TWI665157B - Hydrogen production device and method - Google Patents
Hydrogen production device and method Download PDFInfo
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- TWI665157B TWI665157B TW106144518A TW106144518A TWI665157B TW I665157 B TWI665157 B TW I665157B TW 106144518 A TW106144518 A TW 106144518A TW 106144518 A TW106144518 A TW 106144518A TW I665157 B TWI665157 B TW I665157B
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- ammonia
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 315
- 239000001257 hydrogen Substances 0.000 title claims abstract description 315
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 284
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 149
- 238000000034 method Methods 0.000 title claims description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 1279
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 636
- 239000007789 gas Substances 0.000 claims abstract description 623
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 152
- 238000010438 heat treatment Methods 0.000 claims abstract description 139
- 230000008929 regeneration Effects 0.000 claims abstract description 139
- 238000011069 regeneration method Methods 0.000 claims abstract description 139
- 238000002485 combustion reaction Methods 0.000 claims abstract description 93
- 238000011084 recovery Methods 0.000 claims abstract description 93
- 238000001179 sorption measurement Methods 0.000 claims abstract description 87
- 239000000567 combustion gas Substances 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 115
- 239000003463 adsorbent Substances 0.000 claims description 70
- 238000001816 cooling Methods 0.000 claims description 57
- 239000001301 oxygen Substances 0.000 claims description 56
- 229910052760 oxygen Inorganic materials 0.000 claims description 56
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 55
- 239000002699 waste material Substances 0.000 claims description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000001784 detoxification Methods 0.000 claims description 31
- 150000002431 hydrogen Chemical class 0.000 claims description 30
- 238000011144 upstream manufacturing Methods 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000008236 heating water Substances 0.000 claims description 13
- 239000002912 waste gas Substances 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000009434 installation Methods 0.000 claims description 2
- 230000001464 adherent effect Effects 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 238000010586 diagram Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 230000001172 regenerating effect Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 2
- 150000001255 actinides Chemical class 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052722 tritium Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- -1 oxides Substances 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 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
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
- C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Separation Of Gases By Adsorption (AREA)
- Fuel Cell (AREA)
Abstract
氫製造裝置，係具備有：廢氣加熱裝置，係與氫回收裝置連接，並將廢氣加熱；和廢氣流路，係使其中一端與廢氣加熱裝置連接，並且另一端與複數之氨吸附器連接，而將廢氣供給至已使用之氨吸附器處而能夠使氨吸附器再生；和吸附材再生氣體流路，係與複數之前述氨吸附器連接，並使從已使用之氨吸附器所流出的吸附材再生氣體流通；和燃燒反應裝置，係與吸附材再生氣體流路連接，並燃燒吸附材再生氣體而使燃燒氣體流出；和燃燒氣體流路，係一端與燃燒反應裝置連接，並且另一端與加熱前述氨分解裝置之加熱機器連接。The hydrogen production device includes: an exhaust gas heating device connected to the hydrogen recovery device and heating the exhaust gas; and an exhaust gas flow path connecting one end to the exhaust gas heating device and the other end to a plurality of ammonia adsorbers, The exhaust gas is supplied to the used ammonia adsorber to regenerate the ammonia adsorber; and the regeneration gas flow path of the adsorption material is connected to a plurality of the aforementioned ammonia adsorbers, and the outflow from the used ammonia adsorber is made. Adsorption material regeneration gas flows; and a combustion reaction device is connected to the adsorption material regeneration gas flow path, and burns the adsorption material regeneration gas to make the combustion gas flow out; and a combustion gas flow path, one end is connected to the combustion reaction device, and the other end It is connected to a heating device for heating the aforementioned ammonia decomposition device.
Description
[0001] 本發明，係有關於從氨而製造出氫氣的氫製造裝置及氫製造方法。[0001] The present invention relates to a hydrogen production apparatus and a hydrogen production method for producing hydrogen from ammonia.
[0002] 氫氣，係被期待能夠作為終極的清淨能源。例如，氫氣，係作為燃料電池用之燃料氣體而被使用。 作為此氫氣之原料，係使用有氨。氨，係作為使氫的儲存以及輸送變得容易的化學物質(氫載體)而受到矚目。氨，係藉由在室溫下而壓縮至1MPa以下，而容易地液化。液體氨，其重量氫密度係為17.8質量％而為極高，並且體積氫密度係為液態氫之1.5～2.5倍，而為非常優良的氫載體。 [0003] 然而，若是氫氣作為雜質而含有未分解之氨，則氨係會對於燃料電池內之電解質膜和觸媒層造成不良影響。因此，係在分解氨並得到氨分解氣體之後，進行有將該分解氣體導入至氨吸附器中將氨除去的工程。 [0004] 例如，在專利文獻1中，係揭示有下述之技術：亦即是，係將氨供給至氨分解裝置處並分解為氫(H2 )和氮(N2 )，之後，供給至氨吸附器處將未反應氨除去。又，在專利文獻1中，係亦記載有：藉由從以氨吸附器將未反應氨作了除去之後的氣體來將氫以外之氣體分離出來，係能夠作為氫來使用。進而，在專利文獻1中，係亦記載有：將複數之氨吸附器作並聯設置，並反覆進行在1個的氨吸附器進行氨之吸附時而使其他的氨吸附器進行氨之脫離附著的工程(切換方式)。 [先前技術文獻] [專利文獻] [0005] [專利文獻1] 日本特開2015-059075號公報[0002] Hydrogen is expected to be the ultimate clean energy source. For example, hydrogen is used as a fuel gas for a fuel cell. As a raw material of this hydrogen, ammonia is used. Ammonia is attracting attention as a chemical substance (hydrogen carrier) that facilitates storage and transportation of hydrogen. Ammonia is easily liquefied by being compressed to 1 MPa or less at room temperature. Liquid ammonia has an extremely high weight hydrogen density of 17.8% by mass, and a volume hydrogen density of 1.5 to 2.5 times that of liquid hydrogen, and is a very good hydrogen carrier. [0003] However, if hydrogen contains undecomposed ammonia as an impurity, the ammonia system will adversely affect the electrolyte membrane and the catalyst layer in the fuel cell. Therefore, after the ammonia is decomposed to obtain an ammonia decomposed gas, a process of introducing the decomposed gas into an ammonia adsorber and removing ammonia is performed. [0004] For example, Patent Document 1 discloses a technique in which ammonia is supplied to an ammonia decomposition device and decomposed into hydrogen (H 2 ) and nitrogen (N 2 ), and then supplied. Go to the ammonia adsorber to remove unreacted ammonia. In addition, Patent Document 1 describes that a gas other than hydrogen can be used as hydrogen by separating unreacted ammonia from the gas by an ammonia adsorber. Furthermore, in Patent Document 1, it is also described that a plurality of ammonia adsorbers are installed in parallel, and when one ammonia adsorber performs ammonia adsorption, other ammonia adsorbers perform desorption of ammonia. Works (switching mode). [Prior Art Document] [Patent Document] [0005] [Patent Document 1] Japanese Patent Laid-Open No. 2015-059075
[發明所欲解決之課題] [0006] 在專利文獻1中，係記載有：藉由從以氨吸附器將未反應氨作了除去之後的氣體來將氫分離出來，係能夠製造氫。但是，針對將氫作了除去之後的廢氣之活用方法，係並未作具體性的記載。 本發明，係有關於能夠對該廢氣作有效利用的氫製造裝置及氫製造方法。 [用以解決課題之手段] [0007] 在本發明者等進行了努力檢討之後，係發現到：藉由將從氨分解氣體除去未反應氨後進而將氫作了分離之後的廢氣，利用於被收容在氨吸附器內之氨吸附劑的再生中，並且使含有脫離附著後之氨的該廢氣燃燒而對於燃燒熱作利用，係能夠對於該廢氣作有效利用。 亦即是，本發明，係有關於以下之[1]～[25]。 [0008] [1]一種氫製造裝置，係具備有：氨供給裝置；和氨分解裝置，係與前述氨供給裝置連接，並分解氨而產生含有氫、氮以及未反應氨之分解氣體；和分解氣體冷卻裝置，係與前述氨分解裝置作連接，並將前述分解氣體冷卻；和氨吸附裝置，係與前述分解氣體冷卻裝置連接，並從前述分解氣體將未反應氨作吸附除去並使氨除去後氣體流出；和氫回收裝置，係與前述氨吸附裝置連接，並從前述氨除去後氣體將氫分離並使其流出，並且將剩餘的廢氣排出；和加熱機器，係加熱前述氨分解裝置，前述氨吸附裝置，係具備有被並聯地作了配設的複數之氨吸附器，並構成為能夠將從前述分解氣體冷卻裝置送來送來之分解氣體供給至前述複數之氨吸附器中之任意的一部分處，該氫製造裝置，其特徵為，係具備有：廢氣加熱裝置，係與前述氫回收裝置連接，並將前述廢氣加熱；和廢氣流路，係一端與前述廢氣加熱裝置連接，並且另一端與前述複數之氨吸附器連接，並且將前述廢氣供給至已使用之氨吸附器處而能夠使氨吸附器再生；和吸附材再生氣體流路，係與複數之前述氨吸附器連接，並使從前述以使用之氨吸附器所流出的吸附材再生氣體作流通；和燃燒反應裝置，係與前述吸附材再生氣體流路連接，並燃燒前述吸附材再生氣體而使燃燒氣體流出；和燃燒氣體流路，係一端與前述燃燒反應裝置連接，並且另一端與前述加熱機器連接。 [0009] 若依據該氫製造裝置，則係能夠從氨而製造出氫，並且係能夠將從氫回收裝置所流出的廢氣作為氨吸附器內之氨吸附材的再生用氣體而有效作利用。又，從氫回收裝置所流出的廢氣，係包含有氮以及氫，又，在將該廢氣利用於氨吸附材的再生之後的吸附材再生氣體，係包含有氮、氫以及氨。藉由以燃燒反應裝置來燃燒包含有此些之氮、氫以及氨的吸附材再生氣體，係能夠得到高溫的燃燒氣體，而能夠使用該高溫的燃燒氣體來充分地加熱氨分解裝置。 [0010] [2]如上述[1]所記載之氫製造裝置，其中，前述分解氣體冷卻裝置與前述廢氣加熱裝置，係為同一之熱交換器，並構成為能夠在從前述氨分解裝置所流出的前述分解氣體與從前述氫回收裝置所流出的前述廢氣之間而進行熱交換。 藉由此熱交換器，係能夠將分解氣體之熱充分地賦予至廢氣處，熱效率係提昇。 [0011] [3]如上述[1]或[2]所記載之氫製造裝置，其中，係具備有：循環氣體流路，係一端與前述加熱機器連接，並且另一端與前述吸附材再生氣體流路連接。 藉由使用該循環氣體流路，係能夠將被使用在氨分解裝置之加熱中的燃燒氣體之一部分或全部，與前述之吸附材再生氣體混合並作燃燒，而再度利用在氨分解裝置之加熱中。藉由此，來將供給至氨分解裝置處之燃燒氣體的流量增多，藉由此，係能夠使熱效率提昇。 又，從燃燒反應裝置所流出的燃燒氣體，由於係已燃燒，因此，氫、氨等之可燃性氣體的含有量係為少。而，係將該燃燒氣體，在使用於氨分解裝置之加熱之後，作為循環氣體來利用，並與前述之吸附材再生氣體混合而藉由燃燒反應裝置來使其燃燒。藉由此，係能夠以不會使被供給至燃燒反應裝置中之氣體進入氫的爆發範圍中的方式來進行調整。 [0012] [4]如上述[3]所記載之氫製造裝置，其中，在前述吸附材再生氣體流路以及前述循環氣體流路之其中一方或雙方處，係連接有氧供給裝置。 藉由從該氧供給裝置而供給含氧氣體，並將使前述吸附材再生氣體、循環氣體以及含氧氣體作混合而對組成作了調整之後的混合氣體供給至燃燒反應裝置處，係能夠在燃燒反應裝置內而使氣體略完全燃燒。 [0013] [5]如上述[3]或[4]所記載之氫製造裝置，其中，係具備有：水流路，係與前述循環氣體流路相交叉；和溫水加熱用熱交換器，係被設置在前述循環氣體流路與前述水流路之交叉點處；和加熱水供給裝置，係被設置在前述水流路之下游端處，使用從該加熱水供給裝置所流出之加熱水，來加溫前述氨供給裝置。 藉由從該加熱水供給裝置來將溫水對於前述氨供給裝置放出，係能夠使氨供給裝置內之液體氨氣化。 [0014] [6]如上述[5]所記載之氫製造裝置，其中，在前述循環氣體流路中之較前述溫水加熱用熱交換器更下游處，係具備有用以將在前述循環氣體流路中流動的循環氣體中之水除去的排泄罐(drain pot)。 藉由以該排泄罐來將水除去，係能夠將在燃燒反應裝置中所產生的水分從循環氣體系內排出。 [0015] [7]如上述[6]所記載之氫製造裝置，其中，在前述循環氣體流路中之位於較前述溫水加熱用熱交換器更上游處的第1點與位於較前述排泄罐更下游處的第2點，係相互交叉並成為交叉點，前述循環氣體流路中之前述第1點與前述第2點之間的部份，係成為環狀流路，在前述交叉點處，係設置有循環氣體用熱交換器。 [8]如上述[6]或[7]所記載之氫製造裝置，其中，在前述循環氣體流路、例如環狀流路中之較前述排泄罐更下游處，係具備有循環氣體之循環機。 [0016] [9]如上述[7]或[8]所記載之氫製造裝置，其中，在前述循環氣體流路、例如前述環狀流路之途中，係連接有用以將前述循環氣體之一部分或全部排出的氣體廢棄流路。 藉由從該氣體廢棄流路將循環氣體之一部分或全部排出，係能夠對於被供給至燃燒反應裝置中之氣體的組成以及流量進行調整。 [0017] [10]如上述[9]所記載之氫製造裝置，其中，前述氣體廢棄流路係具備有氨除害設備，該氨除害設備，係具備有：第1氣體廢棄流路，係一端與前述環狀流路連接；和輔助氨吸附裝置，係與前述第1氣體廢棄流路之另外一端連接；和第2氣體廢棄流路，係與前述輔助氨吸附裝置連接，並使從前述輔助氨吸附裝置所排出的氣體流通。 藉由以氨除害裝置來將氣體中之氨除害，係能夠將對環境所造成的負擔為更少的氣體排出至系外。 [0018] [11]如上述[10]所記載之氫製造裝置，其中，前述輔助氨吸附裝置，係具備有被並聯地作配設的複數之輔助氨吸附器，前述第1氣體廢棄流路，係使上游端與前述環狀流路連接，並使下游端分歧而成為第1分歧流路並且與前述複數之輔助氨吸附器連接，前述第2氣體廢棄流路之上游端，係分歧而成為第2分歧流路並且與前述複數之輔助氨吸附器連接，前述氨除害設備，係更進而具備有：再生氣體供給裝置，係對於前述複數之輔助氨吸附器供給再生氣體；和再生氣體流路，係一端與前述再生氣體供給裝置連接，並且另一端分歧而與前述第2分歧流路連接；和再生氣體加熱器，係被設置在前述再生氣體流路之途中，並加熱前述再生氣體；和脫離附著氣體流路，係一端分歧而與前述第1分歧流路連接；和廢氣燃燒反應器，係與前述脫離附著氣體流路之另外一端連接，並燃燒從前述複數之氨吸附器之各者所排出的前述吸附材脫離附著氣體而使燃燒氣體流出；和回送流路，係將從前述廢氣燃燒反應器所排出的燃燒氣體回送至前述第2氣體廢棄流路處。 [12]如上述[11]所記載之氫製造裝置，其中，前述廢氣燃燒反應器，係為前述燃燒反應裝置。 [13]如上述[11]或[12]所記載之氫製造裝置，其中，係具備有：廢氣冷卻器，係被設置在前述回送流路處，並將從前述廢氣燃燒反應器所流出的前述燃燒氣體冷卻。 [14]如上述[1]～[13]中之任一者所記載之氫製造裝置，其中，係具備有：氫流路，係與前述氫回收裝置連接，並使藉由前述氫回收裝置分離出的氫流出；和壓力控制閥，係被設置在前述氫流路處。 藉由該壓力控制閥，係能夠對於氫回收裝置、氨吸附裝置以及氨分解裝置之壓力作調整。 [0019] [15]如上述[1]～[14]中之任一者所記載之氫製造裝置，其中，係具備有：氨流路，係與前述氨供給裝置以及前述氨分解裝置連接；和流量控制閥，係被設置在前述氨流路處。 藉由該流量控制閥，係能夠對於從氨供給裝置所供給至氨分解裝置處之氨流量作控制。 [0020] [16]如上述[15]所記載之氫製造裝置，其中，係具備有：氨加熱用熱交換器，係被設置在前述氨流路處；和分解氣體流路，係將前述氨分解裝置以及前述氨吸附裝置連接，前述分解氣體流路之途中係與前述氨加熱用熱交換器相流通，在前述分解氣體流路中之較前述氨加熱用熱交換器的設置位置更上游側處，係設置有前述分解氣體冷卻裝置。 [0021] [17]如上述[1]～[16]中之任一者所記載之氫製造裝置，其中，係具備有：分解氣體流路，係將前述氨分解裝置以及前述複數之氨吸附器連接；和氨除去後氣體流路，係將前述複數之氨吸附器與前述氫回收裝置連接，在前述分解氣體流路之途中處，係設置有前述分解氣體冷卻裝置，前述分解氣體流路以及前述氨除去後氣體流路，係並不具備有加壓裝置。 如此這般，由於係並不具備有加壓裝置，因此係能夠使設備成本以及運轉成本降低。 [0022] [18]一種氫製造方法，係為使用有如上述[1]～[17]中之任一者所記載之氫製造裝置之氫製造方法，其特徵為，係實施：氨分解工程，係使從前述氨供給裝置送來之前述氨流通至前述氨分解裝置處，並將氨分解而產生含有氫、氮以及未反應氨之前述分解氣體；和氨吸附工程，係使從前述氨分解裝置流出的前述分解氣體流通至前述分解氣體冷卻裝置處並作冷卻，之後，流通至前述複數之氨吸附器之一部分處，而從前述分解氣體來將未反應氨作吸附除去並得到前述氨除去後氣體；和氫回收工程，係使從前述複數之氨吸附器之前述一部分流出的前述氨除去後氣體流通至前述氫回收裝置處，並從前述氨除去後氣體將氫分離並流出，並且將剩餘的廢氣排出；和氨吸附器再生工程，係使從前述氫回收裝置流出的前述廢氣流通至前述廢氣加熱裝置以及前述複數之氨吸附器的剩餘部分中之一部分或全部處，而使氨吸附器再生；和氨分解裝置之加熱工程，係使從前述氨吸附器所流出的吸附材再生氣體流通至前述燃燒反應裝置、前述燃燒氣體流路以及前述加熱機器處，並加熱前述氨分解裝置。 [0023] 若依據該氫製造裝置，則係能夠從氨而製造出氫，並且係能夠將從氫回收裝置所流出的廢氣作為氨吸附器內之氨吸附材的再生用氣體而有效作利用。又，從氫回收裝置所流出的廢氣，係包含有氮以及氫，又，在將該廢氣利用於氨吸附材的再生之後的吸附材再生氣體，係包含有氮、氫以及氨。藉由以燃燒反應裝置來燃燒包含有此些之氮、氫以及氨的吸附材再生氣體，係能夠得到高溫的燃燒氣體，而能夠使用該高溫的燃燒氣體來充分地加熱氨分解裝置。 [0024] [19]如上述[18]所記載之氫製造方法，其中，前述廢氣加熱裝置，係為前述分解氣體冷卻裝置，藉由前述分解氣體冷卻裝置，來將前述分解氣體之熱賦予至前述廢氣處而加熱前述廢氣。 藉由此熱交換器，係能夠將分解氣體之熱充分地賦予至廢氣處，熱效率係提昇。 [0025] [20]如上述[18]或[19]所記載之氫製造方法，其中，係具備有：循環氣體流路，係一端與前述加熱機器連接，並且另一端與前述吸附材再生氣體流路連接，使前述燃燒氣體經由前述燃燒氣體流路、前述加熱機器以及前述循環氣體流路而流通至前述吸附材再生氣體流路中，而作成與前述吸附材再生氣體之混合氣體，並使前述混合氣體流通至前述燃燒反應裝置處而使其燃燒。 藉由使用該循環氣體流路，係能夠將被使用在氨分解裝置之加熱中的燃燒氣體之一部分或全部，與前述之吸附材再生氣體混合並作燃燒，而再度利用在氨分解裝置之加熱中。藉由此，來將供給至氨分解裝置處之燃燒氣體的流量增多，藉由此，係能夠使熱效率提昇。 又，從燃燒反應裝置所流出的燃燒氣體，由於係已燃燒，因此，氫、氨等之可燃性氣體的含有量係為少。而，係將該燃燒氣體，在使用於氨分解裝置之加熱之後，作為循環氣體來利用，並與前述之吸附材再生氣體混合而藉由燃燒反應裝置來使其燃燒。藉由此，係能夠以不會使被供給至燃燒反應裝置中之氣體進入氫的爆發範圍中的方式來進行調整。 [0026] [21]如上述[20]所記載之氫製造方法，其中，在前述吸附材再生氣體流路以及前述循環氣體流路之其中一方或雙方處，係連接有氧供給裝置，將從前述氧供給裝置所供給之含氧氣體，作成與前述循環氣體以及前述吸附材再生氣體之混合氣體，並使前述混合氣體流通至前述燃燒反應裝置處而使其燃燒。 藉由從該氧供給裝置而供給含氧氣體，並將使前述吸附材再生氣體、循環氣體以及含氧氣體作混合而對組成作了調整之後的混合氣體供給至燃燒反應裝置處，係能夠在燃燒反應裝置內而使氣體略完全燃燒。 [0027] [22]如上述[20]或[21]所記載之氫製造方法，其中，係具備有：水流路，係與前述循環氣體流路相交叉；和溫水加熱用熱交換器，係被設置在前述循環氣體流路與前述水流路之交叉點處；和加熱水供給裝置，係被設置在前述水流路之下游端處，在將水或溫水流通至前述溫水加熱用熱交換器處並作成加熱水之後，從前述加熱水供給裝置來將加熱水供給至前述氨供給裝置處，而使氨氣化。 藉由從該加熱水供給裝置來將加熱水對於前述氨供給裝置放出，係能夠使氨供給裝置內之液體氨氣化。 [0028] [23]如上述[22]所記載之氫製造方法，其中，在前述循環氣體流路中之較前述溫水加熱用熱交換器更下游處，係具備有用以將前述循環氣體中之水除去的排泄罐，在使前述循環氣體流通至前述排泄罐處並將水除去之後，與前述吸附材再生氣體一同地流通至前述燃燒反應裝置處並使其燃燒。 藉由以該排泄罐來將水除去，係能夠將在燃燒反應裝置中所產生的水分從循環氣體系內排出。 [0029] [24]如上述[18]～[23]中之任一者所記載之氫製造方法，其中，係具備有：氫流路，係與前述氫回收裝置連接，並使藉由前述氫回收裝置分離出的氫流出；和壓力控制閥，係被設置在前述氫流路處，藉由對於前述壓力控制閥作控制，來將前述氨分解裝置之壓力P1、前述氨吸附裝置之壓力P2以及前述氫回收裝置之壓力P3的各者，控制於會滿足 P1≧P2≧P3 之關係的特定之壓力範圍。 如此這般，藉由設為P1≧P2≧P3，係成為不需要加壓裝置，而能夠使設備成本以及運轉成本降低。 藉由從該氧供給裝置而供給含氧氣體，並將使前述吸附材再生氣體以及含氧氣體作混合而對組成作了調整之後的混合氣體供給至燃燒反應裝置處，係能夠在燃燒反應裝置內使氣體略完全燃燒。 [25]如上述[18]～[24]中之任一者所記載之氫製造方法，其中，前述氫製造裝置，係為如申請專利範圍第10～13項中之任一項所記載之氫製造裝置，該氫製造方法，係具備有：氨除害工程，係將在前述氣體廢棄流路中流通的氣體供給至前述氨除害設備處並將氨除害。 [發明之效果] [0030] 若依據本發明，則係提供一種能夠將在分解氨並製造出氫氣時所產生的廢氣作有效利用之氫製造裝置及氫製造方法。[Problems to be Solved by the Invention] 专利 [0006] Patent Document 1 describes that hydrogen can be produced by separating hydrogen from a gas obtained by removing unreacted ammonia with an ammonia adsorber. However, there is no specific description on the utilization method of the exhaust gas after removing hydrogen. The present invention relates to a hydrogen production apparatus and a hydrogen production method capable of effectively utilizing the exhaust gas. [Means to Solve the Problem] [0007] After intensive review by the present inventors, it was found that, by removing unreacted ammonia from the ammonia decomposed gas, and then separating hydrogen into waste gas, it was used During the regeneration of the ammonia adsorbent contained in the ammonia adsorber, the exhaust gas containing the ammonia after desorption is burned and used for the heat of combustion, which can effectively utilize the exhaust gas. That is, the present invention relates to the following [1] to [25]. [0008] A hydrogen production device comprising: an ammonia supply device; and an ammonia decomposition device connected to the ammonia supply device and decomposing ammonia to generate a decomposition gas containing hydrogen, nitrogen, and unreacted ammonia; and The decomposition gas cooling device is connected to the ammonia decomposition device and cools the decomposition gas; and the ammonia adsorption device is connected to the decomposition gas cooling device, and removes unreacted ammonia from the decomposition gas and removes ammonia. After the removal, the gas flows out; and a hydrogen recovery device is connected to the ammonia adsorption device, and the hydrogen is separated from the ammonia to separate the hydrogen and flow out, and the remaining exhaust gas is discharged; and a heating device is used to heat the ammonia decomposition device The ammonia adsorption device is provided with a plurality of ammonia adsorbers arranged in parallel, and is configured to be capable of supplying the decomposition gas sent from the decomposition gas cooling device to the plurality of ammonia adsorbers. In any part, the hydrogen production device is provided with an exhaust gas heating device connected to the hydrogen recovery device, And heating the exhaust gas; and an exhaust gas flow path, one end of which is connected to the exhaust gas heating device, and the other end of which is connected to the plurality of ammonia adsorbers, and the ammonia is adsorbed by supplying the exhaust gas to a used ammonia adsorber And regeneration of the adsorbent material; the regeneration gas flow path of the adsorption material is connected to the aforementioned ammonia adsorber, and the regeneration gas of the adsorption material flowing out of the aforementioned ammonia adsorber is circulated; and a combustion reaction device is connected to the adsorption The regeneration gas flow path is connected to the combustion material and the combustion gas is burned to flow out; and the combustion gas flow path is connected at one end to the combustion reaction device and at the other end to the heating device. [0009] According to this hydrogen production device, hydrogen can be produced from ammonia, and the exhaust gas flowing out of the hydrogen recovery device can be effectively used as a regeneration gas for the ammonia adsorbent in the ammonia adsorber. The exhaust gas flowing out of the hydrogen recovery device includes nitrogen and hydrogen, and the adsorbent regeneration gas after using the exhaust gas for regeneration of the ammonia adsorbent includes nitrogen, hydrogen, and ammonia. The combustion reaction device is used to burn the regeneration material of the adsorbent containing nitrogen, hydrogen, and ammonia to obtain a high-temperature combustion gas, and the ammonia decomposition device can be sufficiently heated using the high-temperature combustion gas. [2] The hydrogen production device according to the above [1], wherein the decomposed gas cooling device and the exhaust gas heating device are the same heat exchanger, and are configured so that they can be separated from the ammonia decomposition device. Heat exchange is performed between the decomposed gas flowing out and the exhaust gas flowing out of the hydrogen recovery device.由此 With this heat exchanger, the heat of the decomposed gas can be sufficiently given to the exhaust gas, and the thermal efficiency is improved. [3] The hydrogen production device according to the above [1] or [2], comprising: a circulating gas flow path, one end of which is connected to the heating device, and the other end of which is connected to the adsorbent regeneration gas Flow path connection. By using this circulating gas flow path, a part or all of the combustion gas used in the heating of the ammonia decomposition device can be mixed with the aforementioned regeneration material of the adsorbent material and combusted, and the heating in the ammonia decomposition device can be reused. in. As a result, the flow rate of the combustion gas supplied to the ammonia decomposition device is increased, whereby the thermal efficiency can be improved. In addition, since the combustion gas flowing out of the combustion reaction device is burned, the content of flammable gases such as hydrogen and ammonia is small. In addition, the combustion gas is used as a circulating gas after being heated in an ammonia decomposition device, and is mixed with the above-mentioned adsorbent regeneration gas to be combusted by a combustion reaction device. This makes it possible to adjust so that the gas supplied to the combustion reaction device does not enter the explosion range of hydrogen. [0012] [4] The hydrogen production device according to the above [3], wherein an oxygen supply device is connected to one or both of the adsorbent regeneration gas flow path and the circulating gas flow path. By supplying an oxygen-containing gas from the oxygen supply device, and mixing the adsorbent regeneration gas, the circulating gas, and the oxygen-containing gas to adjust the composition, the mixed gas is supplied to the combustion reaction device. Combustion of the gas in the reaction device causes the gas to burn slightly completely. [5] The hydrogen production device according to the above [3] or [4], further comprising: a water flow path intersecting the circulation gas flow path; and a warm water heating heat exchanger, It is installed at the intersection of the circulating gas flow path and the water flow path; and a heating water supply device is provided at the downstream end of the water flow path, and the heating water flowing from the heating water supply device is used to The aforementioned ammonia supply device is warmed.温 By releasing warm water from the heated water supply device to the ammonia supply device, it is possible to vaporize liquid ammonia in the ammonia supply device. [6] The hydrogen production device according to the above [5], wherein the circulating gas flow path is further downstream of the warm water heating heat exchanger than A drain pot for removing water from the circulating gas flowing in the flow path.除去 By removing water with this drain tank, it is possible to discharge the water generated in the combustion reaction device from the circulation gas system. [7] The hydrogen production device according to the above [6], wherein the first point in the circulating gas flow path which is located upstream of the heat exchanger for warm water heating and the drain is located above the drain The second point further downstream of the tank crosses each other and becomes an intersection point, and the part between the first point and the second point in the circulating gas flow path becomes an annular flow path, at the foregoing intersection point A heat exchanger for circulating gas is provided. [8] The hydrogen production device according to the above [6] or [7], wherein the circulating gas flow path, for example, a ring-shaped flow path, further downstream of the drain tank, is provided with a circulating gas circulation machine. [9] The hydrogen production device according to the above [7] or [8], wherein a part of the circulating gas is connected to the circulating gas flow path, for example, the annular flow path, to connect a part of the circulating gas. Or all exhausted gas is discarded.排出 By discharging part or all of the circulating gas from the gas waste flow path, the composition and flow rate of the gas supplied to the combustion reaction device can be adjusted. [0017] The hydrogen production device according to the above [9], wherein the gas waste flow path is provided with an ammonia detoxification device, and the ammonia removal device is provided with a first gas waste flow path, One end is connected to the annular flow path; and an auxiliary ammonia adsorption device is connected to the other end of the first gas waste flow path; and a second gas waste flow path is connected to the auxiliary ammonia absorption device, and the The gas discharged from the auxiliary ammonia adsorption device flows. (2) By using ammonia detoxification device to detoxify ammonia in the gas, the system can discharge the gas with less burden on the environment to the outside. [11] The hydrogen production device according to the above [10], wherein the auxiliary ammonia adsorption device includes a plurality of auxiliary ammonia adsorbers arranged in parallel, and the first gas waste flow path The upstream end is connected to the annular flow path, and the downstream end is branched to become the first branched flow path and connected to the plurality of auxiliary ammonia adsorbers. The upstream end of the second gas waste flow path is branched and The second branched flow path is connected to the plurality of auxiliary ammonia adsorbers. The ammonia detoxification device further includes a regeneration gas supply device for supplying regeneration gas to the plurality of auxiliary ammonia adsorbers; and a regeneration gas. One end of the flow path is connected to the regeneration gas supply device, and the other end is branched to connect to the second branched flow path. The regeneration gas heater is installed in the middle of the regeneration gas flow path and heats the regeneration gas. ; And the detached gas flow path, one end of which is connected to the first branch flow path; and the exhaust gas combustion reactor, which is in addition to the detached gas flow path, It is connected at the end and burns the adsorption material discharged from each of the plurality of ammonia adsorbers to remove the adhered gas to make the combustion gas flow out; and the return flow path is to return the combustion gas discharged from the exhaust gas combustion reactor to the The second gas waste flow path. [12] The hydrogen production device according to the above [11], wherein the exhaust gas combustion reactor is the combustion reaction device. [13] The hydrogen production device according to the above [11] or [12], further comprising: an exhaust gas cooler which is installed at the return flow path and flows out of the exhaust gas combustion reactor; The aforementioned combustion gas is cooled. [14] The hydrogen production device according to any one of the above [1] to [13], further comprising: a hydrogen flow path, which is connected to the hydrogen recovery device, and passes through the hydrogen recovery device. The separated hydrogen flows out; and a pressure control valve is provided at the aforementioned hydrogen flow path.该 The pressure control valve can adjust the pressure of the hydrogen recovery device, ammonia adsorption device, and ammonia decomposition device. [15] The hydrogen production device according to any one of the above [1] to [14], further comprising: an ammonia flow path connected to the ammonia supply device and the ammonia decomposition device; And a flow control valve are provided at the aforementioned ammonia flow path.该 The flow control valve can control the ammonia flow rate from the ammonia supply device to the ammonia decomposition device. [16] The hydrogen production device according to the above-mentioned [15], further comprising: an ammonia heating heat exchanger provided at the ammonia flow path; and a decomposed gas flow path including the foregoing The ammonia decomposition device and the ammonia adsorption device are connected, and the decomposed gas flow path is communicated with the ammonia heating heat exchanger, and the decomposed gas flow path is further upstream than the installation position of the ammonia heating heat exchanger. At the side, the aforementioned decomposition gas cooling device is provided. [17] The hydrogen production device according to any one of the above [1] to [16], further comprising a decomposition gas flow path for adsorbing the ammonia decomposition device and the plurality of ammonia. It is connected to the gas flow path after the ammonia is removed, which is to connect the plurality of ammonia adsorbers to the hydrogen recovery device, and in the middle of the decomposition gas flow path, the decomposition gas cooling device and the decomposition gas flow path are provided. And the gas flow path after the ammonia removal is not provided with a pressurizing device. In this way, because the system does not have a pressurizing device, the system can reduce equipment costs and operating costs. [0022] [18] A hydrogen production method is a hydrogen production method using the hydrogen production device described in any one of the above [1] to [17], and is characterized in that: an ammonia decomposition project is performed, The ammonia is sent from the ammonia supply device to the ammonia decomposition device, and the ammonia is decomposed to generate the decomposition gas containing hydrogen, nitrogen, and unreacted ammonia; and the ammonia adsorption process is to decompose the ammonia from the ammonia. The decomposed gas flowing out of the device flows to the decomposed gas cooling device for cooling, and then flows to a part of the plurality of ammonia adsorbers, and the unreacted ammonia is adsorbed and removed from the decomposed gas to obtain the ammonia removal. The rear gas; and the hydrogen recovery process, which allows the gas after the ammonia removal flowing out of the part of the plurality of ammonia adsorbers to flow to the hydrogen recovery device, and the hydrogen after the ammonia removal gas separates and flows out, and The remaining exhaust gas is discharged; and the ammonia adsorber regeneration process is to circulate the exhaust gas flowing out of the hydrogen recovery device to the exhaust gas heating device and the recovery device. One or all of the remaining parts of the ammonia adsorber are used to regenerate the ammonia adsorber; and the heating process of the ammonia decomposition device is to circulate the regeneration gas of the adsorption material flowing out of the ammonia adsorber to the combustion reaction device, The combustion gas flow path and the heating device heat the ammonia decomposition device. [0023] According to this hydrogen production device, hydrogen can be produced from ammonia, and the exhaust gas flowing out of the hydrogen recovery device can be effectively used as a regeneration gas for the ammonia adsorbent in the ammonia adsorber. The exhaust gas flowing out of the hydrogen recovery device includes nitrogen and hydrogen, and the adsorbent regeneration gas after using the exhaust gas for regeneration of the ammonia adsorbent includes nitrogen, hydrogen, and ammonia. The combustion reaction device is used to burn the regeneration material of the adsorbent containing nitrogen, hydrogen, and ammonia to obtain a high-temperature combustion gas, and the ammonia decomposition device can be sufficiently heated using the high-temperature combustion gas. [19] The method for producing hydrogen according to the above [18], wherein the exhaust gas heating device is the decomposed gas cooling device, and the decomposed gas cooling device is used to impart heat of the decomposed gas to The exhaust gas is heated at the exhaust gas.由此 With this heat exchanger, the heat of the decomposed gas can be sufficiently given to the exhaust gas, and the thermal efficiency is improved. [20] The hydrogen production method according to the above [18] or [19], further comprising: a circulating gas flow path, one end of which is connected to the heating device, and the other end of which is connected to the adsorbent regeneration gas The flow path is connected so that the combustion gas flows through the combustion gas flow path, the heating device, and the circulation gas flow path into the adsorption material regeneration gas flow path, and a mixed gas with the adsorption material regeneration gas is prepared, and The mixed gas flows to the combustion reaction device and is burned. By using this circulating gas flow path, a part or all of the combustion gas used in the heating of the ammonia decomposition device can be mixed with the aforementioned regeneration material of the adsorbent material and combusted, and the heating in the ammonia decomposition device can be reused. in. As a result, the flow rate of the combustion gas supplied to the ammonia decomposition device is increased, whereby the thermal efficiency can be improved. In addition, since the combustion gas flowing out of the combustion reaction device is burned, the content of flammable gases such as hydrogen and ammonia is small. In addition, the combustion gas is used as a circulating gas after being heated in an ammonia decomposition device, and is mixed with the above-mentioned adsorbent regeneration gas to be combusted by a combustion reaction device. This makes it possible to adjust so that the gas supplied to the combustion reaction device does not enter the explosion range of hydrogen. [21] The method for producing hydrogen according to the above [20], wherein an oxygen supply device is connected to one or both of the adsorbent regeneration gas flow path and the circulating gas flow path, and The oxygen-containing gas supplied by the oxygen supply device is made into a mixed gas with the circulating gas and the adsorbent regeneration gas, and the mixed gas is passed to the combustion reaction device to be burned. By supplying an oxygen-containing gas from the oxygen supply device, and mixing the adsorbent regeneration gas, the circulating gas, and the oxygen-containing gas to adjust the composition, the mixed gas is supplied to the combustion reaction device. Combustion of the gas in the reaction device causes the gas to burn slightly completely. [22] The hydrogen production method according to the above [20] or [21], further comprising: a water flow path intersecting the circulation gas flow path; and a warm water heating heat exchanger, It is installed at the intersection of the circulating gas flow path and the water flow path; and a heating water supply device is installed at the downstream end of the water flow path, and circulates water or warm water to the warm water heating heat. After heating water is prepared at the exchanger, the heated water is supplied from the heated water supply device to the ammonia supply device, and ammonia is vaporized.放 By releasing the heated water from the heated water supply device to the ammonia supply device, it is possible to vaporize the liquid ammonia in the ammonia supply device. [23] The method for producing hydrogen according to the above [22], wherein the circulating gas flow path is further downstream of the warm water heating heat exchanger than the heat exchanger for warming water, and is provided with After the water is removed from the drain tank, the circulating gas is circulated to the drain tank and the water is removed, and then circulated to the combustion reaction device together with the adsorbent regeneration gas and burned.除去 By removing water with this drain tank, it is possible to discharge the water generated in the combustion reaction device from the circulation gas system. [24] The method for producing hydrogen according to any one of the above [18] to [23], further comprising a hydrogen flow path connected to the hydrogen recovery device, and passing the The outflow of hydrogen separated by the hydrogen recovery device; and the pressure control valve are provided at the hydrogen flow path, and the pressure of the ammonia decomposition device P1 and the pressure of the ammonia adsorption device are controlled by controlling the pressure control valve. Each of P2 and the pressure P3 of the aforementioned hydrogen recovery device is controlled within a specific pressure range that satisfies the relationship of P1 ≧ P2 ≧ P3. In this way, by setting P1 ≧ P2 ≧ P3, it becomes unnecessary to pressurize the device, and the cost of equipment and operation can be reduced. The oxygen-containing gas is supplied from this oxygen supply device, and the mixed gas obtained by mixing the adsorbent regeneration gas and the oxygen-containing gas to adjust the composition is supplied to the combustion reaction device. The inside causes the gas to burn slightly completely. [25] The hydrogen production method according to any one of the above [18] to [24], wherein the hydrogen production device is the one described in any one of items 10 to 13 of the scope of patent application A hydrogen production apparatus including the ammonia detoxification project, which supplies the gas flowing through the gas waste flow path to the ammonia detoxification facility and detoxifies ammonia. [Effects of the Invention] [0030] According to the present invention, there is provided a hydrogen production apparatus and a hydrogen production method capable of effectively utilizing exhaust gas generated when ammonia is decomposed to produce hydrogen.
[0032] [第1實施形態] 〈氫製造裝置〉 圖1，係為第1實施形態的氫製造裝置1之概略圖。 本實施形態之氫製造裝置1，係具備有：氨供給裝置2；和氨分解裝置3，係與該氨供給裝置2連接，並分解氨而產生含有氫、氮以及未反應氨之分解氣體；和分解氣體冷卻裝置4a，係與該氨分解裝置3連接，並將分解氣體冷卻；和氨吸附裝置5，係與該分解氣體冷卻裝置4a連接，並從分解氣體將未反應氨作吸附除去並使以氫氣和氮氣作為主成分之氨除去後氣體流出；和氫回收裝置6，係與該氨吸附裝置5連接，並從氨除去後氣體將氫分離並使其流出，並且將含有氫氣和氮氣之剩餘的廢氣排出；和加熱機器8，係將前述氨分解裝置加熱。 [0033] 該氨吸附裝置5，係具備有被並聯地作配設的複數之氨吸附器5a、5b，並設為能夠將從前述分解氣體冷卻裝置4a送來之分解氣體供給至該複數之氨吸附器5a、5b中的任意之一者處。 另外，在本實施形態中，氨吸附器5a、5b之數量雖係為2個，但是，係亦可為3個以上。 [0034] 氫製造裝置1，係更進而具備有：廢氣加熱裝置4b，係與前述氫回收裝置6連接，並加熱前述廢氣。 另外，在本實施形態中，該廢氣加熱裝置4b與前述分解氣體冷卻裝置4a，係為同一之熱交換器(分解氣體冷卻用熱交換器)4，並構成為能夠在從前述氨分解裝置3所流出的前述分解氣體與從前述氫回收裝置6所流出的前述廢氣之間而進行熱交換。藉由此，熱效率係提昇。 [0035] 前述氨供給裝置2與前述氨分解裝置3，係經由氨流路11連接。 前述氨分解裝置3與前述氨吸附裝置5，係經由分解氣體流路12連接，在該分解氣體流路12之途中，係連接有前述分解氣體冷卻裝置4a。另外，該分解氣體流路12之下游端，係分歧為複數根(在本實施形態中係為2根)的分歧流路12a、12b並與複數(在本實施形態中係為2個)之氨吸附器5a、5b的全部連接。 前述氨吸附裝置5與前述氫回收裝置6，係經由氨除去後氣體流路14連接。另外，氨除去後氣體流路14之上游端，係分歧為複數根(在本實施形態中係為2根)的分歧流路14a、14b並與複數(在本實施形態中係為2個)之氨吸附器5a、5b的全部連接。此些之分歧流路12a、12b以及分歧流路14a、14b之各者，係具備有開閉閥。 前述氫製造裝置1，係更進而具備有：氫流路15，係與前述氫回收裝置6連接，並使從氨除去後氣體所分離出的氫流出；和連接流路21，係使在從氨除去後氣體將氫作了分離之後的剩餘之廢氣流出。此連接流路21之其中一端(上游端)，係與氫回收裝置6連接，另外一端(下游端)，係被與前述廢氣加熱裝置4b(分解氣體冷卻用熱交換器4)連接。 [0036] 又，氫製造裝置1，係具備有：廢氣流路22，係一端與該廢氣加熱裝置4b(分解氣體冷卻用熱交換器4)連接，並且另一端與前述複數之氨吸附器5a、5b連接，並且將前述廢氣供給至已使用之氨吸附器5a、5b處而能夠再生氨吸附器；和吸附材再生氣體流路23，係與複數之前述氨吸附器5a、5b連接，並使從前述已使用之氨吸附器5a、5b所流出的吸附材再生氣體(主要成份為氫氣、氮氣以及氨)流通；和燃燒反應裝置7，係與該吸附材再生氣體流路23連接，並燃燒前述吸附材再生氣體而使燃燒氣體流出；和燃燒氣體流路24，係一端與前述燃燒反應裝置7連接，並且另一端與前述加熱機器8連接。 上述廢氣流路22之下端，係分歧為複數根(在本實施形態中係為2根)的分歧流路22a、22b並與複數根(在本實施形態中係為2根)的分歧流路14a、14b中之較開閉閥更上游側連接。吸附材再生氣體流路23之上游端，係分歧為複數根(在本實施形態中係為2根)的分歧流路23a、23b並與複數(在本實施形態中係為2個)的分歧流路12a、12b中之較開閉閥更下游側連接。此些之分歧流路22a、22b以及分歧流路23a、23b之各者，係具備有開閉閥。 [0037] 另外，在本實施形態中，前述分解氣體流路12以及前述氨除去後氣體流路14，係並不具備有加壓裝置。藉由此，係能夠削減設備成本以及運轉成本。另外，在本實施形態中，氫製造裝置1係並不具備有加壓裝置。 但是，係亦可在分解氣體流路12以及氨除去後氣體流路14之至少其中一者處，設置加壓裝置。藉由此，係能夠將氨分解裝置3之壓力降低而使氨分解效率提昇，並且將流入至氫回收裝置6處之氨除去後氣體的壓力提高而使氫回收效率提昇。在設置該加壓裝置的情況時，較理想，係僅在分解氣體流路12以及氨除去後氣體流路14中之氨除去後氣體流路14處作設置。 [0038] (氨供給裝置2) 在本實施形態中，氨供給裝置2，係具有液體氨槽。 [0039] (氨分解裝置3) 氨分解裝置3，係收容有氨分解觸媒。 作為氨分解觸媒，只要是在氨分解反應中具有觸媒活性者，則係並不特別作限定，但是，例如，係可列舉出作為組成而包含有卑金屬系變遷金屬(鐵、鈷、鎳、鉬等)、稀土類系(鑭、鈰、釹等)、貴金屬系(釕、銠、銥、鈀、鉑等)的觸媒。上述卑金屬系變遷金屬，係可作為金屬單體、合金、氮化物、碳化物、氧化物、複合氧化物來使用，上述稀土類系，係可作為氧化物來使用，係能夠將該卑金屬系變遷金屬以及該稀土類系一同擔持於氧化鋁、二氧化矽、氧化鎂、氧化鋯、二氧化鈦等之具有高比表面積的載體中使用。又，上述貴金屬系，係亦可擔持於氧化鋁、二氧化矽、氧化鎂、氧化鋯、二氧化鈦等之具有高比表面積的載體中使用。又，係亦可在上述變遷金屬系及／或上述稀土類系中，含有少量的上述貴金屬系而使用。此些之觸媒，係能夠以單體來使用，亦可併用2種以上。 [0040] (氨吸附裝置5) 構成氨吸附裝置5之氨吸附器5a、5b，係收容有氨吸附材。 作為氨吸附材，只要是能夠將分解氣體中之氨除去並且能夠進行再生者，則係並未特別作限定，較理想，係為沸石、活性炭、氧化鋁、二氧化矽、複合氧化物。 [0041] (氫回收裝置6) 氫回收裝置6，只要是能夠從分解氨所成之分解氣體(主要成份為氫氣及氮氣)中將氫分離並取出者，則係並不特別作限定。例如，氫回收裝置6，係可列舉出壓力變動吸附分離裝置(PSA裝置)、溫度變動吸附分離裝置(TSA裝置)、具有氫分離膜之氫分離膜裝置等。 [0042] (燃燒反應裝置7) 燃燒反應裝置7，只要是能夠將從再生中之氨吸附器5a、5b所流出的吸附材再生氣體作燃燒者，則係並未特別作限定，例如，係可列舉出於內部收容有燃燒觸媒之燃燒反應裝置、直接燃燒裝置等。 作為在燃燒反應裝置中所使用的觸媒，係可列舉出鈀、鉑等，但是，從成本的觀點來看，係以鈀為理想。又，在直接燃燒裝置的情況時，係能夠在吸附材再生氣體中混合燈油、天然瓦斯等而進行燃燒。 (加熱機器8) 加熱機器8，係為將從燃燒反應裝置7送來之燃燒氣體供給至氨分解裝置3之周圍並加熱氨分解裝置3之機器。 作為加熱機器8，係可例示有對於將氨分解裝置3之周圍作覆蓋的外套而供給燃燒氣體之裝置或者是將使燃燒氣體通過的配管捲繞於氨分解裝置3之周圍者等。 [0043] 〈氫製造方法〉 接著，針對使用有前述之氫製造裝置1的氫製造方法之其中一例作說明。 在本實施形態之氫製造方法中，係反覆進行後述之第1運轉和第2運轉。 [0044] (第1運轉) 在第1運轉中，係使用氨吸附器5a而實施氫氣之製造，並且實施氨吸附器5b內之氨吸附材的再生。 亦即是，第1運轉，係具備有後述之氨分解工程、和氨吸附工程、和氫回收工程、和氨吸附器再生工程、以及氨分解裝置之加熱工程。 [0045] [氨分解工程] 氨分解工程，係為使從前述氨供給裝置2送來之氨流通至氨分解裝置3處，並將氨分解，而產生含有氫、氮以及未反應氨之前述分解氣體之工程。 氨分解裝置3內之溫度，較理想係為400～800℃。若是該溫度為400℃以上，則氨的分解係被促進，在分解氣體中之未反應氨的含有量係變少。又，若是該溫度為800℃以下，則氨分解觸媒的劣化係被抑制，並且消耗的能量係被抑制。從該觀點來看，氨分解裝置3內之溫度，更理想，係為430～650℃，又更理想，係為450～550℃，再更理想，係為480～520℃。 [0046] 氨分解裝置3內之壓力，較理想係為0.0～1.0MPaG(表壓力)。若是該壓力為0.0MPaG以上，則係能夠防止大氣漏入至裝置內。若是該壓力為1.0MPaG以下，則由於氨分解反應係為使分子數增加的平衡反應，因此係能夠使在分解氣體中之未反應氨的含有量降低。 從該觀點來看，氨分解裝置3內之壓力，更理想，係為0.2～0.8MPaG，又更理想，係為0.3～0.7MPaG，再更理想，係為0.45～0.55MPaG。 [0047] [氨吸附工程] 氨吸附工程，係為在將藉由前述氨分解工程之實施而從前述氨分解裝置3所流出的前述分解氣體流通至前述分解氣體冷卻裝置4a(分解氣體冷卻用熱交換器4)處並作了冷卻之後，使其流通至前述複數之氨吸附器5a、5b的其中一者(氨吸附器5a)處並從前述分解氣體將未反應氨吸附除去而得到前述氨除去後氣體之工程。 氨吸附器5a內之溫度，較理想係為10～100℃。若是該溫度為10℃以上，則係成為不需要氣體之冷卻裝置，而能夠削減能量之消耗量。又，若是該溫度為100℃以下，則氨之吸附量係變大。 從該觀點來看，氨吸附器5a內之溫度，更理想，係為15～80℃，又更理想，係為20～60℃，再更理想，係為25～50℃。 [0048] 氨吸附器5a內之壓力，較理想係為0.1～1.0MPaG。若是該壓力為0.1MPaG以上，則氨吸附材之每單位的氨吸附量係變大。又，若是該壓力為1.0MPaG以下，則係能夠削減用以進行氣體之升壓的能量之消耗量。 從該觀點來看，氨吸附器5a內之壓力，更理想，係為0.15～0.8MPaG，又更理想，係為0.2～0.6MPaG，再更理想，係為0.25～0.5MPaG。 [0049] 又，係亦可將前述氨分解裝置3之壓力P1以及氨吸附器5a內之壓力P2，設為P1≧P2。 藉由此，係成為不需要在氨分解裝置3與氨吸附器5a之間設置加壓裝置，運轉成本以及設備成本係被抑制。 又，從利用該氨吸附器5a之壓力來在下游之氫回收裝置6處進行氫回收的觀點來看，氨吸附器5a內之壓力，更理想，係為0.2～0.8MPaG，又更理想，係為0.25～0.6MPaG，再更理想，係為0.3～0.5MPaG。 [0050] [氫回收工程] 氫回收工程，係為使從前述複數之氨吸附器5a、5b的前述其中一者(氨吸附器5a)所流出的前述氨除去後氣體流通至前述氫回收裝置6處並從前述氨除去後氣體而分離出氫並使其流出並且將剩餘之廢氣排出之工程。 [0051] 氫回收裝置6內之溫度，較理想係為10～60℃。 氫回收裝置6內之壓力，較理想係為0.1～1.0MPaG。 係亦可使前述氨分解裝置3之壓力P1、前述氨吸附裝置5(氨吸附器5a)之壓力P2以及前述氫回收裝置6之壓力P3的各者，設為會滿足 P1≧P2≧P3 之關係。藉由此，係成為不需要在氨分解裝置3與氨吸附器5a之間以及氨吸附器5a與氫回收裝置6之間設置加壓裝置，運轉成本以及設備成本係被抑制。 [0052] [氨吸附器再生工程] 氨吸附器再生工程，係為將從前述氫回收裝置6所流出的前述廢氣，流通至前述廢氣加熱裝置4b(分解氣體冷卻用熱交換器4)以及前述複數之氨吸附器5a、5b的剩餘部分(例如，當正在使用氨吸附器5a的情況時，係為氨吸附器5b)處並使氨吸附器(氨吸附器5b)再生之工程。當氨吸附器5為存在有3個以上的情況時，係能夠對於並非為氨之吸附中的裝置群之中之至少1者而適用此再生工程。 如同前述一般，被供給至氫回收裝置6處之氨除去後氣體，係在氨吸附裝置5處，從氨分解氣體(氫、氮以及未反應氨)中使氨被作了除去。故而，在從氫回收裝置6所流出的廢氣中之氨含有量，係為少量。因此，藉由在將該廢氣加熱之後使其流通至氨吸附器5b處，係能夠使吸附在氨吸附材上的氨良好地脫離附著，而能夠使氨吸附材再生。 又，當正在使氨吸附器5b再生的期間中，係能夠使用氨吸附器5a而從分解氣體來將氨作吸附除去。 [0053] 在使氨脫離附著時的氨吸附器5b內之溫度，較理想係為100～500℃。若是該溫度為100℃以上，則係能夠使氨吸附材充分地再生。又，若是該溫度為500℃以上，則會有導致吸附材的劣化之虞。從該觀點來看，氨吸附器5b內之溫度，更理想，係為200～450℃，又更理想，係為300～430℃，再更理想，係為380～420℃。 [0054] 氨吸附器5b內之壓力，較理想係為0.0～0.5MPaG。若是該壓力為0.0MPaG以上，則係成為不需要進行真空抽氣，而並不需要耗費能量。又，若是該壓力為0.5MPaG以下，則係能夠充分地使氨脫離附著。從該觀點來看，氨吸附器5b內之壓力，更理想，係為0.0～0.45MPaG，又更理想，係為0.0～0.4MPaG，再更理想，係為0.0～0.3MPaG。 [0055] [氨分解裝置之加熱工程] 氨分解裝置之加熱工程，係為藉由以前述燃燒反應裝置7來燃燒從前述氨吸附器5b所流出的吸附材再生氣體來產生熱能，並將此燃燒氣體經由前述燃燒氣體流路4來流通至前述加熱機器8處而加熱前述氨分解裝置3之工程。 從前述氨吸附器5b所流出的吸附材再生氣體，係包含有從前述氨吸附器5b而脫離了附著的氨。又，係亦包含有並未被氫回收裝置6所回收而在廢氣中所含有之氫。故而，藉由以燃燒反應裝置7來燃燒該吸附材再生氣體，係能夠得到高溫的燃燒氣體。又，藉由使用此高溫的燃燒氣體來加熱氨分解裝置3，係能夠充分地加熱氨分解裝置3。 [0056] (第2運轉) 在繼續了前述第1運轉之後，係實施下述之第2運轉。 在第2運轉中，係使用在第1運轉中所再生了的氨吸附器之一部分或是全部(氨吸附器5b)，來進行氨吸附工程，又，係對於在第1運轉中而於氨吸附工程中所使用了的氨吸附器(氨吸附器5a)，而實施氨吸附器再生工程。另外，其他之工程、亦即是氨分解工程、氫回收工程以及氨分解裝置之加熱工程，係與第1運轉相同。 如此這般，藉由反覆進行第1運轉和第2運轉，係能夠進行連續運轉。 [0057] [第2實施形態] 〈氫製造裝置〉 圖2，係為第2實施形態的氫製造裝置30之概略圖，圖3，係為對於使用有圖2之氫製造裝置30的第1運轉作說明之概略圖。 本實施形態之氫製造裝置30，係具備有氨供給裝置31、和氨分解裝置32、和分解氣體冷卻裝置33a(分解氣體冷卻用熱交換器33)、和氨吸附裝置34、和氫回收裝置35、以及加熱機器38。 該氨吸附裝置34，係具備有被並聯地作配設的複數(在本實施形態中係為2個)之氨吸附器34a、34b。 此些之裝置31、32、33a(33)、34、35、38之詳細構成，係如同在第1實施形態中所作了說明一般。 如同後述一般，在本實施形態中，分解氣體冷卻裝置33a，係為分解氣體冷卻用熱交換器33，並兼作為廢氣加熱裝置33b。 [0058] 又，氫製造裝置30，係具備有將氨供給裝置31與氨分解裝置32連接之氨流路41、和將氨分解裝置32與氨吸附裝置34連接之分解氣體流路42、和將氨吸附裝置34與氫回收裝置35連接之氨除去後氣體流路43、以及使藉由氫回收裝置35所分離出的氫流出之氫流路44。 上述分解氣體流路42，係一端(上游端)與氨分解裝置32連接，並且另一端側分歧而成為分歧流路42a、42b，分歧流路42a係與氨吸附器34a連接，分歧流路42b係與氨吸附器34b連接。分歧流路42a、42b之各者，係具備有開閉閥。 又，上述氨除去後氣體流路43，係一端(上游端)分歧而成為分歧流路43a、43b，分歧流路43a係與氨吸附器34a連接，分歧流路43b係與氨吸附器34b連接。又，氨除去後氣體流路43之另外一端，係會合並與氫回收裝置35連接。分歧流路43a、43b之各者，係具備有開閉閥。 在上述氨流路41處，係設置有流量控制閥V1。又，在上述氫流路44處，係設置有壓力控制閥V2。 [0059] 在上述氨流路41中之較流量控制閥V1更下游側處，係從上游側(氨供給裝置31側)起依序設置有氨加熱用熱交換器51以及氨輔助加熱用熱交換器52。 在上述分解氣體流路42中之較分歧流路42a、42b更上游側處，係從上游側(氨分解裝置32側)起依序設置有分解氣體冷卻裝置33a(分解氣體冷卻用熱交換器33)、上述氨加熱用熱交換器51以及水加熱用熱交換器54。 亦即是，上述氨流路41與分解氣體流路42係相互交叉，在該交叉場所處，係設置有上述氨加熱用熱交換器51。故而，在上述氨加熱用熱交換器51之管側以及殼側的其中一者處，係流通有氨，在另外一者處，係流通有分解氣體，並成為能夠在氨與分解氣體之間進行熱交換。 [0060] 進而，氫製造裝置30，係具備有：與氫回收裝置35連接之連接流路61、和經由該連接流路61而與氫回收裝置35連接並且將從氫回收裝置35而經由連接流路61所流出的廢氣加熱之廢氣加熱裝置33b(分解氣體冷卻用熱交換器33)。 在本實施形態中，前述分解氣體冷卻裝置33a與該廢氣加熱裝置33b，係為同一之熱交換器(分解氣體冷卻用熱交換器33)，並構成為能夠在從氨分解裝置32所流出的分解氣體與從前述氫回收裝置35所流出的廢氣之間而進行熱交換。 [0061] 又，氫製造裝置30，係具備有：廢氣流路62，係一端與廢氣加熱裝置33b(分解氣體冷卻用熱交換器33)連接，並且另一端分歧而與前述複數之氨吸附器34a、34b連接，並且將前述廢氣供給至已使用之氨吸附器處而能夠使氨吸附器再生。 亦即是，該廢氣流路62之其中一端(上游端)，係與上述廢氣加熱裝置33b(分解氣體冷卻用熱交換器33)連接，另外一端係分歧而成為分歧流路62a、62b，分歧流路62a係與上述氨除去後氣體流路43之分歧流路43a中的較開閉閥更上游側連接，分歧流路62b係與上述氨除去後氣體流路43之分歧流路43b中的較開閉閥更上游側連接。此些之分歧流路43a、43b之各者，係具備有開閉閥。 [0062] 又，氫製造裝置30，係具備有：吸附材再生氣體流路63，係與複數之前述氨吸附器34a、34b連接，並使從前述已使用之氨吸附器所流出的吸附材再生氣體作流通；和燃燒反應裝置36，係與吸附材再生氣體流路63連接，並燃燒前述吸附材再生氣體而使燃燒氣體流出；和燃燒氣體流路64，係一端與前述燃燒反應裝置36連接，並且另一端與前述加熱機器38連接。 詳細而言，該吸附材再生氣體流路63，係一端(上游端)分歧而成為分歧流路63a、63b，分歧流路63a係與前述之分解氣體流路42之分歧流路42a中的較開閉閥更下游側連接，分歧流路63b係與前述之分解氣體流路42之分歧流路42b中的較開閉閥更下游側連接。亦即是，吸附材再生氣體流路63，係經由前述之分解氣體流路42之分歧流路42a、42b而與氨吸附器34a、34b連接。該吸附材再生氣體流路63，係使另外一端會合並與燃燒反應裝置36連接。此些之分歧流路63a、63b之各者，係具備有開閉閥。 [0063] 在本實施形態中，於該吸附材再生氣體流路63中之較分歧流路63a、63b更下游的位置處，係設置有氧供給裝置37。 [0064] 進而，氫製造裝置30，係具備有：循環氣體流路71，係一端與前述加熱機器38連接，並且另一端與前述吸附材再生氣體流路63連接。 在前述吸附材再生氣體流路63以及前述循環氣體流路71之其中一方或雙方處，係連接有氧供給裝置37。另外，在本實施形態中，於吸附材再生氣體流路63處係連接有氧供給裝置37。 [0065] 氫製造裝置30，係具備有加熱水供給裝置80。該加熱水供給裝置80，係具備有與前述循環氣體流路71相交叉之水流路81、和被設置在該循環氣體流路71與該水流路80之交叉點處的溫水加熱用熱交換器73、和被設置在該水流路81之下游端處的噴淋頭82。故而，藉由在此溫水加熱用熱交換器73之管側以及殼側的其中一者處流通循環氣體並在另外一者處使溫水通過，係成為能夠在循環氣體與溫水之間進行熱交換，在該水流路81中流動的溫水係被加熱並成為加熱水。 另外，係將存在於從水加熱用熱交換器54起直到溫水加熱用熱交換器73處的內部流體，稱作「溫水」，並將較此更下游之內部流體，稱作「加熱水」。 [0066] 又，在水流路81中之較該溫水加熱用熱交換器73更上游的位置處，係與前述之分解氣體流路42中之較分歧並成為分歧流路42a、42b的位置更上游側並且較氨加熱用熱交換器51更下游的位置相交叉，而成為交叉點，在該交叉點處，係設置有水加熱用熱交換器54。藉由在此水加熱用熱交換器54之管側以及殼側的其中一者處流通分解氣體並在另外一者處使水通過，係成為能夠在分解氣體與水之間進行熱交換。 在前述循環氣體流路71中之較前述溫水加熱用熱交換器73更下游處，係具備有用以將前述循環氣體中之水除去的排泄罐74。 [0067] 前述循環氣體流路71，係使其之位於較前述溫水加熱用熱交換器73更上游處的第1點與位於較前述排泄罐74更下游處的第2點相互交叉，而成為交叉點，前述循環氣體流路71中之前述第1點與前述第2點之間的部份，係成為環狀流路71a，在該交叉點處，係設置有循環氣體用熱交換器72。故而，從燃燒氣體流路64經由加熱機器38而流入至循環氣體流路71中的燃燒氣體(循環氣體)，係成為能夠在通過了循環氣體用熱交換器72之管側以及殼側的其中一者之後，在循環氣體流路71中之環狀流路71a中流通，接著，通過循環氣體用熱交換器72之管側以及殼側的另外一者。 在此環狀流路71a處，係從上游側起依序設置有前述之溫水加熱用熱交換器73、排泄罐74以及循環機75。 [0068] 又，從該循環氣體流路71中之排泄罐74之下游並且循環機75之上游側的位置起，係分歧有氣體廢棄流路76。但是，該氣體廢棄流路76，不論是從該循環氣體流路71之何一位置而分歧出來均可。 [0069] 在前述之燃燒氣體流路64的途中場所和前述之循環氣體流路71中之較前述循環氣體用熱交換器72更上游的場所處，係分別連接有旁通流路77之其中一端以及另外一端。 該旁通流路77，係與前述之氨流路41相交叉，在該交叉點處，係設置有前述之氨輔助加熱用熱交換器52。故而，藉由在此氨輔助加熱用熱交換器52之管側以及殼側的其中一者處流通氨並在另外一者處使燃燒氣體通過，係成為能夠藉由氨與燃燒氣體之間之熱交換來將氨加熱。 [0070] 另外，在本實施形態中，前述分解氣體流路42以及前述氨除去後氣體流路43，係並不具備有加壓裝置。藉由此，係能夠削減設備成本以及運轉成本。 但是，係亦可在分解氣體流路42以及氨除去後氣體流路43之至少其中一者處，設置加壓裝置。藉由此，係能夠將氨分解裝置32之壓力降低而使氨分解效率提昇，並且將流入至氫回收裝置35處之氨除去後氣體的壓力提高而使氫回收效率提昇。在設置該加壓裝置的情況時，較理想，係僅在分解氣體流路42以及氨除去後氣體流路43中之氨除去後氣體流路43處作設置。 [0071] (燃燒反應裝置) 燃燒反應裝置36，只要是能夠燃燒氫以及氨者，則係並未特別作限定，但是，從有效率地進行燃燒的觀點來看，較理想，係為收容燃燒觸媒者。 作為在燃燒反應裝置中所使用的觸媒，係可列舉出鈀、鉑等，但是，從成本的觀點來看，係以鈀為理想。 [0072] (氧供給裝置) 關於從氧供給裝置37所供給的含氧氣體，係並未特別作限定，而可列舉出空氣、從氧氣瓶等所供給之氧等，但是，從安全性以及經濟性的觀點來看，係以空氣為理想。 氧供給裝置37，只要是能夠對於吸附材再生氣體流路36供給氧者，則係並未特別作限定，而可列舉出各種壓縮機。 (循環機) 關於循環機75，係並未特別作限定，而可列舉出鼓風機、風扇、各種壓縮機。 (加熱水供給裝置) 加熱水供給裝置80，係如同前述一般，具備有水流路81、和被設置在該水流路81之前端處的噴淋頭82、以及被設置在水流路81處之水加熱用熱交換器54和溫水加熱用熱交換器73。藉由此裝置，係能夠將加熱後之水對於氨供給裝置31作供給並將內部的氨加熱。 [0073] 〈氫製造方法〉 接著，針對使用有前述之氫製造裝置30的氫製造方法之其中一例作說明。 在本實施形態之氫製造方法中，係反覆進行後述之第1運轉和第2運轉。 [0074] (第1運轉) 在第1運轉中，係使用氨吸附器34a而實施氫氣之製造，並且實施氨吸附器34b內之氨吸附材的再生。 亦即是，第1運轉，係具備有後述之氨分解工程、和氨吸附工程、和氫回收工程、和氨吸附器再生工程、和氨分解裝置之加熱工程、和燃燒氣體循環工程、以及水加熱工程。 [0075] [氨分解工程] 氨分解工程，係為使從前述氨供給裝置31送來之氨流通至氨分解裝置32處，並將氨分解，而產生含有氫、氮以及未反應氨之前述分解氣體之工程。 亦即是，首先，在氨分解工程之前，係如同在後述之水加熱工程中所說明一般地，從加熱水供給裝置80之噴淋頭82來對於氨供給裝置31供給加熱水。藉由此，氨供給裝置31內之液體氨係氣化，並在氨流路41中流通。 氨流路41內之氨，係在藉由流量控制閥V1而作了流量調整之後，藉由氨加熱用熱交換器51以及氨輔助加熱用熱交換器52而被加熱，並接著流通至氨分解裝置32處。在該氨分解裝置32內，氨係分解，並產生含有氫、氮以及未反應氨之前述分解氣體。 關於氨分解裝置32內之溫度以及壓力，係如同在第1實施形態中所作了說明一般。 [0076] [氨吸附工程] 氨吸附工程，係為在將藉由前述氨分解工程之實施而從前述氨分解裝置32所流出的前述分解氣體流通至前述分解氣體冷卻裝置33a(分解氣體冷卻用熱交換器33)、氨加熱用熱交換器51以及水加熱用熱交換器54處並作了冷卻之後，使其流通至前述複數之氨吸附器34a、34b的其中一者(氨吸附器34a)處並從前述分解氣體將未反應氨吸附除去而得到前述氨除去後氣體之工程。 關於氨吸附器34a內之溫度以及壓力，係如同在前述之第1實施形態中所作了說明一般。 [0077] [氫回收工程] 氫回收工程，係為使從前述複數之氨吸附器34a、34b的前述其中一者(氨吸附器34a)所流出的前述氨除去後氣體流通至前述氫回收裝置35處並從前述氨除去後氣體而分離出氫並使其流出並且將剩餘之廢氣排出之工程。 關於氫回收裝置35內之溫度以及壓力，係如同在前述之第1實施形態中所作了說明一般。 [0078] 另外，在本實施形態中，係具備有：氫流路44，係與前述氫回收裝置35連接，並使藉由前述氫回收裝置35分離出的氫流出；和壓力控制閥V2，係被設置在氫流路44處。又，在本實施形態中，於從氨供給裝置31起經由氨流路41、氨分解裝置32、分解氣體流路42、氨吸附裝置34直至氨除去後氣體流路43為止的流路中，係並不存在有熱交換器以外之加熱裝置，亦即是並不存在有能量供給形態之加熱器類。故而，藉由對於壓力控制閥V2作控制，係可將前述氨分解裝置32之壓力P1、前述氨吸附裝置34(氨吸附器34a)之壓力P2以及前述氫回收裝置35之壓力P3的各者，設為會滿足 P1≧P2≧P3 之關係的特定之壓力範圍。 [0079] [氨吸附器再生工程] 氨吸附器再生工程，係為將從前述氫回收裝置35所流出的前述廢氣，流通至前述廢氣加熱裝置33b(分解氣體冷卻用熱交換器33)處並將其加熱，之後使其流通至前述複數之氨吸附器34a以及34b的剩餘部分(例如，當正在使用氨吸附器34a的情況時，係為氨吸附器34b)處並使氨脫離附著而使氨吸附器(氨吸附器34b)再生之工程。 [0080] 如同前述一般，被供給至氫回收裝置35處之氨除去後氣體，係在其之上游的氨吸附裝置34處，從氨分解氣體(氫、氮以及未反應氨)中使氨被作了除去。故而，在從氫回收裝置35所流出的廢氣中之氨含有量，係為少量。因此，藉由在將該廢氣加熱之後使其流通至氨吸附器34b處，係能夠使吸附在氨吸附材上的氨良好地脫離附著，而能夠進行再生。 又，當正在使氨吸附器34b再生的期間中，係能夠使用氨吸附器34a而從分解氣體來將氨作吸附除去。 關於氨吸附器34b內之溫度以及壓力，係如同在前述之第1實施形態中所作了說明一般。 [0081] [氨分解裝置之加熱工程] 在氨分解裝置32之加熱工程中，首先係將從前述氨吸附器34b所流出的吸附材再生氣體，與從氧供給裝置37送來之含氧氣體以及從後述之循環氣體流路71送來的循環氣體作混合而作成混合氣體。接著，將該混合氣體供給至前述燃燒反應裝置36處並使其燃燒，而得到高溫的燃燒氣體。接著，使該燃燒氣體經由燃燒氣體流路64來流通至加熱機器38處。 如此這般，在本實施形態中，係藉由燃燒反應裝置36，使將吸附材再生氣體、後述之循環氣體以及含氧氣體作了混合的混合氣體燃燒。故而，藉由對於循環氣體以及含氧氣體之混合量作調整而對於混合氣體之組成進行調整，係能夠使該混合氣體有效率地作燃燒。又，藉由對於循環氣體之一部分或全部作利用，係能夠將與氨分解裝置32進行熱交換之氣體量作增量，藉由此，係能夠使能量效率提昇。 關於被供給至燃燒反應裝置36處之吸附材再生氣體之溫度、燃燒反應裝置36內之溫度以及燃燒反應裝置36內之壓力，係如同在前述之第1實施形態中所作了說明一般。 [0082] [燃燒氣體循環工程] 燃燒氣體循環工程，係為使將前述氨分解裝置32作了加熱之後的前述燃燒氣體作為循環氣體而流通至循環氣體用熱交換器72以及溫水加熱用熱交換器73處並作了冷卻之後，將藉由冷卻而凝結的水藉由排泄罐74而除去，接著使冷卻後之循環氣體的一部分或全部再度流通至循環氣體用熱交換器72處並進行加熱，並與前述吸附材再生氣體以及含氧氣體一同地流通至前述燃燒反應裝置36而被燃燒的工程。 藉由如此這般地將循環氣體冷卻，係能夠降低循環氣體之體積，藉由此，係能夠將循環機75小型化。 另外，在使將該氨分解裝置32作了加熱之後的前述循環氣體之一部分與前述吸附材再生氣體一同地流通至前述燃燒反應裝置36處並被作燃燒的情況時，係只要將該循環氣體之剩餘部分經由氣體廢棄流路76來排出至系外即可。 於此，將在燃燒氣體通過了氨分解裝置之後而於循環氣體流路中所流通的氣體，稱作循環氣體。 [0083] 若是藉由前述燃燒反應裝置36而燃燒前述混合氣體，則混合氣體中之氫以及氨的至少1種與氧係起反應並產生水。故而，在本實施形態中，係在藉由被設置於前述循環氣體流路71處之排泄罐74將該水除去之後，與前述吸附材再生氣體一同地流通至前述燃燒反應裝置36處並使其燃燒。 [0084] [水加熱工程] 水加熱工程，係為藉由加熱水來加熱氨之工程，更具體而言，係為在使水在前述水加熱用熱交換器54以及溫水加熱用熱交換器73中流通並作成加熱水之後，從前述噴淋頭82來將加熱水供給至前述氨供給裝置31處，使氨氣化之工程。 從噴淋頭82所流出的加熱水之溫度，較理想，係為0～80℃，更理想，係為10～60℃，又更理想，係為20～50℃，再更理想，係為30～45℃。 [0085] (第2運轉) 在繼續了前述第1運轉之後，係實施下述之第2運轉。 在第2運轉中，係使用在第1運轉中而再生了的氨吸附器34b來進行氨吸附工程，並且使用在第1運轉中而進行了氨吸附工程之氨吸附器34a來實施氨吸附器再生工程。另外，其他之工程、亦即是氨分解工程、氫回收工程以及氨分解裝置之加熱工程，係與第1運轉相同。 如此這般，藉由反覆進行第1運轉和第2運轉，係能夠進行連續運轉。 [0086] [第3實施形態] 〈氫製造裝置〉 圖4，係為第3實施形態的氫製造裝置30A之概略圖。 圖4之氫製造裝置30A，係在圖2以及圖3之氫製造裝置30中，如同下述一般地進行了改造：亦即是，係並不將燃燒氣體作循環利用，亦即是係使加熱氨分解裝置32之通過了加熱機器38之後的燃燒氣體並不再度回到燃燒反應裝置36處地而廢棄至氫製造裝置外，並且將吸附劑再生氣體以及含氧氣體之混合氣體供給至燃燒反應裝置36處而使其燃燒。 亦即是，氫製造裝置30A，係在氫製造裝置30處，將循環氣體流路71和被設置在該循環氣體流路71處之配管與裝置類以及氧供給裝置37作省略，並且設置了後述之配管以及裝置類。 [0087] 〈在氫製造裝置30A中所並不存在之裝置類〉 亦即是，圖4之氫製造裝置30A，係並不具備有在氫製造裝置30處之循環氣體流路71、循環氣體用熱交換器72、溫水加熱用熱交換器73、排泄罐74、循環機75、氣體廢棄流路76以及氧供給裝置37。 [0088] 〈在氫製造裝置30A中所追加之裝置類〉 如同圖4中所示一般，氫製造裝置30A，係具備有：熱回收流路71A，係一端與加熱機器38連接，並且另一端與排泄罐74A連接。又，在排泄罐74A處，係連接有氣體廢棄流路76A。 熱回收流路71A，係與氧供給流路37B相交叉，在該交叉點處，係設置有氧氣加熱用熱交換器72A。熱回收流路71A內之氣體，係通過該氧氣加熱用熱交換器72A之管側以及殼側之其中一者，氧供給流路37B內之氣體係通過另外一者。該氧供給流路37B之其中一端，係與氧供給裝置37A連接，另外一端，係與吸附劑再生氣體流路63中之較分歧流路63a、63b更下游側處連接。 又，熱回收流路71A中之較前述氧氣加熱用熱交換器72A更下游側的場所，係與水流路81中之較水加熱用熱交換器54更下游側的場所相交叉，在該交叉點處，係設置有溫水加熱用熱交換器73A。熱回收流路71A內之氣體，係通過該溫水加熱用熱交換器73A之管側以及殼側之其中一者，水流路81B之溫水係通過另外一者。該水流路81之下游端，係與噴淋頭82連接。 另外，係將存在於從水加熱用熱交換器54起直到溫水加熱用熱交換器73A處的內部流體，稱作「溫水」，並將較此更下游之內部流體，稱作「加熱水」。 氫製造裝置30A之上述以外的構成，係與氫製造裝置30相同，同樣的元件符號，係代表相同的裝置或配管類。 [0089] 〈氫製造方法〉 接著，針對使用有前述之氫製造裝置30A的氫製造方法之其中一例作說明。 在本實施形態之氫製造方法中，係反覆進行後述之第1運轉和第2運轉。 [0090] (第1運轉) 在第1運轉中，係使用氨吸附器34a而實施氫氣之製造，並且實施氨吸附器34b內之氨吸附材的再生。 亦即是，第1運轉，係具備有後述之氨分解工程、和氨吸附工程、和氫回收工程、和氨吸附器再生工程、和氨分解裝置之加熱工程、和熱回收工程、以及水加熱工程。 [0091] [氨分解工程] 係與第2實施形態相同。 [氨吸附工程] 係與第2實施形態相同。 [氫回收工程] 係與第2實施形態相同。 [氨吸附器再生工程] 係與第2實施形態相同。 [0092] [氨分解裝置之加熱工程] 在氨分解裝置32之加熱工程中，首先係將從前述氨吸附器34b所流出的吸附材再生氣體，與從氧供給裝置37A送來之含氧氣體作混合而作成混合氣體。接著，將該混合氣體供給至前述燃燒反應裝置36處並使其燃燒，而得到高溫的燃燒氣體。接著，使該燃燒氣體經由燃燒氣體流路64來流通至加熱機器38處，藉由此，來加熱氨分解裝置32。 如此這般，在本實施形態中，係藉由燃燒反應裝置36，使將吸附材再生氣體以及含氧氣體作了混合的混合氣體燃燒。故而，藉由對於含氧氣體之量作調整而對於混合氣體之組成進行調整，係能夠使該混合氣體有效率地作燃燒。 關於被供給至燃燒反應裝置36處之吸附材再生氣體之溫度、燃燒反應裝置36內之溫度以及燃燒反應裝置36內之壓力，係如同在前述之第1實施形態中所作了說明一般。 [0093] [熱回收工程] 熱回收工程，係為使將前述氨分解裝置32作了加熱之後的前述燃燒氣體流通至氧氣加熱用熱交換器72A以及溫水加熱用熱交換器73A處並作了冷卻之後，將藉由冷卻而凝結的水藉由排泄罐74A而除去，接著經由氣體廢棄流路76A而排出至系外的工程。 [0094] 若是藉由前述燃燒反應裝置36而燃燒前述混合氣體，則混合氣體中之氫以及氨的至少1種與氧係起反應並產生水。故而，在本實施形態中，係在藉由被設置於前述熱回收流路71A處之排泄罐74A將該水除去之後，排出至系外。 [0095] [水加熱工程] 水加熱工程，係為藉由加熱水來加熱氨之工程，更具體而言，係為在使水在前述水加熱用熱交換器54以及溫水加熱用熱交換器73A中流通並作成加熱水之後，從前述噴淋頭82來將加熱水供給至前述氨供給裝置31處，使氨氣化之工程。 從噴淋頭82所流出的加熱水之溫度，較理想，係為0～80℃，更理想，係為10～60℃，又更理想，係為20～50℃，再更理想，係為30～45℃。 [0096] (第2運轉) 在繼續了前述第1運轉之後，係實施下述之第2運轉。 在第2運轉中，係使用在第1運轉中而再生了的氨吸附器34b而進行氨吸附工程，並且使用在第1運轉中而進行了氨吸附工程之氨吸附器34a來實施氨吸附器再生工程。另外，其他之工程，係與第1運轉相同。 如此這般，藉由反覆進行第1運轉和第2運轉，係能夠進行連續運轉。 [0097] [第4實施形態] 〈氫製造裝置〉 圖5，係為第4實施形態的氫製造裝置30B之概略圖。 圖5之氫製造裝置30B，係為在圖2以及圖3之氫製造裝置30中，於氣體廢棄流路76處設置有氨除害設備90者。 [0098] 亦即是，氣體廢棄流路76，係具備有氨除害設備90，該氨除害設備90，係具備有：第1氣體廢棄流路91，係一端與環狀流路71a連接；和輔助氨吸附裝置92，係與第1氣體廢棄流路91之另外一端連接；和第2氣體廢棄流路93，係與輔助氨吸附裝置92連接，並使從輔助氨吸附裝置92所排出的氣體流通。 [0099] 在本實施形態中，前述輔助氨吸附裝置92，係具備有被並聯地作配設的複數(2個)之輔助氨吸附器92a、92b。 前述第1氣體廢棄流路91，係使上游端與前述環狀流路71a連接，並使下游端分歧而成為複數(2根)的第1分歧流路91a、91b並與前述複數之輔助氨吸附器92a、92b連接。 前述第2氣體廢棄流路93之上游端，係分歧而成為複數(2根)的第2分歧流路93a、93b並與前述複數之輔助氨吸附器92a、92b連接。 [0100] 氨除害設備90，係更進而具備有：再生氣體供給裝置94，係對於前述複數之輔助氨吸附器92a、92b供給再生氣體；和再生氣體流路96(96a、96b)，係一端與前述再生氣體供給裝置94連接，並且另一端分歧為複數(2根)並且與前述第2分歧流路93a、93b連接；和再生氣體加熱器95，係被設置在前述再生氣體流路96之途中，並加熱前述再生氣體。 又，氨除害設備90，係具備有：脫離附著氣體流路97(97a、97b)，係一端分歧為複數(2根)並與前述第1分歧流路91a、91b連接；和廢氣燃燒反應器98，係與前述脫離附著氣體流路97之另外一端連接，並燃燒從前述複數之氨吸附器92a、92b的各者所排出之前述吸附材脫離附著氣體而使燃燒氣體流出；以及回送流路100，係將從前述廢氣燃燒反應器98所排出的燃燒氣體回送至前述第2氣體廢棄流路93處。 在回送流路100處，係設置有將從前述廢氣燃燒反應器所流出的前述燃燒氣體冷卻之廢氣冷卻器99。 又，氨除害設備90，係具備有：旁通流路101，係一端與第1氣體廢棄流路91連接，並且另一端與第2氣體廢棄流路93連接。 [0101] 〈氫製造方法〉 在本實施形態中，係除了能夠實施與第2實施形態相同之氫製造方法以外，更進而能夠實施下述之氨除害工程、輔助氨吸附器之再生工程、以及旁通運轉工程。 [0102] [氨除害工程] 氨除害工程，係為將在前述氣體廢棄流路76中流通的氣體供給至氨除害設備90處並將氨除害之工程。在本實施形態中，係存在有使用輔助氨吸附器92a來將氨除害的情況和使用輔助氨吸附器92b來將氨除害的情況。 例如，係可構成為：將在氣體廢棄流路76中流通之氣體經由第1氣體廢棄流路91以及第1分歧流路91a而供給至輔助氨吸附器92a處，並將氨除害，之後，經由第2分歧流路93a、第2氣體廢棄流路93而排出。 又，亦可構成為：將在氣體廢棄流路76中流通之氣體經由第1氣體廢棄流路91以及第1分歧流路91b而供給至輔助氨吸附器92b處，並將氨除害，之後，經由第2分歧流路93b、第2氣體廢棄流路93而排出。 [0103] 在氨除害工程中，在輔助氨吸附器92a或92b處的運轉條件(溫度、壓力等)，係與在前述之由氨吸附器5a、5b所進行的氨吸附工程中之運轉條件相同。 [0104] 另外，通常，在氣體廢棄流路76內之氣體中的氨濃度，係為就算是直接廢棄也不會造成環境上的問題之程度。故而，係亦可在氫製造裝置30B之運轉開始作業時或運轉停止作業時之非定常運轉時，因應於需要而實施該氨除害工程。藉由此，係能夠確實地防止氨之對於系外的流出。 經由第2氣體廢棄流路93而被排出至系外的氣體中之氨量，係以為25體積ppm以下為理想。故而，較理想，當在第1氣體廢棄流路91中之氣體中的氨量為超過25體積ppm的情況時，係實施該氨除害工程。 [0105] [輔助氨吸附器之再生工程] 輔助氨吸附器之再生工程，係為使在上述之氨除害工程中所使用的輔助氨吸附器92a、92b再生之工程。 例如，在使輔助氨吸附器92a再生的情況時，係在藉由再生氣體加熱器95將從再生氣體供給裝置94送來之含氧氣體作了加熱之後，經由再生氣體流路96、96a、第2分歧流路93a來供給至輔助氨吸附器92a處，並使輔助氨吸附器92a再生。從該輔助氨吸附器92a所排出的氣體，係經由第1分歧流路91a、脫離附著氣體流路97a、97而被供給至廢氣燃燒反應器98處，並使氣體中之可燃性氣體燃燒。燃燒後的氣體，係在藉由廢氣冷卻器99而作了冷卻之後，經由回送流路100以及第2氣體廢棄流路93而被排出。 又，在使輔助氨吸附器92b再生的情況時，係在藉由再生氣體加熱器95將從再生氣體供給裝置94送來之含氧氣體作了加熱之後，經由再生氣體流路96、96b、第2分歧流路93b來供給至輔助氨吸附器92b處，並使輔助氨吸附器92b再生。從該輔助氨吸附器92b所排出的氣體，係經由第1分歧流路91b、脫離附著氣體流路97b、97而被供給至廢氣燃燒反應器98處，並使氣體中之可燃性氣體燃燒。燃燒後的氣體，係在藉由廢氣冷卻器99而作了冷卻之後，經由回送流路100以及第2氣體廢棄流路93而被排出。 [0106] 在輔助氨吸附器之再生工程中，輔助氨吸附器92a或92b的再生條件(溫度、壓力等)，係與在前述之進行氨吸附器5a、5b之再生的氨吸附器再生工程中之運轉條件相同。 又，廢氣燃燒反應器98之運轉條件(溫度、壓力等)，係與前述之燃燒反應裝置36的運轉條件相同。 [0107] (旁通運轉工程) 如同前述一般，在非定常運轉時，係以因應於需要而實施氨除害工程為理想，又，在定常運轉時，係以實施旁通運轉工程為理想。 在旁通運轉工程中，係將在氣體廢棄流路76中流通之氣體經由第1氣體廢棄流路91以及旁通流路101而供給至第2氣體廢棄流路93處，並從第2氣體廢棄流路93將氣體排出。 藉由此，係能夠降低對於氨除害設備90所造成的負擔。 [0108] [第5實施形態] 〈氫製造裝置〉 圖6，係為第5實施形態的氫製造裝置30C之概略圖。 圖6之氫製造裝置30C，係為在圖5之氫製造裝置30B中，代替氨除害設備90而設置有氨除害設備90A者。 氨除害設備90A，係為代替在氨除害設備90中之廢氣燃燒反應器98而使用了燃燒反應裝置36者。 亦即是，在氨除害設備90A中，該脫離附著氣體配管97之其中一端，係分歧為複數(2根：97a、97b)，並與第1分歧流路91a、91b連接。又，該脫離附著氣體配管97之另外一端，係與吸附材再生氣體流路63中之氧供給裝置37之連接位置與燃燒反應裝置36之連接位置之間的位置連接。 又，燃燒氣體流路64和第2氣體廢棄流路93，係經由具備有廢氣冷卻器103之廢氣流路104連接。 [0109] 〈氫製造方法〉 在本實施形態中，係除了能夠實施與第2實施形態相同之氫製造方法以外，更進而能夠實施下述之氨除害工程、輔助氨吸附器之再生工程、以及旁通運轉工程。 [0110] [氨除害工程] 係與第4實施形態相同。 [0111] [輔助氨吸附器之再生工程] 輔助氨吸附器之再生工程，係為使在上述之氨除害工程中所使用的輔助氨吸附器92a、92b再生之工程。 在使輔助氨吸附器92a再生的情況時，係在藉由再生氣體加熱器95將從再生氣體供給裝置94送來之含氧氣體作了加熱之後，經由再生氣體流路96、96a、第2分歧流路93a來供給至輔助氨吸附器92a處，並使輔助氨吸附器92a再生。從該輔助氨吸附器92a所排出的氣體，係經由第1分歧流路91a、脫離附著氣體流路97a、97以及吸附材再生氣體流路63而被供給至燃燒反應裝置36處，並使氣體中之可燃性氣體燃燒。從燃燒反應裝置36所被排出的氣體之一部分，係在藉由廢氣冷卻器103作了冷卻之後，經由第2氣體廢棄流路93而被排出。 又，在使輔助氨吸附器92b再生的情況時，係在藉由再生氣體加熱器95將從再生氣體供給裝置94送來之含氧氣體作了加熱之後，經由再生氣體流路96、96b、第2分歧流路93b來供給至輔助氨吸附器92b處，並使輔助氨吸附器92b再生。從該輔助氨吸附器92b所排出的氣體，係經由第1分歧流路91b、脫離附著氣體流路97b、97以及吸附材再生氣體流路63而被供給至燃燒反應裝置36處，並使氣體中之可燃性氣體燃燒。從燃燒反應裝置36所被排出的氣體之一部分，係在藉由廢氣冷卻器103作了冷卻之後，經由第2氣體廢棄流路93而被排出。 但是，係亦可將從燃燒反應裝置36所被排出的氣體之全部，經由燃燒氣體流路64來供給至加熱機器38處。於此情況，係亦可將具備有廢氣冷卻器103之廢氣流路104省略。 [0112] (旁通運轉工程) 係與第4實施形態相同。 [0113] [第6實施形態] 〈氫製造裝置〉 圖7，係為第6實施形態的氫製造裝置30D之概略圖。 圖7之氫製造裝置30D，係為在圖4之氫製造裝置30A中，設置有氨除害設備90B者。 該氨除害設備90B，係與在第4實施形態中之氨除害設備90相同。 [0114] 〈氫製造方法〉 在本實施形態中，係能夠實施與第3實施形態相同之氫製造方法。 又，在本實施形態中，係能夠實施氨除害工程、輔助氨吸附器之再生工程、以及旁通運轉工程。另外，此些之工程，係與第4實施形態相同。 [0115] [第7實施形態] 〈氫製造裝置〉 圖8，係為第7實施形態的氫製造裝置30E之概略圖。 圖8之氫製造裝置30E，係為在圖4之氫製造裝置30A中，設置有氨除害設備90C者。 該氨除害設備90C，係與在第5實施形態中之氨除害設備90A相同。 [0116] 〈氫製造方法〉 在本實施形態中，係能夠實施與第3實施形態相同之氫製造方法。 又，在本實施形態中，係能夠實施氨除害工程、輔助氨吸附器之再生工程、以及旁通運轉工程。另外，此些之工程，係與第5實施形態相同。[First Embodiment] <Hydrogen Production Apparatus> FIG. 1 is a schematic diagram of a hydrogen production apparatus 1 according to a first embodiment. The hydrogen production device 1 of this embodiment includes: an ammonia supply device 2; and an ammonia decomposition device 3, which is connected to the ammonia supply device 2 and decomposes ammonia to generate decomposed gas containing hydrogen, nitrogen, and unreacted ammonia; The decomposed gas cooling device 4a is connected to the ammonia decomposing device 3 and cools the decomposed gas; and the ammonia adsorption device 5 is connected to the decomposed gas cooling device 4a, and removes unreacted ammonia from the decomposed gas and removes The gas after the removal of ammonia containing hydrogen and nitrogen as the main components is allowed to flow out; and a hydrogen recovery device 6 is connected to the ammonia adsorption device 5 to separate the hydrogen from the gas after the ammonia is removed and flow out, and contains hydrogen and nitrogen The remaining exhaust gas is discharged; and the heating device 8 heats the aforementioned ammonia decomposition device. [0033] The ammonia adsorption device 5 includes a plurality of ammonia adsorbers 5a and 5b arranged in parallel, and is configured to be capable of supplying the decomposed gas sent from the decomposed gas cooling device 4a to the plurality of desorbed gas. Any one of the ammonia adsorbers 5a and 5b. In this embodiment, although the number of the ammonia adsorbers 5a and 5b is two, it may be three or more. [0034] The hydrogen production device 1 further includes an exhaust gas heating device 4b connected to the hydrogen recovery device 6 and heating the exhaust gas. In this embodiment, the exhaust gas heating device 4b is the same heat exchanger (decomposition gas cooling heat exchanger) 4 as the decomposed gas cooling device 4a, and is configured so that Heat exchange is performed between the decomposed gas that has flowed out and the exhaust gas that has flowed out of the hydrogen recovery device 6. As a result, the thermal efficiency is improved. [0035] The ammonia supply device 2 and the ammonia decomposition device 3 are connected via an ammonia flow path 11. (2) The ammonia decomposition device 3 and the ammonia adsorption device 5 are connected via a decomposition gas flow path 12, and in the middle of the decomposition gas flow path 12, the decomposition gas cooling device 4a is connected. In addition, the downstream end of the decomposed gas flow path 12 is divided into a plurality of branched flow paths 12a and 12b (compared with two in this embodiment) and a plurality of (composed in this embodiment with two) All of the ammonia adsorbers 5a and 5b are connected. The ammonia adsorption device 5 and the hydrogen recovery device 6 are connected via a gas flow path 14 after ammonia removal. In addition, the upstream end of the gas flow path 14 after ammonia removal is divided into a plurality of branched flow paths 14a and 14b (compared with two in this embodiment) and a plurality of (in this embodiment, two) All of the ammonia adsorbers 5a and 5b are connected. Each of these branched flow paths 12a, 12b and the branched flow paths 14a, 14b is provided with an on-off valve. The hydrogen production device 1 further includes: a hydrogen flow path 15 connected to the hydrogen recovery device 6 and flowing out hydrogen separated from the gas after the ammonia is removed; and a connection flow path 21 connected between the After the ammonia is removed, the remaining waste gas after the hydrogen has been separated from the gas. One end (upstream end) of the connection flow path 21 is connected to the hydrogen recovery device 6, and the other end (downstream end) is connected to the exhaust gas heating device 4b (decomposed gas cooling heat exchanger 4). [0036] The hydrogen production device 1 includes an exhaust gas flow path 22, one end of which is connected to the exhaust gas heating device 4b (decomposed gas cooling heat exchanger 4), and the other end of which is connected to the plurality of ammonia adsorbers 5a. And 5b are connected, and the aforementioned exhaust gas is supplied to the used ammonia adsorbers 5a, 5b to regenerate the ammonia adsorber; and the adsorption material regeneration gas flow path 23 is connected to a plurality of the aforementioned ammonia adsorbers 5a, 5b, and Circulate the adsorbent regeneration gas (main components are hydrogen, nitrogen, and ammonia) flowing out of the used ammonia adsorbers 5a and 5b; and the combustion reaction device 7 is connected to the adsorbent regeneration gas flow path 23, and The regeneration gas of the adsorbent is burned to cause the combustion gas to flow out; and the combustion gas flow path 24 is connected at one end to the combustion reaction device 7 and at the other end to the heating device 8. The lower end of the above-mentioned exhaust gas flow path 22 is a branched flow path branched into a plurality of branched flow paths (a two in this embodiment) and a branched flow path with a plurality of (two in this embodiment). 14a and 14b are connected more upstream than the on-off valve. The upstream end of the adsorbent regeneration gas flow path 23 is divided into a plurality of branched flow paths 23a, 23b and a plurality of (in this embodiment, two) branched flow paths. The flow paths 12a and 12b are connected further downstream than the on-off valve. Each of these branched flow paths 22a, 22b and the branched flow paths 23a, 23b is provided with an on-off valve. [0037] In this embodiment, the decomposed gas flow path 12 and the ammonia-removed gas flow path 14 are not equipped with a pressurizing device. This makes it possible to reduce equipment costs and operating costs. In this embodiment, the hydrogen production apparatus 1 does not include a pressurizing device. However, a pressurizing device may be provided in at least one of the decomposition gas flow path 12 and the ammonia gas removal path 14. This makes it possible to reduce the pressure of the ammonia decomposition device 3 to increase the ammonia decomposition efficiency, and to increase the pressure of the gas after removing the ammonia flowing into the hydrogen recovery device 6 to improve the hydrogen recovery efficiency. In the case of installing the pressurizing device, it is preferable to install the pressurizing device only at the degassed gas flow path 12 and the ammonia-removed gas flow path 14 after the ammonia-removed gas flow path 14. [0038] (Ammonia Supply Device 2) In this embodiment, the ammonia supply device 2 has a liquid ammonia tank. [0039] (Ammonia Decomposition Device 3) The ammonia decomposition device 3 contains an ammonia decomposition catalyst. The ammonia decomposition catalyst is not particularly limited as long as it has a catalytic activity in the ammonia decomposition reaction, but for example, the system may include a base metal-containing transition metal (iron, cobalt, Nickel, molybdenum, etc.), rare earths (lanthanum, cerium, neodymium, etc.), precious metals (ruthenium, rhodium, iridium, palladium, platinum, etc.) catalysts. The aforementioned base metal transition metals can be used as metal monomers, alloys, nitrides, carbides, oxides, and composite oxides, and the above-mentioned rare earth systems can be used as oxides. The transition metal and the rare earth system are used in a carrier having a high specific surface area such as alumina, silica, magnesia, zirconia, and titania. Moreover, the above-mentioned noble metal system can also be used in a carrier having a high specific surface area such as alumina, silica, magnesia, zirconia, and titania. In addition, the above-mentioned transition metal system and / or the above-mentioned rare earth system may be used by containing a small amount of the noble metal system. These catalysts can be used alone or in combination of two or more. [0040] (Ammonia Adsorption Device 5) 之 The ammonia adsorbers 5a and 5b constituting the ammonia adsorption device 5 contain an ammonia adsorption material. As the ammonia adsorbent, it is not particularly limited as long as it can remove ammonia from the decomposed gas and can be regenerated, and is preferably zeolite, activated carbon, alumina, silica, and composite oxide. [0041] (Hydrogen Recovery Device 6) The hydrogen recovery device 6 is not particularly limited as long as it can separate and take out hydrogen from a decomposed gas (main components: hydrogen and nitrogen) formed by decomposing ammonia. Examples of the hydrogen recovery device 6 include a pressure swing adsorption separation device (PSA device), a temperature swing adsorption separation device (TSA device), and a hydrogen separation membrane device having a hydrogen separation membrane. [Combustion reaction device 7] (i) The combustion reaction device 7 is not particularly limited as long as it can burn the regenerating gas of the adsorbent material flowing out of the ammonia adsorbers 5a and 5b being regenerated, for example, the system Examples thereof include a combustion reaction device and a direct combustion device in which a combustion catalyst is contained. As the catalyst used in the combustion reaction device, palladium may be palladium, platinum, or the like. However, from the viewpoint of cost, palladium is preferable. In the case of a direct combustion device, it is possible to perform combustion by mixing kerosene, natural gas, etc. in the regeneration gas of the adsorbent. (Heating device 8) The heating device 8 is a device that supplies the combustion gas sent from the combustion reaction device 7 to the periphery of the ammonia decomposition device 3 and heats the ammonia decomposition device 3. As the heating device 8, a device for supplying combustion gas to a jacket covering the periphery of the ammonia decomposition device 3, or a pipe for passing the combustion gas around the ammonia decomposition device 3 may be exemplified. [0043] <Hydrogen Production Method> Next, an example of a hydrogen production method using the aforementioned hydrogen production device 1 will be described. In the hydrogen production method of this embodiment, the first operation and the second operation described later are repeatedly performed. [0044] (First operation) In the first operation, the production of hydrogen is performed using the ammonia adsorber 5a, and the regeneration of the ammonia adsorbent in the ammonia adsorber 5b is performed. That is, the first operation is a heating process including an ammonia decomposition process, an ammonia adsorption process, a hydrogen recovery process, an ammonia adsorber regeneration process, and an ammonia decomposition device described later. [Ammonia Decomposition Project] Ammonia decomposition project is to circulate the ammonia sent from the ammonia supply device 2 to the ammonia decomposition device 3 and decompose the ammonia to produce the foregoing containing hydrogen, nitrogen, and unreacted ammonia. Decomposition of gas. The temperature in the ammonia decomposition device 3 is preferably 400 to 800 ° C. If the temperature is 400 ° C or higher, the decomposition system of ammonia is promoted, and the content of unreacted ammonia in the decomposition gas is reduced. If the temperature is 800 ° C. or lower, the degradation system of the ammonia decomposition catalyst is suppressed, and the energy consumption system is suppressed. From this point of view, the temperature in the ammonia decomposition device 3 is more preferably 430 to 650 ° C, more preferably 450 to 550 ° C, and even more preferably 480 to 520 ° C. [0046] The pressure in the ammonia decomposition device 3, more preferably 0. 0 to 1. 0 MPaG (gauge pressure). If the pressure is 0. Above 0 MPaG, it is possible to prevent the atmosphere from leaking into the device. If the pressure is 1. Below 0 MPaG, the ammonia decomposition reaction is a balanced reaction that increases the number of molecules, so that the content of unreacted ammonia in the decomposition gas can be reduced. From this point of view, the pressure in the ammonia decomposition device 3 is more preferably 0. 2 to 0. 8MPaG, which is more ideal, is 0. 3 to 0. 7MPaG, even more ideal, is 0. 45 to 0. 55MPaG. [Ammonia adsorption process] Ammonia adsorption process is to circulate the decomposition gas flowing out of the ammonia decomposition device 3 by the implementation of the ammonia decomposition project to the decomposition gas cooling device 4a (for decomposition gas cooling). After cooling at the heat exchanger 4), it is made to flow to one of the plurality of ammonia adsorbers 5a and 5b (ammonia adsorber 5a), and the unreacted ammonia is adsorbed and removed from the decomposition gas to obtain the foregoing. Engineering of gas after ammonia removal. The temperature in the ammonia adsorber 5a is preferably 10 to 100 ° C. If the temperature is 10 ° C or higher, it becomes a cooling device that does not require gas, and energy consumption can be reduced. When the temperature is 100 ° C or lower, the amount of ammonia adsorbed becomes large. From this point of view, the temperature in the ammonia adsorber 5a is more preferably 15 to 80 ° C, more preferably 20 to 60 ° C, and even more preferably 25 to 50 ° C. [0048] The pressure inside the ammonia adsorber 5a, more preferably 0. 1 to 1. 0MPaG. If the pressure is 0. Above 1 MPaG, the ammonia adsorption amount per unit of the ammonia adsorbent becomes large. Also, if the pressure is 1. Below 0 MPaG, it is possible to reduce the amount of energy used to boost the gas. From this point of view, the pressure inside the ammonia adsorber 5a is more preferably 0. 15 to 0. 8MPaG, which is more ideal, is 0. 2 to 0. 6MPaG, even more ideal, is 0. 25 to 0. 5MPaG. [0049] The pressure P1 of the ammonia decomposition device 3 and the pressure P2 in the ammonia adsorber 5a may be set to P1 ≧ P2. As a result, it becomes unnecessary to provide a pressurizing device between the ammonia decomposition device 3 and the ammonia adsorber 5a, and the running cost and the equipment cost are suppressed. Also, from the viewpoint of using the pressure of the ammonia adsorber 5a to perform hydrogen recovery at the downstream hydrogen recovery device 6, the pressure inside the ammonia adsorber 5a is more preferably 0. 2 to 0. 8MPaG, which is more ideal, is 0. 25 to 0. 6MPaG, even more ideal, is 0. 3 to 0. 5MPaG. [Hydrogen Recovery Project] A hydrogen recovery project is to circulate a gas to the hydrogen recovery device after removing the ammonia flowing out of one of the plurality of ammonia adsorbers 5a and 5b (ammonia adsorber 5a). Six processes for removing hydrogen from the aforementioned ammonia to separate the hydrogen and let it flow out, and discharge the remaining waste gas. [0051] The temperature in the hydrogen recovery device 6 is preferably 10 to 60 ° C. The pressure in the tritium hydrogen recovery device 6 is more preferably 0. 1 to 1. 0MPaG. The pressure P3 of the ammonia decomposition device 3, the pressure P2 of the ammonia adsorption device 5 (ammonia adsorber 5a), and the pressure P3 of the hydrogen recovery device 6 can also be set to satisfy P1 ≧ P2 ≧ P3. relationship. As a result, it is not necessary to provide a pressurizing device between the ammonia decomposition device 3 and the ammonia adsorber 5a, and between the ammonia adsorber 5a and the hydrogen recovery device 6, and the running cost and equipment cost are suppressed. [Ammonia Adsorber Regeneration Project] Ammonia adsorber regeneration project is to circulate the exhaust gas flowing out of the hydrogen recovery device 6 to the exhaust gas heating device 4b (decomposed gas cooling heat exchanger 4) and the foregoing. A process for regenerating the ammonia adsorber (ammonia adsorber 5b) at the remainder of the plurality of ammonia adsorbers 5a, 5b (for example, when the ammonia adsorber 5a is being used, the ammonia adsorber 5b). When three or more ammonia adsorbers 5 are present, the regeneration process can be applied to at least one of the device groups that are not ammonia adsorbers. As described above, the ammonia-removed gas supplied to the hydrogen recovery device 6 is removed from the ammonia decomposition gas (hydrogen, nitrogen, and unreacted ammonia) at the ammonia adsorption device 5. Therefore, the ammonia content in the exhaust gas flowing out from the hydrogen recovery device 6 is small. Therefore, by circulating the exhaust gas to the ammonia adsorber 5b after heating the exhaust gas, the ammonia adsorbed on the ammonia adsorbent can be well desorbed and adhered, and the ammonia adsorbent can be regenerated. In addition, while the ammonia adsorber 5b is being regenerated, the ammonia adsorber 5a can be used to adsorb and remove ammonia from the decomposed gas. [0053] The temperature in the ammonia adsorber 5b when the ammonia is desorbed is preferably 100 to 500 ° C. If the temperature is 100 ° C or higher, the ammonia adsorbent can be sufficiently regenerated. If the temperature is 500 ° C. or higher, the adsorbent may be deteriorated. From this point of view, the temperature in the ammonia adsorber 5b is more preferably 200 to 450 ° C, more preferably 300 to 430 ° C, and even more preferably 380 to 420 ° C. [0054] The pressure inside the ammonia adsorber 5b, more preferably 0. 0 to 0. 5MPaG. If the pressure is 0. Above 0 MPaG, it is not necessary to perform vacuum pumping, and it does not need to consume energy. Also, if the pressure is 0. Below 5 MPaG, ammonia can be sufficiently desorbed. From this point of view, the pressure inside the ammonia adsorber 5b is more preferably 0. 0 to 0. 45MPaG, which is more ideal, is 0. 0 to 0. 4MPaG, even more ideal, is 0. 0 to 0. 3MPaG. 005 [0055] [Heating engineering of ammonia decomposition device] 装置 Heating engineering of ammonia decomposition device, It is to generate thermal energy by burning the regeneration gas of the adsorbent flowing out of the ammonia adsorber 5b with the combustion reaction device 7, This combustion gas is passed through the combustion gas flow path 4 to the heating device 8 to heat the ammonia decomposition device 3. Regeneration gas from the adsorbent flowing out of the ammonia adsorber 5b, The system contains ammonia that has been removed from the ammonia adsorber 5b. also, The system also includes hydrogen contained in the exhaust gas, which is not recovered by the hydrogen recovery device 6. Therefore, By burning the adsorbent regeneration gas with the combustion reaction device 7, System can get high temperature combustion gas. also, The ammonia decomposition device 3 is heated by using this high-temperature combustion gas, The system can sufficiently heat the ammonia decomposition device 3. [0056] (Second operation) After continuing the aforementioned first operation, The second operation described below is performed. In the second operation, Part or all of the ammonia adsorber regenerated in the first operation (ammonia adsorber 5b), To carry out the ammonia adsorption project, also, The ammonia adsorber (ammonia adsorber 5a) used in the ammonia adsorption process in the first operation And the ammonia adsorber regeneration project is implemented. In addition, Other works, That is, ammonia decomposition project, Hydrogen recovery project and heating project of ammonia decomposition plant, The system is the same as the first operation. So this, By repeatedly performing the first operation and the second operation, The system is capable of continuous operation. [0057] [Second Embodiment] <Hydrogen Production Device> FIG. 2 This is a schematic view of a hydrogen production apparatus 30 according to the second embodiment. image 3, It is a schematic diagram for explaining a first operation using the hydrogen production apparatus 30 of FIG. 2. 氢 The hydrogen production device 30 of this embodiment, Is equipped with an ammonia supply device 31, And ammonia decomposition device 32, And decomposed gas cooling device 33a (decomposed gas cooling heat exchanger 33), And ammonia adsorption device 34, And hydrogen recovery device 35, And heating machine 38. The ammonia adsorption device 34, There are a plurality of ammonia adsorbers 34a (two in this embodiment) arranged in parallel, 34b. 装置 These devices 31, 32, 33a (33), 34, 35, The detailed composition of 38, This is as described in the first embodiment. As described below, In this embodiment, Decomposed gas cooling device 33a, Is a decomposed gas cooling heat exchanger 33, It also serves as the exhaust gas heating device 33b. [0058] Again, Hydrogen production device 30, Is equipped with an ammonia flow path 41 connecting the ammonia supply device 31 and the ammonia decomposition device 32, And a decomposition gas flow path 42 connecting the ammonia decomposition device 32 and the ammonia adsorption device 34, And the gas flow path 43 after removing the ammonia connecting the ammonia adsorption device 34 and the hydrogen recovery device 35, And a hydrogen flow path 44 through which the hydrogen separated by the hydrogen recovery device 35 flows out. The above-mentioned decomposition gas flow path 42, One end (upstream end) is connected to the ammonia decomposition device 32, And the other end side diverges to become a branched flow path 42a, 42b, The branch flow path 42a is connected to the ammonia adsorber 34a. The branch flow path 42b is connected to the ammonia adsorber 34b. Branch flow path 42a, Each of 42b, It is equipped with an on-off valve. Alas, After the ammonia is removed, the gas flow path 43, One end (upstream end) diverges to become a branched flow path 43a, 43b, The branch flow path 43a is connected to the ammonia adsorber 34a. The branch flow path 43b is connected to the ammonia adsorber 34b. also, The other end of the gas flow path 43 after the ammonia is removed, The system is connected to the hydrogen recovery device 35 in combination. Branch flow path 43a, 43b each, It is equipped with an on-off valve. At the above-mentioned ammonia flow path 41, A flow control valve V1 is provided. also, In the above-mentioned hydrogen flow path 44, A pressure control valve V2 is provided. [0059] On the downstream side of the ammonia flow path 41 than the flow control valve V1, From the upstream side (the ammonia supply device 31 side), an ammonia heating heat exchanger 51 and an ammonia auxiliary heating heat exchanger 52 are provided in this order. 较 In the above-mentioned decomposition gas flow path 42, the branched flow path 42a, 42b is more upstream, The decomposed gas cooling device 33a (decomposed gas cooling heat exchanger 33) is sequentially installed from the upstream side (the ammonia decomposition device 32 side), The ammonia heating heat exchanger 51 and the water heating heat exchanger 54. Is also, The ammonia flow path 41 and the decomposed gas flow path 42 intersect each other. At the intersection, The above-mentioned ammonia heating heat exchanger 51 is provided. Therefore, On one of the tube side and the shell side of the ammonia heating heat exchanger 51, There is ammonia in circulation, At the other, There is decomposed gas in circulation, And it becomes possible to perform heat exchange between ammonia and decomposed gas. [0060] Further, Hydrogen production device 30, The department has: Connection flow path 61 connected to the hydrogen recovery device 35, An exhaust gas heating device 33b (decomposed gas cooling heat exchanger 33) which is connected to the hydrogen recovery device 35 via the connection flow path 61 and heats the exhaust gas flowing from the hydrogen recovery device 35 through the connection flow path 61. In this embodiment, The aforementioned decomposed gas cooling device 33a and the exhaust gas heating device 33b, Is the same heat exchanger (decomposed gas cooling heat exchanger 33), In addition, it is configured to allow heat exchange between the decomposed gas flowing out of the ammonia decomposition device 32 and the exhaust gas flowing out of the hydrogen recovery device 35. [0061] Again, Hydrogen production device 30, The department has: Waste gas flow path 62, One end is connected to the exhaust gas heating device 33b (decomposed gas cooling heat exchanger 33), And the other end is different from the aforementioned plural ammonia adsorbers 34a, 34b connection, Furthermore, by supplying the exhaust gas to the used ammonia adsorber, the ammonia adsorber can be regenerated. Is also, One end (upstream end) of the exhaust gas flow path 62, It is connected to the exhaust gas heating device 33b (decomposed gas cooling heat exchanger 33), The other end is divided and becomes a branched flow path 62a, 62b, The branched flow path 62a is connected to the branched flow path 43a of the gas flow path 43 after the ammonia is removed, which is more upstream than the on-off valve, The branched flow path 62b is connected to the branched flow path 43b of the gas flow path 43 after the ammonia removal described above on the upstream side of the on-off valve. These divergent flow paths 43a, 43b each, It is equipped with an on-off valve. [0062] Again, Hydrogen production device 30, The department has: Adsorption material regeneration gas flow path 63, The above-mentioned ammonia adsorber 34a, 34b connection, Make the regeneration gas of the adsorbent material flowing out of the previously used ammonia adsorbent circulate; And combustion reaction device 36, It is connected to the regeneration gas flow path 63 of the adsorbent material. And burn the regeneration gas of the adsorption material to make the combustion gas flow out; And combustion gas flow path 64, One end is connected to the aforementioned combustion reaction device 36, The other end is connected to the aforementioned heating device 38. In detail, The adsorbent regeneration gas flow path 63, The one end (upstream end) diverges and becomes a branched flow path 63a, 63b, The branch flow path 63a is connected to the branch flow path 42a of the aforementioned decomposed gas flow path 42 on the downstream side of the on-off valve, The branch flow path 63b is connected to the branch flow path 42b of the decomposed gas flow path 42 described above on the downstream side from the on-off valve. That is, Adsorption material regeneration gas flow path 63, It is a branched flow path 42a via the aforementioned decomposed gas flow path 42, 42b and ammonia adsorber 34a, 34b connected. The adsorbent regeneration gas flow path 63, The other end is connected to the combustion reaction device 36. These divergent flow paths 63a, Each of 63b, It is equipped with an on-off valve. [0063] In this embodiment, In the adsorbent regeneration gas flow path 63, the branched flow path 63a, 63b Further downstream, The system is provided with an oxygen supply device 37. [0064] Further, Hydrogen production device 30, The department has: Circulating gas flow path 71, One end is connected to the aforementioned heating machine 38, The other end is connected to the adsorption material regeneration gas flow path 63. At one or both of the adsorbent regeneration gas flow path 63 and the circulating gas flow path 71, The system is connected to an oxygen supply device 37. In addition, In this embodiment, An oxygen supply device 37 is connected to the adsorbent regeneration gas flow path 63. [0065] Hydrogen production device 30, The system includes a heated water supply device 80. The heated water supply device 80, Is provided with a water flow path 81 intersecting the circulation gas flow path 71, And a warm water heating heat exchanger 73 provided at an intersection of the circulating gas flow path 71 and the water flow path 80, And a shower head 82 provided at a downstream end of the water flow path 81. Therefore, By circulating circulating gas through one of the tube side and the shell side of the warm water heating heat exchanger 73 and passing warm water through the other, To be able to exchange heat between circulating gas and warm water, The warm water system flowing through the water flow path 81 is heated and becomes heated water. Also, The internal fluid existing from the water heating heat exchanger 54 to the warm water heating heat exchanger 73, Called "warm water", And the internal fluids that are more downstream than that, Called "heated water." [0066] Again, At a position upstream of the hot water heating heat exchanger 73 in the water flow path 81, It is different from the aforementioned decomposed gas flow path 42 and becomes a branched flow path 42a, The position of 42b is more upstream and intersects with a position further downstream than the ammonia heat exchanger 51, And become an intersection, At that intersection, A water heating heat exchanger 54 is provided. By passing decomposed gas through one of the tube side and the shell side of the water heating heat exchanger 54 and passing the water through the other, It is possible to exchange heat between the decomposed gas and water. In the circulating gas flow path 71, further downstream than the warm water heating heat exchanger 73, A drainage tank 74 is provided to remove water from the circulating gas. [0067] The aforementioned circulating gas flow path 71, The first point located further upstream from the warm water heating heat exchanger 73 and the second point located further downstream from the drain tank 74 intersect each other. And become an intersection, A portion between the first point and the second point in the circulating gas flow path 71, Becomes an annular flow path 71a, At that intersection, A heat exchanger 72 for circulating gas is provided. Therefore, Combustion gas (circulation gas) flowing from the combustion gas flow path 64 into the circulating gas flow path 71 through the heating device 38, After passing through one of the tube side and the shell side of the heat exchanger 72 for circulating gas, Circulates in the annular flow path 71a in the circulating gas flow path 71, then, Pass the other of the tube side and the shell side of the heat exchanger 72 for circulating gas. At this annular flow path 71a, The above-mentioned warm water heating heat exchangers 73, The drain tank 74 and the circulation machine 75. [0068] Again, From a position downstream of the drain tank 74 in the circulating gas flow path 71 and upstream of the circulation machine 75, The system has a gas waste flow path 76. but, This gas waste flow path 76, Whatever the position of the circulating gas flow path 71 is, it may diverge. [0069] At the midway point of the aforementioned combustion gas flow path 64 and at the site further upstream of the circulation gas heat exchanger 72 in the aforementioned circulation gas flow path 71, One end and the other end of the bypass flow path 77 are connected respectively. 该 bypass 流 路 77 ， The bypass flow path 77, Intersects the aforementioned ammonia flow path 41, At that intersection, The aforementioned ammonia-assisted heating heat exchanger 52 is provided. Therefore, By passing ammonia through one of the tube side and the shell side of the ammonia-assisted heating heat exchanger 52 and passing the combustion gas through the other, It is possible to heat ammonia by heat exchange between ammonia and combustion gases. [0070] In addition, In this embodiment, The decomposed gas flow path 42 and the ammonia-removed gas flow path 43, The system is not equipped with a pressure device. With this, The system can reduce equipment costs and operating costs. But, It is also possible to use at least one of the decomposition gas flow path 42 and the ammonia gas removal path 43 after removal of ammonia, Install a pressurizing device. With this, It is able to reduce the pressure of the ammonia decomposition device 32 and improve the efficiency of ammonia decomposition. In addition, the pressure of the gas after removing the ammonia flowing into the hydrogen recovery device 35 is increased to improve the hydrogen recovery efficiency. When this pressurizing device is installed, More ideally, It is provided only in the decomposed gas flow path 42 and the ammonia-removed gas flow path 43 in the ammonia-removed gas flow path 43. [0071] (combustion reaction device) combustion reaction device 36, As long as it can burn hydrogen and ammonia, Is not specifically limited, but, From the standpoint of efficient combustion, More ideally, Department of containment of combustion catalysts. As a catalyst used in a combustion reaction device, Examples include palladium, Platinum, etc. but, From a cost perspective, It is preferably palladium. [0072] (Oxygen Supply Device) Regarding the oxygen-containing gas supplied from the oxygen supply device 37, Department is not specifically limited, And can list air, Oxygen, etc. supplied from an oxygen cylinder, but, From a safety and economic standpoint, Air is ideal. Oxygen supply device 37, As long as it can supply oxygen to the adsorbent regeneration gas flow path 36, Is not specifically limited, Various compressors can be cited. (Circulation machine) About the circulation machine 75, Department is not specifically limited, Examples include blowers, fan, Various compressors. (Heated water supply device) heated water supply device 80, As before With water flow path 81, And a shower head 82 provided at the front end of the water flow path 81, And a water heating heat exchanger 54 and a warm water heating heat exchanger 73 provided in the water flow path 81. With this device, The heated water can be supplied to the ammonia supply device 31 and the ammonia inside can be heated. [0073] <Hydrogen Manufacturing Method> Next, An example of a hydrogen production method using the aforementioned hydrogen production apparatus 30 will be described. In the hydrogen production method of this embodiment, The first operation and the second operation described later are repeatedly performed. [0074] (First operation) During the first operation, The production of hydrogen is performed using the ammonia adsorber 34a, In addition, regeneration of the ammonia adsorbent in the ammonia adsorber 34b is performed. Is also, The first operation, It is equipped with ammonia decomposition process described later, And ammonia adsorption engineering, And hydrogen recovery engineering, And ammonia adsorber regeneration project, And ammonia decomposition plant heating project, And combustion gas cycle engineering, And water heating works. [0075] [Ammonia Decomposition Project] Ammonia Decomposition Project, In order to circulate the ammonia sent from the ammonia supply device 31 to the ammonia decomposition device 32, And decompose ammonia, Which contains hydrogen, The aforementioned decomposition of nitrogen and unreacted ammonia. Is also, First of all, Before the ammonia decomposition project, As explained in the water heating process described later, Heating water is supplied to the ammonia supply device 31 from the shower head 82 of the heating water supply device 80. With this, Liquid ammonia type gasification in the ammonia supply device 31, It flows through the ammonia flow path 41. 氨 ammonia in ammonia flow path 41, After the flow is adjusted by the flow control valve V1, It is heated by the ammonia heating heat exchanger 51 and the ammonia auxiliary heating heat exchanger 52, Then, it flows to the ammonia decomposition device 32. In the ammonia decomposition device 32, Ammonia decomposition, And produce hydrogen, The aforementioned decomposition gas of nitrogen and unreacted ammonia. Regarding the temperature and pressure in the ammonia decomposition device 32, This is as described in the first embodiment. [0076] [Ammonia adsorption project] Ammonia adsorption project, This is to circulate the decomposed gas flowing out of the ammonia decomposition device 32 by the implementation of the ammonia decomposition project to the decomposed gas cooling device 33a (decomposed gas cooling heat exchanger 33) After the ammonia heating heat exchanger 51 and the water heating heat exchanger 54 are cooled, Circulate it to the plurality of ammonia adsorbers 34a, 34b (ammonia adsorber 34a) is a process of adsorbing and removing unreacted ammonia from the aforementioned decomposed gas to obtain the aforementioned ammonia-removed gas. Regarding the temperature and pressure in the ammonia adsorber 34a, This is as described in the first embodiment. 007 [0077] [hydrogen recovery project] hydrogen recovery project, It is for the ammonia adsorbers 34a, The ammonia-removed gas flowing out of one of the aforementioned 34b (ammonia adsorber 34a) flows to the hydrogen recovery device 35 and the hydrogen-removed gas separates the hydrogen and flows out, and discharges the remaining exhaust engineering. Regarding the temperature and pressure in the hydrogen recovery device 35, This is as described in the first embodiment. [0078] In addition, In this embodiment, The department has: Hydrogen flow path 44, Is connected to the aforementioned hydrogen recovery device 35, And cause the hydrogen separated by the aforementioned hydrogen recovery device 35 to flow out; And pressure control valve V2, The system is provided at the hydrogen flow path 44. also, In this embodiment, From the ammonia supply device 31 through the ammonia flow path 41, Ammonia decomposition device 32, Decomposed gas flow path 42, In the flow path from the ammonia adsorption device 34 to the gas flow path 43 after the ammonia is removed, There is no heating device other than a heat exchanger, That is, there are no heaters in the form of energy supply. Therefore, By controlling the pressure control valve V2, The pressure P1 of the ammonia decomposition device 32 can be Each of the pressure P2 of the ammonia adsorption device 34 (ammonia adsorber 34a) and the pressure P3 of the hydrogen recovery device 35, It is set to a specific pressure range satisfying the relationship of P1 ≧ P2 ≧ P3. 00 [0079] [Ammonia adsorber regeneration project] Ammonia adsorber regeneration project, Is the aforementioned exhaust gas flowing from the aforementioned hydrogen recovery device 35, Circulates to the exhaust gas heating device 33b (decomposed gas cooling heat exchanger 33) and heats it, Thereafter, it is circulated to the remainder of the plurality of ammonia adsorbers 34a and 34b (for example, When the ammonia adsorber 34a is being used, It is a process for removing ammonia from the ammonia adsorber 34b) and regenerating the ammonia adsorber (ammonia adsorber 34b). [0080] As before, The ammonia-removed gas supplied to the hydrogen recovery device 35, At the ammonia adsorption device 34 upstream from it, Decompose gas from ammonia (hydrogen, Nitrogen and unreacted ammonia). Therefore, The ammonia content in the exhaust gas flowing from the hydrogen recovery device 35, Department is a small amount. therefore, By circulating the exhaust gas to the ammonia adsorber 34b after heating the exhaust gas, It is able to make the ammonia adsorbed on the ammonia adsorbent detach and adhere well. Instead, regeneration is possible. Alas, While the ammonia adsorber 34b is being regenerated, The ammonia adsorber 34a can be used to adsorb and remove ammonia from the decomposed gas. Regarding the temperature and pressure in the ammonia adsorber 34b, This is as described in the first embodiment. [0081] [Heating Engineering of Ammonia Decomposing Device] In the heating engineering of ammonia decomposing device 32, First, the adsorbent regenerating gas flowing from the ammonia adsorber 34b is regenerated. An oxygen-containing gas sent from the oxygen supply device 37 and a circulating gas sent from a circulating gas flow path 71 described later are mixed to prepare a mixed gas. then, This mixed gas is supplied to the aforementioned combustion reaction device 36 and burned, A high-temperature combustion gas is obtained. then, This combustion gas is caused to flow through the combustion gas flow path 64 to the heating device 38. So this, In this embodiment, Thanks to the combustion reaction device 36, Regenerating the adsorbent gas, A mixed gas in which a circulating gas and an oxygen-containing gas described later are mixed is burned. Therefore, The composition of the mixed gas is adjusted by adjusting the mixing amount of the circulating gas and the oxygen-containing gas, This enables the mixed gas to be efficiently burned. also, By using part or all of the circulating gas, The amount of gas that can be heat exchanged with the ammonia decomposition device 32 can be increased. With this, The system can improve energy efficiency. Regarding the temperature of the adsorbent regeneration gas supplied to the combustion reaction device 36, The temperature in the combustion reaction device 36 and the pressure in the combustion reaction device 36, This is as described in the first embodiment. 008 [0082] [Combustion gas cycle engineering] Combustion gas cycle engineering, In order to circulate the combustion gas heated by the ammonia decomposition device 32 as a circulating gas to the circulating gas heat exchanger 72 and the warm water heating heat exchanger 73 and cool it, The water condensed by cooling is removed by the drain tank 74, Next, a part or all of the cooled circulating gas is recirculated to the circulating gas heat exchanger 72 and heated, A process in which the regeneration gas and the oxygen-containing gas are passed to the combustion reaction device 36 and burned together with the adsorbent regeneration gas and the oxygen-containing gas. By cooling the circulating gas in this way, Can reduce the volume of circulating gas, With this, The miniaturization of the cycle machine 75 is possible. Also, When a part of the circulating gas heated by the ammonia decomposition device 32 is circulated to the combustion reaction device 36 and burned together with the adsorbent regeneration gas, The system only needs to discharge the remainder of the circulating gas to the outside of the system through the gas waste flow path 76. Stop here, The gas flowing in the circulating gas flow path after the combustion gas has passed through the ammonia decomposition device, It is called circulating gas. [0083] If the aforementioned mixed gas is combusted by the aforementioned combustion reaction device 36, At least one of hydrogen and ammonia in the mixed gas reacts with the oxygen system and generates water. Therefore, In this embodiment, After the water is removed by the drain tank 74 provided in the circulation gas flow path 71, Together with the adsorbent regeneration gas, it flows to the combustion reaction device 36 and is burned. 008 [0084] [Water heating project] Water heating project, It is a project to heat ammonia by heating water. More specifically, After the water is made to flow through the water heating heat exchanger 54 and the warm water heating heat exchanger 73 to form heated water, The heated water is supplied from the shower head 82 to the ammonia supply device 31, Process for gasifying ammonia. 温度 The temperature of the heated water flowing from the shower head 82, More ideally, 0 ～ 80 ℃, More ideally, 10 ～ 60 ℃, And more ideally, It is 20 ～ 50 ℃, Even more ideally, The temperature is 30 to 45 ° C. [0085] (Second operation) After continuing the aforementioned first operation, The second operation described below is performed. In the second operation, The ammonia adsorption process is performed using the ammonia adsorber 34b that was regenerated during the first operation. Then, the ammonia adsorber 34a that has been subjected to the ammonia adsorption process during the first operation is used to perform the ammonia adsorber regeneration process. In addition, Other works, That is, ammonia decomposition project, Hydrogen recovery project and heating project of ammonia decomposition plant, The system is the same as the first operation. So this, By repeatedly performing the first operation and the second operation, The system is capable of continuous operation. [0086] [Third Embodiment] <Hydrogen Production Device> FIG. 4 This is a schematic view of a hydrogen production apparatus 30A according to the third embodiment. 30 FIG. 4 hydrogen production device 30A, It is attached to the hydrogen production device 30 in FIG. 2 and FIG. 3, Remodeled as follows: That is, System does not use combustion gas for recycling, That is, the combustion gas after the heating ammonia decomposition device 32 passes through the heating device 38 is no longer returned to the combustion reaction device 36 and is discarded outside the hydrogen production device. Then, the mixed gas of the adsorbent regeneration gas and the oxygen-containing gas is supplied to the combustion reaction device 36 to be burned. Is also, Hydrogen production device 30A, At the hydrogen production facility 30, The circulating gas flow path 71 and the piping and devices and the oxygen supply device 37 provided in the circulating gas flow path 71 are omitted. In addition, piping and devices described later are installed. [0087] <devices that do not exist in the hydrogen production device 30A> Hydrogen production apparatus 30A of FIG. 4, The system does not have a circulating gas flow path 71 at the hydrogen production device 30. Circulating gas heat exchanger 72, Hot water heating heat exchanger 73, Excretion tank 74, Cycle machine 75, The gas waste channel 76 and the oxygen supply device 37. [0088] <Apparatus added to hydrogen production apparatus 30A> As shown in FIG. 4, Hydrogen production device 30A, The department has: Heat recovery flow path 71A, One end is connected to the heating machine 38, And the other end is connected to the drain tank 74A. also, At the drain tank 74A, A gas waste flow path 76A is connected. Heat recovery flow path 71A, Intersects the oxygen supply flow path 37B, At that intersection, An oxygen heat exchanger 72A is provided. Gas in heat recovery flow path 71A, By one of the tube side and the shell side of the oxygen heating heat exchanger 72A, The gas system in the oxygen supply flow path 37B passes the other. One end of the oxygen supply flow path 37B, Is connected to the oxygen supply device 37A, At the other end, It is a branched flow path 63a, which is different from the adsorbent regeneration gas flow path 63. 63b is connected further downstream. Alas, In the heat recovery flow path 71A, a place further downstream than the aforementioned oxygen heat exchanger 72A, It intersects the place in the water flow path 81 which is further downstream than the water heating heat exchanger 54, At that intersection, A warm water heating heat exchanger 73A is provided. Gas in heat recovery flow path 71A, One of the tube side and the shell side of the warm water heating heat exchanger 73A, The warm water of the water flow path 81B passes the other. The downstream end of the water flow path 81, It is connected to the shower head 82. Also, The internal fluid existing from the water heating heat exchanger 54 to the warm water heating heat exchanger 73A, Called "warm water", And the internal fluids that are more downstream than that, Called "heated water." The structure other than the above of the tritium hydrogen production apparatus 30A, Is the same as the hydrogen production device 30, Same component symbol, Departments represent the same devices or piping. [0089] <Hydrogen Production Method> Next, An example of a hydrogen production method using the aforementioned hydrogen production apparatus 30A will be described. In the hydrogen production method of this embodiment, The first operation and the second operation described later are repeatedly performed. [0090] (First operation) During the first operation, The production of hydrogen is performed using the ammonia adsorber 34a, In addition, regeneration of the ammonia adsorbent in the ammonia adsorber 34b is performed. Is also, The first operation, It is equipped with ammonia decomposition process described later, And ammonia adsorption engineering, And hydrogen recovery engineering, And ammonia adsorber regeneration project, And ammonia decomposition plant heating project, And heat recovery engineering, And water heating works. [0091] [Ammonia Decomposition Process] The system is the same as the second embodiment. [Ammonia Adsorption Process] The actinide system is the same as the second embodiment. [Hydrogen Recovery Process] The actinide system is the same as the second embodiment. [Ammonia adsorber regeneration process] The system is the same as the second embodiment. [0092] [Heating Engineering of Ammonia Decomposing Device] First, the adsorbent regenerating gas flowing from the ammonia adsorber 34b is regenerated. It is mixed with the oxygen-containing gas sent from the oxygen supply device 37A to form a mixed gas. then, This mixed gas is supplied to the aforementioned combustion reaction device 36 and burned, A high-temperature combustion gas is obtained. then, This combustion gas is passed through the combustion gas flow path 64 to the heating device 38, With this, To heat the ammonia decomposition device 32. So this, In this embodiment, Thanks to the combustion reaction device 36, A mixed gas that mixes the regeneration gas of the adsorbent and the oxygen-containing gas is burned. Therefore, By adjusting the amount of oxygen-containing gas and adjusting the composition of the mixed gas, This enables the mixed gas to be efficiently burned. Regarding the temperature of the adsorbent regeneration gas supplied to the combustion reaction device 36, The temperature in the combustion reaction device 36 and the pressure in the combustion reaction device 36, This is as described in the first embodiment. 009 [0093] [Heat recovery project] Heat recovery project, This is to allow the combustion gas heated by the ammonia decomposition device 32 to flow through the oxygen heat exchanger 72A and the warm water heat exchanger 73A and cool them. The water condensed by cooling is removed by the drain tank 74A, Next, it is discharged out of the system through the gas waste flow path 76A. [0094] If the mixed gas is burned by the combustion reaction device 36, At least one of hydrogen and ammonia in the mixed gas reacts with the oxygen system and generates water. Therefore, In this embodiment, After the water is removed by the drain tank 74A provided in the heat recovery flow path 71A, Drained out of the system. 009 [0095] [Water heating project] Water heating project, It is a project to heat ammonia by heating water. More specifically, After the water is made to flow through the water heating heat exchanger 54 and the warm water heating heat exchanger 73A and heated water is produced, The heated water is supplied from the shower head 82 to the ammonia supply device 31, Process for gasifying ammonia. 温度 The temperature of the heated water flowing from the shower head 82, More ideally, 0 ～ 80 ℃, More ideally, 10 ～ 60 ℃, And more ideally, It is 20 ～ 50 ℃, Even more ideally, The temperature is 30 to 45 ° C. [0096] (Second operation) After continuing the aforementioned first operation, The second operation described below is performed. In the second operation, The ammonia adsorption process is performed using the ammonia adsorber 34b that was regenerated during the first operation. Then, the ammonia adsorber 34a that has been subjected to the ammonia adsorption process during the first operation is used to perform the ammonia adsorber regeneration process. In addition, Other works, The system is the same as the first operation. So this, By repeatedly performing the first operation and the second operation, The system is capable of continuous operation. [0097] [Fourth Embodiment] <Hydrogen Production Apparatus> FIG. 5 This is a schematic view of a hydrogen production apparatus 30B according to the fourth embodiment. The hydrogen production device 30B of FIG. 5, In the hydrogen production device 30 shown in Figs. 2 and 3, An ammonia detoxification device 90 is provided at the gas waste flow path 76. [0098] That is, Gas waste flow path 76, Equipped with ammonia detoxification equipment 90, The ammonia removal equipment 90, The department has: The first gas waste flow path 91, One end of the system is connected to the annular flow path 71a; And auxiliary ammonia adsorption device 92, It is connected to the other end of the first gas waste flow path 91; And the second gas waste flow path 93, Is connected to the auxiliary ammonia adsorption device 92, The gas discharged from the auxiliary ammonia adsorption device 92 is circulated. [0099] In this embodiment, The aforementioned auxiliary ammonia adsorption device 92, There are a plurality of auxiliary ammonia adsorbers 92a arranged in parallel (two), 92b. The aforementioned first gas waste flow path 91, The upstream end is connected to the annular flow path 71a, The first branched flow path 91a, where the downstream end diverges into a plurality (two), 91b and the aforementioned auxiliary ammonia adsorbers 92a, 92b connection. 上游 The upstream end of the second gas waste flow path 93, The second branched flow path 93a, which is a plural (two), is divided. 93b and the aforementioned plurality of auxiliary ammonia adsorbers 92a, 92b connection. [0100] ammonia removal equipment 90, The department further has: Regeneration gas supply device 94, For the aforementioned plurality of auxiliary ammonia adsorbers 92a, 92b supply regeneration gas; And regeneration gas flow path 96 (96a, 96b), One end is connected to the aforementioned regeneration gas supply device 94, And the other end diverges into a complex number (2) and is different from the second divergent flow path 93a, 93b connection; And regeneration gas heater 95, It is installed in the middle of the regeneration gas flow path 96, And the aforementioned regeneration gas is heated. Alas, Ammonia removal equipment 90, The department has: Disengage the attached gas flow path 97 (97a, 97b), One end of the system diverges into a complex number (2) and is different from the first branched flow path 91a, 91b connection; And exhaust gas combustion reactor 98, Is connected to the other end of the aforementioned detachment gas flow path 97, And burn the ammonia adsorbers 92a, The aforementioned adsorbent discharged by each of 92b detaches from the attached gas and causes the combustion gas to flow out; And loopback flow path 100, The combustion gas discharged from the exhaust gas combustion reactor 98 is returned to the second gas waste flow path 93. At 100 loopback flow paths, An exhaust gas cooler 99 is provided to cool the combustion gas flowing from the exhaust gas combustion reactor. Alas, Ammonia removal equipment 90, The department has: Bypass flow path 101, One end of the system is connected to the first gas waste flow path 91, The other end is connected to the second gas waste flow path 93. [0101] <Hydrogen Production Method> In this embodiment, Except that the same hydrogen production method as the second embodiment can be implemented, Furthermore, the following ammonia detoxification projects can be implemented, Auxiliary ammonia adsorption regeneration project, And bypass operation works. [0102] [Ammonia harm removal project] This is a process for supplying the gas flowing through the gas waste flow path 76 to the ammonia detoxification facility 90 and detoxifying ammonia. In this embodiment, There are cases where the auxiliary ammonia adsorber 92a is used to detoxify ammonia, and cases where the auxiliary ammonia adsorber 92b is used to detoxify ammonia. E.g, The department can be composed as: The gas flowing through the gas waste flow path 76 is supplied to the auxiliary ammonia adsorber 92a through the first gas waste flow path 91 and the first branch flow path 91a. And harm ammonia, after that, Via the second branched flow path 93a, The second gas is discarded and discharged. Alas, It can also be constituted as: The gas flowing through the gas waste flow path 76 is supplied to the auxiliary ammonia adsorber 92b through the first gas waste flow path 91 and the first branch flow path 91b. And harm ammonia, after that, Via the second branched flow path 93b, The second gas is discarded and discharged. [0103] In the ammonia detoxification project, Operating conditions at the auxiliary ammonia adsorber 92a or 92b (temperature, Stress, etc.), Related to the aforementioned ammonia adsorber 5a, The operating conditions in the ammonia adsorption project carried out in 5b are the same. [0104] In addition, usually, The ammonia concentration in the gas in the gas waste flow path 76, This is to the extent that it does not cause environmental problems even if it is directly discarded. Therefore, It can also be used during the unsteady operation when the operation of the hydrogen production device 30B is started or when the operation is stopped. The ammonia detoxification project is implemented as needed. With this, The system can reliably prevent ammonia from flowing out of the system. 量 The amount of ammonia in the gas discharged out of the system through the second gas waste flow path 93, It is preferably 25 ppm by volume or less. Therefore, More ideally, When the amount of ammonia in the gas in the first gas waste flow path 91 exceeds 25 ppm by volume, Department of this ammonia detoxification project. [0105] [Regeneration project of auxiliary ammonia adsorber] Regeneration project of auxiliary ammonia adsorber, In order to make the auxiliary ammonia adsorber 92a used in the above-mentioned ammonia detoxification project, 92b regeneration project. E.g, When the auxiliary ammonia adsorber 92a is regenerated, After the oxygen-containing gas sent from the regeneration gas supply device 94 is heated by the regeneration gas heater 95, Via regeneration gas flow path 96, 96a, The second branched flow path 93a is supplied to the auxiliary ammonia adsorber 92a, The auxiliary ammonia adsorber 92a is regenerated. The gas discharged from this auxiliary ammonia adsorber 92a, Via the first branch flow path 91a, Disengaged gas flow path 97a, 97 and supplied to the exhaust combustion reactor 98, And make the combustible gas in the gas burn. Burned gas, After cooling by the exhaust gas cooler 99, It is discharged through the return flow path 100 and the second gas waste flow path 93. Alas, When the auxiliary ammonia adsorber 92b is regenerated, After the oxygen-containing gas sent from the regeneration gas supply device 94 is heated by the regeneration gas heater 95, Via regeneration gas flow path 96, 96b, The second branched flow path 93b is supplied to the auxiliary ammonia adsorber 92b, The auxiliary ammonia adsorber 92b is regenerated. The gas discharged from this auxiliary ammonia adsorber 92b, Via the first branch flow path 91b, Disengaged gas flow path 97b, 97 and supplied to the exhaust combustion reactor 98, And make the combustible gas in the gas burn. Burned gas, After cooling by the exhaust gas cooler 99, It is discharged through the return flow path 100 and the second gas waste flow path 93. [0106] In the regeneration project of the auxiliary ammonia adsorber, Auxiliary ammonia adsorber 92a or 92b regeneration conditions (temperature, Stress, etc.), Related to the ammonia adsorber 5a, The operating conditions in the regeneration process of the ammonia adsorber of 5b regeneration are the same. Alas, Operating conditions of exhaust gas combustion reactor 98 (temperature, Stress, etc.), The operating conditions are the same as those of the combustion reaction device 36 described above. [0107] (Bypass operation process) As before, During unsteady operation, It is ideal to implement ammonia detoxification projects in response to needs. also, During normal operation, It is ideal to implement bypass operation. In the bypass operation project, The gas flowing in the gas waste flow path 76 is supplied to the second gas waste flow path 93 through the first gas waste flow path 91 and the bypass flow path 101, Then, the gas is discharged from the second gas waste flow path 93. With this, The system can reduce the burden on the ammonia detoxification device 90. [0108] [Fifth Embodiment] <Hydrogen Production Device> FIG. 6, This is a schematic diagram of a hydrogen production apparatus 30C according to the fifth embodiment. 30The hydrogen production device 30C of FIG. 6, In the hydrogen production device 30B of FIG. 5, Instead of the ammonia detoxification device 90, an ammonia detoxification device 90A is provided. Ammonia removal equipment 90A, A combustion reaction device 36 is used instead of the exhaust gas combustion reactor 98 in the ammonia detoxification facility 90. Is also, In the ammonia detoxification equipment 90A, One end of the detachment-attached gas pipe 97, The division is plural (2: 97a, 97b), And the first branch flow path 91a, 91b connection. also, The other end of the detachment-attached gas pipe 97, It is connected to the connection position between the oxygen supply device 37 and the combustion reaction device 36 in the adsorbent regeneration gas flow path 63. Alas, The combustion gas flow path 64 and the second gas waste flow path 93, It is connected via an exhaust gas flow path 104 provided with an exhaust gas cooler 103. [0109] <Hydrogen Production Method> In this embodiment, Except that the same hydrogen production method as the second embodiment can be implemented, Furthermore, the following ammonia detoxification projects can be implemented, Auxiliary ammonia adsorption regeneration project, And bypass operation works. [0110] [Ammonia Removal Project] The system is the same as the fourth embodiment. 01 [0111] [Regeneration project of auxiliary ammonia adsorber] Regeneration project of auxiliary ammonia adsorber, In order to make the auxiliary ammonia adsorber 92a used in the above-mentioned ammonia detoxification project, 92b regeneration project. When regenerating the auxiliary ammonia adsorber 92a, After the oxygen-containing gas sent from the regeneration gas supply device 94 is heated by the regeneration gas heater 95, Via regeneration gas flow path 96, 96a, The second branched flow path 93a is supplied to the auxiliary ammonia adsorber 92a, The auxiliary ammonia adsorber 92a is regenerated. The gas discharged from this auxiliary ammonia adsorber 92a, Via the first branch flow path 91a, Disengaged gas flow path 97a, 97 and the adsorbent regeneration gas flow path 63 are supplied to the combustion reaction device 36, And make the combustible gas in the gas burn. A part of the gas exhausted from the combustion reaction device 36, After cooling by the exhaust gas cooler 103, It is discharged through the second gas waste flow path 93. Alas, When the auxiliary ammonia adsorber 92b is regenerated, After the oxygen-containing gas sent from the regeneration gas supply device 94 is heated by the regeneration gas heater 95, Via regeneration gas flow path 96, 96b, The second branched flow path 93b is supplied to the auxiliary ammonia adsorber 92b, The auxiliary ammonia adsorber 92b is regenerated. The gas discharged from this auxiliary ammonia adsorber 92b, Via the first branch flow path 91b, Disengaged gas flow path 97b, 97 and the adsorbent regeneration gas flow path 63 are supplied to the combustion reaction device 36, And make the combustible gas in the gas burn. A part of the gas exhausted from the combustion reaction device 36, After cooling by the exhaust gas cooler 103, It is discharged through the second gas waste flow path 93. But, The entire gas discharged from the combustion reaction device 36, It is supplied to the heating device 38 via the combustion gas flow path 64. In this case, The exhaust gas flow path 104 provided with the exhaust gas cooler 103 may be omitted. [0112] (Bypass operation process) The system is the same as the fourth embodiment. [0113] [Sixth Embodiment] <Hydrogen Production Device> FIG. 7 This is a schematic diagram of a hydrogen production apparatus 30D according to the sixth embodiment. The hydrogen production device 30D of FIG. 7, In the hydrogen production device 30A of FIG. 4, Those who have ammonia detoxification equipment 90B. The ammonia removal equipment 90B, This is the same as the ammonia detoxification equipment 90 in the fourth embodiment. [0114] <Method for Producing Hydrogen> In this embodiment, It is possible to implement the same hydrogen production method as the third embodiment. Alas, In this embodiment, Department can implement ammonia detoxification project, Auxiliary ammonia adsorption regeneration project, And bypass operation works. In addition, These projects, This is the same as the fourth embodiment. [0115] [Seventh Embodiment] <Hydrogen Production Device> FIG. 8 This is a schematic diagram of a hydrogen production apparatus 30E according to the seventh embodiment. The hydrogen production device 30E of FIG. 8, In the hydrogen production device 30A of FIG. 4, Those who are equipped with 90C ammonia detoxification equipment. The ammonia removal equipment 90C, This is the same as the ammonia detoxification device 90A in the fifth embodiment. [0116] <Hydrogen Production Method> 中 In this embodiment, It is possible to implement the same hydrogen production method as the third embodiment. Alas, In this embodiment, Department can implement ammonia detoxification project, Auxiliary ammonia adsorption regeneration project, And bypass operation works. In addition, These projects, This is the same as the fifth embodiment.
[0117][0117]
1‧‧‧氫製造裝置1‧‧‧ Hydrogen production equipment
2‧‧‧氨供給裝置2‧‧‧Ammonia supply device
3‧‧‧氨分解裝置3‧‧‧Ammonia decomposition device
4‧‧‧分解氣體冷卻用熱交換器4‧‧‧ Decomposed gas cooling heat exchanger
4a‧‧‧分解氣體冷卻裝置4a‧‧‧ Decomposed gas cooling device
4b‧‧‧廢氣加熱裝置4b‧‧‧ exhaust gas heating device
5‧‧‧氨吸附裝置5‧‧‧Ammonia adsorption device
5a、5b‧‧‧氨吸附器5a, 5b‧‧‧Ammonia adsorber
6‧‧‧氫回收裝置6‧‧‧Hydrogen recovery device
7‧‧‧燃燒反應裝置7‧‧‧Combustion reaction device
8‧‧‧加熱機器8‧‧‧Heating machine
11‧‧‧氨流路11‧‧‧Ammonia flow path
12‧‧‧分解氣體流路12‧‧‧ Decomposed gas flow path
14‧‧‧氨除去後氣體流路14‧‧‧ gas flow path after ammonia removal
15‧‧‧氫流路15‧‧‧ Hydrogen flow path
21‧‧‧連接流路21‧‧‧ connected to the flow path
22‧‧‧廢氣流路22‧‧‧ exhaust gas flow path
23‧‧‧吸附材再生氣體流路23‧‧‧Adsorption material regeneration gas flow path
24‧‧‧燃燒氣體流路24‧‧‧Combustion gas flow path
30‧‧‧氫製造裝置30‧‧‧ Hydrogen production facility
31‧‧‧氨供給裝置31‧‧‧Ammonia supply device
32‧‧‧氨分解裝置32‧‧‧Ammonia decomposition device
33‧‧‧分解氣體冷卻用熱交換器33‧‧‧ Decomposed gas cooling heat exchanger
33a‧‧‧分解氣體冷卻裝置33a‧‧‧ Decomposed gas cooling device
33b‧‧‧廢氣加熱裝置33b‧‧‧Exhaust gas heating device
34‧‧‧氨吸附裝置34‧‧‧Ammonia adsorption device
34a、34b‧‧‧氨吸附器34a, 34b‧‧‧Ammonia adsorber
35‧‧‧氫回收裝置35‧‧‧Hydrogen recovery device
36‧‧‧燃燒反應裝置36‧‧‧Combustion reaction device
37‧‧‧氧供給裝置37‧‧‧ oxygen supply device
38‧‧‧加熱機器38‧‧‧Heating machine
41‧‧‧氨流路41‧‧‧Ammonia flow path
42‧‧‧分解氣體流路42‧‧‧ Decomposed gas flow path
43‧‧‧氨除去後氣體流路43‧‧‧Gas flow path after ammonia removal
44‧‧‧氫流路44‧‧‧ Hydrogen flow path
51‧‧‧氨加熱用熱交換器51‧‧‧Ammonia heating heat exchanger
52‧‧‧氨輔助加熱用熱交換器52‧‧‧Heat exchanger for ammonia auxiliary heating
54‧‧‧水加熱用熱交換器54‧‧‧Water heat exchanger
61‧‧‧連接流路61‧‧‧Connecting the flow path
62‧‧‧廢氣流路62‧‧‧ exhaust gas flow path
63‧‧‧吸附材再生氣體流路63‧‧‧Adsorption material regeneration gas flow path
64‧‧‧燃燒氣體流路64‧‧‧Combustion gas flow path
71‧‧‧循環氣體流路71‧‧‧Circulating gas flow path
71a‧‧‧環狀流路71a‧‧‧Circular flow path
72‧‧‧循環氣體用熱交換器72‧‧‧Circulating gas heat exchanger
73‧‧‧溫水加熱用熱交換器73‧‧‧Heat water heating heat exchanger
74‧‧‧排泄罐74‧‧‧ Drain tank
75‧‧‧循環機75‧‧‧Circulator
76‧‧‧氣體廢棄流路76‧‧‧Gas waste stream
77‧‧‧旁通流路77‧‧‧Bypass
80‧‧‧加熱水供給裝置80‧‧‧ heating water supply device
81‧‧‧水流路81‧‧‧Water stream
82‧‧‧噴淋頭82‧‧‧ sprinkler
V1‧‧‧流量控制閥V1‧‧‧Flow Control Valve
V2‧‧‧壓力控制閥V2‧‧‧Pressure Control Valve
30A‧‧‧氫製造裝置30A‧‧‧ Hydrogen production equipment
37A‧‧‧氧供給裝置37A‧‧‧ oxygen supply device
37B‧‧‧氧供給流路37B‧‧‧ oxygen supply flow path
71A‧‧‧熱回收流路71A‧‧‧Heat recovery flow path
72A‧‧‧氧氣加熱用熱交換器72A‧‧‧ oxygen heat exchanger
73A‧‧‧溫水加熱用熱交換器73A‧‧‧Heat water heating heat exchanger
74A‧‧‧排泄罐74A‧‧‧Drain tank
76A‧‧‧氣體廢棄流路76A‧‧‧Gas waste stream
[0031] [圖1] 係為第1實施形態的氫製造裝置之概略圖。 [圖2] 係為第2實施形態的氫製造裝置之概略圖。 [圖3] 係為針對使用有圖2的氫製造裝置之第1運轉作說明之概略圖。 [圖4] 係為第3實施形態的氫製造裝置之概略圖。 [圖5] 係為第4實施形態的氫製造裝置之概略圖。 [圖6] 係為第5實施形態的氫製造裝置之概略圖。 [圖7] 係為第6實施形態的氫製造裝置之概略圖。 [圖8] 係為第7實施形態的氫製造裝置之概略圖。[0031] FIG. 1 is a schematic diagram of a hydrogen production apparatus according to a first embodiment. [Fig. 2] is a schematic view of a hydrogen production apparatus according to a second embodiment. [Fig. 3] is a schematic diagram for explaining the first operation using the hydrogen production apparatus of Fig. 2. [Fig. 4] is a schematic view of a hydrogen production apparatus according to a third embodiment. [Fig. 5] is a schematic diagram of a hydrogen production apparatus according to a fourth embodiment. [Fig. 6] is a schematic diagram of a hydrogen production apparatus according to a fifth embodiment. [Fig. 7] is a schematic diagram of a hydrogen production apparatus according to a sixth embodiment. [Fig. 8] is a schematic diagram of a hydrogen production apparatus according to a seventh embodiment.
Claims (20)
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| JP7226972B2 (en) * | 2018-11-09 | 2023-02-21 | 好朗 岩井 | Hydrogen gas production equipment |
| EP4304980A1 (en) * | 2021-03-11 | 2024-01-17 | Topsoe A/S | Method and system for producing hydrogen from ammonia cracking |
| JP6934126B1 (en) * | 2021-06-15 | 2021-09-08 | 三菱重工環境・化学エンジニアリング株式会社 | Hydrogen and ammonia production system |
| WO2023054964A1 (en) * | 2021-09-29 | 2023-04-06 | 주식회사 에이이에스텍 | Ammonia electrolysis system and control method therefor |
| WO2023153040A1 (en) * | 2022-02-10 | 2023-08-17 | 株式会社Ihi | Flare stack and system provided with flare stack |
| KR20230132302A (en) | 2022-03-08 | 2023-09-15 | 현대자동차주식회사 | Preparing method of hydrogen gas |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5523073A (en) * | 1978-08-08 | 1980-02-19 | Daido Steel Co Ltd | Ammonia decomposed gas generating apparatus and regeneration exhaust gas returning method in said apparatus |
| JP2015059075A (en) * | 2013-09-20 | 2015-03-30 | 株式会社日本触媒 | System for producing hydrogen by decomposing ammonia |
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| JPS6054881B2 (en) * | 1978-08-07 | 1985-12-02 | 大同特殊鋼株式会社 | Ammonia decomposition gas generator and method of utilizing recycled exhaust gas in the device |
| JP5523069B2 (en) | 2009-11-19 | 2014-06-18 | 日本写真印刷株式会社 | Method for manufacturing power receiving housing in wireless charging system |
| CN102910580B (en) * | 2012-11-09 | 2015-03-11 | 湖南高安新材料有限公司 | Energy-saving device and method for decomposing ammonia to prepare high-purity hydrogen-nitrogen mixture gas |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5523073A (en) * | 1978-08-08 | 1980-02-19 | Daido Steel Co Ltd | Ammonia decomposed gas generating apparatus and regeneration exhaust gas returning method in said apparatus |
| JP2015059075A (en) * | 2013-09-20 | 2015-03-30 | 株式会社日本触媒 | System for producing hydrogen by decomposing ammonia |
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| TW201829295A (en) | 2018-08-16 |
| JP7006886B2 (en) | 2022-01-24 |
| JPWO2018116982A1 (en) | 2019-10-24 |
| WO2018116982A1 (en) | 2018-06-28 |
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