 80°C). After the polymerization, the organic solvent is removed by centrifugal dewatering or the like, and furthermore, the moisture is removed with a dryer or the like, thereby affording a pearl-like cationic w / o emulsion polymer.On the other hand, the aqueous solution polymerization method includes a thermal insulation type polymerization method in which water is used as the solvent, and themonomer described above, a polymerization catalyst, and a mixed solution containing a crosslinking agent and other materials are used and polymerized in a reaction vessel, and a belt type polymerization method in which the mixed solution described above is polymerized on a continuously moving conveyor belt. After the polymerization, the polymerized product obtained by the aqueous solution polymerization method is dried to remove the moisture, and then ground (crushed) to adjust the particle size distribution.The emulsion polymerization method is a method in which an oil phase containing an oily solvent and a surfactant is prepared, and an aqueous solution of the monomer is added to the oil phase, followed by stirring and mixing for emulsification and polymerization. In the case where the polymerization initiator is water soluble, it may be mixed into the aqueous solution of the monomer described above, or in the case where it is oil soluble, it may be added after the emulsification.

[0029] (Transfer and treatment facility)There is no particular limitation on the transfer and treatment facility referred to in the present invention, and for example, it refers to a facility in transfer lines, in which the mineral raw material is fed by predetermined lines from a hold to a facility where the mineral raw material is used through a mineral raw material storage space such as a raw material yard. Specific examples thereof include a hold, an unloader, a stacker, a raw material yard, a reclaimer, a piping, a conveyor belt, a conveyor belt transfer portion, a conveyor chain, a chute, a hopper, a silo, a blending tank, a grinding machine, a coal moisture control facility, and a larry car. One type of these may be used alone, or two or more types thereof may be used in combination. Note that, here, the transfer and treatment facility includes those having the function of temporary storage, such as a chute, a hopper, and a silo, as well, and is distinguished from transport by a ship, a truck, or the like, conveyance by a bucket, and the like.In the present invention, a good adhesion and clogging prevention effect can be obtained particularly in places where inconveniences due to adhesion and clogging are likely to occur, specifically, pipings, conveyor belts, conveyor chains, chutes, hoppers, silos, and the like, of the transfer and treatment facility.The mineral raw material is likely to cause adhesion and clogging in the transfer and treatment facility, and when clogging occurs, it is necessary to stop the operation of the lines and then eliminate clogging, as described above, and effort is required.In contrast, according to the present invention, the mineral raw material is less likely to adhere to the contact surfaces of the transfer and treatment facility, and therefore, clogging with the mineral raw material in the transfer and treatment facility can be simply preventedwithout stopping the operation of the lines and conveyability can be improved efficiently and stably.

[0030] (Raw material mixture)The raw material mixture is a mixture of the mineral raw material and the cationic w / o emulsion polymer obtained by bringing the cationic w / o emulsion polymer into contact with the mineral raw material.When the cationic w / o emulsion polymer is brought into contact with the mineral raw material, at least some of the contained moisture in the mineral raw material is absorbed by the cationic w / o emulsion polymer and the contained moisture on the surface of the mineral raw material is reduced, and the adhesiveness of the mineral raw material to the contact surfaces of the transfer and treatment facility is reduced. Note that it is sufficient if the adhesiveness to the contact surfaces of the transfer and treatment facility is suppressed, and it is not necessary that the entire amount of the contained moisture in the mineral raw material be absorbed by the cationic w / o emulsion polymer.

[0031] Although there is no particular limitation on the method for bringing the cationic w / o emulsion polymer into contact with the mineral raw material to obtain the raw material mixture, it is preferable that the raw material mixture is obtained in a state where the mineral raw material and the cationic w / o emulsion polymer are uniformly mixed and in contact with each other.There is no particular limitation on the position at which the cationic w / o emulsion polymer is brought into contact, and examples thereof include before the transfer of the mineral raw material by a transfer and treatment facility such as a conveyor belt, during the transfer, and after the transfer. This may be performed at one location alone or at two or more locations in combination.For example, the raw material mixture can be obtained by spraying the cationic w / o emulsion polymer on the mineral raw material at least either before transfer or during transfer (before transfer, during transfer, or both before and during transfer) in the transfer and treatment facility such as a conveyor belt. Among the above, from the viewpoint of man- hour reduction and convenience, it is preferable to spray the cationic w / o emulsion polymer on the mineral raw material before transfer or during transfer, and it is more preferable to spray the cationic w / o emulsion polymer on the mineral raw material from above the mineral raw material during transfer by the transfer and treatment facility such as a conveyor belt.The raw material mixture can also be obtained by adding the cationic w / o emulsion polymer into a predetermined container accommodating the mineral raw material, followed by stirring and mixing.Furthermore, the raw material mixture can also be obtained by spraying the cationic w / o emulsion polymer onto the yard where the raw material is stored and mixing them with heavy machines, kneaders, or other equipment.

[0032] There is no particular limitation on the method for bringing the cationic w / o emulsion polymer into contact with the mineral raw material, and examples thereof include spraying, air pressure feed, and a screw feeder.There is no particular limitation on the method for mixing the cationic w / o emulsion polymer and the mineral raw material either, and examples thereof include a method in which the mineral raw material and the cationic w / o emulsion polymer are mixed using a heavy machine, a method in which they are mixed utilizing the impact of a conveyor belt transfer portion, and a method in which they are mixed using a mixing apparatus such as a mixer.Examples

[0033] The present invention will be specifically described below by Examples, but the present invention is not limited by the following Examples.

[0034] <Measurement of water content rate in mineral raw material>The water content rate of the mineral raw material was calculated according to the following expression by measuring the mass (A) for about 5 g of the mineral raw material, measuring the mass (B) after drying it with a dryer at 105°C for 2 hours, and taking the amount of reduction (A - B) as the amount of moisture: moisture content [% by mass] = (A - B) / A x 100.

[0035] <Measurement of particle diameter in mineral raw material>The particle diameter of the mineral atom was measured using the sieving test method (dry sieving method) of JIS Z 8815:1994.

[0036] <Measurement of intrinsic viscosity of cationic w / o emulsion polymer>The intrinsic viscosity of the cationic w / o emulsion polymer was determined according to the following procedures (i) to (v).(i) Five Cannon-Fenske viscometers (manufactured by Kusano Kagaku K.K., No. 75) were immersed in neutral detergent for glassware for one day or longer, then thoroughly washed with water and dried.(ii) The cationic w / o emulsion polymer was diluted with water to prepare an aqueous solution with a polymer concentration of 0.2% by mass.(iii) To 50 mL of the aqueous solution with a polymer concentration of 0.2% by mass prepared in (ii), 50 mL of a 2 mol / L aqueous sodium nitrate solution was added, and the mixture was stirred with a magnetic stirrer at 500 rpm for 20 minutes to obtain a 1 mol / Laqueous sodium nitrate solution with a polymer concentration of 0.1% by mass. This was diluted with a 1 mol / L aqueous sodium nitrate solution to prepare polymer solution samples with five levels of polymer concentration: 0.02, 0.04, 0.06, 0.08, and 0.1% by mass. Note that a 1 mol / L aqueous sodium nitrate solution with no polymer added was used as the blank solution.(iv) In a thermostatic bath adjusted to a temperature of 30°C (within ±0.02°C), the five viscometers provided in (i) were attached vertically. After placing 10 mL of blank solution in each viscometer with a whole pipette, they were allowed to stand still for about 30 minutes in order to make the temperature constant. Thereafter, the solution was suctioned up by using a dropper plug, allowed to fall naturally, and the time it took to pass through the marked line was measured to the nearest 1 / 100 second with a stopwatch. This measurement was repeated 5 times for each viscometer and the average value was taken as a blank value (to).(v) 10 mL of each of the polymer solution samples with five levels of polymer concentration prepared in (iii) was placed in the five viscometers by which the measurement of the blank solution had been carried out, and allowed to stand still for about 30 minutes in order to make the temperature constant. Thereafter, the same operation as in the measurement of the blank solution was repeated 3 times, and the average value of the passing times for each concentration was taken as a measurement value (t). From the blank value to, the measurement value t, and the concentration [mass / volume %] (= C [g / dL]) of the polymer solution sample, the relative viscosity the specific viscosity and the reduced viscositywere determined according to the relational expressions shown in the followingexpressions (II) and (III).From these values, the intrinsic viscosityof each polymer was determined according to the method for determining intrinsic viscosity based on the followingHuggins equation. Note that the method for determining intrinsic viscosity describedabove means a method in which multiple polymer solution samples with different polymer concentrations are prepared, the specific viscosity of the polymer solution sample witheach concentration is determined and plotted on a graph with as the vertical axis and Cas the horizontal axis, and the intercept (intrinsic viscosity is determined by extrapolatingC to 0. Huggins equationk' = Huggins constant

[0037] <Measurement of colloid equivalent value of cationic w / o emulsion polymer>As for the colloid equivalent value of the cationic w / o emulsion polymer, the colloid equivalent value at pH 4 was determined according to the following procedures (1) to (8).(1) While stirring deionized water using a magnetic stirrer at 1500 rpm at room temperature 25°C, the cationic w / o emulsion polymer was quickly poured in along the inner surface of the vortex to a polymer concentration of 0.2% by mass, and the mixture was stirred for 1 hour. Note that, if dissolution was insufficient, the mixture was further stirred for 1 hour. Thereafter, the solution was allowed to stand still overnight at room temperature for dissolution.(2) 25 mL of the aqueous solution with a polymer concentration of 0.2% by mass prepared in (1) was measured out with a whole pipette, placed in a 200 mL measuring cylinder, diluted using deionized water, and stirred by inversion to prepare an aqueous solution (measurement sample) with a polymer concentration of 250 mg / L.(3) Four conical beakers were provided, 80 mL of deionized water was placed in each of the conical beakers, 20 mL of the measurement sample prepared in (2) was further added, and the mixture was thoroughly stirred with a magnetic stirrer and used as a sample to be titrated.(4) While checking with a pH meter, an aqueous hydrochloric acid solution or an aqueous sodium hydroxide solution was added to the sample to be titrated to reach a pH of 3, 5, 7, or 9, thereby adjusting the pH of the respective samples to be titrated.(5) To each of the samples to be titrated whose pH had been adjusted to 3, 5, 7, or 9, 1 to 2 drops of toluidine blue were immediately added as an indicator in advance, and the mixture was stirred for 10 seconds.(6) Next, the titration was immediately carried out using a 0.0025 mol / L (1 / 400 N) potassium polyvinyl sulfate standard solution as the titrant while stirring at a rate of 2 mL / min, and the titration volume, D mL, was determined at the endpoint where the color changed from blue to pink and the pink color was retained for 10 seconds or longer.(7) In the meantime, deionized water was also titrated by the same method as for the samples to be titrated described above to determine a blank titration volume, E mL. From the results of titration volume D mL and blank titration volume E mL, the colloid equivalent value of the samples to be titrated whose pH had been adjusted to 3, 5, 7, and 9 was calculated, respectively, according to the following expression: colloid equivalent value [meq / g] = (titrant concentration (0.0025 mol / L) x (D mL - E mL)) / amount of polymer in measurement sample (g).(8) For each of the samples to be titrated whose pH had been adjusted to pH 3, 5, 7, and 9, the pH value was measured after the titration was completed, and the measured pH value and the colloid equivalent value calculated according to the expression described above were plottedon the X axis of a graph and on the Y axis of a graph, respectively. The colloid equivalent value at the value corresponding to pH 4 was read from the curve formed by connecting the four points plotted on the graph, and was taken as the colloid equivalent value (meq / g) at pH 4.

[0038] <Measurement of colloid equivalent value of anionic w / o emulsion polymer>As for the colloid equivalent value of the anionic w / o emulsion polymer, the colloid equivalent value at pH 10.5 was determined according to the following procedures (1) to (8).(1) While stirring deionized water using a magnetic stirrer at 1500 rpm at room temperature 25°C, the anionic w / o emulsion polymer was quickly poured in along the inner surface of the vortex to a polymer concentration of 0.2% by mass, and the mixture was stirred for 1 hour. Note that, if dissolution was insufficient, the mixture was further stirred for 1 hour. Thereafter, the solution was allowed to stand still overnight at room temperature for dissolution.(2) 25 mL of the aqueous solution with a polymer concentration of 0.2% by mass prepared in (1) was measured out with a whole pipette, placed in a 200 mL measuring cylinder, diluted using deionized water, and stirred by inversion to prepare an aqueous solution (measurement sample) with a polymer concentration of 250 mg / L.(3) Conical beakers were provided, 80 mL of deionized water was placed in each of the conical beakers, and a sodium hydroxide solution was added to adjust the pH to 10 to 11 using a pH meter.(4) 10 mL of a 0.0025 mol / L (1 / 400 N) methyl glycol chitosan solution was added dropwise and the mixture was stirred for 1 minute.(5) With stirring, 20 mL of the sample was added, and after stirring for 5 minutes, the solution was confirmed to have a pH of 10 or more.(6) To each of the prepared samples to be titrated, 1 to 2 drops of toluidine blue were immediately added as an indicator in advance, and the mixture was stirred for 10 seconds.(7) Next, the titration was immediately carried out using a 0.0025 mol / L (1 / 400 N) potassium polyvinyl sulfate standard solution as the titrant while stirring at a rate of 2 mL / min, and the titration volume, F mL, was determined at the endpoint where the color changed from blue to pink and the pink color was retained for 10 seconds or longer. The pH after the titration was confirmed to be 10 or more.(8) In the meantime, deionized water was also titrated at pH = 10 by the same method as for the samples to be titrated described above to determine a blank titration volume, G mL. From the results of titration volume F mL and blank titration volume G mL, the colloidequivalent value of the samples to be titrated whose pH had been adjusted to 10 or more was calculated, respectively, according to the following expression: colloid equivalent value [meq / g] = (titrant concentration (0.0025 mol / L) x (F mL - G mL)) / amount of polymer in measurement sample (g).

[0039] [Synthesis of cationic w / o emulsion polymers and anionic w / o emulsion polymers]Using the following monomers, cationic w / o emulsion polymers (modifying agents 1 to 3, 6, and 7) and anionic w / o emulsion polymers (modifying agents 4 and 5) were synthesized as shown in Synthesis Examples below. Also, the synthesis below was carried out using the emulsion polymerization method.

[0040] (Monomers)· DAA: ethyl 2-acrylate trimethylammonium chloride (2-(acryloyloxy)ethyl trimethylammonium chloride): the following structural formula (1) [Formula 1]• DAM: ethyl 2 -methacrylate trimethylammonium chloride (2-(methacryloyloxy)ethyl trimethylammonium chloride): the following structural formula (2) [Formula 2]· AAM: acrylamide• AAN : ammonium acrylate

[0041] (Synthesis Example 1)40 parts by mass of DAM, 30 parts by mass of normal paraffin, and 30 parts by mass of water were stirred and mixed for emulsification. This was adjusted to 50°C with stirring, and nitrogen gas was bubbled for 30 minutes. In a nitrogen gas stream, a 4 mass% toluene solution of 2, 2'-azobis(2 -methylpropionamidine) dihydrochloride was added as a polymerization initiator, and polymerization was performed at 45 to 55°C for 8 hours toobtain a modifying agent 1. Note that the monomer used in the synthesis of the modifying agent 1 and various physical properties are shown in Table 1.

[0042] (Synthesis Example 2)In Synthesis Example 1, DAA and AAM were used in a mass ratio of 60 / 40 in place of DAM. In addition, a crosslinking agent (N,N'-methylenebisacrylamide), which was not used in Synthesis Example 1, was stirred and mixed together with DAA and AAM for emulsification.By the same method as in Synthesis Example 1 , except for the above, a modifying agent 2 was obtained. Note that the monomers used in the synthesis of the modifying agent 2 and various physical properties are shown in Table 1.

[0043] (Synthesis Examples 3 to 7)By the same method as in Synthesis Example 1 , except that the monomers and mass ratios shown in Table 1 were used in place of DAM in Synthesis Example 1, modifying agents 3 to 7 were obtained. Note that the monomers used in the synthesis of the modifying agents 3 to 7 and various physical properties are shown in Table 1.

[0044] [Table 1]Table 1

[0045] [Mineral raw materials]· Coal 1; water content rate: adjusted to 15% by mass in 100% by mass of coal, particle diameter: adjusted to 5 mm or less, wet coal (wet mineral raw material), particle form· Coal 2; water content rate: adjusted to 20% by mass in 100% by mass of coal, particle diameter: adjusted to 5 mm or less, slurry-like coal (slurry-like mineral raw material), particle form· Iron ore 1; water content rate: adjusted to 8.5% by mass in 100% by mass of iron ore, particle diameter: adjusted to 5 mm or less, wet iron ore (wet mineral raw material), particle form

[0046] [Vibration test apparatus]The <Adhesiveness evaluation test> and <Modification ability evaluation test> described later were performed by using the following vibration test apparatus for measurement and evaluation.The vibration test apparatus is one in which, in place of a vibrating sieve, a simulated hopper (inverted truncated quadrangular pyramid outer shape (length: 160 mm, vertical distance: 110 mm, inner surface area: 65600 mm2, angle: 70°) with charge port: 140 mm x 180 mm and discharge port: 30 mm x 60 mm; made of steel) was attached to the upper portion of an electric sieve (manufactured by Nitto Kagaku Co., Ltd., "ANF-30").

[0047] (Example 1)<Adhesiveness evaluation test>A raw material mixture was prepared by adding 1 g of the modifying agent 1 to 500 g of the coal 1 or coal 2 mineral raw material, or adding 2 g of the modifying agent 1 to 1000 g of the iron ore 1 mineral raw material, and stirring and mixing the mixture uniformly. Note that the above-described amount of the modifying agent 1 added is based on the assumption that the modifying agent is added in an excessive amount, which is a condition that may cause spinnability due to the modifying agent to occur and increase the adhesiveness of the mineral raw material, depending on the type of modifying agent and mineral raw material, and other factors.An adhesiveness evaluation test was carried out using the above-described vibration test apparatus. Adhesiveness was evaluated by charging the raw material mixture into the simulated hopper of the vibration test apparatus, applying vibration, and measuring the time required for all of the material mixture to be discharged from the simulated hopper (discharge time). A shorter discharge time indicates that an excellent modification effect (reduction of adhesiveness) is exhibited even when an excessive amount of w / o emulsion polymer is brought into contact with the mineral raw material. Note that the discharge time for only coal 1 (500 g), coal 2 (500 g), or iron ore 1 (1000 g) was non-detectable.Note that the above-described non-detectable means that the discharge time could not be measured because some or all of the raw material mixture or mineral raw material could not be discharged even after 60 seconds due to adhesion and clogging, and the adhesiveness evaluation test was interrupted.Also, using the discharge time, the presence or absence of clogging was evaluated according to the evaluation criterion 1 below. The results are shown in Table 2.Furthermore, the appearance of the raw material mixture adjusted as described above was visually observed and the presence or absence of spinnability due to the modifying agent was evaluated according to the evaluation criterion 2 below. The results are shown in Table 2.[Evaluation criterion 1 (presence or absence of clogging)] Absent: discharge time of less than 13.0 seconds Slightly present: discharge time of 13.0 to 20.0 seconds Present: discharge time of more than 20.0 secondsIf the evaluation is "Absent" to "Slightly present", it can be said that the expression of clogging is suppressed. On the other hand, if the evaluation is "Present", it cannot be said that the expression of clogging is suppressed.[Evaluation criterion 2 (appearance)]A: No spinnability (no spinning was visible or spinning did not occur to the extent that it was visible)B: Spinnability observed (spinning is observed to the extent that it was visible) <Modification ability evaluation test>Using the above-described vibration test apparatus, the required minimum amount of the modifying agent 1 added (% by mass) that results in a discharge time of 10 seconds or less for the raw material mixture composed of 500 g of the coal 1, coal 2, or iron ore 1 mineral raw material and the modifying agent 1 was verified. The same method as described in <Adhesiveness evaluation test> above was used for the preparation of the raw material mixture (except for the amount of the modifying agent 1 added) and for the measurement of discharge time. The verified results (the required minimum amount of the modifying agent 1 added (% by mass) with respect to 100% by mass of the coal 1, coal 2, or iron ore 1 mineral raw material) are shown in Table 2. A smaller amount of the modifying agent required to result in a discharge time of 10 seconds or less indicates higher modification ability.Also, the appearance of the raw material mixture composed of the coal 1, coal 2, or iron ore 1 and the modifying agent 1 in a required minimum amount was visually observed and the presence or absence of spinnability due to the modifying agent was evaluated according to the evaluation criterion 3 below. The results are shown in Table 2.[Evaluation criterion 3 (appearance)]A: No spinnability (no spinning was visible or spinning did not occur to the extent that it was visible)B: Spinnability observed (spinning is observed to the extent that it was visible)

[0048] (Examples 2 to 3 and Comparative Examples 1 to 4)By the same method as in Example 1 , the <Adhesiveness evaluation test> and <Modification ability evaluation test> were carried out, except that the modifying agents 2 to 7 shown in Table 2 were each used in place of the modifying agent 1 in Example 1.

[0049] The various results of each of the above-described Examples and Comparative Examples are shown together in Table 2.

[0050] [Table 2]

[0051] As can be seen from the results shown in Table 2, it was confirmed that Examples of the present invention (Examples 1 to 3 in which cationic w / o emulsion polymers with an intrinsic viscosity of 10.0 dL / g or less were used) had shorter discharge times in the adhesiveness evaluation test compared to Comparative Examples that are not of the present invention (Comparative Examples 4 to 5 in which anionic w / o emulsion polymers were used and Comparative Examples 6 to 7 in which cationic w / o emulsion polymers with an intrinsic viscosity of more than 10.0 dL / g were used), that is, an excellent modification effect (reduction of adhesiveness) was exhibited even when an excessive amount of w / o emulsion polymer was brought into contact with the mineral raw material.In addition to the above, it was confirmed that Examples of the present invention (Examples 1 to 3 in which cationic w / o emulsion polymers with an intrinsic viscosity of 10.0 dL / g or less were used) had smaller % by mass in the modification ability evaluation test, that is, higher modification ability, compared to Comparative Examples that are not of the present invention (Comparative Examples 4 to 5 in which anionic w / o emulsion polymers were used and Comparative Examples 6 to 7 in which cationic w / o emulsion polymers with an intrinsic viscosity of more than 10.0 dL / g were used), when using the coal 2 (slurry-like mineral raw material (coal)).Coal mainly has an aromatic structure, contains phenolic hydroxy groups and carbonyl groups, and exhibits anionicity. Therefore, it is presumed that cationic w / o emulsions are more likely to demonstrate a modification effect by being adsorbed onto the coal by charge neutralization (the % by mass of Examples 1 and 2 is 0.08 to 0.12 in the modification ability evaluation test for the coal 2).When the intrinsic viscosity of cationic w / o emulsion polymers is greater than 10 dL / g, it is presumed that intermolecular interactions are increased and molecules are entangled with each other, increasing the viscosity of the polymer solution and also resulting in spinnability (the appearance of Comparative Examples 3 and 4 is B in the adhesiveness evaluation test for the coal 1).

Claims

CLAIMS

1. A method for preventing adhesion of and clogging with a mineral raw material by performing at least any of transfer and treatment of a raw material mixture in which a mineral raw material has been brought into contact with a cationic w / o emulsion polymer in a transfer and treatment facility and preventing adhesion of and clogging with the mineral raw material in the transfer and treatment facility, wherein the cationic w / o emulsion polymer has an intrinsic viscosity of 10.0 dL / g or less.

2. The method for preventing adhesion of and clogging with a mineral raw material according to claim 1, wherein the cationic w / o emulsion polymer has a colloid equivalent value of 5.0 meq / g or less.

3. The method for preventing adhesion of and clogging with a mineral raw material according to claim 1 or 2, wherein a ratio of a colloid equivalent value to an intrinsic viscosity of the cationic w / o emulsion polymer (colloid equivalent value / intrinsic viscosity) is 0.5 meq / dL or more when the colloid equivalent value is 3.0 meq / g or more and the intrinsic viscosity is 4.0 to 10.0 dL / g.

4. The method for preventing adhesion of and clogging with a mineral raw material according to claim 1 or 2, wherein the transfer and treatment facility is at least one selected from the group consisting of a hold, an unloader, a stacker, a raw material yard, a reclaimer, a piping, a conveyor belt, a conveyor belt transfer portion, a conveyor chain, a chute, a hopper, a silo, a blending tank, a grinding machine, a coal moisture control facility, and a larry car.

5. The method for preventing adhesion of and clogging with a mineral raw material according to claim 1 or 2, wherein the mineral raw material is at least one selected from the group consisting of coal, ore, dust, coke, and limestone.

6. The method for preventing adhesion of and clogging with a mineral raw material according to claim 1 or 2, wherein the mineral raw material contains water, and a content of the water is 1.0% by mass or more in 100% by mass of the mineral raw material.

7. The method for preventing adhesion of and clogging with a mineral raw material according to claim 1 or 2, comprising a step of spraying the cationic w / o emulsion polymer on the mineral raw material at least either before transfer or during transfer in the transfer and treatment facility to obtain the raw material mixture.

8. The method for preventing adhesion of and clogging with a mineral raw material according to claim 1 or 2, comprising a step of adding the cationic w / o emulsion polymer into a container accommodating the mineral raw material, followed by stirring and mixing to obtain the raw material mixture.

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