JP2013527295A - フィッシャー−トロプッシュ生成物流のオレフィン含有量を低減する方法及びシステム - Google Patents
フィッシャー−トロプッシュ生成物流のオレフィン含有量を低減する方法及びシステム Download PDFInfo
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- JP2013527295A JP2013527295A JP2013512070A JP2013512070A JP2013527295A JP 2013527295 A JP2013527295 A JP 2013527295A JP 2013512070 A JP2013512070 A JP 2013512070A JP 2013512070 A JP2013512070 A JP 2013512070A JP 2013527295 A JP2013527295 A JP 2013527295A
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- Prior art keywords
- catalyst
- catalyst bed
- synthesis gas
- cobalt
- component
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Images
Classifications
-
- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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Abstract
Description
本発明は、合成ガスを、留出燃料及び/又は潤滑油基油として有用な液体炭化水素混合物に転化する方法に関し、当該方法は、合成ガスを触媒と接触させて、それにより、オレフィン成分及びパラフィン成分を含有する液体を製造し、そして、当該液体を水素化触媒と接触させることにより当該オレフィン成分を飽和させることを含む。
今日世界で使用される可燃性液体燃料の大部分は、原油に由来する。しかし、原油を燃料源として使用する上でのいくつかの制限がある。例えば、原油は、有限的供給下にある。
一形態によれば、本発明は、合成ガスを炭化水素混合物に転化する方法であって、
一酸化炭素と水素の混合物を含むフィードを、下流の触媒床でオレフィン飽和触媒と及び上流の触媒床で酸性成分及びフィッシャー−トロプッシュ合成成分を含む合成ガス転化触媒と、接触させることを含み、
しかも、パラフィン及びオレフィンを含みそして約5重量%以下のC21+ノルマルパラフィンを含む中間炭化水素混合物が、前記合成ガス転化触媒によって形成され、そして、
しかも、前記オレフィンが、前記オレフィン飽和触媒によって飽和され、それにより、約5重量%以下のC21+ノルマルパラフィンを含み約25重量%以下のオレフィンを含む最終炭化水素混合物になる、前記方法に関する。
図1を参照すると、一形態によれば、単一固定床反応器で上流の触媒床4及び下流の触媒床8上を合成ガス2のフィードを通過させることにより、留出燃料及び/又は潤滑油基油範囲の液体パラフィンの合成方法が開示される。固定床反応器内では、複数の小径管が、共通の冷媒中に入っている。オレフィン族及びパラフィン系炭化水素の中間混合物は、合成ガスを、上流の触媒床4の中の合成ガス転化触媒と接触させることにより、形成される。そのように形成された炭化水素混合物は、メタンから、30以上の炭素数を痕跡量(<0.5重量%)しか含まない軽ワックスまで多岐にわたり得るのであり、そして、直鎖状、分岐、及び環状化合物を含み得る。ここで定義するように、用語「ワックス」及び「固体ワックス」は、C21+ノルマルパラフィンに言及する。中間炭化水素混合物をその後、下流の触媒床8の中で、オレフィン飽和触媒としても言及される水素化触媒と、接触させる。この形態によれば、合成ガス転化とその後のオレフィン飽和との両方は、オレフィン飽和用の別個の反応器を提供する必要なく、本質的に共通の反応条件下で、単一の反応器の中で実施される。「本質的に共通の反応条件」とは、反応器の中の冷媒の温度が、点ごとに数℃(例えば、0−3℃)の中で一定であり、反応器の中の圧力が、当該2つの床の間で釣り合っていることを、意味する。場合により、好ましくないが、1を超える冷却システムが、お互いに物理的に分離した1を超える冷媒を利用して、使用でき、その場合には、当該冷媒は異なる温度であってもよい。上流及び下流の床の温度及び圧力を別個に制御する必要がないことは有利ではあるが、当該2つの床の温度及び圧力は、幾らか異なることができる。当該床温度は、それらの中で進行する反応の相対的な発熱に依存するであろう。合成ガス転化により発生する発熱は、オレフィン飽和により発生する発熱よりも大きく、平均の上流床温度は平均の下流床温度よりも一般的に高いであろう。当該床の間の温度の相違は、様々な反応器設計要因に依存するであろう。様々な反応器設計要因は、冷媒の温度、反応器中の管の直径、及び反応器を通るガス流の速度を含むが、それらに限定されない。適切な熱制御のために、当該2つの床の温度は、冷媒温度の約10℃の範囲内に好ましくは維持され、したがって、上流の床と下流の床との間の温度の相違は、好ましくは約20℃未満であり、更に約10℃未満である。上流の床の末端での圧力は、下流の床の先頭での圧力に等しい。なぜなら、当該2つの床はお互いに開いているからである。ガスは反応器の中の細い管を通ることが強制されるので、上流の床の上部から下流の床の底部への圧力降下があろうということに注目するように。反応器を横断する圧力降下は、約50psi(約3.4気圧)のように高いことがあり得るのであり、したがって、当該床の間の圧力の平均の相違は、約25psi(約1.7気圧)までであり得る。この形態によれば、上流の触媒床及び下流の触媒床は、直列に、積重ね床構成で配置される。
0−20、例えば、5−15又は8−12、重量%CH4;
0−20、例えば、5−15又は8−12、重量%C2−4;
60−95、例えば、70−90又は76−84、重量%C5+;及び
0−5重量%C21+ノルマルパラフィン類。
20重量%アルミナ及び80重量%ZSM−12の上に担持された7.5重量%Co−0.19重量%Ruを含む触媒の調製
ZSM−12粉末を最初に550℃で2時間焼成した。50gの当該焼成したZSM−12粉末と12.5gのcatapal Bアルミナ粉末をミキサーに添加して10分間混合した。30.6gの脱イオン水及び0.89gの硝酸を、当該混合粉末に添加して、10分間混合した。当該混合物を、その後、The Bonnot Company(Uniontown,Ohio)から市販されている1インチBBガン押出機に移送し、48個の1/16インチ(0.16cm)の穴を含むダイプレートを通して押し出した。当該ZSM−12押出物を、最初に70℃で2時間、その後、120℃で2時間乾燥させ、そして、最後に600℃で2時間気流中で焼成した。
55重量%アルミナ及び45重量%SSZ−32の上に担持された1.0%Pdを含む水素化触媒の調製
1.61gの硝酸パラジウム塩を120ccの水に溶解した。当該パラジウム溶液を、120gのアルミナ(55%アルミナ)結合SSZ−32ゼオライトに添加した。水を65℃にゆっくりと加熱しながらロータリーエバポレーターの中で除去した。当該減圧乾燥した材料を、一晩中120℃でオーブン中で空気中で乾燥させ、最終的に、マッフル炉の中で2時間300℃で焼成した。
実施例1及び実施例2の合成ガス転化触媒を使用する合成ガス転化及びオレフィン水素化
6gのガンマ−アルミナで希釈された実施例1に記載した触媒2gと実施例2に記載した触媒2gとの混合物を、少量のガラスウールによって分離され実施例1からの触媒の下流に配置した実施例2の触媒と直列の0.5インチ(1.27cm)内径の316−SS管反応器に、移送した。その後、当該反応器を反応器炉の中に配置した。当該触媒床を、2時間アルゴンの下向きの流れでフラッシュさせ、その後、ガスフィードを流速100sccmの純粋な水素に切り替えた。温度を、1℃/分の温度間隔でゆっくりと120℃に上昇させ、そこで1時間保持し、その後、1℃/分の温度間隔で250℃に上昇させ、10時間一定に保持した。この後、純粋な水素ガス流の下で保持しながら、当該触媒床を180℃に冷却した。すべての流は下向きに向けた。
6gのアルファアルミナ(450−850μm)で希釈された実施例1に記載した2.0g 7.5%Co/0.19Ru/ZSM−12を2gと0.3gの5%Pd/Al2O3(0.9gのAl2O3で希釈された、Alfa/Aesarから市販)との混合物を、少量のガラスウールによって分離され実施例1からの触媒の下流に配置したPd/Al2O3触媒と直列の0.5インチ(1.27cm)内径の316−SS管反応器に、移送した。その後、当該反応器を反応器炉の中に配置した。当該触媒床を、2時間アルゴンの下向きの流れでフラッシュさせ、その後、ガスフィードを流速100sccmの純粋な水素に切り替えた。温度を、1℃/分の温度間隔でゆっくりと120℃に上昇させ、1時間一定に保持し、その後、1℃/分の温度間隔で250℃に上昇させ、10時間一定に保持した。この後、純粋な水素ガス流の下で保持しながら、当該触媒床を180℃に冷却した。すべての流は下向きに向けた。
実施例1の合成ガス転化触媒を使用したリサイクル有り及び無しでの合成ガス転化
6gのガンマ−アルミナで希釈された実施例1に記載した2.0gの触媒の混合物を、0.5”(1.27cm)内径の316−SS管反応器に、移送した。その後、当該反応器を反応器炉の中に配置した。当該触媒床を、2時間アルゴンの下向きの流れでフラッシュさせ、その後、ガスフィードを流速100sccmの純粋な水素に切り替えた。温度を、1℃/分の温度間隔でゆっくりと120℃に上昇させ、1時間一定に保持し、その後、1℃/分の温度間隔で250℃に上昇させ、10時間一定に保持した。この後、純粋な水素ガス流の下で保持しながら、当該触媒床を180℃に冷却した。すべての流は下向きに向けた。
Claims (15)
- 合成ガスを炭化水素混合物に転化する方法であって、
一酸化炭素と水素の混合物を含むフィードを、下流の触媒床でオレフィン飽和触媒と及び上流の触媒床で酸性成分及びフィッシャー−トロプッシュ合成成分を含む合成ガス転化触媒と、接触させることを含み、
しかも、パラフィン及びオレフィンを含みそして約5重量%以下のC21+ノルマルパラフィンを含む中間炭化水素混合物が、前記合成ガス転化触媒によって形成され、そして、
しかも、前記オレフィンが、前記オレフィン飽和触媒によって飽和され、それにより、約5重量%以下のC21+ノルマルパラフィンを含み約25重量%以下のオレフィンを含む最終炭化水素混合物になる、前記方法。 - 前記上流の触媒床と前記下流の触媒床との間で、前記中間炭化水素混合物をセパレーターに通過させて、前記下流の触媒床に通す液体炭化水素、除去される水及び前記上流の触媒床にリサイクルするガスに分離する、請求項1に記載の方法。
- 前記上流の触媒床及び前記下流の触媒床が、単一の反応器内にあり、そして、本質的に共通の反応器温度及び本質的に共通の反応器圧力を有する、請求項1に記載の方法。
- 前記最終炭化水素混合物が約5重量%以下のオレフィンを含む、請求項1に記載の方法。
- 前記フィッシャー−トロプッシュ合成成分が、ルテニウム、レニウム、白金、パラジウム、金及び銀から成る群から選択されるプロモーターを更に含む、請求項1に記載の方法。
- 前記酸性成分がゼオライトを含む、請求項1に記載の方法。
- 前記合成ガス転化触媒が、コバルト、鉄またはルテニウムと、酸性成分との混合物を含む、請求項1に記載の方法。
- 前記合成ガス転化触媒が、酸性成分担体上のコバルト、鉄及び/又はルテニウムを含む、請求項1に記載の方法。
- 前記オレフィン飽和触媒が、白金、パラジウム、ロジウム、イリジウム、銀、オスミウム及び金、それらの組合せ、及び、ルテニウムを含む金属の組合せから成る群から選択される、請求項1に記載の方法。
- 前記下流の触媒床の前記オレフィン飽和触媒が、金属硫化物を含む、請求項2に記載の方法。
- 前記オレフィン飽和触媒が、鉄、ニッケル、亜鉛、モリブデン、タングステン、銅、鉛、コバルト、ニッケル−モリブデン、コバルト−モリブデン、ニッケル−タングステン、及びコバルト−タングステンから成る群から選択される金属を含む、請求項2に記載の方法。
- 前記オレフィン飽和触媒が、ゼオライト担体を含む、請求項1に記載の方法。
- 製造された前記最終炭化水素混合物が:
0〜20重量%のCH4;
0〜20重量%のC2−C4;及び
60〜95重量%のC5+
を含む、請求項1に記載の方法。 - 前記最終炭化水素混合物が、周囲条件で固体ワックスを実質的に含まない、請求項1に記載の方法。
- 前記最終炭化水素混合物が、15℃以下の曇り点を有する、請求項1に記載の方法。
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US12/797,773 US8461220B2 (en) | 2010-06-10 | 2010-06-10 | Process and system for reducing the olefin content of a fischer-tropsch product stream |
PCT/US2011/039851 WO2011156636A2 (en) | 2010-06-10 | 2011-06-09 | Process and system for reducing the olefin content of a fischer-tropsch product stream |
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US20130253078A1 (en) * | 2012-03-23 | 2013-09-26 | Chevron U.S.A. Inc. | Improved hybrid fischer-tropsch catalysts and processes for use thereof |
US9023899B2 (en) * | 2012-03-23 | 2015-05-05 | Chevron U.S.A. Inc. | Hybrid fischer-tropsch catalysts and processes for use thereof |
CN104232139B (zh) * | 2013-06-07 | 2016-12-07 | 中国海洋石油总公司 | 一种由炭质材料生产甲烷联产液体燃料的方法 |
WO2017197515A1 (en) | 2016-05-16 | 2017-11-23 | Meg Energy Corp. | Direct olefin reduction of thermally cracked hydrocarbon streams |
WO2019183444A1 (en) * | 2018-03-23 | 2019-09-26 | Southern Research Institute | Hydrogenation and oligomerization process |
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