經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（/ ) 發明詳述： 本發明係有關於除去原油中金屬的方法，特別是具沸 石性載體與鎳、鉬或鈷鉬合金之觸媒，藉接觸而移除油中 之金屬物。 原油中已知含有數百萬分之一的金屬，如鎳、釩、鐵 、鈷等。大體而言，此類金屬成份大都存於殘油中最重的 部份，亦即是殘油中沸點最高的部份。這代表此類金屬成 份濃縮於底部之特稱為常壓或真空殘油中。 金屬化合物的存在對許多後續性常用以在精煉廠轉化 或處理常壓或真空殘油之精煉步驟（例如脫硫、殘油氫化 裂解或殘油FCC等）具有毒性。 含有金屬化合物之重油部份具有攝氏350度K上之常 壓沸點。此重油部份通常含有百萬分之50至500主要為鎳 及釩之金屬。此痕跡量之金屬通常藉由一固定座式觸媒程 序移除，其中殘油在通常為攝氏300至4 50度之高溫以及高 氫氣壓力下（例如20至2Q0巴）KQ.25至4小時分之一（ h- 1 )之空間速度與脫金屬觸媒接觸。當此油料與脫金屬 接觸，油料內所含之金屬將產生反應而累積於觸媒表面。 為了能有效率地處理殘油，將殘油中之金屬化合物移 除是非常重要的。傳統性之脫金屬觸媒乃以礬土上附鎳Μ 及鉬或鈷鉬合金。至今發現當使用沸石性載體之脫金屬觸 媒，則在原油脫金屬程序中對金靥的移除具有高效率。 -3- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ;-- - ' i < n n In m «n n - 1 n n n .»!1 n m τ I 一0, (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（i ) 據此本發明提出一種利用原油Μ及氫氣與至少含一種 屬於元素週期表中第八族或第六族之金屬或化合物為活性 物質並附於載體上之觸媒接觸之原油脫金屬程序，其中觸 媒之載體包含二氧化矽與三氧化二鋁，比值至少為5且單 位细胞大小為介於24.30及24.60埃間之沸石。建議使用於 本程序中之金屬為鎳、鉬、鈷鉬合金或其混合物。 更進一步建議使用之觸媒載體材值為包含百分之30至 70重量百分率之上述沸石材料Μ及百分之30至70重量百分 率之攀土。 觸媒可由任何傳統性製作法製作，其中包括Μ —種或 多種活性金屬之鹽類水溶液使鍛燒過之載體呈飽和，再使 此浸透之載體變乾*最後鍛燒此載體Μ獲得活性觸媒。 在本發明之操作程序中，觸媒係Μ固定座之型式安置 於一脫金屬反應器中，而原油與氫則通常Μ 2 0 0 - 2 Q (3 Q Ν 1 / 1 之比例通過此觸媒座。在脫金屬過程中，觸媒座則保持在 攝氏350度至450度與12D至170大氫壓之高溫高壓下。 原油在通過觸媒座後，其金屬含量將下降至數百萬分 之一。 例一： Κ70 克之乾燥 CBV 5 0 0 HY Zeolite (P.Q· Zeolites 出品），其中單位细胞大小為2 4 . 5 3埃同時二氧化矽與三 氧化二鋁之比例為5.4，混Μ 29克之Cat apal (Vista -4- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---一------—裝------IT------^ (請先聞讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（3 )Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (/) Detailed description of the invention: The present invention relates to a method for removing metals from crude oil, especially a zeolite carrier and nickel, molybdenum or cobalt-molybdenum alloy. A catalyst that removes metal objects from the oil by contact. Crude oil is known to contain millions of metals, such as nickel, vanadium, iron, and cobalt. Generally speaking, most of these metals are in the heaviest part of the residual oil, which is the part with the highest boiling point in the residual oil. This means that such metal components are concentrated in the bottom, which is called atmospheric or vacuum residual oil. The presence of metal compounds is toxic to many subsequent refining steps (such as desulfurization, residual hydrocracking, or residual FCC, etc.) commonly used in refineries to transform or process atmospheric or vacuum residual oil. The heavy oil portion containing metal compounds has an atmospheric boiling point at 350 ° C. This heavy oil portion usually contains 50 to 500 parts per million of metals mainly nickel and vanadium. This trace amount of metal is usually removed by a fixed seat catalyst process, where the residual oil is at a high temperature of usually 300 to 450 degrees Celsius and high hydrogen pressure (for example, 20 to 2Q0 bar) KQ. 25 to 4 hours One-half (h-1) space velocity is in contact with the demetallic catalyst. When this oil comes into contact with demetal, the metals contained in the oil will react and accumulate on the catalyst surface. In order to efficiently treat the residual oil, it is very important to remove the metal compounds in the residual oil. Traditional demetalization catalysts are nickel alumina and molybdenum or cobalt molybdenum alloys attached to alumina. So far, it has been found that when a zeolite-based demetalization catalyst is used, the removal of gold moth has a high efficiency in a crude metal demetalization process. -3- This paper size applies to China National Standard (CNS) A4 (210X297 mm);--'i < nn In m «nn-1 nnn.»! 1 nm τ I a 0, (Please read first Note on the back, please fill out this page again) Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (i) Based on this, the present invention proposes a method that uses crude oil M and hydrogen and contains at least one of the eighth in the periodic table. Group 6 or Group 6 metals or compounds are active materials and are attached to the carrier in contact with the catalyst for the demetallization of crude oil, wherein the carrier of the catalyst contains silicon dioxide and aluminum oxide with a ratio of at least 5 and a unit cell size It is a zeolite between 24.30 and 24.60 angstroms. The metals recommended for use in this procedure are nickel, molybdenum, cobalt-molybdenum alloys, or mixtures thereof. It is further suggested that the value of the catalyst carrier material to be used includes 30 to 70% by weight of the above zeolite material M and 30 to 70% by weight of climbing soil. The catalyst can be made by any traditional manufacturing method, including M—a salt solution of one or more active metals to saturate the calcined carrier, then dry the soaked carrier * and finally calcining the carrier M to obtain active catalyst Media. In the operating procedure of the present invention, the type of the catalyst M fixed seat is placed in a demetallization reactor, and crude oil and hydrogen are usually passed through the M 2 0 0-2 Q (3 Q Ν 1/1 ratio). Catalyst holder. During the demetalization process, the catalyst holder is maintained at a high temperature and pressure of 350 degrees Celsius to 450 degrees Celsius and 12D to 170 hydrogen pressure. After crude oil passes through the catalyst holder, its metal content will drop to millions. Example 1: K70 grams of dry CBV 5 0 0 HY Zeolite (produced by PQ · Zeolites), where the unit cell size is 2 4. 5 3 angstroms and the ratio of silicon dioxide to alumina is 5.4, mixed Μ 29 grams of Cat apal (Vista -4- This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm)) ------------------------------------------- -^ (Please read the notes on the back before filling out this page) A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (3)
Corporation出品）與18克百分之65之硝酸W及78克水而成 之凝膠以製作觸媒座。在一Z型揉合器中將上述成份與11 克之Catapal充份混合直至形成麵糰狀物為止。再將此麵 糰狀物擠壓通過一三十二分之一英吋之擠壓機。宪成擠壓 程序後，將此擠出物在室溫下乾燥16小時。然後在實驗室 爐中將乾燥後之擠出物K攝氏5 5 0度鍛燒兩小時。 將此鍛燒過之載體Μ大量填充溶液施Μ毛细浸漬。此 浸漬疲包含18.3克之六水合亞硝酸鈷以及15克之二鉬酸銨 ，再以蒸餾水加至82毫升。在完成浸漬程序後，再將此觸 媒在室溫下乾燥16小時。最後將此浸漬且乾燥後之觸媒在 攝氏5QQ度下锻燒2小時。Μ上述程序製作之觸媒稱作觸媒 Α ° 例二： Μ類似例一中之程序製作觸媒，其中觸媒載體係以3 0 克之乾煉 HY Zeolite CBV 500 混 Κ62 克之 Versal 300 礬土 Μ及1 2 6克之礬土膠而成。再K例一中所述相同條件下之 乾燥、鍛燒、浸漬Μ及分解程序處理觸媒載體。Μ此法所 .製作之觸媒稱作觸媒Β。 例三： Μ例二中所逑程序製作觸媒，其中原本使用之CBV500 沸石成份則Μ單位细胞大小為2 4 . 3 4埃且二氧化矽與三氧 本紙張尺度適用令國國家標準（CNS ) Α4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) - ί I m *1Ti m I— · 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（+ ) 化二鋁之比為5 . 4之CBV 5 0 0 ( P . Q · 2eo 1 i tes出品），以 此法製作之觸媒稱作觸媒C。 例四： 使用市售三氣化二鋁為基礎之觸媒為對照組Μ評量例 一至三中所製作之觸媒。這些觸媒為Haldor Topsoe A/S 公司出品，其商品名稱為TK-711/TK-751M及TK-771。 上述諸觸媒移除殘油中金屬之能力乃於一固定座式中 間工廠從事測試。測試中採用中東原油之殘油6測試油料 之諸特性詳見表一。 表 一 油料性質 比重 0.9513 硫，重量百分率 2.964 氮，百萬分之 1850 鎳與釩，百萬分之 38 CCR ，重量百分率 -6- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） ----------.裝-------訂------鉍 (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（$ ) 瀝青，重量百分率 2.0 碳，重量百分率 11.60 氫，重量百分率 84.8 GC 蒸餾 IBP至攝氐190度，重量百分率 2.1 IBP至攝氏190度，重量百分率 7,3 IBP至攝氏19Q度，重量百分率 2 7.6 IBP至攝氐19Q度，重量百分率 60.6 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 測試所使用的條件列於表二中。由表二可清楚看出測 試乃於攝氐3 8 5度至4 Q 5度不同溫度下完成。為使觸媒達到 穩定活性位準，每一測試溫度位準乃維持一個星期之久。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7 B7 五、發明説明（6 ) 程序條件 表 LHS V 0 . 2 6小時分之一 氫 油比 50 0 壓 力 150大氣壓 溫 度 攝氐 385/400/405/385度 為了控制本發明中使用觸媒上之金屬沈積量*例一至 三中所製作之觸媒乃於一固定座上與商品化之脫金屬媒所 形成之小保護層實施測試。測試中所用觸媒之佈置狀況概 述於表三。 IJ,裝 訂 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 表 三 觸媒座佈置狀況 1) 體積百分 負載物一 負載物二 負載物三 負載物四 本紙張尺度適用中國國家標隼（CNS ) Α4規格（210Χ 297公釐） A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（7 ) 10 TK-711 1/32”C 2 5 TK-7 1 1 1/32 ”C 60 觸媒A 觸媒B 觸媒C 對照用 Cat .TK-771 1) 總負載物中所佔之體積百分率。 圖一至圖三顯示觸媒負載物一至三與傳統性K三氧化 二鋁為基底者之觸媒活性比較。 圖一至三為Arrhenius圖，其中顯示.脫金屬之一·次速 率常數。而此一次速率常數仍係依據下列方程式（1)計算 之。(Produced by Corporation) and 18 g of 65% nitric acid and 78 g of water to make a catalyst seat. The ingredients were thoroughly mixed with 11 g of Catapal in a Z-kneader until a dough was formed. This dough was then extruded through a 132 1/2 inch extruder. After an extrusion procedure, the extrudate was dried at room temperature for 16 hours. The dried extrudate K was then calcined in a laboratory furnace at 50 ° C for two hours. This calcined support M was filled with a large amount of a solution by capillary immersion. The impregnation solution contained 18.3 g of cobalt nitrite hexahydrate and 15 g of ammonium dimolybdate, and was then added to 82 ml with distilled water. After the impregnation procedure was completed, the catalyst was dried at room temperature for another 16 hours. The impregnated and dried catalyst was calcined at 5QC for 2 hours. The catalyst produced by the above procedure is called catalyst A ° Example 2: The catalyst produced by the procedure similar to that in Example 1, where the catalyst carrier is 30 grams of dried HY Zeolite CBV 500 mixed with 62 grams of Versal 300 alumina. And 1 2 6 grams of alumina glue. The catalyst carrier was treated with the drying, calcination, impregnation and decomposition procedures under the same conditions as described in Example 1. The catalyst produced by this method is called Catalyst B. Example 3: The catalyst was prepared by the procedure described in Example 2. In the original CBV500 zeolite component, the unit cell size was 2 4. 3 4 angstroms and the size of the silicon dioxide and trioxide paper was adapted to national standards (CNS ) Α4 specification (210X297 mm) (Please read the notes on the back before filling out this page)-ί I m * 1Ti m I— · Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (+) CBV 5 0 0 (manufactured by P. Q · 2eo 1 ites) at a ratio of 5.4 is called catalyst C. Example 4: A commercially available trialuminous aluminum-based catalyst was used as the control group M to evaluate the catalyst produced in Examples 1 to 3. These catalysts are produced by Haldor Topsoe A / S, and their trade names are TK-711 / TK-751M and TK-771. The ability of these catalysts to remove metals from residual oil was tested in a fixed-type intermediate plant. See Table 1 for the characteristics of the test oil used in the test. Table 1. Specific gravity of oil: 0.9513 sulfur, weight percentage 2.964 nitrogen, 1850 ppm nickel and vanadium, 38 CCR, weight percentage -6- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) ) ----------. Packing ------- Order ------ Bismuth (Please read the notes on the back before filling this page) A7 B7 V. Description of the invention ($) Asphalt, 2.0% by weight carbon, 11.60% by weight hydrogen, 84.8% by weight GC Distilled IBP to 190 ° C, 2.1% IBP to 190 ° C, 7.3% IBP to 19Q ° C, 2 7.6 IBP to Photographed 19Q degrees, weight percentage 60.6 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The conditions used in the tests are listed in Table 2. It can be clearly seen from Table 2 that the tests were performed at different temperatures ranging from 38 ° to 4Q °. In order for the catalyst to reach a stable level of activity, each test temperature level is maintained for a week. This paper scale applies Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of invention (6) Procedure condition table LHS V 0.2. Hydrogen-oil ratio 1 / 6-hour ratio 50 0 pressure 150 atmosphere pressure temperature 385/400/405/385 degrees In order to control the amount of metal deposited on the catalyst used in the present invention * The catalysts produced in Examples 1 to 3 are small protective layers formed on a fixed base and commercialized demetallic media Implement the test. The layout of the catalysts used in the test is summarized in Table 3. IJ, binding (please read the precautions on the back before filling this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs of the Consumer Cooperatives Co., Ltd. 3 The layout of the catalyst seat 1) Volume percent load 1 load 2 load 3 load 4 This paper size applies to China National Standards (CNS) A4 specifications (210 × 297 mm) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (7) 10 TK-711 1/32 ”C 2 5 TK -7 1 1 1/32 ”C 60 Catalyst A Catalyst B Catalyst C Control Cat .TK-771 1) Volume percentage of total load. Figures 1 to 3 show the catalytic activity comparisons of catalyst loadings 1 to 3 and traditional K2O3 based substrates. Figures 1 to 3 are Arrhenius diagrams showing one of the demetallization rate constants. The primary rate constant is still calculated according to the following equation (1).
Kl=LHSV*ln(MeF/MeP) (1) 其中： K1 :脫金屬一次速率常數 LHSV :空間速度，為油料流速（毫升每小時）與觸媒體 積（毫升）之比 M e F , M e P :進料與成品之金屬含量，K百萬分之一為單位 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I IT I- In I - n I - n - I I - T - In tn - I I 永 、-口 泠 (請先閲讀背面之注意事項再填寫本頁) 394789 A7 __B7五、發明説明（/ ) 三能。可 至之 4 良 一 屬之改 圖金分之 。 脫百力 示良至能 表改20屬 線顯之金 實明分脫 Μ 媒百此 現觸為，。 表之度下物 之用 良件化 媒.使改條氫 觸明此試碳 性發，測屬 統本較及金 傳示比料脫 中顯媒油之 三 時觸試全 至同知測完 1 料已之當 圖資與定相 之。即致 中力在獲 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公嫠）Kl = LHSV * ln (MeF / MeP) (1) where: K1: primary metal removal rate constant LHSV: space velocity, which is the ratio of oil flow rate (ml per hour) to contact medium volume (ml) M e F, M e P: Metal content of incoming and finished products, K parts per million. Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) I IT I- In I-n I-n-II-T -In tn-II Yong,-Kou Ling (Please read the notes on the back before filling this page) 394789 A7 __B7 V. Description of the invention (/) Sanneng. It can be changed to 4% of the total. Debaili showed good to be able to change the 20 belong to the line of the display of the line, the real separation of Μ media is now in touch. Use a good piece of media to make the material below the table. Make the modified hydrogen test the carbon properties of the test. The test belongs to the three times when the test is complete. It is expected that the map materials and phasing will be used. Immediately obtained by Zhongli (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) Α4 size (210 × 297 cm)