Effects of the addition of coal ash on the transformation of different types of inorganic K in biomass during gasification
HE Zimeng;DENG Yujie;SHI Wenju;CAO Jingpei;ZHAO Xiaoyan
钾(K)是生物质中一种主要无机元素,在生物质气化过程中它的迁移转化会造成结渣、积灰和灰团聚等问题,掺杂富含硅(Si)和铝(Al)的煤灰是解决这些问题的有效途径之一。大部分生物质中K主要以K2CO3、K2SO4和KCl等水溶性无机盐形式存在,但不同种类生物质中这几种无机K盐组成差异较大,导致气化过程中灰团聚、结渣行为有较大差异。因此,该研究利用了负载K2CO3、K2SO4和KCl的松木模拟含不同无机形态K的生物质,在水蒸气和CO2气氛下,系统研究了气化过程中煤灰对不同无机形态K迁移转化和在流化床条件下(石英砂为床料)灰团聚行为的影响。研究发现,尽管2种煤灰的晶体矿物组成不同,在气化过程中它们均与负载K2CO3和K2SO4的松木反应形成了钾霞石(KAlSiO4)。然而,对于负载KCl的松木,相比于水蒸气气氛,由于煤灰在CO2气氛下生成钾霞石的能力较弱,因此大部分KCl主要通过物理吸附保留,导致K保留比较低。另外,负载KCl的松木气化残渣中K的保留比显著低于负载K2CO3或K2SO4的松木,说明生物质中KCl易挥发且与煤灰的反应较弱,更易造成灰沉积和腐蚀等问题。然而,热力学平衡计算表明3种K盐和煤灰反应主要生成白榴石或长石,与实验结果差别较大。最后,尽管煤灰的加入不能阻止团聚物形成,但抑制了负载K盐的松木和石英砂生成低温熔融硅酸钾的过程,使形成的团聚物更易破碎,可以有效缓解流化床中的灰团聚等问题。
Potassium (K) is a major inorganic element in biomass. The transformation of K during biomass gasification can cause slagging, ash deposition and agglomeration problems. The addition of coal ash rich in Si and Al is one of the effective methods to solve these problems. In most biomass, K mainly exists in the form of water-soluble inorganic salts, such as K2CO3, K2SO4 and KCl. However, the content of these K salts varies significantly with the species of biomass, which leads to the significant differences in the agglomeration and slagging behaviors during gasification. Therefore, the research utilized pine wood doped with K2CO3, K2SO4 and KCl to simulate different types of inorganic K in biomass. The effect of coal ash on the agglomeration in the fluidized-bed reactors (silica sand as the bed material) and the transformation of different types of inorganic K in biomass was studied systematically during steam and CO2 gasification. Although two kinds of coal ash with different mineral compositions were used, the K2CO3-doped and K2SO4-doped pine wood react with both kinds of ash to form kaliophilite (KAlSiO4) during gasification. However, under the CO2 atmosphere, for the KCl-doped pine wood, most of KCl is mainly retained by physical adsorption because the ability to form KAlSiO4 is weaker than that under the steam atmosphere, which results in a lower K retention ratio under the CO2 atmosphere. In addition, the K retention ratio of KCl-doped pine wood is significantly lower than that of pine wood loaded with K2CO3 and K2SO4, which suggests that KCl in biomass tends to release and reacts with coal ash only to a limited extent. Therefore, KCl in biomass is more likely to cause ash deposition or corrosion problems. However, the results of thermodynamic equilibrium calculations indicate that the reaction between the three types of K salts and coal ash mainly forms leucite or feldspar, which are significantly different from the experimental results. Lastly, although the addition of coal ash cannot stop the formation of agglomerates, it inhibits the formation process of low melting-point K silicates generated from the reaction between silica sand and K-salt-doped pine wood. Also, coal ash makes the agglomerates to be broken more easily, thus mitigating the agglomeration problem in fluidized-bed reactors effectively.
biomass;coal ash;inorganic potassium;gasification;migration and transformation;ash agglomeration
主办单位:煤炭科学研究总院有限公司 中国煤炭学会学术期刊工作委员会