負(fù)載金屬催化劑的制備及其合成油醇和異辛醇的研究
發(fā)布時(shí)間：2018-07-25 08:38
【摘要】：脂肪醇和異辛醇都是非常重要的化工產(chǎn)品基礎(chǔ)原料和工業(yè)輔助原料,是具有廣泛應(yīng)用前景的綠色化學(xué)品。隨著我國經(jīng)濟(jì)的快速發(fā)展,脂肪醇和異辛醇在我們?nèi)粘Ｉ钪衅鹬豢苫蛉钡淖饔�。因�?對(duì)于脂肪醇和異辛醇的研制與開發(fā)已成為當(dāng)前社會(huì)不可避免的一種主流趨勢。在加氫反應(yīng)中采用的原料為油酸甲酯和辛烯醛,其中,油酸甲酯作為脂肪酸甲酯的重要組成成分,分子結(jié)構(gòu)比較單一,而且同時(shí)具有雙鍵和酯鍵,更有利于考察催化劑的催化性能,因此我們選用油酸甲酯作為原料制備油醇。目前在油酸甲酯和辛烯醛的加氫反應(yīng)過程中,多數(shù)采用常見的金屬氧化物作為催化劑(如CuO、ZnO、CuO/Cr_2O_3等),其缺點(diǎn)是對(duì)加氫反應(yīng)條件要求比較苛刻,催化劑難以實(shí)現(xiàn)回收利用,最重要的是在催化劑制備過程中有毒金屬的流失會(huì)污染環(huán)境,不符合綠色化學(xué)的發(fā)展理念。負(fù)載金屬催化劑因其具有較高的穩(wěn)定性、反應(yīng)活性及選擇性,良好的重復(fù)使用性能,在加氫、氧化及裂解等催化反應(yīng)中具有普遍的應(yīng)用。因此,本文的主要研究內(nèi)容是采用負(fù)載金屬催化劑催化油酸甲酯和辛烯醛加氫制備油醇和異辛醇。本文首先合成了ZrO_2、CeO_2、MCM-41和SBA-15四種負(fù)載載體,然后分別以ZrO_2、CeO_2、Al_2O_3、MCM-41和SBA-15為載體合成了負(fù)載金屬Ru的催化劑并用于油酸甲酯的催化加氫。實(shí)驗(yàn)表明不同載體對(duì)催化劑的選擇性和活性均具有較大的影響,Al_2O_3是最好的催化加氫催化劑載體。油酸甲酯4.0 g、催化劑Ru/Al_2O_3 0.20 g(Ru的質(zhì)量分?jǐn)?shù)為2.6%)、反應(yīng)溫度270℃、反應(yīng)時(shí)間6 h、氫氣壓力5 MPa為最佳反應(yīng)條件,產(chǎn)物羥值150 mgKOH/g和碘值18mgI2/100g。以Al_2O_3為載體考察了助劑Sn的加入對(duì)油酸甲酯加氫的影響,合成了Ru/Sn/Al_2O_3、Pd/Sn/Al_2O_3、Rh/Sn/Al_2O_3催化劑進(jìn)一步考察負(fù)載雙金屬催化劑對(duì)加氫的影響并篩選出最佳催化劑,結(jié)果表明Ru/Sn/Al_2O_3是最佳的加氫催化劑,在最佳優(yōu)化條件下產(chǎn)物羥值為191 mgKOH/g,碘值為9 mgI2/100g。進(jìn)一步考察了Ru/Sn/Al_2O_3催化劑的重復(fù)使用性能,結(jié)果表明未經(jīng)處理的催化劑在重復(fù)使用6次后,所得產(chǎn)物的羥值、碘值分別為183 mgKOH/g和10 mgI2/100g。采用XRD、TEM、TPR和BET手段對(duì)使用前后的Ru/Sn/Al_2O_3和Ru/Al_2O_3催化劑進(jìn)行了表征,結(jié)果表明雙金屬催化劑的成功合成,而且新制催化劑和重復(fù)使用后的催化劑在結(jié)構(gòu)上未發(fā)生較明顯的變化。以ZrO_2、CeO_2、Al_2O_3、MCM-41、MAS-7和SBA-15為載體合成了負(fù)載金屬Pd的催化劑并用于辛烯醛的催化加氫反應(yīng),篩選出最佳的加氫催化載體為ZrO_2,然后以ZrO_2為載體制備了Ni/Zr O_2、Co/ZrO_2、Rh/ZrO_2和Ru/ZrO_2催化劑并考察了活性金屬對(duì)醛加氫反應(yīng)的影響,結(jié)果表明Pd/ZrO_2催化劑具有較佳的加氫催化性能,在原料辛烯醛2.0 g、催化劑Pd/ZrO_2 0.1 g(Pd質(zhì)量分?jǐn)?shù)為1.0%)、反應(yīng)溫度240℃、反應(yīng)時(shí)間7 h、氫氣壓力6 MPa的反應(yīng)條件下,辛烯醛的轉(zhuǎn)化率和異辛醇的選擇性分別為100%和99.1%,而且在催化劑重復(fù)使用6次后,加氫反應(yīng)的轉(zhuǎn)化率和選擇性仍然高達(dá)99.7%和97.0%。采用XRD、FT-IR和BET手段對(duì)新制Pd/Zr O_2催化劑和重復(fù)使用8次之后的催化劑進(jìn)行表征,說明成功合成了Pd/ZrO_2催化劑,而且催化劑的重復(fù)利用未使催化劑的結(jié)構(gòu)遭到破壞。另外,采用HR-TEM和TPR手段對(duì)Pd/ZrO_2、Ni/ZrO_2、Co/ZrO_2、Rh/ZrO_2和Ru/ZrO_2催化劑進(jìn)行表征,解釋說明了Pd在載體ZrO_2上具有最佳的分散性和Pd/ZrO_2催化劑中金屬氧化物易于還原的特性,從而使得Pd/ZrO_2表現(xiàn)出最理想的催化活性。由此可見,負(fù)載金屬催化劑對(duì)催化酯加氫和醛加氫反應(yīng)具有較好的效果,并且具有良好的穩(wěn)定性和重復(fù)使用性能,為克服傳統(tǒng)的加氫制醇工藝存在的缺陷提供了新的方向,為加氫催化劑的進(jìn)一步研究提供了參考價(jià)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.
【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36;TQ223.1
本文編號(hào)：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.
【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36;TQ223.1
【參考文獻(xiàn)】
相關(guān)期刊論文 前10條
1 王青春;劉振朋;安勝利;王瑞芬;王艷玲;徐拓;;Effect of CeO_2-ZrO_2 on Pt/C electrocatalysts for alcohols oxidation[J];Journal of Rare Earths;2016年03期
2 王沾祺;周志明;張銳;李莉;程振民;;Pd-Cu/γ-Al_2O_3催化苯乙炔選擇性加氫反應(yīng)[J];物理化學(xué)學(xué)報(bào);2014年12期
3 姚琳;劉仕偉;李露;于世濤;;銅鉻催化劑催化脂肪酸甲酯加氫制備脂肪醇的研究[J];化工科技;2014年04期
4 陳彥;李露;于鳳麗;解從霞;;乙醇-水體系下MAS-7介孔分子篩的合成及其催化木質(zhì)素液化的性能[J];青島科技大學(xué)學(xué)報(bào)(自然科學(xué)版);2014年03期
5 張加贏;辛忠;孟鑫;陶淼;;基于MCM-41的鎳基甲烷化催化劑活性與穩(wěn)定性[J];化工學(xué)報(bào);2014年01期
6 石艷芝;張娜;羅孟飛;魯繼青;;Pt/CeO_2催化劑上甲醛催化氧化[J];中國稀土學(xué)報(bào);2011年03期
7 袁鵬;劉仲毅;孫海杰;劉壽長;;焙燒溫度對(duì)酯加氫制醇Cu-Al-Ba催化劑性能的影響(英文)[J];物理化學(xué)學(xué)報(bào);2010年08期
8 曹淵;白英豪;周純;;Pd-MCM-41介孔材料的合成、表征及催化性能研究[J];化學(xué)世界;2008年11期
9 鄭修成;袁程遠(yuǎn);趙文平;楊春艷;葉文豪;王向宇;;介孔分子篩SBA-15的合成與表征[J];鄭州大學(xué)學(xué)報(bào)(理學(xué)版);2008年01期
10 楊萬才;李悅;;含Pd類水滑石催化劑的活性研究[J];遼寧化工;2008年02期
相關(guān)碩士學(xué)位論文 前2條
1 姜蕊;溫控相轉(zhuǎn)移催化脂肪酸甲酯/辛烯醛加氫反應(yīng)的研究[D];青島科技大學(xué);2010年
2 麻春艷;負(fù)載型Au-Pd雙金屬催化劑的制備及其CO氧化與噻吩加氫脫硫反應(yīng)性能的研究[D];煙臺(tái)大學(xué);2007年
，本文編號(hào)：2143246
本文鏈接：http://sikaile.net/kejilunwen/huaxue/2143246.html
最近更新
教材專著
