JP2009512550A - 原油生成物の分解による追加の原油生成物の製造方法 - Google Patents
原油生成物の分解による追加の原油生成物の製造方法 Download PDFInfo
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- B60L1/00—Supplying electric power to auxiliary equipment of vehicles
- B60L1/02—Supplying electric power to auxiliary equipment of vehicles to electric heating circuits
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- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
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- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
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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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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- E21B43/2401—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection by means of electricity
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- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/28—Dissolving minerals other than hydrocarbons, e.g. by an alkaline or acid leaching agent
- E21B43/281—Dissolving minerals other than hydrocarbons, e.g. by an alkaline or acid leaching agent using heat
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- C10G2300/20—Characteristics of the feedstock or the products
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Abstract
【解決手段】地表下現場熱処理法で地層流体を製造する工程、地層流体を分離して、液体流及び第一ガス流を製造する工程、液体流を分離して、1種以上の原油生成物を製造する工程、沸点範囲分布が343℃を超える原油生成物を接触分解して、1種以上の追加の原油生成物を製造する工程を含む原油生成物の製造方法。第一ガス流はオレフィンを含有してよい。原油生成物の少なくとも1種は343℃を超える沸点を有する、及び/又は追加の原油生成物の少なくとも1種は第二ガス流である。
【選択図】図2
Description
1.発明の分野
本発明は、一般に炭化水素含有地層のような各種の地表下地層から炭化水素、水素及び/又はその他の生成物を製造する方法及びシステムに関する。
地下地層から得られる炭化水素は、エネルギー資源、供給原料及び消費製品として使用されることが多い。有用な炭化水素資源の枯渇に対する関心及び製造した炭化水素の品質低下に対する関心から、有用な炭化水素資源の一層効率的な回収法、処理法及び/又は使用法が発展した。地下地層中の炭化水素の化学的及び/又は物理的特性は、地下地層から炭化水素材料を一層容易に取出せるように変化させる必要があるかも知れない。このような化学的物理的変化としては、取出し可能な液体を製造する現場反応、地層中の炭化水素材料の組成変化、溶解度変化、密度変化、相変化、及び/又は粘度変化が挙げられる。限定されるものではないが、流体はガス、液体、エマルジョン、スラリー、及び/又は液体流と同様な流れ特性を有する固体粒子の流れであってよい。
幾つかの実施態様では本発明は、地表下現場熱分解熱処理法で地層流体を製造する工程、地層流体を分離して、液体流、及びオレフィン含有第一ガス流を製造する工程、液体流を分留して、1種以上の原油生成物を製造する工程であって、原油生成物の少なくとも1種は、38〜343℃の沸点範囲分布を有する該工程、沸点範囲分布が38〜343℃の該原油生成物を接触分解して、1種以上の追加の原油生成物を製造する工程であって、該追加の原油生成物の少なくとも1種は0.101MPaにおいて38℃以下の沸点を有する第二ガス流である該工程(但し、沸点範囲分布はASTM法D5307で測定)を提供する。
別の実施態様では、地表下地層の処理は、ここで説明した方法、システム又はヒーターのいずれかを用いて行なわれる。
別の実施態様では、ここで説明した特定の実施態様に追加の特徴を加えることができる。
本発明の利点は、以下の詳細な説明により、また添付図面を参照すれば、当業者に明らかとなり得る。
図1は、炭化水素含有地層を処理するための現場熱処理システムの一部の一実施態様の概略図である。
図2は、現場熱処理法で製造された混合物を処理するためのシステムの一実施態様の概略図である。
図3は、現場熱処理法で製造された液体流を処理するためのシステムの一実施態様の概略図である。
以下の説明は、一般に地層中の炭化水素を処理するシステム及び方法に関する。このような地層は、炭化水素生成物、水素、その他の生成物を生成させるために処理できる。
以下の説明は、一般に現場熱処理法を用いて炭化水素含有地層から製造した地層流体を処理するシステム及び方法に関する。炭化水素含有地層は、炭化水素生成物、水素、メタン、その他の生成物を生成させるために処理できる。
“現場(での)転化法”とは、炭化水素含有地層中に熱分解流体が生成するように、地層の少なくとも一部を熱分解温度より高い温度に上がるまで、炭化水素含有地層を熱源で加熱する方法のことである。
“炭素数”とは、分子中の炭素原子の数のことである。炭化水素流体は、炭素数分布により説明できる。炭素数分布は、真の沸点分布及び/又は気液クロマトグラフィーにより測定できる。
“現場熱処理法”とは、炭化水素含有地層中に流動化流体、粘度低減化流体、及び/又は熱分解流体が生成するように、地層の少なくとも一部を、流動化流体、炭化水素含有材料の粘度低減化(visbreaking)、及び/又は熱分解が生じる温度より高い温度に上がるまで、炭化水素含有地層を熱源で加熱する方法のことである。
“熱分解”は、加熱により化学結合を破壊することである。熱分解は、例えば1つの化合物を熱単独で1種以上の他の化合物に変成することである。熱は、地層の或る部分に伝達させて、熱分解を起こすことができる。幾つかの地層、地層の幾つかの部分、及び/又は地層中の他の材料は、触媒活性により熱分解を促進する可能性がある。
“粘度低減化”とは、熱処理中の流体に分子の絡み合いを解いて、及び/又は熱処理中、大きい分子から小さい分子に破壊して、流体の粘度を低下させることである。
“閉塞”とは、処理容器又は導管中の1種以上の組成物の流れを邪魔又は防止することである。
“ガソリン炭化水素”とは、沸点範囲が32℃(90°F)〜約204℃(400°F)の炭化水素のことである。ガソリン炭化水素としては、限定されるものではないが、直留ガソリン、ナフサ、流動化した又は熱接触的に分解したガソリン、VBガソリン、及びコーカーガソリンが挙げられる。ガソリン炭化水素の含有量は、ASTM法D2887により測定される。
“ケロシン”とは、0.101MPaでの沸点範囲分布が204〜260℃の炭化水素のことである。ケロシン含有量は、ASTM法D2887により測定される。
“ディーゼル”とは、0.101MPaでの沸点範囲分布が260〜343℃(500〜650°F)の炭化水素のことである。ディーゼル含有量は、ASTM法D2887により測定される。
“品質向上”とは、炭化水素の品質を向上させることである。例えば重質炭化水素を品質向上すると、重質炭化水素のAPI比重が増大する。
“API比重”とは、15.5℃(60°F)でのAPI比重のことである。API比重はASTM法D6822により測定される。
“X欄金属”とは、周期律表X欄の1種以上の金属、及び/又は周期律表X欄の1種以上の金属の1種以上の化合物のことである。ここで、Xは、周期律表の欄数(例えば1〜12)に相当する。例えば“6欄金属”とは、周期律表6欄の金属、及び/又は周期律表6欄の1種以上の金属の化合物のことである。
“品質向上”とは、炭化水素の品質を向上させることである。例えば重質炭化水素を品質向上すると、重質炭化水素のAPI比重が増大する可能性がある。
“セノスフェア(cenosphere)”とは、高温の熱処理で有機成分の揮発により溶融成分が気球のように膨らんだ際に形成される中空粒子のことである。
特定の実施態様では、地層流体は粒子の分布を含有してよい。粒子の分布は、限定されるものではないが、3様式又は2様式であってよい。例えば粒子の3様式分布としては、サイズ5〜10μmの粒子が1〜50ppm、サイズ50〜80μmの粒子が2〜2000ppm、及びサイズ100〜200μmの粒子が1〜100ppmが挙げられる。粒子の2様式分布としては、サイズ50〜60μmの粒子が1〜60ppm、及びサイズ100〜200μmの粒子が2〜2000ppmが挙げられる。
幾つかの実施態様では、製造された流体中の粒子の全部又は一部は、製造流体から除去してよい。これらの粒子は遠心、洗浄、酸洗浄、濾過、静電集塵、泡立て(起泡)浮遊、及び/又は他の種類の分離法を用いて除去できる。
液体流234から閉塞性組成物の分離中、膜の圧力差は、5〜60バール、10〜50バール、又は20〜40バールの範囲であってよい。分離温度は、液体流の流動点から100℃まで、約−20〜約100℃、10〜90℃、20〜85℃の範囲であってよい。連続分離中、透過液(permeate)フラックス速度は、初期フラックスの50%以下、70%以下、又は90%以下であってよい。供給原料に対する透過液の重量回収率は、50〜97重量%、60〜90重量%、又は70〜80重量%の範囲であってよい。
地層流体から製造した流れの利用を高めるため、液体流の分留で製造された炭化水素及びプロセスガスの分離で製造された炭化水素ガスは、更に炭素数の大きい炭化水素を形成するため、配合してよい。製造された炭化水素ガス流は、アルキル化反応に受入れ可能なレベルのオレフィンを含有できる。
追加のC3〜C5炭化水素流254’は、販売に好適なガソリンを製造するため、アルキル化ユニット266に送って、C3〜C5炭化水素流254と配合し、及び/又は炭化水素ガス流224と配合してよい。幾つかの実施態様では炭化水素ガス流224中のオレフィン含有量は受入れ可能で、追加のオレフィン源は必要としない。
分離された使用済み触媒流288は、分離システム286を出て、再生ユニット290に入る。再生ユニット290では、使用済み触媒は、炭素燃焼条件下で、例えば酸素及び/又は空気のような酸素源292と接触して、再生分解触媒流282及び燃焼ガス294を生成する。燃焼ガスは炭素及び/又はその他、接触分解工程で触媒上に形成された不純物を除去する際の副生物として形成できる。
幾つかの実施態様では第二接触分解システムの幾何構造は、概略円筒形になるような構造であり、ストリッピング帯域の長さ対直径比は、ストリッピング帯域内では所望の高い水蒸気速度を与えると共に、第二接触分解システムから取出される使用済み再生触媒の所望のストリッピングに対し、ストリッピング帯域内で充分な接触時間を与えるような比である。こうして、ストリッピング帯域の長さ対直径の寸法比は、1:1〜25:1、2:1〜15:1、又は3:1〜10:1の範囲であってよい。
図3では使用済み分解触媒280は第二接触分解システム284を出て、接触分解システム278に入る。使用済み分解触媒流280は、再生分解触媒282の触媒上にある炭素の濃度よりも僅かに高い炭素濃度を持ってよい。触媒上の炭素濃度が高いと、接触分解システム278からのオレフィンの収率を向上させる接触分解触媒を部分的に失活させる可能性がある。使用済み再生触媒のコークス含有量は、0.1重量%以上又は0.5重量%以上であってよい。使用済み再生触媒のコークス含有量は、0.1〜約1重量%又は0.1〜0.6重量%の範囲であってよい。
幾つかの実施態様では図2、3に記載のユニットから製造した残留物は、エネルギー源として使用できる。残留物は、燃焼する(例えばタービン中で燃焼する)及び/又は表面下の地層に注入する(例えば製造したガスを表面下の地層に注入)ガスを製造するため、ガス化できる。特定の実施態様では残留物は、アスファルトを製造するため、脱アスファルトされる。アスファルトはガス化できる。
実施例1:現場熱処理法液体流のナノ濾過
現場熱処理法で液体サンプル(500ml、398.68g)を得た。この液体サンプルは、液体サンプル1g当たり硫黄を0.0069g、窒素を0.0118g含有する。液体サンプルの最終沸点は481℃、密度は0.8474である。サンプルの濾過に用いた膜分離ユニットは、CM Celfa Membrantechnik A.G.(スイス)から得られる実験室用の平坦なシート膜タイプP28である。濾過媒体として、単一の2μ厚ポリジメチルシロキサン膜(GKSS Forschungszentrum GmbH,Geesthact,ドイツ)を使用した。濾過システムは、50℃で操作し、膜上の圧力差は10バールであった。透過液側の圧力は、ほぼ大気圧とした。透過液を収集し、連続法にシミュレートするため、濾過システム経由で再循環した。周囲の空気との接触を防止するため、透過液は窒素でガスシールした。濃縮液も分析のため収集した。濾過中、2kg/m3/バール/hrの平均線束(flux)は、初期の線束から或る程度、下降しなかった。濾過液(298.15g、74.4%回収)は、濾過液1g当たり硫黄を0.007g、窒素を0.0124g含有し、また密度は0.8459、最終沸点は486℃であった。濃縮液(56.46g、14.16%回収)は、濃縮液1g当たり硫黄を0.0076g、窒素を0.0158g含有し、また密度は0.8714、最終沸点は543℃であった。
実施例1の非濾過液サンプル及び濾過液サンプルについて汚染挙動をテストした。汚染挙動は、Alcor熱汚染テスターを用いて測定した。Alcor熱汚染テスターは、使用前にNorton R22サンドペーパーで擦った(grated)1018鋼製の小型多管式熱交換器である。テスト中、熱交換器温度(Te)を一定値に維持しながら、サンプル出口温度(Tout)を監視した。汚染が生じて管表面に物質が沈着すれば、サンプルの熱抵抗が増大し、その結果、出口温度は低下する。所定時間後、出口温度の低下は、汚染の酷さの尺度となる。2時間操作後の温度を汚染の酷さの指標として使用する。ΔT=Tout(0)−Tout(2h)。ここでTout(0)はテスト開始時に得られた最大(安定)出口温度として定義し、Tout(2h)は、出口温度の最初に示された低下後、又は出口温度が少なくとも2時間安定であった時点で記録された2時間である。
本例は現場熱処理法で製造した液体流のナノ濾過により、閉塞性組成物の少なくとも一部は除去されることを示す。
実験的パイロットシステムを用いて実験を行なった。このパイロットシステムは供給原料供給システム、触媒装填・輸送システム、第一流動立上り管反応器、ストリッパー、生成物分離・収集システム、及び再生器を備える。立上がり管反応器は、内径11〜19mm、長さ約3.2mの断熱性立上がり管である。立上がり管反応器の出口は、ストリーパーと流通可能に接続し、ストリッパーは立上がり管反応器の出口流と同じ温度で、かつ本質的に100%のストリッピング効率が得られるように操作した。再生器は、使用済み触媒の再生に使用される多段連続再生器である。使用済み触媒は、制御された温度で再生器に供給し、再生された触媒は容器に収集した。30分間隔での各実験運転中、物質バランスが得られた。複合ガスサンプルは、オンラインガスクロマトグラフを用いて分析し、また液体生成物サンプルは収集し、一晩で分析した。コークスの収量は、ユニットの操作が定常状態の時、各運転で採取した使用済み再生触媒サンプル上のコークスを測定する場合と同様、触媒流を測定し、触媒上のデルタコークスを測定することにより測定した。
熱分解したナフサを使用して、現場熱処理法で製造した沸点範囲分布が30〜182℃の液体流をシミュレートした。このナフサは、ナフサ1g当たり、ナフテンを0.186g、イソパラフィンを0.238g、n−パラフィンを0.328g、シクロパラフィンを0.029g、イソオレフィンを0.046g、n−オレフィンを0.064g、及び芳香族を0.109g含有する。ナフサ流を前述の接触分解システム中で10%ZSM−5含有FCC E−Catと接触させて原油生成物を製造した。立上がり管反応器の温度は593℃(1100°F)に維持した。原油生成物は、原油生成物1g当たり、エチレンを0.1308g、エタンを0.0139g、C4オレフィンを0.0966g、C4イソオレフィンを0.0343g、ブタンを0.0175g、イソブタンを0.0299g、C5オレフィンを0.0525g、C5イソオレフィンを0.0309g、ペンタンを0.0442g、イソペンタンを0.0384g、C6炭化水素と沸点232℃(450°F)以下の炭化水素との混合物を0.4943g、沸点範囲分布が232〜343℃(450〜650°F)の炭化水素を0.0201g、沸点範囲分布が343〜399℃(650〜750°F)の炭化水素を0.0029g、及び沸点範囲分布が399℃以上(750°F以上)の炭化水素を0.00128g、及びコークスを0.00128g含有していた。C3〜C5オレフィンの合計量は、ナフサ1g当たり0.2799gであった。
214 流体分離ユニット
216 現場熱処理法液体流
218 場熱処理法ガス流
220 水性流
222 ガス分離ユニット
224 ガス炭化水素流
226 液体分離ユニット
228 ガス(炭化水素)流
230 塩含有プロセス液体流
232 脱塩ユニット
234 液体流
236 濾過システム
238 濾過液流
240 再循環液流
242 廃棄物流242
244 水素源
248 水素化処理ユニット
250 水素化処理液体流
252 分留ユニット
254 C3〜C5炭化水素流
256 ナフサ流
258 ケロシン流
262 ディーゼル流
264 塔底流
266 アルキル化ユニット又は配合流
268 炭化水素流
270 接触分解ユニット
272 ガソリン炭化水素流
274 液体流
276 水蒸気
278 接触分解システム
280 (使用済み)再生接触分解触媒流
282 再生分解触媒流
284 第二接触分解システム
286 分離システム
288 使用済み触媒流
290 再生ユニット又は再生器
292 酸素源
294 燃焼ガス
296 原油生成物
298 液体分離ユニット
300 ガソリン炭化水素流
302 (軽質)サイクル油流
304 塔底流
306 ガス油炭化水素流
308 粗製オレフィン流
310 オレフィン分離システム
312 エチレン生成物又はオレフィン流
314 プロピレン生成物又はオレフィン流
316 ブチレン生成物又はオレフィン流
Claims (20)
- 地表下現場熱分解熱処理法で地層流体を製造する工程、
地層流体を分離して、液体流、及びオレフィン含有第一ガス流を製造する工程、
液体流を分留して、1種以上の原油生成物を製造する工程であって、原油生成物の少なくとも1種は、ASTM法D5307で測定して38〜343℃の沸点範囲分布を有する該工程、
沸点範囲分布が38〜343℃の該原油生成物を接触分解して、1種以上の追加の原油生成物を製造する工程であって、該追加の原油生成物の少なくとも1種は0.101MPaにおいて38℃以下の沸点を有する第二ガス流である該工程、
を含む原油生成物の製造方法。 - 第二ガス流が、炭素数3以上の炭化水素を含有する請求項1に記載の方法。
- 追加の原油生成物の少なくとも1種が、ASTM法D5307で測定して38〜200℃の沸点範囲分布を有する請求項1又は2に記載の方法。
- 追加の原油生成物の少なくとも1種が、ガソリン炭化水素を含有する請求項1〜3のいずれか1項に記載の方法。
- ガソリン炭化水素のオクタン価が70以上である請求項4に記載の方法。
- 地表下現場熱処理法で地層流体を製造する工程、
地層流体を分離して、液体流を製造する工程、
第一接触分解システム中で該液体流を接触分解触媒と接触させて液体流を接触分解することにより、原油生成物流及び使用済み接触分解触媒を製造する工程、
使用済み接触分解触媒を再生して、再生接触分解触媒を製造する工程、
第二接触分解システム中でガソリン炭化水素流を再生接触分解触媒と接触させて、ガソリン炭化水素流を接触分解することにより、炭素数2以上の炭化水素を含有する粗製オレフィン流及び使用済み再生接触分解触媒を製造する工程、
粗製オレフィン流から炭素数2〜5のオレフィンを分離する工程、及び
第二接触分解システムからの使用済み再生接触分解触媒を第一接触分解システムに供給する工程、
を含む炭化水素の製造方法。 - 接触分解触媒が、非晶質シリカアルミナとゼオライトとを含む請求項6に記載の方法。
- 第二接触分解システムにZSM?5を供給する工程を更に含む請求項6又は7に記載の方法。
- 再生接触分解触媒のコークス含有量が、0.01〜0.5重量%の範囲である請求項6〜8のいずれか1項に記載の方法。
- 使用済み再生接触分解触媒と再生接触分解触媒との重量比が、0.1:1〜100:1の範囲である請求項6〜9のいずれか1項に記載の方法。
- 第一及び/又は第二接触分解システムに水蒸気を供給する工程を更に含む請求項6〜10のいずれか1項に記載の方法。
- 原油生成物を1種以上の炭化水素流に分離する工程であって、炭化水素流の少なくとも1種はガソリン炭化水素流である該工程を更に含む請求項6〜11のいずれか1項に記載の方法。
- 炭化水素流の少なくとも1種がサイクル油流であって、該サイクル油流の少なくとも一部を第一接触分解システムに供給する請求項6〜12のいずれか1項に記載の方法。
- 炭素数3〜5のオレフィンの少なくとも一部をアルキル化ユニットに供給する工程を更に含む請求項6〜13のいずれか1項に記載の方法。
- 炭素数3〜5のオレフィンの少なくとも一部をアルキル化ユニットに供給し、次いで該オレフィンをアルキル化して、輸送用燃料にブレンドするのに好適な炭化水素を製造する工程を更に含む請求項6〜13のいずれか1項に記載の方法。
- 輸送用燃料がガソリンである請求項15に記載の方法。
- 前記オレフィンの少なくとも一部を重合ユニットに供給する工程を更に含む請求項6〜16のいずれか1項に記載の方法。
- 前記液体流の少なくとも一部を、閉塞性組成物の除去に充分な条件で水素化処理する工程を更に含む請求項1〜17のいずれか1項に記載の方法。
- 請求項1〜18のいずれか1項に記載の方法で製造した原油生成物の1種以上を用いて輸送用燃料を製造する方法。
- 請求項1〜19のいずれか1項に記載の方法で製造した炭化水素を含有する輸送用燃料。
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