1374875 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種選擇性氫化含烯烴及芳香族化合物之 含經原料中之稀烴的方法。 【先前技術】 本發明之技術領域係關於選擇性氫化含歸烴及芳香族化 合物之烴流中之烯烴的方法。氫化方法業經煉油公司及石 ^ 油化學生產公司使用以製造更有價值的含烴產物。僅在可 選擇性氫化該等烯烴，且不會同時氫化該等芳香族化合物 下，含烯烴及芳香族化合物之含烴流才有用。先前，已使 用含包括第VIII族金屬（特別為鎳）之承載觸媒進行選擇性 氫化反應。然而，鎳觸媒並不具充份選擇性，因為當選擇 性氫化烯烴時，其有可氫化大部份該等芳香族化合物之顯 著傾向。甚至當於約30至5〇巴之低壓及於5〇。〇與18〇(^間 之低溫度下進行該氫化方法時，該選擇率並未能令人滿意 :i也改進。該先前技藝已教示可藉由在該觸媒與該反應性原 料接觸之前加入硫化合物而改善這些觸媒之選擇率。 雖然在烯烴系烴之選擇性氫化反應中已使用多種方法流 程圖、操作條件及觸媒，但是對於可提供較低成本及所需 產物品質之新選擇性氫化法總是有需求。 美國專利5,417,844 Bl(BoitiaUX等人）揭示—種於鎳觸媒 存在下在蒸氣裂解汽油中選擇性氫化二烯烴之方法，且其 特徵在使用該反應器之前，在使用該觸媒之前將含硫有機 化合物併入在該反應器外之該觸媒内。 106544.doc 【發明内容】 性烴及芳香族化合物之—選擇 法。+κ寻方香族化合物之改良方 法頃出乎預期地發現，當於相# 化學計量比下，使該原料與元辛;對烯烴之低 之撰堪“ 麵觸媒反應時，該等稀烴 、擇性餘和高，且該等芳香族化合物之氫化低。 八本發明係關於一種選擇性氫化含烯烴及芳香族化合物之 f原料中之烯烴的方法，該方法包括以下步驟：⑷於包 括溫度為自2Gt至m：、1力為自618千帕心)至7_千 帕及氫料烴之化學計量比為自1:⑴：烴氯化條 件下’在含有包含元素鎳之觸媒的選擇性氫化區内使該含 烴原料與氫反應；及（b)时含转族化合物及具有減少濃 度之烯烴的含烴產物流。 【實施方式】 旦頃發現可藉由於溫和操作條件及氫對烯烴之有限化學計 里比下’使含烯烴與芳香族化合4勿之含烴原料與含元素鎳 之觸媒反應而達成烯烴之改良選擇性氫化。 雖W本發明特別適周於選擇性氫化石油腦沸點範圍之含 烃原料中所含之烯烴，但是任何合適之含烴原料皆可用於 本發明。較佳原料為沸點範圍自38»c至2〇4〇c内及烯烴含 量為自0.1至5重量。/。之石油腦。 根據本發明，係將該含烯烴及芳香族化合物之含烴原料 與氮一起加入含有包含元素鎳之選擇性氫化觸媒之選擇性 氮化區内’並於選擇性氫化條件（其包括溫度為自2〇〇c至 106544.doc 1374875 、屋力為自618千帕至7_千帕及氫對浠烴之化學計 夏比為。自1:1至5:1)下操作。更佳之氫化區溫度為自50 C至90°c。另-較佳氫化區溫度為自2〇t至耽。 本發明中之合適選擇性氫化觸媒含有較佳承載於高表面 積承載物質(較佳為氧化銘)上之元素錦。若該元素錦存在 於載體上，該錦之存在量較佳為總觸媒重量之自2至40重 量％ » 含芳香m合物及稀烴之含烴流係用於下游處理中，立 中該等稀煙之存在對用於後續處理之觸媒有害或在產物流 中係不宜。因此，較佳且最好當使用此等烴流時，可選擇 性地飽和該等稀烴’同時防止該等芳香族化合物之飽和或 至少使該飽和減至最低。合適之含烴流可衍生自任何來 源，且此種含烴流之-般來源為得自處理石油腦原料之觸 媒：組器的液體流出物、就觸媒重組器流出物流而言，該 等芳香族化合物有價值’但是該等同時產生之烯烴被認為 是污染物’當保留該等芳香族化合物時，必需移除該等污 染物，用本發明選擇性氫化法以減少含芳香族化合物 及烯煙之含烴原料中的烯烴濃度。 因此’提供一種選擇性氫化稀煙之方法，其包括於選擇 性氫化條件下在反應區内使含芳香族化合物及烤烴之原料 接觸含元素錦之觸媒以產生實質上不含稀烴系化合物之產 物。該選擇性氫化條件包括溫度為自2〇它至9〇艺、壓力為 自61 8千帕至7000千帕及氫對烴之化學計量比為自1 :〖I 5:卜該最佳條件組可選自這些條件，且取決於該原料流 106544.doc 1374875 之組合物。在任何情況下，得自_擇性氣化反應區之產 物可實質上不含烯烴。該名詞"實質上不含”意指少於麵 wppm重量基礎之該烯烴系化合物（〇丨重量％)。此外，較佳 該含烴原料中少於〇.5重量％之該等芳香族化合物經氫北。1374875 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for selectively hydrogenating a dilute hydrocarbon containing a olefin and an aromatic compound. [Prior Art] The technical field of the present invention relates to a process for the selective hydrogenation of olefins in hydrocarbon streams containing hydrocarbon-derived and aromatic compounds. The hydrogenation process is used by refining companies and petroleum chemical production companies to produce more valuable hydrocarbon-containing products. The hydrocarbon-containing stream containing olefins and aromatics is useful only when the olefins can be selectively hydrogenated without hydrogenating the aromatic compounds simultaneously. Previously, selective hydrogenation reactions have been carried out using a supported catalyst comprising a Group VIII metal, particularly nickel. However, nickel catalysts are not sufficiently selective because when selectively hydrogenating olefins, they have a significant tendency to hydrogenate most of these aromatic compounds. Even at a low pressure of about 30 to 5 baht and at 5 〇. The selectivity is not satisfactory when the hydrogenation process is carried out at a low temperature between 18 Torr and ii: i is also improved. This prior art has taught that by contacting the catalyst with the reactive starting material. The addition of sulfur compounds improves the selectivity of these catalysts. Although various process schemes, operating conditions and catalysts have been used in the selective hydrogenation of olefinic hydrocarbons, new ones are available that provide lower cost and desired product quality. There is always a need for a selective hydrogenation process. U.S. Patent 5,417,844, Bl. (Boitia UX et al.) discloses a process for the selective hydrogenation of diolefins in steam cracked gasoline in the presence of a nickel catalyst, and which is characterized prior to the use of the reactor. The sulfur-containing organic compound is incorporated into the catalyst outside the reactor before the catalyst is used. 106544.doc [Summary of the invention] Hydrocarbon and aromatic compound-selection method. The improved method unexpectedly found that when the phase is stoichiometric, the raw material is made with the elemental octane; when the olefin is low, the dilute hydrocarbon, the selectivity and the high, And The hydrogenation of the aromatic compounds is low. The present invention relates to a process for the selective hydrogenation of olefins in a feedstock containing olefins and aromatic compounds, the process comprising the steps of: (4) including temperatures from 2 Gt to m:, The stoichiometric ratio of 1 force from 618 kPa to 7 kPa and hydrogen hydrocarbons is from 1: (1): under hydrocarbon chlorination conditions 'in the selective hydrogenation zone containing the catalyst containing elemental nickel The hydrocarbon-containing feedstock reacts with hydrogen; and (b) contains a transductant compound and a hydrocarbon-containing product stream having a reduced concentration of olefins. [Embodiment] It has been found that due to mild operating conditions and limited chemistry of hydrogen to olefins The selective hydrogenation of olefins is achieved by reacting a hydrocarbon-containing feedstock containing an olefin and an aromatic compound with a catalyst containing elemental nickel. Although the invention is particularly suitable for the selective boiling of the boiling range of the petroleum brain The olefins contained in the hydrocarbon feedstock, but any suitable hydrocarbonaceous feedstock can be used in the present invention. Preferred feedstocks have a boiling point ranging from 38»c to 2〇4〇c and an olefin content of from 0.1 to 5 wt%. Petroleum brain. According to this issue The hydrocarbon-containing feedstock containing an olefin and an aromatic compound is added together with nitrogen to a selective nitridation zone containing a selective hydrogenation catalyst containing elemental nickel' and under selective hydrogenation conditions (including temperatures from 2〇) 〇c to 106544.doc 1374875, the house is from 618 kPa to 7 kPa and the stoichiometric ratio of hydrogen to terpene hydrocarbons is from 1:1 to 5:1). The preferred hydrogenation zone temperature is From 50 C to 90 ° C. Another preferred hydrogenation zone temperature is from 2 Torr to 耽. Suitable selective hydrogenation catalysts in the present invention are preferably supported on a high surface area bearing material (preferably oxidized). Elemental gold. If the element is present on the carrier, the amount of the element is preferably from 2 to 40% by weight based on the total catalyst weight. » The hydrocarbon-containing stream containing aromatic m compounds and dilute hydrocarbons is used for downstream processing. In the middle, the presence of such flue-cured tobacco is detrimental to the catalyst used for subsequent processing or unsuitable in the product stream. Accordingly, it is preferred and preferred to selectively saturate the dilute hydrocarbons while using such hydrocarbon streams while preventing or at least saturating the saturation of the aromatic compounds. Suitable hydrocarbon-containing streams can be derived from any source, and the general source of such hydrocarbon-containing streams is the catalyst effluent from the processing of petroleum brain feedstock: in the case of a catalyst recombiner effluent stream, Equivalent aromatic compounds are valuable 'but these simultaneously occurring olefins are considered to be contaminants'. When retaining such aromatic compounds, it is necessary to remove such contaminants, using the selective hydrogenation process of the invention to reduce aromatic compounds And the concentration of olefins in the hydrocarbon-containing feedstock of the olefin. Therefore, a method for selectively hydrogenating a dilute smoke is provided, which comprises contacting a raw material containing an aromatic compound and a roasted hydrocarbon in a reaction zone with a catalyst containing elemental quinone in a reaction zone to produce a substantially free hydrocarbon-free system. The product of the compound. The selective hydrogenation conditions include a temperature from 2 Torr to 9 、, a pressure of from 6 8 kPa to 7000 kPa, and a stoichiometric ratio of hydrogen to hydrocarbons from 1: I 5: These conditions can be selected and depend on the composition of the feed stream 106544.doc 1374875. In any event, the product from the selective gasification reaction zone may be substantially free of olefins. The term "substantially free" means the olefinic compound (% by weight) based on less than the wppm by weight of the surface. Further, it is preferred that less than 0.5% by weight of the aromatics in the hydrocarbon-containing raw material. The compound is hydrogenated north.
根據本發明，該選擇性氫化觸媒較佳用於含有含觸媒之 柱形床的固定床反應器中，於其中該等反應物係以垂直方 向移動。該觸媒可以以，例如，小粒、球狀物、擠出物或 不規則开> 狀顆粒存在於該反應器内。為了使用該觸媒，較 佳使該等反應物之溫度達至該反應區之所欲入口溫度，與 氫混合然後進入並通過該反應器。 或者’該等反應物可以與所欲數量之氫混合，然後經加 熱至該所欲入口溫度。在兩種情況下，該反應區之流出物 皆可進入產物回收設備内以移除殘留氫或若可接受該殘留 氫（如果有的話），則可直接進入下游產物利用區内。可藉 由於較低壓力下驟沸該流出物流或藉由使該流出物流進入 汽提塔或單階段驟沸塔内而移除氫。 該較佳之觸媒形式為直徑在0.4毫米與6·3毫米間之球狀 杨=可以使用許多種不同方法（其包括軋製及壓寬技術）以 製得固體觸媒載體物質之球狀體。然而，最佳使用球狀氧 化铭顆粒作為該觸媒載劑，且藉由可以使氧化鋁溶膠凝膠 化之方法而形成。該使氧化鋁膠化以形成球狀體之方法為 本項技藝中一般所知之油滴法。亦可以使用許多種不同方 法以形成該氧化鋁溶膠。典型的方法為使用約氯化氫 之水性溶液浸提鋁金屬以產生氯化鋁溶膠。另一種方法包 106544.doc U/4875 括使氯化鋁溶液在電解槽内電解。製備氧化鋁溶膠之一般 方法為添加鋁金屬至氯化鋁之水性溶液内，使該混合物經 加熱並於其沸點下浸提。 使該溶料化的較佳方法包括以下步驟：於在該谬化溫 度以下之皿度下混合該溶膠及膠化劑，然&將所形成混合 物以小滴分散在熱油浴中，藉此發生膠化作用，並形成堅 硬的球狀凝膠顆章立。然後使該等氧化铭水凝膠球狀物進行 特定熟化處理以得到所欲物理特性。一般而言，完全熟化 處理包括在熱浴内熟化至少1G小時，在合適液體驗性介質 内熟化至少1G小時’最後經水沖洗以降低該驗性介質之濃 度。在用於形成並熟化氧化鋁顆粒的此種方法中，於在該 液體鹼性彳質内熟化之冑，該等水凝膠球狀體並未與水接 觸。於該方法之這些早期階段下’該等球狀物具水溶性， 且一旦接觸水時，可被破壞。可以於自49°C至260°C之溫 度下進行該熟化處理，且高s1〇〇<t，有快速排放氣體之 傾向，其會導致該等水凝膠球狀體破裂或變脆弱。於該形 成及熟化步驟期間，藉由維持超大氣壓力，可使用較高溫 度Μ進行热化。較高溫度之使用的優點為可不必使闬在液 體鹼性洛液中進行熟化之步驟。因此在該油熟化步驟後可 立即使用水沖洗該等球狀體。典型上，於自9〇。〇至】5 〇它 之溫度及範圍為自常壓至1〇〇〇千帕之壓力下在該油浴内熟 化已膠化之顆粒，費時自1至24小時。若於常壓條件下進 仃油热化，該等已膠化顆粒通常在稀水性氨溶液内進一步 熟化2至4小時。熟化後，該等顆粒經水沖洗、乾燥並煅 106544.doc 1374875 燒。 可藉由混合該溶膠及六亞f基四胺（HMT，其係為一種 於自4至1〇之pH下具有強緩衝作用之弱鹼）而進行該氧化鋁 水溶膠之膠化。於高溫下該物質之水解速率會增加，且不 會急速排出氣體（其有利於該膠化程度）。亦已知可使用尿 素及HMT之混合物作為該膠化劑。一旦將該混合物加熱至 高溫時，該膠化劑可分解並形成氨，其會導致該水溶膠固 ^ 化成凝膠並形成氧化鋁水凝膠球狀體。膠化及熟化後，可 以於110°c下以烘箱乾燥該等顆粒，然後逐漸加熱至65〇 C，並於該溫度下在空氣中煅燒2小時。經該空氣煅燒 後，所形成物質本質上為7氧化鋁。該名詞"本質上，，意指 所形成氧化鋁載劑含有至少9〇重量。/。之7氧化鋁。為了確 保該載體物質本質上為r氧化鋁，該載體物質最好不暴露 於超過850°C之溫度下❶暴露於超過85〇艺之溫度下會導致 該氧化紹之相變，使其自該7 -轉化成5 0 -，及可能甚 f 至α _氧化鋁。此種相變通常連帶使小細孔（小於100埃）崩 散而產生較大之細孔，因此導致總孔隙度增加。然而，由 於該表面積與該等小孔之數量及孔度成正比，所以這些細 孔之朋散導致該載體物質之表面積急劇下降。因此，藉由 使用該油滴法，可形成總孔隙度大於14立方厘米/克且表 面積超過150米2/克之7氧化鋁載體物質，所以可避免與另 外形成技術有關之剛才所述的附帶問題。 除了驗性氧化紹載體物質外，就用於本發明之該觸媒之 性能而δ，需要元素鎳《該鎳僅可存在於該氧化鋁載體物 106544.doc / Μ在該㈣之外表 經表面沉積，藉此本質上所有存在於該載體 、係集中於該載體之最外的200微米層内。以該元素 、屬為基準，該觸媒成品令之錄濃度較佳在5與25重量％ 2間。於m體形成料期間若有必要，可將該錄組份 :加入該觸媒内。然而’如同浸潰法(其中係將已形成之 氧化紹球狀體浸入錄化合物之溶液内），較佳添加該觸媒 之鎳組份至先前已形成之氧化紹球狀體内。該等所形成锻 燒氧化紹球狀體較佳浸在硝酸錦'氯化録、硫酸録或醋酸 錦或其它可溶性鎳化合物之水性溶液内。然後使用旋轉蒸 氣蒸發器，使該溶液與該等球狀體接觸，並蒸發至乾燥。 接著可以於i5〇r之溫度下煅燒該乾燥顆粒，費時一小 時，然後於525 〇C下煅燒一小時。接著乾燥所形成球狀 體，並經氮滌洗，且較佳與含氫氣體接觸以進行還原步 驟。雖然球狀氧化鋁球狀體為該觸媒之鎳組份的較佳^ 體’但是任何合適载體皆可用於本發明。 本發明方法藉由以下實例而進一步說明。這些實例並非 阳以不g地rpc制本發明該方法，而是進一步說明上述星體 實施例之優點。 實例1 在於選擇性氫化條件（其包括壓力為5600千帕、溫度為 40°C、液體時空速度為10及氫到:稀烴之莫耳比為15)下操 作之含T氧化鋁載體載元素鎳之選擇性氫化反應區内，使 含99重量％甲苯及1重量ο/。。至eg烯烴系烴之示範原料反 106544.doc 12 1374875 應。該原料之溴指數（Bromine Index)(其係為該稀烴含量之 直接關係）為1000，且得自該選擇性氫化反應區之流出物 的分析確定該產物之溴指數僅為20。雖然本質上可轉化所 有該等原料烯烴，但是該原料中僅少於〇.2重量〇/〇之曱苯經 飽和〇 . 實例2 . 在於壓力為5600千帕、液體時空速度為10及氫對烯烴之 f 冑耳比為1.5下操作之含r氧化鋁載體載元素鎳的選擇性 氫化反應區内，使含99重量％甲苯及】重量。/。匕至“烯烴系 烴之示範原料反應。藉由將該反應區溫度增加9〇<t而開始 s亥氫化反應，且該產物流之溴指數被認為是15〇。在不改 變任何其它插作條件下，使該反應區溫度自9〇它減至 c，且該溴指數非可預期地自15〇減為4〇。進一步使該反 應，溫度自5(TC減為4(rc可以使該漠指數自4〇減為2〇。在 本實例中4原料中僅少於Q 2重量％之甲苯經飽和。 ‘ 上述說月及實例清楚地說明藉由本發明該方法所包含之 優點及其用途所帶來的好處。According to the present invention, the selective hydrogenation catalyst is preferably used in a fixed bed reactor containing a catalyst-containing cylindrical bed in which the reactants are moved in a vertical direction. The catalyst may be present in the reactor in, for example, pellets, spheres, extrudates or irregularly shaped particles. In order to use the catalyst, it is preferred to bring the temperature of the reactants to the desired inlet temperature of the reaction zone, mix with hydrogen and then enter and pass through the reactor. Alternatively, the reactants may be mixed with the desired amount of hydrogen and then heated to the desired inlet temperature. In either case, the effluent from the reaction zone can be passed to the product recovery unit to remove residual hydrogen or, if acceptable, the residual hydrogen, if any, to the downstream product utilization zone. Hydrogen can be removed by abating the effluent stream at a lower pressure or by passing the effluent stream into a stripper or single stage boiler column. The preferred catalyst form is spheroidal yang having a diameter between 0.4 mm and 6.3 mm. Spheres of solid catalyst carrier material can be prepared using a variety of different methods including rolling and pressure stretching techniques. . However, spheroidal oxide particles are preferably used as the catalyst carrier, and are formed by a method in which an alumina sol can be gelated. The method of gelling alumina to form a spheroid is an oil drop method generally known in the art. A variety of different methods can also be used to form the alumina sol. A typical method is to extract aluminum metal using an aqueous solution of about hydrogen chloride to produce an aluminum chloride sol. Another method package 106544.doc U/4875 involves electrolyzing an aluminum chloride solution in an electrolytic cell. A general method for preparing an alumina sol is to add an aluminum metal to an aqueous solution of aluminum chloride, and the mixture is heated and leached at its boiling point. A preferred method for the solubilization comprises the steps of: mixing the sol and the gelling agent at a temperature below the deuteration temperature, and then dispersing the formed mixture as a droplet in a hot oil bath, borrowing This gelatinization occurs and forms a hard, spherical gel. The oxidized gelatin gel spheres are then subjected to a specific ripening treatment to obtain the desired physical properties. In general, the complete curing treatment consists of curing in a hot bath for at least 1 G hours, aging in a suitable liquid experiential medium for at least 1 G hour, and finally rinsing with water to reduce the concentration of the test medium. In such a method for forming and aging alumina particles, the hydrogel globules are not in contact with water after aging in the liquid alkaline enamel. At these early stages of the process, the spheres are water soluble and can be destroyed upon contact with water. The curing treatment can be carried out at a temperature of from 49 ° C to 260 ° C, and the high s1 〇〇 < t has a tendency to rapidly vent gas, which causes the hydrogel spheroids to rupture or become weak. By maintaining superatmospheric pressure during the formation and maturation steps, higher temperatures can be used for heating. The advantage of the use of higher temperatures is that the step of aging the mash in the liquid alkaline solution is not necessary. Therefore, the spheroids can be washed immediately with water after the oil ripening step. Typically, at 9〇. 〇 】 5 5 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 。 。 。 。 。 。 。 。 。 。 。 。 If the eucalyptus oil is heated under normal pressure conditions, the gelled granules are usually further aged in a dilute aqueous ammonia solution for 2 to 4 hours. After aging, the granules were rinsed with water, dried and calcined at 106544.doc 1374875. The alumina hydrosol can be gelled by mixing the sol and hexamethylene f-tetramine (HMT, which is a weak base having a strong buffering action at a pH of 4 to 1 Torr). The rate of hydrolysis of the material increases at elevated temperatures and does not rapidly vent the gas (which favors the degree of gelation). It is also known to use a mixture of urea and HMT as the gelling agent. Once the mixture is heated to an elevated temperature, the gelling agent decomposes and forms ammonia which causes the hydrosol to solidify into a gel and form an alumina hydrogel spheroid. After gelation and aging, the granules may be dried in an oven at 110 ° C, then gradually heated to 65 ° C, and calcined in air at this temperature for 2 hours. After calcination through the air, the material formed is essentially 7 alumina. The term "essentially, means that the formed alumina carrier contains at least 9 gram by weight. /. 7 alumina. In order to ensure that the carrier material is essentially r alumina, the carrier material is preferably not exposed to temperatures in excess of 850 ° C. Exposure to temperatures above 85 °C results in a phase change in the oxidation, 7 - converted to 50 - and possibly even f to alpha alumina. Such phase transitions are usually associated with the collapse of small pores (less than 100 angstroms) to produce larger pores, thus resulting in an increase in total porosity. However, since the surface area is proportional to the number and pore size of the pores, the pores of these pores cause a sharp drop in the surface area of the carrier material. Therefore, by using the oil droplet method, an alumina carrier material having a total porosity of more than 14 cubic centimeters per gram and a surface area exceeding 150 m 2 /g can be formed, so that the incidental problems just described in connection with the additional formation technique can be avoided. . In addition to the oxidizing carrier material, the performance of the catalyst used in the present invention, δ, requires elemental nickel "the nickel may only be present in the alumina carrier 106544.doc / Μ outside the surface of the surface Deposition, whereby essentially all of the carrier is present in the outermost 200 micron layer of the carrier. Based on the element and the genus, the concentration of the catalyst is preferably between 5 and 25% by weight. The recording component can be added to the catalyst if necessary during the formation of the m body. However, as with the impregnation method in which the formed oxidized spheroid is immersed in the solution of the recorded compound, it is preferred to add the nickel component of the catalyst to the previously formed oxidized spheroid. Preferably, the calcined oxidized spheroids formed are immersed in an aqueous solution of nitric acid chlorinated chloride, sulfuric acid or acetic acid or other soluble nickel compound. The solution was then contacted with the spheroids using a rotary vapor evaporator and evaporated to dryness. The dried granules can then be calcined at a temperature of i5 〇r for a period of one hour and then calcined at 525 〇C for one hour. The formed spheroids are then dried and washed with nitrogen and preferably contacted with a hydrogen containing gas to carry out the reduction step. While spherical alumina spheroids are preferred for the nickel component of the catalyst, any suitable carrier can be used in the present invention. The method of the invention is further illustrated by the following examples. These examples are not intended to produce the method of the present invention, but to further illustrate the advantages of the above-described embodiment of the star. Example 1 consists of a selective hydrogenation condition comprising a T-containing alumina carrier element operating at a pressure of 5600 kPa, a temperature of 40 ° C, a liquid hourly space velocity of 10, and a hydrogen to: molar ratio of 15 for the hydrocarbon. The selective hydrogenation reaction zone of nickel is made to contain 99% by weight of toluene and 1% by weight. . Demonstration raw materials to olefin hydrocarbons. 106544.doc 12 1374875 should be. The Bromine Index of the feedstock, which is the direct relationship of the dilute hydrocarbon content, was 1000, and analysis of the effluent from the selective hydrogenation zone determined that the product had a bromine index of only 20. Although essentially all of these feedstock olefins can be converted, only less than 0.2 wt% of rhodium in the feedstock is saturated with rhodium. Example 2 is at a pressure of 5,600 kPa, a liquid hourly space velocity of 10 and hydrogen to olefins. The f-ear ratio is 1.5 in the selective hydrogenation reaction zone of the r-containing alumina carrier-supporting element nickel, and contains 99% by weight of toluene and the weight. /. The reaction to the exemplary raw material of the olefinic hydrocarbon is started. The hydrogenation reaction is started by increasing the temperature of the reaction zone by 9 〇 < t, and the bromine index of the product stream is considered to be 15 〇 without changing any other insertion. Under the conditions, the temperature of the reaction zone is reduced from 9 〇 to c, and the bromine index is unpredictably reduced from 15 为 to 4 〇. Further, the reaction is further reduced from 5 (TC to 4) (rc can The desert index is reduced from 4 to 2. In this example, only less than Q 2% by weight of the toluene is saturated. 'The above-mentioned month and examples clearly illustrate the advantages and uses of the method by the present invention. The benefits.
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