JPWO2011108212A1 - 合成ガスの製造方法 - Google Patents
合成ガスの製造方法 Download PDFInfo
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- JPWO2011108212A1 JPWO2011108212A1 JP2012502990A JP2012502990A JPWO2011108212A1 JP WO2011108212 A1 JPWO2011108212 A1 JP WO2011108212A1 JP 2012502990 A JP2012502990 A JP 2012502990A JP 2012502990 A JP2012502990 A JP 2012502990A JP WO2011108212 A1 JPWO2011108212 A1 JP WO2011108212A1
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- carbon dioxide
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 49
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 122
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 88
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 87
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 61
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 55
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 49
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 42
- 230000023556 desulfurization Effects 0.000 claims abstract description 42
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims description 194
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000006057 reforming reaction Methods 0.000 claims description 30
- 239000003345 natural gas Substances 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000003463 adsorbent Substances 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 230000003009 desulfurizing effect Effects 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 238000007872 degassing Methods 0.000 claims 1
- 238000005038 synthesis gas manufacturing Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 35
- 238000002407 reforming Methods 0.000 abstract description 26
- 230000006866 deterioration Effects 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- 231100000572 poisoning Toxicity 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 22
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 22
- 239000002994 raw material Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000000629 steam reforming Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- -1 naphtha Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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Abstract
Description
式(1): CH4 + H2O → CO + 3H2
式(2): CH4 + CO2 → 2CO + 2H2
式(4): R−NH2 + H2S → R−NH3 + + HS−
SUS反応管21中に脱硫剤22を充填し(図2)、装置上部から炭酸ガス、メタン、水素、硫化水素からなる模擬ガス23を流通させ、脱硫剤(主成分ZnO)による脱硫効果について検討した。なお、炭酸ガス濃度は20%とした。脱硫後のガス中の硫黄化合物濃度は、反応管出口からガス24をサンプリングし、硫黄化学発光検出器を備えたガスクロマトグラフ(SCD−GC)で測定した。脱硫剤の性状を表1に、試験条件と結果を表2に記す。
実施例1において、炭酸ガス濃度を40%に変更した以外は同様にして試験を行った。
本発明の実施形態1において、脱硫セクションにおいて脱硫されたガスにより改質触媒の劣化が抑えられることを確認するため、以下の実施例3を行った。
従来技術において、硫化水素を含む炭酸ガスを合成ガス製造セクションにリサイクルすることにより改質触媒が劣化することを確認するため、以下の比較例を行った。
本比較例より、脱硫剤を使用しない場合は急速な触媒劣化が生じることが確認された。
本発明の実施形態2において、吸着剤によって分離回収ガス中の硫黄化合物が脱硫されることを示すために、以下の試験を行った。
本発明の実施形態2において、吸着剤によって脱硫した分離回収ガスが改質触媒を劣化させずに改質反応に使用できることを示すために、以下の試験を行った。
本発明の実施形態2において、脱硫しなかった分離回収ガスを使用することで改質触媒が劣化することを確認するため、以下の試験を行った。
22 脱硫剤
23 模擬ガス
24 出口ガス
31 SUS反応管
34 合成ガス
35 改質触媒
44 合成ガス
61 SUS反応管
63 模擬ガス
64 出口ガス
66 吸着剤
71 SUS反応管
74 合成ガス
75 改質触媒
84 合成ガス
Claims (13)
- 脱硫装置を用いて天然ガス中の硫黄化合物を脱硫する脱硫工程、脱硫された天然ガスを含むガスとスチーム及び炭酸ガスとの改質反応により合成ガスを製造する合成ガス製造工程、製造された合成ガスから炭酸ガスを主成分とする分離回収ガスを分離回収する脱炭酸工程を含み、さらに該分離回収ガスを合成ガス製造工程にリサイクルする合成ガスの製造方法において、該分離回収ガスを前記脱硫装置へ導入して脱硫することを特徴とする、合成ガスの製造方法。
- 前記脱硫装置は、天然ガスに含まれる硫黄化合物を水素化処理する第1の工程、及び第1の工程において水素化された硫黄化合物を脱硫剤によって吸着する第2の工程からなり、前記分離回収ガスは、第1の工程の後、第2の工程の前に導入されることを特徴とする請求項1に記載の合成ガスの製造方法。
- 前記脱硫装置において用いられる脱硫剤の主成分は酸化亜鉛であることを特徴とする請求項2に記載の合成ガスの製造方法。
- 前記合成ガス製造工程に導入されるガス中に含有される硫黄化合物の濃度は、硫黄原子換算で10vol−ppb未満であることを特徴とする請求項1から3のいずれか1項に記載の合成ガスの製造方法。
- 前記分離回収ガスは、脱硫装置に導入される時点での温度が300−400℃、圧力が2.1〜2.7MPaG、GHSVが1,000−2,000h−1であることを特徴とする請求項1から4のいずれか1項に記載の合成ガスの製造方法。
- 前記合成ガス製造工程に導入されるガスのH2O/Cモル比は0より大きく3.0以下、CO2/Cモル比は0より大きく1.0以下であることを特徴とする請求項1〜5のいずれか1項に記載の合成ガスの製造方法。
- 請求項1〜6のいずれか1項に記載の方法により製造した合成ガスをフィッシャー・トロプシュ反応に供し、フィッシャー・トロプシュ反応生成物からガス状生成物を分離してフィッシャー・トロプシュ油を製造し、該フィッシャー・トロプシュ油を水素化処理して得られた水素化処理物を蒸留して軽質炭化水素ガスと最終製品である灯軽油とを分離することを特徴とする、天然ガスから合成炭化水素を製造する方法。
- 天然ガス中の硫黄化合物を脱硫する脱硫工程、脱硫された天然ガスを含むガスとスチーム及び炭酸ガスとの改質反応により合成ガスを製造する合成ガス製造工程、製造された合成ガスから炭酸ガスを主成分とする分離回収ガスを分離回収する脱炭酸工程を含み、さらに該分離回収ガスを合成ガス製造工程にリサイクルする合成ガスの製造方法において、該分離回収ガスを吸着装置に導入して硫黄化合物を除去した後に合成ガス製造工程にリサイクルすることを特徴とする、合成ガスの製造方法。
- 前記吸着装置は活性炭又はゼオライトを吸着剤として用いることを特徴とする、請求項8に記載の合成ガスの製造方法。
- 前記合成ガス製造工程にリサイクルされるガス中に含有される硫黄化合物の濃度は、硫黄原子換算で10vol−ppb未満であることを特徴とする、請求項8又は9に記載の合成ガスの製造方法。
- 前記吸着装置における操作条件は、温度が常温〜50℃、圧力が0.0〜0.3MPaG、GHSVが1,000〜3,000h−1であることを特徴とする、請求項8から10のいずれか1項に記載の合成ガスの製造方法。
- 前記合成ガス製造工程に導入されるガスのH2O/Cモル比は0より大きく3.0以下、CO2/Cモル比は0より大きく1.0以下であることを特徴とする、請求項8〜11のいずれか1項に記載の合成ガスの製造方法。
- 請求項8〜12のいずれか1項に記載の方法により製造した合成ガスをフィッシャー・トロプシュ反応に供し、フィッシャー・トロプシュ反応生成物からガス状生成物を分離してフィッシャー・トロプシュ油を製造し、該フィッシャー・トロプシュ油を水素化処理して得られた水素化処理物を蒸留して軽質炭化水素ガスと最終製品である灯軽油とを分離することを特徴とする、天然ガスから合成炭化水素を製造する方法。
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