煤炭、生物质选择性催化氧化制备化学品的研究
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摘要
随着世界上石油资源的日益衰竭,竞争愈演愈烈,煤炭和生物质作为最有可能的石油替代品,以其为原料制备化学品的研究具有重要意义。本课题以氧化反应为手段,在高温水中将煤炭和生物质转化为具有高附加值的化学品,在此方面开展了一系列研究。主要的研究内容和结果如下：
1.研究了褐煤在高温水中以氧气为氧化剂氧化制备苯羧酸的规律。考察了氧化条件对褐煤在高温水中氧化为苯羧酸的影响,对氧化的过程及机理进行了深入的研究。结果表明,氧化温度、反应碱煤比、氧化时间和氧气初始压力是影响苯羧酸产率的主要因素,苯羧酸是通过褐煤中芳香团簇结构的氧化破裂生成的。
2.针对煤氧化过程中碱的消耗量过大的问题,通过提高氧化温度,发现随着氧化温度的提高,所需碱量逐渐降低,而且反应时间也可大大缩短,这主要是由于盐析效应造成的。对比褐煤由传统的240℃氧化时所需碱煤比3/1,我们发现在300℃氧化时所需碱煤比仅为0.8/1,反应时间也由30分钟缩短为1分钟。氧化温度越高越需要较低的盐析效应即较低的碱浓度来避免中间产物被过度氧化。
3.褐煤由于煤化度较低,经过氧化所得苯羧酸收率较低,但褐煤中脂肪结构相对丰富,有可能会得到高收率的小分子脂肪酸。研究结果表明,以褐煤为原料,在得到约20wt%苯羧酸的同时可以得到20-40wt%的小分子脂肪酸收率,主要包括草酸、甲酸和乙酸,这些小分子脂肪酸是通过芳香环的破裂和脂肪结构的氧化得到的。
4.为了完全避免碱在氧化过程中的使用和消耗,筛选了大量作为褐煤氧化制备苯羧酸和小分子脂肪酸的催化剂。最终发现,在完全不使用碱的情况下,当以偏钒酸钠水溶液体系为催化系统,褐煤的氧化反应可以很好的进行,氧化产物中得到了高收率的苯羧酸和小分子脂肪酸,氧化体系中的钒氧物种是催化褐煤氧化反应的关键。
5.将偏钒酸钠水溶液催化体系应用到碳水化合物生物质的氧化反应中,在以硫酸为添加剂的条件下,结果表明以氧气为氧化剂时碳水化合物在此体系中可以被高效的氧化为甲酸。多糖在此催化体系中先发生水解反应生成单糖,单糖通过氧化碳-碳键的断裂生成醛类中间物,这些中间物被快速氧化为甲酸。以纤维素为原料时,甲酸收率可达65%(碳收率),以半纤维素为原料时,甲酸收率可达63.5%(碳收率),而且产物中除二氧化碳外无其他副产物,催化剂体系也可以很容易的进行回收使用。
6.考察了木质素、小麦秸秆、玉米芯等在偏钒酸钠水溶液体系中以氧气为氧化剂制备甲酸的效果。结果表明木质素、小麦秸秆和玉米芯可以被高选择性的氧化为甲酸,以小麦秸秆和玉米芯为原料时可以得到甲酸的收率可达50%以上(碳收率)。
As the depeting of petroleum resource, coal and biomass becoming the potential substitute of petroleum, thus the study on the conversion of coal and biomass into chemicals that required by human beings is significant. This study focuses on the selective oxidation of coal and biomass into high-valued chemicals in hot water. The main content and results are as follows:
1. The oxidation reaction of lignite in the hot water using oxygen was studied. The effect of parameters on the yield of benzene polycarboxylic acids (BPCAs) were investigated, and the process and mechanism of the oxidation were deeply studied. The results showed that the oxidation temperature, alkali/coal mass ratio, oxidation time and initial oxygen pressure are the primary factors that affect the BPCAs yield. The BPCAs are derived from the oxidative breakage of the aromatic clusters in the lignite.
2. The primary problem of the production of BPCAs from coals is the large amount of alkali consumed in the process. The method to decrease the consumed alkali was investigated in this section. It was found that with the oxidation temperature increased, the consumed alkali in the process was decreased dramatically; meanwhile, the oxidation time was shortened obviously. For example, the conventional method to oxidize lignite requires a temperature of240℃and an alkali/coal mass ratio of3/1; however, when the oxidation temperature was increased to300℃, merely an alkali/coal mass ratio of0.8/1was required. Besides, the reaction time of30min was shortened to1min. This new method dramatically improves the economic and production efficiency of the BPCAs from coals. A higher oxidative temperature demands lower salting out effect to avoid deep oxidation of the intermediates.
3. The utilization of lignite is a world problem due to its low colification and high water content. With respect to the method studied in our work, however, the yield of BPCAs is low with lignite as the substrate because of its low content of aromatic clusters. But the content of aliphatic structures is relatively rich in lignite, there may be lots of small-molecular fatty acids in the products accompanied with BPCAs. The results show that20-40wt%of small-molecular fatty acids including oxalic acid, formic aicd and acetic acid was obtained in addition to ca.20wt%of BPCAs. These small-molecular fatty acids are derived from the opening of aromatic rings and the oxidation of aliphatic structures.
4. For the purpose of avoiding alkali used in the oxiation process of lignite, lots of catalytic system was screened to produce BPCAs and small molecular fatty acids from coals using oxygen. The results show that when using sodium metavanadate dissolving in water as the catalytic system, the lignite can be converted to BPCAs and small-molecular fatty acids with high selectivity. The V-O species are critical for the catalytic oxidation of lignites. This method shows an effective way to utilize the low-colification coals such as lignite.
5. The catalytic system for oxidation using sodium metavanadate in water was applied into the oxidation of biomass-based carbohydrates. The results show that this catalytic system has an excellent performance for conversion of carbohydrates into formic acid. A65%yield was obtained from cellulose and64%yield was obtained from hemicellulose. The products in the liquid phase only included formic acid, and which can be separated by extraction method. The recoved catalytic system can be reused for many times without any substantial decrease in the selectivity of formic acid.
6. The lignin and lignocellulose including wheat straw and corncob were were chosen as the substrate to be oxidized in the aquous solutions of sodium metavanadate. The results show that yield of formic acid exceed50%can be obtained in addition to small amount of acetic acid with wheat straw and corncob as the substrates.
1.研究了褐煤在高温水中以氧气为氧化剂氧化制备苯羧酸的规律。考察了氧化条件对褐煤在高温水中氧化为苯羧酸的影响,对氧化的过程及机理进行了深入的研究。结果表明,氧化温度、反应碱煤比、氧化时间和氧气初始压力是影响苯羧酸产率的主要因素,苯羧酸是通过褐煤中芳香团簇结构的氧化破裂生成的。
2.针对煤氧化过程中碱的消耗量过大的问题,通过提高氧化温度,发现随着氧化温度的提高,所需碱量逐渐降低,而且反应时间也可大大缩短,这主要是由于盐析效应造成的。对比褐煤由传统的240℃氧化时所需碱煤比3/1,我们发现在300℃氧化时所需碱煤比仅为0.8/1,反应时间也由30分钟缩短为1分钟。氧化温度越高越需要较低的盐析效应即较低的碱浓度来避免中间产物被过度氧化。
3.褐煤由于煤化度较低,经过氧化所得苯羧酸收率较低,但褐煤中脂肪结构相对丰富,有可能会得到高收率的小分子脂肪酸。研究结果表明,以褐煤为原料,在得到约20wt%苯羧酸的同时可以得到20-40wt%的小分子脂肪酸收率,主要包括草酸、甲酸和乙酸,这些小分子脂肪酸是通过芳香环的破裂和脂肪结构的氧化得到的。
4.为了完全避免碱在氧化过程中的使用和消耗,筛选了大量作为褐煤氧化制备苯羧酸和小分子脂肪酸的催化剂。最终发现,在完全不使用碱的情况下,当以偏钒酸钠水溶液体系为催化系统,褐煤的氧化反应可以很好的进行,氧化产物中得到了高收率的苯羧酸和小分子脂肪酸,氧化体系中的钒氧物种是催化褐煤氧化反应的关键。
5.将偏钒酸钠水溶液催化体系应用到碳水化合物生物质的氧化反应中,在以硫酸为添加剂的条件下,结果表明以氧气为氧化剂时碳水化合物在此体系中可以被高效的氧化为甲酸。多糖在此催化体系中先发生水解反应生成单糖,单糖通过氧化碳-碳键的断裂生成醛类中间物,这些中间物被快速氧化为甲酸。以纤维素为原料时,甲酸收率可达65%(碳收率),以半纤维素为原料时,甲酸收率可达63.5%(碳收率),而且产物中除二氧化碳外无其他副产物,催化剂体系也可以很容易的进行回收使用。
6.考察了木质素、小麦秸秆、玉米芯等在偏钒酸钠水溶液体系中以氧气为氧化剂制备甲酸的效果。结果表明木质素、小麦秸秆和玉米芯可以被高选择性的氧化为甲酸,以小麦秸秆和玉米芯为原料时可以得到甲酸的收率可达50%以上(碳收率)。
As the depeting of petroleum resource, coal and biomass becoming the potential substitute of petroleum, thus the study on the conversion of coal and biomass into chemicals that required by human beings is significant. This study focuses on the selective oxidation of coal and biomass into high-valued chemicals in hot water. The main content and results are as follows:
1. The oxidation reaction of lignite in the hot water using oxygen was studied. The effect of parameters on the yield of benzene polycarboxylic acids (BPCAs) were investigated, and the process and mechanism of the oxidation were deeply studied. The results showed that the oxidation temperature, alkali/coal mass ratio, oxidation time and initial oxygen pressure are the primary factors that affect the BPCAs yield. The BPCAs are derived from the oxidative breakage of the aromatic clusters in the lignite.
2. The primary problem of the production of BPCAs from coals is the large amount of alkali consumed in the process. The method to decrease the consumed alkali was investigated in this section. It was found that with the oxidation temperature increased, the consumed alkali in the process was decreased dramatically; meanwhile, the oxidation time was shortened obviously. For example, the conventional method to oxidize lignite requires a temperature of240℃and an alkali/coal mass ratio of3/1; however, when the oxidation temperature was increased to300℃, merely an alkali/coal mass ratio of0.8/1was required. Besides, the reaction time of30min was shortened to1min. This new method dramatically improves the economic and production efficiency of the BPCAs from coals. A higher oxidative temperature demands lower salting out effect to avoid deep oxidation of the intermediates.
3. The utilization of lignite is a world problem due to its low colification and high water content. With respect to the method studied in our work, however, the yield of BPCAs is low with lignite as the substrate because of its low content of aromatic clusters. But the content of aliphatic structures is relatively rich in lignite, there may be lots of small-molecular fatty acids in the products accompanied with BPCAs. The results show that20-40wt%of small-molecular fatty acids including oxalic acid, formic aicd and acetic acid was obtained in addition to ca.20wt%of BPCAs. These small-molecular fatty acids are derived from the opening of aromatic rings and the oxidation of aliphatic structures.
4. For the purpose of avoiding alkali used in the oxiation process of lignite, lots of catalytic system was screened to produce BPCAs and small molecular fatty acids from coals using oxygen. The results show that when using sodium metavanadate dissolving in water as the catalytic system, the lignite can be converted to BPCAs and small-molecular fatty acids with high selectivity. The V-O species are critical for the catalytic oxidation of lignites. This method shows an effective way to utilize the low-colification coals such as lignite.
5. The catalytic system for oxidation using sodium metavanadate in water was applied into the oxidation of biomass-based carbohydrates. The results show that this catalytic system has an excellent performance for conversion of carbohydrates into formic acid. A65%yield was obtained from cellulose and64%yield was obtained from hemicellulose. The products in the liquid phase only included formic acid, and which can be separated by extraction method. The recoved catalytic system can be reused for many times without any substantial decrease in the selectivity of formic acid.
6. The lignin and lignocellulose including wheat straw and corncob were were chosen as the substrate to be oxidized in the aquous solutions of sodium metavanadate. The results show that yield of formic acid exceed50%can be obtained in addition to small amount of acetic acid with wheat straw and corncob as the substrates.
引文
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