JP5559428B2 - 液体重質炭化水素フィードストックのガス状生成物への変換 - Google Patents
液体重質炭化水素フィードストックのガス状生成物への変換 Download PDFInfo
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Description
(a)ガス状担体中に液体重炭化水素材料を分散させて分散重炭化水素フィード(feed)を生成する工程;
(b)熱エネルギー及びスチーム、並びに場合により一酸化炭素及び水素を含む過熱ガスフィード流を、アルカリ金属含浸炭素質担体の床を含む反応器に導入する工程;
(c)場合により酸素リッチ流を反応器に導入して熱エネルギー、並びに場合により、一酸化炭素及び水素をその場で生じさせる工程;
(d)分散重質炭化水素フィードを、アルカリ金属含浸炭素質担体の床の存在下、高圧で、そして約1100°Fから約1400°Fまでの温度でスチーム、一酸化炭素及び水素と接触させてメタン、エチレン及びプロピレンの一方又は両方、並びにエタン及びプロパンの一方又は両方を含む原ガス状混合物(raw gaseous mixture)を生じさせる工程;及び
(e)ガス状原生成物流として反応器から原ガス状混合物の流れを取出す工程、
を含み、
ここにおいて、工程(d)中の反応が、合成ガス要求(syngas demand)を有し、そして合成ガス要求が過熱ガスフィード流中に存在しうる一酸化炭素及び水素によって、そして工程(c)で生じうる一酸化炭素及び水素によって少なくとも実質的に満たされる、上記方法を提供する。
本発明は、液体重質炭化水素材料を最終的に有意量の軽質オレフィン及び軽質アルカンを含むガス状生成物流に変換する方法に関する。さらなる詳細を下に提供する。
本発明は、「液体重質炭化水素材料」の処理に関するものであって、それは、本発明によれば、本発明の方法に使用するために、材料をガス状担体中に分散することができるように、周囲条件で流動可能な液体であるか又は本方法の供給条件(下にさらに詳細に議論する)として用いられる高められた温度条件で流動可能な液体にすることができる粘性液体若しくは半固体炭素質材料である。
本発明の実施態様において、図1及び2に説明するように、混合容器又は機器(120)中で液体重質炭化水素材料流(10)をガス状担体流(15)と合わせ、ここで、液体重質炭化水素材料をガス状担体中に分散させて分散重質炭化水素フィード流(20)を生じさせる。一実施態様において、液体重質炭化水素材料をガス状担体中で霧化して霧化された重質炭化水素フィード流を生じさせる。
幾つかのタイプのガス化反応器のいずれかを、反応器(100/200)に用いることができる。適した反応器には、向流固定床、並流固定床、流動床、又は噴流若しくは移動床反応室である反応室を有するものが含まれる。図1の反応器(100)は、縦型の配置であり、そして典型的に流動床反応器である。
スチーム炭素:C+H2O→CO+H2 (I)
水性ガスシフト:CO+H2O→H2+CO2 (II)
COメタン化:CO+3H2→CH4+H2O (III)
水素添加ガス化:2H2+C→CH4 (IV)
2C+2H2O→CH4+CO2 (V)
床(110/210)に用いられるアルカリ金属含浸炭素質材料は、メタン、エタン、プロパン、エチレン及びプロピレンが反応から生じる主な炭化水素ガス状生成物であるように、反応器(100/200)中で行われる反応に触媒作用を及ぼすのに有効な量のアルカリ金属を含む粒状バイオマス及び/又は非バイオマスのような粒状炭素質担体材料である。
反応器(100)のような流動床反応器では、典型的に、汚染物質が蓄積されるため、床(110)の一部を除去し、そして時々交換する必要がある。床交換の量及び頻度は、主にどれくらいのコークスが炭素質担体上に付着し、そして残るかという要因による。他の要因としては、例えば、灰分の量及び担体粒子上に付着しうる液体重質炭化水素フィードの他の汚染物質含量又は他に「停滞(tie-up)」触媒成分が含まれる。
0217588A1、US2009/0218424A1、US2009/0217589A1、US2009/0217575A1、US2009/0229182A1、US2009/0217587A1、US2009/0246120A1、US2009/0259080A1、US2009/0260287A1、US2009/0324458A1、US2009/0324459A1、US2009/0324460A1、US2009/0324461A1、US2009/0324462A1、US2010/0121125A1、US2010/0120926A1、US2010/0071262A1、US2010/0168495A1、US2010/0168494A1、US2010/0292350A1、US2010/0287836A1、US2010/0287835A1、US2011/0031439A1、US2011/0062012A1、US2011/0062722A1、US2011/0064648A1、US2011/0088896A1、US2011/0088897A1、WO2010/048493A2及びGB1599932;それぞれ2010年12月16日に出願された米国特許出願第12/970,105号(代理人整理番号FN−0057 US NP1,表題Integrated Enhanced Oil Recovery Process)及び同第12/970,111号(代理人整理番号FN−0058 US NP1,表題Integrated Enhanced Oil Recovery Process);2011年2月21日に出願された米国特許出願第13/031486号(代理人整理番号FN−0059 US NP1,表題Integrated Hydromethanation Fuel Cell Power Generation);2011年3月3日に出願された米国特許出願第13/039995号(代理人整理番号FN−0060 US NP1,表題Integrated Hydromethanation Fuel Cell Power Generation);並びに2011年4月26日に出願された米国特許出願第13/094438号(代理人整理番号FN−0061 US NP1,表題Hydromethanation of a Carbonaceous Feedstock with Vanadium Recovery)に開示されている。
反応器(100/200)を出るガス状原生成物流(50)は、反応器(100/200)の運転温度及び圧力付近である。
of Natural Gas to Synthesis Gas, Reference: KBR Paper #2031,”Sandia National Laboratory Publication No. SAND2007-2331 (2007); 及び Bogdan, “Reactor Modeling and Process Analysis for Partial Oxidation of Natural Gas”, printed by Febodruk, B.V., ISBN: 90-365-2100-9 (2004)を参照のこと。
本発明のプロセスにおいて、各プロセスは、1つ又はそれ以上の処理ユニットで実施してもよい。例えば、1つ又はそれ以上のフィードストック調製単位操作からのフィードストックを用いて1つ又はそれ以上の反応器に供給してもよい。同様に、1つ又はそれ以上の反応器によって生じた原生成物ガス流を、1つ又はそれ以上のガス処理ユニット中で別々に又はそれらの組み合わせにより処理又は精製してもよい。
方法の特定の実施態様は、方法が、工程(a)、(b)、(d)及び(e)が連続的なやり方で操作される連続法であるものである。
内径2インチ、高さ4フィートのカラムに、カリウム触媒を含浸させた炭素チャー(900g)を充填した。チャーは、パウダーリバー盆地(powder river basin)(PRB)石炭に由来し、そして約0.29K/C含量を含んだ。
また、床材料として無触媒活性化炭素を用いて1回運転を行った。
第1の運転を1300°F及び150psigで行って触媒床対無触媒床の効果を比較した。表1に結果を示す。
上に記載された条件であるが、様々な圧力50psig、150psig、295psig及び500psigで触媒床を用いて4回運転を行った。
結果を、表2及び3に示す。
Claims (10)
- 液体重炭化水素材料からガス状原生成物流を生じさせる方法であって、
(a)ガス状担体中に液体重炭化水素材料を分散させて分散重炭化水素フィードを生成する工程;
(b)熱エネルギー及びスチームを含む過熱ガスフィード流を、アルカリ金属含浸炭素質担体の床を含む反応器に導入する工程;
(d)分散重質炭化水素フィードを、アルカリ金属含浸炭素質担体の床の存在下、高圧で、そして1100°F(593℃)から1400°F(760℃)までの温度でスチーム、一酸化炭素及び水素と接触させてメタン、エチレン及びプロピレンの一方又は両方、並びにエタン及びプロパンの一方又は両方を含む原ガス状混合物を生じさせる工程;及び
(e)ガス状原生成物流として反応器から原ガス状混合物の流れを取出す工程、を含み、
ここにおいて、
(1)(A)過熱ガスフィード流はさらに一酸化炭素及び水素を含む、又は
(B)当該方法はさらに(c)酸素を反応器に導入して熱エネルギー、一酸化炭素及び水素をその場で生じさせる工程を含む、又は、
(C)上記(A)と(B)の両方である;そして
(2)工程(d)中の反応において要求される合成ガスは、工程(b)の過熱ガスフィード流中に存在しうる一酸化炭素及び水素によって、工程(c)で生じうる一酸化炭素及び水素によって、そして工程(d)のその場で生じうる一酸化炭素及び水素によって満たされる、
上記方法。 - 液体重炭化水素材料を1つ又はそれ以上の供給点で反応器に送り、ガス状原生成物流を1つ又はそれ以上の取出し点で反応器から取出し、そして供給点から取出し点までの蒸気滞留時間が、2秒未満であることを特徴とする、請求項1に記載の方法。
- 原ガス状生成物流が、メタン+エタン+プロパンの合計(乾量基準)で少なくとも30mol%、及びエチレン+プロピレンの合計(乾量基準)で少なくとも8mol%を含むことを特徴とする、請求項1又は2に記載の方法。
- 液体重炭化水素材料をガス状担体中で霧化して分散重炭化水素フィードを生じさせることを特徴とする、請求項1〜3のいずれか1項に記載の方法。
- ガス状担体が、過熱スチームを主に含むことを特徴とする、請求項1〜4のいずれか1項に記載の方法。
- 高圧が最大で1000psig(6996kPa)までであることを特徴とする、請求項1〜5のいずれか1項に記載の方法。
- 酸素リッチガス流を反応器に送ることを特徴とする、請求項1〜6のいずれか1項に記載の方法。
- 反応器が反応器の底部に捕集ゾーンを含み、そして酸素リッチガス流を捕集ゾーンに送ることを特徴とする、請求項1〜7のいずれか1項に記載の方法。
- 床のブリード流を反応器から取出し、そしてブリード流を水添メタン化してメタン富化合成ガス流及び副生成物チャーを生じさせることを特徴とする、請求項1〜8のいずれか1項に記載の方法。
- 副生成物チャーの少なくとも一部を再利用触媒床として反応器に戻すことを特徴とする、請求項9に記載の方法。
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AU2011258204A1 (en) | 2012-11-29 |
AU2011258204B2 (en) | 2013-11-07 |
WO2011150217A2 (en) | 2011-12-01 |
WO2011150217A3 (en) | 2012-05-31 |
CA2793893A1 (en) | 2011-12-01 |
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