經濟部中央標準局f工消费合作社印製 457229 A7 . _____B7 五、發明説明（） 發明背景 本發明係有關於將原油中含有大量苯之芳香族烴作爲 起始原料，使用特別配方的釕觸媒，進行催化性部份氫化 反應之方法。該方法可獲得較高的環己烯選擇率及產率， 應用於工業化大量生產環己烯具有相當經濟效益^ 環己烯的雙鍵’具有較高的反應活性，極易與其他反 應物反應，利用價値很高，是極佳的化學品原料，可被廣 泛應用於生產醫藥、食品、農業化學品 '飼料、特用化學 口口等新τ>頁域*將本部汾氯化成環己嫌後可再水合(j^ydration) 成環己醇（Cyclogexanol)，環己醇經脫氫反應可得環己酮 (Cyclohexanone)。另可將環己烯在適當條件下，直接氧化製 造己二酸(Adipic acid)。此製程選擇性極高，製法簡化，相 .較於傳統環己酮/環己醇混合物(KA-oil)製程.，可縮短己二 酸之生產流程’故具有相當的經濟效益。己二酸爲尼龍_66 之原料’尼龍-66爲泛用型工程塑膠，被廣泛應用於各項民 生用品，例如汽車零件、蓮動器材、電子產品等。 以苯爲起始原料以生成環己烯，再製造環己醇之新穎 方法與傳統方法比較，例如：環己烷氧化或酚氫化製程， 經濟效益較佳。因苯的價格比酚或環己烷便宜，另製程選 擇性(selectivity)高，可簡化最終產物之分離精製步驟。 環己烯可由許多方法製造，例如鹵化環烷類脫氫，及 鹵素環己烷脫氫，及環己醇脫水等，但以上方法需要較複 雜之步驟，生產成本較高。但若能藉適當觸媒及反應條件 ’由苯部份氫化辰應而合成，則可簡化製程，在工業上極 ___ 3______ 本紙張尺度適用中國國家.：)票準（CNS ) Λ4現格（210X297公釐） —^^1 II - - - .^—^1 —^^1 νΛ I J I -1 I: 1 \r tl_l. n z*fT**^- (請先間讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作社印製 457229 at B7 五、發明説明（） 有價値β由於熱力學平衡之限制，苯氫化之主要產物爲環 己烷 ΟίΗβ—^CeHio, △ G。： =-22 KJ/mol; AG° =-75KJ/mol; ΟεΗβ—^CeHi2, △ G。= =-97 KJ/mol 熱力平衡極不利環己烯之生成，若無適當觸媒及反應 條件，苯部分氫化成環己烯之產率均不高1 一般氫化觸媒多爲貴重金屬或其化合物分散在擔體表 面。觸媒的活性和選擇性與活成份、顆粒大小、分佈方式 及與反應物、產物產生化學吸附力的強弱等因素有關。 一般常用的氫化觸媒爲： 1.金屬硫化物系（metalsulfides)，此類觸媒中最常見者 爲硫化鉬(MoS2)或硫化鎢(WS2)，常用於原油處理的加氫脫 硫(HDS)、加氫脫金屬(HDM)、加氫脫氮(HDN)等。 2·鐵系觸媒：於週期表第八族第一列鐵、鈷、鎳三金 屬中鎳之氫化能力較強，也最常用，以雷內鎳（Raney Nickel)最有名。鎳觸媒甚早即被使用於食用油脂的選擇氫 化以去除不飽和鍵之自氧化（auto-oxidation)，在芳香族煙部 份氫化反應方面仍需要較高反應性觸媒。 3.貴重金屬觸媒：包括週期表第八族第二、三列六種 過渡金屬所組成之鉑族元素(Pt、Pd、Ph、Ir、Ru、Os)，其 中以鉑(Pt)及鈀(Pd)、釕(Ru)、鍺(Rh)較常使用，雖然pt、 Pd之氫化活性比上述金屬硫化物及鐵系強，但在油料的加 氫處理上，則易受含硫或含氮化合物之毒化影響而漸失活 (請先閏讀背面之注意事項再填寫本頁) 衣 訂 本紙張尺度適用中國囤家標率（CNS ) Λ4規格（210X297公:t ) A7 B7 457229 五、發明説明（） 性。Pd觸媒的活性次於鉑觸媒，但對硫化物之抗毒性較Pt 佳，於高溫氫氣環境下穩定性則比Pt差。苯之部份氫化反 應若使用Pd或Pt，則因觸媒反應性不易調整，通常環己烯 產率很低。 本發明中苯的部份氫化觸媒，主要以釕爲主，償格比 Pt或Pd低。欲獲得高環己烯產率，則需避免過度氫化成環 己烷，如何調整使觸媒氫化能力適中及維持一定的觸媒壽 命，爲最重要的課題。氫化能力太強會過度氫化苯成環己 烷，氫化能力太弱則會使反應速率過低，不合經濟效益。 —般需藉助於修飾劑之幫助才能獲較高產率β 利用芳香族烴之苯作爲起始原料，進行部份氫化反應 生成環己烯之數種製程已被揭示，其等並將被倂於本文內 .爲參考： ⑴以液態氨爲介質，於鹼金屬下進行氫化反應〔美國 專利 USP 3274272, 3321539;日本專利 JP-406864, 406865, 438102〕。本法液態氨及鹼金屬需回收是其缺點。 ⑵以低碳醇爲溶劑，於釕觸媒下進行氫化反應〔美國 專利USP 3391206〕。本法環己烯之選擇率較低。 ⑶以含有週期表la或Ha金屬、錳及鋅之氯鹽或硫酸 鹽之中性或酸性水溶液，以釕觸媒進行氫化反應〔日本專 利〗P-5198243〕。本法環己烯之選擇率低。 ⑷以含有鈷、鎳或銅之碳酸鹽水溶液，於釕觸媒進行 氫化反應〔日本專利；ίΡ-5346939〕。本法環己烯之選擇率 低。 ___ 5 (諳先閱讀背面之注意^項再填寫本頁) ，-'° 經濟部中央標準局貝工消费合作社印製 本紙浪尺度適用中國國家標準（CNS ) Λ4規格（2]ΟΧ297公着） 457229 Μ Β7 經濟部令央標準局員工消费合作社印¾ 五、發明説明（） ⑸以含有添加劑之鹼性水溶液，於週期表第M族中至 少一種金屬元素爲觸媒進行氫化反應〔美國專利usp_ 3767720〕。本法環己烯之產率雖高，但需較大量之添加劑 及鹼性溶液’擔體中之金屬離子易溶於鹼性溶液。 ⑹將溶解有氯化鋅、氯化鈦等添加物之鹼性水性溶液 加入苯’以釕、鍺或鈀爲觸媒進行氫化反應〔荷蘭專利 NLP 7205832〕。 ⑺以釕一鐵系金屬，如鈷、鐵、鎳之合金，含浸在 AbCh上’於水存在下進行部份氫化反應〔美國專利USP 3793383, 3912787, 4401640〕。本法環己烯之產率最高約爲 18% ◊ ⑻以釕-鐵、鈷-銅或銀爲活性金屬，BaSO*爲擔體，於 添加銘、鐵、鋅之硫酸鹽水溶液進行氫化反應〔美國專利 USP 455572 ;歐洲專利EP 170915, 214530〕。本法觸媒製備 較爲複雜及性質不易均一是其缺點》 ⑼以釕、釕-鐵或釕-鋅等超細微粒金屬爲觸媒，於 添加鋅之硫酸鹽或氬氧化物之溶液進行氫化反應〔日本專 利JP-62201830, 624544〕。本法觸媒回收分離困難。 (10) 以釕爲活性金屬，含有鑭系稀土金屬，如鑭、鈽 、鍇，之氧化物、氫氧化物或碳氧化物中至少一種爲擔體 ，利用氫氣氣相還原法將釕還原，於添加鋅或鋁之氯鹽、 硫酸鹽、氧化物或氫氧化物之鹼性水溶液進行氫化反應[ 美國專利USP 4678861〕。 (11) 以所謂“化學混合物”（Chemical mixing)方法，混 (請先聞讀背面之注意事項再填寫本頁) 訂Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Industrial Cooperatives Co., Ltd. 457229 A7. _____B7 V. Description of the invention () Background of the invention The present invention relates to the use of a specially formulated ruthenium catalyst as a starting material for aromatic hydrocarbons containing a large amount of benzene in crude oil. , A method for performing a catalytic partial hydrogenation reaction. This method can obtain higher selectivity and yield of cyclohexene, and it has considerable economic benefits when applied to industrial mass production of cyclohexene. The double bond of cyclohexene has high reactivity and is easy to react with other reactants. , The use price is very high, is an excellent chemical raw material, can be widely used in the production of pharmaceuticals, food, agricultural chemicals' feed, special chemical mouth and other new τ > page domain * Chlorinated Fenfen into cyclohexanone After that, it can be rehydrated (Cyclogexanol), and cyclohexanol can be obtained through the dehydrogenation reaction. Alternatively, cyclohexene can be directly oxidized to produce adipic acid under appropriate conditions. This process has extremely high selectivity and simplified manufacturing method. Compared with the traditional cyclohexanone / cyclohexanol mixture (KA-oil) process, it can shorten the production process of adipic acid, and therefore has considerable economic benefits. Adipic acid is the raw material of nylon 66. Nylon-66 is a general-purpose engineering plastic, which is widely used in various consumer goods, such as automobile parts, lotus equipment, and electronic products. Compared with traditional methods, such as cyclohexane oxidation or phenol hydrogenation process, the novel method that uses benzene as the starting material to generate cyclohexene and then regenerate cyclohexanol is more economical. Because the price of benzene is cheaper than that of phenol or cyclohexane, and the selectivity of the other process is high, the separation and purification steps of the final product can be simplified. Cyclohexene can be produced by many methods, such as halogenated cycloalkanes dehydrogenation, halogenated cyclohexane dehydrogenation, and cyclohexanol dehydration. However, the above method requires more complicated steps and higher production costs. However, if it can be synthesized from benzene partially hydrogenated by appropriate catalysts and reaction conditions, the process can be simplified. It is extremely industrially ___ 3______ This paper size is applicable to Chinese countries. :) Ticket standard (CNS) Λ4 (210X297 mm) — ^^ 1 II---. ^ — ^ 1 — ^^ 1 νΛ IJI -1 I: 1 \ r tl_l. Nz * fT ** ^-(Please read the precautions on the back first (Fill in this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 457229 at B7 V. Description of the invention () Valence 値 β Due to the limitation of thermodynamic equilibrium, the main product of benzene hydrogenation is cyclohexane 〇ίΗβ— ^ CeHio, △ G : = -22 KJ / mol; AG ° = -75KJ / mol; ΟεΗβ— ^ CeHi2, △ G. = = -97 KJ / mol Thermal balance is extremely unfavorable for the formation of cyclohexene. Without proper catalysts and reaction conditions, the yield of partial hydrogenation of benzene to cyclohexene is not high. 1 Generally, hydrogenation catalysts are precious metals or their precious metals. The compound is dispersed on the surface of the support. The activity and selectivity of the catalyst are related to factors such as active ingredients, particle size, distribution mode, and the strength of the chemical adsorption force produced by the reactants and products. The commonly used hydrogenation catalysts are: 1. Metal sulfides (metalsulfides), the most common of these catalysts are molybdenum sulfide (MoS2) or tungsten sulfide (WS2), commonly used in crude hydrodesulfurization (HDS) ), Hydrodemetal (HDM), hydrodenitrogenation (HDN), etc. 2. Iron-based catalysts: In the first column of the eighth group of the periodic table, the nickel, the three metals of iron, cobalt, and nickel have strong hydrogenation ability and are most commonly used. Raney Nickel is the most famous. Nickel catalysts have long been used in the selective hydrogenation of edible oils and fats to remove the auto-oxidation of unsaturated bonds. A highly reactive catalyst is still required for the partial hydrogenation of aromatic cigarettes. 3. Precious metal catalysts: including platinum group elements (Pt, Pd, Ph, Ir, Ru, Os) composed of six transition metals in the second and third columns of the eighth group of the periodic table, of which platinum (Pt) and palladium (Pd), ruthenium (Ru), and germanium (Rh) are more commonly used. Although the hydrogenation activity of pt and Pd is stronger than the above-mentioned metal sulfides and iron systems, it is susceptible to sulfur or Nitrogen compounds are gradually inactivated due to the poisoning effect (please read the precautions on the back before filling this page). The size of the bound paper is applicable to the Chinese household standard rate (CNS) Λ4 specification (210X297 male: t) A7 B7 457229 V. Invention Description () Sex. The activity of Pd catalyst is inferior to that of platinum catalyst, but it has better resistance to sulfide than Pt, and its stability is worse than Pt under high temperature hydrogen environment. If Pd or Pt is used for the partial hydrogenation reaction of benzene, the catalyst reactivity is not easy to adjust, and usually the yield of cyclohexene is very low. The partial hydrogenation catalyst of benzene in the present invention is mainly ruthenium, and its compensating ratio is lower than Pt or Pd. To obtain a high cyclohexene yield, it is necessary to avoid excessive hydrogenation to cyclohexane. How to adjust the catalyst hydrogenation capacity to be moderate and maintain a certain catalyst life is the most important issue. Too strong hydrogenation ability will over-hydrogenate benzene to cyclohexane, and too weak hydrogenation ability will make the reaction rate too low, which is not economical. —Generally, the help of modifiers is needed to obtain higher yields. Β Several processes using benzene as the starting material for the partial hydrogenation of aromatic hydrocarbons to produce cyclohexene have been revealed. Herein, for reference: ⑴ Hydrogenation reaction using liquid ammonia as a medium under alkali metal [US Patent Nos. 3274272, 3321539; Japanese patents JP-406864, 406865, 438102]. The liquid ammonia and alkali metals need to be recovered in this method are its disadvantages. ⑵Using a low-carbon alcohol as a solvent, a hydrogenation reaction is performed under a ruthenium catalyst [US Patent No. 3391206]. The selectivity of cyclohexene in this method is low. (3) The hydrogenation reaction is performed with a ruthenium catalyst in a neutral or acidic aqueous solution containing a chloride or sulfate of the periodic table 1a or Ha metal, manganese and zinc [Japanese Patent No. P-5198243]. The selectivity of cyclohexene in this method is low. ⑷ Hydrogenation is carried out with an aqueous carbonate solution containing cobalt, nickel, or copper in a ruthenium catalyst [Japanese Patent; ί-5346939]. The selectivity of cyclohexene in this method is low. ___ 5 (谙 Please read the note on the back ^ before filling in this page),-'° The paper scale printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) Λ4 specification (2) 0 × 297. 457229 Μ Β7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Ⅴ. Description of the invention () ⑸ Hydrogenation reaction using an alkaline aqueous solution containing additives and at least one metal element in Group M of the periodic table as a catalyst [US patent usp_ 3767720]. Although the yield of cyclohexene in this method is high, a relatively large amount of additives and metal ions in the carrier of the alkaline solution 'are easily soluble in the alkaline solution. ⑹An alkaline aqueous solution in which additives such as zinc chloride and titanium chloride are dissolved is added to benzene 'to perform a hydrogenation reaction using ruthenium, germanium or palladium as a catalyst [Netherlands Patent NLP 7205832]. Thorium is impregnated with ruthenium-iron-based metals, such as cobalt, iron, and nickel alloys, on AbCh 'in the presence of water to perform a partial hydrogenation reaction [US Patent Nos. 3793383, 3912787, 4401640]. The maximum yield of cyclohexene in this method is about 18%. ⑻ ⑻ Use ruthenium-iron, cobalt-copper or silver as the active metal, BaSO * as the support, and perform hydrogenation reaction by adding an aqueous solution of sulfate, iron, and zinc [ US patent 455572; European patent EP 170915, 214530]. The preparation of the catalyst of this method is more complicated and its properties are not easy to be uniform. 缺点 Using ultrafine particles of ruthenium, ruthenium-iron or ruthenium-zinc as catalysts, hydrogenation is carried out in the solution of zinc sulfate or argon oxide. Reaction [Japanese Patent JP-62201830, 624544]. This method is difficult to recover and separate the catalyst. (10) Taking ruthenium as an active metal and containing at least one of oxides, hydroxides, or carbon oxides of lanthanide-based rare earth metals such as lanthanum, osmium and osmium as a support, and reducing ruthenium by a hydrogen gas phase reduction method, Hydrogenation is performed in an alkaline aqueous solution containing zinc or aluminum chloride, sulfate, oxide or hydroxide [US Patent USP 4678861]. (11) Use the so-called "chemical mixing" method to mix (please read the notes on the back before filling this page)
C 本紙张尺度適用中國國家標準（CNS ) Λ4现格（210X 297公釐） 457229 A7 經濟部中央標準局I工消t含作社印製 五、發明説明（） 合兩種觸媒前軀物(即溶膠·凝膠法），使釕金屬顆粒(d<:20 A)嵌入擔體(二氧化矽或氧化鋁），於水溶液中進行氫化反 應〔美國專利USP 4495373〕。 發明槪述 因’本發明的一個目的爲提供一種芳香族烴，例如苯 ’部份氫化的方法’其包含芳香族烴於鹼性水溶液下與氫 氣辰應以生成環烷烯，其特徵在於使用週期表第观族金屬 載於鑭及鋅雙氧化物之擔體爲觸媒進行氫化作用，其中鑭 及鋅之莫耳比率爲1:1至1:5，及載於擔體上之金屬含量爲 總觸媒量之1至5重量百分率。 本發明的另一個目的係提供一種製備使用於芳香族烴 ’例如苯’部份氫化的觸媒’其包含以週期表第Vffi族金屬 載於鑭及鋅雙氧化物之擔體，其中鑭及鋅之莫耳比率爲1:1 至1:5 ’及載於擔體上之金屬含量爲總觸媒量之丨至5重量 百分率。 載於鐮及鋅雙氧化物之擔體爲釕。相較於以上之專利 ’本發明之觸媒具有較高之環己烯選擇率及產率。更甚者 ’除了添加少量之鹼水溶液外’該觸媒無須像大部份之專 利須加入其他金屬鹽類，在操作上較爲簡化。 本發明的另一個目的係提供一種製備本發明觸媒之方 法’其包含以碳酸鹽水溶液共沈澱鑭及鋅硝酸鹽水溶液以 得到鑭及鋅莫耳比率爲1:1至1:5之擔體，鍛燒該擔體，含 浸釘使之載於所得擔體並得到觸媒前軀物爲含有釕爲觸媒 (請先閱讀背面之注意事項再填寫本頁} d • 11 J— . 訂 本紙张尺度適用中國國家標導（CNS ) Λ4規格（210X297公釐） 4S7229 經濟部中央標準爲員工消費合作社印製 A7 ___ B7____________ 五、發明説明（） 前軀物之1至5重量百分率，分散於水中，藉由氫硼化鈉 還原以得到經活化觸媒。 共沈澱係進行於混合適當莫耳比率之鑭及鋅硝酸鹽水 溶液，於升高溫度及攪拌之情況下，加入適量碳酸鹽水溶 液產生沉澱，經過濾1水洗及乾燥後，送入鍛燒爐中至少 鍛燒5小時，以確保觸媒擔體之穩定性。 金屬載於擔體可藉由初濕含浸法（incipient wetness impregnation)或濕式含浸法。於初濕含浸法中，定量RuCh .充分溶解於所需初濕體積純水中，所得溶液慢慢滴 入擔體中，同時充分攪拌，由於毛細現象，釕溶液被吸入 擔體孔洞中，而後於室溫下靜置二小時。將所得之泥狀混 合物置於拱箱中於i〇〇°C乾燥過液備用。 於本發明的另一個較佳具體實施例中，初濕含浸法之 釕來源係得自硝酸釕。 於濕式含浸法中，純水1公升與20克擔體混合，攪拌 分散時慢慢將適量l%Ru水溶液倒入後再攪拌2小時。靜 置至暗棕色消失，然後過濾、水洗及乾燥備用（S〇°C ’過夜） 〇 鋸燒及還原條件、觸媒前軀物中所含有之氯離子或其 他雜質可能對觸媒之辰應活性與選擇性產生嚴重影響。除 此之後，觸媒性質可受表面積、微孔徑(Pore size)分佈、金 屬顆粒大小及分佈、活性金屬分散度(metal dispersion)，結 晶性(crystallinity)、擔體組成、觸媒前軀物還原性、金屬擔 體交互作用（metal support interaction，MSI)、氫溢流（hydrogen __§____________ 本紙張尺度適用中國國家操準（CNS ) Λ4泥格（210 X 297公釐） (請先聞讀背面之注意事項再填寫本頁) '裝. 訂 457229 Α7 Β7 娌濟部中央標準局員工消贽合作社印" 五、發明説明（） spill-over)、微量的修飾劑等因素。 本發明觸媒的顆粒大小依鑭及鋅莫耳比率而定，且至 多爲20微米’及平均大小爲2至5微米。表面積亦依鑭及 鋅莫耳比率而定’且約爲1〇_30 m2/g，BET面積（於液態氮， -78K)。釕之顆粒大小可X光繞射測定且約爲 所得之觸媒前物可經還原活化。將含浸烘乾後之觸媒 前軀物秤量’依10克粉體/100毫升純水比率放入三頸瓶 中。於N2氣堤下，將NaBH,分批放入燒瓶內。續攪拌1 小時後過濾、水洗及乾燥(80°C，6小時)儲存備用。因氯化釕 (RuCL·· H2〇)之氯離子，一般認爲對觸媒之活性有影響。當 使用初濕含浸法時，其淸洗步驟須持績至濾液需無法檢出 氯離子濃度0適當之觸媒組成爲1%〜5%wtRu » 本發明之製程條件爲加入水及適量之鹼液，反應溫度 爲150〜250°C，氫氣壓力爲20〜lOOkg/cm2。鹼液加入量爲 維持水溶液濃度0.2〜1M，加入之總水量爲苯體積之0.2〜2 %的範圍之內。 苯轉化率及選擇率之計算公式如下： 轉化率(％) =苯反應消耗之總莫耳數/苯全部供給之總 莫耳數 選擇率=生成之環己烯之莫耳數/苯反應消耗之總 莫耳數 部份氫化程度及環己烯選擇率依觸媒性質、原料性質 及反應條件而定。苯的部份氫化反應產物中，含有未反應 的苯、環己烯、環己烷，其等可以GC/FID將產物分離，並 9 本紙悵尺度適用中國國家標隼（CNS )八4規格（210Χ 297公釐） (請先閲讀背面之注意事項再填寫本頁) Λ衣 丁 ,c 467229 A7 經濟部中央標準局員工消费合作社印试 五、發明説明（） 於適當條件進行定量分析，所使用之分析條件爲： ⑴管柱：管長4.5M，直徑1/8”， _ 10%聚乙二醇苯基醚於80/100網目 Chromorb PAW不銹鋼管柱。 ⑵操作條件：試樣注入量1微升，注射溫度!50°C， 偵測溫度17(TC，烘箱溫度7(TC， 載體氣體N2,管柱壓力1.4巴。 ⑶各成份滯留時間：環己烷6分鐘，環己烯8.9分鐘， 苯18.5分鐘。 ⑷定量校正：於相同GC條件中，各成份於火焰離子偵測 器(FID)之應答訊號(irespones)不同，故須加以校正，以取樣 瓶各秤取等量之苯、環己烯、環己烷充分混合後，於前述 條件下注射至GC，各成份之應答訊號爲苯0,937045，環己 烯 1.013852，環己烷 1.056235。 (5)反應結果計算：由訊華電腦數據處理系統，讀取各成份 GC面積。 苯GC面積X苯應答訊號因子=A 環己烯GC面積X環己烯應答訊號因子=B 環己烯GC面積X環己烷應答訊號因子=C 苯 wt% = [A/(A+B+C)] X 100%=P 環己烯 wt% = [B/(A+B+C)]X100%=Q 環己烷 wt% = [C/(A+B+C)]X100%=R 苯轉化率(Conyersion)=i-P 環己嫌選擇率(Selectivity)=Q/l-P __10___ 本紙張尺度適闲中國國家標準（CNS ) Λ4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 装-- 訂ϊί 457229 Α7 Β7 經濟部中央檩準局員工消贽合作社印製 五、發明説明（） 環己烯產率(Yidd)=Q 實施例 下列實施例用以說明本發明。除非特別指出，擔體成 份之比率係爲莫耳比率。 實施例一 鑭及鋅雙氧化物之製備（鑭：鋅=1:1) 30公克硝酸鑭及18公克硝酸鋅加至500毫升蒸餾水中 ’攪拌混合且增高溫至7〇°C ’並以預先調配之30%硫酸鈉 水溶液，逐滴滴入攪拌中之混合液中’至紅色石蕊試紙由 紅變藍色，此時雙氧化物逐漸結晶沉澱。加料完畢繼續擦 拌一小時並冷卻之，過濾且以蒸餾水洗淨置於珙箱中過夜 烘乾，次將乾燥後之雙氧化物置於鍛燒爐中，於室溫下， 以每分鐘1CTC之速率升溫至500°C，維持5小時鍛燒後約可 得公克雙氧化物。 實施例二 觸媒A之製備（2wt% Ru) 秤取氯化釕0.883公克，溶於13.8毫升之蒸餾水中， 充分攪拌後，逐滴加入實施例一中所製備之18.8公克雙氧 化物中，充分攪拌後靜置兩小時，置於烘箱中於80°C過夜 乾燥。乾燥後之觸媒於200毫升蒸餾水中，以5.5公克氫硼 化鈉分批加入以還原，經水洗及過濾等步驟，於烘箱中 °C乾燥6小時後儲存備用。 實施例三 部份氫化反應之活性與選擇性（鑭：鋅=1:1) 本紙張尺」 44- :尺度適用中國國家標準（CNS ) Λ4規格（2丨Οχ”7公釐） (請先閱讀背面之注意事項再填窝本頁j ，•衣 訂 A7 457229 B7 五、發明説明（） 將氫氧化鈉2.48公克加入100毫升之蒸餾水中，攪拌 溶解後，倒入容量300毫升之高壓反應器中並加入苯75毫 升及觸媒A 2.5公克，於氫氣分壓3J2Mpa及辰應溫度150 t下以半批式法進行氫化反應6結果示於表1。 表1 (請先閲讀背面之注意事項再填寫本頁) 如實施例三所述之步驟，惟觸媒擔體之鑭：鋅莫耳比 爲1:5。結果示於表2。 表2 反應時間 (min') 苯轉化率 (%) 環己烯選擇率 (%) 環己烯產率 (%) 20 21.25 75.76 16.02 80 57.75 55.07 31.80 140 77.02 41.15 31.69 嘗施例四C鑭： 鋅=1:5) 經濟部中央標隼局貝工消资合作让i 反應時間 (min、 苯轉化率 (%) 環己烯選擇率 (Ψ〇) 環己烯產率 (Ψο) 20 21.17 73.90 15.64 80 56.63 56.20 31.82 140 73.38 46.48 34.11 實施例Τί.〔鑭： 鋅=2:1) 如實施例三所述之步驟，惟觸媒擔體之鑭·.鋅莫耳比 爲2:1 °結果不於表3。 —------------- -12 本紙張尺度適用中國國家標皁（CNS ) Λ4規格（210 X297公釐） 457229 A 7 B7 五、發明説明（) 經濟部中央標隼局貝工消费合作社印製 表3 反應時間 苯轉化率 環己烯選擇率 環己烯產率 (min) (%) (%) (Ψ〇) 20 17.60 76.90 13.53 80 49.43 58.69 29.01 140 66.40 46.45 30.84 窨施例六（鑭 :鋅=1:5) 如實施例三所述之步驟 ’惟觸媒擔體之鑭：鋅莫耳比 爲1:5及反應溫度爲133°C 〇 結果示於表4。 表4 反應時間 苯轉化率 環己烯選擇率 環己烯產率 (min') (%) —m (%) 20 6.91 84.27 5.82 80 18.38 80.63 15.19 140 28.51 78.47 22.38 實施例七（鑭 :鋅=1:5) 如實施例. 三所述之步驟 ’惟觸媒擔體之鑭：鋅莫耳比 爲1:5及反應温度爲175°C。 結果示於表5。 表5 反應時間 苯轉化率 環己烯選擇率 環己烯產率 (min、 (%) 20 28.27 71.83 20.31 80 57.72 56.88 32.83 140 69.84 46.68 32.65 13 本紙張尺度適用中國國家榇嗥（|：、奶）/\4現格（210/297公釐} (請先閲讀背面之注意事項再填寫本頁) .1 457229 A7 B7 五、發明説明（） 比較實施例一 如實施例三所述之步驟，惟觸媒擔體僅爲鑭。結果示 於表6。 表6 反應時間 (min) 苯轉化率 (%) 環己烯選擇率 環己烯產率 (Ψο) 20 29.52 29.90 8.83 60 60.11 16.14 9.71 120 99.02 7.36 7,29 比鮫實施例二 如實施例三所述之步驟，惟觸媒擔體僅爲鋅。結果示 於表7。 表7 ----------!装-- (請先間讀背面之注意事項再填寫本頁)C This paper size applies to Chinese National Standards (CNS) Λ4 is present (210X 297 mm) 457229 A7 Central Standards Bureau of the Ministry of Economic Affairs I Industrial Consumers t Printed by Zuozuosha V. Description of invention () Combination of two catalyst precursors (That is, the sol-gel method), ruthenium metal particles (d <: 20 A) are embedded in a support (silicon dioxide or alumina), and a hydrogenation reaction is performed in an aqueous solution [US Patent No. 4495373]. According to the invention, one of the objectives of the present invention is to provide an aromatic hydrocarbon, such as benzene, which is a 'partial hydrogenation method', which comprises an aromatic hydrocarbon and hydrogen in an alkaline aqueous solution to form a cycloalkene, which is characterized by using The lanthanum and zinc double oxide-supported metal of the Group I metal of the periodic table is a catalyst for hydrogenation, in which the molar ratio of lanthanum and zinc is 1: 1 to 1: 5, and the metal content on the support is It is 1 to 5 weight percent of the total catalyst amount. Another object of the present invention is to provide a catalyst for partially hydrogenated aromatic hydrocarbons, such as benzene, which comprises a lanthanum and zinc double oxide supported by a Group Vffi metal of the periodic table, wherein lanthanum and zinc The molar ratio of zinc is 1: 1 to 1: 5 'and the metal content on the support is from 5 to 5 weight percent of the total catalyst amount. The support carried on sickle and zinc double oxide is ruthenium. Compared with the above patent, the catalyst of the present invention has higher selectivity and yield of cyclohexene. What's more, the catalyst does not need to add other metal salts like most patents except for adding a small amount of alkaline aqueous solution, and the operation is simplified. Another object of the present invention is to provide a method for preparing the catalyst of the present invention, which comprises co-precipitating an aqueous solution of lanthanum and zinc nitrate with an aqueous carbonate solution to obtain a support having a lanthanum and zinc molar ratio of 1: 1 to 1: 5. , Burn the support, impregnate the nail to load it on the obtained support and get the catalyst precursor containing ruthenium as the catalyst (please read the precautions on the back before filling this page} d • 11 J—. Zhang scale is applicable to China National Standards (CNS) Λ4 specification (210X297 mm) 4S7229 The central standard of the Ministry of Economic Affairs prints A7 ___ B7____________ for employee consumer cooperatives V. Description of the invention () 1 to 5 weight percent of the precursor, dispersed in water Co-precipitation is performed by mixing an appropriate mol ratio of lanthanum and zinc nitrate aqueous solution, and adding an appropriate amount of carbonate aqueous solution to produce precipitation under the condition of increasing temperature and stirring After filtering, washing, and drying, it is sent to a calcining furnace for at least 5 hours to ensure the stability of the catalyst support. The metal can be carried on the support by the incipient wetness impregnat method. ion) or wet impregnation method. In the initial wet impregnation method, RuCh is quantified. It is fully dissolved in the required initial wet volume of pure water, and the resulting solution is slowly dropped into the support while being fully stirred. Due to the capillary phenomenon, the ruthenium solution It is sucked into the pores of the carrier, and then left to stand at room temperature for two hours. The obtained mud-like mixture is placed in an arch box and dried at 100 ° C for use. Another preferred embodiment of the present invention The source of ruthenium in the primary wet impregnation method is obtained from ruthenium nitrate. In the wet impregnation method, 1 liter of pure water is mixed with 20 grams of the carrier. When stirring and dispersing, slowly pour an appropriate amount of 1% Ru aqueous solution and stir 2 Hours. Allow to stand until the dark brown disappears, then filter, wash and dry (S0 ° C 'overnight). Saw burning and reducing conditions, chloride ions or other impurities contained in the catalyst precursor may affect the catalyst. Chen Ying's activity and selectivity have a serious impact. In addition, the catalyst properties can be affected by surface area, Pore size distribution, metal particle size and distribution, active metal dispersion, crystallinity, crystallinity, Carrier composition, catalyst Forebody reduction, metal support interaction (MSI), hydrogen overflow (hydrogen __§ ____________) This paper size is applicable to China National Standards (CNS) Λ4 mud box (210 X 297 mm) (please Read the precautions on the back before filling in this page) 'Packing. Order 457229 Α7 Β7 Employees of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China eliminate the cooperative seal " V. Invention Description () spill-over), trace modifiers and other factors. The particle size of the catalyst of the present invention depends on the lanthanum and zinc mole ratio, and is at most 20 m 'and the average size is 2 to 5 m. The surface area is also determined by the lanthanum-zinc mole ratio 'and is about 10-30 m2 / g, and the BET area (in liquid nitrogen, -78K). The particle size of ruthenium can be determined by X-ray diffraction and about the obtained catalyst precursor can be reduced and activated. The catalyst precursor body weight after impregnation and drying was weighed into a three-necked bottle according to a ratio of 10 g of powder / 100 ml of pure water. Under a N2 gas bank, NaBH was placed into the flask in batches. Continue to stir for 1 hour, then filter, wash and dry (80 ° C, 6 hours) for storage. Due to the chloride ion of ruthenium chloride (RuCL · · H2O), it is generally considered that it affects the catalyst's activity. When using the initial wet impregnation method, the washing step must be performed until the filtrate cannot detect the chloride ion concentration. The appropriate catalyst composition is 1% ~ 5% wtRu. »The process conditions of the present invention are adding water and an appropriate amount of alkali. Liquid, the reaction temperature is 150 ~ 250 ° C, and the hydrogen pressure is 20 ~ 100kg / cm2. The amount of lye added is 0.2 ~ 1M to maintain the concentration of the aqueous solution, and the total amount of water added is within the range of 0.2 ~ 2% of the volume of benzene. The calculation formula of benzene conversion rate and selectivity is as follows: Conversion rate (%) = total mole number of benzene reaction consumption / total mole number of benzene supply selection rate = mole number of cyclohexene produced / consumption of benzene reaction The total mole number and the degree of hydrogenation and cyclohexene selectivity depend on the nature of the catalyst, the nature of the raw materials, and the reaction conditions. The partially hydrogenated reaction product of benzene contains unreacted benzene, cyclohexene, and cyclohexane, which can be separated by GC / FID. The paper size is applicable to China National Standard (CNS) 8-4 specifications ( 210 × 297 mm) (Please read the notes on the back before filling out this page) Λ Yiding, c 467229 A7 Printing test by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () Quantitative analysis under appropriate conditions, used The analysis conditions are as follows: ⑴Column: 4.5M in length, 1/8 ”in diameter, _ 10% polyethylene glycol phenyl ether in 80/100 mesh Chromorb PAW stainless steel column. ⑵ Operating conditions: 1 micron of sample injection Liters, injection temperature! 50 ° C, detection temperature 17 ° C, oven temperature 7 ° C, carrier gas N2, column pressure 1.4 bar. ⑶ Retention time of each component: 6 minutes of cyclohexane, 8.9 minutes of cyclohexene, Benzene is 18.5 minutes. ⑷ Quantitative calibration: In the same GC condition, the response signals (irespones) of each component in the flame ion detector (FID) are different, so it must be calibrated. Take the same amount of benzene and ring in each sample bottle. After hexene and cyclohexane are mixed well, bet under the above conditions To the GC, the response signals of each component are benzene 0,937045, cyclohexene 1.013852, and cyclohexane 1.056235. (5) Calculation of reaction results: The data area of each component's GC is read by Xunhua computer data processing system. Benzene GC area X Benzene response signal factor = A cyclohexene GC area X cyclohexene response signal factor = B cyclohexene GC area X cyclohexane response signal factor = C benzene wt% = [A / (A + B + C)] X 100% = P cyclohexene wt% = [B / (A + B + C)] X100% = Q cyclohexane wt% = [C / (A + B + C)] X100% = R benzene conversion rate ( Conyersion) = iP Selectivity = Q / lP __10___ This paper is a Chinese standard (CNS) Λ4 size (210X 297 mm) (Please read the precautions on the back before filling this page) -Order: 457229 Α7 Β7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention () Yield of cyclohexene (Yidd) = Q Examples The following examples are used to illustrate the present invention. Unless otherwise specified, The ratio of the carrier components is the Mohr ratio. Example 1 Preparation of lanthanum and zinc double oxide (lanthanum: zinc = 1: 1) 30 grams of lanthanum nitrate and 18 grams of zinc nitrate were added to 500 ml of distilled water and stirred. Combine and increase the temperature to 70 ° C 'and use a 30% sodium sulfate aqueous solution prepared in advance, and drop into the stirring mixture dropwise' until the red litmus paper turns from red to blue, at this time the double oxide gradually crystallizes Precipitation. Continue to scrub for one hour after cooling and cool, filter, wash with distilled water, and place in an oven overnight to dry, and then place the dried double oxide in a calcining furnace at room temperature, every minute The rate of 1CTC is increased to 500 ° C, and about 5 grams of double oxide can be obtained after 5 hours of calcination. Example 2 Preparation of Catalyst A (2wt% Ru) Weigh 0.883 g of ruthenium chloride, dissolve it in 13.8 ml of distilled water, stir it thoroughly, and add it dropwise to the 18.8 g of double oxide prepared in Example 1, Stir well for two hours and place in an oven at 80 ° C overnight to dry. The dried catalyst was added to 200 ml of distilled water in batches of 5.5 g of sodium borohydride for reduction, washed with water and filtered, and dried in an oven at ° C for 6 hours before storage. Example 3 Activity and selectivity of partial hydrogenation reaction (lanthanum: zinc = 1: 1) The paper rule ”44-: The scale is applicable to the Chinese National Standard (CNS) Λ4 specification (2 丨 〇χ” 7 mm) (please first Read the precautions on the back of the page and then fill in this page j. • Bookbinding A7 457229 B7 V. Description of the invention () Add 2.48 grams of sodium hydroxide to 100 ml of distilled water, stir and dissolve, and pour into a high-pressure reactor with a capacity of 300 ml. 75 ml of benzene and 2.5 g of catalyst A were added to the mixture, and the hydrogenation reaction was performed in a semi-batch method at a hydrogen partial pressure of 3J2Mpa and a temperature of 150 ° C. The results are shown in Table 1. Table 1 (Please read the notes on the back first Fill in this page again) The procedure described in Example 3, except that the lanthanum: zinc mole ratio of the catalyst support is 1: 5. The results are shown in Table 2. Table 2 Reaction time (min ') Benzene conversion (% ) Cyclohexene selectivity (%) Cyclohexene yield (%) 20 21.25 75.76 16.02 80 57.75 55.07 31.80 140 77.02 41.15 31.69 Example 4C Lanthanum: Zinc = 1: 5) Shellfish, Central Bureau of Standards, Ministry of Economic Affairs Consumption cooperation let i reaction time (min, benzene conversion (%), cyclohexene selectivity (Ψ〇), cyclohexene yield (Ψο) 20 21.17 73.90 15.64 80 56.63 56.20 31.82 140 73.38 46.48 34.11 Example Τ. [Lanthanum: zinc = 2: 1) The procedure described in the third embodiment, except that the lanthanum of the catalyst support .. Zinc Molar ratio is 2: The results at 1 ° are not in Table 3. —------------- -12 This paper size applies to China National Standard Soap (CNS) Λ4 specification (210 X297 mm) 457229 A 7 B7 V. Invention Note () Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Table 3 Reaction time benzene conversion rate cyclohexene selectivity rate cyclohexene yield (min) (%) (%) (Ψ〇) 20 17.60 76.90 13.53 80 49.43 58.69 29.01 140 66.40 46.45 30.84 窨 Example 6 (lanthanum: zinc = 1: 5) The procedure described in Example 3 except that the lanthanum: zinc mole ratio of the catalyst carrier is 1: 5 and the reaction temperature is 133 ° C 〇 Results are shown in Table 4. Table 4 Reaction time benzene conversion rate cyclohexene selectivity rate cyclohexene yield (min ') (%) -m (%) 20 6.91 84.27 5.82 80 18.38 80.63 15.19 140 28.51 78.47 22.38 Example 7 (lanthanum: zinc = 1: 5) The steps described in Example 3. except that the lanthanum: zinc molar ratio of the catalyst support is 1: 5 and the reaction temperature is 175 ° C. The results are shown in Table 5. Table 5 Reaction time benzene conversion rate cyclohexene selectivity rate cyclohexene yield (min, (%) 20 28.27 71.83 20.31 80 57.72 56.88 32.83 140 69.84 46.68 32.65 13 This paper standard is applicable to Chinese national tincture (| :, milk) / \ 4present (210/297 mm) (please read the notes on the back before filling this page). 1 457229 A7 B7 V. Description of the invention () Comparative Example The steps described in Example 3 are the same, but The catalyst support is only lanthanum. The results are shown in Table 6. Table 6 Reaction time (min) benzene conversion (%) cyclohexene selectivity cyclohexene yield (烯 ο) 20 29.52 29.90 8.83 60 60.11 16.14 9.71 120 99.02 7.36 7,29 Compared with the second embodiment, the steps described in the third embodiment, except that the catalyst carrier is only zinc. The results are shown in Table 7. Table 7 ----------! (Please read the notes on the back before filling in this page)
,1T 經滴部中夾標準局貝工消费合作社印製 反應時間 fmin) 苯轉化率 (%) 環己烯選擇率 (%) 環己烯產率 (%) 20 26.83 25.53 6.85 60 58.76 11.95 7.02 100 79.7 10.95 8.73 14 本紙張尺度適ffl中國®家標隼（CNS ) Λ4規格（210X29?公釐）, 1T Printed reaction time fmin printed by the Ministry of Standards and Standards Shellfish Consumer Cooperative Co., Ltd. Benzene conversion (%) Cyclohexene selectivity (%) Cyclohexene yield (%) 20 26.83 25.53 6.85 60 58.76 11.95 7.02 100 79.7 10.95 8.73 14 This paper is suitable for ffl China® House Standard (CNS) Λ4 size (210X29? Mm)