KR101842581B1 - Stand-alone Heat-exchanger Type Modular Self-sustaining Reformer - Google Patents

Stand-alone Heat-exchanger Type Modular Self-sustaining Reformer Download PDF

Info

Publication number
KR101842581B1
KR101842581B1 KR1020160069729A KR20160069729A KR101842581B1 KR 101842581 B1 KR101842581 B1 KR 101842581B1 KR 1020160069729 A KR1020160069729 A KR 1020160069729A KR 20160069729 A KR20160069729 A KR 20160069729A KR 101842581 B1 KR101842581 B1 KR 101842581B1
Authority
KR
South Korea
Prior art keywords
self
catalyst
reaction
sustaining
heat exchange
Prior art date
Application number
KR1020160069729A
Other languages
Korean (ko)
Other versions
KR20170137497A (en
Inventor
양정일
박지찬
정헌
정헌도
천동현
이호태
Original Assignee
한국에너지기술연구원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 한국에너지기술연구원 filed Critical 한국에너지기술연구원
Priority to KR1020160069729A priority Critical patent/KR101842581B1/en
Publication of KR20170137497A publication Critical patent/KR20170137497A/en
Application granted granted Critical
Publication of KR101842581B1 publication Critical patent/KR101842581B1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16—Controlling the process
    • C01B2203/1614—Controlling the temperature
    • C01B2203/1623—Adjusting the temperature
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16—Controlling the process
    • C01B2203/1642—Controlling the product
    • C01B2203/1647—Controlling the amount of the product
    • C01B2203/1652—Measuring the amount of product
    • C01B2203/1657—Measuring the amount of product the product being hydrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention relates to a heat exchanger-type reaction heat supplier for supplying heat of reaction and a hydrogen foam designed as a metal foam filled in a catalyst layer for absorbing heat for a high endothermic reaction for producing hydrogen using a gas in a deep- The present invention relates to a modular reformer of a self-sustained self-sustaining type heat exchange or other type capable of producing hydrogen, which can fluctuate the production amount of hydrogen. The present invention can stably supply a reaction heat for high endothermic reaction continuously and stably without additional external heat source, It is possible to stably maintain the reaction temperature of the reaction mixture.

Description

(Stand-alone Heat-exchanger Type Modular Self-sustaining Reformer)

The present invention relates to a self-sustaining self-sustaining type heat exchange and other modular modular reformer, and more particularly, to a heat exchanger type reaction heat supplier for supplying reaction heat and a hydrogen generator for generating hydrogen utilizing a gas in a deep- The present invention relates to a modular reformer of a self-sustaining self-sustaining type heat exchange or other type capable of producing hydrogen that can produce hydrogen designed as a metal foam filled in a catalyst layer for absorbing heat for a high endothermic reaction.

Steam reforming technology using methane as a hydrogen production technology is a major technology of interest in areas rich in natural gas. Generally, hydrogen production technology is classified into thermal process, electrolytic process, and light source process. The thermal process uses energy such as natural gas, coal, and biomass to release hydrogen. In particular, heat is used in closed chemical cycles to produce hydrogen from water during the thermochemical process. Electrolytic processes use electricity to divide water into hydrogen and oxygen, using electric energy from a zero carbon source using wind and solar energy, and processes using high temperature nuclear electrolysis. The optical process uses light energy to decompose water into hydrogen and oxygen. Such photoprocessing is known as a major category of photobiological and photoelectric chemistry. In addition, the seven key technical paths are biological production, photoelectrochemical production, thermo-chemical production, water electrolysis, coal and biomass gasification, bio-derived liquid fuel reforming, and natural gas reforming. Table 1 summarizes the forms of hydrogen production for the feed fuels, energy sources, production and seven major reaction paths.

Technology Supply fuel Energy source Production scale Form of hydrogen production Distributed natural gas reforming Natural gas Natural gas Distributed type Thermal process Bio-derived
Liquid fuel reforming Biomass Biomass Distributed type
Semi-concentrated type Thermal process Coal and biomass gasification Coal
Biomass Coal
Biomass Semi-concentrated type
Concentration type Thermal process Water electrolysis water power
wind force
Sun
nuclear power Distributed type
Semi-concentrated type
Concentration type Electrolytic process Thermochemical production water Sun
nuclear power Semi-concentrated type
Concentration type Thermal process Optoelectrochemical
production water Sun Semi-concentrated type
Concentration type Optical process Biological production water
Biomass Sun
Biomass Semi-concentrated type
Concentration type Optical process

For the purpose of this technical review, a prior art reference will be made to Korean Patent Registration No. 10-1487387 (Feb. 21, 2015) to prepare a suspension by mixing a Mo precursor, a Ni precursor and a porous carbon material in water; Adjusting the pH of the suspension; Stirring the pH controlled suspension to adsorb a Mo precursor and a Ni precursor to the porous carbon material; Filtering the suspension containing the Mo precursor and the Ni precursor to the porous carbon material to recover and dry the catalyst precursor; Calcining the recovered and dried catalyst precursor; And carburizing the calcined catalyst precursor. The present invention also relates to a method for producing a metal carbide-based methane-reforming catalyst.

Korean Patent Publication No. 10-1386418 (Apr. 4, 2014) discloses an alumina (Al2O3) catalyst support modified with magnesium oxide (MgO); The catalytically active components nickel and cobalt; And calcium oxide as a catalyst promoter, wherein the catalytically active component and a catalyst promoter are supported on the catalyst support, and the magnesium oxide forms a spinel structure with alumina. The present invention also provides a method for producing a catalyst for steam reforming of methane, which comprises the steps of producing an alumina catalyst support, producing a catalyst primary molded body, and producing a catalyst final molded body, and a method for producing steam reforming of methane contained in a steel by- / RTI >

In Korean Patent Registration No. 10-0818592 (Apr. 04, 2014), a mixed gas supply part for a catalyst exothermic reaction, which injects or mixes air and fuel supplied for exothermic reaction of a catalyst, and a gas-sound foaming reaction (catalyst endothermic reaction) (Catalytic endothermic reaction), which is the main reaction, and the mixture gas supplied from the mixed gas supply part for the catalyst exothermic reaction and the mixed gas for the catalytic endothermic reaction, And an exothermic reaction for heat supply and an endothermic reaction for hydrogen production using catalytic combustion including a simultaneous exothermic / endothermic reaction part in which a catalytic exothermic reaction is generated.

In WO WO2007058855 (May 04, 2007), a reforming catalyst member comprising an elongated main body having a plurality of vertexes and a valley region on the outer surface thereof in order to increase the area of the outer surface of the main body to enhance the catalyst usability, Wherein the reforming catalyst member is attached to the current collector using an adhesive and is dried using infrared rays while the catalyst member is held in the current collector And a unit for forming the catalytic material on a reforming catalyst member having an elongated body, wherein the outer surface of the body is formed on the outer surface of the body Having a plurality of vertex and valley regions to increase the area to enhance catalyst availability, A loading assembly for loading the member into the fuel cell current collector and for attaching the reforming catalyst member to the current collector using an adhesive, and a drying assembly for drying using the infrared while holding the reforming catalyst member in the current collector The system comprising:

WO International Publication No. WO999064150 (June, 1999) discloses an autothermal reforming process for producing hydrogen or syngas, comprising contacting a raw material and a reforming gas comprising oxygen and steam with a catalyst Wherein the amount of ruthenium supported on the carrier is 0.05 to 20% by weight based on the whole catalyst, and the ratio of steam and raw material introduced into the reaction system is " water molecule number / Quot; number of carbon atoms ", and the ratio of the oxygen to the raw material to be introduced into the reaction system is 0.1 to 1 in terms of the number of oxygen atoms / the number of carbon atoms in the raw material.

Also, Dincer I, Acar C. Review and evaluation of hydrogen production methods for better sustainability. Int J Hydrogen Energy 2015, Vol. 40, 11094-111 reviewed various potential methods of hydrogen production using regenerated and non-regenerated sources and evaluated environmental impact, cost, energy efficiency and exergy efficiency. In particular, it has been suggested that natural gas-based hydrogen production in large industrial plants is considered as a low-cost method. Of the three technologies using steam reforming, partial oxidation, and natural reforming fossil fuels, steam reforming is presented as the lowest cost and common technology for hydrogen production.

Also, Herron JA, Kim J, Upadhye AA, Huber GW, Maravelias CT. A general framework for the assessment of solar fuel technologies. Energy Environ Sci. 2015, Vol. 8, 26-57, reviewed various methods of producing hydrogen from water using electrolysis, photoelectrochemical water decomposition, photo-catalytic water decomposition, thermochemical water decomposition, and solar energy.

Also, Schjølberg I, Hulteberg C, Yasuda I, and Nelsson C. Small scale reformers for on-site hydrogen supply. Energy Procedia 2012, Vol. 29, 559-66., Suggested that in-situ hydrogen production technology using small-scale reformers would be an important intermediate technology for the transition to a hydrogen-based infrastructure.

However, the self-sustaining self-sustaining type heat exchanger for generating hydrogen of 1 Nm 3 per hour designed as a metal foam filled with a catalyst layer for absorbing heat for a high endothermic reaction by constituting a reaction heat supplier of its own heat exchange type, There is no proposed type-based reformer.

Korean Registered Patent No. 10-1487387 (2015.01.22) Korean Registered Patent No. 10-1386418 (April 4, 2014) Korean Registered Patent No. 10-0818592 (April 4, 2014) WO International Publication No. WO2007058855 (2007.05.24) WO International Publication No. WO999064150 (June, 1999)

Dincer I, Acar C. Review and evaluation of hydrogen production methods for better sustainability. Int J Hydrogen Energy 2015, Vol. 40, 11094-111. Herron JA, Kim J, Upadhye AA, Huber GW, Maravelias CT. A general framework for the assessment of solar fuel technologies. Energy Environ Sci 2015, Vol. 8, 26-57. Schjølberg I, Hulteberg C, Yasuda I, Nelsson C. Small scale reformers for on-site hydrogen supply. Energy Procedia 2012, Vol. 29, 559-66.

The main object of the present invention to solve the above-mentioned problems of the prior art is to provide a reaction heat supplier of its own heat exchange type, which is designed to be a metal foam filled with a catalyst layer for absorbing heat for a high endothermic reaction, Self-standing self-sustaining type heat exchange and other modular modular reamers for the production of self-sustaining self-sustaining type heat exchangers.

The present invention also relates to a self-sustaining self-sustaining catalyst structure comprising a porous metal foam housing catalyst structure which is formed in a state where a catalyst is directly charged in pores formed in a porous metal foam structure and which is stable and highly reactive even without high- Type heat exchanger and other modular modular reformers.

According to an aspect of the present invention, there is provided a self-sustaining self-sustaining type heat exchange or other modular modular reformer, comprising: an inlet (110) through which reactant flows into one end; A catalyst layer 120 for reacting the introduced reactants under predetermined reaction conditions; And a discharge part (130) through which the product generated while passing through the catalyst layer is discharged to the other end of the first reactor (100); A cooling trap (200) for cooling the unreacted steam; And a storage tank (300) for storing and storing unreacted materials that have passed through the cooling trap. The self-sustaining self-sustaining type heat exchange or other mooring modular type reformer is provided.

The present invention also relates to a gas turbine comprising: a first feeder (410) for supplying one or more gases; A water storage tank (420) for storing water; A first pump (430) for supplying water of the water storage tank; An evaporator 440 for converting the water supplied from the first pump into a gas phase; And a mixer 450 in which the combustible gas and the water supplied from the first pump are mixed and supplied to the evaporator.

In addition, the present invention provides a fuel cell system comprising: a fuel supplier (510) for an exothermic reaction; An oxidizer feeder 520 for reacting with the fuel; An igniter (530) for initiating an exothermic reaction of the fuel and the oxidant; And a reaction heat supplier 500 including a chamber 540 in which the exothermic reaction proceeds, one end of the chamber may be in contact with the first reactor for heat exchange.

Further, the present invention may include a flow meter 610 for measuring a flow rate of a product passing through the reservoir associated with the discharge unit; An analyzer 620 for measuring the composition of the product; And a purification device 630 for separating and collecting the product.

In the present invention, the gas is methane, and the feed ratio of steam and methane supplied as the reactant may have a feed ratio of 1: 1 vol% to 10: 1 vol%.

In the present invention, steam supplied to the reactant may be 100 to 400 ° C and 100 kPa to 40 MPa.

Further, in the present invention, the catalyst amount of the catalyst layer may be 10 g to 60 g at 1 L / min of methane.

Further, in the present invention, the catalyst of the catalyst layer may be impregnated with an aqueous solution of nickel nitrate in an alumina support.

In the present invention, the catalyst layer is formed by pressing a catalyst, which has been processed into a predetermined shape into pores of a porous metal foam structure in the form of a catalyst sheet, by pressurizing and pressing to form a unit porous metal foam housing catalyst structure, Wherein the porous metal foil structure has a thickness of 1 to 10 mm and a pore size of 0.1 to 10 mm, and each of the porous metal foams has a thickness of 0.1 to 10 mm. The porosity is filled in a quantity such that a portion of the catalyst surface is in direct contact with the porous metal foam structure, and the porosity of the porous metal foam housing catalyst structure filled with the catalyst may be 10 to 75%.

The present invention is also a reaction heat supplier in which the exothermic reaction is a combustion or partial oxidation reaction of the fuel and the oxidant and is capable of generating an exhaust gas for heat exchange to maintain the temperature of the catalyst layer at 500 ° C to 900 ° C .

In addition, the present invention further includes a controller 700 for controlling the reactant supply unit, the first reactor, and the reaction heat supplier by comparing the target flow rate and the composition condition of the product with the flow rate and composition information of the flow meter and analyzer .

The evaporator may be a heat exchanger for performing heat exchange with the exhaust gas discharged from the first reactor through the heat exchanger.

Also, the number of heat exchange or other modular reformer channels may be controlled according to the amount of methane supplied to the self-sustaining self-sustaining type heat exchange or other modular reformer and / or the required amount of hydrogen produced .

The present invention can stably supply reaction heat for high endothermic reaction continuously and stably without additional external heat source supply, so that the reaction temperature of the catalyst layer can be stably maintained. Accordingly, the product is produced at a high yield in the reforming reaction There is an effect that can be done.

In addition, the reforming catalyst is enclosed in the metal structure, so that the catalytic desorption is not damaged during the high endothermic reaction, so that the durability is enhanced. Moreover, the endothermic reaction heat supplied due to the metal structure can be effectively transferred to the inside of the catalyst layer.

Further, the reactivity can be maintained stably during the endothermic reaction, and the reformed product can be economically produced.

In addition, the heat exchanger type modular reformer is effective in supplying the heat of reaction to the catalyst bed.

Also, there is no pressure drop even at high GHSV of the reactant.

In addition, when the heat exchanger or other reformer is operated as a modular system, the energy required for the entire process can be reduced by designing the reactor.

FIG. 1 is a view showing the self-sustained self sustaining type heat exchange and other modular modular reformer of the present invention.
FIG. 2 is a diagram illustrating a self-sustaining self sustaining type heat exchange guitar modular reformer according to an exemplary embodiment of the present invention.
3 is a general reformer configuration diagram in which reaction heat is supplied by an external heat source, which is a comparative example of the present invention.
FIG. 4 is a graph showing steam methane reforming and burner operating conditions according to the reactant GSHV according to an embodiment of the present invention.
5 is a graph showing the reaction yield of a compact reactor packed with a 15 wt% Ni / γ-Al 2 O 3 catalyst according to an embodiment of the present invention.
FIG. 6 is a graph showing a reaction yield of a compact reactor filled with 20 wt% Ni / γ-Al 2 O 3 catalyst according to an embodiment of the present invention.
FIG. 7 is a graph showing the reaction yields of a heat exchanger type reactor packed with a 20 wt% Ni / γ-Al 2 O 3 catalyst according to an embodiment of the present invention.
Figure 8 is a graph of the reaction yield of reactant GSHV in a heat exchanger type reactor, which is one embodiment of the present reaction.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to the accompanying drawings. It should be understood, however, that the appended drawings illustrate only the contents and scope of technology of the present invention, and the technical scope of the present invention is not limited thereto. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea of the present invention based on these examples.

In addition, terms and words used in the present specification and claims should not be construed to be limited to ordinary or dictionary meanings, and the inventor should appropriately define the concept of the term to describe its invention in the best way. It should be construed as meaning and concept consistent with the technical idea of the present invention. Therefore, the embodiments described herein are merely the most preferred embodiments of the present invention, and are not intended to represent all of the technical ideas of the present invention, so that various equivalents and modifications may be made thereto .

FIG. 1 is a view showing the self-sustained self sustaining type heat exchange and other modular modular reformer of the present invention.

An inlet 110 into which the reactant flows at one end; A catalyst layer 120 for reacting the introduced reactants under predetermined reaction conditions; And a discharge part (130) through which the product produced while passing through the catalyst layer is discharged to the other end of the first reactor (100); A cooling trap (200) for cooling the unreacted steam; And a reservoir 300 for removing unreacted water passing through the cooling trap and storing the unreacted material. The self-sustaining self-sustaining type heat exchange or other mooring modular type reformer may be used. The incoming reactant is not particularly limited as long as it is capable of reforming. Methane, naphthene, paraffin, naphthene, paraffin, etc., heavy oil, crude oil and water vapor. The predetermined reaction condition is not particularly limited so long as it is a reaction condition required for proceeding the catalytic reforming. And may be 1 atm to 60 atm at a temperature condition of 50 deg. C to 900 deg. Preferably from 1 atm to 10 atm at a temperature condition of 400 < 0 > C to 850 < 0 > C. And more preferably from 1 atm to 2 atm at a temperature condition of 650 deg. C to 750 deg.

If the reaction condition is higher or lower than the above-mentioned reaction conditions, the activity of the catalyst and the reactant decreases, so that the conversion of the reactant becomes lower and the yield of the product becomes lower.

The form of the first reactor is not particularly limited as long as the reaction yield can be increased. Continuous stirred tank reactors, tubular reactors, plug flow reactors, fixed bed reactors. Preferably a tubular reactor.

The catalyst constituting the catalyst layer is not particularly limited as long as the reaction yield can be increased. Platinum, cobalt, iron, and nickel. Based catalyst. Preferably, it is a nickel-based catalyst.

The catalyst support constituting the catalyst layer is not particularly limited as long as the reaction yield can be increased. Silicon oxide, alumina, tin oxide, titanium oxide, and indium oxide. It is preferably gamma alumina.

The housing of the catalyst layer is not particularly limited as long as it can maintain the catalyst layer and increase the reaction yield. Preferably a porous metal foam. The material of the porous metal may be at least one thermally conductive metal selected from the group consisting of aluminum, iron, stainless steel, nickel, iron-chromium-aluminum alloy, nickel-chromium alloy, copper and copper-nickel alloy.

It is obvious that a valve, a temperature sensor, a pressure sensor, a flow meter, and the like may be installed to control reaction conditions in the inlet, the catalyst layer, the outlet, the first reactor, the cooling trap, and the storage tank.

A first feeder (410) for supplying one or more gases; A water storage tank (420) for storing water; A first pump (430) for supplying water of the water storage tank; An evaporator 440 for converting the water supplied from the first pump into a gas phase; And a mixer 450 in which the combustible gas, the combustible gas, and water supplied from the first pump are mixed and supplied to the evaporator.

Various types of water may be supplied to the water reservoir. Additional additives may be present. Aliphatic hydrocarbons such as pure water, fresh water, brackish water, brine, or a mixture of alcohol and water in the form of water and aliphatic hydrocarbons such as hexane; Aromatic hydrocarbons such as benzene, toluene, xylene and methylnaphthalene; Heterocyclic compounds such as quinoline and pyridine, ketones such as acetone, methyl ethyl ketone and cyclohexanone; Esters such as methyl acetate and methyl acrylate; Amines such as diethylenetriamine and N, N-dimethylaminopropylamine; Ethers such as diethyl ether, propylene oxide and tetrahydrofuran (THF); amides such as N-methylpyrrolidone (NMP), dimethylformamide and dimethylacetamide; And an organic solvent such as an aprotic polar solvent such as hexamethylphosphoramide, dimethylsulfoxide, or the like.

The first pump is for supplying the water and is not particularly limited as long as the above object can be achieved. A centrifugal pump, a hydraulic pump, a drain pump, a pressure pump, a motor pump, and an underwater pump. It may be a bucket pump of a volute pump, an axial flow pump, a turbo pump of a turbo pump, a flinger pump, a wash pump, a reciprocating pump of a bucket pump, a gear pump, and a screw pump.

The evaporator is not particularly limited as long as it can phase-change the supplied water to the vapor phase. The evaporator may be a dry type, a semi-liquid type, a bare liquid type, or a liquid circulating type. The evaporator may be a heat exchanger.

The heat exchanger can perform heat exchange with the exhaust gas after the reaction of the reaction heat supplier.

The reactant supply unit may further comprise a cooler for cooling the reactants.

The mixer is not particularly limited as long as it can mix two or more fluids. Rotary mixers, stationary mixers, spot mixers, fluidized bed mixers.

A fuel supplier 510 for an exothermic reaction; An oxidizer feeder 520 for reacting with the fuel; An igniter (530) for initiating an exothermic reaction of the fuel and the oxidant; And a reaction heat supplier (500) including a chamber (540) in which the exothermic reaction proceeds, and one end of the chamber may be in contact with the first reactor for heat exchange.

The exothermic reaction may be a gasification reaction which is a combustion or partial oxidation reaction.

The fuel supply is not particularly limited as long as it is a fuel having a calorific value for an exothermic reaction. It may be solid, liquid, or weather fossil fuel. It can be preferably a vapor fossil fuel. More preferably methane.

The oxidizing agent feeder is not particularly limited as long as it is a compound containing oxygen capable of reacting with the fuel. Preferably air, oxygen, carbon monoxide. More preferably oxygen.

The igniter is not particularly limited as long as it can start the reaction. A pilot burner, a plasma igniter, a spark igniter, and a resistor.

FIG. 2 is a diagram illustrating a self-sustaining self sustaining type heat exchange guitar modular reformer according to an exemplary embodiment of the present invention.

A flow meter (610) for measuring the flow rate of the product passing through the reservoir, the flow rate of the product passing through the reservoir; An analyzer 620 for measuring the composition of the product; And a purification device 630 for separating and collecting the product.

Fig. 3 is a compact type reformer configuration diagram of a comparative example of the present invention.

The compact type reformer supplies reaction heat using an electric heater unlike the self-sustaining self-sustaining modular reformer.

FIG. 4 is a graph showing steam methane reforming and burner operating conditions according to the reactant GSHV according to an embodiment of the present invention.

5 is a graph showing the reaction yield of a compact reactor packed with a 15 wt% Ni / γ-Al 2 O 3 catalyst according to an embodiment of the present invention.

FIG. 6 is a graph showing a reaction yield of a compact reactor filled with 20 wt% Ni / γ-Al 2 O 3 catalyst according to an embodiment of the present invention.

FIG. 7 is a graph showing the reaction yields of a heat exchanger type reactor packed with a 20 wt% Ni / γ-Al 2 O 3 catalyst according to an embodiment of the present invention.

Figure 8 is a graph of the reaction yield of reactant GSHV in a heat exchanger type reactor, which is one embodiment of the present reaction.

In the present invention, the gas is methane, and the feed ratio of steam and methane supplied as the reactant may have a feed ratio of 1: 1 vol% to 10: 1 vol%. And preferably from 1.5: 1 vol% to 5: 1 vol%. And more preferably from 2: 1 vol% to 4: 1 vol%. If the feed ratio is exceeded, the yield due to the reforming reaction may be lowered.

In the present invention, steam supplied to the reactant may be 100 to 400 ° C and 100 kPa to 40 MPa. Preferably 100 占 폚 to 300 占 폚, 100 kPa to 20 MPa. And more preferably 100 캜 to 200 캜, 100 kPa to 10 MPa. If it is outside the above range, additional reaction heat must be supplied to the reactant, which may increase the process cost and lower the reforming reactivity.

Further, in the present invention, the catalyst amount of the catalyst layer may be 10 g to 60 g at 1 L / min of methane. Preferably 15 g to 40 g at 1 L / min of methane. More preferably, it may be 20 g to 30 g at 1 L / min of methane.

In the present invention, the molar ratio of the hydrocarbon compound to the catalyst may be 1 to 6 g / mol. Preferably 1.5 to 4 g / mol. More preferably 2 to 3 g / mol.

In addition, the hydrocarbon compound may be an alkane, an alkane, or an alkene compound having 1 to 6 carbon atoms. Preferably an alkane, alkane, or alkene compound having 1 to 3 carbon atoms. More preferably methane.

Further, in the present invention, the catalyst of the catalyst layer may be impregnated with an aqueous solution of nickel nitrate in an alumina support.

In the present invention, the catalyst layer may be formed by pressing a catalyst, which has been processed into a predetermined shape in the pores of a porous metal foam structure in the form of a catalyst sheet, by pressurizing and pressing to form a unit porous metal foam housing catalyst structure, Wherein the porous metal foil structure has a thickness of 1 to 10 mm, a pore size of 0.1 to 10 mm, a pore size of 0.1 to 10 mm, A portion of the surface of the catalyst is filled in a quantity sufficient to make direct contact with the porous metal foam structure, and the porosity of the porous metal foam housing catalyst structure filled with the catalyst may be 10 to 75%.

In the present invention, the exothermic reaction may be a reaction or partial oxidation reaction of the fuel and the oxidant, and may be a reaction heat supplier capable of producing an exhaust gas for heat exchange to maintain the temperature of the catalyst layer at 500 ° C to 900 ° C.

In addition, the present invention further includes a controller 700 for controlling the reactant supply unit, the first reactor, and the reaction heat supplier by comparing the target flow rate and the composition condition of the product with the flow rate and composition information of the flow meter and analyzer .

The evaporator may be a heat exchanger for performing heat exchange with the exhaust gas discharged from the first reactor through the heat exchanger.

(Example)

In this experiment, Ni / γ-Al alloy with 15 wt% and 20 wt%2O3Catalyst.

The Ni / γ-Al 2 O 3 catalyst packed with 15 wt% and 20 wt% Ni precursor Ni (NO 3 ) 2 6H 2 O (Aldrich) and γ-Al 2 O 3 beads And prepared by incipient wetness method. First, in order to remove surface adsorption impurities, γ-Al 2 O 3 The support was calcined at 400 ° C for 8 hours. An appropriate amount of Ni nitrate hexahydrate (Ni (NO 3 ) 2 6H 2 O aqueous solution was added to the pretreated γ-Al 2 O 3 The support was impregnated with incipient wetness so that the support was filled with 15 wt% and 20 wt% nickel. The impregnated catalyst was dried at 120 ° C for 24 hours and then calcined at 800 ° C for 8 hours.

Finally, the treated catalyst was pulverized to have an average particle size of 0.15 mm, thereby reducing the effect of reducing internal diffusion. Before the experiment using the prepared catalyst, hydrogen was treated at 800 ° C with hydrogen at a flow rate of 200 mL / min for 24 hours.

The heat exchanger and the modular reformer are designed such that the burner of FIG. 2 supplies a reaction heat to the reformer, and a pilot burner and a main burner for ignition are formed to stably form a flame. The supplied fuel is methane, and the supply ratio of methane and air is 1:10, and the feed rates of methane and air are 5.00 and 50.0 L / min, respectively. The initial temperature of the reaction is 850 ° C, and when the reaction gas for the reforming reaction is injected, the temperature is lowered from 850 ° C to 700 ° C below. To increase the reaction temperature of the catalyst layer, the amount of methane and air injected from the burner is increased from 6.99 L / min to 69.9 L / min. The temperature of the final catalyst layer is 798 占 폚.

FIG. 7 shows that the steam / methane injection ratio was 167.9 g of a Ni / γ-Al 2 O 3 catalyst of 3: 1 (18.5 L / min: 6.17 L / min), GHSV = 6,300 h -1 and 20 wt% Deg.] C, and a pressure of 1 atm. The methane conversion rate was 99.7%, and the composition ratios of H 2 , CO and CO 2 (drying conditions) were 74.7%, 15.9% and 7.76%, respectively. The amount of H 2 produced increases to 1.21 Nm 3 / hr. The above high methane conversion rate is considered to be due to a high reaction temperature.

The methane mole ratio as a fuel per unit mole of H 2 is 0.65, and the burner conditions are the same as those described above. The fuel demand is greater than that in a typical Cu-Cl thermochemical cycle, but as the supply of methane and air to the burner decreases, the fuel demand may decrease as the reforming reaction temperature decreases by 650 ° C. In this case, the methane conversion rate is estimated to be 90.6%, and the amount of H 2 produced will be lowered by 3%.

When these heat exchangers are operated as a modular system, reactor design can reduce the amount of energy required for the entire process. In addition, the heat exchange and other modular modular reformers can independently produce hydrogen using the utilization gas secured in the off-shore or deep-sea environment. Therefore, it would be possible to develop a facility for the production of dispersed hydrogen.

As the gas hourly space velocity (GHSV) of the reactant increases, the endothermic reaction heat of the steam methane reforming also increases. GHSV is limited to 5,000 ~ 20,000 h -1 . If the reactant is too small at 5,000 h -1 or less, the reactant is too large compared to the amount of hydrogen produced. If the reaction rate is too high at 20,000 h -1 , It is difficult to evaluate the effect of GHSV on the reactants in a typical electric heater, but heat exchange and other modular modifiers are effective to provide a high endothermic reaction heat to the reactor surface and catalytic metal foam through methane combustion . In addition, the heat exchange and other modular modular reformers do not have a pressure drop due to reactant flow, even at the high reactant GHSV due to the three channels of metal foam in the tube side to the reactant stream.

Figure 8 represents the effect GHSV of the reactant of the heat exchange reformer is Other mouth modular GHSV of the reactant from 6,300 10,000h - the result of the time increase to 1. At various GHSV conditions, the reaction temperatures of the heat exchanger and other modular reformers were controlled by increasing the feed rate of methane to 6.99, 7.99 and 10.9 L / min while maintaining a constant methane: air ratio of 10: 1. The conversion of methane to GHSV was reduced from 99.7% to 98%, but the hydrogen concentration remained almost constant at 75.5%. At GHSW 6,300 and 8,000 h -1 , the reaction equilibrium was found at 798 ° C and 760 ° C, respectively. At GHSW 10,000 h -1 , methane conversion was> 98% and the reaction temperature was 745 ° C. The hydrogen production was increased from 6,300 h -1 to 1.97 Nm 3 / hr at 1.21 Nm 3 / hr from 10,000 h -1 .

(Comparative Example 1)

The two catalyst characteristics for obtaining the production amount of 1 Nm 3 / h of hydrogen were tested using the compact reformer of FIG. A typical electric heater was used as a reformer.

The loading of the 15 wt% Ni / γ-Al 2 O 3 catalyst is 167.8 g at 655 ° C of 1 Nm 3 / h of hydrogen at a methane conversion of 90% or higher. The steam to methane injection ratio is 3: 1. When the catalyst bulk density was 0.72 g / mL, a reformer having a diameter of 1 inch and a length of 613 mm was used. The flow rates of methane and steam are 6.17 L / min and 18.5 L / min, respectively.

The temperature of the catalyst layer using an external electric heater was flushed with nitrogen while being maintained at 800 ° C. When methane and steam mixtures are fed to start the reaction, the reaction temperature drops sharply to 701 ° C. Thereafter, the temperature during the reaction is maintained at 691 캜 to 692 캜.

5 shows the results of reforming at a steam to methane injection ratio of 3: 1 (18.5 L / min: 6.17 L / min), a catalyst of 167.9 g, a reaction temperature of 692 ° C, and a pressure of 1 atm.

The production flow rate of hydrogen is more than 1 Nm 3 / h and the reaction is stable for 2 hours. Methane conversion was 94.4% and hydrogen concentration was 73.4%. The maximum hydrogen production rate was 1.19 Nm 3 / h at 692 ℃.

(Comparative Example 2)

The two catalyst characteristics for obtaining the production amount of 1 Nm 3 / h of hydrogen were tested using the compact reformer of FIG. A typical electric heater was used as a reformer.

The loading of the 20 wt% Ni / γ-Al 2 O 3 catalyst is 167.8 g at 655 ° C. of 1 Nm 3 / h of hydrogen at a methane conversion of 90% or higher. The steam to methane injection ratio is 3: 1. When the catalyst bulk density was 0.72 g / mL, a reformer having a diameter of 1 inch and a length of 613 mm was used. The flow rates of methane and steam are 6.17 L / min and 18.5 L / min, respectively.

The temperature of the catalyst layer using an external electric heater was flushed with nitrogen while being maintained at 850 ° C. When the methane and steam mixture is fed to start the reaction, the reaction temperature falls sharply to 738 캜 and is stabilized at the above temperature.

FIG. 6 shows the reforming characteristics at a steam to methane injection ratio of 3: 1 (18.5 L / min: 6.17 L / min), a catalyst of 167.9 g, a reaction temperature of 738 ° C, and a pressure of 1 atm.

The production flow rate of hydrogen is more than 1 Nm 3 / h and the reaction is stable for 2 hours. The methane conversion was 97.9% and the hydrogen concentration was 75%. The maximum hydrogen production rate was 1.22 Nm 3 / h at 692 ℃.

The resultant difference of Comparative Example 1 and Comparative Example 2 due to the high activity of the 20 wt% Ni / γ-Al 2 O 3 catalyst was that the higher ratio of the γ / Al 2 O 3 support of the Ni / γ-Al 2 O 3 catalyst And the number of nickel particles dispersed in the water.

Although the present invention has been described with reference to the accompanying drawings and embodiments, it is to be understood that the present invention is not limited to the above-described embodiments, but may be modified and changed without departing from the scope and spirit of the invention. It is clear that the present invention is not limited to the above-described embodiments. Accordingly, the scope of protection of the present invention should be construed according to the following claims, and all technical ideas which fall within the scope of equivalence by alteration, substitution, substitution, Range.

In addition, it should be clarified that some configurations of the drawings are intended to explain the configuration more clearly and are provided in an exaggerated or reduced size than the actual configuration.

100: first reactor 110: inlet
120: catalyst layer 130:
200: cooling trap 300: storage tank
400: reactant supply unit 410: first feeder
420: water storage tank 430: first pump
440: Evaporator 450: Mixer
500: reaction heat supplier 510: fuel supplier
520: oxidizer feeder 530: igniter
540: chamber 600: post-processor
610: Flow meter 620: Analyzer
630: Purification apparatus 700: Controller

Claims (13)

Self-sustained Self-sustaining Heat Exchange Miscellaneous As a modular reformer,
An inlet 110 into which the reactant flows at one end; A catalyst layer 120 for reacting the introduced reactants under predetermined reaction conditions; And a discharge part (130) through which the product produced while passing through the catalyst layer is discharged to the other end of the first reactor (100);
A cooling trap 200 for cooling unreacted steam through the first reactor 100; And
And a storage tank (300) for storing the product from which the unreacted product having passed through the cooling trap (200) has been removed. The self-sustaining self sustaining type heat exchange orifice modular type reformer
The catalyst layer is formed by pressing a catalyst formed into a predetermined shape into the pores of a porous metal foam structure in the form of a catalyst sheet by pressurizing the mixture to form a unit porous metal foam housing catalyst structure, Respectively,
The catalyst is in the form of spheres or pellets having a diameter of 0.1 to 10 mm. The porous metal foam structure in the form of a sheet has a thickness of 1 to 10 mm and a pore size of 0.1 to 10 mm. Wherein the porous metal foam housing catalyst structure has a porosity of 10 to 75%, the porous metal foam housing catalyst structure being charged in a quantity such that it can be in direct contact with the porous metal foam structure, Modular Reformer. The method according to claim 1,
A first feeder (410) for supplying one or more gases; A water storage tank (420) for storing water; A first pump (430) for supplying water of the water storage tank; An evaporator 440 for converting the water supplied from the first pump into a gas phase; And a mixer (450) for mixing the gas and the water supplied from the first pump and supplying the mixed gas to the evaporator. The self sustaining self-sustaining type Heat exchange other mouth modular reformer. 3. The method of claim 2,
A fuel supplier 510 for an exothermic reaction; An oxidizer feeder 520 for reacting with the fuel; An igniter (530) for initiating an exothermic reaction of the fuel and the oxidant; And a reaction heat supplier (500) including a chamber (540) in which the exothermic reaction proceeds, one end of the chamber being in contact with the first reactor for heat exchange therewith, Type heat exchange other mouth modular reformer. The method of claim 3,
A flow meter (610) for measuring the flow rate of the product passing through the reservoir, the flow rate of the product passing through the reservoir; An analyzer 620 for measuring the composition of the product; And a purification device (630) for separating and collecting the product. ≪ Desc / Clms Page number 24 > The self-sustaining self sustained-mode heat exchange < RTI ID = 0.0 > 3. The method of claim 2,
Wherein the gas is methane, and the feed ratio of steam to methane supplied to the reactants is 1: 1 vol% to 10: 1 vol% feed ratio. 3. The method of claim 2,
Wherein the steam supplied to the reactant is 100 ° C to 400 ° C and 100 kPa to 40 MPa, and the self-sustaining self-sustaining type heat exchange or other mooring modular reformer. 6. The method of claim 5,
Wherein the amount of catalyst in the catalyst bed is 10 g to 60 g at 1 L / min of methane. The method according to claim 1,
Wherein the catalyst in the catalyst bed is an alumina support impregnated with an aqueous solution of nickel nitrate, the self-sustaining self-sustaining type heat exchange or other modular modular reformer. delete The method of claim 3,
Wherein the exothermic reaction is a combustion or partial oxidation reaction of the fuel and the oxidant and a reaction heat supplier capable of producing an exhaust gas for heat exchange to maintain the temperature of the catalyst layer at 500 to 900 ° C. Staining type heat exchange other mouth modular reformer. 5. The method of claim 4,
And a controller (700) for controlling the reactant supply unit, the first reactor, and the reaction heat supplier by comparing the target flow rate and the composition condition of the product with the flow rate and composition information of the flow meter and the analyzer, Self-sustaining self-sustaining heat exchange with other mouth modular reformers. The method of claim 3,
Wherein the evaporator is a heat exchanger for exchanging heat with exhaust gas discharged from the first reactor through the heat exchanger after heat exchange. 12. The method of claim 1, wherein the self-sustaining self-sustaining type heat exchange or other inlet modular reformer is operated in accordance with the amount of methane supplied and / And the number of channels is adjusted.
KR1020160069729A 2016-06-03 2016-06-03 Stand-alone Heat-exchanger Type Modular Self-sustaining Reformer KR101842581B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020160069729A KR101842581B1 (en) 2016-06-03 2016-06-03 Stand-alone Heat-exchanger Type Modular Self-sustaining Reformer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020160069729A KR101842581B1 (en) 2016-06-03 2016-06-03 Stand-alone Heat-exchanger Type Modular Self-sustaining Reformer

Publications (2)

Publication Number Publication Date
KR20170137497A KR20170137497A (en) 2017-12-13
KR101842581B1 true KR101842581B1 (en) 2018-03-27

Family

ID=60944282

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020160069729A KR101842581B1 (en) 2016-06-03 2016-06-03 Stand-alone Heat-exchanger Type Modular Self-sustaining Reformer

Country Status (1)

Country Link
KR (1) KR101842581B1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002255506A (en) * 2001-02-26 2002-09-11 Corona Corp Production method for high purity hydrogen from heavy hydrocarbon fuel and its apparatus
KR100818592B1 (en) * 2006-11-30 2008-04-01 한국에너지기술연구원 Module type compact hydrogen reformer including both exothermic reaction and endothermic reaction using catalytic combustion
KR101494796B1 (en) 2014-08-22 2015-02-23 고등기술연구원연구조합 System and method for transforming synthesis gas

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002255506A (en) * 2001-02-26 2002-09-11 Corona Corp Production method for high purity hydrogen from heavy hydrocarbon fuel and its apparatus
KR100818592B1 (en) * 2006-11-30 2008-04-01 한국에너지기술연구원 Module type compact hydrogen reformer including both exothermic reaction and endothermic reaction using catalytic combustion
KR101494796B1 (en) 2014-08-22 2015-02-23 고등기술연구원연구조합 System and method for transforming synthesis gas

Also Published As

Publication number Publication date
KR20170137497A (en) 2017-12-13

Similar Documents

Publication Publication Date Title
Nanda et al. Insights on pathways for hydrogen generation from ethanol
Lin Catalytic valorization of glycerol to hydrogen and syngas
Evans et al. A nickel doped perovskite catalyst for reforming methane rich biogas with minimal carbon deposition
Liu et al. Selective catalytic methanation of CO in hydrogen-rich gases over Ni/ZrO2 catalyst
JP5659537B2 (en) Catalyst for reforming tar-containing gas, method for producing the same, and method for reforming tar-containing gas
Gokon et al. Kinetics of methane reforming over Ru/γ-Al2O3-catalyzed metallic foam at 650–900° C for solar receiver-absorbers
JP5780271B2 (en) Catalyst for reforming tar-containing gas, method for producing the same, and method for reforming tar-containing gas
Liu et al. Hydrogen production by glycerol reforming in supercritical water over Ni/MgO-ZrO2 catalyst
Zhang et al. Experimental investigation of steam reforming of methanol over La2CuO4/CuZnAl-oxides nanocatalysts
US20220115682A1 (en) Carbon-neutral process for generating electricity
Yan et al. Hydrogen production by steam reforming of dimethyl ether and CO-PrOx in a metal foam micro-reactor
Deng et al. Producing hydrogen by catalytic steam reforming of methanol using non-noble metal catalysts
AU2022270020A1 (en) Improved catalytic reactor system and catalyst for conversion of captured co2 and renewable h2 into low-carbon syngas
US6713032B2 (en) Catalyst for removing carbon monoxide in hydrogen rich gas and production method therefor
JP6680431B2 (en) An engine that burns hydrogen and oxygen.
Levikhin et al. High-temperature reactor for hydrogen production by partial oxidation of hydrocarbons
JP2017197399A (en) Carbon circulation utilization system
WO2017051610A1 (en) Internal combustion engine
KR101842581B1 (en) Stand-alone Heat-exchanger Type Modular Self-sustaining Reformer
TWI551542B (en) Photocatalysis induced partial oxidation of methanol reaction for producing hydrogen and photocatalyst thereof
Yusuf et al. Recent Advances in Bimetallic Catalysts for Methane Steam Reforming in Hydrogen Production: Current Trends, Challenges, and Future Prospects
Lee et al. Catalytic ammonia decomposition to produce hydrogen: A mini-review
Blinov et al. Metal hydride flow-through hydrogen purification method for renewable energy production and storage
Uy An Exploration of Flow Deflection and Heated Length for Pelletized and Structured Catalysts in Steam-Reforming Reactors
US20240059978A1 (en) One-step process for the production of hydrocarbons from carbon dioxide

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant