【正文】 McGrawHill: New York, 1975。 Isogai, N.。 Happel, J.。 Ito, H.。 Hsieh, C. R. Catal. Lett. 1996, 41,213. [13]Girolamo, M.。 Vol. 13, p 390. [8]Palekar, V. M.。 Stamhuis, E. J.。 5060％的轉(zhuǎn)換，實(shí)現(xiàn)了在一個(gè)流動(dòng)型半批式反應(yīng)器，低溫甲醇合成沒有熱力學(xué)的限制。 這是很難確定，現(xiàn)在純 CO + H2的反應(yīng)路線， CO插入乙醇形成的酯被排除。 從上面的反應(yīng)機(jī)制，水是唯一的中間，類似作用的 CO 2中的步驟（ 1） （ 3）。 流動(dòng)氣體被用來作為一個(gè)純 H2（ 20毫升 /分鐘， 30桿）的流動(dòng)。 為第一個(gè)反應(yīng)條件類似以上所述的甲醇合成反應(yīng)。 另一方面，異丁醇在其氧原子的電子密度高，這應(yīng)該加速反應(yīng)。 例如，在 443 K時(shí)，在 2 丙醇溶劑的總轉(zhuǎn)換是高達(dá) ％，其中甲醇和 2 丙基甲酸產(chǎn)量分別占 ％和 ％。 這些醇類反應(yīng)溫度顯著降低，加速了反應(yīng)，但不影響整體反應(yīng)步驟（ 1）化學(xué)計(jì)量學(xué) （ 3）上面列出的。反應(yīng)時(shí)間為 2小時(shí) 。 反應(yīng)后，反應(yīng)堆冷卻冰水，然后在反應(yīng)器內(nèi)的氣體被釋放非常緩慢，收集在氣包進(jìn)行分析。 以確認(rèn)催化劑鈍化的影響，在原位的催化劑乙醇引進(jìn)前減少提供量身定制的反應(yīng)堆，用于執(zhí)行了催化劑的還原和反應(yīng)，但沒有反應(yīng)行為的差異進(jìn)行了觀察。 同時(shí)加入 300毫升的水不斷攪拌的水溶液，含有銅，鋅硝酸鹽（銅 /鋅的摩爾比 = 1），碳酸鈉水溶液。 考慮到水氣轉(zhuǎn)移反應(yīng)在較低溫度下很容易對(duì) Cu / ZnO催化劑 。 然而，這個(gè)過程中的一個(gè)顯著的缺點(diǎn)是，即使是二氧化碳 和水的進(jìn)氣或反應(yīng)體系中的微量盡快將停用強(qiáng)堿性催化劑 [4,5]導(dǎo)致成本高，從完整的合成氣凈化來自改革者，激活失活的催化劑。 Chapter 20. 外文資料原文 9 一種新的低溫甲醇合成路線： 酒精 溶劑的催化效應(yīng) 1 簡(jiǎn)介 世界各地每年氣相甲醇 的 工業(yè)生產(chǎn) 3040萬噸， 由 一氧化碳 /二氧化碳 /氫 氣 ，在 523? 573 K的溫度范圍和 50100 bar 的 壓力范 圍，采用銅 鋅 氧化物 的 催化劑。 Gruver, V. S. Ki. Katal. 1969,10, 862. [26]Tsubaki, N.。 1973, 77, 1601. [22]Mezaki, R.。 Waugh, K. C. . 1995, 30, 99. [19]Yoshihara, J.。 Cheng, W. H.。 Li, H.。 Jung, H.。 the difference ing from the influence of molar numbers of different alcoholic solvents can be ignored. Concerning the alcohols with the same carbon number but different structure, the second alcohol had highest activity, as shown in the reactions in 2propanol, 2butanol, and 2pentanol separately. 2Propanol exhibited highest activity among these three 2alcohols. For example, at 443 K, the total conversion in the solvent of 2propanol was high up to %, among which methanol and 2propyl formate yields accounted for % and %, respectively. For alcohols with larger spatial obstacle, the reaction had lower activity, as shown in the cases of isobutanol, tertbutyl alcohol, and cyclopentanol. In addition, for ethylene glycol and benzyl alcohol, no activity was observed. But the reason is not very clear now. On the reasons for different behaviors of the alcohols with the same carbon number but different structure, it is considered that different alcohol type affected step(2) by both the electronic effect and spatial effect. For 1butanol, the electron density of oxygen atom in ROH is lower. As a result, ROH attacked the carbon atom of HCOOCu, the intermediate of step (2), more slowly. But the spatial obstacle of 1butanol is the smallest among all butanols, and this is favorable to the nucleophilic attack in the esterification reaction. On the other hand, isobutanol has high electronic density in its oxygen atom and this should accelerate the reaction. But its large molecular volume became a severe spatial obstacle in the nucleophilic attack. So its esterification rate was low. As a balanced effect between electronic factor and spatial factor, 2butanol exhibited highest activity among 4 butanols, in the ratedetermining step (2). As the opposite example, tertbutyl alcohol gave the yield of methanol as low as % here. It should be pointed out that the accumulated ester (HCOOR) can be easily transferred to methanol and ROH under higher H2 partial pressure. Two experiments were conducted to demonstrate this. One was the hydrogenation of ethyl formate in a batch reactor and the other was the hydrogenation of 2butyl formate in a flowtype semibatch autoclave reactor. For the first one, the reaction conditions were similar to those used in the synthesis reaction of methanol described above. A mixture gas of H2 and N2 with a total initial pressure of 30 bar (20 bar H2 and 10 bar N2) was used as feed gas. Ethyl formate ( mL) and mL of cyclohexane were mixed and poured into the reactor instead of 20 mL of alcohol. After 2 h reaction, the total 外文資料原文 6 conversion of ethyl formate was % and the yield of methanol was %. Methyl formate and CO were byproducts. Methyl formate might e from the transesterification of ethyl formate and the methanol produced. CO might e from the deposition of ethyl formate. For the latter experiment, mL of 2butyl formate (5 times amount in volume of ethyl formate used in the first experiment) and mL of cyclohexane were poured in the reactor. A flow of pure H2 (20 mL/min, 30 bar) was used as flowing gas. After 8 h continuous reaction at 443 K, % of 2butyl formate was transferred to methanol and 2butanol. The total conversions were high while 2alcohols were utilized. But the yields to ester were also high, especially for 2pentanol. It is referred that step (3) above was slower if 2alcohols were used. In other cases, the rate of step (3) was much faster than that of step (2), resulting in the disappearance or very low yield of the corresponding esters. If the water was added to ethanol with the same molar amount as that