WO2019234991A1 - 不飽和炭化水素製造装置 - Google Patents
不飽和炭化水素製造装置 Download PDFInfo
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- WO2019234991A1 WO2019234991A1 PCT/JP2019/006331 JP2019006331W WO2019234991A1 WO 2019234991 A1 WO2019234991 A1 WO 2019234991A1 JP 2019006331 W JP2019006331 W JP 2019006331W WO 2019234991 A1 WO2019234991 A1 WO 2019234991A1
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- WIPO (PCT)
- Prior art keywords
- heating furnace
- heat
- unsaturated hydrocarbon
- gas
- hydrocarbon production
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 229930195735 unsaturated hydrocarbon Natural products 0.000 title claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 121
- 239000007789 gas Substances 0.000 claims abstract description 116
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 33
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 30
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 29
- 239000005977 Ethylene Substances 0.000 claims description 29
- 238000000926 separation method Methods 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000011810 insulating material Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 230000012447 hatching Effects 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000005691 oxidative coupling reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000013336 microporous metal-organic framework Substances 0.000 description 2
- -1 naphtha Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/127—Sunlight; Visible light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/008—Pyrolysis reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/062—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes being installed in a furnace
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0871—Heating or cooling of the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0892—Materials to be treated involving catalytically active material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J7/00—Apparatus for generating gases
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/12—Refinery or petrochemical off-gas
Definitions
- Ethylene or acetylene is a raw material for plastics. Ethylene or acetylene is produced by heating raw materials such as kerosene, naphtha, propane, and ethane to about 900 ° C. and causing thermal decomposition.
- raw materials are heated by burning fossil fuels such as petroleum with a burner (for example, Patent Document 1).
- the present disclosure aims to provide an unsaturated hydrocarbon production apparatus capable of reducing carbon dioxide emissions.
- an unsaturated hydrocarbon production apparatus includes a light collecting device that collects sunlight and converts it into solar heat, methane and hydrogen, methane and oxygen, and ethane.
- a heating furnace that heats at least 700 ° C. to 2000 ° C. of the source gas containing at least one of these groups with solar heat generated by a light collecting device.
- the heating furnace may contain a catalyst that promotes the reaction of the raw material gas to one or both of ethylene and acetylene.
- a preheating unit that preheats the source gas with the heat released from the heating furnace may be provided.
- the 1st heat exchange part which heat-exchanges the product gas produced
- the raw material gas heat-exchanged by the 1st heat exchange part may be introduce
- a second heat exchange unit that exchanges heat between the generated gas generated in the heating furnace and the raw material gas preheated by the preheating unit may be provided.
- a separation unit that separates ethylene or acetylene from the product gas generated in the heating furnace may be provided.
- the heating furnace may heat the source gas to 1000 ° C. or more and 1200 ° C. or less.
- FIG. 1 is a diagram illustrating an unsaturated hydrocarbon production apparatus according to the first embodiment.
- FIG. 2A is a diagram illustrating the appearance of the light collecting device and the heating unit.
- FIG. 2B is a perspective view in which a part of the heating unit is cut away.
- FIG. 3 is a diagram illustrating the unsaturated hydrocarbon production apparatus according to the second embodiment.
- FIG. 1 is a diagram illustrating an unsaturated hydrocarbon production apparatus 100 according to the first embodiment.
- solid arrows indicate the flow of the source gas.
- broken arrows indicate the flow of product gas.
- dashed-dotted arrow in FIG. 1 shows the flow of ethylene and acetylene.
- white arrows indicate the condensed sunlight.
- the unsaturated hydrocarbon production apparatus 100 includes a light collecting device 110, a heating unit 120, a first heat exchange unit 130, a second heat exchange unit 140, a cooling unit 150, A separation unit 160 and a second separation unit 170 (separation unit) are included.
- the condensing device 110 condenses sunlight and guides it to the heating unit 120 (lighting window 212).
- the heating unit 120 includes a casing 210, a furnace chamber 220, a heat transfer material 222, a heating furnace 230, a preheating unit 250, and a heat insulating material 260.
- the heat transfer material 222 is indicated by hatching
- the heat insulating material 260 is indicated by cross hatching.
- FIG. 2A is a diagram illustrating the external appearance of the light collecting device 110 and the heating unit 120.
- FIG. 2B is a perspective view in which a part of the heating unit 120 is cut away.
- the heat transfer material 222 is indicated by hatching
- the heat insulating material 260 is indicated by cross hatching.
- the condensing device 110 is a device that condenses sunlight and converts it into solar heat.
- the light concentrator 110 includes one or more heliostats (plane mirrors) 112, a parabolic curved mirror 114, and a furnace wall 220a described later.
- the heliostat 112 reflects the sunlight and guides it to the parabolic curved mirror 114.
- the parabolic curved mirror 114 is a mirror having a concave reflecting surface.
- the parabolic curved mirror 114 condenses the sunlight reflected by the heliostat 112 and guides it to the heating unit 120 (lighting window 212).
- the casing 210 of the heating unit 120 has a cylindrical shape.
- the casing 210 is provided such that the axial direction is the horizontal direction.
- a lighting window 212 is provided on the side surface of the housing 210.
- the furnace chamber 220 is provided inside the casing 210 continuously to the daylighting window 212. That is, the daylighting window 212 divides the furnace chamber 220 from the outside.
- the furnace chamber 220 is a space extending in the horizontal direction.
- the furnace wall 220a that forms the furnace chamber 220 is made of an endothermic material (an inorganic material having high heat resistance such as black ceramics).
- the heating furnace 230 and the preheating unit 250 have a tube shape.
- the heating furnace 230 and the preheating unit 250 are provided so as to penetrate the furnace chamber 220.
- the heating furnace 230 is provided at a position closest to the lighting window 212.
- the preheating unit 250 is adjacent to the heating furnace 230. That is, the heating furnace 230 and the preheating unit 250 are provided in the furnace chamber 220 in order from the side closer to the daylighting window 212.
- the heat transfer material 222 is provided between the heating furnace 230 and the preheating unit 250 and between the preheating unit 250 and the heat insulating material 260. That is, the heat transfer material 222 is separated from the heating furnace 230 and surrounds the preheating unit 250.
- the heat transfer material 222 is, for example, graphite or ceramics.
- the sunlight that has passed through the daylighting window 212 and led into the furnace chamber 220 is irradiated to the heating furnace 230, or irradiated to the furnace wall 220 a that forms the furnace chamber 220, etc. And the heating furnace 230 and the furnace wall 220a are heated. Thereby, the heating furnace 230 is maintained at 1000 ° C. or more and 2000 ° C. or less. Note that, since the heat transfer material 222 is not in contact with the heating furnace 230, the entire circumference of the heating furnace 230 is exposed to radiation. Thereby, the heating furnace 230 is efficiently heated by sunlight.
- the heat (heat radiation) released from the heating furnace 230 is transmitted to the preheating unit 250 by the heat transfer material 222 and is maintained at a predetermined preheating temperature (temperature exceeding room temperature (25 ° C.)).
- a predetermined preheating temperature temperature exceeding room temperature (25 ° C.)
- the heat insulating material 260 is provided in the housing 210.
- the heat insulating material 260 surrounds the furnace chamber 220.
- the heat insulating material 260 suppresses the outflow (heat radiation) of heat from the furnace chamber 220 to the outside.
- the first heat exchanging unit 130 generates a generated gas (which will be described later in detail) generated in the heating furnace 230 and removed by the second heat exchanging unit 140 described later, and a source gas. Heat exchange. Thereby, the raw material gas is heated by the heat of the generated gas, and the generated gas is cooled.
- the source gas is a gas containing at least methane and hydrogen.
- the source gas is, for example, a mixture of natural gas and hydrogen.
- the source gas heated by the first heat exchange unit 130 is sent to the preheating unit 250.
- the product gas cooled by the first heat exchange unit 130 is sent to a second separation unit 170 described later.
- the preheating unit 250 is maintained at the preheating temperature by the heat radiation of the heating furnace 230. Therefore, the preheating unit 250 can preheat (heat) the source gas heated by the first heat exchange unit 130 to the preheating temperature.
- the second heat exchanging unit 140 exchanges heat between the raw material gas preheated by the preheating unit 250 and the generated gas discharged from the heating furnace 230. Thereby, the raw material gas is heated by the heat of the generated gas, and the generated gas is cooled.
- the source gas heated by the second heat exchange unit 140 is introduced into the heating furnace 230.
- the product gas cooled by the second heat exchange unit 140 is introduced into the first heat exchange unit 130.
- the raw material gas heated by the first heat exchange unit 130, the preheating unit 250, and the second heat exchange unit 140 is introduced into the heating furnace 230.
- the source gas introduced into the heating furnace 230 is maintained at 1000 ° C. or more and 2000 ° C. or less by the light collecting device 110 as described above. Then, for example, the reactions shown in the following reaction formula (1) and reaction formula (2) proceed, and methane (CH 4 ) contained in the raw material gas becomes ethylene (C 2 H 4 ) and acetylene (C 2 H 2 ). Is converted to 2nCH 4 + 6nH 2 ⁇ nC 2 H 2 + 9nH 2 ... Reaction formula (1) 2nCH 4 + 6nH 2 ⁇ nC 2 H 4 + 8nH 2 ... Reaction formula (2) In addition, in reaction formulas including reaction formula (1) and reaction formula (2), n is an integer of 1 or more.
- Hydrogen in the raw material gas introduced into the heating furnace 230 is 0.1 mol or more and 8 mol or less with respect to methane (1 mol) in the raw material gas. Hydrogen in the source gas is preferably 3 mol or more with respect to methane in the source gas. By introducing 3 moles or more of hydrogen with respect to methane, the heating furnace 230 can improve the yield of ethylene and acetylene.
- the condensing device 110 may heat the source gas in the heating furnace 230 to 1000 ° C. or more and 1200 ° C. or less.
- the condensing device 110 is good to heat the raw material gas in the heating furnace 230 at 1200 to 1600 degreeC.
- a product gas containing at least ethylene, acetylene, and unreacted hydrogen is generated.
- the cooling unit 150 rapidly cools the generated gas generated in the heating furnace 230 to 600 ° C. or lower. Thereby, the cooling unit 150 can suppress thermal decomposition of ethylene and acetylene contained in the generated gas.
- the product gas rapidly cooled by the cooling unit 150 is introduced into the first separation unit 160.
- the first separation unit 160 includes a ceramic hydrogen separation membrane (for example, a porous ceramic hydrogen separation membrane).
- the first separation unit 160 separates and removes hydrogen from the product gas. With the configuration including the first separation unit 160, the unsaturated hydrocarbon production apparatus 100 can reduce the amount of hydrogen in the product gas.
- the product gas from which hydrogen has been removed by the first separation unit 160 is heat-exchanged by the second heat exchange unit 140 and the first heat exchange unit 130 and then introduced into the second separation unit 170.
- the second separation unit 170 includes, for example, a microporous metal-organic framework material.
- the second separation unit 170 separates the product gas into ethylene and acetylene.
- the unsaturated hydrocarbon production apparatus 100 can increase the purity of ethylene and at the same time increase the purity of acetylene.
- the ethylene separated by the second separation unit 170 is sent to a subsequent facility (for example, a plastic (resin) production plant).
- acetylene separated by the second separation unit 170 is sent to a subsequent facility (for example, a fuel production plant).
- the condensing device 110 heats the raw material gas in the heating furnace 230.
- the unsaturated hydrocarbon production apparatus 100 can reduce the amount of carbon dioxide emission to almost 0 (zero) when producing ethylene and acetylene (unsaturated hydrocarbon). That is, the unsaturated hydrocarbon production apparatus 100 generates new carbon dioxide in the process of obtaining the heating source, unlike the case of using the combustion heat of fossil resources or the electric energy derived therefrom to obtain the heating source. There is no. Therefore, the unsaturated hydrocarbon production apparatus 100 can improve the carbon dioxide reduction effect. Furthermore, the unsaturated hydrocarbon production apparatus 100 does not need to consume valuable fossil resources to obtain a heating source, and can greatly reduce the cost required for heating.
- solid carbon may be generated in the heating furnace 230 depending on the hydrogen content in the source gas.
- the shape of the heating furnace 230 is such that the diameter of the upper opening 232 is smaller than the diameter of the lower opening 234, and the channel cross-sectional area (horizontal cross-sectional area) is directed from the upper opening 232 to the lower opening 234. It is designed to gradually increase in shape.
- the heating furnace 230 is made of a material having a linear expansion coefficient different from that of solid carbon.
- the heating furnace 230 is formed of a ceramic material such as alumina, stearite, forsterite, or zirconia, for example.
- the amount of thermal expansion of the heating furnace 230 and the heating are changed by changing the temperature in the heating furnace 230 during the period when the production of unsaturated hydrocarbons (ethylene, acetylene) is stopped.
- a difference can be made between the thermal expansion amount of the solid carbon adhering to the inner wall of the furnace 230. Therefore, even if the solid carbon is attached to the inner wall of the heating furnace 230, the unsaturated hydrocarbon production apparatus 100 causes a contact between the heating furnace 230 and the solid carbon due to a difference in the amount of thermal expansion between them. A shearing force can be applied along the surface.
- the unsaturated hydrocarbon production apparatus 100 can reduce the adhesion between the inner wall of the heating furnace 230 and the solid carbon, and can induce the separation of the solid carbon from the inner wall of the heating furnace 230.
- the separated solid carbon falls outside the heating furnace 230 by its own weight through the lower opening 234.
- the unsaturated hydrocarbon production apparatus 100 includes the first heat exchange unit 130. Thereby, the 1st heat exchange part 130 can heat source gas with the heat which generated gas has. Furthermore, the unsaturated hydrocarbon production apparatus 100 includes a preheating unit 250. Thereby, the preheating unit 250 can preheat the source gas with the heat released from the heating furnace 230. Moreover, the unsaturated hydrocarbon production apparatus 100 includes a second heat exchange unit 140. Thereby, the 2nd heat exchange part 140 can heat source gas with the heat which generated gas has. As described above, the unsaturated hydrocarbon production apparatus 100 can heat the raw material gas with exhaust heat, so that the cost required for heating can be suppressed.
- the heating furnace 230 of the first embodiment does not contain a catalyst. However, the heating furnace 330 may accommodate the catalyst.
- FIG. 3 is a diagram for explaining an unsaturated hydrocarbon production apparatus 300 according to the second embodiment.
- the solid line arrows indicate the flow of the source gas.
- the broken arrow indicates the flow of the product gas.
- the one-dot chain line arrows indicate the flow of ethylene and acetylene.
- white arrows indicate the concentrated sunlight.
- the unsaturated hydrocarbon production apparatus 300 includes a light collecting device 110, a heating unit 320, a first heat exchange unit 130, a second heat exchange unit 140, a first separation unit 160, A second separation unit 170.
- the heating unit 320 includes a casing 210, a furnace chamber 220, a heat transfer material 222, a heating furnace 330, a preheating unit 250, and a heat insulating material 260.
- symbol is attached
- the heat transfer material 222 is indicated by hatching
- the heat insulating material 260 is indicated by cross hatching.
- the heating furnace 330 is a catalyst that promotes the reaction of the raw material gas to one or both of ethylene and acetylene (for example, the reaction shown in the reaction formula (1) or the reaction shown in the reaction formula (2)). To accommodate.
- the heating furnace 330 contains a catalyst as a packed bed.
- Catalysts that promote the reaction of source gas to either or both of ethylene and acetylene include, for example, molybdenum (Mo), tungsten (W), iron (Fe), vanadium (V), and chromium (Cr). Or one or more selected from the group.
- the unsaturated hydrocarbon production apparatus 300 can omit the cooling unit 150. Therefore, the unsaturated hydrocarbon production apparatus 300 can improve the heat recovery efficiency of the product gas by the second heat exchange unit 140.
- the hydrogen in the raw material gas is preferably 0.5 mol or more, more preferably 1 mol or more, relative to methane in the raw material gas, More preferably, it is at least mol.
- the source gas is a gas containing at least methane and hydrogen
- the source gas may be a gas containing at least methane and oxygen.
- the condensing device 110 may heat the source gas in the heating furnace 330 to 700 ° C. or more and 2000 ° C. or less.
- the oxidative coupling reaction shown in the following reaction formula (3) proceeds, and methane contained in the raw material gas is converted to ethylene. 2nCH 4 + nO 2 ⁇ nC 2 H 4 + 2nH 2 O ... reaction formula (3)
- the heating furnace 330 accommodates a catalyst that promotes the oxidative coupling reaction shown in the reaction formula (3).
- Catalysts that promote oxidative coupling reactions are SrO / La 2 O 3 , Mn / Na 2 WO 4 / SiO 2 , Li / MgO, BaF 2 / Y 2 O 3 , Rb 2 WO 4 / SiO 2 , La 2 O One or more selected from the group of 3- CeO 2 and Na 2 WO 4 / SiO 2 .
- the raw material gas is a gas containing at least methane and oxygen
- methane in the raw material gas may be partially oxidized, and the reaction shown in the following reaction formula (4) may be advanced to convert methane to acetylene. . 2nCH 4 + nO 2 ⁇ nC 2 H 2 + nH 2 + 2nH 2 O ... reaction formula (4)
- the condensing device 110 may heat the source gas in the heating furnace 230 to about 1500 ° C.
- the source gas may be a gas containing at least ethane (C 2 H 6 ).
- the condensing device 110 may heat the source gas in the heating furnaces 230 and 330 to 1000 ° C. or more and 2000 ° C. or less. Then, for example, a pyrolysis (cracking) reaction shown in the following reaction formula (5) proceeds, and ethane contained in the raw material gas is converted into ethylene.
- the source gas may be a gas containing at least ethane and hydrogen.
- the condensing device 110 may heat the source gas in the heating furnaces 230 and 330 to 1000 ° C. or more and 2000 ° C. or less. Then, for example, the thermal decomposition (cracking) reaction shown in the following reaction formula (6) and reaction formula (7) proceeds, and ethane contained in the raw material gas is converted into ethylene and acetylene.
- the source gas may be a gas containing at least ethane and oxygen.
- ethane in the raw material gas may be partially oxidized and the reaction shown in the following reaction formula (8) may be advanced to convert ethane to acetylene.
- the condensing device 110 may heat the source gas in the heating furnace 230 to about 1500 ° C.
- the heating furnaces 230 and 330 have been described by taking as an example the case where the flow path cross-sectional area gradually increases from the upper opening 232 toward the lower opening 234.
- the flow path cross-sectional area at the location arranged in the furnace chamber 220 may be smaller than other flow path cross-sectional areas. Thereby, the heating furnaces 230 and 330 can shorten the residence time of the source gas in a temperature environment of 700 ° C. or more and 2000 ° C. or less.
- the laminar convection heat transfer condition is switched to the turbulent convection heat transfer condition, and the heat transfer rate from the heating furnaces 230 and 330 to the source gas is increased (rapidly). Can be heated).
- the residence time is shortened, that is, the heating time is shortened, the time until the raw material gas is heated and cooled is shortened (can be rapidly cooled).
- the heating furnaces 230 and 330 in which the flow passage cross-sectional area of the portion disposed in the furnace chamber 220 is smaller than the other flow passage cross-sectional areas, the raw material gas can be rapidly cooled immediately after being rapidly heated. it can.
- the heating furnaces 230 and 330 are preferably filled with inert particles at locations disposed in the furnace chamber 220, thereby narrowing the cross-sectional area of the flow path. In this case, the inert particles in contact with the inner walls of the heating furnaces 230 and 330 are heated by heat conduction from the inner walls of the heating furnaces 230 and 330.
- the source gas is heated from the surface of the inert particles in addition to the surfaces of the inner walls of the heating furnaces 230 and 330 (that is, the heat transfer area is increased). Thereby, the heating furnaces 230 and 330 can further rapidly heat the source gas.
- the case where the casing 210 of the heating units 120 and 320 has a cylindrical shape has been described as an example.
- the shape of the casing 210 of the heating units 120 and 320 is not limited.
- the case 210 is described as an example in which the casing 210 is provided so that the axial direction is the horizontal direction.
- the installation direction of the housing 210 is not limited.
- the housing 210 may be provided so that the axial direction intersects the horizontal direction.
- the heating furnaces 230 and 330 are arranged in the furnace chamber 220, and the indirect heating type heating parts 120 and 320 in which the source gas passing through the heating furnaces 230 and 330 is indirectly heated are exemplified.
- the unsaturated hydrocarbon production apparatuses 100 and 300 include a daylighting window 212 having airtightness, and the raw gas is directly heated by directly introducing the raw material gas into the furnace chamber 220. You may provide a heating part of a formula.
- the light collecting device 110 including the heliostat 112 and the parabolic curved mirror 114 has been described as an example.
- the condensing device 110 can condense sunlight and generate solar heat, its type and configuration are not limited.
- the light collecting device 110 may be a tower-type light collecting device.
- the condensing device 110 was mentioned as an example and demonstrated as a heating source of the heating furnace 230,330.
- the heating source of the heating furnaces 230 and 330 is not limited to the light collecting device 110.
- a heating source for the heating furnaces 230 and 330 a combustion device, an electric heater, or the like may be used instead of or in addition to the light collecting device 110.
- heat sources of heating furnaces 230 and 330 may be switched to a combustion device or an electric heater.
- the combustion apparatus may combust the source gas or hydrogen separated by the first separation unit 160.
- the unsaturated hydrocarbon manufacturing apparatuses 100 and 300 demonstrated and demonstrated the structure provided with the preheating part 250 as an example.
- the preheating unit 250 is not an essential configuration.
- the unsaturated hydrocarbon production apparatuses 100 and 300 have been described using the configuration including the first heat exchange unit 130 as an example.
- the 1st heat exchange part 130 is not an essential structure.
- the unsaturated hydrocarbon manufacturing apparatuses 100 and 300 demonstrated and demonstrated the structure provided with the 2nd heat exchange part 140 as an example.
- the second heat exchange unit 140 is not an essential configuration.
- heating furnaces 230 and 330 and the preheating unit 250 extend in the vertical direction
- any one or more of the heating furnaces 230 and 330 and the preheating unit 250 may extend in a direction intersecting the vertical direction (for example, the horizontal direction).
- the second separation unit 170 has been described by taking as an example a configuration including a microporous metal-organic framework material.
- the configuration of the second separation unit 170 is not limited as long as it can separate ethylene or acetylene from the product gas.
- the second separation unit 170 may include an absorbent that dissolves acetylene, for example.
- the raw material gas may be preheated with the heat recovered by the cooling unit 150.
- hydrogen separated by the first separation unit 160 may be used as a raw material gas.
- This disclosure can be used for unsaturated hydrocarbon production equipment.
- Unsaturated hydrocarbon production apparatus 110 Condensing apparatus 130: 1st heat exchange part 140: 2nd heat exchange part 150: Cooling part 170: 2nd separation part (separation part) 230: Heating furnace 250: Preheating part 300 : Unsaturated hydrocarbon production system 330: Heating furnace
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Abstract
Description
図1は、第1の実施形態の不飽和炭化水素製造装置100を説明する図である。なお、図1中、実線の矢印は、原料ガスの流れを示す。図1中、破線の矢印は、生成ガスの流れを示す。また、図1中、一点鎖線の矢印は、エチレンおよびアセチレンの流れを示す。図1中、白抜き矢印は、集光された太陽光を示す。
2nCH4 + 6nH2 → nC2H2 + 9nH2 …反応式(1)
2nCH4 + 6nH2 → nC2H4 + 8nH2 …反応式(2)
なお、反応式(1)、反応式(2)をはじめとする反応式中、nは1以上の整数である。
上記第1の実施形態の加熱炉230は、触媒を収容していない。しかし、加熱炉330が触媒を収容してもよい。
2nCH4 + nO2 → nC2H4 + 2nH2O …反応式(3)
また、この場合、加熱炉330は、上記反応式(3)に示す酸化カップリング反応を促進する触媒を収容する。酸化カップリング反応を促進する触媒は、SrO/La2O3、Mn/Na2WO4/SiO2、Li/MgO、BaF2/Y2O3、Rb2WO4/SiO2、La2O3-CeO2、および、Na2WO4/SiO2の群から選択される1または複数である。
2nCH4 + nO2 → nC2H2 + nH2 + 2nH2O …反応式(4)
この場合、集光装置110は、1500℃程度に、加熱炉230内の原料ガスを加熱してもよい。
nC2H6 → nC2H4 + nH2 …反応式(5)
nC2H6 + 3nH2 → nC2H2 + 5nH2 …反応式(6)
nC2H6 + 3nH2 → nC2H4 + 4nH2 …反応式(7)
nC2H6 + nO2 → nC2H2 + 2nH2O …反応式(8)
この場合、集光装置110は、1500℃程度に、加熱炉230内の原料ガスを加熱してもよい。
Claims (8)
- 太陽光を集光して太陽熱に変換する集光装置と、
メタンと水素、メタンと酸素、および、エタンの群のうちいずれかを少なくとも含む原料ガスを、前記集光装置によって発生させた太陽熱で700℃以上2000℃以下に加熱する加熱炉と、
を備える不飽和炭化水素製造装置。 - 前記加熱炉で生成された生成ガスを600℃以下まで急冷する冷却部を備える請求項1に記載の不飽和炭化水素製造装置。
- 前記加熱炉は、前記原料ガスの、エチレンおよびアセチレンのいずれか一方または両方への反応を促進する触媒を収容する請求項1に記載の不飽和炭化水素製造装置。
- 前記加熱炉から放出された熱で前記原料ガスを予熱する予熱部を備える請求項1から3のいずれか1項に記載の不飽和炭化水素製造装置。
- 前記加熱炉で生成された生成ガスと、前記原料ガスとを熱交換させる第1熱交換部を備え、
前記予熱部には、前記第1熱交換部で熱交換された前記原料ガスが導入される請求項4に記載の不飽和炭化水素製造装置。 - 前記加熱炉で生成された生成ガスと、前記予熱部によって予熱された前記原料ガスとを熱交換させる第2熱交換部を備える請求項4または5に記載の不飽和炭化水素製造装置。
- 前記加熱炉で生成された生成ガスからエチレンまたはアセチレンを分離する分離部を備える請求項1から6のいずれか1項に記載の不飽和炭化水素製造装置。
- 前記加熱炉は、前記原料ガスを1000℃以上1200℃以下に加熱する請求項1から7のいずれか1項に記載の不飽和炭化水素製造装置。
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AU2019281557A AU2019281557B2 (en) | 2018-06-05 | 2019-02-20 | Unsaturated hydrocarbon production device |
EP19815257.1A EP3816144A4 (en) | 2018-06-05 | 2019-02-20 | DEVICE FOR THE PRODUCTION OF UNSATURATED HYDROCARBONS |
JP2020523511A JP7028320B2 (ja) | 2018-06-05 | 2019-02-20 | 不飽和炭化水素製造装置 |
US17/108,456 US20210080176A1 (en) | 2018-06-05 | 2020-12-01 | Unsaturated hydrocarbon production apparatus |
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