负载金属催化剂的制备及其合成油醇和异辛醇的研究
发布时间：2018-07-25 08:38
【摘要】：脂肪醇和异辛醇都是非常重要的化工产品基础原料和工业辅助原料,是具有广泛应用前景的绿色化学品。随着我国经济的快速发展,脂肪醇和异辛醇在我们日常生活中起着不可或缺的作用。因此,对于脂肪醇和异辛醇的研制与开发已成为当前社会不可避免的一种主流趋势。在加氢反应中采用的原料为油酸甲酯和辛烯醛,其中,油酸甲酯作为脂肪酸甲酯的重要组成成分,分子结构比较单一,而且同时具有双键和酯键,更有利于考察催化剂的催化性能,因此我们选用油酸甲酯作为原料制备油醇。目前在油酸甲酯和辛烯醛的加氢反应过程中,多数采用常见的金属氧化物作为催化剂(如CuO、ZnO、CuO/Cr_2O_3等),其缺点是对加氢反应条件要求比较苛刻,催化剂难以实现回收利用,最重要的是在催化剂制备过程中有毒金属的流失会污染环境,不符合绿色化学的发展理念。负载金属催化剂因其具有较高的稳定性、反应活性及选择性,良好的重复使用性能,在加氢、氧化及裂解等催化反应中具有普遍的应用。因此,本文的主要研究内容是采用负载金属催化剂催化油酸甲酯和辛烯醛加氢制备油醇和异辛醇。本文首先合成了ZrO_2、CeO_2、MCM-41和SBA-15四种负载载体,然后分别以ZrO_2、CeO_2、Al_2O_3、MCM-41和SBA-15为载体合成了负载金属Ru的催化剂并用于油酸甲酯的催化加氢。实验表明不同载体对催化剂的选择性和活性均具有较大的影响,Al_2O_3是最好的催化加氢催化剂载体。油酸甲酯4.0 g、催化剂Ru/Al_2O_3 0.20 g(Ru的质量分数为2.6%)、反应温度270℃、反应时间6 h、氢气压力5 MPa为最佳反应条件,产物羟值150 mgKOH/g和碘值18mgI2/100g。以Al_2O_3为载体考察了助剂Sn的加入对油酸甲酯加氢的影响,合成了Ru/Sn/Al_2O_3、Pd/Sn/Al_2O_3、Rh/Sn/Al_2O_3催化剂进一步考察负载双金属催化剂对加氢的影响并筛选出最佳催化剂,结果表明Ru/Sn/Al_2O_3是最佳的加氢催化剂,在最佳优化条件下产物羟值为191 mgKOH/g,碘值为9 mgI2/100g。进一步考察了Ru/Sn/Al_2O_3催化剂的重复使用性能,结果表明未经处理的催化剂在重复使用6次后,所得产物的羟值、碘值分别为183 mgKOH/g和10 mgI2/100g。采用XRD、TEM、TPR和BET手段对使用前后的Ru/Sn/Al_2O_3和Ru/Al_2O_3催化剂进行了表征,结果表明双金属催化剂的成功合成,而且新制催化剂和重复使用后的催化剂在结构上未发生较明显的变化。以ZrO_2、CeO_2、Al_2O_3、MCM-41、MAS-7和SBA-15为载体合成了负载金属Pd的催化剂并用于辛烯醛的催化加氢反应,筛选出最佳的加氢催化载体为ZrO_2,然后以ZrO_2为载体制备了Ni/Zr O_2、Co/ZrO_2、Rh/ZrO_2和Ru/ZrO_2催化剂并考察了活性金属对醛加氢反应的影响,结果表明Pd/ZrO_2催化剂具有较佳的加氢催化性能,在原料辛烯醛2.0 g、催化剂Pd/ZrO_2 0.1 g(Pd质量分数为1.0%)、反应温度240℃、反应时间7 h、氢气压力6 MPa的反应条件下,辛烯醛的转化率和异辛醇的选择性分别为100%和99.1%,而且在催化剂重复使用6次后,加氢反应的转化率和选择性仍然高达99.7%和97.0%。采用XRD、FT-IR和BET手段对新制Pd/Zr O_2催化剂和重复使用8次之后的催化剂进行表征,说明成功合成了Pd/ZrO_2催化剂,而且催化剂的重复利用未使催化剂的结构遭到破坏。另外,采用HR-TEM和TPR手段对Pd/ZrO_2、Ni/ZrO_2、Co/ZrO_2、Rh/ZrO_2和Ru/ZrO_2催化剂进行表征,解释说明了Pd在载体ZrO_2上具有最佳的分散性和Pd/ZrO_2催化剂中金属氧化物易于还原的特性,从而使得Pd/ZrO_2表现出最理想的催化活性。由此可见,负载金属催化剂对催化酯加氢和醛加氢反应具有较好的效果,并且具有良好的稳定性和重复使用性能,为克服传统的加氢制醇工艺存在的缺陷提供了新的方向,为加氢催化剂的进一步研究提供了参考价值。
[Abstract]:Fatty alcohols and isooctyl alcohols are both very important basic raw materials for chemical products and industrial auxiliary materials and are widely used as green chemicals. With the rapid development of our economy, fatty alcohols and ISO octanol play an indispensable role in our daily life. Therefore, the development and development of fatty alcohol and isooctanol have been developed. It is an inevitable trend in the current society. The raw materials used in the hydrogenation reaction are methyl oleate and Xin Xiquan, in which methyl oleate is an important component of fatty acid methyl ester, with a single molecular structure and double bonds and ester bonds at the same time, which is more conducive to the catalytic performance of the catalyst. Therefore, we choose oleic acid. In the process of hydrogenation of methyl oleate and ocenenal, most of the common metal oxides are used as catalysts (such as CuO, ZnO, CuO/Cr_2O_3, etc.) in the process of hydrogenation of methyl oleate and ocenenal. The disadvantage is that the requirements for the hydrogenation reaction are very demanding, and the catalyst is difficult to be recycled. The most important thing is that the catalyst is prepared in the process of preparation. The loss of toxic metals will pollute the environment and do not conform to the concept of green chemistry. Supported metal catalysts are widely used in the catalytic reactions such as hydrogenation, oxidation and cracking because of their high stability, reactive activity and selectivity and good reuse performance. Four loading carriers of ZrO_2, CeO_2, MCM-41 and SBA-15 were synthesized by hydrogenation of methyl oleate and octyl aldehyde. The catalysts supported by ZrO_2, CeO_2, Al_2O_3, MCM-41 and SBA-15 were synthesized to catalyze the catalytic hydrogenation of methyl oleate with ZrO_2, CeO_2, Al_2O_3, MCM-41 and SBA-15. The experiments showed that the different carriers were catalyzed. The selectivity and activity of the agent have great influence. Al_2O_3 is the best catalyst for catalytic hydrogenation. The methyl oleate is 4 g, the catalyst Ru/Al_2O_3 0.20 g (the mass fraction of Ru is 2.6%), the reaction temperature is 270, the reaction time is 6 h, the hydrogen pressure 5 MPa is the best reaction condition, the product of the hydroxyl value 150 mgKOH/g and the iodine value 18mgI2/100g. are Al_2O_3. The effect of the addition of auxiliary Sn on the hydrogenation of methyl oleate was investigated. The effect of Ru/Sn/Al_2O_3, Pd/Sn/Al_2O_3 and Rh/Sn/Al_2O_3 catalysts on the hydrogenation of the supported bimetallic catalyst was further investigated and the best catalyst was screened. The results showed that Ru/Sn/Al_2O_3 was the best hydrogenation catalyst, and the hydroxyl value of the product under the optimal optimum conditions was determined. 191 mgKOH/g and an iodine value of 9 mgI2/100g. further investigated the reuse performance of the Ru/Sn/Al_2O_3 catalyst. The results showed that the hydroxyl value of the product was 183 mgKOH/g and 10 mgI2/100g., respectively, after 6 times of reuse of the untreated catalyst, and XRD, TEM, TPR and BET were used to catalyze the Ru/Sn/Al_2O_3 and Ru/Al_2O_3 before and after use. The catalyst was characterized. The results showed the successful synthesis of the bimetallic catalyst, and the catalyst and the reused catalyst had no obvious changes in the structure. ZrO_2, CeO_2, Al_2O_3, MCM-41, MAS-7 and SBA-15 were used as the carrier to synthesize the catalytic agent of the metal Pd and the catalytic hydrogenation reaction of the ocenal aldehyde. The hydrogenation catalyst carrier is ZrO_2, then the catalyst of Ni/Zr O_2, Co/ZrO_2, Rh/ZrO_2 and Ru/ZrO_2 is prepared with ZrO_2 as the carrier and the effect of active metal on the hydrogenation of aldehyde is investigated. The results show that the catalyst has a better catalytic performance for hydrogenation, 2 g in the raw material of octyl aldehyde, and the catalyst Pd/ZrO_2 0.1 g (Pd mass fraction is 1%). At 240 C, reaction time 7 h and hydrogen pressure 6 MPa, the conversion rate of octyl aldehyde and the selectivity of isooctanol are 100% and 99.1% respectively, and the conversion and selectivity of hydrogenation reaction are still 99.7% and XRD, FT-IR and BET methods are used for the new Pd/Zr O_2 catalyst and repeat after the catalyst is reused for 6 times. The catalyst was characterized after 8 times, indicating that the Pd/ZrO_2 catalyst was successfully synthesized, and the catalyst's reutilization did not destroy the structure of the catalyst. In addition, the Pd/ZrO_2, Ni/ZrO_2, Co/ZrO_2, Rh/ZrO_2 and Ru/ZrO_2 catalysts were characterized by HR-TEM and TPR, explaining that Pd is best on the carrier ZrO_2. The dispersivity and the easy reduction of the metal oxide in the Pd/ZrO_2 catalyst make the Pd/ZrO_2 exhibit the most ideal catalytic activity. Thus, the supported metal catalyst has a good effect on the catalytic hydrogenation of ester and aldehyde hydrogenation, and has good stability and reuse performance, which is to overcome the traditional hydrogenation of alcohol. The defects in the process provide a new direction, which provides a reference for further research of hydrogenation catalyst.
【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;TQ223.1
本文编号：2143246
[Abstract]:Fatty alcohols and isooctyl alcohols are both very important basic raw materials for chemical products and industrial auxiliary materials and are widely used as green chemicals. With the rapid development of our economy, fatty alcohols and ISO octanol play an indispensable role in our daily life. Therefore, the development and development of fatty alcohol and isooctanol have been developed. It is an inevitable trend in the current society. The raw materials used in the hydrogenation reaction are methyl oleate and Xin Xiquan, in which methyl oleate is an important component of fatty acid methyl ester, with a single molecular structure and double bonds and ester bonds at the same time, which is more conducive to the catalytic performance of the catalyst. Therefore, we choose oleic acid. In the process of hydrogenation of methyl oleate and ocenenal, most of the common metal oxides are used as catalysts (such as CuO, ZnO, CuO/Cr_2O_3, etc.) in the process of hydrogenation of methyl oleate and ocenenal. The disadvantage is that the requirements for the hydrogenation reaction are very demanding, and the catalyst is difficult to be recycled. The most important thing is that the catalyst is prepared in the process of preparation. The loss of toxic metals will pollute the environment and do not conform to the concept of green chemistry. Supported metal catalysts are widely used in the catalytic reactions such as hydrogenation, oxidation and cracking because of their high stability, reactive activity and selectivity and good reuse performance. Four loading carriers of ZrO_2, CeO_2, MCM-41 and SBA-15 were synthesized by hydrogenation of methyl oleate and octyl aldehyde. The catalysts supported by ZrO_2, CeO_2, Al_2O_3, MCM-41 and SBA-15 were synthesized to catalyze the catalytic hydrogenation of methyl oleate with ZrO_2, CeO_2, Al_2O_3, MCM-41 and SBA-15. The experiments showed that the different carriers were catalyzed. The selectivity and activity of the agent have great influence. Al_2O_3 is the best catalyst for catalytic hydrogenation. The methyl oleate is 4 g, the catalyst Ru/Al_2O_3 0.20 g (the mass fraction of Ru is 2.6%), the reaction temperature is 270, the reaction time is 6 h, the hydrogen pressure 5 MPa is the best reaction condition, the product of the hydroxyl value 150 mgKOH/g and the iodine value 18mgI2/100g. are Al_2O_3. The effect of the addition of auxiliary Sn on the hydrogenation of methyl oleate was investigated. The effect of Ru/Sn/Al_2O_3, Pd/Sn/Al_2O_3 and Rh/Sn/Al_2O_3 catalysts on the hydrogenation of the supported bimetallic catalyst was further investigated and the best catalyst was screened. The results showed that Ru/Sn/Al_2O_3 was the best hydrogenation catalyst, and the hydroxyl value of the product under the optimal optimum conditions was determined. 191 mgKOH/g and an iodine value of 9 mgI2/100g. further investigated the reuse performance of the Ru/Sn/Al_2O_3 catalyst. The results showed that the hydroxyl value of the product was 183 mgKOH/g and 10 mgI2/100g., respectively, after 6 times of reuse of the untreated catalyst, and XRD, TEM, TPR and BET were used to catalyze the Ru/Sn/Al_2O_3 and Ru/Al_2O_3 before and after use. The catalyst was characterized. The results showed the successful synthesis of the bimetallic catalyst, and the catalyst and the reused catalyst had no obvious changes in the structure. ZrO_2, CeO_2, Al_2O_3, MCM-41, MAS-7 and SBA-15 were used as the carrier to synthesize the catalytic agent of the metal Pd and the catalytic hydrogenation reaction of the ocenal aldehyde. The hydrogenation catalyst carrier is ZrO_2, then the catalyst of Ni/Zr O_2, Co/ZrO_2, Rh/ZrO_2 and Ru/ZrO_2 is prepared with ZrO_2 as the carrier and the effect of active metal on the hydrogenation of aldehyde is investigated. The results show that the catalyst has a better catalytic performance for hydrogenation, 2 g in the raw material of octyl aldehyde, and the catalyst Pd/ZrO_2 0.1 g (Pd mass fraction is 1%). At 240 C, reaction time 7 h and hydrogen pressure 6 MPa, the conversion rate of octyl aldehyde and the selectivity of isooctanol are 100% and 99.1% respectively, and the conversion and selectivity of hydrogenation reaction are still 99.7% and XRD, FT-IR and BET methods are used for the new Pd/Zr O_2 catalyst and repeat after the catalyst is reused for 6 times. The catalyst was characterized after 8 times, indicating that the Pd/ZrO_2 catalyst was successfully synthesized, and the catalyst's reutilization did not destroy the structure of the catalyst. In addition, the Pd/ZrO_2, Ni/ZrO_2, Co/ZrO_2, Rh/ZrO_2 and Ru/ZrO_2 catalysts were characterized by HR-TEM and TPR, explaining that Pd is best on the carrier ZrO_2. The dispersivity and the easy reduction of the metal oxide in the Pd/ZrO_2 catalyst make the Pd/ZrO_2 exhibit the most ideal catalytic activity. Thus, the supported metal catalyst has a good effect on the catalytic hydrogenation of ester and aldehyde hydrogenation, and has good stability and reuse performance, which is to overcome the traditional hydrogenation of alcohol. The defects in the process provide a new direction, which provides a reference for further research of hydrogenation catalyst.
【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;TQ223.1
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