WO2007114438A1 - 反応デバイス - Google Patents
反応デバイス Download PDFInfo
- Publication number
- WO2007114438A1 WO2007114438A1 PCT/JP2007/057463 JP2007057463W WO2007114438A1 WO 2007114438 A1 WO2007114438 A1 WO 2007114438A1 JP 2007057463 W JP2007057463 W JP 2007057463W WO 2007114438 A1 WO2007114438 A1 WO 2007114438A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reaction
- catalyst
- fluid
- water
- gas
- Prior art date
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 308
- 239000012530 fluid Substances 0.000 claims abstract description 120
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910001868 water Inorganic materials 0.000 claims abstract description 93
- 239000003054 catalyst Substances 0.000 claims abstract description 68
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000000470 constituent Substances 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 90
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 74
- 235000011187 glycerol Nutrition 0.000 description 37
- 239000000203 mixture Substances 0.000 description 34
- 239000007788 liquid Substances 0.000 description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 238000001816 cooling Methods 0.000 description 23
- 229910052739 hydrogen Inorganic materials 0.000 description 23
- 239000001257 hydrogen Substances 0.000 description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 21
- 239000000126 substance Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 229920002620 polyvinyl fluoride Polymers 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000011027 product recovery Methods 0.000 description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229960004063 propylene glycol Drugs 0.000 description 5
- 235000013772 propylene glycol Nutrition 0.000 description 5
- 229940044613 1-propanol Drugs 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- -1 conoret Chemical compound 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000000629 steam reforming Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 description 1
- 241000282994 Cervidae Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910001039 duplex stainless steel Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910001055 inconels 600 Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- 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
- B01J16/00—Chemical processes in general for reacting liquids with non- particulate solids, e.g. sheet material; Apparatus specially adapted therefor
- B01J16/005—Chemical processes in general for reacting liquids with non- particulate solids, e.g. sheet material; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
- C01B2203/1017—Packed bed of catalytic structures, e.g. particles, packing elements characterised by the form of the structure
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1035—Catalyst coated on equipment surfaces, e.g. reactor walls
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a reaction device used for producing water gas from polyhydric alcohol and water, and a method for producing water gas using the reaction device.
- Glycerin is a raw material produced as a by-product in the production of biodiesel, which is expected to be put to practical use in the future, and is also used in energy situations considering environmental protection derived from natural products called carbon neutral. It is a substance that has increased significance.
- synthesizing hydrogen by reaction reforming using glycerin has a very high social significance.
- the synthesized hydrogen is used in chemical raw materials for fuel cells, hydrogenation reaction applications, hydrogen automobiles, etc. It can be applied to a fuel source or the like.
- Non-Patent Document 1 reports that a catalytic metal species excellent in steam reforming from glycerin was considered in a fixed bed reactor.
- Non-Patent Document 2 reports the possibility of hydrogen synthesis with glycerin power using a nickel catalyst in a sub-critical water field.
- Non-Patent Documents 1 and 2 there is a problem in production in terms of time and yield required for a force reaction that can obtain hydrogen with a certain degree of purity.
- Patent Document 1 discloses a microreactor for reforming a raw material to obtain hydrogen gas, a metal substrate having a fine groove on one surface, and the other surface of the metal substrate.
- a heating element provided via an insulating film, a catalyst carried in the fine groove, and a cover member joined to the metal substrate so as to cover the fine groove and having a raw material inlet and a gas outlet.
- Patent Document 2 discloses a chemical reaction apparatus having a reaction channel formed continuously, and is temperature adjusted to supply a predetermined amount of heat formed corresponding to a region including the reaction channel.
- a first electrode layer stacked in a first region on the temperature adjustment layer, and an insulating layer stacked on a second region other than the first region on the temperature adjustment layer A second electrode layer that is laminated on the first electrode layer and supplies electric power for generating a predetermined amount of heat in the temperature adjustment layer via the first electrode layer, and an insulating layer
- an insulating material that is integrated with the first electrode layer and is obtained by subjecting the conductive material of the same layer to an acid treatment.
- Non-Patent Document 1 Petroleum 'Abstracts of Petrochemical Discussion, 2005, 34, 248
- Non-Patent Document 2 Proceedings of the Chemical Society of Japan, 2005, 85, 2, page 1430
- Patent Document 1 Japanese Patent Laid-Open No. 2004-256387
- Patent Document 2 JP 2004-63131 A
- the reaction device of the present invention is used to generate water gas from a polyhydric alcohol and water
- the method for producing a water gas of the present invention is a method for producing a water gas from a polyhydric alcohol and water,
- Water gas is generated by reacting a reaction fluid containing polyhydric alcohol and water in a reaction field provided with a catalyst having a surface formed so as to extend along the flow direction of the reaction fluid. The step of carrying out is provided.
- FIG. 1 is a diagram showing a configuration of a reaction device according to a first embodiment.
- FIG. 2 is a cross-sectional view of a reaction part.
- FIG. 3 is a perspective view of a reaction unit.
- FIG. 4 is a diagram showing a configuration of a reaction device of Embodiment 2.
- FIG. 1 shows a reaction device 10 according to the first embodiment.
- This reaction device 10 is a continuous type that continuously obtains a reaction product, and is provided with a tube that extends to a reaction fluid supply unit 11 force product recovery unit 15 as a reaction fluid supply source,
- a fluid supply pump 12 and a reaction unit 13 are arranged in series in the pipe in order from upstream to downstream, and a heating unit 16 is provided so that the reaction unit 13 can be heated. Yes.
- This reaction device 10 includes a reaction fluid that is a mixture of polyhydric alcohol (eg, glycerin, propanediol, etc.) and water as raw materials from a reaction fluid supply unit 11 via a fluid supply pump 12. 13 is used to produce a water gas by reacting polyhydric alcohol and water in the reaction unit 13 and recovering the reaction fluid containing the generated water gas in the product recovery unit 15 Is.
- polyhydric alcohol eg, glycerin, propanediol, etc.
- the reaction section 13 has an inflow section into which the reaction fluid flows in and an outflow section through which the reaction fluid flows out, and an elongated reaction channel 13a formed between the inflow section and the outflow section.
- This reaction channel 13a constitutes a reaction field 14 in which the reaction fluid flows and reacts.
- the reaction unit 13 may be configured such that the reaction channel 13a is formed by bringing a face piece having a groove formed on the surface by cutting or the like into close contact with another different face piece, or a square tube or a circular tube.
- the reaction flow path 13a may be constituted by a pre-made tube.
- Examples of the cross-sectional shape of the reaction channel 13a include a circular shape, a semi-circular shape, an elliptical shape, a semi-elliptical shape, a square shape, a rectangular shape, a trapezoidal shape, a parallelogram shape, and an indefinite shape.
- Examples of the shape of the trajectory in the length direction from the inflow portion to the outflow portion of the reaction channel 13a include a straight shape, a circular shape, a meandering shape, and a helical shape.
- the area surrounded by the outer periphery of the cross section of the reaction channel 13a is preferably 0.05 to 50 mm in terms of equivalent diameter. Heat transfer can be improved in order to proceed appropriately.
- 0.05-: LOmm is more preferred 0. l-3m Particularly preferred is m.
- the equivalent diameter is a diameter of a perfect circle having the same area as the area of the reaction channel 13a.
- a catalyst 17 is provided in the reaction channel 13a constituting the reaction field 14.
- the catalyst 17 has a surface formed so as to extend along the flow direction of the reaction fluid.
- a metal used for steam reforming of alcohol can be suitably used, and among these, any metal of Group 8 to 12, preferably Group 8 to 10, is industrially suitable.
- Can be used for Examples include iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc.
- those of group 8 to 10 are industrial cost, availability, safety.
- nickel, ruthenium, nickel and platinum are more preferable.
- these can be used in combination, and the surface is treated with a pretreatment such as a reduction treatment using hydrogen or an oxidation treatment using oxygen or air. It is also possible to control and use the state.
- the catalyst 17 is, for example, as shown in FIGS. 2 (a) and 2 (b), a linear structure such as a metal wire, a wire bundle or a stranded wire, an elongated structure such as a plate-like structure, As shown in 2 (c), it is constituted by the inner wall of the reaction channel 13a in the reaction section 13 and the like.
- the catalyst 17 may be formed so as to continuously extend along the flow direction of the reaction fluid, or may be configured by a plurality of portions provided intermittently along the flow direction of the reaction fluid. .
- the outer peripheral surface corresponds to a surface formed so as to extend along the flow direction of the reaction fluid.
- the reaction section 13 in which the reaction flow path 13a is configured by the assembly of the face pieces the reaction section 13 in which the reaction flow path 13a is configured by a pre-made tube, which is sufficient if the catalyst 17 is disposed in the groove of one face face. Therefore, the catalyst 17 may be inserted into the reaction channel 13a. Further, as shown in FIG. 3, the catalyst 17 may be provided in the reaction channel 13a so as to form a spiral having a pitch in the flow direction of the reaction fluid.
- a plurality of catalyst metals may be provided intermittently along the flow direction of the reaction fluid, and they may constitute a surface formed so as to extend along the flow direction of the reaction fluid as a whole. Further, the catalyst 17 may be provided all over the inflow portion of the reaction portion 13 to reach the outflow portion, or may be provided only in a part thereof, or may be displaced.
- the inner wall surface is along the flow direction of the reaction fluid. It corresponds to the surface formed to extend.
- a catalytic metal may be applied to the metal forming the inner wall of the reaction channel 13a, or the inner wall of the reaction channel 13a may be formed later with the catalyst 17 by a technique such as plating, sputtering, coating and drying.
- the inner wall may be formed of a catalytic metal intermittently along the flow direction of the reaction fluid.
- the catalyst 17 may be provided all over the reaction part 13 from the inflow part to the outflow part, or may be provided only in a part thereof, or may be displaced.
- the surface area S of each catalyst structural unit is perpendicular to the flow direction of the reaction fluid of the catalyst structural unit.
- ⁇ AZ ⁇ S «0 to 0.2 (—) force is preferred, 0 to 0.1 (—) is more preferred 0 to 0.07 (—) is more preferred 0 to 0.05 (—) Is particularly preferred.
- the catalyst 17 is provided in the reaction channel 13a so that the catalyst 19 exists within a radius of 10 mm at any position in the cross section. More preferably, 7 is provided. According to such a configuration, the catalyst 17 can have a distance of 20 mm or less at any position of the reaction field 14. Thus, a state suitable for reactivity and aldehyde selectivity can be obtained.
- FIG. 2 (d) there is a reaction channel 13a having an inner wall formed of a catalyst 17 and having a cross-sectional shape formed in an elongated gap shape having a spacing of 20 mm or less.
- the reaction flow path 13a provided with the catalyst 17 having a plurality of catalyst constituent unit forces is configured so that the reaction fluid flows in a stagnation state in the vicinity of the catalyst 17. I like that. If there is no stagnation area (so-called dead space) in the vicinity of the catalyst 17, the reaction residence time distribution of the reaction fluid can be narrowed. The reaction can be suppressed.
- the catalyst 17 is preferably arranged so that the catalyst constituent units do not have a narrow gap between the point contact portions. More specifically, it is preferable that the catalyst constituent units are arranged with a minimum distance of 0.2 mm or more, more preferably 0.5 mm or more, and more preferably 1 mm or more. More preferably.
- a reactor called a microreactor has a narrow flow path of less than 1 mm, but this does not apply if there is no stagnation in the flow path.
- the fluid supply pump 12 supplies the reaction fluid from the reaction fluid supply unit 11 to the reaction unit 13.
- the fluid supply pump 12 include a centrifugal pump, a differential user pump, a spiral mixed flow pump, a mixed flow pump, an axial flow pump, a gear pump, a screw pump, a cam pump, a vane pump, and a piston pump when the reaction fluid is a liquid.
- Plunger pumps, diaphragm pumps, vortex pumps, viscous pumps, bubble pumps, jet pumps, and electromagnetic pumps are Among these, the type with less pulsating flow is preferable.
- reaction fluid when a reaction fluid is circulated in the flow path without pulsating flow, a uniform and stable flow is maintained in each part of the flow path, a stable mixing phenomenon occurs, and the reaction is defective. This is because there is obtained a reaction advantage that the stoichiometric conditions having a desired reactivity and high selectivity without causing the reaction can be uniformly achieved.
- the reaction fluid may be supplied to the reaction unit 13 by a method using a pressure difference.
- each member constituting the reaction device 10 needs to be formed of a material having a melting point higher than the reaction temperature. Further, considering that the reaction temperature is reached at an early stage, it is preferably formed of a material having excellent thermal conductivity. For these reasons, the material of each member constituting the reaction device 10 is preferably a metal.
- Such metals include single-composition metals such as aluminum, titanium, chromium, iron, conoret, nickel, copper, zinc, and zirconium, and alloys containing these in combination.
- Specific examples of alloys include, for example, austenitic steel represented by SUS304 and SUS316, martensitic steel represented by SUS420, duplex stainless steel of ferrite and austenite represented by SUS329, stainless steel, and stainless steel.
- Examples include Ni alloys such as C276 and Inconel 600, and titanium alloys such as 6-4 titanium alloy. Of course, each member can be formed of these materials singly or in combination of two or more.
- This method for producing a water gas is to produce a mixed gas of polyhydric alcohol, water, hydrogen and hydrogen monoxide, which is called a strong water gas.
- the polyhydric alcohol refers to a compound having a structure having 2 or more carbon atoms and two or more hydroxyl groups bonded thereto. If these conditions are satisfied, a carboxylic acid group or an aldehyde group may be bonded in addition to the hydroxyl group.
- the polyhydric alcohol for example, dihydric alcohols such as ethylene diglycol, 1,2 propanediol, 1,3 prononediol, 2,3 hydroxypropanal, 1,2 butanediol, 1, 3 Butanediol, 1,4 butanediol, tartaric acid, etc., and trivalent alcohols such as glycerin, 1,2,4 butane diol, 1,2,6 hexane diol, etc. Examples of the alcohol include pentaerythritol. Of these, the use of ethylene glycol and glycerin is desirable from the viewpoint of economy.
- the polyhydric alcohol generates water gas based on the following chemical reaction formula (1).
- the produced carbon monoxide and carbon can react with water to produce hydrogen secondarily based on the water gas shift reaction of the following chemical reaction formula (2).
- a reaction fluid which is a mixture of polyhydric alcohol as a raw material and water, is supplied from the reaction fluid supply unit 11 to the reaction unit 13 via the fluid supply pump 12.
- the phase state of the reaction fluid may be any of liquid, gas, and supercritical fluid, or may be a state in which these are mixed.
- the phase state of the reaction fluid is adjusted by setting the heating temperature of the reaction unit 13 by the heating unit 16 and setting the exhaust pressure of the reaction fluid by the pressure regulator provided in front of the product recovery unit 15.
- the mixing ratio of the polyhydric alcohol and water in the reaction fluid is such that the molar ratio of water to carbon atoms contained in the polyhydric alcohol is 0.3 to 10 in order to allow the reaction to be performed suitably. More preferably, it is more preferably 1 to 6 (for example, when the polyhydric alcohol is glycerin, the mixing ratio of glycerin and water in the reaction fluid is glycerin in order to allow the reaction to be carried out suitably). It is preferable to set the molar ratio of water to 0.9-30, more preferably 3-18.
- reaction fluid contains organic acids such as organic acids, hydrocarbons, alcohols and aldehydes, salts thereof, or inorganic salts that do not impair the essential reactivity. May be.
- the reaction unit 13 reacts with the polyhydric alcohol and water to produce water gas.
- the reaction time between the polyhydric alcohol and water in the reaction fluid is preferably about 0.1 seconds to 1 hour, more preferably 1 second to 10 minutes (for example, when the polyhydric alcohol is glycerin, the reaction fluid The reaction time between glycerin and water is preferably about 0.1 seconds to 1 hour, more preferably 1 second to 10 minutes.
- the reaction fluid propanediol
- the reaction time of 0.1 second to 1 hour is preferable, and 1 second to 10 minutes is more preferable.
- the reaction time of the polyhydric alcohol and water of the reaction fluid is Since it is defined by the residence time, it is adjusted by setting the liquid feed rate of the reaction fluid by the fluid supply pump 12 according to the volume of the reaction field 14.
- the reaction temperature of the reaction fluid with the polyhydric alcohol and water is preferably 200 to 1000 ° C force S, more preferably 300 to 700 ° C (for example, when the polyhydric alcohol is glycerin, the reaction fluid glycerin is glycerin).
- the reaction temperature between water and water is preferably 200 to 1000, more preferably 300 to 700 ° C.
- the reaction temperature between propanediol and water in the reaction fluid is 200 to 1000 ° C force is preferable, and 300 to 700 ° C force is more preferable.
- the reaction temperature between the polyhydric alcohol of the reaction fluid and water is adjusted by the heating temperature setting of the reaction unit 13 by the heating unit 16.
- reaction fluid containing the produced water gas is recovered by the product recovery unit 15.
- the recovered water gas is purified so as to achieve the required quality according to the use of the fuel cell, hydrogen engine fuel, chemical raw material, and the like.
- purification methods include a method using a gas permeable membrane, PSA or the like.
- FIG. 4 shows a reaction device 10 according to the second embodiment. Parts having the same names as those in the first embodiment are denoted by the same reference numerals as those in the first embodiment.
- This reaction device 10 is a continuous type that continuously obtains a reaction product
- the body supply section 11 is provided with a pipe that extends to the product recovery section 15, and the pipe is provided with a fluid supply pump 12, a preheating section 18, a reaction section 13 and a cooling section 19 in order from the upstream to the downstream.
- a heating unit 16 is provided so that the preheating unit 18 and the reaction unit 13 can be heated.
- This reaction device 10 includes a reaction fluid that is a mixture of polyhydric alcohol (eg, glycerin, propanediol, etc.) and water as raw materials from a reaction fluid supply unit 11 via a fluid supply pump 12. 18, the reaction fluid preheated in the preheating unit 18 is supplied to the reaction unit 13, and the reaction unit 13 reacts with polyhydric alcohol and water to generate water gas, and the reaction fluid containing the generated water gas is The product is supplied to the cooling unit 19 to be cooled, and used for the production of water gas in which the cooled reaction fluid is recovered by the product recovery unit 15.
- polyhydric alcohol eg, glycerin, propanediol, etc.
- this method for producing a water gas is also a method of generating a mixed gas of hydrogen and carbon monoxide, called water gas, from a polyhydric alcohol and water.
- reaction fluid preheated in the preheating unit 18 is supplied to the reaction unit 13.
- the preheating time of the reaction fluid is preferably 0.1 second to 1 hour, more preferably 1 second to 10 minutes (for example, when the polyhydric alcohol is glycerin, the preheating time of the reaction fluid is 0. 1 second to 1 hour is preferred 1 second to 10 minutes is more preferred When the polyhydric alcohol is propanediol, the preheating time of the reaction fluid is preferably 0.1 second to 1 hour 1 second to 10 minutes ) 0
- the reaction fluid preheating time is defined by the residence time of the reaction fluid in the preheating section 18, so that the force that can be adjusted by selecting the capacity of the preheating section 18 is determined. In this case, it is determined by the setting of the liquid feeding speed of the reaction fluid by the fluid supply pump 12.
- the preheating temperature of the reaction fluid is preferably 200 to 1000 ° C, more preferably 300 to 700 ° C (for example, when the polyhydric alcohol is glycerin, the preheating temperature of the reaction fluid is 200 to 1000 ° C. Preferably 300-700 ° C force S.
- the preheating temperature of the reaction fluid is preferably 200-1000 ° C, more preferably 300-700 ° C.
- the preheating temperature of the reaction fluid depends on the heating temperature setting of the reaction section 13 by the heating section 16. It is adjusted at the same time.
- the reaction fluid containing the water gas generated in the reaction unit 13 is supplied to the cooling unit 19 and cooled.
- the cooling time of the reaction fluid is preferably 0.1 second to 1 hour, more preferably 1 second to 10 minutes.
- the cooling time of the reaction fluid is defined by the residence time of the reaction fluid in the cooling section 19, so that the force that can be adjusted by selecting the capacity of the cooling section 19 is determined. It depends on the setting of the pumping speed of the reaction fluid by the pump 12.
- the temperature after cooling of the reaction fluid is preferably 0 to 200 ° C, more preferably 20 to 100 ° C.
- the temperature of the reaction fluid after cooling is adjusted by setting the cooling temperature of the reaction fluid in the cooling section 19.
- reaction consumption rate of the reaction raw materials were determined.
- the reaction consumption rate, water gas yield and carbon residue of the reaction raw materials were determined as follows.
- the reaction raw materials are specifically glycerin, 1,2-propanediol, and 1 propanol.
- the unreacted raw material concentration was quantified by gas chromatographic analysis with respect to the collected liquid, and the unreacted raw material discharge amount that required the product with the liquid collection amount was calculated.
- the reaction consumption rate was calculated by subtracting the ratio of unreacted material discharge to reaction material input from 100%.
- the concentration of each gas component such as hydrogen, carbon monoxide, and carbon dioxide was calculated.
- the amount of reaction raw material input force The ratio of the actual yield to the theoretically required water gas yield was defined as the water gas yield.
- the amount of water gas that can be theoretically generated from 1 mol of glycerin is 7 mol. 1 , 2 Propanediol
- the water gas that can theoretically generate 1 mol force is 5 mol. 1-Propanol 1 molar force
- the theoretically generated water gas is 6 moles.
- the collected gas is quantified by gas chromatographic analysis to determine the concentration of each gas component containing carbon atoms such as carbon monoxide, carbon dioxide, methane, ethane, ethylene, propane, propylene, etc.
- the number of moles of each product is calculated.
- the collected liquid is subjected to gas chromatographic analysis to determine the number of moles of unreacted raw materials and reaction products.
- the number of moles of each component is converted into the number of moles of carbon atoms contained in each component, and these are summed, and the total number of moles of carbon atoms with respect to the value obtained by converting the input amount of the reaction raw material into the number of moles of carbon atoms.
- the value obtained by subtracting this ratio from 100% was taken as the carbon residue rate. If the carbon residual ratio is large, the reactor may be clogged or the catalytic activity may be deactivated, and it is desirable that the carbon residual ratio be small for stable water gas production. is there.
- the fluid supply pump is a microfeeder
- the preheating part is made of SUS316 material with an inner diameter of 1. Omm and a length of 2 m of a circular pipe channel
- the part is made of nickel material (nickel purity> 99.0%) with a circular channel with an inner diameter of 2.18mm and a length of 0.10m
- the cooling part has an inner diameter of 1. Omm and a length of 0.5m
- the reaction device was made of SUS316 material with a circular channel and made of air-cooling system, and equipped with an electric furnace that heated and kept constant at 600 ° C in a radiant heat transfer format as a heating part.
- the inner wall of the reaction section constitutes a metal catalyst.
- This reaction device was subjected to a treatment as a pre-reaction treatment A in which the temperature was raised to 600 ° C and maintained for 1 hour while circulating hydrogen.
- reaction device after this pretreatment A 36.2 g of glycerin (manufactured by Kishida Chemical Co., Ltd., special grade) and 63.8 g of distilled water (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed in advance.
- the prepared solution was supplied as a reaction fluid to the preheating section at 0.218 mLZh using a microfeed pump.
- the gas-liquid mixed reaction fluid obtained from the cooling section is collected in a Tedlar bag, and the liquid composition And gas composition were analyzed respectively.
- the reaction section is made of SUS 316 material with a circular reaction channel with a circular tube with an inner diameter of 1.78 mm and a length of 0.10 m.
- the reaction channel of the reaction section has a diameter of 100 m and a length of 0.10 m.
- 20 wires PURATRONIC, nickel purity 99.994%
- the total sum ⁇ of the projected area A on the surface perpendicular to the flow direction of the reaction fluid is calculated by the total surface area S of the surface area S. divided by, Shigumaeizuishigumaesu is 2. was 5 X 10- 4.
- this reaction device was subjected to a treatment of raising the temperature to 600 ° C and maintaining it for 1 hour while circulating hydrogen.
- reaction device after this pretreatment A 36.2 g of glycerin (manufactured by Kishida Chemical Co., Ltd., special grade) and 63.8 g of distilled water (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed in advance.
- the prepared solution was supplied as a reaction fluid to the preheating section at 0.136 mLZh using a microfeed pump.
- the gas-liquid mixed reaction fluid obtained from the cooling section was collected in a Tedlar bag, and the liquid composition and gas composition were analyzed.
- the reaction consumption rate of glycerin was 100%.
- the collected gas composition is shown in Table 1.
- the yield of water gas was 71.0%.
- the carbon residue rate was 4.9%.
- the preheating part is made of SUS316 material with a circular pipe channel with an inner diameter of 1. Omm and a length of lm, and the reaction part is made of nickel material with a circular pipe channel with an inner diameter of 4.35 mm and a length of 0.10 m.
- a reaction device identical to that of Example 1 was constructed except that the nickel content was 99.0%.
- This reaction device was subjected to a treatment as a pre-reaction treatment A in which the temperature was raised to 600 ° C and maintained for 1 hour while circulating hydrogen.
- a treatment as a pre-reaction treatment A in which the temperature was raised to 600 ° C and maintained for 1 hour while circulating hydrogen.
- 1,2-propanediol manufactured by Shidama Aldrich Japan Co., Ltd., SAJ-class
- SAJ-class 1,2-propanediol
- a solution prepared by mixing 68. lg in advance was supplied as a reaction fluid to the preheating section at 0.880 mLZh by a microfeed pump.
- the gas-liquid mixed reaction fluid obtained from the cooling section was collected in a Tedlar bag, and the liquid composition and gas composition were analyzed.
- the reaction consumption rate of 1,2-propanediol was 99.3%.
- the collected gas composition is shown in Table 1.
- the yield of water gas was 73.2%.
- the carbon residue rate was 2.4%.
- This reaction device was subjected to a treatment as a pre-reaction treatment A in which the temperature was raised to 600 ° C and maintained for 1 hour while circulating hydrogen.
- the gas-liquid mixed reaction fluid obtained from the cooling section was collected in a Tedlar bag, and the liquid composition and gas composition were analyzed.
- the reaction consumption rate of glycerin was 100%.
- the collected gas composition is shown in Table 1.
- the yield of water gas was 91.0%.
- the carbon residue rate was 4.8%.
- reaction part was made of a nickel material having a circular pipe channel with an inner diameter of 4.35 mm and a length of 0.10 m, which was plated with platinum. .
- the inner wall of the reaction part constitutes a metal catalyst.
- This reaction device was subjected to a treatment as a pre-reaction treatment B after removing the residue on the inner wall surface and raising the temperature to 600 ° C while maintaining the hydrogen flow for 3 hours.
- the gas-liquid mixed reaction fluid obtained from the cooling section was collected in a Tedlar bag, and the liquid composition and gas composition were analyzed.
- the reaction consumption rate of glycerin was 100%.
- the collected gas composition is shown in Table 1.
- the yield of water gas was 78.4%.
- the carbon residue rate was 0%.
- the same reaction device as in Example 3 was constructed except that the reaction part was made of a nickel material having a circular pipe channel with an inner diameter of 4.35 mm and a length of 0.10 m, which was subjected to iridium plating. .
- This reaction device was subjected to a pre-reaction treatment B after removing the residue on the inner wall surface and then raising the temperature to 600 ° C and maintaining for 3 hours while circulating hydrogen.
- the gas-liquid mixed reaction fluid obtained from the cooling unit was collected in a Tedlar bag, and the liquid composition and gas composition were analyzed.
- the reaction consumption rate of glycerin was 100%.
- the collected gas composition is shown in Table 1.
- the yield of water gas was 81.6%.
- the carbon residue rate was 0%.
- This reaction device was subjected to a pre-reaction treatment B after removing the residue on the inner wall surface and then raising the temperature to 600 ° C and maintaining for 3 hours while circulating hydrogen.
- the reaction consumption rate of glycerin was 99.7%.
- the collected gas composition is shown in Table 1.
- the yield of water gas was 88.7%.
- the carbon residue rate was 0%.
- Example 2 and Example 2 except that 0.9442 g of nickel powder (manufactured by Wako Pure Chemical Industries, Ltd.) having a particle size of 150 m or less was placed in the reaction channel of the reaction section instead of nickel wire as the metal catalyst. The same reaction device was constructed. The calculation is made assuming that the catalyst is a true sphere. 25.
- nickel powder manufactured by Wako Pure Chemical Industries, Ltd.
- This reaction device was subjected to a treatment as a pre-reaction treatment A in which the temperature was raised to 600 ° C and maintained for 1 hour while circulating hydrogen.
- reaction device after this pretreatment A 36.2 g of glycerin (manufactured by Kishida Chemical Co., Ltd., special grade) and 63.8 g of distilled water (manufactured by Wako Pure Chemical Industries, Ltd.) were prepared in advance.
- the solution was supplied as a reaction fluid to the preheating section at 0.083 mLZh by a microfeed pump.
- the gas-liquid mixed reaction fluid obtained from the cooling section was collected in a Tedlar bag, and the liquid composition and gas composition were analyzed.
- the reaction section is made of SUS 316 material with a circular reaction channel with a circular tube with an inner diameter of 2.18 mm and a length of 0.10 m, and a particle size of 2 m or less instead of nickel wire as a metal catalyst (optical).
- the same reaction device as in Example 2 was constructed except that 0.1366 g of platinum black powder (visually confirmed by a microscope) (manufactured by Wako Pure Chemical Industries, Ltd.) was placed. Assuming that the catalyst is a true sphere, the total surface area S of the surface area S is divided by the total area ⁇ A of the projected area A onto the surface perpendicular to the flow direction of the reaction fluid. Met.
- reaction pretreatment A the temperature was raised to 600 ° C while hydrogen was circulated. The process which hold
- the gas-liquid mixed reaction fluid obtained from the cooling section was collected in a Tedlar bag, and the liquid composition and gas composition were analyzed.
- This reaction device was subjected to a treatment as a pre-reaction treatment A in which the temperature was raised to 600 ° C and maintained for 1 hour while circulating hydrogen.
- the gas-liquid mixed reaction fluid obtained from the cooling section was collected in a Tedlar bag, and the liquid composition and gas composition were analyzed.
- Table 1 shows the configuration of the reaction channel of the reaction part of the reaction device used in Examples 1 to 7 and Comparative Examples 1 to 3, and the test evaluation results.
- the present invention is useful for a reaction device used for producing water gas from a polyhydric alcohol and water and a method for producing water gas using the reaction device.
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Abstract
Description
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JP2007537053A JP5143560B2 (ja) | 2006-04-05 | 2007-04-03 | 反応デバイス |
CN2007800005268A CN101321690B (zh) | 2006-04-05 | 2007-04-03 | 反应器 |
EP07740899.5A EP2008968B1 (en) | 2006-04-05 | 2007-04-03 | Method for producing water gas |
US12/226,014 US8114174B2 (en) | 2006-04-05 | 2007-04-03 | Reaction device |
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JP2009298619A (ja) * | 2008-06-11 | 2009-12-24 | Ihi Corp | グリセリン改質装置および改質方法 |
JP2009298616A (ja) * | 2008-06-11 | 2009-12-24 | Ihi Corp | グリセリン改質装置および改質方法 |
WO2010055687A1 (ja) | 2008-11-14 | 2010-05-20 | 花王株式会社 | 水性ガス用原料 |
WO2011058746A1 (ja) | 2009-11-12 | 2011-05-19 | 花王株式会社 | 水性ガスの製造方法 |
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JP5143438B2 (ja) * | 2007-01-31 | 2013-02-13 | 花王株式会社 | 反応デバイス |
EP2980015B1 (en) * | 2013-03-29 | 2018-07-04 | JFE Steel Corporation | High-calorie gas manufacturing process |
EP3136488B1 (en) | 2013-07-02 | 2019-11-13 | Asahi Kasei Kabushiki Kaisha | Electrolyte solution and processes for preparing electrolyte membrane, electrode catalyst layer, membrane-electrode assembly, and fuel cell |
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- 2007-04-03 CN CN2007800005268A patent/CN101321690B/zh not_active Expired - Fee Related
- 2007-04-03 JP JP2007537053A patent/JP5143560B2/ja not_active Expired - Fee Related
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JP2009298619A (ja) * | 2008-06-11 | 2009-12-24 | Ihi Corp | グリセリン改質装置および改質方法 |
JP2009298616A (ja) * | 2008-06-11 | 2009-12-24 | Ihi Corp | グリセリン改質装置および改質方法 |
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JP2010116307A (ja) * | 2008-11-14 | 2010-05-27 | Kao Corp | 水性ガス用原料 |
US8652436B2 (en) | 2008-11-14 | 2014-02-18 | Kao Corporation | Material for water gas |
WO2011058746A1 (ja) | 2009-11-12 | 2011-05-19 | 花王株式会社 | 水性ガスの製造方法 |
JP2011105523A (ja) * | 2009-11-12 | 2011-06-02 | Kao Corp | 水性ガスの製造方法 |
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CN101321690A (zh) | 2008-12-10 |
JPWO2007114438A1 (ja) | 2009-08-20 |
EP2008968B1 (en) | 2017-08-30 |
JP5143560B2 (ja) | 2013-02-13 |
EP2008968A4 (en) | 2012-02-29 |
US20090249692A1 (en) | 2009-10-08 |
CN101321690B (zh) | 2012-03-14 |
US8114174B2 (en) | 2012-02-14 |
EP2008968A1 (en) | 2008-12-31 |
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