CAJ | 학술논문

以红松松子壳为原料，采用连续热解装置研究了热解反应温度和时间对生物油得率的影响规律，在反应温度为450℃、反应时间为6 min时，生物油得率可达到40.74%，热值可达到22.66 MJ/kg。采用气相色谱质谱联用仪对生物油成分进行了分析，其成分以酚类为主，质量分数约为33.5%；选用HZSM-5及NiO/HZSM-5分子筛催化剂对热解重质油部分分别进行催化改性试验，结果表明：经NiO/HZSM-5分子筛催化剂催化后其中高沸点有机物质量分数降低约13个百分点；其黏度由原来的约3290 mPa·s大幅度地降低至450 mPa·s，热值则由原来的约26.16 MJ/kg增加到30.33 MJ/kg，增加了16%，同时提高了重质油的燃烧性和稳定性；负载物氧化镍（NiO）的添加提高了HZSM-5催化剂的抗积碳能力。该研究也为后续生物油改性提供了参考。
이홍송송자각위원료，채용련속열해장치연구료열해반응온도화시간대생물유득솔적영향규률，재반응온도위450℃、반응시간위6 min시，생물유득솔가체도40.74%，열치가체도22.66 MJ/kg。채용기상색보질보련용의대생물유성분진행료분석，기성분이분류위주，질량분수약위33.5%；선용HZSM-5급NiO/HZSM-5분자사최화제대열해중질유부분분별진행최화개성시험，결과표명：경NiO/HZSM-5분자사최화제최화후기중고비점유궤물질량분수강저약13개백분점；기점도유원래적약3290 mPa·s대폭도지강저지450 mPa·s，열치칙유원래적약26.16 MJ/kg증가도30.33 MJ/kg，증가료16%，동시제고료중질유적연소성화은정성；부재물양화얼（NiO）적첨가제고료HZSM-5최화제적항적탄능력。해연구야위후속생물유개성제공료삼고。
With the consumption of fossil fuels, it would be more and more difficult to depend on fossil fuels for energy, which together with the environment problems forces people to find a clean and renewable alternative energy. Because of the huge amount, the environmental friendly and renewable features, the biomass has aroused considerable attention. Bio-oil is one of the products from biomass pyrolysis. As a kind of promising alternative energy, bio-oil has showed some good characteristics of high energy density, convenient storage and transportation. In generally, bio-oil is brown acid liquid with smoke and irrigating smell. The major components of bio-oil are acids, phenols, and hydrocarbon and so on. Based on the different component characteristics, bio-oil could be divided into two parts:the light part which is called pyroligneous, and the heavy part. The heavy part consists of large molecules from the procedure of pyrolysis, which is difficult to use for its high viscosity and high oxygen content. Catalytic cracking is one of the useful methods for bio-oil upgrading, although the lifetime of the catalyst is influenced by the char deposit. More and more promising materials are used for catalyst cracking, however, the absence of theoretical support makes the upgrading process blind. In this paper, pine-nut shell was pyrolyzed through continuous pyrolysis device. In order to gain more liquid product, the reaction parameters of temperature (350-650℃) and time (2-8 min) were researched. The GC-MS was used to analyze the major constituent of the pine-nut shell bio-oil produced at the suitable situation, as well as its properties including viscosity, heat value, water content and pH. The heavy part of bio-oil was divided from the bio-oil for the upgrading experiment. The catalytic cracking experiment was carried out on the fixed bed reactor. In the experiment HZSM-5 and NiO/HZSM-5 zeolite were used to catalyze the heavy oil respectively. The heavy oil was compared with the catalyzed one on the composition and properties. The results showed that in the range of 350-650℃, the yield of bio-oil had a trend that increased initially and decreased afterwards as the increase of temperature. In the range of 2-8 min, the yield of bio-oil had a similar trend with time passing. Besides the influence on bio-oil yield, the results also indicated the suitable temperature and time was 450℃ and 6 min, respectively, at which the yield could be 40.74%. The GC-MS result showed that the major constituent of pine-nut bio-oil was phenol, some acids and arena. The upgrading experiment also proved that the heavy component was decreased by 10%, the viscosity was decreased to 400 mPa·s and the heat value was increased by 13%-16% by the catalysis upgrading of the HZSM-5 and NiO/HZSM-5 zeolite. The combustion stability of the upgrading oil was improved as well. Although the catalysis result was good, the deposit of char still existed, and the addition of NiO improved the resistance ability of the catalyst to carbon deposition. All of the above results provided a theoretical basis for experimental study of upgrading bio-oil.