JP7190486B2 - 還元剤の非存在下での水蒸気の通過による失活に対する耐性を有する予備改質触媒の調製プロセス及び予備改質触媒 - Google Patents
還元剤の非存在下での水蒸気の通過による失活に対する耐性を有する予備改質触媒の調製プロセス及び予備改質触媒 Download PDFInfo
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- JP7190486B2 JP7190486B2 JP2020519354A JP2020519354A JP7190486B2 JP 7190486 B2 JP7190486 B2 JP 7190486B2 JP 2020519354 A JP2020519354 A JP 2020519354A JP 2020519354 A JP2020519354 A JP 2020519354A JP 7190486 B2 JP7190486 B2 JP 7190486B2
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- 239000003054 catalyst Substances 0.000 title claims description 84
- 238000002407 reforming Methods 0.000 title claims description 51
- 239000003638 chemical reducing agent Substances 0.000 title claims description 19
- 230000009849 deactivation Effects 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 14
- 238000000034 method Methods 0.000 claims description 62
- 230000008569 process Effects 0.000 claims description 49
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 238000001816 cooling Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000571 coke Substances 0.000 description 10
- 229910052707 ruthenium Inorganic materials 0.000 description 10
- 238000000629 steam reforming Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003921 particle size analysis Methods 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- -1 magnesium aluminate Chemical class 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 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
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical group O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
Classifications
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01J37/18—Reducing with gases containing free hydrogen
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—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
- C01B3/38—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 using catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
CnHm+nH2O=nCO+(n+1/2m)H2(吸熱反応) 反応1
CH4+H2O=CO+3H2(吸熱、206.4kJ/mol) 反応2
CO+H2O=CO2+H2(発熱、-41.2kJ/mol) 反応3
- 炭化水素フィードが失敗した場合の、装置の即時停止。典型的に、反応器のバイパスに繋がり、自動操作機能を持つ高価なバルブを必要とするインターロック論理回路を使用、又は触媒と装置に対する危険性がある装置の急速減圧の使用を伴う。
- 還元雰囲気を保証するために、反応器の入口への再循環水素のフィードが失敗した場合、装置を即座に停止するため、全体としてのプロセスの信頼性が低下する。選択的に、緊急事態に供給するための保存された水素又はメタノールを維持及び使用する高価な戦略を必要とし得る。
- 装置の起動手順中に、一次改質等の予備改質反応器及び下流反応器の蒸気加熱が不可能となり、熱衝撃による機器、特に一次改質器、の完全性に対するより大きなリスクを有するより複雑な論理回路の原因となる。
- 無機Ru塩の溶液、好適には水溶液を調製する工程と、
- 前記無機Ru塩の前記溶液でシータアルミナ担体を含浸して、含浸材料を提供する工程と、
- 1乃至24時間、30°C乃至200°Cで変化する温度で、空気中で前記含浸材料を乾燥させる工程と、を備える予備改質触媒の調製プロセスに関する。
- 無機Ru塩の水溶液を調製する工程
- 100乃至200メッシュ(0.075mm乃至0.150mmに相当)、好適には、100乃至150メッシュ(0.105mm乃至0.150mmに相当)の粒度分析範囲のシータアルミナ担体を含浸する工程
- Ruを含有する含浸された材料を、1乃至24時間、30乃至200°C、好適には、50°C乃至150°Cで変化する温度で、空気中で乾燥させる工程
この例は、先行技術で既知の市販の触媒の調製を説明する。
以下の実施例1乃至5は、本発明のプロセスによる水蒸気予備改質触媒の調製を説明する。
この実施例は、本発明による予備改質触媒の調製を説明する。100乃至150メッシュの粒度分析範囲で事前に粉砕された、40グラムのシータアルミナ(アクセンス(Axens)社 SPH 508F)を、0.9gのRuCl3.xH2Oを含有する水溶液28mlで細孔容積の技術により含浸した。材料は、12時間、90乃至120°Cの温度で乾燥させられ、1wt%のRuを含有し、N2吸着法によって決定される比表面積が62m2/gのRu/シータアルミナタイプの予備改質触媒を得た。
この実施例は、本発明による予備改質触媒の調製を説明する。100乃至150メッシュの粒度分析範囲で事前に粉砕された、30グラムのシータアルミナ(アクセンス(Axens)社 SPH 508F)を、0.68gのRuCl3.xH2O及び0.15gのAgNO3を含有する水溶液21mlで細孔容積の技術により含浸した。材料は、12時間、90乃至120°Cの温度で乾燥させられ、1wt%のRu及び0.30wt%のAgを含有し、N2吸着法によって決定される比表面積が58m2/gのAgRu/シータアルミナタイプの予備改質触媒を得た。
この実施例は、還元剤の非存在下での水蒸気の通過(スチーミング)によって、予備改質触媒が影響を受ける加速された失活の方法を説明する。
この実施例は、還元剤の非存在下での水蒸気の通過による失活に対する本発明による触媒の優れた耐性を説明する。
表1:比較例及び実施例1及び2によって調製された触媒の触媒活性の結果
この例は、コークスの堆積による失活に対する本発明による触媒の優れた耐性を説明する。
表2:比較例及び実施例1及び2により調製された触媒に堆積したコークスの含有量
Claims (13)
- 還元剤の非存在下での蒸気の通過による失活に対する耐性を有する予備改質触媒の調製プロセスであって、
無機Ru塩の溶液を調製する工程と、
前記無機Ru塩の前記溶液でシータアルミナ担体を含浸して、含浸材料を提供する工程と、
1乃至24時間、30°C乃至200°Cの温度で、空気中で前記含浸材料を乾燥させる工程と、
を備え、
前記含浸材料の前記乾燥工程の結果生成された前記材料を取り出し、前記材料を、1乃至5時間、300乃至500°Cの温度条件で、水素、ホルムアルデヒド、及びメタノールから選択される還元剤のストリームの中で還元し、還元材料を提供する工程と、
前記還元材料を冷却し、1乃至5時間、20乃至60°Cの温度で気流に曝す工程と、をさらに備える、予備改質触媒の調製プロセス。 - 前記溶液は水溶液である、請求項1に記載のプロセス。
- 前記無機Ru塩の溶液は、RuCl3.H2Oである、請求項1又は2に記載のプロセス。
- 前記含浸材料を乾燥させる工程での乾燥温度が90乃至120℃である、請求項1乃至3のいずれか一項に記載のプロセス。
- 前記含浸は、初期湿潤含浸による技術又は過剰溶液法による、請求項1乃至4のいずれか一項に記載のプロセス。
- 前記含浸は、初期湿潤含浸による、請求項5に記載のプロセス。
- 前記担体は、さらに、前記担体の重量に基づいて、0.1乃至10wt%のアルカリ金属を含んでいる、請求項1乃至6のいずれか1項に記載のプロセス。
- 前記アルカリ金属はカリウムである、請求項7に記載のプロセス。
- 前記無機Ru塩の前記溶液は、さらにAgを含んでいる、請求項1乃至8のいずれか1項に記載のプロセス。
- 前記無機Ru塩の前記溶液は、さらにAgNO3を含んでいる、請求項9に記載のプロセス。
- 炭化水素が、水素を含む生成物のストリームを生成する水蒸気と反応する工程を備える予備改質プロセスであって、
前記プロセスは、400乃至550°Cの温度で実施され、
前記生成物ストリームは、前記生成物ストリームの重量に基づいて、20wt%を上回るメタン含有量を有し、
前記予備改質は、請求項1乃至10のいずれか1項に記載のプロセスにより取得できる触媒の存在下で行われる、予備改質プロセス。 - 前記プロセスは、430乃至490°Cの温度で行われる、請求項11に記載の予備改質プロセス。
- 炭化水素が、水素を含む生成物ストリームを生成する水蒸気と反応する予備改質プロセスにおいて、請求項1乃至10のいずれか1項に記載のプロセスにより取得される触媒の使用であって、
前記プロセスは、400乃至550°Cの温度で実施され、
前記生成物ストリームは、前記生成物ストリームの重量に基づいて、20wt%を上回るメタン含有量を有する、触媒の使用。
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