生物质气化焦油在高温木炭床上的裂解试验研究

在高温木炭床裂解炉上,对以木粉为原料的120Kw鼓泡流化床气化炉产生的气化气中的焦油进行了裂解研究,采用溶剂冷态捕集焦油和称重分析相结合的方法对裂解前、后的焦油含量进行了测量.结果表明,在高温木炭床上发生的木炭吸附焦油、焦油的高温裂解和木炭灰催化裂解焦油等一系列的物理化学过程,可有效降低燃气中的焦油含量,同时可以获得热值为5MJ/m^3的可燃气.     

生物质焦油裂解的技术关键

生物质焦油是生物质气化过程中有害的副产物，它会降低气化效率，影响设备运行，所以必须加以有效利用和处理。本文介绍了国内外焦油催化裂解的研究现状，详细地分析了讨论了催化裂解的关键过程和工艺件，总结出了焦油催化裂解的最佳条件和比较有前景的工艺路线。     

两段气化对降低生物质气化过程焦油生成量的影响

在分析焦油生成和裂解的有关机理的基础上，研究开发了两段气化装置，对一段供风和两段供风气化过程进行了大量的对比试验，探讨了温度分布和气化强度等因素对气化中焦油含量的影响。研究结果表明，在同样的试验条件下，两段供风显著提高了气化炉内的最高温度和还原区的温度，气体中焦油的含量仅为常规供风方式的1／10左右，改善了气化机组的性能。     

CaO催化裂解生物质气化焦油实验研究

以谷壳气化发电产生焦油为研究对象,考查了CaO作为焦油裂解催化剂对其催化裂解的影响。实验研究结果表明:CaO作为焦油裂解催化剂可使焦油裂解率明显提高,在800℃时,其裂解率可由热裂解的28.66%提高到65.60%,焦油催化裂解后可使燃气成份中的H2、CO、CH4以及CO2含量提高。但焦油裂解过程中,其积炭率可达30.51%;扫描电镜显示:因焦油裂解积炭包裹CaO催化剂,易使其催化活性失效,同时由于积炭,使床层压降增加,给焦油催化裂解运行带来困难。     

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。     

生物质热解煤气中焦油含量的影响因素

采用稻杆、稻壳和木屑作为原料，对生物质材料热解产生的煤气中的焦油含量进行了系统研究。采用冷态捕集方法进行焦油取样；焦油样品用重度分析方法确定煤气中焦油含量。结果表明，由于各种生物质原料的组成及结构不同，热解煤气中，焦油含量存在较大差异，热解温度由550℃升高到900℃以上，热解煤气中焦油含量迅速下降，下降幅度甚至达到70％，随生物质原料在热解反应器内滞留时间的延长，焦油含量也下降，同时给出并分析了焦油含量随热解温度和滞留时间变化的情况。     

助剂改性Ru-Ni-CeO2/HZSM-5催化剂裂解秸秆气化焦油性能研究

用助剂Fe、Mn、Co以及Cu调变浸渍法制备Ru-Ni-CeO2/HZSM-5催化剂,并对催化裂解秸秆气化焦油的活性和选择性进行研究。结果表明,助剂影响焦油裂解的活性和选择性,Cu对提高Ni-Ru-CeO2/HZSM-5催化剂焦油裂解活性和燃气质量具有最佳效果。     

热解和气化过程焦油析出的影响因素分析

在热解和气化过程中产生的焦油给气化工业带来极大的不便。讨论了温度、停留时间、压力、气氛、拉径以及床料等对热裂解和催化裂解产生的影响。催化剂的加入对上述因素又产生了新的影响。同时介绍了不同研究者对催化剂性能的研究，在此作出对比。     

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。     

整体式焦油裂解催化剂的制备及性能研究

以堇青石为载体,采用真空浸渍法制备整体式镍基催化剂,研究了不同干燥方法对整体式催化剂内表面活性组分轴向分布的影响及不同工艺条件下的催化性能。结果表明:微波干燥法所得催化剂内表面活性组分轴向分布最均匀;重时空速对焦油裂解率的影响较大,当重时空速为177kg/(h.m3)时,焦油裂解率高达92.62%,H2的体积分数为46.53%;在较低温度条件(700~800℃)下,催化温度对焦油裂解的影响较小,当催化温度上升到900℃时,焦油裂解率大幅上升,单位质量生物质气体产率高达1.22Nm3/kg。     

Experimental study on influence of operating parameters on tar components from corn straw gasification in fluidized bed

Gasification is a promising approach for converting solid fuel sources, including renewable ones like biomass, for use. The main problem in biomass gasification is the formation of condensable tars, including polycyclic aromatic hydrocarbons (PAHs). This paper investigated the conversion of tar components during corn straw gasification. It analyzed collected tar components using a gas chromatograph-mass spectrograph (GC-MS). Experimental results indicate that, with increasing temperature from 700°C to 900°C, the concentrations of benzene, indene, phenanthrene, naphthalene, acenaphthylene, fluorene, and pyrene increased whereas those of toluene, phenol, 1-methylnaphthalene, and 2-methylnaphthalene decreased. As the equivalence ratio (ER) increased from 0.21 to 0.34, the concentrations of indene and phenanthrene increased from 0.148% and 0.087% to 0.232% and 0.223%, respectively. Further, the phenol content increased as ER increased from 0.21 to 0.26 and then decreased as the ER increased further to 0.34. Other parameters like the steam/biomass (S/B) ratio and catalyst also played a critical role in tar reduction. This paper demonstrates the conversion of some tar components and elucidates their chemical properties during gasification.     

生物质炭催化裂解焦油的性能研究

采用管式反应器研究了生物质炭作为焦油裂解催化剂的性能,选用白云石和石英砂作对比试验。通过对焦油转换率、裂解产物、裂解气气体组分和动力学参数的分析对比可知:在所选用的3种材料中,生物质炭作为催化剂的焦油转化率最高,裂解产物中气体所占比重最大,且可燃气体的组分较高,反应动力学参数最小。生物质炭的催化性能显著高于石英砂,稍好于白云石,是一种高效的焦油裂解催化剂。     

Experimental study on the coal tar hydrocracking process over different catalysts

In the paper, the results of the study on a laboratory process of hydrocracking of coal tar are presented. High-temperature coal tar was hydrocracked in an autoclave reactor, at 400–413 °C and 7,3–9,6 MPa over 5 different, hydrocracking catalysts to study the yields and characteristics of the products. Liquid products were obtained with a yield of 88–92 wt.% and gas products with a yield of 12–8 wt.%. After dehydration by azeotropic distillation, liquid products were separated on the oil fraction boiling below 360 °C, and pitch fractions boiling above this temperature. In the balance of distillation, it is clear that only the cracking activity of NiW/Al₂O₃ and Y zeolite catalysts is so high that the raw material containing 5 vol.% fraction boiling below 200 °C provides a product comprising approx. 12,5 vol.% of this fraction. The influence of five different catalysts on the yield of 18 poly aromatic hydrocarbons (PAHs) in the hydrocracking products have been investigated by GC/MS. The results indicate that NiW/Al₂O₃ and Y zeolite catalysts have the highest catalytic activity for light aromatic formation (the highest yield of fraction boiling below 200 °C) and aromatic condensed aromatic cracking (PAHs). After the hydrocracking NiW/Al₂O₃ catalyst, the total yields of PAHs decrease 52.7% as that of raw coal tar.     

Study on solid waste pyrolysis coke catalyst for catalytic cracking of coal tar

Low value solid waste pyrolysis coke was used as a catalyst to catalytically crack gas-phase tar to improve tar yield and gas production. Pyrolysis coke with different pyrolysis final temperature and pyrolysis time were prepared, the effect of tar cracking products was studied, and the optimal pyrolysis coke were screened. The pyrolysis coke catalyst was characterized by BET, FTIR, SEM. The results show that the optimal preparation final temperature of pyrolysis coke is 750 °C, and the optimal preparation pyrolysis time is 2 h. Compared with the pyrolysis of raw coal, the tar cracking rate increased by 9.3%, after added the pyrolysis coke catalyst, the gas increased by 23.2%, and the light component increased to 36.6%. And the OH, C–N and C–O–C functional groups present on coke are the factors that affect the catalytic cracking.     

生物质气化气中焦油催化裂解模型

生物质流化床气化气中焦油的催化裂解模型一般采用简单的一阶集总动力学反应,在一些应用方面不够完善.文章在Shamsi和Aznar的模型之上引出了微观反应动力学模型.该模型建立在二集总或焦油的不同种类基础之上,它有4个动力学常数.每一个集总反应都包括热裂解和催化裂解反应.选择Corella的试验为对象,催化温度为840 ℃左右,将硅藻土和镍基水蒸气重整型催化剂(ICI 46-1)在小型试验台上所得到的数据应用于此微观模型,得到的4个动力学常数是相互关联的,并且符合试验结果,在焦油催化裂解研究方面取得了一大进步.     

生物质气化发电燃气焦油脱除方法的探讨

生物质气化发电技术的最大难点之一就是如何除去燃气中含有的焦油等污染物,这些成分会对燃气轮机或内燃机等设备造成一定的影响.因此生物质气化发电过程中燃气焦油的脱除是目前国内外重点研究和解决的课题之一.文章在研究国内外大量有关文献资料的基础上,深入阐述了气化过程中焦油产生的机理、影响焦油生成的因素以及焦油的脱除方法,重点探讨了目前较为有效的焦油热化学脱除方法,即焦油的热裂解和催化裂解方法,以期为生物质气化发电燃气焦油的脱除提供一些思路和参考.     

复合式低焦油固定床生物质气化装置研究

综合分析上吸式固定床及下吸式固定床生物质气化装置各自特点,提出复合式低焦油固定床生物质气化装置,建立生物质原料处理量为600 kg/h的中试规模试验装置并开展研究。研究结果表明:复合式低焦油固定床生物质气化装置具有结构简单、气化效率高、热效率高、碳转化率高、原料适用性广等优点,极大程度提高了燃气清洁程度,对于生物质气化、发电、供热、化石燃料替代等领域的工业化应用起到了极大的推动作用。     

Experimental study on coal multi-generation in dual fluidized beds

An atmospheric test system of dual fluidized beds for coal multi-generation was built.One bubbling fluidized bedis for gasification and a circulating fluidized bed for combustion.The two beds are combined with two valves:one valve to send high temperature ash from combustion bed to the gasification bed and another valve to sendchar and ash from gasification bed to combustion bed.Experiments on Shenhua coal multi-generation were madeat temperatures from 1112 K to 1191 K in the dual fluidized beds.The temperatures of the combustor are stableand the char combustion efficiency is about 98%.Increasing air/coal ratio to the fluidized bed leads to theincrease of temperature and gasification efficiency.The maximum gasification efficiency is 36.7% and thecalorific value of fuel gas is 10.7 MJ/Nm3.The tar yield in this work is 1.5%,much lower than that of pyrolysis.Carbon conversion efficiency to fuel gas and flue gas is about 90%.