WO2015198186A1 - An autothermal reformer reactor and a feeding system thereof - Google Patents

An autothermal reformer reactor and a feeding system thereof Download PDF

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Publication number
WO2015198186A1
WO2015198186A1 PCT/IB2015/054541 IB2015054541W WO2015198186A1 WO 2015198186 A1 WO2015198186 A1 WO 2015198186A1 IB 2015054541 W IB2015054541 W IB 2015054541W WO 2015198186 A1 WO2015198186 A1 WO 2015198186A1
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autothermal reformer
catalyst bed
enables
reformer reactor
natural gas
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PCT/IB2015/054541
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French (fr)
Inventor
Atilla ERSÖZ
Aslı KAYTAZ
Fehmi AKGÜN
Göktuğ Nezihi ÖZYÖNÜM
Murat BARANAK
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Tubitak
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0285Heating or cooling the reactor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0207Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly horizontal
    • B01J8/0221Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly horizontal in a cylindrical shaped bed
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0278Feeding reactive fluids
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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
    • C01B3/382Multi-step processes
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    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00026Controlling or regulating the heat exchange system
    • B01J2208/00035Controlling or regulating the heat exchange system involving measured parameters
    • B01J2208/00044Temperature measurement
    • B01J2208/00061Temperature measurement of the reactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00168Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00176Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles outside the reactor
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    • B01J2208/00017Controlling the temperature
    • B01J2208/00389Controlling the temperature using electric heating or cooling elements
    • B01J2208/00407Controlling the temperature using electric heating or cooling elements outside the reactor bed
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    • B01J2208/00017Controlling the temperature
    • B01J2208/00389Controlling the temperature using electric heating or cooling elements
    • B01J2208/00415Controlling the temperature using electric heating or cooling elements electric resistance heaters
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00477Controlling the temperature by thermal insulation means
    • B01J2208/00495Controlling the temperature by thermal insulation means using insulating materials or refractories
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/0053Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00628Controlling the composition of the reactive mixture
    • B01J2208/00646Means for starting up the reaction
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796Details of the reactor or of the particulate material
    • B01J2208/00823Mixing elements
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2208/00796Details of the reactor or of the particulate material
    • B01J2208/00823Mixing elements
    • B01J2208/00831Stationary elements
    • B01J2208/00849Stationary elements outside the bed, e.g. baffles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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    • C01B2203/08Methods of heating or cooling
    • C01B2203/0872Methods of cooling
    • C01B2203/0888Methods of cooling by evaporation of a fluid
    • C01B2203/0894Generation of steam
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235Hydrocarbons
    • C01B2203/1241Natural gas or methane
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    • C01B2203/1276Mixing of different feed components
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288Evaporation of one or more of the different feed components
    • CCHEMISTRY; METALLURGY
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    • C01B2203/1614Controlling the temperature
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    • C01B2203/1619Measuring the temperature
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    • C01B2203/1628Controlling the pressure
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    • C01B2203/169Controlling the feed
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus

Definitions

  • the present invention relates to an autothermal reformer reactor which enables to produce a gas mixture with enriched hydrogen content and a feeding system of an autothermal reformer reactor which enables to supply optimum flow regime to the said reactor.
  • Hydrogen (H 2 ) can be produced catalytically by water vapour from other hydrocarbon fuels (methanol, LPG, naphtha, gasoline) in addition to natural gas.
  • reaction no. 1 is endothermic whereas the reactions no. 2 and 3 are exothermic. Heat required for the reaction no. 1 is met by the heat produced in the reactions no. 2 and 3. Therefore, autothermal reformer system is provided without the need for heat supply to the system or heat removal.
  • autothermal reformer reactors have a simple design because they do not need an additional heat exchanger.
  • autothermal reformer systems are quite advantageous in terms of start-up time and time of being able to respond to capacity changes which are two of the most critical parameters.
  • the most important parameters determining operation conditions of the process and the product composition can be defined as ratio of the water supplied to the reactor to the total carbon inside the fuel (S/C), ratio of the molecular oxygen supplied to the reactor to the total carbon inside the fuel (0 2 /C), operating temperature of the reactor, operating pressure of the reactor and space velocity (GHSV) of the gas mixture supplied to the reactor.
  • S/C total carbon inside the fuel
  • GHSV space velocity
  • Control of amount of oxygen (0 2 ) supplied to the system is quite important in order that the operating temperature is kept in desired range. Oxidation reactions and conversion reaction by water vapour take place in temperatures above 500°C very quickly by means of catalysts. In these systems, a product composition close to the thermodynamic equilibrium conditions is obtained.
  • temperature distribution in autothermal reformer reactor is characterized by a sudden increase in inlet. Fast oxidation reactions occur in this region where temperature increases. Following this region, temperature decreases because of endothermic reactions.
  • Catalytic combustion can be used as a start-up step for autothermal reformer reactors. Thus, heat required for initiating autothermal reformer reactions is provided by catalytic combustion of methane (CH 4 ).
  • the reaction region is designed as a turnaround chamber and a turn-around wall. Accordingly, the stream of product obtained at the end of the reactor can be returned to the reactant stream. Thus, the stream supplied from the opposite direction and the turn-around stream is in a stream axially.
  • This design provides creation of a low-velocity zone and offers advantages by stabilizing location of a flame.
  • the Japanese patent document no. JP2007326777 discloses a catalyst pre-heating apparatus for start-up of a compact fuel processor unit and a method for providing this. The apparatus described in the said patent document is used for heating the catalyst area in a time elapsed until the heat needed for starting-up the reactions is reached.
  • An electrically-powered heating element is used for heating the catalyst bed directly or indirectly. Direct heating incident is ensured by direct contact of the electrical heating element with the catalyst. Whereas indirect heating incident is ensured by direct heating of the fluid (process flow) sent to the reactor and then passing this fluid through the catalyst bed. Additionally, the electrical heating may be placed within a sheath coating in direct contact with the catalyst or the fluid sent to the catalyst bed.
  • catalysts of many forms, including pellets, extrudates, spheres, and monoliths may be used together with the said catalyst heater.
  • the catalyst heater may be in the form of a resistive wire, cartridge or rod, in a double form such that it may be coupled to a power source.
  • An objective of the present invention is to realize an autothermal reformer reactor which enables to produce a gas mixture with enriched hydrogen content.
  • Another objective of the present invention is to realize a feeding system of an autothermal reformer reactor which enables to supply optimum flow regime to the said reactor.
  • Figure 1 is a front view of the inventive autothermal reformer reactor.
  • Figure 2 is a schematic view of the inventive feeding system of an autothermal reformer reactor.
  • An autothermal reformer reactor (1) which enables to produce a gas mixture with enriched hydrogen content essentially comprises:
  • At least one second inlet port (3) where how water is supplied
  • at least one mixing chamber (4) where hot natural gas, superheated water vapour and air are mixed homogeneously and which is located under the first inlet port (2) and the second inlet port (3);
  • At least one catalyst bed (5) where chemical reactions enabling to produce a gas mixture with enriched hydrogen from mixture of hot natural gas, superheated water vapour and air are realized;
  • At least one outlet port (6) which is located on the lower part of the catalyst bed (5) and where the product obtained in the catalyst bed (5) exits;
  • At least one feeding chamber (7) which is located between the mixing chamber (4) and the catalyst bed (5) and ensures that the mixture of hot natural gas, superheated water vapour and air becoming homogeneous in the mixing chamber (4) is supplied to the catalyst bed (5);
  • At least two distribution plates (8) which are located on the inlet and outlet of the catalyst bed (5), ensures that the stream arriving the catalyst bed (5) from the feeding chamber (7) and the stream leading from the catalyst bed
  • At least one heating unit (9) which is located on the outlet of the feeding chamber (7), ensures that the mixture of hot natural gas, superheated water vapour and air supplied from the feeding chamber (7) to the catalyst bed (5) is heated to the temperature level that will create the reaction to occur in the catalyst bed (5).
  • the inventive autothermal reformer reactor (1) which enables to produce a gas mixture with enriched hydrogen content also comprises at least one first insulating layer (10) which is located on the outer part of the mixing chamber (4) and the feeding chamber (7) and enables generation of heat insulation in the said mixing chamber (4) and the feeding chamber (7).
  • the first insulating layer (10) is made of glass wool.
  • the inventive autothermal reformer reactor (1) which enables to produce a gas mixture with enriched hydrogen content also comprises at least one second insulating layer (11) which wraps the outer part of the catalyst bed (5), enables the catalyst bed (5) to remain stable and ensures heat insulation by minimizing heat transfer from the walls of the catalyst bed (5) outwards.
  • the second insulating layer (11) is made of an insulating layer of a ceramic blanket type.
  • the inventive autothermal reformer reactor (1) which enables to produce a gas mixture with enriched hydrogen content also comprises a plurality of temperature measurement devices (12) enabling to measure temperatures of the inlet of the catalyst bed (5), the inner of the catalyst bed (5), the outlet of the catalyst bed (5) and the outer part of the catalyst bed (5).
  • a thermocouple is used as the temperature measurement devices (12).
  • the heating unit (9) included in the inventive autothermal reformer reactor (1) which enables to produce a gas mixture with enriched hydrogen content is preferably an electric heater.
  • the feeding system (13) which enables to supply optimum flow regime to the inventive autothermal reformer reactor (1) described above comprises:
  • At least one natural gas feeding line (14) which enables to provide the natural gas to be supplied to the autothermal reformer reactor (1);
  • At least one water feeding line (15) which enables to provide the demineralised water to be supplied to the autothermal reformer reactor (1); at least one air feeding line (16) which enables to provide the hot air to be supplied to the autothermal reformer reactor (1);
  • At least one catalytic burner unit (17) which enables to pre-heat the natural gas received from the natural gas feeding line (14) and gives only hot exhaust gas (EGR) as output;
  • At least one first heat exchanger (18) which enables to turn the water (DW) received from the water feeding line (15) into saturated water vapour (SV) by heating it by means of the exhaust gas (EG) exiting the catalytic burner unit (17);
  • At least one second heat exchanger (19) which enables to heat the natural gas (NG) received from the natural gas feeding line (14), by means of the exhaust gas (EG) exiting the catalytic burner unit (17);
  • At least one pre-mixture unit (20) which enables to mix the saturated water vapour (SV) exiting the first heat exchanger (18) and the natural gas (NG) exiting the second heat exchanger (19); and
  • At least one third heat exchanger (21) which enables to heat the mixture of water vapour natural gas (SV+NG) exiting the pre-mixture unit (20) to higher temperatures by means of the gas mixture with enriched hydrogen exiting the autothermal reformer reactor (1).
  • the feeding system (13) which enables to supply optimum flow regime to the inventive autothermal reformer reactor (1) also comprises at least one first control valve (22) which is located between the first heat exchanger (18) and the pre- mixture unit (20) and enables to control temperature and pressure of the saturated water vapour (SV) exiting the first heat exchanger (18).
  • the feeding system (13) which enables to supply optimum flow regime to the inventive autothermal reformer reactor (1) also comprises at least one second control valve (23) which is located between the second heat exchanger (19) and the pre-mixture unit (20) and enables to control temperature and pressure of the hot natural gas (NG) exiting the second heat exchanger (19).
  • the feeding system (13) which enables to supply optimum flow regime to the inventive autothermal reformer reactor (1) also comprises at least one third control valve (24) which is located on the hot air feeding line (16) and enables to control temperature and pressure of the air passing through the line (16).
  • the natural gas feeding line (14) is opened and the natural gas (NG) stream is transmitted to the catalytic burner unit (17).
  • the hot exhaust gas (EG) generated after the catalytic burner unit (17) fires the natural gas (NG) is sent to the first heat exchanger (18) and the second heat exchanger (19).
  • the water feeding line (15) is in off-position and no water supply is realized to the system (1).
  • the natural gas (NG) heated by the hot air received from the hot air feeding line (16) and the gas exiting the catalytic burner unit (17) is supplied into the autothermal reformer reactor (1) from the first inlet port (2) and the second inlet port (3) of the autothermal reformer reactor (1).
  • the streams supplied to the autothermal reformer reactor (1) are almost at temperature of 150°C.
  • the said streams are mixed in the mixing chamber (4) inside the autothermal reformer reactor (1) in a homogeneous way.
  • the mixture reaches the temperature value defined as the ignition moment, it is supplied into the catalyst bed (5) over the distribution plate (8) and partial oxidation reaction starts here.
  • the autothermal reformer reactor (1) is supplied such that desired oxygen/carbon (CVC) value, preferably 0.5, is provided.
  • CVC desired oxygen/carbon
  • the demineralised water feeding line (15) is opened and the demineralised water is (DW) supplied to the first heat exchanger (18).
  • the temperature of the water (DW) heated by means of the exhaust gas (EG) reaches a value predetermined in the outlet of the first heat exchanger (18)
  • the natural gas feeding line (14) is opened.
  • Temperature of the natural gas (NG) supplied from the natural gas feeding line (14) is increased to a predetermined value in the second heat exchanger (19) and the saturated water vapour (SV) and the heated natural gas (NG) obtained in the first heat exchanger (18) are supplied to the pre- mixture unit (20) simultaneously and they are mixed with each other here.
  • the mixture of water vapour natural gas (SV+NG) prepared in the pre-mixture unit (20) also passes through the third heat exchanger (21) before the autothermal reformer reactor (1) is supplied and the temperature of the mixture is increased to almost 450°C.
  • the high-temperature water vapour-natural gas mixture (SV+NG) is supplied from the first inlet port (2) of the autothermal reformer reactor (1) and the hot water is supplied into the autothermal reformer reactor (1) from the second inlet port (3).
  • the mixture of high-temperature water vapour- natural gas mixture (SV+NG) and hot air supplied to the autothermal reformer reactor (1) is mixed with each other in the mixing chamber (4) homogeneously and supplied to the catalyst bed (5) over the distribution plate (8) without needing to operate the heating unit (9) and water vapour conversion reaction starts in the catalyst bed (5).
  • the autothermal reformer reactor (1) switches to autothermal mode.
  • Suitable steam/carbon adjustment is made by natural gas (NG) and water vapour (SV) until the temperature in the outlet port (6) of the autothermal reformer reactor (1) switching to the autothermal mode reaches around 750°C.
  • suitable ratio is between the values of 3-3,5.

Abstract

The present invention relates to an autothermal reformer reactor (1) which enables to produce a gas mixture with enriched hydrogen content and a feeding system of an autothermal reformer reactor which enables to supply optimum flow regime to the said autothermal reformer reactor (1). The reactor comprises at least two inlets (2, 3) that lead to a mixing chamber (4) which in turn is connected to a feeding chamber (7) placed upstream at least one catalyst bed (5). The catalyst bed (5) is located between two distribution plates (8). The reactor further comprises at least one heating unit (9), which is located on the outlet of the feeding chamber (7).

Description

DESCRIPTION
AN AUTOTHERMAL REFORMER REACTOR AND A FEEDING
SYSTEM THEREOF
Technical Field
The present invention relates to an autothermal reformer reactor which enables to produce a gas mixture with enriched hydrogen content and a feeding system of an autothermal reformer reactor which enables to supply optimum flow regime to the said reactor.
Background of the Invention Today, researches on alternative energy sources and their use have gained speed due to the fact that fossil fuels will run out in the near future and because of environmental pollution problems which are created as a result of carbon dioxide, C02, sulphur oxides, SOx, nitrogen oxides, NOx, etc. emissions resulting from fossil fuels. Hydrogen (H2), which is an alternative energy carrier, is a synthetic fuel and production sources thereof are highly plentiful and diversified. Water, coal and natural gas are the primary ones of these sources.
Majority of hydrogen produced in the world is obtained from natural gas by catalytic conversion of methane (CH4) with water vapour. Carbon monoxide (CO), carbon dioxide (C02) and methane (CH4) - which is not converted into product during reaction - are released together with hydrogen during production. The carbon monoxide released is converted into hydrogen (H2) and carbon dioxide (C02) by high and low temperature water-gas conversion reactions and selective oxidation reaction. Hydrogen (H2) can be produced catalytically by water vapour from other hydrocarbon fuels (methanol, LPG, naphtha, gasoline) in addition to natural gas. As average molecular weight of hydrocarbon fuel increases, difficulties (energy need for vaporization, coking etc.) in production process of hydrogen (H2) increase as well. Sulphur (S) content of hydrocarbon leads to significant catalyst poisoning problems in the process. As an alternative for production of hydrogen (H2) through conversion of hydrocarbon fuels by water vapour, it can also be produced through partial oxidation, pyrolysis and autothermal reformer reactions by pure oxygen (02) or air. Autothermal reformer reaction takes place by realizing conversion reaction through water vapour which is endothermic, and partial oxidation reaction which is exothermic, inside the same reactor by using suitable catalyst synchronously. Autothermal reformer reactors (ATR) are the leading thermo-chemical methods used for production of hydrogen (H2) from natural gas.
It is observed that catalytic complete combustion reaction of methane (CH4) starts around 350°C when it is initiated to supply the gas mixture in a stoichiometric ratio before the temperature of experiment is reached while heating the reactor.
Water-gas conversion reactions occur in autothermal reformer reactor environment as well.
Natural gas, water and air/02 are supplied to autothermal reformer reactors together in certain proportions and a gas mixture with enriched hydrogen (H2) content is obtained in conclusion. Mainly, the following reactions occur in the said reactors:
CH4 + H20 CO + 3 H2 ΔΗ = + 206 kJ/kmole (1)
CH4 + ½ 02 CO + 2 H2 ΔΗ = - 247 kJ/mole (2)
CO + H20 - C02 + H2 ΔΗ = - 41,2 kJ/mole (3) The reaction no. 1 is endothermic whereas the reactions no. 2 and 3 are exothermic. Heat required for the reaction no. 1 is met by the heat produced in the reactions no. 2 and 3. Therefore, autothermal reformer system is provided without the need for heat supply to the system or heat removal.
The fact that all heat required in conversion reactions can be provided by partial oxidation reactions is the most important advantage of this method. Therefore, autothermal reformer reactors have a simple design because they do not need an additional heat exchanger. In addition, when residential micro cogeneration applications based on fuel cell are in question, autothermal reformer systems are quite advantageous in terms of start-up time and time of being able to respond to capacity changes which are two of the most critical parameters.
The most important parameters determining operation conditions of the process and the product composition can be defined as ratio of the water supplied to the reactor to the total carbon inside the fuel (S/C), ratio of the molecular oxygen supplied to the reactor to the total carbon inside the fuel (02/C), operating temperature of the reactor, operating pressure of the reactor and space velocity (GHSV) of the gas mixture supplied to the reactor.
Control of amount of oxygen (02) supplied to the system is quite important in order that the operating temperature is kept in desired range. Oxidation reactions and conversion reaction by water vapour take place in temperatures above 500°C very quickly by means of catalysts. In these systems, a product composition close to the thermodynamic equilibrium conditions is obtained. In general, temperature distribution in autothermal reformer reactor is characterized by a sudden increase in inlet. Fast oxidation reactions occur in this region where temperature increases. Following this region, temperature decreases because of endothermic reactions. Catalytic combustion can be used as a start-up step for autothermal reformer reactors. Thus, heat required for initiating autothermal reformer reactions is provided by catalytic combustion of methane (CH4). Stoichiometric combustion of methane (CH4) is ensured in the first two steps and then it is switched to autothermal reformer operation mode. Water vapour, natural gas and air as oxygen (02) source are supplied to the autothermal reformer reactor; and synthesis gas having hydrogen (H2), carbon monoxide (CO), carbon dioxide (C02), unconverted methane (CH4) and airborne nitrogen (N2) in content thereof is obtained. The oxygen (02) included in the air supplied is completely consumed during reaction. The International patent document no. WO2008131562 discloses sending fuel and oxygen streams to a mixing unit and then sending them to a reaction region axially in order to produce a hydrogen-enriched gas mixture. In the invention disclosed in the said patent document, the reaction region is designed as a turnaround chamber and a turn-around wall. Accordingly, the stream of product obtained at the end of the reactor can be returned to the reactant stream. Thus, the stream supplied from the opposite direction and the turn-around stream is in a stream axially. This design provides creation of a low-velocity zone and offers advantages by stabilizing location of a flame. The Japanese patent document no. JP2007326777 discloses a catalyst pre-heating apparatus for start-up of a compact fuel processor unit and a method for providing this. The apparatus described in the said patent document is used for heating the catalyst area in a time elapsed until the heat needed for starting-up the reactions is reached. An electrically-powered heating element is used for heating the catalyst bed directly or indirectly. Direct heating incident is ensured by direct contact of the electrical heating element with the catalyst. Whereas indirect heating incident is ensured by direct heating of the fluid (process flow) sent to the reactor and then passing this fluid through the catalyst bed. Additionally, the electrical heating may be placed within a sheath coating in direct contact with the catalyst or the fluid sent to the catalyst bed. In this context, catalysts of many forms, including pellets, extrudates, spheres, and monoliths, may be used together with the said catalyst heater. The catalyst heater may be in the form of a resistive wire, cartridge or rod, in a double form such that it may be coupled to a power source.
Summary of the Invention
An objective of the present invention is to realize an autothermal reformer reactor which enables to produce a gas mixture with enriched hydrogen content.
Another objective of the present invention is to realize a feeding system of an autothermal reformer reactor which enables to supply optimum flow regime to the said reactor.
Detailed Description of the Invention "An Autothermal Reformer Reactor and A Feeding System Thereof realized to fulfil the objectives of the present invention is shown in the figures attached, in which:
Figure 1 is a front view of the inventive autothermal reformer reactor.
Figure 2 is a schematic view of the inventive feeding system of an autothermal reformer reactor.
The components illustrated in the figures are individually numbered, where the numbers refer to the following:
1. Autothermal reformer reactor
2. First inlet port
3. Second inlet port
4. Mixing chamber
5. Catalyst bed
6. Outlet port 7. Feeding chamber
8. Di stributi on pi ate
9. Heating unit
10. First insulating layer
11. Second insulating layer
12. Temperature measurement device
13. Feeding system
14. Natural gas feeding line
15. Water feeding line
16. Air feeding line
17. Catalytic burner unit
18. First heat exchanger
19. Second heat exchanger
20. Pre-mixture unit
21. Third heat exchanger
22. First control valve
23. Second control valve
24. Third control valve
DW: demineralised water
SV: saturated water vapour
NG: natural gas
EG: exhaust gas
An autothermal reformer reactor (1) which enables to produce a gas mixture with enriched hydrogen content essentially comprises:
at least one first inlet port (2) where mixture of hot natural gas and superheated water vapour are supplied;
at least one second inlet port (3) where how water is supplied; at least one mixing chamber (4) where hot natural gas, superheated water vapour and air are mixed homogeneously and which is located under the first inlet port (2) and the second inlet port (3);
at least one catalyst bed (5) where chemical reactions enabling to produce a gas mixture with enriched hydrogen from mixture of hot natural gas, superheated water vapour and air are realized;
at least one outlet port (6) which is located on the lower part of the catalyst bed (5) and where the product obtained in the catalyst bed (5) exits;
at least one feeding chamber (7) which is located between the mixing chamber (4) and the catalyst bed (5) and ensures that the mixture of hot natural gas, superheated water vapour and air becoming homogeneous in the mixing chamber (4) is supplied to the catalyst bed (5);
at least two distribution plates (8) which are located on the inlet and outlet of the catalyst bed (5), ensures that the stream arriving the catalyst bed (5) from the feeding chamber (7) and the stream leading from the catalyst bed
(5) to the outlet port (6) are uniform; and
at least one heating unit (9) which is located on the outlet of the feeding chamber (7), ensures that the mixture of hot natural gas, superheated water vapour and air supplied from the feeding chamber (7) to the catalyst bed (5) is heated to the temperature level that will create the reaction to occur in the catalyst bed (5).
The inventive autothermal reformer reactor (1) which enables to produce a gas mixture with enriched hydrogen content also comprises at least one first insulating layer (10) which is located on the outer part of the mixing chamber (4) and the feeding chamber (7) and enables generation of heat insulation in the said mixing chamber (4) and the feeding chamber (7). In a preferred embodiment of the invention, the first insulating layer (10) is made of glass wool. The inventive autothermal reformer reactor (1) which enables to produce a gas mixture with enriched hydrogen content also comprises at least one second insulating layer (11) which wraps the outer part of the catalyst bed (5), enables the catalyst bed (5) to remain stable and ensures heat insulation by minimizing heat transfer from the walls of the catalyst bed (5) outwards. In a preferred embodiment of the invention, the second insulating layer (11) is made of an insulating layer of a ceramic blanket type.
The inventive autothermal reformer reactor (1) which enables to produce a gas mixture with enriched hydrogen content also comprises a plurality of temperature measurement devices (12) enabling to measure temperatures of the inlet of the catalyst bed (5), the inner of the catalyst bed (5), the outlet of the catalyst bed (5) and the outer part of the catalyst bed (5). In a preferred embodiment of the invention, a thermocouple is used as the temperature measurement devices (12).
The heating unit (9) included in the inventive autothermal reformer reactor (1) which enables to produce a gas mixture with enriched hydrogen content, is preferably an electric heater.
The feeding system (13) which enables to supply optimum flow regime to the inventive autothermal reformer reactor (1) described above comprises:
at least one natural gas feeding line (14) which enables to provide the natural gas to be supplied to the autothermal reformer reactor (1);
at least one water feeding line (15) which enables to provide the demineralised water to be supplied to the autothermal reformer reactor (1); at least one air feeding line (16) which enables to provide the hot air to be supplied to the autothermal reformer reactor (1);
at least one catalytic burner unit (17) which enables to pre-heat the natural gas received from the natural gas feeding line (14) and gives only hot exhaust gas (EGR) as output;
at least one first heat exchanger (18) which enables to turn the water (DW) received from the water feeding line (15) into saturated water vapour (SV) by heating it by means of the exhaust gas (EG) exiting the catalytic burner unit (17);
at least one second heat exchanger (19) which enables to heat the natural gas (NG) received from the natural gas feeding line (14), by means of the exhaust gas (EG) exiting the catalytic burner unit (17);
at least one pre-mixture unit (20) which enables to mix the saturated water vapour (SV) exiting the first heat exchanger (18) and the natural gas (NG) exiting the second heat exchanger (19); and
at least one third heat exchanger (21) which enables to heat the mixture of water vapour natural gas (SV+NG) exiting the pre-mixture unit (20) to higher temperatures by means of the gas mixture with enriched hydrogen exiting the autothermal reformer reactor (1).
The feeding system (13) which enables to supply optimum flow regime to the inventive autothermal reformer reactor (1) also comprises at least one first control valve (22) which is located between the first heat exchanger (18) and the pre- mixture unit (20) and enables to control temperature and pressure of the saturated water vapour (SV) exiting the first heat exchanger (18).
The feeding system (13) which enables to supply optimum flow regime to the inventive autothermal reformer reactor (1) also comprises at least one second control valve (23) which is located between the second heat exchanger (19) and the pre-mixture unit (20) and enables to control temperature and pressure of the hot natural gas (NG) exiting the second heat exchanger (19).
The feeding system (13) which enables to supply optimum flow regime to the inventive autothermal reformer reactor (1) also comprises at least one third control valve (24) which is located on the hot air feeding line (16) and enables to control temperature and pressure of the air passing through the line (16). In order that a gas mixture with enriched hydrogen content is produced by the autothermal reformer reactor (1) in the feeding system (13) which enables to supply optimum flow regime to the autothermal reformer reactor (1), firstly the natural gas feeding line (14) is opened and the natural gas (NG) stream is transmitted to the catalytic burner unit (17). The hot exhaust gas (EG) generated after the catalytic burner unit (17) fires the natural gas (NG) is sent to the first heat exchanger (18) and the second heat exchanger (19). While the hot exhaust gas (EG) is being supplied to the first heat exchanger (18) and the second heat exchanger (19), the water feeding line (15) is in off-position and no water supply is realized to the system (1). Upon production of the mixture with enriched hydrogen content is started, the natural gas (NG) heated by the hot air received from the hot air feeding line (16) and the gas exiting the catalytic burner unit (17) is supplied into the autothermal reformer reactor (1) from the first inlet port (2) and the second inlet port (3) of the autothermal reformer reactor (1). In a preferred embodiment of the invention, the streams supplied to the autothermal reformer reactor (1) are almost at temperature of 150°C. The said streams are mixed in the mixing chamber (4) inside the autothermal reformer reactor (1) in a homogeneous way. The mixture of natural gas (NG) air mixed homogeneously passes from the mixing chamber (4) to the heating unit (9) and the mixture is heated here by the heating unit (9) such that it will reach the temperature value defined as the first ignition moment, preferably 450°C. When the mixture reaches the temperature value defined as the ignition moment, it is supplied into the catalyst bed (5) over the distribution plate (8) and partial oxidation reaction starts here. The autothermal reformer reactor (1) is supplied such that desired oxygen/carbon (CVC) value, preferably 0.5, is provided. The flow temperature of the outlet port (6) of the autothermal reformer reactor (1) also reaches temperature of almost 500°C when desired ratio is provided. When the temperature of the outlet port (6) of the autothermal reformer reactor (1) reaches the value of almost 500°C and the temperature of the catalytic burner unit (17) also reaches the values of between 480-500°C, the demineralised water feeding line (15) is opened and the demineralised water is (DW) supplied to the first heat exchanger (18). When the temperature of the water (DW) heated by means of the exhaust gas (EG) reaches a value predetermined in the outlet of the first heat exchanger (18), the natural gas feeding line (14) is opened. Temperature of the natural gas (NG) supplied from the natural gas feeding line (14) is increased to a predetermined value in the second heat exchanger (19) and the saturated water vapour (SV) and the heated natural gas (NG) obtained in the first heat exchanger (18) are supplied to the pre- mixture unit (20) simultaneously and they are mixed with each other here. The mixture of water vapour natural gas (SV+NG) prepared in the pre-mixture unit (20) also passes through the third heat exchanger (21) before the autothermal reformer reactor (1) is supplied and the temperature of the mixture is increased to almost 450°C. After this, the high-temperature water vapour-natural gas mixture (SV+NG) is supplied from the first inlet port (2) of the autothermal reformer reactor (1) and the hot water is supplied into the autothermal reformer reactor (1) from the second inlet port (3). The mixture of high-temperature water vapour- natural gas mixture (SV+NG) and hot air supplied to the autothermal reformer reactor (1) is mixed with each other in the mixing chamber (4) homogeneously and supplied to the catalyst bed (5) over the distribution plate (8) without needing to operate the heating unit (9) and water vapour conversion reaction starts in the catalyst bed (5). Thus, the autothermal reformer reactor (1) switches to autothermal mode. Suitable steam/carbon adjustment is made by natural gas (NG) and water vapour (SV) until the temperature in the outlet port (6) of the autothermal reformer reactor (1) switching to the autothermal mode reaches around 750°C. In a preferred embodiment of the invention, suitable ratio is between the values of 3-3,5. When the temperature in the outlet port (6) of the autothermal reformer reactor (1) is 750°C, the mixture with enriched hydrogen is sent from the outlet port (6) to the hydrogen purification reactors at the temperature of 450°C.
In a preferred embodiment of the invention, it is ensured that the system is cleaned entirely by pumping nitrogen (N2) to all lines and units before the feeding system (13) which enables to supply optimum flow regime to the inventive autothermal reformer reactor (1) is run.
Within these basic concepts, it is possible to develop a great variety of embodiments of the inventive "An Autothermal Reformer Reactor and A Feeding System Thereof; it cannot be limited to the examples disclosed herein and it is essentially according to the claims.

Claims

An autothermal reformer reactor (1) which enables to produce a gas mixture with enriched hydrogen content essentially comprising:
at least one first inlet port (2) where mixture of hot natural gas and superheated water vapour are supplied;
at least one second inlet port (3) where how water is supplied;
at least one mixing chamber (4) where hot natural gas, superheated water vapour and air are mixed homogeneously and which is located under the first inlet port (2) and the second inlet port (3);
at least one catalyst bed (5) where chemical reactions enabling to produce a gas mixture with enriched hydrogen from mixture of hot natural gas, superheated water vapour and air are realized;
at least one outlet port (6) which is located on the lower part of the catalyst bed (5) and where the product obtained in the catalyst bed (5) exits;
at least one feeding chamber (7) which is located between the mixing chamber (4) and the catalyst bed (5) and ensures that the mixture of hot natural gas, superheated water vapour and air becoming homogeneous in the mixing chamber (4) is supplied to the catalyst bed (5);
at least two distribution plates (8) which are located on the inlet and outlet of the catalyst bed (5), ensures that the stream arriving the catalyst bed (5) from the feeding chamber (7) and the stream leading from the catalyst bed
(5) to the outlet port (6) are uniform;
and characterized by
at least one heating unit (9) which is located on the outlet of the feeding chamber (7), ensures that the mixture of hot natural gas, superheated water vapour and air supplied from the feeding chamber (7) to the catalyst bed (5) is heated to the temperature level that will create the reaction to occur in the catalyst bed (5).
2. An autothermal reformer reactor (1) according to Claim 1; characterized by at least one first insulating layer (10) which is located on the outer part of the mixing chamber (4) and the feeding chamber (7) and enables generation of heat insulation in the said mixing chamber (4) and the feeding chamber (7).
3. An autothermal reformer reactor (1) according to Claim 1; characterized by at least one first insulating layer (10) which is made of glass wool.
4. An autothermal reformer reactor (1) according to any of Claim 1 to 3;
characterized by at least one second insulating layer (11) which wraps the outer part of the catalyst bed (5), enables the catalyst bed (5) to remain stable and ensures heat insulation by minimizing heat transfer from the walls of the catalyst bed (5) outwards.
5. An autothermal reformer reactor (1) according to Claim 4; characterized by at least one second insulating layer (11) which is an insulating layer of a ceramic blanket type.
6. An autothermal reformer reactor (1) according to any of the preceding claims; characterized by a plurality of temperature measurement devices (12) which enable to measure temperatures of the inlet of the catalyst bed (5), the inner of the catalyst bed (5), the outlet of the catalyst bed (5) and the outer part of the catalyst bed (5).
7. An autothermal reformer reactor (1) according to Claim 6; characterized by the temperature measurement device (12) which is a thermocouple.
8. An autothermal reformer reactor (1) according to any of the preceding claims; characterized by the heating unit (9) which is an electric heater.
9. A feeding system (13) which enables to supply optimum flow regime to an autothermal reformer reactor (1) according to any of the preceding claims comprising:
at least one natural gas feeding line (14) which enables to provide the natural gas to be supplied to the autothermal reformer reactor (1);
at least one water feeding line (15) which enables to provide the demineralised water to be supplied to the autothermal reformer reactor (1); at least one air feeding line (16) which enables to provide the hot air to be supplied to the autothermal reformer reactor (1);
and characterized by
at least one catalytic burner unit (17) which enables to pre-heat the natural gas received from the natural gas feeding line (14) and gives only hot exhaust gas (EGR) as output;
at least one first heat exchanger (18) which enables to turn the water (DW) received from the water feeding line (15) into saturated water vapour (SV) by heating it by means of the exhaust gas (EG) exiting the catalytic burner unit (17);
at least one second heat exchanger (19) which enables to heat the natural gas (NG) received from the natural gas feeding line (14), by means of the exhaust gas (EG) exiting the catalytic burner unit (17);
at least one pre-mixture unit (20) which enables to mix the saturated water vapour (SV) exiting the first heat exchanger (18) and the natural gas (NG) exiting the second heat exchanger (19); and
at least one third heat exchanger (21) which enables to heat the mixture of water vapour natural gas mixture (SV+NG) exiting the pre-mixture unit
(20) to higher temperatures by means of the gas mixture with enriched hydrogen exiting the autothermal reformer reactor (1).
10. An autothermal reformer reactor (1) according to Claim 9; characterized by at least one first control valve (22) which is located between the first heat exchanger (18) and the pre-mixture unit (20) and enables to control temperature and pressure of the saturated water vapour (SV) exiting the first heat exchanger (18).
11. An autothermal reformer reactor (1) according to Claim 9 or 10;
characterized by at least one second control valve (23) which is located between the second heat exchanger (19) and the pre-mixture unit (20) and enables to control temperature and pressure of the hot natural gas (NG) exiting the second heat exchanger (19).
12. An autothermal reformer reactor (1) according to any of Claim 9 to 11;
characterized by at least one third control valve (24) which is located on the hot air feeding line (16) and enables to control temperature and pressure of the air passing through the line (16).
PCT/IB2015/054541 2014-06-23 2015-06-16 An autothermal reformer reactor and a feeding system thereof WO2015198186A1 (en)

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