JP2016074603A - 一酸化炭素変成装置及び方法並びに水素製造装置 - Google Patents
一酸化炭素変成装置及び方法並びに水素製造装置 Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 280
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 244
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 228
- 239000001257 hydrogen Substances 0.000 title claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 497
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 134
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 64
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 64
- 231100000572 poisoning Toxicity 0.000 claims abstract description 47
- 230000000607 poisoning effect Effects 0.000 claims abstract description 47
- 230000007423 decrease Effects 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims description 112
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 65
- 239000012495 reaction gas Substances 0.000 claims description 38
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical group [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 28
- 229910052697 platinum Inorganic materials 0.000 claims description 28
- 238000011144 upstream manufacturing Methods 0.000 claims description 27
- 239000007800 oxidant agent Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000011426 transformation method Methods 0.000 claims description 2
- 238000002715 modification method Methods 0.000 claims 1
- 239000000376 reactant Substances 0.000 abstract 3
- 230000000052 comparative effect Effects 0.000 description 33
- 230000000694 effects Effects 0.000 description 26
- 230000003197 catalytic effect Effects 0.000 description 16
- 238000005259 measurement Methods 0.000 description 16
- 239000000446 fuel Substances 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 12
- 230000035945 sensitivity Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 239000006200 vaporizer Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000011701 zinc Substances 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
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
Description
CO + H2O → H2 +CO2
2CO+O2 → 2CO2
(化3)
2H2+O2 → 2H2O
2: 反応管
3: 第1触媒層
4: 第2触媒層
5: 入口
6: 出口
11〜13: 供給管
14: 混合ガス供給管
15: 気化器
16: 水タンク
17: 水供給管
18: 電気炉
19: マントルヒータ
20,22: 排気管
21: ドレインタンク(冷却器)
23: ガスクロマトグラフィー分析装置
24: 一酸化炭素選択酸化器
25: 空気ポンプ
26: 冷却水ポンプ
G0: 被処理ガス(反応ガス)
G1、G1’: 処理済ガス
G2: 処理済ガス(選択酸化後)
Claims (19)
- 反応ガス中に含まれる一酸化炭素と水蒸気を反応させて二酸化炭素と水素に転化させる一酸化炭素変成装置であって、
変成触媒層を少なくとも上流側と下流側の2段に分割して、上流側に第1触媒、下流側に第2触媒を夫々備え、
前記第1触媒が、供給される反応ガス中の一酸化炭素濃度及び反応温度が一定の場合において、当該供給される反応ガス中の二酸化炭素濃度が高い程、一酸化炭素転化率が低下する二酸化炭素被毒の特性を有し、
供給される反応ガス中の二酸化炭素濃度の同じ増加に対し、前記第2触媒における前記二酸化炭素被毒による一酸化炭素転化率の低下の程度が、前記第1触媒における前記二酸化炭素被毒による一酸化炭素転化率の低下の程度より小さいことを特徴とする一酸化炭素変成装置。 - 供給される反応ガス中の二酸化炭素濃度の同じ増加に対し、前記第2触媒における前記二酸化炭素被毒による一酸化炭素転化率の低下の程度が、前記第1触媒における前記二酸化炭素被毒による一酸化炭素転化率の低下の程度より小さくなる条件下で前記第2触媒が使用されることを特徴とする請求項1に記載の一酸化炭素変成装置。
- 前記第1触媒が銅亜鉛系触媒で、前記第2触媒が貴金属系触媒であることを特徴とする請求項1または2に記載の一酸化炭素変成装置。
- 前記第2触媒が白金系触媒であって、前記第2触媒の担体が酸化セリウムであることを特徴とする請求項3に記載の一酸化炭素変成装置。
- 前記第2触媒の体積が前記第1触媒の体積以下であることを特徴とする請求項3または4に記載の一酸化炭素変成装置。
- 前記第1触媒と前記第2触媒の反応温度が共通に制御されることを特徴とする請求項1〜5の何れか1項に記載の一酸化炭素変成装置。
- 前記第1触媒と前記第2触媒の反応温度が夫々独立に制御されることを特徴とする請求項1〜5の何れか1項に記載の一酸化炭素変成装置。
- 前記第1触媒と前記第2触媒が同じ組成及び構造であり、前記第1触媒と前記第2触媒の各反応温度を、前記第2触媒における供給される反応ガス中の二酸化炭素濃度の増加に対する一酸化炭素転化率の低下の程度が、前記第1触媒における供給される反応ガス中の二酸化炭素濃度の増加に対する一酸化炭素転化率の低下の程度より小さくなるように夫々独立に制御することを特徴とする請求項1または2に記載の一酸化炭素変成装置。
- 前記第1触媒及び前記第2触媒が銅亜鉛系触媒であることを特徴とする請求項8に記載の一酸化炭素変成装置。
- 反応ガス中に含まれる一酸化炭素と水蒸気を反応させて二酸化炭素と水素に転化させる一酸化炭素変成方法であって、
変成反応工程を連続する少なくとも2つの変成反応工程に分割し、上流側の第1の変成反応工程で第1触媒を用い、下流側の第2の変成反応工程で第2触媒を用い、
前記第1触媒が、供給される反応ガス中の一酸化炭素濃度及び反応温度が一定の場合において、当該供給される反応ガス中の二酸化炭素濃度が高い程、一酸化炭素転化率が低下する二酸化炭素被毒の特性を有し、
供給される反応ガス中の二酸化炭素濃度の同じ増加に対し、前記第2触媒における前記二酸化炭素被毒による一酸化炭素転化率の低下の程度が、前記第1触媒における前記二酸化炭素被毒による一酸化炭素転化率の低下の程度より小さいことを特徴とする一酸化炭素変成方法。 - 供給される反応ガス中の二酸化炭素濃度の同じ増加に対し、前記第2触媒における前記二酸化炭素被毒による一酸化炭素転化率の低下の程度が、前記第1触媒における前記二酸化炭素被毒による一酸化炭素転化率の低下の程度より小さくなる条件下で前記第2触媒を使用することを特徴とする請求項10に記載の一酸化炭素変成方法。
- 前記第1触媒が銅亜鉛系触媒で、前記第2触媒が貴金属系触媒であることを特徴とする請求項10または11に記載の一酸化炭素変成方法。
- 前記第2触媒が白金系触媒であって、前記第2触媒の担体が酸化セリウムであることを特徴とする請求項12に記載の一酸化炭素変成方法。
- 前記第2触媒の体積が前記第1触媒の体積以下であることを特徴とする請求項12または13に記載の一酸化炭素変成方法。
- 前記第1触媒を通過した反応ガスが温度調整されずに前記第2触媒に送入されることを特徴とする請求項10〜14の何れか1項に記載の一酸化炭素変成方法。
- 前記第1触媒と前記第2触媒の反応温度を夫々独立に制御することを特徴とする請求項10〜14の何れか1項に記載の一酸化炭素変成方法。
- 前記第1触媒と前記第2触媒が同じ組成及び構造であり、前記第1触媒と前記第2触媒の各反応温度を、前記第2触媒における供給される反応ガス中の二酸化炭素濃度の増加に対する一酸化炭素転化率の低下の程度が、前記第1触媒における供給される反応ガス中の二酸化炭素濃度の増加に対する一酸化炭素転化率の低下の程度より小さくなるように夫々独立に制御することを特徴とする請求項10または11に記載の一酸化炭素変成方法。
- 前記第1触媒及び前記第2触媒が銅亜鉛系触媒であることを特徴とする請求項17に記載の一酸化炭素変成方法。
- 請求項1〜9の何れか1項に記載の一酸化炭素変成装置と、前記一酸化炭素変成装置で処理されたガス中の一酸化炭素濃度を選択酸化により低下させる一酸化炭素選択酸化器とを備えてなることを特徴とする水素製造装置。
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