JP6082175B2 - 石油原料からのプロピレン生成量を最大化するための過酷度流動接触分解方法の高度制御方法 - Google Patents
石油原料からのプロピレン生成量を最大化するための過酷度流動接触分解方法の高度制御方法 Download PDFInfo
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- JP6082175B2 JP6082175B2 JP2009536277A JP2009536277A JP6082175B2 JP 6082175 B2 JP6082175 B2 JP 6082175B2 JP 2009536277 A JP2009536277 A JP 2009536277A JP 2009536277 A JP2009536277 A JP 2009536277A JP 6082175 B2 JP6082175 B2 JP 6082175B2
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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Description
本明細書に記載するように、本明細書における最良のプロピレン生成のための教示に従って適切に改変された流動接触分解装置は、軽質オレフィンを製造するのに用いることができる。そのような流動接触分解装置を用いることは、特に、石油化学工業と密接に結びついている石油精製において経済的に有利となり得る。
本発明の流動接触分解において、原料油として石油を使用する。石油は、直留ガスオイル、減圧ガスオイル、常圧残油、減圧残油、コーカー・ガスオイル、及び上記残油及びガスオイルを水素化精製又は水素化処理をすることにより得られた石油を含む。上記の石油は、単独で用いるか、又は少量の軽質分留油との混合物として用いてもよい。
しばしば“触媒/油比”と呼ばれる反応装置中の触媒濃度の増加は、触媒の最大転化率の可能性を増大させる。これは、反応装置の熱負荷を上げるか又は比較的低いコークス選択性(すなわち、より低いデルタコークス)触媒に切り替えることにより達成することができる。反応装置の熱負荷は、反応装置の上昇温度又はより低い供給速度によって上げることができる。これは、触媒/油比を上げることになり、装置の熱平衡を維持する。
再生触媒上炭素(CRC)が低ければ低いほど、酸分解サイトをブロックするコークスが少ないから、分解サイトの有効性がより高くなる。CRCは、一酸化炭素酸化促進剤を用いて再生効率を高めることにより減らせる。再生装置の床レベルを上げても滞留時間が増えてCRCを改善するが、これは、短縮された希薄相分離器滞留時間及び触媒の損失量増加の可能性とバランスさせなければならない。
触媒は、予め決められたスケジュールに基づいて一定間隔でFCC装置に加えることができる。本発明の一つの特定の側面において、供給触媒は、連続的に調整される。しかし、自動システムにおいて、新しい触媒の投入時期及び量は、FCCプロセス中に増量して生成収率、生成混合物を最良のものとするための規定とともに制御装置にプログラムすることができる。供給原料油の化学組成、及びその他のFCCシステムに加わる変数のような、生成プロセスに関わる不確実要因により、排出物、エネルギー使用、生成混合物は、従来技術の流動分解プロセスでの目的対象とするところから変移することがある。
分解に有効な反応時間を増やすと、転化率も増える。新規原料供給速度、上向流管水蒸気速度、及び圧力は、所定の装置の形状について反応時間に影響する主な操作変数である。転化率は、分解に供される反応装置の限定された大きさとは逆に変動する。転化率は、幾つかの装置において、新規原料供給速度の3〜5%の相対値減少に対して絶対値1%だけ増加することが観察された。本明細書において使用される接触時間は、原料油と再生触媒との接触開始と、触媒からの分解生成物の離脱との間の時間、又は、分解生成物が分離域の上流直近で急冷される場合には、原料油と再生触媒との接触開始と急冷との間の時間のどちらかを意味する。好ましい態様において、接触時間は、約0.1〜1.5秒の範囲、より好ましくは、約0.2〜0.9秒の範囲である。接触時間が0.1秒未満の場合には、重質留分油の転化率が低いために、軽質留分オレフィンは、高収率で得られないであろう。逆に、接触時間が1.5秒よりも長い場合には、供給された石油の熱分解は、過剰になることがあり、それにより、乾性ガスの発生量が過度に増大する。しかしながら、接触時間は、供給システムに依存しており、最良の反応時間は、以下に詳細に説明するプロセスモデルにより予測することができる。
反応装置の温度が増大すると、主として吸熱分解反応にとって反応速度が高まることにより、また、触媒/油比が増加することにより転化率を増大する。反応装置温度が約10°F上昇すると、転化率が絶対値約1〜2%増大させる。反応装置温度がより高いと、ガソリンのオクタン価を増大し、LPGのオレフィン率を上昇させる。これは、この方法による転化率の最大化の非常に望ましい副次的利益である。オクタン価がより高くなるということは、ガソリンの沸点範囲でオレフィンを飽和させ、ガソリンのオクタン価を低下させる二次的水素移動反応に比べて、主分解反応速度が大きいことによるものである。一般的に、反応装置温度が10°F上昇すると、リサーチオクタン価及びモーターオクタン価がそれぞれ0.8及び0.4まで上昇することができる。
転化率及びコークス収率がより高いことは、より高い圧力では熱力学的に好ましい。しかしながら、転化率は、装置の圧力により有意に影響されない。なぜなら、実質的な圧力上昇が、転化率を有意に上げるのに必要だからである。ある態様において、FCC装置は、好ましくは1〜3kg/cm2の反応圧力かつ約650℃〜720℃の再生域温度で操作される。
本発明の本態様で使用される流動接触分解装置は、再生域(再生装置)、下向流型反応装置(下向流反応装置又は“下向流管”)、分離域(分離装置)、及びストリップ域(ストリップ装置)を包含し得る。反応装置は、反応装置の性能に基づいて触媒投入及び排出実時間を制御する手段ばかりでなく、オンラインで生成物及び供給物の組成を監視する複数のセンサーを備えることができ、制御システムと一体化する。
FCC装置のコークス形成は、熱平衡を維持する最重要パラメーターである。上向流管又は下向流管内で生成したコークスは、再生装置中の空気の存在で燃焼する。吸熱性のコークス燃焼反応により生じた熱は、反応装置の熱需要、すなわち、蒸発熱、及び原料の関連顕熱、分解吸熱等を供給する。例えば、従来のFCC装置における減圧ガスオイル残物を含むコークス収量は、約4.5〜5.5重量%の範囲に入ることができる。完全燃焼から生じる熱は、反応装置の熱負荷を十分まかない得る。しかしながら、FCC装置の残油においては、原料は、コンラドソン・コークス及び芳香族環をより多く含む大量のコークス前駆物を含むので、コークスの生成はかなり増大する。このことにより、再生装置の温度を、従来のFCC装置の約650℃〜860℃から残油分解装置の約720℃〜250℃に上昇させる。
本発明は、一側面において、“プロピレン生成を最適化する”ことを目的とする。このことは、“最低の生産コストでプロピレン生成を最大化する”ことを意味する。FCC装置における炭化水素転化率は、多くの変数の複雑な関数である。例えば、ガソリンのLPG及び乾性ガスへの過剰分解は、反応装置の対流時間の増大により起こることがある。潜在的な過剰分解を止める有効な手段は、さらなる上向流管水蒸気を加えてより選択的な分解のために炭化水素分圧を低下させること、反応装置の圧力を下げること、循環速度を増加して滞留時間を下げること、触媒/油比を下げて接触分解サイトの有効性を減じること、上記条件を組み合わせることを含む。
管理制御回路は、設備自動化階層の基礎としての役割を持つ。保守及び制御技術要員は、転化率資産の能力を維持しようと努力する。装置及び技術の信頼性の課題、設備作業者の変更、上記資産の監視・保守のための熟練技術資産が少ないことは、すべて共通の問題である。その結果は、品質、エネルギー消費、装置の摩損・破損、設備の処理量、最後に収益性にとって不利な要因を抱える。能力を監視することにより、(1)業界標準に対して流量制御能力のベンチマークテストを行い、(2)問題を確認し、優先順位をつけて保守情報源に焦点を当て、(3)オンライン及びオフラインの記録について問題を分析、診断し、(4)規定の制御装置及び高度制御装置の両方について全セットのツールにより制御能力を改良し、(5)包括的な、自動化された記録について改善を監視、維持するツールを提供する。例えば、マトリコン(Matrikon)社製プロセスドクター(ProcessDoctor)、ハネウェル(Honeywell)社製ループスカウト(LoopScout)又は横河社製MDダイアグノスチック(Diagnostic)は、そのような機能を提供する。
初期撹乱(incipient disturbances)のある連続方法の処理量と制御を改良する高度ソフトウェアを用いてFCC装置を最適化することができる。そのようなソフトウェアのパッケージは、従来の自動化技術では制御が難しい連続方法に対して自動制御を提供する。従来の手動又は自動制御にとって対応するには余りにも開始が速すぎる撹乱を生じる方法が多く存在する。モデル化と最適化のパッケージを使用すると、通常の工程中の優れた制御により、また、停止させることがある工程の混乱状態を避けるか又は減ずることにより、処理量を増やし、かつエネルギー消費を減らす結果となる。また、工程に責任を持つ操作者の手作業の関わりを少なくする必要があり、そこで、操作者は、より高いレベルの製造制御活動に注意を集中することができる。本発明のある態様の方法は、例えば、ユーメトリック(Umetric)社のSIMCA P11及びマス・ワークス・インク(Math Works Inc.)社のマトラブ(Matlab)の最適化ツールのようなソフトウェアパッケージを利用することができる。
本発明の一つの具体的態様において、システムは、種々のセンサー信号を用いて操作条件を決定し、流れ操作を最も良く表現するプロセスモデルを選択することができる。モデルは、以然に開発したプロセスモデルから選択することができる。次いで、選択されたモデルを、最適化アルゴリズムにおいて用いて最適なプロセス設定値を計算する。
原料: ハイドロ脱硫アラビアンライト減圧ガスオイル
触媒: HARMOREX(CCIC)
反応域温度: 600℃
反応圧力: 1.0Kg/cm2G
触媒対油比: 15.5重量/重量
接触時間: 0.4秒
再生域触媒温度: 720℃
事例Aの結果:
転化率(重量%):95.6%
収率(重量%):
乾性ガス 4.1
プロピレン 18.2
ブテン 22.5
ガソリン 42.5
LCO+ 4.4
コークス 1.0
反応域出口温度: 600℃
水素分圧: 65Kg/cm2G
触媒/油比: 14.9重量/重量
事例Bの結果:
転化率: 86.3%(比較例2)
収率(重量%):
乾性ガス 3.8
プロピレン 11.3
ブテン 15.0
ガソリン 48.7
LCO+ 13.7
コークス 2.7
転化率(重量%) 97.6(APCでの例)
収率(重量%):
乾性ガス 4.2
プロピレン 18.7
ブテン 22.95
ガソリン 41.65
LCO+ 4.3
コークス 0.98
2 気固分離域、
3 ストリップ域、
4 再生域、
5 ライン(上向流型再生装置)、
6 触媒ホッパー、
7 混合域、
8 第二分離装置、
9 ディップレッグ、
10 ライン(原料)、
11、12、13、14 ライン、
15 第二分離装置、
16 バイパスライン、
17、19 ライン、
20 バイパスライン、
22、23、24、25、26、27 ライン、
30 プロセス制御(DSC)、
40 制御バルブ(バルブ入口)、
41、42、43、44、45、46、47 流量制御バルブ
Claims (15)
- 石油供給原料の流動接触分解方法であって、
(A)石油供給原料を分解触媒混合物と接触させる工程であって、
該分解触媒混合物は
(i)5〜50重量%の安定Y型ゼオライトと0.6重量%未満の希土類金属酸化物とを含む基本分解触媒55〜95重量%、
(ii)20〜70重量%の形状選択性ゼオライトを含有する添加物5〜45重量%、及び
(iii)リン含有化合物10重量%以下
を含む工程、
(B)500℃〜650℃の温度、0.05〜3.0秒の接触時間に維持した流動接触分解装置の反応域において、該分解触媒混合物と供給原料油とを反応させ、生成物流、未反応供給原料油及び消費済み触媒の混合物を得る工程であって、
該反応域への供給原料油及び触媒の添加は、プロセス制御により制御される工程、
及び
(C)消費済み触媒及び未反応供給原料油から、生成物流を分離及び収集する工程、
を含む方法であって、
該プロセス制御が
(a)合成反応装置の原料データ、触媒対油比、再生触媒上炭素量、触媒供給速度、反応時間、反応装置温度、圧力、熱平衡、及び生成物物性データの運転パラメータを連続監視するステップ、
(b)ステップ(a)で監視された運転パラメータに基づいて、プロセスモデルを、分散制御システム(DCS)、モデル予測制御(MPC)、並びに操作条件の検出およびプロセスモデル選択(SPM)を用いて、予測及び選択するステップ、
(c)ステップ(a)で監視された運転パラメータに基づくプロセスと該プロセスモデルとを、実時間最適化および動的最適化(RTO)並びにエネルギー管理技術(PMS)を用いて、比較するステップ、及び
(d)最適化されたプロピレン生成が得られるように操作条件を、実時間最適化および動的最適化(RTO)並びにエネルギー管理技術(PMS)を用いて、調整するステップ
を含む
方法。 - 流動接触分解装置が下向流型流動接触分解反応装置である、請求項1に記載の方法。
- 流動接触分解装置が、さらに、再生域、分離域及びストリップ域を包含する、請求項1に記載の方法。
- 分離域がサイクロン分離装置を含む、請求項3に記載の方法。
- 流動接触分解装置が、さらに、分離域に結合した第二分離装置を含む、請求項3に記載の方法。
- 流動接触分解装置が、さらに、新しい触媒を反応域に供給するための触媒ホッパーを含む、請求項3に記載の方法。
- さらに、未反応供給原料油を反応域に再循環する、請求項1に記載の方法。
- さらに、再生域において消費済み触媒を再生する工程を含む、請求項1に記載の方法。
- 生成物流の少なくとも一部を反応域に再循環する、請求項1に記載の方法。
- 反応域出口温度が500℃よりも高い、請求項1に記載の方法。
- 反応域における触媒と石油供給原料との接触時間が0.1〜1.5秒である、請求項1に記載の方法。
- 反応域における触媒と石油供給原料との接触時間が0.2〜0.9秒である、請求項1に記載の方法。
- 流動接触分解装置における触媒/油比が10〜50重量/重量である、請求項1に記載の方法。
- 石油供給原料が、ナフサ、原油、脱瀝油、減圧ガスオイル、ガスオイル、石油残油、水素化処理石油製品、及びそれらの混合物からなる群から選ばれる油からなる群から選ばれる、請求項1に記載の方法。
- 分解触媒混合物と供給原料油との反応が1〜5気圧で行われる、請求項1に記載の方法。
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| Application Number | Priority Date | Filing Date | Title |
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| US85730006P | 2006-11-07 | 2006-11-07 | |
| US60/857,300 | 2006-11-07 | ||
| PCT/US2007/023405 WO2008057546A2 (en) | 2006-11-07 | 2007-11-07 | Advanced control of severe fluid catalytic cracking process for maximizing propylene production from petroleum feedstock |
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| JP2010509329A JP2010509329A (ja) | 2010-03-25 |
| JP6082175B2 true JP6082175B2 (ja) | 2017-02-15 |
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| CA (1) | CA2668541C (ja) |
| EA (1) | EA016421B1 (ja) |
| MX (1) | MX2009004863A (ja) |
| WO (1) | WO2008057546A2 (ja) |
Families Citing this family (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2009004863A (es) | 2006-11-07 | 2009-10-26 | Saudi Arabian Oil Co | Control avanzado de proceso severo de desintegracion catalitica de fluidos para maximizar la produccion de propileno a partir de materiales de alimentacion de petroleo. |
| US20090095657A1 (en) * | 2006-11-07 | 2009-04-16 | Saudi Arabian Oil Company | Automation and Control of Energy Efficient Fluid Catalytic Cracking Processes for Maximizing Value Added Products |
| US9764314B2 (en) * | 2006-11-07 | 2017-09-19 | Saudi Arabian Oil Company | Control of fluid catalytic cracking process for minimizing additive usage in the desulfurization of petroleum feedstocks |
| EP1970825A1 (en) * | 2006-12-22 | 2008-09-17 | Bp Oil International Limited | System and method for prediction of deterioration |
| JP2009009538A (ja) * | 2007-10-01 | 2009-01-15 | Yokogawa Electric Corp | 運転状況分析方法および運転状況分析システム |
| BRPI0804120A2 (pt) * | 2008-09-09 | 2010-07-06 | Petróleo Brasileiro S/A - Petrobras | método para produção de eteno e gás de sìntese em leito fluidizado circulante |
| BRPI0803617A2 (pt) * | 2008-09-19 | 2010-06-15 | Petroleo Brasileiro Sa | Aditivo com sistema múltiplo de zeólitas e método de preparo |
| BRPI0805566B1 (pt) * | 2008-12-18 | 2018-02-14 | Petróleo Brasileiro S/A - Petrobras | Processo integrado para a fabricação de olefinas e intermediários para a produção de amônia e uréia |
| JP2010167349A (ja) * | 2009-01-21 | 2010-08-05 | Uop Llc | 軽質オレフィン製造のためのfcc触媒 |
| US20110174694A1 (en) * | 2010-01-15 | 2011-07-21 | Schlumberger Technology Corporation | Producing hydrocarbons from oil shale based on conditions under which production of oil and bitumen are optimized |
| CN101794119B (zh) * | 2010-03-08 | 2012-05-23 | 浙江中控软件技术有限公司 | 瓦斯系统平衡与优化调度方法、装置及系统 |
| US20120029966A1 (en) * | 2010-07-30 | 2012-02-02 | Accenture Global Services Gmbh | Monitoring and evaluating the production of a conversion facility |
| US9101853B2 (en) * | 2011-03-23 | 2015-08-11 | Saudi Arabian Oil Company | Integrated hydrocracking and fluidized catalytic cracking system and process |
| US9101854B2 (en) | 2011-03-23 | 2015-08-11 | Saudi Arabian Oil Company | Cracking system and process integrating hydrocracking and fluidized catalytic cracking |
| CN102193548A (zh) * | 2011-04-09 | 2011-09-21 | 太原罗克佳华工业有限公司 | 污染物排放及净化设施实时监测系统 |
| US20130026065A1 (en) | 2011-07-29 | 2013-01-31 | Omer Refa Koseoglu | Integrated Selective Hydrocracking and Fluid Catalytic Cracking Process |
| CN102393636B (zh) * | 2011-09-22 | 2013-09-25 | 任季明 | 一种对石油炼制过程的控制系统及方法 |
| FR3016370B1 (fr) * | 2014-01-10 | 2017-06-16 | Ifp Energies Now | Procede de craquage catalytique permettant une valorisation amelioree des calories des fumees de combustion. |
| KR102317620B1 (ko) * | 2014-05-23 | 2021-10-26 | 에스케이이노베이션 주식회사 | 디젤 수율이 극대화된 rfcc 공정 |
| JP6329436B2 (ja) * | 2014-05-30 | 2018-05-23 | Jxtgエネルギー株式会社 | 重質油の流動接触分解法 |
| EP3277779A4 (en) * | 2015-03-31 | 2018-09-26 | Hindustan Petroleum Corporation Ltd. | Fluid catalytic cracking process |
| US9981888B2 (en) * | 2016-06-23 | 2018-05-29 | Saudi Arabian Oil Company | Processes for high severity fluid catalytic cracking systems |
| US10679484B2 (en) * | 2017-02-01 | 2020-06-09 | Fisher Controls International Llc | Methods and apparatus for communicating alert notifications using discrete input channels |
| CN108732940B (zh) * | 2017-04-24 | 2021-05-07 | 西门子(中国)有限公司 | 优化汽油柴油切割过程的催化裂化分馏塔的顶循环油流量的方法和系统 |
| WO2018229621A1 (en) * | 2017-06-14 | 2018-12-20 | Sabic Global Technologies B.V. | A hybrid machine learning approach towards olefins plant optimization |
| JP7021995B2 (ja) * | 2018-03-28 | 2022-02-17 | コスモ石油株式会社 | Fcc装置の生成物の得率を提供する装置、方法、プログラム、非一時的コンピュータ可読記録媒体 |
| JP7042132B2 (ja) * | 2018-03-28 | 2022-03-25 | コスモ石油株式会社 | Fcc装置に用いる推奨触媒を提案する装置、方法、プログラム、非一時的コンピュータ可読記録媒体 |
| US11318438B2 (en) | 2018-03-29 | 2022-05-03 | Bharat Petroleum Corporation Limited | Advanced process control in a continuous catalytic regeneration reformer |
| JPWO2020066309A1 (ja) * | 2018-09-28 | 2021-09-24 | 富士フイルム株式会社 | フロー反応設備及び方法 |
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| EP3892604A4 (en) * | 2018-12-03 | 2022-08-17 | Furukawa Electric Co., Ltd. | DEVICE FOR PRODUCING GAS CONTAINING LIGHT OLEFINS AND METHOD FOR PRODUCING GAS CONTAINING LIGHT OLEFINS |
| CN110209091B (zh) * | 2019-06-14 | 2025-04-25 | 南京天石能源科技有限公司 | 一种催化剂加剂物联网智能测控器及其使用方法 |
| FR3097555B1 (fr) * | 2019-06-24 | 2021-11-26 | Europeenne De Biomasse | Procédé de production d’un biocombustible par vapocraquage |
| US10899972B1 (en) * | 2019-12-18 | 2021-01-26 | Saudi Arabian Oil Company | Fluid catalytic cracking of petroleum oil with reduced emissions |
| KR102338443B1 (ko) | 2020-08-21 | 2021-12-09 | 이진숙 | 촉매 분배 장치 |
| CN112224308B (zh) * | 2020-09-28 | 2021-10-22 | 大唐互联科技(武汉)有限公司 | 一种车辆装配工艺防错系统 |
| KR20220154371A (ko) | 2021-05-13 | 2022-11-22 | 태광산업주식회사 | 파라핀의 촉매 탈수소화에 의한 올레핀 제조 공정에서의 촉매 재생 시스템 및 촉매 재생 방법 |
| KR102478101B1 (ko) | 2021-12-06 | 2022-12-14 | 이진숙 | 촉매 분배 장치 |
| WO2024129222A1 (en) | 2022-12-12 | 2024-06-20 | Chevron U.S.A. Inc. | Process for stable blend of waste plastic with petroleum feed for feeding to oil refinery units and process of preparing same |
| CN119546687A (zh) * | 2022-12-12 | 2025-02-28 | 雪佛龙美国公司 | 用于进料至炼油厂单元的废塑料与石油进料的稳定共混物的方法及其制备方法 |
| US20240417633A1 (en) * | 2023-06-15 | 2024-12-19 | Kellogg Brown & Root Llc | Process for debottlenecking fcc wet gas compressor and gas plant |
Family Cites Families (65)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2626233A (en) * | 1950-08-05 | 1953-01-20 | Standard Oil Dev Co | Catalytic cracking of hydrocarbons in the presence of added gaseous olefins |
| US3074878A (en) * | 1957-10-18 | 1963-01-22 | Exxon Research Engineering Co | Short contact time system |
| US3175968A (en) * | 1961-06-23 | 1965-03-30 | Phillips Petroleum Co | Automatic control and optimization of a fluidized catalytic cracker |
| US3213014A (en) * | 1962-06-14 | 1965-10-19 | Phillips Petroleum Co | Computer control of hydrocarbon conversion |
| US3629097A (en) * | 1970-01-06 | 1971-12-21 | Continental Oil Co | Control system for fluid catalytic cracking process |
| US3728526A (en) * | 1971-07-08 | 1973-04-17 | Texaco Inc | Means and method for controlling independent operating parameters in a process system |
| US3828171A (en) * | 1972-08-14 | 1974-08-06 | Phillips Petroleum Co | Process apparatus control system for optimizing objective variable quality |
| US4092722A (en) * | 1976-10-18 | 1978-05-30 | Phillips Petroleum Company | Fluid catalytic cracking with automatic temperature control |
| US4144189A (en) * | 1978-04-13 | 1979-03-13 | Kirkbride Chalmer G | Process for regenerating spent cracking catalyst |
| US4243630A (en) * | 1979-03-19 | 1981-01-06 | Texaco Inc. | Fluid catalytic cracking unit yield monitor |
| US4354957A (en) * | 1980-10-03 | 1982-10-19 | Phillips Petroleum Company | Regenerator temperature control |
| US4345993A (en) * | 1980-12-30 | 1982-08-24 | Phillips Petroleum Company | Control of a fluid catalytic cracking unit |
| US4419221A (en) * | 1981-10-27 | 1983-12-06 | Texaco Inc. | Cracking with short contact time and high temperatures |
| US4532026A (en) * | 1982-07-06 | 1985-07-30 | Chevron Research Company | Method to improve circulation control in fluidized systems |
| US4437977A (en) * | 1982-09-29 | 1984-03-20 | Phillips Petroleum Company | Control of a catalytic cracking unit |
| CN1004878B (zh) * | 1987-08-08 | 1989-07-26 | 中国石油化工总公司 | 制取低碳烯烃的烃类催化转化方法 |
| US4985136A (en) | 1987-11-05 | 1991-01-15 | Bartholic David B | Ultra-short contact time fluidized catalytic cracking process |
| WO1989007487A1 (en) * | 1988-02-16 | 1989-08-24 | Bartholic David B | Fluid catalytic cracking (fcc) catalyst and additive loading and control system |
| US4992614A (en) * | 1988-06-30 | 1991-02-12 | Mobil Oil Corp. | Reactivation of partially deactivated catalyst employing ultrasonic energy |
| US4929337A (en) * | 1988-12-30 | 1990-05-29 | Mobil Oil Corporation | Process for catalytic cracking of heavy hydrocarbon feed to lighter products |
| US5073349A (en) * | 1989-12-21 | 1991-12-17 | Mobil Oil Corporation | High efficiency catalytic cracking stripping apparatus |
| US5298155A (en) * | 1990-02-27 | 1994-03-29 | Exxon Research & Engineering Co. | Controlling yields and selectivity in a fluid catalytic cracker unit |
| CA2036067A1 (en) * | 1990-02-27 | 1991-08-28 | Exxon Research And Engineering Company | Process and apparatus for controlling a fluid catalytic cracking unit |
| CA2044074C (en) * | 1990-07-03 | 2003-01-21 | Craig Y. Sabottke | Controlling temperature, yields and selectivity in a fluid hydrocarbon conversion and cracking apparatus and process comprising a novel feed injection system |
| US5774381A (en) * | 1992-03-04 | 1998-06-30 | Meier; Paul F. | Modeling and simulation of catalytic cracking |
| ES2123052T3 (es) | 1992-05-04 | 1999-01-01 | Mobil Oil Corp | Craqueo catalitico fluidizado. |
| US5402333A (en) * | 1992-06-15 | 1995-03-28 | E. I. Du Pont De Nemours & Co., Inc. | System and method for improving model product property estimates |
| CN1031646C (zh) * | 1992-10-22 | 1996-04-24 | 中国石油化工总公司 | 石油烃的催化转化方法 |
| US5322619A (en) * | 1992-11-30 | 1994-06-21 | Exxon Research And Engineering Company | FCC for producing low emission fuels from high hydrogen and low nitrogen and aromatic feeds with rare earth promoted catalyst |
| US5389236A (en) * | 1993-04-21 | 1995-02-14 | Bartholic; David B. | Method and apparatus for controlling introduction of catalysts into FCC units |
| JPH0713611A (ja) * | 1993-06-24 | 1995-01-17 | Hitachi Ltd | プロセスモデル評価装置およびプロセスモデル評価方法 |
| US5462652A (en) * | 1993-09-24 | 1995-10-31 | Uop | Short contact FCC process with catalyst blending |
| JP3580518B2 (ja) * | 1996-06-05 | 2004-10-27 | 新日本石油株式会社 | 重質油の流動接触分解法 |
| US5904837A (en) * | 1996-10-07 | 1999-05-18 | Nippon Oil Co., Ltd. | Process for fluid catalytic cracking of oils |
| US6045690A (en) * | 1996-11-15 | 2000-04-04 | Nippon Oil Co., Ltd. | Process for fluid catalytic cracking of heavy fraction oils |
| US5846402A (en) * | 1997-05-14 | 1998-12-08 | Indian Oil Corporation, Ltd. | Process for catalytic cracking of petroleum based feed stocks |
| US6093867A (en) * | 1998-05-05 | 2000-07-25 | Exxon Research And Engineering Company | Process for selectively producing C3 olefins in a fluid catalytic cracking process |
| EP1116775A1 (en) * | 2000-01-12 | 2001-07-18 | Akzo Nobel N.V. | Catalyst composition with high efficiency for the production of light olefins |
| ES2168208B1 (es) * | 2000-03-24 | 2003-04-01 | Univ Valencia Politecnica | Catalizadores de craqueo basados en zeolitas. |
| US20020019722A1 (en) * | 2000-07-19 | 2002-02-14 | Wim Hupkes | On-line calibration process |
| US6735541B2 (en) * | 2001-02-16 | 2004-05-11 | Exxonmobil Research And Engineering Company | Process unit monitoring program |
| JP3948905B2 (ja) | 2001-02-21 | 2007-07-25 | 財団法人 国際石油交流センター | 重質油の流動接触分解法 |
| JP4223690B2 (ja) * | 2001-02-21 | 2009-02-12 | 財団法人 国際石油交流センター | 重質油の流動接触分解方法 |
| US6835302B2 (en) * | 2001-03-23 | 2004-12-28 | Uop Llc | FCC process and apparatus with automatic catalyst recycle control |
| WO2002093439A1 (en) * | 2001-05-15 | 2002-11-21 | Akzo Nobel N.V. | Method of product specification for a processing chemical |
| US6656346B2 (en) * | 2001-06-07 | 2003-12-02 | King Fahd University Of Petroleum And Minerals | Fluid catalytic cracking process for heavy oil |
| US20020195373A1 (en) * | 2001-06-07 | 2002-12-26 | Takashi Ino | Heavy oil fluid catalytic cracking process |
| US7145051B2 (en) * | 2002-03-22 | 2006-12-05 | Exxonmobil Chemical Patents Inc. | Combined oxydehydrogenation and cracking catalyst for production of olefins |
| US7369959B2 (en) * | 2002-11-26 | 2008-05-06 | Intercat Equipment, Inc. | Fluid catalytic cracking catalyst injection system and method for communicating with same |
| US20040099572A1 (en) * | 2002-11-26 | 2004-05-27 | Martin Evans | FCC catalyst injection system having closed loop control |
| US7507686B2 (en) * | 2002-12-03 | 2009-03-24 | W. R. Grace & Co. - Conn. | Gasoline sulfur reduction in fluid catalytic cracking |
| JP2004261628A (ja) | 2003-01-24 | 2004-09-24 | Idemitsu Petrochem Co Ltd | 炭化水素類の接触分解触媒及びそれを用いた軽質オレフィン類の製造方法 |
| JP2006513843A (ja) * | 2003-02-05 | 2006-04-27 | エクソンモービル・ケミカル・パテンツ・インク | 接触分解のための混合した分解及び選択的水素燃焼 |
| US20040215697A1 (en) * | 2003-04-11 | 2004-10-28 | Vasileios Vergopoulos | Systems and methods for managing unit operating data |
| US7589041B2 (en) * | 2004-04-23 | 2009-09-15 | Massachusetts Institute Of Technology | Mesostructured zeolitic materials, and methods of making and using the same |
| US7351872B2 (en) * | 2004-05-21 | 2008-04-01 | Exxonmobil Chemical Patents Inc. | Process and draft control system for use in cracking a heavy hydrocarbon feedstock in a pyrolysis furnace |
| RU2399648C2 (ru) * | 2004-08-10 | 2010-09-20 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Способ для получения среднедистиллятного продукта и низших олефинов из углеводородного сырья и устройство для его осуществления |
| US20060060504A1 (en) * | 2004-09-08 | 2006-03-23 | Vierheilig Albert A | Additives for metal contaminant removal |
| AR052122A1 (es) * | 2004-11-05 | 2007-03-07 | Grace W R & Co | Catalizadores para olefinas livianas y glp gas licuado de petroleo en unidades de craqueo catalitico fluidizado |
| US7601254B2 (en) * | 2005-05-19 | 2009-10-13 | Uop Llc | Integrated fluid catalytic cracking process |
| BRPI0503182B1 (pt) * | 2005-08-04 | 2014-03-04 | Petroleo Brasileiro Sa | Aditivo multifuncional para maximização de propriedades relevantes a um processo de craqueamento catalítico fluido e processo de preparação do mesmo |
| US7460915B2 (en) * | 2006-06-21 | 2008-12-02 | Honeywell International Inc. | Methods and apparatus for process control using catalyst state estimation |
| US20080078694A1 (en) * | 2006-09-29 | 2008-04-03 | Marathon Petroleum Company Llc | Method and apparatus for controlling FCC effluent with near-infrared spectroscopy |
| MX2009004863A (es) | 2006-11-07 | 2009-10-26 | Saudi Arabian Oil Co | Control avanzado de proceso severo de desintegracion catalitica de fluidos para maximizar la produccion de propileno a partir de materiales de alimentacion de petroleo. |
| US20090095657A1 (en) * | 2006-11-07 | 2009-04-16 | Saudi Arabian Oil Company | Automation and Control of Energy Efficient Fluid Catalytic Cracking Processes for Maximizing Value Added Products |
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Also Published As
| Publication number | Publication date |
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| JP2010509329A (ja) | 2010-03-25 |
| BRPI0718870A2 (pt) | 2014-09-09 |
| WO2008057546A3 (en) | 2009-02-26 |
| KR101586093B1 (ko) | 2016-01-15 |
| EP2099880A2 (en) | 2009-09-16 |
| US9701914B2 (en) | 2017-07-11 |
| EA016421B1 (ru) | 2012-04-30 |
| WO2008057546A9 (en) | 2009-09-03 |
| EA200970458A1 (ru) | 2009-12-30 |
| CA2668541C (en) | 2016-12-13 |
| WO2008057546A2 (en) | 2008-05-15 |
| BRPI0718870A8 (pt) | 2017-02-07 |
| KR20090098805A (ko) | 2009-09-17 |
| CN101611118A (zh) | 2009-12-23 |
| US20080128325A1 (en) | 2008-06-05 |
| MX2009004863A (es) | 2009-10-26 |
| CA2668541A1 (en) | 2008-05-15 |
| CN101611118B (zh) | 2013-11-20 |
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