JP7490851B2 - バイオベース素材の処理方法及びそれを処理するための装置 - Google Patents
バイオベース素材の処理方法及びそれを処理するための装置 Download PDFInfo
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Images
Classifications
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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
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- C—CHEMISTRY; METALLURGY
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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
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- C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
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Description
本発明の詳細な例について、添付図面を参照に説明する。ここで使用する用語は、詳細な例を説明するためであり、本発明の範囲を限定するものではない。更に、特に定義されていない場合は、ここで使用される技術的・科学的な用語は、当業者が一般的に理解している意味と同じである。可能であれば、同じ参照用の符号は、明確性や整合性のため、複数の図面を通して使用される。
酸性の多孔質固体支持体(担体)上に異なる触媒を担持させたものを用いて、得られた影響/結果を表1に示す。
触媒の性能に影響を及ぼすファクターを検討し、表2に示す。
本発明の方法の一例を、パームオレイン(パーム油)を供給原料とし、水素を用い、更に使用する触媒としてAl2O3上にNiMOを担持したものを用いて実施して、処理済油を調製した。反応器の温度は、30~70barの圧力で300℃~360℃に変化させ、空間速度を1.0hr-1とし、パームオレインに対する水素ガスの比を0.06g水素/g油とした。
処理済油の特性の選択例を表3に示す。
本発明の他の方法の一例を実施して、処理済油を調製する方法における、例えばNiMo/Al2O3及びNiCoMo/Al2O3のような異なる触媒を用いた場合の影響を示す。反応器の温度は、圧力35バールで330℃、空間速度は1.0hr-1で、パームオレインに対する水素の比を0.06g水素/g油とした。
得られた処理済油の特性を表4に示す。
本発明の方法の他の複数の例を、パームオレインを供給原料とし、水素を用い、更にAl2O3上にNiMOを担持した触媒を用いて実施して、PCMを調製するのに適切な処理済油を調製した。反応器の温度は、圧力35barで330℃、空間速度は1.0hr-1で、パームオレインに対する水素の比を0.06g水素/g油とした。
本発明の方法の一例を、種々のバイオベース素材を供給原料とし、水素を用い、更にAl2O3上にNiMOを担持した触媒を用いて実施して、グリーンディーゼルを調製するのに適切な処理済油を調製した。反応器の温度は、圧力35barで350℃、空間速度は1.0hr-1で、バイオベース素材に対する水素の比を0.06g水素/gバイオベース素材とした。
本発明の方法の一例を、実施例4の処理済油を更に処理することを実施し、PCM及び工業用溶媒を産出した。NiCo/Al2O3を触媒として用い、図1及び図2に示すと同様の方法を実施した。その結果として、工業用溶媒(GTR1)及び3種のPCM(PCM#01、#02、#03)(それぞれストリーム121,124,127及び130)を産出した。
本発明の方法により得られたグリーンディーゼルの蒸留範囲を表10に示す。特に、実施例4で得られた処理済油を用い、触媒としてNiCoMo/Al2O3を用いて、当該処理済油を蒸留装置(装置139)に通過させ、次いで吸着カラム(装置140)に通過させた。表10に示すように、グリーンディーゼルの蒸留範囲は、約200℃~約350℃で、特に約260.5℃~約323.0℃である。市場で入手し得るグリーンディーゼルと比較して、本発明のグリーンディーゼルのIBPは、相対的に高い。特に、本発明のグリーンディーゼルのIBPは、約260.5℃である。一方、例えば、市場で入手できた第1のグリーンディーゼルのIBPは180℃であり、市場で入手できた第2のグリーンディーゼルのIBPは173℃である。従って、このことは、本発明のグリーンディーゼルは、市場で入手し得るグリーンディーゼルよりも炭素原子数が高いノーマルパラフィン(例えばn-C15~n-C18)を多く含むことを示している。
本発明の工業用溶媒である、実施例7のGTR1を、一連の脂肪族系ミネラルスピリット、ShellSolTMD38(A1)、ShellSolTMD40(A2)、ShellSolTMD60(A3)、ShellSolTMD70(A4)、ShellSolTMD80(A5)、ShellSolTMD90(A6)及びShellSolTMD100(A7)と比較した(表11)。A1~A7の一連の脂肪族系ミネラルスピリットに関する情報は、シェルTM(ShellTM)によるテクニカルデータシートによるものであり、試験方法は次の方法である:米国材料試験協会(ASTM)D56をA1~A3の引火点を測定するのに用い、ASTM D93をA4~A7の引火点を測定するのに用い、ASTM D4052をA1~A7の密度を測定するのに用い、ガスクロマトグラフィー(GC)をA1~A3の芳香族含量及び硫黄含量の測定に用い、シェルメソッドシリーズ(SMS)2728をA4~A7の芳香族含量を測定するのに用い、国際標準規格(ISO)20846をA1~A7の硫黄含量を測定するのに用い、ASTM D86をA1~A7の蒸留範囲を測定するのに用いた。脂肪族ミネラルスピリットは、石油製油所の産物であり、(i)粗ナフサ(virgin naphtha)及びフルレンジ(full range)ナフサのような石油供給原料の水素化及び分別により、又は(ii)天然ガス供給原料のフィッシャー-トロプシュプロセスにより調製される。これらは、粘性が低い溶媒であって、芳香族含量は少ない。
最も市場で入手できる工業用溶媒は、石油ベースである。それにもかかわらず、バイオマス由来の工業用溶媒が研究され商業的に生産されてきた。かかる工業用溶媒は、スターチ、カルス、炭水化物、リグニン、テルペン及びプロテインのようなバイオマスから生成される。しかし、かかるバイオマス由来の工業用溶媒は、GTR1のような本発明の工業用溶媒が有する特性は有してない。
リグニンは、主としてフェノールポリマーを含有するバイオマスで、水素化分解又は熱分解により工業用溶媒に調製されることができる。これらのプロセスは、リグニンをフェノール化合物に転換させるものである。このように、実施例7からのGTR1のような本発明の工業用溶媒と代表的なリグニン由来の溶媒とを比較すると、リグニン由来の溶媒には、主として芳香族化合物が含まれる。従って、リグニン由来の溶媒の特性及び適用は、GTR1とはかなり異なる。
Claims (7)
- トリグリセリド及び遊離脂肪酸を含む動物油及び/又は植物油を含有する実質的に再生可能な供給原料から形成された再生可能なバイオベース素材の処理方法であって、該方法は次の工程:
所定の流量及び圧力を有する新鮮なバイオベース素材からなる第1のストリームを第1の熱交換器に通過させ、該第1の熱交換器からは反応器の入口に流れる加熱された新鮮なバイオベース素材からなる第1の加熱ストリームが産出され.
所定の流量及び圧力を有する新鮮な水素からなる第2のストリームを第1の熱交換器とは別の第2の熱交換器に通過させ、該第2の熱交換器からは加熱された新鮮な水素からなる別の第2のストリームが産出され、該第2のストリームは該第1のストリームかから独立して反応器の入口に流れ、
反応器の入口において、(a)加熱された新鮮なバイオベース素材からなる該第1の加熱されたストリーム、及び、(b)加熱された新鮮な水素からなる別の第2の加熱されたストリームであって、該第1のストリームから独立して流れる第2のストリームは、(水素0.03~0.10g)/(g バイオベース素材)の割合で、それぞれ、反応物の並流として導入され、該反応器は一連の反応床を備え、各床は支持体上に担持されている触媒が設置されており、
該反応器内に導入された反応物を、200~400℃の範囲に制御された温度及び25~40barの範囲に制御された圧力で、触媒の存在下で反応させることにより、ワンステップ水素化処理が行われ、処理油が該反応器より産出され、
該反応器から産出された該処理油を、該処理済油の温度を低下させるために、第1の熱交換器および第2の熱交換器の各々とは異なる第3の熱交換器に通過させ、該第3の熱交換器から、所定の温度に低下した処理油が産出され、
該温度が低下した処理済油を高圧分離器に通過させて、該温度が低下した処理済油からガス状成分を分離し、該高圧分離器からガス状成分と精製された処理済油をそれぞれ独立して産出し、次いで該精製された処理済油を低圧分離器に通過させることにより、水成分を該精製された処理済油から分離し、該低圧分離器から水成分と更に精製された処理済油とをそれぞれ独立して産出し、
(i)該更に精製された処理油を蒸留ユニットに通過させ、蒸留ユニットによって産出されたストリームの第1の部分を吸着ユニットに更に通過させて、少なくとも100のセタン価を有するグリーンディーゼルを産出し、及び/又は(ii)該更に精製された処理油または蒸留ユニットによって産出されたストリームの第2の部分を第1の蒸留カラムに通過させて、炭素数16未満のストリーム及び第1の追加のストリームを生成し、該炭素数16未満のストリームを第1の吸着カラムに通過させて、少なくとも99質量%のn-パラフィンを含む工業用溶媒を生成し、さらに、第1の追加のストリームを第2の蒸留カラムおよび対応する第2の吸着カラムに通過させて、n-ヘキサデカンからなり、0質量%以上1質量%以下のイソパラフィン含量を有する第1の相転移材料(PCM)を産出し、
該吸着ユニットは、活性炭素、イオン交換樹脂及びモレキュラーシーブからなる群より選ばれる少なくとも1つの吸着剤を含み、更に
該反応器は、冷却物質を反応器中に、該反応物の流れと逆ではなく、該反応物の流れに垂直及び並流する間の角度で導入するノズルを介して、該反応器の温度を制御するための内部冷却機能を備える、
ことを特徴とする、方法。 - 請求項1に記載の方法において、該支持体は、アルミナ(Al2O3)、シリカ(SiO2)又はアルミナ-シリカ(Al2O3-SiO2)であり、該支持体がAl2O3の場合に、Al2O3上の触媒は、NiMo/Al2O3及びNiW/Al2O3からなる群から選択されるか、又はAl2O3上の触媒は、NiCoMo/Al2O3、NiMoP/Al2O3及びCoMo/Al2O3からなる群より選択されることを特徴とする、方法。
- 請求項1の方法において、反応器内の空間速度は、0.5h-1から2h-1であることを特徴とする、方法。
- 請求項1乃至3のいずれかの方法において、水素と該バイオベース素材との比は、0.05g水素/gバイオベース素材~0.07g水素/gバイオベース素材であることを特徴とする、方法。
- 請求項1乃至4のいずれかの方法において、該吸着カラムは、活性炭素、イオン交換樹脂及びモレキュラーシーブよりなる群から選ばれる少なくとも一つの吸着剤を含むことを特徴とする、方法。
- 請求項1乃至5のいずれかの方法において、
該バイオベース素材はパームオレインを含み、該工業用溶媒は1ppm未満の硫黄含有量を有し、前記第1のPCMは1ppm未満の硫黄含有量を有する、
ことを特徴とする、方法。 - トリグリセリド及び遊離脂肪酸を含む動物油及び/又は植物油を含有する実質的に再生可能な供給原料から形成された再生可能なバイオベース素材の処理を行うシステムであって、該システムは:
入口を有する反応器、
所定の流量及び圧力を有する新鮮なバイオベース素材からなる第1のストリームを受け入れるように構成され、更に、反応器の入口に流れる加熱された新鮮なバイオベース素材からなる第1の加熱ストリームが産出されるように構成される、第1の熱交換器、
所定の流量及び圧力を有する新鮮な水素からなる第2のストリームを受け入れるように構成され、更に、加熱された新鮮な水素からなる別の第2の加熱されたストリームが産出され、該第2のストリームは該第1の加熱ストリームから独立して反応器の入口に流れるように構成される、第1の熱交換器とは別の第2の熱交換器、
該反応器の入口で、(a)加熱された新鮮なバイオベース素材からなる該第1の加熱されたストリーム、及び(b)加熱された新鮮な水素からなる別の加熱された第2のストリームであって該第1の加熱ストリームから独立して流れる第2のストリームのそれぞれは、(水素0.03~0.10g)/(g バイオベース素材)の割合で、反応器に流入して反応する反応物の並流として導入される入口を備える反応器であって、該反応器は一連の反応床を備え、各床は支持体上に担持されている触媒が設置されており、該反応器内の供給原料と水素とを、200~400℃の範囲に制御された温度及び25~40barの範囲に制御された圧力で該触媒の存在下で反応させて、ワンステップ水素化処理により処理済油が該反応器の出口で産出されるように構成される反応器、
該反応器から産出された該処理済油を受け入れて、所定の低下した温度を有する処理済油が産出されるように、該処理済油の温度を低下させるように構成された、第1の熱交換器及び第2の熱交換器の各々とは異なる第3の熱交換器、
該温度が低下した処理済油を受け入れ、そこからガス状成分を分離し、更に該ガス状成分と精製された処理済油をそれぞれ独立して産出し、次いで、該精製された処理済油を受け入れて、水成分と更に精製された処理済油とをそれぞれ独立して産出するように構成された低圧分離器に続くように構成される高圧分離器、
(i)該更に精製された処理油を通過させて、蒸留ユニット出口ストリームを提供するように構成された蒸留ユニットと、少なくとも100のセタン価を有するグリーンディーゼルを生成するために蒸留出口ストリームの第1の部分を通過させるように構成された吸着ユニット、及び/又は、(ii)該更に精製された処理油または蒸留ユニット出口ストリームの第2の部分を通過させて、炭素数16未満のストリームおよび第1の追加ストリームを生成するように構成された第1の蒸留カラム、および炭素数16未満のストリームを通過させて、少なくとも99質量%のn-パラフィンを含む工業用溶媒を産出するように構成された第1の吸着カラム、更に、n-ヘキサデカンを含み、0質量%~1質量%のイソパラフィン含有量を有する第1の相転移材料(PCM)を産出するために、第1の追加ストリームを通過させるように構成された第2の蒸留カラムおよび対応する第2の吸着カラム、
を備え、
該吸着ユニットは、活性炭素及びイオン交換樹脂からなる群より選ばれる少なくとも1つの吸着剤を含み、更に
該反応器は、冷却物質を反応器中に、該反応物の流れと逆ではなく、該反応物の流れに垂直及び並流する間の角度で導入するノズルを備え、これにより該反応器に、該反応器の温度を制御するための内部冷却機能を反応器に提供する、
ことを特徴とする、システム。
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EP3746523A1 (en) | 2020-12-09 |
CA3092622C (en) | 2024-01-23 |
BR112020017866A2 (pt) | 2020-12-22 |
NZ766567A (en) | 2023-11-24 |
CA3092622A1 (en) | 2019-11-07 |
JP2021518859A (ja) | 2021-08-05 |
MY184991A (en) | 2021-04-30 |
SG10201803633UA (en) | 2019-11-28 |
US11674096B2 (en) | 2023-06-13 |
AU2019262567B2 (en) | 2023-11-16 |
TW202003820A (zh) | 2020-01-16 |
SG10201805293XA (en) | 2019-11-28 |
KR20220123553A (ko) | 2022-09-07 |
RU2020125852A (ru) | 2022-02-04 |
ZA202005558B (en) | 2024-06-26 |
US20210054292A1 (en) | 2021-02-25 |
CN111630136A (zh) | 2020-09-04 |
AU2019262567A1 (en) | 2020-08-20 |
MX2020008726A (es) | 2020-09-28 |
SG11202006046WA (en) | 2020-07-29 |
MY195388A (en) | 2023-01-18 |
PH12020551011A1 (en) | 2021-09-01 |
TWI793315B (zh) | 2023-02-21 |
KR20200100838A (ko) | 2020-08-26 |
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