TW201522608A - 製造汽油或芳香族化合物之整合製程 - Google Patents

製造汽油或芳香族化合物之整合製程 Download PDF

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TW201522608A
TW201522608A TW103124042A TW103124042A TW201522608A TW 201522608 A TW201522608 A TW 201522608A TW 103124042 A TW103124042 A TW 103124042A TW 103124042 A TW103124042 A TW 103124042A TW 201522608 A TW201522608 A TW 201522608A
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Gregory A Funk
Steven T Arakawa
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Uop Llc
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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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural parallel stages only
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    • C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
    • C10G61/02—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only
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    • C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
    • C10G61/02—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only
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    • C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
    • C10G61/08—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural parallel stages only
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    • C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
    • C10G61/10—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen processes also including other conversion steps
    • 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
    • C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
    • C10G63/06—Treatment of naphtha by at least one reforming process and at least one other conversion process plural parallel stages only
    • 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
    • C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
    • C10G63/06—Treatment of naphtha by at least one reforming process and at least one other conversion process plural parallel stages only
    • C10G63/08—Treatment of naphtha by at least one reforming process and at least one other conversion process plural parallel stages only including at least one cracking step
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • C10G67/0409—Extraction of unsaturated hydrocarbons

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Abstract

本發明呈現用於增加烴組分自烴原料至汽油摻配池之產率之製程。該製程包含將石腦油原料分離為較易於在裂解單元中加工之呈第一流之組分及較易於在重組單元中加工之呈第二流之組分。該製程包含將組分自裂解流轉化為重組流之能力。

Description

製造汽油或芳香族化合物之整合製程 優先權之聲明
本申請案主張2014年4月24日提出申請之美國申請案第14/260,784號之優先權，該美國申請案主張2013年8月7日提出申請之美國臨時申請案第61/863,025號之權益，該兩個申請案之內容以全文引用方式併入本文中。
本發明係關於用於自較重烴流製造芳香族化合物之製程及系統。特定而言，此製程提供自烴原料製造芳香族化合物及輕烯烴之增加產率及靈活性。
石油原材料之重組係用於製造有用產品之重要製程。在汽油之製造中，一個重要製程係對用於馬達燃料之烴之分離及升級，諸如製造石腦油進料流及升級石腦油之辛烷值。然而，來自原油來源之烴進料流包含有用化學前驅物之製造以供在塑膠、清潔劑及其他產品之製造中使用。
汽油之升級係重要製程，且已在美國專利第3,729,409號、第3,753,891號、第3,767,568號、第4,839,024號、第4,882,040號及第5,242,576號中呈現對石腦油進料流之轉化之改良以增加辛烷數目。此等製程涉及用以增強辛烷數目及特定而言用於增強汽油芳香族化合物 含量之多種構件。
製程包含使用諸如用於較低沸點烴之單金屬觸媒或非酸觸媒及用於較高沸點烴之雙金屬觸媒之不同觸媒來分裂進料及操作數個重組器。如在美國專利第4,677,094號、第6,809,061號及第7,799,729號中所呈現，其他改良包含新觸媒。然而，存在對此等專利中所呈現之方法及觸媒之限制，且該等限制可需要成本之顯著增加。
傳統上已透過流加工或觸媒裂解來製造輕烯烴，且輕烯烴包括乙烯及丙烯。輕烯烴亦自與汽油相同之原料衍生。由於石油來源之有限可用性及高成本，因此自此等石油來源製造輕烯烴之成本已穩步地增加。使輕烯烴及汽油池之原料中之組分轉移之能力使得生產者能夠經濟地挑選最重要產品線且能夠以有效方式使烴組分中之某些烴組分轉移。
呈現用於改良汽油產率之製程。本發明之第一實施例係用於轉化經處理烴進料流之製程，該製程包括：將該經處理烴進料流傳遞至分離單元以產生富含直鏈烷烴之萃取物流及具有減小之直鏈烴含量之萃餘物流；將該萃取物流傳遞至萃取物分離系統以產生包括nC5及nC6化合物之萃取物頂部流、包括nC7至nC11化合物之萃取物中間流及包括去吸附劑之萃取物底部流；將該萃餘物流傳遞至萃餘物分離系統以產生包括iC5及iC6化合物之萃餘物頂部流、包括C6至C11碳範圍中之芳香族化合物及非直鏈烴之中間萃餘物流以及包括去吸附劑之萃餘物底部流；及將該中間萃餘物流傳遞至重組單元以產生芳香族化合物流。本發明之實施例係向上貫穿此段落中之第一實施例的此段落中之先前實施例中之一項、任何或所有先前實施例，該實施例進一步包括：將烴進料流傳遞至分餾單元以產生包括C4及較輕烴之頂部流以及包括C5+烴之底部流；對該底部流進行氫化處理以產生經處理氫化 流；將該經處理氫化流傳遞至該分離單元。本發明之實施例係向上貫穿此段落中之第一實施例的此段落中之先前實施例中之一項、任何或所有先前實施例，該實施例進一步包括將該萃取物頂部流之一部分傳遞至異構化單元以產生包括C5及C6化合物之經異構化流。本發明之實施例係向上貫穿此段落中之第一實施例的此段落中之先前實施例中之一項、任何或所有先前實施例，該實施例進一步包括將該經異構化流傳遞至該分離單元。
本發明之第二實施例係用於轉化石腦油進料流之製程，該製程包括：將該石腦油進料流分餾以產生包括C4及較輕烴之石腦油頂部流以及包括C5+烴之石腦油底部流；對該石腦油底部流進行氫化處理以產生具有減少之乙炔、二烯、硫及氮含量之經氫化流；將該經氫化流傳遞至分離單元以產生富含直鏈烴之萃取物流及萃餘物流；將該萃取物流傳遞至萃取分離系統以產生包括nC5及nC6化合物之萃取物頂部流、包括nC7至nC11化合物之萃取物中間流以及包括去吸附劑之萃取物底部流；將該萃餘物流傳遞至萃餘物分離系統以產生包括iC5及iC6化合物之萃餘物頂部流、包括C6至C11芳香族化合物及非直鏈烴之中間萃餘物流以及包括去吸附劑之萃餘物流；將該中間萃取物流及該石腦油頂部流傳遞至石腦油裂解單元以產生輕烯烴；及將該中間萃餘物流傳遞至重組單元以產生芳香族化合物流。本發明之實施例係向上貫穿此段落中之第二實施例的此段落中之先前實施例中之一項、任何或所有先前實施例，該實施例進一步包括將該萃取物頂部流之一部分傳遞至異構化單元以產生包括C5及C6化合物之經異構化流。本發明之實施例係向上貫穿此段落中之第二實施例的此段落中之先前實施例中之一項、任何或所有先前實施例，該實施例進一步包括將該經異構化流傳遞至該分離單元。
依據以下詳細說明及圖式，熟習此項技術者將明瞭本發明之其 他目標、優點及應用。
8‧‧‧經處理烴流/流
10‧‧‧分離單元/分離系統/吸收分離單元/吸收分離系統
12‧‧‧萃取物流
14‧‧‧萃餘物流
20‧‧‧萃取物分離系統/萃取分離系統
22‧‧‧萃取物頂部流/頂部流
24‧‧‧萃取物中間流
26‧‧‧萃取物底部流/循環流
30‧‧‧萃餘物分離系統
32‧‧‧萃餘物頂部流
34‧‧‧中間萃餘物流
36‧‧‧萃餘物底部流
40‧‧‧裂解單元
42‧‧‧輕烯烴產品流/輕烯烴
50‧‧‧重組單元
52‧‧‧重組油流/重組油
60‧‧‧異構化單元
62‧‧‧經異構化流
70‧‧‧分餾單元
72‧‧‧頂部流
74‧‧‧底部流/石腦油底部流
76‧‧‧石腦油進料流
80‧‧‧氫化處理單元
圖1係製程之流程示意圖；且圖2係本發明製程之特定實施例。
本發明實施例提供烴原料之有效使用。自較低價值烴原料製造有用較高價值產品對石油加工廠之經濟而言係重要的。吾人期望較高價值產品之製造之靈活性以回應不同產品線之需求轉換。
本發明實施例提供加工烴進料流以製造輕烯烴及/或芳香族化合物之靈活性。如圖1中所展示，該製程包含將經處理烴流8傳遞至分離單元10。分離單元10產生富含直鏈烴之萃取物流12及具有減少之直鏈烴含量之萃餘物流14。將萃取物流12傳遞至萃取物分離系統20以產生萃取物頂部流22。萃取物分離系統20亦可產生萃取物中間流24及萃取物底部流26。
烴流中之直鏈組分比非直鏈組分更易於裂解以形成輕烯烴。直鏈組分亦比非直鏈組分更難以重組為芳香族化合物。與將不同流傳遞至適當下游加工單元組合之直鏈組分與非直鏈組分之分離改良了裂解及重組石腦油之靈活性及經濟。將直鏈組分轉化為非直鏈組分之能力允許將烴組分自進料至裂解單元之流轉移至用於產生汽油組分之流。
萃取物頂部流22可包括直鏈C5及C6化合物，萃取物中間流24可包括直鏈C7及較重化合物，且萃取物底部流26可包括傳遞回至分離單元10之循環流。將萃取物中間流24傳遞至裂解單元40以產生輕烯烴。在一項實施例中，裂解單元40係石腦油流裂解單元。
在一項實施例中，分離單元10係吸收分離單元，且循環流26係自萃取物分離系統20至分離單元10循環之去吸附劑。萃取物分離系統20可包括用於自去吸附劑分離萃取物流之一或多個分餾塔。萃取物分 離系統20亦可將萃取物流12分離成多個流。分離製程之選項包含分隔壁蒸餾塔或用於分離烴流之其他構件。
將萃餘物流14傳遞至萃餘物分離系統30以產生萃餘物頂部流32、中間萃餘物流34及萃餘物底部流36。萃餘物頂部流32將包括異戊烷及異己烷，中間萃餘物流34包括C6至C11範圍中之芳香族化合物、環烷及非直鏈烴，且萃餘物底部流36包括返回至分離單元10之循環流。
藉助吸收分離系統10，萃餘物循環係吸收分離製程中所使用之去吸附劑。將中間萃餘物流34傳遞至重組單元50以產生包括芳香族化合物之重組油流52。
在特定實施例中，如圖2中所展示，該製程加工石腦油進料流。石腦油進料流包括諸多烴組分，且通常被傳遞至裂解單元以製造輕烯烴。然而，石腦油流之組成包含不良地裂解為輕烯烴之組分且此導致進一步加工。石腦油進料流亦包含用於轉化為芳香族化合物之有用烴。本發明實施例試圖分離石腦油進料流以增加石腦油裂解單元及重組單元之產率及效率。將石腦油進料流76傳遞至分餾單元70以產生包括C4及較輕烴之頂部流72以及包括C5及較輕烴之底部流74。將頂部流72傳遞至裂解單元40以產生輕烯烴產品流42。
石腦油進料流將通常包括C4至C11範圍中之烴。吸收分離單元10將因此利用通常在此範圍之外的適當去吸附劑。對具有C4至C11範圍中之組分之輕石腦油起作用之一種去吸附劑係n-C12。
將石腦油底部流74傳遞至氫化處理單元80以產生經處理烴流8。對石腦油底部流74之氫化處理移除硫雜質及氮雜質。氫化處理亦可執行諸如乙炔及二烯之反應性組分之某一氫化。氫化處理或氫化之後，將流8傳遞至吸收分離單元10以產生萃取物流12及萃餘物流14。選擇吸收分離單元10中之吸附劑以自非直鏈烴分離直鏈烴及特定而言直鏈 烷烴。萃取物流12包括直鏈烴且萃餘物流14包括非直鏈及芳香烴。
將萃餘物流14傳遞至萃餘物分離系統30。萃餘物分離系統30產生萃餘物頂部流32、中間萃餘物流34及萃餘物底部流36。萃餘物分離系統30可包括兩個分餾塔、分隔壁蒸餾塔或用於將混合物分離成兩個或三個流之其他構件。分餾係較佳的，此乃因萃餘物流中之組分因其沸點差而易於分離。吸收分離系統10使用去吸附劑，且萃餘物底部流36包括循環至吸收分離系統10之去吸附劑。萃餘物頂部流包括iC5及iC6化合物，且可用於下游加工，包含添加至汽油摻配池。將包括具有比iC5或iC6化合物高之沸點之芳香族化合物及非直鏈烴之中間萃餘物流34傳遞至重組單元50以產生具有增加之芳香族化合物含量之重組油52。
將萃取物流12傳遞至萃取分離系統20以產生萃取物頂部流22、萃取物中間流24及萃取物底部流26。萃取物分離系統20可包括多個分餾塔以及使用分隔壁蒸餾塔之較佳系統。萃取物底部流26包含循環至分離單元10之去吸附劑。將萃取物中間流24傳遞至裂解單元40以將直鏈烷烴轉化為輕烯烴42。典型裂解單元係石腦油流裂解單元，但亦可包括觸媒裂解單元。亦可將萃取物頂部流22傳遞至裂解單元40，但在替代方案中，可將萃取物頂部流傳遞至異構化單元60。
異構化單元60將具有直鏈C5及C6烷烴之頂部流22轉化為具有直鏈及iso-C5及C6烷烴之混合物之經異構化流62。將經異構化流62傳遞至分離單元10，其中然後在萃餘物流14中移除經異構化流62之非直鏈組分。此提供較多烴傳遞至重組單元50以增加重組油52或傳遞至萃餘物頂部流32以供下游處理(包含傳遞至重組單元50作為選項)。
較佳實施例係用於將分離系統、異構化系統及觸媒重組製程整合至整合式煉油廠石油操作中。該製程提供在用以產生輕烯烴之裂解製程與用於產生芳香族化合物之重組製程之間之烴轉移。因此給工廠 提供產生所要產品流之靈活性。
在較佳實施例中，萃取物分離系統或萃餘物分離系統將利用分隔壁蒸餾塔來製造三個分離流。此將節省資金及操作成本。此製程將透過石腦油進料流中之烴組分以及(特定而言)C5及C6組分自裂解流至重組流之轉移或引導至汽油摻配池而允許汽油製造領域之靈活性。
雖然已藉助當前視為較佳實施例之內容而闡述本發明，但應理解，本發明並不限於所揭示實施例，而意欲涵蓋隨附申請專利範圍之範疇內所包含之各種修改及等效配置。
8‧‧‧經處理烴流/流
10‧‧‧分離單元/分離系統/吸收分離單元/吸收分離系統
12‧‧‧萃取物流
14‧‧‧萃餘物流
20‧‧‧萃取物分離系統/萃取分離系統
22‧‧‧萃取物頂部流/頂部流
24‧‧‧萃取物中間流
26‧‧‧萃取物底部流/循環流
30‧‧‧萃餘物分離系統
32‧‧‧萃餘物頂部流
34‧‧‧中間萃餘物流
36‧‧‧萃餘物底部流
40‧‧‧裂解單元
42‧‧‧輕烯烴產品流/輕烯烴
50‧‧‧重組單元
52‧‧‧重組油流/重組油

Claims (10)

  1. 一種用於轉化經處理烴進料流之製程，其包括：將該經處理烴進料流傳遞至分離單元以產生富含直鏈烷烴之萃取物流及具有減少之直鏈烴含量之萃餘物流；將該萃取物流傳遞至萃取物分離系統以產生包括nC5及nC6化合物之萃取物頂部流、包括nC7至nC11化合物之萃取物中間流以及包括去吸附劑之萃取物底部流；將該萃餘物流傳遞至萃餘物分離系統以產生包括iC5及iC6化合物之萃餘物頂部流、包括芳香族化合物及非直鏈烴之中間萃餘物流以及包括去吸附劑之萃餘物底部流；及將該中間萃餘物流傳遞至重組單元以產生芳香族化合物流。
  2. 如請求項1之製程，其進一步包括：將烴進料流傳遞至分餾單元以產生包括C4及較輕烴之頂部流以及包括C5+烴之底部流；對該底部流進行氫化處理以產生經處理氫化流；將該經處理氫化流傳遞至該分離單元。
  3. 如請求項2之製程，其進一步包括將該頂部流傳遞至裂解單元。
  4. 如請求項1之製程，其進一步包括將該萃取物中間流傳遞至裂解單元。
  5. 如請求項1之製程，其進一步包括將該萃取物頂部流之一部分傳遞至異構化單元以產生包括C5及C6化合物之經異構化流。
  6. 如請求項5之製程，其進一步包括將該經異構化流傳遞至該分離單元。
  7. 如請求項1之製程，其進一步包括將該萃取物頂部流之一部分傳遞至裂解單元。
  8. 如請求項7之製程，其中該烴進料流係石腦油進料流。
  9. 如請求項7之製程，其中該裂解單元係石腦油裂解單元。
  10. 如請求項1之製程，其進一步包括將該萃餘物頂部流傳遞至汽油摻配池。
TW103124042A 2013-08-07 2014-07-11 製造汽油或芳香族化合物之整合製程 TWI557220B (zh)

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