KR20180012296A - Pulverized coal treatment method and composition - Google Patents

Abstract

The present invention provides methods and compositions for treating coal. Nitroxyl radical compounds are added to coal to inhibit coal autoxidation. In addition, nitrosyl radical compounds can be used in conjunction with conventional dust control agents to inhibit fugitive pulverulent particle dissemination. When a foaming treatment is required to treat the pulverized coal, the nitrosyl radical compound can be used jointly with the foamable composition together with various foam enhancing surfactants such as amphoteric, nonionic and anionic surfactants.

Description

Pulverized coal treatment method and composition

Cross reference of related application

This application claims benefit of priority to Indian Provisional Application No. 2615 / CHE / 2015 filed on May 25, 2015.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a method of treating coal and coal piles to prevent fugitive pulverulent coal dissemination and auto-oxidation. In addition, the stability of the foam used for dust control and automatic oxidation treatment has also been improved.

Coal is a carbonaceous solid fossil fuel. It is extracted (mined) by open-pit mining or surface or underground methods. Coal, which has not yet been mined but is exposed to or exposed to external conditions in the earth, is called in-situ coal. The mined coal is usually crushed to a smaller size for transportation, handling and storage. The typical size of this pulverized coal is less than 8 inches (less than 200 mm). The present invention treats both in-situ coal and extracted (mined) coal during transportation, handling and storage. During transportation, handling and storage, mined coal may produce pulverized coal. Pulverized coal diffusion poses safety, health and environmental concerns. Pulverized coal inhibition is desirable to minimize pulverulent coal diffusion that can occur during coal storage or transportation. Airborne spiked fine particulate matter can cause pneumoconiosis and other diseases.

Also, when coal is exposed to air, it slowly oxidizes and forms heat with CO ₂ . Oxidation is promoted in the presence of moisture and elevated temperature. Oxidation is a detrimental process because it reduces the calorific value of coal and can cause spontaneous combustion or coal self-ignition. In some cases where coal self-ignition occurs in the presence of suspended charcoal, a pulverized coal explosion may also occur.

Coal has traditionally been stored in piles to reduce the penetration of air and moisture, thereby alleviating the oxidation process. Piling up does not stop coal oxidation, it is just an attempt to slow down the oxidation rate. The ideal coal pile is large enough to reduce the surface-to-volume ratio of the coal exposed to the air, but is sufficiently small that the heat generated within the coal pile will disappear into the surrounding environment. Unfortunately, in large coal processing plants such as those present in coal-fired power plants, it is difficult to achieve ideal conditions because coal is used in large quantities, and coal self-ignition due to coal oxidation is common. Coal fires and pulverized coal explosions pose a serious risk to employees and cost a lot in terms of equipment damage and coal consumption.

In many cases, coal can be treated with aqueous based foams to inhibit the diffusion of fine pulverized coal particles or to aid in the application of dust control binders. These foams can be formed and applied, for example, as described in U.S. Patent No. 4,400,220 (Cole). Certain foaming agents such as amphoteric surfactants, anionic surfactants, and nonionic surfactants can be used to assist foam formation and dust inhibition. Stability of the foam is an important characteristic for maximum surface area contact with coal surfaces during application.

In general, with regard to coal storage and transportation problems as mentioned above, a versatile product is required to address this problem, and preferably such a product will also improve foam life stability in situations where foaming applications are utilized .

Gist of invention

In one embodiment, there is provided a method of treating a coal in which a nitrosyl radical compound (NRC), an amine-functionalized tannin or a quaternary ammonium compound is added to the coal. Typically, the NRC is added to the coal in an amount of about 0.001 to 10 pounds per ton of coal and the addition rate of about 0.005 to 1 pound of NRC per ton of coal is also mentioned by way of example.

In some cases it is desirable to provide a foaming treatment of the coal and in this connection a foaming agent such as those selected from the group of amphoteric, nonionic and anionic surfactants may be used. In this case, NRC can be used with surfactants to improve the stability and durability of the foam. In one embodiment, the blowing agent comprises an anionic surfactant and long chain C ₁₀ -C ₁₈ alkenyl sulfonate salts such as C ₁₁ -C ₁₆ alkenyl sodium sulfonate.

In another embodiment, the NRC can be used with a dust control agent (DCA) and can be applied to coal. The DCA may, for example, comprise a variety of different polymers. In one embodiment, DCA comprises i) epichlorohydrin (EPI) / polyalkylene polyamine / adipic acid terpolymer; an aminoalkylated polyacrylamide, ii) an aminoalkylated polyacrylamide, and iii) a quaternary ammonium polymer and a copolymer.

In most cases, the NRC will be applied to coal in the form of an aqueous solution or dispersion. an aqueous composition consisting of a) a nitroxyl radical (NRC) and b) a dust control agent and c) a blowing agent may be used, wherein a) and b) are present, a) 1 to 5 parts ) B) from 1 to 100 parts. When a) and c) are present, a) from 1 to 5 parts c) from 0.01 to 10 parts are present. When all three of a) and b) and c) are present, a) from 1 to 5 parts b) from 1 to 100 parts and c) from 0.01 to 10 parts. In another embodiment, the composition is composed of the ingredients described above, wherein a) and b) are present, if present: a) from 1 to 20 parts per part b). If a) and c) are present, a) from 0.15 to 2 parts per 1 part of c) are present. When all three of a) and b) and c) are present, there is a) between 1 and 20 parts per part and c) between 0.15 and 2 parts per part.

details

In one embodiment of the present invention, a nitrosyl radical compound (NRC) is provided that treats coal surfaces such as coal piles to delay auto-oxidation of coal, self-heating and spontaneous combustion. In another embodiment, nitrosyl radical compounds are used in conjunction with DCA, such as polymers, to improve dust control efficacy in the ability to aggregate fine particles and inhibit dust diffusion.

In another embodiment of the present invention where foam application to coal is desired, the NRC is added to the DCA along with the anionic blowing agent. The NRC and blowing agent may be added without DCA. Using NRC with blowing agent improves foam quality and stability.

In one embodiment, the NRC may have the following structure:

here

R ₂ , R ₃ , R ₈ and R ₉ are each independently of the other substituted or unsubstituted C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, or C ₂ -C ₁₈ alkynyl; or

R ₂ and R ₃ and / or R ₈ and R _{9 taken} together with the connecting carbon form a C ₃ -C ₁₂ cycloalkyl radical;

R ₄ , R ₅ , R ₆ and R ₇ are each independently of the other hydrogen, substituted or unsubstituted C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, or C ₂ -C ₁₈ alkynyl;

X is -O-, -OC (O) -, = O, -NR ₁₀ - or -NR ₁₀ -C (O) -;

R ₁₀ is hydrogen, phenyl, or substituted or unsubstituted C ₁ -C ₁₈ alkyl;

R ₁ is hydrogen, phenyl, substituted or unsubstituted C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, or C ₂ -C ₁₈ alkynyl.

In another embodiment, R ₂ , R ₃ , R ₈ and R ₉ are each independently of the other substituted or unsubstituted C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, or C ₂ -C ₆ alkynyl ; R ₂ and R ₃ and / or R ₈ and R _{9 taken} together with the connecting carbon form a C ₃ -C ₁₂ cycloalkyl radical; R ₄ , R ₅ , R ₆ and R ₇ are each independently of the other hydrogen, substituted or unsubstituted C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, or C ₂ -C ₆ alkynyl; X is -O-, -OC (O) -, = O, -NR ₁₀ - or -NR ₁₀ -C (O) -; R ₁₀ is hydrogen, phenyl, or substituted or unsubstituted C ₁ -C ₆ alkyl, R ₁ is hydrogen, substituted or unsubstituted C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, or C ₂ - C ₆ alkynyl.

Exemplary nitroxyl radical compounds (NRC) include derivatives of dialkyl nitrosyl radicals and 1-oxyl-2,2,6,6-tetraalkylpiperidine compounds such as 1-oxyl-2,2,6,6- Tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol (4-HT), 1-oxyl-2,2,6,6-tetramethylpiperidine Oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate, 1-oxyl-2,2,6,6-tetramethylpiperidin- 2-ethylhexanoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-oxyl-2,2,6,6-tetramethylpiperidin- -Yl benzoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 4- tert -butylbenzoate, bis (1 -oxyl-2,2,6,6-tetra Methylpiperidin-4-yl) succinate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin- , 6-tetramethylpiperidin-4-yl) sebacate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin- Bis (1-oxyl-2,2,6,6-tetramethylpiperidinyl-4-yl) phthalate, bis Bis (1-oxyl-2,2,6,6-tetramethylpiperidinyl-4-yl) terephthalate, bis 4-yl) hexahydroterephthalate, N, N'-bis (1-oxyl-2,2,6,6-tetramethylpiperidin- 2,6,6-tetramethylpiperidin-4-yl-dodecylsuccinimide, 1-oxyl-4-methoxy-2,2,6,6-tetramethylpiperidine, 1- -Amino-2,2,6,6-tetramethylpiperidine, 4-butoxy-2,2,6,6-tetramethylpiperidine and 1-oxyl-4-acetamino- , 6-tetramethylpiperidine. In one embodiment, the nitroxyl radical compound is 4HT.

In one aspect of the present invention, in situations where dust controlled diffusion is desired, a polymeric dust control agent (DCA) may be used in conjunction with the NRC. Such polymeric dust control agents are well known and are disclosed, for example, in U.S. Patent No. 5,256,444, the disclosure of which is herein incorporated by reference. Exemplary Polymeric DCAs include: i) polymers having at least two monomers of epichlorohydrin (epi), polyalkylene polyamine and adipic acid; ii) polymers comprising aminoalkylated polyacrylamides; And iii) quaternary ammonium polymers and copolymers. In another embodiment, the DCA polymer has three of the following monomers: epichlorohydrin (epi), polyalkylene polyamine and adipic acid; ii) polymers comprising aminoalkylated polyacrylamides; And iii) quaternary ammonium polymers and copolymers. Exemplary members of the monomers in i) above are diethyltriamine, adipic acid and epichlorohydrin (epi), and other examples of DCA are ii) aminomethylated polyacrylamides and iii) quaternary amines, dimethyl Amine and epi. ≪ / RTI > In one embodiment, the molecular weight of these polymers is from 100,000 to 5,000,000. In yet another embodiment, the molecular weight of these polymers is from 300,000 to 2,500,000.

Typically, about 0.001 to 10 lbs of nitrosyl radical compound, based on one ton of coal, is added to the coal. In another embodiment, the NRC per tonne of coal is added in an amount of 0.002 to 5 lbs. In another embodiment, the NRC per tonne of coal is added in an amount of 0.0035 to 2.5 lbs. In another embodiment, the NRC per tonne of coal is added in an amount of 0.005 to 1.0 lbs.

When foaming applications to coal are used, the NRC may be combined with known blowing agents such as nonionic surfactants such as alkyl polyglucosides, amphoteric surfactants such as ether amines, or anionic surfactants such as long chain alkenyl Can be used. In one embodiment, the blowing agent is an anionic surfactant having a long alkenyl (C ₁₁ -C ₁₈ ) chain. One such anionic surfactant is sodium olefin (C ₁₄ -C ₁₆ ) sulfonate.

In situations where the NRC is used with DCA and / or a blowing agent, the composition may comprise one or more of a), b) and c).

a) = NRC

b) = DCA

c) = blowing agent

In one embodiment, when a) and b) are present, a) from 1 to 5 parts b) from 1 to 100 parts are present. When a) and c) are present, a) from 1 to 5 parts c) from 0.01 to 10 parts are present. When all three of a) and b) and c) are present, a) from 1 to 5 parts b) from 1 to 100 parts and c) from 0.01 to 10 parts.

In another embodiment, when a) and b) are present, a) from 1 to 5 parts b) from 1 to 75 parts are present. When a) and c) are present, a) from 1 to 5 parts c) from 0.075 to 7.5 parts are present. When all three of a) and b) and c) are present, there is a) from 1 to 75 parts b) from 1 to 5 parts and c) from 0.075 to 7.5 parts.

In another embodiment, when a) and b) are present, a) from 1 to 5 parts b) from 1 to 50 parts are present. When a) and c) are present, a) from 1 to 5 parts c) from 0.1 to 5 parts are present. When all three of a) and b) and c) are present, a) from 1 to 5 parts b) from 1 to 50 parts and c) from 0.1 to 5 parts.

In one embodiment, when a) and b) are present, there is a) from 1 to 20 additions per part b). If a) and c) are present, a) from 0.15 to 2 parts per 1 part of c) are present. When all three of a) and b) and c) are present, there is a) between 1 and 20 parts per part and c) between 0.15 and 2 parts per part.

In one embodiment, the water-based composition has the components a): b): c) and the remaining composition comprises water and possibly other minor components.

The NRC and other components may be in-situ or extracted (mined) during transportation, handling and storage at the mine site and / or any subsequent location, for example, a terminal, quay, reservoir, Lt; / RTI > Waterborne sprays are often used for coal applications. In one embodiment, the NRC is applied alone or with or without the DCA applied as a foam. For foaming applications, blowing agents such as those mentioned above are used with NRC.

Example

Coal auto oxidation inhibition

Example 1 - Coal self-heating test was conducted to evaluate the efficacy of a substance that inhibits pulverized coal self-ignition. This is an accelerated test method in which the coal sample is heated to a pre-set temperature with a known quantity and air flow to be supplied. This method promotes natural coal oxidation and leads to thermal runaway of the coal.

Coal samples:

-250 micron pulverized coal

Solution and application:

The chemicals are prepared in water at two different concentrations of 0.5% and 2%. The chemical is applied to the coal at a rate such that the same amount of moisture (4%) is added to all coal samples.

Measure:

Measure and record the temperature of the coal sample. Record the time at which the coal sample reaches thermal runaway (typically at 200F). The time delay to thermal run-up for the treated coal samples versus blank and samples with only water added is used to evaluate the antioxidant efficacy.

step:

The weight of the coal sample is 50 g. Apply the desired chemical substance (or moisture blank) to the coal as a droplet. The coal is thoroughly mixed with the solution using a stainless steel spatula. Mix until the sample is uniform, then transfer to the reaction vessel. The test device consists of six slots for the rectangular container (reaction chamber) and the reaction container and is connected to the automatic temperature recorder. The reaction chamber has a heater and is filled with silicone oil for heating. Set the required temperature of the oil bath and place the reaction vessel in the chamber. Then the air flow starts. Reaction chamber heating is started and heating of the coal sample begins. Place the thermocouple in a day bath to measure the set temperature of the day bath and record the bath temperature continuously in the data acquisition system. Each reaction vessel is provided with two thermocouples at different points and the temperature data is recorded continuously. One blank coal sample and one moisture blank sample are included as a control with the treated sample. Data is continuously recorded until the coal reaches thermal runaway.

The results are shown in Table 1.

Time to reach thermal runaway

C1 = comparison = aqueous polymer, diethylamine triamine / adipic acid / epichlorohydrin terpolymer

C2 = comparison = aqueous polymer, aminomethylated polyacrylamide

EX1 = 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol (4HT)

EX2 = quaternary amine / dimethylamine / epichlorohydrin

EX3 = tannin / monoethanolamine / formaldehyde

The time lag compared to the untreated control for the onset of heat runaway indicates inhibition of autoxidation. In this example, EX-1 exhibits a level of inhibition comparable to known auto-oxidation inhibition polymers, which is surprising since conventional antioxidant products are polymeric and EX-1 is a monomer.

Example 2 - Dust control enhancement

Instrument:

Dust Monitor - The laboratory dust monitor uses white light to determine the level of dust in the material being loaded into the sampling chamber.

Substrate:

Coal samples, a mixture of size fractions to produce sufficient dust for the study.

step:

A solution of various concentrations of each product is prepared. An untreated coal matrix sample is prepared with a spinning riffler so that the particle size of each sample is uniformly distributed. Apply the product to coal. The sample is dried at 140F for 30 minutes. Cool for 30 minutes at room temperature. Pass the sample through the dust monitor and record the dust value. The reported value is the dust area plus the maximum value, which is the combined area under the curve of the sample measured over 30 seconds plus the maximum dust level recorded for the sample. Low dust area + maximum value indicates excellent dust control.

In these examples, EX-1, or 4HT, was added to the coal without any particulate control agent and, in addition, a known dust control agent, i.e., aqueous aminomethylated polyacrylamide (labeled "C2") was added. Dust control improvements are shown in Tables 2 and 3 below.

Table 2 shows that when added to 4HT only coal, it has a negative impact on dust generation compared to water. When 4HT is added as an adjuvant to C2, a known polymeric dust modifier (DCA), the dust reduction performance of DCA is synergistically improved.

Table 3 shows that a small dosage of 4HT added as an adjuvant to C2, a known polymeric dust control agent (DCA), synergistically enhances the dust reduction performance of DCA.

Example 3 - Foam Stability - To determine the effect on foam stability, 4HT was added to a known foaming agent, "C4", anionic surfactant, sodium olefin (C ₁₄ -C ₁₆ ) sulfonate.

solution:

At ambient temperature (72 ° F), 200 mL solution

Instrument:

Waring Commercial Blender (Model 7011G) with 50 mL scale

Measure:

- Maximum foam height (up to 25mL)

- the half-life (in seconds) - the time the 100 mL solution is drained back into the liquid phase

step:

200 mL of the solution was poured into the blender. The blender was operated at low speed for 30 seconds. The blender was then held until half of the sample (100 mL) was returned to the liquid phase. The elapsed time until the liquid-foam interface reached the 100 mL scale was reported as "foam 1/2 life time ".

The results are shown in Tables 3 and 4.

[Table 3]

C2 = aqueous polymer, aminomethylated polyacrylamide

C4 = anionic surface active agent, sodium olefin (C ₁₄ -C ₁₆₎ sulfonate

From Table 3 it can be seen that foam stability was improved by adding 4HT to C4, to the anionic surfactant and to the combination of C4 and C2. As can be seen in Table 4, no significant foaming properties are found in 4HT itself. Surprisingly, the combination of 4HT and C4 provided a synergistic effect with respect to foam stabilization.

Additional experiments were performed on water of various hardnesses. In this experiment, a mixture of 40 ppm of CaCO ₃ , an intermediate of CaCO ₃ 80ppm Ca) and very dense (600ppm Ca as CaCO ₃ ) were observed. Changes in hardness can affect the production of stable foams. As can be seen in Table 5, the combination of C4 (0.3% or 0.5%) and 4HT (various concentrations) at all three hardness levels improved foam stability.

Claims (27)

A method of treating coal, comprising adding nitroxyl radical compound (NRC) to coal. The method of claim 1, wherein the NRC has the following structure:

In the above formulas,
R ₂ , R ₃ , R ₈ and R ₉ are each independently of the other substituted or unsubstituted C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, or C ₂ -C ₁₈ alkynyl;
R ₂ and R ₃ and / or R ₈ and R _{9 taken} together with the connecting carbon form a C ₃ -C ₁₂ cycloalkyl radical;
R ₄ , R ₅ , R ₆ and R ₇ are each independently of the other hydrogen, substituted or unsubstituted C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, or C ₂ -C ₁₈ alkynyl;
X is -O-, -OC (O) -, = O, -NR ₁₀ - or -NR ₁₀ -C (O) -; here
R ₁₀ is hydrogen, phenyl, or C ₁ -C ₁₈ alkyl;
R ₁ is hydrogen, phenyl, substituted or unsubstituted C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, or C ₂ -C ₁₈ alkynyl. The method of claim 1, wherein the NRC is added to the coal in an amount of about 0.001 to 10 lbs per tonne of coal. The method of claim 1, wherein the NRC is selected from the group consisting of dialkyl nitropyl radicals, 1-oxyl-2,2,6,6-tetraalkylpiperidine compounds, 1-oxyl-2,2,6,6-tetramethylpiperidine (4-HT), 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one , 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate, 1-oxyl-2,2,6,6-tetramethylpiperidin- Octyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ylbenzoate , 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 4- tert -butylbenzoate, bis (1-oxyl-2,2,6,6-tetramethylpiperidine (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) n-butyl malonate, bis (1-oxyl- 2,6,6-tetramethylpiperidine (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N, N'-bis -Oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipamide, N-loxyl-2,2,6,6-tetramethylpiperidin- 4-methoxy-2,2,6,6-tetramethylpiperidine, 1-oxyl-4-amino-2,2,6,6-tetramethylpiperidine, 4-butoxy-2,2,6,6-tetramethylpiperidine and 1-oxyl-4-acetamino-2,2,6,6-tetramethylpiperidine and derivatives thereof , Coal treatment method. 5. The method of claim 4, wherein the NRC is 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol (4HT). The method of claim 1, further comprising adding to said coal a blowing agent selected from amphoteric, nonionic and anionic surfactants. 7. The method of claim 6, wherein the blowing agent comprises an anionic surfactant. 8. The method of claim 7, wherein the anionic surfactant comprises an alkane sulfonate or an alkenyl sulfonate. The method of claim 1, wherein the method further comprises adding a dust control agent (DCA) to the coal. 10. The method of claim 9, wherein the DCA comprises a polymer. 11. The composition of claim 10, wherein the polymer is selected from the group consisting of i) a polymer containing two or more of epichlorohydrin, polyalkylene polyamine and adipic acid monomer, ii) aminoalkylated polyacrylamide, and iii) quaternary ammonium polymer ≪ / RTI > and a copolymer. 12. The method according to claim 11, wherein the polymer containing two or more of i) epichlorohydrin, polyalkylene polyamine and adipic acid monomer comprises diethyltriamine, adipic acid and epichlorohydrin monomer, ii) the aminoalkylated polyacrylamide comprises an aminomethylated polyacrylamide, and iii) the quaternary ammonium polymer and copolymer comprises a reaction product of a quaternary amine, dimethylamine and epichlorohydrin, Way. A composition comprising at least one of a) a nitroxyl radical composition (NRC) and b) a dust control agent and c) a foaming agent, wherein a) and b) are present: a) from 1 to 5 parts per A) from 1 to 5 parts, c) from 0.01 to 10 parts, and when a) and b) and c) are both present, a) a) and c) ) 1 to 5 parts b) 1 to 100 parts and c) 0.01 to 10 parts. 14. The composition of claim 13, wherein the NRC has the structure:

In the above formulas,
R ₂ , R ₃ , R ₈ and R ₉ are each independently of the other substituted or unsubstituted C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, or C ₂ -C ₁₈ alkynyl;
R ₂ and R ₃ and / or R ₈ and R _{9 taken} together with the connecting carbon form a C ₃ -C ₁₂ cycloalkyl radical;
R ₄ , R ₅ , R ₆ and R ₇ are each independently of the other hydrogen, substituted or unsubstituted C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, or C ₂ -C ₁₈ alkynyl;
X is -O-, -OC (O) -, = O, -NR ₁₀ - or -NR ₁₀ -C (O) -; here
R ₁₀ is hydrogen, phenyl, or C ₁ -C ₁₈ alkyl;
R ₁ is hydrogen, phenyl, substituted or unsubstituted C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, or C ₂ -C ₁₈ alkynyl. 14. The method of claim 13, wherein said a) NRC is selected from the group consisting of a dialkylnitroxyl radical, 1-oxyl-2,2,6,6-tetraalkylpiperidine compound, 1-oxyl-2,2,6,6- Piperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol (4-HT), 1-oxyl-2,2,6,6-tetramethylpiperidin- Oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate, 1-oxyl-2,2,6,6-tetramethylpiperidin- Ethylhexanoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-oxyl-2,2,6,6-tetramethylpiperidin- Benzoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 4- tert -butylbenzoate, bis (1-oxyl-2,2,6,6- Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) n-butylmalonate, bis (1-oxyl- 2,2,6,6-tetramethyl Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N, N'-bis Oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipamide, N-1-oxyl- 1-oxyl-4-methoxy-2,2,6,6-tetramethylpiperidine, 1-oxyl-4-amino-2,2,6,6-tetramethylpiperidine , 4-butoxy-2,2,6,6-tetramethylpiperidine and 1-oxyl-4-acetamino-2,2,6,6-tetramethylpiperidine and derivatives thereof ≪ / RTI > 16. The composition of claim 15, wherein the NRC is 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol (4HT). 14. The composition of claim 13, wherein the blowing agent is selected from amphoteric, nonionic and anionic surfactants. 18. The composition of claim 17, wherein the blowing agent comprises an anionic surfactant. 19. The composition of claim 18, wherein the anionic surfactant comprises an alkanesulfonate or an alkenylsulfonate. 14. The composition of claim 13, wherein the dust modifier comprises a polymer. 21. The composition of claim 20, wherein the polymer is selected from the group consisting of i) a polymer containing two or more of epichlorohydrin, polyalkylene polyamine and adipic acid monomer, ii) aminoalkylated polyacrylamide, and iii) quaternary ammonium polymer And a copolymer. The method according to claim 21, wherein the polymer containing two or more of i) epichlorohydrin, polyalkylene polyamine and adipic acid monomer comprises diethyltriamine, adipic acid and epichlorohydrin monomer, ii) the aminoalkylated polyacrylamide comprises an aminomethylated polyacrylamide, and iii) the quaternary ammonium polymer and copolymer comprises the reaction product of a quaternary amine, dimethylamine and epichlorohydrin. A) a nitrosyl radical composition (NRC), b) a dust control agent, and c) a foaming agent, wherein a) and b) are present, wherein a) from 1 to 5 parts b) A) from 1 to 100 parts, and if a) and c) are present, a) from 1 to 5 parts c) from 0.01 to 10 parts, and if a) and b) and c) B) from 1 to 100 parts per 1 to 5 parts, and c) from 0.01 to 10 parts, wherein a) per ton of coal is present in an amount of from 0.001 to 10 lbs. And adding a quaternary ammonium compound to the coal. 25. The method of claim 24, wherein the quaternary ammonium compound is a quaternary amine / dimethylamine / epichlorohydrin. Adding an amine-functionalized tannin to the coal. 27. The method of claim 26, wherein the amine-functionalized tannin is tannin / monoethanolamine / formaldehyde.