TW202039805A - 用於將稀釋蒸汽與液體烴類在蒸汽裂解前混合之方法 - Google Patents

用於將稀釋蒸汽與液體烴類在蒸汽裂解前混合之方法 Download PDF

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TW202039805A
TW202039805A TW109108651A TW109108651A TW202039805A TW 202039805 A TW202039805 A TW 202039805A TW 109108651 A TW109108651 A TW 109108651A TW 109108651 A TW109108651 A TW 109108651A TW 202039805 A TW202039805 A TW 202039805A
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steam
hydrocarbons
hydrocarbon
crude oil
whole crude
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TW109108651A
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迪尼斯 馬隆尼
肯達沙米 桑達蘭
拉古 納拉延
阿卜杜 Ｒ Ｚ 阿克拉斯
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美商魯瑪斯科技有限責任公司
沙烏地阿拉伯商沙烏地阿美科技公司
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Abstract

一種用於蒸汽裂解全原油之方法，其包含用以維持一相對較大烴滴液尺寸而實施之一揮發步驟。此方法可包含將一全原油與蒸汽接觸而揮發一部份之烴類，其中烴原料與蒸汽之接觸係以，例如，少於30m/s之一初始相對速率進行。然後，形成之含有經揮發之烴類及蒸汽的蒸氣相可與包含未經蒸發之烴類的一液體相分離。然後，蒸氣相中之烴類可前進至一蒸汽熱解反應器，以蒸汽裂解蒸氣相中之烴類。

Description

用於將稀釋蒸汽與液體烴類在蒸汽裂解前混合之方法
揭露領域
此處揭露之實施例一般係有關於將諸如全原油或包括非揮發性烴類之其它烴混合物的烴混合物加工生產烯烴類。
背景
具有非揮發性組份，諸如具有超過550°C之一終沸點者，的烴混合物一般不是直接於一蒸汽熱解反應器中加工生產烯烴類，因為反應器相當快速地結焦。雖然限制反應條件可降低結垢傾向，但不太嚴苛之條件造成產率重大損失。
此項技藝之普遍共識係具有一廣沸點範圍之烴混合物及/或具有一高終沸點之烴類需將烴類初始分離成數種分餾物，諸如，氣體/輕烴類、石油腦範圍之烴類、汽油等，然後將每一分餾物於此等分餾物特別條件下裂解，諸如，於個別蒸汽熱解爐。雖然諸如經由一蒸餾塔之分餾及個別另工會係資薩本及能量密集，但一般相信有關於方法控制及產率，分餾物之分開及個別之加工係提供最高利益。
對於需要使一烴分餾物與稀釋蒸汽接觸之重烴加工及其它蒸汽裂解方法，各種習知技文獻在於以0.5至1.0(蒸汽對烴類)之重量比例與稀釋蒸汽混合之前，將液體烴原料部份蒸發。對於傳統原料，混合係以高速率進行，且造成原料全部蒸發。但是，諸如全原油之含有非揮發性烴類之供料，全部蒸發未被達成或並不合意。
於此等混合及蒸發方法期間，蒸汽及烴類典型上係以通當高達或高於100m/s之相對速率(蒸汽速率減掉烴速率)接觸。此等接觸速率造成小液滴形成，合意地誘發烴類與蒸汽緻密地接觸，達成一高蒸發度。不幸地，此等小液滴難以自蒸氣移除。因此，需要特別蒸氣液體分離器，諸如，一重油加工系統(HOPS)，以於經分離之蒸氣送至蒸汽裂解器之輻射區段之前移除此等小液滴。
各種習知技藝文獻可包括US3617493、US4498629、US6632351、US7097758、US8070938及Ludwig Kniel等人之“Ethylene: Keystone to the Petrochemical Industry”，Marcel Dekker, Inc.，紐約，1980，第85頁，及Mal J. Maddock，Ph.D.，“Improved Field Condensate Cracking Trends in Industrial Application”，Paper presented at Refining，LNG and Petrochem Asia 92，1992年12月1-4日，新加坡。
揭露概要
已發展出用於選擇之加工條件靈活地加工含有非揮發性烴類及/或高沸點焦炭先質之全原油及其它烴混合物的方法。更特別地，液體烴供料可依據此處之實施例預熱，不會形成顯著蒸氣，同時避免高的相對速率。稀釋蒸汽以低的相對速率添加至烴而蒸發更多揮發性烴類，未產生小的難以分離之液滴。此處之實施例可於進一步加工期間有利地降低結焦及結垢，諸如，於熱裂解，即使於高度嚴苛條件，達到合意產率，同時顯著降低與預分餾及個別加工有關之資本及能量需求。
於一方面，此處揭露之實施例係有關於一種用於蒸汽裂解全原油之方法。此方法可包括使一全原油與蒸汽接觸以揮發其內一部份之烴類。烴原料與蒸汽之接觸可於少於30m/s之一初使相對速率進行。此方法亦可包括使包含經揮發之烴類及蒸汽的一蒸氣相與一包含未經蒸發之烴類的一液體相分離，及蒸汽裂解於蒸氣相中之烴類。
於某些實施例，全原油與蒸汽之接觸可於範圍從約1m/s至約15m/s之一初始相對速率進行。於其它實施例，全原油與蒸汽之接觸可於範圍從約2m/s至約10m/s之一初始相對速率進行。
蒸汽與烴類之接觸於某些實施例可進一步包括形成具有大於約 1000微米之一D50的一滴液尺寸分佈之烴滴液，其中，50重量%之液體係以具有小於D50之直徑的滴液被包含。於不同實施例，此方法可包括形成具有大於約20微米之一D10的烴滴液，其中，10重量%之液體係以具有小於D1之直徑的滴液被包含，且90重量%之液體係以具有大於D10之直徑的滴液被包括。此處之實施例亦可包括於接觸步驟之前將全原油預熱至低於其起泡點溫度之一溫度。
於某些實施例，接觸可包括使蒸汽與全原油以同向流混合，且分離可包括於一氣旋分離器中使蒸氣相與液體相分離。於其它實施例，蒸汽與全原油可以逆向流接觸。
此方法可包括控制一蒸汽溫度及蒸汽供料速率，例如，於某些實施例係足以揮發全原油中之5至90重量%的烴類。於其它實施例，此方法可包括控制一蒸汽溫度及蒸汽供料速率而足以揮發全原油中之10至30重量%的烴類。
於另一方面，此處揭露之實施例係有關於一種蒸汽裂解一全原油或其部份以生產烯烴類及/或芳香族化合物之方法。此方法可包括使一全原油與蒸汽接觸以揮發一部份的烴類。全原油與蒸汽之接觸可被進行，使得具有大於約15微米之一D10的烴滴液被形成。此方法亦可包括回收包括經蒸發之烴類及蒸汽的一蒸氣相，及包括未經蒸發之烴類的一液體相。然後，蒸氣相可供應至一蒸汽熱解反應器，以將其內一部份之烴類轉化成烯烴類及/或芳香族化合物。
於某些實施例，全原油之接觸形成具有大於約20微米之一D10的烴滴液。於不同實施例，全原油之接觸形成具有大於約25微米之一D10的烴滴液。
於某些實施例，此方法可包括使全原油通過蒸汽熱解反應器之一對流區段，以於接觸步驟之前將全原油預熱。此預熱可包括，例如，將全原油加熱至低於其起泡點溫度之一溫度。
此方法可進一步包括控制一蒸汽溫度及蒸汽供料速率，而足以蒸發烴原料中之5至90重量%的烴類。於其它實施例，蒸汽溫度及流速可控制於蒸發烴原料中之10至30重量%的烴類。於其它實施例，此方法可包括控制蒸汽溫度及蒸汽流速，以於蒸氣分餾物中回收全原油中之70至98重量%的具有160°C或更少之正常沸點的烴類。
於另一方面，此處揭露之實施例係有關於一種用於自一廣沸點範圍之烴原料生產烯烴類之系統。此系統包括一揮發裝置，其具有一蒸汽入口、一烴入口、一蒸氣相出口，及一液體相出口。一控制系統可被設置及建構，以使經由烴入口引入之烴原料與經由蒸汽入口引入之蒸汽的一流速維持於，例如，少於30m/s之一相對接觸速率。此系統亦可包括一蒸汽熱解反應器，以供經由蒸氣相出口回收之經揮發的烴類轉化形成烯烴類及芳香族化合物。
於某些實施例，例如，控制系統可被建構成使經由烴入口引入之烴原料與經由蒸汽入口引入之蒸汽的一流速維持於少於15m/s之一相對接觸速率。
揮發裝置可包括蒸汽入口及烴入口，其於某些實施例係建構成配置於一同向流結構中之同心管。揮發裝置可進一步包括一氣旋分離器，其係建構成用以接收來自同心入口之同向流的蒸汽及烴。於其它實施例，揮發裝置可建構成具有配置於一逆流結構中之蒸汽入口及烴入口。
於另一方面，此處揭露之實施例係有關於一種用於蒸汽裂解廣沸點範圍烴原料之方法。此方法使可包括原始或經先前加工或氫加工之流體的一廣沸點範圍烴原料與蒸汽接觸，以揮發一部份之烴類。烴原料與蒸汽之接觸可以少於30m/s之一初始相對速率進行。此方法可進一步包括使包括經揮發之烴類及蒸汽的一蒸氣相與包括未經蒸發之烴類的一液體相分離，與蒸汽裂解蒸氣相中之烴類。
於上述實施例之每一者，其中，蒸汽係用以與一液體烴流混合， 此接觸係以低速率進行，以蒸發更多揮發性烴類，且不會產生小的難以分離之液體滴液。
於所附圖式中顯示之此方法流程圖對於特別之原油及產品構成可作些微修改。其它方面及優點由下列說明及所附申請專利範圍會係明顯的。
詳細說明
於一方面，此處揭露之實施例係有關於使一廣沸點範圍之烴原料與蒸汽控制式揮發之系統及方法。如上所示，當一烴混合物之終沸點高，諸如，超過550°C，此烴混合物會含有不合意或難以處理之化合物。例如，高沸點組份無法於一蒸汽熱解反應器中直接加工產生烯烴類，因為此等重烴類存在造成於反應器中形成焦炭，其中，結焦會發生在對流區預熱線圈或過熱線圈、於輻射線圈，或於傳輸線路交換器之一或多者，且其中，此結焦會快速發生，諸如，於最小時內。
當將烴類揮發以供分離及供應至下游方法，發現使蒸汽與烴類“溫和”接觸可有利地蒸發混合物中之較輕烴類，同時使會干擾下游加工之較重烴類的滴液形成及挾帶達最小或避免。於此使用時，“溫和”可指烴與蒸汽之接觸係於，例如，少於30m/s之一初始相對速率進行，產生一可分離混合物，其包括包含未經蒸發之烴類的一液體相及包含經揮發之烴類及蒸汽的一蒸氣相。於某些實施例，烴原料與蒸汽之接觸可於範圍從約1m/s至約30m/s，諸如，範圍從約1m/s至約15m/s之一初始相對速率進行。於其它實施例，烴原料與蒸汽之接觸可於範圍從約2m/s至約10m/s，諸如，範圍從約3.5m/s至約10m/s或從約6.5m/s至約9.5m/s之一初始相對速率進行。蒸汽與烴類之初始接觸可以，例如，少於30m/s，例如，少於25m/s，少於20m/s，少於18m/s，少於15m/s，少於12m/s，或少於10m/s之一相對速率發生，諸如，於範圍從1、2、3、4、5、6、7、8、9，或10m/s之一下限至5、6、7、8、9、10、12、15、18、20，或25m/s之一上限的一相對速率，其中，任何下限可與任何上限組合。於此使用時，初始相對速率係指初始混合時之個別流體速率之差值。
欲被揮發之烴類的量會衝擊此速率之下限。一熱量係於與烴類之一特定溫度差時之一特別體積的蒸汽內可獲得。因此，藉由蒸汽之流動面積及體積流速決定之蒸氣速率需充分而足以將烴原料內之一合意量的烴類揮發。因此，訂定用於使蒸汽與烴類接觸之組件的尺寸可以其等之用於達成一合意揮發量所需之個別流速為基準而決定。
於某些實施例，在烴原料與蒸汽接觸之前，可以一些蒸氣將烴原料預熱至低於其起泡點溫度、於此溫度，或高於此溫度之一溫度。此預熱可，例如，於一熱交換器，諸如，一供料/流出物熱交換器，與置於，例如，一加熱器之一對流區段中之加熱線圈中發生。
蒸汽與烴原料之接觸於某些實施例中可以同向流之蒸汽及烴類進行。例如，蒸汽及烴類可經由同心管件混合，其中，於外管件中流動之蒸汽或烴類可與流至一內管件之一終端處的蒸汽或烴類之另一者接觸。於某些實施例，蒸汽可於外管件中，且烴類可於內管件中流動。於其它實施例，烴可於外管件中流動，且蒸汽可於內管件中流動。於某些實施例，諸如，一靜式混合器之混合裝置可設置於內管件終端處的下游。
混合後，直接加熱可造成烴類部份揮發。形成之二相混合物可被供應至一分離器，以便使包括未經揮發之烴類的液體相與包括蒸汽及經揮發之烴類的一蒸氣相分離。因為蒸汽及烴類係以一溫和方式混合，最小或沒有會挾帶較重烴類至蒸氣相出口的滴液會被形成。因此，蒸汽與烴類之同向接觸可允許低相對速率，諸如，少於30m/s或少於15m/s，且可允許液體烴滴液直徑主要係高於，例如，25微米。此液體烴滴液直徑能允許輕組份蒸發，且不會蒸發或挾帶重組份。
於某些實施例，分離器可為一閃蒸器。於某些實施例，接觸後之蒸汽與烴類的混合物可供應至一圓柱形閃蒸器，使得此流體之大部份係以切線方向引至閃蒸器內，產生一氣旋流，因此促進蒸氣與含有於混合方法期間會形成的任何滴液之液體相的分離。氣旋分離腔室可包括用於回收蒸氣相之一上出口，及用於回收液體相之一出口。
於其它實施例，蒸汽與烴原料可逆向流接觸。例如，蒸汽與烴類可於一垂直式容器之相反端引入，其中，向下流之烴類可與向上流之蒸氣接觸。於某些實施例，垂直式容器可含有質量/熱轉移內部及/或分配器，以供引入蒸汽及/或烴類。於垂直式容器內之速率可被維持低到足以避免小液滴(即，具有少於25微米之直徑的滴液)大量形成，但高到足以維持輕組份之一合意揮發度。
如上所述，依據此處實施例之蒸汽與烴類同向流及逆向流接觸可於用以避免大量之會被挾帶的小烴滴液形成之相對速率進行。但是，公認接觸會造成一滴液尺寸分佈。於某些實施例，依據此處實施例之蒸汽與烴類接觸可於使得形成之滴液具有大於大於100微米，大於150微米，大於200微米，大於250微米，大於300微米，或大於350微米之一D50的相對速率進行。於其它實施例，形成之滴液具有大於5微米之一D10，即，諸如，大於10微米，大於15微米，大於20微米，大於25微米，大於30微米，大於35微米，大於85微米，或大於200微米。於某些實施例，形成之滴液可具有範圍從約60至約150微米之一D10，及範圍從約200至約350微米之一D50。於其它實施例，蒸汽與烴接觸可於使得少於5%，少於10%，或少於15%之滴液具有少於25微米之一直徑進行。
上述之一廣沸點範圍烴原料揮發可有利地施用於一用以熱裂解烴類而生產烯烴類及/或芳香族化合物之系統。可用於此處堨露之實施例的烴混合物可包括各種烴混合物，其包括具有其中混合物之終沸點可為大於450°C或大於500°C，諸如，大於525°C，550°C，或575°C之一沸點範圍者。高沸點烴類，諸如，於超過550°C沸騰之烴類，的量可為少至0.1重量%，1重量%，或2重量%，但可高達10重量%，25重量%，50重量%，或更大。此處之實施例可關於原油作說明，但任何高沸騰終點之烴混合物，諸如，原油及濃縮物，可被使用。此處揭露之方法可施用於具有一廣沸點曲線及高於500°C之端點的原油、濃縮物，及烴，或含有微量的具有低達150°C之一終沸點的污染物之供料。此等烴混合物可包括全原油、原始原油、加氫處理之原油、汽油、真空汽油、加熱油、噴射燃料、柴油、煤油、汽油、合成石油腦、萃餘物重組油、費雪缺卜夕(Fischer-Tropsch)液體、費雪缺卜夕氣體、天然汽油、蒸餾物、原始石油腦、天然氣體冷凝物、大氣管餾器底部物、真空管餾器之包括底部物的流體、廣沸點範圍之石油腦到汽油冷凝物、來自精煉廠之重非原始烴流體、真空汽油、重汽油、大氣殘油、加氫裂解爐蠟，及費雪缺卜夕蠟等。於某些實施例，烴混合物可包括從石油腦範圍或更輕到真空汽油範圍或更重沸騰之烴類。若要的話，此等供料可被預加工以移除此處揭露方法之一部份的硫、氮、金屬，及康拉遜碳(Conradson Carbon)上游物，或加氫處理增加氫含量或降低分子量。
當烴混合物之終沸點高，諸如，超過550°C，烴混合物無法於一蒸汽熱解反應器中直接加工生產烯烴類。此等重烴類的存在造成於反應器中形成焦炭，其中，結焦會發生在一或多個對流區預熱線圈或過熱線圈、於輻射線圈，或於轉移管線交換器，且此結焦會快速發生，諸如，於數小時內。全原油未被商業化地裂解，因為其並不具經濟性。其被一般地分餾，且僅特別餾分被用於一蒸汽熱解反應器中生產烯烴類。其餘者被用於其它方法。具有較低終點之受污染供料亦會影響蒸汽熱解反應器，或產物回收區段，或二者中之烯烴設備。
裂解反應係經由一自由基機構進行。因此，高乙烯產率可於其在高溫度裂解時達成。如丁烷類及戊烷類之較輕供料需要一高反應器溫度達成高烯烴產率。如汽油及真空汽油(VGO)之重供料需要較低溫度。原油含有從丁烷類至VGO及殘餘物(具有超過550°C之一正常沸點的物料)之化合物的一分佈。使全原油無分離而接受高溫產生一高產率之焦炭(高嚴苛性之裂解烴類的副產物)及使反應器阻塞。蒸汽熱解反應器需週期性停機及藉由蒸汽/空氣去結焦而移除焦炭。生產烯烴類時二清理期之間的時間稱為執行長度。當原油無分離地裂解時，焦炭會沉積於對流區段線圈(蒸發流體)、輻射區段(其間係生產烯烴類之反應發生)及/或轉移管線交換器(於其間反應藉由冷卻快速停止以保持烯烴類產率)。此處之分離裝置及方法可促進全原油分餾成合意之分餾物，以供蒸汽熱解反應器中之改良式加工。
當揮發烴類以供分離及供應至一蒸汽裂解器，已發現蒸汽與烴類溫和接觸會有利地蒸發混合物中之較輕烴類，同時使較重烴類之滴液形成及挾帶達最小或避免。此處揭露之實施例可用以將供料烴混合物預熱及分離成二或更多分餾物。例如，此處之實施例可使一全原油與蒸汽接觸而揮發一輕烴分餾物，諸如，具有少於90°C，少於120°C，少於140°C，少於150°C，少於160°C，少於180°C，少於200°C，少於220°C，少於250°C，少於300°C，少於350°C，少於400°C，或少於450°C之一正常沸點溫度之烴類。於與蒸汽接觸之前，烴原料可被預熱，諸如，於一熱交換器中或藉由使此原料通過一蒸汽熱解反應器之對流區段(或一加熱器)以使供料烴混合物預熱，促進分離成合意之分餾物。
蒸汽可以一低相對速率(蒸汽減掉烴速率)注射至烴原料內，以增加烴混合物之蒸發及控制達成之加熱及分離度。烴類之蒸發可於相對較低溫度發生。蒸汽與烴類之初始接觸可，例如，以如上所述之低相對速率發生，其中，相對速率可為，例如，少於30m/s，少於25m/s，少於20m/s，少於15m/s，少於12m/s，或少於10m/s。
於某些實施例，蒸汽溫度及蒸汽供料速率可為足以使，例如，烴原料中之最高達5，最高達10，最高達15，最高達20，最高達25，最高達30，最高達35，或最高達40重量%之烴類揮發。於某些實施例，蒸汽溫度與蒸汽流速可為足以使70至90，95，或甚至98重量%之具有160°C或更少之一正常沸點的烴類揮發，諸如，75至85重量%之具有160°C或更少之一正常沸點的烴類揮發。於其它實施例，蒸汽溫度及蒸汽流速可為足以使70至90，95，或98重量%之具有200℃或更少，或220℃或更少之一正常沸點的烴類揮發，諸如，75至85重量%之具有200℃或220℃或更少之一正常沸點的烴類揮發。
依據此處實施例之蒸汽與廣沸點範圍之烴的接觸可使焦炭先質之揮發及/或焦炭先質之挾帶達最小或去除。例如，對於一特定分餾點溫度，此處之實施例可有效率地揮發主要為具有等於或少於意欲分餾點溫度之一正常沸點的烴類。例如，烴“餾分”會相對乾淨，意指經蒸發之分餾物會不具有任何大量(於此使用時係＞10重量%)之高於意欲沸騰溫度目標沸騰之化合物。例如，一160°C餾分會不具有任何大量之高於160°C沸騰之烴化合物(即，＞10重量%)。於其它實施例，意欲目標“餾分”溫度可為一95%沸點溫度，或於其它實施例，為一85%沸點溫度，諸如，可使用ASTM D86或ASTM D2887，或，例如，依據ASTM D2892之一真實沸點(TBP)分析測量。於此等實施例，可具有最高達5重量%，最高達15重量%，或最高達25重量%之化合物高於意欲之“分餾”點溫度。
用於熱裂解諸如一全原油之一廣沸點範圍的烴混合物之方法因此可包括使具有最高達450°C或更大之一沸點範圍的一烴原料與蒸汽接觸，以使一部份之烴類揮發。烴原料與蒸汽接觸可於少於15m/s或少於12m/s之一初始相對速率進行，諸如，於如上所述之例如9m/s之一相對速率。回收之後，形成之蒸氣相可供應至一蒸汽熱解反應器，以使其它之至少一部份的烴類轉化成烯烴類。烴原料可通過此蒸汽熱解反應器之一對流區段，用以在與蒸汽接觸之前預熱此烴原料。於某些實施例，進行此預熱用以使烴原料之加熱限於低於其起泡點溫度之一溫度。
於另一方面，此處之實施例係有關於一種用於揮發一廣沸點範圍的烴原料之系統，及用於從一廣泡點範圍的烴原料生產烯烴類及芳香族化合物之系統。此處之此等系統可包括一揮發裝置，其包含一蒸汽入口、一烴入口、一蒸氣相出口，及一液體相出口。
於某些實施例，此揮發裝置包含建構成以一同向流結構配置之同心管線的蒸汽入口及烴入口。一同向流揮發裝置可進一步包括一氣旋分離器，其係建構成用以接收來自同心入口之同向流的蒸汽及烴。於其它實施例，此揮發裝置可建構成具有以一逆向流結構配置之蒸汽入口及烴入口。
此處之系統亦可包括一控制系統，以控制經由烴入口引入之烴原料的一流速，及經由蒸汽入口引入之蒸汽的一流速。此控制系統可建構成用以維持烴原料及蒸汽之流速，及使此等流體之接觸控制於少於30m/s，少於15m/s，少於12m/s，少於10m/s之一相對速率，或於如上所述之其它相對速率。
系統可進一步包括一蒸汽熱解反應器，其係用於將經由蒸氣相出口回收之經揮發的烴類轉化形成烯烴類及芳香族化合物。
上述之部份蒸發系統及方法因此可形成一蒸氣-液體混合物。蒸氣烴類可與液體烴類分離，且僅經分離之蒸氣可供應至一蒸汽熱解反應器之一或多個輻射單元中之輻射線圈。
若要的話，加熱及分離步驟可用以將烴混合物分離成二或更多的烴分餾物。此可使每一餾分最佳地裂解，使得產量、蒸汽對油之比例、加熱器入口及出口之溫度，及其它變數可控制在合意量，以達成合意反應結果，諸如，至一合意產物分佈，同時限制輻射圈及相關下游設備中之結焦。剩餘液體可被移除以供進一步加工，諸如，調節原料之較重部份，以將難以處理之較重組份轉化成適於至輻線圈之另外供料的烴類，以供生產烯烴類及芳香族化合物。
烴原料可以來自處理流之廢熱預熱，其包括來自裂解方法之流出物或來自蒸汽熱解反應器/加熱器之煙道氣體。另外，原油加熱器可用於預熱。於此等情況，為使蒸汽熱解反應器之熱效率達最大，其它冷流體(如鍋爐供應水(BFW)或空氣預熱或節熱器)可作為對流區段之最上冷卻散熱片。
一蒸汽熱解反應器中之裂解烴類的處理可分成三部份，即，一對流區段、一輻射區段，及一驟冷區段，諸如，於一轉移管線交換器(TLE)內。於對流區段，供料被預熱，與蒸汽混合，及部份蒸發。於輻射區段，供料被裂解(於其中，主要裂解反應發生)。於TLE，反應流體被快速驟冷以停止反應及控制產物混合物。替代經由熱交換之間接驟冷，以油之直接驟冷亦可接受。
此處之實施例有效率且選擇性地蒸發一烴原料，以限制或去除較重烴類的挾帶，增強裂解處理。於某些實施例，所有加熱可於單一反應器中之一對流區段中實施。於某些實施例，原油進入對流管束之最上排，且以加熱器之輻射區段中產生之熱煙道氣體，於操作壓力預熱至中間溫度，且未添加任何蒸汽。出口溫度可從150°C至230°C作改變，其係依原料之沸點範圍、壓力，及生產量而定。於此等條件，極少或無烴類會被蒸發，使烴原料維持在低於或於其起泡點。例如，此第一加熱步驟之出口溫度可為使得如同石油腦一樣輕之組份(具有最高達約200°C之一正常沸點)未被蒸發，或僅最小地蒸發。因為烴混合物係以加熱器之輻射區段中產生之熱煙道氣體預熱，出口溫度之有限溫度變化及不確定性可被預期。
於某些實施例，一小量之蒸汽可與供料烴一起添加且進一步預熱達到大於200°C之一溫度，且部份蒸發此供料。添加小量之蒸汽可避免焦炭形成，且同時能使供料加熱至高溫度，而能回收一較高產率之原油或原始供料，以供生產烯烴類及芳香族化合物。
然後，經預熱之烴混合物可如上所述般與蒸汽以低的相對速率混合，以便僅部份蒸發烴原料，且經蒸發之部份可與未經蒸發之部份分離。蒸氣可進一步過熱，與稀釋蒸汽混合，然後供應至輻射線圈用於裂解。
於某些實施例，例如，具有160℃或更少之一正常沸點的烴類可被揮發。此經揮發之輕烴分餾物及稀釋蒸汽混合物可於對流區段中進一步過熱，然後進入輻射線圈。輻射線圈可於一不同單元中，或於單一單元內之一組輻射線圈可用以裂解此輕烴分餾物。稀釋蒸汽的量可被控制以使總能量達最小。典型上，蒸汽對輕烴分餾物係控制在約0.5w/w之一蒸汽對油之比例，諸如，從0.2w/w至1.0w/w或諸如，從約0.3w/w至約0.7w/w。
於某些實施例，未經蒸發之液體烴類可進一步加工或送至燃料。若未經蒸發之液體的熱裂解係合意以產生另外之烯烴類及芳香族化合物，未經蒸發之液體可先於其它精煉方法調節，諸如，可得自Chevron Lummus Global之一LC-FINING方法或一LC-SLURRY方法，產生適用於一蒸汽熱解反應器之供料。替代加氫處理，亦可考慮其它路徑，諸如，延遲結焦及/或流體催化裂解(FCC)。另外，可於此流體獲得之熱能可用以預熱其它處理流或產生蒸汽。
輻射油技術可為具有範圍從90毫秒至1000毫秒之整體滯留時間，具有數列及數個平行通道及/或分流線圈配置之任何型式。其等可為垂直或水平。線圈材料可為高強度合金，具有裸及鰭片式或內部熱轉換改良管。熱交換器可由具有多數個線圈之一個輻射箱及/或於每一箱中具有多個線圈之二個輻射箱所組成。每一箱中的輻射線圈之幾何形狀及尺寸與線圈數量可為相同或不同。若成本不是一因素，可使用多個流體加熱器/交換器。
於輻射線圈裂解之後，一或多個轉移管線交換器可用以極快速地冷卻產品及產生(超)高壓蒸汽。一或多個線圈可被組合及連接至每一交換器。交換器可為雙管式或多殼式及管式交換器。
替代間接冷卻，亦可使用直接驟冷。對於此等情況，油可於輻射線圈之出口注射。於油驟冷之後，亦可使用一水驟冷。替代油驟冷，一全水式驟冷亦可接受。驟冷之後，產品被送至一回收區段。
圖1係例示依據此處實施例之一裂解系統的一簡化方法流程圖。一明火管式爐1係用於將烴類裂解成乙烯及及其烯烴類及芳香族化合物。明火管式爐1可具有一對流區段或區域2及一裂解區段或區域3。爐1含有一或多個處理管線4(輻射線圈)，藉此等管線，於施加熱時，一部份之經由烴供應管線22初始供應之烴類裂解產生氣體。輻射及對流熱係藉由經加熱媒介入口8，諸如，膛爐、地板爐或壁爐，引至爐1的裂解區段3的一加熱媒介的燃燒而供應，且經由一排氣裝置10離開。
烴原料，諸如，一全原油或包括從石油腦範圍之烴類至具有大於大於450°C之一正常沸點溫度的烴類而沸騰的烴類之一烴混合物，可經由入口22引至一加熱線圈24，其係置於蒸汽熱解加熱器1之對流區段2。例如，具有一廣沸點範圍之烴類，其包括具有大於475°C，大於500°C，大於525°C，或大於550°C之一正常沸點溫度之烴類，可被引至加熱線圈24。於加熱線圈24，烴原料可被預熱，諸如，到少於烴原料之一起泡點的一溫度。然後，經加熱之烴原料26係以一低相對速率與蒸汽50接觸，且供應至一分離器27，以分離成一蒸氣分餾物28及一液體分餾物30。雖未明確例示，以圖1例示之實施例考量到於供應至一氣旋分離器27前的蒸汽50及經預熱的烴26之同向流接觸。
蒸汽可經由流程線32供應至此方法。此方法之各部份可使用低溫或飽和之蒸汽，而其它可使用高溫過熱蒸汽。欲被過熱之蒸汽可經由流程線32供應至加熱線圈34，於蒸汽熱解加熱器1之對流區2中加熱，且經由流程線36以過熱蒸汽回收。蒸汽50可自流程線32供應，或另外可為來自流程線50A之過熱蒸汽。
蒸汽50或50A與經預熱之烴原料26以低相對速率接觸可揮發，例如，最輕之10至30重量%的烴組份，其等可於流程線28與蒸汽一起回收。一部份之蒸汽可經由流程線40供應，且與蒸氣分餾物28於管線42中混合形成一蒸汽/烴混合物。然後，於流體42中之蒸汽/烴混合物可經由系統(A)供應至一加熱線圈44。然後，形成之過熱混合物經由流程線46，經由系統(B)，供應至一裂解線圈4，其係置於蒸汽熱解加熱器1之一輻射區3中。然後，經裂解之烴產物可經由供熱回收、驟冷，及產物回收之流程線12回收。系統(A)及(B)可為一簡單導管，或可包括一或多個加熱器、另外之蒸汽注射、次要之烴供料，或中間加工。例如，替代經由流程線40供應且與蒸氣分餾物28混合之另外蒸汽，蒸汽可於系統(A)中混合。
液體分餾物30，其係於加熱線圈24中未被揮發之為烴原料之70至90重量%的最重物，其後可被供應至一系統(C)，用以調節較重組份以供熱裂解。於系統(C)中調節之後，形成之將被熱裂解的烴類可於線圈52預熱，於置於蒸汽熱解反應器1之對流區2的加熱線圈52之前或之後與蒸汽53混合。於加熱線圈52，經調節之烴類可被部份或完全蒸發。如上所示，於某些實施例,，一小量之蒸汽(未示出)可於加熱重供料之前添加。將蒸汽注射至經調節之液體分餾物30內可助於避免焦炭於加熱線圈52形成。經加熱之液體分餾物54可選擇性地供應至一分離器56，用以分離成一蒸氣分餾物58及一液體分餾物60。如所示般，流體(C)可於相同蒸汽裂解爐中熱裂解。於其它實施例，流體(C)可於一不同加熱器中熱裂解，其提供額外溫度控制。另外，流體(C)可於一加氫處理單元或一FCC單元中加工。於其它實施例，流體(C)可與其它流體摻合形成一燃料。
一部份的過熱蒸汽可經由流程線62供應且與蒸氣分餾物58混合於管線64中形成一蒸汽/烴混合物。然後，流體64中之蒸汽/烴混合物可供應至一加熱線圈66。然後，形成之過熱混合物可經由流程線68供應至一裂解線圈4，其係置於蒸汽熱解加熱器1之一輻射區3。然後，經裂解之烴產物經由用於熱回收、驟冷，及產物回收之流程線13回收。
過熱蒸汽可經由流程線74直接注射至分離器56中。將過熱蒸汽注射至分離器中可降低分壓及增加蒸氣分餾物58中烴類的量。
除了加熱烴及蒸汽流外，對流區2可用以加熱其它處理流及蒸汽流，諸如，經由線圈80，82，84。例如，線圈80，82，84可用以加熱BFW(鍋爐供水)及預熱SHP(超高壓)蒸汽及其它。
線圈24，52，34，44，66，80，82，84的位置及數量可依可用的設計及預期原料作改變。以此方式，對流區段可被設計成使自煙道氣體的能量回收達最大。於某些實施例，可能意欲將超加熱線圈44置於比超加熱線圈66更高之一煙道氣體溫度位置。較輕烴類的裂解可以較高嚴苛度及藉由適當地置放超加熱線圈而進行，裂解條件可對特別蒸氣餾分作增強或修整。
如上所述，分離器27可金構成與經預熱之烴原料以一同向流或逆流向方式，以一低相對速率接觸。此接觸可達成一低提升(lift)(諸如，少於30重量%之烴類揮發)，且亦可形成一高平均烴滴液直徑(諸如，高於25微米)。
分離器56可被操作達成一高揮發度。當意欲一高揮發度時，第二分離器56可為一重油加工系統(HOPS)塔，其可用以使經調節之烴類達到大於95%揮發。另外，可使用與分離器27相似之一分離器，以達成一高揮發度。另外，雖然圖1顯示輕流體及高沸點流體於單一加熱器或多個加熱器中熱裂解，高沸點分餾物可另外於如上所示般之一加氫處理單元中加工。
於每一上述實施例，液體烴供料可被預熱及與蒸汽混合。此處之實施例係進一步有關於形成蒸汽與液體烴類之一混合物，其中，液體烴類被加熱且未形成大量蒸氣，因此避免高速率。然後，稀釋蒸汽係以低速率添加至烴，以蒸發更多揮發性烴類，且未產生小且難蝌分離之液體滴液。
例如，此處之實施例可包括將原油或其它烴分餾物於一蒸汽裂解爐之對流區段預熱至低於其起泡點溫度之一溫度。然後，經預熱之原油可於含有質量及/或熱轉移內部之一垂直式容器中接觸，蒸汽與原油以低速率接觸。於某些實施例，蒸汽及原油可以逆向流式流動。於垂直式容器中之速率可保持低到足以使具有直徑少於25微米之小液滴的形成達最小或避免。然後，來自容器頂部之包括蒸汽及經揮發之烴類的蒸氣可導引至蒸汽裂解器之過熱及/或輻射區段，用以轉化成烯烴類。垂直式容器及接觸部能使液體烴分餾物與蒸汽接觸，以使該烴原料之一分餾物以低速率蒸發，以避免小滴液形成。然後，無滴液或基本上無滴液之蒸氣分餾物可於一蒸汽裂解器輻射區裂解。
此處之實施例因此可提供靈活地加工含有高沸點之焦炭先質的全原油及其它烴混合物。有利地，此處之系統及方法可提供使廣沸點範圍之混合物控制式揮發。此處之實施例可於預熱、過熱，及裂解方法期間，甚至於高嚴苛條件時，有利地降低結焦及結垢。此處之實施例可達成合意產率，同時明顯減少與分餾物於多個加熱器中之預分餾及分離加工有關之資本及能量需求。
依據此處實施例於整個裂解方法抑制結焦且同時增加烯烴類產率提供重大優點，其包括增加執行長度(減少停機時間)及處理含有重烴類之供料的能力。再者，顯著能量效率可優於包括蒸餾分離及個別裂解反應器之傳統方法而獲得。
雖然本揭露包括有限數量之實施例，但具有本揭露利益之熟習此項技藝者會瞭解未偏離本揭露之範圍的其它實施例可被想出。
1:明火管式爐/蒸汽熱解加熱器 2:對流區段或區域 3:裂解區段或區域/輻射區 4:處理管線/裂解線圈 8:加熱媒介入口 10:排氣裝置 12:流程線 13:流程線 22:烴供應管線/入口 24:加熱線圈 26:烴原料 27:分離器 28:蒸氣分餾物/流程線 30:液體分餾物 32:流程線 34:加熱線圈 36:流程線 40:流程線 42:管線/流體 44:加熱線圈 46:流程線 50:蒸汽 50A:流程線 52:加熱線圈 53:蒸汽 54:液體分餾物 56:分離器 58:蒸氣分餾物 60:液體分餾物 62:流程線 64:管線/流體 66:加熱線圈 68:流程線 74:流程線 80,82,84:線圈 A,B,C:系統
圖1係依據此處實施例之用於熱裂解烴混合物的一系統之一簡化方法流程圖。
1:明火管式爐/蒸汽熱解加熱器
2:對流區段或區域
3:裂解區段或區域/輻射區
4:處理管線/裂解線圈
8:加熱媒介入口
10:排氣裝置
12:流程線
13:流程線
22:烴供應管線/入口
24:加熱線圈
26:烴原料
27:分離器
28:蒸氣分餾物/流程線
30:液體分餾物
32:流程線
34:加熱線圈
36:流程線
40:流程線
42:管線/流體
44:加熱線圈
46:流程線
50:蒸汽
50A:流程線
52:加熱線圈
53:蒸汽
54:液體分餾物
56:分離器
58:蒸氣分餾物
60:液體分餾物
62:流程線
64:管線/流體
66:加熱線圈
68:流程線
74:流程線
80,82,84:線圈
A,B,C:系統

Claims (25)

  1. 一種用於蒸汽裂解全原油之方法，該方法包含： 將一全原油與蒸汽接觸以揮發一部份之烴類，其中，該烴原料與該蒸汽之該接觸係以少於30m/s之一初始相對速率進行； 將包含經揮發之烴類及蒸汽之一蒸氣相與包含未經蒸發之烴類的一液體相分離； 蒸汽裂解於該蒸氣相中之烴類。
  2. 如請求項1之方法，其中該全原油與該蒸汽之該接觸係以範圍從約1m/s至約15m/s之一初始相對速率進行。
  3. 如請求項1之方法，其中該全原油與蒸汽之該接觸係以範圍從約2m/s至約10m/s之一初始相對速率進行。
  4. 如請求項1之方法，進一步包含形成具有大於約100微米之一D50的烴滴液。
  5. 如請求項1之方法，進一步包含形成具有大於約20微米之一D10的烴滴液。
  6. 如請求項1之方法，進一步包含於該接觸步驟之前將該全原油預熱至低於其起泡點溫度之一溫度。
  7. 如請求項1之方法，其中該接觸包含將該蒸汽與該全原油以同向流混合，且其中該分離包含於一氣旋分離器中將該蒸氣相與該液體相分離。
  8. 如請求項1之方法，其中該蒸汽與該全原油係以逆向流接觸。
  9. 如請求項1之方法，進一步包括控制一蒸汽溫度及蒸汽供料速率而足以揮發該全原油中之5至90重量%的烴類。
  10. 如請求項1之方法，進一步包括控制一蒸汽溫度及蒸汽供料速率而足以揮發該全原油中之10至30重量%的烴類。
  11. 一種用於蒸汽熱解全原油或其一部份而生產烯烴類及/或芳香族化合物之方法，該方法包含： 將一全原油與蒸汽接觸而揮發一部份之烴類，其中該全原油與蒸汽之該接觸形成具有大於約30微米之一D10的烴滴液； 回收包含經揮發之烴類及蒸汽之一蒸氣相及包含未經蒸發之烴類的一液體相； 將該蒸氣相供應至一蒸汽熱解反應器而將其內至少一部份之該烴類轉化成烯烴類及/或芳香族化合物。
  12. 如請求項11之方法，其中該烴原料之該接觸形成具有大於約85微米之一D10的烴滴液。
  13. 如請求項11之方法，其中該烴原料之該接觸形成具有大於約200微米之一D10的烴滴液。
  14. 如請求項11之方法，進一步包含於該接觸步驟之前，使該烴原料通過該蒸汽熱解反應器之一對流區段以預熱該烴原料。
  15. 如請求項14之方法，其中該預熱包含將該烴原料加熱至低於其起泡點溫度之一溫度。
  16. 如請求項11之方法，其中該接觸包含將該蒸汽與該烴原料以同向流混合，且該分離包含於一氣旋分離器中使該蒸氣相與該液體相分離。
  17. 如請求項11之方法，其中該蒸汽與烴原料係以逆向流接觸。
  18. 如請求項11之方法，進一步包括控制一蒸汽溫度及蒸汽供料速率而足以揮發該烴原料中之5至90重量%的該烴類。
  19. 如請求項11之方法，進一步包括控制一蒸汽溫度及蒸汽供料速率而足以揮發該烴原料中之10至30重量%的該烴類。
  20. 如請求項11之方法，進一步包含控制蒸汽溫度及蒸汽供料速率，以於該蒸氣分餾物中回收70至98重量%之具有160°C或更少之一正常沸點的烴類。
  21. 一種用於自一廣沸點範圍之烴原料生產烯烴類之系統，該系統包含： 一揮發裝置，其包含一蒸汽入口、一烴入口、一蒸氣相出口，及一液體相出口； 一控制系統，其係建構成將經由該烴入口引入之該烴原料及經由該蒸汽入口引入之蒸汽的一流速維持於少於30m/s之一相對接觸速率；及 一蒸汽熱解反應器，其係用於將經由該蒸氣相出口回收之經揮發的烴類轉化，形成烯烴類及芳香族化合物。
  22. 如請求項21之系統，其中該控制系統係建構成將經由該烴入口引入之該烴原料及經由該蒸汽入口引入之該蒸汽的一流速維持於少於15m/s之一相對接觸速率
  23. 如請求項21之系統，其中該揮發裝置包含該蒸汽入口及該烴入口，其等係以一同向流結構配置之同心管線而建構。
  24. 如請求項23之系統，其中該揮發裝置進一步包含一氣旋分離器，其係建構成用於接收來自該等同心的入口之同向流的蒸汽及烴。
  25. 如請求項21之系統，其中該揮發裝置係建構成具有以一逆向流結構配置之該蒸汽入口及該烴入口。
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