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摘要: 采用热重红外质谱联用法(TG-FTIR-MS)和水平管式热解炉/化学吸收法,对比研究了矿化垃圾(ARDF)和常规垃圾(NRDF)衍生燃料热解过程腐蚀性气体(HCl和H2S)的析出特性,分析了热解温度及热解类型对析出行为的影响并对热解固相产物腐蚀性元素的赋存特点进行了考察。结果表明,慢速热解过程,两者腐蚀性气体的析出特征温度区间相似,均分为两段,HCl析出区间为200-400和420-500 ℃,H2S析出区间为230-370和380-670 ℃,而ARDF表现为较低的HCl和H2S析出率;快速热解过程,两者腐蚀性气体的析出受热解温度影响较大,且规律有所差别:随热解温度的升高,HCl析出率呈S型变化(先高后低再高),而H2S析出率呈正相关,均在850 ℃达到峰值,其中,HCl析出率分别为48.8%(ARDF)和29.4%(NRDF),H2S析出率分别为6.8%(ARDF)和44.6%(NRDF)。因腐蚀性气体差异性的析出规律,两类垃圾热解固相产物腐蚀性元素的赋存与热解温度相关,ARDF的Cl和S元素最高赋存率分别可达59.4%(450 ℃)和84.3%(750 ℃),而NRDF的Cl和S元素最高赋存率分别仅为36.7%(850 ℃)和15.2%(650 ℃)。说明在合适的热解条件下,相比NRDF,ARDF腐蚀性元素不易释放,倾向于固相赋存,此为不同垃圾衍生燃料的热利用提供了一定依据和参考。Abstract: Based on the horizontal tubular reactor-chemical absorption together with TG-FTIR-MS methods, release characteristics of corrosive gases, viz., HCl and H2S, during pyrolysis of refuse derived-fuels were investigated. The effects of pyrolysis temperature and pyrolysis type on their release behaviors for the aged (ARDF) and normal (NRDF) categories were compared. Meanwhile, the occurrence properties of corrosive elements (Cl and S) in solid products were also explored. The results indicate that the release of each corrosive gas has similar characteristic temperature range for slow pyrolysis of two categories. The release of HCl occurs at 200-400 and 420-500℃, respectively, while the emission of H2S is observed at 230-370 and 380-670℃, respectively. In addition, ARDF has a lower emission amounts of both HCl and H2S compared to NRDF under this condition. With regard to fast pyrolysis, the release of corrosive gases show different regularities, which largely depends on pyrolysis temperature. With increasing temperature, the emission of HCl and H2S present a nonlinear and an increasing trends, respectively, reaching peak values at 850℃; It is 48.8% (ARDF) and 29.4% (NRDF) for HCl, 6.8% (ARDF) and 44.6% (NRDF) for H2S. Subsequently, due to the distinctive release characteristics of corrosive gases, the occurrence of corrosive elements in solid phase relating to temperature differs in two categories. The retained amounts of Cl and S reach to 59.4% (450℃) and 84.3% (750℃) for ARDF, respectively. But for NRDF, that is 36.7% (850℃) and 15.2% (650℃), repetitively. It can be inferred that ARDF has the more stable corrosive elements difficult to be released into gases, which could provide some guidelines on thermal utilization of refuse derived-fuels.
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Key words:
- HCl /
- H2S /
- aged refuse derived-fuels /
- normal refuse derived-fuels /
- pyrolysis
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表 1 ARDF和NRDF的元素分析与工业分析
Table 1 Ultimate and proximate analysis of ARDF and NRDF
Sample Ultimate analysis wdb*/% Proximate analysis wdb*/% C H N O** total
Sinorganic
Stotal
Clinorganic
ClA V FC ARDF 35.95 2.56 0.85 18.29 0.65 0.103 0.95 0.46 41.68 40.75 17.57 NRDF 57.26 6.23 0.87 22.64 0.15 0.007 1.37 0.14 11.48 75.96 12.56 *: dried basis;**: calculated by difference 表 2 ARDF和NRDF的HCl红外吸收峰峰面积及HCl相对析出率计算值RHCl
Table 2 Absorbance area of HCl and RHCl of HCl from ARDF and NRDF
Sample Area of
peak AArea of
peak BResult
of RHClARDF 0.6632 0.4344 115.5 NRDF 2.973 0.7283 270.2 表 3 ARDF及NRDF的H2S离子吸收峰峰面积及H2S相对析出率计算值RH2S值
Table 3 Ion current area of H2S and RH2S of ARDF and NRDF
Sample Area of
peak A
/ 1×10-11Area of
peak B
/ 1×10-11Result of
RH2S
/ 1×10-9ARDF 0.861 0.316 1.811 NRDF 1.276 1.792 20.453 -
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