微藻/核桃壳混合热解需热量及制备芳烃研究
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摘要
利用热重分析仪(TG)、气相色谱-质谱联用仪(GC/MS)与固定床反应器,考察了微藻、核桃壳及混合物主要热解阶段的需热量特性,以及混合比、温度、催化剂种类对二者混合热解制备芳烃的影响规律。结果表明:在不同升温速率下,核桃壳热解在180~270℃和380~485℃处存在两个吸热峰,整体表现为吸热效应(378.56~596.45k J·kg~(-1));微藻热解在280~450℃处存在一个放热峰,整体表现为放热效应(-814.76~~(-1)191.52 k J·kg~(-1))。微藻/核桃壳热解呈现较低的放热效应(-99.05~~(-1)58.04 k J·kg~(-1)),表明二者混合热解可以实现一定程度的热量耦合。微藻/核桃壳热解在制备芳烃上表现出明显的协同效应,且芳烃相对含量在600℃、混合比1:1下达到最大值,为20.51%;加入Cu/HZSM-5可进一步提高混合热解的芳烃相对含量,达到35.74%。为微藻与核桃壳的高值化利用提供了新思路。
In this study, Nannochloropsis sp.(NS) and walnut shell(WS) were used as raw materials for mixed pyrolysis, and the characteristics of thermal demanding during pyrolysis of NS, WS and NS/WS were initially investigated by a thermogravimetric analyzer and a fixed-bed reactor. Then the effects of mass ratio, reaction temperature, and catalysts on the preparation of aromatic hydrocarbons from NS/WS mixed pyrolysis were studied by a GC/MS method. Results showed that the two endothermic peaks were observed from WS pyrolysis at 180—270℃ and 380—485℃, the overall performance of WS pyrolysis took on the endothermic effect with thermal demanding values of 378.56—596.45 k J·kg~(-1) under different heating rates. An endothermic peak was obtained from NS pyrolysis at 280—450℃, the overall performance of NS pyrolysis took on exothermic effect with thermal demanding values of-814.76—~(-1)191.52 k J·kg~(-1). The pyrolysis of NS/WS presented low exothermic effect with thermal demanding values of-99.05—~(-1)58.04 k J·kg~(-1), indicating that the mixed pyrolysis achieved a certain degree of thermal coupling. The mixed pyrolysis of NS/WS demonstrated a synergistic effect in the preparation of aromatic hydrocarbons. The optimum condition for aromatics preparation with a value of 20.51% was achieved at a temperature of 600℃ and a NS/WS mass ratio of 1:1. By introducing Cu/HZSM-5 catalyst, the relative content of aromatics was further improved(35.74%). This study provided a new approach for high-value utilization of NS and WS.
In this study, Nannochloropsis sp.(NS) and walnut shell(WS) were used as raw materials for mixed pyrolysis, and the characteristics of thermal demanding during pyrolysis of NS, WS and NS/WS were initially investigated by a thermogravimetric analyzer and a fixed-bed reactor. Then the effects of mass ratio, reaction temperature, and catalysts on the preparation of aromatic hydrocarbons from NS/WS mixed pyrolysis were studied by a GC/MS method. Results showed that the two endothermic peaks were observed from WS pyrolysis at 180—270℃ and 380—485℃, the overall performance of WS pyrolysis took on the endothermic effect with thermal demanding values of 378.56—596.45 k J·kg~(-1) under different heating rates. An endothermic peak was obtained from NS pyrolysis at 280—450℃, the overall performance of NS pyrolysis took on exothermic effect with thermal demanding values of-814.76—~(-1)191.52 k J·kg~(-1). The pyrolysis of NS/WS presented low exothermic effect with thermal demanding values of-99.05—~(-1)58.04 k J·kg~(-1), indicating that the mixed pyrolysis achieved a certain degree of thermal coupling. The mixed pyrolysis of NS/WS demonstrated a synergistic effect in the preparation of aromatic hydrocarbons. The optimum condition for aromatics preparation with a value of 20.51% was achieved at a temperature of 600℃ and a NS/WS mass ratio of 1:1. By introducing Cu/HZSM-5 catalyst, the relative content of aromatics was further improved(35.74%). This study provided a new approach for high-value utilization of NS and WS.
引文
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[29]杨文衍,曾燕,罗嘉,等.微拟球藻热解及其催化热解制备生物油研究[J].燃料化学学报,2011,39(9):664-669.YANG W Y,ZENG Y,LUO J,et al.Production of bio-oil by direct and catalytic pyrolysis of Nannochloropsis sp.[J].Journal of Fuel Chemistry and Technology,2011,39(9):664-669.
[30]ONLY O,BEIS S,KOCKAR O M.Pyrolysis of walnut shell in a well-swept fixed-bed reactor[J].Energy Sources,2004,26(8):771-782.
[31]LIU S Y,XIE Q L,ZHANG B,et al.Fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with Ca O and HZSM-5 as the catalyst[J].Bioresource Technology,2016,204:164-170.
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[33]VESES A,AZNAR M,MARTINEZ I,et al.Catalytic pyrolysis of wood biomass in an auger reactor using calcium-based catalysts[J].Bioresource Technology,2014,162(6):250-258.
[2]孟晓晓,孙锐,袁皓,等.不同热解温度下玉米秸秆中碱金属K和Na的释放及半焦中赋存特性[J].化工学报,2017,68(4):1600-1607.MENG X X,SUN R,YUAN H,et al.Effect of different pyrolysis temperature on alkali metal K and Na emission and existence in semichar[J].CIESC Journal,2017,68(4):1600-1607.
[3]VISPUTE T P,ZHANG H Y,SANNA A,et al.Renewable chemical commodity feedstocks from integrated catalytic processing of pyrolysis oils[J].Science,2010,330:1222-1227.
[4]HEW K L,TAMIDI A M,YUSUP S,et al.Catalytic cracking of biooil to organic liquid product(OLP)[J].Bioresource Technology,2010,101(22):8855-8858.
[5]CHAGAS B M E,DORADO C,SERAPIGLIA M J,et al.Catalytic pyrolysis-GC/MS of spirulina:evaluation of a highly proteinaceous biomass source for production of fuels and chemicals[J].Fuel,2016,179:124-134.
[6]ZHOU Y,WANG Y P,FAN L L,et al.Fast microwave-assisted catalytic co-pyrolysis of straw stalk and soapstock for bio-oil production[J].Journal of Analytical and Applied Pyrolysis,2017,124:35-41.
[7]董丽.生物质制芳烃技术进展与发展前景[J].化工进展,2013,32(7):1526-1533.DONG L.Development of aromatics production from biomass[J].Chemical Industry and Engineering Progress,2013,32(7):1526-1533.
[8]闵恩泽,吴巍.可再生生物质资源[J].化工进展,2002,21(5):357-359.MIN E Z,WU W.Renewable biomass resources[J].Chemical Industry and Engineering Progress,2002,21(5):357-359.
[9]CHEN N Y,DEGNAN T F,KOENIG L R.Liquid fuel from carbohydrates[J].Chemtech,1986,16(8):506-511.
[10]ZHU X L,LOBBAN L L,MALLINSON R G,et al.Bifunctional transalkylation and hydrodeoxygenation of anisole over a Pt/HBeta catalyst[J].Journal of Catalysis,2011,281(1):21-29.
[11]LI X Y,ZHANG H F,LI J,et al.Improving the aromatic production in catalytic fast pyrolysis of cellulose by co-feeding low-density polyethylene[J].Applied Catalysis A General,2013,455(2):114-121.
[12]WARREN C.The burning question[J].Science,2017,355:18-21.
[13]SINGH A,NIGAM P S,MURPHY J D.Renewable fuels from algae:an answer to debatable land based fuels[J].Bioresource Technology,2011,102(1):10-16.
[14]ALAM F,DATE A,RASJIDIN R,et al.Biofuel from algae-is it a viable alternative?[J].Procedia Engineering,2012,49(29):221-227.
[15]SHI F,WANG P,DUAN Y,et al.Recent developments in the production of liquid fuels via catalytic conversion of microalgae:experiments and simulations[J].RSC Advances,2012,2(26):9727-9747.
[16]PIRT S J.The thermodynamic efficiency(quantum demand)and dynamics of photosynthetic growth[J].New Phytologist,1986,102(1):3-37.
[17]GHASEMI Y,RASOUL-AMINI S,NASERI A T,et al.Microalgae biofuel potentials[J].Applied Biochemisty Microbiology,2012,48(2):126-144.
[18]王楷,郭庆杰,杨林.微拟球藻脂肪热解及对全组分制备生物油的影响[J].燃料化学学报,2016,44(1):60-68.WANG K,GUO Q J,YANG L.Pyrolysis of fat from Nannochloropsis sp.and its effect on bio-oil from pyrolysis of all components[J].Journal of Fuel Chemistry and Technology,2016,44(1):60-68.
[19]HUA M Y,LI B X.Co-pyrolysis characteristics of the sugarcane bagasse and Enteromorpha prolifera[J].Energy Conversion and Management,2016,120:238-246.
[20]THANGALAZHY-GOPAKUMAR S,ADHIKARI S,CHATTANATHAN S A,et al.Catalytic pyrolysis of green algae for hydrocarbon production using H+ZSM-5 catalyst[J].Bioresource Technology,2012,118(4):150-157.
[21]DU Z Y,MA X C,LI Y,et al.Production of aromatic hydrocarbons by catalytic pyrolysis of microalgae with zeolites:catalyst screening in a pyroprobe[J].Bioresource Technology,2013,139(7):397-401.
[22]WANG S,WANG Q,HU Y M,et al.Study on the synergistic copyrolysis behaviors of mixed rice husk and two types of seaweed by a combined TG-FTIR technique[J].Journal of Analytical and Applied Pyrolysis,2015,114:109-118.
[23]常国璋,黄艳琴,赖喜锐,等.棕榈壳焦CO2气化过程中反应性及结构特性研究[J].燃料化学学报,2015,43(8):947-954.CHANG G Z,HUANG Y Q,LAI X R,et al.Experimental study on the structure and reactivity of palm kernel shell chars during CO2gasification[J].Journal of Fuel Chemistry and Technology,2015,43(8):947-954.
[24]LUO S P,BAO G R,WANG H,et al.TG-DSC-FTIR analysis of cyanobacteria pyrolysis[J].Physics Procedia,2012,33:657-662.
[25]WANG J,WANG G,ZHANG M,et al.A comparative study of thermolysis characteristics of seaweed and fir wood[J].Process Biochemistry,2006,41(8):1883-1886.
[26]ZHAO H,YAN H X,DONG S S,et al.Thermogravimetry study of the pyrolytic characteristics and kinetics of macro-algae Macrocystis pyrifera residue[J].Journal of Thermal Analysis&Calorimetry,2013,111(3):1685-1690.
[27]ANCA-COUCE A,SCHARLER R.Modelling heat of reaction in biomass pyrolysis with detailed reaction schemes[J].Fuel,2017,206:572-579.
[28]SHEN J C,IGATHINATHANE C,YU M L,et al.Biomass pyrolysis and combustion integral and differential reaction heats with temperatures using thermogravimetric analysis/differential scanning calorimetry[J].Bioresource Technology,2015,185:89-98.
[29]杨文衍,曾燕,罗嘉,等.微拟球藻热解及其催化热解制备生物油研究[J].燃料化学学报,2011,39(9):664-669.YANG W Y,ZENG Y,LUO J,et al.Production of bio-oil by direct and catalytic pyrolysis of Nannochloropsis sp.[J].Journal of Fuel Chemistry and Technology,2011,39(9):664-669.
[30]ONLY O,BEIS S,KOCKAR O M.Pyrolysis of walnut shell in a well-swept fixed-bed reactor[J].Energy Sources,2004,26(8):771-782.
[31]LIU S Y,XIE Q L,ZHANG B,et al.Fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with Ca O and HZSM-5 as the catalyst[J].Bioresource Technology,2016,204:164-170.
[32]ZHENG Y W,WANG F,YANG X Q,et al.Study on aromatics production via the catalytic pyrolysis vapor upgrading of biomass using metal-loaded modified H-ZSM-5[J].Journal of Analytical and Applied Pyrolysis,2017,126:169-179.
[33]VESES A,AZNAR M,MARTINEZ I,et al.Catalytic pyrolysis of wood biomass in an auger reactor using calcium-based catalysts[J].Bioresource Technology,2014,162(6):250-258.