海藻生物质热解与燃烧的试验与机理研究
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摘要
随着化石能源的日益枯竭和环境恶化问题的日趋严重,开发洁净的可再生能源已经成为了当前全球紧迫的问题。生物质能作为一种丰富的可再生能源,受到世界各国的重视,诸如丹麦、荷兰、德国、法国、加拿大、芬兰等国,多年来一直在进行各自的研究,并形成了各具特色的生物质能源研究与开发体系。但目前全世界大范围对能源植物的利用主要是木材与农作物,实际上美国《科学》杂志称,在某些情况下,用粮食作物等制造生物燃料不仅达不到减缓气候变化的目的,反而有可能增加温室气体排放。同时发展生物质能要处理好能源与粮食的关系,因此开发新型的生物质就显得尤其重要。海藻类生物质生活在海洋里,不占用耕地,其资源开发的潜力巨大。特别是我国拥有广阔的海洋优势,高效、清洁、合理地利用丰富的海藻资源,对于我国在日后国际能源竞争中占据有利的地位有重大的理论意义与工程应用价值。当今世界范围内,各国对海藻这类海洋生物质的研究还比较少,属于崭新课题。本文主要对典型大型海藻热化学转化过程(燃烧和热解)进行了系统的试验与理论研究。
研究海藻的燃料特性是进行海藻生物质利用的基础。第二章从工业分析和元素分析上分析了海藻生物质,发现其高灰低热值,高含水量,含氧量低于陆上生物质。海藻生物质灰熔点普遍不高,尤其长松藻极低的灰熔点导致其不适合热化学利用。我国国家标准(GB)与美国ASTM标准规定的灰化温度都不适合海藻类生物质,同时江蓠与马尾藻在较高灰化温度下,生成了较多的高熔点物,影响了灰熔点的判断。低温(530℃)下制得灰样的灰熔点更具有参考性。通过灰成分分析、X射线衍射方法、热显微镜观察及TG-DTG-DTA联用试验,对3种海洋生物质——海藻的灰熔融过程进行了研究。研究表明:海藻灰渣中都有大量碱金属氯化物结晶相,随着灰化温度的升高,结晶相强度减弱,发生了碱金属的蒸发,因而海藻热化学转化能源利用时必须考虑碱金属的蒸发问题。
同时文中还使用NETZSCH DSC404型差示量热扫描仪(DSC)测定了3种海洋生物质-海藻在40~550℃温度范围内的比热容,并在传统求解方法的基础上根据失重值对结果进行了修正。结果表明:海藻在升温过程中水分挥发,挥发分大量释放,半焦状态3个主要区间内的比热容相差较大,其原因为其残留物性质发生了变化。3种海藻总体相比较而言,江蓠的比热容最大,条浒苔次之,马尾藻最小。文中还给出了海藻在40~550℃温度范围内的比热容与温度的关联式。研究结果可供大型海藻生物质热化学转换能源利用及其相应的数值模拟参考使用。
热分析是分析海藻热解与燃烧过程的重要方法,因而第三章主要在DTG-60H热分析仪上进行了海藻生物质的热解与燃烧试验。海藻热解失重过程由脱水,快速失重和慢速失重以及固体残留物的分解过程。海藻热解温度比陆上生物质低,因为海藻的主要成分不同于陆上生物质的纤维素、半纤维素、木质素。FTIR分析用于测量样品热解时成分的变化;TG-MS用来分析海藻热解过程中的气体产物。随着升温速率增加,海藻热解初析温度提高,最大热解速率值增大,对应的峰值温度后移,挥发分热解活化能也随之增加。对海藻生物质的热解过程使用Coats–Redfern积分法处理。二级反应机理函数适用于江蓠与海带的热解动力学分析;条浒苔和马尾藻热解低温区采用Zhuralev,Lesokin and Tempelman机理函数,高温区仍采用二级反应机理。海藻的着火方式为均相着火,着火温度较低容易着火。海藻的燃烧过程由脱水阶段,挥发分析出与燃烧阶段,过渡阶段,固定碳燃烧和高温反应阶段组成。文中还分析了着火温度、最大燃烧速率、燃尽温度等燃烧参数。海藻燃烧特性与方式与陆上木质类生物质存在差异,究其原因为挥发分的不同。TG-MS也用来分析燃烧的气体产物。各海藻CO_2和NO_2释放趋势与DTG曲线相吻合。SO_2释放曲线稍有差异,燃烧段的生成主要与含硫多糖有关,高温阶段主要是含硫灰分的分解作用。海藻低温段生成的含氮化合物(NOx)主要是由于挥发分分解阶段蛋白质的分解。最后利用一元二次方法计算了海藻的燃烧活化能。
本文第四章在小型流化床试验台上研究了海藻颗粒(条浒苔与马尾藻)的流化床燃烧。海藻在流化床内的挥发分析出燃烧时间较短,都在1分钟左右。条浒苔颗粒在流化床中燃烧先进行脱水和挥发分的燃烧;接着发生焦炭燃烧,其燃烧过程符合缩核模型,炭核由外向内逐层燃烧,而灰层半径几乎不变。但马尾藻颗粒进入流化床后,由于挥发分的大量快速释放而迅速膨胀破碎成屑。另外通过对条浒苔颗粒及不同燃烧时间后收集的焦炭颗粒剖面的SEM扫描电镜观察,发现随着燃烧的进行,颗粒内孔隙增大,微孔表面粗糙,但局部甚至出现融化。在进行流化床连续燃烧海藻颗粒燃料实验时,当条浒苔给料与配风搭配合适时,能在750℃左右稳定燃烧,无结渣,温度波动不大。底灰中灰分粒径分布主要集中较大值和较小值左右。而马尾藻虽然在低温下能够燃烧,但随着燃烧的进行会出现严重结渣,主要是由于其灰熔点太低的缘故。因而可见条浒苔适合流化床燃烧而马尾藻不太适合。最后对条浒苔原样和流化床燃烧后收集的底灰进行孔隙结构分析,燃烧后灰比原样孔隙增多,内部孔隙扩张,孔容积和比表面积增大。通过分形分析可知海藻原样表面光滑,燃烧后表面粗糙不规则。
为了进一步了解海藻单颗粒燃料在流化床内的燃烧特征,第五章详细研究了两种单颗粒海藻颗粒(条浒苔与马尾藻)在流化床内单次投料下的焚烧试验。随着床温的升高,条浒苔释放NOx相对浓度增加,CO相对浓度减少。而马尾藻释放气体中SO_2与NOx含量相对条浒苔有所增加,随着床温的升高,CO相对浓度减少。床温的升高使得床内传热速率加快,两种海藻挥发分的析出提前,燃尽时间缩短。条浒苔与马尾藻随着风速的升高各烟气相对浓度无床温影响般明显规律性变化。风速的升高使得两种海藻燃烧容易,燃尽时间缩短。随着床层高度的变化,两种海藻各气体析出都没有出现明显规律性变化。床高的升高使得热载体增多也一定程度上有利于燃烧,燃尽时间也有缩短。通过分析床高、床温、流化风速三种因素对条浒苔颗粒燃烧后剩余质量和固定碳残留率的影响,可以看出床高因素对海藻颗粒在流化床内燃烧的影响最小。利用灰色关联分析得到各工况因素影响固定碳燃尽主次依次是:床层温度(℃)>流化数>床层高度(mm),可见在研究工况范围内床层温度是影响燃烧的最主要因素。最后建立了条浒苔单颗粒在流化床内燃烧的数学模型,模拟结果与试验对比基本符合。
第六章里详细研究了海藻类生物质的快速热裂解过程,分析了各工况参数对海藻类生物质热裂解特性的影响规律。热解反应温度对海藻生物油的产率有一定影响。反应温度的增加有利于热解气的生成而不利于生成炭。在500℃左右存在最大产油率。停留时间(载气流量)对海藻生物油产率影响不大;停留时间减少,生物油产率略有提高。蛋白质快速热裂解产油率很高,产生焦炭很少,试验结果表明蛋白质容易裂解。热解反应温度升高,热解生成炭中挥发分的比例下降,而固定碳的比例则增加,这说明在较高温度时有更多的挥发分析出。检测结果表明海藻类生物油相比陆上一般生物质具有较高的碳氢含量,较低的含氧量的优点。最后讨论认为海藻热裂解中得到的炭和不凝气能够提供热裂解的热量需求,实现海藻热解制油-半焦与不凝气燃烧供热能量自平衡。
为了进一步了解海藻生物油的特点,第七章通过对海藻生物质(条浒苔、马尾藻)不同工况下热解制得的生物油进行GC-MS分析,得到了海藻油的主要成分。海藻类生物油的主要成分为一些烃类、酮类、醛类、醇类和酚类化合物,以及较大分子量的羧酸及其衍生物,并包含了少量呋喃、吡喃、吡啶等衍生物的杂环化合物。条浒苔油中羧酸及其衍生物和烃类物质较多,而马尾藻生物油中甾族和醇类化合物较多,也检测出油酸和棕榈酸酯,花生酸。不同工况下产生的生物油在组成成分上非常相似,只是相对含量有所不同。热解温度对海藻油组分的分布起了重要作用,而载气流量对热解海藻油成分分布的影响就不明显了。
本章还初步研究了海藻生物质热解产油的机理。海藻热解油中大多数含氮化合物的形成都是与蛋白质的热分解有关。海藻油中的烃类物质生成主要与碳水化合物和脂类物质有关。蛋白质的热解一般包括肽和氨基酸分子的热解。氨基酸热解主要机理是分子中脱去CO_2反应,以及Strecker聚解反应,继续进行裂解反应,形成含羰基和双羰基化合物。海藻含量较少的脂类物质也能在热解过程中发生脱羧、取代等反应生成烃类或酯类等。
本文最后总结了全文,展望了今后的研究工作。
As a limited energy source, fossil fuel could hardly afford long-lasting consumption. And environmental contamination becomes an apparent and serious issue. All facts hasten a growing concern to the exploitation and application of biomass. Many countries pay attention to the importance of biomass that is an abundant renewable energy resource. Such as Denmark, the Netherlands, Germany, France, Canada, Finland and other countries has been conducting their own research and formed a distinctive biomass energy R&D system for many years. But the energy plants around the world is mainly focus on wood and crops, in fact the U.S. Science magazine said that in some cases, the use of food crops such as bio-fuel, not only fail to mitigate climate change, it actually are likely to increase greenhouse gas emissions.
The development of biomass energy properly handles the relationship between energy and food, so the development of new biomass sources becomes particularly important. Seaweed biomass live in the sea, not occupy area land. Its resources development has great potential. In particular, China are surrounded by wide coastal areas and territorial seas. If those rich seaweeds sources are explored efficiently and put into clean and proper use, they may contribute a lot to the future of our country in the competition of the worldwide energy usage, both theoretically and industrially.
The research on this seaweed biomass is still relatively small around world, which is a novel topic. In this paper, the thermochemical conversion processes (combustion and pyrolysis) of the typical large seaweed were studied using a systematic experimental and theoretical method.
Researching fuel characteristics is the foundation of studying seaweed biomass. In chapter 2, the seaweed biomass is studied from proximate and ultimate analysis. It is found that the heating values of the seaweed samples are low and the moisture and ash contents of seaweed are high. In relation to the elementary analysis, seaweed has a lower oxygen content than terrestrial biomass. The low ash fusion temperatures of seaweed make the ashing temperatures recommended by both GB and ASTM norms to exceed the limit of temperature to prepare seaweed ash. At a high ashing temperature, Gracilaria cacalia and Sargassum natans will generate some high-melting matters which influence the identification of the ash fusion points. So it is more exact and referenced that the seaweed biomasses were ashed at a lower temperature (such as 530oC). The ash fusing characteristics on three sorts of seaweed (a kind of marine biomass) were studied by using thermal microscope, X-ray diffractometer, ash composition analysis, and simultaneous thermogravimetry/differential thermal analysis. It was presented that there were lots of alkali metals especially K and Na in all seaweed ash samples. XRD analysis shows that the crystalline phase intensities of alkali chlorides reduce with increasing the ashing temperature, due to the evaporization of alkali chlorides. Therefore the evaporization of alkali chlorides in seaweed biomass should be considered during the thermal conversion.
At the same time, the specific heat capacities of three sorts of seaweed (a kind of marine biomass) during 40 oC -550 oC were measured by using the NETZSCH DSC404 differential scanning calorimeter, which were modified with the mass loss on the base of traditional solution method. The results show that the heating process are composed of three main intervals, dehydration, large devolatilization seni-coke state, during which the specific heat capacities are great different. The cause is that the residues in every interval are changed. Comparing the specific heat capacities of three sorts of seaweed, Gracilaria cacalia is the largest, Enteromorpha clathrata the second and Sargassum natans the lowest. In this paper, the mathematic relations for specific heat capacities and temperatures are presented during 40 oC -550 oC. The results can be a reference for the thermal chemical conversion energy utilization and numerical simulation of seaweed biomass.
Thermal analysis was a important method used to analyze the pyrolysis and combustion process. In chapter 3, pyrolysis and combustion experiments of Enteromorpha clathrata (ENT) (a species of seaweed) have been conducted using a DTG-60H Thermal Analyzer. The results indicated that the non-isothermal mass loss process of samples is composed of dehydration, rapid mass loss, slow mass loss and solid residue decomposition. The devolatilization stage of ENT started earlier than that of woody biomass because the basic components in seaweed are preferable for pyrolysis compared to lignocellulosic materials. The FTIR analysis was employed to investigate the changes in the main components of sample, while the TG-MS analysis was used for the gaseous products analysis during the pyrolysis. The characteristic parameters of pyrolysis at different heating rates showed that the maximum rate of pyrolysis mass loss, the peak temperature, the initial and final temperature for devolatilization, and the heat release would increase with increasing heating rate. The kinetic parameters were calculated by using the Coats–Redfern method, which indicated that the second order mechanism function was suitable for the pyrolysis of Gracilaria cacalia and Laminaria japonica. The Zhuralev,Lesokin and Tempelman mechanism function was suitable for the pyrolysis of Enteromorpha clathrata and Sargassum natans at a low temperature; the second order mechanism function was also suitable for their pyrolysis at a high temperature. The ignition mode of seaweed was homogeneous and the ignition temperature was low. The combustion process was composed of dehydration, the pyrolysis and combustion of volatile, transition stage, the combustion of char and the reaction at high temperature. And the combustion characteristic parameters were obtained such as ignition temperature, maximum rate of combustion, burnout temperature etc. The combustion models of these seaweeds were also analyzed. The combustion characteristics and model differences between the seaweed and woody biomass were caused by the differences of volatile components. TG-MS analysis was used for the gaseous products analysis during the combustion. During the combustion of seaweeds, NO2 emissions were similar with CO2 emission. They were both accord the mass loss peaks in DTG curve and exothermic peaks in DTA curve.
The obvious SO2 in the combustion stage were likely caused from the decomposition and oxidization of sulfated polysaccharide. However the SO2 emission at the high temperature was about the decomposition of S-containing ash. Several NO emission peaks in the low temperature region were obvious. The cause was mainly associated with the protein in seaweed. At last, activation energies were determined using Arrhrnius model that was solved by binary linear regression method.
In the chapter 4, the fluidized bed combustion of seaweed particles (Enteromorpha clathrata and Sargassum natans) was studied in a bench scale combustor. The devolatilization times of seaweed in fluidized were short, are about 1 minute. When Enteromorpha clathrata particles were put into the fluidized bed, dehydration and the release and combustion of volatile happened, followed by burning char that accorded with the shrinking core model. The carbon burnt layer by layer from outside to inside the nuclear, while the ash layer was almost constant radius. Sargassum natans particles fractured immediately soon after they were fed into the fluidized bed, which was due to the release of a large number of volatile. SEM analysis was used to study the cross-sections of Enteromorpha clathrat particles at different fluidization times. With the combustion of EN particle, the pores inside the particle increase. The micro-pore surface appeared rough, and even partial happened to melt. During the continuous combustion experiments in fluidized bed, if the feeding Enteromorpha clathrat matched the air, they can burn stability at 750 oC. Slagging and big temperature fluctuations were not been found. Particle size distribution of bottom ash mainly concentrated around the value of larger and smaller values. Sargassum natans can burn at low temperatures, but there would be a serious slagging with the combustion process, which mainly due to its low ash melting point. Therefore the fluidized bed combustion was suitable for Enteromorpha clathrata, while Sargassum natan was opposite. At last, Enteromorpha clathrata and its bottom ash were collected for pore structure analysis. The number of porosity, pore volume and specific surface area increased after combustion. The expansion internal pore can be seen in ash. Fractal analysis showed that original seaweed has smooth surface. After combustion, the surface was irregular and rough.
In order to know more about the combustion characteristics of single seaweed particle in fluidized bed, the fluidized combustion experiment of several seaweed particles (Enteromorpha clathrata, while Sargassum natan) were studied. When Enteromorpha clathrata particles were burning, the relative concentration of NOx increases, while the relative concentration of CO decreased. The SO2 and NOx released from Sargassum natan were more than that from Enteromorpha clathrata. The CO concentration also decreased with increasing the bed temperature. The devolatilization of two kinds of seaweed in advance, and the burnout times are both shorten, because the rate of heat transfer increases due to the raise of bed temperature. However the velocity of air flow had no regular influence as bed temperature on the gas concentration of Enteromorpha clathrata and Sargassum natan. Increasing the velocity of air flow made two kinds of seaweed burn easily. With the change in bed height, two kinds of seaweed were not found in the gas precipitation significant to change regularly. The increasing in bed height made the heat carrier increase, which helped to burn. The combustion time had also been shortened.
By analyzing the influence of three factors (bed height, bed temperature, fluidized air velocity) on the fixed carbon residue of Enteromorpha clathrata particles after combustion, the result showed that the bed height is the minimum factor on the fluidized combustion of seaweed. The influential extent of operating parameters on the burnout of fixed carbon was sequenced by the gray relation analysis: bed temperature (℃)> fluidized air velocity(m/s) > bed height (mm). The result showed that the bed temperature was the main influence factor on the combustion in the range of working conditions.
At last, the mathematical model for the fluidized bed combustion of Enteromorpha clathrata single particle was established. The simulation resulted generally consistent with the experimental comparison.
In chapter 6, seaweed biomass fast pyrolysis process was studied. Analysis of working parameters of various types of seaweed biomass pyrolysis characteristics were investigated. This chapter analyzed the effects of main factors of seaweed biomass pyrolysis work condition on pyolysis characteristics.
Pyrolysis reaction temperature had a certain influence on the bio-oil yield of seaweed. The increase in reaction temperature was benefit to generate pyrolysis and no good for generation of carbon. At about 500℃, there was the maximum liquid yield. Retention time (carrier gas flow rate) had little effect on the seaweed bio-oil yield. The bio-oil yield increased slightly with reducing the residence time. The liquid yield from protein pyrolysis was high. The fast pyrolysis of protein produced little char. The result indicated that the protein was easier to pyrolysis. The volatile proportion in char pyrolyized decreased with the increasing the pyrolytic reaction temperature, while the fixed carbon proportion increased, which indicated that the higher temperatures had more volatile released. The testing results showed that seaweed bio-oil has high hydrocarbon content and the advantage of low oxygen content compared with the general land biomass. At last, the chapter discussed that the char and incondensable gas obtained from pyrolysis of seaweed can provide the heat that is needed in pyrolysis process. Therefore the energy self-balance, seaweed fast pyrolysis for bio-oil production and combustion of semi-coke and incondensable gas, can be achieved.
To further understand the characteristics of seaweed bio-oil, Chapter 7 analyzed two kinds of seaweed bio-oil (Enteromorpha clathrata and Sargassum natans) obtained under different conditions by using GC-MS analysis. The main components of seaweed bio-oil were obtained. A number of major components of seaweed bio-oil were hydrocarbon, ketones, aldehydes, alcohols and phenolic compounds, as well as large molecular weight carboxylic acids and their derivatives, and includes a small amount of heterocyclic compounds (derivatives of furan, pyran, pyridine, etc.).
There were lots of hydrocarbons, carboxylic acids and their derivatives in Enteromorpha clathrata oil. While Sargassum natans oil contains many steroids and alcohols compounds. The oleic acid, palmitate, and peanut acid were also detected in Sargassum natans oil. The bio-oils pyrolyzed under different work conditions were very similar in composition, but the relative contents of compositions were different. Pyrolysis temperature played an important role on the distribution of seaweed oil compositions, while the influence function of the carrier gas flow rate was not obvious.
The chapter also studied the mechanism of fast pyrolysis of seaweed biomass. The majority of nitrogen-containing compounds in seaweed oil are related to the thermal decomposition of the protein. The hydrocarbon materials are mainly consistent with carbohydrate and lipid substances. Pyrolysis of proteins includes the thermal decomposition of peptides and amino acids in general. The main mechanism of pyrolysis of amino acids is draw off CO2 molecules reaction, as well as the Strecker reaction of poly solution, and then continue to pyrolysis reaction resulting the formation of carbonyl-containing and two carbonyl compounds. Little lipid in seaweed can also generate hydrocarbons and esters from the decarboxylation and substitution reaction during pyrolysis process.
The dissertation ends with summary and research prospects.
研究海藻的燃料特性是进行海藻生物质利用的基础。第二章从工业分析和元素分析上分析了海藻生物质,发现其高灰低热值,高含水量,含氧量低于陆上生物质。海藻生物质灰熔点普遍不高,尤其长松藻极低的灰熔点导致其不适合热化学利用。我国国家标准(GB)与美国ASTM标准规定的灰化温度都不适合海藻类生物质,同时江蓠与马尾藻在较高灰化温度下,生成了较多的高熔点物,影响了灰熔点的判断。低温(530℃)下制得灰样的灰熔点更具有参考性。通过灰成分分析、X射线衍射方法、热显微镜观察及TG-DTG-DTA联用试验,对3种海洋生物质——海藻的灰熔融过程进行了研究。研究表明:海藻灰渣中都有大量碱金属氯化物结晶相,随着灰化温度的升高,结晶相强度减弱,发生了碱金属的蒸发,因而海藻热化学转化能源利用时必须考虑碱金属的蒸发问题。
同时文中还使用NETZSCH DSC404型差示量热扫描仪(DSC)测定了3种海洋生物质-海藻在40~550℃温度范围内的比热容,并在传统求解方法的基础上根据失重值对结果进行了修正。结果表明:海藻在升温过程中水分挥发,挥发分大量释放,半焦状态3个主要区间内的比热容相差较大,其原因为其残留物性质发生了变化。3种海藻总体相比较而言,江蓠的比热容最大,条浒苔次之,马尾藻最小。文中还给出了海藻在40~550℃温度范围内的比热容与温度的关联式。研究结果可供大型海藻生物质热化学转换能源利用及其相应的数值模拟参考使用。
热分析是分析海藻热解与燃烧过程的重要方法,因而第三章主要在DTG-60H热分析仪上进行了海藻生物质的热解与燃烧试验。海藻热解失重过程由脱水,快速失重和慢速失重以及固体残留物的分解过程。海藻热解温度比陆上生物质低,因为海藻的主要成分不同于陆上生物质的纤维素、半纤维素、木质素。FTIR分析用于测量样品热解时成分的变化;TG-MS用来分析海藻热解过程中的气体产物。随着升温速率增加,海藻热解初析温度提高,最大热解速率值增大,对应的峰值温度后移,挥发分热解活化能也随之增加。对海藻生物质的热解过程使用Coats–Redfern积分法处理。二级反应机理函数适用于江蓠与海带的热解动力学分析;条浒苔和马尾藻热解低温区采用Zhuralev,Lesokin and Tempelman机理函数,高温区仍采用二级反应机理。海藻的着火方式为均相着火,着火温度较低容易着火。海藻的燃烧过程由脱水阶段,挥发分析出与燃烧阶段,过渡阶段,固定碳燃烧和高温反应阶段组成。文中还分析了着火温度、最大燃烧速率、燃尽温度等燃烧参数。海藻燃烧特性与方式与陆上木质类生物质存在差异,究其原因为挥发分的不同。TG-MS也用来分析燃烧的气体产物。各海藻CO_2和NO_2释放趋势与DTG曲线相吻合。SO_2释放曲线稍有差异,燃烧段的生成主要与含硫多糖有关,高温阶段主要是含硫灰分的分解作用。海藻低温段生成的含氮化合物(NOx)主要是由于挥发分分解阶段蛋白质的分解。最后利用一元二次方法计算了海藻的燃烧活化能。
本文第四章在小型流化床试验台上研究了海藻颗粒(条浒苔与马尾藻)的流化床燃烧。海藻在流化床内的挥发分析出燃烧时间较短,都在1分钟左右。条浒苔颗粒在流化床中燃烧先进行脱水和挥发分的燃烧;接着发生焦炭燃烧,其燃烧过程符合缩核模型,炭核由外向内逐层燃烧,而灰层半径几乎不变。但马尾藻颗粒进入流化床后,由于挥发分的大量快速释放而迅速膨胀破碎成屑。另外通过对条浒苔颗粒及不同燃烧时间后收集的焦炭颗粒剖面的SEM扫描电镜观察,发现随着燃烧的进行,颗粒内孔隙增大,微孔表面粗糙,但局部甚至出现融化。在进行流化床连续燃烧海藻颗粒燃料实验时,当条浒苔给料与配风搭配合适时,能在750℃左右稳定燃烧,无结渣,温度波动不大。底灰中灰分粒径分布主要集中较大值和较小值左右。而马尾藻虽然在低温下能够燃烧,但随着燃烧的进行会出现严重结渣,主要是由于其灰熔点太低的缘故。因而可见条浒苔适合流化床燃烧而马尾藻不太适合。最后对条浒苔原样和流化床燃烧后收集的底灰进行孔隙结构分析,燃烧后灰比原样孔隙增多,内部孔隙扩张,孔容积和比表面积增大。通过分形分析可知海藻原样表面光滑,燃烧后表面粗糙不规则。
为了进一步了解海藻单颗粒燃料在流化床内的燃烧特征,第五章详细研究了两种单颗粒海藻颗粒(条浒苔与马尾藻)在流化床内单次投料下的焚烧试验。随着床温的升高,条浒苔释放NOx相对浓度增加,CO相对浓度减少。而马尾藻释放气体中SO_2与NOx含量相对条浒苔有所增加,随着床温的升高,CO相对浓度减少。床温的升高使得床内传热速率加快,两种海藻挥发分的析出提前,燃尽时间缩短。条浒苔与马尾藻随着风速的升高各烟气相对浓度无床温影响般明显规律性变化。风速的升高使得两种海藻燃烧容易,燃尽时间缩短。随着床层高度的变化,两种海藻各气体析出都没有出现明显规律性变化。床高的升高使得热载体增多也一定程度上有利于燃烧,燃尽时间也有缩短。通过分析床高、床温、流化风速三种因素对条浒苔颗粒燃烧后剩余质量和固定碳残留率的影响,可以看出床高因素对海藻颗粒在流化床内燃烧的影响最小。利用灰色关联分析得到各工况因素影响固定碳燃尽主次依次是:床层温度(℃)>流化数>床层高度(mm),可见在研究工况范围内床层温度是影响燃烧的最主要因素。最后建立了条浒苔单颗粒在流化床内燃烧的数学模型,模拟结果与试验对比基本符合。
第六章里详细研究了海藻类生物质的快速热裂解过程,分析了各工况参数对海藻类生物质热裂解特性的影响规律。热解反应温度对海藻生物油的产率有一定影响。反应温度的增加有利于热解气的生成而不利于生成炭。在500℃左右存在最大产油率。停留时间(载气流量)对海藻生物油产率影响不大;停留时间减少,生物油产率略有提高。蛋白质快速热裂解产油率很高,产生焦炭很少,试验结果表明蛋白质容易裂解。热解反应温度升高,热解生成炭中挥发分的比例下降,而固定碳的比例则增加,这说明在较高温度时有更多的挥发分析出。检测结果表明海藻类生物油相比陆上一般生物质具有较高的碳氢含量,较低的含氧量的优点。最后讨论认为海藻热裂解中得到的炭和不凝气能够提供热裂解的热量需求,实现海藻热解制油-半焦与不凝气燃烧供热能量自平衡。
为了进一步了解海藻生物油的特点,第七章通过对海藻生物质(条浒苔、马尾藻)不同工况下热解制得的生物油进行GC-MS分析,得到了海藻油的主要成分。海藻类生物油的主要成分为一些烃类、酮类、醛类、醇类和酚类化合物,以及较大分子量的羧酸及其衍生物,并包含了少量呋喃、吡喃、吡啶等衍生物的杂环化合物。条浒苔油中羧酸及其衍生物和烃类物质较多,而马尾藻生物油中甾族和醇类化合物较多,也检测出油酸和棕榈酸酯,花生酸。不同工况下产生的生物油在组成成分上非常相似,只是相对含量有所不同。热解温度对海藻油组分的分布起了重要作用,而载气流量对热解海藻油成分分布的影响就不明显了。
本章还初步研究了海藻生物质热解产油的机理。海藻热解油中大多数含氮化合物的形成都是与蛋白质的热分解有关。海藻油中的烃类物质生成主要与碳水化合物和脂类物质有关。蛋白质的热解一般包括肽和氨基酸分子的热解。氨基酸热解主要机理是分子中脱去CO_2反应,以及Strecker聚解反应,继续进行裂解反应,形成含羰基和双羰基化合物。海藻含量较少的脂类物质也能在热解过程中发生脱羧、取代等反应生成烃类或酯类等。
本文最后总结了全文,展望了今后的研究工作。
As a limited energy source, fossil fuel could hardly afford long-lasting consumption. And environmental contamination becomes an apparent and serious issue. All facts hasten a growing concern to the exploitation and application of biomass. Many countries pay attention to the importance of biomass that is an abundant renewable energy resource. Such as Denmark, the Netherlands, Germany, France, Canada, Finland and other countries has been conducting their own research and formed a distinctive biomass energy R&D system for many years. But the energy plants around the world is mainly focus on wood and crops, in fact the U.S. Science magazine said that in some cases, the use of food crops such as bio-fuel, not only fail to mitigate climate change, it actually are likely to increase greenhouse gas emissions.
The development of biomass energy properly handles the relationship between energy and food, so the development of new biomass sources becomes particularly important. Seaweed biomass live in the sea, not occupy area land. Its resources development has great potential. In particular, China are surrounded by wide coastal areas and territorial seas. If those rich seaweeds sources are explored efficiently and put into clean and proper use, they may contribute a lot to the future of our country in the competition of the worldwide energy usage, both theoretically and industrially.
The research on this seaweed biomass is still relatively small around world, which is a novel topic. In this paper, the thermochemical conversion processes (combustion and pyrolysis) of the typical large seaweed were studied using a systematic experimental and theoretical method.
Researching fuel characteristics is the foundation of studying seaweed biomass. In chapter 2, the seaweed biomass is studied from proximate and ultimate analysis. It is found that the heating values of the seaweed samples are low and the moisture and ash contents of seaweed are high. In relation to the elementary analysis, seaweed has a lower oxygen content than terrestrial biomass. The low ash fusion temperatures of seaweed make the ashing temperatures recommended by both GB and ASTM norms to exceed the limit of temperature to prepare seaweed ash. At a high ashing temperature, Gracilaria cacalia and Sargassum natans will generate some high-melting matters which influence the identification of the ash fusion points. So it is more exact and referenced that the seaweed biomasses were ashed at a lower temperature (such as 530oC). The ash fusing characteristics on three sorts of seaweed (a kind of marine biomass) were studied by using thermal microscope, X-ray diffractometer, ash composition analysis, and simultaneous thermogravimetry/differential thermal analysis. It was presented that there were lots of alkali metals especially K and Na in all seaweed ash samples. XRD analysis shows that the crystalline phase intensities of alkali chlorides reduce with increasing the ashing temperature, due to the evaporization of alkali chlorides. Therefore the evaporization of alkali chlorides in seaweed biomass should be considered during the thermal conversion.
At the same time, the specific heat capacities of three sorts of seaweed (a kind of marine biomass) during 40 oC -550 oC were measured by using the NETZSCH DSC404 differential scanning calorimeter, which were modified with the mass loss on the base of traditional solution method. The results show that the heating process are composed of three main intervals, dehydration, large devolatilization seni-coke state, during which the specific heat capacities are great different. The cause is that the residues in every interval are changed. Comparing the specific heat capacities of three sorts of seaweed, Gracilaria cacalia is the largest, Enteromorpha clathrata the second and Sargassum natans the lowest. In this paper, the mathematic relations for specific heat capacities and temperatures are presented during 40 oC -550 oC. The results can be a reference for the thermal chemical conversion energy utilization and numerical simulation of seaweed biomass.
Thermal analysis was a important method used to analyze the pyrolysis and combustion process. In chapter 3, pyrolysis and combustion experiments of Enteromorpha clathrata (ENT) (a species of seaweed) have been conducted using a DTG-60H Thermal Analyzer. The results indicated that the non-isothermal mass loss process of samples is composed of dehydration, rapid mass loss, slow mass loss and solid residue decomposition. The devolatilization stage of ENT started earlier than that of woody biomass because the basic components in seaweed are preferable for pyrolysis compared to lignocellulosic materials. The FTIR analysis was employed to investigate the changes in the main components of sample, while the TG-MS analysis was used for the gaseous products analysis during the pyrolysis. The characteristic parameters of pyrolysis at different heating rates showed that the maximum rate of pyrolysis mass loss, the peak temperature, the initial and final temperature for devolatilization, and the heat release would increase with increasing heating rate. The kinetic parameters were calculated by using the Coats–Redfern method, which indicated that the second order mechanism function was suitable for the pyrolysis of Gracilaria cacalia and Laminaria japonica. The Zhuralev,Lesokin and Tempelman mechanism function was suitable for the pyrolysis of Enteromorpha clathrata and Sargassum natans at a low temperature; the second order mechanism function was also suitable for their pyrolysis at a high temperature. The ignition mode of seaweed was homogeneous and the ignition temperature was low. The combustion process was composed of dehydration, the pyrolysis and combustion of volatile, transition stage, the combustion of char and the reaction at high temperature. And the combustion characteristic parameters were obtained such as ignition temperature, maximum rate of combustion, burnout temperature etc. The combustion models of these seaweeds were also analyzed. The combustion characteristics and model differences between the seaweed and woody biomass were caused by the differences of volatile components. TG-MS analysis was used for the gaseous products analysis during the combustion. During the combustion of seaweeds, NO2 emissions were similar with CO2 emission. They were both accord the mass loss peaks in DTG curve and exothermic peaks in DTA curve.
The obvious SO2 in the combustion stage were likely caused from the decomposition and oxidization of sulfated polysaccharide. However the SO2 emission at the high temperature was about the decomposition of S-containing ash. Several NO emission peaks in the low temperature region were obvious. The cause was mainly associated with the protein in seaweed. At last, activation energies were determined using Arrhrnius model that was solved by binary linear regression method.
In the chapter 4, the fluidized bed combustion of seaweed particles (Enteromorpha clathrata and Sargassum natans) was studied in a bench scale combustor. The devolatilization times of seaweed in fluidized were short, are about 1 minute. When Enteromorpha clathrata particles were put into the fluidized bed, dehydration and the release and combustion of volatile happened, followed by burning char that accorded with the shrinking core model. The carbon burnt layer by layer from outside to inside the nuclear, while the ash layer was almost constant radius. Sargassum natans particles fractured immediately soon after they were fed into the fluidized bed, which was due to the release of a large number of volatile. SEM analysis was used to study the cross-sections of Enteromorpha clathrat particles at different fluidization times. With the combustion of EN particle, the pores inside the particle increase. The micro-pore surface appeared rough, and even partial happened to melt. During the continuous combustion experiments in fluidized bed, if the feeding Enteromorpha clathrat matched the air, they can burn stability at 750 oC. Slagging and big temperature fluctuations were not been found. Particle size distribution of bottom ash mainly concentrated around the value of larger and smaller values. Sargassum natans can burn at low temperatures, but there would be a serious slagging with the combustion process, which mainly due to its low ash melting point. Therefore the fluidized bed combustion was suitable for Enteromorpha clathrata, while Sargassum natan was opposite. At last, Enteromorpha clathrata and its bottom ash were collected for pore structure analysis. The number of porosity, pore volume and specific surface area increased after combustion. The expansion internal pore can be seen in ash. Fractal analysis showed that original seaweed has smooth surface. After combustion, the surface was irregular and rough.
In order to know more about the combustion characteristics of single seaweed particle in fluidized bed, the fluidized combustion experiment of several seaweed particles (Enteromorpha clathrata, while Sargassum natan) were studied. When Enteromorpha clathrata particles were burning, the relative concentration of NOx increases, while the relative concentration of CO decreased. The SO2 and NOx released from Sargassum natan were more than that from Enteromorpha clathrata. The CO concentration also decreased with increasing the bed temperature. The devolatilization of two kinds of seaweed in advance, and the burnout times are both shorten, because the rate of heat transfer increases due to the raise of bed temperature. However the velocity of air flow had no regular influence as bed temperature on the gas concentration of Enteromorpha clathrata and Sargassum natan. Increasing the velocity of air flow made two kinds of seaweed burn easily. With the change in bed height, two kinds of seaweed were not found in the gas precipitation significant to change regularly. The increasing in bed height made the heat carrier increase, which helped to burn. The combustion time had also been shortened.
By analyzing the influence of three factors (bed height, bed temperature, fluidized air velocity) on the fixed carbon residue of Enteromorpha clathrata particles after combustion, the result showed that the bed height is the minimum factor on the fluidized combustion of seaweed. The influential extent of operating parameters on the burnout of fixed carbon was sequenced by the gray relation analysis: bed temperature (℃)> fluidized air velocity(m/s) > bed height (mm). The result showed that the bed temperature was the main influence factor on the combustion in the range of working conditions.
At last, the mathematical model for the fluidized bed combustion of Enteromorpha clathrata single particle was established. The simulation resulted generally consistent with the experimental comparison.
In chapter 6, seaweed biomass fast pyrolysis process was studied. Analysis of working parameters of various types of seaweed biomass pyrolysis characteristics were investigated. This chapter analyzed the effects of main factors of seaweed biomass pyrolysis work condition on pyolysis characteristics.
Pyrolysis reaction temperature had a certain influence on the bio-oil yield of seaweed. The increase in reaction temperature was benefit to generate pyrolysis and no good for generation of carbon. At about 500℃, there was the maximum liquid yield. Retention time (carrier gas flow rate) had little effect on the seaweed bio-oil yield. The bio-oil yield increased slightly with reducing the residence time. The liquid yield from protein pyrolysis was high. The fast pyrolysis of protein produced little char. The result indicated that the protein was easier to pyrolysis. The volatile proportion in char pyrolyized decreased with the increasing the pyrolytic reaction temperature, while the fixed carbon proportion increased, which indicated that the higher temperatures had more volatile released. The testing results showed that seaweed bio-oil has high hydrocarbon content and the advantage of low oxygen content compared with the general land biomass. At last, the chapter discussed that the char and incondensable gas obtained from pyrolysis of seaweed can provide the heat that is needed in pyrolysis process. Therefore the energy self-balance, seaweed fast pyrolysis for bio-oil production and combustion of semi-coke and incondensable gas, can be achieved.
To further understand the characteristics of seaweed bio-oil, Chapter 7 analyzed two kinds of seaweed bio-oil (Enteromorpha clathrata and Sargassum natans) obtained under different conditions by using GC-MS analysis. The main components of seaweed bio-oil were obtained. A number of major components of seaweed bio-oil were hydrocarbon, ketones, aldehydes, alcohols and phenolic compounds, as well as large molecular weight carboxylic acids and their derivatives, and includes a small amount of heterocyclic compounds (derivatives of furan, pyran, pyridine, etc.).
There were lots of hydrocarbons, carboxylic acids and their derivatives in Enteromorpha clathrata oil. While Sargassum natans oil contains many steroids and alcohols compounds. The oleic acid, palmitate, and peanut acid were also detected in Sargassum natans oil. The bio-oils pyrolyzed under different work conditions were very similar in composition, but the relative contents of compositions were different. Pyrolysis temperature played an important role on the distribution of seaweed oil compositions, while the influence function of the carrier gas flow rate was not obvious.
The chapter also studied the mechanism of fast pyrolysis of seaweed biomass. The majority of nitrogen-containing compounds in seaweed oil are related to the thermal decomposition of the protein. The hydrocarbon materials are mainly consistent with carbohydrate and lipid substances. Pyrolysis of proteins includes the thermal decomposition of peptides and amino acids in general. The main mechanism of pyrolysis of amino acids is draw off CO2 molecules reaction, as well as the Strecker reaction of poly solution, and then continue to pyrolysis reaction resulting the formation of carbonyl-containing and two carbonyl compounds. Little lipid in seaweed can also generate hydrocarbons and esters from the decarboxylation and substitution reaction during pyrolysis process.
The dissertation ends with summary and research prospects.
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