KR100992868B1 - Gasification method and apparatus for generating hydrogen by recycling carbon dioxide separated from psa - Google Patents

Abstract

PURPOSE: A gasification device and a method thereof are provided to control the carbon dioxide concentration by recirculating the carbon dioxide which is divided in a PSA(Pressure swing Absorbent), thereby enhancing the hydrogen generation amount by increasing the generation amount of hydrogen and carbon monoxide. CONSTITUTION: A gasification device which generates the hydrogen includes a gas phase or liquid carbon dioxide storage tank(80), a gasification device(10), a boiler(20), a cooler(30), a collector(40), a refiner(50), a water gas shift reactor(60), a PSA gas separator(70), a gas circulation pipe, a concentration controller(100). The boiler collects the heat of the decomposition gas which is flown out from gasification device. The cooler cools the decomposition gas of the high temperature exhausted from the boiler. The refiner removes the acidic gas and oxidizing substances by contacting the decomposition gas with the washed object. The water gas shift reactor changes the carbon monoxide and steam of the decomposition gas into the carbon dioxide and hydrogen. The PSA gas separator absorbs the carbon dioxide among the converted carbon dioxide and hydrogen and divides the hydrogen gas. The gas circulation pipe recirculates the carbon dioxide of the PSA gas separator inside the gasification device. If the gas density inside the gasification device measured in the density measurement sensor(101) is less than the reference concentration, the controller respectively and successively controls the opening and closing angle of a second electronic valve which is installed to the gas circulation pipe and a first electronic valve(103) which is installed to the gas supply pipe and recirculates the carbon dioxide of the PAS gas separator to the first tank. If the gas density inside the gasification device measured in the density measurement sensor is lower than the reference concentration even in recirculation of the carbon dioxide of the PSA gas divider, the controller recirculates the carbon dioxide of the gas storing tank to the second rank. The concentration controller comprised of controller maintaining the gas concentration inside the gasification device in range of reference concentration.

Description

GASIFICATION METHOD AND APPARATUS FOR GENERATING HYDROGEN BY RECYCLING CARBON DIOXIDE SEPARATED FROM PSA}

The present invention relates to a gasification method and apparatus, and in particular, water (H ₂ O) and oxygen (O ₂ ) and carbon dioxide (CO ₂ ) is supplied to the gasifier, and separated in a PSA (Pressure Swing Absorbent) gas separator CO-gasifier to produce hydrogen and recycling the carbon dioxide separated in the PSA that to (CO ₂₎ to increase the amount of gasification group recycled while carbon dioxide (CO ₂₎ carbon monoxide (CO) and hydrogen (H ₂₎ by adjusting the concentration of the A method and apparatus are disclosed.

Gasification of polymer liquid waste such as waste oil and waste organic solvent generated from industrial factories, and polymer solid organic matter such as coal and waste tire is mainly performed by carbon monoxide and hydrogen gas, which are gaseous fuels. It means to convert to syngas.

That is, when oxygen is injected into and combusted with high molecular weight organic materials such as waste oil, waste plastic, coal, and waste tire, an oxidation reaction occurs, and steam (H ₂ O) and carbon dioxide (CO ₂ ) generated through the oxidation reaction are 1200 ° C. When reacted with the polymer organic material in a closed space maintained at a high temperature exceeding the reduction reaction (reformation reaction) occurs to gasify into hydrogen (H ₂ ), carbon monoxide (CO) and carbon dioxide (CO ₂ ) as fuel gas. In other words, all the carbonized materials are reformed at 1200 ° C. or higher to gasify hydrogen (H ₂ ), carbon monoxide (CO), and carbon dioxide (CO ₂ ).

In this gasification process, as shown in FIG. 1, a high-molecular liquid waste such as waste oil, waste organic solvent, or polymer solid organic matter such as coal and waste tire, water (H ₂ O) and oxygen (O ₂ ) are supplied to the gasifier. Gasification is carried out. This is represented by the following formula.

Then, the sensible heat of the decomposition gas flowing out of the gasifier 10 is recovered through the sensible heat boiler 20 and then the decomposition gas is cooled through the cooler 30. At this time, the sensible heat boiler 20 is a boiler for recovering the amount of heat held by the decomposition gas to generate and utilize water vapor to cool the decomposition gas to 200 ℃. The steam produced can be used by itself or as a steam turbine to produce power for its own processes.

After the cooling is completed, the dust is collected through the dust collector 40, and then supplied to the purifier 50 to bring the decomposition gas into contact with the cleaning product to oxidize acidic gases such as hydrogen sulfide and hydrogen chloride, and oxidation such as dioxins, SOx, and NOx. Remove the material.

Then, carbon monoxide (CO) and water vapor (H ₂ O) of the decomposition gas are reacted in a water gas shift reactor (WGS) 60 to form carbon dioxide (CO ₂ ) and hydrogen (H). ₂ ).

Then, the conversion of carbon dioxide (CO ₂₎ and hydrogen (H ₂₎ of carbon dioxide (CO ₂₎ the PSA (Pressure swing Absorbent: a pressure swing adsorption), the gas separator 70, the liquid absorption by using the new amine, ammonium hydroxide, carbonates such as in Hydrogen gas is separated and other gases are released.

Meanwhile, as the social structure becomes more complex and sophisticated, energy consumption in each country continues to increase. However, the depletion of fossil energy such as oil and natural gas, which is the basis of energy consumption, is approaching gradually, and global environmental problems such as global warming are being highlighted. In the 21st century, many countries have recognized hydrogen (H ₂ ) as a viable alternative, a chemical that can be obtained from abundant resources and allows combustion products to store and transport energy without contaminating the environment.

Although the natural gas reforming process is widely used as a method of producing hydrogen resources, research and development for producing hydrogen from coal are being expanded due to price instability and regional variations in natural gas landfills. In particular, hydrogen technology through coal gasification has gained great attention as a core process for expanding carbon dioxide storage technology.

However, in such a conventional gasification method, it is more common to use a complex power generation or a hydrogen production plant itself, which can directly use the energy of all the synthesis gases, rather than using hydrogen in the produced synthesis gas. This is a problem in that the economic efficiency of the hydrogen produced in the synthesis gas is produced in a small amount or a large amount is not much economical because the additional cost is too much for use after compressing, storing, transporting.

The present invention is to solve the above problems, supplying water (H ₂ O) and oxygen (O ₂ ) and carbon dioxide (CO ₂ ) to the gasifier, carbon dioxide separated from the pressure swing absorber (PSA) gas separator By recycling the (CO ₂ ) to the gasifier while controlling the concentration of carbon dioxide (CO ₂ ) by increasing the amount of carbon monoxide (CO) and hydrogen (H ₂ ) generated by recycling the carbon dioxide separated from the PSA to increase the production of hydrogen It is an object of the present invention to provide a gasification method and apparatus for generating hydrogen.

Features of the present invention for achieving the above object,

A gas storage tank in which gaseous or liquid carbon dioxide (CO ₂ ) is stored; A gasifier connected to water (H ₂ O), oxygen (O ₂ ), and the gas storage tank and a gas supply pipe to a polymer liquid waste or a polymer solid organic material to receive carbon dioxide and perform gasification; A boiler for recovering sensible heat of the decomposition gas flowing out of the gasifier; A cooler for cooling the hot decomposition gas discharged from the boiler; A dust collector for collecting dust of the decomposition gas after cooling is completed; A purifier for removing the acid gas and the oxide by contacting the decomposed gas, which has been collected, with the cleaning material; A water gas shift reactor for converting carbon monoxide (CO) and steam (H ₂ O) of the cracked gas into carbon dioxide and hydrogen (H ₂ ); And a pressure swing adsorption (PSA) gas separator for liquid-phase absorption of the converted carbon dioxide and carbon dioxide in hydrogen and separating hydrogen gas.

Here, the gasifier for generating hydrogen by recycling the carbon dioxide separated from the PSA according to the present invention interconnects the PSA gas separator and the gasifier, the gas circulation to recycle the carbon dioxide inside the PSA gas separator to the gasifier Further provided with a tube.

Here, the gasifier for generating hydrogen by recycling carbon dioxide separated from the PSA according to the present invention further includes a concentration controller for maintaining a constant carbon dioxide concentration inside the gasifier.

Here, the concentration controller may include a concentration measuring sensor for measuring a gas concentration of any one of carbon dioxide, hydrogen, and carbon monoxide in the gasifier; A first solenoid valve installed on the gas supply pipe; A second solenoid valve installed in the first gas circulation pipe; And a controller for controlling the first solenoid valve and the second solenoid valve to maintain the carbon dioxide concentration inside the gasifier within a reference concentration range.

Here, when the gas concentration in the gasifier measured by the concentration measuring sensor is less than a reference concentration, the controller controls the opening and closing degree of the second solenoid valve and the first solenoid valve sequentially to the first priority. The carbon dioxide of the PSA gas separator is recycled, and the carbon dioxide of the gas storage tank is recycled secondly if the carbon dioxide of the PSA gas separator is less than the reference concentration.

Here, the gas storage tank stores liquid carbon dioxide absorbed by the PSA gas separator or gaseous carbon dioxide converted into gas, or external carbon dioxide when the amount of carbon dioxide cannot be supplied in the process.

According to another aspect of the present invention,

In the gasification method of generating hydrogen by recycling the carbon dioxide separated from the PSA using a gasifier that generates hydrogen by recycling the carbon dioxide separated from the PSA, water (H ₂₎ into the gasifier in which the polymer liquid waste or the polymer solid organic material is introduced. A gasification process for performing gasification by supplying O), oxygen (O ₂ ), and carbon dioxide (CO ₂ ); A sensible heat recovery step of recovering sensible heat of the decomposition gas flowing out of the gasifier through a boiler; A cooling step of cooling the hot decomposition gas discharged from the boiler through a cooler; A dust collecting step of collecting dust of the decomposed gas which has been cooled through a dust collector; A purifying step of removing the acid gas and the oxide material by contacting the decomposed gas, which has been collected, with the washings in a purifier; A water gas shift reaction step of converting carbon monoxide (CO) and water vapor (H ₂ O) of the cracked gas into a carbon dioxide and hydrogen (H ₂ ) by reacting the same through a water gas shift reactor; And a separation process in which the converted carbon dioxide and carbon dioxide in hydrogen are absorbed in a liquid phase through a PSA (Pressure Swing Absorbent) gas separator, and the hydrogen gas is separated.

Here, the gasification process recycles carbon dioxide inside the PSA gas separator to the gasifier or supplies gaseous or liquid carbon dioxide stored in a gas storage tank to the gasifier.

Therefore, although the carbon dioxide separated in the PSA gas separator may be used as a demand source for the chemical process, in the present invention, a predetermined amount of carbon dioxide is continuously circulated in the process itself by recycling or reinjecting the recovered carbon dioxide into the gas for gasification in the gasifier. As a result, emissions from the final exit can be reduced.

According to the gasification method and apparatus for generating hydrogen by recycling the carbon dioxide separated from the PSA of the present invention configured as described above, the gasifier is supplied with water (H ₂ O) and oxygen (O ₂ ) and carbon dioxide (CO ₂ ) The amount of hydrogen produced by increasing the generation of carbon monoxide (CO) and hydrogen (H ₂ ) by controlling the concentration of carbon dioxide (CO ₂ ) while recycling the carbon dioxide (CO ₂ ) separated from the pressure swing absorber (PSA) gas separator into the gasifier. There is an advantage that can be increased.

1 is a schematic diagram schematically showing the configuration of a conventional gasifier.
Figure 2 is a schematic diagram schematically showing the configuration of a gasifier for generating hydrogen by recycling the carbon dioxide separated from the PSA according to the present invention.
3 is a process diagram illustrating a gasification method for generating hydrogen by recycling carbon dioxide separated from the PSA according to the present invention.

Hereinafter, the configuration of a gasifier for generating hydrogen by recycling carbon dioxide separated from the PSA according to the present invention will be described in detail with reference to the accompanying drawings.

In the following description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted. The following terms are defined in consideration of the functions of the present invention, and may be changed according to the intentions or customs of the user, the operator, and the like. Therefore, the definition should be made based on the contents throughout the specification.

Figure 2 is a schematic diagram schematically showing the configuration of a gasifier for generating hydrogen by recycling the carbon dioxide separated from the PSA according to the present invention.

Referring to FIG. 2, a gasifier 1 for generating hydrogen by recycling carbon dioxide separated from a PSA according to the present invention includes a gasifier 10, a boiler 20, a cooler 30, and a dust collector 40. ), A purifier 50, a water gas shift reactor 60, a PSA gas separator 70, a gas storage tank 80, a gas circulation tube 90, and a concentration controller 100.

First, the gasifier 10, the boiler 20, the cooler 30, the dust collector 40, the purifier 50, the water gas shift reactor 60, and the PSA gas separator 70 are conventionally The same reference numerals are assigned to the same components as those, and the description thereof will be omitted. In addition, the cooler 30 may not be an essential installation equipment in some cases, and equipment that performs the function may be installed at the front and rear ends of the cooler. In addition, the purifier 50 may be installed divided into one process or each process performing the same function.

In addition, the gas storage tank 80 stores gaseous or liquid carbon dioxide (CO ₂ ), and supplies it to the gasifier 10 through the gas supply pipe 81. Here, the gas storage tank 80 preferably stores liquid carbon dioxide absorbed by the PSA gas separator 70 or gaseous carbon dioxide converted into a gas, and may store and utilize carbon dioxide supplied from the outside according to a selection. .

In addition, the gas circulation pipe 90 interconnects the PSA gas separator 70 and the gasifier 10, and recycles carbon dioxide inside the PSA gas separator 70 to the gasifier 10.

On the other hand, the concentration regulator 100 is a concentration measuring sensor 101, the first solenoid valve 103, the second solenoid valve 105, the controller to maintain a constant carbon dioxide concentration inside the gasifier 10 It consists of 107.

The concentration sensor 101 measures the gas concentration of any one of carbon dioxide, hydrogen, and carbon monoxide in the gasifier 10, and outputs a measurement signal to the controller 107.

Opening and closing degree of the first solenoid valve 103 is controlled according to the control of the controller 107, the amount of carbon dioxide supplied to the gasifier 10 from the gas storage tank 80 is installed in the gas supply pipe 81 Adjust.

The second solenoid valve 105 is controlled to open and close and open and close according to the control of the controller 107, and installed in the gas circulation pipe 90 to supply carbon dioxide supplied from the PSA gas separator 70 to the gasifier 10. Adjust the supply.

When the gas concentration in the gasifier 10 measured by the concentration measuring sensor 101 is less than the reference concentration, the controller 107 sequentially opens and closes the opening and closing views of the second solenoid valve 105 and the first solenoid valve 103, respectively. The carbon dioxide of the PSA gas separator 70 is recycled in the first order, and the carbon dioxide of the gas storage tank 80 is recycled when the carbon dioxide of the PSA gas separator 70 is less than the reference concentration. At this time, the reference concentration can be varied according to the selection.

On the contrary, the controller 107 operates the first solenoid valve 103 and the second solenoid valve in the same manner as described above even when the gas concentration in the gasifier 10 measured by the concentration measuring sensor 101 exceeds the reference concentration. The opening and closing degrees of the 105 are sequentially controlled.

Hereinafter, a gasification method for generating hydrogen by recycling carbon dioxide separated from PSA according to the present invention will be described in detail with reference to FIGS. 2 and 3.

3 is a process diagram illustrating a gasification method for generating hydrogen by recycling carbon dioxide separated from the PSA according to the present invention.

First, water (H ₂ O), oxygen (O ₂ ), and carbon dioxide (CO ₂ ) are supplied into the gasifier 10 into which the polymer liquid waste or the polymer solid organic material is injected (S100). At this time, the controller 107 sequentially controls the opening and closing degrees of the second solenoid valve 105 and the first solenoid valve 103 to supply carbon dioxide into the gasifier 10, but the concentration measurement sensor 101 is performed. When the carbon dioxide concentration inside the gasifier 10 measured from the reference concentration is less than the reference concentration, as described above, the opening and closing degrees of the second solenoid valve 105 and the first solenoid valve 103 are sequentially controlled, respectively. 10) Adjust the concentration of carbon dioxide inside.

Then, the sensible heat of the decomposition gas flowing out from the gasifier 10 is recovered through the boiler 20 (S110), and the high-temperature decomposition gas discharged from the boiler is cooled through the cooler 30 (S120).

When the cooling of the decomposition gas is completed, dust of the decomposition gas is collected through the dust collector 40 (S130), and the collected decomposition gas is brought into contact with the cleaning material in the purifier 50 to acid gas (hydrogen sulfide or hydrogen chloride), Oxides (dioxin, SOx, NOx) are removed (S140).

Then, carbon monoxide (CO) and water vapor (H ₂ O) of the decomposition gas is reacted through the water gas shift reactor 60 to convert carbon dioxide and hydrogen (H ₂ ) (S150), the converted carbon dioxide and carbon dioxide in hydrogen To absorb the liquid through the PSA gas separator 70, and separates the hydrogen gas (S160).

As those skilled in the art would realize, the described embodiments may be modified in various ways, all without departing from the spirit or scope of the present invention. It is to be understood, however, that the present invention is not limited to the specific forms referred to in the description, but rather includes all modifications, equivalents, and substitutions within the spirit and scope of the invention as defined by the appended claims. Should be.

10: gasifier 20: boiler
30: cooler 40: dust collector
50: purifier 60: water gas conversion reactor
70: PSA gas separator 80: gas storage tank
90: gas circulation tube 100: concentration regulator
101: concentration measurement sensor 103, 105: first, second solenoid valve
107: controller

Claims (8)

A gas storage tank in which gaseous or liquid carbon dioxide (CO 2) is stored;
A gasifier connected to water (H 2 O), oxygen (O 2), and the gas storage tank and a gas supply pipe to a polymer liquid waste or a polymer solid organic material to receive carbon dioxide and perform gasification;
A boiler for recovering sensible heat of the decomposition gas flowing out of the gasifier;
A cooler for cooling the hot decomposition gas discharged from the boiler;
A dust collector for collecting dust of the decomposition gas after cooling is completed;
A purifier for removing the acid gas and the oxide by contacting the decomposed gas, which has been collected, with the cleaning material;
A water gas shift reactor for reacting carbon monoxide (CO) and water vapor (H 2 O) of the cracked gas to convert carbon dioxide and hydrogen (H 2);
A pressure swing adsorption (PSA) gas separator for absorbing the converted carbon dioxide and carbon dioxide in hydrogen in a liquid phase and separating hydrogen gas;
A gas circulation pipe interconnecting the PSA gas separator and the gasifier and recycling carbon dioxide inside the PSA gas separator to the gasifier; And
A concentration sensor for measuring the concentration of any one of carbon dioxide, hydrogen, carbon monoxide in the gasifier, a first solenoid valve provided in the gas supply pipe, a second solenoid valve provided in the gas circulation pipe, and When the gas concentration in the gasifier measured from the concentration sensor is less than the reference concentration, the second solenoid valve and the first solenoid valve are sequentially controlled so that the carbon dioxide of the PSA gas separator is recycled first. And a concentration controller including a controller for controlling carbon dioxide of the gas storage tank to be recycled at a second priority when the carbon dioxide of the PSA gas separator is less than the reference concentration, thereby maintaining the gas concentration within the gasifier within the reference concentration range. Recycling the separated carbon dioxide from the PSA, characterized in that Gasifier for generating a hydrogen-W. delete delete delete delete The method of claim 1,
The gas storage tank,
The liquid carbon dioxide absorbed by the PSA gas separator or gaseous carbon dioxide converted into a gas is stored, or external carbon dioxide is stored when the amount of carbon dioxide cannot be supplied in the process. Gasification device for generating. In the gasification method using a gasification apparatus for generating hydrogen by recycling the carbon dioxide separated from the PSA of claim 1,
A gasification process for performing gasification by supplying water (H ₂ O), oxygen (O ₂ ), and carbon dioxide (CO ₂ ) into a gasifier in which a polymer liquid waste or a polymer solid organic material is introduced;
A sensible heat recovery step of recovering sensible heat of the decomposition gas flowing out of the gasifier through a boiler;
A cooling step of cooling the hot decomposition gas discharged from the boiler through a cooler;
A dust collecting step of collecting dust of the decomposed gas which has been cooled through a dust collector;
A purifying step of removing the acid gas and the oxide material by contacting the decomposed gas, which has been collected, with the washings in a purifier;
A water gas shift reaction step of converting carbon monoxide (CO) and water vapor (H ₂ O) of the cracked gas into a carbon dioxide and hydrogen (H ₂ ) by reacting the same through a water gas shift reactor; And
Hydrogen is recycled by recycling the carbon dioxide separated from the PSA, which includes a separation process in which the converted carbon dioxide and carbon dioxide in hydrogen are absorbed in a liquid phase through a pressure swing adsorption (PSA) gas separator, and the hydrogen gas is separated. Gasification method that occurs. The method of claim 7, wherein
The gasification process,
Recycling the carbon dioxide inside the PSA gas separator to the gasifier, or supplying gaseous or liquid carbon dioxide stored in the gas storage tank to the gasifier to recycle the carbon dioxide separated from the PSA gas generation method.

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