WO2022167591A1 - Heating unit, in particular for a device for water thermolysis - Google Patents

Heating unit, in particular for a device for water thermolysis Download PDF

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Publication number
WO2022167591A1
WO2022167591A1 PCT/EP2022/052732 EP2022052732W WO2022167591A1 WO 2022167591 A1 WO2022167591 A1 WO 2022167591A1 EP 2022052732 W EP2022052732 W EP 2022052732W WO 2022167591 A1 WO2022167591 A1 WO 2022167591A1
Authority
WO
WIPO (PCT)
Prior art keywords
heating unit
ceramic material
thermal coefficient
electric conductive
hollow tube
Prior art date
Application number
PCT/EP2022/052732
Other languages
French (fr)
Inventor
Nils Kongmark
Original Assignee
Ultra High Temperature Processes Ltd
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 Ultra High Temperature Processes Ltd filed Critical Ultra High Temperature Processes Ltd
Priority to EP22704893.1A priority Critical patent/EP4304978A1/en
Publication of WO2022167591A1 publication Critical patent/WO2022167591A1/en

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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
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C01B3/045—Decomposition of water in gaseous phase
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0203—Preparation of oxygen from inorganic compounds
    • C01B13/0207—Water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0251—Physical processing only by making use of membranes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/141—Conductive ceramics, e.g. metal oxides, metal carbides, barium titanate, ferrites, zirconia, vitrous compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/22—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible
    • H05B3/28—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor embedded in insulating material
    • H05B3/283—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor embedded in insulating material the insulating material being an inorganic material, e.g. ceramic

Definitions

  • the invention relates to a heating unit which can withstand very elevated temperatures and/or highly oxidative and/or corrosive atmospheres .
  • the invention also pertains to the use of such a heating unit in a device for splitting water into hydrogen and oxygen by thermolysis .
  • US patent No . 7 , 935 , 254 discloses a device for the thermolysis or thermal decomposition of water at temperatures exceeding 2000 ° C .
  • the material of the heating unit has di f ficulties in withstanding not only the elevated temperature but also the oxidative atmosphere due to the presence of steam which, at a temperature of 2250 ° C (which is the economic temperature ) , is aggressive .
  • the main goal of the invention is to provide a heating unit which has a better ability to withstand ultrahigh temperatures as well as oxidative and/or corrosive atmospheres .
  • a heating unit comprising :
  • the invention also concerns a process for making the above heating unit , comprising a step of applying on the surface of the ceramic material facing the interior of the heating unit a coating of a high thermal resistive material .
  • the invention deals with the use of the heating unit in a device for splitting water into hydrogen and oxygen by thermolysis .
  • FIG. 1 a front view of a heating unit according to the invention.
  • FIG. 2 a side sectional view along A-A of the heating unit of figure 1 .
  • the heating unit may have a general rectangular parallelepipedal closed shape and it comprises a ceramic material 1 preferably having the form of a rectangular parallelepiped with no upper face , having a high thermal coef ficient , that is , usually greater than 170 W/m/ °K and preferably greater than 200 W/m/ °K; - an electric conductive ceramic material 2 , preferably also having the form of a rectangular parallelepiped with no upper face , surrounding the ceramic material 1 and having a high electrical conductivity, that is , usually greater than 37 . 10 6 Siemens/m and preferably greater than 50 .
  • an electrical heating element 3 preferably is an electrical resistor, embedded in the electric conductive ceramic material 2 , preferably almost along the entire surface thereof , and preferably also having the form of a rectangular parallelepiped with no upper face , a ceramic material 4 having a general rectangular parallelepipedal closed shape and a low thermal coe f ficient , that is , usually lower than 10 W/m/ °K and preferably lower than 5 W/m/ °K, entirely surrounding the electric conductive ceramic material 3 as well as the ceramic material 1 , an external insulating material 5 having a general rectangular parallelepipedal closed shape , entirely surrounding the ceramic material 4 , and having a low thermal coef ficient , that is , usually lower than 10 W/m/ °K and preferably lower than 4 W/m/ °K, and an electrical conductor 6 connecting the electrical heating element 3 with the exterior of the heating unit and preferably located in the center of one face of the heating unit
  • the preferred ceramic materials are as follows :
  • the external insulating material 5 is preferably made of ZrO2 materials in form of panels so placed that the heat radiation frequency can choke the heat trans fer .
  • the dimensions of the heating unit may be for example 50 cm (width) x 80 cm ( length) x 50 cm (height ) .
  • the electrical conductor 6 may be a ultra-high temperature conductor (UHTC ) having for example a circular cross-section of 15 mm .
  • UHTC ultra-high temperature conductor
  • ceramic material 1 The role of ceramic material 1 is to protect ceramic material 2 and also to trans fer a maximum of the developed heat energy in the heating elements to the reactor space where the coating protects it against the steam or other matter in the rector space , i . e . , it shall have a high thermal conductivity .
  • the heating device comprises at least one hollow tube 8 extending through the heating unit and having one closed end 9 , the other end 10 being opened.
  • the diameter of tube 8 is generally comprised between 20 and 40 mm, preferably between 25 mm and 40 mm.
  • the hollow tubes 8 preferably consist in a mixed ionic- electronic conducting (MIEC) ceramic, which make them permeable to oxygen at high temperatures especially at high temperatures, i.e. at least 2000°C.
  • MIEC mixed ionic- electronic conducting
  • the surface of ceramic material 1 facing the interior of the heating unit advantageously has a coating (not shown on the figures) having a heat resistance greater than 3000°C, preferably at least 3245°C.
  • the material of the coating is preferably a mixture of boride and carbide.
  • the thickness of the coating is usually about 2-3 nm.
  • the coating may have been applied on at least a part of the surface of ceramic material 1, preferably by atomic vapor deposition (AVD) .
  • ALD atomic vapor deposition
  • the heating unit further comprises at least one inlet and at least one outlet (not shown on the figures) , for example for the entry and the exit of gases.
  • the electrical conductor 6 is supplied with a direct current (DC) , having for example an intensity (amperage) of >100 A and with a voltage of 4 V by a usual supply cable connected to the free end of electrical conductor 6.
  • DC direct current
  • the heating unit of the invention may advantageously be used in a device for splitting water into hydrogen and oxygen by thermolysis, like that disclosed in the above US patent No. 7,935,254. It is most preferably used in the device and process as described in European patent application filed by the Applicant on 4 th February 2021 under filing number EP21315016 . 2 . In that latter case , the heating unit advantageously is the reactor of the device , the free end 10 of the hollow tube 8 is connected to the oxygen mani fold of the device ( i f any) and/or the electrical conductor 6 is connected to a DC power source .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Analytical Chemistry (AREA)
  • Resistance Heating (AREA)

Abstract

The invention relates to a heating unit which can withstand very elevated temperatures and/or highly oxidative and/or corrosive atmospheres. This heating unit comprises: a ceramic material (1) having a thermal coefficient greater than 170 W/m/°K, - an electric conductive ceramic material (2) surrounding the ceramic material (1) and having a thermal coefficient greater than 37.106 Siemens/m, - an electrical heating element (3) embedded in the electric conductive ceramic material (2), - a ceramic material (4) having a thermal coefficient lower than 10 W/m/°K and surrounding the electric conductive ceramic material (2) and the ceramic material (1), an external insulating material (5) surrounding the ceramic material (4) and having a thermal coefficient lower than 10 W/m/°K, an electrical conductor (6) connecting the electrical heating element (3) with the exterior of the heating unit, and - at least one hollow tube (8) extending through the heating unit. The invention also pertains to the use of the above heating unit.

Description

HEATING UNIT , IN PARTICULAR FOR A DEVICE FOR WATER
THERMOLYSIS
The invention relates to a heating unit which can withstand very elevated temperatures and/or highly oxidative and/or corrosive atmospheres .
The invention also pertains to the use of such a heating unit in a device for splitting water into hydrogen and oxygen by thermolysis .
Background of the Invention
US patent No . 7 , 935 , 254 discloses a device for the thermolysis or thermal decomposition of water at temperatures exceeding 2000 ° C . However, at such temperatures , the material of the heating unit has di f ficulties in withstanding not only the elevated temperature but also the oxidative atmosphere due to the presence of steam which, at a temperature of 2250 ° C (which is the economic temperature ) , is aggressive .
Summary of the Invention
The main goal of the invention is to provide a heating unit which has a better ability to withstand ultrahigh temperatures as well as oxidative and/or corrosive atmospheres .
To this ef fect , the inventor has developed a heating unit comprising :
- a ceramic material having a high thermal coef ficient ,
- an electric conductive ceramic material surrounding the ceramic material having a high thermal coef ficient ,
- an electrical heating element embedded in the electric conductive ceramic material , a ceramic material having a low thermal coef ficient surrounding the electric conductive ceramic material and the ceramic material having a high thermal coef ficient ,
- an external insulating material surrounding the ceramic material having a low thermal coef ficient and
- an electrical conductor connecting the electrical heating element with the exterior of the heating unit .
The invention also concerns a process for making the above heating unit , comprising a step of applying on the surface of the ceramic material facing the interior of the heating unit a coating of a high thermal resistive material .
According to another aspect , the invention deals with the use of the heating unit in a device for splitting water into hydrogen and oxygen by thermolysis .
Other features and advantages of the invention will now be described in detail in the following description, which refers to the appended figures that schematically shows an embodiment of the device of the invention :
[ Fig . 1 ] : a front view of a heating unit according to the invention; and
[ Fig . 2 ] : a side sectional view along A-A of the heating unit of figure 1 .
Detailed description of the invention
An embodiment of the invention is shown in the appended figures .
The heating unit may have a general rectangular parallelepipedal closed shape and it comprises a ceramic material 1 preferably having the form of a rectangular parallelepiped with no upper face , having a high thermal coef ficient , that is , usually greater than 170 W/m/ °K and preferably greater than 200 W/m/ °K; - an electric conductive ceramic material 2 , preferably also having the form of a rectangular parallelepiped with no upper face , surrounding the ceramic material 1 and having a high electrical conductivity, that is , usually greater than 37 . 106 Siemens/m and preferably greater than 50 . 106 Siemens/m, having a general rectangular parallelepipedal closed shape/ an electrical heating element 3 preferably is an electrical resistor, embedded in the electric conductive ceramic material 2 , preferably almost along the entire surface thereof , and preferably also having the form of a rectangular parallelepiped with no upper face , a ceramic material 4 having a general rectangular parallelepipedal closed shape and a low thermal coe f ficient , that is , usually lower than 10 W/m/ °K and preferably lower than 5 W/m/ °K, entirely surrounding the electric conductive ceramic material 3 as well as the ceramic material 1 , an external insulating material 5 having a general rectangular parallelepipedal closed shape , entirely surrounding the ceramic material 4 , and having a low thermal coef ficient , that is , usually lower than 10 W/m/ °K and preferably lower than 4 W/m/ °K, and an electrical conductor 6 connecting the electrical heating element 3 with the exterior of the heating unit and preferably located in the center of one face of the heating unit .
The preferred ceramic materials are as follows :
- ceramic material 1 : doped AIN ( aluminum nitride ) /
- electric conductive ceramic material 2 : lead dioxide mixture/
- ceramic material 4 : SiC . The external insulating material 5 is preferably made of ZrO2 materials in form of panels so placed that the heat radiation frequency can choke the heat trans fer .
The dimensions of the heating unit may be for example 50 cm (width) x 80 cm ( length) x 50 cm (height ) .
Examples of thicknesses of the ceramic materials may be as follows : for the ceramic material 1 : 20 mm; for the electric conductive ceramic material 2 : 30 mm; for the electrical heating element 3 : 5 mm; for the ceramic material 4 : 40 - 50 mm; and for the external insulating material 5 the thickness can vary with the temperature and the use of air ( k = 0 . 06 ) . It is preferably equal to the distance between ceramic material 4 and the vessel double wall . It varies with the capacity of the heating unit and the installation of the heating unit . Finally the distances of air (between the insulation panels ) depend on the heat radiation wave length so the thickness should be seen as a distance .
The electrical conductor 6 may be a ultra-high temperature conductor (UHTC ) having for example a circular cross-section of 15 mm .
The role of ceramic material 1 is to protect ceramic material 2 and also to trans fer a maximum of the developed heat energy in the heating elements to the reactor space where the coating protects it against the steam or other matter in the rector space , i . e . , it shall have a high thermal conductivity .
According to a preferred embodiment , the heating device comprises at least one hollow tube 8 extending through the heating unit and having one closed end 9 , the other end 10 being opened. The diameter of tube 8 is generally comprised between 20 and 40 mm, preferably between 25 mm and 40 mm.
The hollow tubes 8 preferably consist in a mixed ionic- electronic conducting (MIEC) ceramic, which make them permeable to oxygen at high temperatures especially at high temperatures, i.e. at least 2000°C.
The surface of ceramic material 1 facing the interior of the heating unit advantageously has a coating (not shown on the figures) having a heat resistance greater than 3000°C, preferably at least 3245°C.
The material of the coating is preferably a mixture of boride and carbide.
The thickness of the coating is usually about 2-3 nm.
The coating may have been applied on at least a part of the surface of ceramic material 1, preferably by atomic vapor deposition (AVD) .
In a preferred embodiment, the heating unit further comprises at least one inlet and at least one outlet (not shown on the figures) , for example for the entry and the exit of gases.
Use of the heating unit
According to the invention, in order for the heating unit to function, the electrical conductor 6 is supplied with a direct current (DC) , having for example an intensity (amperage) of >100 A and with a voltage of 4 V by a usual supply cable connected to the free end of electrical conductor 6.
The heating unit of the invention may advantageously be used in a device for splitting water into hydrogen and oxygen by thermolysis, like that disclosed in the above US patent No. 7,935,254. It is most preferably used in the device and process as described in European patent application filed by the Applicant on 4th February 2021 under filing number EP21315016 . 2 . In that latter case , the heating unit advantageously is the reactor of the device , the free end 10 of the hollow tube 8 is connected to the oxygen mani fold of the device ( i f any) and/or the electrical conductor 6 is connected to a DC power source .

Claims

7 Claims
1.- A heating unit comprising: a ceramic material (1) having a thermal coefficient greater than 170 W/m/°K,
- an electric conductive ceramic material (2) surrounding the ceramic material (1) and having a thermal coefficient greater than 37.106 Siemens/m,
- an electrical heating element (3) embedded in the electric conductive ceramic material (2) ,
- a ceramic material (4) having a thermal coefficient lower than 10 W/m/°K and surrounding the electric conductive ceramic material (2) and the ceramic material (1) , an external insulating material (5) surrounding the ceramic material (4) and having a thermal coefficient lower than 10 W/m/°K, an electrical conductor (6) connecting the electrical heating element (3) with the exterior of the heating unit, and
- at least one hollow tube (8) extending through the heating unit .
2.- The heating unit of claim 1, wherein the thermal coefficient of the ceramic material (1) is greater than 200 W/m/°K.
3.- The heating unit of claim 1 or 2, wherein the ceramic material (1) is doped AIN.
4.- The heating unit of any one of claims 1 to 3, wherein the thermal coefficient of the electric conductive ceramic material (2) is greater than 50.106 Siemens/m. 8
5.- The heating unit of any one of claims 1 to 4, wherein the electric conductive ceramic material (2) is a lead dioxide mixture.
6.- The heating unit of any one of claims 1 to 5, wherein the ceramic material (4) has a thermal coefficient lower than 5 W/m/°K.
7 The heating unit of any one of claims 1 to 6, wherein the ceramic material (4) is SiC.
8.- The heating unit of any one of claims 1 to 7, wherein one end (9) of tube (8) is closed.
9.- The heating unit of any one of claims 1 to 8, wherein the hollow tube (8) is permeable to oxygen.
10.- The heating unit of any one of claims 1 to 9, wherein the hollow tube (8) consists in a mixed ionic-electronic conducting (MIEC) ceramic.
11.- The heating unit of any one of claims 1 to 10 having a rectangular parallelepipedal shape.
12.- The heating unit of any one of claims 1 to 11, wherein the surface of the ceramic material (1) facing the interior of the heating unit has a coating having a heat resistance greater than 3000°C.
13.- The heating unit of claims 12, wherein the coating has a heat resistance greater than 3245°C.
14.- The heating unit of claim 12 or 13, wherein the coating is a mixture of boride and carbide.
15.- The heating unit of any one of claims 12 to 14, wherein said coating has a thickness of about 2-3 nm.
16.- The heating unit of any one of claims 1 to 15, further comprising at least one inlet and at least one outlet.
17.- Process for making a heating unit of claims 12 to 15, or of claim 16 when depending on claims 12 to 15, wherein the coating is applied by atomic vapor deposition.
18.- Use of a heating unit according to any one of claims 1 to 16, wherein the electrical conductor (6) is supplied with a direct current (DC) .
19.- Use of a heating unit according to any one of claims 1 to 16 in a device for splitting water into hydrogen and oxygen by thermolysis.
20.- Use of claim 19, wherein the heating unit is the reactor of the device.
21.- Use according to any one of claims 18 to 20, wherein the hollow tube (8) is permeable to oxygen.
22.- Use according to any one of claims 18 to 20, wherein the hollow tube (8) consists in a mixed ionic-electronic conducting (MIEC) ceramic. 10
23.- Use of claim 21 or 22, wherein the free end (10) of the hollow tube (8) is connected to an oxygen manifold.
24.- Use according to any one of claims 20 to 23, wherein the electrical conductor (6) is connected to a DC power source .
PCT/EP2022/052732 2021-02-05 2022-02-04 Heating unit, in particular for a device for water thermolysis WO2022167591A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP22704893.1A EP4304978A1 (en) 2021-02-05 2022-02-04 Heating unit, in particular for a device for water thermolysis

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21315017 2021-02-05
EP21315017.0 2021-02-05

Publications (1)

Publication Number Publication Date
WO2022167591A1 true WO2022167591A1 (en) 2022-08-11

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2022/052732 WO2022167591A1 (en) 2021-02-05 2022-02-04 Heating unit, in particular for a device for water thermolysis

Country Status (2)

Country Link
EP (1) EP4304978A1 (en)
WO (1) WO2022167591A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB370198A (en) * 1927-08-07 1932-04-07 Gottfried Fuchs Apparatus for splitting up water into hydrogen and oxygen
US7935254B2 (en) 2004-12-16 2011-05-03 H2 Power Systems Ltd Reactor for simultaneous separation of hydrogen and oxygen from water
US20150251905A1 (en) * 2014-03-07 2015-09-10 Stellar Generation, Inc. Separating Hydrogen From Disassociated Water

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB370198A (en) * 1927-08-07 1932-04-07 Gottfried Fuchs Apparatus for splitting up water into hydrogen and oxygen
US7935254B2 (en) 2004-12-16 2011-05-03 H2 Power Systems Ltd Reactor for simultaneous separation of hydrogen and oxygen from water
US20150251905A1 (en) * 2014-03-07 2015-09-10 Stellar Generation, Inc. Separating Hydrogen From Disassociated Water

Also Published As

Publication number Publication date
EP4304978A1 (en) 2024-01-17

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