摘要
松香分别与磷钨酸、硅钨酸、活性白土、膨润土等催化剂,在一定试验条件下进行热裂解反应。以裂解油的酸值为主要指标,考察上述催化剂对松香裂解反应程度的差异。结果表明:磷钨酸、硅钨酸以及活性白土催化剂能够使松香彻底裂解。
考察反应时间、反应温度和催化剂用量对松香裂解反应的影响,并采用三因素三水平正交试验研究活性白土催化剂的最佳工艺条件,得到磷钨酸、硅钨酸、活性白土三种催化剂催化松香裂解反应的最佳试验条件为:磷钨酸催化剂用量为0.25%,反应温度240℃,反应时间2 h,得到的裂解产物酸值为0.80 mg/g,硅钨酸催化剂用量为1%,反应温度240℃,反应时间2 h,得到的裂解产物酸值为0.55 mg/g,活性白土pH值为3.5~4.5时,用量10%,反应温度240℃,反应时间1.5 h,得到裂解产物酸值为0.62 mg/g。
采用气相色谱/质谱(GC/MS)分析裂解油和挥发油的化学成分,裂解油主要由双环芳烃、苯环类、萘环类和菲环类等芳香族化合物组成,挥发油主要由环烷烃、环烷烯、萘类、苯类等化合物组成。
参照GB252-2000《轻柴油》对裂解油各项理化性能进行分析,将其分别与0#柴油和生物柴油进行复配试验,试验证明,松香裂解油的体积分数为1%时,与棕榈油生物柴油和0#柴油进行复配制备生物质燃料油,符合GB/T20828-2007《柴油机燃料调合用生物柴油(BD100)》和GB252-2000《轻柴油》国家标准要求。
Catalytic cracking of rosin with phosphotungstic acid hydrate, silicotungstic acid hydrate, activated clay, bentonite and other catalysts was studied. Estimated the extent of reaction by acid value of cracked products as the main index. The final results demonstrated that rosin can be completely cracked with phosphotungstic acid hydrate, silicotungstic acid hydrate and activated clay catalysts. Whereas phosphotmolybdic acid hydrate, zeolite molecule sieve and bentonite were not suitable for cracking of rosin. Best conditions for cracking reaction were a reaction temperature of 240℃, phosphotungstic acid hydrate catalyst weight of 0.25% of rosin and a reaction time of 2 h, reduced the acid value of products to 0.80 mg/g, silicotungstic acid hydrate catalyst weight of 1% of rosin, a reaction temperature of 240℃and a reaction time of 2 h, reduced the acid value of products to 0.55 mg/g, the pH of the activated clay catalyst was 3.5~4.5, best reaction codition were a temperature of 240℃, activated clay catalyst weight of 10% of rosin, and a reaction time of 1.5 h, reduced the acid value of products to 0.62 mg/g.
Chemical compositions of the cracked products from rosin were analyzed with gas chromatography-mass spectrometry(GC/MS). The main compositions of the pyrolysis oil were bicyclitic compounds, benzene derivatives, naphthalene derivatives, phenanthrene derivatives and other aromatic compounds. The main compostions of the volatile oil were naphthenic hydrocarbon, naphthenic alkene hydrocarbon, benzene derivatives, naphthalene derivatives and other low molecular weight compounds.
Chemical and physical properties of pyrolysis oil was analyzed refer to national standard of BG252-2000. And two kinds of good quality bio-fuel oil which met the national standard of GB/T20828-2007 and GB252-2000 were made by mixing 1% colume fraction of the pyrolysis oil with palm bio-diesel and0#diesel oil respectivly.
引文
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