JP5914588B2 - トリグリセリドを含有する原材料の連続的水素化方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims description 51
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 41
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- 150000003626 triacylglycerols Chemical class 0.000 title claims description 14
- 239000003054 catalyst Substances 0.000 claims description 122
- 239000001257 hydrogen Substances 0.000 claims description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims description 56
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 53
- 239000003085 diluting agent Substances 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 33
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
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- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 239000002600 sunflower oil Substances 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
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- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
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- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
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- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
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Description
通常の周知のディーゼルの水素化処理に従って、ジャトロファオイル(表1に特徴付けられている)を、3個の触媒床を有するパイロット反応器内で、1.0のLHSV(liquid hourly space velocity:液体の毎時空間速度)、40barg、かつ新鮮な供給原料体積(リットル)あたりH2700リットルで水素化処理した。3個の触媒床は、1:2:4の比で市販のCoMo触媒を含有していた。
植物油のための公知の技術に従って、パーム油(表1に特徴付けられている)を、3個の触媒床を有する反応器内で、1.0のLHSV、50barg、かつ新鮮な供給原料体積(リットル)あたりH2800リットルで水素化処理した。3個の触媒床は、1:2:4の比で市販のNiMo触媒を含有していた。
植物油のための公知の技術に従って、パーム油(表1に特徴付けられている)を、5個の触媒床を有する反応器内で、0.3のLHSV、50barg、かつ新鮮な供給原料体積(リットル)あたりH2900リットルで水素化処理した。5個の触媒床は、1:1.5:2:2.5:3の比で市販のNiMo触媒を含有していた。
実施例2および3におけるのと同じパーム油を、新鮮な供給原料をベースとして0.3のLHSV、50bargおよび新鮮な供給原料体積(リットル)あたりH2900リットルで、5個の触媒床(図1の(3)〜(7))を有する断熱反応器内で用いた。5個の触媒床は、実施例2および3におけるのと同一の市販のNiMo触媒を、1:1.5:2:3:4.5の比で含有していた。
実施例2、3および4におけるのと同じパーム油を、新鮮な供給原料をベースとして1.0のLHSV、50bargおよび新鮮な供給原料の体積(リットル)当たりH2900リットルで、3個の触媒床を有する断熱反応器において用いた。3個の触媒床は、実施例2、3および4と同じ市販のNiMo触媒を、1:1.3:1.6の比で含有していた。
Claims (16)
- 水素化触媒を含むいくつかの触媒床を有する固定床反応器システムにおいて、トリグリセリドを含有する原材料を連続的に水素化する方法であって、該床は、直列に配列され、原材料供給原料、水素含有ガス、および希釈剤が一緒に、水素化条件で反応器システムの触媒床に通過させられ、
a)原材料供給原料流れが、反応器システム内で80℃未満の温度で触媒床の数nと等しい多くの異なる分流F1〜Fnに分けられ、水素含有ガス流れもまた、110℃未満の温度で同じ数の異なる分流H1〜Hnに分けられ、その後、原材料供給原料の分流F1および水素含有ガスの分流H1は、第一触媒床に送られ、原材料供給原料の分流F2および水素含有ガスの分流H2は、第二触媒床に送られ、以下、同様に送られ、nが2超である場合、下流方向に流れる原材料供給原料の各分流は、先行する流れより大きいものであり、希釈剤対原材料供給原料の重量比が、すべての触媒床の入口において本質的に同じでありかつ4:1を超えず、該希釈剤は、各触媒床中に形成された水素化生成物を含む生成希釈剤と、下記b)に定義された追加希釈剤とからなり、
b)反応器入口における第一触媒床の温度(始動期間後)が追加希釈剤で調整され、該希釈剤は本方法によって得られる水素化生成の一部であり、該希釈剤は、制御された圧力の低減を伴わない、高温分離器(8)での145〜280℃ついで低温分離器(9)での15〜60℃の2つの工程における分離によって、反応器出口の生成物混合物から液状で回収され、
c)追加希釈剤は、反応器入口に入りかつ第一触媒床を通過する、原材料供給原料流F1と水素含有ガス流H1の流れにのみ添加され、かつ、
d)理論的水素消費量を超える水素が用いられる
ことを特徴とする、方法。 - 原材料供給原料の各分流は、対応する水素含有ガスの分流と混合されて、混合分流(F1+H1、F2+H2、等)を形成した後に、反応器システムに入る、請求項1に記載の方法。
- 下流方向に流れるそれぞれの水素含有ガスの分流は、それらが混合される対応原材料供給原料分流と実質的に同一倍、先行の流れより多い、請求項1または2に記載の方法。
- 水素過剰は、少なくとも50%である、請求項1〜3のいずれか1つに記載の方法。
- 追加希釈剤対全原材料供給原料の重量比は、1未満である、請求項1〜4のいずれか1つに記載の方法。
- 供給原料分流および対応する水素含有ガス分流はすべて、ガスの標準立方メートル対原材料供給原料の立方メートルの同じ比で混合される、請求項1〜5のいずれか1つに記載の方法。
- 第二触媒床および存在する場合次の触媒床への分流または混合分流の量は、全ての触媒床の入口における温度を、反応器入口における第一触媒床と本質的に同一の温度に調節するように制御される、請求項1〜6のいずれか1つに記載の方法。
- 反応器システムは、3個超20個未満の触媒床を含む、請求項1〜7のいずれか1つに記載の方法。
- 水素化触媒は、周期律表の第6、8、9、および10族の1種以上の硫化元素から選択される、請求項1〜8のいずれか1つに記載の方法。
- 水素化は、1〜8MPaの範囲の水素分圧で行われる、請求項1〜9のいずれか1つに記載の方法。
- 水素化は、145〜280℃の範囲の温度で行われる、請求項1〜10のいずれか1つに記載の方法。
- 原材料供給原料のLHSVは、0.1〜1m3/m3(触媒)/時である、請求項1〜11のいずれか1つに記載の方法。
- 液体材料の線速度は、各床において1〜6mm/秒である、請求項1〜12のいずれか1つに記載の方法。
- 反応器入口における追加希釈剤対原材料供給原料の重量比は、4:1以下であり、新鮮な原材料供給原料の各分流並びに水素含有ガスの各分流は、1.25倍以上、前の分流より大きい、請求項1〜13のいずれか1つに記載の方法。
- トリグリセリドを含有する原材料は、鉱物油と一緒に処理される、請求項1〜14のいずれか1つに記載の方法。
- 水素化生成物の一部は、反応器入口で入りかつ第一触媒床を通過する原材料供給原料F1および水素含有ガスH1の流れへの追加のために再循環させられず、異性化または水素化分解並びに精製所成分との調合に付されて、品質向上したケロシンまたはディーゼル燃料が得られる、請求項1〜15のいずれか1つに記載の方法。
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EP2428547B1 (en) | 2010-09-08 | 2018-09-05 | IFP Energies nouvelles | Process for the continuous hydrogenation of triglyceride containing raw materials using a nickel and molybdenum based catalyst |
EP2428548A1 (en) * | 2010-09-08 | 2012-03-14 | IFP Energies nouvelles | Process for the continuous hydrogenation of triglyceride containing raw materials using a molybdenum based catalyst |
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FR2969642B1 (fr) * | 2010-12-22 | 2012-12-28 | IFP Energies Nouvelles | Production de carburants paraffiniques a partir de matieres renouvelables par un procede d'hydrotraitement en continu |
ES2626658T5 (es) | 2011-01-18 | 2021-01-26 | Neste Oyj | Método y disposición para alimentar materiales sensibles al calor a reactores de lecho fijo |
US8785709B2 (en) | 2011-03-30 | 2014-07-22 | University Of Louisville Research Foundation, Inc. | Catalytic isomerisation of linear olefinic hydrocarbons |
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FR2992326B1 (fr) * | 2012-06-21 | 2014-06-20 | IFP Energies Nouvelles | Procede de production de tensio-actifs a partir de matieres renouvelables comprenant une etape d'hydrotraitement et une etape de transformation de paraffines en tensio-actifs |
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JP6306370B2 (ja) * | 2014-02-25 | 2018-04-04 | 千代田化工建設株式会社 | 芳香族化合物の水素化システムおよび水素化方法 |
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CN105273747B (zh) * | 2015-11-18 | 2017-05-03 | 北京中科诚毅科技发展有限公司 | 一种浆态床加氢反应器的控温措施及其设计方法和用途 |
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