KR102561052B1 - Hydrothermal Gasify Fluidized Bed Reactor for Hydrogen and Methane Gas Generation - Google Patents

Abstract

The present invention relates to a hydrothermal gasification fluidized bed reactor for producing hydrogen and methane, in particular, a fluidized bed reactor using organic waste or woody biomass as a raw material and having a hydrothermal gasification zone therein, comprising a reaction zone and a gasification zone. And, the reaction region and the gasification region are separated by an intermediate separator body portion; An air supply unit supplying external air, high-temperature air and nitrogen heated by a pre-heater to the fluidization zone to raise the temperature of the fluidized bed to form a hydrothermal gasification atmosphere; a raw material supply unit supplying wood-based biomass or organic waste to the reaction zone for hydrothermal liquefaction and gasification; An oxidizing agent supply unit for supplying an oxidizing agent through a rotary injection nozzle installed inside the body unit; and a heater provided outside the reactor to control an internal reaction temperature of the fluidized bed reactor.
According to the present invention, the efficiency of the hydrothermal gasification process is increased, the condensation of the oxidizing agent is prevented, the size of the oxidation reaction is controlled, and the hydrothermal gasification and catalytic chemical reaction area is expanded to obtain hydrogen (H ₂ ) and methane (CH _{4 )} . ) can provide a fluidized bed reactor capable of producing gas.

Description

Hydrothermal Gasify Fluidized Bed Reactor for Hydrogen and Methane Gas Generation}

The present invention relates to a fluidized bed reactor using a catalyst capable of generating hydrogen and methane from organic waste by enabling a hydrothermal gasification reaction under subcritical conditions.

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

Many studies are being conducted on environmentally friendly treatment and energy conversion of various types of biomass or organic wastes generated in daily life.

Biomass refers to various types of wood, by-products, and waste wood, and organic waste refers to various food processing wastes such as alcohol residue, coffee grounds, bean curd, beans, red beans, sweet potatoes, and potatoes; Agricultural waste such as mushroom broth, vegetables and fruits; Livestock waste such as cow manure, pig manure, chicken manure, and animal carcasses; aquatic wastes such as fish, oysters, seaweed, and seaweed; Wastewater sludge, food waste, coffee grounds, and household waste such as garden waste, etc. It refers to waste generated daily in life, agriculture, fisheries, and industry.

Various methods for utilizing organic waste have been attempted, and the most representative is a technology for energy conversion or fuel conversion. Energy recovery through incineration, fuel conversion through dry or wet hydrothermal carbonization, low-temperature/high-temperature pyrolysis, anaerobic digestion, and gaseous fuel production through hydrothermal gasification. Pyrolysis is widely used as a method of direct combustion of the generated gas, and the disadvantage is that residues such as charcoal still remain and organic waste with a lot of moisture must first be dried before application of the technology is possible. Anaerobic digesters can produce methane and use it as a fuel for gas engines and for electricity production, but there is a problem in that the gas production period takes from a few weeks to a month or more. Hydrothermal gasification is a technology that can produce hydrogen under supercritical conditions (above 374°C), that is, supercritical water, and is a basic research step that requires a lot of research for commercialization in the future. In the meantime, many studies on solid fuel conversion using hydrothermal carbonization technology have been conducted and have reached the commercialization stage, but hydrothermal liquefaction or gasification technology is at an extremely basic laboratory level.

Depending on the production method, gray hydrogen represented by reformed hydrogen that reforms natural gas and by-product hydrogen generated as a by-product of oil refineries, blue hydrogen that reduces greenhouse gases by capturing and storing carbon dioxide generated during gray hydrogen production, and renewable It is divided into green hydrogen produced through water electrolysis as energy power. Of these, green hydrogen is the most environmentally friendly, but water electrolysis technology itself requires high costs. The by-product hydrogen production method among gray hydrogen is a very anti-environmental technology that emits 10 tons of carbon dioxide per ton of hydrogen produced, but it is a hydrogen production method that can be supplied immediately. Among the current hydrogen production methods, the most commonly used method is the reformed hydrogen method. Most reformed hydrogen produces hydrogen through reforming (reforming) from C1-chemistry of methane (CH4). There are technologies such as steam catalytic reforming, catalytic and non-catalytic partial oxidation, carbon dioxide reforming, and pyrolysis. Steam catalytic reforming is the most commonly used.

Patent Application No. 10-2011-0050251/ 10-1251025-0000 Syngas production device and method for pyrolysis and gasification using dry fluidized bed method using waste tangerines Patent Application No. 10-2011-0053056/ 10-1285879-0000 Apparatus for obtaining bio-crude oil through fluidized bed rapid pyrolysis Patent application No. 10-2014-7031052 biomass gasification device Patent application No. 10-2013-0066396 Tar removal device and method for biomass waste reformer

The problem to be solved by the present invention is a wet process that conventional pyrolysis technology could not do for gasification of biomass and organic waste, and in a much shorter time than an anaerobic digester, but not raised to a high supercritical state like hydrothermal gasification To produce methane and hydrogen within 1-2 hours, we want to achieve gasification that was only possible under supercritical conditions by using a solid catalyst in a subcritical liquefaction state of 300 ° C - 400 ° C.

The reactor used in conventional hydrothermal carbonization was a batch method in which the reaction temperature and pressure were raised to a maximum of 250℃ and 40 bar, and the reactants were taken out after 1-4 hours in a closed state to separate solids and wastewater, but hydrogen/methane gasification The reactor must be able to raise the temperature up to 400℃ and 215 bar, and mixing is required so that the solid catalyst and reactants to be used can sufficiently react, and the hydrogen and methane produced can be continuously recovered even before the reaction is completed. Continuous hydrothermal It must be a gasification reactor.

The fluidized bed reactor achieved through the present invention in order to achieve the above object,

A fluidized bed reactor using biomass or organic waste such as wood as a raw material and having a hydrothermal gasification region therein,

A main body having a reaction region and a gasification region, the reaction region and the gasification region being separated by an intermediate separator;

An air supply unit supplying external air, high-temperature air and nitrogen heated by a pre-heater to the fluidization zone to raise the temperature of the fluidized bed to form a hydrothermal gasification atmosphere;

a raw material supply unit supplying biomass or organic waste to the reaction zone for thermal decomposition;

An oxidizing agent supply unit for supplying an oxidizing agent through a rotary injection nozzle installed inside the body unit; and

and a heater provided outside the reactor to control the internal reaction temperature of the fluidized bed reactor.

It is characterized in that a control valve is installed in the vent line to control the pressure and flow rate of the fluidizing agent (nitrogen), air, and oxidizing agent (steam) supplied to the reaction area of the main body.

A control unit is further included as needed, and the control unit controls driving of the control valve and the heater.

It is characterized in that the prebed is filled and operated by using a solid raw material supplied to the reaction zone and a catalyst that induces an exothermic reaction by replacing a general layer material to improve the performance of liquefaction and gasification in the hydrothermal liquefaction process.

The injection nozzle of the oxidizing agent supply unit extends and is formed in a rotary spraying method at the inner lower part of the reaction region, and the heater is mounted outside the main body to prevent condensation of the oxidizing agent.

The raw materials supplied from the raw material supply unit include various types of wood-based wood and by-products, biomass such as waste wood, alcohol residue, coffee grounds, bean curd, beans, red beans, sweet potatoes, potatoes, and various food processing wastes; Agricultural waste such as mushroom broth, vegetables and fruits; Livestock waste, such as cow manure, pig manure, chicken manure, and animal carcasses; aquatic wastes such as fish, oysters, seaweed, and seaweed; It includes at least one of domestic wastes such as sewage sludge, food waste, and garden waste.

The reaction zone is characterized by utilizing subcritical water (300 ° C to 400 ° C) in thermodynamic phase equilibrium. The gasification process using a nickel (Ni) catalyst is as follows.

Cellulose --- (decomposition) --> water soluble liquefied -- (gasification/Ni) --> gas (H ₂ + CO ₂ )

--(methanation/Ni)--> gas (CH ₄ + CO ₂ )

In an embodiment of the present invention, the sample supply device is configured horizontally at the bottom of the fluidized bed reactor to increase the efficiency of the hydrothermal gasification process, and the fluidizing agent (nitrogen) and gasifying agent (air) are preheated in a gas preheater and introduced from the bottom of the reactor , The supplying part of the oxidizing agent (steam) is placed between them (between the pre-beds) and wrapped with a ceramic board heater to prevent condensation of the oxidizing agent (steam), and the supply method of the oxidizing agent is changed to a rotary injection method, Existing reaction layer material capable of producing hydrogen (H ₂ ) and methane (CH ₄ ) by controlling the size of the oxidation reaction by making it easy to mix with the supplied gas and expanding the area of hydrothermal gasification and catalytic chemical reaction It is possible to provide a fluidized bed reactor in which (sand, alumina) is replaced with a solid catalyst.

In addition, the hydrothermal gasification fluidized bed reactor for methane production, which is produced in just a few hours through the present invention, can replace anaerobic digesters that require several weeks of treatment time for current food waste, sewage sludge, and livestock wastewater treatment. In addition, when carbon dioxide (CO ₂ ) produced together with methane is reacted to syngas, additional hydrogen production using the Water-Gas Shift method using methane and carbon monoxide is possible. The hydrogen produced in this way can be used for industrial purposes in a low purity state, and can lead to high purity hydrogen production through a PSA (Pressure Swing Adsorption) device.

In addition, the hydrogen produced through the present invention is expected to greatly reduce the cost of hydrogen production because biomass or various organic wastes as raw materials have no cost or can receive treatment costs. Currently, it is difficult to reduce the total hydrogen production cost to less than 2,000 won/kg in the steam reforming method that reforms and uses natural gas of 1,000 won/kg or more. It is expected to provide a decisive opportunity to lower the price to less than 1,000 won/kg.

1 is a block diagram of a fluidized bed reactor according to an embodiment of the present invention.
2 is a side cross-sectional view of a main body of a fluidized bed reactor according to an embodiment of the present invention.
3 is a plan view of a main body of a fluidized bed reactor according to an embodiment of the present invention.
4 is a cross-sectional view of a separator of a fluidized bed reactor according to an embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. However, the present invention may be implemented in many 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 certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

1 to 4, the fluidized bed reactor according to an embodiment of the present invention,

A fluidized bed reactor using woody biomass or organic waste as a raw material and having a reaction zone 101 for hydrothermal gasification therein,

a body portion 100 having a reaction region 101 and a gasification region 102, the reaction region 101 and the gasification region 102 separated by an intermediate separator 103;

An air supply unit 130 for forming a hydrothermal gasification atmosphere by supplying external air, high-temperature air and nitrogen heated by a pre-heater as a fluidization region to increase the temperature of the fluidized bed;

Quantitatively supplying biomass (wood, sawdust, waste wood) or various organic wastes (agricultural and livestock industrial waste, sewage sludge, food waste) to the hydrothermal gasification reaction region 101 to perform hydrothermal liquefaction and gasification reactions A raw material supply unit 110 for;

An oxidizing agent supply unit 120 for inducing an activation reaction of hydrothermal liquefied biomass/organic waste gas by supplying an oxidizing agent (steam) through a rotary injection nozzle installed inside the main body unit 100;

In order to control the internal reaction temperature of the body part 100, a heater 150 provided outside the reactor is included.

Characterized in that a control valve is installed in the vent line to control the pressure and flow rate of the fluidizing agent (nitrogen), air and oxidizing agent (steam) supplied to the reaction area 101 of the main body part 100 do.

A controller 140 is further included as needed, and the controller 140 controls driving of the control valve 160 and the heater 150 .

In order to improve the performance of hydrothermal liquefaction and gasification in the process of hydrothermal liquefaction and gasification in the solid raw material supplied to the reaction zone 101 and hydrothermal gasification, a catalyst inducing an exothermic reaction is used as a layer material to fill the prebed and operate it. to be characterized

The injection nozzle of the oxidizing agent supply unit 120 is extended and formed in a rotary injection method at the inner lower part of the reaction region 101, and the heater 150 is installed outside the body part 100 to prevent condensation of the oxidizing agent. is fitted

The raw material supply unit supplies raw materials by means of a screw and a feeder, and the combustibles meet the high-temperature air introduced from the air supply unit 130 and chemically react with the oxidizing agent introduced through the injection nozzle in the reaction area 101 of the main body unit 100. Organic waste is cracked with carbon compounds to form hydrocarbons.

Here, in the reaction zone 101 of the reactor main body 100, organic waste or wood-based biomass is hydrothermally liquefied and gasified with high-temperature steam inside, and the gas generated during hydrothermal gasification is in the middle of the reaction zone 101. From the gasification zone 102 through the separation plate 103, it exits through a gas passage.

The gas generated in the reaction region 101 moves to the gasification region 102, is recycled through the gas furnace, and is introduced into the reaction region 101 again through the air supply unit 130 to increase efficiency and yield.

In the embodiment of the present invention, a catalytic chemical reaction can occur in a short time with the hydrothermal gas generated by hydrothermal liquefaction and gasification in the reaction zone 101 of the main body 100, and the gasification zone under conditions where the temperature and pressure do not drop. 102 and the hydrothermal gasification reaction region 101 are integrally formed inside the main body 100, so that the size of the oxidation reaction of hydrogen, methane and carbon dioxide gas can be controlled.

To this end, it is possible to increase the efficiency of the hydrothermal gasification reaction by replacing the conventional layer material (sand), which is a heating medium, with a hydrothermal gasification solid catalyst at the bottom of the reaction region 101 and filling the prebed with the layer material. Catalysts useful in catalytic cracking with a fluidized bed reactor include (i) a support and/or an additive and a cocatalyst, and (ii) at least one transition metal catalyst on the cocatalyst (additive), wherein the transition metal catalyst is tungsten, and a transition metal catalyst selected from cobalt, molybdenum, nickel, and combinations thereof. A corresponding fluidized bed reaction process and catalytic reactor apparatus are described, wherein the catalyst is purified to enable the production and production of hydrogen and methane gas. Here, the fluidized bed reactor catalyst is characterized in that it contains Na, 1.35 to 3.45% by weight of Ni, 1.24 to 2.73% by weight.

In addition, the fluidizing agent (nitrogen) and the gasifying agent (air) are preheated in a gas preheater and introduced from the lower part of the reaction region 101, and the supply part of the oxidizing agent (steam) is positioned between the pre-bed and the ceramic board heater ( 150) to prevent condensation of the oxidizing agent (steam), and change the supply method of the oxidizing agent to a rotary injection method so that the gas is recirculated and introduced to facilitate mixing. In this way, the size of the oxidation reaction can be adjusted, and the hydrothermal gasification and catalytic chemical reaction zone 101 can be enlarged to produce hydrogen (H ₂ ) and methane (CH 4 ).

Referring to FIG. 4, the thickness of the separator 103 is preferably 2 to 4 mm, specifically about 2.5 mm, and the diameter of the hole 104 formed on the upper part of the separator is preferably 0.5 to 1 mm, specifically 0.8 mm. mm. In addition, the inlet of the hole 104 may be larger than the outlet if necessary, so that the gas can be moved conveniently.

The material of the separator 103 may be steel.

The operation of the fluidized bed reactor according to an embodiment of the present invention having such a configuration will be described as follows.

First, in a state in which the layer material is filled with the catalyst in the pre-bed of the main body 100, the air supply unit 130 injects the fluidizing agent (nitrogen/air) through the preheater, and then the raw material supply unit transfers the raw material to the reaction zone 101. supply

Thereafter, the raw material undergoes a hydrothermal liquefaction process while being fluidized with gas, a heat source supplied from a fluidizing agent (nitrogen and air), and a layer material, which is a heat source filled in the prebed.

When the hydrothermal liquefaction process proceeds smoothly in the reaction zone 101, the gasification agent (air) is mixed with the fluidization agent (nitrogen) and supplied, and the air is partially oxidized in the fluidization zone to supply heat necessary for the gasification reaction, which is an endothermic reaction. , it causes an endothermic reaction with steam to produce hydrogen and methane gas.

Here, the synthesis gas may move from the upper portion to the gas region 102 through the micropores of the separator 103 and be fed back to the lower portion of the reaction region 101 .

In addition, the supply rate of the fluidizing agent for determining the type and amount of the layer material filled in the prebed and fluidizing the layer material can be controlled through the control unit 140.

The fluidization rate may be determined by measuring the minimum flow and pressure fluctuations of the layer material in the reaction region 101 of the main body 100 and using the minimum fluidization rate obtained in the experiment.

In the gasification reaction, the gas generated from the bioreactant is recycled and introduced into the reaction area to recycle the unreacted gas and increase the yield, efficiency and heat.

In the future, it is possible to produce and manufacture a second hydrogen gas by producing hydrogen (H ₂ ) and carbon monoxide (CO), which are syngas, using unreacted gas.

In order to maintain the reaction, a heat source must be supplied from the outside, and in the present invention, a jacket-type electric heat source is installed to supply the required heat source.

The controller 140 supplies biomass while checking the pressure, fluidization speed, and temperature in the reaction zone 101 .

Therefore, in the preheating of the fluidized bed reactor, the gas preheater and the reaction zone 101 are heated in the gasification zone 102 by supplying woody biomass or organic waste and supplying air to raise the temperature of the reaction zone 101 to 190-240 ° C. to produce hydrothermal gasification.

In the present invention, it can be used regardless of the type of organic waste and woody biomass, and it is possible to produce high value-added gas from organic waste. Hydrogen (H ₂ ) produced through a fluidized bed reactor without a separate treatment device is 30-39%, methane (CH ₄ ) is 10-17%, and carbon dioxide (CO ₂ ) is 40-49%.

The fluidized bed reactor according to an embodiment of the disclosed technology has been described with reference to the embodiment shown in the drawings to aid understanding, but this is only exemplary, and various modifications and equivalents from this to those of ordinary skill in the art It will be appreciated that other embodiments are possible. Therefore, the true technical scope of protection of the disclosed technology will be determined by the appended claims.

Claims (4)

A fluidized bed reactor that uses organic waste and wood-based biomass as raw materials and produces hydrogen and methane through hydrothermal gasification.
A main body having a reaction region and a gasification region, the reaction region and the gasification region being separated by an intermediate separator;
An air supply unit supplying external air, high-temperature air and nitrogen heated by a pre-heater to the fluidization zone to raise the temperature of the fluidized bed to form a hydrothermal gasification atmosphere;
a raw material supply unit supplying wood-based biomass and organic waste to the reaction zone for hydrothermal gasification;
An oxidizing agent supply unit for supplying an oxidizing agent through a rotary injection nozzle installed inside the body unit; and
Including a heater provided outside the reactor to control the internal reaction temperature of the fluidized bed reactor,
Further comprising a control unit, the control unit controls the driving of the control valve and the heater,
The control unit supplies the raw material while checking the pressure, fluidization speed and temperature in the reaction zone,
A catalyst that induces an exothermic reaction is used as a layer material to fill the prebed and operate it.
The fluidized bed reactor catalyst contains Na, 1.35 to 3.45% by weight of Ni, 1.24 to 2.73% by weight,
The reaction zone is a fluidized bed reactor, characterized in that utilizing a subcritical fluid of 300 ℃ - 400 ℃ in thermodynamic phase equilibrium.
According to claim 1,
Fluidized bed reactor, characterized in that a control valve is installed in the vent line to control the pressure and flow rate of the fluidizing agent, air and oxidizing agent supplied to the reaction area of the main body.
According to claim 1,
The fluidized bed reactor in which the spray nozzle of the oxidizing agent supply unit extends and is formed in a rotary spraying method at the inner lower part of the reaction zone.
According to claim 1,
The raw materials supplied from the raw material supply unit include wood-based biomass such as various woods, by-products, and waste wood, and various food processing wastes such as alcohol residue, coffee grounds, bean curd, beans, red beans, sweet potatoes, and potatoes; Agricultural waste such as mushroom broth, vegetables and fruits; Livestock waste such as cow manure, pig manure, chicken manure, and animal carcasses; aquatic wastes such as fish, oysters, seaweed, and seaweed; A fluidized bed reactor containing at least one of domestic waste such as wastewater sludge, food waste, coffee grounds, and garden waste.