TWI482851B - 協同的酸摻合物萃取助劑及其使用方法 - Google Patents

協同的酸摻合物萃取助劑及其使用方法 Download PDF

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TWI482851B
TWI482851B TW098105841A TW98105841A TWI482851B TW I482851 B TWI482851 B TW I482851B TW 098105841 A TW098105841 A TW 098105841A TW 98105841 A TW98105841 A TW 98105841A TW I482851 B TWI482851 B TW I482851B
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acid
extraction
extraction aid
crude oil
water
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Alan E Goliaszewski
Cato R Mcdaniel
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Gen Electric
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    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
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    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
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    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content

Description

協同的酸摻合物萃取助劑及其使用方法
本發明係關於萃取助劑、及其在石油生產及精煉脫鹽製程中之用途。更具體而言，本發明係關於在製造及處理期間去除原油中污染物(尤其係金屬及胺)之萃取助劑。
液態烴介質(例如原油及粗餾分)包括石腦油、汽油、煤油、噴射機燃料、燃料油、柴油及減壓渣油，其通常含有會損害處理或產品品質之污染物。在精煉及其他製程中，污染物會導致腐蝕、熱交換器結垢、爐結焦、觸媒失活及產品降格。污染物大體上分為鹽、底部沈積物及水、固體及金屬。該等雜質之量隨特定原油及其處理而變化。
脫鹽或脫水係在運輸及精煉之前去除原油中污染物(主要為水及無機鹽)之製程。初始脫水步驟通常在使用諸如游離水分離器(Free Water Knockout)(FWKO)等裝置之情況下實施以自油中分離產生的水。通常，產出油所含水的量遠遠超過0.5%的典型管線規格且FWKO之目的係去除水以低於管線規格。精煉廠中之脫鹽步驟係藉由以下提供：添加少量體積百分比之淡水並將其與原油混合以作為乳液接觸留於原油中之鹽水並去除該鹽水。脫鹽為原油處理或精煉所提供之益處包括：減少原油蒸餾單元(crude unit)腐蝕；減少原油預熱系統結垢；減少對蒸餾塔之潛在損壞；降低能源成本；並減少下游製程及產品污染。
在原油脫鹽中，借助與佔原油的約四(4)-約十(10)體積%之水混合來有意形成油包水乳液。將水添加至原油中並充分混合以使原油中之雜質轉移至水相中。由於小水滴逐漸合併成較大液滴且最終油與在下面的水相重力分離，從而發生相分離。
在美國專利第4,778,589號中揭示去除含烴原料中金屬污染物(尤其係鈣)之製程。該製程包含將原料與金屬掩蔽劑(尤其係羥基羧酸，且更具體而言係檸檬酸、或其鹽或混合物)之水溶液混合及分離出含有金屬之水溶液形成脫金屬原料。
美國專利第5,078,858號揭示並主張自液態烴(例如原油)中萃取含鐵物質(例如環烷酸鐵及鐵硫化物)之方法。將選自由草酸或檸檬酸組成之群之螯合劑直接添加至液態烴中並與其混合。添加洗滌水以形成油包水乳液，使該乳液分解，並分離出負載鐵之水相。
在美國專利申請公開案第2004/0045875 A1號中，已發現金屬及/或胺可在破乳製程中藉由使用含有水溶性羥基酸之組合物自烴相除去或轉移至水相中。該組合物亦可包括至少一種無機酸以降低脫鹽設備洗滌水之pH。該組合物可視情況包括溶劑。該製程使金屬及/或胺轉移至水相中，而幾乎沒有或不會將烴相夾帶至水相中。
因此，仍需要顯示改良優於原油中污染物萃取之製程以使污染物在脫鹽製程中不會分配至原油中，該製程使用水溶性、不會在原油蒸餾單元頂部餾出物中產生可使中和劑需求量增加的酸、於高溫下穩定且易於施用之組份。
已發現一種可提供增強之自原油中去除污染物(例如金屬及胺)之萃取助劑，其使用之組份為水可溶、具有低毒性、高度生物可降解並展示高的熱穩定性故為生產及脫鹽製程中所需。
根據本發明一個實施例，提供增強萃取性質之萃取助劑係由酸、尤其水溶性酸之摻合物組成。更具體而言，兩種選自乙酸、硫酸、羥基乙酸、檸檬酸及甲磺酸組成之群之酸之組合。
在萃取中顯示協同作用之替代實施例係由甲磺酸(MSA)及檸檬酸組成，已發現該組合比使用單一酸(例如檸檬酸)效果更佳。
在本發明又一替代實施例中，藉由探究已發現當甲磺酸以萃取助劑的約5至約50體積%之量存在時，甲磺酸與檸檬酸之組合的協同作用明顯。當甲磺酸以介於約10體積%與約20體積%間之量存於萃取助劑中時，協同作用表現最大。
表徵本發明之各種新穎特徵於形成本揭示內容一部分的隨附申請專利範圍中特別指出。為更好地理解本發明、其操作優點及藉由使用其可達成之益處，應參照隨附圖及描述性內容。隨附圖意欲顯示本發明之實例。該等圖並非意欲顯示本發明可實施或使用之所有方式之限制。當然可對本發明之各種組份做出改變及替代。本發明亦關於所闡述要素之子組合及子系統、及其使用方法。
本文中在整個說明書及申請專利範圍所使用之近似用語可用於修飾可允許改變而不引起其所涉及之基本功能改變之任何數量表示。因此，由一個術語或若干個術語(例如「約」)修飾之數值並不限於所規定之精確數值。在至少一些情況下，近似用語可對應於用於量測數值之儀器之精度。除非上下文或語言中另外指明，否則範圍限制可經組合及/或互換，且該等範圍係經識別且包括其中所包括之所有子範圍。除在操作實例中外或除非另有說明，否則在說明書及申請專利範圍中所使用之所有表示成份數量、反應條件及諸如此類之數字或表達應理解為在所有情況下均由詞語「約」修飾。
本文中所用術語「包含(comprises,comprising)」、「包括(includes,including)」、「具有(has,having)」或其任何其他變形皆意欲涵蓋非排他性包括之內容。例如，包含一系列要素之製程、方法、物件或設備無需僅限於彼等要素，而可包括該製程、方法、物件或設備之其他未明確列出的或所固有的要素。
根據本發明之一個實施例，提供經增強萃取性質之萃取助劑係由酸、尤其水溶性酸之摻合物組成，其在油精煉中之脫鹽製程期間用於去除原油中之污染物。已發現在精煉廠中當原油流經脫鹽設備時，將酸之組合添加至原油中可顯著降低烴中鈣及其他金屬之量與胺之量。已發現當使用酸之組合作為萃取助劑時，其使得烴中污染物(尤其金屬及胺污染物)之減少量比僅用單一酸高。
隨原油進入精煉設備中之各種化學物質可能對處理或產品品質有害。一類該群組或化學實體係胺家族。視相對沸點而定，例如某些烷基胺在脫鹽之後可留在原油中並經蒸餾沿常壓塔向上。該等胺之HCl鹽可導致沈積物並導致極具侵蝕性之沈積物下腐蝕(under-deposit corrosion)或熔鹽腐蝕。經鑒定速率大於1000mpy(密爾/年腐蝕穿透)。若胺HCl鹽之鹽點在於塔頂部或抽出管線中於水露點之前，則此尤其成問題。胺之來源很多且包括來自酸性氣體清洗單元、排放物或洩漏物中之胺。由於胺來自脫鹽設備洗滌水並在脫鹽設備中分配至原油中，故其亦可能進入原油塔中。存在並顯示該等特性、且藉由添加萃取助劑而顯著降低之胺已為業內所熟知，且其包括(但不限於)乙醇胺、二乙醇胺、三乙醇胺、N-甲基乙醇胺、N,N-二甲基乙醇胺、嗎啉、N-甲基嗎啉、乙二胺、甲氧基丙胺、N-乙基嗎啉、N-甲基乙醇胺、N-甲基二乙醇胺、二丁胺、及其組合。
在原油處理中不期望並導致諸多問題的另一種化學物質係金屬。本發明中所提及之金屬意欲包括(但不限於)彼等週期表(CAS版本)之IA、IIA、VB、VIII、IIB及IVA族者。在另一非限制性實施例中，金屬包括(但不限於)鈣、鐵、鋅、矽、鎳、鈉、鉀、釩及其組合。在脫鹽設備中未自油中萃取出之金屬(例如鐵)最終會進入常壓蒸餾塔之底部沈積物中及由該等底部沈積物構成之焦炭中。此產生焦炭，此對於金屬而言不合規格。殘留之鈣可導致煉焦爐結垢，使殘留燃料對於金屬含量而言不合規格或在FCC進料中作為觸媒毒。
通常使用脫鹽製程作為去除原油中不期望物質之方式。僅用水洗滌可萃取出一些污染物，包括一些金屬及胺。酸通常可藉由使胺質子化並使其更溶於水促進污染物(尤其係胺)之去除。在使用親水性胺之情況下酸之有益作用更顯著。提供增強萃取性質之萃取助劑係由酸、尤其水溶性酸之摻合物組成。更具體而言，兩種選自由乙酸、硫酸、羥基乙酸、檸檬酸及甲磺酸組成之群之酸之組合。
該等酸較佳為水溶性酸、尤其檸檬酸，其不僅展示水溶性且亦不溶於烴，且因此使得酸不會留在或進入原油蒸餾單元頂部餾出物中。此一作用將導致需要增加中和劑之量。檸檬酸(C6 H8 O7 )係弱有機酸，其水溶解度為133g/100ml(20℃)、且不溶於烴、且環境友好，且因此為較佳酸。
甲磺酸(CH3 SO2 OH)係磺酸家族之成員，且其為有機酸。其水可溶，但不溶於烴，於高溫下展示穩定性且生物可降解。
藉由組合兩種酸以產生萃取助劑，其對原油中污染物之萃取展示協同作用，尤其對於金屬(例如但不限於鐵及鋅)及/或胺之萃取而言。組合酸之協同值隨萃取助劑之組成而發生變化。由約5體積%至約50體積%之甲磺酸與包含檸檬酸之第二酸組成之萃取助劑展示協同作用。本發明一個實施例包含含甲磺酸及檸檬酸之萃取助劑，其中該萃取助劑包含約10體積%至約20體積%之甲磺酸。
當與僅用洗滌水或單一酸萃取助劑(例如檸檬酸)相比時，可看出組合酸萃取助劑具有協同作用。在其中甲磺酸與檸檬酸組合成萃取助劑之實施例中，發現萃取增強超過未經處理洗滌水多達約70%。此一實施例中之平均萃取增強超過未經處理洗滌水約20%至約40%。在展示多種污染物(包括各種胺)之多種原油中皆可看到該等協同作用。該等原油之實例包括(但不限於)Syncrude PZ、Maya、Arab Medium及Heidrun。協同作用亦隨不同胺(例如二丁胺(DBA)、二甲基乙醇胺(DMEA)、嗎啉(MORPH)、二乙醇胺(DEA)、及單乙醇胺(MEA))而發生變化。
藉由使用由甲磺酸及檸檬酸組成之萃取助劑亦展示協同作用，其優於使用僅由一種酸(例如檸檬酸)組成之萃取助劑。此對胺萃取而言尤其理想，且對極性胺而言甚至更係如此。
實例
在若干不同性質之原油(具體而言該等原油係Syncrude PZ、Maya、Arab Medium及Heidrun)中使用5種工業上相關之胺(DBA、DMEA、MORPH、DEA及MEA)來實施脫鹽設備模擬。該等原油定量添加200ppm之胺，使用經處理或未經處理之洗滌水來實施實驗室脫鹽設備模擬。該製程於240-300℉下使用4-8%洗滌水，同時進行剪切。結果示於下表中。
隨附圖1中顯示超過未經處理洗滌水胺萃取增強作用之百分比，而圖3顯示超過使用單一酸(尤其檸檬酸)的萃取助劑經增強的萃取作用。圖2顯示本發明組合酸之協同作用。儘管已參照較佳實施例對本發明進行闡述，但彼等熟悉此項技術者可在不背離本發明技術範圍之情況下對該等實施例做出各種改變或替代。因此，本發明之技術範圍不僅涵蓋上述彼等實施例，而且涵蓋屬於隨附申請專利範圍範圍內之所有內容。
圖1係根據本發明之實施例經增強胺萃取作用對未經處理之洗滌水之圖形顯示。
圖2係顯示根據本發明之實施例組合酸萃取助劑協同作用之圖形。
圖3係顯示根據本發明之實施例經增強胺萃取作用對檸檬酸萃取助劑之圖形。
(無元件符號說明)

Claims (7)

  1. 一種用於在精煉製程中自原油去除污染物之萃取助劑，其中該萃取助劑係由甲磺酸及檸檬酸組成。
  2. 如請求項1之萃取助劑，其中該萃取係於脫鹽製程中實施。
  3. 如請求項1之萃取助劑，其中該甲磺酸係以該助劑的約5至約50體積%之量存在。
  4. 如請求項1之萃取助劑，其中該甲磺酸係以該助劑的約10至約20體積%之量存在。
  5. 如請求項1之萃取助劑，其中該等經萃取污染物包含金屬及/或胺。
  6. 一種用於在精煉廠中之脫鹽製程期間增強污染物去除之萃取助劑，其中該萃取助劑係由甲磺酸及檸檬酸組成。
  7. 一種在原油精煉廠中去除污染物之方法，其中用於脫鹽製程之萃取助劑係由甲磺酸及檸檬酸組成。
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