WO2010035651A1

WO2010035651A1 - Method for manufacturing hyper-coal

Info

Publication number: WO2010035651A1
Application number: PCT/JP2009/066019
Authority: WO
Inventors: 眞基濱口; 憲幸奥山; 康爾堺; 信行小松
Original assignee: 株式会社神戸製鋼所
Priority date: 2008-09-29
Filing date: 2009-09-14
Publication date: 2010-04-01
Also published as: AU2009297631A1; JP2010083907A; KR20110047264A; JP4708463B2; KR101246505B1; CN102165049B; CN102165049A

Abstract

A method for manufacturing hyper-coal is characterized by comprising a first slurry heating step (S1) for heat-treating slurry prepared by mixing coal and an aromatic solvent, a first separation step (S2) for separating the heat-treated slurry into a liquid component and a solid component, a second slurry heating step (S3) for heat-treating slurry prepared by adding and mixing a hydrogen donor solvent into the solid component at a temperature higher than or equal to the temperature of the heat treatment in the first slurry heating step (S1), a second separation step (S4) for separating the heat-treated slurry into a liquid component and a solid component, and an upgraded coal acquisition step (S5) for acquiring hyper-coal by removing the solvent from the liquid component, and further acquiring hyper-coal by removing the solvent from the liquid component separated in the first separation step.

Description

Production method of ashless coal

The present invention relates to a method for producing a non-ferrous metal reducing agent, structural material charcoal, electric material charcoal, or ashless charcoal used as a raw material thereof.

Conventionally, carbon materials have been widely used as structural materials and electrical materials because of their excellent heat resistance and chemical stability and electrical conductivity. Further, since carbon exhibits an action of reducing many metal oxides at a high temperature, it is also used as a reducing agent in refining silicon and titanium. The characteristics required for the carbon material vary depending on its use. However, since the characteristics of the carbon material are not deteriorated, high quality characteristics such as low ash concentration and excellent thermal fluidity are required. Thus, attempts have been made to extract a component soluble in a solvent from coal as a raw material coal for the carbon material to obtain a high quality extracted coal from the raw material coal.

As the raw coal for such a low ash carbon material, so-called ashless coal (Hyper Coal), which has been actively developed recently, can be cited (for example, see Patent Document 1). Here, ashless coal is produced by extracting coal with a solvent, separating only the components soluble in the solvent, and then removing the solvent. Structurally, this ashless coal has a wide molecular weight distribution from a relatively low molecular weight component having 2 to 3 condensed aromatic rings to a high molecular weight component having about 5 or 6 rings. In addition, since ash is not dissolved in a solvent, ashless coal does not substantially contain ash, exhibits high fluidity under heating, and is excellent in thermal fluidity. Some coals, like caking coal, exhibit thermoplasticity at around 400 ° C., but ashless coal generally melts at 200 to 300 ° C. regardless of the quality of the raw coal. This ashless coal can be used as a raw material for carbon material, and the carbon material is used as a reducing agent for metallurgy including iron making, a structural material, and an electrical material such as an electrode.

However, in the production of ashless coal, there is a problem that it is not always possible to obtain ashless coal from all types of coal in a high yield. For example, among bituminous coal, coal with a relatively low degree of coalification is easy to dissolve in a solvent, and generally a high yield (about 50% by mass or more) is obtained. However, like subbituminous coal and lignite, the degree of coalification is low. Among coal and bituminous coal, those with a high degree of coalification are difficult to dissolve in the solvent and the yield is low.

On the other hand, it is known that a method using a hydrogen donating solvent is effective in order to realize a high extraction rate (ratio of coal components extracted into the solvent) regardless of the coal type (brand). Examples of the hydrogen donating solvent include partially hydrogenated aromatic compounds such as tetralin and tetrahydroquinoline, or hydrogenated liquefied oil of coal. Since these solvents have the effect of hydrogenating and stabilizing coal radicals generated by thermal decomposition in the extraction process, the polycondensation of coal is suppressed, and extracted coal can be obtained in a high yield (hydrogen to the solvent). If there is no donating property, it is inevitable that a considerable amount of insoluble matter is generated by the polycondensation of coal).

JP 2001-26791 A

However, the conventional method for producing ashless coal has the following problems.
As described above, depending on the coal type of coal used as a raw material, there are some that are not easily dissolved in a solvent, and there are cases where a high ashless coal yield cannot be obtained as compared with a coal type that is easily dissolved in a solvent.
In addition, the method using a hydrogen donating solvent is effective in terms of dissolving coal, but (1) the hydrogen donating solvent is generally more expensive than an ordinary solvent having no hydrogen donating property, (2) Since the solvent once used for extraction loses most of its hydrogen donating capacity, it must be regenerated (hydrogenation treatment) and costly for the treatment, and (3) the hydrogen donating solvent For components that can be extracted even if they are not used, hydrogen in the hydrogen-donating solvent is consumed, so that the utilization efficiency of the hydrogen-donating solvent is low. However, there are problems such as the generation of a relatively large amount of light components, and it has not been put into practical use.

This invention is made | formed in view of the said subject, The objective is the manufacturing method of the ashless coal which can obtain an ashless coal with high yield and low cost irrespective of the coal kind of raw material coal. It is to provide.

As a result of diligent research, the present inventors have made a process for obtaining extracted coal (ashless coal) at a low yield in a high yield while making the best use of the properties of a hydrogen-donating solvent and reducing the disadvantages as much as possible. Succeeded in building.

That is, the method for producing ashless coal according to the present invention is a method for producing ashless coal used as a nonferrous metal reducing agent, structural material coal, electric material coal, or these raw materials, 1st slurry heating process which heat-processes the slurry which mixed this, The slurry heat-processed by the said 1st slurry heating process is isolate | separated into the liquid component in which coal melt | dissolved, and the solid component containing ash and insoluble coal A hydrogen-donating solvent is added to and mixed with the solid component separated in the first separation step and the first separation step, and the mixed slurry is heated at a temperature equal to or higher than the temperature of the heat treatment in the first slurry heating step. The second slurry heating step to be processed, and the slurry heat-treated in the second slurry heating step are separated into a liquid component in which coal is dissolved and a solid component containing ash and insoluble coal. A modified coal acquisition step of removing a solvent from the liquid component separated in the second separation step and acquiring ashless coal that is a modified coal, and the modified coal acquisition step In addition to obtaining the ashless coal, in the modified coal obtaining step, the solvent is further removed from the liquid component separated in the first separation step, and the ashless coal that is the modified coal is obtained. It is characterized by acquiring.

According to such a manufacturing method, in the first slurry heating step, the slurry is heat-treated at a lower temperature than the heat treatment in the second slurry heating step, thereby comparing substituents such as alkyl groups having a relatively low molecular weight. A component containing a large amount is extracted. Also, in the second slurry heating step, the slurry obtained by adding the hydrogen-donating solvent to the solid component separated in the first separation step and mixing is heated at a temperature equal to or higher than the temperature of the heat treatment in the first slurry heating step. Thus, depolymerization of coal proceeds, and components that have a relatively large molecular weight and are difficult to melt are extracted. Moreover, since the hydrogen transfer from the hydrogen donating solvent is performed, the polycondensation of coal is suppressed and the coal components are easily extracted.
The ashless coal obtained from the liquid component separated in the first separation step is hereinafter also referred to as “first ashless coal”, and the ashless coal obtained from the liquid component separated in the second separation step. Hereinafter also referred to as “second ashless coal”.

The method for producing ashless coal according to the present invention hydrotreats the solvent removed in the modified coal acquisition step, supplies the hydrotreated solvent to the second slurry heating step, and circulates it. It is characterized by that.

According to such a manufacturing method, the solvent removed in the modified coal acquisition step, that is, the solvent separated from the liquid component is subjected to hydrogenation treatment, whereby a part of the aromatic aromatic compound in the solvent component is aromatized. The ring is partially hydrogenated and modified as a hydrogen donating solvent. By recycling this modified solvent, the production cost of ashless coal can be reduced.

According to the method for producing ashless coal according to the present invention, the use of an aromatic solvent and a hydrogen-donating solvent in combination with the extraction of coal components reduces the cost regardless of the coal type of the raw coal, and Ash coal yield can be improved.
Furthermore, the production cost of ashless coal can be reduced by circulating the solvent used for coal extraction.

It is a flowchart explaining the process of the manufacturing method of ashless coal. It is a schematic diagram which shows the outline of the manufacturing method of ashless coal. It is the schematic at the time of using the gravity sedimentation method in the manufacturing method of ashless coal.

Next, the method for producing ashless coal according to the present invention will be described in detail with reference to the drawings. In the drawings to be referred to, FIG. 1 is a flowchart for explaining the steps of the method for producing ashless coal, FIG. 2 is a schematic diagram showing an outline of the method for producing ashless coal, and FIG. It is the schematic at the time of using the gravity sedimentation method in a method.

≪Production method of ashless coal≫

The method for producing ashless coal according to the present invention is a method for producing non-ferrous metal reducing agent, structural material coal, electric material coal, or ashless coal used as a raw material thereof, as shown in FIGS. The first slurry heating step (S1), the first separation step (S2), the second slurry heating step (S3), the second separation step (S4), and the modified coal obtaining step (S5). Is included.
Hereinafter, each step will be described.

<First slurry heating step (S1)>
The first slurry heating step (S1) is a step of preparing a slurry by mixing coal and an aromatic solvent, and heat-treating the slurry containing the coal and the aromatic solvent (first slurry heating treatment). And a coal component is heat-extracted by the aromatic solvent by heat-processing a slurry.

[coal]
Coal to be used as raw material (hereinafter also referred to as “raw coal”) should be non-slightly caking coal that has little softening and melting properties, or low quality coal such as lignite or sub-bituminous coal. Is preferable from an economic viewpoint. By using inexpensive coal such as these, ashless coal can be produced at a lower cost, so that economic efficiency can be improved. However, the coal used is not limited to these inferior coals, and bituminous coals may be used.

In addition, inferior coal here refers to coal, such as non-slightly caking coal, steam coal, and low-grade coal. The low-grade coal is coal that contains 20% by mass or more of water and is desired to be dehydrated. Examples of such low-grade coal include lignite, lignite, and sub-bituminous coal. For example, lignite coal includes Victoria coal, North Dakota coal, Belga coal, etc., and sub-bituminous coal includes West Banco coal, Binungan coal, Samarangau coal, and the like. The low-grade coal is not limited to those exemplified above, and any coal containing a large amount of water and desired to be dehydrated is included in the low-grade coal referred to in the present invention.

[Aromatic solvent]
Generally, aromatic solvents that dissolve coal include monocyclic aromatic compounds such as benzene, toluene, xylene, naphthalene, methylnaphthalene, dimethylnaphthalene, trimethylnaphthalene, alkylnaphthalene, anthoselan, phenanthrene, ethylnaphthalene, etc. These 2- to 3-ring aromatic compounds or mixtures thereof are used. The bicyclic aromatic compound includes other naphthalenes having an aliphatic side chain, and biphenyl and alkylbenzene having a long aliphatic side chain. It is preferable to use a bicyclic aromatic compound that is a non-hydrogen-donating solvent.

The non-hydrogen donating solvent is a coal derivative that is a solvent mainly composed of a bicyclic aromatic and purified mainly from a coal carbonization product. Since this non-hydrogen donating solvent is stable even in a heated state and has excellent affinity with coal, the proportion of coal components extracted into the solvent (hereinafter also referred to as “extraction rate”) is high. It is a solvent that can be easily recovered by methods such as distillation. Then, in order to improve the economic efficiency, the recovered solvent can be supplied to the second slurry heating step (S3) after being subjected to a hydrogenation treatment as described later, and can be circulated and used repeatedly. Or it can supply to a 1st slurry heating process (S1), and it can circulate and use repeatedly, without performing a hydrogenation process. In addition, since the aromatic solvent is less expensive than the hydrogen donating solvent described later, the use of the aromatic solvent in the first slurry heating step (S1) can improve economic efficiency.

The aromatic solvent preferably has a boiling point of 180 to 330 ° C. When the boiling point is less than 180 ° C., the required pressure in the heat extraction or in the first separation step (S2) described later increases, and the loss due to volatilization increases in the step of recovering the solvent. The recovery rate decreases. Furthermore, the extraction rate in the heat extraction decreases. On the other hand, when the temperature exceeds 330 ° C., it becomes difficult to separate the solvent from the liquid component or the solid component in the modified coal acquisition step (S5), and the solvent recovery rate decreases. The boiling point of the hydrogen donating solvent in the second slurry heating step (S3) described later is the same as described above.

Although the ratio of coal to aromatic solvent depends on the type of raw material coal, it is preferable that the ratio of raw material coal to aromatic solvent (aromatic solvent / coal) is adjusted to 3 to 10. The higher the coal concentration, the better. However, when the “aromatic solvent / coal” is less than 3, the viscosity of the slurry increases, and the liquid component and the solid component are separated in the movement of the slurry and the first separation step (S2). Tends to be difficult. On the other hand, if the “aromatic solvent / coal” exceeds 10, the ratio (extraction rate) of the coal component extracted into the aromatic solvent is less than the amount of the aromatic solvent, which is not economical. The ratio of the solid component to the hydrogen donating solvent (hydrogen donating solvent / solid component) in the second slurry heating step (S3) described later is the same as described above.

[Processing conditions]
The heat treatment (heat extraction) of the slurry in the first slurry heating step (S1) is preferably 320 to 450 ° C. Heat treatment in this temperature range using an aromatic solvent extracts components that are relatively soluble in raw coal, that is, components that contain relatively many substituents such as alkyl groups with relatively low molecular weight. The If the extraction of the low molecular weight component is insufficient in the first slurry heating step (S1), in order to treat many insoluble components in the second slurry heating step (S3), many hydrogen donating solvents are used. It becomes necessary, and the load in the second slurry heating step (S3) increases.

Further, if the processing conditions in the first slurry heating step (S1) are made harsh, that is, when extraction processing is performed at a relatively high temperature for a long time, the polymerization of coal proceeds, so the second slurry heating step ( Even if a hydrogen donating solvent is used in S3), the extraction rate (yield) of the second ashless coal is lowered and the total yield is also lowered. Accordingly, not only the second slurry heating step (S3) but also the conditions of the first slurry heating step (S1) are appropriately adjusted so that the yield of the second ashless coal does not decrease (for example, less than 10% by mass). That is important.

If the heating temperature of the slurry is 320 ° C. or higher, the amount of low molecular weight components separated in the first slurry heating step (S1) increases, and the components that melt in the first slurry heating step (S1) are sufficiently extracted. The load in the second slurry heating step (S3) can be reduced. On the other hand, if it is 450 degrees C or less, the polymerization of coal does not advance, and the extraction rate (yield of the second ashless coal is obtained by using a hydrogen donating solvent in the second slurry heating step (S3). ) Is not too low and the total yield is not reduced. In order to secure a more appropriate extraction rate, the temperature is more preferably 340 to 440 ° C. However, the above-mentioned heating temperature is a standard, and is appropriately adjusted depending on the type of coal or solvent used, the properties of the desired product, and the like.

Here, the total yield of the first ashless coal and the second ashless coal is preferably at least 45% by mass in consideration of the productivity of the ashless coal. And it is preferable that the yield of the 1st ashless coal (the yield with respect to the raw material coal of the obtained 1st ashless coal) is 20 mass% or more on an anhydrous and ashless coal basis.
If the yield is less than 20% by mass, the yield of the first ashless coal is relatively low, and the load in the second slurry heating step (S3) becomes large as described above. Therefore, the extraction rate in the first slurry heating step (S1) is appropriately adjusted so that the second ashless coal has a desired yield. In addition, the desired yield in 1st ashless coal is a standard, and it changes with the kind of coal to be used, the kind of solvent, the property of the product calculated | required, etc.

The heating time (extraction time) is a time until reaching the dissolution equilibrium, but it is economically disadvantageous to realize it. Therefore, since it varies depending on conditions such as the particle size of the coal and the type of solvent, it cannot be generally stated, but it is usually about 0 to 120 minutes after reaching a predetermined extraction temperature. It is preferable to prepare within this range based on various conditions such as coal and solvent. Even if the heating time exceeds 120 minutes, the extraction does not proceed any further, which is not economical. The heating time of 0 minutes means that the temperature is raised to a desired temperature and extracted, and then immediately cooled as follows.

Before proceeding to the first separation step (S2), the heated slurry may be cooled to a temperature at which the solute eluted from the coal does not reprecipitate, for example, about 150 ° C. or more and less than about 200 ° C. By cooling the slurry, subsequent handling is facilitated, and excessive thermal decomposition in the first slurry heating step (S1) can be avoided. In addition, the pressure in the sedimentation tank can be lowered, and the specification level of valves and the like can be lowered.

In this heat extraction, the pyrolysis of coal produces aromatic-rich components mainly having an average boiling point (Tb50: 50% distillation temperature) of 200 to 300 ° C. Can be used as part.

It is preferable to perform the heat extraction in a non-oxidizing atmosphere. Specifically, it is performed in the presence of an inert gas. This is because, in the case of heat extraction, if it comes into contact with oxygen, it may ignite, and if hydrogen is used, the cost increases. However, as will be described later, when a coke oven gas (Coke Oven Gas: COG) is used for hydrogenation of the solvent, it is not necessary to replace the used COG with an inert gas without oxygen. It is also possible to carry out in a COG atmosphere.

As the inert gas used in the heat extraction, it is preferable to use inexpensive nitrogen, but it is not particularly limited. As described above, COG may be used as it is. The pressure in the heat extraction is preferably 1.0 to 5.0 MPa, although it depends on the temperature at the time of heat extraction and the vapor pressure of the aromatic solvent used. When the pressure is lower than the vapor pressure of the aromatic solvent, the aromatic solvent volatilizes and is not trapped in the liquid phase and cannot be extracted. In order to confine the aromatic solvent in the liquid phase, a pressure higher than the vapor pressure of the aromatic solvent is required. On the other hand, if the pressure is too high, the cost of the equipment and the operating cost increase, which is not economical.

<First separation step (S2)>
The first separation step (S2) is a step of separating the slurry heated in the first slurry heating step (S1) into a liquid component and a solid component (first slurry separation).
Here, the liquid component means a solution in which coal is dissolved, that is, a solution containing a coal component dissolved (extracted) in an aromatic solvent, and the solid component means ash and insoluble coal insoluble in the aromatic solvent. A slurry containing

The method for separating the slurry into a liquid component and a solid component in the first separation step (S2) is not particularly limited, and a known method can be used. For example, a filtration method, a centrifugal separation method, a gravity sedimentation method, or the like can be used, and a plurality of these methods may be combined. However, it is preferable to use a gravity sedimentation method as a solid-liquid separation method (the gravity sedimentation method will be described later).

As a method for separating a slurry into a liquid component and a solid component, various filtration methods and centrifugal separation methods are generally known. However, the filtration method requires frequent replacement of the filter, and the centrifugation method tends to cause clogging with undissolved coal components, and it is not easy to implement these methods industrially. Therefore, it is preferable to use a gravity sedimentation method that allows continuous operation of fluid and is suitable for a large amount of processing at low cost. As a result, a liquid component (hereinafter also referred to as “supernatant liquid”) containing a coal component extracted into the solvent from the upper part of the gravity settling tank, and an insoluble ash and insoluble in the solvent from the lower part of the gravity settling tank. A solid component (hereinafter, also referred to as “solid content concentrate”) that is a slurry containing coal can be obtained. Note that the gravity sedimentation method is one of the options, and other methods may be used.

<Second slurry heating step (S3)>
In the second slurry heating step (S3), a hydrogen donating solvent is added to and mixed with the solid component separated in the first separating step (S2) to prepare a slurry, which includes the solid component and the hydrogen donating solvent. In this step, the slurry is heated at a temperature equal to or higher than the temperature of the heat treatment in the first slurry heating step (S1) (second slurry heat treatment). And a coal component is heat-extracted by the hydrogen-donating solvent by heat-processing a slurry.

[Solid component]
The solid component is separated in the first separation step (S2) and includes a coal component that has not been extracted into the aromatic solvent in the first slurry heating step (S1).

[Hydrogen-donating solvent]
As the hydrogen donating solvent for dissolving coal, compounds such as 1,2,3,4-tetrahydronaphthalene, 1,2-dihydronaphthalene, tetrahydromethylnaphthalene or a mixture thereof are generally used.

The hydrogen donating solvent is a fragrance of a part of an aromatic compound having two or more rings having or not having an aliphatic side chain, such as naphthalene, methylnaphthalene, dimethylnaphthalene, trimethylnaphthalene, alkylnaphthalene, anthoselan, phenanthrene, and ethylnaphthalene. The ring is a partially hydrogenated aromatic compound that is partially hydrogenated and has a high hydrogen donating property. The bicyclic aromatic compound includes other naphthalenes having an aliphatic side chain, and biphenyl and alkylbenzene having a long aliphatic side chain.
In addition to these, hydrotreated products such as coal liquefied oil and tar fractions and petroleum refining by-products can also be used as the hydrogen donating solvent.

A hydrogen-donating solvent is heated and heated, and is stabilized by giving hydrogen to radical fragments generated by thermal decomposition of some of the coal molecules, thereby suppressing the polycondensation of coal, resulting in extraction into the solvent. The amount of coal components can be increased. Therefore, the extraction rate becomes high. The hydrogen-donating solvent is a solvent that can be easily recovered by a method such as distillation. The hydrogen-donating solvent has the property that after donating hydrogen to the coal radical, it loses itself and turns into an aromatic solvent.
For example, “1,2,3,4-tetrahydronaphthalene → naphthalene + 2H ₂ ”.

Then, in order to improve the economic efficiency, the recovered solvent after the heat treatment is supplied to the second slurry heating step (S3) after being subjected to a hydrogenation treatment as described later, and can be circulated and used repeatedly. it can. Or it can supply to a 1st slurry heating process (S1), and it can circulate and use repeatedly, without performing a hydrogenation process. The recovered solvent may contain a small amount of a hydrogen-donating solvent in the aromatic solvent. However, such a solvent does not lower the economy, and the first slurry heating step (S1) It is possible to supply and use.

The pressure in the heat extraction is preferably 1.0 to 20.0 MPa, although it depends on the temperature at the time of heat extraction and the vapor pressure of the hydrogen donating solvent used. When the pressure is lower than the vapor pressure of the hydrogen donating solvent, the hydrogen donating solvent volatilizes and is not trapped in the liquid phase and cannot be extracted. In order to confine the hydrogen donating solvent in the liquid phase, a pressure higher than the vapor pressure of the hydrogen donating solvent is required. On the other hand, if the pressure is too high, the cost of the equipment and the operating cost increase, which is not economical.
About other conditions etc., it is the same as that of the description about the aromatic solvent in said 1st slurry heating process (S1).

[Processing conditions]
In the second slurry heating step (S3), the heat treatment is performed at a temperature equal to or higher than the temperature of the heat treatment in the first slurry heating step (S1).
Thereby, depolymerization of coal progresses, and a component that is more difficult to dissolve, that is, a component that has a relatively large molecular weight and is difficult to melt, is extracted as compared with the case of heat extraction in the first slurry heating step (S1). Moreover, since hydrogen transfer from the hydrogen donating solvent is performed, polycondensation of coal is suppressed, and ashless coal can be obtained with high yield.
In the second slurry heating step (S3), ashless charcoal is obtained from the components remaining undissolved in the first slurry heating step (S1), and components that could not be extracted in the first slurry heating step (S1) are extracted. Since extraction is performed, a small yield in the second slurry heating step (S3) leads to a small overall yield.

When the heating temperature in the second slurry heating step (S3) is lower than the temperature in the heat treatment in the first slurry heating step (S1), components that cannot be extracted in the first slurry heating step (S1) are extracted. The extraction rate (yield) cannot be improved, and the overall yield decreases.

The heating temperature in the second slurry heating step (S3) is not particularly limited as long as it is equal to or higher than the heating temperature in the first slurry heating step (S1), but it is preferably performed at a temperature of 350 to 500 ° C. . By setting the heating temperature within this range, in the presence of the hydrogen donating solvent, the bonds between the molecules constituting the coal are loosened, mild thermal decomposition occurs, and the extraction rate increases. The heating temperature in the first slurry heating step (S1) and the heating temperature in the second slurry heating step (S3) may be the same.

If the heating temperature of the slurry is 350 ° C. or higher, it is sufficient to weaken the bonds between the molecules constituting the coal in the presence of the hydrogen donating solvent, and the extraction rate (yield) is likely to be improved. On the other hand, if the temperature is 500 ° C. or lower, the rate of the thermal decomposition / carbonization (polymerization) reaction tends to decrease. . In order to improve the extraction rate, it is more preferably 340 to 440 ° C.
However, the above-mentioned heating temperature is a standard, and is appropriately adjusted depending on the type of coal or solvent used, the properties of the desired product, and the like.

Here, the yield in the second slurry heating step (S3) (the yield of the obtained second ashless coal relative to the raw coal) is preferably 10% by mass or more based on anhydrous / ashless coal.
If the yield is less than 10% by mass, the extraction rate (yield) of the component that could not be extracted in the first slurry heating step (S1) is low, and the overall yield is lowered. In addition, the effect of using a hydrogen donating solvent is small. Therefore, the extraction rate in the second slurry heating step (S3) is appropriately adjusted so that the second ashless coal has a desired yield. Note that the desired yield in the second ashless coal is a guideline and varies depending on the type of coal and solvent used, the properties of the desired product, and the like.

Further, before the transition to the second separation step (S4), the heated slurry may be cooled to a temperature at which the solute eluted from the coal does not reprecipitate, for example, about 200 to 360 ° C. By cooling the slurry, subsequent handling is facilitated, and excessive thermal decomposition in the second slurry heating step (S3) can be avoided. In addition, the pressure in the sedimentation tank can be lowered, and the specification level of valves and the like can be lowered.
Other conditions are the same as the processing conditions in the first slurry heating step (S1).
In addition, although the same processing apparatus can be used for 1st slurry heating process (S1) and 2nd slurry heating process (S3), you may use a separate processing apparatus.

<Second separation step (S4)>
The second separation step (S4) is a step of separating the slurry heated in the second slurry heating step (S3) into a liquid component and a solid component (second slurry separation).
Here, the liquid component means a solution in which coal is dissolved, that is, a solution containing a coal component dissolved (extracted) in a hydrogen donating solvent, and the solid component is an ash component insoluble in the hydrogen donating solvent and A slurry containing insoluble coal.

Since the second separation step (S4) is the same as the first separation step (S2), description thereof is omitted here. In addition, the method in the case of using the gravity sedimentation method in the second separation step (S4) will be described later.
The same solid-liquid separation device can be used for both the first separation step (S2) and the second separation step (S4), but separate solid-liquid separation devices may be used.

<Modified coal acquisition process (S5)>
In the modified coal acquisition step (S5), the solvent is removed from the liquid component separated in the second separation step (S4) to obtain ashless coal (second ashless coal) which is the modified coal. It is.
Further, in addition to obtaining the second ashless coal, the solvent is removed from the liquid component separated in the first separation step (S2), and ashless coal (first ashless coal that is modified coal) is obtained. ).

The method for separating and removing the solvent from the liquid component (supernatant liquid) is not particularly limited, and a known method can be used, for example, a general distillation method or evaporation method (spray drying method, etc.). Etc. can be used. Then, the separated and recovered solvent can be circulated to the first slurry heating step (S1) and repeatedly used. Or after hydrotreating, it can circulate to a 2nd slurry heating process (S3), and can be used repeatedly. By separating and recovering the solvent (solid-liquid separation), ashless coal with an extremely low ash concentration can be obtained from the supernatant. This ashless coal contains almost no ash, has no moisture, and exhibits performance (thermal fluidity) far superior to that of raw coal.

The ashless coal obtained by the production method of the present invention is used as a non-ferrous metal reducing agent, structural material charcoal, or electric material charcoal. Or it uses as a raw material of nonferrous metal reducing agent, structural material charcoal, or electric material charcoal. Here, the non-ferrous metal reducing agent refers to a reducing agent used for reduction of non-ferrous metals such as silicon and titanium, and the structural material charcoal is, for example, a carbon heat insulating material or a raw material for a carbon structural material such as a crucible. The electric material charcoal is a carbon material used as a raw material for a carbon electric material such as a carbon electrode or an anode for aluminum refining. The reason for using these raw materials is, for example, that it may be necessary to subject the ashless coal to a secondary treatment such as heat treatment.

If necessary, in the modified coal acquisition step (S5), ashless from the liquid component separated in the first separation step (S2) and the liquid component separated in the second separation step (S4). In addition to obtaining charcoal (first ashless charcoal and second ashless charcoal), the solvent is removed from the solid component separated in the second separation step (S4) to produce by-product coal that is reformed charcoal. May be manufactured (by-product charcoal acquisition step).

This by-product charcoal is free of oxygen-containing functional groups, has ash, has no water, and has a sufficient calorific value. Therefore, this by-product charcoal can be used for a known method, for example, for various fuels.

The method for separating and removing the solvent from the solid component (solid concentrate) is a known method, for example, a general distillation method or evaporation method, as in the case of obtaining ashless coal from the liquid component described above. The solvent that can be used and separated and recovered can be circulated to the first slurry heating step (S1) and repeatedly used. Or after hydrotreating, it can circulate to a 2nd slurry heating process (S3), and can be used repeatedly. By separation and recovery of the solvent (solid-liquid separation), by-product charcoal in which ash is concentrated can be obtained from the solid concentrate.

The solvent (solvent separated from the liquid component) removed in the modified coal acquisition step (S5) is hydrotreated (hydrotreating step), and the hydrotreated solvent is used in the second slurry heating step (S3). It is preferable to use it by supplying it to the circulation. The solvent to be hydrotreated is a solvent removed from the liquid component separated in the first separation step (S2), a solvent removed from the liquid component separated in the second separation step (S4), and a by-product coal acquisition step. The solvent removed from the solid component may be all, but only one or two may be hydrotreated. The same applies to the case of recycling without hydrotreating.

The hydrotreating method is not particularly limited. For example, the solvent is brought into contact with coke oven gas (COG) and pressurized, and the reaction is performed at a predetermined temperature in the presence of a catalyst. Hydrogenation methods can be used.
As a specific example, a fixed bed catalyst reaction tower (fixed bed hydrogenation reactor filled with a known hydrogenation catalyst such as NiMo, NiCo, CoMo, etc., which is a hydrogenation reaction tower as in a so-called petroleum refining plant. ), And COG is mixed with the solvent to be circulated, then, for example, sent to a fixed bed catalytic reaction tower holding a pressure of 5 to 10 MPa using a pressure pump, and reacted at a temperature of about 320 to 370 ° C. To do.

By this hydrogenation treatment, a part (one) of the aromatic rings of two or more aromatic compounds is partially hydrogenated (two or more aromatic compounds are partially hydrogenated), and hydrogen donating properties are improved. It is modified as a solvent. And since a solvent has hydrogen donating property, the radical produced | generated by thermal decomposition under extraction temperature is stabilized, the polycondensation reaction by thermal decomposition of coal is suppressed, and the extraction rate of coal increases. Thereby, the expected amount of ashless coal production can be stably obtained corresponding to the properties of the coal and the coal type.

COG is a by-product gas emitted from a coke oven that is generated when coal is distilled to produce coke. The COG usually contains 50 to 70% by mass of hydrogen, and other methane, carbon monoxide, and ammonia.
The COG discharged from the coke oven is about 800 ° C., and by using this sensible heat to raise the temperature of the contacted solvent, the heating load in the hydrotreatment can be suppressed.

The temperature of the hydrogenation treatment is preferably 320 to 370 ° C. This is because of a temperature generally used as a reaction for efficiently producing a partially hydrogenated aromatic in the presence of a catalyst, that is, naphthenating an aromatic ring. By performing the hydrogenation treatment at 320 to 370 ° C., a part of the aromatic rings of the two or more aromatic compounds in the solvent component is likely to be partially hydrogenated and easily modified as a solvent having a hydrogen donating property. Become. The hydrotreatment pressure is preferably 5 to 10 MPa, and LHSV (propylene standard) is preferably about ¹ hr ⁻¹ .

The catalyst used in the hydrotreatment may be the same as the catalyst used in a general petroleum refining process, such as a NiMo / Al ₂ O ₃ catalyst, a NiCo / Al ₂ O ₃ catalyst, a CoMo / Al ₂ O ₃ catalyst, etc. Use it.

Thus, the solvent removed / recovered in the modified coal acquisition step (S5) is subjected to a hydrogenation process, and then supplied to the second slurry heating step (S3), and separated in the first separation step (S2). The mixed slurry is mixed, the mixed slurry is heat-treated, and the coal component is heated and extracted into a solvent. Thereafter, the solvent is removed and recovered again through the second separation step (S4) and the modified coal acquisition step (S5). The recovered solvent is again hydrogenated and supplied to the second slurry heating step (S3). By repeating this, the solvent is circulated and used.
Note that the solvent removed and recovered in the modified coal acquisition step (S5) can be supplied to the first slurry heating step (S1) as an aromatic solvent without performing a hydrogenation treatment.

Next, an example of using the gravity sedimentation method in the method for producing ashless coal will be described with reference to FIGS.
As shown in FIG. 3, in the gravity sedimentation method, in the solid-liquid separator 100, first, powder coal as a raw material of ashless coal charged from the coal storage tank 1 in a coal slurry preparation tank 3, and a solvent The aromatic solvent thrown from the storage tank 2 is mixed and stirred with the stirrer 12a to prepare a slurry. Next, a predetermined amount of this slurry is supplied to the first extraction tank 4 and heated at 320 to 450 ° C. for a predetermined time while being stirred by the stirrer 12b. Then, if necessary, the slurry is brought to a predetermined temperature by a cooler (not shown). Cool (first slurry heating step (S1)). Note that a cooling mechanism may be provided in the first extraction tank 4 in order to cool the slurry. Further, a predetermined amount of slurry may be supplied from the coal slurry preparation tank 3 to a preheater (not shown) and heated to 320 to 450 ° C. before being supplied to the first extraction tank 4.

And the slurry which performed this extraction process is supplied to the 1st gravity sedimentation tank 5, a slurry is isolate | separated into a supernatant liquid and solid content concentrate (1st separation process (S2)), and the 1st gravity sedimentation tank 5 is discharged to the second extraction tank 6 and the upper supernatant is discharged to the reformed coal separator 7 by a predetermined amount.

Here, in the first gravity settling tank 5, in order to prevent reprecipitation of components eluted from the raw material coal, the temperature at which the slurry is heated, and when the slurry is cooled after being heated, the temperature is maintained at the cooled temperature after being heated. In addition, the pressure is preferably in the range of 1.0 to 5.0 MPa. Further, the time for maintaining at a predetermined temperature in the first gravity settling tank 5 is a time required for separating the slurry into a supernatant and a solid concentrate, and is generally 60 to 120 minutes. However, it is not particularly limited.

In addition, by increasing the number of the first gravity settling tanks 5, it is possible to recover components soluble in the aromatic solvent accompanying the concentrated solid solution. It is appropriate to arrange the tanks 5 in two stages.

The solid concentrate is mixed with the hydrogen-donating solvent hydrogenated in the stationary hydrogenation reactor 10 in the second extraction tank 6, and 350 to 500 ° C. (however, the first extraction tank 4 is stirred with the stirrer 12c). And then cooled to a predetermined temperature by a cooler (not shown) as necessary (second slurry heating step (S3)). Note that a cooling mechanism may be provided in the second extraction tank 6 in order to cool the slurry. In addition, a predetermined amount of slurry may be supplied from the first gravity settling tank 5 to a preheater (not shown) before being supplied to the second extraction tank 6, and the slurry may be heated to 350 to 500 ° C.

And the slurry which performed this extraction process is supplied to the 2nd gravity sedimentation tank 8, a slurry is isolate | separated into a supernatant liquid and solid content concentrate (2nd separation process (S4)), and the 2nd gravity sedimentation tank 8 is discharged to the by-product coal separator 9 and the upper supernatant liquid is discharged to the reformed coal separator 7 by a predetermined amount.
The pressure in the second gravity settling tank 8 is the same as described for the first gravity settling tank 5 except that the pressure is preferably in the range of 1.0 to 20.0 MPa.

The supernatant liquid separated in the first gravity settling tank 5 and the supernatant liquid separated in the second gravity settling tank 8 are separated from the solvent by the reformed coal separator 7, and the first and second ashless coals are separated. (Modified coal acquisition step (S5)). If necessary, the by-product coal separator 9 may separate and recover the solvent from the solid component (solid content concentrate) to obtain a by-product coal in which the ash that is the modified coal is concentrated.

The solvent (collected solvent) separated and recovered by the reformed coal separator 7 and the byproduct coal separator 9 is circulated to the solvent storage tank 2 as necessary. This recovered solvent is mixed (contacted) with a hydrogen source (for example, COG) supplied from a hydrogen source supply tank 11 in a fixed hydrogenation reactor 10 filled with a catalyst and pressurized at a pressure of 5 to 10 MPa. After that, the temperature is raised to 320 to 370 ° C. and hydrogenation is performed. Thereafter, the pressure is reduced and the second extraction tank 6 is supplied. The mixing with COG, the control of temperature and pressure, etc. may be performed in the fixed hydrogenation reactor 10, but before and after supplying the fixed hydrogenation reactor 10 with a booster pump, a solvent heating device or the like. You may make it carry out. Further, the recovered solvent may be supplied to the coal slurry preparation tank 3 without performing a hydrogenation treatment.

Although the present invention is as described above, in carrying out the present invention, within the range that does not adversely affect the respective steps, for example, a coal pulverization step of pulverizing raw coal between or before and after the respective steps, You may include other processes, such as an unnecessary object removal process which removes unnecessary objects, such as garbage, and a drying process which dries the obtained ashless coal.

Next, an example is given and the manufacturing method of ashless coal concerning the present invention is explained concretely.
<Procedure>
Coal and solvent were charged into an autoclave with a pressure filtration mechanism having an internal volume of 5 liters, and the coal was extracted by heating and stirring over the temperature, pressure (nitrogen pressure), and time shown in Table 1 (first extraction process). First extraction process). Then, while maintaining this extraction temperature, pressure filtration was performed to discharge only the extract, leaving only the insoluble components in the autoclave. Next, a predetermined amount of solvent was added and the mixture was heated and stirred over the temperature, pressure (nitrogen pressure), and time shown in the second extraction process of Table 1 to extract coal (second extraction process). Then, while maintaining this extraction temperature, pressure filtration was performed to discharge only the extract, leaving only the insoluble components in the autoclave. In Table 1, No. For 10 and 11, only the first extraction process was performed.

The used coal is subbituminous coal (carbon content 74.5% by mass (daf basis)), and the solvent used is 1-methylnaphthalene (MN), which is an aromatic solvent, or tetrahydro-, which is a hydrogen-donating solvent. 1-methylnaphthalene (THMN). Moreover, the ratio of the coal and the solvent in the first extraction process (solvent / coal) is 4 (2.0 kg / 0.5 kg), and the ratio of the insoluble component to the solvent in the second extraction process (solvent / insoluble component). Was 4 (2.0 kg / 0.5 kg).
The solid-liquid separation method was performed by high-temperature filtration (pressure filtration with a 0.5 μm mesh filter at the extraction temperature).

<Product recovery and analysis>
The extraction liquids obtained by the first extraction process and the second extraction process were each heated to 200 ° C. in a nitrogen stream to remove the solvent, and further heated to 300 ° C. to remove the product oil. (First ashless coal and second ashless coal) were collected and weighed. The solvent and produced oil were each collected by a cooling trap and weighed.
In each extraction process, the gas in the autoclave after the treatment is collected while measuring the volume, and analyzed by a gas chromatograph, and the generated gas components (water, methane, ethane, hydrogen, CO, CO _2). ) Was quantitatively analyzed. The gas yield and oil yield were determined.

The gas yield was calculated by measuring the volume of the generated gas by an ordinary method. In addition, the oil yield is determined by calculating the total mass of the solvent and product oil collected in the step of recovering the product, and defining the amount of oil added above the mass of the charged solvent as the amount of oil produced. / Mass of charged coal (raw coal) × 100.

And about the obtained 1st ashless coal, the ashless coal yield (extraction rate) was calculated | required.
Specifically, it was determined by the formula: (mass of first ashless coal / mass of raw coal) × 100.
Moreover, about the obtained 2nd ashless coal, the ashless coal yield (extraction rate) was calculated | required.
Specifically, it was determined by the formula (mass of second ashless coal / mass of raw coal) × 100.
The raw coal is based on anhydrous / ashless coal.

The first ashless coal yield is 20% by mass or more, the first ashless coal yield is good, and the second ashless coal yield is 10% by mass or more. The yield of ashless coal was considered good, and the total yield of the first ashless coal and the second ashless coal was 45% by mass or more, and the total yield was good.

<Calculation of hydrogen consumption>
The recovered solvent was subjected to quantitative analysis of the composition by gas chromatography. When hydrogen-donating tetrahydro-1-methylnaphthalene is used as the solvent, after extraction, in addition to the starting solvent, 1-methylnaphthalene and dihydro-1-methylnaphthalene that have lost hydrogen (the hydrogen substitution position is specified) Production) was observed. In this case, the hydrogen consumption was calculated by the following formula.

In the above formula,
HC: Hydrogen consumption (mg / g-coal)
W _S : Recovered solvent mass (g)
C _DHMN : _fraction of dihydro-1-methylnaphthalene in the recovered solvent (% by mass)
C _MN : fraction of 1-methylnaphthalene in the recovered solvent (% by mass)
W _C: coal charged amount (g)
It is.

These results are shown in Table 1. In addition, about what does not satisfy | fill the conditions of this invention, it shows by underlining a numerical value etc. Further, in the comparative example, those for which a preferable result was not obtained are shown by underlining the numerical value at that location.

As shown in Table 1, no. Examples 1 to 6 are examples that satisfy the requirements of the present invention, and the yields of the first ashless coal and the second ashless coal are good at 20% by mass or more and 10% by mass or more, respectively. The total yield of 1st ashless coal and 2nd ashless coal was as favorable as 45 mass% or more.
In addition, No. In No. 6, since the temperature of the first extraction treatment and the temperature of the second extraction treatment are the same, the yield of the second ashless coal and the total yield of the first ashless coal and the second ashless coal are No. Compared to 1-5, it was slightly lower.

No. 7 to 11 are comparative examples not satisfying the requirements of the present invention, and the following results were obtained.
No. In No. 7, since no hydrogen-donating solvent was used as the solvent in the second extraction treatment, the yield of the second ashless coal was low, and the total yield of the first ashless coal and the second ashless coal was also low. . No. In No. 8, since the hydrogen donating solvent was used as the solvent in the first extraction treatment, the yield of the first ashless coal was high, but no hydrogen donating solvent was used as the solvent in the second extraction treatment. Therefore, the yield of the second ashless coal was low, and as a result, the total yield of the first ashless coal and the second ashless coal was also low.

No. No. 9, since the temperature in the second extraction process was lower than the temperature in the first extraction process, the yield of the second ashless coal was slightly inferior, resulting in the total yield of the first ashless coal and the second ashless coal. The rate was low. No. Since 10 and 11 performed only the 1st extraction process, the total yield of the 1st ashless coal and the 2nd ashless coal was low.

As mentioned above, although the best embodiment and the example were shown and explained in detail about the manufacturing method of ashless coal concerning the present invention, the meaning of the present invention is not limited to the above-mentioned contents, and the scope of right is patent. It should be interpreted broadly based on the claims. Needless to say, the contents of the present invention can be widely modified and changed based on the above description.

S1 first slurry heating step S2 first separation step S3 second slurry heating step S4 second separation step S5 modified coal acquisition step 1 coal storage tank 2 solvent storage tank 3 coal slurry preparation tank 4 first extraction tank 5 first gravity Sedimentation tank 6 Second extraction tank 7 Reformed coal separator 8 Second gravity sedimentation tank 9 Byproduct coal separator 10 Fixed hydrogenation reactor 11 Hydrogen

source supply tank

12a, 12b, 12c Stirrer 100 Solid-liquid separator

Claims

Nonferrous metal reducing agent, structural material charcoal, electric material charcoal, or a production method of ashless charcoal used as these raw materials,
A first slurry heating step of heating a slurry in which coal and an aromatic solvent are mixed;
A first separation step of separating the slurry heat-treated in the first slurry heating step into a liquid component in which coal is dissolved and a solid component containing ash and insoluble coal;
Second slurry heating, in which a hydrogen-donating solvent is added to and mixed with the solid component separated in the first separation step, and the mixed slurry is heat-treated at a temperature equal to or higher than the temperature of the heat treatment in the first slurry heating step. Process,
A second separation step of separating the slurry heat-treated in the second slurry heating step into a liquid component in which coal is dissolved and a solid component containing ash and insoluble coal;
Removing the solvent from the liquid component separated in the second separation step to obtain ashless coal that is reformed coal,
In the modified coal acquisition step, in addition to acquiring the ashless coal, in the modified coal acquisition step, the solvent is further removed from the liquid component separated in the first separation step. A method for producing ashless charcoal, comprising obtaining ashless charcoal.
The solvent removed in the reformed coal acquisition step is hydrotreated, and the hydrotreated solvent is supplied to the second slurry heating step and circulated for use. The manufacturing method of ashless coal of description.