WO2014085598A1 - Systèmes et procédés pour produire du gaz hydrogène - Google Patents
Systèmes et procédés pour produire du gaz hydrogène Download PDFInfo
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- WO2014085598A1 WO2014085598A1 PCT/US2013/072248 US2013072248W WO2014085598A1 WO 2014085598 A1 WO2014085598 A1 WO 2014085598A1 US 2013072248 W US2013072248 W US 2013072248W WO 2014085598 A1 WO2014085598 A1 WO 2014085598A1
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- WO
- WIPO (PCT)
- Prior art keywords
- hydrocarbon feedstock
- volume
- reaction chamber
- carrier gas
- ultrasonic agitation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 96
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 223
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 223
- 239000012159 carrier gas Substances 0.000 claims abstract description 218
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 181
- 238000006243 chemical reaction Methods 0.000 claims abstract description 172
- 230000001590 oxidative effect Effects 0.000 claims abstract description 23
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 79
- 229910052799 carbon Inorganic materials 0.000 claims description 79
- 239000000126 substance Substances 0.000 claims description 73
- 238000010438 heat treatment Methods 0.000 claims description 63
- 238000013019 agitation Methods 0.000 claims description 57
- 238000000354 decomposition reaction Methods 0.000 claims description 47
- 230000008021 deposition Effects 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 177
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 3
- 229910002090 carbon oxide Inorganic materials 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 26
- 238000002347 injection Methods 0.000 description 22
- 239000007924 injection Substances 0.000 description 22
- 238000000926 separation method Methods 0.000 description 19
- 238000002485 combustion reaction Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 238000001914 filtration Methods 0.000 description 14
- 239000012530 fluid Substances 0.000 description 14
- 238000010586 diagram Methods 0.000 description 12
- 230000008878 coupling Effects 0.000 description 9
- 238000010168 coupling process Methods 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000012466 permeate Substances 0.000 description 5
- 230000001172 regenerating effect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000003303 reheating Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003738 black carbon Substances 0.000 description 2
- 238000004590 computer program Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 239000003570 air Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013479 data entry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 i.e. Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
-
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- 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
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition 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
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
-
- 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
- C01B2203/0833—Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
-
- 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
-
- 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
- Y02P20/10—Process efficiency
Definitions
- the present application is related to and/or claims the benefit of the earliest available effective filing date(s) from the following listed application(s) (the“Priority Applications”), if any, listed below (e.g., claims earliest available priority dates for other than provisional patent applications or claims benefits under 35 USC ⁇ 119(e) for provisional patent applications, for any and all parent, grandparent, great-grandparent, etc. applications of the Priority Application(s)).
- the present application is related to the“Related Applications,” if any, listed below.
- Priority Applications is related to and/or claims the benefit of the earliest available effective filing date(s) from the following listed application(s) (the“Priority Applications”), if any, listed below (e.g., claims earliest available priority dates for other than provisional patent applications or claims benefits under 35 USC ⁇ 119(e) for provisional patent applications, for any and all parent, grandparent, great-grandparent, etc. applications of the Priority Application(s)).
- the present application is related
- the present disclosure relates generally to systems and methods for producing hydrogen gas. More particularly, the present disclosure relates to systems and methods for producing hydrogen gas from the thermal decomposition of hydrocarbons.
- the various embodiments disclosed herein relate to the production of hydrogen gas.
- the disclosure provides for both systems and methods for producing hydrogen gas from the thermal decomposition of hydrocarbons.
- the thermal decomposition reaction occurs in a substantially oxidant- free environment thereby eliminating or greatly reducing the production of carbon oxide byproducts.
- An exemplary system may comprise hydrocarbon feedstock, a supply of non- oxidative carrier gas, one or more heat exchangers, and a reaction chamber.
- the hydrocarbon feedstock is the source of hydrogen gas to be produced.
- the carrier gas may be used to transfer heat to the hydrocarbon feedstock.
- the one or more heat exchangers may be configured to heat the carrier gas.
- the reaction chamber may be configured to receive a volume of hydrocarbon feedstock and a volume of heated carrier gas.
- the hydrocarbon feedstock and the heated carrier gas may directly mix with one another. Mixing the hydrocarbon feedstock with the heated carrier gas may result in heat being transferred from the heated carrier gas to the hydrocarbon feedstock. When a sufficient amount of heat has been transferred to the hydrocarbon feedstock, the hydrocarbon feedstock may thermally decompose to a product that includes hydrogen gas and carbon substances.
- a gaseous product stream may thereafter be collected and removed from the reaction chamber.
- the gaseous product stream may comprise hydrogen gas and carrier gas.
- the gaseous product stream also may be relatively hot.
- the heat within the gaseous product stream may be further utilized by the system.
- the gaseous product stream may be thermally coupled to a volume of carrier gas that is to be used in subsequent thermal decomposition reactions.
- Hydrogen gas may be separated from the gaseous product stream, and at least a portion of the gaseous product stream may be recycled through the system.
- the carrier gas may be heated either directly or indirectly.
- one or more heat exchangers may be configured to transfer heat from one or more heat sources to the carrier gas.
- the one or more heat sources may generate heat.
- Exemplary heat sources include combustion heating systems, electrical heating systems, radiative heating systems, and plasma heating systems.
- the heat sources may further be either catalytic or non-catalytic.
- the carrier gas may be delivered into the reaction chamber using either a high speed injection system or method or a low speed injection system or method.
- the high speed injection system or method may comprise one or more discrete injectors, and each discrete injector may have a nozzle.
- the low speed injection system or method may comprise a reaction chamber having one or more porous walls.
- the reaction chamber may further be configured such that the carrier gas may permeate through the one or more porous walls and into the reaction chamber.
- the hydrocarbon feedstock may be heated without the use of a carrier gas.
- the hydrocarbon feedstock may be heated by contacting a hot surface.
- the hot surface may be a wall of the reaction chamber.
- the hot surface may be a surface of the thermal matrix of a regenerative heat exchanger.
- the hot surface may be a surface of a heat exchanger.
- ultrasonic agitation may be used to disrupt the buildup of the carbon substances.
- the ultrasonic agitation may be generated from a variety of sources including mechanical, electrical, piezoelectric, and/or magnetostrictive generators. One or more parameters of the ultrasonic agitation may be varied as needed or desired.
- FIG. 1 is a schematic diagram of a system for producing hydrogen gas, according to an embodiment of the present disclosure.
- FIG. 2 is a schematic diagram of a system for producing hydrogen gas, according to another embodiment of the present disclosure.
- FIG. 3 is a schematic diagram of a system for producing hydrogen gas, according to another embodiment of the present disclosure.
- FIG. 4 is a schematic diagram of a system for producing hydrogen gas, according to another embodiment of the present disclosure.
- FIG. 5 is a schematic diagram of a system for producing hydrogen gas, according to another embodiment of the present disclosure.
- FIG. 6 is a schematic diagram of a system for producing hydrogen gas, according to another embodiment of the present disclosure.
- a system may comprise hydrocarbon feedstock, a supply of non-oxidative carrier gas, one or more heat exchangers, and a reaction chamber.
- the hydrocarbon feedstock is the source of hydrogen gas to be produced.
- the carrier gas may be used to transfer heat to the hydrocarbon feedstock.
- the one or more heat exchangers may be configured to heat the carrier gas.
- the reaction chamber may be configured to receive a volume of hydrocarbon feedstock and a volume of heated carrier gas. Additionally, the reaction chamber may provide an environment for the thermal decomposition reaction to occur.
- the system may be configured such that a volume of hydrocarbon feedstock and a volume of carrier gas may each be individually delivered to the reaction chamber.
- the carrier gas Before entering the reaction chamber, the carrier gas may pass through the one or more heat exchangers.
- the one or more heat exchangers may be coupled to one or more heat sources. By being coupled to one or more heat sources and the carrier gas, the one or more heat exchangers may be configured to draw heat from the one or more heat sources and transfer the heat to the carrier gas.
- the carrier gas may therefore be substantially hot when it is delivered into the reaction chamber.
- the hydrocarbon feedstock and the heated carrier gas may rapidly mix or otherwise blend with one another. Mixing the hydrocarbon feedstock with the heated carrier gas in this manner may result in heat being transferred from the carrier gas to the hydrocarbon feedstock.
- a potential advantage of transferring heat to the hydrocarbon feedstock in this fashion is a reduction of carbon buildup on the walls of the reaction chamber, as may occur if heat transfer is based upon thermal conduction from such walls.
- the hydrocarbon feedstock may thermally decompose to a product that comprises hydrogen gas and carbon substances.
- a gaseous product stream may thereafter be collected and removed from the reaction chamber.
- the gaseous product stream may comprise hydrogen gas and carrier gas.
- the gaseous product stream may be relatively hot.
- the heat within the gaseous product stream may be further utilized by the system.
- the gaseous product stream may be thermally coupled to a volume of carrier gas that is to be used in subsequent thermal decomposition reactions, thereby reducing the net energy required to produce a given amount of hydrogen gas.
- thermally coupling the gaseous product stream to the carrier gas comprises use of a heat exchanger.
- Hydrogen gas may be separated from the gaseous product stream either before or after thermally coupling the gaseous product stream to the carrier gas. At least a portion of the gaseous product stream may further be recycled through the system.
- the carrier gas may be heated either directly or indirectly.
- one or more heat exchangers may be configured to transfer heat from one or more heat sources to the carrier gas.
- the one or more heat sources may generate heat.
- Exemplary heat sources include combustion heating systems, electrical heating systems, radiative heating systems, and plasma heating systems.
- the heat source(s) may further be either catalytic or non-catalytic.
- the carrier gas may be delivered into the reaction chamber using either a high speed injection system or method or a low speed injection system or method.
- the high speed injection system or method may comprise one or more discrete injectors. Each discrete injector may have a nozzle.
- the low speed injection system or method may comprise a reaction chamber having one or more porous walls. The reaction chamber may further be configured such that the carrier gas may permeate through the one or more porous walls and into the reaction chamber.
- the hydrocarbon feedstock may be heated without the use of a carrier gas.
- the hydrocarbon feedstock may be heated by contacting a hot surface.
- the hot surface may be a surface of a fluid or a solid.
- the hot surface may be a wall of the reaction chamber.
- the hot surface may be a surface of the thermal matrix of a regenerative heat exchanger.
- the hot surface may be a surface of a heat exchanger.
- ultrasonic agitation may be used to disrupt the buildup of the carbon substances.
- the ultrasonic agitation may be generated from a variety of sources including mechanical, electrical, piezoelectric, and/or magnetostrictive generators. One or more parameters of the ultrasonic agitation may be varied as needed or desired.
- FIG. 1 is a schematic diagram of a system 100 for producing hydrogen gas 120 according to an embodiment of the present disclosure.
- the system 100 may comprise a hydrocarbon feedstock 102, a supply of non-oxidative carrier gas 104, one or more heat exchangers 108, 110, and a reaction chamber 106.
- the hydrocarbon feedstock 102 is the originating source of the hydrogen gas 120 that may be produced in accordance with the present disclosure.
- the hydrocarbon feedstock 102 comprises gaseous hydrocarbons such as natural gas.
- the hydrocarbon feedstock 102 may include any variety of hydrocarbons.
- the hydrocarbon feedstock 102 comprises saturated hydrocarbons.
- the hydrocarbon feedstock 102 comprises unsaturated hydrocarbons.
- the hydrocarbon feedstock 102 comprises aromatic hydrocarbons.
- the hydrocarbon feedstock 102 comprises two or more of the following: saturated hydrocarbons, unsaturated hydrocarbons, and aromatic hydrocarbons.
- the hydrocarbon feedstock 102 comprises one or more light hydrocarbons having the general formula C n H m , wherein n is 1 , 2, 3 or 4, and m is independently selected from 2, 4, 6, 8 or 10.
- the hydrocarbon feedstock 102 comprises CH 4 .
- the hydrocarbon feedstock 102 comprises C 2 H 2 .
- the hydrocarbon feedstock 102 comprises C 2 H 4 .
- the hydrocarbon feedstock 102 comprises C 2 H 6 .
- the hydrocarbon feedstock 102 comprises C 3 H 8 .
- the hydrocarbon feedstock 102 comprises C 4 H 10 .
- the hydrocarbon feedstock 102 comprises one of more of the following: CH 4 , C 2 H 2 , C 2 H 4 , C 2 H 6 , C 3 H 8 , and C 4 H 10 .
- the hydrocarbon feedstock 102 comprises a mixture of two or more of the following: CH 4 , C 2 H 2 , C 2 H 4 , C 2 H 6 , C 3 H 8 , and C 4 H 10 .
- the hydrocarbon feedstock 102 need not be limited to only light hydrocarbons. Rather, the hydrocarbon feedstock 102 may comprise one or more hydrocarbons that are not light hydrocarbons.
- the hydrocarbon feedstock 102 comprise one or more hydrocarbons that have a relatively high hydrogen to carbon content.
- the hydrocarbon feedstock 102 comprise hydrocarbons that have a hydrogen to carbon ratio of at least 2:1 , 3:1 , or 4:1.
- the hydrocarbon feedstock 102 may be filtered or otherwise purified prior to being introduced into the system 100.
- thermal decomposition of hydrocarbon feedstock 102 that is substantially pure may have a higher hydrogen gas yield as compared to hydrocarbon feedstock 102 that contains a high amount of impurities.
- the hydrocarbon feedstock 102 is substantially free of impurities.
- the hydrocarbon feedstock 102 is substantially free of non-hydrocarbons.
- the hydrocarbon feedstock 102 is substantially free of oxidative compounds.
- the hydrocarbon feedstock 102 need not be substantially pure and may contain minor amounts of impurities.
- the hydrocarbon feedstock 102 may comprise a mixture of one or more hydrocarbons and one or more non-hydrocarbons.
- the non-oxidative carrier gas 104 may be used to transfer heat or thermal energy to the hydrocarbon feedstock 102.
- a non-oxidative carrier gas 104 to heat the hydrocarbon feedstock 102, the thermal decomposition reaction may occur in a substantially oxidant-free environment thereby eliminating or greatly reducing the production of carbon oxide byproducts.
- a wide variety of non-oxidative gases may be used as the carrier gas 104.
- any non-oxidative gas that does not easily undergo chemical reactions when being subjected to heat can be used as the carrier gas 104.
- the carrier gas 104 may comprise one or more inert gases.
- the inert gases may be, for example, noble gases.
- the carrier gas comprises hydrogen, i.e., hydrogen may serve both as the carrier gas as well as a product of the hydrocarbon decomposition.
- the carrier gas comprises nitrogen.
- the carrier gas comprises argon.
- the carrier gas comprises helium.
- the carrier gas comprises a mixture of two or more of the following: hydrogen, nitrogen, argon, and helium.
- the carrier gas 104 may be substantially free of impurities. Alternatively, the carrier gas 104 need not be substantially pure and may contain minor amounts of impurities and/or additional compounds. Notwithstanding, it is desirous that the carrier gas 104 be substantially free of oxidative compounds. Accordingly, in some embodiments, the carrier gas 104 is substantially free of oxidative compounds.
- the hydrocarbon feedstock 102 may be heated without the use of a carrier gas 104.
- the hydrocarbon feedstock 102 may be heated by contacting a hot surface.
- the hot surface may be a surface of a fluid, such as a liquid.
- the hot surface may be a surface of a solid.
- the hot surface may be one or more walls of the reaction chamber 106.
- the hot surface may be a surface of the thermal matrix of a regenerative heat exchanger.
- the hot surface may be one or more surfaces of a heat exchanger.
- the heat exchanger may be coupled to one or more heat sources. Exemplary heat exchangers and heat sources that may be used in accordance with the present disclosure are further discussed below.
- the hydrocarbon feedstock 102 may be heated by one or more heat sources directly, without the use of a heat exchanger. In still other embodiments, the hydrocarbon feedstock 102 may be preheated prior to delivery into the reaction chamber 106.
- the system 100 may be configured such that a first volume of hydrocarbon feedstock 102 and a first volume of carrier gas 104 may each individually be delivered to the reaction chamber 106.
- the system 100 may further be configured such that the first volume of carrier gas 104 passes through one or more heat exchangers 108, 110 before entering the reaction chamber 106.
- the first volume of carrier gas 104 is delivered to and passes through a first heat exchanger 108 and a second heat exchanger 110.
- Each of the heat exchangers 108, 110 may be configured to transfer heat or thermal energy to the first volume of carrier gas 104. Accordingly, the first volume of carrier gas 104 may be substantially hot when it enters the reaction chamber 106.
- the system 100 may comprise a cyclical flow regenerative heat exchanger commonly known as a regenerator.
- the system 100 may comprise a countercurrent heat exchanger (e.g., recuperator).
- the system may comprise a continuous flow heat exchanger.
- the system may comprise two or more different types of heat exchangers (e.g., one regenerative heat exchanger and one countercurrent heat exchanger).
- Each heat exchanger may comprise one or more heat exchanger fluids.
- the heat exchanger fluids may be gaseous; in other embodiments, the heat exchanger fluids may be liquid.
- the heat exchanger fluid may be enclosed within the heat exchanger.
- the heat exchanger fluid may therefore circulate within the heat exchanger.
- the heat exchanger fluid may not be enclosed within the heat exchanger; rather, the heat exchanger fluid may flow in and out of the heat exchanger. It is contemplated that the heat exchanger fluid may circulate in a closed-loop manner. By circulating in a closed-loop manner, the heat exchanger fluid may be retained and recycled. Further, energy loss may be minimized when circulating the heat exchanger fluid in a closed-loop manner.
- the system may further comprise one or more heat sources 118.
- the one or more heat sources 118 may generate and provide the system 100 with the heat or thermal energy that is necessary for the decomposition reaction to occur.
- the one or more heat sources 118 may be coupled to one or more heat exchangers 108, 110.
- the heat source 118 is coupled to the first heat exchanger 108.
- the heat source 118 may comprise an electrical heating system, a radiative heating system (including thermal and/or optical radiation systems), a combustion heating system, or a plasma heating system.
- the heat source 118 may further be either catalytic or non-catalytic. It is contemplated that the thermal energy or heat generated by the heat source 118 may be transferred to the first heat exchanger 108.
- the first heat exchanger 108 may then transfer heat to the first volume of carrier gas 104.
- the heat source 118 may transfer heat directly to the first volume of carrier gas 104, or directly to the first volume of hydrocarbon feedstock 102, without the use of a heat exchanger 108.
- an exemplary heat source 118 may comprise a combustion heating system.
- the combustion heating system may generate heat or energy from the combustion of one or more combustible gases.
- the one or more combustible gases may comprise a portion of the hydrocarbon feedstock 102, as is illustrated in FIG.1.
- the one or more combustible gases comprise hydrocarbon feedstock 102 and a second combustible gas that is other than hydrocarbon feedstock 102.
- the second combustible gas may comprise air.
- the second combustible gas may comprise oxygen.
- the one or more combustible gases comprise hydrogen gas.
- the hydrogen gas may be at a temperature that is greater than ambient temperature.
- the hydrogen gas used by the combustion system may be derived from the first gaseous product stream 116. Accordingly, a portion of the hydrogen gas 120 produced by the system 100 may be delivered to the heat source 118 and used by the combustion system to generate heat.
- the one or more combustible gases comprise hydrogen gas and a second combustible gas that is other than hydrogen gas.
- the second combustible gas may comprise air.
- the second combustible gas may comprise oxygen.
- the first volume of carrier gas 104 may be delivered to the reaction chamber 106.
- the first volume of carrier gas 104 may be delivered into the reaction chamber 106 through the use of a high speed injection system or method.
- the high speed injection system or method may convert at least a portion of the static pressure of the first volume of carrier gas 104 into dynamic pressure.
- Exemplary high speed injection systems or methods may comprise one or more discrete injectors through which the first volume of carrier gas may be passed.
- the one or more discrete injectors each comprise a nozzle. Any variety and shape of nozzles may be utilized in accordance with the present disclosure.
- the one or more discrete injectors may be coupled or otherwise connected to the reaction chamber 106 at one or more injection sites.
- the one or more discrete injectors may further be configured and aligned such that injection of, or passing, the first volume of carrier gas 104 through the one or more discrete injectors may aid in keeping the byproducts of the thermal decomposition reaction (e.g., carbon substances) from depositing on and blocking the one or more injection sites.
- the thermal decomposition reaction e.g., carbon substances
- the first volume of carrier gas 104 may be delivered into the reaction chamber 106 through the use of a low speed injection system or method.
- exemplary low speed injection systems or methods comprise a reaction chamber 106 comprising one or more porous walls.
- the first volume of carrier gas 104 may permeate or otherwise be passed into the reaction chamber 106 through the one or more porous walls.
- the rate at which the first volume of carrier gas 104 permeates or is otherwise passed through the one or more porous walls of the reaction chamber 106 may be varied by controlling and adjusting the pressure differential between the inside and the outside of the reaction chamber 106. The higher the pressure differential (i.e., higher pressure on the outside of the reaction chamber than on the inside of the reaction chamber), the faster the first volume of carrier gas 104 may permeate through the one or more porous walls.
- the high speed and low speed injection systems or methods disclosed herein may be used to deliver the first volume of carrier gas 104 into the reaction chamber 106 either continuously or in batches.
- the injection systems or methods may continuously and constantly deliver the first volume and subsequent volumes carrier gas 104 into the reaction chamber 106.
- the injection systems or methods disclosed herein may be used to deliver only batches or certain volumes (e.g., a first volume, a second volume, etc.) of the carrier gas 104 into the reaction chamber 106 at specified time intervals.
- substantially all of the first volume of carrier gas 104 that has been heated by the one or more heat exchangers 108, 110 may be delivered into the reaction chamber 106 by either the high speed or low speed injection system or method.
- only a portion of the first volume of carrier gas 104 may be delivered to the reaction chamber 106 by either the high speed or low speed injection system or method.
- the reaction chamber 106 may be configured to receive the first volume of heated carrier gas 104 and the first volume of hydrocarbon feedstock 102.
- the reaction chamber 106 may be made of any suitable material that is able to withstand the extreme temperatures necessary to thermally decompose the hydrocarbon feedstock 102.
- the size and shape of the reaction chamber 106 may be varied.
- the reaction chamber 106 may be substantially cylindrical.
- the reaction chamber 106 also may be mounted horizontally or vertically. Inside the reaction chamber 106, the first volume of carrier gas 104 and the first volume of hydrocarbon feedstock 102 may directly mix or otherwise blend with one another.
- the first volume of hydrocarbon feedstock 102 may thermally decompose into a product comprising hydrogen gas and carbon substances.
- the decomposition product further comprises hydrocarbons. These hydrocarbons may be residual hydrocarbons originating from the hydrocarbon feedstock 104 and may include unreacted hydrocarbons and/or partially decomposed hydrocarbons.
- the carbon substances 114 may be collected and removed from the reaction chamber 106. All or a portion of the carbon substances 114 may then be discarded from the system 100.
- the carbon substances 114 may include a variety of carbonaceous materials and are naturally free from oxygen, as sources of oxygen are excluded from the decomposition reaction.
- the carbon substances 114 comprise black carbon.
- the carbon substances 114 comprise elemental carbon.
- the carbon substances 114 comprise pyrocarbon.
- the carbon substances 114 comprise soot.
- the carbon substances 114 comprise one or more of black carbon, pyrocarbon, elemental carbon, and soot.
- At least a portion of the carbon substances 114 may be used as a catalyst in the decomposition of hydrocarbon feedstock 102.
- at least a portion of the carbon substances may act as a catalyst in the decomposition of the remaining portion of the first volume of hydrocarbon feedstock 102 within the reaction chamber.
- at least a portion of the carbon substances 114 may act as a catalyst in the decomposition of subsequent volumes (e.g., a second or third volume) of hydrocarbon feedstock 102 that may be delivered to the reaction chamber for subsequent decomposition reactions.
- At least a portion of the carbon substances 114 that have been collected and removed from the reaction chamber 106 may be delivered back into the reaction chamber 106 and used as a catalyst in the subsequent decomposition of subsequent volumes (e.g., a second or third volume) of hydrocarbon feedstock 102, as illustrated in FIG. 1.
- Carbon substances may be deposited on various surfaces of the reaction chamber 106.
- ultrasonic agitation may be used to disrupt a buildup of the carbon substances on one or more selected surfaces within the reaction chamber 106.
- ultrasonic agitation may be used to disrupt the buildup of carbon substances on the surfaces of the reaction chamber or on the one or more discrete injectors or nozzles that may be used in delivering the carrier gas 104 into the reaction chamber 106.
- a first gaseous product stream 116 may be collected and removed from the reaction chamber 106.
- the first gaseous product stream 116 may comprise hydrogen gas produced from the decomposition reaction.
- the first gaseous product stream 116 may further comprise carrier gas 104.
- the carrier gas 104 may be derived from the first volume of carrier gas 104 that was used to transfer heat to the first volume of hydrocarbon feedstock 102 in the decomposition reaction.
- the first gaseous product stream 116 further comprises hydrocarbons. These hydrocarbons may be residual hydrocarbons originating from the hydrocarbon feedstock 102 that was not fully decomposed in the reaction chamber 106.
- these hydrocarbons may include unreacted hydrocarbons and/or partially decomposed hydrocarbons.
- the first gaseous product stream 116 is substantially free from hydrocarbons.
- the first gaseous product stream 116 may be filtered to remove hydrocarbons.
- the first gaseous product stream 116 may further comprise gasborne carbon substances.
- gasborne carbon substances For example, carbon substances produced from the decomposition reaction may be suspended in the gaseous product stream 116.
- the first gaseous product stream 116 may be substantially free from gasborne carbon substances.
- the first gaseous product stream 116 may be filtered to remove gasborne carbon substances.
- the first gaseous product stream 116 may be relatively hot. Accordingly, the first gaseous product stream 116 may be at a temperature that is above ambient temperature. It may be desirous to recapture energy from the hot first gaseous product stream 116 and further use it within the system 100. This may be accomplished in several ways. For example, heat from at least a portion of the first gaseous product stream 116 may be thermally coupled to a second volume of carrier gas 104 that is to be used in subsequent decomposition reactions.
- Thermal coupling heat from a portion of the first gaseous product stream 116 to the second volume of carrier gas 104 may be accomplished in a variety of ways.
- the first gaseous product stream 116 may be delivered to the second heat exchanger 110.
- the second heat exchanger 110 may be any variety of heat exchangers previously discussed (e.g., a regenerator, recuperator, continuous flow heat exchanger, etc.), and may be configured such that it removes heat from the first gaseous product stream 116 and transfers the heat to the second volume of carrier gas 104 that is being delivered to the reaction chamber for subsequent decomposition reactions.
- the second volume of carrier gas 104 may be delivered to second heat exchanger 110 prior to being delivered to the reaction chamber 106. Still further, the second volume of carrier gas 104 may be delivered to the second heat exchanger 110 prior to being delivered to the first heat exchanger 108. Accordingly, the second volume of carrier gas 104 may be first heated by the second heat exchanger 110, which is coupled to the first gaseous product stream 116, after which the second volume of carrier gas 104 may be further heated by the first heat exchanger 108, which is coupled to a heat source 118. It is contemplated that the first heat exchanger 108, coupled to a heat source 118, may be configured to heat the second volume of carrier gas 104 to a higher temperature than the second heat exchanger 110 which is coupled to the first gaseous product stream 116.
- the system 100 comprises first and second heat exchangers 108, 110.
- the first and second heat exchangers 108, 110 may be configured such that they share common components. Accordingly, the first and second heat exchangers 108, 110 may, in a sense, overlap one another.
- a system 100 may comprise only one heat exchanger with two or more sections that may be analogous to the first and second heat exchangers 108, 110 that are illustrated in FIG. 1.
- the system 100 may comprise one or more additional heat exchangers, such as a third heat exchanger.
- each of the heat exchangers (e.g., the first, second, and third) may be configured such that it shares common components with one or more of the other heat exchangers.
- the first gaseous product stream 116 may be filtered or otherwise separated into one or more components either before or after it is thermally coupled to the second volume of carrier gas 104.
- the separation system 112 may comprise any known systems or methods for separating and/or filtering gases.
- the separation system comprises a series of filters.
- the filters may be, for example, filter bags.
- one or more filtration systems and/or separation systems 112 may be used.
- the first gaseous product stream 116 may be delivered to a separation system 112 after being coupled to the second volume of carrier gas 104 through the second heat exchanger 110.
- the first gaseous product stream 116 may be delivered to a separation system 112 before being delivered to the second heat exchanger 110 or otherwise thermally coupled to the second volume of carrier gas 104.
- the first gaseous product stream 116 may be delivered to one or more filtration and/or separation systems 112 prior to being delivered to the second heat exchanger 110, and delivered to one or more filtration and/or separation systems 112 after being delivered to the second heat exchanger 110. Accordingly, depending on the placement of the filtration and/or separation systems 112, either the full first gaseous product stream 116, or only a portion of the first gaseous product stream 116, may be thermally coupled to the second volume of carrier gas 104.
- the hydrocarbons 124 and the carbon substances 126 may be removed from the first gaseous product stream 116 prior to delivering at least a portion of the first gaseous product stream 116 to the heat exchanger 110 for use in thermally coupling heat to the second volume of carrier gas 104.
- the portion of the first gaseous product stream 116 delivered to the heat exchanger 110 may primarily comprise remnants of the first volume of carrier gas 104 and hydrogen gas 120.
- At least a portion of hydrogen gas 120 may be removed from the first gaseous product stream 116 prior to delivering at least a portion of the first gaseous product stream 116 to the second heat exchanger 110 for use in thermally coupling heat to the second volume of carrier gas 104.
- the hydrocarbons 124, carbon substances 126, and at least a portion of hydrogen gas 120 may be removed from the first gaseous product stream 116 prior to delivering at least a portion of the first gaseous product stream 116 to the heat exchanger 110 for use in thermally coupling heat to the second volume of carrier gas 104.
- the separation system 112 may be configured such that at least a portion of hydrogen gas 120 is removed from the first gaseous product stream 116.
- the portion of hydrogen gas 120 may be stored, sold, or further used in the system 100.
- a portion of hydrogen gas 120 may be delivered to the heat source 118 and used in the generation of additional heat for the system 100.
- the hydrogen gas 120 may be removed from the system 100 and either sold or used for other applications.
- the separation system 112 may be configured such that at least a portion of the first volume of carrier gas 104 is removed from the first gaseous product stream 116.
- the first volume of carrier gas 104 may thereafter be recycled through the system 100 as desired.
- the first gaseous product stream 116 may be recycled and reused in the system 100.
- the first gaseous product stream 116 may be converted into a smaller portion (e.g., a second portion) of the first gaseous product stream 116 by at least partially removing, or completely removing, hydrocarbons 124, carbon substances 126, and/or hydrogen gas 120 from the first gaseous product stream 116 through use of the separation system 112. As shown in FIG.
- this smaller portion of the first gaseous product stream 116 may be delivered to the first heat exchanger 108 where it is reheated and thereafter delivered to the reaction chamber 106 for use in subsequent decomposition reactions.
- a portion of the first gaseous product stream 116 may be delivered to another heat exchanger, e.g., a third heat exchanger.
- the third heat exchanger may be any of the types of heat exchangers previously discussed and may be configured such that it shares one or more common components with the first heat exchanger 108.
- a heat source may be configured to transfer thermal energy to the third heat exchanger prior to heating the portion of the first gaseous product stream 116 with the third heat exchanger.
- the heat source may be any the above mentioned heat sources, such as a combustion heating system.
- the first gaseous product stream 116 when recycling a portion of the first gaseous product stream 116 back through the system 100, it may be desirous to filter the first gaseous product stream 116 to remove any and all hydrocarbons and/or carbon substances either before reheating the portion of the gaseous product stream 116, or before completion of the reheating. Doing so will help prevent decomposition of hydrocarbons inside the first heat exchanger 108 (or any other heat exchanger configured to heat the first gaseous product stream 116) or on any other undesirable areas within the system 100.
- recycling at least a portion of the first gaseous product stream 116 may comprise delivering at least a portion of the reheated first gaseous product stream 116 to the reaction chamber 106. Recycling at least a portion of the first gaseous product stream 116 may further comprise adding or otherwise combining at least a portion of the first gaseous product stream 116 with a second volume of carrier gas 104 that is being delivered to the reaction chamber 106 for use in a subsequent decomposition reaction. For example, in an embodiment, the portion of first gaseous product stream 116 may be combined with the second volume of carrier gas 104 prior to delivering the second volume of carrier gas 104 into the reaction chamber 106.
- first gaseous product stream 116 may be combined with the second volume of carrier gas 104 prior to heating the second volume of carrier gas with first heat exchanger 108. In yet another embodiment, the portion of first gaseous product stream 116 may be combined with the second volume of carrier gas 104 prior to completion of the heating of the second volume of carrier gas with first heat exchanger 108. [0066] As previously discussed, at least a portion of the first volume of carrier gas may be separated or otherwise removed from the first gaseous product stream 116 by the separation system 112. The portion of the first volume of carrier gas may then be recycled and reused in the system 100 in similar fashion to the portion of first gaseous product stream 116 previously discussed.
- the portion of the first volume of carrier gas may be combined with the second volume of carrier gas 104 that is being delivered to the reaction chamber 106 for use in a subsequent decomposition reaction.
- the portion of the first volume of carrier gas may be combined with a second volume of carrier gas 104 prior to delivering the second volume of carrier gas 104 into the reaction chamber 106.
- the portion of first volume of carrier gas may be combined with the second volume of carrier gas 104 prior to heating the second volume of carrier gas with the first heat exchanger 108.
- the portion of first volume of carrier gas may be combined with the second volume of carrier gas 104 prior to completion of the heating of the second volume of carrier gas with first heat exchanger 108.
- the portion of the first gaseous product stream, or the portion of first volume of carrier gas removed from the first gaseous product stream 116 may be compressed prior to being added or otherwise combined with the second volume of carrier gas 104.
- the portion of the first gaseous product stream, or the portion of first volume of carrier gas removed from the first gaseous product stream 116 may further be cooled prior to the compression. It is further contemplated that the heat removed during the cooling may be used to heat the second volume of carrier gas 104.
- a second volume of hydrocarbon feedstock 102 may thereafter be delivered to the reaction chamber 106 and mixed with a portion of the first gaseous product stream 116.
- the second volume of hydrocarbon feedstock 102 may comprise the same composition as the first volume of hydrocarbon feedstock 102. Heat may be transferred from the portion of the first gaseous product stream 116 to the second volume of hydrocarbon feedstock 102 thereby thermally decomposing the second volume of hydrocarbon feedstock 102 into a product comprising hydrogen gas and carbon substances.
- a second gaseous product stream 116 comprising hydrogen gas 120 and carrier gas 104 may thereafter be collected and further cycled and recycled through the system 100 as discussed above with respect to the first gaseous product stream 116.
- first carrier gas 104 removed from the first gaseous product stream 116 may be mixed with a second volume of hydrocarbon feedstock 102 thereby thermally decomposing the second volume of hydrocarbon feedstock 102 into a product comprising hydrogen gas and carbon substances. It is therefore contemplated that the systems and methods disclosed herein may be continuous and cyclical systems such that the carrier gas 104 and gaseous product streams 116 may be cycled and recycled through the system and used to transfer heat to additional volumes of hydrocarbon feedstock 102 within the reaction chamber 106.
- FIG. 2 is a schematic diagram of a system 200, according to another embodiment of the present disclosure.
- the system 200 may comprise a hydrocarbon feedstock 202, a supply of carrier gas 204, a heat exchanger 208, and a reaction chamber 206.
- a first volume of carrier gas 204 and a first volume of hydrocarbon feedstock 202 may each independently be delivered to the reaction chamber 206.
- the first volume of carrier gas 204 Prior to being delivered to the reaction chamber 206, the first volume of carrier gas 204 may be heated by the heat exchanger 208.
- the heat exchanger 208 may be configured such that it comprises two or more sections 208a, 208b. Each section 208a, 208b may be configured to individually transfer heat to the carrier gas 204 being passed there through. Each section 208a, 208b may further obtain heat from different sources. For example, section 208a of the heat exchanger 208 may obtain heat from at least a portion of the first gaseous product stream 216. Section 208b may obtain heat from a separate heat source 218. Thus sections 208a and 208b of the heat exchanger 208 may be analogous in some respects with the first and second exchangers 108 and 110 discussed above in FIG. 1.
- sections 208a and 208b of the heat exchanger 208 may comprise overlapping components. In other embodiments, sections 208a and 208b of the heat exchanger may comprise two separate and independent heat exchangers, with or without overlapping components.
- carbon substances 214 may be collected and removed from the system 200 as described above with respect to FIG. 1.
- only a portion of the first gaseous product stream 216 may be thermally coupled to the second volume of carrier gas 204.
- forming the portion of the first gaseous product stream 216 may comprise removing hydrocarbons 224 and/or gasborne carbon substances 226 from the first gaseous product stream 216 through use of a filtration system 230.
- the portion of the first gaseous product stream 216 may be thermally coupled to the second volume of carrier gas 204 through use of the heat exchanger 208. After passing through the heat exchanger 208, the portion of the first gaseous product stream 216 may be delivered to a separation system 212.
- the separation system 212 may be configured to remove at least a portion of hydrogen gas 220 from the gaseous product stream 216.
- the portion of hydrogen gas 220 may be stored, sold, or used in the system 200.
- a portion of the hydrogen gas 220 may be delivered to the heat source 218 and used in the generation of additional heat for the system 200.
- the hydrogen gas 220 may also be removed from the system 200 and used in other applications.
- the portion of the first gaseous product stream 216 may be converted into a second smaller portion of the first gaseous product stream 216, which may consist primarily of remnants of the first volume of carrier gas 204.
- the second portion of the first gaseous product stream 216 may then be added to or otherwise combined with a second volume of carrier gas 204 and recycled through the system, or it may be discarded.
- FIG. 3 is a schematic diagram of a system 300, according to another embodiment of the present disclosure.
- the system 300 may comprise a hydrocarbon feedstock 302, a supply of carrier gas 304, a heat exchanger 308, and a reaction chamber 306.
- a first volume of carrier gas 304 and a first volume of hydrocarbon feedstock 302 may each independently be delivered to the reaction chamber 306.
- the first volume of carrier gas 304 may be heated by the heat exchanger 308.
- the heat exchanger 308 may be configured such that it comprises two or more sections 308a, 308b. Similar to FIG. 2, each section 308a, 308b may be configured to individually transfer heat to the carrier gas 304 being passed there through. Each section 308a, 308b may further obtain heat from different sources. For example, section 308a of the heat exchanger 308 may obtain heat from at least a portion of the first gaseous product stream 316. Section 308b may obtain heat from a separate heat source 318. Thus sections 308a and 308b of the heat exchanger 308 may be analogous in some respects with the first and second exchangers 108 and 110 discussed above in FIG. 1. In some embodiments, sections 308a and 308b of the heat exchanger 308 may comprise overlapping components. In other embodiments, sections 308a and 308b of the heat exchanger may comprise two separate and independent heat exchangers, with or without overlapping components.
- carbon substances 314 may be collected and removed from the system 300 as described above with respect to FIG. 1.
- only a portion of the first gaseous product stream 316 may be thermally coupled to the second volume of carrier gas 304.
- Forming the portion of the first gaseous product stream 316 may comprise removing hydrocarbons 324 and/or gasborne carbon substances 326 from the first gaseous product stream 316 through use of a filtration system 330.
- Forming the portion of the first gaseous product stream 316 may further comprise removing at least a portion of hydrogen gas 320 through use of a separation system 312.
- the portion of hydrogen gas 320 may be stored, sold, or used in the system 300.
- a portion of the hydrogen gas 320 may be delivered to the heat source 318 and used in the generation of additional heat for the system 300.
- the hydrogen gas 320 may also be removed from the system 300 and used in other applications.
- the portion of the first gaseous product stream 316 which may consist primarily of remnants of the first volume of carrier gas 304, may thereafter be thermally coupled to the second volume of carrier gas 304 through use of the heat exchanger 308. As shown in FIG. 1 , the portion of the first gaseous product stream 316 may then exit the heat exchanger 308 and may be added to or otherwise combined with a second volume of carrier gas 304 and recycled through the system, or it may be discarded.
- FIG. 4 is a schematic diagram of a system 400, according to another embodiment of the present disclosure.
- the system 400 may comprise a hydrocarbon feedstock 402, a supply of carrier gas 404, a heating system 432, and a reaction chamber 406.
- a first volume of carrier gas 404 and a second volume of hydrocarbon feedstock 402 may each independently be delivered to the reaction chamber 406.
- the first volume of carrier gas 404 may be heated by the heating system 432.
- the heating system 432 may comprise a heat source that is configured to heat the first volume of carrier gas 404. Any variety of heat sources previously discussed may be used by the heating system 432.
- the heating system 432 comprises a combustion heating system.
- the heating system 432 comprises an electrical heating system.
- the heating system 432 comprises a radiative heating system.
- the heating system 432 comprises a plasma heating system.
- the heating system 432 may be catalytic or non-catalytic.
- heat or thermal energy generated from the heating system 432, or the heat source within the heating system 432 may be directly transferred to the first volume of carrier gas 404; in other embodiments, the heat or thermal energy generated from the heating system 432, or the heat source within the heating system 432, may be indirectly transferred to the first volume of carrier gas 404.
- Exemplary methods of indirectly transferring heat or thermal energy include the use of a heat exchanger.
- carbon substances 414 may be collected and removed from the system 400 as described above with respect to FIG. 1.
- a first gaseous product stream 416 may be collected from the reaction chamber 406.
- the first gaseous product stream 416 may thereafter be thermally coupled to a second volume of carrier gas 404.
- the first gaseous product stream 416 may be delivered to a heat exchanger 408.
- the heat exchanger 408 may be configured to remove heat from the first gaseous product stream 416 and transfer it to a second volume of carrier gas 404.
- the second volume of carrier gas 404 may be delivered to the heat exchanger 408 prior to being delivered into the reaction chamber 406. Further, the second volume of carrier gas 404 may exit or otherwise leave the heat exchanger 408 prior to being heated by the heating system 432 or any other heat source.
- the first gaseous product stream 416 may be delivered to a separation system 412 that may be configured to remove or otherwise separate hydrocarbons 424, carbon substances 426, and/or hydrogen gas 420 from the first gaseous product stream 416.
- a portion of the first gaseous product stream 416 may thereafter be combined with the second volume of carrier gas 404 and delivered to the heating system 432 for reheating and reuse in subsequent decomposition reactions.
- FIG. 5 is a schematic diagram of a system 500, according to another embodiment of the present disclosure.
- the system 500 may comprise a hydrocarbon feedstock 502, a supply of carrier gas 504, a first heat exchanger 508, and a reaction chamber 506.
- a first volume of carrier gas 504 and a first volume of hydrocarbon feedstock 502 may each independently be delivered to the reaction chamber 506.
- the first volume of carrier gas 504 Prior to being delivered to the reaction chamber 506, the first volume of carrier gas 504 may pass through a first heat exchanger 508, and a second heat exchanger 510.
- carbon substances 514 may be collected and removed from the system 500 and used as described above with respect to FIG. 1.
- a first gaseous product stream 516 may be collected and delivered to a filtration system 530 prior to being thermally coupled to the second volume of carrier gas 504.
- the filtration system 530 may be configured to filter or otherwise remove one or more components from the first gaseous product stream 516.
- the filtration system 530 may be configured to remove hydrocarbons 524 and carbon substances 526 from the first gaseous product stream 516.
- a portion of the first gaseous product stream 516 may thereafter be thermally coupled to a second volume of carrier gas 504 by the second heat exchanger 510. After thermally coupling heat to the second volume of carrier gas 504 through the second heat exchanger 510, the portion of the first gaseous product stream 516 may be delivered to a separation system 512 that may be configured to remove at least a portion, or all, of the hydrogen gas 520 from the portion of the first gaseous product stream 516.
- the portion of the first gaseous product stream 516 may be converted into a second smaller portion of the first gaseous product stream 516, which may consist primarily of remnants of the first volume of carrier gas 504.
- the second portion of the first gaseous product stream 516 may thereafter be delivered to a third heat exchanger 511 that may be configured to heat the second portion of the first gaseous product stream 516.
- the third heat exchanger may be configured such that it shares one or more common components with the first and/or second heat exchanger 508, 510.
- a heat source 518 may be coupled to third heat exchanger 511. The heat source 518 may provide heat or otherwise transfer thermal energy to the third heat exchanger 511 prior to heating the second portion of the first gaseous product stream 516 with the third heat exchanger 511.
- the heat source 518 may be any of the above-mentioned heat sources, such as a combustion heating system that generates heat from the combustion of one or more combustible gases. Further, as shown in FIG. 5, in some embodiments, the heat source 518 may be coupled to both the first heat exchanger 508 and the third heat exchanger 511. In other embodiments, separate and independent heat sources 518 may be used to transfer thermal energy to each heat exchanger (e.g., the first heat exchanger 508 and the third heat exchanger 511 ).
- the second portion of the gaseous product stream 516 may thereafter be delivered to the reaction chamber 506 for use in subsequent decomposition reactions, or may be added to or otherwise combined with a second volume of carrier gas 504 that is to be used in subsequent decomposition reactions.
- the second portion of the gaseous product stream 516 is added to or otherwise combined with the second volume of carrier gas 504 prior to heating the second volume of carrier gas 504 with the first heat exchanger 508. Accordingly, the combined second portion of the first gaseous product stream 516 and the second volume of carrier gas 504 may be heated by the first heat exchanger 508 and thereafter delivered to the reaction chamber 506 for use in subsequent decomposition reactions.
- FIG. 6 is a schematic diagram of a system 600, according to another embodiment of the present disclosure.
- the system 600 may comprise a hydrocarbon feedstock 602, a supply of carrier gas 604, a first heat exchanger 608, and a reaction chamber 606.
- a first volume of carrier gas 604 and a first volume of hydrocarbon feedstock 602 may each independently be delivered to the reaction chamber 606.
- the first volume of carrier gas 604 may be heated by the heat exchanger 608.
- carbon substances 614 may be collected and removed from the system 600 and used as described above with respect to FIG. 1.
- a first gaseous product stream 616 may be collected from the reaction chamber 606 and delivered to a filtration system 630.
- the filtration system 630 may be configured to filter or otherwise remove one or more components from the first gaseous product stream 616.
- the filtration system 630 may be configured to remove hydrocarbons 624 and carbon substances 626 from the first gaseous product stream 616.
- the filtration system 630 may be configured to remove carbon substances 626 from the first gaseous product stream 616, while leaving some or all of hydrocarbons 624 within the first gaseous product stream 616.
- a portion of the first gaseous product stream 616 may thereafter be delivered to a separation system 612.
- the separation system 612 may be configured to remove at least a portion, or all, of the hydrogen gas 620 from the portion of the first gaseous product stream 616.
- the portion of hydrogen gas 620 may be stored, sold, or used in the system 600.
- a portion of the hydrogen gas 620 may be delivered to the heat source 618 and used in the generation of additional heat for the system 600.
- the hydrogen gas 620 may also be removed from the system 600 and used in other applications.
- the portion of the first gaseous product stream 616 may be converted into a second smaller portion of the first gaseous product stream 616, which may consist primarily of remnants of the first volume of carrier gas 604 and optionally some or all of hydrocarbons 624.
- the second portion of the first gaseous product stream 616 may thereafter be delivered to a second heat exchanger 610 that may be configured to heat the second portion of the first gaseous product stream 616.
- the second heat exchanger may be configured such that it shares one or more common components with the first heat exchanger 608.
- the second portion of the gaseous product stream 616 may thereafter be delivered to the reaction chamber 606 for use in subsequent decomposition reactions.
- the second portion of the first gaseous product stream 616 may be added to or otherwise combined with a second volume of carrier gas 604 prior to entry into the reaction chamber 606.
- a heat source 618 may be coupled to the second heat exchanger 610.
- the heat source 618 may provide heat or otherwise transfer thermal energy to the second heat exchanger 610 prior to heating the second portion of the first gaseous product stream 616 with the second heat exchanger 610.
- the heat source 618 may be any of the above-mentioned heat sources, such as a combustion heating system that generates heat from the combustion of one or more combustible gases.
- the heat source 618 may be coupled to both the first heat exchanger 608 and the second heat exchanger 610. In other embodiments, separate and independent heat sources 618 may be used to transfer thermal energy to each heat exchanger (e.g., the first heat exchanger 608 and the second heat exchanger 610).
- At least a portion of the gaseous product stream may be delivered to a heat exchanger that is coupled to the hydrocarbon feedstock.
- the heat exchanger may be configured such that it removes heat from the gaseous product stream and transfers the heat to a volume of hydrocarbon feedstock that is being delivered to the reaction chamber for use in decomposition reactions.
- at least a portion of the gaseous product stream may be delivered to a heat exchanger that is coupled to a combustible gas.
- the heat exchanger may be configured to transfer heat from the portion of the gaseous product stream to the combustible gas.
- the combustible gas may thereafter be delivered to a second heat exchanger.
- a second combustible gas may also be delivered to the second heat exchanger, and the first and second combustible gases may combust with one another.
- the combustion of the first combustible gas and the second combustible gas may serve as a heat source for the second heat exchanger.
- the second heat exchanger may thereafter be used to heat the carrier gas prior to delivering the carrier gas to the reaction chamber.
- the first and second combustible gases may comprise air, oxygen, hydrocarbon feedstock, or hydrogen gas, or mixtures thereof.
- the hydrogen gas may be derived from the first gaseous product stream and may be at a temperature that is greater than ambient temperature.
- the source of the ultrasonic agitation may be a generator.
- the generator may be, for example, a mechanical generator, an electrical generator, a piezoelectric generator, or a magnetostrictive generator.
- one or more parameters of the ultrasonic wave may be varied as needed or desired.
- Such parameters include the frequency, amplitude, duration and site of the ultrasonic agitation.
- the variable parameter may be a frequency of the ultrasonic agitation. Typical ultrasonic wave frequencies may be in the range of about 1 to about 800 kHz.
- the variable parameter may be an amplitude of the ultrasonic agitation.
- the variable parameter may be a duration of the ultrasonic agitation.
- the variable parameter may be a site of the ultrasonic agitation.
- one or more parameters of the ultrasonic agitation may be varied based on the amount of carbon substances that are deposited on a selected surface. This may be influenced by reaction conditions such as temperature and rate of decomposition, etc. One or more parameters of the ultrasonic agitation may also be varied based on reaction conditions and the time the ultrasonic agitation is being applied. One or more parameters of the ultrasonic agitation may also be varied based on the deposition rate of the carbon substances on a selected surface, or based on the type of carbon substances deposited on a selected surface.
- the ultrasonic wave generator may be coupled to the reaction chamber.
- the ultrasonic wave generator may be disposed substantially perpendicularly to the exterior of the reaction chamber. However, the ultrasonic wave generator may also be disposed in any other suitable orientation.
- the ultrasonic wave generator may further be protected by one or more fluids. The ultrasonic waves may therefore be transmitted through the one or more fluids as necessary.
- ultrasonic agitation may be applied to a variety of selected surfaces.
- the selected surfaces may be surfaces that are within the reaction chamber.
- the reaction chamber may comprise one or more walls. Each wall may comprise an inner surface and an outer surface. The inner surface is directed toward the inside of the reaction chamber.
- at least one selected surface to which ultrasonic agitation may be applied may be a wall or an inner surface of the reaction chamber.
- the reaction chamber may further comprise one or more windows. Each window may have an inner surface that is directed toward the inside of the reaction chamber.
- at least one of the selected surfaces to which ultrasonic agitation may be applied may be the inner surface of a window.
- the reaction chamber may further comprise additional components such as one or more inlet ports, one or more outlet ports, discrete injectors, nozzles, etc. that are coupled or otherwise attached thereto.
- the one or more inlet ports may be configured to allow the introduction of carrier gas and/or hydrocarbon feedstock into the reaction chamber; the one or more outlet ports may be configured to allow the gaseous product stream and/or carbon substances out of the reaction chamber; and the discrete injectors and nozzles may be configured to deliver the carrier gas into the reaction chamber.
- each of these components may comprise one or more surfaces that are directed toward the inside of the reaction chamber. It is contemplated that each of their surfaces directed toward the inside of the reaction chamber may be a selected surface to which ultrasonic agitation may be applied.
- At least one selected surface to which ultrasonic agitation may be applied may be an electrode; in some embodiments, at least one selected surface to which ultrasonic agitation may be applied may be the surface of a heat exchanger; and in some embodiments, at least one selected surface to which ultrasonic agitation may be applied may be a catalyst surface. It is therefore contemplated that virtually any surface that may be used in accordance with the thermal decomposition reaction may be a selected surface to which ultrasonic agitation may be applied.
- a method for thermally decomposing hydrocarbon feedstock may comprise a step of heating a first volume of non-oxidizing carrier gas with a first heat exchanger.
- the method may further comprise a step of delivering a first volume of hydrocarbon feedstock into a reaction chamber.
- the method may comprise a step of delivering the first volume of carrier gas into the reaction chamber such that the first volume of carrier gas and the first volume of hydrocarbon feedstock mix within the reaction chamber and the first volume of carrier gas transfers heat to the first volume of hydrocarbon feedstock within the reaction chamber causing the decomposition of the first volume of hydrocarbon feedstock, and wherein the decomposition of the first volume of hydrocarbon feedstock results in a product comprising hydrogen gas and carbon substances.
- the method may comprise a step of collecting a first gaseous product stream from the reaction chamber, wherein the first gaseous product stream comprises hydrogen gas and carrier gas.
- the method may yet further comprise a step of thermally coupling heat from at least a portion of the first gaseous product stream into a second volume of carrier gas before delivering the second volume of carrier gas into the reaction chamber.
- a method for thermally decomposing hydrocarbon feedstock may comprise a step of heating a first volume of non-oxidizing carrier gas with a first heat exchanger.
- the method may further comprise a step of delivering a first volume of hydrocarbon feedstock into a reaction chamber.
- the method may further comprise a step of delivering the first volume of carrier gas into the reaction chamber such that the first volume of carrier gas and the first volume of hydrocarbon feedstock mix within the reaction chamber and the first volume of carrier gas transfers heat to the first volume of hydrocarbon feedstock within the reaction chamber causing the decomposition of the first volume of hydrocarbon feedstock, and wherein the decomposition of the first volume of hydrocarbon feedstock results in a product comprising hydrogen gas and carbon substances.
- the method may further comprise the step of collecting a first gaseous product stream, wherein the first gaseous product stream comprises hydrogen gas and carrier gas.
- the method may further comprise the step of delivering at least a portion of the first gaseous product stream to a second heat exchanger.
- the method may comprise a step of heating the portion of the first gaseous product stream using the second heat exchanger.
- the method may still further comprise a step of delivering a second volume of hydrocarbon feedstock into the reaction chamber.
- the method may comprise a step of delivering the portion of the first gaseous product stream into the reaction chamber such that the portion of the first gaseous product stream and the second volume of hydrocarbon feedstock mix within the reaction chamber and the portion of the first gaseous product stream transfers heat to the second volume of hydrocarbon feedstock within the reaction chamber causing the decomposition of the second volume of hydrocarbon feedstock, and wherein the decomposition of the second volume of hydrocarbon feedstock results in a product comprising hydrogen gas and carbon substances.
- the method may further comprise a step of collecting a second gaseous product stream, wherein the second gaseous product stream comprises hydrogen gas and carrier gas.
- the method may further comprise a step of repeating the steps of delivering the portion of the first gaseous product stream to the second heat exchanger, heating the portion of the first gaseous product stream using the second heat exchanger, delivering a second volume of hydrocarbon feedstock into the reaction chamber, delivering the portion of the first gaseous product stream into the reaction chamber, and collecting a second gaseous product stream.
- a method for thermally decomposing hydrocarbon feedstock may comprise a step of heating a non-oxidative carrier gas.
- the method may further comprise a step of delivering a first volume of hydrocarbon feedstock into a reaction chamber.
- the method may further comprise a step of delivering the carrier gas into the reaction chamber using a high speed injection method such that the carrier gas and the first volume of hydrocarbon feedstock mix within the reaction chamber and the carrier gas transfers heat to the first volume of hydrocarbon feedstock within the reaction chamber causing the decomposition of the first volume of hydrocarbon feedstock, and wherein the decomposition of the first volume of hydrocarbon feedstock results in a product comprising hydrogen gas and carbon substances.
- a method for thermally decomposing hydrocarbon feedstock may comprise a step of delivering a volume of hydrocarbon feedstock into a reaction chamber.
- the method may further comprise a step of heating the volume of hydrocarbon feedstock in a non-oxidative manner within the reaction chamber, wherein heating the volume of hydrocarbon feedstock causes the decomposition of the volume of hydrocarbon feedstock, and wherein the decomposition of the volume of hydrocarbon feedstock results in a product comprising hydrogen gas and carbon substances.
- the method may further comprise a step of applying ultrasonic agitation to the reaction chamber to disrupt a buildup of carbon substances on one or more selected surfaces.
- a method for thermally decomposing hydrocarbon feedstock may comprise a step of heating a volume of non-oxidizing carrier gas with a first heat exchanger.
- the method may further comprise a step of delivering a volume of hydrocarbon feedstock into a reaction chamber.
- the method may comprise a step of delivering the volume of carrier gas into the reaction chamber such that the volume of carrier gas and the volume of hydrocarbon feedstock mix within the reaction chamber and the volume of carrier gas transfers heat to the volume of hydrocarbon feedstock within the reaction chamber causing the decomposition of the volume of hydrocarbon feedstock, and wherein the decomposition of the volume of hydrocarbon feedstock results in a product comprising hydrogen gas and carbon substances.
- the method may yet further comprise a step of collecting a first gaseous product stream, wherein the first gaseous product stream comprises hydrogen gas and carrier gas.
- the method may further comprise a step of applying ultrasonic agitation to the reaction chamber to disrupt a buildup of carbon substances on one or more selected surfaces.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Hydrogen, Water And Hydrids (AREA)
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Abstract
L'invention concerne des systèmes et des procédés pour décomposer thermiquement une charge hydrocarbonée. Un système peut comprendre une charge hydrocarbonée, un gaz porteur non oxydant, un ou plusieurs échangeur(s) de chaleur et une chambre de réaction. Le gaz porteur peut être utilisé pour transférer de la chaleur à charge hydrocarbonée. Le/les échangeur(s) de chaleur peut/peuvent être conçu(s) pour chauffer le gaz porteur. La chambre de réaction peut être conçue pour recevoir la charge hydrocarbonée et le gaz porteur chauffé. A l'intérieur de la chambre de réaction, la charge hydrocarbonée et le gaz porteur chauffé peuvent se mélanger l'un avec l'autre, ce qui entraîne une réaction de décomposition thermique. La réaction de décomposition thermique se produit dans un environnement sensiblement exempt d'oxydant, ce qui permet d'éliminer ou de réduire grandement la production de sous-produits d'oxyde de carbone. Le gaz hydrogène peut être séparé du flux de produits gazeux et ensuite collecté depuis la chambre de réaction. Une partie du flux de produits gazeux peut être couplée thermiquement au gaz porteur et peut ensuite être recyclée via le système.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
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US13/691,552 | 2012-11-30 | ||
US13/691,543 | 2012-11-30 | ||
US13/691,543 US9156688B2 (en) | 2012-11-30 | 2012-11-30 | Systems and methods for producing hydrogen gas |
US13/691,552 US9434612B2 (en) | 2012-11-30 | 2012-11-30 | Systems and methods for producing hydrogen gas |
US13/691,585 US20140154170A1 (en) | 2012-11-30 | 2012-11-30 | Systems and methods for producing hydrogen gas |
US13/691,585 | 2012-11-30 |
Publications (1)
Publication Number | Publication Date |
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WO2014085598A1 true WO2014085598A1 (fr) | 2014-06-05 |
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ID=50828464
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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PCT/US2013/072248 WO2014085598A1 (fr) | 2012-11-30 | 2013-11-27 | Systèmes et procédés pour produire du gaz hydrogène |
PCT/US2013/072240 WO2014085594A2 (fr) | 2012-11-30 | 2013-11-27 | Systèmes et procédés pour la production d'hydrogène gazeux |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US2013/072240 WO2014085594A2 (fr) | 2012-11-30 | 2013-11-27 | Systèmes et procédés pour la production d'hydrogène gazeux |
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WO (2) | WO2014085598A1 (fr) |
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US1717354A (en) * | 1927-08-22 | 1929-06-18 | Alox Chemical Corp | Production of hydrogen and carbon by thermal decomposition of hydrocarbons |
US2791990A (en) * | 1954-05-21 | 1957-05-14 | Daniel A Grieb | Ultrasonic mixing method and apparatus therefor |
US4341598A (en) * | 1979-08-14 | 1982-07-27 | Occidental Research Corporation | Fluidized coal pyrolysis apparatus |
US20030223305A1 (en) * | 2002-06-03 | 2003-12-04 | Halsall Richard W. | Method for continuous internal agitation of fluid within hot water heaters or other fluid containing vessels |
WO2008155538A2 (fr) * | 2007-06-18 | 2008-12-24 | Otter Controls Limited | Récipient chauffant pour liquide et commande |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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DE3585325D1 (de) * | 1984-12-31 | 1992-03-12 | Oliver Michael Gondouin | Umwandlungssystem fuer naturgas. |
NO175718C (no) * | 1991-12-12 | 1994-11-23 | Kvaerner Eng | Fremgangsmåte ved spalting av hydrokarboner samt apparat for bruk ved fremgangsmåten |
EP1214459B1 (fr) * | 1999-08-17 | 2009-01-07 | Tokyo Electron Limited | Traitement au plasma pulse et appareil a cet effet |
WO2001046067A1 (fr) * | 1999-12-21 | 2001-06-28 | Bechtel Bwxt Idaho, Llc | Production d'hydrogene et de carbone elementaire a partir de gaz naturel et d'autres hydrocarbures |
EP2425915B1 (fr) * | 2010-09-01 | 2015-12-02 | Directa Plus S.p.A. | Complexe de production multimode pour nanoparticules de métal |
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2013
- 2013-11-27 WO PCT/US2013/072248 patent/WO2014085598A1/fr active Application Filing
- 2013-11-27 WO PCT/US2013/072240 patent/WO2014085594A2/fr active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1717354A (en) * | 1927-08-22 | 1929-06-18 | Alox Chemical Corp | Production of hydrogen and carbon by thermal decomposition of hydrocarbons |
US2791990A (en) * | 1954-05-21 | 1957-05-14 | Daniel A Grieb | Ultrasonic mixing method and apparatus therefor |
US4341598A (en) * | 1979-08-14 | 1982-07-27 | Occidental Research Corporation | Fluidized coal pyrolysis apparatus |
US20030223305A1 (en) * | 2002-06-03 | 2003-12-04 | Halsall Richard W. | Method for continuous internal agitation of fluid within hot water heaters or other fluid containing vessels |
WO2008155538A2 (fr) * | 2007-06-18 | 2008-12-24 | Otter Controls Limited | Récipient chauffant pour liquide et commande |
Also Published As
Publication number | Publication date |
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WO2014085594A3 (fr) | 2014-07-17 |
WO2014085594A2 (fr) | 2014-06-05 |
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