201224132 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種處理液態烴以將酸性雜質（例如硫醇） 轉化為氣味較少之硫化合物之方法。更明確而言，在氧氣 之存在下，藉由使該烴與包括多價螯合金屬觸媒、醇及鹼 金屬氫氧化物之水性處理溶液接觸而將該等雜質氧化成_ 硫化物油。尤其較佳之處理溶液亦包含缓酸。 【先前技術】 已知含有不希望之酸性物種（例如硫醇）之液態烴之處 理，且可利用萃取或轉化方法來進行。t亥等轉化方法被稱 為「脫硫」方法，其中在含氧氣體之存在下，含有鹼金屬 氫氧化物（例如氫氧化鈉）及螯合金屬觸媒之混合物之水溶 液係與烴流接觸。發生氧化反應從而將該等硫醇轉化成二 硫化物油，其在隨後分離該烴與該水性溶液之步驟期間係 保留於該烴相中。該等脫硫方法對於具有輕質硫醇雜質之 輕質烴進料有效。 例如美國專利第 6,860,99、6,960,291、7,014,751、及 7’〇29,573號所述之該等萃取方法需要在厭氧條件下（即在 無貫質額外氧存在中）使該等硫醇自該烴液_液質量傳送至 水溶液中。該等方法對於移除通常含於較重液態烴進料之 高分子量硫醇（C4及更高碳數）特別有效。該水溶液較佳具 有兩相，其中烷基酚，例如甲酚（呈鹼金屬鹽形式）係在水 性萃取劑城實質上不可混合於該萃取劑中之較稠密的水 性底相中與多價金屬觸媒及鹼金屬氫氧化物組合。該等烷 152836.doc 201224132 基酚係用於提高該等較重硫醇之萃取。該金屬觸媒係包含 於該溶液中以最小化該處理烴中所夾帶之水溶液，尤其在 較高驗金屬氫氧化物濃度下所遇到之較高黏性。在與「酸 性」液態烴進料混合期間，該等硫醇係經物理方式萃取 (非轉化）至該水性萃取劑相中，且在分離後獲得硫醇含量 實質上低於該進料之升級烴產物。隨後，將該萃取劑相水 性溶液送至氧化製程中，其中加入含氧氣體且存在於該溶 液中之金屬觸媒將該等硫醇轉化成二硫化物。該等基於燒 基酚之萃取方法係更複雜且難以操作，主要因為需使用兩 相水性萃取溶液，或組成位於該一與二相區域間之相界的 單相。 因此，仍然存在對最小化操作難度及最小化對處理硫污 染物之二次加工之需要的新穎烴處理方法的需求。 【發明内容】 本發明係關於一種經改良之液態烴處理方法，其組合傳 統脫硫方法之精華與更複雜之萃取方法的精華。本方法係 利用水性處理溶液及氧化反應將包含較高分子量之硫醇 (a及更高碳數）之硫醇轉化（與萃取相反）成二硫化物油。 該等二硫化物油係保留在自該方法所移除之分離烴產物流 中。更明確而’本發明包含一種包括用於處理含硫醇之 烴之方法的製程中將含硫醇之液態烴與含氧氣體組合 以形細斗流。在接觸器容器中使該進料與一包括水二 金屬氫氧化物、多價餐合金属觸媒及至少—種醇，較佳具 有100C至210C之大氣壓彿點者之水性處理溶液接觸其 152836.doc 201224132 中使用該觸媒及氧以传兮梦设γ 2 使”亥#硫酵經由氧化反應轉化成二硫 化物油。該接觸步驟形成一㈣入至少-個分離區域（其 中將含該等二硫化物油之升級烴流與該摻合物分離)之產 物摻合物。必要時，扃、太4 ^ 在添加補充觸媒及/或該處理溶液之 其他成份以後，再游·王夢4 k + 衮s亥水性處理溶液以處理更多酸性 烴。 在另一實施例中，本發明包含用於處理含硫醇之烴之二 階段方法，其包括：使液態烴與空氣混合以形成第—進 料；隨後使該第-進料在第一階段接觸器中與m 鹼金屬氫氧化物、螯合多價金屬觸媒及至少一種醇，較佳 具有ioomot之大氣㈣點者之水性處理溶液接觸。 存於該空氣之氧及該觸媒氧化該第_進料中之大部份硫醇 以形成第-摻合物。隨後’使該摻合物沉降於第_分離區 域中，其中自該沉降之第-摻合物分離出含該等二硫化: 油之升級烴流。隨後，使該經分離之升級烴流與附加 混合以形成第二進料。該第二進料係在第二階段接觸二 進一步與該水性處理溶液之第二流接觸以將任何殘留硫醇 氧化成二硫化物油，從而形成第二摻合物。該第二摻人 係沉降在第二分離區域中，其中分離出含該等二硫化：4: 之第二升級烴流並以產物流形式自該製程中移除。必要 時’第三及第四階段可重複使用類似步驟。 較佳地，制減少水相夾帶之接觸器進行該等接 驟。該等接觸器係經配置以幾乎或完全不會引起攪動， 種該接觸方法係使用一包含安裝於遮罩中 =。— «質連續延長 152836.doc 201224132 纖維之質量傳送儀器。首先以該水性處理溶液濕潤該等纖 維’隨後使大表面積呈現於該烴中，而使該水相無實質分 散於該烴中。 本發明之觸媒組合物較佳為液態螯合多價金屬觸媒溶 液°多價觸媒包含（但不限於）金屬酞菁，其中該金屬陽離 子係選自由錳（Μη)、鐵（Fe)、鈷（Co)、鎳（Ni)、銅（Cu)、鋅 (Zn)、釕（ru)、鍺（Rh)、鈀（pd)、銀（Ag)等組成之群。觸媒 濃度為約10至1〇,〇〇〇 ppm，較佳約2〇至約4〇〇〇 ppm。於製 備該處理溶液期間可包含該經選擇之特定觸媒及/或隨後 將其添加至該溶液中其使用處。 本發明之水性處理溶液亦包含一或多種具有8〇<t至2251 之大氣壓沸點之醇。該等醇包含（但不限於）甲醇、乙醇、 1丙醇、2-丙醇、2 -甲基-1-丙醇、2-甲基-2-丁醇、環己 醇盼、甲紛、一曱盼、對苯二紛、間苯二紛、鄰苯二 酚、苯甲基醇、乙二醇、丙二醇。當與鹼金屬氫氧化物混 0時，形成該醇之鹼金屬鹽，其濃度較佳為約5至約4〇重 量/° ’最佳為約1 0至約3 5重量❶/〇。一種較佳醇之類型為芳 族醇，其係以通式芳基_〇H表示之化合物^該芳基可為苯 基、苯硫基、吲哚基、甲苯基、二甲苯基及類似物。較佳 芳族醇包含紛、？盼、二甲紛、甲基乙基紛、三甲基紛、 萘酚院基萘酚、硫酚、烧基硫酚及類似酚類。非芳族醇 可為第一、第二或第三醇，包含甲醇、乙醇、正丙醇、異 丙知、環己醇、2-f基_丨·丙醇、2_甲基_2_丁醇。亦可使用 不同醇之混合物。該等較佳醇具有約1〇(rc至約21〇。匸之大 152836.doc 201224132 氣壓沸點。該等較佳醇之鹼金屬鹽包含（但不限於）環己醇 鉀、異丙醇鉀、丙二醇二鉀、甲苯酚鉀及其混合。 在最佳處理溶液調配物中，包含一或多種羧酸。該等酸 包含（但不限於）脂肪酸、環烷酸、胺基酸、酮酸、α經 酸、二羧酸及三羧酸。該等酸亦與該等鹼金屬氫氧化物反 應以形成濃度為約0至約40重量％、較佳約5至約25重量％ 之其專驗金屬鹽。一般而言，該等缓酸可包含炫酸及環炫 酸’其中該等烷酸係以R_C〇〇H表示，其中R為氫或範圍 從CH3-(即乙酸）至CH3(CH2)18-(即二十烷酸）之烷基。環 烷酸係多種環戊基及環己基羧酸之混合物，其中其等之主 要部份較佳具有9至20個碳原子之碳主鏈。多種叛酸化合 物之混合物亦可用作該處理溶液之一部份。 本發明之該水性處理溶液含有一選自氫氧化鋰（u〇H)、 氫氧化鈉（NaOH)、氫氧化鉀（K0H)、氫氧化铷（Rb〇H)及氫 氧化鉋（CsOH)之鹼金屬氫氧化物。該鹼金屬氫氧化物以大 於足以確保所有醇及羧酸形成其等對應鹼金屬鹽之濃度存 在。以氫氧化鈉及尤其氫氧化鉀為較佳。 又 可藉由任何液-液混合裝置（例如填料塔、泡罩盤、攪拌 容器、栓塞流反應器等）實現烴進料與該水性處理溶:之 接觸。較佳地，利用實現快速液·液質量傳送而不導致難 以在該烴與該水性處理溶液之間獲得快速且乾淨相分離之 接觸器來進行該接觸。該等接觸器係經配^乎或—入 不會引起《，並減少該烴夾帶水溶液…種該接觸= 使用一包含安裝於—遮罩中之實質連續延長纖維的質量傳 152836.doc 201224132 送儀器。S亥·#纖維首先係經該水性處理溶液濕潤以於纖維 表面上形成薄膜’並隨後使大表面積呈現於該烴而該水相 無實質分散於該烴t。藉由該大表面積及該水性溶液之功 旎性可快速液-液質量傳送，其因此使該等硫醇能夠自該 烴轉移至與該水性處理溶液之薄膜接觸。如先前所述般， 可採用二或更多階段與水性處理溶液之接觸來實現更大程 度之處理效率。 可利用本水性處理溶液以本方法處理任何數量之沸點高 達約350°c之烴進料，其包含（但不限於）煤油 '喷射燃料、 柴油、輕質及重質石腦油。其他進料可包含直餾或裂解或 選擇性氫化處理之LPG、石腦油、原油、原油冷凝物及該 等類似物質。 自下文所含之較佳實施例之詳細描述將更加明白該等及 其他實施例。 【實施方式】 如所述般，本發明包含藉由氧化方法處理一含硫醇之酸 性液態烴流，其中使該等烴與含氧氣體接觸並在接觸器中 與-水性處理溶液混合以將該等硫醇轉化成二硫化物油， 其係保留在該烴中。自該水性處理溶液中分離出升級煙流 (含有該等二硫化物油）並自該製程移除。在另—實施例 中’如以下更完整揭示般’該方法包含至少兩階段之接 觸、氧化及分離。 經本方法處理之該等烴係沸點高達約35〇。〇之液體且含 有酸性物種’例如硫醇。示例性烴包含直顧或裂解或選擇 152836.doc 201224132 性氫化處理之天然氣冷凝物、液化石油氣（LPG)、丁烷、 丁烯、汽油流、喷射燃料、煤油、柴油、石腦油及類似物 中之一或多種。一實例性烴為沸點在約35°C至約230。(：之 範圍内之裂解石腦油，例如FCC石腦油或焦化石腦油。該 等烴流一般可含有一或多種硫醇化合物，例如甲基硫醇、 乙基硫醇、正丙基硫醇、異丙基硫醇、正丁基硫醇、硫酚 及較高分子量之硫醇。該硫醇化合物經常以符號RSH表 示，其中R為一般或分枝烷基或芳基。該硫醇硫係以欲處 理之液悲烴流計範圍從約2〇 ppm至約4〇〇〇 ppm(以重量計） 之量存在於該等烴中。該等硫醇之分子量係由約^或匕向 上變化且可以直鏈 '分枝或兩者形式存在。可經本發明氧 化方法轉化成二硫化物物質之特定硫醇類型將包含甲基硫 醇、乙基硫醇、丙基硫醇、丁基硫醇、戊基硫醇、己基硫 醇、庚基硫醇、辛基硫醇、壬基硫醇、癸基硫醇、十一烷 基硫醇、十二烧基硫醇、十三烧基硫醇、十四烧基硫醇、 十五院基硫醇、十六燒基硫醇、十七烧基硫醇、十八烧基 硫醇、十九烧基硫醇、各種疏基苯并㈣、經基硫醇（如 疏基乙醇）、半耽胺酸、芳族硫醇（如硫驗、經甲基取代之 硫紛異構體、經乙基取代之硫紛異構體、經丙基取代之硫 酚異構體）等。 在某些情況下’欲以本方法虛神—斗缺 、，必 万沄處理之該等烴已經氫化處理 1除不希望之硫物種及其他來自裂解石腦油之雜原子。 在氮化處理期間所形成之硫化氫係與稀煙反應而 形成硫醇’其《為反轉硫醇或重組硫醇以區分其等 152836.doc 201224132 在於引入該加氫處理器之裂解石腦油中的該等硫醇。該等 反轉硫醇一般具有範圍從約9〇至約160 g/莫耳之分子量， 且通常超過重油、汽油及殘渣油裂解或焦化期間所形成之 硫醇的分子量，因為其等通常在48至約76 g/莫耳之分子量 範圍内。該等反轉硫醇之較高分子量及其等烴成份之分枝 特性使其等更難利用傳統腐蝕性萃取自該石腦油中移除。 利用含至少一種醇及驗金屬氫氧化物之水性處理溶液之 本改良氧化方法可處理沸點在約55 〇C至約1 8〇。〇之範圍内 且含有範圍在約10至約100 wppm(基於該經氫化處理之石 腦油之重量）之反轉硫醇硫之經氫化處理的石腦油。同樣 地，本方法可處理經選擇性氫化處理之烴，即相較於該氫 化處理器進料超過80重量％(較佳9〇重量％及更佳95重量％) 脫硫，但基於該氫化處理器進料之烯烴量，保留超過 30%(較佳5 0%且更佳60。/。之該等稀烴者。 不同於先前慣用在無氧存在下使用兩相處理溶液之方 法，本方法使用一與所加含氧氣體組合之水性處理溶液， 其使該烴進料中之硫醇氧化成二硫化物油，而該等二硫化 物油係保留於該烴相中。可藉由將金屬酞菁觸媒添加至鹼 金屬氫氧化物及至少一種醇之水溶液中來製備該處理溶 液。另-較佳處理溶液另外包含至少一種羧酸，例如環烷 酸或乙基己酸a 本文包含之圖1示意地顯示僅一種可能進行之製程流程 圖’其係適用於實施藉由本發明教示轉化烴流中所發現之 硫化σ物之方法。將結合該顯示流程圖之描述詳細描述本 152836.doc •10- 201224132 發明方法。然而，在轉至該圖細節以前，應瞭解雖然可使 用該圖所顯示之單元操作之特定配置來將含硫雜質轉化成 氣味較小之硫化合物，但熟悉此項技術者將易於了解如何 • &良該流程圖以允許催化氧化職態煙進料流中之硫化合 物。 圖1顯示使含硫醇之液態烴進料丨與含氧氣流6(如空氣） 混合之二階段方法。隨後將該混合物2饋送至接觸器3，其 中使該空氣/烴混合物與含有本發明之水性處理溶液之流5 接觸。該處理溶液與該烴之間之接觸為液_液接觸，且可 經傳統接觸設備（例如填料塔，泡罩盤，攪拌容器，纖維 接觸、轉動圓盤接觸器或其他接觸儀器）完成。如所示 般，以Merichem Company銷售之FIBER FILM®接觸器3為 較佳。該等接觸器之特徵為由垂直遮罩中所含之大量金屬 或其他材料之懸掛薄帶所提供之大表面積，其允許以非分 散方式進行質量傳送。該類型之接觸器係描述在美國專利 第3,997,829、3,992，156及4,753,722號中。雖然接觸溫度 及壓力可在約〇0C至約15〇〇C及0 psig至約500 psig之範圍 内’該接觸較佳係發生在約25。(：至約100°C之範圍内之溫 度及約0 psig至約300 pSig之範圍内之壓力下。當該烴進料 * 具有低大氣壓沸點時，可能希望接觸期間之較高壓力以確 保與該烴之接觸發生在該液相中。 在該接觸步驟期間，使該等硫醇氧化成二硫化物油，其 最終保留於該烴相中。烴與處理溶液7之摻合物移出接觸 器3之底部並將其導入第一分離區域4中，其中令含該等二 152836.doc 201224132 硫化物油之液態烴與該水性處理溶液經由重力沉降而分 離。藉由路線8移出該分離之升級液態烴並隨後與第二空 氣流9組合以形成進入第二FIBEr film®接觸器U之流 10。將流10之該空氣/烴混合物與處理溶液14之第二流組 合。處理溶液流5及14包括自分離區域4及17移除之循環處 理溶液及補充新鮮處理溶液13及觸媒15。自第一分離區域 4移出一部份該處理溶液作為流19以供處置用，並自第二 分離區域17移出一部份該處理溶液作為欲與流12混合之流 21。在第二接觸器丨丨中進一步將該烴中之任何殘留硫醇氧 化成二硫化物油。將摻合物20自接觸器11導入分離區域17 中，其中將含該二硫化物油之產物烴流丨8自該製程移除。 該等特定實施例之以上描述將如此全面地揭示本發明之 一般特性以致在不脫離該一般概念下，其他人可施用現有 知識輕易地修改及/或調整以供各種應用該等特定實施例 用，且因此，該等調整及修改意欲涵蓋於該等揭示實施例 之等效物之涵義及範圍中。應瞭解，本文之措辭或術語係 基於描述之目的且非限制目的。 ' 參考以下實例將可更完整理解並瞭解本發明之多個熊 樣》該等實例不僅在本發明教示方法中所使用之該水性^ 理溶液與某些製程變數之間的相互關係，而且顯示與先: 技術方法相比，本發明在減少受污染之進料 | τ <硫醇硫 化合物濃度的顯著改良效果。 實例 提供四組對比實例來顯示本發明水性處理溶液之增強處 \ 52836.doc 12 201224132 理效率。在第—組中’使用慣用苛性溶液來處理—酸性 射燃料以供脫硫用。在第二組中顯示—本處理溶液之實施 例以實質提高該處理效率。在第三組中，使用本處理溶液 之五種不同組合物來處理該酸性嘴射燃料以顯示藉由包含 羧酸可進一步實質提高該處理效率。 在貫驗室工作台之批錢應器^實驗方式心處理溶 液之處理（即脫硫）效率。自一煉油廠獲得彿點為12代至 343t之酸性噴射燃料。將五個該酸性烴體積裝至批次反 應器中各體積之水性處理溶液中，並混合該等内含物。在 超過將硫醇完全氧化成二硫化物油所需要之化學計量之氧 氣的存在下，將該反應器内含物保持在38。(：下。在指定反 應時間長度之後’自該水相分離出該烴相並分析之以：定 其硫醇濃度。將使作為反應時間函數之該硫醇濃度與動力 速度方程式相關以測定氧化速度常數。 該測試處理溶液之性能優勢係由增強因子E(其實質上大 於1)來表示。該增強因子係定義為在相同條件下以本發明 處理溶液所獲得之速度常數與以慣用15重量％ Na〇H所獲 得之速度常數之比。換言之，該增強因子表示相對於15重 量％ NaOH之處理效率的提高程度。 實例1-3 在商業貫施之脫硫技術中’氫氧化鈉溶液通常係用作該 水性處理溶液。氫氧化鉀極少用於該目的。儘管如此，仍 製備各含15重量％ NaOH、22重量％ KOH及3 5重量％ k〇h 之三種苛性溶液。將相同濃度之酞菁鈷觸媒添加至各溶液 152836.doc -13- 201224132 令並測试處理一含3 8 ppm重量之硫醇硫之酸性煤油樣品。 增強因子E之結果係列於表i中。該酞菁鈷觸媒可自 Merichem購得。 根據定義，該15重量°/。NaOH溶液之增強因子£為丨〇。 表1顯示22重量％ KOH處理溶液不改變該增強因子且提供 貫質上與1 5重量％ NaOH溶液相同之處理效率。增加該苛 性強度至35重量％ KOH使該增強因子輕微提高至3 5，其 指示更高濃度之KOH溶液與1 5重量％ Na〇H相比在某種程 度上確實可增加該處理效率。 表1 實例 實例2 實例3201224132 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for treating liquid hydrocarbons to convert acidic impurities such as mercaptans into sulfur compounds which are less odorous. More specifically, the impurities are oxidized to _ sulfide oil by contacting the hydrocarbon with an aqueous treatment solution comprising a sequestration metal catalyst, an alcohol and an alkali metal hydroxide in the presence of oxygen. Particularly preferred treatment solutions also contain a slow acid. [Prior Art] A liquid hydrocarbon containing an undesired acidic species such as a mercaptan is known and can be carried out by an extraction or conversion method. The conversion method such as thai is called a "desulfurization" method in which an aqueous solution containing a mixture of an alkali metal hydroxide (for example, sodium hydroxide) and a chelate metal catalyst is contacted with a hydrocarbon stream in the presence of an oxygen-containing gas. . An oxidation reaction occurs to convert the thiol to a disulfide oil which is retained in the hydrocarbon phase during the subsequent step of separating the hydrocarbon from the aqueous solution. These desulfurization processes are effective for light hydrocarbon feeds with light mercaptan impurities. Such extraction methods as described in U.S. Patent Nos. 6,860,99, 6,960,291, 7, 014, 751, and 7' 〇 29, 573, require the thiol to be derived from the hydrocarbon under anaerobic conditions (i.e., in the absence of permeate additional oxygen). The liquid-liquid mass is transferred to the aqueous solution. These methods are particularly effective for removing high molecular weight mercaptans (C4 and higher carbon numbers) typically contained in heavier liquid hydrocarbon feeds. The aqueous solution preferably has two phases, wherein the alkylphenol, such as cresol (in the form of an alkali metal salt), is substantially immiscible in the aqueous extractant city in the denser aqueous base phase and polyvalent metal in the extractant. Catalyst and alkali metal hydroxide combination. The alkane 152836.doc 201224132 phenol is used to enhance the extraction of these heavier thiols. The metal catalyst is included in the solution to minimize the aqueous solution entrained in the treated hydrocarbon, especially at higher organometallic hydroxide concentrations. During mixing with the "acidic" liquid hydrocarbon feed, the thiols are physically extracted (non-converted) into the aqueous extractant phase, and after separation the thiol content is substantially lower than the upgrade of the feed. Hydrocarbon product. Subsequently, the extractant phase aqueous solution is sent to an oxidation process in which an oxygen-containing gas is added and the metal catalyst present in the solution converts the mercaptans to disulfides. Such phenol-based extraction processes are more complex and difficult to handle, primarily because of the need to use a two-phase aqueous extraction solution or to form a single phase at the phase boundary between the one and two phase regions. Therefore, there remains a need for a novel hydrocarbon processing method that minimizes operational difficulties and minimizes the need for secondary processing of sulfur contaminants. SUMMARY OF THE INVENTION The present invention is directed to an improved liquid hydrocarbon processing method that combines the essence of conventional desulfurization methods with the essence of more complex extraction methods. The process converts (in contrast to the extraction) a mercaptan comprising a higher molecular weight mercaptan (a and higher carbon number) into a disulfide oil using an aqueous treatment solution and an oxidation reaction. The disulfide oils are retained in the separated hydrocarbon product stream removed from the process. More specifically, the present invention encompasses a process comprising a process for treating a hydrocarbon containing a mercaptan in which a mercaptan-containing liquid hydrocarbon is combined with an oxygen-containing gas to form a stream. The feed is contacted in a contactor vessel with an aqueous treatment solution comprising a water dimetal hydroxide, a polyvalent meal metal catalyst and at least an alcohol, preferably having an atmospheric pressure of from 100 C to 210 C. 152836 .doc 201224132 uses the catalyst and oxygen to transfer γ 2 to make "Hai # sulfur fermentation converted to disulfide oil via oxidation reaction. The contacting step forms one (four) into at least one separation region (which will be included) a product blend of an upgraded hydrocarbon stream of the disulfide oil and the blend. If necessary, 扃, 太 4 ^ After adding the supplementary catalyst and/or other components of the treatment solution, Dreaming 4 k + 衮shai aqueous treatment solution to treat more acidic hydrocarbons. In another embodiment, the invention comprises a two-stage process for treating thiol-containing hydrocarbons comprising: mixing liquid hydrocarbons with air Forming a first feed; subsequently, the first feed is in the first stage contactor with m alkali metal hydroxide, chelated polyvalent metal catalyst and at least one alcohol, preferably having an atmosphere of ioomot (four) Contact with aqueous treatment solution. Oxygen stored in the air And the catalyst oxidizes a majority of the mercaptan in the first feed to form a first blend. Subsequently, the blend is allowed to settle in the first separation zone, wherein the precipitated first blend An upgraded hydrocarbon stream comprising the disulfide:oil is separated. The separated upgraded hydrocarbon stream is then mixed with additional to form a second feed. The second feed is contacted with the second phase in the second stage. The second stream of the treatment solution is contacted to oxidize any residual mercaptan to a disulfide oil to form a second blend. The second incorporation is settled in a second separation zone wherein the disulfide is separated : 4: The second upgraded hydrocarbon stream is removed from the process as a product stream. If necessary, the third and fourth stages may be reused in a similar step. Preferably, the contactor for reducing the water phase entrainment is performed. The contactors are configured to cause little or no agitation, and the contact method uses a mass transfer instrument that includes a fiber that is mounted in the mask to replace the 152836.doc 201224132 fiber. First moisturizing the aqueous treatment solution The iso-fibers then present a large surface area in the hydrocarbon, so that the aqueous phase is not substantially dispersed in the hydrocarbon. The catalyst composition of the present invention is preferably a liquid chelate multivalent metal catalyst solution. Including, but not limited to, a metal phthalocyanine, wherein the metal cation is selected from the group consisting of manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), and ruthenium (ru). a group consisting of rhodium (Rh), palladium (pd), silver (Ag), etc. The catalyst concentration is about 10 to 1 Torr, 〇〇〇 ppm, preferably about 2 〇 to about 4 〇〇〇 ppm. The selected particular catalyst may be included during the preparation of the treatment solution and/or subsequently added to the solution for its use. The aqueous treatment solution of the present invention also comprises one or more atmospheric pressures having 8 Torr < t to 2251 The boiling point of the alcohol. The alcohols include, but are not limited to, methanol, ethanol, 1 propanol, 2-propanol, 2-methyl-1-propanol, 2-methyl-2-butanol, cyclohexanol, and a A look forward to, benzodiazepine, isophthalic acid, catechol, benzyl alcohol, ethylene glycol, propylene glycol. When mixed with an alkali metal hydroxide, an alkali metal salt of the alcohol is formed, preferably at a concentration of from about 5 to about 4 Torr/°' optimum of from about 10 to about 35 ❶/〇. A preferred alcohol type is an aromatic alcohol, which is a compound represented by the formula aryl_〇H. The aryl group may be a phenyl group, a phenylthio group, a decyl group, a tolyl group, a xylyl group and the like. . Preferred aromatic alcohols contain a variety of? Pan, Dimethyl, methyl ethyl, trimethyl, naphthol, naphthol, thiophenol, mercaptothiophenol and similar phenols. The non-aromatic alcohol may be the first, second or third alcohol, and comprises methanol, ethanol, n-propanol, isopropanol, cyclohexanol, 2-f-based hydrazine, 2-methyl-2_ Butanol. Mixtures of different alcohols can also be used. The preferred alcohols have a boiling point of from about 1 Torr (rc to about 21 Å. 匸 152 836.doc 201224132). The alkali metal salts of such preferred alcohols include, but are not limited to, potassium cyclohexoxide, potassium isopropoxide , propylene glycol dipotassium, potassium cresyl and mixtures thereof. In an optimal treatment solution formulation, one or more carboxylic acids are included. These acids include, but are not limited to, fatty acids, naphthenic acids, amino acids, keto acids, Alpha acid, dicarboxylic acid and tricarboxylic acid. The acids are also reacted with the alkali metal hydroxides to form a concentration of from about 0 to about 40% by weight, preferably from about 5 to about 25% by weight. Metal salts. In general, the buffer acids may comprise leucoic acid and cyclosuccinic acid, wherein the alkanoic acids are represented by R_C〇〇H, wherein R is hydrogen or ranges from CH3-(ie acetic acid) to CH3 (CH2) An alkyl group of 18-(ie, eicosanoic acid). The naphthenic acid is a mixture of a plurality of cyclopentyl groups and cyclohexylcarboxylic acids, wherein a major portion thereof preferably has a carbon backbone of 9 to 20 carbon atoms. A mixture of a plurality of oleic acid compounds may also be used as part of the treatment solution. The aqueous treatment solution of the present invention contains a selected from the group consisting of hydrogen peroxide. Alkali metal hydroxide of lithium (u〇H), sodium hydroxide (NaOH), potassium hydroxide (K0H), barium hydroxide (Rb〇H) and hydroxide planer (CsOH). It is greater than the concentration sufficient to ensure that all alcohols and carboxylic acids form their corresponding alkali metal salts. Sodium hydroxide and especially potassium hydroxide are preferred. Also by any liquid-liquid mixing device (eg packed column, blister tray) , a stirred vessel, a plug flow reactor, etc.) to effect contact of the hydrocarbon feed with the aqueous treatment solution. Preferably, rapid liquid-liquid mass transfer is achieved without causing difficulty in obtaining between the hydrocarbon and the aqueous treatment solution. Quick and clean phase-separated contactors to make the contact. These contactors are either fitted or not introduced, and the hydrocarbon entrained aqueous solution is reduced...the contact is replaced by a containment-mounted The essence of the continuous extension of the quality of the fiber is 152,836.doc 201224132. The instrument is first wetted by the aqueous treatment solution to form a film on the surface of the fiber' and then the large surface area is presented to the hydrocarbon without the aqueous phase. Substantially dispersed The hydrocarbon t can be transported by rapid liquid-liquid mass by the large surface area and the workability of the aqueous solution, which thereby enables the mercaptans to be transferred from the hydrocarbon to contact with the film of the aqueous treatment solution. As described, a greater degree of processing efficiency can be achieved by contacting two or more stages with an aqueous treatment solution. Any aqueous hydrocarbon feed having a boiling point of up to about 350 ° C can be treated in this manner using the aqueous treatment solution. Including, but not limited to, kerosene 'jet fuel, diesel, light and heavy naphtha. Other feeds may include straight run or cracked or selectively hydrogenated LPG, naphtha, crude oil, crude oil condensate and These and other embodiments will become more apparent from the detailed description of the preferred embodiments. [Embodiment] As described, the present invention comprises treating a mercaptan-containing acidic liquid hydrocarbon stream by an oxidation process, wherein the hydrocarbons are contacted with an oxygen-containing gas and mixed with an aqueous treatment solution in a contactor to The thiols are converted to a disulfide oil which is retained in the hydrocarbon. An upgraded soot stream (containing the disulfide oil) is separated from the aqueous treatment solution and removed from the process. In another embodiment, the method comprises, as described more fully below, the method comprising at least two stages of contacting, oxidizing, and separating. The hydrocarbons treated by the process have a boiling point of up to about 35 Torr. It is a liquid and contains acidic species such as mercaptans. Exemplary hydrocarbons include direct or cracked or selected 152836.doc 201224132 Hydrogenated natural gas condensate, liquefied petroleum gas (LPG), butane, butene, gasoline stream, jet fuel, kerosene, diesel, naphtha, and the like One or more of them. An exemplary hydrocarbon has a boiling point of from about 35 °C to about 230. Pyrolysis naphtha in the range of (eg, FCC naphtha or coker naphtha. These hydrocarbon streams may generally contain one or more thiol compounds such as methyl mercaptan, ethyl mercaptan, n-propyl Mercaptan, isopropyl mercaptan, n-butyl mercaptan, thiophenol and higher molecular weight thiols. The thiol compound is often represented by the symbol RSH, where R is a general or branched alkyl or aryl group. The mercaptan is present in the hydrocarbons in an amount ranging from about 2 ppm to about 4 ppm by weight of the liquid hydrocarbon stream to be treated. The molecular weight of the mercaptans is about匕 varies upwards and may exist as a linear 'branched or both. The particular thiol type that can be converted to a disulfide species by the oxidation process of the present invention will comprise methyl mercaptan, ethyl mercaptan, propyl mercaptan, Thiol, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, mercapto mercaptan, mercapto mercaptan, undecyl mercaptan, dodecyl mercaptan, thirteen burn Thiol, tetradecyl mercaptan, fifteen-chamber mercaptan, hexadecanolyl mercaptan, heptadecyl mercaptan, octadecyl mercaptan, nineteen Alkyl mercaptan, various mercaptobenzoic (tetra), mercapto mercaptan (such as mercaptoethanol), hemi-amic acid, aromatic mercaptan (such as sulfur, methyl substituted sulfur isomer, ethyl Substituted sulfur isomers, propyl substituted thiophenol isomers, etc. In some cases, 'the method is intended to be a virtual god-------------------------------------- Except for undesired sulfur species and other heteroatoms from cracked naphtha. The hydrogen sulfide formed during the nitriding process reacts with the dilute fumes to form thiols, which are distinguished by inverting mercaptans or recombinant mercaptans. 152836.doc 201224132 is the introduction of such mercaptans in the cracked naphtha of the hydrotreater. The inverting mercaptans generally have a molecular weight ranging from about 9 〇 to about 160 g/mol, and usually Exceeding the molecular weight of the mercaptan formed during the cracking or coking of heavy oil, gasoline and residual oil, as it is usually in the molecular weight range of 48 to about 76 g/mol. The higher molecular weight of the inverted mercaptan and its etc. The branched nature of the hydrocarbon component makes it more difficult to extract from the stone brain using traditional corrosive properties. The present modified oxidation process using an aqueous treatment solution containing at least one alcohol and a metal hydroxide can be treated to have a boiling point in the range of from about 55 〇C to about 18 〇, and in a range from about 10 to about 100 wppm (based on the weight of the hydrotreated naphtha) of the hydrotreated naphtha of the reversed mercaptan sulfur. Similarly, the process can treat the selectively hydrotreated hydrocarbon, ie compared to the The hydrogenation processor feeds more than 80% by weight (preferably 9% by weight and more preferably 95% by weight) desulfurization, but remains above 30% (preferably 50% and more based on the amount of olefin fed to the hydrogenation processor) a method of using a two-phase treatment solution in the absence of oxygen, the method uses an aqueous treatment solution combined with an oxygen-containing gas, which allows the hydrocarbon to enter. The mercaptans in the feed are oxidized to disulfide oils, and the disulfide oils remain in the hydrocarbon phase. The treatment solution can be prepared by adding a metal phthalocyanine catalyst to an aqueous solution of an alkali metal hydroxide and at least one alcohol. Further, the preferred treatment solution additionally comprises at least one carboxylic acid, such as naphthenic acid or ethylhexanoic acid. A Figure 1 contained herein schematically shows that only one possible process flow diagram is suitable for implementation by the teachings of the present invention. A method of sulphide sulphide found in a hydrocarbon stream. The method of the invention will be described in detail in conjunction with the description of the display flow chart. 152836.doc • 10-201224132. However, before moving to the details of this figure, it should be understood that although the specific configuration of the unit operation shown in the figure can be used to convert sulfur-containing impurities into odorous sulfur compounds, those skilled in the art will be readily aware of how to • & The flow chart is to allow for the catalytic oxidation of sulfur compounds in the feed stream of the present smoke. Figure 1 shows a two-stage process for mixing a mercaptan-containing liquid hydrocarbon feed crucible with an oxygen-containing stream 6 (e.g., air). This mixture 2 is then fed to a contactor 3 in which the air/hydrocarbon mixture is contacted with stream 5 containing the aqueous treatment solution of the invention. The contact between the treatment solution and the hydrocarbon is liquid-liquid contact and can be accomplished by conventional contacting equipment such as packed towers, blister trays, stirred vessels, fiber contacts, rotating disk contactors or other contacting instruments. As shown, the FIBER FILM® contactor 3 sold by the Merichem Company is preferred. The contactors are characterized by a large surface area provided by a plurality of suspended strips of metal or other material contained in the vertical mask that permit mass transfer in a non-dispersive manner. Contactors of this type are described in U.S. Patent Nos. 3,997,829, 3,992,156 and 4,753,722. Although the contact temperature and pressure may range from about C0C to about 15 〇〇C and from 0 psig to about 500 psig, the contact preferably occurs at about 25. (: to a temperature in the range of about 100 ° C and a pressure in the range of about 0 psig to about 300 pSig. When the hydrocarbon feed* has a low atmospheric boiling point, it may be desirable to have a higher pressure during the contact to ensure The contacting of the hydrocarbon takes place in the liquid phase. During the contacting step, the mercaptans are oxidized to a disulfide oil which is ultimately retained in the hydrocarbon phase. The blend of hydrocarbon and treatment solution 7 is removed from the contactor. The bottom of 3 is introduced into the first separation zone 4, wherein the liquid hydrocarbon containing the two 152836.doc 201224132 sulfide oil is separated from the aqueous treatment solution by gravity sedimentation. The upgrade of the separation is removed by route 8. The liquid hydrocarbon is then combined with the second air stream 9 to form a stream 10 into the second FIBEr film® contactor U. The air/hydrocarbon mixture of stream 10 is combined with a second stream of treatment solution 14. Process stream 5 and 14 includes a circulating treatment solution removed from the separation zones 4 and 17 and a replenishing fresh treatment solution 13 and a catalyst 15. A portion of the treatment solution is removed from the first separation zone 4 as a stream 19 for disposal, and from the second Separation area 17 moves out of one The treatment solution is used as stream 21 to be mixed with stream 12. Further residual thiol in the hydrocarbon is oxidized to disulfide oil in a second contactor crucible. Blend 20 is introduced into and separated from contactor 11. In the region 17, wherein the product hydrocarbon stream 8 containing the disulfide oil is removed from the process. The above description of the specific embodiments will fully disclose the general characteristics of the invention so as not to depart from the general concept. And the other persons can use the existing knowledge to easily modify and/or adjust the meanings and scopes of the equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology herein is for the purpose of description and not for the purpose of the purpose of the invention. The relationship between the aqueous solution and certain process variables, and shows that the present invention reduces the contaminated feed compared to the prior: technical method | τ < mercaptan sulfide Significantly improved effect of concentration. Examples provide four sets of comparative examples to show the enhancement of the aqueous treatment solution of the present invention. In the first group, 'use a conventional caustic solution to treat - acid fuel for the purpose of taking off Used in the second group - the embodiment of the treatment solution is used to substantially increase the efficiency of the treatment. In the third group, the five different compositions of the treatment solution are used to treat the acid injection fuel for display by The inclusion of the carboxylic acid can further substantially improve the efficiency of the treatment. The processing of the treatment of the solution (ie, desulfurization) efficiency in the laboratory of the laboratory is carried out. The point of the Buddha from 12 to 343 t is obtained from a refinery. Acidic fuel injection. Five volumes of this acidic hydrocarbon are charged to each volume of the aqueous treatment solution in the batch reactor and the contents are mixed. The reactor contents were maintained at 38 in the presence of more than the stoichiometric amount of oxygen required to completely oxidize the thiol to the disulfide oil. (: below. After the specified reaction time length, 'the hydrocarbon phase is separated from the aqueous phase and analyzed to determine its thiol concentration. The thiol concentration as a function of reaction time is correlated with the dynamic velocity equation to determine oxidation. Velocity constant. The performance advantage of the test treatment solution is represented by an enhancement factor E (which is substantially greater than 1.) The enhancement factor is defined as the rate constant obtained by treating the solution of the invention under the same conditions and is 15 weights conventionally used. The ratio of the rate constant obtained by % Na〇H. In other words, the enhancement factor indicates the degree of improvement with respect to the treatment efficiency of 15% by weight of NaOH. Examples 1-3 In the commercial desulfurization technology, the sodium hydroxide solution is usually Used as the aqueous treatment solution. Potassium hydroxide is rarely used for this purpose. Nevertheless, three caustic solutions each containing 15% by weight of NaOH, 22% by weight of KOH and 35 % by weight of k〇h are prepared. Cobalt phthalocyanine catalyst was added to each solution 152836.doc -13- 201224132 and tested to treat an acid kerosene sample containing 38 ppm by weight of mercaptan sulfur. In Table i, the cobalt phthalocyanine catalyst is commercially available from Merichem. By definition, the enhancement factor of the 15 weight % / NaOH solution is 丨〇. Table 1 shows that the 22% by weight KOH treatment solution does not change the enhancement factor and The treatment efficiency is the same as that of the 15 wt% NaOH solution. Increasing the caustic strength to 35% by weight KOH slightly increases the enhancement factor to 35, which indicates a higher concentration of KOH solution and 15 wt% Na〇. H can certainly increase the processing efficiency compared to some extent. Table 1 Example Example 2 Example 3
水溶液_ 15 重量％NaOHAqueous solution _ 15% by weight NaOH
22重量％KOH 35重量％κ〇Η 增強因子，Ε 1.0*_ 1.0 **_ 3.5 ** *根據定義；**相較於15重量％1^〇11 實例4 此貫例顯示含有多僧雜上甘 畀夕價觸媒、方族醇及鹼金屬氫氧化物之 本發明水溶液之優勢 ^徹底混合125.2克45%氫氧化鉀、 克曱酚及37.2克水。所得溶液含24 9重量 18.6重量。/。游離氫氡 ⑽及 水溶液I 將G.8G纽料觸媒添加至該 測試如以上製備之命 处理洛液以處理含約38 ppm重量之硫 醇硫之Sx性噴射姆料 α 中。 ‘、、、科樣°°，並計算增強因子且報告在表2 152836.doc 201224132 表2 實例 表”肩示#本發明水性處理溶液提供丨5.3之增強因子。 ' 田以本發明水溶液處理時，該喷射燃料之脫琉係 比15重量％ NaOH快15倍。 實例5-9 該等實例顯示藉由在醇之存在下包含羧酸可進一步實質 ，高本發明處理溶液之效率。環炫酸及乙基己酸係缓酸之 實例％己醇、異丙醇、丙二醇及烷基酚係該等醇之實 例。 實例5 :徹底混合125.2克45%氫氧化鉀、从2克環己 醇、34.2克環烧酸及5.6克水。所得溶液含有江6重量。環 己醇鉀、U.5重量％游離氫氧化鉀及2〇6重量％環烷酸鉀。 將0.80克酞菁鈷觸媒添加至該溶液中。 實例6 :徹底混合！25·2克氫氧化鉀、2〇4克異丙 醇、34.2克環烷酸及19.3克水。所得溶液含有16.7重量％異 丙醇鉀、13.5重量％游離氫氧化鉀及2〇6重量％環烷^卸°。' 將0.80克酞菁鈷觸媒添加至該溶液中。 實例7 :徹底混合I25.2克45%氫氧化鉀' % 〇克丙一 醇、34.2克環烧酸及13.9克水。所得溶液含有25 θ 重量％丙 二醇二鉀' 13.5重量％游離氫氧化鉀及2〇 6重量％環浐酽 斜。將0.8 0克酜菁鈷觸媒添加至該溶液中。 實例8 :徹底混合I25.2克45%氫氧化鉀；％ 8克人η重 152836.doc -15- 201224132 量％酚、49重量％曱酚、17重量0/〇二甲酚、7重量0/〇乙基酚 及3重量％三甲基酚之混合甲苯酚；34.2克環烷酸；及3.〇 克水。所得溶液含有24.9重量％甲苯酚鉀、13.5重量％游離 氫氧化鉀及20·6重量％環烷酸鉀。將0·80克酞菁鈷觸媒添 加至該溶液中。 實例9 :徹底混合125.2克45%氫氧化鉀、36.8克甲酚、 26.4克乙基環己酸及ι〇·8克水。所得溶液含有24.9重量。/0甲 苯酚鉀、13.5重量。/。游離氩氧化鉀及16.7重量％環乙基環己 酸鉀。將0.80克酞菁鈷觸媒添加至該溶液。 以含約38 ppm重量之硫醇硫之酸性喷射燃料樣品個別測 試實例5至9之水性處理溶液。該等增強因子之結果係列於 表3中。如表3清楚顯示般，本發明之水性處理溶液提供 33.6至75.7之增強因子。換言之，與15重量％]^〇]9相比， 當利用本發明處理溶液處理之時，該喷射燃料之脫硫比15 重量％ NaOH快34至76倍。 表3 在實例10至11中顯示本發 屬氫氧化物的基本作用。 明水性處理溶液中之醇及鹼金 實例 增強因子，E ~ 實例5 51.1 實例6 42.0 實例7 71.5 實例8 75.7 實例9 33.6 —* --------[ 實例10-11 152836.doc •16· 201224132 實例10 :徹底混合117.3克30%氫氧化銨、36 8克曱酚、 34.2克環烧酸及10.9克水。所得溶液含有21.3重量％曱苯酴 銨、8.4重量％游離氫氧化銨及18.7重量％環烧酸銨。將 〇.8〇克酞菁鈷觸媒添加至該溶液。 貫例11 .徹底混合125.2克45%氫氧化鉀、34.2克環烧酸 及39.8克水。所得溶液含有23.0重量％游離氫氧化鉀及2〇·6 重星。/〇環烧酸鉀。將〇. 8 0克酞菁始觸媒添加至該溶液。 個別測试貫例10至11之溶液以處理含約3 8卯爪重量之硫 醇硫之酸性噴射燃料樣品。該等增強因子之結果係列於表 4中。表4顯示以氫氧化銨替代鹼金屬氫氧化物（實例1〇)或 無醇存在（貫例11)皆導致處理效率大幅降低，而增強因子 各自降至0,7及5.1。其如表3所示與本發明之該等水性處理 溶液之33.6至75.7的增強因子形成鮮明對比。 表4 實例 增強因子，E 實例10 0.7 實例11 5.1 實例12 本發明顯示相較於慣用15重量％ Na〇H溶液，利用本發 明水溶液處理酸性噴射燃料係在大量生產之削狀⑧ 接觸器中進^。FIBER FILM⑧接觸器係如多項美國專利所 示般由Merichem所發明並商業化之專利性非分散液-液質 量傳送裝置。該酸性噴射燃料含有26剛重量之硫醇酸性 物質。當使用慣用15重量％㈣⑽，該噴射燃料係經處 152836.doc -17- 201224132 理至18 ppm重量之硫醇硫或31%減少量。相反地，當使用 本發明水性處理溶液時，該喷射燃料係經處理至2卯爪重 量之硫醇硫或92°/。減少量。 在不脫離本發明之情況下，用於實現多種揭示功能之該 等方法、材料及步驟皆可採用多種替代形式。因此，該等 表述「…之方法」及「供…用之方法」或可在以上說明書 或以下緊接功能闡述之專利申請範圍中發現之任何方法步 驟語言皆意欲定義並涵蓋現在或將來可存在而實現所列功 能之任何結構、物理、化學或電元件或結構，或任何方法 步驟，無論是否為以上說明書中所揭示之一或多個實施例 之精確等效物，即可使用其他實現該相同功能之方法或步 驟；且意欲該等表達係在整個以下專利申請範圍内提供其 等最寬廣之解釋。 【圖式簡單說明】 圓1示意地顯示本發明之一可能實施例之製程流程圖。 【主要元件符號說明】 2 3 4 5 6 7 8 152836.doc 含硫醇之液態煙進料 混合物 接觸器 第一分離區域 含本發明水性處理溶液之流 含氧氣流 處理溶液 路線 201224132 9 第二空氣流 10 進入第二接觸器之流 11 第二接觸器 12 流 13 補充新鮮處理溶液 14 處理溶液流 15 觸媒 17 第二分離區域 18 產物烴流 19 供處置用之流 20 摻合物 21 與流12混合之流 -19- 152836.doc22% by weight KOH 35wt% κ〇Η Enhancement factor, Ε 1.0*_ 1.0 **_ 3.5 ** * By definition; ** compared to 15% by weight 1^〇11 Example 4 This example shows that it contains many impurities Advantages of the aqueous solution of the present invention of the upper phthalic acid, the aromatic alcohol and the alkali metal hydroxide ^ thoroughly mixed 125.2 g of 45% potassium hydroxide, ketone and 37.2 g of water. The resulting solution contained 24 9 weights of 18.6 by weight. /. Free Hydroquinone (10) and Aqueous Solution I G.8G catalyzed catalyst was added to the test as described above for the treatment of Sx-injected sulphur alpha containing about 38 ppm by weight of thiol sulphur. ',,, and the sample °°, and calculate the enhancement factor and report in Table 2 152836.doc 201224132 Table 2 Example Table “Shoulder # The aqueous treatment solution of the present invention provides an enhancement factor of 丨5.3. The off-gassing of the injected fuel was 15 times faster than 15% by weight of NaOH. Examples 5-9 These examples show that the efficiency of the treatment solution of the present invention can be further substantially higher by including a carboxylic acid in the presence of an alcohol. And examples of ethylhexanoic acid-based acid retardation % hexanol, isopropanol, propylene glycol and alkyl phenol are examples of such alcohols. Example 5: Thoroughly mixing 125.2 grams of 45% potassium hydroxide from 2 grams of cyclohexanol, 34.2 g of ring-burning acid and 5.6 g of water. The obtained solution contained 6 parts by weight of potassium, potassium hexoxide, 5% by weight of free potassium hydroxide and 2 6% by weight of potassium naphthenate. 0.80 g of cobalt phthalocyanine catalyst Add to the solution. Example 6: Thoroughly mix! 25·2 g of potassium hydroxide, 2 4 g of isopropanol, 34.2 g of naphthenic acid and 19.3 g of water. The resulting solution contains 16.7 wt% potassium isopropoxide, 13.5 % by weight of free potassium hydroxide and 2〇6 wt% of naphthenic acid. ' 0.80 g of cobalt phthalocyanine catalyst To this solution. Example 7: Thoroughly mix I25.2 g of 45% potassium hydroxide '% ketone propanol, 34.2 g of sulphuric acid and 13.9 g of water. The resulting solution contains 25 θ wt% propylene glycol dipotassium' 13.5 weight % free potassium hydroxide and 2 〇 6 wt% cyclic skew. 0.80 g of cobalt phthalocyanine catalyst was added to the solution. Example 8: Thoroughly mixing I25.2 g of 45% potassium hydroxide; % 8 g η重152836.doc -15- 201224132 Amount of phenol, 49% by weight of decyl phenol, 17% by weight of oxime, 7 parts by weight of ruthenium ethoxylate and 3% by weight of cresol mixed cresol; 34.2 a solution of naphthenic acid; and 3. gram of water. The resulting solution contains 24.9% by weight of potassium methoxide, 13.5% by weight of free potassium hydroxide and 20.6 % by weight of potassium naphthenate. 0. 80 grams of cobalt phthalocyanine catalyst Add to the solution. Example 9: Thoroughly mix 125.2 g of 45% potassium hydroxide, 36.8 g of cresol, 26.4 g of ethylcyclohexanoic acid and 10 g of water. The resulting solution contained 24.9 wt. /0 potassium methoxide 13.5 wt./. free potassium argon oxide and 16.7 wt% potassium cyclohexacyclohexanoate. 0.80 g of cobalt phthalocyanine catalyst was added to the solution to contain about 38 ppm by weight. Acid-injected fuel samples of mercaptan sulfur Individually tested aqueous treatment solutions of Examples 5 to 9. The results of these enhancement factors are summarized in Table 3. As clearly shown in Table 3, the aqueous treatment solution of the present invention provides an enhancement of 33.6 to 75.7. In other words, the desulfurization of the injected fuel is 34 to 76 times faster than the 15% by weight NaOH when treated with the treatment solution of the present invention, compared to 15% by weight. Table 3 shows the basic effects of the hydroxide of the present invention in Examples 10 to 11. Examples of alcohol and alkali gold enhancement factors in clear water treatment solutions, E ~ Example 5 51.1 Example 6 42.0 Example 7 71.5 Example 8 75.7 Example 9 33.6 —* -------- [Example 10-11 152836.doc • 16· 201224132 Example 10: 117.3 g of 30% ammonium hydroxide, 36 8 g of indophenol, 34.2 g of ring-burning acid and 10.9 g of water were thoroughly mixed. The resulting solution contained 21.3% by weight of anthraquinone ammonium, 8.4% by weight of free ammonium hydroxide and 18.7% by weight of ammonium sulfonate. 〇.8 gram of cobalt phthalocyanine catalyst was added to the solution. Example 11. Thoroughly mix 125.2 grams of 45% potassium hydroxide, 34.2 grams of ring burn acid, and 39.8 grams of water. The resulting solution contained 23.0% by weight of free potassium hydroxide and 2〇·6 heavy stars. / 〇 ring burning potassium. 〇. 80 g of phthalocyanine starting catalyst was added to the solution. The solutions of Examples 10 through 11 were individually tested to treat acidic injected fuel samples containing sulphur sulphur of about 38 lbs. The results of these enhancement factors are summarized in Table 4. Table 4 shows that the replacement of the alkali metal hydroxide (Example 1) with ammonium hydroxide or the absence of alcohol (Example 11) resulted in a significant reduction in the treatment efficiency, with the enhancement factors being reduced to 0, 7 and 5.1, respectively. It is in sharp contrast to the enhancement factor of 33.6 to 75.7 of the aqueous treatment solutions of the present invention as shown in Table 3. Table 4 Example Enhancement Factor, E Example 10 0.7 Example 11 5.1 Example 12 The present invention shows that the acidic injection fuel system is treated with the aqueous solution of the present invention in a mass-produced shape 8 contactor compared to the conventional 15% by weight Na〇H solution. ^. The FIBER FILM8 contactor is a patented non-dispersive liquid-liquid mass transfer device invented and commercialized by Merichem as shown in various U.S. patents. The acidic jet fuel contains 26 weight percent of the thiol acid. When 15% by weight (4) (10) is used, the injected fuel is 152836.doc -17-201224132 to 18 ppm by weight of thiol sulfur or 31% reduction. Conversely, when the aqueous treatment solution of the present invention is used, the injected fuel is treated to a sulphur sulphur or 92 deg. Reduce the amount. The methods, materials, and steps for implementing the various disclosed functions can be employed in various alternative forms without departing from the invention. Therefore, the words "methods of" and "methods for use" or any method step language that may be found in the above description or the scope of the patent application described immediately below the function are intended to define and cover the present or future existence. Any structural, physical, chemical, or electrical component or structure, or any method step, for implementing the listed functions, whether or not it is an exact equivalent of one or more embodiments disclosed in the above specification, may be used in other implementations. Methods or steps of the same function; and such expressions are intended to provide the broadest interpretation throughout the scope of the following patent applications. BRIEF DESCRIPTION OF THE DRAWINGS A circle 1 schematically shows a process flow diagram of a possible embodiment of the present invention. [Main component symbol description] 2 3 4 5 6 7 8 152836.doc Mercury-containing liquid smoke feed mixture contactor First separation zone containing the aqueous treatment solution of the present invention containing oxygen flow treatment solution route 201224132 9 second air Flow 10 into the second contactor flow 11 second contactor 12 flow 13 replenishing fresh treatment solution 14 treatment solution flow 15 catalyst 17 second separation zone 18 product hydrocarbon stream 19 for disposal stream 20 blend 21 and flow 12 mixed streams -19- 152836.doc