CN116930441A - Method for accurately judging heavy metal sources in mine water of coal mine - Google Patents
Method for accurately judging heavy metal sources in mine water of coal mine Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 138
- 239000003245 coal Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002386 leaching Methods 0.000 claims abstract description 13
- 238000004458 analytical method Methods 0.000 claims abstract description 6
- 238000002474 experimental method Methods 0.000 claims abstract description 4
- 239000003673 groundwater Substances 0.000 claims description 28
- 230000009189 diving Effects 0.000 claims description 23
- 239000002352 surface water Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 17
- -1 diving Substances 0.000 claims description 10
- 230000009897 systematic effect Effects 0.000 claims description 8
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004364 calculation method Methods 0.000 claims description 6
- 229910052805 deuterium Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000012512 characterization method Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-NJFSPNSNSA-N oxygen-18 atom Chemical compound [18O] QVGXLLKOCUKJST-NJFSPNSNSA-N 0.000 claims description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000005065 mining Methods 0.000 description 5
- 239000011435 rock Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910002975 Cd Pb Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010219 correlation analysis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1813—Specific cations in water, e.g. heavy metals
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Abstract
The invention discloses a method for accurately judging the source of heavy metals in mine water of a coal mine, and relates to the field of mine water treatment. The method can accurately and quantitatively characterize the heavy metals in the mine water, and further achieves the purpose of obtaining the heavy metal sources of the mine water. The method comprises the following steps: step 1, acquiring water chemistry index parameters; step 2, determining and defining the types of the excessive heavy metals; step 3, primarily judging the potential sources of heavy metals in mine water; step 4, judging the potential sources of heavy metals in the mine water again; step 5, judging possible sources of heavy metals in mine water; step 6, performing coincidence analysis on the judgment result in the step 3-5, wherein the coincidence object is a heavy metal key source in mine water; step 7, taking a coal sample for carrying out a heavy metal leaching experiment to obtain typical heavy metal leaching parameters; and 8, finally judging the true source of the heavy metals in the mine water. Finally, the sources of heavy metals in the mine water can be accurately identified, so that the mine water recycling treatment is facilitated.
Description
Technical Field
The invention relates to the field of mine water treatment, in particular to a method for accurately judging the source of heavy metals in mine water of a coal mine.
Background
Along with the high-intensity exploitation of coal in China, the mine water discharge amount is also increased sharply. Many toxic and harmful heavy metal elements exist in mine water, so that the mine water cannot be directly utilized, however, the mine water is directly discharged, so that not only is the water resource of a coal production area seriously wasted, but also surrounding water bodies can be polluted, and the ecological environment of the mining area is destroyed. Therefore, the method has the advantages of accurately judging the heavy metal source in the mine water to carry out the recycling treatment on the mine water, relieving the contradiction between the mine water waste and the water environment protection and water resource utilization, avoiding the ecological environment damage of the mining area, and realizing the green exploitation of the coal resource.
Heavy metals in mine water mainly originate from surrounding coal and rock masses, and on one hand, the coal and rock masses interact with underground water for a long time, and heavy metals enriched in the coal and rock masses are dissolved into the mine water; on the other hand, the coal mining activities change the occurrence environment of the original coal rock mass, and heavy metals can also enter mine water. At present, the technical research of heavy metal underground water in coal mines mainly focuses on the fields of a process, a technology and a device for removing heavy metals in mine water, and the research on heavy metal sources in mine water is relatively few. Conventional methods such as element concentration analysis and correlation analysis only can form qualitative or semi-quantitative conclusions when judging the heavy metal source of mine water, but cannot realize accurate and quantitative characterization.
Therefore, how to accurately and quantitatively characterize heavy metals in mine water becomes a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
Aiming at the problems, the invention provides a method for accurately judging the source of heavy metal in mine water of a coal mine, which can accurately and quantitatively characterize the heavy metal in the mine water, thereby achieving the purpose of acquiring the source of the heavy metal in the mine water.
The technical scheme of the invention is as follows: the method comprises the following steps:
step 1, collecting and detecting coal mine rainwater, surface water, diving, groundwater of each aquifer and mine water, and obtaining water chemical index parameters of the groundwater;
step 2, determining out-of-standard heavy metal types according to water chemistry index parameters of mine water and defining the out-of-standard heavy metal types as typical heavy metals of the mine;
step 3, comparing the mine water with rainwater, surface water, diving, the water chemistry type, delta D and delta of the groundwater of each aquifer 18 O value, primarily judging the potential source of heavy metals in mine water;
step 4, judging the potential sources of heavy metals in the mine water again according to the typical heavy metal concentrations of rainwater, surface water, diving and groundwater of each aquifer;
step 5, classifying rainwater, surface water, diving, groundwater of each aquifer and mine water according to the water chemistry index parameters by adopting a systematic clustering method, and judging possible sources of heavy metals in the mine water;
step 6, performing coincidence analysis on the judgment result in the step 3-5, wherein the coincidence object is a heavy metal key source in mine water;
step 7, taking a coal sample for carrying out a heavy metal leaching experiment to obtain typical heavy metal leaching parameters;
if the total number of typical heavy metals is more than or equal to +1 of the total number of key sources, carrying out the next step; if the total number of typical heavy metals is less than the total number of key sources +1, judging the result of the step 6 as the real source of the heavy metals in the mine water;
and 8, calculating the contribution rates of the heavy metals in the mine water by adopting a chemical mass balance method according to typical heavy metal leaching parameters of the coal sample and typical heavy metal parameters of key sources, and finally judging the real sources of the heavy metals in the mine water.
The above mentioned:
and 3, judging that the potential source conditions of heavy metals in mine water are simultaneously as follows:
the water chemistry type of the condition 1 and the mine water is the same;
condition 2, δd= (90% -110%) δd Mine water ；
Condition 3, delta 18 O＝(90％～110％)δ 18 O Mine water ；
In the above, δD is the value of deuterium, which is a stable isotope of hydrogen, δD Mine water Value delta of stable isotope deuterium of hydrogen in mine water 18 Stable isotope of O as oxygen 18 O value, delta 18 O Mine water Is a stable isotope of oxygen in mine water 18 O value.
And step 4, judging that the potential source conditions of the heavy metals in the mine water are any one of the following conditions:
condition 1, any typical heavy metal concentration exceeds standard;
condition 2, any typical heavy metal concentration reaches 10% of the typical heavy metal concentration in mine water.
And 5, judging that the possible source conditions of heavy metals in the mine water are as follows: is classified into the most recent category with mine water;
the equations involved in the systematic clustering method are:
according to the conventional ions, typical heavy metals, delta D and delta in rainwater, surface water, diving, groundwater in various aquifers and mine water 18 O parameter construction matrix:
wherein x is mn For the nth water chemistry index parameter in the mth water sample, m=4+total number of aquifers, n=9+total number of typical heavy metals;
eliminating the dimensional difference equation:
wherein x is ij Corresponding values after dimension differences are eliminated for the water chemistry index parameters in the raw water sample;
similarity characterization equation:
d is the similarity distance between two types of water samples, i is the ith water sample, j is the jth chemical index parameter, and k is the kth water sample.
And 7, judging the real source conditions of heavy metals in mine water as follows:
condition 1, contribution rate greater than 5%;
the equations involved in the chemical mass balance method are as follows:
the contribution concentration calculation equation:
wherein j=1+ total number of key sources; c (C) i Is the typical heavy metal i concentration in mine water; f (F) ij The mass proportion of the typical heavy metal i in the coal sample or the key source j to all the typical heavy metals; s is S j The contribution concentration of the coal sample or the key source j;
the contribution rate calculation equation:
the beneficial effects of the invention are as follows:
the method is suitable for rapidly and accurately judging the sources of heavy metals in mine water in a coal mine, and aims at the difference between the water chemical index parameters of each water source water chemical environment in a mining area and the water chemical index parameters in the mine water, comprehensive analysis is performed to rapidly and accurately identify the sources of the heavy metals in the mine water, so that the pollution of the heavy metals in the mine water and the recycling treatment of the mine water are reduced, the contradiction between the waste of the mine water, the water environment protection and the water resource utilization is further relieved, the ecological environment damage of the mining area is avoided, and the purpose of green exploitation of coal resources is realized.
Drawings
FIG. 1 is a lineage diagram of the systematic clustering method in this case.
Detailed Description
In order to clearly illustrate the technical features of the present patent, the following detailed description will make reference to the accompanying drawings.
The purpose of the scheme is to find out which of rainwater, surface water, diving and groundwater in each aquifer is the main source of heavy metals in mine water, and the scheme comprises the following steps:
step 1, collecting and detecting coal mine rainwater, surface water, diving, groundwater of each aquifer and mine water, and obtaining water chemical index parameters of the groundwater;
specifically collecting and detecting coal mine rainwater, surface water, fourth-system diving, and system straight Luo Zu aquifer (hereinafter referred to as an I aquifer) groundwater and mine water in a dwarf system, and acquiring water chemistry index parameters of the groundwater and the mine water in a sandstone aquifer (hereinafter referred to as an II aquifer) between coals, wherein the water chemistry index parameters are shown in table 1;
TABLE 1 Water chemistry index parameter table
| Rainwater | Surface water | Diving device | I aqueous phase | II aqueous phase | Mine water | |
| K + | 8.64 | 19.16 | 17.59 | 20.31 | 28.93 | 31.67 |
| Ca 2+ | 16.47 | 64.84 | 216.17 | 127.56 | 197.45 | 203.32 |
| Na + | 7.16 | 498.15 | 945.97 | 1756.18 | 3690.75 | 4860.17 |
| Mg 2+ | 4.52 | 37.24 | 145.76 | 97.86 | 160.73 | 207.41 |
| SO 4 2- | 17.55 | 375.62 | 617.97 | 1256.81 | 3142.22 | 4057.16 |
| HCO 3 - | 37.89 | 235.18 | 364.14 | 504.43 | 424.14 | 396.17 |
| Cl - | 9.31 | 443.29 | 794.24 | 1597.71 | 3071.57 | 3475.77 |
| Fe | ND | ND | ND | ND | 0.03 | 0.05 |
| Mn | ND | ND | ND | ND | ND | ND |
| Cu | ND | ND | ND | ND | ND | ND |
| Zn | ND | ND | ND | 0.06 | 0.12 | 0.16 |
| Hg | ND | ND | ND | 0.00005 | 0.00011 | 0.00014 |
| As | ND | ND | ND | ND | ND | ND |
| Se | ND | ND | 0.00003 | 0.00004 | 0.00023 | 0.0003 |
| Cd | ND | ND | ND | ND | 0.009 | 0.05 |
| Cr | ND | ND | ND | ND | ND | ND |
| Pb | ND | ND | ND | 0.0097 | 0.19 | 0.27 |
| δD/％ | -100.43 | -117.35 | -101.45 | -123.48 | -124.51 | -121.51 |
| δ 18 O/％ | -12.45 | -13.11 | -16.12 | -16.54 | -14.69 | -15.72 |
| Type of water chemistry | Ca 2+ -HCO 3 - | Na + -Cl - | Na + -SO 4 2- -Cl - | Na + -SO 4 2- -Cl - | Na + -SO 4 2- -Cl - | Na + -SO 4 2- -Cl - |
Units: mg/L, ND: the detection result is lower than the detection limit of the method and is calculated by 0 value.
The water chemistry index parameter comprises seven conventional ions K + 、Ca 2+ 、Na + 、Mg 2+ 、SO 4 2- 、HCO 3 - 、Cl - Mine water is commonly 10 heavy metals Fe, mn, cu, zn, hg, as, se, cd, cr, pb and delta D and delta 18 O。
Step 2, determining out-of-standard heavy metal types according to water chemistry index parameters of mine water and defining the out-of-standard heavy metal types as typical heavy metals of the mine; specifically, the specified value of the class III of the groundwater quality standard (GB/T14848-2017) is used as a typical heavy metal determination condition, and in the scheme, the standard exceeding heavy metals Cd and Pb are determined to be typical heavy metals according to the water chemistry index parameters of mine water.
Step 3, comparing the mine water with rainwater, surface water, diving, the water chemistry type, delta D and delta of the groundwater of each aquifer 18 O value, primarily judging the potential source of heavy metals in mine water;
the potential source conditions of the heavy metals in the mine water are judged to be simultaneously meeting the following three conditions:
the water chemistry type of the condition 1 and the mine water is the same;
condition 2, δd= (90% -110%) δd Mine water ；
Condition 3, delta 18 O＝(90％～110％)δ 18 O Mine water ；
In the above, δD is the value of deuterium, which is a stable isotope of hydrogen, δD Mine water Value delta of stable isotope deuterium of hydrogen in mine water 18 Stable isotope of O as oxygen 18 O value, delta 18 O Mine water Is a stable isotope of oxygen in mine water 18 O value.
In this example, the mine water was compared with rainwater, surface water, diving, I aquifer groundwater, II aquifer groundwater for the water chemistry type, δD and δ 18 And (3) the O value is preliminarily determined that the water-bearing layer I and the water-bearing layer II are potential sources of heavy metals in mine water.
Step 4, judging the potential sources of heavy metals in the mine water again according to the typical heavy metal concentrations of rainwater, surface water, diving and groundwater of each aquifer;
judging that the potential source conditions of the heavy metals in the mine water are any one of the following conditions:
condition 1, any typical heavy metal concentration exceeds standard;
condition 2, any typical heavy metal concentration reaches 10% of the typical heavy metal concentration in mine water.
In this embodiment, the ii aquifer is determined to be a potential source of heavy metals in mine water according to typical heavy metal concentrations of rainwater, surface water, diving, i aquifer groundwater, ii aquifer groundwater.
Step 5, classifying rainwater, surface water, diving, groundwater of each aquifer and mine water according to the water chemistry index parameters by adopting a systematic clustering method, and judging possible sources of heavy metals in the mine water;
the conditions for judging the possible sources of the heavy metals in the mine water are as follows: is classified into the most recent category with mine water;
the equations involved in the systematic clustering method are:
according to the conventional ions, typical heavy metals, delta D and delta in rainwater, surface water, diving, groundwater in various aquifers and mine water 18 O parameter construction matrix:
wherein x is mn For the nth water chemistry index parameter in the mth water sample, m=4+total number of aquifers, n=9+total number of typical heavy metals;
eliminating the dimensional difference equation:
wherein x is ij Corresponding values after dimension differences are eliminated for the water chemistry index parameters in the raw water sample;
similarity characterization equation:
d is the similarity distance between two types of water samples, i is the ith water sample, j is the jth chemical index parameter, and k is the kth water sample.
In this embodiment, rainwater, surface water, diving, groundwater in aquifer I, groundwater in aquifer II and mine water are classified, and as shown in FIG. 1 and Table 2, aquifer II is judged as a possible source of heavy metals in mine water.
Table 2 systematic clustering distance characterization table
| Rainwater | Surface water | Diving device | I contains | II contains | Mine water | |
| Rainwater | 0 | 0.87 | 1.75 | 2.12 | 2.87 | 3.67 |
| Surface water | 0.87 | 0 | 1.31 | 1.42 | 2.34 | 3.23 |
| Diving device | 1.75 | 1.31 | 0 | 1.30 | 2.12 | 2.93 |
| I contains | 2.12 | 1.42 | 1.30 | 0 | 1.68 | 2.57 |
| II contains | 2.87 | 2.34 | 2.12 | 1.68 | 0 | 1.16 |
| Mine water | 3.67 | 3.23 | 2.93 | 2.57 | 1.16 | 0 |
Step 6, performing coincidence analysis on the judgment result in the step 3-5, wherein the coincidence object is a heavy metal key source in mine water;
in the embodiment, the water-bearing layer of the superposition object II is judged to be a heavy metal key source in mine water.
Step 7, taking a coal sample for carrying out a heavy metal leaching experiment, and obtaining typical heavy metal leaching parameters of the coal sample, wherein the typical heavy metal leaching parameters are shown in table 3;
TABLE 3 typical heavy metal leaching parameter values for coal samples
| Cd | Pb | |
| Coal sample | 0.039 | 0.011 |
Units: mg/L
And 8, calculating the contribution rates of the heavy metals in the mine water by adopting a chemical mass balance method according to typical heavy metal leaching parameters of the coal sample and typical heavy metal parameters of key sources, and finally judging the real sources of the heavy metals in the mine water.
The real source conditions of heavy metals in mine water are judged as follows:
condition 1, contribution rate greater than 5%;
the equations involved in the chemical mass balance method are as follows:
the contribution concentration calculation equation:
wherein j=1+ total number of key sources; c (C) i Is the typical heavy metal i concentration in mine water; f (F) ij The mass proportion of the typical heavy metal i in the coal sample or the key source j to all the typical heavy metals; s is S j The contribution concentration of the coal sample or the key source j;
the contribution rate calculation equation:
the above mentioned:
when the total number of typical heavy metals is more than or equal to the total number of key sources +1; the chemical mass balance method is solved, and all steps 1-8 are completed to judge the heavy metal source in the mine water;
when the typical total heavy metal is less than the total key source +1; the chemical mass balance method has no solution, and only the steps 1-6 are needed to be completed, and the important source is judged to be the source of heavy metals in mine water.
In this example, table 4, it was finally determined that the II aquifer and the coal seam were the actual sources of heavy metals in mine water.
TABLE 4 heavy metal contribution rate Table
| II aquifer | Coal seam | |
| Contribution rate/% | 84.89 | 15.11 |
While there have been described what are believed to be the preferred embodiments of the present invention, it will be apparent to those skilled in the art that many more modifications are possible without departing from the principles of the invention.
Claims (5)
1. The method for accurately judging the source of the heavy metal in the mine water of the coal mine is characterized by comprising the following steps of:
step 1, collecting and detecting coal mine rainwater, surface water, diving, groundwater of each aquifer and mine water, and obtaining water chemical index parameters of the groundwater;
step 2, determining out-of-standard heavy metal types according to water chemistry index parameters of mine water and defining the out-of-standard heavy metal types as typical heavy metals of the mine;
step 3, comparing the mine water with rainwater, surface water, diving, the water chemistry type, delta D and delta of the groundwater of each aquifer 18 O value, primarily judging the potential source of heavy metals in mine water;
step 4, judging the potential sources of heavy metals in the mine water again according to the typical heavy metal concentrations of rainwater, surface water, diving and groundwater of each aquifer;
step 5, classifying rainwater, surface water, diving, groundwater of each aquifer and mine water according to the water chemistry index parameters by adopting a systematic clustering method, and judging possible sources of heavy metals in the mine water;
step 6, performing coincidence analysis on the judgment result in the step 3-5, wherein the coincidence object is a heavy metal key source in mine water;
step 7, taking a coal sample for carrying out a heavy metal leaching experiment to obtain typical heavy metal leaching parameters;
if the total number of typical heavy metals is more than or equal to +1 of the total number of key sources, carrying out the next step; if the total number of typical heavy metals is less than the total number of key sources +1, judging the result of the step 6 as the real source of the heavy metals in the mine water;
and 8, calculating the contribution rates of the heavy metals in the mine water by adopting a chemical mass balance method according to typical heavy metal leaching parameters of the coal sample and typical heavy metal parameters of key sources, and finally judging the real sources of the heavy metals in the mine water.
2. The method for accurately determining the source of heavy metals in mine water of a coal mine according to claim 1, wherein the conditions for determining the potential source of heavy metals in mine water in step 3 are three conditions simultaneously:
the water chemistry type of the condition 1 and the mine water is the same;
condition 2, δd= (90% -110%) δd Mine water ；
Condition 3, delta 18 O＝(90％～110％)δ 18 O Mine water ；
In the above, δD is the value of deuterium, which is a stable isotope of hydrogen, δD Mine water Value delta of stable isotope deuterium of hydrogen in mine water 18 Stable isotope of O as oxygen 18 O value, delta 18 O Mine water Is a stable isotope of oxygen in mine water 18 O value.
3. The method for accurately determining the source of heavy metals in mine water of a coal mine according to claim 1, wherein the determination in step 4 is that the potential source condition of heavy metals in mine water is any one of the following conditions:
condition 1, any typical heavy metal concentration exceeds standard;
condition 2, any typical heavy metal concentration reaches 10% of the typical heavy metal concentration in mine water.
4. The method for accurately determining the source of heavy metals in mine water of coal mine according to claim 1, wherein the conditions for determining the possible source of heavy metals in mine water in step 5 are as follows: is classified into the most recent category with mine water;
the equations involved in the systematic clustering method are:
according to the conventional ions, typical heavy metals, delta D and delta in rainwater, surface water, diving, groundwater in various aquifers and mine water 18 O parameter construction matrix:
wherein x is mn For the nth water chemistry index parameter in the mth water sample, m=4+total number of aquifers, n=9+total number of typical heavy metals;
eliminating the dimensional difference equation:
wherein x is ij Corresponding values after dimension differences are eliminated for the water chemistry index parameters in the raw water sample;
similarity characterization equation:
d is the similarity distance between two types of water samples, i is the ith water sample, j is the jth chemical index parameter, and k is the kth water sample.
5. The method for accurately judging the source of heavy metals in mine water of a coal mine according to claim 1, wherein the condition for judging the true source of heavy metals in mine water in step 7 is as follows:
condition 1, contribution rate greater than 5%;
the equations involved in the chemical mass balance method are as follows:
the contribution concentration calculation equation:
wherein j=1+ total number of key sources; c (C) i Is the typical heavy metal i concentration in mine water; f (F) ij The mass proportion of the typical heavy metal i in the coal sample or the key source j to all the typical heavy metals; s is S j The contribution concentration of the coal sample or the key source j;
the contribution rate calculation equation:
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