JP5703096B2 - スラリー中の微粒子含有量の見積もり方法及び炭化水素油の製造方法 - Google Patents
スラリー中の微粒子含有量の見積もり方法及び炭化水素油の製造方法 Download PDFInfo
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- JP5703096B2 JP5703096B2 JP2011080619A JP2011080619A JP5703096B2 JP 5703096 B2 JP5703096 B2 JP 5703096B2 JP 2011080619 A JP2011080619 A JP 2011080619A JP 2011080619 A JP2011080619 A JP 2011080619A JP 5703096 B2 JP5703096 B2 JP 5703096B2
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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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- 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
- C10G2/34—Apparatus, reactors
- C10G2/342—Apparatus, reactors with moving solid catalysts
- C10G2/344—Apparatus, reactors with moving solid catalysts according to the "fluidised-bed" technique
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- 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
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
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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
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Description
工程S1では、まず、脱硫装置(図示省略。)により、天然ガス中に含まれる硫黄化合物を除去する。通常この脱硫装置は、公知の水素化脱硫触媒が充填された水素化脱硫反応器及びその後段に配設された、例えば酸化亜鉛等の硫化水素の吸着材が充填された吸着脱硫装置から構成される。天然ガスは水素とともに水素化脱硫反応器に供給され、天然ガス中の硫黄化合物は硫化水素に転化される。続いて吸着脱硫装置において硫化水素が吸着除去されて、天然ガスが脱硫される。この天然ガスの脱硫により、改質器に充填された改質触媒、工程S2で使用されるFT合成触媒等の硫黄化合物による被毒を防止する。
CH4+H2O→CO+3H2 (1)
CH4+CO2→2CO+2H2 (2)
工程S2においては、工程S1において製造された合成ガスが気泡塔型スラリー床反応器C2に供給され、合成ガス中の水素ガスと一酸化炭素ガスから炭化水素が合成される。
2nH2+nCO→(−CH2−)n+nH2O (3)
工程S3では、上記反応器C2の外部に設けられた分離システムによって重質液体炭化水素を抜き出し、後段へと供給する。当該システムは、流出管L6を介して抜き出されたスラリーを重質液体炭化水素とFT合成触媒粒子とに分離する触媒分離器D4と、触媒分離器D4により分離されたFT合成触媒粒子及び一部の炭化水素油を反応器C2に返送する返送管L10とを主として含む。
工程S4では、触媒分離器D4から供給された重質液体炭化水素と、気液分離器D2から供給された軽質液体炭化水素との混合物を第1精留塔C4において分留する。この分留により、FT合成油を、と概ねC5〜C10であり沸点が約150℃よりも低い粗ナフサ留分と、概ねC11〜C21であり沸点が約150〜360℃である粗中間留分と、概ねC22以上であり沸点が約360℃を超える粗ワックス留分とに分離する。
第1精留塔C4から工程S4により移送された粗ワックス留分は、ラインL12に接続される水素ガスの供給ライン(図示省略。)により供給される水素ガスとともに、ラインL12の中途に設置された熱交換器H4により粗ワックス留分の水素化分解に必要な温度まで加熱された後、水素化分解装置C6へ供給されて水素化分解される。なお、水素化分解装置C6において水素化分解を十分に受けなかった粗ワックス留分(以下、場合により「未分解ワックス留分」という。)は、工程S8において第2精留塔C12の塔底油として回収され、ラインL38によりラインL12にリサイクルされ、水素化分解装置C6へ再び供給される。
第1精留塔C4からラインL18により抜き出された粗中間留分は、ラインL18に接続される水素ガスの供給ライン(図示省略。)により供給される水素ガスとともに、ラインL18に設置された熱交換器H6により粗中間留分の水素化精製に必要な温度まで加熱された後、中間留分水素化精製装置C8へ供給され、水素化精製される。
第1精留塔C4の塔頂からラインL14により抜き出された粗ナフサ留分は、ラインL14に接続される水素ガスの供給ライン(図示省略。)により供給される水素ガスとともに、ラインL14に設置された熱交換器H8により粗ナフサ留分の水素化精製に必要な温度まで加熱された後、ナフサ留分水素化精製装置C10へ供給され、水素化精製される。
水素化分解装置C6からの流出油から得られる液体炭化水素及び中間留分水素化精製装置C8からの流出油から得られる液体炭化水素からなる混合油は、ラインL32に設置された熱交換器H10で加熱された後に、第2精留塔C12へ供給され、概ねC10以下である炭化水素と、灯油留分と、軽油留分と、未分解ワックス留分とに分留される。概ねC10以下の炭化水素は沸点が約150℃より低く、第2精留塔C12の塔頂からラインL44により抜き出される。灯油留分は沸点が約150〜250℃であり、第2精留塔C12の中央部からラインL42により抜き出され、タンクT4に貯留される。軽油留分は沸点が約250〜360℃であり、第2精留塔C12の下部からラインL40により抜き出され、タンクT2に貯留される。未分解ワックス留分は沸点が約360℃を超え、第2精留塔C12の塔底から抜き出され、ラインL38により水素化分解装置C6の上流のラインL12にリサイクルされる。第2精留塔C12の塔頂から抜き出された概ねC10以下の炭化水素はラインL44及びL36によりナフサ・スタビライザーに供給され、ナフサ留分水素化精製装置C10より供給された液体炭化水素とともに分留される。
工程S9では、流出管L6を介して抜き出されたスラリーの一部を採取し、本発明に係るスラリー中の微粒子含有量の見積もり方法によりスラリーにおける所定の粒子径以下の微粒子の含有量を見積もる。この工程は、定期的に及び/又は随時行うことができる。
工程S10では、逆洗液槽(図示省略。)に貯留されている液体炭化水素をポンプ等(図示省略。)によって触媒分離器D4内のフィルターF1に流通方向と逆方向に流通させる。そして、フィルターに堆積した触媒粒子を逆洗液である液体炭化水素とともに返送管L10を介して反応器C2内のスラリー床中に戻す。
未使用のFT合成触媒(シリカ担体にコバルト酸化物を担持した触媒、平均粒子径は96μm)をボールミルで粉砕し、更に乾式振動篩い器で篩い分けを行って、粒子径が10μm以下の触媒微粒子を得た。
上記の各標準試料を100℃に加熱して炭化水素を溶融状態に保持し、撹拌しながら5mlの試料を石英ガラス製セルに導入した。そして、10分間の静置後に、日本分光社製可視・紫外光分光分析装置V−660を用いて、セル内の試料液面から1cm深いところの可視光透過率をそれぞれ測定した。なお、測定波長は550nmとし、測定中は試料の温度を100℃に保持した。
各標準試料中の微粒子濃度と、上記で得られた可視光透過率との関係をプロットすることにより検量線を作成した。図3は、標準試料中の微粒子濃度と可視光透過率との関係をプロットしたグラフである。図3中のAで示される線は、微粒子濃度が250質量ppmを下回る試料の結果からランバート・ベール法に基づいて作成された検量線(y=106.97e−0.0064x)を示し、Bで示される線は、微粒子濃度が250質量ppm以上の試料の結果からランバート・ベール法に基づいて作成された検量線(y=32.641e−0.0022x)を示す。
未使用のFT合成触媒(前述の標準試料の作成に使用したものと同一)をボールミルで粉砕し、更に乾式振動篩い器で篩い分けを行って、粒子径が10μm以下の触媒微粒子を得た。一方で、乾式振動篩い器の篩い上サンプルを回収することにより粒子径が10μmを超える触媒粒子を得た。
(実施例1)
測定用スラリー試料を、100℃に加熱して炭化水素を溶融状態に保持し、撹拌しながら5mlのスラリー試料を石英ガラス製セルに導入した。そして、10分間の静置後に、日本分光社製可視・紫外光分光分析装置V−660を用いて、セル内の試料液面から1cm深いところの可視光透過率をそれぞれ測定した。なお、測定波長は550nmとし、測定中は試料の温度を100℃に保持した。
所定の時間FT合成反応に使用した後の触媒からの微粒子の発生状況について、下記の焼き飛ばし法及び溶剤洗浄法でスラリーを処理し評価を試みた。
FT合成反応塔からFT合成触媒(前述の標準試料の作成に使用したものと同一のものを使用。)及び生成油を含有するスラリーを採取した。なお、生成油は、炭素数C20〜C100からなるノルマルパラフィンの含有量が99質量%であるFTワックスの組成を有していた。
比較例1と同様にスラリーを採取した。採取したスラリー試料を100℃に加熱して炭化水素を融解させ、ここに加熱した大過剰(500ml×3回)のトルエンを加え、ろ紙を用いてスラリー試料のろ過・洗浄した。更に、トルエンをノルマルヘキサンに置換してトルエンを除去し、ろ紙上の触媒粒子を回収した。回収した触媒粒子は、ノルマルヘキサンを除去するため、60℃で3時間減圧乾燥させた。
比較例1と同様にスラリーを採取した。採取したスラリー試料を100℃に加熱して炭化水素を溶融状態に保持し、撹拌しながら5mlのスラリー試料を石英ガラス製セルに導入した。そして、10分間の静置後に、日本分光社製可視・紫外光分光分析装置V−660を用いて、セル内の試料液面から1cm深いところの可視光透過率をそれぞれ測定した。なお、測定波長は550nmとし、測定中は試料の温度を100℃に保持した。
Claims (5)
- ワックスを含む炭化水素に固体粒子が分散してなるスラリーにおける所定の粒子径以下の微粒子の含有量を見積もる方法であって、
ワックスを含む炭化水素に前記所定の粒子径以下の固体粒子を分散させたときの、前記炭化水素が液体となる温度における可視光透過率と前記所定の粒子径以下の固体粒子の含有量との相関に基づいて、
前記スラリーを前記温度に静置したときの上澄み部の可視光透過率から前記スラリーにおける所定の粒子径以下の微粒子の含有量を見積もる、スラリー中の微粒子含有量の見積もり方法。 - 前記固体粒子が、無機酸化物担体にコバルト及び/又はルテニウムが担持されてなるフィッシャー・トロプシュ合成触媒である、請求項1に記載のスラリー中の微粒子含有量の見積もり方法。
- 触媒粒子と液体炭化水素とを含むスラリーを内部に保持し、前記スラリーの上部に気相部を有する気泡塔型スラリー床反応器を用いてフィッシャー・トロプシュ合成反応により炭化水素油を製造する方法であって、
前記反応器の内部および/または外部に配置されたフィルターに前記スラリーを流通させて触媒粒子と重質液体炭化水素とを分離し、重質液体炭化水素を抜き出す工程と、
前記フィルターに前記スラリーの流通方向と逆方向に液体炭化水素を流通させ、前記フィルターに堆積した触媒粒子を前記反応器内のスラリー床中に戻す逆洗工程と、
請求項1又は2に記載の方法により前記スラリーにおける所定の粒子径以下の微粒子の含有量を見積もる監視工程と、を備える、炭化水素油の製造方法。 - 前記監視工程で得られる前記スラリーにおける所定の粒子径以下の微粒子の含有量の見積もり結果に基づいて、前記逆洗工程を実施する頻度を決定する、請求項3に記載の炭化水素油の製造方法。
- 前記監視工程で得られる前記スラリーにおける所定の粒子径以下の微粒子の含有量の見積もり結果に基づいて、前記抜き出された重質液体炭化水素に同伴する微粒子を除去するためのフィルターの交換又は洗浄の時期を決定する、請求項3に記載の炭化水素油の製造方法。
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CA2831743A CA2831743C (en) | 2011-03-31 | 2012-03-26 | Method for estimating content of fine particles in slurry and process for producing hydrocarbon oil |
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KR100992835B1 (ko) * | 2008-02-29 | 2010-11-08 | 한국화학연구원 | 피셔-트롭쉬 합성반응용 고체촉매와 생성물의 연속분리배출장치 및 방법 |
JP5501706B2 (ja) * | 2009-09-16 | 2014-05-28 | 独立行政法人石油天然ガス・金属鉱物資源機構 | 炭化水素の製造方法及び合成反応システム |
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EP2693191B1 (en) | 2016-12-28 |
US20140080926A1 (en) | 2014-03-20 |
EP2693191A1 (en) | 2014-02-05 |
BR112013025303B1 (pt) | 2020-10-13 |
CN103430008B (zh) | 2016-04-13 |
AP2013007201A0 (en) | 2013-10-31 |
ZA201307566B (en) | 2014-07-30 |
US9193917B2 (en) | 2015-11-24 |
AU2012233962C1 (en) | 2016-04-21 |
EA028779B1 (ru) | 2017-12-29 |
CN103430008A (zh) | 2013-12-04 |
AU2012233962B2 (en) | 2015-11-26 |
CA2831743A1 (en) | 2012-10-04 |
EA201391433A1 (ru) | 2014-02-28 |
EP2693191A4 (en) | 2014-10-08 |
WO2012133324A1 (ja) | 2012-10-04 |
BR112013025303A2 (pt) | 2016-12-13 |
AU2012233962A1 (en) | 2013-10-24 |
MY161300A (en) | 2017-04-14 |
JP2012214609A (ja) | 2012-11-08 |
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