Fractional pyrolysis and one-step pyrolysis of natural algae Cyanobacteria from Taihu Lake were comparatively studied from 200 to 500 ℃. One-step pyrolysis produced bio-oil with complex composition and low high heati...Fractional pyrolysis and one-step pyrolysis of natural algae Cyanobacteria from Taihu Lake were comparatively studied from 200 to 500 ℃. One-step pyrolysis produced bio-oil with complex composition and low high heating value （HHV〈30.9 MJ/kg）. Fractional pyrolysis separated the degradation of different components in Cyanobacteria and improved the selectivity to products in bio-oil. That is, acids at 200 ℃, amides and acids at 300 ℃, phenols and nitriles at 400 ℃, and phenols at 500 ℃, were got as main products, respectively. HZSM-5 could promote the dehydration, cracking and aromatization of pyrolytic intermediates in fractional pyrolysis. At optimal HZSM-5 catalyst dosage of 1.0 g, the selectivity to products and the quality of bio-oil were improved obviously. The main products in bio-oil changed to nitriles （47.2%） at 300 ℃, indoles （51.3%） and phenols （36.3%） at 400 ℃. The oxygen content was reduced to 7.2 wt% and 9.4 wt%, and the HHV was raised to 38.1 and 37.3 MJ/kg at 300 and 400 ℃, respectively. Fractional catalytic pyrolysis was proposed to be an efficient method not only to provide a potential solution for alleviating environmental pressure from water blooms, but also to improve the selectivity to products and obtain high quality bio-oil.展开更多
In situ catalytic conversion of biomass fast pyrolysis vapors was carried out on HZSM-5 with varying Si/Al ratios(ranging from 20 to 300) at 450 °C. The effects of Si/Al ratios of HZSM-5 zeolites on the distribut...In situ catalytic conversion of biomass fast pyrolysis vapors was carried out on HZSM-5 with varying Si/Al ratios(ranging from 20 to 300) at 450 °C. The effects of Si/Al ratios of HZSM-5 zeolites on the distribution of biomass fast pyrolysis products and carbon deposits on catalysts were investigated. It was quite remarkable that after in situ catalytic conversion the amount of light phenols and hydrocarbons increased significantly while that of heavy phenols decreased a lot. Besides, the yield of cyclopentenones with relatively low oxygen content generally increased. It also indicated that as the Si/Al ratios of HZSM-5 increased, the amount of hydrocarbons and light phenols was found to drop greatly. The amount of carbon deposits was found to be around 8.5% with the exception of HZSM-5 with the Si/Al ratio of 300,which is much lower. Moreover, the carbon deposits yield dropped gradually with increasing Si/Al ratios of HZSM-5.Calcination of spent catalysts at 600 °C helped to restore the catalytic activity to a large extent despite a relatively lower efficiency of deoxygenation. Results indicated that HZSM-5 with relatively high acidity displayed great catalytic performance.展开更多
Fast pyrolysis of biomass will produce various furan derivatives, among which 5-hydroxymethyl furfural（5-HMF） and furfural（FF） are usually the two most important compounds derived from holocellulose. In this study...Fast pyrolysis of biomass will produce various furan derivatives, among which 5-hydroxymethyl furfural（5-HMF） and furfural（FF） are usually the two most important compounds derived from holocellulose. In this study, density functional theory（DFT） calculations are utilized to reveal the formation mechanisms and pathways of 5-HMF and FF from two hexose units of holocellulose, i.e., glucose and mannose. In addition, fast pyrolysis experiments of glucose and mannose are conducted to substantiate the computational results, and the orientation of 5-HMF and FF is determined by 13C-labeled glucoses. Experimental results indicate that C1 provides the aldehyde group in both 5-HMF and FF, and FF is mainly derived from C1 to C5 segment. According to the computational results, glucose and mannose have similar reaction pathways to form 5-HMF and FF with d-fructose（DF） and 3-deoxy-glucosone（3-DG） as the key intermediates. 5-HMF and FF are formed via competing pathways. The formation of 5-HMF is more competitive than that of FF, leading to higher yield of 5-HMF than FF from both hexoses. In addition, compared with glucose,mannose can form 5-HMF and FF via extra pathways because of the epimerization at C2 position. Therefore, mannose pyrolysis results in higher yields of 5-HMF and FF than glucose pyrolysis.展开更多
The method for pyrolysis of biomass to manufacture hydrocarbon-rich fuel remains challenging in terms of conversion of multifunctional biomass with high oxygen content and low thermal stability into a high-quality com...The method for pyrolysis of biomass to manufacture hydrocarbon-rich fuel remains challenging in terms of conversion of multifunctional biomass with high oxygen content and low thermal stability into a high-quality compound, featuring high content of hydrocarbons, low oxygen content, few functional groups, and high thermal stability. This study offers a promising prospect to derive hydrocarbon-rich oil through microwave-assisted fast catalytic pyrolysis by improving the effective hydrogen to carbon ratio(H/Ceff) of the raw materials. The proposed technique can promote the production of high-quality bio-oil through the molecular sieve catalyzed reduction of oxygenated compounds and mutagenic polyaromatic hydrocarbons. This work aims to review and summarize the research progress on microwave copyrolysis and microwave catalytic copyrolysis to demonstrate their benefits on enhancement of bio-oils derived from the biomass. This review focuses on the potential of optimizing the H/Ceff ratio, the microwave absorbent, and the HZSM-5 catalyst during the microwave copyrolysis to produce the valuable liquid fuel. This paper also proposes future directions for the use of this technique to obtain high yields of bio-oils.展开更多
利用隔壁精馏塔替代混合碳五馏分原有分离流程中的脱丁烷塔和碳五预分离塔,通过Aspen Plus V12软件对混合碳五馏分的提纯流程进行稳态模拟,在此基础上运用灵敏度分析工具,对隔壁精馏塔的操作参数进行优化。结果表明:采用隔壁精馏塔替代...利用隔壁精馏塔替代混合碳五馏分原有分离流程中的脱丁烷塔和碳五预分离塔,通过Aspen Plus V12软件对混合碳五馏分的提纯流程进行稳态模拟,在此基础上运用灵敏度分析工具,对隔壁精馏塔的操作参数进行优化。结果表明:采用隔壁精馏塔替代脱丁烷塔和碳五预分离塔,最佳原料进料位置为第11块塔板、最佳质量回流比为5、最佳侧线采出位置为第7块塔板、最佳侧线采出量为500 kg h,气相回流位置为第37块塔板,液相回流位置为第12块塔板;在相同进料条件和相同碳五馏分纯度的前提下,与采用常规精馏工艺相比,采用隔壁塔精馏工艺时冷却能耗降低17.04%,加热能耗降低16.69%。展开更多
基金supported by the National Basic Research Program of China(973 Program,No.2013CB228103)
文摘Fractional pyrolysis and one-step pyrolysis of natural algae Cyanobacteria from Taihu Lake were comparatively studied from 200 to 500 ℃. One-step pyrolysis produced bio-oil with complex composition and low high heating value （HHV〈30.9 MJ/kg）. Fractional pyrolysis separated the degradation of different components in Cyanobacteria and improved the selectivity to products in bio-oil. That is, acids at 200 ℃, amides and acids at 300 ℃, phenols and nitriles at 400 ℃, and phenols at 500 ℃, were got as main products, respectively. HZSM-5 could promote the dehydration, cracking and aromatization of pyrolytic intermediates in fractional pyrolysis. At optimal HZSM-5 catalyst dosage of 1.0 g, the selectivity to products and the quality of bio-oil were improved obviously. The main products in bio-oil changed to nitriles （47.2%） at 300 ℃, indoles （51.3%） and phenols （36.3%） at 400 ℃. The oxygen content was reduced to 7.2 wt% and 9.4 wt%, and the HHV was raised to 38.1 and 37.3 MJ/kg at 300 and 400 ℃, respectively. Fractional catalytic pyrolysis was proposed to be an efficient method not only to provide a potential solution for alleviating environmental pressure from water blooms, but also to improve the selectivity to products and obtain high quality bio-oil.
基金supported by the National Basic Research Program of China(2013CB228104)
文摘In situ catalytic conversion of biomass fast pyrolysis vapors was carried out on HZSM-5 with varying Si/Al ratios(ranging from 20 to 300) at 450 °C. The effects of Si/Al ratios of HZSM-5 zeolites on the distribution of biomass fast pyrolysis products and carbon deposits on catalysts were investigated. It was quite remarkable that after in situ catalytic conversion the amount of light phenols and hydrocarbons increased significantly while that of heavy phenols decreased a lot. Besides, the yield of cyclopentenones with relatively low oxygen content generally increased. It also indicated that as the Si/Al ratios of HZSM-5 increased, the amount of hydrocarbons and light phenols was found to drop greatly. The amount of carbon deposits was found to be around 8.5% with the exception of HZSM-5 with the Si/Al ratio of 300,which is much lower. Moreover, the carbon deposits yield dropped gradually with increasing Si/Al ratios of HZSM-5.Calcination of spent catalysts at 600 °C helped to restore the catalytic activity to a large extent despite a relatively lower efficiency of deoxygenation. Results indicated that HZSM-5 with relatively high acidity displayed great catalytic performance.
基金financial support from the National Natural Science Foundation of China (51576064, 51676193)Beijing Nova Program (Z171100001117064)+2 种基金Beijing Natural Science Foundation (3172030)the Foundation of Stake Key Laboratory of Coal Combustion (FSKLCCA1706)the Fundamental Research Funds for the Central Universities (2017MS071, 2016YQ05)
文摘Fast pyrolysis of biomass will produce various furan derivatives, among which 5-hydroxymethyl furfural（5-HMF） and furfural（FF） are usually the two most important compounds derived from holocellulose. In this study, density functional theory（DFT） calculations are utilized to reveal the formation mechanisms and pathways of 5-HMF and FF from two hexose units of holocellulose, i.e., glucose and mannose. In addition, fast pyrolysis experiments of glucose and mannose are conducted to substantiate the computational results, and the orientation of 5-HMF and FF is determined by 13C-labeled glucoses. Experimental results indicate that C1 provides the aldehyde group in both 5-HMF and FF, and FF is mainly derived from C1 to C5 segment. According to the computational results, glucose and mannose have similar reaction pathways to form 5-HMF and FF with d-fructose（DF） and 3-deoxy-glucosone（3-DG） as the key intermediates. 5-HMF and FF are formed via competing pathways. The formation of 5-HMF is more competitive than that of FF, leading to higher yield of 5-HMF than FF from both hexoses. In addition, compared with glucose,mannose can form 5-HMF and FF via extra pathways because of the epimerization at C2 position. Therefore, mannose pyrolysis results in higher yields of 5-HMF and FF than glucose pyrolysis.
基金the financial support from the National Natural Science Foundation of China (No. 21766019, 21466022)the Key Research and Development Program of Jiangxi Province(20171BBF60023)+2 种基金the International Science&Technology Cooperation Project of China(2015DFA60170-4)the Science and Technology Research Project of Jiangxi Province Education Department(No.GJJ150213)the Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development Program (No. Y707sb1001)”
文摘The method for pyrolysis of biomass to manufacture hydrocarbon-rich fuel remains challenging in terms of conversion of multifunctional biomass with high oxygen content and low thermal stability into a high-quality compound, featuring high content of hydrocarbons, low oxygen content, few functional groups, and high thermal stability. This study offers a promising prospect to derive hydrocarbon-rich oil through microwave-assisted fast catalytic pyrolysis by improving the effective hydrogen to carbon ratio(H/Ceff) of the raw materials. The proposed technique can promote the production of high-quality bio-oil through the molecular sieve catalyzed reduction of oxygenated compounds and mutagenic polyaromatic hydrocarbons. This work aims to review and summarize the research progress on microwave copyrolysis and microwave catalytic copyrolysis to demonstrate their benefits on enhancement of bio-oils derived from the biomass. This review focuses on the potential of optimizing the H/Ceff ratio, the microwave absorbent, and the HZSM-5 catalyst during the microwave copyrolysis to produce the valuable liquid fuel. This paper also proposes future directions for the use of this technique to obtain high yields of bio-oils.
文摘利用隔壁精馏塔替代混合碳五馏分原有分离流程中的脱丁烷塔和碳五预分离塔,通过Aspen Plus V12软件对混合碳五馏分的提纯流程进行稳态模拟,在此基础上运用灵敏度分析工具,对隔壁精馏塔的操作参数进行优化。结果表明:采用隔壁精馏塔替代脱丁烷塔和碳五预分离塔,最佳原料进料位置为第11块塔板、最佳质量回流比为5、最佳侧线采出位置为第7块塔板、最佳侧线采出量为500 kg h,气相回流位置为第37块塔板,液相回流位置为第12块塔板;在相同进料条件和相同碳五馏分纯度的前提下,与采用常规精馏工艺相比,采用隔壁塔精馏工艺时冷却能耗降低17.04%,加热能耗降低16.69%。
