生物油催化重整制氢和草酸二甲酯加氢合成乙二醇研究
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摘要
生物质能源是一种绿色清洁的可再生能源,随着全球化石资源的日渐枯竭和环境污染问题的日趋严重,生物质能的高效开发利用变得越来越重要。生物质快速热裂解技术可以将能量密度低的固体生物质转化为能量密度相对较高并易于运输的液体燃料生物油,其产率可以高达70%以上。然而,生物油具有水分含量高、氧含量高、pH值低和粘度大等特性,无法直接作为动力燃料油使用,因此需要对其进行提质改性。催化重整技术可以将富含水的生物油高效地转化为用途广泛的氢气。氢气不仅可直接用于内燃机与燃料电池,也可用于生物油提质改性的氢源供应。因此,本论文重点对生物油催化重整制氢技术开展了研究,同时还开展了草酸二甲酯加氢合成乙二醇的研究。
首先选取乙醇为模化物,比较不同制备方法对Ni/Al2O3催化剂活性的影响。研究发现,由共沉淀法得到的催化剂,具有优良的反应活性,对乙醇进行重整反应时,其H2产率可以达到88%,乙醇转化率达到99%。同时通过密度泛函理论(DFT)计算确定了乙醇在Ni(111)面上最优的分解途径CH3CH2OH*→CH3CH2O*→CH3CH2*→CH3C*→CH3*+C*。
随后选取了乙酸、羟基丙酮和苯酚,在Ni/nano-Al2O3催化剂上开展了催化重整制氢研究。以纳米A1203为载体的Ni/Al2O3催化剂,对这三种模化物均具有较高的反应活性,当反应温度达到700℃时,乙酸的转化率达到98.2%，氢气产率为87%；羟基丙酮的转化率为98.7%,氢气产率为97.2%;苯酚的转化率略低,为84.2%,氢气产率为69%。同时,此催化剂对三种模化物的稳定性均超过了10h。随后以模拟生物油为反应物,开展了催化重整制氢反应初步能耗分析。
制备了系列无负载的Co-Fe催化剂,以乙酸为生物油模化物开展催化重整制氢实验研究。结果表明,纯Co催化剂具有最高的反应活性,在低温400℃时,(?)酸的转化率100%,氢气产率达到96%,催化剂稳定性超过了65h。确定了乙(?)Co(111)面上最优的分解反应路径：CH3COOH*→CH3OO*→CH3CO*→CH3*+CO*。
利用分子蒸馏技术,将稻壳热解原始生物油分离成两个不同的组分,富水蒸馏组分和低水残留组分。在Ni/Al2O3催化剂上开展的富水蒸馏组分催化重整买验结果表明,在最优的反应工况下,碳转化率达到95%,氢气质量得率达到135(?)mg g-1organics),催化剂的寿命达到11个小时。在该重整过程中不需要额外的水蒸汽供应.反应所需的H2O全部来源于原始生物油中的水分。通过DFT计算得出了乙酸、羟基丙酮、糠醛和苯酚四种化合物在Ni(111)面上最优的分解反应路径。
最后,利用尿素水解法制备了Cu/SiO2催化剂,并在其上开展了草酸二甲酯加氢合成乙二醇研究。在15.6%的Cu负载量以及优化的反应条件下,草酸二甲酯的转化率达到100%,乙二醇选择性达到98%。
Biomass energy is a green, clean and renewable energy. With the global depletion of fossil resources and deterioration of environment, efficient utilization of biomass energy has become increasingly important. Biomass fast pyrolysis can convert solid biomass of low energy density to liquid bio-oil of relatively high energy density and transport convenience. The bio-oil yield can be up to70%. However, bio-oil has several disadvantages associated with high water content, high oxygen content, low pH value and high viscosity. Thus it cannot be directly used as power fuel oil and must be upgraded. Catalytic reforming technology can efficiently convert bio-oil of rich water into widely-used hydrogen. The produced hydrogen can be used not only in the field of internal combustion engines and fuel cells but also as hydrogen resource for bio-oil upgrading process. Therefore, this thesis focuses on the bio-oil catalytic reforming for hydrogen production and the synthesis of ethylene glycoly via dimethyl oxalate hydrogenation.
Firstly, ethanol was selected as a bio-oil model compound to carry out studies of the influence of different catalyst preparation methods on the performance of Ni/Al2O3catalyst. It was found that the catalyst prepared by coprecipitation method had high activity. For ethanol reforming reaction, hydrogen yield was maximized to88%and ethanol conversion reached99%. The opimized decomposition route of ethanol on the Ni(111) surface was identified via density functional theory (DFT) calculation:CH3CH2OH→CH3CH2O*→CH3CH2*→CH3C*-→CH3*+C*.
Secondly, acetic acid, hydroxylacetone and phenol were selected to study the catalytic reforming for hydrogen production over Ni/nano-Al2O3catalyst. The Ni/nano-Al2O3catalyst exhibited high activity for all the three above organics. At the temperature of700℃. acetic acid conversion reached98.2%with hydrogen yield of87%and hydroxylacetone conversion reached98.7%with hydrogen yield of97.2%. Phenol had a slightly lower conversion of84.2%and the hydrogen yield was69%. Meanwhile, for these three organics, the stability of catalyst was more than10h. Subsequently, preliminary analysis of energy consumption of catalytic reforming was carried out.
Series of Co-Fe catalysts without support were prepared and used for catalytic reforming of acetic acid for hydrogen production. The results indicated that pure cobalt catalyst had highest activity. Acetic acid can be converted completely, and the hydrogen yield can reach highly to96%at the low reaction temperature of400℃. The stability of catalyst was more than65h. Furthermore, the optimized decomposition route of acetic acid on the Co(111) surface was identified by DFT calculation:CH3COOH→CH3COO*→CH3CO*→CH3*+CO*.
Molecular distillation technology was adopted to separate the rice husk bio-oil into two different fractions:water-rich distillation fraction and water-less residual fraction. Results of catalytic reforming of the water-rich distillation fraction on Ni/Al2O3catalyst revealed that the carbon conversion of95%and hydrogen mass yield of135(mg g-1organics) were obtained under the optimum reaction conditions. The catalyst stability reached11hours. Besides, an interesting found was that all the water invovled in the reforming reaction came from the crude bio-oil without any extra supply, which contributed to significant reduction in water consumption of the catalytic reforming for hydrogen production. Furthermore, the most likely decomposition pathway of acetic acid, hydroxyacetone, furfural and phenol on the Ni(111) surface were identified via DFT calculations.
Finally, ethylene glycol synthesis from dimethyl oxalate hydrogenation over Cu/SiO2catalysts was studied. The Cu/SiO2catalysts were prepared by urea hydrolysis method. The100%conversion of dimethyl oxalate and98%selectivity of ethylene glycol were obtained over the catalyst with Cu loading content of15.6%.
首先选取乙醇为模化物,比较不同制备方法对Ni/Al2O3催化剂活性的影响。研究发现,由共沉淀法得到的催化剂,具有优良的反应活性,对乙醇进行重整反应时,其H2产率可以达到88%,乙醇转化率达到99%。同时通过密度泛函理论(DFT)计算确定了乙醇在Ni(111)面上最优的分解途径CH3CH2OH*→CH3CH2O*→CH3CH2*→CH3C*→CH3*+C*。
随后选取了乙酸、羟基丙酮和苯酚,在Ni/nano-Al2O3催化剂上开展了催化重整制氢研究。以纳米A1203为载体的Ni/Al2O3催化剂,对这三种模化物均具有较高的反应活性,当反应温度达到700℃时,乙酸的转化率达到98.2%，氢气产率为87%；羟基丙酮的转化率为98.7%,氢气产率为97.2%;苯酚的转化率略低,为84.2%,氢气产率为69%。同时,此催化剂对三种模化物的稳定性均超过了10h。随后以模拟生物油为反应物,开展了催化重整制氢反应初步能耗分析。
制备了系列无负载的Co-Fe催化剂,以乙酸为生物油模化物开展催化重整制氢实验研究。结果表明,纯Co催化剂具有最高的反应活性,在低温400℃时,(?)酸的转化率100%,氢气产率达到96%,催化剂稳定性超过了65h。确定了乙(?)Co(111)面上最优的分解反应路径：CH3COOH*→CH3OO*→CH3CO*→CH3*+CO*。
利用分子蒸馏技术,将稻壳热解原始生物油分离成两个不同的组分,富水蒸馏组分和低水残留组分。在Ni/Al2O3催化剂上开展的富水蒸馏组分催化重整买验结果表明,在最优的反应工况下,碳转化率达到95%,氢气质量得率达到135(?)mg g-1organics),催化剂的寿命达到11个小时。在该重整过程中不需要额外的水蒸汽供应.反应所需的H2O全部来源于原始生物油中的水分。通过DFT计算得出了乙酸、羟基丙酮、糠醛和苯酚四种化合物在Ni(111)面上最优的分解反应路径。
最后,利用尿素水解法制备了Cu/SiO2催化剂,并在其上开展了草酸二甲酯加氢合成乙二醇研究。在15.6%的Cu负载量以及优化的反应条件下,草酸二甲酯的转化率达到100%,乙二醇选择性达到98%。
Biomass energy is a green, clean and renewable energy. With the global depletion of fossil resources and deterioration of environment, efficient utilization of biomass energy has become increasingly important. Biomass fast pyrolysis can convert solid biomass of low energy density to liquid bio-oil of relatively high energy density and transport convenience. The bio-oil yield can be up to70%. However, bio-oil has several disadvantages associated with high water content, high oxygen content, low pH value and high viscosity. Thus it cannot be directly used as power fuel oil and must be upgraded. Catalytic reforming technology can efficiently convert bio-oil of rich water into widely-used hydrogen. The produced hydrogen can be used not only in the field of internal combustion engines and fuel cells but also as hydrogen resource for bio-oil upgrading process. Therefore, this thesis focuses on the bio-oil catalytic reforming for hydrogen production and the synthesis of ethylene glycoly via dimethyl oxalate hydrogenation.
Firstly, ethanol was selected as a bio-oil model compound to carry out studies of the influence of different catalyst preparation methods on the performance of Ni/Al2O3catalyst. It was found that the catalyst prepared by coprecipitation method had high activity. For ethanol reforming reaction, hydrogen yield was maximized to88%and ethanol conversion reached99%. The opimized decomposition route of ethanol on the Ni(111) surface was identified via density functional theory (DFT) calculation:CH3CH2OH→CH3CH2O*→CH3CH2*→CH3C*-→CH3*+C*.
Secondly, acetic acid, hydroxylacetone and phenol were selected to study the catalytic reforming for hydrogen production over Ni/nano-Al2O3catalyst. The Ni/nano-Al2O3catalyst exhibited high activity for all the three above organics. At the temperature of700℃. acetic acid conversion reached98.2%with hydrogen yield of87%and hydroxylacetone conversion reached98.7%with hydrogen yield of97.2%. Phenol had a slightly lower conversion of84.2%and the hydrogen yield was69%. Meanwhile, for these three organics, the stability of catalyst was more than10h. Subsequently, preliminary analysis of energy consumption of catalytic reforming was carried out.
Series of Co-Fe catalysts without support were prepared and used for catalytic reforming of acetic acid for hydrogen production. The results indicated that pure cobalt catalyst had highest activity. Acetic acid can be converted completely, and the hydrogen yield can reach highly to96%at the low reaction temperature of400℃. The stability of catalyst was more than65h. Furthermore, the optimized decomposition route of acetic acid on the Co(111) surface was identified by DFT calculation:CH3COOH→CH3COO*→CH3CO*→CH3*+CO*.
Molecular distillation technology was adopted to separate the rice husk bio-oil into two different fractions:water-rich distillation fraction and water-less residual fraction. Results of catalytic reforming of the water-rich distillation fraction on Ni/Al2O3catalyst revealed that the carbon conversion of95%and hydrogen mass yield of135(mg g-1organics) were obtained under the optimum reaction conditions. The catalyst stability reached11hours. Besides, an interesting found was that all the water invovled in the reforming reaction came from the crude bio-oil without any extra supply, which contributed to significant reduction in water consumption of the catalytic reforming for hydrogen production. Furthermore, the most likely decomposition pathway of acetic acid, hydroxyacetone, furfural and phenol on the Ni(111) surface were identified via DFT calculations.
Finally, ethylene glycol synthesis from dimethyl oxalate hydrogenation over Cu/SiO2catalysts was studied. The Cu/SiO2catalysts were prepared by urea hydrolysis method. The100%conversion of dimethyl oxalate and98%selectivity of ethylene glycol were obtained over the catalyst with Cu loading content of15.6%.
引文
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