LOW-SULFUR COAL PRODUCTION METHOD

- JFE STEEL CORPORATION

A low-sulfur coal production method having an excellent desulfurization effect includes bringing coal into contact with a chemical material that is a mixed solution of hydrogen peroxide and acetic anhydride to remove sulfur in the coal. It is preferred that the molar ratio of the acetic anhydride to the hydrogen peroxide is 0.5 to 12.0 inclusive. It is preferred that the acetic anhydride is mixed with the hydrogen peroxide before the chemical material is brought into contact with the coal and the chemical material is brought into contact with the coal after 10 minutes or more has elapsed since the mixing.

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Description
BACKGROUND OF THE INVENTION

The present invention relates to a low-sulfur coal production method.

BACKGROUND ART

In an iron manufacturing process, when coal is used as a reducing material for iron ore, a part of sulfur contained in the coal dissolves as a solid in iron obtained by reducing the iron ore. If sulfur remains, toughness and workability of steel deteriorates, so that a great amount of effort has been made to remove sulfur from iron.

When coal is used as a heat source, a sulfur oxide is mixed in an exhaust gas, so that a great amount of effort has been required to remove a sulfur content from an exhaust gas from the standpoint of prevention of air pollution.

From such background, the industrial value is high if sulfur (sulfur content) in coal can be removed before the coal is used.

As a method of producing coal having a reduced sulfur content (low-sulfur coal), the claim of Patent Literature 1 describes “a chemical desulfurization method for coal, characterized in that an aqueous solution of caustic soda or caustic potash alone, or an aqueous solution of a mixture thereof is mixed with pulverized coal, and the resultant mixture is heated and reacted at a high temperature under an atmosphere of an oxygen gas or air or a mixture thereof, thereby removing a sulfur content in the coal.”

CITATION LIST Patent Literatures

  • Patent Literature 1: JP 3-275795 A

SUMMARY OF INVENTION Technical Problems

In producing low-sulfur coal by desulfurizing coal (removing sulfur in coal), the conventional method had an insufficient desulfurization effect in some cases.

An object of the present invention is therefore to provide a low-sulfur coal production method having an excellent desulfurization effect.

Solution to Problems

The present inventors have made an intensive study and as a result found that when the configuration described below is employed, the foregoing object is achieved. The invention has been thus completed.

Specifically, the present invention provides the following [1] to [11].

[1] A low-sulfur coal production method comprising bringing coal into contact with a chemical agent which is a mixed solution of hydrogen peroxide and acetic anhydride to thereby remove sulfur in the coal.

[2] The low-sulfur coal production method according to [1] above, wherein a molar ratio between the acetic anhydride and the hydrogen peroxide (acetic anhydride/hydrogen peroxide) is not less than 0.5 and not more than 12.0.

[3] The low-sulfur coal production method according to [1] or [2] above, wherein the acetic anhydride and the hydrogen peroxide are mixed before the chemical agent is brought into contact with the coal, and

wherein when 10 minutes or more have elapsed after the acetic anhydride and the hydrogen peroxide are mixed, the chemical agent is brought into contact with the coal.

[4] The low-sulfur coal production method according to any one of [1] to [3] above, wherein a mass ratio between the chemical agent and the coal (chemical agent/coal) is not less than 1.0.

[5] The low-sulfur coal production method according to any one of [1] to [4] above, wherein a temperature of the chemical agent at a time of being brought into contact with the coal is not less than 5° C.

[6] The low-sulfur coal production method according to any one of [1] to [5] above, wherein a temperature of the chemical agent at a time of being brought into contact with the coal is not more than 30° C.

[7] The low-sulfur coal production method according to any one of [1] to [6] above, wherein the coal comprises sub-bituminous coal.

[8] The low-sulfur coal production method according to any one of [1] to [7] above, wherein the coal that has been brought into contact with the chemical agent is heat-treated at a heat treatment temperature of not less than 150° C.

[9] The low-sulfur coal production method according to [8] above, wherein a heating rate at which the coal that has been brought into contact with the chemical agent is heated to the heat treatment temperature is not less than 10° C./min.

[10] The low-sulfur coal production method according to any one of [1] to [7] above, wherein the coal that has been brought into contact with the chemical agent is brought into contact with a hydrogen peroxide solution having a temperature of not more than 40° C.

[11] The low-sulfur coal production method according to [10] above,

wherein a concentration of the hydrogen peroxide solution is not less than 2.0 mass %, and

wherein a mass ratio between the hydrogen peroxide solution and the coal (hydrogen peroxide solution/coal) is not less than 1.0.

Advantageous Effects of Invention

The present invention can provide a low-sulfur coal production method having an excellent desulfurization effect.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing a desulfurization rate with respect to a mass ratio between a chemical agent and coal (chemical agent/coal).

FIG. 2 is a graph (lower part) showing an amount of peracetic acid generated with respect to a temperature of a chemical agent, and a graph (upper part) showing a desulfurization rate (solid line) and a carbon yield (dashed line) with respect to a temperature of a chemical agent.

FIG. 3 is a schematic view showing an example of a facility for producing low-sulfur coal.

 DETAILED DESCRIPTION OF THE INVENTION [Low-Sulfur Coal Production Method]

The low-sulfur coal production method of the invention (hereinafter, also simply referred to as “the method of the invention”) is a low-sulfur coal production method comprising bringing coal into contact with a chemical agent which is a mixed solution of hydrogen peroxide and acetic anhydride to thereby remove sulfur in the coal.

<Primary Treatment (Chemical Treatment)>

First, described below is a primary treatment (chemical treatment) in which coal is brought into contact with a chemical agent which is a mixed solution of hydrogen peroxide and acetic anhydride.

Sulfur in coal is roughly classified into inorganic sulfur (inorganic sulfur content) and organic sulfur (organic sulfur content).

A typical example of inorganic sulfur is FeS2. Examples of organic sulfur include: an aromatic sulfur compound in which sulfur is present inside an aromatic ring such as dibenzothiophene; an aliphatic sulfur compound such as mercaptan. Of these, sulfur present inside an aromatic ring constituting coal is known to be particularly difficult to be removed.

The present inventors studied various chemical agents (desulfurization agents). As a result, it was found that peracetic acid effectively acts on thiophene form sulfur which is a component particularly difficult to be removed among organic sulfurs in coal, thereby successfully removing sulfur from coal or increasing an efficiency of converting sulfur into an easily removable form. It is assumed that by the action of peracetic acid, thiophene form sulfur is oxidized to be, for example, sulfone form sulfur or sulfide form sulfur, and a bond between carbon and sulfur is relatively weakened to be easily cut off, whereby the sulfur becomes easy to be separated.

Meanwhile, peracetic acid is easy to decompose. In the invention, therefore, a mixed solution of hydrogen peroxide and acetic anhydride (hereinafter, also simply referred to as “mixed solution”) is used as a chemical agent. The mixed solution generates peracetic acid which is a reaction product of hydrogen peroxide and acetic anhydride. The mixed solution as above is brought into contact with coal.

A reaction of hydrogen peroxide (H2O2) and acetic anhydride ((CH3CO)2O) to obtain peracetic acid (CH3COO2H) and water (H2O) is represented by Formula (I) below.


2H2O2+(CH3CO)2O⇔2CH3COO2H+H2O  (I)

In Formula (I) above, an equilibrium state changes depending on various conditions such as a temperature and a mixing ratio of a chemical agent. Therefore, the concentration of each component varies depending on the combination of the conditions. Suitable conditions will be described in detail below.

When a chemical agent is brought into contact with coal, inorganic sulfur which is easy to be removed dissolves and leaches into the chemical agent in the form of, for example, a sulfate ion. Similarly, a part of organic sulfur is also oxidized and leaches into the chemical agent in the form of, for example, a sulfate ion. Coal is desulfurized (i.e., sulfur in coal is removed) in this manner to thereby obtain coal having a reduced sulfur content (low-sulfur coal).

<<Molar Ratio (Acetic Anhydride/Hydrogen Peroxide)>>

A molar ratio between acetic anhydride and hydrogen peroxide (acetic anhydride/hydrogen peroxide) in a chemical agent is preferably not less than 0.1 and more preferably not less than 0.5 because peracetic acid which is a reaction product can be formed in a proper amount and the desulfurization effect can become more excellent.

Further, when the molar ratio (acetic anhydride/hydrogen peroxide) is within the foregoing range, acetic anhydride can be prevented from becoming excessive with respect to hydrogen peroxide, and residual hydrogen peroxide in the mixed solution can be minimized (as described below, hydrogen peroxide decreases a carbon yield of coal).

The molar ratio (acetic anhydride/hydrogen peroxide) is preferably not more than 15.0 and more preferably not more than 12.0. When the molar ratio (acetic anhydride/hydrogen peroxide) is within the foregoing range, as in the above, peracetic acid which is a reaction product can be formed in a proper amount, so that the desulfurization effect can become more excellent. Further, the generated peracetic acid is prevented from being diluted with excessive acetic anhydride.

The molar ratio (acetic anhydride/hydrogen peroxide) is calculated as follows.

First, a molar amount [mol] of each component (acetic anhydride or hydrogen peroxide) in a chemical agent is represented by Formula (a) below. Therefore, the molar ratio between acetic anhydride and hydrogen peroxide (acetic anhydride/hydrogen peroxide) in the chemical agent is calculated by Formula (b) below.


Molar amount=(Li×Ci)/(100×Mi)  (a)


Molar ratio=(L1×C1×M2)/(L2×C2×M1)  (b)

Li: amount of i aqueous solution [g/h]

Ci: concentration of i aqueous solution [mass %]

Mi: molecular weight of i [g/mol]

Here, i is 1 or 2, 1 is acetic anhydride and 2 is hydrogen peroxide.

The molecular weight of acetic anhydride is assumed to be 102, and the molecular weight of hydrogen peroxide is assumed to be 34. The amount of an aqueous solution Li is adjusted such that the desired molar ratio (acetic anhydride/hydrogen peroxide) is obtained.

<<Elapsed Time after Mixing>>

The reaction (forward reaction) of Formula (I) above has a relatively slow rate. Therefore, generation of peracetic acid is insufficient immediately after acetic anhydride and hydrogen peroxide are mixed in some cases.

The present inventors determined the quantities of various reaction rates and found out that it takes about 10 minutes for the reaction of Formula (I) above to settle into a steady state.

In the invention, therefore, it is preferable that acetic anhydride and hydrogen peroxide are mixed before a chemical agent is brought into contact with coal, and when 10 minutes or more have elapsed after this mixing, the chemical agent is brought into contact with the coal. This allows peracetic acid to be sufficiently generated, whereby the desulfurization effect of removing sulfur in coal can become more excellent. Further, this allows peracetic acid hydrogen to be decreased, whereby decrease in a carbon yield due to a reaction of hydrogen peroxide with coal can be minimized.

The elapsed time after mixing is more preferably not less than 20 minutes and even more preferably not less than 30 minutes and, at the same time, preferably not more than 120 minutes, more preferably not more than 90 minutes, and even more preferably not more than 60 minutes.

<<Mass Ratio (Chemical Agent/Coal)>>

The present inventors studied a mass ratio between a chemical agent and coal (chemical agent/coal). In this study, a chemical agent having a molar ratio between acetic anhydride and hydrogen peroxide (acetic anhydride/hydrogen peroxide) of 5.0 was used.

FIG. 1 is a graph showing a desulfurization rate with respect to a mass ratio between a chemical agent and coal (chemical agent/coal). As shown in the graph of FIG. 1, as the amount of a chemical agent with respect to coal increases, the desulfurization rate increases, so that the desulfurization effect becomes more excellent. Therefore, the mass ratio (chemical agent/coal) is preferably not less than 0.5, more preferably not less than 1.0 and even more preferably not less than 2.0.

As shown in the graph of FIG. 1, when the amount of a chemical agent becomes excessive with respect to the amount of coal, the desulfurization rate barely changes. The mass ratio (chemical agent/coal) is preferably not more than 100.0 and more preferably not more than 50.0 for the sake of reducing the amount of a chemical agent used.

When a mass of coal (solid content) before desulfurization is W1 [kg], a sulfur content of coal (solid content) before desulfurization is % S1 [mass*], a mass of coal (solid content) after desulfurization is W2 [kg], and a sulfur content of coal (solid content) after desulfurization is % S2 [mass %], the desulfurization rate [mass %] is defined by Formula (1) below.


Desulfurization rate[mass %]=100×{1−(W2×% S2)/(W1×% S1)}  (1)

<<Temperature of Chemical Agent>>

The present inventors also studied a temperature of a chemical agent at the time of being brought into contact with coal (hereinafter, also simply referred to as “a temperature of a chemical agent”). In this study, a chemical agent having a molar ratio between acetic anhydride and hydrogen peroxide (acetic anhydride/hydrogen peroxide) of 5.0 was used.

FIG. 2 provides a graph (lower part) showing an amount of peracetic acid generated with respect to a temperature of a chemical agent, and a graph (upper part) showing a desulfurization rate (solid line) and a carbon yield (dashed line) with respect to a temperature of a chemical agent. The amount of peracetic acid generated is an index obtained by setting a calculated value at the time when the reaction contributing substances (hydrogen peroxide and acetic anhydride) completely react to 1.0.

As shown in the graphs (lower and upper parts) of FIG. 2, when the temperature of a chemical agent at the time of being brought into contact with coal is high, the amount of peracetic acid generated is large, and the desulfurization rate is high, so that the desulfurization effect becomes more excellent. In connection with this, the temperature of a chemical agent is preferably not less than 5° C., more preferably not less than 10° C., even more preferably not less than 20° C. and particularly preferably not less than 25° C.

On the other hand, as shown in the graph (upper part) of FIG. 2, the temperature of a chemical agent is preferably not too high in order to maintain a high carbon yield. Specifically, the temperature is preferably not more than 40° C., more preferably not more than 35° C. and even more preferably not more than 30° C. because the carbon yield can become more excellent.

When a carbon content of coal (solid content) before desulfurization is % C1 [mass %] and a carbon content of coal (solid content) after desulfurization is % C2 [mass %], the carbon yield [mass %] is defined by Formula (2) below.


Carbon yield[mass %]=100×(W2×% C2)/(W1×% C1)   (2)

The presumable reason why the carbon yield decreases is described below.

Hydrogen peroxide and peracetic acid may become an oxidizing agent which may destroy a skeleton of coal, and in this case, the carbon yield unintentionally decreases simultaneously with removal of sulfur. The present inventors found, through a study, that peracetic acid first causes cutting off of a bond between sulfur and carbon of thiophene form sulfur, and thereafter destroy of a carbon skeleton (carbon-carbon bond) occurs. The degree of destroy of a carbon skeleton is low with peracetic acid and high with hydrogen peroxide. In particular, it is remarkable with hydrogen peroxide having a high temperature.

Therefore, by appropriately controlling a condition when a chemical agent is brought into contact with coal (for example, preventing the temperature of a chemical agent from becoming too high, or appropriately adjusting the mixing ratio of hydrogen peroxide in a mixed solution), the thiophene form sulfur can be effectively removed while the destroy of a carbon skeleton is minimized.

<Coal>

While the coal used in the invention is not particularly limited and a wide variety of coals can be used, the coal preferably includes coal having a moderate degree of coalification such as sub-bituminous coal, more preferably includes sub-bituminous coal and even more preferably is sub-bituminous coal.

When such coal is used, the desulfurization effect tends to be more excellent than that in the case where coal having a high degree of coalification such as anthracite coal is used, and the carbon yield tends to be more excellent than that in the case where coal having a low degree of coalification such as brown coal is used.

The grain size (mean grain size) of coal used in the invention is not particularly limited. For example, even when the grain size of coal is on the order of several millimeters, there is no significant change in desulfurization performance. When the grain size of coal is equal to or larger than this, a mild pulverization treatment may be performed as necessary.

The primary treatment (chemical treatment) for desulfurizing coal was described above.

Next, two types of secondary treatments are described as a treatment for further removing sulfur remaining in coal having been desulfurized by the primary treatment.

<Secondary Treatment (Heat Treatment)>

By the action of peracetic acid which is a reaction product of hydrogen peroxide and acetic anhydride, thiophene form sulfur which is difficult to be removed is changed into an easily removable form; therefore, the thiophene form sulfur can be removed by a heat treatment at a relatively low temperature (about 150° C.)

That is, it is preferable that a heat treatment is further performed on coal which has been brought into contact with a chemical agent because the desulfurization effect can become more excellent. The heat treatment temperature is preferably not less than 150° C., more preferably not less than 250° C., and even more preferably not less than 350° C.

Note that a hydrocarbon-containing gas derived from coal and generated by a heat treatment can be recovered and used as a part of a gaseous fuel in an iron manufacturing process. In consideration of performing a heat treatment using, for example, exhaust heat generated at a factory such as ironworks, a heat treatment at a temperature of up to several hundreds Celsius is preferred.

One example of a furnace for subjecting coal to a heat treatment in iron manufacturing process is a coke oven. The heat treatment temperature in a coke oven is about 1000 to 1200° C., and the coke oven may be operated at a temperature at or above 1200° C. Coal that has been brought into contact with a chemical agent and desulfurized may be introduced into a coke oven to produce low-sulfur coke. While a hydrocarbon gas and a sulfur-containing gas are generated in this case, the sulfur-containing gas can be separately removed. The generated gas after the sulfur-containing gas is removed can be reused as a fuel gas.

Among processes for subjecting coal to a heat treatment, a process having the highest temperature is probably substantially a process of producing coke. As a result of experiments conducted by the present inventors, it was confirmed that a sufficient desulfurization effect was also exhibited even with a heat treatment temperature in a coke oven.

Therefore, the heat treatment temperature is, for example, not more than 1300° C.

Coal that has been subjected to a heat treatment at about 600° C. is generally called semi-coke. Coal that has been brought into contact with a chemical agent and desulfurized can also be used in producing semi-coke. Since semi-coke is generally inferior in strength to coke, it can hardly be used as coke for a blast furnace, but it can be used for other applications. In particular, semi-coke containing less sulfur is useful as, for example, a heating agent (carburizing material) used for heating in a converter.

It is preferable that a heating rate at which coal that has been brought into contact with a chemical agent is heated to the heat treatment temperature (hereinafter, also simply referred to as “heating rate”) is higher. This is because a sulfur compound which has been changed into a form allowing desulfurization by the action of a mixed solution of hydrogen peroxide and acetic anhydride may be resynthesized into thiophene form sulfur which is difficult to desulfurize under heating, and this resynthesis is suppressed. Specifically, the heating rate is preferably not less than 10° C./min and more preferably not less than 20° C./min.

While the upper limit of the heating rate is not particularly limited, realization of an excessively high heating rate is difficult for technical and industrial (cost) reasons. Therefore, the heating rate is, for example, not more than 100° C./min.

<Secondary Treatment (Hydrogen Peroxide Treatment)>

The present inventors found, through the study, that for further desulfurizing coal that has been brought into contact with a chemical agent, a treatment using low-temperature hydrogen peroxide may be performed separately from the above-described heat treatment.

When hydrogen peroxide acts on coal that has not been subjected to the primary treatment (chemical treatment), as described above, a carbon skeleton is destroyed, and the carbon yield decreases. However, since a sulfur content remaining in coal that has been subjected to the primary treatment is in an easily removable form, the coal can be easily additionally desulfurized with hydrogen peroxide.

That is, it is preferable that the coal that has been brought into contact with the chemical agent is further brought into contact with a hydrogen peroxide solution having a low temperature.

The temperature of a hydrogen peroxide solution is preferably not more than 50° C. and more preferably not more than 40° C. The oxidizing ability of hydrogen peroxide becomes increasingly strong as the temperature of the hydrogen peroxide becomes high, and not only the desulfurization effect but also the carbon yield tends to decrease. When the temperature of a hydrogen peroxide solution is within the above range, the desulfurization effect is further excellent, and the carbon yield is also good.

The lower limit thereof is not particularly limited, and the temperature of a hydrogen peroxide solution is, for instance, not less than 5° C.

The concentration of a hydrogen peroxide solution (the content of hydrogen peroxide in a hydrogen peroxide solution) is preferably not less than 2.0 mass % and more preferably not less than 3.0 mass % because the desulfurization effect can become more excellent.

When the concentration of a hydrogen peroxide solution is not less than 3.0 mass %, the effect thus obtained is substantially constant regardless of the concentration of a hydrogen peroxide solution. Therefore, the upper limit thereof is not particularly limited, and the concentration of a hydrogen peroxide solution is preferably not more than 35.0 mass %, for instance.

Hydrogen peroxide is often commercially available as an aqueous solution of 30 to 35 mass % because it is easy to decompose on the high concentration side. In the present invention, such a commercially available aqueous solution may be appropriately diluted and used.

[Facility for Producing Low-Sulfur Coal]

Next, an example in which the present invention is implemented using a specific facility will be described with reference to FIG. 3.

FIG. 3 is a schematic view showing an example of a facility for producing low-sulfur coal (hereinafter, also simply referred to as “production facility”).

The production facility shown in FIG. 3 has a hydrogen peroxide storage tank 1 for storing hydrogen peroxide and an acetic anhydride storage tank 3 for storing acetic anhydride.

The hydrogen peroxide inside the hydrogen peroxide storage tank 1 is supplied to a chemical agent mixing tank 5 via a hydrogen peroxide transport pipe 2. The acetic anhydride inside the acetic anhydride storage tank 3 is supplied to the chemical agent mixing tank 5 via an acetic anhydride transport pipe 4. The hydrogen peroxide transport pipe 2 and the acetic anhydride transport pipe 4 are each provided with a suitable flow rate control device (not shown), and the flow rates of the hydrogen peroxide and the acetic anhydride can be controlled.

The chemical agent mixing tank 5 is provided with a heating device 6 and a mixing device 7. The hydrogen peroxide and the acetic anhydride supplied to the chemical agent mixing tank 5 are heated to a predetermined temperature using the heating device 6 as necessary and mixed using the mixing device 7.

A chemical agent which is a mixed solution obtained by mixing in the chemical agent mixing tank 5 is supplied to a desulfurization treatment tank 9 via a chemical agent transport pipe 8. The chemical agent transport pipe 8 is provided with a suitable flow rate control device (not shown), and the flow rate of the chemical agent can be controlled.

The desulfurization treatment tank 9 is further supplied with coal from a coal storage tank 10 for storing coal via a coal transport pipe 11. The coal transport pipe 11 is provided with a suitable flow rate control device (not shown), and the flow rate of the coal can be controlled.

The desulfurization treatment tank 9 is provided with a heating device 12. The heating device 12 controls the chemical agent supplied from the chemical agent mixing tank 5 and the coal supplied from the coal storage tank 10 to an appropriate temperature as necessary. Further, the desulfurization treatment tank 9 is provided with a mixing device 13. The mixing device 13 mixes the chemical agent and the coal well as necessary.

Thus, in the desulfurization treatment tank 9, the coal is brought into contact with the chemical agent and desulfurized, thereby obtaining coal with low sulfur content (low-sulfur coal) (hereinafter, also referred to as “chemical-treated coal”)

The desulfurization treatment tank 9 is provided with discharge holes at two places. A chemical agent circulation pipe 14 is provided at one discharge hole. Peracetic acid may remain in a part of the chemical agent after use in desulfurization of the coal. In this case, the chemical agent may be flown back from the desulfurization treatment tank 9 to the chemical agent mixing tank 5 and reused.

However, sulfur may leach into the chemical agent after desulfurization. Reuse of the chemical agent into which sulfur leaches may adversely affect desulfurization. Therefore, a chemical agent discharge pipe 15 is connected to the chemical agent circulation pipe 14, and a part or all of the chemical agent after desulfurization can be discharged through the chemical agent discharge pipe 15.

A chemical-treated coal transport pipe 16 is provided at the other discharge hole of the desulfurization treatment tank 9. The chemical-treated coal transport pipe 16 is further branched into three pipes, i.e., a chemical-treated coal discharge pipe 16a, a heat treatment device connection pipe 16b and a hydrogen peroxide treatment device connection pipe 16c.

The chemical-treated coal discharge pipe 16a discharges the chemical-treated coal obtained in the desulfurization treatment tank 9 without performing the secondary treatment. The heat treatment device connection pipe 16b transports the chemical-treated coal to a heat treatment device 17. The hydrogen peroxide treatment device connection pipe 16c transports the chemical-treated coal to a hydrogen peroxide treatment device 23.

First, the heat treatment device 17 will be described.

When low-sulfur coal (chemical-treated coal) is subjected to a heat treatment in the heat treatment device 17, sulfur is further volatilized, so that the desulfurization proceeds further. The coal that has been subjected to the heat treatment in the heat treatment device 17 and has been further reduced in sulfur content (hereinafter, also referred to as “heat-treated coal”) is taken out through a heat-treated coal discharge pipe 18 and used for a predetermined use.

Further, the heat treatment device 17 is provided with a heat treatment gas exhaust pipe 19. A gas generated by a heat treatment may include a combustible gas. In this case, the gas can be taken out through the heat treatment gas discharge pipe 19 and used for a predetermined use.

Next, the hydrogen peroxide treatment device 23 will be described.

The hydrogen peroxide treatment device 23 is supplied with the chemical-treated coal via the hydrogen peroxide treatment device connection pipe 16c. In the hydrogen peroxide treatment device 23, the chemical-treated coal is subjected to the above-described secondary treatment (hydrogen peroxide treatment).

The hydrogen peroxide treatment device 23 is supplied with the hydrogen peroxide via a hydrogen peroxide supply pipe 20. The hydrogen peroxide supply pipe 20 is connected to the hydrogen peroxide storage tank 1. When the hydrogen peroxide is diluted, water may be supplied from a dilution water tank 21 through a dilution water supply pipe 22. Another hydrogen peroxide storage tank (not shown) may be provided exclusively for the hydrogen peroxide treatment device 23.

The hydrogen peroxide treatment device 23 is provided with a cooling device 24. The cooling device 24 controls a temperature inside the hydrogen peroxide treatment device 23 to an appropriate temperature as necessary.

Further, the hydrogen peroxide treatment device 23 is provided with a mixing device 25. The mixing device 25 mixes the hydrogen peroxide solution and the chemical-treated coal well as necessary.

The hydrogen peroxide treatment device 23 is provided with discharge holes at two places.

A hydrogen peroxide circulation pipe 27 is provided at one discharge hole. Hydrogen peroxide may remain in a part of the hydrogen peroxide solution after use in desulfurization of the coal (chemical-treated coal). In this case, the hydrogen peroxide solution may be flown back from the hydrogen peroxide treatment device 23 to the hydrogen peroxide storage tank 1 and reused. A destination of the flowback may be a separately provided hydrogen peroxide storage tank (not shown) or the chemical agent mixing tank 5.

However, sulfur may leach into the hydrogen peroxide solution after desulfurization. Reuse of the hydrogen peroxide solution into which sulfur leaches may adversely affect desulfurization. Therefore, a hydrogen peroxide discharge pipe 28 is connected to the hydrogen peroxide circulation pipe 27, and a part or all of the hydrogen peroxide solution after desulfurization can be discharged through the hydrogen peroxide discharge pipe 28.

A discharge pipe 26 is connected to the other discharge hole of the hydrogen peroxide treatment device 23. Coal that has been further desulfurized inside the hydrogen peroxide treatment device 23 (hereinafter, also referred to as “hydrogen peroxide-treated coal”) is taken out through the discharge pipe 26 and used for a predetermined use.

Note that since the chemical-treated coal transported to the heat treatment device 17 or the hydrogen peroxide treatment device 23 is already reduced in sulfur content, it may be taken out through the heat-treated coal discharge pipe 18 or the discharge pipe 26 without being subjected to the secondary treatment (heat treatment or hydrogen peroxide treatment).

Each part of the production facility described with reference to FIG. 3 need not have a special specification, and existing devices can be used as appropriate. For example, the heat treatment device 17 may be a heat exchanger using exhaust heat as a heat source, and it may be a furnace such as a semi-coke oven or a coke oven.

EXAMPLES

The present invention is specifically described below with reference to examples. However, the present invention should not be construed as being limited to the following examples.

Examples 1 to 16 and Comparative Example 1

By using the production facility described with reference to FIG. 3, a test was conducted in which coal was desulfurized to produce low-sulfur coal by the method of the present invention.

As the coal, at least one selected from the group consisting of Coal A (sub-bituminous coal), Coal B (sub-bituminous coal) and Coal C (semi-anthracite coal) was used. The details of the coals used are shown in Table 1 below. The granularity of each coal was about 300 μm in a mean grain size. With all coals, permeability of peracetic acid is high, and the desulfurization performance did not vary greatly depending on the granularity.

TABLE 1 Industrial analysis value Industrial analysis value [mass % d.a.f.] [mass % d.b.] C H N S V.M Ash Coal A 78.5 4.6 0.8 0.2 38.2 6.8 Coal B 77.1 4.9 1.5 0.5 33.2 6.7 Coal C 82.1 1.2 1.4 2 9.4 8.1

In Table 1 above, “d.a.f” indicates a dry ash free basis, and means an analytical value of net coal excluding moisture and ash.

“d.b.” means an analysis value on a dry basis.

“V.M” means a content of volatile matter in industrial analysis.

“Ash” means a content of ash in industrial analysis.

Test conditions such as supply amounts (flow rates) of coal, hydrogen peroxide and acetic anhydride are shown in Table 2 below.

In Examples 1 to 7 and Comparative Example 1, only the above-described primary treatment (chemical treatment) was performed. That is, the coal after being brought into contact with the chemical agent was taken out, and the desulfurization rate and the carbon yield were determined.

In Examples 8 to 11, the above-described secondary treatment (heat treatment) was further performed. That is, after the primary treatment (chemical treatment), the coal was further introduced into the heat treatment device capable of raising the temperature to 1200° C. and then subjected to heat treatment under a nitrogen atmosphere, and the desulfurization rate and the carbon yield after the heat treatment were determined.

In Examples 12 to 16, the above-described secondary treatment (hydrogen peroxide treatment) was further performed. That is, after the primary treatment (chemical treatment), the coal was further introduced into the hydrogen peroxide treatment device and then subjected to the hydrogen peroxide treatment, and the desulfurization rate and the carbon yield after the hydrogen peroxide treatment were determined.

In the primary treatment, an aqueous solution having a concentration of hydrogen peroxide of 35 mass % was used as hydrogen peroxide. As acetic anhydride, acetic anhydride having a purity of 99 mass % was used.

TABLE 2 Example Example Unit 1 2 3 4 5 6 7 8 9 Coal Coal A g/h 100 50 0 100 100 100 100 100 100 Coal B g/h 0 50 0 0 0 0 0 0 0 Coal C g/h 0 0 100 0 0 0 0 0 0 Total amount g/h 100 100 100 100 100 100 100 100 100 Chemical Hydrogen peroxide g/h 50 100 50 95 50 20 240 50 50 agent and Acetic anhydride g/h 265 55 265 40 350 70 60 265 265 primary Molar ratio mol/mol 5.0 0.5 5.0 0.4 6.6 3.3 0.2 5.0 5.0 treatment (acetic anhydride/ (chemical hydrogen peroxide) treatment) Elapsed time after min 30 60 30 30 8 30 30 30 30 mixing Mass ratio (chemical g/g 3.2 1.6 3.2 1.4 4.0 0.9 3.0 3.2 3.2 agent/coal) Chemical agent ° C. 20 22 20 20 17 20 35 20 20 temperature Desulfurization rate mass % 52 51 50 48 51 45 58 52 52 (after primary treatment) Carbon yield mass % 96 93 97 96 94 96 90 96 96 (after primary treatment) Secondary Heat treatment ° C. — — — — — — — 150 1200 treatment temperature (heat Heating rate ° C./min — — — — — — — 20 25 treatment) Desulfurization rate mass % — — — — — — — 65 68 (after secondary treatment) Carbon yield mass % — — — — — — — 95 94 (after secondary treatment) Secondary Temperature of ° C. — — — — — — — — — treatment hydrogen peroxide (hydrogen solution peroxide Concentration of mass % — — — — — — — — — treatment) hydrogen peroxide solution Mass ratio (hydrogen g/g — — — — — — — — — peroxide solution/coal) Desulfurization rate mass % — — — — — — — — — (after secondary treatment) Carbon yield mass % — — — — — — — — — (after secondary treatment) Comparative Example Example Example Unit 10 11 12 13 14 15 16 1 Coal Coal A g/h 100 100 100 100 100 100 100 100 Coal B g/h 0 0 0 0 0 0 0 0 Coal C g/h 0 0 0 0 0 0 0 0 Total amount g/h 100 100 100 100 100 100 100 100 Chemical Hydrogen peroxide g/h 50 50 50 50 50 50 50 300 agent and Acetic anhydride g/h 265 265 265 265 265 265 265 0 primary Molar ratio mol/mol 5.0 5.0 5.0 5.0 5.0 5.0 5.0 0.0 treatment (acetic anhydride/ (chemical hydrogen peroxide) treatment) Elapsed time after min 30 30 30 30 30 30 30 — mixing Mass ratio (chemical g/g 3.2 3.2 3.2 3.2 3.2. 3.2 3.2 3.0 agent/coal) Chemical agent ° C. 20 20 20 20 20 20 20 20 temperature Desulfurization rate mass % 52 52 52 52 52 52 52 2.8 (after primary treatment) Carbon yield mass % 96 96 96 96 96 96 96 96 (after primary treatment) Secondary Heat treatment ° C. 100 150 — — — — — — treatment temperature (heat Heating rate ° C./min 10 5 — — — — — — treatment) Desulfurization rate mass % 53 61 — — — — — — (after secondary treatment) Carbon yield mass % 95 95 — — — — — — (after secondary treatment) Secondary Temperature of ° C. — — 20 40 45 30 30 — treatment hydrogen peroxide (hydrogen solution peroxide Concentration of mass % — — 35.0 35.0 5.0 1.5 3.0 — treatment) hydrogen peroxide solution Mass ratio (hydrogen g/g — — 2.5 2.5 2.5 2.5 0.9 — peroxide solution/coal) Desulfurization rate mass % — — 65 66 55 62 63 — (after secondary treatment) Carbon yield mass % — — 95 93 71 95 95 — (after secondary treatment)

<Summary of Test Results>

It was revealed that Examples 1 to 16 using a mixed solution of hydrogen peroxide and acetic anhydride as a chemical agent exhibited a higher desulfurization rate than that of Comparative Example 1 in which such a solution was not used, thus having a sufficient desulfurization effect. The carbon yield was also good.

The comparison between Example 1 and Example 4 revealed that Example 1 in which a molar ratio (acetic anhydride/hydrogen peroxide) was 5.0 had a higher desulfurization rate than that of Example 4 in which a molar ratio (acetic anhydride/hydrogen peroxide) was 0.4, thus having a more excellent desulfurization effect.

The comparison between Example 1 and Example 5 revealed that Example 1 in which the elapsed time after mixing of acetic anhydride and hydrogen peroxide was 30 minutes had a higher desulfurization rate than that of Example 5 in which the time was 8 minutes, thus having a more excellent desulfurization effect.

The comparison between Example 1 and Example 6 revealed that Example 1 in which the mass ratio (chemical agent/coal) was 3.2 had a higher desulfurization rate than that of Example 6 in which the mass ratio (chemical agent/coal) was 0.9, thus having a more excellent desulfurization effect.

The comparison between Example 1 and Example 7 revealed that Example 1 in which the temperature of the chemical agent at the time of being brought into contact with coal was 20° C. had a better carbon yield than that of Example 7 in which the temperature was 35° C.

The desulfurization rates (after the secondary treatment) of Examples 8 to 11 were equal to or higher than the desulfurization rates (after the primary treatment) of Examples 1 to 7.

The comparison between Example 8 and Example 10 revealed that Example 8 in which the heat treatment temperature was 150° C. had a higher desulfurization rate (after the secondary treatment) than that of Example 10 in which the heat treatment temperature was 100° C., thus having a more excellent desulfurization effect.

The comparison between Example 8 and Example 11 revealed that Example 8 in which the heating rate at which the temperature was raised to the heat treatment temperature was 20° C./min had a higher desulfurization rate (after the secondary treatment) than that of Example 11 in which the heating rate was 5° C./min, thus having a more excellent desulfurization effect.

The desulfurization rates (after the secondary treatment) of Examples 12 to 16 were equal to or higher than the desulfurization rates (after the primary treatment) of Examples 1 to 7.

The comparison between Example 12 and Example 14 revealed that Example 12 in which the temperature of the hydrogen peroxide solution was 20° C. had a higher desulfurization rate (after the secondary treatment) than that of Example 14 in which the temperature was 45° C., thus having a more excellent desulfurization effect.

The comparison between Example 12 and Example 15 revealed that Example 12 in which the concentration of the hydrogen peroxide solution was 35.0 mass % had a higher desulfurization rate (after the secondary treatment) than that of Example 15 in which the concentration was 1.5 mass %, thus having a more excellent desulfurization effect.

The comparison between Example 12 and Example 16 revealed that Example 12 in which a mass ratio (hydrogen peroxide solution/coal) was 2.5 had a higher desulfurization rate (after the secondary treatment) than that of Example 16 in which a mass ratio (hydrogen peroxide solution/coal) was 0.9, thus having a more excellent desulfurization effect.

REFERENCE SIGNS LIST

    • 1: Hydrogen peroxide storage tank
    • 2: Hydrogen peroxide transport pipe
    • 3: Acetic anhydride storage tank
    • 4: Acetic anhydride transport pipe
    • 5: Chemical agent mixing tank
    • 6: Heating device
    • 7: Mixing device
    • 8: Chemical agent transport pipe
    • 9: Desulfurization treatment tank
    • 10: Coal storage tank
    • 11: Coal transport pipe
    • 12: Heating device
    • 13: Mixing device
    • 14: Chemical agent circulation pipe
    • 15: Chemical agent discharge pipe
    • 16: Chemical-treated coal transport pipe
    • 16a: Chemical-treated coal discharge pipe
    • 16b: Heat treatment device connection pipe
    • 16c: Hydrogen peroxide treatment device connection pipe
    • 17: Heat treatment device
    • 18: Heat-treated coal discharge pipe
    • 19: Heat treatment gas exhaust pipe
    • 20: Hydrogen peroxide supply pipe
    • 21: Dilution water tank
    • 22: Dilution water supply pipe
    • 23: Hydrogen peroxide treatment device
    • 24: Cooling device
    • 25: Mixing device
    • 26: Discharge pipe
    • 27: Hydrogen peroxide circulation pipe
    • 28: Hydrogen peroxide discharge pipe

Claims

1.-11. (canceled)

12. A low-sulfur coal production method comprising:

bringing coal into contact with a chemical agent which is a mixed solution of hydrogen peroxide and acetic anhydride to thereby remove sulfur in the coal,
wherein a molar ratio between the acetic anhydride and the hydrogen peroxide (acetic anhydride/hydrogen peroxide) is not less than 0.5 and not more than 12.0,
wherein the acetic anhydride and the hydrogen peroxide are mixed before the chemical agent is brought into contact with the coal, and
wherein when 10 minutes or more have elapsed after the acetic anhydride and the hydrogen peroxide are mixed, the chemical agent is brought into contact with the coal.

13. The low-sulfur coal production method according to claim 12,

wherein a mass ratio between the chemical agent and the coal (chemical agent/coal) is not less than 1.0, and
wherein a temperature of the chemical agent at a time of being brought into contact with the coal is not less than 5° C. but not more than 30° C.

14. The low-sulfur coal production method according to claim 12,

wherein the coal comprises sub-bituminous coal.

15. The low-sulfur coal production method according to claim 13,

wherein the coal comprises sub-bituminous coal.

16. The low-sulfur coal production method according to claim 12,

wherein the coal that has been brought into contact with the chemical agent is heat-treated at a heat treatment temperature of not less than 150° C., and
wherein a heating rate at which the coal that has been brought into contact with the chemical agent is heated to the heat treatment temperature is not less than 10° C./min.

17. The low-sulfur coal production method according to claim 13,

wherein the coal that has been brought into contact with the chemical agent is heat-treated at a heat treatment temperature of not less than 150° C., and
wherein a heating rate at which the coal that has been brought into contact with the chemical agent is heated to the heat treatment temperature is not less than 10° C./min.

18. The low-sulfur coal production method according to claim 14,

wherein the coal that has been brought into contact with the chemical agent is heat-treated at a heat treatment temperature of not less than 150° C., and
wherein a heating rate at which the coal that has been brought into contact with the chemical agent is heated to the heat treatment temperature is not less than 10° C./min.

19. The low-sulfur coal production method according to claim 15,

wherein the coal that has been brought into contact with the chemical agent is heat-treated at a heat treatment temperature of not less than 150° C., and
wherein a heating rate at which the coal that has been brought into contact with the chemical agent is heated to the heat treatment temperature is not less than 10° C./min.

20. The low-sulfur coal production method according to claim 12,

wherein the coal that has been brought into contact with the chemical agent is brought into contact with a hydrogen peroxide solution having a temperature of not more than 40° C.,
wherein a concentration of the hydrogen peroxide solution is not less than 2.0 mass %, and
wherein a mass ratio between the hydrogen peroxide solution and the coal (hydrogen peroxide solution/coal) is not less than 1.0.

21. The low-sulfur coal production method according to claim 13,

wherein the coal that has been brought into contact with the chemical agent is brought into contact with a hydrogen peroxide solution having a temperature of not more than 40° C.,
wherein a concentration of the hydrogen peroxide solution is not less than 2.0 mass %, and
wherein a mass ratio between the hydrogen peroxide solution and the coal (hydrogen peroxide solution/coal) is not less than 1.0.

22. The low-sulfur coal production method according to claim 14,

wherein the coal that has been brought into contact with the chemical agent is brought into contact with a hydrogen peroxide solution having a temperature of not more than 40° C.,
wherein a concentration of the hydrogen peroxide solution is not less than 2.0 mass %, and
wherein a mass ratio between the hydrogen peroxide solution and the coal (hydrogen peroxide solution/coal) is not less than 1.0.

23. The low-sulfur coal production method according to claim 15,

wherein the coal that has been brought into contact with the chemical agent is brought into contact with a hydrogen peroxide solution having a temperature of not more than 40° C.,
wherein a concentration of the hydrogen peroxide solution is not less than 2.0 mass %, and
wherein a mass ratio between the hydrogen peroxide solution and the coal (hydrogen peroxide solution/coal) is not less than 1.0.
Patent History
Publication number: 20220220404
Type: Application
Filed: Apr 20, 2020
Publication Date: Jul 14, 2022
Applicant: JFE STEEL CORPORATION (Tokyo)
Inventors: Ryota MURAI (Tokyo), Ikuhiro SUMI (Tokyo), Katsuyasu SUGAWARA (Akita-shi), Takahiro KATO (Akita-shi)
Application Number: 17/605,950
Classifications
International Classification: C10L 9/06 (20060101);