201247320 六、發明說明： 【發明所屬之技術領域】 本發明係、關於-種藉由在包括成形含銀纖維及/或絲線 之成形觸媒體上氧化脫氫c,至ClQ醇來製備匕至心〇醛之方 • 法，其中該等含銀纖維及/或絲線之平均直徑在30 4出至 200 μηι之範圍内。 【先前技術】 很早已知藉由在銀觸媒上氧化/脫氫甲醇來製備曱醛之 方法’參見（例如Encycl〇pedia of IndustHai Chemistry，第 1 頁 ff。 所使用之銀觸媒可以多種形式使用。例如，作為顆粒狀 晶體銀，但是亦可以銀網或銀薄紗之形式。 US4,076,754(Du Pont)描述一種自甲醇、空氣及水製備 曱醛之二階段方法。所使用之觸媒包括由直徑為〇 〇丨4英 寸（即350 μηι或0.35 mm)之銀絲製成之20目銀薄紗（即網目 大小為1·25 mm)之40片層疊片。該銀薄紗之密度或空隙分 率未揭示於US 4,076,754中。 DE 2829035 Al(Heraeus)描述一種包括催化活性金屬纖 • 維之觸媒’該金屬纖維由銀、鉑、铑、鈀或基於其中之一 , 之合金組成’其中該金屬纖維係類毛氈以針軋複合物之方 式相互交織。該觸媒可應用於氨氧化及製造氫氰酸或甲 醛。帶狀纖維之橫截面可係具有100 μηι及50 μηι之尺寸之 矩形’長度可係介於10 cm與1 m之間°未描述該相互交織 之金屬纖維體之密度或空隙分率。 163874.doc 201247320 DE 3047193 Al(J〇hnS〇n Matthey)描述一種由銀或銀合 金製成之觸媒。該觸媒體係藉由熔紡方法或炫化提取方法 而製備。例如，藉由捲曲及切割加工宽為1至2 mm且厚為 50至60 μηι之帶狀物以形成長約1 cm且因此為相當短之纖 維之波狀觸媒體。DE 3〇47193八丨未揭示自該類觸媒體形 成之編織物、織造物 '毛氈或類似物。 雖然早已知曉醇催化氧化/脫氫為醛，更特定言之甲醇 催化氧化/脫氫為甲醛，但仍存在改良空間，例如，提高 觸媒活性 '甲醛選擇性（對於未改變觸媒活性有利）、或增 加在觸媒上下降之壓力。 申請者研究已顯示，特定言之就甲醇氧化脫氫為甲醛而 言，使用包含纖維或絲之結構作為觸媒並非是件簡單的事 情。此係因為成形觸媒體的構造必須可在（例如甲醇氧化 脫氫為甲醛之）工業製程之操作條件下建立穩定的引發反 應區。然而，當前技術水準尚未揭示此成形觸媒體之必要 特徵》 【發明内容】 由本發明所解決之問題係藉由使用包含成形含銀纖維及 /或絲線之成形觸媒體，提高醇氧化脫氫為醛（更特定言之 甲醇氧化脫氫為曱醛）之醛產量。 適用的C|至C|〇醇包括具有1至1〇個碳原子及一或多個， 較佳2至3個OH基團之醇。該等醇較佳具有丨或？個〇H基 團該等醇可係脂肪族、直鍵、分支鍵或環狀分子中包 括一或多個C-C雙鍵或三鍵，其可係芳烷基醇或烷芳基 163874.doc 201247320 醇。其較佳係—級醇或在多元醇之情況下為鄰位之c,至 C丨〇二醇。 所述及之（^至c1()醇之實例係甲醇、乙醇、丨_丙醇、異丙 醇、正丁醇、異丁醇、第二丁醇、第三丁醇、“2-乙二 醇、丙二醇、婦丙醇、戊二稀醇、卩戊二稀醇。甲醇 為特別佳。 適用的祕包括藉由氧化脫氫上述CjCi〇醇而獲 得之醛。該等醛分子中可具有一或多個醛基較佳分子中 含有1或2個醛基。根據本發明之Cl至C|Q醛之實例係蟻醛 (甲醛）、乙二醛（HCO-CHO)、戊二烯醛或異戊二烯醛。 在特別佳的實施例中，本發明之方法係用於自曱醇製 備蟻醛（曱醛）’如以下所描述。然而，針對上述^至^⑺醛 而言，亦可以類似形式進行此曱醇氧化製程。 用於甲醇氧化製程之適宜起始物質係藉由高壓或低壓方 法製備之純甲醇、工業級甲醇、粗曱醇、或有利係其與水 之混合物；起始物質中水性混合物之甲醇濃度有利地係在 60重量/〇至95重量0/〇之範圍内，及較佳係在7〇重量。、至 重量％之範圍内。一有利實施例使用根據DE_B_12 77 834、DE-C-12 35 881 與DE-C1 1 36 3 18 中所述之方法’藉 由移除低沸點餾分或分別用氧化劑與/或鹼金屬處理而純 化之粗曱醇。 將甲醇以蒸汽形式，有利地以與水蒸汽及可選的惰性氣 體之混合物添加至反應器空間。例如，氬氣適合用作該方 法之惰性氣體。 163874.doc 201247320 所使用之氧化劑可不僅係純氧，而且較佳係含氧氣體， 更特定言之空氣。有利地以0 25至06之莫耳比且更特定 言之0.35至0.5 mol氧氣/莫耳甲醇，使用氧氣及曱醇。水 蒸汽總量較佳不多於3.0，且有利係〇 67至i 75 m〇1/莫耳甲 醇。 在甲醛之工業操作方法中，通常將以上所述之反應混合 物在介於5(TC與20〇t之間的溫度下且通常介於ι匕訂與之 bar之間的絕對壓力下引入反應器。 隨後，通常將所提及之起始物質傳入本發明之觸媒體位 於其中的一或多個區中。 本發明之成形觸媒體係三維結構，其可藉由於含銀纖維 或含銀絲線之空間中之三維成形及/或排列而獲得。 該含銀纖維或絲線包含銀（其含量範圍在5〇重量％至1〇〇 重量。/。，較佳90重量❶/。至100重量％，且更佳98重量％至1〇〇 重量％)及元素週期表之第1 〇或第丨丨族之其他金屬，較佳係 選自含銅 '鈀、鈦之金屬（其含量範圍在〇重量％至5〇重量 %，較佳0重量％至1〇重量％，更佳〇重量％至2重量％)。 極適宜之含銀纖維或絲線包含幾乎1〇〇重量％之銀。 根據本發明之含銀纖維之長度通常為約1 mm至丨〇〇 mm ’而根據本發明之含銀絲線理論上可為無限長，然而 事實上其長度通常在幾釐米至數千米之範圍内。 該含銀纖維或絲線之平均直徑（在基本上圓形橫截面之 情況下）或平均對角線長度（在基本上矩形或方形橫截面之 情況下）係在30至200 μηι之範圍内，較佳在3〇至15〇从爪之 163874.doc 201247320 範圍内，且更佳在30至70 μπι之範圍内。 使用臟 ISO 4782「Nominal Wire 叫则咖如 w〇ven Screens」之方法，測定平均直徑或平均對角線長度。 含銀纖維或絲線係為熟習此項技術者所知，係可購得，201247320 VI. Description of the Invention: [Technical Field] The present invention relates to the preparation of bismuth to nucleate by oxidative dehydrogenation of c to a CQ alcohol on a shaped contact medium comprising shaped silver-containing fibers and/or filaments. The method of furfural, wherein the average diameter of the silver-containing fibers and/or filaments is in the range of from 30 4 to 200 μη. [Prior Art] A method for preparing furfural by oxidizing/dehydrogenating methanol on a silver catalyst is known very early [see, for example, Encycl〇pedia of IndustHai Chemistry, page 1 ff. The silver catalyst used can be in various forms. For example, as a granular crystalline silver, but also in the form of a silver mesh or a silver tissue. US 4,076,754 (Du Pont) describes a two-stage process for the preparation of furfural from methanol, air and water. Includes 40 laminate sheets of 20 mesh silver tissue (ie mesh size of 1·25 mm) made of 〇〇丨4 inch (ie 350 μηι or 0.35 mm) silver. The density of the silver tissue Or a void fraction is not disclosed in US 4,076,754. DE 2829035 Al (Heraeus) describes a catalyst comprising a catalytically active metal fiber. The metal fiber is composed of silver, platinum, rhodium, palladium or an alloy based on one of them. 'The metal fiber-based felts are interwoven with a needle-rolled composite. The catalyst can be applied to ammonia oxidation and to produce hydrocyanic acid or formaldehyde. The cross-section of the ribbon fibers can be 100 μηιη and 50 μηι Rectangular The length may be between 10 cm and 1 m. The density or void fraction of the interwoven metal fiber bodies is not described. 163874.doc 201247320 DE 3047193 Al(J〇hnS〇n Matthey) describes a type of silver or silver a catalyst made of an alloy prepared by a melt spinning method or a smear extraction method, for example, by crimping and cutting a ribbon having a width of 1 to 2 mm and a thickness of 50 to 60 μm. A wavy contact medium having a length of about 1 cm and thus a relatively short fiber is formed. DE 3〇47193 丨 丨 does not disclose a woven fabric, woven fabric felt or the like formed from such a contact medium. Although alcoholic catalytic oxidation has long been known /dehydrogenation to aldehyde, more specifically methanol catalytic oxidation / dehydrogenation to formaldehyde, but there is still room for improvement, for example, to improve catalyst activity 'formaldehyde selectivity (for unaltered catalyst activity), or increase in catalyst The pressure of the drop. Applicant's research has shown that, in particular, the oxidative dehydrogenation of methanol to formaldehyde, it is not a simple matter to use a structure containing fibers or filaments as a catalyst. This is because the formation of the shaped contact medium must be Available at For example, a stable initiation reaction zone is established under the operating conditions of an industrial process such as oxidative dehydrogenation of methanol to formaldehyde. However, the current state of the art has not revealed the necessary features of the shaped contact medium. [Disclosure] The problem solved by the present invention is The use of a shaped contact medium comprising shaped silver-containing fibers and/or filaments to increase the aldehyde yield of oxidative dehydrogenation of an alcohol to an aldehyde (more specifically, oxidative dehydrogenation of methanol to furfural). Suitable C| to C| sterols include An alcohol having 1 to 1 carbon atom and one or more, preferably 2 to 3, OH groups. Preferably, the alcohols have hydrazine or ? The hydrazine H group may be one or more CC double or triple bonds in an aliphatic, straight bond, branched bond or cyclic molecule, which may be an aralkyl alcohol or an alkylaryl group 163874.doc 201247320 alcohol. It is preferably a grade alcohol or an ortho c to a C diol in the case of a polyol. Examples of the (^ to c1() alcohols are methanol, ethanol, hydrazine-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, "2-ethane Alcohol, propylene glycol, propylene glycol, pentane dilute alcohol, pentylene dilute alcohol. Methanol is particularly preferred. Applicable secrets include aldehydes obtained by oxidative dehydrogenation of the above CjCi sterols. Or a plurality of aldehyde groups preferably have 1 or 2 aldehyde groups. Examples of Cl to C|Q aldehydes according to the invention are aldehyde (formaldehyde), glyoxal (HCO-CHO), pentadienal or Isoprene aldehyde. In a particularly preferred embodiment, the process of the invention is used to prepare formic aldehyde (furfural) from decyl alcohol as described below. However, for the above-mentioned oxime (7) aldehyde, The sterol oxidation process can be carried out in a similar manner. Suitable starting materials for the methanol oxidation process are pure methanol, technical grade methanol, crude sterol, or a mixture thereof with water prepared by a high pressure or low pressure process; The methanol concentration of the aqueous mixture in the starting material is advantageously in the range of from 60% by weight to 95% by weight, and preferably 7 〇 weight., to the range of % by weight. An advantageous embodiment uses the method described in DE_B_12 77 834, DE-C-12 35 881 and DE-C1 1 36 3 18 'by removing low boiling fractions or The crude sterol purified by treatment with an oxidizing agent and/or an alkali metal, respectively. The methanol is advantageously added to the reactor space in the form of a vapor, preferably with water vapor and optionally an inert gas. For example, argon is suitable for use as the The inert gas of the method. 163874.doc 201247320 The oxidizing agent used may be not only pure oxygen, but also preferably oxygen-containing gas, more specifically air. Advantageously, a molar ratio of 0 25 to 06 and more specifically 0.35 To 0.5 mol of oxygen per mole of methanol, using oxygen and sterol. The total amount of water vapor is preferably not more than 3.0, and is advantageously 〇67 to i 75 m〇1/mol methanol. In the industrial operation method of formaldehyde, The reaction mixture described above is usually introduced into the reactor at an absolute pressure between 5 (TC and 20 Torr) and usually between ι and bar. Subsequently, it will usually be mentioned The starting material is introduced into the touch medium of the present invention The one or more zones of the present invention. The shaped contact media of the present invention is a three-dimensional structure which can be obtained by three-dimensional forming and/or arranging in a space containing silver fibers or silver-containing wires. The silver-containing fiber or wire comprises Silver (the content of which ranges from 5% by weight to 1% by weight, preferably 90% by weight to 100% by weight, and more preferably from 98% by weight to 1% by weight) and the 1 〇 or other metals of the 丨丨 family, preferably selected from the group consisting of copper-palladium, titanium metal (the content of which ranges from 〇% by weight to 5% by weight, preferably from 0% by weight to 1% by weight, more 〇% by weight to 2% by weight.) A very suitable silver-containing fiber or thread contains almost 1% by weight of silver. The length of the silver-containing fiber according to the present invention is usually from about 1 mm to 丨〇〇mm ', and the silver-containing thread according to the present invention may theoretically be infinitely long, but in fact its length is usually in the range of several centimeters to several kilometers. Inside. The average diameter of the silver-containing fibers or filaments (in the case of a substantially circular cross section) or the average diagonal length (in the case of a substantially rectangular or square cross section) is in the range of 30 to 200 μηι, It is preferably in the range of 3〇 to 15〇 from the 163874.doc 201247320 of the claw, and more preferably in the range of 30 to 70 μπι. The average diameter or average diagonal length is determined using the method of dirty ISO 4782 "Nominal Wire called w〇ven Screens". Silver-containing fibers or silk threads are known to those skilled in the art and are commercially available,
* 且可用作（例如）高價值紡織品或抗腐蝕感測應用（例如pH . 測定）中之導電材料。 可有序或無序達成該等含銀纖維或絲線在空間中之三维 成形及/或排歹〇 無序成形及/或排列根據本發明之含銀纖維或較佳根據 本發明之含料線itt導致所謂H料可藉由例如 纖維或絲以形成統計上非均勻排列之線團，且隨後使用多 種壓力進步壓縮’以於線團中達到所需之線團密度或所 需之空隙分率而獲得。 此等.線團中’根據本發明之含銀纖維或絲線在空間中以 無規律排列，且亦可如&般彼此互相接合，且藉此獲得 (例如）其特疋的機械穩定性。此類型之線團在下文中亦稱 為「本發明含銀線團」。 a:纖維或線之該有序成形及/或排列導致具有週期性 5複早t單70 (例如網孔或小孔）之本f上規則及有序的結 在工間中有序成形及/或排列含銀纖維或較佳絲線之 極適合方法係針織或編織等及隨後增密化。 由含銀纖維或較佳含銀絲線形成之極適宜的有序結構係 所謂之編織物戍姻此 ’、 飞騎物，例如其具有在300至50目（80㈣ 至5〇〇 μπι)範圍，赫社 較佳在300至1〇〇目（80 0111至25〇 μηι)範圍 163874.doc 201247320 的網格尺寸。該等編織物或網狀物在下文中係亦稱為「本 發明含銀編織物料」。 本發明含銀編織物料或本發明含銀線團之密度一般係在 2 g/cm3至4 g/cm3之範圍内，且較佳在3 §/〇1113至4 g/cm3之 範圍内。 在本發明含銀編織物料或本發明含銀線團中，該密度一 般對應於在60。/〇至80% ’較佳60%至75%之範圍内之空隙分 率。 咼於80%之空隙分率係不利的。本發明含銀編織物料或 本發明含銀線團之空隙分率亦有利於確保在極低溫度（例 如，350°C或以下且有利地在2〇〇至35〇〇c之範圍）下甲醇之 催化氧化/脫氫反應之「引發」。通常言之，預熱本發明 含銀編織物料或本發明含銀線團，直至反應（甲醇氧化脫 氫為甲醛）引發。其後，所提及之反應一般係於隔熱條件 下自行維持》 本發明含銀編織物料或本發明含銀線團之上述密度及空 隙分率係由如下方法測定：稱重已知幾何體。其重量與由 其所佔之體積之比率確定密度。相對於由相同材料組成之 幾何上相同粗厚體之重量之比率定義其空隙分率。 本發明之成形觸媒體可以多種空間形式存在。 例如，形成本發明之成形觸媒體之本發明含銀線團或較 佳本發明含銀編織物料可作為墊或圓盤（即長度和寬度為 其高度之許多倍的類片結構）存在。視情況，複數個2形 觸媒體可彼此堆疊於頂部上或以分段方式置於 163874.doc 201247320 在。 例如，形成本發明之成形觸媒體之本發明含銀線團或較 佳本發明含銀編織物料亦可以拉西環（Raschig ring)及/或 螺旋線形式存在。 本發明之成形觸媒體之絕對測量值一般取決於其中使用 該成形觸媒體之反應器之尺寸。 本發明之成形觸媒體之示例性尺寸為長度在丨2〇至cm 之範圍内，寬度在1至10⑽之範圍内，且高度在1至丨〇 cm 且較佳在2至4 cm之範圍内。 本發明之成形觸媒體之幾何形狀一般係可變。 以上述尺寸之矩形/長方體或圓形/圓盤形或圓柱形觸媒 體為較佳，例如，圓形觸媒體之直徑係在2 cm至3〇() em之 範圍内，較佳在25 cm至300 cm之範圍内，更佳在5〇 (^至 300 cm之範圍内。 通常言之，該成形觸媒體係用於反應空間中，其中上述 起始物質（例如醇（如甲醇）、含氧氣體）係安置於載體裝置 上反應。 此載體裝置係為人所知，例如不同材料，較佳金屬（例 如不銹鋼或銀）之網格、籃子或穿孔板、或牢固網狀物。 本發明之成形觸媒體可作為唯一催化活性成分存在於反 應區中，該反應區中使用包括曱醇、氧氣及水之上述起始 物質/流。然而，本發明之成形觸媒體亦可在顆粒銀觸媒 及/或用於醇氧化脫氫為醛之其他觸媒之存在下存在。 例如，可存在根據本發明之成形觸媒體之層狀結構"顆 163874.doc 201247320 粒銀觸媒。 、。使用複數個反應區，該反應區中使用上述起始物質/ 流，例如醇（如甲贿、. 、甲醇）、含氧氣體，且其包含「串聯連接」 之本發明之觸姐。 ^ 可在一個反應器中或反應器級聯中實現 串聯連接。 此外該方法係以習知方式進行，例如，藉由在約550 C更特定言之595至71〇°c之溫度下，使以上述含 量之曱醇蒸汽、空氣、可選之惰性氣體及有利之水蒸汽之 Hi 穿過包含本發明之觸媒體之反應區。一般而 β ’在介於0.5與2 bar ’且較佳介於丨^與丨8 ^『之間的絕 對壓力下，以連續操作方式進行該方法。此處宜在短時間 内將離開催化區之反應氣體冷卻至例如至3 5〇。匸之溫 度。氣體混合物已經冷卻後，將其饋入吸收塔中，其中利 用水自氣體混合物中洗滌出甲醛（有利地逆流）。 該方法亦更特定言之描述於觸WUllmanaE卿d〇pedia of Industrial Chemistry，第 1 頁及之後 _。 根據本發明之方法之優點特定言之係·· 與習知觸媒相I，提高C丨至Cl。醛(尤其是甲醛)產率(例 如，甲醛的較高選擇性，及例如在較低觸媒量時之相當的 甲醇轉化率）。 就層厚度與材料密度而言，提高觸媒填裝之均一性。 藉由特定調整該成形體之幾何形狀，更特定言之絲/纖 維結構（關於該成形體之直徑及密度），可影響本發明之成 形觸媒體之催化特性。 l63S74.doc -10- 201247320 ‘驚人的是’在成形觸媒體之幾何學及結構參數與提高化 學生產率之間產生關係。在此關係中可觀察到，例如，在 氧化脫氫甲醇時，隨著絲直徑變小，單次穿過催化床之甲 酸產量増加。 【實施方式】 實例 實例1 將具有水/曱醇等於^之莫耳比之氣態水_甲醇混合物與 空氣（140Nl/h)及氮氣（5〇Nl/h)混合，使得甲醇與氧氣之莫 耳比係2.5。將該混合物在反應器上游的預熱器中加熱至 14 0 C，隨後通過編織銀觸媒。該觸媒由成形圓柱體組 成’其具有10 mm之高度及20 mm之直徑。該成形體由壓 縮銀織品組成，其具有〇.〇5 mm之纖維直徑（成形體密度： 3 g/cm3，空隙分率：75〇/0) 〇在石英玻璃反應器（内部直徑 為20 mm)内隔熱進行操作。該反應器之絕熱藉由被動絕緣 及完全免除任何補償性加熱而達成。爲了確保在銀觸媒上 絕熱進行之反應之引發，將曱醇·水-空氣-氮氣混合物加熱 至300t，在該溫度下，曱醇/氧氣之莫耳比係7:1，且氮氣 係計量為300 Nl/h。隔熱引發確保係在3〇〇°c ^隨後，遞增 計量水/曱醇/空氣/氮氣之上述組合物。在如上所述設置該 計量及預熱器溫度時，在已引發之隔熱反應中，催化床溫 度達到595°C。達成在觸媒上之95 OOOh·1之每小時重量空 間速度。將自催化床形成之產物混合物在熱交換器中冷卻 至120t。藉由氣相層析分析該產物混合物之組成。在所 I63874.doc 201247320 述條件下’可達成99〇/〇之曱醇轉化率與90%之曱醛選擇 性°習知使用之電解製備之顆粒銀觸媒（片段大小〇.5至2 mm)在990/〇之曱醇轉化率時，達成87〇/〇之甲醛選擇性。 實例2 關於反應物計量與觸媒引發，重複實例1。所使用之觸 媒係由壓縮銀網狀物製成之三維成形圓柱體。該銀絲之直 徑係0.076 mrr^該成形觸媒體之高度係2〇 mm，直徑係2〇 mm。在所述條件下，達成98〇/〇之曱醇轉化率與9〇0/〇之曱醛 選擇性。習知使用之電解製備之顆粒銀觸媒（片段大小0.5 至2 mm)在98%之曱醇轉化率時，達成87%之曱醛選擇性。 實例3 關於反應物計量及觸媒引發，重複實例丨。所使用之觸 媒係由先編織後壓縮之銀絲製成之三維成形圓柱體。該銀 絲直徑係0_ 1 mm。壓製的編織物料之密度係3 g/cm3 ^該成 形觸媒體的高度係10 mm，直徑係2〇 mm。在所述條件 下，達成96〇/〇之甲醇轉化率與91 〇/0之曱醛選擇性。習知使 用之電解製備之顆粒銀觸媒（片段大小〇5至2 mm)在96%之 甲醇轉化率時，達成90%之甲醛選擇性。 實例1至3之參數係於以下圖1中說明。 【圖式簡單說明】 圆1:觸媒性能（基於甲醇之曱酸產率）對形成該成形觸 媒體之所使用絲之直控的依賴性。所有成形體具有相同體 積與相同密度。該反應條件為同一。 163874.doc •12·* and can be used as a conductive material in, for example, high value textiles or corrosion resistant sensing applications such as pH. The three-dimensional forming and/or drainage disorder forming and/or arranging of the silver-containing fibers or filaments in space may be ordered or disordered, and the silver-containing fibers according to the invention or preferably the feed lines according to the invention may be arranged. Itt causes the so-called H material to be formed by, for example, fibers or filaments to form a statistically non-uniformly aligned coil, and then progressively compresses using a variety of pressures to achieve the desired cluster density or desired void fraction in the coil. And get. In the above-mentioned coils, the silver-containing fibers or threads according to the present invention are arranged irregularly in space, and may also be joined to each other as & and thereby obtain, for example, their characteristic mechanical stability. This type of coil is also referred to hereinafter as "the silver-containing coil of the present invention". a: the orderly shaping and/or arranging of the fibers or wires results in a regular and regular formation of the regular and ordered knots in the process with periodicity 5, early t-single 70 (eg, mesh or small holes) and / or the most suitable method of arranging silver-containing fibers or preferred threads is knitting or weaving, etc. and subsequent densification. A highly suitable ordered structure formed of silver-containing fibers or preferably silver-containing filaments is a so-called woven fabric, such as a flying object, for example, having a range of 300 to 50 mesh (80 (four) to 5 〇〇 μπι). Hertz preferably has a mesh size of 163874.doc 201247320 in the range of 300 to 1 item (80 0111 to 25 〇 μηι). These braids or webs are also referred to hereinafter as "the silver-containing woven material of the present invention". The density of the silver-containing woven material of the present invention or the silver-containing wire group of the present invention is generally in the range of 2 g/cm3 to 4 g/cm3, and preferably in the range of 3 §/〇1113 to 4 g/cm3. In the silver-containing woven material of the present invention or the silver-containing wire group of the present invention, the density generally corresponds to 60. /〇 to 80% 。 preferably a void fraction in the range of 60% to 75%. A gap of 80% is unfavorable. The void fraction of the silver-containing woven material of the present invention or the silver-containing wire group of the present invention is also advantageous for ensuring methanol at an extremely low temperature (for example, 350 ° C or below and advantageously in the range of 2 〇〇 to 35 〇〇 c). The "initiation" of the catalytic oxidation/dehydrogenation reaction. In general, the silver-containing woven material of the present invention or the silver-containing wire group of the present invention is preheated until the reaction (oxidation of methanol to deoxygenation to formaldehyde) is initiated. Thereafter, the reactions referred to are generally self-sustaining under insulating conditions. The above-described density and void fraction of the silver-containing woven material of the present invention or the silver-containing filaments of the present invention are determined by weighing the known geometry. The density is determined by the ratio of the weight to the volume occupied by it. The void fraction is defined relative to the ratio of the weight of the geometrically identical thick body composed of the same material. The shaped touch media of the present invention can exist in a variety of spatial forms. For example, the silver-containing braid of the present invention or the silver-containing woven material of the present invention which forms the shaped contact medium of the present invention can be present as a mat or disc (i.e., a sheet-like structure having a length and width many times its height). Optionally, a plurality of 2-touch media can be stacked on top of each other or in a segmented manner at 163874.doc 201247320. For example, the silver-containing wire cluster of the present invention or the silver-containing woven material of the present invention which forms the shaped contact medium of the present invention may also be present in the form of a Raschig ring and/or a spiral. The absolute measurement of the shaped touch media of the present invention will generally depend on the size of the reactor in which the shaped touch media is used. Exemplary dimensions of the shaped touch media of the present invention are in the range of 丨2〇 to cm, widths in the range of 1 to 10 (10), and heights in the range of 1 to 丨〇cm and preferably 2 to 4 cm. . The geometry of the shaped touch media of the present invention is generally variable. Preferably, a rectangular/cuboid or circular/disc or cylindrical contact medium of the above size is used. For example, the diameter of the circular contact medium is in the range of 2 cm to 3 〇 () em, preferably 25 cm. In the range of up to 300 cm, more preferably in the range of 5 〇 (^ to 300 cm). Generally speaking, the shaped contact medium is used in the reaction space, wherein the above starting materials (for example, alcohol (such as methanol), The oxygen gas is disposed on a carrier device. The carrier device is known, for example, a mesh of different materials, preferably a metal such as stainless steel or silver, a basket or perforated plate, or a solid mesh. The shaped contact medium may be present as the sole catalytically active component in the reaction zone in which the above starting materials/streams including decyl alcohol, oxygen and water are used. However, the shaped contact medium of the present invention may also be in the silver contact of particles The medium and/or other catalyst for oxidative dehydrogenation of the alcohol to the aldehyde is present. For example, there may be a layered structure of the shaped contact medium according to the present invention "163163.doc 201247320 granule silver catalyst. Using a plurality of reaction zones, The above starting materials/streams, such as alcohols (e.g., bribes, methanol, methanol), oxygen-containing gases, and the "series-connected" of the present invention are used in the zone. ^ Can be reacted in a reactor or in a reactor The series connection is achieved in the cascade. Further, the method is carried out in a conventional manner, for example, by decyl alcohol vapor, air at a temperature of about 550 C, more specifically 595 to 71 ° C. The optional inert gas and the advantageous water vapor Hi pass through the reaction zone comprising the touch medium of the present invention. Typically, β 'is between 0.5 and 2 bar 'and preferably between 丨^ and 丨8 ^ The method is carried out in a continuous operation under absolute pressure. The reaction gas leaving the catalytic zone is preferably cooled in a short time to, for example, a temperature of 35 Torr. After the gas mixture has been cooled, it is fed into the absorption. In the column, wherein formaldehyde is eluted from the gas mixture by means of water (advantageously countercurrent). The method is also described more specifically in the context of U.S. Patent No. 1, pp. 1 and after. The method according to the invention Advantage In conclusion, · · Improve the yield of aldehydes (especially formaldehyde) from C 丨 to Cl. (for example, higher selectivity of formaldehyde, and equivalent, for example, at lower catalyst amounts) Methanol conversion rate). Improve the uniformity of the catalyst packing in terms of layer thickness and material density. By specifically adjusting the geometry of the shaped body, more specifically the filament/fiber structure (with respect to the diameter of the shaped body and Density) can affect the catalytic properties of the shaped contact media of the present invention. l63S74.doc -10- 201247320 'Amazingly' is the relationship between the geometry and structural parameters of the shaped contact media and the increased chemical productivity. It can be observed in this relationship that, for example, in the oxidative dehydrogenation of methanol, as the wire diameter becomes smaller, the yield of formic acid passing through the catalyst bed a single time is increased. [Examples] Example 1 A gaseous water-methanol mixture having a molar ratio of water/sterol equal to 2 was mixed with air (140 Nl/h) and nitrogen (5 〇Nl/h) to make methanol and oxygen. The ratio is 2.5. The mixture was heated to 140 C in a preheater upstream of the reactor and subsequently passed through a woven silver catalyst. The catalyst consists of a shaped cylinder having a height of 10 mm and a diameter of 20 mm. The shaped body consists of a compressed silver fabric having a fiber diameter of 〇.〇5 mm (shape density: 3 g/cm3, void fraction: 75 〇/0) 〇 in a quartz glass reactor (internal diameter 20 mm) ) Internal insulation for operation. The insulation of the reactor is achieved by passive insulation and complete elimination of any compensating heating. In order to ensure the initiation of the adiabatic reaction on the silver catalyst, the sterol-water-air-nitrogen mixture is heated to 300 t, at which temperature the molar ratio of sterol/oxygen is 7:1, and the nitrogen is metered. It is 300 Nl/h. The insulation initiation ensures that the above composition is metered in water/sterol/air/nitrogen at a temperature of 3 °C. When the metering and preheater temperatures were set as described above, the temperature of the catalyst bed reached 595 ° C in the initiated heat insulation reaction. Achieved an hourly weight space velocity of 95 OOOh·1 on the catalyst. The product mixture formed from the autocatalytic bed was cooled to 120 t in a heat exchanger. The composition of the product mixture was analyzed by gas chromatography. Under the conditions described in I63874.doc 201247320, '99 〇 / 〇 sterol conversion and 90% valence selectivity can be achieved. The electrolytically prepared granule silver catalyst is used (fragment size 〇 5 to 2 mm At a 990/〇 sterol conversion, a formaldehyde selectivity of 87 Å/〇 was achieved. Example 2 Example 1 was repeated with respect to reactant metering and catalyst initiation. The catalyst used is a three-dimensional shaped cylinder made of a compressed silver mesh. The diameter of the silver wire is 0.076 mrr. The height of the shaped contact medium is 2 mm and the diameter is 2 mm. Under the conditions described, a 98 〇/〇 sterol conversion rate and a 〇0/〇 valence selectivity were achieved. The electrolytically prepared particulate silver catalyst (fragment size 0.5 to 2 mm) used in the prior art achieves 87% furfural selectivity at 98% sterol conversion. Example 3 Example 丨 is repeated for reactant metering and catalyst initiation. The catalyst used is a three-dimensionally shaped cylinder made of woven and then compressed silver. The silver wire diameter is 0_ 1 mm. The density of the pressed woven material is 3 g/cm3 ^ The height of the shaped contact medium is 10 mm and the diameter is 2 mm. Under the conditions described, a methanol conversion of 96 〇/〇 and a selectivity to furfural of 91 〇/0 were achieved. The electrolytically prepared particulate silver catalyst (fragment size 〇 5 to 2 mm) is conventionally used to achieve 90% formaldehyde selectivity at a methanol conversion of 96%. The parameters of Examples 1 to 3 are illustrated in Figure 1 below. BRIEF DESCRIPTION OF THE DRAWINGS Circle 1: Catalyst performance (based on methanolic citric acid yield) dependence on the direct control of the filaments used to form the shaped contact medium. All shaped bodies have the same volume and the same density. The reaction conditions are the same. 163874.doc •12·