耦合法制备γ-丁内酯和2-甲基呋喃的研究
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摘要
单独的1，4-丁二醇脱氢制γ-丁内酯反应和糠醛加氢制2-甲基呋喃反应具有一些缺点，如：因单独过程的强吸、放热，易导致局部反应温度过冷或过热，降低目的产物选择性、低的能量和氢的利用率等。针对两反应的上述缺点，朱玉雷开发了常压脱氢加氢耦合一体化制γ-丁内酯和2-甲基呋喃的新工艺，在耦合过程中，糠醛加氢反应释放出来的热可以被1，4-丁二醇脱氢反应所用，而1，4-丁二醇脱出的氢可以被糠醛加氢所用。脱氢加氢耦合一体化体现了一个高效节能的过程，但目前仍然缺乏对这一过程的全面和深入的认识，因此对其进行详细地研究非常必要，本文从反应和催化剂两方面着手，对脱氢加氢耦合一体化制γ-丁内酯和2-甲基呋喃作了进一步的研究，以期能为其工业化提供一些基础参数。主要研究结果如下：
1．利用应用广泛的Cu-Cr体系催化剂对1，4-丁二醇和糠醛单独脱氢加氢反应分别进行了详细地研究，得到了这两个反应的最佳操作条件，XRD和TG-DTG表征发现，Cu~0为催化剂的活性中心，Cr的存在促进了Cu的高度分散，助剂Ca和Ba的加入，降低了催化剂的还原温度，提高了目的产物的选择性，整体上提高了催化剂的性能。
2．采用脱氢和加氢效果皆好的Cu-Cr-Ca-Ba催化剂对耦合反应进行了详细地研究。得到了耦合反应最佳的操作条件。
3．采用不同铝源制备了一系列Cu-Zn-Al催化剂，考察了各自的耦合反应性能，结果表明：采用氧化铝溶胶作为Al源的催化剂，反应性能较好。考察了焙烧温度对此催化剂耦合反应性能的影响，结果表明：350℃焙烧的催化剂的催化性能最好。低温不利于催化剂前驱体的完全分解，温度过高将会降低催化剂的比表面积，最终导致目的产物选择性的降低。
4．1，4-丁二醇脱氢、糠醛加氢的比活性随着焙烧温度的提高而增大，但是同时表面积的降低又抵消了催化剂的比活性的增加，导致催化剂总的活性的降低。
There are many deficiencies existing in the conventional individual dehydrogenation of 1,4-butanediol and hydrogenation of furfural, such as poor hydrogen utilization, hardly controlled reaction temperature, and low selectivity to desired products. In order to solve these problems, a novel coupling process of the dehydrogenation of 1,4-butanediol and the hydrogenation of furfural has been invented for the synthesis of y-butyrolactone and 2-methylfuran simultaneously by Zhu Yulei. In this coupling process, the heat released by the hydrogenation of furfural can be used for the dehydrogenation of 1,4-butanediol, and the H2 released by the dehydrogenation of 1,4-butanediol can be utilized by the hydrogenation of furfural, leading to much easier temperature control and more perfect hydrogen mass balance (with hydrogen recycle but no hydrogen supply and release). However, a full understanding of the process and the mechanism for this reaction is still lacking. Thus the detailed study of this coupling process shows
great interest. In this paper, the coupling process is studied further in term of reaction and catalyst. The results and corresponding conclusion obtained in this work are summarized as follow:
1. The dehydrogenation of 1,4-butanediol and the hydrogenation of furfural over the Cu-Cr catalysts are studied in detail respectively and the proper reaction conditions of the two reactions are achieved. The XRD and TG-DTG characterization results show that Cu?is the active site of reaction, and the presence of Cr is in favor of high dispersion of Cu, which results in increasing of the reaction activity and selectivity. The reduction temperature is lowed by the addition of calcium and barium promoters, leading to an increased yield of the desired products.
2. Over a Cu-Cr-Ca-Ba catalyst with excellent dehydrogenation and hydrogenation performance, the coupling process is investigated in detail, and the proper reaction conditions are achieved.
3. A series of Cu-Zn-Al catalysts are prepared by using different aluminium compounds, and the performance of them is studied through the coupling process.
The results show that the Cu-Zn-Al catalyst which prepared by alumina gel has the better reaction performance. The effect of calcination temperatures on this optimal catalyst is investigated in detail, and the results show that the suitable calcination temperature for Cu-Zn-Al catalyst is about 350癈. Lower temperature cannot facilitate the precursor to complete decomposition and higher calcination temperature will decline the surface area of the catalyst, which finally declines the yield for desired products.
4. The experimental results show that the specific activities for 1,4-butanediol and furfural conversion are improved at high temperature, but the simultaneous loss of surface area offsets the gain in specific activity and final causes the decline in the overall activity of catalyst.
1．利用应用广泛的Cu-Cr体系催化剂对1，4-丁二醇和糠醛单独脱氢加氢反应分别进行了详细地研究，得到了这两个反应的最佳操作条件，XRD和TG-DTG表征发现，Cu~0为催化剂的活性中心，Cr的存在促进了Cu的高度分散，助剂Ca和Ba的加入，降低了催化剂的还原温度，提高了目的产物的选择性，整体上提高了催化剂的性能。
2．采用脱氢和加氢效果皆好的Cu-Cr-Ca-Ba催化剂对耦合反应进行了详细地研究。得到了耦合反应最佳的操作条件。
3．采用不同铝源制备了一系列Cu-Zn-Al催化剂，考察了各自的耦合反应性能，结果表明：采用氧化铝溶胶作为Al源的催化剂，反应性能较好。考察了焙烧温度对此催化剂耦合反应性能的影响，结果表明：350℃焙烧的催化剂的催化性能最好。低温不利于催化剂前驱体的完全分解，温度过高将会降低催化剂的比表面积，最终导致目的产物选择性的降低。
4．1，4-丁二醇脱氢、糠醛加氢的比活性随着焙烧温度的提高而增大，但是同时表面积的降低又抵消了催化剂的比活性的增加，导致催化剂总的活性的降低。
There are many deficiencies existing in the conventional individual dehydrogenation of 1,4-butanediol and hydrogenation of furfural, such as poor hydrogen utilization, hardly controlled reaction temperature, and low selectivity to desired products. In order to solve these problems, a novel coupling process of the dehydrogenation of 1,4-butanediol and the hydrogenation of furfural has been invented for the synthesis of y-butyrolactone and 2-methylfuran simultaneously by Zhu Yulei. In this coupling process, the heat released by the hydrogenation of furfural can be used for the dehydrogenation of 1,4-butanediol, and the H2 released by the dehydrogenation of 1,4-butanediol can be utilized by the hydrogenation of furfural, leading to much easier temperature control and more perfect hydrogen mass balance (with hydrogen recycle but no hydrogen supply and release). However, a full understanding of the process and the mechanism for this reaction is still lacking. Thus the detailed study of this coupling process shows
great interest. In this paper, the coupling process is studied further in term of reaction and catalyst. The results and corresponding conclusion obtained in this work are summarized as follow:
1. The dehydrogenation of 1,4-butanediol and the hydrogenation of furfural over the Cu-Cr catalysts are studied in detail respectively and the proper reaction conditions of the two reactions are achieved. The XRD and TG-DTG characterization results show that Cu?is the active site of reaction, and the presence of Cr is in favor of high dispersion of Cu, which results in increasing of the reaction activity and selectivity. The reduction temperature is lowed by the addition of calcium and barium promoters, leading to an increased yield of the desired products.
2. Over a Cu-Cr-Ca-Ba catalyst with excellent dehydrogenation and hydrogenation performance, the coupling process is investigated in detail, and the proper reaction conditions are achieved.
3. A series of Cu-Zn-Al catalysts are prepared by using different aluminium compounds, and the performance of them is studied through the coupling process.
The results show that the Cu-Zn-Al catalyst which prepared by alumina gel has the better reaction performance. The effect of calcination temperatures on this optimal catalyst is investigated in detail, and the results show that the suitable calcination temperature for Cu-Zn-Al catalyst is about 350癈. Lower temperature cannot facilitate the precursor to complete decomposition and higher calcination temperature will decline the surface area of the catalyst, which finally declines the yield for desired products.
4. The experimental results show that the specific activities for 1,4-butanediol and furfural conversion are improved at high temperature, but the simultaneous loss of surface area offsets the gain in specific activity and final causes the decline in the overall activity of catalyst.
引文
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