秸秆慢速裂解液态产物物性分析及分馏试验研究
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摘要
我国是一个农业大国,农作物秸秆产量丰富,能否有效利用农作物秸秆等生物质能源,关系到解决我国农村生活用能的重要问题。加快秸秆裂解工业化利用和大力发展生态农业,是新时期农业发展的主题,也是在农村全面建设小康社会的有效途径。农作物秸秆裂解产物的特点是固态、液态、气态均有产物,而且均能利用。相对于固态碳和裂解气的利用便捷性,液态产物的利用就相对复杂。秸秆裂解所产生的生物油中含有一些所不希望有的特性给生物油直接作为高品位能源的应用带来了一些难免的问题,如热稳定性差、热值低、低挥发性和腐蚀性,必须经过进一步的改性处理才能应用。为了生物油的直接应用和进一步改性,对液态产物理化特性进行试验分析以及对其进行分馏试验是非常必要的。
本文以常见的玉米秸秆、玉米芯、小麦秸秆为研究对象,通过严谨的科学试验和认真、精确的数据处理,对秸秆慢速裂解液态产物物性及分馏进行实验研究,得到的以下主要内容与研究结论:
(1)秸秆慢速裂解液态产物物性分析。通过实验测量,液态产物的含水率较高,接近25%,在后续开发时要注意水分的分离。液态产物具有较强酸性,pH值2.6左右,在储存、运输时要注意器具的选择。液态产物密度值在1100 Kg/m3～1200 Kg/m3之间,干基热值约为20 MJ/Kg,能够体现出热裂解过程对生物质能量密度的增加。
(2)秸秆慢速裂解液态产物分子蒸馏馏分分析。通过对各个馏分物理性质的分析,并与未分馏的液态产物作对比,发现各个工况的轻质馏分均表现出较高的酸性,液态产物中的水分经过分子蒸馏全部馏出且几乎都在轻质馏分中,其含水量达到50～70wt%,不可燃。热值则是重质馏分的最高,其中一个热值达到25.4MJ/Kg,比原液态产物提高了60%以上。
(3)通过横向对比三个不同工况蒸馏温度下同种馏分各族类的百分含量,以及纵向对比同一工况下三种馏分的族类百分含量,分析分馏后各馏分成分分布情况以及蒸馏温度对各馏分成分分布的影响。馏分A中酮类占比最大,液态产物中绝大部分轻质组分都在其中;馏分B中只有ketones和酚类含量较高,其它族类占比都较小;馏分C不含acids和U-alcohols外,酚类中只有catechols占到绝对大的比例外,其它均匀分布在5%左右。由此可见蒸馏温度的改变对酮类、邻苯二酚类、苯酚类的影响最为显著。
China is a large agricultural country, rich in crop straw yield, the effective use of crop stalks and other biomass energy, related to the settlement of rural life, the important issue of energy use. Speed up the industrialization of straw decomposition, and to develop ecological agriculture use, is the subject of the Agricultural Development is also building a well in the rural areas an effective way. Straw pyrolysis products are characterized by solid, liquid, gaseous products are, and can use. Relative to the solid carbon and the use of pyrolysis gas convenience, the use of liquid products is relatively complicated. Straw produced by pyrolysis bio-oil contains some of the undesirable characteristics to the bio-oil directly as a high-grade energy resources brought some unavoidable problems, such as poor thermal stability, low heat value, low-volatile and corrosive, must be applied for further modification. For the direct application of bio-oil and further modification, physical and chemical properties of the liquid products to test for fractional analysis and tests of its very necessary.
In this paper, a common corn stalk, corn cob, wheat straw as the research object, through rigorous scientific testing and careful, accurate processing of straw slow pyrolysis liquid products and fractionation properties of the experimental study, obtained the following main elements and Research Conclusion:
(1) Straw slow pyrolysis properties of liquid products. The experimental measurements, the higher the moisture content of liquid products, nearly 25% in the subsequent development should pay attention to water separation. Strong acid liquid products, pH, around 2.6, in the storage, transportation should pay attention to the choice of equipment. Density of liquid products in between 1100 Kg/m3~1200Kg/m3, dry basis calorific value of approximately 20 MJ/Kg, to reflect the amount of biomass pyrolysis process on the increase in density.
(2) Slow pyrolysis liquid products of straw fractions of molecular distillation. By analyzing the physical properties of the various fractions, and fractionation of liquid products with and without compare, was found in all light conditions showed a higher fraction of acidic, liquid products through the molecular distillation of the water and almost all of distillate are light fraction, its water content to 50 ~ 70wt%, non-combustible. Calorific value is the heavy fraction of the maximum, one of the calorific value to 25.4MJ/Kg, than the original liquid products increased by 60% or more.
(3)By comparing three different lateral conditions hereinafter kind of distillation temperature fractions, the contents of all classes, and the comparison between the condition of three fractions with the same percentages of ethnic categories, analysis of various fractions after fractionation component distribution and the distillation temperature on the fraction composition distribution. Fraction A, the largest proportion ketones, most of the liquid products of the light components which are; fraction B, only ketones and phenols were higher, accounting for all other ethnic categories less; fraction C does not contain acids and U-alcohols, the phenols, only catechols account for a large proportion of the absolute, the other uniformly distributed in about 5%. Distillation temperature change shows that ketones, catechol, phenol of the most significant.
本文以常见的玉米秸秆、玉米芯、小麦秸秆为研究对象,通过严谨的科学试验和认真、精确的数据处理,对秸秆慢速裂解液态产物物性及分馏进行实验研究,得到的以下主要内容与研究结论:
(1)秸秆慢速裂解液态产物物性分析。通过实验测量,液态产物的含水率较高,接近25%,在后续开发时要注意水分的分离。液态产物具有较强酸性,pH值2.6左右,在储存、运输时要注意器具的选择。液态产物密度值在1100 Kg/m3～1200 Kg/m3之间,干基热值约为20 MJ/Kg,能够体现出热裂解过程对生物质能量密度的增加。
(2)秸秆慢速裂解液态产物分子蒸馏馏分分析。通过对各个馏分物理性质的分析,并与未分馏的液态产物作对比,发现各个工况的轻质馏分均表现出较高的酸性,液态产物中的水分经过分子蒸馏全部馏出且几乎都在轻质馏分中,其含水量达到50～70wt%,不可燃。热值则是重质馏分的最高,其中一个热值达到25.4MJ/Kg,比原液态产物提高了60%以上。
(3)通过横向对比三个不同工况蒸馏温度下同种馏分各族类的百分含量,以及纵向对比同一工况下三种馏分的族类百分含量,分析分馏后各馏分成分分布情况以及蒸馏温度对各馏分成分分布的影响。馏分A中酮类占比最大,液态产物中绝大部分轻质组分都在其中;馏分B中只有ketones和酚类含量较高,其它族类占比都较小;馏分C不含acids和U-alcohols外,酚类中只有catechols占到绝对大的比例外,其它均匀分布在5%左右。由此可见蒸馏温度的改变对酮类、邻苯二酚类、苯酚类的影响最为显著。
China is a large agricultural country, rich in crop straw yield, the effective use of crop stalks and other biomass energy, related to the settlement of rural life, the important issue of energy use. Speed up the industrialization of straw decomposition, and to develop ecological agriculture use, is the subject of the Agricultural Development is also building a well in the rural areas an effective way. Straw pyrolysis products are characterized by solid, liquid, gaseous products are, and can use. Relative to the solid carbon and the use of pyrolysis gas convenience, the use of liquid products is relatively complicated. Straw produced by pyrolysis bio-oil contains some of the undesirable characteristics to the bio-oil directly as a high-grade energy resources brought some unavoidable problems, such as poor thermal stability, low heat value, low-volatile and corrosive, must be applied for further modification. For the direct application of bio-oil and further modification, physical and chemical properties of the liquid products to test for fractional analysis and tests of its very necessary.
In this paper, a common corn stalk, corn cob, wheat straw as the research object, through rigorous scientific testing and careful, accurate processing of straw slow pyrolysis liquid products and fractionation properties of the experimental study, obtained the following main elements and Research Conclusion:
(1) Straw slow pyrolysis properties of liquid products. The experimental measurements, the higher the moisture content of liquid products, nearly 25% in the subsequent development should pay attention to water separation. Strong acid liquid products, pH, around 2.6, in the storage, transportation should pay attention to the choice of equipment. Density of liquid products in between 1100 Kg/m3~1200Kg/m3, dry basis calorific value of approximately 20 MJ/Kg, to reflect the amount of biomass pyrolysis process on the increase in density.
(2) Slow pyrolysis liquid products of straw fractions of molecular distillation. By analyzing the physical properties of the various fractions, and fractionation of liquid products with and without compare, was found in all light conditions showed a higher fraction of acidic, liquid products through the molecular distillation of the water and almost all of distillate are light fraction, its water content to 50 ~ 70wt%, non-combustible. Calorific value is the heavy fraction of the maximum, one of the calorific value to 25.4MJ/Kg, than the original liquid products increased by 60% or more.
(3)By comparing three different lateral conditions hereinafter kind of distillation temperature fractions, the contents of all classes, and the comparison between the condition of three fractions with the same percentages of ethnic categories, analysis of various fractions after fractionation component distribution and the distillation temperature on the fraction composition distribution. Fraction A, the largest proportion ketones, most of the liquid products of the light components which are; fraction B, only ketones and phenols were higher, accounting for all other ethnic categories less; fraction C does not contain acids and U-alcohols, the phenols, only catechols account for a large proportion of the absolute, the other uniformly distributed in about 5%. Distillation temperature change shows that ketones, catechol, phenol of the most significant.
引文
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