WO2015072637A1 - Method for preparing ash-free composite coal having increased reactivity and ash-free composite coal prepared thereby - Google Patents

Abstract

The present invention relates to a method for preparing ash-free composite coal by uniformly mixing an organic component extracted from coking coal with oil in an extraction separation step and solidifying the mixture, and ash-free composite coal prepared thereby. The ash-free composite coal of the present invention exhibits high reactivity since vegetable or animal oil containing C8 to C20 fatty acid, fatty acid ester or triglyceride components, having a significantly higher reactivity than coal, is present by being uniformly mixed with the organic component extracted from coal. Since the ash-free composite coal of the present invention exhibits high reactivity, in a case where a catalytic gasification reaction is carried out, it is possible to carry out the reaction under milder conditions when compared to existing ash-free coal. The ash-free composite coal of the present invention is reusable since catalyst activation is not significantly lowered even when the catalytic gasification reaction is carried out, thereby being very economical. The ash-free composite coal of the present invention contains a carbon neutral biomass component, that is, vegetable or animal oil, thereby reducing CO₂ emissions.

Description

Manufacturing method of ashless composite carbon with increased reactivity, thereby ashless composite carbon

The present invention relates to a method for manufacturing ashless composite coal having increased reactivity and to ashless composite carbon, and more particularly, to an ashless composite in which organic components and oil extracted from raw coal are uniformly mixed and solidified in an extraction separation step. The present invention relates to a method for producing coal, and to ashless composite coal.

Coal gasification is one of the most economical ways to produce hydrogen gas on a commercial scale. The production of hydrogen from coal accounts for about 20% of the world's total production. Current commercial coal gasifiers generally convert hydrogen at temperatures above 1000, high pressure to obtain hydrogen. However, in order to respond to such extreme conditions, the device must be made of a material that can withstand high temperature / high pressure, which requires a lot of device cost, risks in operation, and a reduction in the effective use of energy. none.

Catalytic gasification of coal is known as a method for producing a rapid reaction at low temperature (less than 900) and low pressure (1 10 bar) through the introduction of a catalyst in syngas production using coal. Since the gasification of coal tar is also activated through the introduction of a catalyst, tar, which reduces process efficiency, can be simultaneously removed by gasification.

Despite these advantages, catalytic gasifiers for coal have not yet been made commercially. The main reason is that it is not easy to recycle expensive catalysts compared to coal. In general, for the catalytic gasification of coal, 3 to 20% by weight of the catalyst should be introduced. It is not possible to obtain a catalyst retaining the original activity from the gasification byproduct obtained after the initial gasification reaction. This is because the catalyst reacts and mineralizes minerals (mineral or ash or minerals) contained in coal during the gasification reaction.

In order to solve the mineralization of these catalysts, there have been attempts to produce ash-free coal containing no ash and apply it to the catalytic gasification process. However, ashless coal produced by the solvent extraction method is generally low in gasification reactivity compared to raw coal, and thus, the catalytic gasification reaction of ashless coal has a problem that it must proceed at a high temperature and high pressure than raw coal.

Prior Patent 10-1209465 discloses a coal reforming method in which palm residue oil is coated on a coal surface to prevent water resorption and increase calorific value. It does not solve the problem.

The present invention is to produce highly reactive ashless coal.

The present invention provides a novel ashless composite coal which can perform a catalytic gasification reaction while rapidly reducing the amount of catalyst used or a gasification reaction in a mild condition without using a catalyst.

The present invention is to provide a ashless composite coal that can reduce the generation of carbon dioxide generated in the gasification reaction of coal.

One aspect of the present invention

Preparing a slurry by mixing raw coal, an organic solvent and an oil;

Extracting the organic component from the slurry with the solvent and solid-liquid separation of the slurry; And

The present invention relates to a method for producing ashless composite coal, which comprises cooling an organic solvent from a separated liquid component and then cooling the organic solvent.

In another aspect, the present invention relates to a method for producing a syngas gas by reacting the ashless composite coal with water vapor at 600 ~ 1000 and 1 ~ 30 bar.

In another aspect, the present invention relates to an ashless composite coal in which vegetable oils or animal oils including triglycerides and organic components extracted from raw coals are uniformly mixed and solidified at a molecular level.

Ash-less composite coal according to the present invention is organic or vegetable oil containing triglyceride component composed of C8 ~ C20 fatty acid which is very reactive to coal, or C8 ~ C20 single fatty acid and fatty acid ester or mixture thereof. Highly reactive due to the presence of uniformly mixed with the powder.

The ashless composite coal of the present invention exhibits high reactivity, so that when the catalytic gasification reaction is carried out, it is possible to reduce the amount of catalyst used or to perform the reaction under mild conditions compared to the conventional ashless coal, and to perform the gasification reaction without the catalyst. Reactions are possible at milder conditions than ash and coal coal.

The ashless composite carbon of the present invention is very economical because it can be reused because there is almost no catalyst activity deterioration even after the catalytic gasification reaction.

The ashless composite carbon of the present invention contains carbon neutral biomass components, that is, vegetable oils and by-products and derivatives thereof, thereby reducing CO 2 emissions.

1 is an extraction separation reactor usable in the present invention.

Figure 2 shows a comparison of the steam gasification reactivity of Example 1 and Comparative Example 1.

Figure 3 shows a comparison of the steam gasification reactivity of Example 2 and Comparative Example 2.

The present invention relates to a method for producing an ash-rich composite coal having increased reactivity produced by uniformly mixing the organic components of vegetable or animal oils or single fatty acids and fatty acid esters or mixtures thereof with coal at the molecular level in the extraction and separation steps. do.

The ashless composite coal production method of the present invention includes a slurry preparation step, organic component extraction and solid-liquid separation step, organic solvent removal and cooling step.

Slurry manufacturing step is to make a slurry by mixing the raw coal, the organic solvent and oil.

The raw coal may be at least one selected from the group consisting of lignite having a ash content of 1 to 50%, sub-bituminous coal, bituminous coal, and anthracite.

The raw coal is used by crushing with a grinder, the size of the crushed coal may have a size of 50 ~ 300, preferably about 100, but is not necessarily limited thereto. In general, when the particle size of the coal is smaller than 50, agglomeration of particles occurs, so that the contact with the solvent is not smooth. If the particle size is larger than 300, a long extraction time is required. The powdery raw coal has a small particle size, which can widen the reaction area with the solvent, and facilitate the inter-process transfer of the slurry produced by mixing with the solvent.

Organic solvents for the extraction of coal have a boiling point of 250 or less, N-methyl 2-pyrrolidinone (NMP), Benzylamine, p-cresol, pyridine, 1-methylnaphthalene (1-MN), tetraline, aniline, light cycle oil, carbon disulfide Etc. may be used as a single material or mixture, but is not necessarily limited thereto.

The oil may be a vegetable oil or an animal oil.

The vegetable oil or animal oil is rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, palm oil, palm residue oil, coconut oil, mustard seed oil, corn oil , Jute oil, sesame oil, shea nut oil, peanut and linseed oil, Waste vegetable oil, tallow, fish oil, tallow, pork oil and chicken oil.

Preferably obtained from vegetable oils such as soybean oil, palm oil and palm residue oil, coconut oil, corn oil, waste vegetable oil, fatty acids obtained from vegetable oils, fatty acid esters, and by-products in oil extraction processes. Sludge oil (palm residue oil), palm sludge oil and fish oil, tallow, lard or animal oil of chicken oil.

The oil may include by-products or derivatives thereof produced from the vegetable or animal oils.

The vegetable or animal oil includes triglycerides composed of fatty acids having 8 to 20 carbon atoms.

The oil may comprise small amounts (within 1%) of fatty acids or fatty acid esters.

The oil is more reactive than the organic components extracted from coal.

Palm residue oil used in the present invention is a residue after palm oil production in Indonesia, Malaysia, etc., palm fatty acid distillate (PFAD), palm sludge oil (PSO), etc., this is a solid at room temperature and high calorific value of 9,000 kcal / kg or more Has

The palm fatty acid distillate (PFAD) is a byproduct obtained from physical purification of crude palm oil, about 81.7% of fatty acids, about 14.4% of triglycerides, about 0.8% of squalene, and about 0.4% of vitamin E 0.5% sterol. And 2.2% (see Production and utilization of palm fatty acid distillate (PFAD), 2010 WILEY-VCH Verlag Gmbh & Co. KgAa, Weinheim).

Palm sludge oil is composed of 30 to 70% free fatty acid and the rest triglycerides.

The waste vegetable oil contains more than 10% free fatty acid.

The boiling point of the vegetable oil and animal oil is 300 or more.

When the slurry is prepared, the mixing ratio of the raw petroleum coal, oil, and the organic solvent is suitably in the range of 1: 0.02 to 1: 2 to 20 by weight.

If the weight ratio of the solvent to the raw coal is more than 1:20, the amount of coal is too small, so it is not economically suitable. If the weight ratio of the solvent is lower than 1: 2, the amount of coal increases and the viscosity of the slurry increases, so that This can be a problem in processes such as filtration.

The weight ratio of palm residue oil to the raw coal may be increased within the above range to exhibit an increased reactivity effect.

The extraction and separation step is the step of extracting the organic component from the slurry with the solvent and solid-liquid separation of the slurry. More specifically, the extraction step is a step of extracting the organic components from the raw coal using the organic solvent and uniformly mixing them at the oil and molecular level. In the solid-liquid separation step, the liquid and solid components are separated.

By the extraction step, the raw coal is separated into an organic component dissolved in an organic solvent and a solid residue material (ash and an organic solvent insoluble substance) that is not dissolved in the organic component. In the case of raw coal (coal), it is preferable to heat the molecules in the particles to 300-400 range, where the intermolecular bonds are loosened by thermal softening. When the organic solvent is heated to the extractable temperature in the liquid state, the pressure increases to the range of 10-25 bar.

Therefore, the extraction step may be performed at 50 ~ 400 and 1 ~ 30 bar pressure.

In addition to the organic components of the raw coal extracted in the extraction step, oil components (fatty acid, fatty acid ester, triglyceride, etc.) are dissolved in the organic solvent, so that the organic components and the oil components are uniformly mixed at the molecular level. Here, molecular level mixing indicates that molecules of organic components and oils of 5 to 100 nanometers are mixed in organic solvents.

The solid-liquid separation step may use a conventionally known solid-liquid separation method, for example, by sedimentation of the solid component by gravity sedimentation method and by discharging the solution component to the top may be used.

The extraction and solid-liquid separation step may be used in combination with a known extraction reactor or separation reactor, preferably the extraction separation reactor of Figure 1 may be used. For the extraction separation reactor of FIG. 1, reference may be made to the patent application filed (Application No. 10-2011-0077779) of the present invention. The organic component extraction separation reactor 100 of FIG. 1 includes a main body 10, an inlet 20, a solid residue discharge 30, an extract 40, and an extract solution discharge 50.

The slurry in which the organic solvent, the raw coal and the oil are mixed is injected into the inlet 20, and the reaction conditions inside the main body are maintained at 50 to 400 and 1 to 30 bar as described above. The extraction part 40 is formed between the solid residue discharge part 30 and the inlet part 20, and includes an agitator 41 to mix the slurry to form an organic component contained in an organic fuel as a solvent. Dissolve. The stirrer 41 may be a magnetic stirrer or an ultrasonic generator.

The slurry (S5) is introduced into the extraction unit 40 to the inlet 20. The organic components in the coal particles included in the slurry introduced into the extraction unit 40 are extracted while contacting the solvent by the stirring action of the stirrer. The oil is also dissolved in an organic solvent. The oil and organic components dissolved in the organic solvent are circulated inside the extraction unit and are pushed by the entire fluid flow to the upper portion of the extraction unit 40, and are discharged to the discharge unit 50 via the precipitation unit 70.

The precipitation unit 70, the filtration unit 80 may refer to the published patent.

The removal and cooling step is a step of cooling after removing the organic solvent from the solution component obtained from the discharge unit (50).

The organic solvent removal is a step of removing the organic solvent by heating the separated liquid component, preferably may be heated to 50 ~ 300 under reduced pressure conditions. In this temperature range, the organic solvent evaporates, but the organic components and oil of coal still remain.

The cooling step is to cool the liquid component from which the organic solvent is removed. That is, in the cooling step, the mixture of the organic component and the oil component is cooled to room temperature and solidified. Since the oil is uniformly mixed at the molecular level with the organic components through the extraction and solid-liquid separation step, these components are evenly distributed even inside the solidified composite coal.

In another aspect, the present invention relates to ashless composite coal produced by the method.

The ashless composite coal is solidified by uniformly mixing organic components extracted from raw coal and vegetable oils or triglycerides, fatty acids, fatty acid esters or animal oils including fatty acid esters at a molecular level.

The ashless composite carbon is solidified by mixing an organic component and an oil in a predetermined weight ratio. The weight ratio of the organic component and the oil may vary depending on the weight ratio of the raw coal and the oil to be added, and may also be adjusted according to the extraction amount of the organic component extracted from the raw coal. For example, the use ratio of raw coal and oil is 1: 0.02-1, and the organic component extracted from the raw coal may be about 30 to 90% of the total raw coal, in which case the organic component and oil are in a weight ratio of 1: 0.03 to 3.5. It may be in the range, preferably 1: 1: may range from 0.05 to 1.

The ashless composite carbon may include trace components such as squalene and vitamin as the oil component.

The composite coal may include a catalyst on the surface or inside thereof, and preferably, the catalyst may be supported on the surface of the composite coal.

As the catalyst, K, Na, which is an alkali group element, Ca, Mg, which is an alkaline group element, and Ni, Fe, or the like, which are transition metals, may be used.

The catalyst may range from 0.1% to 30% of the total weight of the composite coal.

Since the catalyst also activates the gasification reaction of coal tar, the tar, which lowers the process efficiency, can be removed by the gasification reaction.

The present invention can produce a synthesis gas by catalytic reaction of ashless composite coal containing the catalyst with water at 600 to 1000 and 1 to 30 bar.

Since the synthesis gasification reaction of the present invention uses a catalyst, it can be carried out in a low temperature low pressure process much lower than the conventional synthesis gas reaction conditions of 1400 ~ 1500, 30bar. The ashless composite coal does not include ash, which is an inorganic substance that degrades the catalytic activity by reacting with the catalyst during the steam gasification reaction, so the catalyst reuse rate is high and the activity hardly drops.

The ashless composite coal contains oil having a higher reactivity than the ashless coal and its by-products and derivatives in a predetermined ratio, thereby further lowering the temperature or pressure of the catalytic gasification reaction.

In addition, many of the existing commercialized entrained-bed type gasifiers undergo a gasification reaction by introducing coal in the form of a coal-water mixture (CWM). At this time, the carbon content of the CWM is very important for determining the efficiency, the increase in the carbon content leads to a decrease in the water content is advantageous for the gasification reaction.

The ashless composite carbon of the present invention includes an oil containing both hydrophilic and hydrophobic groups at the same time, and thus plays a role of increasing the carbon content in CWM because it plays a function of a surfactant to some extent.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are provided to illustrate the present invention, but the present invention is not intended to limit the scope thereof.

Example 1

     Crushed dried raw coal (bituminous coal) with a calorific value of 6,700 kcal / Kg was filtered through 200 mesh to prepare 30 g of raw coal having a size of 75 or less, 6 g of palm fatty acid distillate (PFAD) and 270 g N-methyl. After mixing with 2-pyrrolidinone (NMP) solvent and organic components were extracted with stirring for 1 hour at 250, 30 bar. After the mixture was naturally cooled to room temperature, organic solvent insolubles and soluble components were separated using a filter paper. The obtained organic solvent solubles were dried for 1 hour in a 100 to 200 dryer to obtain a final ashless composite coal (17% of palm residue oil).

Example 2

     Compared to Example 1, 30 g of lignite, a low grade coal, was dried instead of bituminous coal, and 2 g of palm fatty acid distillate (PFAD) and 270 g of N-methyl 2-pyrrolidinone (NMP) solvent were used. Except for using was carried out in the same manner as in Example 1 (palm residue oil content of 6%).

Comparative Examples 1 and 2

     The same procedure as in Examples 1 and 2 was performed except that no palm residue oil was added.

Experiment

      The steam gasification reactivity of Examples 1 and 2 and Comparative Examples 1 and 2 was evaluated using a fixed bed gasification reactor. Steam gasification is the reaction of water vapor with coal or hydrocarbons to produce H2, CO, CO2 and small amounts of CH4. Steam gasification reactivity was evaluated by the carbon conversion rate indicating the rate at which the reactant carbon fuel is converted to the product gas. The fixed bed gasification reactor was manufactured by mounting a frit in the middle of a quartz tube, and 0.1 g of samples (Examples 1 and 2 Comparative Examples 1 and 2) were placed on the frit to allow only the product gas to pass. The reactor temperature was controlled by placing a thermocouple directly on top of the sample. The temperature rise was 30 / min speed. The reaction by-products tar and water were removed through an oil filter and 2 chillers at the bottom of the reactor, so that only the product gas reached GC.

     FIG. 2 shows the steam gasification reactivity of Example 1 and Comparative Example 1, and FIG. 3 shows the steam gasification reactivity of Example 2 and Comparative Example 2. FIG.

     2 and 3, it can be seen that the conversion ratio of Examples 1 and 2 is much increased as the reaction time is increased compared to Comparative Examples 1 and 2, so that the reactivity of the composite coal is improved.

Although the above has been described in detail with reference to a preferred embodiment of the present invention, this description is merely to describe and disclose an exemplary embodiment of the present invention. Those skilled in the art will readily recognize that various changes, modifications and variations can be made from the above description and the accompanying drawings without departing from the scope and spirit of the invention.

The ashless composite coal of the present invention is capable of reacting in a mild condition or reducing catalyst usage compared to conventional ashless coal when performing a catalytic gasification reaction, and when performing a gasification reaction without a catalyst, conventional ashless coal and coal raw coal. Compared to milder conditions, the reaction is possible.

Claims (16)

1. Preparing a slurry by mixing raw coal, an organic solvent and an oil;

   Extracting the organic component from the slurry with the solvent and solid-liquid separation of the slurry; And

   Removing the organic solvent from the separated liquid component and then cooling the ash-free composite carbon comprising the step of cooling.
2. The method of claim 1, wherein the oil is a vegetable oil or an animal oil.
3. According to claim 1, wherein the vegetable oil or animal oil is rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, palm oil, palm residue oil, coconut oil , Mustard seed oil, corn oil, jute oil, sesame oil, shea nut oil, peanut and linseed oil, waste vegetable oil, tallow, fish oil, tallow, pork oil and chicken oil Method for producing ashless composite coal, characterized in that one.
4. The method of claim 1, wherein the vegetable oil is a triglyceride having 8 to 20 carbon atoms (triglyceride) and its production method characterized in that the ashless carbon composite.
5. The method of claim 1, wherein the oil comprises a small amount of fatty acids or fatty acid esters.
6. The method of claim 1, wherein the raw coal, oil, and an organic solvent are mixed in a weight ratio of 1: 0.02 to 1: 2 to 20 by weight.
7. The method of claim 1, wherein the organic solvent has a boiling point of 250 or less N-methyl 2-pyrrolidinone (NMP), Benzylamine, p-cresol, pyridine, 1-methylnaphthalene (1-MN), tetraline, aniline, light cycle oil and carbon Method for producing ashless composite carbon, characterized in that at least one selected from disulfide.
8. According to claim 1, wherein the raw coal is one kind selected from the group consisting of lignite having a ash content of 1 to 50%, sub-bituminous coal, bituminous coal, and anthracite. A method for producing ashless composite coal, characterized in that above.
9. The method of claim 1, wherein the extraction step is ash-free composite coal production method characterized in that carried out at 50 ~ 450 and 1 ~ 30bar pressure.
10. 2. The method of claim 1, wherein the organic component extracted from the raw coal and the organic component of the oil are dissolved in a solvent and mixed uniformly.
11. 2. The method of claim 1, wherein the cooling step cools the liquid component to room temperature to solidify the organic component.
12. A method for producing a synthesis gas in which the ashless composite carbon prepared according to any one of claims 1 to 11 is subjected to catalytic reaction with water vapor at 600 to 1000 and 1 to 30 bar for gasification.
13. Organic components extracted from raw coal and

    Ash-free composite coal, characterized in that the vegetable oil or animal oil containing triglyceride is uniformly mixed and solidified at the molecular level.
14. The ashless composite coal of claim 13, wherein the organic component and the oil are in a weight ratio of 1: 0.03 to 3.5.
15. The ashless composite coal according to claim 13, wherein the composite coal is supported on a surface thereof, and the catalyst is at least one metal of an alkali compound, an alkali earth metal compound, and a transition metal.
16. The ashless composite coal of claim 13, wherein the catalyst is 0.1% to 30% of the total weight of the composite coal.

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