Correlation mechanism between structure and gasification characteristics of typical municipal solid waste (MSW) disposable bamboo chopsticks hydrochar
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摘要: 由于城市生活垃圾(MSW)成分复杂、物料特性波动大、能量密度低，导致对其水热炭的气化特性认识不足，研究单一成分的水热炭气化特性具有重要意义。本文以MSW的典型成分一次性竹筷子(DBC)为原料，研究水热炭化(HTC)条件对DBC水热炭结构性质与气化反应特性的影响规律。结果表明，HTC提高了DBC的能量品质，水热处理后DBC-230-60的高位热值(HHV)是DBC的1.62倍，H/C和O/C从DBC的1.57和0.76下降到DBC-230-60的1和0.33。表征发现水热炭和水热炭半焦的芳构化程度比DBC原样更高，水热炭的比表面积要低于DBC原样，但水热炭半焦的比表面积却要高于DBC原样半焦。相比于水热时间，水热温度对水热炭结构和气化反应性的影响更加显著。更高的水热温度增大了水热炭的芳构化程度，降低了水热炭的气化反应性。水热炭的气化反应性要比DBC原样更差，主要是因为水热炭半焦芳构化程度增大对气化反应性的消极作用大于孔隙结构丰富的促进作用。Abstract: Due to the complex composition, large fluctuation of material characteristics and low energy density of MSW, the gasification characteristics of its hydrochars are not well understood. Therefore, it is of great significance to study the gasification characteristics of single component hydrochars. In this paper, a typical component of MSW, disposable bamboo chopsticks (DBC), was used as raw material to study the effect of hydrothermal carbonization (HTC) conditions on the structural properties and gasification reaction characteristics of DBC hydrochars. The results showed that HTC improved the energy quality of DBC, the HHV of DBC-230-60 sample was 1.62 times of that of DBC, and H/C and O/C decreased from 1.57 and 0.76 of original sample to 1 and 0.33 of DBC-230-60. The results of characterization also demonstrate that the aromatization degree of hydrochar and hydrochar semicoke is higher than that of the DBC original one. The specific surface area of hydrochar is lower than that of DBC original sample, but hydrochar semicoke is higher than that of DBC original sample semicoke Compared with hydrothermal time, hydrothermal temperature had the more significant effect on the structure and gasification reactivity of hydrochar. Higher hydrothermal temperature increases the aromatization degree of hydrochar and decreases the gasification reactivity of hydrochar. The gasification reactivity of hydrochar is worse than that of DBC original sample, mainly because the increase of the degree of semicoke arbulization of hydrochar has a greater negative effect on the gasification reactivity than the abundance of pore structure.
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Key words:
- msw /
- hydrochar /
- gasification behavior /
- reactivity
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图 1 (a)不同水热温度(120、150、180、200、230 ℃)，水热时间为60 min条件下水热炭的收率曲线；(b)不同水热时间(30、60、90 min)，水热温度为200 ℃条件下水热炭的收率曲线
Figure 1 (a) Yield curves of hydrochar under different hydrothermal temperatures (120, 150, 180, 200, 230 ℃) and hydrothermal time of 60 min; (b) Yield curves of hydrochar at 200 ℃ for different hydrothermal time (30, 60, 90 min)
图 3 不同工艺条件水热炭的范式原子比例图
Figure 3 Van Krevelen diagram of hydrochar with different process conditions
图 4 不同工艺条件水热炭的红外曲线
Figure 4 FT-IR curve of hydrochar with different process conditions
图 5 不同工艺条件水热炭的XRD曲线
Figure 5 XRD curves of hydrochar with different process conditions
图 6 不同工艺条件水热炭的拉曼曲线
Figure 6 Raman curves of hydrochar with different process conditions
图 7 不同工艺条件水热炭拉曼峰的面积比
Figure 7 Area ratio of Raman peak of hydrochar with different process conditions
图 8 不同工艺条件水热炭的TG(a)、DTG(b)曲线
Figure 8 TG(A) and DTG(B) curves of hydrochar under different process conditions
图 9 CO2气氛下水热炭在900 ℃的炭转化率曲线
Figure 9 Carbon conversion curve of hydrochar in CO2 atmosphere at 900 ℃
图 10 不同工艺条件水热炭热解半焦的红外曲线
Figure 10 FT-IR curves of pyrolysis semi-coke of hydrochar under different process conditions
图 11 DBC-900、DBC-120-60-900、DBC-230-60-900半焦的扫描电镜图。(a, c, e)为三个样品在1K放大倍率下的扫描电镜图；(b, d, f)为三个样品在10K放大倍率下的扫描电镜图。
Figure 11 SEM images of DBC-900, DBC-120-60-900, DBC-230-60-900 pyrolysis semi-coke. (a, c, e) are SEM images of three samples at 1 K magnification; (b, d, f) are SEM images of three samples at 10 K magnification
图 12 不同工艺条件水热炭热解半焦比表面积与气化平均转化速率关系曲线
Figure 12 Relationship between specific surface area and average gasification conversion rate of pyrolysis semi-coke of hydrochar under different process conditions
图 13 不同工艺条件水热炭热解半焦拉曼峰面积比与气化平均转化速率关系曲线
Figure 13 Relationship between Raman peak area ratio and average gasification conversion rate of pyrolysis semi-coke of hydrochar under different process conditions
表 1 DBC的基本性质
Table 1 Basic properties of DBC
Sample Ultimate analysis wd/% Proximate analysis wd/% Atomic ratio HHV(MJ/kg) C H O N S A V FC O/C H/C DBC 45.85 6.01 46.43 0.6 0.36 0.75 85.48 13.76 0.76 1.57 14.63 
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表 2 水热炭制备的工况参数
Table 2 Operating parameters of hydrochar preparation
Sample Hydrothermal temperature (℃） Hydrothermal time (time) Stirring speed (r/min) Heating rate (℃/min) Solid-liquid ratio DBC-120-60 120 60 150 3 1∶10 DBC-180-60 180 60 150 3 1∶10 DBC-200-30 200 30 150 3 1∶10 DBC-200-60 200 60 150 3 1∶10 DBC-200-90 200 90 150 3 1∶10 DBC-230-60 230 60 150 3 1∶10
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表 3 DBC水热炭的元素分析、原子比和C回收率
Table 3 Elemental analysis, atomic ratio and C recovery of DBC hydrocar
Sample Ultimate analysis wd/% Atomic ratio C recovery rate/% C H O N S O/C H/C DBC 45.85 6.01 46.43 0.60 0.36 0.76 1.57 100.00 DBC-120-60 48.41 6.10 44.92 0.46 0.08 0.72 1.51 82.55 DBC-180-60 52.29 6.10 41.03 0.54 0.02 0.59 1.40 65.86 DBC-200-30 52.98 5.86 40.59 0.54 0.02 0.58 1.33 66.12 DBC-200-60 54.79 5.85 38.76 0.58 0.01 0.53 1.28 67.41 DBC-200-90 53.90 5.96 39.51 0.58 0.04 0.55 1.32 67.97 DBC-230-60 65.25 5.43 28.64 0.67 0.00 0.33 1.00 60.68
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表 4 DBC水热炭的工业分析、热值、能量密度和能量回收率
Table 4 Industrial analysis, HHV, energy density and energy recovery of DBC hydrochar
Sample Proximate analysis wd/% Atomic ratio HHV(MJ/kg) ED/% ERE/% A V FC O/C H/C DBC 0.75 85.48 13.76 0.76 1.57 14.63 100.00 100.00 DBC-120-60 0.03 91.09 8.88 0.72 1.51 15.88 108.54 84.86 DBC-180-60 0.02 87.29 12.70 0.59 1.40 17.90 122.35 65.10 DBC-200-30 0.01 83.60 16.39 0.58 1.33 17.91 122.42 57.25 DBC-200-60 0.01 81.00 18.99 0.53 1.28 18.85 128.84 59.37 DBC-200-90 0.01 83.07 16.93 0.55 1.32 18.55 126.79 56.90 DBC-230-60 0.01 65.35 34.64 0.33 1.00 23.70 162.00 54.48
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表 5 XRD的结构参数
Table 5 Structural parameters of XRD
Sample Lc/nm Iπ/Iγ Aromaticity DBC 0.22 0.68 0.38 DBC-180-60 0.50 2.01 0.60 DBC-200-60 0.60 1.79 0.46 DBC-230-60 0.61 1.98 0.53
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表 6 水热炭的比表面积及平均孔径
Table 6 Specific surface area and average pore size of hydrochar
Sample SBET/(m2·g−1) Average pore size(nm) DBC 94.14 15.09 DBC-120-60 18.28 39.46 DBC-180-60 13.43 65.34 DBC-200-60 21.94 34.56 DBC-230-60 10.94 47.02
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表 7 水热炭热解半焦的比表面积及平均孔径
Table 7 Specific surface area and average pore size of pyrolysis semi-coke of hydrochar
Sample SBET/(m2·g−1) Average pore size(nm) DBC-900 117.80 2.50 DBC-120-60-900 540.60 1.65 DBC-180-60-900 510.71 1.59 DBC-200-60-900 515.29 1.60 DBC-230-60-900 475.74 1.61
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