KR20190030044A - Apparatus for producing hydrogen gas through steam reforming reaction of organic and method for producing hydrogen gas using the same - Google Patents

Abstract

The present invention relates to an apparatus for generating hydrogen gas through a steam reforming reaction of an organic material, which comprises: an organic raw material supply unit for a steam reforming reaction, including an organic raw material chamber and a first preheater for preheating an organic raw material; a steam supply unit for a steam reforming reaction, including a water chamber and a second preheater for preheating water; a mixing unit for generating a mixture of the organic raw material and steam through the organic raw material supply unit and the steam supply unit; and a reaction unit including a reactor for performing a steam reforming reaction of the mixture. According to the apparatus of the present invention, a process can be operated at a lower pressure than a hydrogen gas generating apparatus by supercritical water gasification by employing a steam reforming reaction, thereby having low operation costs of a process, being safe, and easily controlling a process. Also, a byproduct that may be generated in the steam reforming reaction is remarkably reduced, such that a clogging phenomenon caused by the byproduct can be prevented even when the apparatus is operated for a long time, and also, hydrogen of a high concentration can be generated. The generated hydrogen is a high concentration to be immediately used as a fuel of a fuel cell, and can be useful as a small scale fuel cell since the generation of the byproduct is significantly less.

Description

[0001] The present invention relates to an apparatus for generating hydrogen gas through steam reforming reaction of an organic material and a method for producing hydrogen gas using the same,

The present invention relates to an apparatus for generating hydrogen gas through steam reforming reaction of an organic substance and a method for producing hydrogen gas using the same.

Recently, a fuel cell has been developed and is expected to be commercialized as an electric production device for various facilities such as automobiles, buildings, and homes. One of the reasons why the fuel cell is receiving the attention of the world is that, unlike the existing electric production method, there is no discharge of environmental pollutants during the electric production process. The principle of producing electricity from a fuel cell is the reaction of hydrogen and oxygen in reaction to the electrolysis of water to produce electricity and water. Therefore, the method of producing hydrogen, which is a fuel for a fuel cell, has become more important than ever.

A typical conventional hydrogen production method is to produce naphtha generated by natural gas or crude oil refining process by steam reforming. Although these methods are well-known commercial hydrogen production methods, both natural gas and naphtha as reaction materials are fossil fuels, and a large amount of carbon dioxide is generated in the steam reforming reaction process thereof. Since carbon dioxide generated in the process of using fossil fuels is known as a representative greenhouse gas that is the cause of global warming, European countries add expensive carbon tax to fossil fuels and adopt carbon emission total amount system and carbon emission trading system. The use of which is limited. As a result, countries are making research and development efforts on how to produce hydrogen for fuel cells from new and renewable energy sources.

Synthetic gas production by supercritical vaporization of organic materials is a method of producing hydrogen from biomass and its derivatives, one of these renewable energy sources. This method has an advantage that microorganism fermentation residue having a high moisture content or sugar waste can be vaporized without being dried. When the organic material is placed in supercritical water, it instantaneously vaporizes to form a synthesis gas containing hydrogen. The reaction principle is similar to the steam reforming of natural gas. However, the supercritical water used for the vaporization of organic materials has a lower temperature (below 750 ° C) and a higher pressure (above 22.1 MPa) than the steam of general reforming reaction. The reason for choosing this reaction condition is that the supercritical water To take advantage of unique properties.

Supercritical water is water present at temperature and pressure conditions of 374 ℃, 221bar, which is the critical point of water. The density of the supercritical water used in the vaporization reaction is higher than that of water vapor by a factor of 10, while the viscosity can be maintained at a very low value, so that higher heat transfer and mass transfer can be expected. The dielectric constant value is very low, And thus a high reaction efficiency can be obtained.

However, the synthesis gas production by supercritical vaporization generally requires a high-pressure pump capable of operating at a pressure of at least 250 bar due to high-pressure reaction characteristics, and the reactor is also manufactured using special nickel alloy tubes such as Inconel 625 and Hastelloy C- The manufacturing cost and the base process energy (especially the pump operating electricity consumption) required for the system operation are high.

In this connection, Korean Patent Registration No. 10-0916210 discloses a method for producing the trium-nickel / activated carbon catalyst and a system and a method for producing hydrogen by supercritical water conversion of an organic material using the trium-nickel / activated carbon catalyst have.

On the other hand, a steam reforming reaction in which the pressure is kept low can be used as a similar reaction, but the steam reforming reaction is often a by-product, and tar or char is generated. The byproducts not only lower the yield of the produced gas but also accumulate in the reactor to lower the catalytic activity and cause plugging of the reactor, so that the possible occurrence should be suppressed.

The inventors of the present invention discovered that hydrogen gas production using an apparatus and method for generating hydrogen gas through steam reforming reaction can minimize the generation of byproducts, and completed the present invention.

It is an object of the present invention to provide a high concentration hydrogen gas generating apparatus through steam reforming reaction of an organic material employing a steam reforming reaction capable of preventing a plugging phenomenon byproduct, a high concentration hydrogen gas generating method using the same, And a battery is further included in the fuel cell.

In order to achieve the above object,

An organic material raw material supply unit for steam reforming reaction, comprising an organic material source chamber and a first preheater for preheating the organic material source;

A water vapor supply unit for water vapor reforming reaction comprising a water chamber and a second preheater for preheating the water;

A mixing unit for generating a mixture of organic material and water vapor through the organic material supply unit and the water vapor supply unit; And

And a reactor for performing the steam reforming reaction of the mixture

/ RTI >

The present invention provides an apparatus for generating hydrogen gas through steam reforming reaction of an organic substance.

In addition,

There is provided a fuel cell electricity production system including a hydrogen gas generation device through a steam reforming reaction of an organic matter and a fuel cell.

Further,

A first preheating of the organic material stock (step 1);

Second preheating the water to produce water vapor (step 2);

Mixing the organic raw material and water produced in the step 1 and the step 2 to form a mixture, and continuously introducing the mixture into the reactor (step 3); And

Performing a steam reforming reaction of said mixture in said reactor (step 4);

And a method for generating hydrogen gas through steam reforming reaction of an organic material.

Since the apparatus for generating hydrogen gas through the steam reforming reaction of the organic material according to the present invention employs the steam reforming reaction, it can operate the process at a lower pressure than the hydrogen gas generating apparatus by the supercritical water system, Process control is easy. In addition, by reducing the byproducts that may occur in the steam reforming reaction, clogging due to by-products can be prevented even if the apparatus is operated for a long period of time, and high concentration of hydrogen can be generated. Since the produced hydrogen has a high concentration, it can be used immediately as a fuel for a fuel cell and is particularly useful for small-scale fuel cells because the generation of by-products is remarkably small.

FIG. 1A is a schematic view showing an apparatus for generating hydrogen gas through a steam reforming reaction of an organic material according to the present invention; FIG.
FIG. 1B is a schematic view showing an apparatus for producing hydrogen gas through a supercritical gasification reaction of an organic substance according to a comparative example of the present invention; FIG.
FIG. 2 is a flowchart showing the steps of a method for generating hydrogen gas through steam reforming reaction of an organic material according to the present invention;
3 is a photograph showing an apparatus for generating hydrogen gas through steam reforming reaction of an organic material according to an embodiment of the present invention;
4A is a graph showing the total gas production rate and hydrogen yield according to the molar ratio of water / methanol in the supercritical gasification reaction of methanol according to the comparative example of the present invention;
4B is a graph showing the carbon gasification efficiency (CGE) and the hydrogen gasification efficiency (HGE) according to the molar ratio of water / methanol in the supercritical gasification reaction of methanol according to the comparative example of the present invention;
4c is a graph showing the gas composition according to the molar ratio of water / methanol in the supercritical gasification reaction of methanol according to the comparative example of the present invention;
FIG. 5A is a graph showing the total gas production rate and hydrogen yield according to the molar ratio of water / methanol in the steam gasification reaction of methanol according to Experimental Example 1 of the present invention; FIG.
5B is a graph showing the carbon gasification efficiency (CGE) and the hydrogen gasification efficiency (HGE) according to the molar ratio of water / methanol in the steam gasification reaction of methanol according to Experimental Example 1 of the present invention;
5c is a graph showing the gas composition according to the molar ratio of water / methanol in the steam gasification reaction of methanol according to Experimental Example 1 of the present invention;
FIG. 6A is a graph showing the total gas production rate and hydrogen yield according to the catalyst bed temperature in the steam gasification reaction of methanol according to Experimental Example 1 of the present invention; FIG.
FIG. 6B is a graph showing carbon gasification efficiency (CGE) and hydrogen gasification efficiency (HGE) according to the catalyst bed temperature in the steam gasification reaction of methanol according to Experimental Example 1 of the present invention;
FIG. 6C is a graph showing the gas composition according to the temperature of the catalyst bed in the steam gasification reaction of methanol according to Experimental Example 1 of the present invention; FIG.
7A is a graph showing total gas production rate and hydrogen yield according to the molar ratio of water / ethanol in the steam gasification reaction of ethanol according to Experimental Example 2 of the present invention;
7B is a graph showing the carbon gasification efficiency (CGE) and the hydrogen gasification efficiency (HGE) according to the molar ratio of water / ethanol in the steam gasification reaction of ethanol according to Experimental Example 2 of the present invention;
FIG. 7C is a graph showing the gas composition according to the molar ratio of water / ethanol in the steam gasification reaction of ethanol according to Experimental Example 2 of the present invention; FIG.
8A is a graph showing total gas production rate and hydrogen yield according to WHSV in the steam gasification reaction of ethanol according to Experimental Example 2 of the present invention;
8B is a graph showing carbon gasification efficiency (CGE) and hydrogen gasification efficiency (HGE) according to WHSV in the steam gasification reaction of ethanol according to Experimental Example 2 of the present invention;
8c is a graph showing gas composition according to WHSV in the steam gasification reaction of ethanol according to Experimental Example 2 of the present invention;
9A is a graph showing the total gas production rate and hydrogen yield according to the catalyst bed temperature change in the steam gasification reaction of glycerol according to Experimental Example 3 of the present invention;
9B is a graph showing carbon gasification efficiency (CGE) and hydrogen gasification efficiency (HGE) according to the catalyst bed temperature in the steam gasification reaction of glycerol according to Experimental Example 3 of the present invention;
9c is a graph showing the gas composition according to the temperature of the catalyst bed in the steam gasification reaction of glycerol according to Experimental Example 3 of the present invention;
10A is a graph showing total gas production rate and hydrogen yield according to WHSV in the steam gasification reaction of glycerol according to Experimental Example 3 of the present invention;
10B is a graph showing carbon gasification efficiency (CGE) and hydrogen gasification efficiency (HGE) according to WHSV in the steam gasification reaction of glycerol according to Experimental Example 3 of the present invention;
FIG. 10C is a graph showing gas composition according to WHSV in the steam gasification reaction of glycerol according to Experimental Example 3 of the present invention. FIG.

The present invention

An organic material raw material supply unit for steam reforming reaction, comprising an organic material source chamber and a first preheater for preheating the organic material source;

A water vapor supply unit for water vapor reforming reaction comprising a water chamber and a second preheater for preheating the water;

A mixing unit for generating a mixture of organic material and water vapor through the organic material supply unit and the water vapor supply unit; And

And a reactor for performing the steam reforming reaction of the mixture

/ RTI >

The present invention provides an apparatus for generating hydrogen gas through steam reforming reaction of an organic substance.

Hereinafter, an apparatus for generating hydrogen gas through a steam reforming reaction of an organic material according to the present invention will be described in detail with reference to FIG. 1A. The hydrogen gas generator 101 includes a raw material supply unit 200, a steam supply unit 300, a mixing unit 400, and a reaction unit 500.

First, the steam reforming reaction organic material feeder 200 includes an organic material source chamber 220, a first pump 240 for pressurizing the organic material source from the organic material source chamber, and a second pump 240 for preheating the organic material source 1 pre-heater (260).

At this time, the organic material raw material may include alcohol, and the alcohol may be derived from biomass, but is not limited thereto.

In addition, the alcohol may be selected from the group consisting of methanol, ethanol, glycerol, and combinations thereof, but is not limited thereto.

The water vapor supply unit 300 for steam reforming includes a water chamber 320, a second pump 340 for applying pressure to the water discharged from the water chamber 320, And a second preheater 360 for delivering the heat.

At this time, the second preheating through the second preheater 360 may be higher than the first preheating through the first preheater 260.

For example, the first preheating may be performed at about 200 ° C to about 500 ° C, and preferably at about 250 ° C to about 300 ° C. If the first preheating is performed at a temperature lower than 200 ° C, the steam reforming reaction of the organic material does not occur smoothly in the subsequent process, and the hydrogen gas production amount may be lowered. If the first preheating is performed at a temperature higher than 500 ° C, the generation of by-products such as tar and char can be increased. If the generation of the by-product increases, the process of generating hydrogen gas by causing clogging in the reactor 520 of the apparatus may not proceed smoothly.

On the other hand, the second preheating may be performed at about 600 ° C to about 800 ° C, preferably about 650 ° C to about 750 ° C. If the second preheating is performed at a temperature lower than 600 ° C., the steam reforming reaction of the organic material does not occur smoothly in the post-process, and the hydrogen gas production amount may be lowered. And the occurrence of by-products such as tar and char may increase. If the generation of the by-product increases, the process of generating hydrogen gas by causing clogging in the reactor 520 of the apparatus may not proceed smoothly.

Next, the mixing unit 400 generates a mixture of organic material and water vapor through the organic material supply unit 200 and the water supply unit 300, and the mixture is continuously supplied to the reaction unit 500. The mixing unit 400 may include a pipe connection port 420 and the reaction unit 500 includes a reactor 520 for performing the steam reforming reaction of the mixture.

At this time, the organic material and the water vapor are preheated to different temperatures, respectively, and then mixed and supplied to the reactor 520, thereby minimizing the generation of byproducts that may occur in the preheating of the organic material raw material. That is, the organic material is first preheated to about 200 ° C to about 500 ° C, mixed with water vapor having a temperature of about 600 ° C or higher, and immediately introduced into the reactor so that the mixture between the mixing part 400 and the reaction part 500 The generation of by-products can be remarkably reduced before the mixture is introduced into the reaction part 500 by minimizing the length. The byproducts are mainly produced by carbonization of the organic material raw material, and the higher the temperature, the higher the production amount. Therefore, the preheating temperature of the organic material raw material is limited to 500 캜 or less. The temperature before the mixture is introduced into the reaction part 500 may be about 250 ° C to about 500 ° C, but is not limited thereto.

The pressure of the mixture before being introduced into the reaction part 500 may be normal pressure, but is not limited thereto. If the pressure exceeds the normal pressure, the by-product may clog the reactor 520 and the pressure may be increased.

At this time, the reactor 520 may include a catalyst for steam reforming reaction, and the catalyst may be at least one selected from the group consisting of trium-nickel / activated carbon, tungsten, carbonitungsten, molybdenum carbide, platinum, ruthenium, iridium, But are not limited to, those selected from the group consisting of palladium, palladium, nickel, and combinations thereof.

In addition, when the reactor 520 includes a catalyst for steam reforming reaction, the reactor 520 may be a fixed bed reactor or a fluidized bed reactor, but is not limited thereto. However, when the reactor 520 is a fixed bed reactor, clogging of the reactor often occurs due to byproducts, compared to a fluidized bed reactor. In this case, the generation of byproducts is remarkably small, thereby preventing the clogging due to byproducts.

At this time, the temperature of the mixture discharged from the reactor 520 may be about 500 ° C to about 750 ° C, but is not limited thereto. The temperature rise of the mixture after the reaction in the reactor 520 may be the temperature rise due to the progress of the steam reforming reaction, but is not limited thereto.

The apparatus for generating hydrogen gas through the steam reforming reaction of the organic material may be used for a fuel cell, and the hydrogen produced by the apparatus may be used as a fuel for a fuel cell.

The hydrogen gas generator 101 through the steam reforming reaction of the organic material may further include the cooling unit 600 and the separation unit 700 following the reaction unit 500, but the present invention is not limited thereto.

In this case, the cooling unit 600 may be connected to the reaction unit 500 and may include a cooler 620. The cooler 620 may cool the high temperature product discharged through the reactor 520 of the reactor 500.

For example, the cooler 620 may cool the temperature of the product to less than about 20 ° C, but is not limited thereto.

The separator 700 may be connected to the cooling unit 600 and the separator 700 may include a separator 720 and a flow meter 740. The separator 720 is used for phase separation of the generated material discharged through the cooling unit 600, and the phase separation may be a liquid-gas phase separation. At this time, when the phase separation is liquid-gas phase separation, the gaseous material (gas) can pass through the flow meter 740 to measure the gas production amount per hour.

In addition,

An apparatus for generating hydrogen gas through a steam reforming reaction of the organic material, and a fuel cell.

Hereinafter, the fuel cell electric system according to the present invention will be described in detail.

Specifically, fuel cells are electrochemical devices that convert the chemical energy of a fuel directly into electrical energy, potentially providing a clean and highly efficient source of electrical vehicle power. The fuel cell may be a solid oxide fuel cell, but is not limited thereto.

The fuel cell reacts with hydrogen and oxygen as an opposite reaction to electrolysis of water to produce electricity and water. Therefore, it is important to produce hydrogen at a high concentration for use as the fuel of the fuel cell.

Therefore, in the present invention, the hydrogen gas generation device through the steam reforming reaction of the organic material and the fuel cell may be connected to supply the hydrogen generated in the device as fuel to the fuel cell immediately. At this time, the fuel cell can be supplied directly to the fuel cell from the reaction part 500 without passing through the cooling part 600, and since the hydrogen generated in the device is high in concentration, a more efficient fuel cell electric system can be constituted.

Further,

A first preheating of the organic material stock (step 1);

Second preheating the water to produce water vapor (step 2);

Mixing the organic raw material and water produced in the step 1 and the step 2 and continuously injecting them into the reactor (step 3); And

Performing a steam reforming reaction of said mixture in said reactor (step 4);

And a method for generating hydrogen gas through steam reforming reaction of an organic material.

Hereinafter, a method of generating hydrogen gas through the steam reforming reaction of an organic material according to the present invention will be described in detail with reference to FIG. 2.

First, in the method for generating hydrogen gas through steam reforming reaction of an organic material according to the present invention, step 1 is a first preheating step (S100) of an organic material raw material.

In the step 1, the steam reforming reaction can be easily performed by first preheating the organic raw material.

Specifically, the organic material raw material of step 1 may include alcohol, and the alcohol may be derived from biomass, but is not limited thereto.

In addition, the alcohol may be selected from the group consisting of methanol, ethanol, glycerol, and combinations thereof, but is not limited thereto.

Next, step 2 is a step (S200) of generating water vapor by second preheating the water.

In the step 2, water is generated by the second preheating of the water, and the steam reforming reaction can be easily performed through the preheating.

At this time, the second preheating through the second preheater may be higher than the first preheating through the first preheater.

For example, the first preheating may be performed at about 200 ° C to about 500 ° C, and preferably at about 250 ° C to about 300 ° C. If the first preheating is performed at a temperature lower than 200 ° C, the steam reforming reaction of the organic material does not occur smoothly in the subsequent process, and the hydrogen gas production amount may be lowered. If the first preheating is performed at a temperature higher than 500 ° C, the generation of by-products such as tar and char can be increased. If the generation of the by-products increases, the process of generating hydrogen gas by causing clogging of the reactor of the apparatus may not proceed smoothly.

On the other hand, the second preheating may be performed at about 600 ° C to about 800 ° C, preferably about 650 ° C to about 750 ° C. If the second preheating is performed at a temperature lower than 600 ° C., the steam reforming reaction of the organic material does not occur smoothly in the post-process, and the hydrogen gas production amount may be lowered. And the occurrence of by-products such as tar and char may increase. If the generation of the by-products increases, the process of generating hydrogen gas by causing clogging of the reactor of the apparatus may not proceed smoothly.

Next, Step 3 is a step (S300) of mixing the organic material and water produced in Step 1 and Step 2 to produce a mixture and continuously injecting the mixture into the reactor (S300).

Specifically, by preheating the organic material and the water vapor to different temperatures and mixing them and supplying them to the reactor, it is possible to minimize the generation of byproducts that may occur in the preheating of the organic material raw material. That is, the organic material is first preheated to about 200 ° C to about 500 ° C, mixed with water vapor having a high temperature of about 600 ° C or higher, and immediately introduced into the reactor to minimize the length of the tube between the mixing part and the reaction part, The occurrence of by-products can be remarkably reduced before being put into the reaction section. The byproducts are mainly produced by carbonization of the organic material raw material, and the higher the temperature, the higher the production amount. Therefore, the preheating temperature of the organic material raw material is limited to 500 캜 or less. The temperature before the mixture is introduced into the reactor may be about 250 ° C to about 500 ° C, but is not limited thereto.

The pressure of the mixture before being introduced into the reaction part 500 may be normal pressure, but is not limited thereto. If the pressure exceeds the normal pressure, the by-product may clog the reactor 520 and the pressure may be increased.

Next, step 4 is a step (S400) of performing the steam reforming reaction of the mixture in the reactor.

Specifically, the reactor may comprise a catalyst for steam reforming reaction, wherein the catalyst is selected from the group consisting of titanium-nickel / activated carbon, tungsten, carbonitungsten, molybdenum carbide, platinum, ruthenium, iridium, , Nickel, and combinations thereof, but is not limited thereto.

In addition, when the reactor includes a catalyst for steam reforming reaction, the reactor may be a fixed bed reactor or a fluidized bed reactor, but is not limited thereto. However, when the reactor is a fixed-bed reactor, clogging of the reactor often occurs due to by-products, compared to a fluidized bed reactor. In this case, the generation of by-products is remarkably small, thereby preventing the clogging due to by-products.

At this time, the temperature of the mixture discharged from the reactor may be about 500 ° C to about 750 ° C, but is not limited thereto. The temperature rise of the mixture after the reaction in the reactor may be a temperature rise due to the progress of the steam reforming reaction, but is not limited thereto.

The hydrogen gas generated through the above steps 1 to 4 (S100 to S400) can be used as the fuel of the fuel cell.

The method for producing hydrogen gas through the steam reforming reaction of the organic material may further comprise a step (step 5) of cooling the product produced through the steam reforming reaction (step 4) of the mixture following the step 4 (step 5) Subsequently, the step of separating the product (step 6) may further be included.

Specifically, high-temperature, high-pressure generating materials can be produced in step 4. The product can be added to the chiller as step 5 to cool the product to a temperature below about 20 ° C, but is not limited thereto.

Then, the product material cooled by the step 5 may contain two or more phases and may be introduced into a separator to cause phase separation of the product (step 6). At this time, the phase separation may be a liquid-gas phase separation, in which the liquid material is discharged to the bottom of the separator and the vapor material (gas) is discharged to the top of the separator. At this time, the vapor phase material may include hydrogen.

Hereinafter, examples and experimental examples of the present invention will be described in more detail.

However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the present invention is not limited by the following Examples and Experimental Examples.

<Examples>

1. Experimental material

Ethanol, methanol, glycerol (ideal purity> 99%) and distilled water were used as reactants. Ni-Y / AC was used as a wet gasification catalyst for alcohols. The catalysts were prepared by loading nickel (25 wt% of AC) and ditrimium (10 wt% of AC) in an activated charcoal (AC) using incipient wetness method and then drying at 105 ° C for 10 hours, 3 hours calcination, and hydrogenation at 400 ° C for 8 hours.

2. Experimental apparatus and method

From the liquid biomass, a hydrogen gas generator was produced by steam reforming reaction of micro scale organic material which can continuously produce high concentration hydrogen gas suitable for solid oxide fuel cell. Referring to FIG. 1A, the apparatus includes an organic material supply unit 200, a water supply unit 300, a mixing unit 400, a reaction unit 500, and a separation unit 700. The apparatus may further include a cooling unit 600 (see comparative example 1b). The pumps used in the organic material supply unit and the water supply unit were a high pressure pump (Waters 515) (240, 340) capable of continuously supplying the organic material and / or water at 600 g / h at a maximum of 400 bar. When the flow rate of the organic material and / or water is 600 g / h, the first preheater 260 and the second preheater 360 are installed to preheat the organic material up to 450 ° C. and water to 720 ° C. Respectively. The volume of the first preheater was 18.2 mL and the volume of the second preheater was 51.4 mL. For comparative experiments, supercritical water gasification was also performed. In this case, the steam generator was removed and preheated to the same temperature using only the raw material preheater.

The reactor was equipped with a reactor 520 made of Inconel 625 SML tubing and the reactor was packed with particulate (20 mesh to 35 mesh) catalyst and was operated at a maximum pressure of 300 bar and 700 ° C. The volume of the reactor thus prepared was 21.3 mL. The product produced after the reaction in the reactor is cooled to below 20 ° C in a condenser 620 and is depressurized to a normal pressure in a back-pressure regulator 640 and then introduced into a separator 720. In the steam gasification experiment of the present embodiment, the backpressure controller 640 is omitted and the cooled product is immediately introduced into the separator 720. On the other hand, in the supercritical gasification of methanol of the comparative example, as shown in FIG. 1B (110), it is operated including the back pressure controller 640. Liquid separating in the separator 720, and the gas separated from the separator is passed through the flow meter 740 to measure the amount of gas produced per hour. A photograph of the hydrogen gas generator is shown in Fig.

3. Analysis method

The product gas was sampled between the gas-liquid separator of the reforming reactor and the wet test meter and analyzed using gas chromatograph (GC, Agilent, DS Science IGC7200). Hydrogen, carbon monoxide, methane and carbon dioxide of the product gases were quantitatively analyzed by using a thermal conductivity detector (TCD), C ₂₊ hydrocarbons and other gases using a flame ionization detector (FID). The analytical column was a Caroxen-1000 packed column. The carrier gas was a mixture of helium and hydrogen of 8 vol%. The quantitative analysis was made by using a calibration curve for each gas component using standard gas.

Preheating temperature of reactant and water, inlet and outlet temperature and pressure of reactor were collected and stored at intervals of 5 seconds through a data logger.

4. Experimental Example and Analysis of Results

(1) Definition of terms

In this example, the terms used are defined as follows:

1) WHSV (h ^-1 ): Biomass Feeding Rate (g / h) / Charged Catalyst (Ni) Amount (g)

2) Total gas production rate (L / h / L): total gas production rate (L / h) / catalyst bed reactor volume (L)

3) Gas yield (mol / mol): gas production rate (mol / h) / organic material input rate (mol / h)

4) Carbon (hydrogen) gasification efficiency (%): [Carbon (hydrogen) production rate (g / h) /

Carbon (hydrogen) input rate (g / h) in organic material] x 100

5) Gas composition (vol%): concentration of each component present in the product gas (vol%)

(2) Comparative Example - Supercritical gasification of methanol

4A to 4C are graphs showing the influence of water / methanol (water / methanol) molar ratio on supercritical gasification of methanol on a Ni-Y / AC catalyst (catalyst: Ni-Y / AC, catalyst layer temperature: WHSV: 100 h ^-1 , pressure: 250 bar). This experiment was performed to compare the results of steam gasification of methanol, which is an experimental example of the present invention described below, as a comparative example. The theoretical water / methanol molar ratio of the steam gasification reaction of methanol (CH ₃ OH + H ₂ O? CO ₂ + 3H ₂ ) is 1. The total gas production rate was 17,613 L / h / L, which is the highest in the theoretical molar ratio, but the hydrogen yield tended to increase with increasing water / methanol, that is, with higher water content. The carbon gasification efficiency (CGE) and hydrogen gasification efficiency (HGE) were low and decreased slightly as the water / methanol molar ratio increased. From the analysis of chemical oxygen demand (COD) of the liquid effluent, it was found to be less than 500 ppm and there was no change in pressure during the operation. As a result, it was confirmed that the side reaction of solid production such as coking did not proceed. Through this, it was estimated that all of the input methanol was gasified. However, the low gas yield was judged to be the result of a malfunction of the BPR, which acts to lower the high pressure of 250 bar to 1 bar. Therefore, it was estimated that the actual total gas production rate was also higher than the values in FIG. 4A. Analysis of the gas composition showed that the hydrogen concentration increased sharply and methane concentration decreased with increasing water / methanol molar ratio. Through this, if the concentration of water is low at supercritical water condition of 250 bar, methane and water are produced as methanation reaction (CO + 3H ₂ → CH ₄ + H ₂ O, CO ₂ + 4H ₂ → CH ₄ + 2H ₂ O) (CO + H ₂ O → H ₂ + CO ₂ ) and methane reforming reaction (methanation reaction) are activated when the concentration of water increases.

(3) Experimental Example 1 - Steam gasification of methanol

5A to 5C show the influence of the water / methanol molar ratio on the steam gasification of methanol (catalyst: Ni-Y / AC, catalyst layer temperature: 650 ° C, WHSV: 160 h ^-1 , pressure: 1 bar). Steam gasification was performed at the initial atmospheric pressure, so no backpressure controller (BPR) was used. Therefore, the production gas velocity can be accurately measured. As a comparative example, the tendency of water / methanol molar ratio was similar to that of supercritical gasification, but it was confirmed that gas generation rate and hydrogen yield were higher in steam gasification. The carbon gasification efficiency (CGE) represented 100% in all water / methanol molar ratios. That is, all of the carbon monoxide was converted to gas. The hydrogen gasification efficiency (HGE) showed a tendency to increase with increasing water / methanol molar ratio and showed up to 130%. This means that at least 30% of the hydrogen in the gas was produced from water. The gas composition in the steam gasification is very different from the supercritical gasification. The hydrogen content increased in proportion to the increase of water / methanol molar ratio, but the sensitivity was lower than that of supercritical gasification. The increase in hydrogen content and carbon dioxide content and the decrease in carbon monoxide content inversely mean that the water gas reaction (CO + H ₂ O → H ₂ + CO ₂ ) was activated as the amount of water increased. The hydrogen content was the highest at 71.4 vol% at the water / methanol molar ratio of 6.7. On the other hand, the methane content in the water / methanol range was 4 vol% or less. Methane - producing reactions were not activated in the steam gasification of methanol.

Therefore, when the supercritical gasification of methanol and the steam gasification experiment are compared, it is confirmed that the steam gasification at atmospheric pressure is preferable in the case of producing the fuel for the small scale SOFC requiring high concentration of methanol gasification.

6A to 6C (catalyst: Ni-Y / AC, water / methanol: 1 mol / mol, WHSV: 142 h ^-1 , pressure: 1 bar) on the steam gasification of methanol. In general, it was judged that there was no significant change in the gas production amount or composition when the reaction temperature was maintained at 550 ° C. or higher. Gas composition showed that the hydrogen concentration remained constant even when the reaction temperature increased, but carbon monoxide decreased and methane and carbon dioxide increased slightly. It was judged that methane production reaction was activated somewhat at high temperature.

(4) Experimental Example 2 - Steam gasification of ethanol

7A to 7C (catalyst: Ni-Y / AC, catalyst layer temperature: 650 DEG C, pressure: 1 bar) were examined by investigating the influence of water / ethanol (W / E) molar ratio on the steam gasification of ethanol. The theoretical W / E molar ratio of the wet gasification of ethanol (C ₂ H ₅ OH + 3H ₂ O → 2CO ₂ + 6H ₂ ) is 3. The total gas production rate was 35,507 L / h / L, which is the highest value at W / E molar ratio 2.4, and then decreased rapidly with increasing W / E molar ratio. The tendency was similar to methanol. However, the hydrogen yield remained constant at about 1.6 mol / mol in the above molar ratio range. Unlike methanol, ethanol showed a tendency to decrease with increasing W / E mole ratio in both carbon gasification efficiency (CGE) and hydrogen gasification efficiency (HGE). It is considered that ethanol is sensitive to the W / E molar ratio in some of the unit reactions involved in the gasification reaction compared to methanol.

As the gas composition increased, the hydrogen content increased and the methane content decreased as the W / E molar ratio increased, similar to that of methanol. The hydrogen content was the lowest at W / E molar ratio of 2.4 to 45 vol%, and the molar ratio was the highest at 9.6 to 57.7 vol%. Ethanol gasification showed higher methane content and lower carbon monoxide content than methanol gasification. It was found that the methanation reaction (CO + 3H ₂ → CH ₄ + H ₂ O) was activated in the steam gasification condition of ethanol. Therefore, it has been confirmed that the technology for suppressing the methane generation reaction is required to produce high-concentration hydrogen.

8A to 8C show the effect of weight hourly space velocity (WHSV) on the steam gasification of ethanol (catalyst: Ni-Y / AC, catalyst layer temperature: 650 ° C, W / E: 3 mol / 1 bar). In the range of 114 h ^-1 to 252 h ^-1 , it can be seen that WHSV does not significantly affect gas production rate and gas composition by ethanol gasification. As shown in the hydrogen gasification efficiency (HGE), the gasification conversion of hydrogen atoms in ethanol was most effective at a theoretical ratio of 3, and the hydrogen concentration in the produced gas was about 47 vol%. The methane content remained high in the studied WHSV range due to the activation mechanism of methane production by the hydrogenation carbon monoxide reaction described above.

(5) Experimental Example 3 - Steam gasification of glycerol

(Catalyst: Ni-Y / AC, W / G: 3 mol / mol, WHSV: 105 h- ¹ , pressure: 1 bar) were investigated to investigate the influence of the catalyst bed temperature on the steam gasification of glycerol. The water / glycerol (W / G) theoretical molar ratio of the wet gasification reaction of glycerol (C ₃ H ₈ O ₃ + 3H ₂ O? 3CO ₂ + 7H ₂ ) is 3 (weight ratio: 0.59). In the theoretical ratio, both the gas production rate and the hydrogen yield by the steam gasification of glycerol were very sensitive to the catalyst bed temperature. This means that the gasification of glycerol has a complex reaction pathway that is sensitive to temperature, which is very different from methanol. As shown by the carbon gasification efficiency (CGE), the complete gasification of the high concentration glycerol was completed at a reaction temperature of 600 ° C or higher. Even when complete gasification occurred, the hydrogen gasification efficiency (HGE) did not exceed 100%, which affected the hydrogen concentration in the product gas. The concentration of major gas components except carbon monoxide was not significantly affected by the temperature of the catalyst bed. The hydrogen concentration was about 42 vol% and the methane content was about 13 vol% lower than that of ethanol. Generally, the methanation reaction was activated at a high temperature of 550 ° C or higher, which was the same as in the case of methanol.

10A to 10C show the results of investigating the effect of WHSV on the gasification of steam of glycerol (catalyst: Ni-Y / AC, catalyst layer temperature: 600 ° C, W / G: 3 mol / mol, pressure: 1 bar). The gas production rate increased linearly with increasing WHSV, but the hydrogen yield tended to decrease somewhat. In other words, most of the generated gas is a component other than hydrogen. Gas conversion of glycerol was higher than that of glycerol, but gas conversion of hydrogen was lower than expected. From this, it can be seen that the reaction route of hydrogen production by the steam gasification of glycerol is much more complicated than methanol or ethanol. The hydrogen concentration in the product gas was 47.3 vol%, which is the highest at WHSV 28 h ^-1 , and 38 vol%, which is the lowest at 110 h ^-1 . In order to obtain a hydrogen concentration of 45 vol% or more, WHSV should be kept below 80 h ^-1 .

(6) Conclusion

Effects of temperature, pressure, water / organic mole ratio and WHSV on the production of hydrogen syngas by steam gasification of alcohols such as methanol, ethanol and glycerol were investigated in a fixed bed continuous reactor. The catalyst used was Ni-Y / AC, which was developed by itself. The supercritical gasification of methanol at a catalyst bed temperature of 600 ° C., a W / M molar ratio of 1, and a WHSV of 100 h ^-1 and 250 bar showed a gas formation rate of about 17,000 L / h / L and a hydrogen concentration of 52 vol% The steam gasification of methanol at a W / M molar ratio of 1 and a WHSV of 160 h ^-1 showed a gas production rate of about 46,000 L / h / L and a hydrogen concentration of 64 vol%. Steam gasification of methanol was not affected by the temperature above 450 ℃. The steam gasification of ethanol showed a gas production rate of about 35,000 L / h / L and a hydrogen content of 47 vol% at 650 ℃, a W / E theoretical molar ratio of 3, and a WHSV of 100 h ^{- 1} . The effect of temperature and W / E mole ratio on the gasification results was higher than methanol. The gasification of glycerol showed a gas formation rate of about 14,000 L / h / L and a hydrogen content of 47 vol% at 600 ℃, W / G theoretical molar ratio of 3 and WHSV of 80 h ^{- 1} . The steam gasification of glycerol was greatly affected by the main operating conditions such as catalyst bed temperature and WHSV. Gas production rate and hydrogen content by steam gasification were higher in order of methanol>ethanol> glycerol.

Through experiments, it was possible to effectively produce syngas containing high concentration hydrogen by performing steam gasification of methanol, ethanol and glycerol in a fixed-bed continuous reactor filled with Ni-Y / AC catalyst. Syngas produced showed a composition that could be used as a fuel for a solid acid fuel cell (SOFC).

101: hydrogen gas generator
110: Supercritical water gasifier
200:
220: organic material chamber
240: first pump
260: First preheater
300: water vapor supply part
320: water chamber
340: Second pump
360: Second preheater
400: mixing part
420: pipe connector
500: Reaction part
520: Reactor
600: cooling section
620: cooler
640: Postpressure controller
700:
720: separator
740: Flow Meter

Claims (16)

An organic material raw material supply unit for steam reforming reaction comprising an organic material chamber and a first preheater for preheating (first preheating) the organic material raw material;
A water chamber for water steam reforming reaction comprising a water chamber and a second preheater for preheating the water (second preheating);
A mixing unit for generating a mixture of organic material and water vapor through the organic material supply unit and the water vapor supply unit; And
And a reactor for performing the steam reforming reaction of the mixture
/ RTI &gt;
An apparatus for generating hydrogen gas through steam reforming reaction of organic substances.
The method according to claim 1,
Wherein the organic material raw material comprises an alcohol derived from biomass.
3. The method of claim 2,
Wherein the alcohol comprises one selected from the group consisting of methanol, ethanol, glycerol, and combinations thereof.
The method according to claim 1,
Wherein the first preheating is performed at 200 ° C to 500 ° C, and the second preheating is performed at 600 ° C to 800 ° C.
The method according to claim 1,
Wherein the reactor comprises a catalyst for steam reforming reaction.
6. The method of claim 5,
Wherein the reactor is a fixed bed reactor or a fluidized bed reactor.
6. The method of claim 5,
The catalyst for steam reforming reaction may be selected from the group consisting of the trium-nickel / activated carbon, tungsten, carbonitungsten, molybdenum carbide, platinum, ruthenium, iridium, rhodium, palladium, nickel, Wherein the reforming reaction is carried out in the presence of oxygen.
The method according to claim 1,
Wherein the apparatus for generating hydrogen gas through the steam reforming reaction of the organic material is for generating fuel of the fuel cell.
9. A fuel cell electricity production system, comprising a hydrogen gas generation apparatus and a fuel cell through steam reforming reaction of an organic material according to any one of claims 1 to 8.
A first preheating of the organic material stock (step 1);
Second preheating the water to produce water vapor (step 2);
Mixing the organic raw material and water produced in the step 1 and the step 2 to form a mixture, and continuously introducing the mixture into the reactor (step 3); And
Performing a steam reforming reaction of said mixture in said reactor (step 4);
A method for producing hydrogen gas through steam reforming reaction of organic material
11. The method of claim 10,
Wherein the organic material source comprises an alcohol derived from biomass.
12. The method of claim 11,
Wherein the alcohol comprises one selected from the group consisting of methanol, ethanol, glycerol, and combinations thereof.
11. The method of claim 10,
Wherein the first preheating is performed at 200 ° C to 500 ° C, and the second preheating is performed at 600 ° C to 800 ° C.
11. The method of claim 10,
Wherein the reactor comprises a catalyst for steam reforming reaction.
15. The method of claim 14,
Wherein the reactor is a fixed bed reactor or a fluid bed reactor.
15. The method of claim 14,
The catalyst for steam reforming reaction may be selected from the group consisting of the trium-nickel / activated carbon, tungsten, carbonitungsten, molybdenum carbide, platinum, ruthenium, iridium, rhodium, palladium, nickel, Wherein the hydrogen gas is a hydrogen gas.

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