生物质闪速热裂解制取生物油的试验研究

基于生物质资源的高效清洁能源化利用目的，对生物质热裂解制取生物油这一具有重要应用前景的技术开展研究。结合流化床的优质和生物质的特殊性，自行研制成功给料速达5kg/h的流化床热裂解反应器，并制取得到产率高达60％的生物油。同时针对木屑和秸秆的系统试验研究得出了反应温度和原料种类等主要参数对生物质闪速热裂解制油的影响规律。     

生物质的热裂解与热解油的精制

生物质能属于可再生能源，其利用符合社会可持续发展的原则。生物质在中等温度下(约500℃)热裂解主要得到热解油。介绍了温度对热裂解过程的影响、热解油——水的二元相图、热裂解过程的机理和热解油的特性，综述了催化剂种类，溶剂等对热解油催化裂解的影响。结果表明，催化剂H-ZSM-5的脱氧效果最好，以四氢萘为溶剂时，精制油的收率大幅提高，达39．4％。     

生物质热裂解制油的动力学及技术研究

在不同升温速率下对水曲柳原料在 30 0～ 12 0 0 K范围内进行了热重分析试验 ,试验显示生物质热裂解随温度升高经历五个不同阶段。采用微商法和积分法对其主体阶段的分析得到相互一致的结果 :活化能为 10 1.4 k J/mol、指数因子为 1.2 2× 10 7s- 1 的一阶一步动力学模型。在所开发的以流化床反应器为主体的生物质热裂解制油系统上对生物质进行热裂解试验 ,得出了温度、粒径、停留时间和木种等几种最为重要的参数对热裂解制油的影响规律 ,并在 773K左右成功制取出产率高达 6 0 %的生物油 ,同时用色质联机分析 (GC- MS)技术对所制取的生物油进行了初步分析。     

生物质及其热裂解产物生物油的特性分析

以红松、白松、落叶松、玉米秸秆等不同生物质为原料,对流化床反应器热裂解制取的生物油进行了研究试验,通过对生物油的物理特性及其成分的分析,得出的实验结果表明:红松制取的生物油品质最好,热值高,含水率低,更适合进一步改性研究和应用,并利用现代精密仪器GC-MS对生物油进行了组分分析,解释了生物油高含氧和高含水特性。     

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。     

生物质油应用技术

介绍了国外生物质油的各种应用技术研究成果。作为燃料，与煤混合用于锅炉可以减少SO2排放，与矿物柴油共同乳化可驱动柴油机，也可直接用于燃气轮机中，但是生物质油有一定的腐蚀性。生物质油可以用于制氢，但目前成本较高，必须结合高附加值的副产品联合生产。生物质油还可以成为一种纤维素气化工艺的中间产品，生产合成气；作为脱硫脱硝剂使用也很有前途。     

生物质热裂解制取液体燃料的实验研究

在对生物质热裂解技术进行系统研究的基础上，率先在国内自行开发研制了以流化床反应器为主体的可连续运行的生物质热裂解制取游液体燃料系统，成功地制取出了产率高达60％的生物油。同时简要介绍了适合于生物油分析的GC－MS分析方法，得出生物油由于高水分含量和高含氧量需作进一步改性处理后才能投入实际应用。     

燃料油的新型替代品——生物质裂解油

从化石能源为主向可再生能源为主过渡,是我国能源发展战略的一项重要任务,其中,燃料油将是可再生能源服务的重要对象之一。生物质裂解油以秸秆等农林废弃物为原料,其特质适于替代燃料油。国际上生物质裂解油已经迈入产业化发展的门槛,我国亦具有广阔的市场前景。当前应该抓住国际技术发展的机遇,推动该技术的研发、示范和产业化。     

生物质裂解油催化裂解精制机理研究(Ⅰ)——生物质裂解油及其催化裂解精制油的物性及组成

通过生物质裂解油和催化裂解精制油的物性和化学分析显示催化裂解精制油的密度、粘度、水含量较生物质裂解油明显降低,而pH值和热值明显提高。催化裂解精制油的碳含量较生物裂解油增加,氧含量降低。催化裂解精制油中的酸、醛、酮、糖和醇含量明显降低,酚和芳烃含量明显增加。说明经过催化裂解精制后的精制油的品质较精制前的生物裂解油明显提高。     

Fractionation of flash pyrolysis condensates by staged condensation

The utilization of condensates from flash pyrolysis is challenging due to several unwanted properties. The condensates consist of a mixture of many high value compounds, but each of them is only contained in a low concentration. As additional challenge instantaneous phase separation into an aqueous and a sludgy heavy organic phase takes place, if agricultural residues like barley straw are used as raw material for pyrolysis. A separation by means of distillation is not possible as the compounds undergo polymerization reactions when exposed to higher temperature. A different approach for separation based on boiling temperature is staged condensation of original vapors. Ablative flash pyrolysis is performed in a laboratory. The pyrolysis vapors are condensed in either two or three stages, each composed of a double-effect cooler followed by an electrostatic precipitator. The higher boiling fractions are low in water and acid and show a high heating value. This makes it applicable as sulfur-free bunker fuel and replacement of heavy fuel oil. It can also serve as fuel for gasification plants for the production of either combined heat and power or 2nd generation biofuels. Depending on condensation configuration the first fractions can also be utilized for the production of rigid polyurethane foams or phenolic resins. The last fraction obtained at the lowest cooling temperature mainly consists of water and acids. The production of pure acetic acid seems economically feasible and utilization in agricultural biogas plants is also possible. This is proved by batch fermentation experiments in the biological laboratories.     

Requirements for transportation of fast pyrolysis bio-oil in Finland

The purpose of this paper is to discuss the requirements and challenges of pyrolysis oil's transportation in Finland. Pyrolysis oil is a new type of renewable liquid fuel that can be utilised in applications such as heat and electricity production. It has never been transported on a large scale in Finland. Possible options are transport by road, rail and waterway. The most significant requirements in its transportation are created by acidity and high density of pyrolysis oil, which impose requirements for the materials and transport equipment. The study described here shows that constant domestic transportation of pyrolysis oil is most reasonably operated with tank trucks. Rail-based transport may have potential for domestic fixed routes, and transport by water could be utilised in exporting. All transportation methods have limitations and advantages relative to each other. Ultimately, the production site and end-user's locations will determine the most suitable transport method.     

Bio-oils from arid land plants: Flash pyrolysis of Euphorbia characias bagasse

The devolatilization of the bagasse obtained by solvent extraction of dried Euphorbia characias, a bushy plant growing in arid land of the Mediterranean area, was investigated under rapid heating conditions at atmospheric pressure using a bench-scale fluidized bed pyrolyser. Particle heating rates exceeded 10⁴°C s⁻¹. Bagasse was fed continuously at the rate of 6 g h⁻¹ directly into a sand bed fluidized by nitrogen operating in the temperature range of 400°–750°C. The yields of oils, gases and chars are reported. A maximum oil yield of 44% (wt/wt) (moisture free bagasse) was obtained at 500°C. Yields of gases, CO, CO₂, C₁–C₄ hydrocarbons increased with the rise in temperature, reaching a maximum at 750°C. Elemental analyses showed that the composition of oils and chars was dependent on pyrolysis temperature. The nitrogen content is fairly high; an upgrading process could be necessary for its remotion before the use of the bio-oil as combustible. The other characteristics of oils fall in the range of oils derived from other biomass feedstocks. Chars have a high HHV (15.36 MJ kg⁻¹ at 500°C), representing a valuable fuel.     

生物质热解液化技术经济分析

我国生物质资源十分丰富，但主要以各类农业残余废弃物为主，其特点是能量密度低、分布不集中，如果采用热解液化技术在产地将其先分散转化成生物油，然后再对生物油进行应用或再加工，则就避免了大规模收集和长距离运输生物质所带来的巨大困难。研究分析表明：热解液化设备的规模以每小时可处理2t农业残余废弃物较为适宜，且这种技术在我国具有良好的市场应用前景。     

生物质热裂解制取液体燃料技术的发展

对生物质热裂解技术进行了系统的研究，阐述了其基本技术要求和发展现状，并将现有的生物质热裂解反应器进行分类，分析了相应的优势与不足。最后评估了生物质热裂解制取液体燃料技术的经济和社会效益，结果表明它具有广泛的应用前景。     

Kinetic modeling and optimization of biomass pyrolysis for bio-oil production

Thermo-kinetic models for biomass pyrolysis were simulated under both isothermal and non-isothermal conditions to predict the optimum parameters for bio-oil production. A comparative study for wood, sewage sludge, and newspaper print pyrolysis was conducted. The models were numerically solved by using the fourth order Runge–Kutta method in Matlab-7. It was also observed that newspaper print acquired least pyrolysis time to attain optimum bio-oil yield followed by wood and sewage sludge under the identical conditions of temperature and heating rate. Thus, at 10 K/min, the optimum pyrolysis time was 21.0, 23.8, and 42.6 min for newspaper print, wood, and sewage sludge, respectively, whereas the maximum bio-oil yield predicted was 68, 52, and 36%, respectively.     

生物质快速热解制取生物油

生物质能源是可再生能源的重要组成部分,具有资源丰富和低污染的特点,它的开发与利用已成为21世纪研究的重要课题。本文概述了生物质快速热解的过程、设备及其产物,并对热解的重要产物——生物油的组成、性质、精制以及转化利用进行了详细的阐述。     

生物质催化热解研究进展

介绍了生物质种类、生物油性质、热解反应条件对生物油产率和油品质的作用以及催化剂对催化热解反应的影响。生物质催化热解技术能够实现资源、能源、环境的高效统一,符舍社会的可持续发展原则,具有很大的开发前景。