第86114480號專利申請案 A7 中文説明書修正頁(87年11月） β7 象正· ---^ 五、發明説明（8 ) 氣導致的氫的損失的方法，以求得離開氣體對進氣的比 率。 氫對丁炔二醇的莫耳比率，在反應器中至少爲3: 1 ， 較佳爲4 : 1到100 : 1。 本發明方法的進行乃是在氣體-循環模式中以固定床觸 媒作用，亦即，離開反應器的氣體，補充新鮮氬氣後若適 當可以再循環，經由壓·縮機返回反應器。經由噴射式壓縮 機可以運送全部的循3哀氣體或部分的循環氣體。在較佳的 具體例中，循環氣體壓縮機爲較不筇貴的噴嘴所取代。經 由如循環液體的導入而完成壓縮的工作。液體需_要增加的 壓力以操作喷射式壓縮機而言，爲由約3到5巴。 施行本發明方法用於觸媒固定床的適當反應器，例如， 圖1所示的固定床反應器或圖2所示的管束反應器。 圖之簡單説明 圖1顯示一種可使用於本發明方法的固定床反應器之配 置。 圖2顯示一種可使用於本發明方法的管束反應器之配 置。 圖3顯示一種可使用於本發明方法的噴射式喷嘴反應 經濟部中央標準局員工消費合作社印製 (請先閡讀背面之注意事項再镇寫本頁) 器。 圖4顯示一種可使用於本發明方法的泡沫式管柱。 圖式主要元件符號之意義 符號 意義 1 反應器 2 觸媒顆粒床 3 鐵網 _u. 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 五、發明説明（1 ) A7 B7 本發明係關於藉1，4-丁炔二醇之催化氫化作用製備η ^二醇的方法’在存有固態氫化催化劑之下，氫氣的壓力_ 馬/至200巴，而液態側體積質量傳遞係數的値由〇土 秒-1至1秒―1，此時液體形成連續相，而氫形成分散相。· 1，4· 丁炔二醇的氫化產生14_ 丁二醇，此乃藉由以下示 意圖的各別步驟而形成。 [催化劑] HOCH2C == CCH2OH + H2--—^ HOCH ΓΤΤ r>rr/-iTT [催化劑] >hoch2ch = chch2oh + h2 經濟部中央標準局員工消費合作社印製 hoch2(ch2)2ch2oh 上式已完成了數十年，且描述過許多A。然而，此—已知 的方法有低的、不經濟的空間—時間產率的缺點，亦即， 當壓力低於2GG巴進行氫化作用時，每—反應器的體積和 單位時間用的起始材料的量呈現低催化劑壽命和低選擇 性。除此之外，當催化劑用於固定床時，氫化需要超過 2〇〇巴的高壓，這也伴隨了高資本的代價。 而且，1，4-丁炔二醇，丁缔二醇和由此衍生出來的 化,物’假如眞有其事，可以從j,4•丁（烷）二醇中困難的 4餾分離出來；例如，藉由丁烯二醇的異構化而形成的曱 醛攸丁（烷）二醇和氫氣化丁醛中蒸餾分離出來。然而，以 1’4 丁一醇的進一步加工而言，在大部份的應用上均嚴格 需求不得有不完全氫化產物之存在。 化學反應中’通常轉化率的升高伴隨著選擇性的降低。 因此辛苦的工作完成此—反應，一方面以儘可能低的溫 度’另一方面以部分轉換率換取儘可能高的選擇性。在丁 (讀先聞讀背面之注意事碩再填寫本頁.) 裝. -訂 丨¥ 經 濟 部 中 央 標 準 員 工 消 費 合 杜 印 製 第86114480號專利申請案 A? 中文説明書修正頁(87年11月） B7 奶年“Ma i 'λ' 1 五、發明説明（& ) 4 液體進料 5 管線 6 混合噴嘴 7 管線 8 管線 9 氣相/液相之兩/相混合物 10 氣體/液體分離器 i 11 氣體流 1 2 次流 13 墨縮機 14 次流 1 5 管 16 熱交換器 2 0 填充 2 1 幫浦 圖1 描繪出可用於本發明方法的固定床反應器的配置。 反應器 1含有平均粒徑1到20毫米（較佳2到5毫米）觸 媒顆粒床2 。爲避免觸媒顆粒由反應器中被攜出，鐵網3 置放於觸媒床的上方末端。液體進料4包含丁炔二醇和 水，經由管線及循環液體經由管線5 以噴射驅動至混合噴 嘴6， 在其中新鮮氫氣經由管線7而循環氧體經由管線8 於其中混合。氣相/液相的兩相混合物 9由反應器1之上 方末端離開，而在氣體/液體分離器 10分離之。氣流11 的次流 12被除去而排出，以避免惰性组份的累積。循環 氣流8 經由壓縮機13再循環而進入混合喷嘴6。假如循 環液體 5藉由幫浦21傳送時，壓縮機可以省略，且能提 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-Ha 請 先 閲 讀 背 I 事 項 再 填 寫 本 頁 A7 B7 异、發明説明（2 ) ~ 炔二醇氫化中，爲了後續工作可接受的產品品質，完全轉 (讀先閱讀背面之注意事項再填寫本頁) 化是基本要求，所以氫化常分散於不同條件下操作的數個 反應器中。 - US-A 5 068 468揭示於固體擔載之鎳/鋼催化劑上令14_ 丁炔二醇氫化，其中空間-時間產率於250巴壓力下爲 〇.3公斤丁二醇/升小時。 BE-B 745 225揭示於2S9巴下以雷尼（Raney)鎳觸媒於固 足床中反應’其達到的空間-時間產率於二階段製程中爲 0.286公斤丁二醇/升小時。 US_A 4 153 578揭示一種二階段製程用於14_ 丁块二醇的 氫化，於21巴壓力下以懸浮的雷尼鎳/鉬觸媒作用，此製 程達到的空間-時間產率爲0.06公斤丁二醇/升小時。 DD-A 272 644揭示以鎳/ SiCb觸媒催化的丁炔二醇水溶液 的懸浮氫化。假設丁块二醇通常使用的濃度爲39到50% 重量分率而且假設完全轉換，計算得空間-時間產率於 15巴壓力下由0.15到0_25公斤丁二醇/升小時。使用的觸 媒僅僅經過50小時卻顯示出活性損失37%。 經濟部中央標準局員工消費合作社印掣 US-A 2 967 8们實例1中，以雷尼鎳-銅觸媒氫化1，4- 丁 块二醇計算所得的空間-時間產率爲約0.01公斤丁二醇/ 升小時。 RU-A 202 913揭示以鎳/ 5鍺觸媒氫化丁決二醇的空間-時間產率爲0.1公斤丁二醇/升小時。 EP-B 0 319 208，DE-A 1 941 633 和 DE-A 2 040 501 揭示 一般可應用於丁块二醇氫化的方法，其中反應器的氣體循 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) 五、發明説明（ A7 B7 經濟部中央標準局員工消費合作社印製 環操作模式爲避免氣相和液相_起由底部向上流過觸媒的 固疋化床。本案以氣相和液相的過渡流的形式流 以液相形成連續相。 ^ 然而，這些方法的缺點爲氫化過程中，丁块二醇的高進 料量，使得反應區末端的反應物無氯可 丁块二醇的轉化不完全，所以產生了由丁二醇 的中間物。若於低的丁块二醇進料量的情形，可以獲得滿 意的產品品質和完全的轉化率，但是卻明顯的降低；空間 -時間產率或需要較高的壓力來作業。 二 本發明的目的之-爲提供-種將…丁炔二醇以觸媒氯 化而製成1，4-丁二醇的方法，藉小^ 2⑼巴壓力，甚至使 =工業級1，4_丁块二醇，仍可獲得高的空間—時間產率及 高選擇性，而高的觸媒操作壽命也可達成。 我們發現此一目標，已藉由連續的觸媒氳化丁炔二 醇製備1，4-丁二醇的方法而達成。此方法包括於2〇到3⑼ °c(較佳爲60至220。(：，更佳爲120至⑽。〇,在液體連 續相中以觸媒氫化M-丁炔二醇，壓力由i到2〇〇巴（較佳 爲3到150巴，而更佳爲5到⑽巴），而液相侧體積質量 傳送係數kLa的値從〇·；[秒-1至丨秒-!，較佳爲從〇 2秒q至 1 秒-1 〇 a) 使用懸浮於反應介質中的催化劑，其中若使用具填充々 泡柱，以上升流體模式操作，而氣體離開反應槽對氣體 進入反應槽之比率由0.99 : 1到0.4 : 1，或 b) 固定床反應器在氣體循環式的操作模式下，液⑲ $ 鱼不1氧體 _ 冬 ^紙張尺度適用中國國家標準rCNsTA4規格（210X297公釐 (諳先聞讀背面之注意事碩再填寫本頁) • _Γ •裝. -訂 經濟部中央標準局員工消費合作社印製 A7 ' B7五、發明説明（4 ) 以上升方向，同向流過反應器，反應槽進氣對氣體排出 的比率保持在0.99 : 1到0.4 : 1。 本發明所揭示的方法可提供1,4- 丁炔二醇以高的空間-- 時間產率並同時具備於低於200巴壓力下的高選擇性，此 法藉由單階或多階氫化達成之。除此之外，長的觸媒工作 壽命也可以獲得。 介於氣相和液相間之液態侧體積質量傳輸係數kLa定義 成 kj,a = k〇L x F〇l > 其中kGL爲氣相-液相質量傳輸的質量傳輸係數，而fgl 是氣相-液相的界面面積。kLa値亦定義爲比吸收率，如 同在 Ullmanns Encyclop技die der. technischen Chemie，Verlag Chemie, 4th edition (1973), Volume 3，從 495 到 499 頁所描述.者。 kLa値由實驗測得，藉由測定於設定的工作溫度下的 .50%重量分率的丁二醇和50%重量分率的水所形成的混合 物的氫吸收。實驗測定kLa的程序已多次描述於特定文獻 中，例如P. Wilkinson等所著："在加壓氣管柱中質量傳輸 和氣泡尺寸分佈"，"Chemical Engineering Science, Vol. 49 (1994) No. 9, pp, 1417-1427, Ullmanns Encyclopadie der technischen Chemie, Verlag Chemie, Weinheim/Bergstr ;第 4 版，1973 ，第 3 卷，495 頁至 499 頁，H. Hoffmann : "Gepackte Aufstrom-Blasensaulen", Chem.-Ing.-Tech. 54, (1982) No. 10, pp. 865-876及A. Marquez等所著："近期化工技術對 (請先閣讀背面之注意事項再填寫本頁) __Γ· 裝· 訂 本紙張尺度適用中國國家標準（CNS ) Α4规格（210Χ297公釐） 經濟部中央標準局員工消費合作社印製 A7 ______B7 五、發明説明（5 ) " 於決定氣體-液體反應器中體積測量法質量-傳輸係數 kLa 的回顧"chemical Engineering and Processing，33 (1994) ρρ· 247-260 〇 如用於本發明所揭示的方法的k^a値高時，氳吸收的測 量於連續操作狀態下較佳。在所欲溫度下，液體混合物的 軋机儘可大量注入沒有氫而懸浮之觸媒中。液體混合物 的流動儘可能足夠高，使得反應器的液體含量至少在2分 鐘内可被代換，最好在j分鐘或更短時間内被代換。同 時，除去帶氫的液體混合物，減壓至大氣壓，溶解的氫排 出時以體積量測法測定。氣相中氫的分壓以相似方法測 定0 本發明方法執行時最好使用工業級1，4- 丁炔二醇，其以 水溶液形式存在，可另含如何溶或不溶之來自丁块二醇合 成的成份，如銅、鉍、鋁或矽化合物。當然，使用已純化 的丁炔二醇也是可以的，例如藉由蒸餾純化。工業生產丁 块二醇可由乙炔和甲醛水溶液而通常以重量分率3〇_6〇0/〇 強度的水溶液氫化。然而，氫化也可以在其他溶劑中進 行，例如醇類，如甲醇 '乙醇、丙醇、丁醇或i，4-丁二 醇。氳化所需的氫最好爲純物質，但是也可以另含其他成 分，例如甲烷和一氧化碳。 依據本發明，使用的觸媒爲能夠氫化碳_碳叁键和雙键 成爲單鍵之物質。他們通常含1或更多的週期表中之過度 元素Ϊ、VI、νπ和vm族的元素。較佳的元素爲銅、 鉻、鉬、鎂'銖、鐵、釕、鈷、鎳、鉑、鈀。更佳的觸媒 — "S- 本紙張尺度適财關家縣（CNS ) A4规格（2!GX297公釐） (請先閱讀背面之注意事項再填寫本頁) -裝· 訂 'tf‘ / A7 經濟部中央標準局負工消費合作社印製 五、發明説明（6 )爲含有選自銅、鉻、鉬、鐵、鎳、鉑和鈀之中至少—種元 素的組成物。 觸媒中之金屬含量通常爲O.i-lOO%重量分率，較佳爲 〇.2_95%重量分率，更佳爲0.5-95%重量分率。觸媒較佳另含有至少一種元素，選自週期表中主要族 II、III、IV和VI，過渡族π、III、IV和ν族中之元 素，而鑭作爲促進劑以增加活性。 觸媒中促進劑的含量通常最高含有5%重量分率，較佳 爲0.001-5%重量分率，更佳爲〇 01_3%重量分率。 支撑型或雷尼型觸媒的製備可以使用沈澱法，製備法描 述如下例，Ullmanns EncycolpMie der technischen Chemie，4th edition，1977, Volume 13, pages 558-665。 可使用的支撑物擔體爲氧化鋁、氧化鈦、二氧化結、二 氧化矽、黏土如微晶高嶺土、矽酸鹽如鎂或鋁矽酸鹽、潍 石和活性碳。較佳的支撑物質爲氧化鋁、二氧化鈥、二氧 化矽、二氧化錐和活性碳。當然，不同支撑物的混合物也 可作爲本發明方法中的觸媒支撑物。 這些觸媒可以不同的形狀，例如圓形、圓柱形環形、 螺旋形或以粉末狀來使用。 合適的雷尼型觸媒有例如雷尼鎳、雷尼銅、雷尼鈷、雷 尼鎳/鉬、雷尼鎳/铜、雷尼鎳/鉻、雷尼鎳/鉻/鐵或海$ 狀錁。雷尼鎳/鉬觸媒可依下述文獻所述的方法製備，例 如US-A 4 153 578 。然而，這些觸媒的售出乃藉由，^ 如，Degussa, 634〇3 Hanau，德國。例如，雷尼鎳絡— _ 9 - 本紙張尺度適财賴家辟（CNS ) A4規格（21GX297公釐)' -----__ (讀先鬩讀背面之注意事項再填寫本頁) -裝. 訂 i¥ A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（7 ) 觸媒以商品名Katalysator Typ 11 112 w@由迪谷撤（Degussa) 公司賣出。 當使用沈澱型或支撑型觸媒時，其於反應初期在氫氣或 氫/惰性氣體中於150到500 °C下即可將觸媒還原。此一還 原反應可以直接在合成反應器中進行。假如還原反應在一 分離的反應器中進行，這些觸媒自分離的反應器移開前能 夠在30 °C下使用含氧的氣體混合物鈍化。在此種情況 下，鈍化之觸媒在使用前於合成反應器中的氮/氫氣流中 於180 C下活化，或不經活化也可以使用。 觸媒可用於固定床或懸浮式。假如觸媒是固定床的型 式，依據本發明，反應器中觸媒不是在習慣的向下流模式 而是使用向上同向流動的液體和氣體，以此種方法，液體 而非氣體以連續相存在。 懸浮式觸媒通常以粒徑0.1-500微米來運用，較佳從〇 5 至200微米，更佳爲1至1〇〇微米。 當使用填充氣泡柱時，若供應懸浮式觸媒，反應的進行 如同使用一向上流的液體和氣體，以此種方法，液體而非 氣體是以連續相型式存在。排出反應容器中的氣體對充入 反應器中氣體的比率，當使用固定床反應器和填充氣泡柱 而觸媒懸浮於反應介質中時，比率爲〇 99 : 1到〇 4 : i。 離開反應器氣體對充入氣體的比率，依據本發明，在固 定床反應器的情況下，觸媒縣浮在反應介質中在填充式氣 泡柱中，藉由量度氫以新鮮氣體存在的大約量或如工業上 較喜好的再循環循環氣體和僅以新鮮氫補足化學反應和廢 ΓΜ——J----:'裝------訂------y f讀先聞讀背面之注意事if再填寫本頁jNo. 86114480 Patent Application A7 Revised Chinese Manual (November 87) β7 Xiangzheng --- ^ V. Description of the invention (8) Method for loss of hydrogen caused by gas, in order to obtain the exit gas to the inlet The ratio. The molar ratio of hydrogen to butynediol in the reactor is at least 3: 1, preferably 4: 1 to 100: 1. The process of the present invention is carried out by using a fixed bed catalyst in a gas-circulation mode, that is, the gas leaving the reactor can be recycled after being replenished with fresh argon if appropriate, and returned to the reactor via a compression / shrinking machine. All or part of the circulating gas can be transported through the jet compressor. In a preferred embodiment, the circulating gas compressor is replaced by a less expensive nozzle. Compression is accomplished by the introduction of, for example, a circulating liquid. The liquid needs to be increased in pressure to operate a jet compressor, from about 3 to 5 bar. A suitable reactor for carrying out the method of the present invention for a catalyst fixed bed, for example, a fixed bed reactor as shown in FIG. 1 or a tube bundle reactor as shown in FIG. 2. Brief Description of the Drawings Figure 1 shows a configuration of a fixed bed reactor that can be used in the process of the present invention. Figure 2 shows a configuration of a tube bundle reactor that can be used in the method of the present invention. Figure 3 shows a spray nozzle that can be used in the method of the present invention. It is printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before writing this page). Figure 4 shows a foamed tubing string that can be used in the method of the present invention. The meaning of the symbols of the main components of the drawing. Symbol meaning 1 reactor 2 catalyst particle bed 3 iron mesh_u. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 5. Description of the invention (1) A7 B7 The present invention relates to a method for preparing η ^ diol by catalytic hydrogenation of 1,4-butynediol '. In the presence of a solid hydrogenation catalyst, the pressure of hydrogen is _ horse / to 200 bar, and the volume and mass transfer on the liquid side The coefficient 値 is from 0 to 1 second to 1 second, at which time the liquid forms a continuous phase and hydrogen forms a dispersed phase. The hydrogenation of 1,4-butynediol yields 14-butanediol, which is formed by separate steps as shown below. [Catalyst] HOCH2C == CCH2OH + H2 --— ^ HOCH ΓΤΤ r > rr / -iTT [Catalyst] > hoch2ch = chch2oh + h2 Printing of hoch2 (ch2) 2ch2oh by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs For decades, many A's have been described. However, this—the known method has the disadvantage of a low, uneconomical space—time yield, that is, when the pressure is below 2 GG bar for hydrogenation, the volume per reactor and the starting time per unit time The amount of material exhibits low catalyst life and low selectivity. In addition, when the catalyst is used in a fixed bed, hydrogenation requires a high pressure of more than 200 bar, which is also accompanied by the cost of high capital. In addition, 1,4-butynediol, butylene glycol, and the derivatized compounds, if there is something wrong, can be separated from the difficult 4-distillate of j, 4 • butanediol; For example, the aldol-butane (alkane) diol formed by the isomerization of butenediol and hydrogenated butyraldehyde are separated by distillation. However, in terms of the further processing of 1'4 butanol, in most applications it is strictly required that no incomplete hydrogenation products be present. In chemical reactions, an increase in 'is usually accompanied by a decrease in selectivity. So the hard work completes this reaction, on the one hand, at the lowest possible temperature ', and on the other hand, the partial conversion rate in exchange for the highest possible selectivity. Ding (Read first, read the notes on the back, and then fill out this page.) Pack.-Order 丨 ¥ Central Standard Staff Consumption of the Ministry of Economic Affairs, Du Duying No. 86114480 Patent Application A? Chinese Manual Correction Sheet (87 November) B7 Milk Year "Ma i 'λ' 1 5. & Invention Description 4 Liquid Feed 5 Line 6 Mixing Nozzle 7 Line 8 Line 9 Gas / Liquid Two / Phase Mix 10 Gas / Liquid Separation Reactor i 11 gas stream 1 2 stream 13 ink shrinker 14 stream 1 5 tube 16 heat exchanger 2 0 packed 2 1 pump Figure 1 depicts the configuration of a fixed bed reactor that can be used in the method of the invention. Reactor 1 A catalyst particle bed 2 containing an average particle diameter of 1 to 20 mm (preferably 2 to 5 mm). To prevent the catalyst particles from being carried out of the reactor, an iron mesh 3 is placed at the upper end of the catalyst bed. Feed 4 contains butynediol and water, and is driven by a line and a circulating liquid via line 5 to the mixing nozzle 6 in a jet, in which fresh hydrogen is circulated through line 7 and oxygen is mixed therein via line 8. Both of the gas / liquid phase Phase mixture 9 by The upper end of the reactor 1 leaves and is separated in the gas / liquid separator 10. The secondary stream 12 of the gas stream 11 is removed and discharged to avoid the accumulation of inert components. The circulating gas stream 8 is recirculated through the compressor 13 to enter the mixing Nozzle 6. If the circulating liquid 5 is conveyed through pump 21, the compressor can be omitted, and the paper size can be applied to the Chinese National Standard (CNS) A4 specification (210X297 mm)-Ha Please read the item I in the back first Fill in this page A7 B7 I. Description of invention (2) ~ In the hydrogenation of acetylene glycol, in order to accept acceptable product quality for subsequent work, completely switch (read the precautions on the back before filling in this page) Chemicalization is the basic requirement, so hydrogenation Often dispersed in several reactors operating under different conditions.-US-A 5 068 468 discloses the hydrogenation of 14_ butynediol on a solid supported nickel / steel catalyst with a space-time yield of 250 bar pressure The following is 0.3 kg of butanediol per liter hour. BE-B 745 225 reveals that the reaction with Raney nickel catalyst in a fixed bed at 2S9 bar 'its space-time yield reached in two stages 0.286 in the process Butanediol / litre hours. US_A 4 153 578 discloses a two-stage process for the hydrogenation of 14_ butanediol, using a suspended Raney nickel / molybdenum catalyst at a pressure of 21 bar. The space-time achieved by this process The yield was 0.06 kg of butanediol per liter of hour. DD-A 272 644 revealed the suspension hydrogenation of an aqueous solution of butynediol catalyzed by a nickel / SiCb catalyst. Assuming butanediol is usually used at a concentration of 39 to 50% by weight and assuming full conversion, the space-time yield is calculated from 0.15 to 0-25 kg butanediol per liter hour at 15 bar pressure. The catalyst used showed a 37% loss of activity after only 50 hours. US-A 2 967 printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. In Example 1, the space-time yield calculated from the Raney nickel-copper catalyst hydrogenated 1,4-butanediol was about 0.01 kg. Butanediol / litre hour. RU-A 202 913 reveals that the space-time yield of hydrogenated butadiene glycol with a nickel / 5 germanium catalyst is 0.1 kg of butanediol / liter hour. EP-B 0 319 208, DE-A 1 941 633 and DE-A 2 040 501 disclose methods generally applicable to the hydrogenation of butanediol, in which the gas in the reactor is in accordance with the Chinese paper standard (CNS) A4 according to this paper standard Specifications (210X297 mm) V. Description of the invention (A7 B7 The printed ring operation mode of the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs is to avoid the gas and liquid phases. The solidified bed that flows through the catalyst from the bottom up. The gas-phase and liquid-phase transition streams form a continuous phase in the liquid phase. ^ However, the disadvantage of these methods is the high feed volume of butanediol during the hydrogenation process, making the reactants at the end of the reaction zone free of chlorine. The conversion of butanediol is not complete, so an intermediate of butanediol is produced. If the amount of butanediol is low, satisfactory product quality and complete conversion can be obtained, but it is obvious Reduced; space-time yield or higher pressure required for operation. 2 The purpose of the present invention is to provide-a method for preparing 1,4-butanediol by chlorinating butynediol with a catalyst By borrowing a small ^ 2⑼ bar pressure, even making = industrial grade 1 4-Butanediol can still obtain high space-time yield and high selectivity, and high catalyst operating life can also be achieved. We found that this goal has been tritiated with butyne This is achieved by a process for the preparation of 1,4-butanediol from diols. This process comprises at 20 to 3 ° C (preferably 60 to 220. (:, more preferably 120 to ⑽ ° C), in the liquid continuous phase. M-butynediol is hydrogenated with a catalyst at a pressure ranging from i to 2000 bar (preferably 3 to 150 bar, and more preferably 5 to ⑽bar), and the volume side mass transfer coefficient kLa of the liquid side is from 〇 ·; [sec-1 to 丨 sec- !, preferably from 0.22q to 1sec-1 〇a) using a catalyst suspended in the reaction medium, wherein if a packed froth column is used to raise the fluid Mode operation, and the ratio of the gas leaving the reaction tank to the gas entering the reaction tank is from 0.99: 1 to 0.4: 1, or b) the fixed bed reactor is in the gas circulation operation mode, the liquid ⑲ $ 鱼 不 1 氧 体 _ 冬^ The paper size applies the Chinese national standard rCNsTA4 specification (210X297 mm (谙 first read the notes on the back before filling in this page) • _Γ • Packing.-Order the Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards A7 'B7 V. Description of the invention (4) Flow through the reactor in the same direction in the same direction, and the ratio of the inlet to the gas exhaust of the reaction tank is maintained at 0.99: 1 to 0.4: 1. The present invention The disclosed method can provide 1,4-butynediol with high space-time yield and high selectivity at pressures below 200 bar. This method is achieved by single-stage or multi-stage hydrogenation. In addition, a long working life of the catalyst can also be obtained. The liquid side bulk mass transfer coefficient kLa between the gas and liquid phases is defined as kj, a = k〇L x F〇l > where kGL is The mass transfer coefficient of the gas-liquid mass transfer, and fgl is the gas-liquid interface area. kLa 値 is also defined as the specific absorption rate, as described in Ullmanns Encyclop technology die der. technischen Chemie, Verlag Chemie, 4th edition (1973), Volume 3, from pages 495 to 499. kLa 値 is measured experimentally by measuring the hydrogen absorption of a mixture of .50% by weight butanediol and 50% by weight water at a set operating temperature. The procedure for experimental determination of kLa has been described many times in specific literatures, for example by P. Wilkinson et al .: "Mass transfer and bubble size distribution in pressurized tracheal columns", "Chemical Engineering Science, Vol. 49 (1994 ) No. 9, pp, 1417-1427, Ullmanns Encyclopadie der technischen Chemie, Verlag Chemie, Weinheim / Bergstr; 4th edition, 1973, vol. 3, pages 495 to 499, H. Hoffmann: " Gepackte Aufstrom-Blasensaulen ", Chem.-Ing.-Tech. 54, (1982) No. 10, pp. 865-876 and A. Marquez, etc .: " Recent chemical technology (please read the precautions on the back before filling in this Page) __Γ · Binding · The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210 × 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ______B7 V. Description of the Invention (5) " Review of the volumetric mass-transmission coefficient kLa in the reactor " chemical Engineering and Processing, 33 (1994) ρρ · 247-260 〇 As k ^ a 値 used in the method disclosed in the present invention is high, Measure Better in continuous operation. At the desired temperature, the rolling mill of the liquid mixture can be injected as much as possible into the suspended catalyst without hydrogen. The flow of the liquid mixture is as high as possible so that the liquid content of the reactor can be replaced within at least 2 minutes, preferably within j minutes or less. At the same time, the hydrogen-containing liquid mixture was removed, the pressure was reduced to atmospheric pressure, and the dissolved hydrogen was measured by a volumetric method when it was discharged. The partial pressure of hydrogen in the gas phase is determined by a similar method. The method of the present invention is best performed using industrial-grade 1,4-butynediol, which is present in the form of an aqueous solution, and can also contain how to be soluble or insoluble from the butanediol. Synthetic ingredients such as copper, bismuth, aluminum or silicon compounds. Of course, it is also possible to use purified butynediol, for example by distillation. Commercially produced butanediols can be hydrogenated from aqueous solutions of acetylene and formaldehyde, but usually at an intensity of 30-60 / 100. However, the hydrogenation can also be performed in other solvents, such as alcohols such as methanol 'ethanol, propanol, butanol, or i, 4-butanediol. The hydrogen required for tritiation is preferably a pure substance, but it may also contain other components such as methane and carbon monoxide. According to the present invention, the catalyst used is a substance capable of hydrogenating a carbon-carbon triple bond and a double bond into a single bond. They usually contain 1 or more elements in the periodic table of elements Ϊ, VI, νπ, and vm. Preferred elements are copper, chromium, molybdenum, magnesium, baht, iron, ruthenium, cobalt, nickel, platinum, and palladium. Better Catalysts-" S- This paper is suitable for Guancai County (CNS) A4 size (2! GX297 mm) (Please read the precautions on the back before filling out this page)-Binding and ordering 'tf' / A7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. The invention description (6) is a composition containing at least one element selected from the group consisting of copper, chromium, molybdenum, iron, nickel, platinum and palladium. The metal content in the catalyst is usually from 0.1 to 100% by weight, preferably from 0.2 to 95% by weight, and more preferably from 0.5 to 95% by weight. The catalyst preferably further contains at least one element selected from the elements of the main groups II, III, IV and VI in the periodic table, the transition groups π, III, IV and ν, and lanthanum as an accelerator to increase activity. The content of the accelerator in the catalyst usually contains a maximum of 5% by weight, preferably 0.001 to 5% by weight, and more preferably 0.01 to 3% by weight. The support type or Raney type catalyst can be prepared by the precipitation method. The preparation method is described in the following example, Ullmanns EncycolpMie der technischen Chemie, 4th edition, 1977, Volume 13, pages 558-665. Usable support supports are alumina, titania, oxide junction, silica, clays such as microcrystalline kaolin, silicates such as magnesium or aluminosilicates, Weisite and activated carbon. The preferred support materials are alumina, dioxide ', silica, cone and activated carbon. Of course, a mixture of different supports can also be used as a catalyst support in the method of the present invention. These catalysts can be used in different shapes, such as circular, cylindrical ring, spiral or powder. Suitable Raney-type catalysts are, for example, Raney nickel, Raney copper, Raney cobalt, Raney nickel / molybdenum, Raney nickel / copper, Raney nickel / chrome, Raney nickel / chrome / iron or sea-like ingot. Raney nickel / molybdenum catalysts can be prepared according to the methods described in, for example, US-A 4 153 578. However, these catalysts were sold by, for example, Degussa, 63403 Hanau, Germany. For example, Raney Nickel — _ 9-This paper is suitable for financial use (CNS) A4 size (21GX297 mm) '-----__ (Read the notes on the back first and then fill out this page)- Order. ¥ 7 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (7) The catalyst was sold under the trade name Katalysator Typ 11 112 w @ Degussa. When a precipitated or supported catalyst is used, it can be reduced at 150 to 500 ° C in hydrogen or hydrogen / inert gas at the beginning of the reaction. This reduction reaction can be carried out directly in the synthesis reactor. If the reduction is carried out in a separate reactor, these catalysts can be passivated with an oxygen-containing gas mixture at 30 ° C before being removed from the separate reactor. In this case, the passivated catalyst is activated at 180 C in a nitrogen / hydrogen stream in the synthesis reactor before use, or it can be used without activation. The catalyst can be used in fixed bed or suspended type. If the catalyst is a fixed-bed type, according to the present invention, the catalyst in the reactor is not in the customary downward flow mode but uses liquids and gases flowing upward in the same direction. In this way, liquids, rather than gases, exist in a continuous phase . Suspended catalysts are generally used with a particle size of 0.1-500 microns, preferably from 05 to 200 microns, and more preferably from 1 to 100 microns. When a packed bubble column is used, if a suspended catalyst is supplied, the reaction proceeds as if an upward flow of liquid and gas were used. In this way, liquid rather than gas exists as a continuous phase. The ratio of the gas discharged from the reaction vessel to the gas filled in the reactor, when the catalyst is suspended in the reaction medium using a fixed-bed reactor and a packed bubble column, the ratio is 〇 99: 1 to 〇 4: i. The ratio of the gas leaving the reactor to the gas filled. According to the present invention, in the case of a fixed-bed reactor, the catalyst is floated in the reaction medium in a packed bubble column, and the approximate amount of hydrogen as a fresh gas is measured by measuring Or, as the industry prefers to recycle the circulating gas and only use fresh hydrogen to make up the chemical reaction and waste ΓΜ——J ----: 'installation ------ order ------ yf Note on the back if fill in this page j
第86114480號專利申請案 A7 中文説明書修正頁(87年11月） β7 象正· ---^ 五、發明説明（8 ) 氣導致的氫的損失的方法，以求得離開氣體對進氣的比 率。 氫對丁炔二醇的莫耳比率，在反應器中至少爲3: 1 ， 較佳爲4 : 1到100 : 1。 本發明方法的進行乃是在氣體-循環模式中以固定床觸 媒作用，亦即，離開反應器的氣體，補充新鮮氬氣後若適 當可以再循環，經由壓·縮機返回反應器。經由噴射式壓縮 機可以運送全部的循3哀氣體或部分的循環氣體。在較佳的 具體例中，循環氣體壓縮機爲較不筇貴的噴嘴所取代。經 由如循環液體的導入而完成壓縮的工作。液體需_要增加的 壓力以操作喷射式壓縮機而言，爲由約3到5巴。 施行本發明方法用於觸媒固定床的適當反應器，例如， 圖1所示的固定床反應器或圖2所示的管束反應器。 圖之簡單説明 圖1顯示一種可使用於本發明方法的固定床反應器之配 置。 圖2顯示一種可使用於本發明方法的管束反應器之配 置。 圖3顯示一種可使用於本發明方法的噴射式喷嘴反應 經濟部中央標準局員工消費合作社印製 (請先閡讀背面之注意事項再镇寫本頁) 器。 圖4顯示一種可使用於本發明方法的泡沫式管柱。 圖式主要元件符號之意義 符號 意義 1 反應器 2 觸媒顆粒床 3 鐵網 _u. 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經 濟 部 中 央 標 準 員 工 消 費 合 杜 印 製 第86114480號專利申請案 A? 中文説明書修正頁(87年11月） B7 奶年“Ma i 'λ' 1 五、發明説明（& ) 4 液體進料 5 管線 6 混合噴嘴 7 管線 8 管線 9 氣相/液相之兩/相混合物 10 氣體/液體分離器 i 11 氣體流 1 2 次流 13 墨縮機 14 次流 1 5 管 16 熱交換器 2 0 填充 2 1 幫浦 圖1 描繪出可用於本發明方法的固定床反應器的配置。 反應器 1含有平均粒徑1到20毫米（較佳2到5毫米）觸 媒顆粒床2 。爲避免觸媒顆粒由反應器中被攜出，鐵網3 置放於觸媒床的上方末端。液體進料4包含丁炔二醇和 水，經由管線及循環液體經由管線5 以噴射驅動至混合噴 嘴6， 在其中新鮮氫氣經由管線7而循環氧體經由管線8 於其中混合。氣相/液相的兩相混合物 9由反應器1之上 方末端離開，而在氣體/液體分離器 10分離之。氣流11 的次流 12被除去而排出，以避免惰性组份的累積。循環 氣流8 經由壓縮機13再循環而進入混合喷嘴6。假如循 環液體 5藉由幫浦21傳送時，壓縮機可以省略，且能提 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-Ha 請 先 閲 讀 背 I 事 項 再 填 寫 本 頁 - A7 ____ B7 ____ 五、發明説明（9 ) 供足夠高的壓力，而混合噴嘴6經設計成噴射壓縮機。循 環液體的次流14取出作爲產物流。反應釋出的熱量藉由 熱交換器16移去。 本發明方法不但能在絕熱操作的固定床反應器（描述於 圖1)中操作’而且可在等溫操作的管束反應器（如圖2)中 進行。 圖2顯示管束反應器的裝置，其中觸媒顆粒2平均粒徑 由約1至20毫米’較佳由2至5毫米，安置在管15中。 循環液體5對產物14的比率是由wo : 1到5〇〇 : 1 ， 較佳爲200 : 1 ，此比率在圖1的固定床反應器和圖2的 管束反應器皆爲同一比率。反應器的直徑使空管中流體建 立的速度範園由100至1000公尺/小時。適當的空-管流 速乃於實驗室設備中對各種觸媒作實驗而決定。以有關於 觸媒磨損所允許的最大流速設定空管流速是適當的。當空 -管流槨大於大約1000公尺/小時時，可發現小顆粒觸媒 有一因增加壓損所作之額外的限制。 經濟部中央標準局員工消費合作社印製 對於固定空管流速的主要影響參數爲觸媒體積，形狀和 顆粒大小分佈和它的磨損行爲。以實驗爲基礎的壓降圖從 約0.02到0.15巴/公尺’可用作指引之用。反應器流出之 氣體量較佳設定爲產生之空管流速約與液體空管流速一 致'。然而，它可能到小於90%。 爲了施行本發明的方法乃使用一觸媒懸浮在反應介質 中，適合的反應器爲噴射式噴嘴反應器。攪拌式容器和填 充有埃充表面積至少500公尺2/公尺3，較佳爲1〇〇〇至 _^________ -12- 本紙張尺度適用中國國家標準（CNS ) Μ规格（210X297^51 ' 經濟部中央標隼局員工消費合作社印製 A7 B7 •五、發明説明（10 ) 2000公尺2/公尺3的填充氣泡管柱。不同種類的噴射式噴 鳴反應器能夠應用，假如以實驗爲基礎能夠確信藉由足夠 高的輸入能量大於2千瓦/公尺3，由氧相到含有懸浮觸媒 -顆粒的液相的高質量傳送，基本上可用於本發明。裝有脈 衝式互換管之噴射式噴嘴反應器尤其適合。噴射式噴嘴反 應器的廣泛流傳的工業敘述。例如反應器描述於EP_A 0 419 419。因爲從3到5千瓦/公尺3的能量輸入値，此反 應器仍可能用無附加裝備的簡單分離器（如泡沫離心機或 旋風式離心機）以完成氣相分離。 圖3顯示一種噴射式噴嘴反應器，其中液相藉由管線5 傳送，且經由—具有熱交換器16和驅動噴射式壓縮機6 而引入氫氣的外加迴路。爲加強質量傳送，二相混合物的 傳送乃經由一脈衝式交換管17。在反應器/較低的末端， 可能有一緩衝板18 ，其使液體轉向，且使氣體分離較容 易。氣體在外部輪狀空間19朝向頂端升起，且藉由驅動 噴射式壓縮機6再次抽出氣體。液體在反應器的較低的末 端被除去，其中氣體基本上已經分離，經由熱交換器16 以移去反應熱，且再注入驅動的.噴射壓縮機6中。 擅掉式谷器適用於施.行本發明方法’此僅適於輸入能量 範園介於2到1〇千瓦/公尺3。爲了轉換攪拌能量以獲得 本發明所品的高kLa値，對於内部適當的携拌式容器是有 用的’其中確信氣體和液體密切混合的攪拌式容器，例如 緩衝板。 除此之外，提供有填充20的泡沫式管柱示於圖4 ，其 - _ __ 五3 本紙張尺度 -~~ --- (請先閱讀背面之注意事項再填寫本頁) -裝. -訂. 經濟部中央標準局員工消費合作社印製 ΑΠ __Β7__ 乒、發明説明（11 ) 也適用於本發明方法。填充物的表面積必需至少500公 尺2/公尺3，較佳由1000至2000公尺2/公尺3。填充物20 可以规則排列或任意排列，已知有规則填充幾何形狀乃來 自於有最低的壓降的蒸餾分離技術。填充包含鐵網，與慣 用於蒸餾技術者類似，鐵網表現出尤其受歡迎的性質。網 狀填充物有例如Sulzer DX®或Sulzer EX®，其由Sulzer Chemteclin·，8404 Winterthur, Switzerland 户斤售出。 所述及的填充物也可以用觸媒活化成份直接塗覆。此種 填充物描述於 EP-A- 068 862，EP-A 201 614 和 EP-A 448 884。固定床反應器使用填充氣泡柱，此種填充物對液體 和氣體具有相似之高空管流速，在每一情況下，從1〇〇到 1000公尺/小時，較佳從200到1000公尺/小時，如同懸浮 .步驟具有相同的高kLa値。 依據本發明設定的kLa値由0· 1秒-1至1秒-1，此一數據 的決定乃是爲了同時獲得高選擇性和高空間時間產率，藉 由目標的技術對各別的反應器種類作合適的測量而施行。 反應器的全部種類，通常於施行此一方法時，和其他方法 相比具有輸入能量的増加^藉由特定的結構組態和操作條 件’導入的能量有效的轉化而改進質量傳遞。 當本發明方法使用攪拌容器中的懸浮觸媒而施行時，攪 拌型具有良好的氣體導入性質，例如碟式攪拌器或針板攪 拌器是眾所週知的，例如，發酵技藝必需使用的設定、& 的値由0.1秒-1至1秒-1。輸入能量的量測爲2到1〇千瓦/ 公尺3，對於小的裝置使用較小値將產生良好的氫化結 ____ -14- 本紙張尺度適用中國國家標準（CNS ) Μ規格（210: 297公遵;) 一 —' ---- (請先閱讀背面之注意事項再填寫本頁) -裝· 訂 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（12 ) 果。反應器尺寸大於〇·5公尺3的情況下，5-10千瓦/公 尺3的輸入量是必需的。在攪拌型容器中藉由攪拌器的驅 動動力導入能量。這些能量輸入的値大於傳統在攪拌容器 中的氣體-導入反應，例如發酵或氫化的輸入能量約0.2 到1千瓦/公尺3。 具有懸浮觸媒的噴射噴嘴反應器需要大於2千瓦/公尺3 的輸入能量，較佳3-5千瓦/公尺3能量的導入乃是藉由迴 成幫浦21中液體的壓力增加，結合驅動噴射壓縮機6的 壓力降。迴流幫浦中所設定的迴流和壓力的變化能夠設定 需要的輸入能量。幫浦中的壓力設定通常爲2到5巴的範 園。 假設在填充氣泡柱中的反應介質内的懸浮觸媒可用於本 發明方法，填充物的單位體積表面積必需至少5〇〇公尺2/ 公尺3，但較佳爲1000-2000公尺2 /公尺3。對於本發明所 需要的kLa値設定爲0.1秒_；1至1秒-1_，同時需要高的液體 和氣體速度，由100到1000公尺/小時。結合填充物的指 定幾何形狀，設定指定的氣體和液體速度以確信需要輸入 的能量。然而，此種裝備的結果低於同樣狀態下的攪拌容 器或噴射式噴嘴反應器。適當的能量輸入値的獲得乃起源 於流動液體和氣體的壓力降，而這可用監視器藉由壓力降 而測得，壓力降爲0.02到0.15巴/米填充物。若需要，液 體流速能改變，以符合設定所需之壓力減少。 每單位體積的表面積的値、填充物中的壓力減少和液體 和氣體的循環速率和上述在填充氣泡柱的懸浮方法也可以 -15- 本紙張尺度適用中國國家標準（CNS; ) A4規格（210X297公釐） ——1-—*---^_丨;'.裝------訂------〔Μ ' 一 (請先閎讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（I3 ) 用於填充物已塗佈有觸媒活化物質的填充氣泡柱中。 當本發明方法使用固定床反應器時，觸媒顆粒的平均粒 徑必須爲1-20毫米，較佳2-5毫米，而液體和氣體流過的 速度必需是100-1000公尺/小時，以設定kLa値由〇1秒心 至1秒-1。固定床的壓力降的設定應爲约〇.〇2_〇 15巴/米。 14- 丁二醇以大量於工業上使用，例如，製備THF或聚 酯中的二醇成分。 本發明方法藉由以下例子作一描述。丁炔二醇除非另行 注明，否則均使用工業級，其以水溶液的54%重量分率的 形式’其中含有不同量的丙炔醇《在實施例中丙炔醇的量 大約依循丙醇在反應產物中的量。在實施例中反應產物的 百分率，除非另行注明，百分率爲以無水爲基礎的重量分 率，藉氣體色層分析決定。 實施例 實施例1 攪拌式壓熱蚤中置有130毫升的液體，其具有二片合適 的缓衝板、碟式攪拌器和内設的液位控制器（具多孔金屬 過濾以防觸媒進入），將10克在50毫升水中的雷尼Ni/M〇 觸媒（以鉬化銨溶液充滿雷尼鎳而成鉬重量分率2%)加 入’接著引入35巴的氫。經由外加油的加熱，内部反應 器溫度升至140 Ό，並將氫氣流設定爲80標準升/小時。 攪拌器設定每分鐘700轉，以確信kLa爲0.2秒-1。1〇〇克 /小時的54%重量分率強度的丁炔二醇水溶液接著以幫浦 打入。内部反應器溫度升至149。(：。獲得反應產物的量爲 -16- (讀先闞讀背面之注意事^再填寫本頁) -裝. ,ιτ 本紙張尺廣il用ΦΜΙ圃倉接5仅/ π·\Τ〇 A4招故r\ - ,π A7 B7 經濟部中央標準局員工消費合作社印製 -17- 五、發明説明（14 ) 103克/小時且含有94.2%重量分率的i，4_ 丁二醇、i 3重 量％的正丁醇、3_3重量％的正丙醇和少量其他產物，每 —產物的量少於0·08重量。/。。STY爲0.4公斤丁二醇/ 升_•小時。 實例2 使用和例1相似的方法，170公克/小時的丁炔二醇溶 液，以10克的Ni/Mo (2.5重量❶/。的鉬）氫化。初溫爲15〇 °C，而反應器溫度在反應期間升至173 。產物以176克/ 小時的量獲得，且包含92.4%重量分率的i，4_ 丁二醇、 0.4%重量分率的2-曱基丁二醇、2%重量分率的正_ 丁醇和 4.7%重量分率的正-丙醇，加些量少於〇〇8%重量分率的 其他產物。STY爲0.7公斤的丁二醇/升.小時。 實施例3 使用和例1相似的方法，60克/小時的丁块二醇溶液以 10 克的雷尼 Ni/Fe/Cr (得自 Degussa 的 type 11 II2 W)氫化 之。反應器中液體量爲85毫升、kLa爲0.2秒―1。初溫爲 140 °C，然後升至144 °C。獲得產物的量爲64克/小時， 且包含95.7%重量分率的丁二醇、0.6%重量分率的正丁醇 和1.8%重量分率的正丙醇，加上量小於〇 〇8%重量分率的 其他產物。STY爲0.25公斤的丁二醇/升.小時。 實施例4 使用和例1相似的方法，60克/小時的丁炔二醇溶液以 每分鐘600轉，kLa爲0· 1秒-1，且反應器溫度爲1〇5 °C來 冗成氫化。反應器輸出包含90%重量分率的丁二醇、 本紙張尺度適用中國國家梯準（CNS )六4^格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁} —.1-^1-----訂------：¾--- 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（15 ) 1.8%重量分率的丁烯二醇、4-羥丁醛和丁二醇形成的5% 重量分率的縮醛、2%重量分率的4-羥丁醛和4%重量分率 的丁醇。反應器溫度升至136 °C後，轉化率增加，且下列 數量的產物在產物中出現：92%重量分率的丁二醇、4-羥 丁醛和丁二醇形成的2.7%重量分率的縮醛、0.7%重量分 率的4-羥丁醛和3%重量分率的丁醇。本發明如實施例4 所示的方法能夠在高轉化率獲得較高的選擇性。 實施例5 一個直徑2.7公分的400毫升油熱管反應器以直徑5毫 米的拉西環填充400毫升，拉西環以 Verein Deutscher Eisenhuttenleute，第 8 版，Verlag Stahleisen mbH，Dusseldorf 1990,（UNS-No. S 32100)所發行的鋼鐵表材料編號1.4541的 金屬網環爲原料所製成。管反應器安裝在反應系統中，其 中反應液體藉由一齒輪幫浦的氣體/液體分離器得以循 環。分離器含有一過濾器，液體和氣體通過此過濾器而保 留觸媒。如實施例1中以200克/小時加入丁炔二醇和100 標準升/小時的新鮮氣體在反應器前加入。反應器以向向 上流的模式操作。液體的空間速度爲170公尺3 /公尺2 · 小時，kLa爲0.25秒_1。 反應前，反應系統以實施例1相似的方法充填20克的 Raney Ni/Mo進入300毫升的水中。反應器在30巴和溫度 由145到151 °C之下，獲得的產物量爲213克/小時，且包 含93.3%重量分率的丁二醇、0.3%重量分率的2-甲基丁二 醇、1.5%重量分率的正丁醇、4.2%重量分率的正丙醇和 -18 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） w!i'— ♦ n nn mt nn nt tm m ^ an— I m I—y nn In i «^^^1 I 厂 i (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（16) ^於〇·〇8/°重量分率的其他產物。STY爲約〇 25公斤的丁 二醇/升.小時。 實施例6 . 重覆實施例5的步驟，以5克的雷尼Ni/Mo安裝其中。 10〇克/小時的丁炔二醇溶液在反應器溫度約l22 t 巴和300升/小時的氫氣之下加以氫化。液體的$間速度 爲225公尺3/公尺2 .小時和〇3秒-!的kLa，而丁块二醇 芫全轉化，產物中含有22_27%重量分率的正丁醇，其中 以77/。重量分率含量的〗，4-丁二醇和殘留物爲中間物。液 體的空間速度增加到263公尺3/公尺2 .小時後，依〇4 秒-1的kLa，正丁醇含量爲13%重量分率時，丁二醇含量 升至88%重量分率。 實施例7 使用如同實施例1的方法，60克/小時的57%重量分率 強度的丁块二醇水溶液（水含量：42%重量分率）在反應器 的溫度127。(：和0.2秒―1的kLa之下氫化。反應時間12S小 時以後’產物包含95·4%重量分率的丁二醇、〇 1%重量分 率的2-甲基丁二醇、1.5%重量分率的縮醛（其由4_羥丁醚 和丁二醇而形成）、2.6%重量分率的丁二醇和〇 3%重量分 率的丙醇。然後，反應器溫度增加至141 °C。接著，中間 產物的轉化持續進行至考全且選擇性升高。操作時間173 小時以後，出現下列内含物：98.8%重量分率的丁二醇、 0.1%重量分率的2-甲基丁二醇、〇 7%重量分率的丁二醇 和0.3%重量分率的丙醇。 _____ -19- 本紙張跋適用中國國家標準（〔邮）八4規格（2獻297公^7 —^^----裝一i-----訂-----—.ml 一 _ (請先閔讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（17 ) 比較實施例1 使用如同實施例1的方法，蒸顧過的丁炔二醇以50%重 量分率強度的水溶液予以氫化。加入溶液的pH以NaOH -調整成6.6。在140 °C的油浴溫度之下，一内部反應器的 溫度設定爲150 °C而進料速率爲100克/小時。經過24小 時的操作以後，反應器輸出含有3%重量分率的正丁醇、 0.5%重量分率的正丙醇和96%重量分率的1,4-丁二醇。降 低攪拌速度至350 rpm以後，kLa爲0.05秒―1、反應器溫度 降至141 °C，而反應器輸出包含10%重量分率的丁炔二 醇、31%重量分率的丁烯二醇、41%重量分率的丁二醇、 3%重量分率的4-經丁酸、0.5%重量分率的丙醇，加上4% 重量分率的丁醇和7%重量分率的丁烯醇。殘留物主要爲 縮塍。 比較實例2 使用如同實施例1的方法，100克/小時的工業級丁炔 二醇溶液在油浴溫度140 °C之下使用10克的雷尼Ni/Mo (1.8%重量分率的鉬，計算如Mo )反應。内反應器的溫度 爲149 °C。反應產物有以下的组成：94.1%重量分率的丁 二醇、0.2%重量分率的2-甲基丁二醇、1.5%重量分率的 丁醇和4.2%重量分率的丙醇。降低攪拌速度至350 rpm以 後，相當於0.05秒·1的kLa ,獲得以下氫化結果：40.3%重 量分率的丁二醇、37%重量分率的丁二醇、2.1%重量分 率的丁炔二醇、3%重量分率的丁醇、2.6%重量分率的丁 烯醇、3.1%重量分率的4-羥丁醛相對於100%重量分率之 _-20-_ 本紙張尺度適用中國國家標準（CNsTa4規格（210X297公釐_) (讀先閱讀背面之注意事碩再填寫本頁) 裝·No. 86114480 Patent Application A7 Revised Chinese Manual (November 87) β7 Xiangzheng --- ^ V. Description of the invention (8) Method for loss of hydrogen caused by gas, in order to obtain the exit gas to the inlet The ratio. The molar ratio of hydrogen to butynediol in the reactor is at least 3: 1, preferably 4: 1 to 100: 1. The process of the present invention is carried out by using a fixed bed catalyst in a gas-circulation mode, that is, the gas leaving the reactor can be recycled after being replenished with fresh argon if appropriate, and returned to the reactor via a compression / shrinking machine. All or part of the circulating gas can be transported through the jet compressor. In a preferred embodiment, the circulating gas compressor is replaced by a less expensive nozzle. Compression is accomplished by the introduction of, for example, a circulating liquid. The liquid needs to be increased in pressure to operate a jet compressor, from about 3 to 5 bar. A suitable reactor for carrying out the method of the present invention for a catalyst fixed bed, for example, a fixed bed reactor as shown in FIG. 1 or a tube bundle reactor as shown in FIG. 2. Brief Description of the Drawings Figure 1 shows a configuration of a fixed bed reactor that can be used in the process of the present invention. Figure 2 shows a configuration of a tube bundle reactor that can be used in the method of the present invention. Figure 3 shows a spray nozzle that can be used in the method of the present invention. It is printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before writing this page). Figure 4 shows a foamed tubing string that can be used in the method of the present invention. The meaning of the symbols of the main components of the drawing. Symbol meaning 1 reactor 2 catalyst particle bed 3 iron mesh _u. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm). No. 86114480 Patent Application A? Chinese Manual Correction Page (November 1987) B7 Milk Year "Ma i 'λ' 1 V. & Description of the Invention 4 Liquid Feed 5 Pipe 6 Mixing Nozzle 7 Pipe 8 Line 9 Gas / liquid two-phase mixture 10 Gas / liquid separator i 11 Gas stream 1 2 Stream 13 Ink shrinker 14 Stream 1 5 Pipe 16 Heat exchanger 2 0 Fill 2 1 Pump Figure 1 depicts The configuration of the fixed-bed reactor that can be used in the method of the present invention is provided. The reactor 1 contains a catalyst particle bed 2 having an average particle diameter of 1 to 20 mm (preferably 2 to 5 mm). In order to prevent the catalyst particles from being carried in the reactor, The iron grid 3 is placed at the upper end of the catalyst bed. The liquid feed 4 contains butynediol and water, and is driven by a line and a circulating liquid to the mixing nozzle 6 via a line 5 to be sprayed, in which fresh hydrogen passes through The circulating oxygen is mixed in line 7 via line 8. The gas / liquid phase two-phase mixture 9 leaves from the upper end of reactor 1 and is separated in gas / liquid separator 10. The secondary stream 12 of gas stream 11 is Remove and discharge to avoid the accumulation of inert components. The circulating air flow 8 is recirculated through the compressor 13 and enters the mixing nozzle 6. If the circulating liquid 5 is transmitted through the pump 21, the compressor can be omitted and the paper can be extracted. The dimensions are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -Ha Please read the back I item before filling out this page-A7 ____ B7 ____ V. Description of the invention (9) Provide a sufficiently high pressure, while the mixing nozzle 6 Designed as a jet compressor. The secondary stream 14 of the circulating liquid is taken out as the product stream. The heat released by the reaction is removed by the heat exchanger 16. The method of the present invention can not only operate in a fixed bed reactor which is operated adiabatically (described in Figure 1) Medium operation 'can also be performed in an isothermally operated tube-bundle reactor (see Figure 2). Figure 2 shows the device of the tube-bundle reactor, in which the average particle diameter of the catalyst particles 2 is from about 1 to 20 mm, preferably from 2 to 5 Meters, placed in tube 15. The ratio of circulating liquid 5 to product 14 is from wo: 1 to 5000: 1, preferably 200: 1, this ratio is in the fixed bed reactor of Fig. 1 and the tube bundle of Fig. 2 The reactors all have the same ratio. The diameter of the reactor enables the velocity range of the fluid in the empty tube to be set from 100 to 1000 meters / hour. Appropriate air-tube flow rates are determined by experiments with various catalysts in laboratory equipment. It is appropriate to set the empty tube flow rate with regard to the maximum flow rate allowed for catalyst wear. When the air-to-tube flow rate is greater than about 1000 m / h, it is found that the small particle catalyst has an additional limitation due to increased pressure loss. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The main parameters affecting the flow rate of the fixed empty pipe are the contact volume, shape and particle size distribution and its abrasion behavior. An experimental-based pressure drop chart from about 0.02 to 0.15 bar / meter 'can be used as a guide. The amount of gas flowing out of the reactor is preferably set such that the generated empty tube flow rate is approximately the same as the liquid empty tube flow rate '. However, it may go to less than 90%. For carrying out the method of the present invention, a catalyst is used to suspend in the reaction medium. A suitable reactor is a jet nozzle reactor. Stirred container and filled with Angstrom surface area of at least 500 meters 2 / meters 3, preferably 1000 to _ ^ ________ -12- This paper size applies the Chinese National Standard (CNS) M specifications (210X297 ^ 51 ' Printed A7 B7 by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs • V. Description of the invention (10) Filled bubble column of 2000 m 2 / m 3. Different types of spray-type snoring reactors can be applied. Based on this, it can be assured that with a sufficiently high input energy greater than 2 kW / m3, high-quality transmission from the oxygen phase to the liquid phase containing suspended catalyst particles is basically applicable to the present invention. Equipped with a pulse-type interchange tube The jet nozzle reactor is particularly suitable. The widely-circulated industrial description of the jet nozzle reactor. For example, the reactor is described in EP_A 0 419 419. Because of the energy input from 3 to 5 kW / m3, this reactor is still It is possible to use a simple separator without additional equipment (such as a foam centrifuge or cyclone centrifuge) to complete the gas phase separation. Figure 3 shows a jet nozzle reactor in which the liquid phase is transmitted through line 5 and via-with heat Converter 16 and external circuit that introduces hydrogen to drive the jet compressor 6. For enhanced mass transfer, the two-phase mixture is transferred via a pulsed exchange tube 17. At the reactor / lower end, there may be a buffer plate 18 It turns the liquid and makes it easier to separate the gas. The gas rises toward the top in the outer wheel-shaped space 19 and extracts the gas again by driving the jet compressor 6. The liquid is removed at the lower end of the reactor, The gas has been basically separated, the reaction heat is removed through the heat exchanger 16 and reinjected into the driven jet compressor 6. The skimming trough is suitable for carrying out the method of the present invention. This is only suitable for inputting energy. Fanyuan ranges from 2 to 10 kW / m3. In order to convert the stirring energy to obtain the high-kLa 値 produced by the present invention, it is useful for a suitable portable mixing container inside. Type container, such as a buffer board. In addition, a foam-filled tubing string filled with 20 is shown in Figure 4, which is _ __ 5 3 paper sizes-~~ --- (Please read the precautions on the back before fill in (Page)-Packing.-Ordering. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Preferably from 1000 to 2000 m2 / m3. The filling 20 can be arranged regularly or arbitrarily. It is known that the regular filling geometry comes from the distillation separation technology with the lowest pressure drop. The filling includes iron mesh, and customary Similar to distillation techniques, iron meshes exhibit particularly popular properties. Reticulated fillers such as Sulzer DX® or Sulzer EX® are sold by Sulzer Chemteclin, 8404 Winterthur, Switzerland. The mentioned fillers can also be directly coated with a catalyst activating component. Such fillers are described in EP-A-068 862, EP-A 201 614 and EP-A 448 884. The fixed-bed reactor uses a packed bubble column. This packing has a similar high-altitude tube flow rate for liquids and gases. In each case, from 100 to 1,000 meters / hour, preferably from 200 to 1,000 meters. / Hour, like suspension. The steps have the same high kLa 値. The kLa 値 set according to the present invention ranges from 0.1 sec-1 to 1 sec-1. The determination of this data is to obtain high selectivity and high space-time yield at the same time. Device type to make appropriate measurement and implementation. For all types of reactors, when this method is implemented, compared with other methods, the energy input has been improved by an effective conversion of energy introduced by specific structural configuration and operating conditions' to improve mass transfer. When the method of the present invention is carried out using a suspended catalyst in a stirring vessel, the stirring type has good gas introduction properties. For example, a dish stirrer or a pin plate stirrer is well known. For example, settings necessary for fermentation techniques,値 from 0.1 seconds -1 to 1 seconds -1. The input energy is measured from 2 to 10 kW / m3. For small devices, using smaller 値 will produce a good hydrogenation ____ -14- This paper size applies to China National Standard (CNS) Μ specifications (210: 297 public compliance;) I — '---- (Please read the notes on the back before filling out this page)-Binding and printing A7 B7 printed by the Staff Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (12). When the reactor size is larger than 0.5 m 3, an input amount of 5 to 10 kW / m 3 is necessary. Energy is introduced into the agitated container by the driving power of the agitator. These energy inputs are larger than conventional gas-introduction reactions in stirred vessels, such as fermentation or hydrogenation, with input energy of about 0.2 to 1 kW / m3. The jet nozzle reactor with suspension catalyst requires an input energy of more than 2 kW / m3, preferably 3-5 kW / m3 is introduced by increasing the pressure of the liquid in the pump 21, The pressure drop driving the jet compressor 6. The reflux and pressure changes set in the reflux pump can set the required input energy. The pressure setting in the pump is usually a range of 2 to 5 bar. Assuming that the suspended catalyst in the reaction medium in the packed bubble column can be used in the method of the present invention, the surface area per unit volume of the packing must be at least 500 m 2 / m 3, but preferably 1000-2000 m 2 / Meters 3. The kLa (R) required for the present invention is set to 0.1 sec .; 1 to 1 sec.-1_, and high liquid and gas velocities are required, from 100 to 1000 m / h. In combination with the specified geometry of the filler, set the specified gas and liquid velocities to be sure that the energy input is required. However, the results of such equipment are lower than those of stirred vessels or jet nozzle reactors in the same state. Appropriate energy input 乃 is derived from the pressure drop of the flowing liquid and gas, which can be measured by the monitor with the pressure drop. The pressure drop is between 0.02 and 0.15 bar / meter filling. If required, the liquid flow rate can be changed to match the required pressure reduction. The surface area per unit volume of radon, the pressure reduction in the filling and the circulation rate of liquids and gases and the above-mentioned suspension method in a filled bubble column can also be -15- This paper size applies to the Chinese National Standard (CNS;) A4 size (210X297 (Mm) ——1 -— * --- ^ _ 丨; '. Loading ------ Order ------ [Μ' One (Please read the precautions on the back before filling this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (I3) It is used to fill a packed air bubble column with a catalyst activated substance. When the method of the present invention uses a fixed-bed reactor, the average particle diameter of the catalyst particles must be 1-20 mm, preferably 2-5 mm, and the speed of liquid and gas flow must be 100-1000 meters / hour. Set kLa 値 to center from 0 to 1 second. The pressure drop of the fixed bed should be set to about 0.002_〇 15 bar / meter. 14-Butanediol is used industrially in large quantities, for example, to prepare diol components in THF or polyesters. The method of the present invention is described by the following examples. Unless otherwise specified, butynediol is of industrial grade, which is in the form of 54% by weight of an aqueous solution, which contains different amounts of propynol. "In the examples, the amount of propynol is approximately the same as that of propanol. Amount in the reaction product. The percentages of reaction products in the examples, unless otherwise noted, are percentages by weight based on anhydrous water, determined by gas chromatography analysis. EXAMPLES Example 1 130 ml of liquid is placed in a stirred autoclave, which has two suitable buffer plates, a disc stirrer, and a built-in level controller (with porous metal filter to prevent catalyst from entering) ), Add 10 grams of Raney Ni / Mo catalyst in 50 ml of water (molybdenum solution filled with Raney nickel to form a molybdenum weight fraction of 2%) and then introduce 35 bar of hydrogen. The temperature of the internal reactor was increased to 140 F by external oil heating, and the hydrogen flow was set to 80 standard liters / hour. The stirrer was set at 700 revolutions per minute to ensure that the 54% by weight strength butyne glycol aqueous solution with a kLa of 0.2 seconds to 1.1 g / hr was then pumped in with a pump. The internal reactor temperature rose to 149. (: The amount of the obtained reaction product is -16- (read the precautions on the back ^ and then fill out this page) -pack., Ιτ This paper rule is used for ΦΜΙ 仓, and only 5 / π · \ Τ〇 A4 Recruitment r \-, π A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -17- V. Description of the invention (14) 103 g / h and containing 94.2% by weight i, 4_ butanediol, i 3% by weight of n-butanol, 3-4% by weight of n-propanol and a small amount of other products, the amount of each product is less than 0 · 08 weight ... STY is 0.4 kg butanediol / liter_ • hour. Example 2 Use Similar to Example 1, a 170 g / h solution of butynediol was hydrogenated with 10 g of Ni / Mo (2.5 wt.% / Mo of molybdenum). The initial temperature was 150 ° C, and the reactor temperature was at the reaction temperature. During the period it rose to 173. The product was obtained in an amount of 176 g / h and contained 92.4% by weight of i, 4-butanediol, 0.4% by weight of 2-fluorenylbutanediol, and 2% by weight of N-butanol and n-propanol at 4.7% by weight, add some other products with less than 0.8% by weight. STY is 0.7 kg of butanediol per liter. Hours. Example 3 Uses and Examples 1 similar Method, a 60 g / h butyl glycol solution was hydrogenated with 10 g of Raney Ni / Fe / Cr (type 11 II2 W from Degussa). The amount of liquid in the reactor was 85 ml and kLa was 0.2 seconds. -1. The initial temperature is 140 ° C, and then it is raised to 144 ° C. The amount of the obtained product is 64 g / hour, and contains 95.7% by weight of butanediol, 0.6% by weight of n-butanol, and 1.8%. Weight fraction of n-propanol, plus other products in an amount of less than 0.8% by weight. STY is 0.25 kg of butanediol per liter. Hours. Example 4 Using a method similar to Example 1, 60 g / The hourly solution of butynediol was 600 rpm, kLa was 0.1 seconds -1, and the reactor temperature was 105 ° C for redundant hydrogenation. The reactor output contained 90% by weight of butanediol. 、 This paper size applies to China National Standards of Standards (CNS) six 4 ^ grid (210X297 mm) (Please read the precautions on the back before filling this page} —.1- ^ 1 ----- Order ---- -: ¾ --- Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (15) 5% of butenediol, 4-hydroxybutyraldehyde and butanediol formed by 1.8% by weight Weight fraction Aldehyde, 2% by weight 4-hydroxybutyraldehyde and 4% by weight butanol. After the reactor temperature rose to 136 ° C, the conversion increased and the following amount of product appeared in the product: 92% by weight Butanol glycol, 4-hydroxybutyraldehyde and butanediol at a fraction of 2.7% by weight, 4-hydroxybutyraldehyde at 0.7% by weight, and butanol at 3% by weight. The method of the present invention as shown in Example 4 can obtain high selectivity at high conversion. Example 5 A 2.7 cm diameter 400 ml oil-heated tube reactor was filled with 400 ml of a 5 mm diameter Raschig ring. The Raschig ring was Verein Deutscher Eisenhuttenleute, 8th edition, Verlag Stahleisen mbH, Dusseldorf 1990, (UNS-No. S 32100) The metal mesh ring of steel watch material number 1.4541 issued is made of raw materials. The tube reactor is installed in a reaction system where the reaction liquid is circulated by a gear-pumped gas / liquid separator. The separator contains a filter through which liquids and gases pass to retain catalyst. As in Example 1, butynediol was added at 200 g / hr and 100 standard liters / hr of fresh gas was added before the reactor. The reactor was operated in an upward flow mode. The space velocity of the liquid is 170 m 3 / m 2 · hour, and kLa is 0.25 second_1. Before the reaction, the reaction system was filled with 20 g of Raney Ni / Mo into 300 ml of water in a similar manner as in Example 1. The reactor was at 30 bar and the temperature was from 145 to 151 ° C. The product obtained was 213 g / h and contained 93.3% by weight butanediol and 0.3% by weight 2-methylbutane. Alcohol, 1.5% by weight n-butanol, 4.2% by weight n-propanol, and -18-This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) w! I'— ♦ n nn mt nn nt tm m ^ an— I m I—y nn In i «^^^ 1 I factory i (Please read the notes on the back before filling out this page) Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5. Description of the invention (16) Other products at a weight fraction of 0.08 / °. The STY was about 0.25 kg of butanediol / liter.h. Example 6. The procedure of Example 5 was repeated, and 5 grams of Raney Ni / Mo was installed therein. A 100 g / h solution of butynediol was hydrogenated under a reactor temperature of about 122 t bar and 300 l / h of hydrogen. The velocity of the liquid is 225 meters 3 / meter 2.hours and 0.33 seconds of kLa, and the butadiene glycol is fully converted. The product contains 22_27% n-butanol by weight, of which 77 /. In terms of weight fraction content, 4-butanediol and the residue are intermediates. The space velocity of the liquid increased to 263 meters 3 / meters 2. After an hour, the kLa content was increased to 88% by weight when the n-butanol content was 13% by weight in terms of kLa of 0.4 seconds-1. . Example 7 Using the same method as in Example 1, a 57% by weight butanediol aqueous solution (water content: 42% by weight) at a strength of 60 g / hr was at a temperature of 127 in the reactor. (: And hydrogenation under kLa of 0.2 seconds -1. After 12S hours of reaction time, the product contains 95.4% by weight butanediol, 0% by weight 2-methylbutanediol, 1.5% Acetal by weight (formed from 4-hydroxybutyl ether and butanediol), 2.6% by weight butanediol and 03% by weight propanol. The reactor temperature was then increased to 141 ° C. Next, the conversion of the intermediate product continued to complete and selectivity increased. After 173 hours of operation, the following inclusions appeared: 98.8% by weight butanediol, 0.1% by weight 2-methyl Butyl glycol, 7% by weight butanediol, and 0.3% by weight propanol. _____ -19- This paper is applicable to the Chinese National Standard ([Postal] 8-4 specification (2 offers 297 public ^ 7 — ^^ ---- Install one i-----Order-------.ml one_ (Please read the notes on the back before filling out this page) Printed by A7, Consumers Cooperative of Central Standards Bureau, Ministry of Economic Affairs B7 V. Description of the invention (17) Comparative Example 1 Using the same method as in Example 1, the butynediol that had been steamed was subjected to hydrogenation in an aqueous solution having a strength of 50% by weight. The solution was added. The pH was adjusted to 6.6 with NaOH-. At an oil bath temperature of 140 ° C, the temperature of an internal reactor was set to 150 ° C and the feed rate was 100 g / h. After 24 hours of operation, the reactor output Contains 3% by weight of n-butanol, 0.5% by weight of n-propanol, and 96% by weight of 1,4-butanediol. After reducing the stirring speed to 350 rpm, kLa is 0.05 seconds -1, the reaction The reactor temperature dropped to 141 ° C, and the reactor output contained 10% by weight butynediol, 31% by weight butenediol, 41% by weight butylene glycol, and 3% by weight 4-butyric acid, 0.5% by weight of propanol, plus 4% by weight of butanol and 7% by weight of butenol. The residue is mainly shrunken. Comparative Example 2 Use as in Example 1 method, a 100 g / h technical grade butynediol solution is reacted at an oil bath temperature of 140 ° C using 10 g of Raney Ni / Mo (1.8% weight fraction of molybdenum, calculated as Mo). The temperature of the reactor was 149 ° C. The reaction product had the following composition: 94.1% by weight butanediol, 0.2% by weight 2-methylbutanediol, 1.5% by weight Butanol and 4.2% by weight propanol. After reducing the stirring speed to 350 rpm, which corresponds to a kLa of 0.05 seconds · 1, the following hydrogenation results were obtained: 40.3% by weight butanediol, 37% by weight Butanediol, 2.1% by weight butynediol, 3% by weight butanol, 2.6% by weight butenol, 3.1% by weight 4-hydroxybutyraldehyde relative to 100% by weight _-20-_ This paper size applies to Chinese national standards (CNsTa4 specification (210X297 mm_) (read the precautions on the back before filling in this page)
、1T 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（IS ) 殘留物主要包含丙醇、丙錦醇和4-輕丁經和二醇形成的縮 酸。 (請先閩讀背面之注意事項再填寫本頁) .裝. 訂 -21- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, 1T A7 B7 V. Description of the Invention (IS) The residue mainly contains propanol, propanol, and 4-acetal and glycols. (Please read the precautions on the reverse side before filling out this page). Packing. Order -21- This paper size applies to China National Standard (CNS) A4 (210X297 mm)