玖、發明說明： t發明所廣之技術領域】 發明領域 本發明是有關於一種純化方法’特別是一種用以由烴燃料 中移除掉硫化合物的方法。 【先前技術3 發明背景 為了環境的原因’對於烴燃料（諸如，例如汽油、柴油及喷 射燃料），在世界上許多地區的現行法令規定燃料内的硫化合物 之含量須有上限。被用來降低硫化合物的含量之主要商業方法 涉及到具一高硫位準的烴燃料在氣態氫與一加氫脫硫催化劑 之存在下的加氫處理，其中有機硫化物被轉化成硫化氫，而硫 化氫隨後被移除。 然而，存在有一持續的要求來改善脫硫製程，俾以生產具 較低硫含量之烴燃料，而本發明提供一種單一液相脫硫方法， 此方法可消除循環氣體壓縮機的需求。 【發明内容2 發明概要 於疋，本發明提供一種用以減少一 態烴進料之硫含量的方法，其中财法包括·· a) h亥包含有有機硫物種的液態烴進料接觸 包含有有機硫物種的液 觸—含氫氣體物 =料俾以生成—包含有有機硫物種與-增高的氫含量之 液態煙 令該包含有有機 b)在—反舰内於升高的溫度與壓力下， 200402467 硫物種與一增高的氫含量之液態烴進料接觸一催化劑，俾以生 成一帶有一降低的有機硫物種含量與一增高的硫化氫含量之 液態烴進料； C)令該帶有一降低的有機硫物種含量與一增高的硫化氫含 5 量之液態烴進料通經一硫化氫移除區，俾以生成一帶有一降低 的有機硫物種含量與一降低的硫化氫含量之液態烴進料。 該包含有有機硫物種之液態烴進料在一為25°C的溫度及 一為1 barg的壓力下通常係為一種液體，並且一般是直接或間 接地衍生自一原油蒸餾。該液態烴進料通常含有飽和烴類，例 10 如有分支與無分支的烷類與脂環烴類以及可變數量的芳族物 和/或諸如烯烴的不飽和化合物。 該包含有有機硫物種之液態烴進料可為一柴油（middle distillate)，該柴油可為一種或多種具一沸點範圍為150-450°C (較佳為190-390°C)之石油餾分。有利地，該柴油物流係為該等 15 石油餾分之一組合。合適的石油餾分之實例包括：輕粗柴油 (LGO)、重粗柴油（HGO)、輕循環油（LCO)、焦化粗柴油（CGO) 及減黏裂化粗柴油（VBGO)。較佳地，該包含有有機硫物種之液 態烴進料是柴油、汽油、煤油或噴射燃料，而有利地是為柴油 或喷射燃料。 20 該有機硫物種通常包含硫醇、硫化物、噻吩、苯並噻吩以 及二苯並噻吩(DBTs)，尤其是受阻烷基取代的二苯並噻吩。該 包含有有機硫物種之液態烴進料通常具有一總硫含量（以元素 硫來表示）為 1000-50000 ppm S (較佳為5000-20000 ppm S，例如 15000 ppm S)，一 DBT 含量為 100-20000 ppm S (較佳為 200402467 1000-5000 ppm S，例如3000 ppm s)，以及一受阻-DBT含量為 50-5000 ppm S (較佳為 loo-iooo ppm S，例如500 ppm S)。當該 包含有有機硫物種之液態烴是柴油時，此柴油可能包含污染性 硫落在10-100 ppm (以元素硫來表示）之範圍内。 5 該包含有有機硫物種之液態烴進料與含氫氣體物流接觸 以生成一包含有有機硫物種與一增高的氫含量之液態烴進料。 該含氫氣體物流可藉由一重整爐出口氣物流來提供，但較 佳地實質上是純氫。該包含有有機硫物種之液態烴進料典型地 於一飽和器容室内為氣態氫所飽和，於該容室當中有氫通經液 10 體之本體。 該包含有有機硫物種之液態烴典型地在一介於250-500°C (例如300_400°(：，如340°(：或380°〔:）之溫度以及一介於1-100 6&『 (較佳是10-60 bar，例如20-40 bar)之壓力下被氣態氫飽和。該 包含有有機硫物種之液態烴通常含有每立方公尺為1 _ 1 〇〇 Nm3 15 (較佳是10-90 Nm3，尤其是20-60 Nm3)之氫。 該包含有有機硫物種之液態烴進料可以在遠離反應區的位 置被氫所飽和。任擇地，該包含有有機硫物種之液態烴進料亦 可立即地在反應區之上游處被氫飽和。 該包含有有機硫物種與一增高的氫含量之液態烴進料接而 20 在一反應區於升高的溫度與壓力下與一催化劑接觸，以生成_ 帶有一降低的有機硫物種含量與一增高的硫化氫含量之液態 烴進料。 任何適當的催化劑均可被使用於反應區内。該一催化劑可 包含一或多個被分散於一催化劑擔體上的活性組分。活性組分 7 200402467 的實例包括：鉬、鎢、鉑、鈀、釕、鎳、鈷、鐵、銅、鈽或銖。 較佳地，該催化劑包含至少二種選自於上述群組的金屬，而最 佳地該催化劑包含鉬或鎢以及至少一種選自於鎳和鈷的額外 金屬。 5 該（等）活性組分可被擔載於任一種適當的催化劑擔體上， 諸如一氧化矽、氧化鋁、二氧化矽_氧化鋁、碳、二氧化鈦、活 性碳或酸鹽（諸如—彿石）。該擔體可以被預處理以併入 -促進劑(諸如喊氟）。該催化劑擔體可被混合以 一黏合劑（如 氧化鋁或二氧化矽）。 1〇 金屬的總重量，以擔體的重量為準，可介於ow/。重量計 (田作至屬）較仏地以擔體的重量為準是介於重量計（當 作金屬）等）金屬可藉由任_種被使用在催化劑製備中的詳 *技衍而被引人至擔體内，例如浸潰處理，其中擔體之孔洞被 至〆4刀地充填以-包含有所欲金屬之一可溶性前驅物鹽 15類m紅所形柄擔贿後被乾燥 ，選擇性地被煅燒與 硫化。該浸潰溶液通常是一由下列所構成之水性溶液 :金屬硝 酉欠#草酉夂鹽甲酉夂鹽、丙酸鹽、醋酸鹽、氣化物、碳酸鹽或 奴酉夂氫孤特別疋金屬峭酉曼鹽、氣化物或碳酸鹽。任擇地， 1又/貝/合液可包3被溶於_有機溶劑内之金屬化合物，例如 20 一有機金屬化合物’像是—金屬乙酿㈣化物、金屬環肢鹽 或羰基金屬。 i亥催化劑含有至少二種金屬之中，第二種金屬在初始金 屬的併入之刚或之後，亦可如上所述被併入至擔體，或者額外 的金屬之併人可與初始金屬之併人係為同時。 200402467 當一包含有鉬或鎢以及至少一種選自於鎳及鈷之額外金屬 的催化劑正在被製備之時，該等浸潰溶液通常是為仲鉬酸銨 (ammonium paramolybdate)以及硝酸鈷或硝酸鎳，而當一包含有 鎢以及至少一種選自於鎳及鈷之額外金屬的催化劑正在被製 5 備之時’該等浸潰溶液通常是為仲嫣酸錄（ammonium paratungstate)以及硝酸鈷或硝酸鎳。 該催化劑通常至少包含1%重量計之鉬或鎢（以擔體重量為 準），通常是介於1-50%重量計之鉬或鎢（較佳為介於20-30%重量 計之鉬或鎢），以及至少0.15%重量計之鎳和/或鈷（以擔體重量 10 為準），通常是介於0.1-20%重量計之鎳和/或鈷（較佳為介於 3-10%重量計之鎳和/或鈷）。 在金屬併入後，該催化劑可予以後處理。該後處理通常涉 及在空氣、氮或氦中，於一落於2〇〇-800°C(較佳為300-70(TC， 例如350-500。〇範圍内之溫度下之煅燒。於煅燒後，該催化劑 15可有利地使用一硫化劑（諸如硫化氫或二甲基二硫化物）予以硫 化。該催化劑通常是在一落於100_400°C範圍内之溫度下被硫 化，較佳是落在250-350°C之範圍内。 在令該包含有有機硫物種與一增高的氫含量之液態烴進料 與該催化劑接觸之前，該催化劑通常會被預處理。該預處理通 20常涉及在空氣、氮或氦中，於一落於200-800°C(較佳為300-700 C，例如350-500。〇範圍内之溫度下之煅燒。選擇性地，該催 化劑於一落於1 〇〇-800°C (較佳為200-700°C)範圍内之溫度下，以 一流動氣體(諸如氩、一氧化碳或一輕烴類，如Ci_C4烴類）予以 還原。任擇地，在煅燒後，該催化劑可使用一硫化劑（諸如硫化(Ii) Description of the invention: [Technical field covered by the invention] The present invention relates to a purification method ', particularly a method for removing sulfur compounds from a hydrocarbon fuel. [PRIOR ART 3 BACKGROUND OF THE INVENTION For environmental reasons' For hydrocarbon fuels (such as, for example, gasoline, diesel, and jet fuels), current statutes in many regions of the world require an upper limit on the amount of sulfur compounds in the fuel. The main commercial method used to reduce the content of sulfur compounds involves hydrotreating a hydrocarbon fuel with a high sulfur level in the presence of gaseous hydrogen and a hydrodesulfurization catalyst, in which organic sulfides are converted to hydrogen sulfide While hydrogen sulfide is subsequently removed. However, there is a continuing need to improve the desulfurization process to produce hydrocarbon fuels with lower sulfur content, and the present invention provides a single liquid phase desulfurization method that can eliminate the need for a cycle gas compressor. [Summary of the Invention 2 Summary of the Invention] The present invention provides a method for reducing the sulfur content of a single-state hydrocarbon feed, wherein the financial method includes ... a) contacting a liquid hydrocarbon feed containing an organic sulfur species Liquid contact of organic sulfur species—hydrogen-containing gas = material to generate—liquid smoke containing organic sulfur species and-increasing hydrogen content makes the organic-containing b) in—anti-ships at elevated temperatures and pressures Next, 200402467 sulfur species contacts a catalyst with a liquid hydrocarbon feed with an increased hydrogen content to generate a liquid hydrocarbon feed with a reduced organic sulfur species content and an increased hydrogen sulfide content; C) the Reduced organic sulfur species content and an increased hydrogen sulfide-containing liquid hydrocarbon feed pass through a hydrogen sulfide removal zone to produce a liquid hydrocarbon with a reduced organic sulfur species content and a reduced hydrogen sulfide content Feed. The liquid hydrocarbon feed containing organic sulfur species is usually a liquid at a temperature of 25 ° C and a pressure of 1 barg, and is generally derived directly or indirectly from a crude distillation. The liquid hydrocarbon feed usually contains saturated hydrocarbons, such as branched and unbranched alkanes and alicyclic hydrocarbons, as well as variable amounts of aromatics and / or unsaturated compounds such as olefins. The liquid hydrocarbon feed containing organic sulfur species may be a middle distillate, which may be one or more petroleum distillates having a boiling point range of 150-450 ° C (preferably 190-390 ° C). . Advantageously, the diesel stream is a combination of these 15 petroleum distillates. Examples of suitable petroleum distillates include: light gas oil (LGO), heavy gas oil (HGO), light cycle oil (LCO), coking gas oil (CGO), and visbreaking gas oil (VBGO). Preferably, the liquid hydrocarbon feed containing organic sulfur species is diesel, gasoline, kerosene or jet fuel, and is advantageously diesel or jet fuel. 20 This organic sulfur species typically contains thiols, sulfides, thiophenes, benzothiophenes, and dibenzothiophenes (DBTs), especially hindered alkyl-substituted dibenzothiophenes. The liquid hydrocarbon feed containing organic sulfur species usually has a total sulfur content (expressed as elemental sulfur) of 1000-50000 ppm S (preferably 5000-20000 ppm S, such as 15000 ppm S), and a DBT content of 100-20000 ppm S (preferably 200402467 1000-5000 ppm S, such as 3000 ppm s), and a blocked-DBT content of 50-5000 ppm S (preferably loo-iooo ppm S, such as 500 ppm S). When the liquid hydrocarbon containing organic sulfur species is diesel, the diesel may contain polluting sulfur that falls within the range of 10-100 ppm (expressed as elemental sulfur). 5 The liquid hydrocarbon feed containing the organic sulfur species is contacted with a hydrogen-containing gas stream to produce a liquid hydrocarbon feed containing the organic sulfur species and an increased hydrogen content. The hydrogen-containing gas stream may be provided by a reformer outlet gas stream, but is preferably substantially pure hydrogen. The liquid hydrocarbon feed containing organic sulfur species is typically saturated with gaseous hydrogen in a saturator vessel, and the body passes through the body of hydrogen in the vessel. The liquid hydrocarbon containing organic sulfur species is typically at a temperature between 250-500 ° C (for example, 300-400 ° (:, such as 340 ° (: or 380 ° [:) and a temperature between 1-100 6 & It is preferably saturated with gaseous hydrogen at a pressure of 10-60 bar, for example 20-40 bar. The liquid hydrocarbon containing organic sulfur species usually contains 1 _ 1 00Nm3 15 (preferably 10- 90 Nm3, especially 20-60 Nm3) of hydrogen. The liquid hydrocarbon feed containing organic sulfur species can be saturated with hydrogen at a location remote from the reaction zone. Optionally, the liquid hydrocarbon feed containing organic sulfur species The feed can also be saturated with hydrogen immediately upstream of the reaction zone. The organic sulfur species is combined with a liquid hydrocarbon feed with an increased hydrogen content and 20 in a reaction zone with a catalyst at elevated temperature and pressure. Contact to produce a liquid hydrocarbon feed with a reduced organic sulfur species content and an increased hydrogen sulfide content. Any suitable catalyst can be used in the reaction zone. The catalyst can include one or more dispersed Active component on a catalyst support. Active component 7 200402 Examples of 467 include: molybdenum, tungsten, platinum, palladium, ruthenium, nickel, cobalt, iron, copper, rhenium, or baht. Preferably, the catalyst comprises at least two metals selected from the above group, and most preferably The catalyst contains molybdenum or tungsten and at least one additional metal selected from nickel and cobalt. 5 The (and other) active components may be supported on any suitable catalyst support, such as silica, alumina, Silica_alumina, carbon, titanium dioxide, activated carbon or acid salt (such as -fossil). The support can be pre-treated to incorporate a promoter (such as fluorine). The catalyst support can be mixed with a Binder (such as alumina or silicon dioxide). 10 The total weight of the metal is based on the weight of the support, which can be between ow /. It must be between weight (as metal), etc.) The metal can be introduced into the carrier by any of the detailed techniques used in the preparation of the catalyst, such as immersion treatment, in which the holes of the carrier Filled with 〆4 knives with-Soluble precursor salt containing one of the desired metals 15 types m The red shaped handle is dried, selectively calcined and sulfided. The immersion solution is usually an aqueous solution composed of the following: metal nitrate # 草 酉 夂 盐 甲 酉 夂 盐, propionate , Acetate, gaseous, carbonate, or sulfonium hydride special metal kryptomanganese salt, gaseous, or carbonate. Optionally, 1 / shellfish / hybrid solution can be dissolved in 3 organic solvents A metal compound, such as 20, an organometallic compound, such as a metal ethyl alcohol, a metal ring, or a metal carbonyl. The catalyst includes at least two metals, and the second metal is incorporated into the original metal. Immediately after, it can also be incorporated into the carrier as described above, or the merger of additional metals can be simultaneous with the merger of the original metal. 200402467 When a catalyst containing molybdenum or tungsten and at least one additional metal selected from nickel and cobalt is being prepared, the impregnation solutions are usually ammonium paramolybdate and cobalt or nickel nitrate And when a catalyst containing tungsten and at least one additional metal selected from nickel and cobalt is being prepared, the impregnation solutions are usually ammonium paratungstate and cobalt nitrate or nitric acid. nickel. The catalyst usually contains at least 1% by weight of molybdenum or tungsten (based on the weight of the support), usually between 1-50% by weight of molybdenum or tungsten (preferably between 20-30% by weight of molybdenum) Or tungsten), and at least 0.15% by weight of nickel and / or cobalt (based on the weight of the support of 10), usually between 0.1-20% by weight of nickel and / or cobalt (preferably between 3 and 3) 10% by weight of nickel and / or cobalt). After the metal is incorporated, the catalyst can be worked up. This post-treatment usually involves calcination in air, nitrogen or helium at a temperature in the range of 2000-800 ° C (preferably 300-70 ° C, for example, 350-500 ° C.). Calcination Thereafter, the catalyst 15 can be advantageously sulfided using a sulfurization agent such as hydrogen sulfide or dimethyl disulfide. The catalyst is usually sulfided at a temperature in the range of 100-400 ° C, preferably In the range of 250-350 ° C. The catalyst is usually pretreated before the liquid hydrocarbon feed containing organic sulfur species and an increased hydrogen content is contacted with the catalyst. The pretreatment usually involves Calcination in air, nitrogen or helium at a temperature in the range of 200-800 ° C (preferably 300-700 C, such as 350-500 ° C). Optionally, the catalyst is It is reduced with a flowing gas (such as argon, carbon monoxide or a light hydrocarbon such as Ci_C4 hydrocarbon) at a temperature within the range of 100-800 ° C (preferably 200-700 ° C). Optionally, After calcination, the catalyst can be
Λ 9 200402467 氫或二甲基二硫化物）予以硫化。該催化劑通常是在一落於 100-400°C範圍内之溫度下被硫化，較佳是落在25〇-350°C之範 圍内。 該包含有有機硫物種與一增高的氫含量之液態烴進料較佳 5地是在一介於250-500°C(例如3〇〇_40(TC，如34CTC或380。〇之溫 度以及一介於1-100 bar (較佳是i〇_6〇 bar，例如20-40 bar)之壓 力下與該催化劑接觸。 该反應區通常包含一被包含在一容室内之固定床催化劑。 該容室可為一種能夠承受高達5〇〇t：的溫度與高達1〇〇 bar的壓 10 力者，例如一鋼壓力容室。 該反應區產生一帶有一降低的有機硫物種含量與一增高的 硫化氫含量之液態烴進料，且這被有利地直接通往至硫化氮移 除區（亦即不存在有任何通向反應區的循環），以生成一帶有一 降低的有機硫物種含量與一降低的硫化氮含量之液態煙進料。 15 誠化氫㈣區可包含-讀_在-比反舰所具者為 低的壓力下之區域。因此，從該反應區而出的液態煙進料内所 存在之硫化氫與氫於該移除區内被蒸發，而由液態煙產物中被 移除。 有利地’一氣體物流可被通經該硫化氫移除區，以加速硫 20化氫的移除。該氣體物流可包含—惰性氣體(諸錢氣），但以 氫氣為佳。 ，在該氣體為氫之中，從該硫化氫移除區而出的氣體可接而 被有利地使用於本發明的（a)步驟中。 在本發明之-較佳具體例中，該硫化氣移除區包含一位於 10 200402467 -吸附區内之吸附劑，其中本案方法包括令該帶有—降低的有 機硫物種含量與-增高的硫化氫含量之㈣烴進料.位於 -吸附區内之吸附劑接觸，俾以生成—帶有_降低的有機硫物 種含量與-降低的硫化氫含量之液態烴進料以及—帶有一增 5 高的硫化氫含量之吸附劑。 10 適當的吸附劑可藉由多孔性氧化物（例如金屬或非金屬氧 化物）來提供。有利地，該金屬氧化物可為二三或四價金屬 其可為過渡鱗過渡金屬或稀土金屬，諸如：氧化鋅、氧化銘、 二氧化鈦、氧化高結(C〇baltic 〇xide：)、氧化錯、氧化鈽、氧化翻、 氧化鎮以及氧化鶴。非金屬氧化物之_實例為二氧切。多於 -種形式的吸_可以存在。有魏，該吸_係選自於氧化 鋅、氧化鋁及氧化鎂或此等之任一組合。 该吸附劑可包含被併入的元素金屬，其通常是選自於 VIIIA、IB、IIB、IIIB、IVB以及VB族金屬，特別是VIIIA族金 15屬（如鎳、姑）’以及尤其是翻族金屬（如始、纪、釕、铑、鐵以 及錶）。5亥專金屬無被描述於F.A· Cotton，G.Wilkinson and P.L.Gaus Publ. John Wiley & Sonsjnc New York 2nd ED. 1986 所著作之Basic Inorganic Chemistry内之週期表。有利地，該吸 附劑包含有鎳加上一或多種鉑族金屬（例如鉑）。 任擇地，該吸附劑可包含有一沸石，這些沸石可為合成的 (例如沸石A、X、Y及L)或為天然存在的沸石，如八面沸石 (faujasite)。該沸石亦可包含有VIIIA族金屬（尤其是鈀或鉑）來作 為元素金屬。 於本發明之另一具體例中，該吸附劑可為以碳為基底者， 200402467 例如活性碳。 该帶有一降低的有機硫物種含量與一增高的硫化氫含量之 液態烴進料較佳地是在一介於50-200°C (有利地為介於100_150 °C，例如120°C或140°C)之溫度以及一介於1-50 bar (較佳是2-20 5 bar，例如1〇_15 bar)之壓力下與該吸附劑接觸。 該吸附區通常包含一被包含在一容室内之固定床吸附劑。 該容室可為一種能夠承受高達500°C的溫度與高達1〇〇 bar的壓 力者，例如一鋼壓力容室。 该具有增南的硫化氫含量之吸附劑較佳地藉由接觸一汽提 10氣體（如氮、氧、氫或蒸汽或一不含硫的烴氣）而將其硫含量汽 提出，俾以生成一實質上不含被吸附的硫化合物的吸附劑。 含有硫的吸附劑通常在一被升高至高於吸附的溫度之溫度 下與汽提氣體接觸。通常該汽提氣體在範圍為100-60(TC(例如 150-350°C)之溫度以及一介於1·100 bar之壓力下與該吸附劑接 15 觸。 在本發明之另一實施例中，該硫化氫移除區可包含一胺或 一苛性鹼溶液，其中本案方法包含令該帶有一降低的有機硫物 種含量與一增高的硫化氫含量之液態烴進料通經一個含有一 胺或一苛性鹼溶液（例如氫氧化鉀溶液或氫氧化鈉溶液）的容 20 室，俾以生成一帶有，降低的有機硫物種含量與一降低的硫化 氫含量之液態烴進料。 該帶有一降低的有機硫物種含量與一降低的硫化氫含量之 液態烴進料通常含有〆含硫化合物之總量為低於500 PPm s，例 如200-400 ppm S，較佳為低於200 PPm S，例如 50-100 ppm S， 12 iJU. / 200402467 更佳為低於50 ppm S，例如20-40 ppm S)，且有利地是低於10 ppm S，例如0·1_5 ppm S (以重量計來表示作為元素硫）。 I：實施方式3 較佳實施例之詳細說明 5 本發明現參照附圖來作描述與解說，其中第1圖顯示一包 含有有機硫物種的液態烴進料之儲槽（1)。該包含有有機硫物種 的液態烴進料經由一液體進料唧筒（3)被通向一氫飽和器（2)，其 中該液態烴進料與經由管線(4)被通向該氫飽和器的氣態氫接 觸，並經由出口（5)而離開該氫飽和器。 10 一包含有有機硫物種與一增高的氫含量之液態烴進料經 由管線(6)而離開該氫飽和器，且被通入至一含有一由加氫脫硫 催化劑所構成之固定床的反應區（7)内。 一帶有一降低的有機硫物種含量與一增高的硫化氫含量 之液態烴進料離開該反應區（7)，並經由管線(8)被通入至一含有 15 一由吸附劑所構成之固定床的吸附區（9)内。一帶有一降低的有 機硫物種含量與一降低的硫化氫含量之液態烴進料經由管線 (10)離開該吸附區。 本發明以下面的實施例來作說明。 實施例1 20 使用一包含有被包含在一用於溫度控制的爐内之下列構 件的測試裝備：一液體進料儲存槽、一液體進料唧筒、一氫供 應器、一飽和器容室以及一反應器。該反應器包含有一具内部 直徑為4 mm與一長度為1.3 m的鋼管，並且含有一由被預硫化 的姑-钥位在氧化銘上之加氫處理催化劑所構成的固定床。反應 13 200402467 器溫度係在360°C-400°C之間變化，而壓力係在30-70 barg之間 變化。 一含有260 ppm的總硫量（以元素硫來表示）的粗柴油被通 向該氫飽和器，於氫飽和器中該粗柴油被氣態氫所飽和，且隨 5 後以一介於1.0-1 ·4 1Γ1之間的液體小時空間速度(LHSV)被通向 該反應器。從該反應器而出的粗柴油被通向硫化氫移除區，於 該移除區中硫化氮被移除。 粗柴油產物的硫含量在不同的反應器溫度與壓力以及不 同的接觸時間下被監測。結果被顯示於表1中。 10 表1 壓力（barg) 溫度（°C) LHSV(h_1) 硫含量(ppm) 30 360 1.0 46 30 370 1.2 35 30 380 1.4 46 30 390 1.2 24 60 400 1.1 4 70 360 1.1 30 實施例2 實施例1被重複。反應器溫度被維持於360°C下，而壓力係 在10-30barg之間變化。 一含有32 ppm的總硫量（以元素硫來表示）的粗柴油被通向 15 該氫飽和器，於氫飽和器中該粗柴油被氣態氫所飽和，且隨後 以一介於1-45 1Γ1之間的液體小時空間速度(LHSV)被通向該反 應器。從該反應器而出的粗柴油被通向硫化氫移除區，於該移 除區中硫化氫被移除。 粗柴油產物的硫含量在不同的反應器壓力以及不同的接 20 觸時間下被監測。結果被顯示於表2中。 4 OrV.*i 1 .5^3. 14 200402467 表2 壓力（barg) 溫度（°C) LHSV (h_1) 硫含量(ppm) 30 360 1.1 <5 30 360 43.1 6 10 360 1.4 <5 10 360 10.1 6 實施例示說明：一帶有低於lOppm的產物可以從一已經被 預處理過的粗柴油來生成。 實施例3 5 該催化劑被置換以一由一含有42%重量計的Al2〇3以及 2.7%重量計的Re203之US_Y沸石所構成的固定床。該沸石於200 °C下以氮氣予以預處理歷時1小時。反應器溫度係在300-360°C 之間變化，而壓力是於10-30 barg之間變化。 一含有3 2 p p m的總硫量（以元素硫來表示）的粗柴油被通向 10 該氫飽和器，於氫飽和器中該粗柴油被氣態氫所飽和，且隨後 以一介於7-35 h_1之間的液體小時空間速度(LHSV)被通向該反 應器。從該反應器而出的粗柴油被通向硫化氫移除區，於該移 除區中硫化氮被移除。 粗柴油產物的硫含量在不同的反應器溫度、壓力以及不同 15 的接觸時間下被監測。結果被顯示於表3中。 表3 壓力（barg) 溫度（°C) LHSV (h_1) 硫含量（ppm) 50 300 8 28 50 330 7 19 50 360 7 11 50 360 35 14 實施例4 該US-Y沸石被置換以一含銅-鈽位在沸石上的催化劑。反 15 200402467 應器溫度係於300-360°C之間變化，而壓力被維持在50barg下。 一含有32 ppm的總硫量（以元素硫來表示）的粗柴油被通向 該氫飽和器，於氫飽和器中該粗柴油被氣態氫所飽和，且隨後 以一介於6.9-7.3 hf1之間的液體小時空間速度(LHSV)被通向該 5 反應器。從該反應器而出的粗柴油被通向硫化氫移除區，於該 移除區中硫化氫被移除。 粗柴油產物的硫含量在不同的反應器溫度、壓力以及不同 的接觸時間下被監測。結果被顯示於表3中。 表4 壓力（barg) 溫度（°C) LHSV (h_1) 硫含量(ppm) 50 300 6.9 18 50 330 7 13 50 360 7.3 8 10 【圖式簡單說明】 第1圖顯示一含有一包含有有機硫物種的液態烴進料之儲 槽⑴。 【圖式之主要元件代表符號表】 1 儲槽 2 氫飽和器 3 液體進料唧筒 4 管線 5 出口 6 管線 7 反應區 8 管線 9 吸附區 10 管線 16Λ 9 200402467 hydrogen or dimethyl disulfide). The catalyst is usually sulfided at a temperature in the range of 100-400 ° C, preferably in the range of 25-350 ° C. The liquid hydrocarbon feed containing organic sulfur species and an increased hydrogen content is preferably at a temperature between 250-500 ° C (for example, 300-40 ° C, such as 34CTC or 388.0 ° C) and an introduction Contact the catalyst at a pressure of 1-100 bar (preferably i0_60 bar, for example 20-40 bar). The reaction zone usually contains a fixed bed catalyst contained in a container. The container It can be a type capable of withstanding temperatures up to 500 t: and pressures up to 100 bar, such as a steel pressure chamber. The reaction zone produces a layer with a reduced content of organic sulfur species and an increased hydrogen sulfide. Content of liquid hydrocarbon feed, and this is advantageously directed directly to the nitrogen sulfide removal zone (that is, there is no circulation to the reaction zone) to produce a reduced organic sulfur species content and a reduced Liquid smoke feed with nitrogen sulphide content. 15 The Chenghua hydrogen plutonium zone may contain -reading-at-lower pressure than that of antiships. Therefore, the liquid smoke feed from the reaction zone The existing hydrogen sulfide and hydrogen are evaporated in the removal area, and the liquid smoke Advantageously, a gas stream may be passed through the hydrogen sulfide removal zone to accelerate the removal of sulfur hydride. The gas stream may include an inert gas (money gas), but hydrogen In the case where the gas is hydrogen, the gas from the hydrogen sulfide removal zone can be advantageously used in step (a) of the present invention. In a preferred embodiment of the present invention The sulfide gas removal zone includes an adsorbent located in the 10 200402467-adsorption zone, wherein the method in this case includes making the sulfonium hydrocarbon feed with -reduced organic sulfur species content and -increased hydrogen sulfide content. The adsorbent in the adsorption zone is contacted to produce—a liquid hydrocarbon feed with—reduced organic sulfur species content and—reduced hydrogen sulfide content and—an adsorbent with an increased hydrogen sulfide content of 5 higher. 10 Appropriate The adsorbent can be provided by a porous oxide (such as a metal or non-metal oxide). Advantageously, the metal oxide can be a two-, three- or four-valent metal which can be a transition scale transition metal or a rare earth metal, such as: Zinc oxide, oxide oxide, two Titanium oxide, Cobaltic oxide: Oxide oxide, Hafnium oxide, Oxidation oxide, Oxidation ball and Oxidation crane. Examples of non-metal oxides are dioxygenation. More than- It can exist. There is Wei. The adsorbent is selected from the group consisting of zinc oxide, aluminum oxide, and magnesium oxide, or any combination thereof. The adsorbent may include an incorporated elemental metal, which is usually selected from the group consisting of VIAA, IB , IIB, IIIB, IVB and VB metals, especially Group VIIIA gold 15 genus (such as nickel, alum) 'and especially turn group metals (such as starting, period, ruthenium, rhodium, iron and watch). None is described in the periodic table in Basic Inorganic Chemistry by FA Cotton, G. Wilkinson and PLGaus Publ. John Wiley & Sonsjnc New York 2nd ED. 1986. Advantageously, the sorbent comprises nickel plus one or more platinum group metals (e.g. platinum). Alternatively, the adsorbent may include a zeolite, which may be synthetic (e.g., zeolites A, X, Y, and L) or a naturally occurring zeolite, such as faujasite. The zeolite may also contain a Group VIIIA metal (especially palladium or platinum) as an elemental metal. In another specific example of the present invention, the adsorbent may be carbon-based, such as 200402467, such as activated carbon. The liquid hydrocarbon feed with a reduced organic sulfur species content and an increased hydrogen sulfide content is preferably at a temperature between 50-200 ° C (favorably between 100-150 ° C, such as 120 ° C or 140 ° C) in contact with the adsorbent at a temperature of between 1 and 50 bar (preferably 2-20 5 bar, for example 10-15 bar). The adsorption zone usually contains a fixed-bed adsorbent contained in a container. The chamber can be a type capable of withstanding temperatures up to 500 ° C and pressures up to 100 bar, such as a steel pressure chamber. The sorbent with increased hydrogen sulfide content in the south is preferably stripped of its sulfur content by contacting a stripping 10 gas (such as nitrogen, oxygen, hydrogen or steam or a sulfur-free hydrocarbon gas) to generate An adsorbent that is substantially free of adsorbed sulfur compounds. The sulfur-containing adsorbent is usually contacted with the stripping gas at a temperature that is elevated above the temperature of the adsorption. Generally, the stripping gas contacts the adsorbent at a temperature in the range of 100-60 (TC (for example, 150-350 ° C)) and a pressure between 1.100 bar. In another embodiment of the present invention, The hydrogen sulfide removal zone may include an amine or a caustic solution, wherein the method of the present case includes passing the liquid hydrocarbon feed with a reduced organic sulfur species content and an increased hydrogen sulfide content through an amine or A caustic solution (such as a potassium hydroxide solution or a sodium hydroxide solution) contains 20 chambers to produce a liquid hydrocarbon feed with a reduced organic sulfur species content and a reduced hydrogen sulfide content. The organic hydrocarbon species content and a reduced hydrogen sulfide content of a liquid hydrocarbon feed usually contain less than 500 PPm s of sulfur compounds, such as 200-400 ppm S, preferably less than 200 PPm S, such as 50-100 ppm S, 12 iJU. / 200402467 more preferably less than 50 ppm S, such as 20-40 ppm S), and advantageously less than 10 ppm S, such as 0.1 · 5 ppm S (expressed by weight As elemental sulfur). I: Embodiment 3 Detailed description of the preferred embodiment 5 The present invention will now be described and illustrated with reference to the accompanying drawings, wherein FIG. 1 shows a storage tank (1) containing a liquid hydrocarbon feed containing organic sulfur species. The liquid hydrocarbon feed containing organic sulfur species is passed to a hydrogen saturator (2) via a liquid feed cartridge (3), wherein the liquid hydrocarbon feed is passed to the hydrogen saturator via line (4) The gaseous hydrogen is contacted and leaves the hydrogen saturator via the outlet (5). 10 A liquid hydrocarbon feed containing organic sulfur species and an increased hydrogen content leaves the hydrogen saturator via line (6) and is passed to a fixed bed containing a hydrodesulfurization catalyst Inside the reaction zone (7). A liquid hydrocarbon feed with a reduced organic sulfur species content and an increased hydrogen sulfide content leaves the reaction zone (7) and is passed through a line (8) to a fixed bed containing 15-an adsorbent Inside the adsorption zone (9). A liquid hydrocarbon feed with a reduced organic sulfur species content and a reduced hydrogen sulfide content leaves the adsorption zone via line (10). The invention is illustrated by the following examples. Example 1 20 A test equipment including the following components contained in a furnace for temperature control was used: a liquid feed storage tank, a liquid feed cartridge, a hydrogen supply, a saturator container, and A reactor. The reactor contains a steel tube with an internal diameter of 4 mm and a length of 1.3 m, and contains a fixed bed consisting of a hydrosulfation catalyst pre-sulfided with an oxidized molybdenum on an oxidized plate. Reaction 13 200402467 The vessel temperature varies between 360 ° C and 400 ° C, while the pressure varies between 30-70 barg. A gas oil with a total sulfur content of 260 ppm (expressed as elemental sulfur) is passed to the hydrogen saturator. In the hydrogen saturator, the gas oil is saturated with gaseous hydrogen. • The liquid hourly space velocity (LHSV) between 4 1Γ1 is passed to the reactor. The gas oil from the reactor is passed to a hydrogen sulfide removal zone where nitrogen sulfide is removed. The sulfur content of gas oil products was monitored at different reactor temperatures and pressures, and at different contact times. The results are shown in Table 1. 10 Table 1 Pressure (barg) Temperature (° C) LHSV (h_1) Sulfur content (ppm) 30 360 1.0 46 30 370 1.2 35 30 380 1.4 46 30 390 1.2 24 60 400 1.1 4 70 360 1.1 30 Example 2 Example 1 is repeated. The reactor temperature was maintained at 360 ° C, while the pressure was varied between 10-30 barg. A gas oil with a total sulfur content of 32 ppm (expressed as elemental sulfur) is passed to 15 the hydrogen saturator, in which the gas oil is saturated with gaseous hydrogen, and then a range of 1-45 1Γ1 The hourly space velocity of liquid (LHSV) is passed to the reactor. The gas oil from the reactor is passed to a hydrogen sulfide removal zone where the hydrogen sulfide is removed. The sulfur content of the gas oil product was monitored at different reactor pressures and different contact times. The results are shown in Table 2. 4 OrV. * I 1 .5 ^ 3. 14 200402467 Table 2 Pressure (barg) Temperature (° C) LHSV (h_1) Sulfur content (ppm) 30 360 1.1 < 5 30 360 43.1 6 10 360 1.4 < 5 10 360 10.1 6 The example illustrates that a product with less than 10 ppm can be produced from a gas oil that has been pretreated. Example 3 5 The catalyst was replaced with a fixed bed consisting of a US_Y zeolite containing 42% by weight of Al203 and 2.7% by weight of Re203. The zeolite was pretreated with nitrogen at 200 ° C for 1 hour. The reactor temperature varies between 300-360 ° C, while the pressure varies between 10-30 barg. A gas oil containing 3 2 ppm total sulfur (expressed as elemental sulfur) is passed to the hydrogen saturator, in which the gas oil is saturated with gaseous hydrogen, and then a range of 7-35 The hourly space velocity of liquid (LHSV) between h_1 is passed to the reactor. The gas oil from the reactor is passed to a hydrogen sulfide removal zone where nitrogen sulfide is removed. The sulfur content of gas oil products was monitored at different reactor temperatures, pressures, and different contact times. The results are shown in Table 3. Table 3 Pressure (barg) Temperature (° C) LHSV (h_1) Sulfur content (ppm) 50 300 8 28 50 330 7 19 50 360 7 11 50 360 35 14 Example 4 The US-Y zeolite was replaced with a copper-containing -Catalysts with zeolite sites. Inverter 15 200402467 The reactor temperature varies between 300-360 ° C, while the pressure is maintained at 50 barg. A gas oil containing 32 ppm of total sulfur (expressed as elemental sulfur) is passed to the hydrogen saturator, in which the gas oil is saturated with gaseous hydrogen and subsequently at a level between An hourly liquid hourly space velocity (LHSV) was passed to the 5 reactor. The gas oil from the reactor is passed to a hydrogen sulfide removal zone where the hydrogen sulfide is removed. The sulfur content of gas oil products was monitored at different reactor temperatures, pressures, and different contact times. The results are shown in Table 3. Table 4 Pressure (barg) Temperature (° C) LHSV (h_1) Sulfur content (ppm) 50 300 6.9 18 50 330 7 13 50 360 7.3 8 10 [Simplified description of the figure] Figure 1 shows one containing one containing organic sulfur Storage tanks for liquid hydrocarbon feeds of species. [Representative symbols for the main components of the figure] 1 Storage tank 2 Hydrogen saturator 3 Liquid feed drum 4 Pipeline 5 Outlet 6 Pipeline 7 Reaction zone 8 Pipeline 9 Adsorption zone 10 Pipeline 16