1286134 A7 - —- _____B7 五、發明説明（1 ) 發明背景 發明領璏 本發明係關一種乙烯氧化為環氧乙烷之觸媒，其係由 銀，械金屬如铯，鹹土金屬如锶，硫組份及選用之氟組份 殿積於載體如α -氧化鋁土所組成；及有關用觸媒生產環氧 乙烷。此觸媒本質上不含鍊或過渡金屬組份。 以往技術之說明 環氧乙院之製法包含用銀在載體如氧化鋁上組成的固態 觸媒以分子氧使乙烯汽相氧化。經許多工作者致力於改進 生產環氧乙烷用銀觸媒之效用與效率β美國專利5,〇51，395 提供以往工作者此等努力的廣泛解析β 此方面以往許多教示中，美國專利第4,〇〇7，135號（亦見 UK 1，491，447)教示生產環氧乙烷與丙烷之各種銀觸媒，其 包括助催量之銅，金，鎂，辞，鎘，汞，锶，鈣，鈮， 組，鉑’鶴，絡，釩與/或較佳鋇，超過任何在預成形載體 内呈固定式雜質或水泥（第2欄1-15行），生產環氧丙烷的 銀觸媒含助催量之至少一種選自鋰，鉀，鈉，铷，铯， 銅，金，鎂，鋅，鎘，鏢，鈣，鈮，钽，鉬，鎢，鉻，釩 及鋇中的助催劑，超過任何在預成形載體内呈固定式雜質 或水泥|第2攔1 6 - 3 4行），以及製造環氧乙烷或環氧丙烷之 銀觸媒含（a)助催量的鈉，铯，铷與/或鉀，及⑻鎂，鋰， 鈣與/或較佳鋇之助催量（第3欄5 - 8行）。 美國專利第5,057,481號與相關第4,908,343號係關銀環氧乙 院觸媒’由铯與一3 b至7b族元素的氧陰離子構成。銘列為 -4- 本纸張尺度逋用中國國家樑準(CNS) A4规格(2IQX 297公#) 1286134 A7 ---—- _ B7 五、發明説明（2 ) 一可能組份。 美國專利第3,888,889號說明適合氧化丙烯成環氧丙烷作 用的觸媒由元素銀經5b與6{3中一元素之化合物改良構成。 雖曾提起使用載體，但無實例。未提到使用铯。 歐洲公開案第266 01 5號係關於載體上的銀觸媒經鍊與一長 列可能的輔催劑助催。 美國專利第5,102,848號論及適用製造環氧乙烷之觸媒含 浸銀載體，其上亦有至少一種陽離子助催劑如铯，與含⑴ 硫酸根陰離子，（ii)氟化物陰離子，及（iii)週期表包括3b至 6b族一元素的氧陰離子之助摧劑。由於在申請專利的觸媒 範圍之外可能為比較用專利於21與22欄處表現一 6號觸媒 在載體上含八§/€3/3/?，其€5量為1〇96?0!11。 美國專利第5,486,628號說明經鹹金屬，銖及稀土或鑭屬 組份助催之銀觸媒。 美國專利第5,502,020號敘述一種環氧乙烯觸媒，其含 銀，鎢，铯與鉋以外的選用鹹金屬，鹹土金屬，稀土金屬 及選自IB-VB與IVA-VIA族之金屬。 在令人感到迷惑的龐大數量之文獻中，許多文獻互相矛 盾，申請人已發現生產環氧乙烯之一種新穎改良的觸媒。 發明之簡述 本發明係關一種改良的載體上銀環氧乙烷觸媒，其含助 催劑組合，其係由重要量之鹹金屬組份，較佳為铯，與硫 組份，鹹土金屬組份與選用之氟組份所組成，及有關觸媒 製備與用途；觸媒本質上不含鍊及過渡金屬組份。 •5- 本紙張尺度逋用中β β家標準(CNS> Α4规格(210 X 297公釐) 1286134 A7 B7 五、發明説明（3 新近研究結果吾人已發現以Cs/S/F及锶所製觸媒超過單獨 用铯，硫（成硫酸鹽）及氟（成氟化物）所製標準觸媒之成 就，尤其穩定性方面。在此情況下有鳃助催的觸媒得到 83.8%以上的選擇度並展現極大改進之安定度。 詳細說明 根據本發明製備的較佳觸媒含最多約35%重量之銀，以 金屬表示，澱積在多孔耐火料載體的表面及遍佈各孔。觸 媒含總重量20%以上之銀係有效的，但造成觸媒價格甚昂 貴。以金屬表示觸媒總重量約5-20%的銀含量為佳，而銀含 量8-15%特佳。 本發明觸媒中除銀外亦含一重要助催組合，其係由一定 量的鹹金屬，硫，氟與勰所組成β鹹金屬助催組份之重要 量以觸媒重量基按鹹金屬表示不超過3000 ppm ;觸媒較佳 含觸媒重量基計400-1500 ppm，尤佳500-1000 ppm械金屬。 鹹金屬宜係鉋，雖亦能用鋰，鈉，鉀，铷及混合物。有利 採用美國專利3,962,136内所述浸透程序添加鎚組份於觸 媒。 本發明實務亦必要供應硫作一助催觸媒組份，硫組份能 用硫酸鹽如硫酸鏠，及硫酸錄之類加入觸媒載體浸潰液。 美國專利4,766,105在例如第10欄53-60行敘述硫助催劑的用 途，此一公告在此引用參考。用硫（以元素表示）量基本上 根據本發明觸媒重量基計宜在5-300 ppm，較佳20-150 ppm ° 觸媒亦能含選用組份之氟助催劑，以觸媒重量基計其量 -6 - 本紙張尺度逋用中a國家揉i|t<CNS) A4规格<210X 297公釐) 12861341286134 A7 - - - _____B7 V. INSTRUCTION DESCRIPTION (1) BACKGROUND OF THE INVENTION The present invention relates to a catalyst for the oxidation of ethylene to ethylene oxide, which is made of silver, a mechanical metal such as barium, a salty metal such as barium, The sulfur component and the selected fluorine component are composed of a carrier such as α-alumina; and the catalyst is used to produce ethylene oxide. This catalyst essentially does not contain a chain or transition metal component. Description of the Prior Art The epoxy resin process involves the vapor phase oxidation of ethylene with molecular oxygen using a solid catalyst composed of silver on a support such as alumina. Through the efforts of many workers to improve the effectiveness and efficiency of silver catalysts for the production of ethylene oxide, US Patent 5, 〇 51,395 provides extensive analysis of the efforts of past workers. In this regard, many of the previous teachings, US Patent No. 4, 〇〇 7,135 (see also UK 1,491,447) teaches the production of various silver catalysts for ethylene oxide and propane, including the amount of copper, gold, magnesium, rhodium, cadmium, mercury,锶, calcium, strontium, group, platinum 'crane, complex, vanadium and/or preferably ruthenium, exceeding any fixed impurities or cement in the preformed carrier (column 2, lines 1-15), producing propylene oxide At least one of the silver catalyst-containing catalyzed doses is selected from the group consisting of lithium, potassium, sodium, rubidium, cesium, copper, gold, magnesium, zinc, cadmium, dart, calcium, strontium, barium, molybdenum, tungsten, chromium, vanadium and strontium. Promoter, more than any fixed impurities or cement in the preformed carrier | 2nd barrier 1 6 - 3 4 row), and silver catalyst for the manufacture of ethylene oxide or propylene oxide (a) The amount of sodium, strontium, barium and/or potassium, and (8) the amount of magnesium, lithium, calcium and/or preferably strontium (column 3, lines 5-8). U.S. Patent No. 5,057,481 and the related U.S. Patent No. 4,908,343 are incorporated herein by reference. It is listed as -4- This paper scale adopts China National Liang Zhun (CNS) A4 specification (2IQX 297 public #) 1286134 A7 ----- _ B7 V. Invention description (2) One possible component. U.S. Patent No. 3,888,889 teaches that a catalyst suitable for the action of propylene oxide to propylene oxide is modified from elemental silver via a compound of 5b and 6{3. Although the use of the carrier has been mentioned, there are no examples. There is no mention of using 铯. European Publication No. 266 01 5 relates to the silver catalyst on the carrier via a chain and a long list of possible cocatalysts. U.S. Patent No. 5,102,848 discloses a catalyst-impregnated silver carrier suitable for the manufacture of ethylene oxide having at least one cationic promoter such as ruthenium, and (1) sulfate anion, (ii) fluoride anion, and (iii) The periodic table includes an aid of an oxygen anion of a group 3b to 6b element. As the scope of the patented catalyst may be compared to the comparative patents in the 21st and 22nd columns, a 6th catalyst contains eight §/€3/3/? on the carrier, and the amount of €5 is 1〇96? 0!11. U.S. Patent No. 5,486,628 describes silver catalysts which are promoted by salty metals, cerium and rare earth or lanthanum components. U.S. Patent No. 5,502,020 describes an ethylene oxide catalyst comprising a salt metal, a salty metal, a rare earth metal and a metal selected from the group consisting of IB-VB and IVA-VIA, in addition to silver, tungsten, tantalum and planer. Among the confusing and large number of documents, many of which contradict each other, the Applicant has discovered a novel and improved catalyst for the production of ethylene oxide. BRIEF SUMMARY OF THE INVENTION The present invention is directed to an improved supported silver oxirane catalyst comprising a cocatalyst combination comprising an important amount of a salty metal component, preferably hydrazine, and a sulphur component, salty. The composition of the earth metal component and the selected fluorine component, and the preparation and use of the catalyst; the catalyst does not substantially contain the chain and transition metal components. • 5- The standard for beta β β in this paper size (CNS> Α4 specification (210 X 297 mm) 1286134 A7 B7 V. Description of invention (3) Recent findings We have found that Cs/S/F and 锶The catalyst exceeds the achievement of standard catalysts made of hydrazine, sulfur (sulphate) and fluorine (formed fluoride), especially in terms of stability. In this case, the catalyst is more than 83.8%. And exhibits greatly improved stability. DETAILED DESCRIPTION Preferred catalysts prepared in accordance with the present invention contain up to about 35% by weight silver, expressed as metal, deposited on the surface of the porous refractory support and throughout the pores. Silver with a total weight of more than 20% is effective, but the catalyst is expensive. The silver content of the catalyst is about 5-20% of the total weight of the catalyst, and the silver content is 8-15%. In addition to silver, the medium also contains an important auxiliary combination, which consists of a certain amount of salt metal, sulfur, fluorine and antimony. The important amount of the beta salt metal promoter component is not more than the salt weight of the catalyst. 3000 ppm; the catalyst is preferably 400-1500 ppm based on the catalyst weight basis, especially 500-1000 ppm The metal is suitable for planing, although lithium, sodium, potassium, strontium and mixtures can also be used. It is advantageous to add the hammer component to the catalyst by the soaking procedure described in U.S. Patent No. 3,962,136. The invention also requires the supply of sulfur as a aid. The catalyst component, the sulfur component can be added to the catalyst carrier impregnation solution with a sulfate such as barium sulfate, and sulfuric acid. The use of sulfur promoters is described, for example, in column 10, lines 53-60 of U.S. Patent 4,766,105. This publication is hereby incorporated by reference. The amount of sulfur (in terms of elements) is preferably from 5 to 300 ppm, preferably from 20 to 150 ppm °, based on the weight of the catalyst of the present invention. Promoter, based on the catalyst weight basis - 6 - This paper scale is used in a country 揉i|t<CNS) A4 size <210X 297 mm) 1286134
發明説明 按疋素F表示最多1〇〇〇 ppm，較佳2(M〇〇 ppm。能用氟化 錄’鹹金屬氧化物之類。 本發明需要一助催量的鹹土金屬組份。適宜鹹土組份為 C a ’ B a與S r，以s r較佳。鹹土組份以元素表示之用量為 觸媒重量基的10-1000 ppm重量比，較佳25-3〇〇沖m，基本 上根據本發明。醋酸勰，溴化鏍，氣化鋰，硝酸锶等以及 C a及B a相對物均能用。 製作觸媒以多孔耐火材料製備載體。較佳載體包括氧化 铭，梦石，矽石-氧化鋁或其組合物，木炭，浮石，碳化 石夕’氧化鎂，氧化錘及氧化鈮。較佳載體為其中主要含a. 氧化铭’特別其中含最多約丨5重量0/〇矽石者。 特佳載體有約〇· b〇 9 cc/g之孔率，約〇·2-〇·7 cc/g較宜。較 佳載體亦有相對低表面積，即用BET法測定約0.2-5.0 m2/g， 較佳 0.4-2.0 m2/g，最好 〇·5-1·3 m2/g。見 J· Am· Chem Soc· 60, 3098-16 (1938)。孔率用汞孔率計法測定；見Drake & Ritter, “Ind. Eng· Chem· anal· Ed·，” 17, 787 (1945)。孔與孔徑分配 係由表面積與表觀孔率測量決定β 在環氧乙烷商業生產實用中載體希望作成正規成形九 片’球形，環狀等。載體粒子宜有“當量直徑，，在3-1〇 mm範 圍，較佳在4-8 mm範圍内，一般能與其中放置觸媒的小管 内徑相容❶‘‘當量直徑”為一如所用載體粒子有相同外表面 (即不計粒子孔隙内表面）對體積比之球徑。 銀宜藉載體沉浸於銀/胺浸潰溶液或用起始潤濕技術加入 載體◊含銀液體藉吸收，毛細作用及/或真空滲入载體的 本紙浪尺度遴用中钃國家樑4KCNS) A4规格(210X 297公釐) 1286134 A7 B7 五、發明説明（5 ) 孔。單一浸潰或連串浸潰附帶或不帶中間乾燥皆可使用’ 分別視溶液中銀鹽濃度而定。欲得銀含量在較佳範圍内之 觸媒，適宜浸液一般可含5-50重量％銀以金屬表示。採用之 確實濃度在許多因數中自然當視所須含銀量’載體性質’ 液體黏度，以及銀化合物的溶解度。 選擇載體之浸潰作用以慣用方式達成。載體材料放在銀 溶液内直到全部溶液為載體吸收。 以上指示的浸潰溶液特徵為一銀/胺溶液，較佳如美國專 利3,702,259中詳述者，此處引用其發表參考。美國專利 3,962，136内所述浸潰程序作鉋組份採用有利。 預澱積，共澱積及澱積後之各種助催劑的已知以往程序 皆可採用。 浸潰後分離一切過多浸液，煅燒或活性化已浸銀之載鱧 與助催劑（等）^本發明的最佳實務中按1996/4/2所頒普通讓 渡之美國專利第5,504,052號及第1996/1/16號提出的審查中申 請案08/587,281號完成，在此引用參考。煅燒作用係藉浸過 之載體加熱達成，宜以漸進程度至200-500°C範圍内溫度歷 時足夠轉化所含之銀成銀金屬並分解有機物及變成揮發物 脫除。 浸過的載體於全部製程期間在300°C以上時隨意保持於惰 性氣氛下•不願受理論約束，相信300°C以上溫度時氧被大 量吸收入大部分銀内對觸媒特性有不利影響。發明内隨意 採用之惰性氣氛為本質上不含氧者。 煅燒的另一選擇方法為在溫度不超過350°C之空氣流内， -8 - 本紙張尺度遴用肀國踽家樣準(CNS) A4規格(21〇X 297公#) 1286134 A7 ——___B7 五、發明説明（6 ) 較佳不超過3 0 0 °C加熱觸媒。 根據本發明所製觸媒有改善功效，特別由分子氧汽相氧 化乙烯製造環氧乙烷之穩定性。此等通常包含約它至4〇〇 °C的溫度，一般約200°C至300°C，及自0·5至35巴範圍間之反 應壓力。反應物進料混合物含〇·5至20%乙烯與3-15%氧，其 他含較惰性物質包括氮，二氧化碳，f烷，乙烷，及氬等 物質。每行程通過觸媒的乙烯通常僅一部分反應，分離所 須環氧乙烷產物後移除適當清洗流體及二氧化碳以防止惰 性物與/或副產物不受控制的累積，未反應物質則送回氧化 反應器。 以往技術助催之觸媒缺點有一與此等觸媒附屬的不穩定 性。根據本發明，不含銖與過渡金屬之觸媒具有利的高選 擇性與高穩定性。 以下實例說明本發明。 實例1 用下列組份製備一銀溶液 (重量比份數）： 氧化銀-834份 草酸-442份 去離子水-2808份 乙二胺-415份 室溫中氧化銀與水混合後徐加草酸。混合物攪1 5分鐘’ 其時氧化銀之黑色懸浮液變為草酸銀之灰/棕色。濾、過混合 物，以3公升脫離子水清洗固體。 -9- 本紙杀尺度逋用t困钃家揲準(CNS) A4規格(210X 297公釐） 1286134DESCRIPTION OF THE INVENTION According to the halogen F, it is at most 1 〇〇〇 ppm, preferably 2 (M 〇〇 ppm. Fluoride can be used to record 'salt metal oxides and the like. The present invention requires a flux-promoting salty metal component. The salty soil component is C a ' B a and S r , preferably sr. The salty soil component is expressed by the element in an amount of 10-1000 ppm by weight based on the catalyst weight basis, preferably 25-3 〇〇m According to the invention, cerium acetate, cerium bromide, lithium hydride, cerium nitrate, etc., and the relatives of Ca and B a can be used. The catalyst is prepared by using a porous refractory material. Dream stone, vermiculite-alumina or its combination, charcoal, pumice, carbon stone, magnesium oxide, oxidized hammer and cerium oxide. The preferred carrier is mainly composed of a. Oxidation Ming 'specially containing up to about 5 weight 0/ vermiculite. The best carrier has a porosity of about 〇·b〇9 cc/g, preferably about 〇·〇·7 cc/g. The preferred carrier also has a relatively low surface area, ie BET The method is about 0.2-5.0 m2/g, preferably 0.4-2.0 m2/g, preferably 5-1·3 m2/g. See J. Am. Chem Soc. 60, 3098-16 (1938). Mercury hole For the determination of the method; see Drake & Ritter, “Ind. Eng·Chem· anal· Ed·,” 17, 787 (1945). The pore and pore size distribution is determined by surface area and apparent porosity measurements. In commercial production, the carrier is expected to be formed into a regular shape of nine pieces of spheres, rings, etc. The carrier particles should have an "equivalent diameter, in the range of 3-1 〇 mm, preferably in the range of 4-8 mm, which can generally be placed therein. The inner diameter of the small tube of the catalyst is compatible with the ''equivalent diameter') as the carrier particles have the same outer surface (ie, excluding the inner surface of the particle pores) and the volume ratio of the spherical diameter. Silver should be immersed in the silver/amine impregnation by the carrier. The solution or the initial wetting technique is added to the carrier, the silver-containing liquid is absorbed, the capillary action and/or the vacuum infiltrates into the carrier, and the paper is used in the medium-sized beam 4KCNS. A4 size (210X 297 mm) 1286134 A7 B7 , invention description (5) holes. Single or continuous dipping with or without intermediate drying can be used depending on the concentration of silver salt in the solution. In order to obtain a catalyst having a silver content within a preferred range, a suitable immersion liquid may generally contain 5 to 50% by weight of silver as a metal. The exact concentration employed is naturally dependent on the amount of silver 'carrier properties' liquid viscosity and the solubility of the silver compound. The impregnation of the selected carrier is achieved in a conventional manner. The carrier material is placed in the silver solution until all of the solution is absorbed by the carrier. The impregnation solution indicated above is characterized by a silver/amine solution, as described in detail in U.S. Patent No. 3,702,259, the disclosure of which is incorporated herein by reference. The impregnation procedure described in U.S. Patent 3,962,136 is advantageous for use as a planing component. Pre-deposition, known conventional procedures for co-deposition and deposition of various promoters can be employed. Separation of all excess immersion liquid after soaking, calcination or activation of immersion silver-loaded ruthenium and co-catalyst (etc.) ^ In the best practice of the invention, U.S. Patent No. 5,504,052, issued in accordance with 1996/4/2 No. 08/587,281, which is hereby incorporated by reference. The calcination is achieved by heating with a immersed carrier. It is preferred to convert the silver-containing silver metal contained in the process to a temperature in the range of 200-500 ° C and decompose the organic matter and become a volatile matter. The impregnated carrier is kept in an inert atmosphere at a temperature above 300 °C during the whole process. • It is not willing to be bound by theory. It is believed that oxygen is absorbed into most of the silver at a temperature above 300 °C, which has an adverse effect on the catalyst properties. . The inert atmosphere which is optionally employed in the invention is essentially oxygen free. Another method of calcination is to use air flow at a temperature not exceeding 350 ° C. -8 - This paper scale is used in the National Standard (CNS) A4 specification (21〇X 297 gong#) 1286134 A7 —— ___B7 V. Description of the invention (6) It is preferred not to heat the catalyst at 300 °C. The catalyst prepared according to the present invention has an improved effect, particularly the stability of ethylene oxide produced by molecular oxygen vapor phase oxidation of ethylene. These typically contain temperatures from about 4 ° C to about 4 ° C, typically from about 200 ° C to 300 ° C, and from -0.5 to 35 bar. The reactant feed mixture contains 〇·5 to 20% ethylene and 3-15% oxygen, and other relatively inert materials include nitrogen, carbon dioxide, f-alkane, ethane, and argon. The ethylene per catalyst through the catalyst is usually only partially reacted, the desired ethylene oxide product is separated and the appropriate cleaning fluid and carbon dioxide are removed to prevent uncontrolled accumulation of inerts and/or by-products, and the unreacted material is returned for oxidation. reactor. The shortcomings of the catalysts used in the past have been associated with the instability of these catalysts. According to the present invention, the catalyst containing no antimony and transition metal has a favorable high selectivity and high stability. The following examples illustrate the invention. Example 1 A silver solution (weight ratio parts) was prepared using the following components: silver oxide - 834 parts of oxalic acid - 442 parts of deionized water - 2808 parts of ethylenediamine - 415 parts of silver oxide mixed with water at room temperature and then added oxalic acid . The mixture was stirred for 15 minutes. At this time, the black suspension of silver oxide was changed to gray/brown oxalic acid. The mixture was filtered, and the mixture was washed with 3 liters of deionized water. -9- The paper is used to kill the scale and is difficult to use (CNS) A4 specification (210X 297 mm) 1286134
將盛此洗清固體的容器置冰浴内，攪拌中緩加乙二胺與 水（呈72%/28%混合物）俾保持反應溫度低於33t。乙二胺'· 水混合物全部添加後室溫中濾過溶液。用透明濾液作製備 觸媒之銀/胺儲液。 實例用載體得自Norton Co·，主要為5/16吋圓筒式α •氧化 鋁製作。載體有表面積0.65 m2/g ,孔隙度.3 cc/g ,及中點孔 徑1 ·5 μ。實例中約185份的銀溶液與不同量下列液體混合· 1· CsOH液（8%Cs重量比水液）， 2 ·氟化銨（3 % F重量比水液）， 3 ·硫酸氫銨（1 % S重量比水液）與锶之水液，助催劑溶液 量經調節得表内所示助催劑濃度。 攪拌銀儲液與助催液的混合物至確實均勻後加進4〇〇份載 體中。濕觸媒混合1 0分鐘後煅燒。 加熱觸媒達銀鹽之分解溫度使銀化合物烺燒並澱積。在 一控制氣氛有幾個加熱區的爐内完成《觸媒裝在移動帶上 於室溫進爐。逐區通過時觸媒漸升溫。上升達4〇〇 °C時觸媒 經過七加熱區。加熱區後移動帶通過冷卻區，觸媒漸冷至 100°C以下溫度。在爐内全部逗留時間22分鐘。爐中氣氛由 不同加熱區中氣流控制。有些例内如下表所示用空氣進行 煅燒。 在用鹽浴加熱之不銹鋼管中試驗觸含15 %乙婦，7 0/〇氧與 7 8%惰氣主要氮與二氧化碳之氣態混合物於300 p.s.i.g·送過 觸媒，調節反應溫度以獲得每小時每m3觸媒（WR-1) 165 kg 的環氧乙烷生產率，此溫度列入表内。 -10- 本纸浪尺度遒用中國國家橾準<CNS) A4规格<21〇x297公釐) 1286134 A7 B7 五、發明説明（8 ) 為測量觸媒之穩定性起見，提高觸媒（WR-2)的生產率至 每小時每m 3觸媒285 kg。選擇性與活性的退化率計算成對 照試樣的退化率百分比。 觸媒試驗結果綜列於下表。 iL· 試驗 載體 煅燒 氣氛 鹹土化物及 量 選擇性 WR-1 時溫度 WR-1 WR-2 選擇性 退化率 WR-2 活性退 化率 1 A n2 無（對照A) 84.4 236 100 100 2 A n2 CaCl2，52 ppm as Ca 84.9 226 61 67 3 A n2 SrCl2，100 ppm as Sr 84.6 231 44 44 4 A n2 SrCl2，110 ppm as Sr 84.6 230 50 28 5 B n2 無（對照B) 84.8 231 100 100 6 B n2 SrCh，105 ppm as Sr 84.5 234 44 20 7 B n2 BaCI2 » 170 ppm as Ba 84.5 237 76 0 8 B air SrCl2，100 ppm as Sr 84.4 235 52 35 [言主] 載體A，低表面積；氧化鋁（1.0 m2/g)，含Al203 97%以上 載體B，低表面積；氧化鋁（0.8 m2/g)，含Al2〇3 99%以上 WR-1=標準工作率（165 kg EO/hr/m3觸媒） WR-2=加速工作率（ 285 kg EO/hr5/m3觸媒） -11 - 本纸蒗尺度遴用+國國家標率(CNS> A4规格<210X297公釐） 1286134 A7 B7 五、發明説明（9 ) 每一觸媒製備使含70 ppm F，35 ppm S，12% Ag及1100 ppm Cs (載體 A)及 780 ppm Cs (載體 B)。 上表中試驗1與5為對照。數據證明經本發明獲得大為改 進之結果，即含鹹土組份的觸媒展現重大進步之穩定性。 含S r的觸媒得到特佳結果。 本紙張尺度逋用中國國家揉準(CNS> A4规格(210X 297公釐)The container in which the solid was washed was placed in an ice bath, and ethylenediamine and water (in a mixture of 72%/28%) were gradually added while stirring to maintain the reaction temperature below 33t. After the ethylenediamine'· water mixture was all added, the solution was filtered at room temperature. A clear filtrate was used as a silver/amine stock solution for the preparation of the catalyst. An example carrier was obtained from Norton Co., primarily 5/16 inch cylindrical alpha alumina. The carrier has a surface area of 0.65 m2/g, a porosity of .3 cc/g, and a midpoint pore diameter of 1. 5 μ. In the example, about 185 parts of the silver solution is mixed with different amounts of the following liquids: 1 · CsOH solution (8% Cs weight ratio water), 2 · ammonium fluoride (3 % F weight ratio water), 3 · ammonium hydrogen sulfate ( The concentration of the cocatalyst solution was adjusted to the concentration of the cocatalyst shown in the table. Stir the mixture of the silver stock solution and the helper solution until it is evenly distributed and add 4 parts of the carrier. The wet catalyst was mixed for 10 minutes and then calcined. The decomposition temperature of the silver catalyst is heated to cause the silver compound to be calcined and deposited. The catalyst is loaded into the moving belt at room temperature in a furnace with several heating zones in a controlled atmosphere. The catalyst gradually warmed up as the zone passed. When the temperature rises up to 4 °C, the catalyst passes through seven heating zones. After the heating zone, the moving belt passes through the cooling zone, and the catalyst gradually cools to a temperature below 100 °C. All stay in the furnace for 22 minutes. The atmosphere in the furnace is controlled by the gas flow in the different heating zones. In some cases, calcination is carried out with air as shown in the following table. In a stainless steel tube heated with a salt bath, the test was carried out with 15% of a woman, 7 0 / 〇 oxygen and 7 8% of inert gas, a mixture of main nitrogen and carbon dioxide at 300 psig · sent through the catalyst, adjust the reaction temperature to obtain each Ethylene oxide productivity per hour of m3 catalyst (WR-1) 165 kg, which is listed in the table. -10- This paper wave scale is used in China National Standard <CNS) A4 Specification <21〇x297 mm) 1286134 A7 B7 V. Invention Description (8) For measuring the stability of the catalyst, improve the catalyst The productivity of (WR-2) is 285 kg per m 3 of catalyst per hour. The rate of degradation of selectivity and activity is calculated as the percentage of degradation rate of the sample. The results of the catalyst test are summarized in the table below. iL· test carrier calcination atmosphere salty soil and quantity selectivity WR-1 temperature WR-1 WR-2 selective degradation rate WR-2 activity degradation rate 1 A n2 none (control A) 84.4 236 100 100 2 A n2 CaCl2 , 52 ppm as Ca 84.9 226 61 67 3 A n2 SrCl2, 100 ppm as Sr 84.6 231 44 44 4 A n2 SrCl2, 110 ppm as Sr 84.6 230 50 28 5 B n2 None (Control B) 84.8 231 100 100 6 B n2 SrCh, 105 ppm as Sr 84.5 234 44 20 7 B n2 BaCI2 » 170 ppm as Ba 84.5 237 76 0 8 B air SrCl2, 100 ppm as Sr 84.4 235 52 35 [Speaker] Carrier A, low surface area; alumina (1.0 M2/g), containing Al203 97% or more carrier B, low surface area; alumina (0.8 m2/g), containing Al2〇3 99% or more WR-1=standard working rate (165 kg EO/hr/m3 catalyst) WR-2=Accelerated working rate (285 kg EO/hr5/m3 catalyst) -11 - Paper size standard + National standard rate (CNS> A4 size <210X297 mm) 1286134 A7 B7 V. Description of invention (9) Each catalyst was prepared to contain 70 ppm F, 35 ppm S, 12% Ag and 1100 ppm Cs (Carrier A) and 780 ppm Cs (Carrier B). Tests 1 and 5 in the above table are controls. The data demonstrates that the results of the invention have been greatly improved, that is, the catalyst containing the salty component exhibits significant progress in stability. The catalyst containing S r gives excellent results. The paper size is based on the Chinese national standard (CNS> A4 specification (210X 297 mm)