Comparative study on evaluation methods of accurate acid production potential of coal gangue
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摘要: 为有效避免重大酸性水污染事故，需提高矿山岩石产酸潜力评价的精度。通过全面阐述矸石中常见含硫矿物的产酸潜力计算方法，采用三步连续提取法测定了多个矿石和煤矸石中产酸矿物的硫含量，对比分析了精确产酸潜力和最大产酸潜力。结果表明：煤矸石的产酸潜力值取决于各产酸硫的质量分数和单位硫产酸值；对大部分样品，用产酸硫含量计算的产酸潜力值不同程度地低于用全硫预测的产酸潜力值；样品SC中的硫成分主要为砷黄铁矿硫，相比黄铁矿的单位硫产酸值更高，导致SC样品计算的精确产酸潜力相比全硫预测的产酸潜力更高；三步连续提取法适用于以铁和铜的硫化物为主要含硫矿物的煤矸石；当矿石中其他硫化物成分增多和空白样品混合不均匀都会对结果产生一定干扰。研究结果为准确评价矿区煤矸石精确产酸潜力提供了依据。Abstract: In order to prevent major acid drainage pollution accidents, this study aims to improve the accuracy of acid production potential evaluation of mine rocks in the prediction of acid drainage. Specifically, this paper introduced existing calculation methods of acid-producing potential, and then determined the acid-producing mineral contents in some sulfur minerals and coal gangue samples by three-step sequential extraction method, which is then compared with the traditional method of calculating the maximum acid-producing potential by measuring total sulfur. Results show that: 1) the acid-producing potential of coal gangue is dependent on the mass percentage content of each acid-producing sulfur and the corresponding unit acid value; 2) except for sample SC, the acid-producing potential calculated by acid-producing sulfur content is lower than(with different degrees) the acid-producing potential predicted by total sulfur. The sulfur in the sample SC is mainly arsenopyrite sulfur, which has a higher acid value per unit than pyrite sulfur, resulting in a higher acid potential calculated by SC sample than predicted by total sulfur; 3) the three-step sequential extraction is suitable for samples with iron and copper sulfides as the main sulfur minerals; 4) when other sulfide components increase and blank samples are unevenly mixed, the results will be disturbed to some extent. This research provides evidences to justify the evaluation of accurate acid production potential of coal gangue in mining area.
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图 2 10个样品的XRD图谱
Q—石英；L—伊利石；K—高岭石；Py—黄铁矿；S—菱铁矿；D—白云石；Pol—多硅锂云母；Mgr—硒砷铜矿；G—方铅矿；Ars—砷黄铁矿；Po—磁黄铁矿；sp—闪锌矿；B—斑铜矿；Ch—黄铜矿；Cas—锡石；C—方解石；H—赤铁矿
Figure 2. XRD patterns of ten samples
图 3 各步骤“实测硫损失值/计算总硫值”
Figure 3. Measured sulfur loss value/calculated total sulfur value in each step
图 4 样品的两种产酸潜力比较
Figure 4. Comparison of acid production potential PPA and MPA of each sample
表 1 常见含硫矿物每摩尔硫的产酸系数[18]
Table 1. Acid production coefficient per mole of sulfur produced by common sulfur-containing minerals[18]
含硫矿物 pH近中性下的理论终产物 单位硫产酸系数 相对黄铁矿的产酸倍数 FeS2和Fe1-xS Fe(OH)3，H+，SO42- 2 1 FeAsS Fe(OH)3，H+，
SO42-，HAsO42-4 2 ZnS Zn2+，SO42- 0 0 PbS Pb2+，SO42- 0 0 CuFeS2 Fe(OH)3，H+，SO42-，
Cu(OH)2，Cu2+1~2 0.5~1 MoS2 MoO42-，
SO42-，H+3 1.5 FeSO4·7H2O Fe(OH)3，H+，
SO42-，H2O2 1 KFe3(SO4)2
(OH)6K+，Fe(OH)3，
H+，SO42-1.5 0.75 
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表 2 XRD检测结果
Table 2. XRD test results of samples
样品编号 矿物成分 MGS 石英、高岭石、菱铁矿 WJL 石英、高岭石、伊利石、黄铁矿 HB 石英、白云石、菱铁矿 HN 石英、高岭石 SC 石英、高岭石、砷黄铁矿、磁黄铁矿、砷铜矿 KW1 石英、菱铁矿、磁黄铁矿、黄铁矿 KW2 方解石、黄铁矿 KW3 石英、斑铜矿、赤铁矿 KW4 黄铜矿、锡石 KW5 方铅矿、闪锌矿
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表 3 硫测定结果占原样的质量分数
Table 3. The ratio of sulfur determination results to the mass of the original sample
% 样品编号 艾士卡全硫 碳硫仪全硫 全硫 水萃取后总硫 焙烧后总硫 酸萃取后总硫 MGS 0.217 0.565 0.565 0.511 0.641 — WJL 3.131 2.411 2.411 4.334 0.058 — HB 0.087 0.203 0.203 0.225 0.581 — HN 2.039 2.248 2.248 1.602 0.086 — SC 8.189 10.277 8.189 7.806 2.739 2.233 KW1 2.780 2.613 2.613 2.360 0.272 0.099 KW2 1.823 3.000 3.000 2.988 0.443 0.486 KW3 0.657 1.111 1.111 1.105 0.702 0.329 KW4 0.459 1.793 1.793 1.756 0.672 0.111 KW5 0.945 1.257 1.257 1.201 1.166 0.941 注：MGS、WJL、HB样品未采用。
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表 4 水萃取液ICP测定结果
Table 4. ICP determination results of water extraction
mg/L 样品编号 Fe Mg Ca S LHN 0.008 1.216 2.664 5.447 LSC 0.410 4.237 4.340 9.693 LKW1 0.695 0.322 0.704 1.579 LKW2 0.052 0.273 1.127 1.286 LKW3 0.002 0.230 0.691 0.141 LKW4 0.002 0.239 2.317 1.209 LKW5 0.009 0.255 0.687 0.335
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表 5 盐酸萃取液ICP测定结果
Table 5. ICP determination results of hydrochloric acid extraction
mg/L 样品编号 Fe S Cu Li As K LHN 4.377 4.146 1.927 LSC 79.551 12.994 0.080 1.168 63.649 LKW1 6.337 3.419 LKW2 4.801 2.017 LKW3 3.429 7.871 38.416 LKW4 8.453 11.013 23.424 LKW5 2.644 3.868
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表 6 各步骤中硫占原样的质量分数
Table 6. The ratio of sulfur loss in each step to the mass of the original sample
% 各步骤中的硫质量分数 HN SC KW1 KW2 KW3 KW4 KW5 全硫 2.248 8.189 2.613 3.000 1.111 1.793 1.257 平行样-水萃取后总硫 1.602 7.806 2.360 2.988 1.105 1.756 1.201 ICP-水萃取硫 0.022 0.039 0.006 0.005 0.001 0.005 0.001 计算总硫(非测定值) 1.624 7.845 2.366 2.993 1.106 1.761 1.202 焙烧损失硫 1.516 5.067 2.088 2.545 0.403 1.084 0.035 ICP-酸萃取硫 0.166 0.520 0.137 0.080 0.315 0.441 0.155 残余硫 未测定 2.233 0.099 0.486 0.329 0.111 0.941 累加硫(非测定值) 1.704 7.859 2.330 3.116 1.048 1.641 1.132
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表 7 各步骤“实测硫损失值/计算总硫值”
Table 7. Measured sulfur loss value/calculated total sulfur value in each step
% 各步骤硫的损失/计算总硫 HN SC KW1 KW2 KW3 KW4 KW5 ICP-水萃取硫/计算总硫 1.35 0.50 0.25 0.17 0.10 0.28 0.10 焙烧损失硫/计算总硫 93.34 64.59 88.25 85.03 36.44 61.55 2.91 ICP-酸萃取硫/计算总硫 10.22 6.63 5.79 2.67 28.48 25.04 12.90 残余硫/计算总硫 0.00 28.46 4.18 16.24 29.75 6.30 78.29 累加硫/计算总硫 104.91 100.18 98.47 104.11 94.77 93.17 94.20
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表 8 三种提取方法对10个单一成分含硫矿物的提取效果[15]
Table 8. Extraction effects by the three extraction methods on 10 single-component sulfur-containing minerals[15]
含硫矿物* 4 mol/L HCl
16 h550 ℃焙烧
1 h550
℃焙烧1 h +
4 mol/L HCl(0.5 h)萃取/损失的硫/% 黄钾铁矾 90 — 100 黄铁矿 0 100 — 砷黄铁矿 8 100 — 闪锌矿 24 5 8 磁黄铁矿 62 86 95 方铅矿 76 1 15 铜蓝 11 50 97 辉铜矿 15 20 85 斑铜矿 21 35 95 黄铜矿 33 45 95 * 由对应含硫矿物(5 %)和石英(95 %)组成。
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