TW385261B

TW385261B - Method of improving catalyst activity, and use of improved catalysts in ammoxidation

Info

Publication number: TW385261B
Application number: TW083108509A
Authority: TW
Inventors: Fernando A P Cavalcanti; Noel L Bremer; James F Brazdil; Linda C Brazdil
Original assignee: Bp America
Priority date: 1993-08-26
Filing date: 1994-09-15
Publication date: 2000-03-21

Abstract

Disclosed is a process comprising the heat treatment of certain V and Sb-containing catalysts at a lower temperature than the previous calcination temperature of the base catalyst to improve catalytic performance; the catalysts resulting from such process; and certain oxidation and ammoxidation reactions in the presence of such a catalyst.

Description

經濟部智慧財產局員工消費合作社印製 A7 _^_B7 ___ 五、發明說明（丨）本發明一方面內容係關於一種製備改良觸媒的方法， κ及所製備的觸媒。本發明的另一方面内容係關於石蠟糸，烯烴和芳香系化合物的氧化和氨氧化反應。含氧化物形式的釩和銻的觸媒通常含錫或鈦，或同時含兩者，其係為金屬氧化物觸媒的一部份，該觸媒一般在用於催化石蠘，烯烴和各種芳香糸的氨氧化反應之前先被煅燒；此煅燒溫度高於7 5 0 °C，並活性組成物Μ製備有效的氨氧化反應觸媒。目前已經發現此觸媒甚至可被進一步活化以提高人料轉化活性Κ及轉化成腈（n i t r i 1 e )的選擇率，其係藉著熱處理先前在高於7 5 0 C被煅燒而活化的觸媒，其中熱處理係在至少低於最高煅燒溫度5 0 t：的有效溫度進行的。在本發明一廣泛的内容方面，吾人發現對用至少5 0 0 °C及至少低於煅燒溫度5 Ot：的溫度，對在高於7 5 0°C 的溫度煅燒的觸媒進行熱處理，使人料如丙烷或丙烯轉化成丙烯腈的活性可獲得改善。本發明一較佳的製備活性更高的觸媒的方法中，在高於7 5 ◦ 的溫度煅燒，然後在較低的溫度進行熱處理的觸媒，與據信為些許微量（一般小於1 %組成物）的含氧化物形式的釩和銻有毒化合物所用溶劑的液體接觸，所有 "溶劑"與觸媒分離。有關本發明的這方面内容，進行7 5 0 °C Μ上煅燒之後可使用有各種"溶劑"來處理氧化物形式的此類釩和銻本紙張尺度適用中國國家標準（CNS)A4規格αίο X 297公釐） (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _ ^ _ B7 ___ V. Description of the Invention (丨) One aspect of the present invention relates to a method for preparing an improved catalyst, κ, and the prepared catalyst. Another aspect of the present invention relates to the oxidation and ammoxidation reactions of paraffin, olefins and aromatic compounds. Catalysts containing vanadium and antimony in the form of oxides usually contain tin or titanium, or both, which are part of metal oxide catalysts. The catalysts are generally used to catalyze ballast, olefins and various Aromatic hydrazone is calcined before the ammonia oxidation reaction; the calcination temperature is higher than 750 ° C, and the active composition M prepares an effective ammonia oxidation reaction catalyst. It has been found that this catalyst can even be further activated to improve the selectivity of human conversion activity K and conversion to nitrile (nitri 1 e). It is a catalyst that was previously activated by calcination at a temperature higher than 7 5 0 C by heat treatment. Medium, wherein the heat treatment is performed at an effective temperature of at least 50 t: below the maximum calcination temperature. In a broad aspect of the present invention, we have found that the catalyst calcined at a temperature higher than 750 ° C is heat-treated at a temperature of at least 500 ° C and at least 5 Ot: The conversion of human feeds such as propane or propylene to acrylonitrile can be improved. In a preferred method for preparing a catalyst with higher activity according to the present invention, the catalyst calcined at a temperature higher than 7 5 ◦ and then heat-treated at a lower temperature is believed to be a trace amount (generally less than 1%). The composition) contains liquids in the form of oxides of vanadium and antimony toxic compounds in liquid contact, and all " solvents " are separated from the catalyst. Regarding this aspect of the present invention, after calcining at 750 ° C, various " solvents " can be used to treat such vanadium and antimony in the form of oxides. This paper is in accordance with China National Standard (CNS) A4 specifications αίο X 297 mm) (Please read the notes on the back before filling in this page)

A7 B7 五、發明說明（少）觸媒。這些包括水，酸或鹼水溶液’洌如隣酸，硫酸和乙酸，K及氨和氫氧化納溶液；美國專利第5 ，094，9 8 9號的羥基化合物；環己醇；環戊醇；單羥基，含1 一 8個碳原子的非環烴；二羥基，含2 ~ 4個碳原子的非環烴。改善的方法所用的觸媒包括下式所示的元素和相對數量：A7 B7 5. Description of invention (less) Catalyst. These include water, acid or alkaline aqueous solutions such as o-acid, sulfuric acid and acetic acid, K and ammonia and sodium hydroxide solutions; hydroxy compounds of US Patent No. 5,094, 898; cyclohexanol; cyclopentanol; Monohydroxy, acyclic hydrocarbon containing 1 to 8 carbon atoms; dihydroxy, acyclic hydrocarbon containing 2 to 4 carbon atoms. The catalyst used in the improved method includes the elements and relative quantities shown in the following formula:

VvSbmAaDdOx 其中若有A時，代表錫和/或鈦；若有D時，代表一或多個鋰，鎂，納，鈣，锶，鋇，鈷，鐵，鉻，鎵，鎳，鋅，緒，鈮，皓’鉬，鎢，銅，締，組’硒，鉍，鈽，絪，砷，硼，鋁和錳； Μ及，其中所有該式元素除了氧Μ外均為陽離子，且 ν為1 ， m 為 0 ， 5 - 1 〇， a為多達1 〇， d為多達1 〇， X由陽離子氧化狀態決定。本發明一更特殊的内容是本方法所用觸媒適合以下關係：v+m+a>〇 . 5d 改善觸媒的方法大部份適合此類前述觸媒，其中a g v + m 0 在上述化學式當中’ 〃若有時"一詞意味著可能沒有 -4- 本紙張尺度適用中國國家標準（CNS)A‘l規格（2.10 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 言· — 1111 — 1彩經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（+ ) A，也可能沒有D。因此，觸媒可以主要只含釩和綈。本發明方法相對低溫熱處理步驟之前之高於7 5 0 t：的觸媒最高煅燒溫度可高到1 2 0 0 °C，但是通常超過 7 5 0°C，並高達10 5 0°C，大部份高達950°C。本發明觸媒可在反應區内對石躐，烯烴和芳香糸化合物進行氧化和氨氧化作用。特別的是，本發明的這方面内容特別有用的反應包括丙烷與氨和氧進行氨氧反應而形成丙烯膳，丙烯與氨和氧進行氨氧反應而形成丙烯腈，甲基 ttfc啶與氧和氨的氨氧化反應形成相對應的氰吡啶，間二甲基與氧和氨的氨氧化反應形成異肽腈。 K下特定的實例旨在說明而不應視為任何的限制。觸媒實例1 27 · 42克的V2 Os粉末添加到盛有1 00毫升的3 0 %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。 V 2 0 5粉末反應完畢之後，加人6 1 · 2 2克的三氧化二銻和2 ‘ 4 0克的熔融二氧化鈦（D e g u s s a P - 2 5 )粉末，蓋上表玻璃，攪拌並加熱混合物約3小時。將8 9 · 5 2 克的1 0 · 1 %二氧化錫溶膠（N a 1 c 〇 C h e in i c a 1 C 〇 .)加入上述分散液。混合物在未加蓋燒杯中攪拌並加熱，以蒸發水份，使體積減為3 0 0毫升，然後在1 2 0 °C的烘箱中乾燥。之後，在6 5 0 °C煅燒8小時，冷卻，壓碎，篩選成 2 0 — 3 5 m e s h 。一部份觸媒在8 1 0 °C煅燒3 小時。然後與異丁醇接觸，每克觸媒有6 . 2 5毫升的異 ~ 5 ~ 本紙張尺度適用中國國家標準（CNS)A.丨規格（2】0 X 297公釐) --------------___ (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（心）丁醇，並將觸媒置於粗玻璃（frit)漏斗中，將異丁酵倒人觸媒*在異丁醇中攪拌觸媒，使觸媒在漏斗底部分散均.句，然後在沒有抽氣情況下使異丁醇通過漏斗，以上過程共進行3次。在最後一次異丁醇通過漏斗後，觸媒在1 20 Ό的烘箱中被加熱，Μ除去觸媒上殘留的異丁醇，然後依本發明所述5 0 0 °C的烘箱中加熱觸媒3小時。煅燒之後的觸媒然後與異丁酵接觸，每克觸媒有 6 * 2 5毫升的異丁醇，並將觸媒置於粗玻璃（frit)漏斗中，將異丁酵倒人觸媒，在異丁醇中撹拌觸媒，使觸媒在漏斗底部分散均勻，然後在沒有油氣情況下使異丁醇通過漏斗，K上過程共進行2次_。在最後一次異丁酵通過漏斗後，觸媒在1 2 ο υ的烘箱中被加熱，κ除去觸媒上殘留的異丁酵。用來氨氧化丙烷的觸媒係外徑3 / 8吋並配餚預熱腳的金屬固定床反懕器，被浸清於溫控熔融鹽浴中，將4 · 0 克觸媒置於反應器中，所有氨氧化作用進行的结果列於表 1和2，如入料比例和溫度。觸媒實例2 ^ 2 7 · 4 2克的V 2 0 s粉末添加到盛有1 0 0毫升的3 0 %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。 V 2 0 s粉末反應完舉之後，加入6 1 . 2 2克的三氧化二銻和2 . 4 0克的熔融二氧化§太（D e g u s s a P - 2 5 )粉末，蓋上表玻璃，攪拌並加熱混合物約3小時。將8 9 . 5 2 本紙張尺度適用中國國家標準（CN‘S)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作杜印製 — — — — — — — — — — — — — — — — — — — — — — — — — — ——II 九SJ·11111!11 — — — — — — — — — — — — — — — — — — — — — — — 五、發明說明（< ) 經濟部智慧財產局員工消費合作社印製克的 1 0 * 1 % 二氧化錫上述分散疲 0 混合物在未 ί 使體積減為 3 0 0 毫升 0 之後在 5 0 V 煅燒 2 0 3 5 m e S h ύ 一 0 然後與異丁酵接觸 t 每 > 並將觸媒置於粗玻璃 (f I 在異丁酵中 m 拌觸媒，後在沒有抽氣情況下使異 3 次 0 在 er 取後 —> 次 .異丁醇烘箱中被加熱 Μ 除去觸明所述 6 5 0 °c 的烘箱中煅燒之後的觸媒妖八、\ 後 6 • 2 5 毫升的異丁醇 9 中 9 將異丁醇倒入觸媒 9 漏斗底部分散均匀 9 然後漏斗以上過程共進行 2 時 9 觸媒在 1 2 0 V 的烘的異丁醇 0 用來氨氧化丙烷的觸的金屬固定床反應器 i 被克觸媒置於反 um 懕器中 0 觸媒實例 8 Λ7 137 溶膠（Nalco Chemical Co.)加入加蓋下攪拌並加熱，以蒸發水份，然後在1 2 0 °C的烘箱中乾燥 8小時，冷卻，壓碎，篩選成部份觸媒在8 1 0 °C煅燒3小時克觸媒有6 · 2 5毫升的異丁醇 r i t)漏斗中，將異丁醇倒入觸媒使觸媒在漏斗底部分散均勻，然丁醇通過漏斗，K上過程共進行通過漏斗時，觸媒在1 2 0 °C的媒上殘留的異丁醇，然後依本發加熱觸媒3小時。與異丁醇接觸，每克觸媒有並將觸媒置於粗玻璃（frit)漏斗在異丁醇中攬拌觸媒，使觸媒在在沒有抽氣情況下使異丁醇通過次。在最後一次異丁醇通過漏斗箱中被加熱，Μ除去觸媒上殘留媒係外徑3 / 8时並配備預熱腳浸清於溫控熔融鹽浴中，將4 . 0 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） (請先閱讀背面之注意事項再填寫本頁) — II — — — — — — U — — — — — — — — — — — — ' I ί I I I I I LSJt I I ϊ I I I I I ^01^1 I n — — — — — — — — — — — — · Λ7 B7 五、發明說明（u) (請先閲讀背面之注意事項再填寫本頁) 2 7 * 4 2克的V 2 0 s粉末添加到盛有1 〇〇毫升的3 0 96雙氧水溶液（於9 〇 0毫升水）的2升燒杯中。 V 2 0 s粉末反應完畢之後，加人6 1 ♦ 2 2克的三氧化二銻和2 · 4 0克的熔融二氧化鈦（Degussa P-25)粉末’ 蓋上表玻璃，撹拌並加熱混合物約3小時。將8 9 · 5 2 克的1 0 · 1%二氧化錫溶膠（N a Uo Chemical Co.)加人上述分散液。混合物在未加蓋下攪拌並加熱，以蒸發水份，使體積減為3 0 0毫升，然後在1 2 0 ”的烘箱中乾燥。之後，在6 5 0 °C煅燒8小時，冷卻，壓碎，篩選成 2 0 — 3 5 m e s h。一部份觸媒在8 1 0 °C煅燒3小時。然後與異丁醇接觸，每克觸媒有6 > 2 5毫升的異丁醇，並將觸媒置於粗玻璃（frit.)漏斗中，將異丁醇倒入觸媒，在異丁醇中攪拌觸媒，使觸媒在漏斗底部分散均勻，然後在沒有抽氣情況下使異丁醇通過漏斗，Μ上過程共進行 3次。在最後一次異丁醇通過漏斗時，觸媒在1 2 〇〇的烘箱中被加熱，以除去觸媒上殘留的異丁醇，然後依本發明所述6 5 0 °C的珙箱中加熱觸媒3小時。經濟部智慧財產局員工消費合作杜印製煅燒之後的觸媒然後與異丁醇接觸，每克觸媒有 6 ‘ 2 5毫升的異丁酵，並將觸媒置於粗玻璃（f r i t)漏斗中，將異丁酵倒入觸媒，在異丁醇中攪拌觸媒，使觸媒在漏斗底部分散均勻，然後在沒有油氣情況下使異丁醇通過漏斗，K上過程共進行2次。在最後一次異丁醇通過漏斗時，觸媒在1 2 0 °C的烘箱中被加熱，以除去觸媒上殘留本紙張尺度適用中國國家標準（CNS)Al規格（2]0 X 297公釐） Α7 Β7 五、發明說明（y) 的異丁醇。用來氨氧化丙烷的觸媒係外徑3 / 8吋並配備預熱腳的金屬固定床反應器，被浸清於溫控熔融鹽浴中，將4 . 5 克觸媒置於反應器中。VvSbmAaDdOx where A represents tin and / or titanium; if D, represents one or more of lithium, magnesium, sodium, calcium, strontium, barium, cobalt, iron, chromium, gallium, nickel, zinc, lead, Niobium, Hao'molybdenum, tungsten, copper, association, group'selenium, bismuth, scandium, thallium, arsenic, boron, aluminum, and manganese; , M is 0, 5-10, a is up to 10, d is up to 10, and X is determined by the cation oxidation state. A more special content of the present invention is that the catalyst used in the method is suitable for the following relationship: v + m + a> 0.5d. Most of the methods for improving the catalyst are suitable for such catalysts, where agv + m 0 is in the above chemical formula. '〃If sometimes " means there may not be -4- this paper size applies Chinese National Standard (CNS) A'l specification (2.10 X 297 mm) (Please read the notes on the back before filling this page) Words — 1111 — 1 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The description of the invention (+) A, there may be no D. Therefore, the catalyst can mainly contain only vanadium and rhenium. Before the method of the relatively low temperature heat treatment step of the method of the present invention, the maximum calcination temperature of the catalyst above 750 ° C can be as high as 120 ° C, but usually exceeds 750 ° C and as high as 105 ° C. Some are up to 950 ° C. The catalyst of the present invention can carry out the oxidation and ammoxidation of ballast, olefins and aromatic thorium compounds in the reaction zone. In particular, reactions that are particularly useful in this aspect of the invention include the reaction of propane with ammonia and oxygen to form propylene, the reaction of propylene with ammonia and oxygen to form acrylonitrile, and the methyl ttfcidine with oxygen and The ammoxidation of ammonia forms the corresponding cyanopyridine, and the ammoxidation of m-dimethyl with oxygen and ammonia forms the isopeptide nitrile. The specific examples under K are intended to illustrate and should not be viewed as limiting. Catalyst Example 1 27. 42 g of V2 Os powder was added to a 2 liter beaker containing 100 ml of a 30% aqueous solution of hydrogen peroxide (in 900 ml of water). After the reaction of the V 2 0 5 powder was completed, add 6 1.2 g of antimony trioxide and 2 ′ 40 g of fused titanium dioxide (D egussa P-2 5) powder, cover the surface glass, stir and heat the mixture. About 3 hours. 89.52 g of a 10.1% tin dioxide sol (N a 1 c o C h e in i c a 1 C 0.) Was added to the above dispersion. The mixture was stirred and heated in an uncovered beaker to evaporate the water to reduce the volume to 300 ml, and then dried in an oven at 120 ° C. After that, it was calcined at 650 ° C for 8 hours, cooled, crushed, and sieved to 20 to 3 5 m e s h. A part of the catalyst was calcined at 8 10 ° C for 3 hours. Then it comes into contact with isobutanol. Each gram of catalyst has 6.25 milliliters of iso ~ 5 ~ This paper size is applicable to China National Standard (CNS) A. 丨 Specifications (2) 0 X 297 mm) ----- ---------___ (Please read the notes on the back before filling this page) A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (Heart) Butanol and catalyst In a coarse glass (frit) funnel, stir the catalyst in isobutanol * and stir the catalyst in isobutanol to disperse the catalyst evenly at the bottom of the funnel. Then pass the isobutanol through without suction. Funnel, the above process was performed a total of 3 times. After the last time isobutanol passed through the funnel, the catalyst was heated in an oven at 120 ° F. The residual isobutanol on the catalyst was removed, and then the catalyst was heated in the oven at 500 ° C according to the present invention. 3 hours. The calcined catalyst is then brought into contact with isobutyrate. Each gram of catalyst has 6 * 2 5 ml of isobutanol, and the catalyst is placed in a coarse glass (frit) funnel. Stir the catalyst in isobutanol to disperse the catalyst evenly at the bottom of the funnel, and then pass isobutanol through the funnel without oil and gas. The process on K is performed 2 times. After the last time the isobutyrate passed through the funnel, the catalyst was heated in an oven of 1 2 ο υ to remove the residual isobutyrate on the catalyst. The catalyst used for the ammoxidation of propane was a metal fixed bed reactor with an outside diameter of 3/8 inches and preheated with food. The catalyst was immersed in a temperature-controlled molten salt bath, and 4.0 grams of catalyst was placed in the reaction. The results of all ammonia oxidation processes in the reactor are shown in Tables 1 and 2, such as feed ratio and temperature. Catalyst Example 2 ^ 2 7 · 42 grams of V 2 0 s powder was added to a 2 liter beaker containing 100 ml of a 30% aqueous solution of hydrogen peroxide (in 900 ml of water). After the reaction of V 2 0 s powder is completed, add 6 1.22 g of antimony trioxide and 2. 40 g of molten dioxide § too (D egussa P-2 5) powder, cover with glass and stir And the mixture was heated for about 3 hours. 8 9. 5 2 This paper size applies the Chinese National Standard (CN'S) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page). System — — — — — — — — — — — — — — — — — — — — — — — — — — — II Nine SJ · 11111! 11 — — — — — — — — — — — — — — — — — — — — — — — — — V. Description of the invention (<) 1 0 * 1% tin dioxide printed by the consumer cooperative of employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, the above-mentioned disperse fatigue mixture was reduced to 3 in volume 0 0 ml 0 then calcined at 5 0 V 2 0 3 5 me S h ύ a 0 and then contact with isobutyrate t each > and place the catalyst in coarse glass (f I in isobutyrate m mix catalyst After that, without isolating the gas, make the iso 3 times 0 after the er is removed— > times. The isobutanol oven is heated Μ to remove the catalyst after the calcination in the oven at 650 ° C. Eighth, after 6 • 2 5 ml of isobutanol 9 in 9 pour isobutanol into the catalyst 9 the bottom of the funnel is dispersed evenly 9 and then the above process of the funnel is carried out for 2 hours 9 the catalyst is baked at 1 2 0 V Butanol 0 A catalytic metal fixed bed reactor for the ammoxidation of propane i The catalyst was placed in a reactor with a catalyst of 0 0 Catalyst Example 8 Λ7 137 Sol (Nalco Chemical Co.) was added under a cap, stirred and heated, Evaporate the water, then dry it in an oven at 120 ° C for 8 hours, cool, crush, and sieve into a portion of the catalyst. Calcined at 8 10 ° C for 3 hours. The catalyst has 6.25 ml of isocyanate. Butanol (ritanol) funnel, pour isobutanol into the catalyst to disperse the catalyst evenly at the bottom of the funnel, but the butanol passes through the funnel, and the process on K is carried out through the funnel, the catalyst is on the medium at 120 ° C. Residual isobutanol was then heated for 3 hours. In contact with isobutanol, place the catalyst in a frit funnel per gram of catalyst. Stir the catalyst in isobutanol to allow the catalyst to pass through isobutanol for several times without pumping. In the last time isobutanol was heated through the funnel box, M removed the remaining media on the catalyst when the outer diameter of the system was 3/8 and equipped with preheated feet to immerse in a temperature-controlled molten salt bath. 4.0 This paper size applies China National Standard (CNS) A4 (210 x 297 mm) (Please read the notes on the back before filling out this page) — II — — — — — — U — — — — — — — — — — — — ' I ί IIIII LSJt II ϊ IIIII ^ 01 ^ 1 I n — — — — — — — — — — — — Λ7 B7 V. Description of the invention (u) (Please read the notes on the back before filling this page) 2 7 * 42 g of V 2 0 s powder was added to a 2 liter beaker containing 100 ml of a 3096 aqueous solution of hydrogen peroxide (in 900 ml of water). After the reaction of V 2 0 s powder is completed, add 6 1 ♦ 2 2 g of antimony trioxide and 2. 40 g of fused titanium dioxide (Degussa P-25) powder '. Cover with glass, stir and heat the mixture for about 3 hour. 8 · 9 · 52 g of a 10 · 1% tin dioxide sol (Na Uo Chemical Co.) was added to the above dispersion. The mixture was stirred and heated without a cap to evaporate the water to reduce the volume to 300 ml, and then dried in a 120 "oven. After that, it was calcined at 650 ° C for 8 hours, cooled, and pressed. Broken and sieved into 20 — 3 5 mesh. A part of the catalyst was calcined at 8 10 ° C for 3 hours. Then it was contacted with isobutanol, and there were 6 > 2 5 ml of isobutanol per gram of catalyst, and Place the catalyst in a coarse glass (frit.) Funnel, pour the isobutanol into the catalyst, and stir the catalyst in isobutanol to make the catalyst evenly dispersed at the bottom of the funnel. The butanol passed through the funnel, and the process of M was performed 3 times. In the last time the isobutanol passed through the funnel, the catalyst was heated in an oven at 12,000 to remove the residual isobutanol on the catalyst. The invention described above is that the catalyst is heated in the oven at 650 ° C for 3 hours. The employee of the Intellectual Property Bureau of the Ministry of Economic Affairs has cooperated with the printing process to print the calcined catalyst and then contact it with isobutanol. Ml of isobutyrate, and place the catalyst in a frit funnel, pour the isobutyrate into the catalyst, in isobutanol Mix the catalyst to disperse the catalyst evenly at the bottom of the funnel, and then pass isobutanol through the funnel without oil and gas. The process on K is performed 2 times. When the last time isobutanol passed the funnel, the catalyst was at 1 2 0. It is heated in an oven at ° C to remove the residue on the catalyst. The paper size is in accordance with Chinese National Standard (CNS) Al specification (2) 0 X 297 mm. Α7 Β7 V. Isobutanol of invention description (y). The catalyst for propane ammoxidation is a metal fixed-bed reactor with an outer diameter of 3/8 inches and equipped with preheated feet. It is immersed in a temperature-controlled molten salt bath and 4.5 grams of catalyst is placed in the reactor.

對照觸媒實例A 27 . 42克的V2 〇5粉末添加到盛有1 ◦〇毫升的3 0 %雙氧水溶液（於g 〇〇毫升水）的2升燒杯中。 V 2 0 s粉末反應完畢之後，加人6 1 , 2 2克的三氧化二銻和2 * 4 0克的熔融二氧化鈦（Degussa P-25)粉末，蓋上表玻璃，攪拌並加熱混合物約3小時。將8 9 . 5 2 克的1 1 % —氧化錫溶膠（N a 1 c 〇 C h e hi i c a 1 C 〇 .)加人上述分散液。混合物在未加蓋下攪拌並加熱，以蒸發水份 ’使體積減為3〇0毫升，然後在1 2 0。〇的烘箱中乾燥。之後，在6 5 0 °C煅燒8小時，冷卻，壓碎，篩選成 2 0 — 3 5 m e s h。一部份觸媒在8 1 0 υ煅燒3小時 0 煅燒之後的觸媒然後與異丁醇接觸，每克觸媒有 6 ‘ 2 5毫升的異丁醇，並將觸媒置於粗玻璃（f Γ丨t)漏斗中’將異丁醇倒入觸媒，在異丁醇中攪拌觸媒，使觸媒在漏底部分散均勻，然後在沒有抽氣情況下使異丁醇通過漏斗’ Μ上過程共進行2次。在最後一次異丁酵通過漏斗時’觸媒在1 2 0 °C的烘箱中被加熱，以除去觸媒上殘留的異丁醇。本紙張尺度適用中國國家標準（CNS)A‘l規格（2]〇χ 297公沒） (請先閱讀背面之注意事項再填寫本頁) ---------訂--------- 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（多）用來氨氧化丙烷的觸媒偽外徑3 / 8时並配備預熱腳的金屬固定床反應器，被浸清於溫控熔融鹽浴中，將2 . 5 克觸媒置於於反應器中。结果簡述於表1 。觸媒實例4 2 7 ♦ 4 4克的V 2 ◦ 5粉末添加到盛有1 0 ◦毫升的3 0 %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。混合物在未加熱情況下攪拌約6小時，產生深紅色溶膠/ 凝膠。然後在室溫下攪拌隔夜，加人61·26克三氧化二綈，加熱所形成的混合物到沸騰，在表玻璃蓋住燒杯情況下沸騰約3小時。定期加水到燒杯中，保持混合物攪拌，混合物體積保持恆定。在加熱混合物期間，混合物先後變成綠色，灰色，然後是灰黒色。此時加人84 · 56克的1 0 · 7 %重量的二氧化錫溶膠和2 * 4克的二氧化鈦，混合物在熱板上保持恆定攪拌，到幾乎蒸乾。所形成的爱狀物在1 2〇υ乾燥隔夜。乾燥的物質在650 °C加熱 8小時，然後被磨碎，篩選，收集20_35me s h的顆粒。一部份在8 1 0 ΐ：煅燒的顆粒被異丁酵沖洗三次，其係用約每8克觸媒5 ◦毫升的異丁醇，此顆粒置於粗表玻璃（frit)漏斗，覆蓋著異丁酵，在沒有抽氣情況下使異丁酵通過漏斗。所形成的物質然後置於120Ό烘箱達數小時，Μ除去殘留的異丁酵。組成物然後在6 5 0 t’加熱 3小時，如實例3所述被沖洗和加熱。從表1可看出來後者6 5 0 °C熱處理與對照觸媒實例Β比較起來在產量和選 -1 0- 本纸張尺度適用中國國家標準（CNS)Al規格（2】0 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) --痛--------旬--------- 經濟部智慧財產局員工消費合作社印製經濟部智慧財產扃員工消費合作社印製 A7 __B7_ _ *1··^ * 五、發明說明（/) 擇性均獲得改善。Comparative Catalyst Example A 27. 42 grams of V2O5 powder was added to a 2 liter beaker containing 1 ml of a 30% aqueous solution of hydrogen peroxide (in g of ml water). After the reaction of the V 2 0 s powder is completed, add 6 1, 2 2 g of antimony trioxide and 2 * 4 0 g of fused titanium dioxide (Degussa P-25) powder, cover the surface glass, stir and heat the mixture for about 3 hour. 8 9 .52 g of a 11% tin oxide sol (N a 1 c o C h e hi c a 1 C 0.) Was added to the above dispersion. The mixture was stirred and heated without a cap to evaporate the water 'to reduce the volume to 3,000 ml, then at 120. 〇 Dry in an oven. After that, it is calcined at 6 50 ° C for 8 hours, cooled, crushed, and sieved to 20-3 5 m e s h. A part of the catalyst was calcined at 8 1 0 υ for 3 hours. The calcined catalyst was then contacted with isobutanol. There was 6 '2 5 ml of isobutanol per gram of catalyst, and the catalyst was placed in coarse glass ( f Γ 丨 t) In the funnel, pour the isobutanol into the catalyst, stir the catalyst in the isobutanol to make the catalyst evenly dispersed at the bottom of the leak, and then pass the isobutanol through the funnel without pumping. Μ The process was performed 2 times. The catalyst was heated in an oven at 120 ° C the last time the isobutyrate passed through the funnel to remove the residual isobutanol from the catalyst. This paper size applies to China National Standard (CNS) A'l specifications (2) 0 × 297 (not available) (Please read the precautions on the back before filling this page) --------- Order ---- ----- Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (multiple) Metal fixed bed reactor equipped with preheated feet when the catalyst has a pseudo-outer diameter of 3/8 , Was immersed in a temperature-controlled molten salt bath, and 2.5 grams of catalyst was placed in the reactor. The results are summarized in Table 1. Catalyst example 4 2 7 ♦ 4 4 g of V 2 ◦ 5 powder was added to a 2 liter beaker containing 10 ◦ ml of a 30% aqueous solution of hydrogen peroxide (in 900 ml of water). The mixture was stirred for about 6 hours without heating, resulting in a dark red sol / gel. Then stir at room temperature overnight, add 61.26 grams of dioxane, heat the resulting mixture to a boil, and boil for about 3 hours with the glass cover the beaker. Add water to the beaker regularly, keep the mixture agitated, and keep the volume of the mixture constant. During the heating of the mixture, the mixture turned green, then gray, and then grayish gray. At this time, 84.56 grams of 10.7% by weight tin dioxide sol and 2 * 4 grams of titanium dioxide were added, and the mixture was kept under constant stirring on a hot plate until almost evaporated. The formed love was dried overnight at 120 °. The dried material was heated at 650 ° C for 8 hours, then it was ground, sieved, and 20-35 me sh particles were collected. A part is at 8 1 0 ΐ: the calcined granules are washed three times with isobutyrate, which is about 5 ◦ ml of isobutanol per 8 g of catalyst, and the granules are placed in a coarse frit funnel and covered Isobutyrate passes isobutyrate through the funnel without suction. The formed material was then placed in an oven at 120 ° F for several hours, and the residual isobutyrate was removed. The composition was then heated at 650 t 'for 3 hours and rinsed and heated as described in Example 3. It can be seen from Table 1 that the latter heat treatment at 65 ° C is compared with the control catalyst example B. The yield and selection are -1 0- This paper size applies to the Chinese National Standard (CNS) Al specification (2) 0 X 297 mm ) (Please read the notes on the back before filling out this page)-Pain -------- Xun --------- The Intellectual Property Department of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the intellectual property of the Ministry of Economic Affairs 经济Printed by the employee consumer cooperative A7 __B7_ _ * 1 ·· ^ * V. Description of the invention (/) Optionality has been improved.

對照觸媒實例B 27 · 44克的V2 Os粉末添加到盛有100毫升的3 ◦ %雙氧水溶液’（於9 0 0毫升水）的2升燒杯中。混合物在未加熱情況下攪拌約6小時，產生深紅色溶膠/ 凝膠。然後在室溫下攪伴隔夜，加人6 1 · 2 6克三氧化二銻，加熱所形成的混合物到沸騰，在表玻璃蓋住燒杯情況下沸騰約3小時。定期加水到燒杯中，保持混合物攪拌，混合物體積保持恆定。在加熱混合物期間，混合物先後變成綠色，灰色，然後是灰黑色。此時加人84 · 56克的1 0 · 7 %重量的二氧化錫溶膠和2，4克的二氧化鈦，混合物在熱板上保持恆定攪伴，到幾乎蒸乾。所形成的蕭狀物在1 20°C乾燥隔夜。乾燥的物質在650C加熱 8小時，然後被磨碎，篩選，收集2 0 — 3 5 m e s h的顆粒。一部份在8 1 0 υ煅燒的顆粒被異丁醇沖洗三次，其係用約每8克觸媒50毫升的異丁醇，此顆粒置於粗表玻璃（f r i t)漏斗，覆蓋著異丁醇，在沒有抽氣情況下使異丁醇通過漏斗。重覆此過程三次。所形成的物質然後置於 1 2 〇υ烘箱達數小時，以除去殘留的異丁醇。觸媒實例5 2 7 . 4 4克的V 2 0 s粉末添加到盛有1 〇 ◦毫升的3 0 %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。混合物在未加熱情況下攪拌約6小時，產生深紅色瑢膠/ -11- 本紙張尺度適用中國國家標準（CNS)A.l規格（21〇χ 297公釐) (請先閱讀背面之注意事項再填寫本頁)Comparative Catalyst Example B 27.44 g of V2 Os powder was added to a 2 liter beaker containing 100 ml of a 3 ◦% hydrogen peroxide solution '(in 900 ml of water). The mixture was stirred for about 6 hours without heating, resulting in a dark red sol / gel. Then stir at room temperature overnight, add 612.26 g of antimony trioxide, heat the resulting mixture to a boil, and boil for about 3 hours with the glass cover the beaker. Add water to the beaker regularly, keep the mixture agitated, and keep the volume of the mixture constant. During the heating of the mixture, the mixture turned green, then grey, then grey-black. At this time, 84.56 grams of 10.7% by weight tin dioxide sol and 2.4 grams of titanium dioxide were added, and the mixture was kept on a hot plate with constant stirring until almost evaporated. The formed scum was dried overnight at 120 ° C. The dried material was heated at 650C for 8 hours, then it was ground, sieved, and 20 to 35 m e sh particles were collected. A part of the particles calcined at 8 1 0 υ was washed three times with isobutanol. It used about 50 ml of isobutanol per 8 grams of catalyst. The particles were placed in a frit funnel and covered with isobutyl alcohol. Alcohol, pass isobutanol through the funnel without suction. Repeat this process three times. The formed material was then placed in a 120 ° oven for several hours to remove residual isobutanol. Catalyst Example 5 27.44 grams of V 2 0 s powder was added to a 2 liter beaker containing 100 ml of a 30% aqueous solution of hydrogen peroxide (in 900 ml of water). The mixture is stirred for about 6 hours without heating, resulting in dark red tan gum / -11- This paper size applies to China National Standard (CNS) Al specifications (21〇χ 297 mm) (Please read the precautions on the back before filling (This page)

A7五、發明說明（凝膠。二銻，況下沸 *混合變成綠的1 〇，混合齋狀物 8小時顆粒。 6 5 0 兗觸媒斗，覆。重覆達數小然後在加熱所騰約3 物體積色，灰 • 7 % 物在熱在1 2 ，然後一部份 υ 3小 5 ◦毫蓋著異此過程時，以室溫下攪拌隔夜，加形成的混合物到沸騰小時。定期加水到燒保持恆定。在加熱混色，然後是灰黒色。重量的二氧化踢溶膠板上保持恆定攪拌， 0 °c乾燥隔夜。乾燥被磨碎，篩選，收集在8 1 0 °C煅燒的顆時，然後被異丁醇沖升的異丁醇，此顆粒丁酵，在沒有抽氣情三次。所形成的物質除去殘留的異丁醇。入6 1 ，2 6克三氧化，在表坡璃蓋住燒杯情杯中，保持混合物攪拌合物期間，混合物先後此時加入84 * 56克和2 · 4克的二氧化鈦到幾乎蒸乾。所形成的的物質在6 5 0 °C加熱 2 0-35 h的粒依本發明方法熱在洗三次，其用量約每8 置於粗表玻璃（frit)漏況下使異丁醇通過漏斗然後置於1 20°C烘箱經濟部智慧財產局員工消費合作杜印製對個兩與理處熱後的時〇小善 3 改 P 得 ο 獲 5 有 6 ^目來而出 C 看和C 可 B 例 1 例實表實媒從媒觸觸照照對升。\ 毫中膠 ο 杯溶 ο 燒色 1 升紅有 2 深盛的生到 } 產加水，添升時末毫小粉 ο 6 S ο 約 09 拌 2 於攪 V C 下的液況克溶情 4 水熱 4 氧加 . 雙未 7 % 在 2 ο 物 3 合的混膠疑綈二化情氧杯三燒克注 6 蓋 2 璃 ’ 坡 1 表 6 在入，加騰，沸夜到隔物拌合搜混下的溫成室形在所後熱然加本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公发） (請先閱讀背面之注意事項再填寫本頁) i I I----訂---------線-^--I--I ------------------ 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（t /) 況下沸騰約3小時。定期加水到燒杯中，保持混合物攪拌，混合物體積保持恆定。在加熱温合物期間，混合物先後變成綠色，灰色，然後是灰黒色。此時加人8 4 * 5 6克的1 0 * 7 %重量的二氧化錫溶膠和2 · 4克的二氧化鈦，混合物在熱板上保持恆定攪拌，到幾乎蒸乾。所形成的莆狀物在1 20 °C乾燥隔夜。乾燥的物質在650 °C加熱 8小時，然後被磨碎，篩選，收集2 0 — 3 5 m e s h的顆粒。一部份2 ◦- 35me s h顆粒在8 1 OC煅燒3 小時，這魷是對照觸媒實例C。Κ丙烷氨氧化作用進行觸媒試驗的結果如表1所示。觸媒實例6 2 7 ，4 4克的V 2 0 5粉末添加到盛有1 0 0毫升的30%雙氧水溶液（於900毫升水）的2升燒杯中。混合物在未加熱情況下攪拌約6小時，產生深紅色溶膠/ 凝膠。然後在室溫下攪拌隔夜，加入6 1 . 2 6克三氧化二銻，加熱所形成的混合物到沸騰，在表玻璃蓋住燒杯情況下沸騰約3小時。定期加水到燒杯中，保持混合物攪拌，混合物體積保持恆定。在加熱混合物期間，混合物先後變成綠色，灰色，然後是灰黒色。此時加人8 4 . 5 6克的1 0 * 7 %重量的二氧化錫溶膠和2 · 4克的二氧化鈦，混合物在熱板上保持恆定撹拌，到幾乎蒸乾。所形成的莆狀物在1 2 0 °C乾燥隔夜。乾燥的物質在6 5 0 °C加熱 8小時，然後被磨碎，篩選，收集2 0 — 3 5 m e s h的 -13- 本紙張尺度適用中國國家標準（CMS)A.l規格（210 χ 297公芨） -------------Φ---- (請先閱讀背面之注意事項再填寫本頁) tTi-------Μά------------------------ 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（丨» 顆粒。一部份2 0 - 3 5 m e s h顆粒在8 1 ◦ °C煅燒3 小時，然後依本發明方法在6 5 0 C熱處理3小時。從表 1可看出來，最後在6 5 O t的低溫熱處理對丙烷的氨氧化作用的產量和選擇性均獲得改善。比較本實例與對照觸媒實例C的結果。觸媒實例7 27 . 44克的V2 Os粉末添加到盛有1 〇〇毫升的3 0 %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。 Vz 〇s粉末反應完畢之後，加入61 ，26克的三氧化二銻，蓋上表玻璃，攪拌並加熱混合物約3小時。將 84 . 5 6 克的 1 0，7%二氧化錫溶膠（Nalco Chemical Co .)和2 . 4 0克的熔融二氧化钛（Degussa P-25)粉末加入上述分散液。混合物在未加蓋下攪拌並加熱，Μ蒸發水份減少體積。當混合物再也攪不動，在1 2 0 t的烘箱中乾燥。之後，在6 5 0 10煅燒8小時，冷卻，壓碎，篩選成20 — 35me s h。一部份觸媒在8 1 0°C煅燒3小時，然後另外再於6 5 0 10處理3小時。煅燒觸媒與異丁醇接觸，每克觸媒有6 · 25毫升的異丁酵，並將觸媒置於粗玻璃（frit)漏斗中，將異丁醇倒入觸媒，在異丁酵中攪拌觸媒，使觸媒在漏斗底部分散均勻，然後在沒有抽氣情況下使異丁醇通過漏斗，K上過程共進行3次。在最後一次異丁醇通過漏斗時，觸媒在 1 2 0 °C的烘箱中被加熱，以除去觸媒上殘留的異丁醇。本紙張尺度適用中國國家標準（CNS)/V1規格αίο X 297公t ) (請先閱讀背面之注意事項再填寫本頁) —--------^ · 1111—I -4g:;r—----—---------------- A7 __B7_ 五、發明說明（Θ) 用來氨氧化丙烷的觸媒係外徑3 / 8时並配備預熱腳的金屬固定床反應器，被浸清於溫控熔融鹽浴中’將 8 . 1 4克觸媒置於反應器中。结果簡示於表1 。觸媒實例8 27 . 29克的V2 Os粉末添加到盛有1 0 ◦毫升的3 0 %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。 V 2 〇 5粉末反應完畢之後，加入5 6 · 8 5克的三氧化二銻，蓋上表玻璃，攪拌並加熱混合物約3小時。將 4 2 . 2 5 克的 1 0 . 7% 二氧化錫溶膠（Nalco Chemical Co.)和2 * 4 0克的熔融二氧化鈦（Degussa P-25)粉末加入上述分散液。混合物在未加蓋下攪伴並加熱，K蒸發水份減少體積。當混合物再也攪不動，在1 2 0 υ的烘箱中乾燥。之後，在6 5 ◦ °C煅燒8小時，冷卻，壓碎，篩選成2 0 — 3 5 m e s h。一部份觸媒在8 1 0 °C煅燒3小時，然後另外再於6 5 0 t：處理3小時。煅燒觸媒與異丁酵接觸，每克觸媒有6 · 25毫升的異丁酵，並將觸媒置於粗玻璃（frit)漏4中，將異丁醇倒入觸媒，在異丁醇中攪拌觸媒，使觸媒在漏斗底部分散均勻，然後在沒有抽氣情況下使異丁醇通過漏斗，Μ上過程共進行3次。在最後一次異丁酵通過漏斗時，觸媒在 1 2 0 〇的烘箱中被加熱，Μ除去觸媒上殘留的異丁醇。用來氨氧化丙烷的觸媒係外徑3 / 8时並配備預熱腳的金屬固定床反應器，被浸清於溫控熔融鹽浴中，將 -15- 本纸張尺度適用+國國家標準（CNS)A.l規格（2〗0 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ------!11---------韓· 經濟部智慧財產局員工消費合作社印製經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明（、少） 8 * 2 8 5克觸媒置於反應器中。結果簡示於表1 。觸媒實例9 2 7 . 4 2克的V 2 ◦ s粉末添加到盛有1 0 0毫升的3 0 %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。 V 2 0 s粉末反應完畢之後，加人6 1 * 2 2克的三氧化二銻和2 ，4 0克的熔融二氧化鈦（D e g u s s a P - 2 5 )粉末，蓋上表玻璃，攬拌並加熱混合物約3小時。將8 4 . 5 Ο 克的1 0 * 7%二氧化錫溶膠（以1(^〇 Chemical Co.)加入上述分散液。混合物在未加蓋下攪拌並加熱，K蒸發水份減少體積。當混合物再也搜不動，在1 2 0 °C的烘箱中乾燥。之後，在6 5 0 °C煅燒8小時，冷卻，壓碎，篩選成20 — 35me s h。一部份觸媒在8 1 0°C煅燒3小時，然後另外再於6 5 0 處理3小時。煅燒觸媒與異丁醇接觸，每克觸媒有6 · 25毫升的異丁醇，並將觸媒置於粗玻璃（frit)漏斗中，將異丁酵倒入觸媒，在異丁酵中搜拌觸媒，使觸媒在漏斗底部分散均勻，然後在沒有抽氣情況下使異丁醇通過漏斗，K上過程共進行3次。在最後一次異丁醇通過漏斗時，觸媒在 1 2 0 °C的烘箱中被加熱，Μ除去觸媒上殘留的異丁醇。用來氨氧化丙烷的觸媒係外徑3 / 8时並配備預熱腳的金屬固定床反應器，被浸清於溫控熔融鹽浴中，將 7 · 5 0克觸媒置於反應器中。结果簡示於表1 。A7 V. Description of the invention (Gel. Diantimonium, in the case of boiling * mixed into green 10, mixed with 8-hour particles. 6 5 0 兖 catalyst bucket, covered. Repeated for a small number and then heated in the Take about 3 things to color, ash • 7% of the material is heated at 1 2, then a part of υ 3 is small 5 ◦ When covering this process, stir at room temperature overnight, add the formed mixture to boiling hours. Regularly add water to the burner to keep it constant. Mix in heat and then gray. Keep the weight of the dioxide dioxide sol on the plate under constant agitation, and dry at 0 ° C overnight. Dry and grind, filter, and collect the calcined at 8 1 0 ° C. When it is smashed, it is then washed with isobutanol by isobutanol. The granules are leaven three times without extraction. The formed substance removes the residual isobutanol. Into 6 1, 2 6 grams of trioxide, in the table Cover the beaker with beaker and keep the mixture under stirring. At this time, 84 * 56g and 2.4g of titanium dioxide are added to the mixture to almost evaporate to dryness. The formed substance is heated at 6 5 0 ° C 2 0-35 h granules are washed three times according to the method of the present invention. Its dosage is approximately every 8 placed in the coarse glass (frit) leakage condition, allowing isobutanol to pass through the funnel and then placed in an oven at 120 ° C. Consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs时〇小善 3 Change P to get ο get 5 There are 6 ^ C coming out of C look and C can B Example 1 Example of the actual media from the touch of the medium to shine. \ 零中胶 ο cup dissolved ο burnt color 1 liter of red has 2 Shengsheng to produce} add water, add powder at the end of time ο 6 S ο about 09 mix 2 under the condition of VC stirring solution 4 water heat 4 oxygen plus. Double 7% in 2 ο The compound 3 mixed with the mixed plastic oxygen cup three burning grams Note 6 Lid 2 Li 'Po 1 Table 6 The temperature-forming chamber under the mixing, mixing, boiling, and mixing with the partition is shaped in the place I will add the paper size to China National Standard (CNS) A4 (210 x 297) (please read the precautions on the back before filling this page) i I I ---- Order ------ --- Line-^-I--I ------------------ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (t /) Boiling for about 3 hours. Add water to the beaker at regular intervals, keep the mixture stirred, and keep the volume of the mixture constant. During the heating of the warm compound, the mixture turns green, gray, and then gray. At this time, 8 4 * 5 6 grams of 1 0 * 7% The weight of the tin dioxide sol and 2.4 grams of titanium dioxide, the mixture was kept under constant stirring on a hot plate until almost evaporated to dryness. The resulting mash was dried overnight at 1 20 ° C. The dried material was heated at 650 ° C for 8 hours, then it was ground, sieved, and 20 to 35 m e s particles were collected. A portion of 2 ◦-35me sh particles were calcined at 8 1 OC for 3 hours. This is the control catalyst example C. Table 1 shows the results of the catalyst test of K-propane ammoxidation. Catalyst Example 6 27, 44 g of V 2 0 5 powder was added to a 2 liter beaker containing 100 ml of a 30% hydrogen peroxide solution (in 900 ml of water). The mixture was stirred for about 6 hours without heating, resulting in a dark red sol / gel. Then stir overnight at room temperature, add 61.26 g of antimony trioxide, heat the resulting mixture to a boil, and boil for about 3 hours with the glass cover the beaker. Add water to the beaker regularly, keep the mixture agitated, and keep the volume of the mixture constant. During the heating of the mixture, the mixture turned green, then gray, and then grayish gray. At this time, 8 4 .56 g of 10 * 7% by weight of tin dioxide sol and 2.4 g of titanium dioxide were added, and the mixture was kept under constant stirring on a hot plate until almost evaporated to dryness. The resulting mash was dried overnight at 120 ° C. The dried material is heated at 650 ° C for 8 hours, then it is ground, sieved, and collected at 20 — 3 5 mesh. -13- This paper size applies the Chinese National Standard (CMS) Al specification (210 χ 297 cm) ------------- Φ ---- (Please read the notes on the back before filling this page) tTi ------- Μά ---------- -------------- A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (丨 »Particles. Part of 2 0-3 5 mesh particles at 8 1 ◦ ° C was calcined for 3 hours, and then heat-treated at 650 C for 3 hours according to the method of the present invention. As can be seen from Table 1, the yield and selectivity of the ammoxidation of propane were improved at the low-temperature heat treatment at 65 Ot. Compare the results of this example with the control catalyst example C. Catalyst Example 7 27. 44 grams of V2 Os powder was added to a 2 liter beaker containing 100 ml of a 30% aqueous solution of hydrogen peroxide (in 900 ml of water). After the reaction of the Vz 〇s powder was completed, 61,26 grams of antimony trioxide was added, covered with a watch glass, and the mixture was stirred and heated for about 3 hours. 84.56 grams of 10,7% tin dioxide sol (Nalco Chemi cal Co.) and 2.40 grams of molten titanium dioxide (Degussa P-25) powder were added to the above dispersion. The mixture was stirred and heated without a cap, and the evaporated water reduced the volume. When the mixture was no longer stirred, the Dry in an oven at 120 t. After that, it is calcined at 6 500 0 for 8 hours, cooled, crushed, and sieved to 20-35mesh. A part of the catalyst is calcined at 8 10 ° C for 3 hours, and then another Treat for 3 hours at 6 5 0 10. The calcined catalyst is in contact with isobutanol. There is 6.25 ml of isobutanol per gram of catalyst, and the catalyst is placed in a frit funnel to dissolve isobutanol. Pour the catalyst, stir the catalyst in isobutyrate to disperse the catalyst evenly at the bottom of the funnel, and then pass isobutanol through the funnel without suction. The process on K is performed 3 times in total. In the last isobutyl When the alcohol passes through the funnel, the catalyst is heated in an oven at 120 ° C to remove the residual isobutanol on the catalyst. This paper is dimensioned to the Chinese National Standard (CNS) / V1 specification αίο X 297mm t) ( Please read the precautions on the back before filling this page) —-------- ^ · 1111—I -4g:; r —----—---------- ------ A7 __B7_ V. Description of the Invention (Θ) The catalyst used for the ammoxidation of propane when the outer diameter of the catalyst system is 3/8 and equipped with a preheated metal fixed bed reactor is immersed in temperature-controlled molten salt In the bath, 8.14 grams of catalyst was placed in the reactor. The results are summarized in Table 1. Catalyst Example 8 27. 29 g of V2 Os powder was added to a 2 liter beaker containing 10 ml of a 30% aqueous solution of hydrogen peroxide (in 900 ml of water). After the reaction of the V205 powder was completed, 56.85 g of antimony trioxide was added, the surface glass was covered, and the mixture was stirred and heated for about 3 hours. To this dispersion was added 4 2.25 grams of 10.7% tin dioxide sol (Nalco Chemical Co.) and 2 * 40 grams of fused titanium dioxide (Degussa P-25) powder. The mixture was stirred and heated without capping, and K evaporated water to reduce volume. When the mixture can no longer be stirred, dry in an oven of 120 °. After that, it is calcined at 65 ° C for 8 hours, cooled, crushed, and sieved to 20 to 35 m e s h. A portion of the catalyst was calcined at 8 10 ° C for 3 hours, and then at another 650 t: treatment for 3 hours. The calcined catalyst is in contact with isobutyrate. There is 6.25 milliliters of isobutyrate per gram of catalyst, and the catalyst is placed in coarse glass (frit) drain 4. Pour isobutanol into the catalyst. The catalyst was stirred in the alcohol to make the catalyst evenly dispersed at the bottom of the funnel, and then isobutanol was passed through the funnel without suction. The above process was performed 3 times. When the isobutyrate passed through the funnel for the last time, the catalyst was heated in an oven at 1200 to remove the residual isobutanol from the catalyst. The catalyst used for the ammoxidation of propane is a metal fixed-bed reactor equipped with preheated feet at an outer diameter of 3/8, which is immersed in a temperature-controlled molten salt bath. Standard (CNS) Al specification (2) 0 X 297 mm (Please read the precautions on the back before filling this page) ------! 11 --------- Korean Ministry of Economic Affairs Printed by the employee's consumer cooperative of the Property Bureau Printed by the consumer's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (, less) 8 * 2 8 5 grams of catalyst is placed in the reactor. The results are summarized in Table 1. Catalyst Example 9 2 7 .42 g of V 2 ◦ s powder was added to a 2 liter beaker containing 100 ml of a 30% aqueous solution of hydrogen peroxide (in 900 ml of water). After the reaction of V 2 0 s powder is completed, add 6 1 * 2 2 g of antimony trioxide and 2, 40 g of molten titanium dioxide (D egussa P-2 5) powder, cover the surface glass, stir and heat The mixture was about 3 hours. 8 4 .50 grams of 10 * 7% tin dioxide sol (as 1 (^ 〇 Chemical Co.) was added to the above dispersion. The mixture was stirred and heated without cap, K evaporated water to reduce the volume. When The mixture can no longer be searched and dried in an oven at 120 ° C. After that, it is calcined at 65 ° C for 8 hours, cooled, crushed, and sieved to 20-35mesh. A part of the catalyst is at 8 1 0 Calcined at 3 ° C for 3 hours, and then treated for another 3 hours at 6 50. The calcined catalyst was contacted with isobutanol with 6.25 ml of isobutanol per gram of catalyst, and the catalyst was placed in coarse glass (frit ) In the funnel, pour the isobutyrate into the catalyst, search for the catalyst in the isobutyrate to make the catalyst evenly dispersed at the bottom of the funnel, and then pass the isobutanol through the funnel without pumping. 3. The last time the isobutanol passed through the funnel, the catalyst was heated in an oven at 120 ° C to remove the isobutanol remaining on the catalyst. The catalyst system used to ammoxidize propane was 3 At 8 o'clock, a metal fixed-bed reactor equipped with preheated feet was immersed in a temperature-controlled molten salt bath, and 7.50 grams of catalyst was placed in the reactor. The results are shown in Table 1. profile.

對照觸媒實例D -1 6 - 本紙張尺度適用中國國ϋ準（CNSM，】規恪⑵0 X 297公髮^ -------------鑄--------訂---------線4Ρ- (請先閱讀背面之注意事項再填寫本頁) A7 ____B7____ , ‘ 五、發明說明 27 · 42克的V2 Os粉末添加到盛有100毫升的3 ◦ %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。 V 2 0 s粉末反應完畢之後，加入6 1 · 2 2克的三氧化二銻和2 . 4 0克的'熔融二氧化鈦（Degussa P-25)粉末，蓋上表玻璃，攪拌並加熱混合物約3小時。將8 4 · 5 0 克的1 0 . 7%二氧化錫溶膠（Nalco Chemical Co.)加入上述分散液。混合物在未加蓋下攪拌並加熱，K蒸發水份減少體積。當混合物再也攪不動，在1 2 0 t的烘箱中乾燥。之後，在6 5 0 °C煅燒8小時，冷卻，壓碎，篩選成20 — 35me s h。一部份觸媒在8 1 0°C煅燒3小時，然後另外再於6 5 0 °C處理3小時。煅燒觸媒與異丁醇接觸，每克觸媒有6·25毫升的異丁醇，並將觸媒置於粗玻璃（frit)漏斗中，將異丁醇倒入觸媒，在異丁醇中攪拌觸媒，使觸媒在漏斗底部分散均勻，然後在沒有油氣倩況下使異丁醇通過漏斗，K上過程共進行3次。在最後一次異丁酵通過漏斗時，觸媒在 1 20亡的烘箱中被加熱，Μ除去觸媒上殘留的異丁酵。用來氨氧化丙烷的觸媒係外徑3 / 8时並配備預熱腳的金屬固定床反應器，被浸清於溫控熔融鹽浴中，將 7 * 125克觸媒置於反應器中。结果簡示於表1 。觸媒實例1 0 2 7 ，2 9克的V 2 〇 5粉末添加到盛有1 〇〇毫升的3 0 %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。本紙張尺度適用中國國家標準（CNS)A'l規格（2〗0 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) — ----訂 --------韓」rl 經濟部智慧財產局員工消費合作社印制衣 A7 B7 五'發明說明（沙） V 2 0 5粉末反應完畢之後，加入5 6 · 8 5克的三氧化二銻，蓋上表玻璃，攬拌並加熱混合物約3小時。將 8 4 * 5 1克的1〇· 7 %二氧化錫溶膠（N a U 〇 C h e πι i c a 1 Co.)和2 ♦ 4 0克的熔融二氣化鈦（Degussa P-25)粉末加入上述分散液。混合物在未加蓋下攪拌並加熱，以蒸發水份減少體積。當混合物再也攪不動，在1 2 0它的烘箱中乾燥。之後，在6 5 0 °C煅燒8小時，冷卻，壓碎，篩選成2 0 — 3 5 m e s h。一部份觸媒在8 1 0 t：煅燒3小時，然後另外再於6 5 0 °C處理3小時。煅燒觸媒與異丁醇接觸，每克觸媒有6 · 2 5毫升的異丁醇，並將觸媒置於粗玻璃（frit)漏斗中，將異丁醇倒入觸媒，在異丁醇中攪拌觸媒，使觸媒在漏斗底部分散均勻，然後在沒有抽氣情況下使異丁醇通過漏斗，K上過程共進行3次。在最後一次異丁醇通過漏斗時，觸媒在 1 20 °C的烘箱中被加熱，K除去觸媒上殘留的異丁醇。用來氨氧化丙烷的觸媒係外徑0 · 5时並配備預熱腳的金屬固定床反應器，被浸清於溫控熔融鹽浴中，將 8.151克觸媒與4毫升石英片（20—35mesh 顆粒尺寸）混合，置於反應器中。结果藺示於表1。觸媒實例1 1 2 7 · 4 2克的V 2 0 5粉末添加到盛有1 ◦ 〇毫升的3 0 %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。 V 2 〇 ε粉末反應完畢之後，加人6 1 · 2 2克的三氧化本紙張尺度適用中國國家標準（CN'S)A，:!規格（2.10 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) n n tl n n 如5、 I n I I · 經濟部智慧財產局員工消費合作社印製 ------------------------ 經濟部智慧財產局員工消費合作社印製 Λ7 — _B7____ 五、發明說明（\/| ) 二銻，再加入◦ * 38克L i OH，H2 0，蓋上表玻璃，攢拌並加熱混合物約3小時。將8 4 . 5 0克的1 〇 . 7 % 二氣化錫溶膠（NalccrChemical Co.)和2 · 4 0克的熔融二氧化鈦（D e g u s s a P - 2 5 )粉末加入上述分散液。混合物在未加蓋下攪拌並加熱，Μ蒸發水份減少體積。當混合物再也攪不動，在1 2 0 °C的烘箱中乾燥。之後，在6 5 ◦它煅燒8小時，冷卻，壓碎，篩選成2 0 _ 3 5 m e s h。一部份觸媒在8 1 ◦ °C椴燒3小時，然後另外再於6 5 0 C 處理3小時。煅燒觸媒與異丁醇接觸，每克觸媒有6 · 2 5毫升的異丁醇，並將觸媒置於粗玻璃（frit)漏斗中，將異丁醇倒入觸媒，在異丁醇中攪拌觸媒，使觸媒在漏斗底部分散均勻*然後在沒有抽氣情況下使異丁醇通過漏斗，K上過程共進行3次。在最後一次異丁醇通過漏斗時，觸媒在 1 2 0°C的烘箱中被加熱，K除去觸媒上_留的異丁酵。用來氨氧化丙烷的觸媒係外徑3/8吋並配備預熱腳的金屬固定床反應器，被浸清於溫控熔融鹽浴中，结果簡示於表2，可與對照觸媒實洌E的結果比較。Comparative catalyst example D -1 6-This paper size is applicable to China National Standards (CNSM) regulations 0 0 297 public hair ^ ------------- cast --------- -Order --------- Line 4P- (Please read the notes on the back before filling this page) A7 ____B7____, 'V. Description of the invention 27 · 42 g of V2 Os powder is added to a container containing 100 ml 3 ◦% hydrogen peroxide solution (in 900 ml of water) in a 2 liter beaker. After the V 2 0 s powder reaction is complete, add 6 1 · 2 2 g of antimony trioxide and 2. 40 g of 'fused titanium dioxide'. (Degussa P-25) powder, cover the surface glass, stir and heat the mixture for about 3 hours. Add 8 4 · 50 grams of 10.7% tin dioxide sol (Nalco Chemical Co.) to the above dispersion. Mixture Stirred and heated without cover, K evaporated water to reduce the volume. When the mixture could not be stirred anymore, it was dried in an oven at 120 t. After that, it was calcined at 6 50 ° C for 8 hours, cooled, and crushed. Screened to 20 — 35me sh. A part of the catalyst was calcined at 8 1 0 ° C for 3 hours, and then treated at 6 50 ° C for 3 hours. The calcined catalyst was contacted with isobutanol at 6 per gram of catalyst. 25 ml Butanol, place the catalyst in a coarse glass (frit) funnel, pour the isobutanol into the catalyst, and stir the catalyst in isobutanol to make the catalyst evenly dispersed at the bottom of the funnel. Isobutanol was passed through the funnel, and the process of K was carried out 3 times. When the last time isobutanol passed through the funnel, the catalyst was heated in an oven at 120 ° C to remove the residual isobutase on the catalyst. The catalyst for propane ammoxidation is a metal fixed bed reactor equipped with preheated feet at an outer diameter of 3/8, and is immersed in a temperature-controlled molten salt bath. 7 * 125 grams of catalyst is placed in the reactor. The results are summarized in Table 1. Catalyst Example 10 27, 29 g of V 2 05 powder was added to a 2 liter beaker containing 100 ml of a 30% aqueous solution of hydrogen peroxide (in 900 ml of water). Medium. This paper size is applicable to China National Standard (CNS) A'l specification (2〗 0 X 297 mm) (Please read the precautions on the back before filling out this page) — ---- Order ------ --Korean "rl Printed clothing A7 B7 of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed clothes A5 B5 Description of invention (sand) V 2 0 5 After powder reaction is completed, add 5 6 · 8 5 Cover antimony trioxide with glass, stir and heat the mixture for about 3 hours. Dissolve 8 4 * 5 1 g of 10.7% tin dioxide sol (N a U OC He π ica 1 Co.) And 2 ♦ 40 g of molten titanium dioxide (Degussa P-25) powder were added to the above dispersion. The mixture was stirred and heated without a cap to reduce the volume by evaporation of water. When the mixture can no longer be stirred, dry in an oven at 120. After that, it was calcined at 650 ° C for 8 hours, cooled, crushed, and sieved to 20 to 35 m e s h. A part of the catalyst was calcined at 810 t: 3 hours, and then treated at 650 ° C for another 3 hours. The calcined catalyst is in contact with isobutanol. There is 6.25 ml of isobutanol per gram of catalyst, and the catalyst is placed in a frit funnel. The isobutanol is poured into the catalyst. The catalyst was stirred in the alcohol to make the catalyst evenly dispersed at the bottom of the funnel, and then isobutanol was passed through the funnel without suction, and the process of K was performed 3 times. When the isobutanol passed the funnel for the last time, the catalyst was heated in an oven at 120 ° C, and K removed the residual isobutanol from the catalyst. The catalyst used for the ammoxidation of propane was a metal fixed-bed reactor equipped with preheated feet at an outer diameter of 0 · 5, which was immersed in a temperature-controlled molten salt bath. 8.151 g of the catalyst and 4 ml of quartz flakes (20 —35mesh particle size) and placed in the reactor. The results are shown in Table 1. Catalyst Example 1 1 2 7 · 42 g of V 2 0 5 powder was added to a 2 liter beaker containing 1 ml of a 30% aqueous solution of hydrogen peroxide (in 900 ml of water). After the V 2 〇ε powder reaction is completed, add 6 1 · 2 2 grams of trioxide paper. The size of the paper applies to China's national standard (CN'S) A,:! Specifications (2.10 X 297 mm) (Please read the precautions on the back first) (Fill in this page again) nn tl nn such as 5, I n II · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ------------ Economy Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau Λ7 — _B7____ V. Description of the Invention (\ / |) Diantimony, and then added ◦ * 38g Li OH, H2 0, cover with glass, stir and heat the mixture for about 3 hours . 84.5 g of 10.7% digassed tin sol (Nalccr Chemical Co.) and 2.40 g of molten titanium dioxide (D e g u s s a P-25) powder were added to the above dispersion. The mixture was stirred and heated without a cap, and the evaporated water reduced the volume. When the mixture can no longer be stirred, dry in an oven at 120 ° C. After that, it was calcined at 6 5 ◦ for 8 hours, cooled, crushed, and sieved to 20 5 35 m e s h. A portion of the catalyst was fired at 81 ° C for 3 hours, and then treated at 650 ° C for another 3 hours. The calcined catalyst is in contact with isobutanol. There is 6.25 ml of isobutanol per gram of catalyst, and the catalyst is placed in a frit funnel. The isobutanol is poured into the catalyst. Stir the catalyst in the alcohol to evenly disperse the catalyst at the bottom of the funnel * and then pass isobutanol through the funnel without pumping. The process on K is performed 3 times. When the isobutanol passed through the funnel for the last time, the catalyst was heated in an oven at 120 ° C, and K removed the isobutyrene left on the catalyst. The catalyst used for the ammoxidation of propane is a metal fixed bed reactor with an outer diameter of 3/8 inches and equipped with pre-heated feet. The catalyst is immersed in a temperature-controlled molten salt bath. The results are shown in Table 2. Comparison of the results of E 洌 E.

對照觸媒實例E 27 ♦ 42克的V2 〇5粉末添加到盛有1 00毫升的3 0 %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。 V 2 0 5粉末反應完畢之後，加入6 1 . 2 2克的三氧化二綈，再加人ϋ · 38克L丨0H · H2 ◦，蓋上表玻璃本纸張尺度適用中國國家標準（CNS)A.l規格（2】0 X 297公釐) -------------C--------訂---------錦-1P· (請先閲讀背面之注意事項再填寫本頁) A7 __B7______ 五、發明說明（#) ，攪拌並加熱混合物約3小時。將8 4 ♦ 5 0克的1 〇 . 7 % 二氧化錫溶膠（Nalco Chemical Co.)和2 ’ 4 0克的熔融二氧化鈦（D e g u s s a P - 2 5 )粉末加人上述分散液°混合物在未加蓋下攪拌並加熱，K蒸發水份減少體積。當混合物再也攪不動，在1 2 0。<0的烘箱中乾爍。之後，在6 5 〇〇煅燒8小時，冷卻，壓碎，篩選成2 0 — 3 5 m e s h。一部份觸媒在8 1 0 °C煅燒3小時，然後另外再於6 5 0 t；處理3小時。煅燒觸媒與異丁醇接觸，每克觸媒有6，25毫升的異丁醇，並將觸媒置於粗玻璃（frit)漏斗中，將異丁酵倒入觸媒，在異丁醇中攪拌觸媒，使觸媒在漏斗底部分散均勻，然後在沒有抽氣情況下使異丁酵通過漏斗，在最後一次異丁酵通過漏斗時，觸媒在1 2 0 °C的烘箱中被加熱，K除去觸媒上殘留的異丁醇。觸媒實例1 2 27，42克的V2 〇s粉末添加到盛有1 ◦〇毫升的3 0 %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。經濟部智慧財產局員工消費合作社印*1^ (請先閱讀背面之沒意事項再填寫本頁) V 2 0 s粉末反應完舉之後，加入6 1 · 2 2克的三氧化二銻，再加人0 · 38克L i 0H · Hz ◦，蓋上表玻璃，攪拌並加熱混合物約3小時。將8 4 · 5 0克的1 〇 ’ 7 % 二氧化錫溶膠（N a 1 c 〇 C h e in i c a 1 C 〇 .)和2 · 4 0克的熔融二氧化钛（1) e g u s s a P - 2 5 )粉末加人上述分散液。混合物在未加蓋下攪拌並加熱，K蒸發水份減少體積。當混合物再 -20- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 B7 五、發明說明（（f) (請先閱讀背面之注意事項再填寫本頁) 也授不動，在1 20¾的烘箱中乾燥。之後，在650 °C 锻燒8小時，冷卻，壓碎，篩選成2〇_35mesh。一部份觸媒在8 1 〇 -C煅燒3小時，然後另外再於6 5 ◦ t：處理3小時。锻燒觸媒與異丁酵接觸，每克觸媒有6 ，2 5毫升的異丁醇，並將觸媒置於粗玻璃（f r i t)漏斗中，將異丁醇倒人觸媒，在異丁酵中攪拌觸媒，使觸媒在漏斗底部分散均匀’然後在沒有抽氣情況下使異丁醇通過漏斗，以上過程共進行3次。在最後一次異丁酵通過漏斗時，觸媒在 1 2 0 t的烘箱中被加熱，以除去觸媒上殘留的異丁醇。用來氨氧化丙焼的觸媒係外徑3 / 8时並配備預熱腳的金屬固定床反應器，被浸清於溫控熔融鹽浴中，结果簡示於表2 ’可與對照觸媒實例f的结果比較。Comparative Catalyst Example E 27 ♦ 42 g of V2 05 powder was added to a 2 liter beaker containing 100 ml of a 30% aqueous solution of hydrogen peroxide (in 900 ml of water). After the reaction of V 2 0 5 powder is completed, add 6 1.2 g of dioxin trioxide, and then add gadolinium · 38 g L 丨 0H · H2 ◦ cover the surface glass. The paper size applies Chinese national standards (CNS ) Al specifications (2) 0 X 297 mm) ------------- C -------- Order --------- Jin-1P · (Please Read the notes on the back before filling this page) A7 __B7______ 5. Description of the Invention (#), stir and heat the mixture for about 3 hours. 8 4 ♦ 50 grams of 10.7% tin dioxide sol (Nalco Chemical Co.) and 2 '40 grams of fused titanium dioxide (D egussa P-2 5) powder were added to the above dispersion. Stir and heat under a lid, K evaporates water to reduce volume. When the mixture can no longer be stirred, it is at 1 2 0. <0 in the oven. After that, it was calcined at 6500 for 8 hours, cooled, crushed, and sieved to 20-50 mmesh. A part of the catalyst was calcined at 810 ° C for 3 hours, and then treated at 650 t for another 3 hours. The calcined catalyst is in contact with isobutanol. There is 6,25 ml of isobutanol per gram of catalyst, and the catalyst is placed in a frit funnel. The isobutanol is poured into the catalyst. Stir the catalyst in the middle of the funnel to evenly disperse the catalyst at the bottom of the funnel, and then pass the isobutyrate through the funnel without suction. When the last time isobutyrate passed through the funnel, the catalyst was washed in an oven at 120 ° C. Heating, K removes the isobutanol remaining on the catalyst. Catalyst Example 1 27. 42 grams of V2Os powder was added to a 2 liter beaker containing 1 ml of a 30% aqueous solution of hydrogen peroxide (in 900 ml of water). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs * 1 ^ (Please read the unintentional matter on the back before filling out this page) V 2 0 s After the powder reaction is completed, add 6 1 · 2 2 g of antimony trioxide, and then Add 0 · 38 g L i 0H · Hz ◦, cover with cover glass, stir and heat the mixture for about 3 hours. 8 4 · 50 g of 1 0 '7% tin dioxide sol (N a 1 c 〇C in in ica 1 C 0.) and 2. 40 g of fused titanium dioxide (1) egussa P-2 5) The powder was added to the above dispersion. The mixture was stirred and heated without a cap, and K evaporated water to reduce the volume. When the mixture is -20- This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) A7 B7 V. Description of the invention ((f) (Please read the precautions on the back before filling this page) Do not move, dry in an oven at 12020. After that, calcined at 650 ° C for 8 hours, cooled, crushed, and sieved to 20-35 mesh. A part of the catalyst was calcined at 8 10-C for 3 hours, and then another Then at 5 5 ◦ t: processing for 3 hours. The calcination catalyst is in contact with isobutyramine, and there is 6.5 ml of isobutanol per gram of catalyst, and the catalyst is placed in a coarse glass (frit) funnel. The isobutanol is poured into the catalyst, and the catalyst is stirred in the isobutyrate so that the catalyst is evenly dispersed at the bottom of the funnel. Then the isobutanol is passed through the funnel without suction. The above process is performed 3 times in total. At the end When the isobutyrate passes through the funnel once, the catalyst is heated in a 120 t oven to remove the residual isobutanol on the catalyst. The catalyst used for the ammoxidation of propidium is equipped with an external diameter of 3/8 The preheated metal fixed-bed reactor was immersed in a temperature-controlled molten salt bath. The results are shown in Table 2 Comparison of results for catalyst instance f.

對照觸媒實例F 27 * 42克的V2 Os粉末添加到盛有1 00毫升的3 0 %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。經濟部智慧財產局員工消費合作社印製 V2 Os粉末反應完畢之後，加入6 1 *22克的三氧化二銻，再加入0 . 38克L i OH. H2 〇，蓋上表坡璃，攪拌並加熱混合物約3小時。將8 4 . 5 0克的1 0 , 7 % 二氧化錫溶膠（Nalco Cheraicai Co.)和2，4 0克的熔融二氧化鈦（D e gu s s a P - 2 5 )粉末加人上述分散液。混合物在未加蓋下攪拌並加熱，K蒸發水份減少體積。當混合物再也攪不動，在1 2 0 °C的烘箱中乾燥。之後，在6 5 0艺 -21- 本纸張尺度適用中國國家標準（CNS)A.l規格（210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 A7 137 五、發明說明（〆0 锻燒8小時，冷卻，壓碎，篩選成2 0 — 3 5 m e s h。一部份觸媒在8 1 0 °C煅燒3小時。煅燒觸媒與異丁醇接觸，每克觸媒有6 · 2 5毫升的異丁醇，並將觸媒查於粗玻璃（frit)漏斗中，將異丁醇倒入觸媒，在異丁醇中攪拌觸媒，使觸媒在漏斗底部分散均勻，然後在沒有油氣情況下使異丁醇通過漏斗，K上過程共進行4次。在最後一次異丁酵通過漏斗時，觸媒在 1 2 Ο υ的烘箱中被加熱，K除去觸媒上殘留的異丁醇。觸媒實例1 3 2 1 ，9 5克的V 2 0 s粉末添加到盛有1 0 0毫升的3 0 %雙氧水溶液（於9 ◦ 0牽升水）的2升燒杯中。 V 2 〇 5粉末反應完畢之後，加入4 9 * Ο 1克的三氧化二綈，蓋上表玻璃，攪拌並加熱混合物約3小時。將 71·67克的10，7%二氧化錫溶膠（NalcoComparative Catalyst Example F 27 * 42 g of V2 Os powder was added to a 2 liter beaker containing 100 ml of a 30% aqueous solution of hydrogen peroxide (in 900 ml of water). After printing the V2 Os powder printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 6 1 * 22 grams of antimony trioxide was added, and 0.38 grams of Li i OH. H2 〇 was added. The mixture was heated for about 3 hours. 8 4 .50 grams of 10,7% tin dioxide sol (Nalco Cheraicai Co.) and 2,40 grams of molten titanium dioxide (D e gu s s a P-2 5) powder were added to the above dispersion. The mixture was stirred and heated without a cap, and K evaporated water to reduce the volume. When the mixture can no longer be stirred, dry in an oven at 120 ° C. After that, at 6 5 0 Yi-21- This paper size applies the Chinese National Standard (CNS) Al specification (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 137 V. Description of the invention Burn for 8 hours, cool, crush, and sieve into 20 — 3 5 mesh. A part of the catalyst is calcined at 8 10 ° C for 3 hours. The calcined catalyst is in contact with isobutanol at a rate of 6.2 per gram of catalyst. 5 ml of isobutanol, check the catalyst in a frit funnel, pour the isobutanol into the catalyst, stir the catalyst in isobutanol to make the catalyst evenly dispersed at the bottom of the funnel, and then In the absence of oil and gas, isobutanol was passed through the funnel, and the process on K was performed 4 times. In the last time the isobutanol passed through the funnel, the catalyst was heated in an oven of 1 2 0 υ, and K removed the residual impurities on the catalyst. Butanol. Catalyst Example 1 3 2 1, 95 g of V 2 0 s powder was added to a 2 liter beaker containing 100 ml of a 30% hydrogen peroxide solution (at 9 ◦ 0 draft water). V 2 After the reaction of the powder was completed, 4 9 * 1 g of dioxin trioxide was added, the surface glass was covered, and the mixture was stirred and heated for about 3 hours. 71 · 67 g of 10.7% tin dioxide sol (Nalco

Chemical Co.)和2 · 4 0克的熔融二氧化鈦粉末加人上述分散液，然後加人66 · 7克之30%重量的二氧化矽溶膠（Nissan N-30)。混合物在未加蓋下攪拌並加熱，K蒸發水份減少體積。當混合物再也攪不動，在1 2 0 t的烘箱中乾燥。之後，在65〇υ煅燒8小時，冷卻，壓碎，篩選成20 — 3 5me s h。一部份觸媒在8 1 0°C煅燒3 小時 > 然後另外再於6 5 0 °C處理3小時。煅燒觸媒與異丁醇接觸，每克觸媒有6 · 2 5毫升的異丁醇，並將觸媒置於粗玻璃（f r it)漏斗中，將異丁醇 -22- 本紙張尺度適用中國國家標準（CNS)Al規格（210x297公釐） (請先閒讀背面之注意事項再填寫本頁) --------訂--------- A7 B7 - — ， _ 五、發明說明（~) 倒入觸媒，在異丁醇中攪拌觸媒，使觸媒在漏斗底部分散均勻，然後在沒有抽氣情況下使異丁醇通過漏斗，以上過程共進行3次。在最後一次異丁酵通過漏斗時，觸媒在 1 2 0 °C的烘箱中被加熱，K除去觸媒上殘留的異丁醇。用來氨氧化丙烷的觸媒係外徑3 / 8时並配備預熱腳的金屬固定床反應器，被浸清於溫控熔融鹽浴中，將3 ♦ 0 克的觸媒置於反應器中，结果簡示於表2，可與對照觸媒實例G的结果比較。Chemical Co.) and 2.40 g of fused titanium dioxide powder were added to the above dispersion, followed by 66.7 g of 30% by weight silica dioxide (Nissan N-30). The mixture was stirred and heated without cap, and K evaporated water to reduce volume. When the mixture can no longer be stirred, it is dried in a 120 t oven. After that, it was calcined at 65 ° for 8 hours, cooled, crushed, and sieved to 20-3 5 me s h. A part of the catalyst was calcined at 810 ° C for 3 hours and then treated at 650 ° C for another 3 hours. The calcined catalyst is in contact with isobutanol. There is 6.25 ml of isobutanol per gram of catalyst, and the catalyst is placed in a frit funnel. Isobutanol-22 is applicable to this paper. China National Standard (CNS) Al Specification (210x297 mm) (Please read the precautions on the back before filling this page) -------- Order --------- A7 B7-—, _ 5. Description of the invention (~) Pour the catalyst, stir the catalyst in isobutanol to make the catalyst evenly dispersed at the bottom of the funnel, and then pass the isobutanol through the funnel without air extraction. The above process is performed in total 3 Times. The catalyst was heated in an oven at 120 ° C for the last time the isobutyrate passed through the funnel, and K removed the residual isobutanol from the catalyst. The catalyst used for the ammoxidation of propane is a metal fixed-bed reactor equipped with preheated feet at an outer diameter of 3/8, which is immersed in a temperature-controlled molten salt bath, and a catalyst of 3.0 g is placed in the reactor. The results are summarized in Table 2 and can be compared with the results of the control catalyst example G.

對照觸媒實例G 2 1 ，95克的V2 05粉末添加到盛有1 00毫升的3 0 %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。 Vz 〇5粉末反應完畢之後，加入49 · 01克的三氧化二銻，蓋上表玻璃，攪拌並加熱混合物約3小時。將 7 1 · 6 7克的1 0 · 7 %二氧化錫溶膠（N a 1 c 〇For the control catalyst example G 2 1, 95 g of V 2 05 powder was added to a 2 liter beaker containing 100 ml of a 30% hydrogen peroxide solution (in 900 ml of water). After the reaction of the Vz 05 powder was completed, 49.01 g of antimony trioxide was added, the surface glass was covered, and the mixture was stirred and heated for about 3 hours. 7 1 · 67 g of 10 · 7% tin dioxide sol (N a 1 c 〇

Chemical Co.)和2 . 4 0克的熔融二氧化鈦粉末加人上述分散液，然後加入6 6 ♦ 7克之3 ◦ %重量的二氧化矽溶膠（Nissan N-3Q)。混合物在未加蓋下攪拌並加熱，Μ蒸發水份減少體積。當混合物再也攪不動，在1 2 0 υ的烘箱中乾燥。之後，在6501C煅燒8小時，冷卻，壓碎，篩選成20 — 35me s h。一部份觸媒在8 1 0它煅燒3 小時，然後另外再於6 5 0 °C處理3小時。煅燒觸媒與異丁醇接觸，每克觸媒有6 · 25毫升的異丁 _，並將觸媒置於粗玻璃（f r i t)漏斗中，將異丁醇 -2 3- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) L0 訂---------LeT . 經濟部智慧財產局員工消費合作社印f Λ7 B7 五、發明說明（ (請先閱讀背面之生意事項再填寫本頁) 倒入觸媒，在異丁醇中攪拌觸媒，使觸媒在漏斗底部分散均勻，然後在沒有抽氣情況下使異丁醇通過漏斗，Μ上過程共進行3次。在最後一次異丁醇通過漏斗時，觸媒在 1 2 〇 °C的烘箱中被加熱，Κ除去觸媒上殘留的異丁醇。用來氨氧化丙烷的觸媒係外徑3 / 8吋並配備預熱腳的金屬固定床反應器，被浸清於溫控熔融鹽浴中，將3 · 0 克的觸媒置於反應器中，結果簡示於表2。觸媒實例1 4 2 7 * 4 2克的V 2 0 5粉末添加到盛有1 0 0毫升的3 0 %雙氧水溶液（於9 0 0毫升水）的2升燒杯中。 V 2 〇 s粉末反應完畢之後，加入6 1 · 2 2克的三氧化二銻，蓋上表玻璃，攪拌並加熱混合物約3小時。將 43·8 9克的20*6%二氣化錫溶膠（Nalco 經濟部智慧財產局員工消費合作社印？衣Chemical Co.) and 2.40 grams of fused titanium dioxide powder were added to the above dispersion, and then 6 6 ♦ 7 grams 3% by weight of silica dioxide (Nissan N-3Q) was added. The mixture was stirred and heated without a cap, and the evaporated water reduced the volume. When the mixture can no longer be stirred, dry in an oven of 120 °. After that, it was calcined at 6501C for 8 hours, cooled, crushed, and sieved to 20-35 me s h. A part of the catalyst was calcined at 810 for 3 hours, and then treated at 650 ° C for another 3 hours. The calcined catalyst is in contact with isobutanol. There is 6.25 ml of isobutyl alcohol per gram of catalyst, and the catalyst is placed in a frit funnel. The isobutanol-2 is used. 3- This paper applies to China National Standard (CNS) A4 Specification (210 X 297 mm) (Please read the notes on the back before filling out this page) L0 Order --------- LeT. Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs f Λ7 B7 V. Description of the invention ((Please read the business matters on the back before filling in this page) Pour the catalyst and stir the catalyst in isobutanol to make the catalyst evenly dispersed at the bottom of the funnel, and then without gas extraction The isobutanol was passed through the funnel, and the above process was performed 3 times. When the isobutanol was passed through the funnel for the last time, the catalyst was heated in an oven at 120 ° C, and K was removed from the catalyst. The catalyst used for the ammoxidation of propane is a 3 / 8-inch metal fixed-bed reactor equipped with preheated feet. It is immersed in a temperature-controlled molten salt bath, and 3.0 grams of catalyst is placed in the reactor. The results are shown in Table 2. Example of catalyst 1 4 2 7 * 4 2 g of V 2 0 5 powder was added to 100 ml of 30% double Oxygen solution (in 900 ml of water) in a 2 liter beaker. After the V 2 0s powder reaction is completed, add 6 1.2 g of antimony trioxide, cover the surface glass, stir and heat the mixture for about 3 hours. .43.9 g of 20 * 6% digassed tin sol (printed by the Consumer Cooperative of the Intellectual Property Bureau of the Nalco Ministry of Economic Affairs?

Chemical Co.)和2 ‘40克的熔融二氧化鈦粉末加人上逑分散液，混合物在未加蓋下攪拌並加熱，K蒸發水份減少體積。當混合物再也攪不動，在1 2 0它的烘箱中乾燥。之後，在6 5 Ot：煅燒8小時，冷卻，壓碎，篩選成2〇 —35me s h。一部份觸媒在8 1 Ot：煅燒3小時，然後另外再於6 5 0 °C處理8小時。煅燒觸媒與異丁醇接觸，每克觸媒有6 . 25毫升的異丁醇，並將觸媒置於粗玻璃（f r i t)漏4中，將異丁酵倒入觸媒，在異丁醇中攪拌觸媒，使觸媒在漏斗底部分散均勻，然後在沒有油氣情況下使異丁醇通過漏4，以上過 -24- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） Λ7 B7 — _ _ 1 1 五、發明說明（y) 程共進行3次。在最後一次異丁醇通過漏斗時，觸媒在 1 2 0 °C的烘箱中被加熱，K除去觸媒上殘留的異丁醇。用來氨氧化丙烷的觸媒係外徑3 / 8时並配備預熱腳的金屬固定床反應器，被浸清於溫控熔融鹽浴中，將5克的觸媒置於反應器中，結果簡示於表2。 (請先閱讀背面之注意事項再填寫本頁) --------訂---------線經濟部智慧財產局員工消費合作社印製本紙張尺度適用中國國家標準（CNS)A.l規格（210 X 297公a ) A7__B7 五、發明說明（y十） Ν】ο. 5 15 16 (5) 17 IS 19 20 (5) 22 (5) 23 24 25 26 27(5) 2S 29 D (5) 1° 1〇 B (5) 5 C (5) li^ No. 1 > s 2 lo/nh-ip/lz 5/1.33/3.350.M 3/M9/3.16/I2.39 C,/NH,/P/N./H.〇 3/1.29/3.01/10.34/2.0 耦：I-t ρ/ΝΤι~/ρ/ΗΓΟ(6) 5/1/2.S/l 460 2.9 , 7.5 so 么60 规1 (赠郝細2 fife (請先閱讀背面之注意事項再填寫本頁) nT馨ill 2.5 1-7 3.2 3.2 3.7 1.7 3.6 0.91.2 •4 -8 3.72.2 § 15.6 H.7 13.OT 1-6 15.1 14.9 14.5 15.5 15.2 30.6 3M 30.6 29-7 17.6 31- 經濟部智慧財產局員工消費合作社印製 sAii 9.6 9b 9.0 9_6 9_5 9.1 9.3 •3 •9 1-2 18.3 1-6 16.211.6 1-0 i 聲s i % ) s 陰 61.7 60-9 65.1 65.6 62.7 61.3 S.2 53.5 5-7 59.5 5-1 57.5 54.7g.3 57-Chemical Co.) and 2 ' 40 grams of molten titanium dioxide powder were added to the scutellariata dispersion. The mixture was stirred and heated without capping, and K evaporated water to reduce the volume. When the mixture can no longer be stirred, dry in an oven at 120. After that, it is calcined at 65 5 Ot for 8 hours, cooled, crushed, and sieved to 20-35 me s h. A part of the catalyst was calcined at 8 1 Ot: 3 hours, and then treated at 6 50 ° C for another 8 hours. The calcined catalyst is in contact with isobutanol. There is 6.25 ml of isobutanol per gram of catalyst, and the catalyst is placed in a frit glass 4. Pour isobutanol into the catalyst. Stir the catalyst in alcohol to make the catalyst evenly disperse at the bottom of the funnel, and then let isobutanol pass through the leak without oil and gas. The above is over -24.-This paper size applies to China National Standard (CNS) A4 (210 X 297) (Mm) Λ7 B7 — _ _ 1 1 V. Description of the invention (y) The process is carried out 3 times. When the isobutanol passed through the funnel for the last time, the catalyst was heated in an oven at 120 ° C, and K removed the residual isobutanol on the catalyst. The catalyst used for the ammoxidation of propane is a metal fixed bed reactor equipped with preheated feet at an outer diameter of 3/8, which is immersed in a temperature-controlled molten salt bath, and 5 grams of the catalyst is placed in the reactor. The results are summarized in Table 2. (Please read the precautions on the back before filling this page) -------- Order --------- The paper printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese national standard ( CNS) Al specifications (210 X 297 male a) A7__B7 V. Description of the invention (y ten) Ν] ο. 5 15 16 (5) 17 IS 19 20 (5) 22 (5) 23 24 25 26 27 (5) 2S 29 D (5) 1 ° 1〇B (5) 5 C (5) li ^ No. 1 > s 2 lo / nh-ip / lz 5 / 1.33 / 3.350.M 3 / M9 / 3.16 / I2.39 C, / NH, / P / N. / H.〇3 / 1.29 / 3.01 / 10.34 / 2.0 Coupling: It ρ / ΝΤι ~ / ρ / ΗΓΟ (6) 5/1 / 2.S / l 460 2.9, 7.5 so mus 60 rule 1 (free hao fine 2 fife (please read the precautions on the back before filling out this page) nTxinill 2.5 1-7 3.2 3.2 3.7 1.7 3.6 0.91.2 • 4 -8 3.72.2 § 15.6 H. 7 13.OT 1-6 15.1 14.9 14.5 15.5 15.2 30.6 3M 30.6 29-7 17.6 31- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy sAii 9.6 9b 9.0 9_6 9_5 9.1 9.3 • 3 • 9 1-2 18.3 1-6 16.211.6 1-0 i sound si%) s Yin 61.7 60-9 65.1 65.6 62.7 61.3 S. 2 53.5 5-7 59.5 5-1 57.5 54.7g. 3 57-

Si ,131¾ --------訂---------. 1 6 本紙張尺度適用中國國家標準（CNS)A.l規格（210 X 297公釐）五、發明說明（；><) S3諫鎇 s 3镟_屝逦(哲) 3 —Ms (6)13締 A7 B7 S9^ _B 30 31(5) 32 33 (5) 3公 35(5) 36 ^1 11ES 12FS. ΠCS - 5/1/2.B- 460 «圳VTrT_ 闲 p/NICOJIIb (6) 一£ OH 2.0 0. 7 2.1 1. 〇 -1 1.9 产0 15..4 14.9 14.5 15.4 17.° 14.3 14.9 AN 9.7 •9 9.1 9.2 10·1 3 9.5 (請先閱讀背面之注意事項再填寫本頁) 遽____Si, 131¾ -------- Order ---------. 1 6 This paper size applies to China National Standard (CNS) Al specification (210 X 297 mm) V. Description of the invention (&> <) S3 谏鎇 s 3 镟 _ 屝逦 (哲) 3 —Ms (6) 13 缔 A7 B7 S9 ^ _B 30 31 (5) 32 33 (5) 3 male 35 (5) 36 ^ 1 11ES 12FS ΠCS-5/1 / 2.B- 460 «Zhen VTrT_ Free p / NICOJIIb (6) 1 £ OH 2.0 0. 7 2.1 1. 〇-1 1.9 Production 0 15..4 14.9 14.5 15.4 17. ° 14.3 14.9 AN 9.7 • 9 9.1 9.2 10 · 1 3 9.5 (Please read the notes on the back before filling this page) 遽 ____

^口·— I — I I I 經濟部智慧財產局員工消費合作杜印製 62.5 59- 62.7 59.7 59_6 57.7 63.5 0-0S f 21^-/- §s) s s ------------------------ 本紙張尺度適用中國國家標準（CNS)A‘l規格（210 X 297公釐） A7 _ B7 五、發明說明（4) 雖然本發明是採用較佳的具體實施例作說明，應該理解的是習知此技人士在閲讀本說明書之後對本案之各種改良相當明顯。因此，應該理解的是本發明在此處欲涵蓋此類改良情況，而在爾後所附申請專利範園所請求範圍之内 (請先閱讀背面之注意事項再填寫本頁) -*\一° 經濟部智慧財產局員工消費合作社印製 -28 本紙張尺度適用中國國家標準（CNS)A4规格（2〗〇x 297公釐）^ 口 · — I — III Intellectual Property Cooperation of Employees of Intellectual Property Bureau of the Ministry of Economic Affairs 62.5 59- 62.7 59.7 59_6 57.7 63.5 0-0S f 21 ^-/-§s) ss ----------- ------------- This paper size applies to China National Standard (CNS) A'l specification (210 X 297 mm) A7 _ B7 V. Description of the invention (4) Although the present invention is It will be understood that the specific embodiments are described, and it should be understood that various modifications of the present case by the person skilled in the art after reading this specification are quite obvious. Therefore, it should be understood that the present invention intends to cover such improvements here, and is within the scope requested by the attached patent application park (please read the precautions on the back before filling this page)-* \ 一 ° Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics -28 This paper size applies to the Chinese National Standard (CNS) A4 specification (2) 0x297 mm

Claims

A8 B8 C8 D8, the scope of patent application of this application is 1 ~~ Improved the calcination at the temperature of 750 ° C to 10501 (please read the precautions on the back before filling ^^) Method, wherein the calcining catalyst includes the elements and relative amounts shown by the following formula: V vS b mA.aD dox where A is tin and titanium; 13 when D is present, it represents one or more of lithium, magnesium, sodium, and calcium , 缌, .barium, inscribed 'iron', 镕, gallium '_, zinc, germanium, silver, zirconium, molybdenum, tungsten, copper, associative molybdenum, selenium, rhenium, indium, indium, arsenic, boron, aluminum and manganese;. M and 'where all elements of the formula are cations other than oxygen' and v is *] _, mg.0, 5-10, a is greater than 0 and up to 1 〇, d is 0 to 1 〇, v + m + a > 0 '5d, x is determined by the cationic oxidation state. After printing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, it is at least 50 ° C and at least below this. Calcination_ effective temperature range of 50 ° C Inside the catalyst, heat treatment. 2 'As claimed in the patent application, the method belongs to item 1, wherein & contains v + m. 3: The method according to item 1 of the patent application park, wherein the heat treatment catalyst is then contacted with a ~ 7 liquid, the liquid system is selected from the group consisting of water, acid or alkaline aqueous solution; cyclohexanol; amyl alcohol; single warp group, containing 1 — Phenanthrene hydrocarbons of 8 carbon atoms; dihydroxy 'acyclic hydrocarbons of 2 to 4 carbon atoms. 4 'As in the method of applying for the second item of the patent scope, where the heat treatment catalyst is followed by I paper money, the Chinese National Standard (CNS) A4 secret (210X297 public love) — A8 B8 C8 D8? A method to improve the calcination of the catalyst previously calcined at a temperature of 750 ° C to 10501 (please read the precautions on the back and fill in the ^^ page), wherein the calcined catalyst includes the element shown in the following formula and Relative amount: V vS b mA.aD dox where A is tin and titanium; 13 when D is present, it represents one or more of lithium, magnesium, sodium, calcium, thallium, barium, inscription 'iron', gallium ' _, Zinc, germanium, silver, zirconium, molybdenum, tungsten, copper, associative molybdenum, selenium, perylene, osmium, indium, arsenic, boron, aluminum, and manganese; .M and 'where all elements of this formula are cations except oxygen 'And v is *] _, mg.0, 5—10, a is greater than 0 and up to 10, d is 0 to 10, v + m + a> 0' 5d, x is determined by the state of cationic oxidation After printing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, at least 500 ° C and at least lower than this. Calcination temperature in the effective temperature range of 50 ° C Into the character, heat treatment. 2 'As claimed in the patent application, the method belongs to item 1, wherein & contains v + m. 3: The method according to item 1 of the patent application park, wherein the heat treatment catalyst is then contacted with a ~ 7 liquid, the liquid system is selected from the group consisting of water, acid or alkaline aqueous solution; cyclohexanol; amyl alcohol; single warp group, containing 1 — Phenanthrene hydrocarbons of 8 carbon atoms; dihydroxy 'acyclic hydrocarbons of 2 to 4 carbon atoms. 4 'As for the method of applying for the second item of the patent scope, in which the heat treatment catalyst is followed by I paper money. Chinese national standard (CNS) A4 secret (210X297 public love) — A8 DO gs8 6. The scope of patent application' Contact with a tired body The fatigue system is selected from the group consisting of water, acid or alkaline water-soluble fatigue; cyclohexanol group and should, when. And should, when. Achieved by the ammonia reaction, the reaction of the ammonia reaction and the reaction of the ammonia reaction and the chemical reaction in the bank and the chemical office; the alkoxy store second into the alkoxy store second into the method 0 / alanine medium 8 8 Alanine medium 8 8 Fang: The contact of the square ring system ♦. The contact of the system * * of the undefined 4 2 of the fixed 4 2 items, select to * \, select to / 1 2 Should be shaped 2 1 Should be shaped 2 1 Chapter. The original anti-central institute. ♦ \ 反中所 * \ Surrounding carbonization and other methods. Oxygen, square-is oxygen, square, is: Lili 8 The degree of hydrocarbon amino nitrile is higher than the degree of ammonia purchased _ cyclic olefinic term warmer olefinic term warmer please please 1 non-line propylene 1 _ 懕莫行丙 2 Ying Mo f, Jia Shen Han's progress into the opposite, progress into the reverse and vice versa, such as, in the child 8 $ Wai ° 0 oxygen in the shape. Wai ° 0 oxygen system / primordial zone 'and Fan ο \ Zone and Fan ο / its Its g carbon should be 8 ammonia. It should be 8 ammonia, which should be anti-anti-specialist 4 / anti-anti-specialist 4 \ media media; 4 in oxygen please I alkane in oxygen please I alkane contact alcohol I am a kind of ammonia string ο Type A ammonia ο Type III S pentam S 1 line 茆 6 and a line such as 6 and a ring containing * enter in 4.K * advance. In 4K. Ο ^ * * ο; Γ 5 oxygen is between 6 oxygen is between 7 \ 8 (Please read the notes on the back of the cabinet first and then fill out this page) The paper printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese national standard (CNS) A4 specification (210 X 297 mm)