JP2008512557A - 重油のアップグレードにおける活性スラリー触媒組成物のリサイクル法 - Google Patents
重油のアップグレードにおける活性スラリー触媒組成物のリサイクル法 Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
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- 238000009835 boiling Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
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- 239000002699 waste material Substances 0.000 claims description 2
- 230000009849 deactivation Effects 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 6
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
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- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、重油のアップグレードにおけるスラリー触媒組成物を用いた方法に関する。これらの重油は、低水素対炭素比および高炭素残留物、ならびに、アスファルテン、窒素、イオウおよび金属の高含量を特徴とする。
重油のアップグレードに使用されるスラリー触媒組成物は、一般に、1〜20ミクロンの範囲の傾向の粒度のためにリサイクルされない。これらの触媒粒子のリサイクルを試みる方法は、最終生成物からの当該触媒の分離および濃縮に複数の工程を必要とする傾向がある。使用工程は、精製技術上周知である。当該方法は、次の工程を含むが、それらに制約されない。即ち、溶媒脱瀝、遠心分離、濾過、沈殿、蒸留および乾燥である。これらの工程で使用される他の設備は、水旋器、押出機、掃引(wiped)液膜蒸発装置を含むことができるが、それらに制約されない。
本発明は、活性スラリー触媒組成物を用いた重油の水素化転換法に向けられるものである。
(a)水素化処理条件下のアップグレード用反応器中で、重質供給材料(heavy feed)、水素ガス、新鮮触媒スラリー組成物およびリサイクルスラリー組成物を配合し、
(b)アップグレード反応器流出液を分離ゾーンに通し、当該ゾーンで、900°F(482℃)までの温度で沸騰する生成物が上方を通され、
(c)前記分離ゾーン中に残った材料を、工程(b)から定速攪拌触媒貯蔵タンクに通し、
(d)当該定速攪拌触媒貯蔵タンク中の材料の少なくとも一部を工程(a)のアップグレード反応器に通す、
(a)(b)(c)(d)の上記4工程を含む。
・触媒を沈殿させないことによる、触媒凝集(触媒失活源)の防止、
・上部での水素化ゾーンからの中間留分の除去(高温高圧分離器からのガス蒸気として)
・当該水素化ゾーンからの無触媒生成物(沈殿、濾過、遠心分離などの必要なし)
・100%転換によって実質的な圧力および/または温度降下が起こった場合、触媒の大幅な失活がない。
・超縮合物(アスファルテン)およびコークの生成量がごくわずかであり、前記触媒組成物の活性にそれほど影響しない。
・前記分離工程での触媒濃縮−追加濃縮が必要ない。
本発明は、同時係属出願T-6344(S.N. )およびT-6393(S.N. )に開示されているものなど、活性スラリー触媒組成物を用いた、重油の水素化転換法に向けられたものである。これらの出願は、参照することによって本明細書に組み入れられている。当該触媒組成物は、モリブデンなどのVIB群金属化合物を含む。スラリー触媒組成物は、触媒の失活がそれほど起こることなく、単一分離工程のみを使用してリサイクルされることができる。当該単一分離工程は、好ましくは、高温高圧分離器を用いる。
アップグレード反応器10に示される第一工程の運転に関して、高転換率を達成するには、重油フィードストックの温度は、普通、約700°F(371℃)よりも高く、好ましくは750°F(399℃)よりも高く、最も好ましくは800°F(427℃)よりも高い。水素分圧は、350〜4500 psiの範囲で、水素対油比は、500〜10,000 SCFBである。重油中の前記活性スラリー触媒の濃度は、通常、重油フィードストック重量に対する金属(モリブデン)重量として表される約100〜20,000 ppmである。典型的には、触媒対油比が高いほど、イオウ、窒素および金属の除去に関して高転換率、ならびに、高分解転換率を生じる。高圧分離器温度は、800°F(427℃)程度であることができる。重油の100%近くの脱金属 (demetalation)転換率および1000°F (538℃)+分解転換率が、適切な方法条件で達成されることができ、一方、コーク収率は、約1%よりも少なく維持されることができる。
Claims (15)
- 沈殿を伴わないスラリー触媒組成物を用いた重油のアップグレード法であって、
(a)水素化処理条件下のアップグレード用反応器中で、重質供給材料(heavy feed)、水素ガス、新鮮触媒スラリー組成物およびリサイクルスラリー組成物を配合し、
(b)アップグレード反応器流出液を分離ゾーンに通し、この分離ゾーンにおいて900°F(482℃)までの温度で沸騰する生成物が上方を通され、
(c)前記分離ゾーン中に残った材料を、工程(b)から定速攪拌触媒貯蔵タンクに通し、
(d)当該定速攪拌触媒貯蔵タンク中の材料の少なくとも一部を工程(a)のアップグレード反応器に通す、
(a)(b)(c)(d)の4工程を含むアップグレード法。 - 前記重質供給物が、常圧軽油、減圧軽油、脱瀝油、オレフィン、タールサンドもしくはビチューメン由来油、石炭由来油、重質原油、フィシャー・トロプシュ法からの合成油およびリサイクル廃油およびポリマー由来油から成る群から選択されることを特徴とする、請求項1に記載の方法。
- 前記アップグレード法が、熱水素化分解、水素化処理、水素化脱硫、水素化脱窒素および水素化脱金属から成る群から選択されることを特徴とする、請求項1に記載の方法。
- 前記分離ゾーンが高温高圧分離器であることを特徴とする、請求項1に記載の方法。
- 製品の少なくとも50重量%が180〜650°F(82〜343℃)の範囲で沸騰することを特徴とする、請求項1に記載の方法。
- 前記アップグレード反応器が定速攪拌タンク反応器または沸騰床であることを特徴とする、請求項1に記載の方法。
- リサイクルスラリー触媒が、前記アップグレード反応器中で使用される触媒の95重量%までを含むことを特徴とする、請求項1に記載の方法。
- 水素化処理条件が750°F(399℃)よりも高温、350〜4500 psiの範囲の水素分圧、および、500〜10,000 SCFBの範囲の水素対油比を含むことを特徴とする、請求項1に記載の方法。
- 前記重油中の活性スラリー触媒濃度が、通常、重油フィードストック重量に対する金属(モリブデン)重量として表される約100〜20,000 ppmであることを特徴とする、請求項1に記載の方法。
- 900°F(482℃)よりも低温で沸騰する製品が触媒の除去に追加分離処理を必要としないことを特徴とする、請求項1に記載の方法。
- 900°F(482℃)よりも低温で沸騰する製品が、へテロ原子の除去のためにさらにアップグレードされることができることを特徴とする、請求項1に記載の方法。
- 前記アップグレードが、移動床反応器、沸騰床反応器および固定床反応器から成る群から選択される反応器中で起こることを特徴とする、請求項10に記載の方法。
- 前記アップグレードが固定床反応器中で起こることを特徴とする、請求項12に記載の方法。
- 脱金属転換率が約99%であることを特徴とする、請求項1に記載の方法。
- コーク収率が約1%よりも低いことを特徴とする、請求項1に記載の方法。
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US10/938,438 US7431824B2 (en) | 2004-09-10 | 2004-09-10 | Process for recycling an active slurry catalyst composition in heavy oil upgrading |
PCT/US2005/031892 WO2006031571A2 (en) | 2004-09-10 | 2005-09-07 | Process for recycling an active slurry catalyst composition in heavy oil upgrading |
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Cited By (3)
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JP2009214013A (ja) * | 2008-03-11 | 2009-09-24 | Ihi Corp | フィッシャー・トロプシュ合成触媒の連続再生方法及び装置 |
JP2014527116A (ja) * | 2011-09-15 | 2014-10-09 | シェブロン ユー.エス.エー. インコーポレイテッド | 水素化処理触媒及びその作製方法 |
JP2015523194A (ja) * | 2012-05-11 | 2015-08-13 | シャンハイ フアチャン エンバイロンメンタル プロテクション カンパニー リミテッドShanghai Huachang Environmental Protection Co., Ltd | 沸騰床残渣油水素化の排出触媒を処理する方法および装置 |
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EP1794265A4 (en) | 2010-09-08 |
WO2006031571A3 (en) | 2007-06-21 |
MX2007002672A (es) | 2007-05-16 |
WO2006031571A2 (en) | 2006-03-23 |
CA2579139C (en) | 2010-12-14 |
EA200700610A1 (ru) | 2007-10-26 |
KR20070051892A (ko) | 2007-05-18 |
NO20071781L (no) | 2007-04-04 |
EA011976B1 (ru) | 2009-06-30 |
KR100930991B1 (ko) | 2009-12-10 |
CN101300325B (zh) | 2012-04-18 |
EP1794265A2 (en) | 2007-06-13 |
JP4874977B2 (ja) | 2012-02-15 |
US20060054533A1 (en) | 2006-03-16 |
CN101300325A (zh) | 2008-11-05 |
US7431824B2 (en) | 2008-10-07 |
CA2579139A1 (en) | 2006-03-23 |
BRPI0515100A (pt) | 2008-07-08 |
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