KR102399818B1 - High Concentration Hydrogen-Methane Gas Generation Reactor System by Hydrothermal Gasification(HTG) and Electromethanogenesis Cell(EMC) Technology - Google Patents

Abstract

The present invention relates to a high concentration hydrogen-methane gas production reactor system using a hydrothermal gasification (HTG) system and electromethanogenesis cell (EMC) technology, which uses waste wood-based biomass as a raw material and comprises hydrothermal gasification (HTG) system, a gas separation membrane system, an electromethanogenesis cell (EMC) system, and a hydrogen-methane mixed gas storage tank system. The present invention shows the effect of producing biogas in a few hours by improving the conventional anaerobic digester-centered biogas production system, which takes a long reaction time, and the effect of providing a new production method that can significantly reduce the hydrogen production cost of the existing hydrogen production cost having a limitation in cost reduction due to the steam reforming method by producing hydrogen from the waste wood-based biomass.

Description

High Concentration Hydrogen-Methane Gas Generation Reactor System by Hydrothermal Gasification(HTG) and Electromethanogenesis Cell(EMC) Technology}

The present invention uses a catalyst to enable hydrothermal gasification at a relatively low temperature (300 to 450° C.) to produce hydrogen and methane from biomass, while electromethanization cell (EMC) reaction of carbon dioxide produced as a by-product in hydrothermal gasification It relates to a reactor system that enables the production of high-concentration hydrogen-methane synthesis gas by synthesizing it with methane.

The content described below merely provides background information related to the present invention and does not constitute the prior art.

A lot of research on eco-friendly treatment and energy conversion of various types of biomass or organic waste generated in daily life is being conducted.

Biomass refers to all plant resources originally generated by photosynthesis. Among them, lignocellulosic biomass refers to various types of wood, by-products, waste wood, and unused forest biomass, and other organic wastes include mushroom medium, vegetables , agricultural waste such as fruits; aquatic waste such as seaweed and seaweed; household waste, such as garden waste; means etc.

In the present invention, other organic wastes are included in the lignocellulosic biomass waste to be referred to as waste lignocellulosic biomass.

Various methods have been tried to utilize such waste wood-based biomass, and the most representative ones are energy conversion technology and fuel conversion technology.

These technologies include energy recovery technology through incineration, fuel conversion technology through dry or wet hydrothermal carbonization, low/high temperature pyrolysis, anaerobic digester, and gas fuel production technology through hydrothermal gasification reaction.

Although the pyrolysis technology is widely used as a method of directly burning the generated gas, there is a problem in that the organic waste with a lot of moisture and residues such as charcoal still remains after combustion, and the technology must be dried first.

Anaerobic digester technology can produce methane and use it as a fuel for a gas engine or use it for electricity production, but there is a problem in that the gas production period is short from a few weeks to a long one month or more.

Hydrothermal gasification reaction technology is a basic research stage that requires a lot of research for commercialization in the future as a technology capable of producing hydrogen under critical conditions (374° C. or higher), that is, in a supercritical water state. In the meantime, research on solid fuel conversion using hydrothermal carbonization technology has progressed a lot and has reached the commercialization stage, but hydrothermal liquefaction or hydrothermal gasification technology remains at the very basic laboratory level, so it is difficult to apply it.

On the other hand, according to the production method, gray hydrogen, which is represented by reformed hydrogen that reforms natural gas and by-product hydrogen produced as a by-product of an oil refinery, is blue, which reduces greenhouse gas by capturing and storing carbon dioxide emitted during the production of gray hydrogen. Hydrogen is divided into green hydrogen produced through water electrolysis as renewable energy power.

Among them, green hydrogen is the most environmentally friendly, but the water electrolysis technology itself has a problem that requires a high cost. The by-product hydrogen production method among gray hydrogen is a hydrogen production method that can be applied immediately, but it has a problem of being a very eco-friendly technology that emits 10 tons of carbon dioxide for 1 ton of hydrogen production.

Currently, the most commonly used method of hydrogen production is the reformed hydrogen method. Most of the reformed hydrogen produces hydrogen through reforming (reforming) from C1-chemistry of methane (CH4), and there are technologies such as steam catalytic reforming, catalytic and non-catalytic partial oxidation, carbon dioxide reforming, and thermal decomposition. Steam catalytic reforming is the most commonly used in

Patent Document 1: Republic of Korea Patent Publication No. 10-1251025 (A device and method for producing syngas that have been pyrolyzed and gasified by dry fluidized bed method using waste tangerines) Patent Document 2: Republic of Korea Patent Publication No. 10-2015-0014917 (biomass gasification device) Patent Document 3: Republic of Korea Patent Publication No. 10-1530662 (tar removal device and removal method for biomass waste reformer) Patent Document 4: Republic of Korea Patent Publication No. 10-1775010 (Anaerobic wastewater treatment system combining pressure delayed osmosis and bioelectrochemical system)

The problem to be solved by the present invention is a wet process that conventional pyrolysis technology could not do for gasification from waste wood-based biomass, and within 1 to 2 hours, which is much shorter than an anaerobic digester, using a solid catalyst. It is to provide a hydrothermal gasification (HTG) system capable of producing methane and hydrogen in a supercritical state of 300° C. to 450° C. without raising it to a high supercritical state like hydrothermal gasification of.

In order to solve the problem that was only possible at the supercritical temperature of 700 to 800 ° C of the existing hydrothermal gasification reaction, by using a solid catalyst and mixing the solid catalyst and reactants to sufficiently react, the hydrothermal gasification reaction temperature can be lowered to 450 ° C or less. It is to provide a hydrothermal gasification (HTG) system to which a solid catalyst is applied.

In addition, since approximately 50% of the gas produced by the hydrothermal gasification (HTG) reaction is carbon dioxide (CO ₂ ) as a by-product, in order to solve the problem of synthesizing it into methane, which is a combustible biogas, in the hydrothermal gasification (HTG) system Electro-methanization cell (EMC), which consumes less energy and combines an electromethanization cell (EMC) that can convert most of carbon dioxide into methane, and at the same time has a slow reaction time compared to hydrothermal gasification, which has a fast reaction time of less than 1 hour It is to provide an improved electromethanization cell (EMC) system that can speed up the methanation reaction of

In order to achieve the above object, the high-concentration hydrogen-methane gas production reactor system utilizing the hydrothermal gasification (HTG) and electro-methanization cell (EMC) technology achieved through the present invention is largely composed of four systems.

That is, first, it is composed of a hydrothermal gasification (HTG) system, second, a gas separation membrane system, third, an electromethanegenesis cell (EMC) system, and fourth, a hydrogen-methane mixed gas storage system.

First, a hydrothermal gasification (HTG) system includes a hydrothermal gasification body; a raw material supply unit for supplying waste wood-based biomass to the hydrothermal gasification body; an oxidizing agent supply unit for supplying an oxidizing agent through a rotary injection nozzle installed inside the hydrothermal gasification body; and a control unit. More specifically, the hydrothermal gasification (HTG) system is a pulverizer that pulverizes waste wood-based biomass to a size of 0.5 mm or less, a raw material supply conveyor, a pretreatment supply device including a water supply device, and energy to a hydrothermal gasification (HTG) reactor. Hydrothermal gasification with a solid catalyst equipped with an energy supply device such as a steam boiler or hot wire to supply It consists of a HTG) reactor and a storage tank that collects the remaining biochar after the reaction.

Second, the gas separation membrane system receives a mixed gas such as hydrogen, methane, and carbon dioxide generated in the hydrothermal gasification system, selectively separates only carbon dioxide, and supplies it to the electromethanization cell (EMC) system, and the hydrogen and methane mixed gas is hydrogen-methane As sent to the mixed gas storage system, the gas separation membrane lowers the temperature of hydrogen, methane, carbon dioxide, and carbon monoxide and other small amounts of other gases produced through the hydrothermal gasification (HTG) reaction through a heat exchanger, and separates carbon dioxide from it to make it smaller. It is pumped through the electromethanization cell (EMC). In this case, a polymer membrane is mainly used, and the mixed gas of hydrogen and methane is stored together in a separate storage device.

Third, the electromethanization cell (EMC) system converts the carbon dioxide supplied from the gas separation membrane system into methane and sends it to the hydrogen-methane mixed gas storage system. An abiotic anode and a bioreduction electrode ( Biocathode) and an external electricity supply device. The electromethanization cell (EMC) is first filled with water. The abiotic anode, which produces hydrogen cations (H+) from water by electrolysis, and microorganisms while blocking the oxygen supply are used as a kind of catalyst. Hydrogen cations (H+) generated at the abiotic anode are combined with electrons (e-) supplied from the outside to make hydrogen, and this hydrogen is combined with carbon dioxide supplied from the product gas separation membrane to convert it to methane a biocathode, and a hydrogen ion selective separation membrane (PEM: Proton Exchange Membrane) that allows only hydrogen cations (H+) to pass from the abiotic anode to the biocathode between these electrodes. ), and a current supply that supplies current at a low voltage from the outside. The methane gas reduced in the electromethanization cell (EMC) is stored in a hydrogen-methane mixed gas storage tank connected to a gas separation membrane. Oxygen and water generated in the electromethanization cell may be used as an oxidizing agent/fluidizing agent in a hydrothermal gasification reactor and a reaction solution in a bioreduction electrode, respectively. The reaction time of an electromethanization cell (EMC) is usually more than 24 hours, which is not suitable for receiving the gas generated in a hydrothermal gasification (HTG) reactor with a reaction time of less than 1 hour. ) and connect in parallel with the separation gas membrane.

A control unit that adjusts the temperature and pressure of hydrothermal gasification (HTG) as needed, a gas supply pump control unit after the gas separation membrane, an electromethanization cell (EMC) current supply unit control unit, an electromethanization cell (EMC) stack A control unit is installed.

The waste wood-based biomass supplied from the raw material supply unit includes wood-based biomass wastes such as various types of wood and by-products, waste wood, and unused forest biomass. And, for convenience, the waste wood-based biomass is agricultural waste such as mushroom medium, vegetables, and fruits; aquatic waste such as seaweed and seaweed; Household waste such as garden waste; shall include organic waste including;

The hydrothermal gasification (HTG) reaction region is characterized by utilizing supercritical water (400° C. to 450° C.) in thermodynamic phase equilibrium. The gasification process using a nickel (Ni) catalyst, etc. is as follows.

Cellulose ---(decomposition)--> aqueous liquid --(gasification/Ni)--> gas (H ₂ + CO ₂ )

--(Methanation/Ni)--> Gas (CH ₄ + CO ₂ )

The methanation reaction of carbon dioxide through the electromethanization cell (EMC) reaction using the electrolysis reaction by external electricity supply with bacteria such as methane bacteria is as follows.

Abiotic Anode: 4H ₂ O <--> 8H ⁺ + 2O ₂

Microorganism: 8H⁺ + 8e^-<--> 4H₂

Biocathode: CO ₂ + 8H ⁺ + 8e ^- <--> CH ₄ + 2H ₂ O

In an embodiment of the present invention, a mixed gas of hydrogen (35%) and methane (55%) produced from waste wood-based biomass may be mixed with LNG used in a combined cycle power plant, and this mixed gas is renewable energy As the mandatory use of renewable energy according to the Renewable Portfolio Standard (RPS) will increase to 10% by 2023 and continue to rise thereafter, the LNG fuel based on the existing fossil fuel will be reduced and the RPS regulation will also be applied. It shows a satisfying effect.

In addition, it exhibits the effect of producing hydrogen and methane by using waste resources such as waste wood-based biomass, and provides an eco-friendly hydrogen and methane production method close to green hydrogen by supplying additional carbon dioxide and methanating it. to indicate the effect.

In addition, the high-concentration hydrogen-methane gas production reactor system using hydrothermal gasification (HTG) and electromethanization cell (EMC) technology, in which waste wood-based biomass is treated in just a few hours through the present invention, is currently It is to provide an effect that can replace the anaerobic digester that takes several weeks to process the mass.

In addition, if the purpose is only to produce hydrogen, carbon dioxide (CO ₂ ) produced together with methane is reacted to form synthesis gas, thereby enabling additional hydrogen production in the Water-Gas Shift method using methane and carbon monoxide. The hydrogen produced in this way can be used not only for industrial purposes, but also has the effect of enabling the production of high-purity hydrogen through a PSA (Pressure Swing Adsorption) device.

And, in the present invention, the waste wood-based biomass, which is a raw material for hydrogen, can rather receive a treatment cost, thereby exhibiting the effect of significantly lowering the hydrogen production cost. Specifically, natural gas, the most common hydrogen production method at present In the steam reforming method used for reforming, the total hydrogen production cost is about 8,000 won per kg, but the high-concentration hydrogen-methane gas production reactor system using the hydrothermal gasification (HTG) and electromethanization cell (EMC) technologies proposed in the present invention Hydrogen production from waste lignocellulosic biomass using

1 is an overall configuration diagram of a high-concentration hydrogen-methane gas production reactor system using hydrothermal gasification (HTG) and electromethanization cell (EMC) technology according to an embodiment of the present invention.
2 is a block diagram of a hydrothermal gasification (HTG) system according to an embodiment of the present invention.
3 is a block diagram of a hydrothermal gasification (HTG) body according to an embodiment of the present invention.
4 is a block diagram of an electromethanization cell (EMC) system according to an embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings, the embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily implement them. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the specification, when a part "includes" a certain element, it means that other elements may be further included, rather than excluding other elements, unless otherwise stated.

1, the high-concentration hydrogen-methane gas production reactor system using hydrothermal gasification (HTG) and electromethanization cell (EMC) technology according to an embodiment of the present invention uses waste wood-based biomass as a raw material, It will include a hydrothermal gasification (HTG) system 100 , a gas separation membrane system 200 , an electromethanization cell (EMC) system 300 , and a hydrogen-methane mixed gas storage system 400 .

It will be described in more detail below.

First, the hydrothermal gasification (HTG) system 100 is a system capable of hydrothermal gasification (HTG) of waste wood-based biomass by receiving external energy (electrical energy or steam) supply, and hydrogen (H ₂ ) 30 to 35 %, methane (CH ₄ ) (10 to 15%), carbon dioxide (CO ₂ ) 40 to 45% are produced, and after the final reaction, biochar is discharged from the hydrothermal gasification (HTG) system 100 .

Second, the gas separation membrane system 200 receives a mixed gas of hydrogen, methane, carbon dioxide, etc. generated in the hydrothermal gasification (HTG) system 100, selectively separates only carbon dioxide, and an electromethanization cell (EMC) system ( 300), and the hydrogen and methane mixed gas are sent to the hydrogen-methane mixed gas storage system 400 and stored.

Third, the electromethanization cell (EMC) system 300 converts the carbon dioxide supplied from the gas separation membrane system 200 into methane and sends it to the hydrogen-methane mixed gas storage system 400, and thus abiotic oxidation Electrode (Abiotic Anode) 34 and bio-reduction electrode (Biocathode) (33), as including the electrical supply device (35), by supplying electrical energy from the outside, 40-45% of carbon dioxide at a time of 35-40% The electromethanization cell (EMC) 31 that converts methane is configured in a parallel stack to process a large amount of carbon dioxide at once, and the produced methane is sent to the hydrogen-methane mixed gas storage system 400 .

2 and 3 , a hydrothermal gasification (HTG) system according to an embodiment of the present invention is a hydrothermal gasification system including a reactor body 110 that uses waste woody biomass as a raw material and performs hydrothermal gasification therein. As a gasification reactor system, a stirrer 14 for mixing raw materials inside the reactor 11, a raw material inlet 16 connected to the raw material supply unit, and a biochar outlet 13 for discharging the remaining biochar after the reaction, are generated Synthesis gas outlet 20 for sending the exhausted gas to the membrane 200, a gas outlet plate 22 made in a tapered shape that leaves the solid catalyst 21 in the reactor and discharges only the syngas, the remaining a gas outlet 18, a thermocouple 17 for temperature measurement, a pressure gauge 15, a safety valve 19, and a body portion 110 consisting of a heating wire 12 for supplying heat to the reactor;

a raw material supply unit 120 for performing a hydrothermal gasification reaction by quantitatively supplying waste wood-based biomass to the hydrothermal gasification reactor 11;

An oxidizing agent supply unit 150 for inducing a gasification activation reaction of the hydrothermal liquefied waste wood-based biomass by supplying an oxidizing agent (steam) through the rotary injection nozzle 23 installed at the lower end of the main body 110;

It is characterized in that a control valve is installed in a vent line to control the pressure and flow rate of the oxidizer (water vapor) supplied to the reactor 11 of the main body 110 .

In order to improve the performance of hydrothermal liquefaction and gasification in the process of hydrothermal liquefaction and gasification with the solid raw material supplied to the reactor 11, the catalyst 21, which induces an exothermic reaction by replacing the general layer material, is used as a layer material and filled in the pre-bed. It is characterized by operation.

A heater 130 provided outside the reactor for supplying heat through a jacket-type heating wire 12 is included in order to control the internal reaction temperature of the main body 110 .

It further includes a control unit 140 as necessary, and controls driving of the raw material supply unit 120 , the oxidizer supply unit 150 , and the heater 130 . In addition, it controls the operation of the stirrer 14 of the main body 110 and displays and stores the data of the thermocouple 17 and the thermometer 15 .

The raw material supply unit supplies the raw material by means of a screw and a feeder, and the raw material meets high-temperature steam and the reactor 11 of the main body 110 to crack the carbon compounds of the waste wood-based biomass to generate hydrogen and methane. .

Here, in the hydrothermal gasification (HTG) reactor 11 of the reactor hydrothermal gasification (HTG) body part 110, the waste wood-based biomass is hydrothermalized and gasified with internal high-temperature steam, and the gas generated during hydrothermal gasification In the hydrothermal gasification (HTG) reactor 11, the hydrogen-methane mixed gas storage tank system 400 ) to exit.

In an embodiment of the present invention, a catalytic chemical reaction may occur in a short time with the hydrothermal gas produced by hydrothermal liquefaction and gasification in the hydrothermal gasification (HTG) reactor 11 of the hydrothermal gasification (HTG) body part 110, the temperature And through the oxidizing agent (steam) supply unit 150 under the condition that the pressure is not lowered, the size of the oxidation reaction of the generated hydrogen, methane, and carbon dioxide gas can be adjusted.

To this end, the catalyst for inducing an exothermic reaction in the hydrothermal gasification (HTG) body part 110 is one or a mixture thereof selected from the group consisting of sodium, tungsten, cobalt, molybdenum, and nickel, for example, 1.35 to 3.45 weight. % of Na and 1.24 to 2.73% by weight of Ni may be mixed, and a cocatalyst may be further included. Here, the catalyst is purified to enable the production and production of hydrogen and methane gas.

The gas separation membrane system 200 that separates carbon dioxide (CO ₂ ) from the gas generated in the hydrothermal gasification (HTG) system 100 has a selectivity of CO ₂ /CH ₄ like DDR type zeolite exceeds 100 and is relatively resistant is less and the transmittance is fast.

Referring to FIG. 4 , the electromethanization cell (EMC) system 300 according to the embodiment of the present invention converts carbon dioxide filtered through the gas separation membrane system 200 into a trace amount of electrical energy and methane bacteria 36 ) as a cell-type electromethanization cell (EMC) 31 system that converts it to methane using

The electromethanization cell (EMC) 31 filled with water is largely composed of an abiotic anode 34 that produces hydrogen cations (H+) from water by electrolysis; and an abiotic anode electrode. Anode) (34), the hydrogen cation (H+) and the electrons (e-) supplied from the outside are combined to make hydrogen, and a biocathode (33) that combines with the supplied carbon dioxide to convert it into methane; and a hydrogen ion selective separation membrane (PEM: Proton Exchange Membrane) that allows only hydrogen cations (H+) to pass from the anode to the cathode between the two (32); and an electric supply device 35 for supplying electricity at a low voltage from the outside.

The abiotic anode 34 receives 4 moles of water through the water inlet 40 and causes electrolysis to produce hydrogen cations (H+) and sends them to the membrane 32, and 2 moles of oxygen (O ₂ ) is discharged through the oxygen outlet (41). In this case, the abiotic anode 34 is made of a carbon-based material such as graphite.

The cation exchange membrane (PEM: Proton Exchange Membrane) (32) serves as a separator that selectively passes only hydrogen cations (H+) between the anode (34) and the biocathode (33). It is made of a fluoropolymer material and used as an ion exchange function do.

The biocathode 33 is used as a kind of catalyst by putting bacteria 36 such as methane bacteria while blocking the oxygen supply, and supplying external electricity to the hydrogen cations (H+) that have passed through the membrane 32 . Combined with electrons (e-) supplied from the device 35, converted into hydrogen (H ₂ ) and combined with 1 mole of carbon dioxide supplied to the carbon dioxide supply pipe 37 from the gas separation membrane system 200 that allows carbon dioxide to pass through Thus, 2 moles of water (H ₂ O) and 1 mole of methane (CH ₄ ) are discharged through the water discharge pipe 39 and the methane exhaust pipe 38, respectively. The methane gas reduced in EMC is stored in the hydrogen-methane mixed gas storage system 400 connected to the gas separation membrane system 200 . Biocathode uses carbon-based materials such as graphite.

EMC reaction time usually takes more than 24 hours, so it is not suitable to receive and process the gas generated from the HTG reactor, which takes only 1 hour. An electric methanation cell stack in which several electric methanation cells are connected in parallel to produce hydrogen and methane mixed gas is provided.

In addition, electrons flow from the abiotic anode to the biocathode 33 through the supply of a small amount of electricity of 1V or less through the electricity supply device 35 that enables electrolysis.

If necessary, the control unit 140 for hydrothermal gasification is connected to the gas separation membrane system 200 and the electromethanization cell (EMC) system 300, and a small pump of the membrane and external electricity supply of the electromethanization cell (EMC) system Controls the operation of the device 35 and other peripheral devices of the electromethanization cell (EMC) system 300 .

The operation of the hydrothermal gasification (HTG) system and the electromethanization cell (EMC) system according to an embodiment of the present invention having such a configuration will be described as follows.

First, in a state in which the hydrothermal gasification (HTG) reactor 11 of the hydrothermal gasification (HTG) body 110 is filled with a layer material with a catalyst, the raw material pulverized into 0.5 mm or less in the raw material supply unit 120 is hydrothermal gasified ( HTG) is supplied to the reactor 11 .

Thereafter, the oxidizing agent (steam) is supplied through the oxidizing agent (steam) supply rotary injection nozzle 23 installed at the bottom of the hydrothermal gasification (HTG) reactor 11, the fuel is stirred with the stirrer 14, and the fuel is stirred with an external heater ( Heat is supplied through the jacket-type heating wire 12 connected to 130). When the temperature of the hydrothermal gasification (HTG) reactor 11 rises to 300-350° C. with a heat source supplied from steam and a hot wire, it first undergoes a hydrothermal liquefaction process by the raw material and steam filled therein.

In the hydrothermal gasification (HTG) reactor 11, the hydrothermal liquefaction process proceeds smoothly, and when the internal temperature is raised to 400-450° C., the heat required for the gasification reaction, which is an endothermic reaction, is supplied, causing an endothermic reaction with steam to generate a maximum of 35 hydrogen. %, methane gas will be produced up to 10%.

Here, the synthesis gas moves from the upper part to the membrane 200 through the micropores of the gas discharge plate 22, and when the reaction is completed within 1-2 hours at most, the residual gas is discharged through the residual gas outlet 18. After the reaction, the remaining solids and liquids are discharged through the biochar outlet 13 .

In addition, the amount of raw material to be filled in the reactor and the purpose of heating in the form of steam as well as the amount and supply speed of the oxidizing agent supplied for fluidization can be adjusted through the control unit 140, and when the target temperature and pressure are reached, the stirrer 14 ) to maintain the flow of raw materials continuously.

The mixed gas generated in the above hydrothermal gasification (HTG) system 100 is hydrogen (H ₂ ) 30 to 35%, methane (CH ₄ ) 10 to 15%, carbon dioxide (CO ₂ ) 40 to 45% is composed of There, this mixed gas passes through a heat exchanger, etc. to lower the temperature, and then is sent to the gas separation membrane system 200 including a DDR-type zeolite membrane, and there, the CO ₂ is separated and sent to the electric methanation cell 300. The remaining hydrogen and methane are sent to the mixed gas storage tank (400). At this time, the gas is moved using the pressure of the gas remaining in the hydrothermal gasification reactor 11 . The carbon dioxide supplied through the DDR type zeolite membrane is moved by a small pump to the electromethanization cell (EMC) system 300 already prepared for the methanation process.

The abiotic anode (34) room of the electromethanization cell (EMC) (31) is pre-filled with pure water or electrolyte supplied to the inlet (40), and the biocathode (33) room is It is marinated in pure water or a microbial culture medium and contains microorganisms such as methane bacteria (36) under anaerobic conditions.

When a small amount of current of 1V or less is supplied through the electricity supply device 35, electrons (e-) flow from the abiotic anode 34 to the biocathode 33, and at this time As electrolysis occurs, hydrogen cations (H+) generated at the anode 34 pass through the hydrogen ion selective permeation membrane (PEM) 32, and hydrogen (H ₂ ) is generated at the biocathode (33) and Methane (CH ₄ ) is formed by meeting with carbon dioxide (CO 2 ) filtered through the membrane 200 and introduced through the carbon dioxide inlet, in which case the methanation rate is about 1 ml/day cm 2 .

At this time, the generated methane is collected in the hydrogen-methane mixed gas storage system 400 through the methane exhaust pipe 38, and the generated water is discarded through the water discharge pipe 39 or to the biocathode 33 room. will be recycled On the other hand, oxygen (O ₂ ) made in the abiotic anode (34) is discarded through the outlet or bitten by the oxidizer (steam) supply rotary injection nozzle (23) of the HTG reactor (11) to the reactor. It may also help the oxidation reaction of

In the system of the present invention, various waste wood-based biomass can be used regardless of the type, and finally produced hydrogen (H ₂ ) is 30 to 35%, methane (CH ₄ ) is 45 to 55%, carbon dioxide (CO ₂ ) ) is 2 to 5%.

Hydrothermal gasification (HTG)-electromethanization cell (EMC) reactor system according to an embodiment of the disclosed technology has been described with reference to the embodiment shown in the drawings for better understanding, but this is only exemplary, and is common in the art It will be understood by those skilled in the art that various modifications and equivalent other embodiments are possible therefrom. Accordingly, the true technical protection scope of the disclosed technology should be defined by the appended claims.

100: Hydrothermal gasification (HTG) system
200: gas separation membrane system
300: electric methanation cell (EMC) system
400: hydrogen-methane mixed gas storage system
110: Hydrothermal gasification (HTG) body part
120: raw material supply unit
130. Heater
140: control unit
150: oxidizing agent (steam) supply unit
11: Hydrothermal gasification (HTG) reactor
12: jacket type heated wire
13: biochar outlet
14: agitator
15: pressure gauge
16: raw material input port
17: thermocouple
18: residual gas outlet
19. Safety valve
20: gas outlet
21: solid catalyst
22: gas exhaust plate
23: Oxidizing agent (steam) supply rotary type injection nozzle
31: electric methanation cell (EMC)
32: hydrogen ion selective separation membrane (PEM)
33: Biocathode
34: Abiotic Anode
35: electricity supply device
36: methane bacteria
37: carbon dioxide supply pipe
38: methane exhaust pipe
39: water discharge pipe
40: water inlet pipe
41: oxygen exhaust pipe

Claims (12)

A hydrothermal gasification (HTG) system using waste wood-based biomass as a raw material and hydrothermal gasification of the biomass to produce a gas containing carbon dioxide, methane and hydrogen, a gas separation membrane system for separating carbon dioxide from the gas; Hydrothermal gasification (HTG) and electromethanization cell (EMC) technology, including an electromethanization cell (EMC) system for converting the separated carbon dioxide into methane, and a hydrogen-methane mixed gas storage system for mixing and storing the hydrogen and the methane In the high-concentration hydrogen-methane gas production reactor system using
The hydrothermal gasification (HTG) system,
Hydrothermal gasification body part comprising 1.35 to 3.45 wt% of Na and 1.24 to 2.73 wt% of Ni as a catalyst for inducing an exothermic reaction, and further comprising a cocatalyst;
a raw material supply unit for supplying waste wood-based biomass to the hydrothermal gasification body;
an oxidizing agent supply unit for supplying an oxidizing agent through a rotary injection nozzle installed inside the hydrothermal gasification body; and a control unit; a high-concentration hydrogen-methane gas production reactor system using hydrothermal gasification (HTG) and electro-methanization cell (EMC) technology, comprising: a.
delete According to claim 1, wherein the gas separation membrane system,
Receive a mixed gas of hydrogen, methane, carbon dioxide, etc. generated in the hydrothermal gasification system, selectively separate only carbon dioxide, supply it to an electromethanization cell (EMC) system, and send the hydrogen and methane mixed gas to a hydrogen-methane mixed gas storage system A high-concentration hydrogen-methane gas production reactor system using hydrothermal gasification (HTG) and electromethanization cell (EMC) technology.
According to claim 1, wherein the electromethanization cell (EMC) system,
Converting carbon dioxide supplied from the gas separation membrane system into methane and sending it to the hydrogen-methane mixed gas storage system, including an abiotic anode and a biocathode, and an external electricity supply device High-concentration hydrogen-methane gas production reactor system using hydrothermal gasification (HTG) and electromethanization cell (EMC) technology, characterized in that.
According to claim 1, wherein the hydrothermal gasification (HTG) system,
Hydrothermal gasification (HTG) and electromethanization cell (EMC) technology, characterized in that a control valve is installed in a vent line to control the pressure and flow rate of air and oxidizer supplied to the hydrothermal gasification body part High-concentration hydrogen-methane gas production reactor system.
delete delete According to claim 1, wherein the hydrothermal gasification (HTG) system,
Hydrothermal gasification (HTG) and electromethanization cell (EMC) technology, characterized in that the injection nozzle of the oxidizing agent supply part is extended and formed in a rotational injection method on the inner lower part of the hydrothermal gasification body to create a fluidized bed. High-concentration hydrogen-methane gas production reactor system.
The method of claim 3, wherein the gas separation membrane system comprises:
Hydrothermal gasification (HTG) characterized in that the temperature of mixed gases such as hydrogen, methane, and carbon dioxide generated in the hydrothermal gasification (HTG) system is lowered through a heat exchanger, and carbon dioxide is separated from it and transferred to an electromethanization cell (EMC) through a small pump ( High-concentration hydrogen-methane gas production reactor system using HTG) and electromethanization cell (EMC) technology.
5. The method of claim 4, wherein the electromethanization cell (EMC) system comprises:
Utilize hydrothermal gasification (HTG) and electromethanization cell (EMC) technology, which facilitates the hydrogenation process of hydrogen ions and promotes methanation of carbon dioxide by injecting and attaching methane bacteria to the biocathode A high-concentration hydrogen-methane gas production reactor system.
5. The method of claim 4, wherein the electromethanization cell (EMC) system comprises:
An electric methanation cell stack in which several electric methanation cells are connected in parallel to produce a hydrogen and methane mixed gas by rapidly processing a mixed gas such as hydrogen, methane, and carbon dioxide, which are rapidly generated in the hydrothermal gasification system, characterized in that High-concentration hydrogen-methane gas production reactor system using hydrothermal gasification (HTG) and electromethanization cell (EMC) technology.
The method of claim 1,
Hydrothermal gasification (HTG) and electromethanization cell (EMC) technology, characterized in that oxygen and water generated in the electromethanization cell are used as an oxidizer/fluidizer of a hydrothermal gasification reactor and a reaction solution of a bioreduction electrode, respectively A high-concentration hydrogen-methane gas production reactor system.

Images