生物质热裂解过程的节能与优化

生物质秸秆是一种洁净的新能源,具有硫、氮含量低,环境污染小等优点.生物质热裂解是一种很有前景的生物质高效利用方式.本文简要介绍了生物质热裂解过程,介绍了夹点技术、自热式热裂解以及移动床闪速热裂解的研究进展情况,并对国内生物质热裂解节能与优化的发展方向提出了建议.     

生物质裂解油催化裂解精制机理研究(Ⅲ)——生物质裂解油模拟物的催化裂解机理

分析生物质油6种模拟物在裂解温度500℃,不同质量空速条件下的催化裂解产物。不含芳环的生物质油模拟物(乙酸、甲醇、环戊酮和糠醛)经过HZSM-5分子筛催化剂催化裂解后的产物中,均含有苯、萘、茚和多环芳烃及其衍生物,而苯酚和间甲酚经过HZSM-5分子筛催化裂解后,产物中主要是酚类化合物。根据模拟物催化裂解产物,推测不同类型化合物的催化裂解反应途径,说明生物质裂解油催化裂解精制反应过程主要发生脱氧和芳烃化反应,为生物质油催化裂解精制机理研究提供了理论依据。     

热解焦对生物质焦油催化裂解的影响

在小型固定床反应器上,以甲苯为模型化合物对生物质焦油在热解焦上的催化裂解反应进行了研究。重点考察了裂解温度、热解焦粒径尺寸、气相停留时间和水蒸气的流量对焦油的转化率和裂解气成分的影响。结果表明,高温条件下,热解焦对甲苯的裂解具有明显的催化作用。850℃时,所用的两种热解焦对甲苯的转化率分别达到了92.7%和97.0%,同时发现,较小粒径的热解焦和较长的气相停留时间更有利于甲苯的深度裂解。另外,随着水蒸气流量的增加,甲苯的转化率和气体中CO的产率均增大,但当蒸汽甲苯比(S/T)超过6.1时,继续增加水蒸气的流量,甲苯转化率并无明显地提高。     

焦炭对焦油模型化合物的催化裂解实验研究

研究焦炭对焦油模型化合物的催化裂解。考察焦炭对甲苯、甲苯与萘、甲苯与苯酚的催化裂解率及析炭率。结果表明:焦炭对甲苯的催化裂解率与同温度下的热裂解率相当,分别为61.68%与59.02%,析炭率有所降低,由8.54%变为4.16%;对萘的催化裂解率也与同温度下的热裂解率相当,分别为57.95%与56.20%,析炭率也有所降低,由20.72%变为11.89%;而焦炭对苯酚的裂解率与同温度下热裂解率相比有明显增加,由38.25%增加到97.41%,析炭率同样有所降低,由10.96%变为7.03%;说明焦炭对焦油中的组分有选择催化裂解作用。对上述反应前后焦炭样的XRD分析,发现反应后析出的炭与作为催化剂的炭是同一晶型的炭,对末裂解冷凝液的GC-MS分析,发现焦油模型化合物通过裂解后有少部分向芳香化程度增加的方向进行转化。     

玉米秸秆沼渣热裂解及热动力学研究

采用热重法(TG)-微分热重法(DTG)-差热分析法(DTA)研究玉米秸秆沼渣热解过程及热裂解反应动力学特征和机理。研究结果表明玉米秸秆沼渣的失重过程分为吸附水蒸发阶段和秸秆裂解、挥发性物质蒸发阶段。热解过程中,加热速率对玉米秸秆沼渣热解有显著作用。使用FWO、KAS和Popescu方法计算出其热解活化能分别为233、359、358 kJ/mol。对41种常用热裂解动力学机理函数分析确定其热裂解动力学机理为三级方程g(α)=(1-α)-2。扫描时电子显微镜(SEM)分析表明,热裂解可破坏玉米秸秆沼渣的木质纤维束状结构,降低木质纤维中的木质素和半纤维素的质量分数,但效果随升温速度的增大而变差。     

生物质热解气重整试验平台设计与试验

针对热解气焦油含量高、热值低的问题,文章基于焦油催化裂解和热解气气化重整原理,提出了生物质热解气重整工艺路线,并设计、搭建了生物质热解气重整试验平台,该试验平台主要由热解、催化重整、产品收集、控制系统等组成。以玉米秸秆为原料,在该试验平台上开展了热解气重整试验,试验结果表明:在以石英砂作为惰性材料的条件(高温裂解)下,热解气产率为33.8%,焦油转化率为64.3%;在玉米秸秆炭催化裂解条件下,热解气产率为37.8%,焦油转化率72.6%;高温裂解和催化裂解条件下生成的热解气的热值均达到了17MJ/m3以上。热解气重整试验平台达到了设计目的,为热解气重整研究提供了理论支持和技术支撑。     

玉米秸秆发酵渣与酚醛树脂热解特性比较

以热重(TG)和裂解器-气/质联用仪(Py-GC/MS)考察了玉米秸秆发酵渣和酚醛树脂热解产物组成分布随热解温度变化的规律性和差异性。结果显示,甲苯、苯酚、甲基酚为两体系主要共有组分,2,3-二氢苯并呋喃、烷氧基化合物及少量羧酸是玉米秸秆发酵渣热解产物中的特有组分,而二甲基酚、9H-氧杂蒽等组分在酚醛树脂热解产物中的含量显著,这是两种原料的组成成分及结构的差异性体现。     

玉米秸秆热裂解试验研究

在热天平分析玉米秸秆热失重行为基础上,利用气相色谱仪分析研究了玉米秸秆在热裂解过程中热解气的组分。分析结果表明:随着温度升高,气体产物中氢气、甲烷的含量增加,二氧化碳、一氧化碳的含量却减少。结合玉米秸秆的化学组分从分子微观结构角度对玉米秸秆热裂解过程进行了分析。     

热重分析法研究水稻秸秆热裂解特性

在氮气氛围下,利用热重分析法研究了水稻秸秆的热裂解过程,考察了升温速率、熔盐种类和盐质比对热裂解特性的影响,计算了热裂解动力学参数。结果表明:随着升温速率的增加,水稻秸秆热裂解的初始温度、最大失重温度和裂解终止温度升高,热滞后现象严重,残炭产率略呈下降趋势,高升温速率对炭的生成有一定的抑制作用;熔盐使热裂解主失重区间变窄,降低了热裂解的终止温度,显著影响最大失重温度;盐质比对热裂解最大失重温度影响显著,盐质比为1∶1时,最大失重温度降为280.7℃,随着盐质比的增大,最大失重温度向右侧偏移。采用积分法分段处理水稻秸秆的热裂解过程。     

在线催化裂解精制生物质裂解油

以木屑为原料,在3种条件下分别制取快速裂解油、二次裂解油和在线精制油,并对三者进行了水分、元素组成、组分测定和分析.由分析结果知:在线精制油的水分含量最低(仅22%),氧含量最低为31.4%(文中百分数如无特殊说明均为质量分数),且其组分中含一或两个苯环的化合物的相对含量明显上升(接近17%).在线催化裂解条件下,比较了390、450和500℃ 3个温度的产物物性,500℃得到的生物质油的物性(密度、粘度、水分、元素组成)明显优于390℃和450℃两个温度下的产物.     

空分装置有效能分析研究

佣分析方法是低温法精馏过程分析，也是空气分离过程节能分析的主要方法。本文使用空分有效能分析（EAASU）系统对唐钢气体公司的40000m。m（标准）空分装置进行了分析，其设计工况的流程效率为45．25％。分析结果表明，气态产品中氧的摩尔l厢最大，液态产品中氩的摩尔炯最大；同种产品中液态摩尔炯大于气态摩尔炯。在相同环境条件和加工空气量的情况下，增加液态产品的产量，尤其是液氩的产量，可以提高空分装置的流程效率。以设计工况作为参照，基于EAASU软件进一步分析了不同产量的流程炯效率，即当液体总产量增加9％，则流程炯效率提高0．65％以上；气氧产量增加10％，则流程炯效率可提高1,56％。     

An integrated process for biomass pyrolysis oil upgrading: A synergistic approach

Biomass pyrolysis is a promising path toward renewable liquid fuels. However, the calorific value of the pyrolysis oil (PO), also known as bio-oil, is low due to the high content of organic oxygenates and water. The oxygen content of PO can be reduced by hydrodeoxygenation, in which hydrogen is used to remove oxygen. An economic disadvantage of hydrodeoxygenation pathway is its dependence on hydrogen as an expensive feedstock. An alternative technology is to upgrade PO in hot, high pressure water, known as hydrothermal processing. The present paper studies upgrading pyrolysis oil derived from Norwegian spruce by (1) hydrodeoxygenation in a liquid hydrocarbon solvent using nanodispersed sulphide catalysts and (2) hydrothermal treatment in near-supercritical water. Experimental results and simulation studies suggested that if water soluble products are reformed for hydrogen production, the hydrodeoxygenation pathway would be a net consumer of hydrogen, whilst the hydrothermal pathway could produce a significant hydrogen excess. By comparison, the fuel yield from hydrodeoxygenation was significantly higher than hydrothermally treated fuel. Therefore, in the present study, an integrated model was proposed which demonstrates that the synergistic integration of hydrothermal and hydrodeoxygenation upgrading technologies can yield an optimal configuration which maximises fuel production, whilst obviating the need to purchase hydrogen. In this optimal configuration, 32% of raw pyrolysis-oil is hydrothermally treated and the rest is sent for hydrodeoxygenation. The results of a techno-economic analysis suggests that if the proposed integrated approach is used, it is possible to produce biofuel (43% gasoline, and 57% diesel) at a very competitive minimum selling price of 428 $ m⁻³ (1.62 $/gallon).     

Large capacity hydrogen production by microwave discharge plasma in liquid fuels ethanol

In situ hydrogen production technologies have attracted attentions because of hydrogen storage and transportation safety issues. Discharge plasma technology for hydrogen production is of fast response, large capacity, small scale and portability, which is suitable for automobiles and ships. In this paper, a method for producing hydrogen by microwave discharge in ethanol solution was introduced. A microwave discharge reactor of direct standing wave coupling (MDRSWC) was designed, which was suitable for on-board hydrogen production. The characteristics of large capacity hydrogen production by applying MDRSWC in liquid ethanol were investigated. Depending on the experimental conditions of ethanol concentration and microwave power, the flow rate of hydrogen production was achieved ranging from 28.93 to 72.48 g/h. In addition to main hydrogen and carbon dioxide, a small amount of methane and acetylene as by-products were detected. By optimizing the experimental conditions, the experimental results showed that the flow rate of hydrogen, the percentage concentration of hydrogen and the energy yield of hydrogen production were 72.48 g/h, 58.1% and 48.32 g/kWh respectively. This work could provide a potentially effective hydrogen production method for on-board hydrogen utilization device.     

Impact of experimentally measured relative permeability hysteresis on reservoir-scale performance of underground hydrogen storage (UHS)

Underground Hydrogen Storage (UHS) is an emerging large-scale energy storage technology. Researchers are investigating its feasibility and performance, including its injectivity, productivity, and storage capacity through numerical simulations. However, several ad-hoc relative permeability and capillary pressure functions have been used in the literature, with no direct link to the underlying physics of the hydrogen storage and production process. Recent relative permeability measurements for the hydrogen-brine system show very low hydrogen relative permeability and strong liquid phase hysteresis, very different to what has been observed for other fluid systems for the same rock type. This raises the concern as to what extend the existing studies in the literature are able to reliably quantify the feasibility of the potential storage projects. In this study, we investigate how experimentally measured hydrogen-brine relative permeability hysteresis affects the performance of UHS projects through numerical reservoir simulations. Relative permeability data measured during a hydrogen-water core-flooding experiment within ADMIRE project is used to design a relative permeability hysteresis model. Next, numerical simulation for a UHS project in a generic braided-fluvial water-gas reservoir is performed using this hysteresis model. A performance assessment is carried out for several UHS scenarios with different drainage relative permeability curves, hysteresis model coefficients, and injection/production rates. Our results show that both gas and liquid relative permeability hysteresis play an important role in UHS irrespective of injection/production rate. Ignoring gas hysteresis may cause up to 338% of uncertainty on cumulative hydrogen production, as it has negative effects on injectivity and productivity due to the resulting limited variation range of gas saturation and pressure during cyclic operations. In contrast, hysteresis in the liquid phase relative permeability resolves this issue to some extent by improving the displacement of the liquid phase. Finally, implementing relative permeability curves from other fluid systems during UHS performance assessment will cause uncertainty in terms of gas saturation and up to 141% underestimation on cumulative hydrogen production. These observations illustrate the importance of using relative permeability curves characteristic of hydrogen-brine system for assessing the UHS performances.     

Comparison of supercritical CO2, liquid CO2, and solvent extraction of chemicals from a commercial slow pyrolysis liquid of beech wood

Innovative extraction methods with supercritical CO₂ and liquid CO₂ have been employed to obtain value-added chemicals from a slow pyrolysis liquid. Sequential solvent extraction with hexane and acetone was carried out for comparison. Pyrolysis liquid was first adsorbed on silica (SiO₂) with weight ratios SiO₂:oil of 100:40 and 100:80. Pyrolysis liquid and extracts were mainly characterized by GC–MS/FID, elemental analysis, and water content. Results show that scCO₂ extraction is mainly controlled by dissolution at the first 3 h during a 6-h extraction period and by combination of dissolution and diffusion at later extraction periods. Around 60–65% of the CO₂ and hexane extracts could be identified by GC compared to 49% of the starting pyrolysis liquid. GC data confirmed that, CO₂ extraction effectively enriched both non-aromatics and aromatic compounds. Hexane extracts contained lower contents of organic acids. Hexane enabled a complete extraction of aromatics. Chemical composition of extracts from scCO₂ and liquid CO₂ are very similar. Extraction with scCO₂ and liquid CO₂ proves to be an effective and innovative pre-treatment process for the production of chemicals from pyrolysis liquid.     

Improved biodiesel manufacture at low temperature and short reaction time

Biodiesel, which is derived from oil/fat by transesterification with alcohol, has attracted considerable attention over the past decades due to its ability to subsidise fossil fuel derived energy as a renewable and carbon neutral fuel. Several approaches for biodiesel fuel production have been developed, among which transesterification using a catalyst gives high yields of methyl ester. This method has therefore been widely utilized for biodiesel production in a number of countries. In this study, a Downflow Liquid Contactor Reactor (DLCR) has been used for the liquid–liquid transesterification reaction of sunflower oil with alcohol with extraordinary results. The reactor provides great potential for chemical reactions, which are normally limited by mass transfer and possesses a number of distinctive advantages over conventional multiphase reactors. Inside the reactor a high velocity liquid jet stream is produced which generates powerful shear and energy, causing vigorous agitation in the upper part of the reactor. The high mixing intensity in the DLCR enabled the manufacture of biodiesel to European Standard EN14214 (ester content 96.5%) in 2.5 min at 40 °C with 0.43 wt.% alkali catalyst and alcohol to oil molar ratio of 4.5 to 1.0. The separation of FAME from glycerol is done by gravity settling only without water washing. The effect of the alcohol type (methanol, ethanol) on biodiesel yield was also investigated. The process offers the advantage of continuous large scale production with limited reactor volume.     

Complete saccharification of cellulose through chemo-enzymatic hydrolysis

A new method for total hydrolysis of cellulose using a chemo-enzymatic system to combine chemical depolymerization and enzymatic hydrolysis, is described in this paper. The approach described herein involves the dissolution of cellulose in an ionic liquid, depolymerization by acidic solid-catalyst, and use of an antisolvent to obtain the resulting cello-oligomers. These were subjected to chemical depolymerization, after which virtually all the soluble cello-oligomers were hydrolyzed to glucose by β-1,4-D-glucan glucohydrolase. This glucohydrolase is newly identified from a species of Paenibacillus (HPL-001), and is different from commercial β-1,4-D-glucosidase. Continuous recycling (99%) of ionic acid and organic solvent completely broke down the cellulose into cello-oligomers (soluble sugars) shorter than six anhydrous glucose units. The cello-oligomers of soluble sugars were easily connected to a new single-enzyme system for complete hydrolysis to glucose. The efficiency of this technology could solve the dissolution and selective deconstruction problem retarding the major production of glucose from cellulose, and could provide a crucial advance in the production of un-degraded glucose as final product. This approach provides an alternative techno-economic process to traditional, expensive, three-enzyme hydrolysis of cellulose.     

Comparing biological and thermochemical processing of sugarcane bagasse: An energy balance perspective

The technical performance of lignocellulosic enzymatic hydrolysis and fermentation versus pyrolysis processes for sugarcane bagasse was evaluated, based on currently available technology. Process models were developed for bioethanol production from sugarcane bagasse using three different pretreatment methods, i.e. dilute acid, liquid hot water and steam explosion, at various solid concentrations. Two pyrolysis processes, namely fast pyrolysis and vacuum pyrolysis, were considered as alternatives to biological processing for the production of biofuels from sugarcane bagasse. For bioethanol production, a minimum of 30% solids in the pretreatment reactor was required to render the process energy self-sufficient, which led to a total process energy demand equivalent to roughly 40% of the feedstock higher heating value. Both vacuum pyrolysis and fast pyrolysis could be operated as energy self-sufficient if 45% of the produced char from fast pyrolysis is used to fuel the process. No char energy is required to fuel the vacuum pyrolysis process due to lower process energy demands (17% compared to 28% of the feedstock higher heating value). The process models indicated that effective process heat integration can result in a 10-15% increase in all process energy efficiencies. Process thermal efficiencies between 52 and 56% were obtained for bioethanol production at pretreatment solids at 30% and 50%, respectively, while the efficiencies were 70% for both pyrolysis processes. The liquid fuel energy efficiency of the best bioethanol process is 41%, while that of crude bio-oil production before upgrading is 67% and 56% via fast and vacuum pyrolysis, respectively. Efficiencies for pyrolysis processes are expected to decrease by up to 15% should upgrade to a transportation fuel of equivalent quality to bioethanol be taken into consideration.     

Review of electrochemical ammonia production technologies and materials

Ammonia, being a good source of hydrogen, has the potential to play a significant role in a future hydrogen economy. The hydrogen content in liquid ammonia is 17.6 wt% compared with 12.5 wt% in methanol. Although a large percentage of ammonia, produced globally, is currently used in fertiliser production, it has been used as a fuel for transport vehicles and for space heating. Ammonia is an excellent energy storage media with infrastructure for its transportation and distribution already in place in many countries. Ammonia is produced at present through the well known Haber–Bosch process which is known to be very energy and capital intensive. In search for more efficient and economical process and in view of the potential ammonia production growth forecast, a number of new processes are under development. Amongst these, the electrochemical routes have the potential to substantially reduce the energy input (by more than 20%), simplify the reactor design and reduce the complexity and cost of balance of plant when compared to the conventional ammonia production route. Several electrochemical routes based on liquid, molten salt, solid or composite electrolytes consisting of a molten salt and a solid phase are currently under investigation. In this paper these electrochemical methods of ammonia synthesis have been reviewed with a discussion on materials of construction, operating temperature and pressure regimes, major technical challenges and materials issues.     

Liquid biofuels potential and outlook in Iran

Iran’s diversity of terrain and climate enables cultivation of a variety of energy crops suitable for liquid biofuels production. In Iran, the easily and readily available biofuel feedstock today for production of bioethanol is molasses from sugar cane and sugar beet. There is also about 17.86 million tons of crops waste from which nearly 5 billion liters of bioethanol could be produced annually. This amount of bioethanol is sufficient to carry out E10 for spark ignition engine vehicles in Iran by 2026. There is also enormous potential for cultivation of energy plants such as cellulosic materials and algae. Iran has 7%of its area covered with forest products which are suitable sources for liquid biofuels such bioethanol and biodiesel. Iran also has a long tradition of fishing in Caspian Sea and Persian Gulf with about 3200 km coastline and on inland rivers. The produced fish oil and other plant oils such as palm tree, jatropha, castor plant and algae are suitable biodiesel feedstock. Out of 1.5 million tons of edible cooking oil consumed in Iran annually, about 20% of it can be considered as waste, which is suitable biodiesel feedstock.This quantity along with the other possible potential feedstock are favorable sources to carry out B10 step by step until 2026.