Utilization of High Calcium Biogas Residue for Biochar Adsorbent Preparation and Its Soil Improvement Properties
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摘要: 为解决酿酒沼渣的资源化问题，采用热解法制备沼渣生物炭，通过批量吸附试验和盆栽试验考察其吸附性能和土壤改良性能.结果表明：700 ℃下限氧热解1.5 h所制备的高钙沼渣生物炭，初始pH为10时，吸附量最大，投加10 g·L-1的沼渣生物炭对实际废水COD、NH4+-N和TP的去除率分别可达45.29%、56.10%和86.33%，吸附符合拟一阶动力学模型和Langmuir等温吸附，属于物理吸附.吸附后生物炭表面C、N、P、O元素含量显著增加，出现新的N-H、P=O基团.当投加5%的吸附后生物炭时，土壤中速效磷、速效钾及有机质的含量均显著提高，小白菜生长得到促进.本研究探索了“一处理两用”的策略，为酿酒沼渣处置和资源回收提供了一种本土方法.Abstract: In order to solve the problem of resource utilization of brewing biogas residue, the biochar prepared by brewing biogas residue was added into garden soil. A batch incubation and absorption experiments were carried out with the amended soils to study the improvement of biochar addition on adsorption availability and soil physicochemical properties. Results show that: the high calcium biochar prepared by oxygen limited pyrolysis method at 700 ℃ for 1.5 h behaved best with initial pH 10, the removal rates of COD, NH4+-N and TP in actual wastewater by adding 10 g·L-1 biogas biochar can reach 45.29%, 56.10% and 86.33%, respectively. Langmuir isothermal model and pseudo-first-order kinetic equation were more consistent with its adsorption characteristics, indicating the physical adsorption were the main adsorption modes. The contents of C, N, P and O elements on the biochar surface increased significantly with new N-H and P=O groups generated after the adsorption. The available phosphorus, available potassium and organic matter in soil were significantly increased with 5% of adsorbed biochar added which could promote the growth of Chinese cabbage well. This study explored a 'one treatment but two uses' approach, which provides an application prospect for the disposal and resource recovery of biogas residue.
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Key words:
- brewing biogas residue /
- biochar /
- adsorbents /
- wastewater treatment /
- soil conditioners
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图 1 BC-2 h在不同温度下热解对吸附效果的影响
Fig. 1. Effect on adsorption of BC-2 h in different temperatures
图 2 BC-700 ℃不同热解时长对吸附效果的影响
Fig. 2. Effect on adsorption of BC-700 ℃ in different pyrolysis times
图 5 BC吸附前后有机废水三维荧光光谱分析图
a.为吸附前；b.为吸附后
Fig. 5. Three-dimensional fluorescence spectra of organic wastewater
图 7 BC吸附磷酸盐和NH4+-N的吸附等温线
Fig. 7. Adsorption isotherm of BC adsorption for phosphate and NH4+-N
图 8 吸附前BC(a~d)与吸附后BC(e~h)的电镜扫描图
Fig. 8. SEM of unabsorbed BC (a-d) and adsorbed BC (e-h)
图 16 吸附前后BC对土壤中碱解氮(a)和全氮(b)的影响
Fig. 16. Effects of BC on alkali-hydrolyzed nitrogen (a) and total nitrogen (b) in soil
图 17 吸附前后BC对土壤中速效磷(a)和全磷(b)的影响
Fig. 17. Effect of BC on available phosphorus (a) and total phosphorus (b) in soil
图 18 吸附前后BC对土壤中速效钾(a)和全钾(b)的影响
Fig. 18. Effect of BC on available potassium (a) and total potassium (b) in soil
图 19 吸附前后BC对土壤中有机质含量的影响
Fig. 19. Effect of BC on the content of organic matter in soil
表 1 试验所用沼渣及废水水质
Table 1. Composition of brewing biogas residue and wastewater
沼渣性质 含量 水质指标 指标范围 灰分(%) 45.96 COD(mg·L-1) 340~370 挥发性固体(%) 54.04 NH4+-N(mg·L-1) 9.5~10.8 有机质(g·Kg-1) 418.30 TN(mg·L-1) 28~30 硅(g·Kg-1) 4.00 TP(mg·L-1) 73~76 钙(g·Kg-1) 11.80 pH 7.6~8.1 镁(g·Kg-1) 14.72 温度(℃) 20~30 pH 6.80 色度(倍数) 200 
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表 2 BC对磷酸盐和NH4+-N的吸附动力学模型拟合参数
Table 2. Fitting parameters of adsorption kinetics model for phosphate and NH4+-N
模型 参数 磷酸盐 NH4+-N Pseudo-first-order
$ {q}_{\mathrm{t}}={q}_{\mathrm{e}}(1-{\mathrm{e}}^{-{k}_{1}t}) $qe(mg·g-1) 2.430 0 0.350 9 k1(min-1) 0.268 4 0.025 7 R2 0.988 24 0.989 5 Pseudo-second-order
$ {q}_{\mathrm{t}}=\frac{{k}_{2}{q}_{\mathrm{e}}^{2}t}{1+{k}_{2}{q}_{\mathrm{e}}t} $qe(mg·g-1) 2.829 0 4.097 3 k2(g·mg-1·min-1) 0.010 7 0.007 0 R2 0.979 4 0.970 9
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表 3 BC对磷酸盐和NH4+-N的吸附等温线拟合参数
Table 3. Fitting parameters of adsorption isotherm for phosphate and NH4+-N
等温线模型 参数 磷酸盐 NH4+-N Langmuir
$ {q}_{\mathrm{e}}=\frac{{q}_{\mathrm{m}\mathrm{a}\mathrm{x}}{K}_{\mathrm{L}}{C}_{\mathrm{e}}}{1+{K}_{\mathrm{L}}{C}_{\mathrm{e}}} $qmax (mg·g-1) 78.001 0 6.183 27 KL (L·mg-1) 0.031 28 0.066 80 R2 0.984 27 0.992 92 Freundlich
$ {q}_{\mathrm{e}}={K}_{\mathrm{F}}{C}_{\mathrm{e}}^{\frac{1}{n}} $KF (mg·g-1) 8.012 5 0.663 29 1/n 0.434 5 0.538 66 R2 0.958 39 0.977 06
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表 4 吸附前后BC对小白菜出苗率、根冠比、比根长、比根表面积影响
Table 4. Effects of BC on seedling emergence rate, root shoot ratio, specific root length and specific root surface area
处理 出苗率(%) 根冠比 比根长(m·g-1) 比根表面积(cm2·g-1) CK 80 0.040 42.93 304.75 BC-1% 90 0.032 111.01 687.94 BC-3% 90 0.035 99.16 534.47 BC-5% 100 0.033 83.58 448.25 吸附后BC-1% 100 0.044 82.06 538.29 吸附后BC-3% 100 0.032 93.22 520.17 吸附后BC-5% 100 0.003 150.25 956.48
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