CN115712990A - Prediction method of fluoride ion concentration, and fluorine removal method and device - Google Patents
Prediction method of fluoride ion concentration, and fluorine removal method and device Download PDFInfo
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- 239000011737 fluorine Substances 0.000 title claims abstract description 81
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- 238000000034 method Methods 0.000 title claims abstract description 81
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 38
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 14
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Abstract
The invention provides a method for predicting the concentration of fluorine ions, a method and a device for removing fluorine, wherein the method for predicting the concentration of fluorine ions comprises the following steps: s10, collecting water samples of a mining working face, a goaf and a driving roadway mine respectively, detecting the concentration of fluorine ions, and calculating the average concentration of the fluorine ions in the water samples of the mining working face, the goaf and the driving roadway mine; s20, respectively determining the water inflow Q of the mining working face and the water inflow Q of the goaf Air conditioner And water gushing of the driving tunnelQuantity Q Digging machine (ii) a S30, determining the water inflow Q of the mining working face and the water inflow Q of the goaf according to the step S20 Air conditioner And water inflow amount Q of tunneling roadway Digging machine And S10, determining the concentration of the fluorine ions in the mine water from each source, and calculating the concentration of the fluorine ions in the mixed mine water of the unexplored coal seam.
Description
Technical Field
The invention belongs to the field of mine water resource treatment and utilization, and particularly relates to a method for predicting fluoride ion concentration, a method for removing fluoride and a device.
Background
Fluorine is a necessary trace element for human bodies, is beneficial to health when being taken in a proper amount, but can cause dental fluorosis and fluoroossicless, even fluorosis, nerve injury and other diseases when being taken in excessively for a long time, and seriously threatens human health. Fluorine is a typical lithophilic element, widely exists in coal seams, rocks and soil, is influenced by regional geology and structures, and has large content difference of fluorine in the coal rocks. In western mining areas of China, along with downward extension mining of coal seams, under dual control of coal mining disturbance and water-coal/rock action, fluorine in coal rocks is released into underground water and gushes into coal mining roadways or working faces through water-flowing fracture zones to form high-fluorine mine water. Surface water resources and underground water resources in western mining areas are in short supply, and mine water is an important resource for guaranteeing local production, ecology and domestic water, so that the treatment and resource utilization of the high-fluorine mine water are very important. In conclusion, the concentration of the fluorine ions in the mine water is accurately predicted, and the treatment process suitable for the concentration is selected, so that the method has important significance for treating and utilizing high-fluorine mine water resources.
The difference of the defluorination process corresponding to mine water with different fluoride concentrations is large, a medicament coagulating sedimentation method is often adopted for medium and high concentrations, the fluoride in the water body can be removed by an adsorption method, a resin method and the like for low concentrations, and in addition, the concentration of the fluoride can directly influence the membrane material type selection for defluorination by a membrane method. Therefore, the accurate prediction of the concentration of the fluorine in the mine water has important guiding significance for designing the fluorine removal process and constructing the fluorine removal system of the mine water treatment station.
The existing prediction methods for the concentration of fluorine in mine water are all based on a solute transport numerical model, focus on the prediction of a fluorine ion diffusion range, cannot accurately predict the concentration of fluorine in mine water, and have high technical threshold, so that the method is difficult to popularize and apply on site. Based on accurate prediction of the concentration of fluorine in mine water, a fluorine removal process is selected and a fluorine removal system is constructed, so that accurate removal of fluoride in mine water can be realized, the operability is high, and the investment and operation cost is low.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a mass coupling-based prediction method for typical ion concentration in mine water, and solve the problems in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for predicting fluoride ion concentration, the method comprising the steps of:
s10, collecting water samples of a mining working face, a goaf and a driving roadway mine respectively, detecting the concentration of fluorine ions, and calculating the average concentration of the fluorine ions in the water samples of the mining working face, the goaf and the driving roadway mine;
s20, respectively determining the water inflow Q of the mining working face and the water inflow Q of the goaf Air conditioner And the water inflow Q of the excavation roadway Digging machine ；
S30, determining the water inflow Q of the mining working face and the water inflow Q of the goaf according to the step S20 Air conditioner And water inflow Q of tunneling roadway Digging machine And S10, determining the concentration of the fluorine ions in the mine water from each source, and calculating the concentration of the fluorine ions in the mixed mine water of the unexplored coal seam.
Preferably, the mining work in S10Average concentration of fluorine ions C Mining A ：
Average concentration C of fluorinion in goaf Empty F ：
Average fluorine ion concentration C of excavation roadway Digging F ：
Wherein, C F1 The average concentration of fluoride ions in the sample 1 of the mining working face is given by the unit: mg/L; c F2 Average concentration of fluoride ions in the mining face sample 2, unit: mg/L; c F3 The average concentration of fluoride ions in the sample 3 of the mining working face is given by the unit: mg/L; c Fn The average concentration of the fluorine ions in the sample n of the mining working face is as follows: mg/L; c Fn1 The average concentration of fluorine ions in n samples in the goaf is as follows: mg/L; c Fn2 The average concentration of fluorine ions in n samples of a roadway is tunneled, and the unit is as follows: mg/L; and n is the number of water samples of the mining working face, the goaf and the tunneling roadway.
Preferably, in S20, the water inflow of the mining face:
Q＝Q 1 +Q 2 (4)
wherein, Q is the water inflow of mining working face, unit: m is a unit of 3 /d；Q 1 Dynamic replenishment quantity for mining working face, unit: m is 3 /d；Q 2 The unit is the static reserve of the mining working face: m is 3 D; k is the permeability coefficient, unit: m/d; m is the aquifer thickness, unit: m; h is the average head height, in units: m; s is a drainage head reduction value in units: m; r 0 To influence the radius, the unit: m; r is 0 For reference to radius, unit: m; b is 0 For adopting the working face trend length, unit: m; b is the working face inclination width, unit: m; eta is the pit shape influence coefficient.
Preferably, the water inflow Q of the goaf is determined in the step S20 Air conditioner Water inflow quantity Q of driving tunnel Digging machine Collecting water inflow data of the mined goaf and the tunneling roadway in history, acquiring the water inflow change rule of the goaf and the tunneling roadway, and predicting the water inflow Q of the goaf in the unexploited area according to the water inflow increasing or attenuating rule Air conditioner And the water inflow Q of the driving tunnel Digging machine 。
Preferably, the proportion K of the water inflow of the mining working face to the total water inflow is as follows:
ratio K of water inflow to total water inflow in goaf Air conditioner ：
Ratio K of water inflow to total water inflow of excavation roadway Digging machine ：
Wherein Q is Air conditioner The unit of water inflow of the goaf is as follows: m is 3 /d；Q Digging machine The unit is the water inflow amount of the tunneling roadway: m is 3 /d。
Preferably, in S30, the concentration of typical ion a in the mixed mine water of the unexplored coal seam:
C A ＝K·C mining of F +K Air conditioner ·C Empty F +K Digging machine ·C Digging F (9)
Wherein K is the proportion of the water inflow of the mining working face to the total water inflow, and K is Air conditioner The ratio of the water inflow to the total water inflow in the goaf, K Digging machine The ratio of water inflow to total water inflow for the driving tunnel, C Mining A The average concentration of ions of the mining working face A is shown as the unit: mg/L; c Null A The average concentration of ions in the goaf A is shown in unit: mg/L; c Digging A Average concentration of ions A in the excavation roadway, unit: mg/L.
A defluorination method adopts a dosing method and an adsorption method to cooperate with defluorination, wherein the dosing method adopts a membrane chemical reactor to defluorinate, the dosing concentration of the membrane chemical reactor is determined according to the fluoride ion concentration obtained by the prediction method of the fluoride ion concentration, and the adsorption method adopts an adsorption tank to defluorinate.
Preferably, when the fluoride ion concentration is more than 2.5mg/L, the dosing concentration of the membrane chemical reactor is as follows:
C＝100+(C1-2.5)×50
wherein, C is the adding concentration of the medicament of the membrane chemical reactor, and the unit is as follows: mg/L; c1 is the concentration of fluorine ions in the inlet water, and the unit is as follows: mg/L.
Preferably, in the adsorption defluorination process, hydroxyapatite is placed in an adsorption tank as an adsorption material.
A fluorine removal device, comprising: the above membrane chemical reactor and adsorption tank further comprise:
the first water inlet pump is connected with the inlet of the membrane chemical reactor;
an inlet of the middle water tank is connected with an outlet of the membrane chemical reactor, an outlet of the middle water tank is connected with an inlet of the adsorption tank through a second water pump, the second water pump is also connected with regenerated liquid, an outlet of the adsorption tank is respectively connected with waste liquid and filtrate,
the two ends of the reflux pump are respectively connected with the outlet of the middle water tank and the inlet of the membrane chemical reactor, the connections are all connected through pipelines, and the pipelines are all provided with valves;
and the ion concentration detector is connected with the filtrate, an adsorption tank is adopted in the adsorption method, and hydroxyapatite is placed in the adsorption tank to serve as an adsorption material.
Compared with the prior art, the invention has the following technical effects:
the method for predicting the fluoride ion concentration fully considers the formation process of the fluoride ions in the mine water, the concentration of the fluoride ions in the mine water is predicted by coupling the mine water quantity and the water quality, based on the concentration, a fluoride removal process corresponding to the fluoride ion concentration is selected, and an adaptive fluoride removal system is constructed. The method solves the problems of accurate prediction and removal of the fluorine ions in the mine water, and ensures the safety of water for ecology, life and production in mining areas.
The fluorine removal method and system provided by the invention combine the membrane chemical reactor and adsorption method combined process, so that the advantages of a medicament method in fluorine removal in a medium-high fluorine ion concentration range and the advantages of an adsorption method in fluorine removal in a low-concentration fluorine ion concentration range can be fully exerted, the fluorine removal efficiency is improved, and the fluorine removal cost is saved.
Drawings
FIG. 1 is a schematic flow diagram of the present invention;
FIG. 2 (a) is a statistical chart of the historical water inflow of the gob of the present invention;
FIG. 2 (b) is a statistical chart of the historical water inflow of the excavation roadway of the invention;
FIG. 3 is a graph showing the concentration of fluoride ions in the product water of a membrane chemical reactor as a function of the concentration of the added agent;
FIG. 4 is a graph of fluoride ion removal rate as a function of concentration of added agent;
FIG. 5 is a graph of mine water treatment cost per ton (ton water cost) as a function of drug addition concentration;
FIG. 6 is a graph of fluoride ion concentration over time;
FIG. 7 is a schematic structural view of the fluorine removal device of the present invention.
The meaning of the individual reference symbols in the figures is:
1-a membrane chemical reactor, 2-an adsorption tank, 3-a first water inlet pump, 4-an intermediate water tank, 5-a second water pump, 6-a regeneration liquid, 7-a waste liquid, 8-a filtering liquid, 9-a reflux pump and 10-an ion concentration detector.
The present invention will be explained in further detail with reference to examples.
Detailed Description
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Herein, ICP-MS represents an inductively coupled plasma emission spectrometer, and the fluorine ion concentration in the mine water is more than 1.0mg/L, and the mine water is called high fluorine mine water.
Example 1:
dan Ge coal mines are located in the northwest of the Shenmu City, shanxi province, and in the northwest of the Hedong Wulanlun where the distance is about 55 kilometers, and the administrative region belongs to the large Liu Da test district of the Shenmu City. The West of the Jingtian is Wulanmuhe, the south of Haragu well field, the north of the Jingtian is connected with the Batuta well field, and the east of the Jingtian is bounded by the seven ditch and the Shanmeng boundary; west is bound by wulanmulen river. East-west length is about 10 kilometers, south-north width is about 8 kilometers, area 65.283 square kilometers. The production capacity of the certifications is 1200 million tons/year, and 22 coals and 31 coals of Jurassic series Yanan group are mainly adopted at present.
The early stage of coal mine mainly comprises 22 coals, but with the exploitation of 31 coals, fluoride detected in a 31-coal roof aquifer exceeds the standard, and the difference from the prior knowledge is large. At present, dan Ge coal mine water treatment plants are about to face reconstruction and expansion, and in order to reasonably determine the defluorination process and device of the mine water treatment plants, the concentration of fluorine ions in future mine water needs to be predicted, and a defluorination method, process and device matched with the concentration are selected.
In the embodiment, the water sample is collected from the working face which is already taken, and the concentration of the fluorine ions in the mine water of the working face which is not taken is predicted. The 31 coal faces to be mined are 10 faces, 31101 (face number), 31102, 31103, 31104, 31105, 31106, 31107, 31108, 31109 and 31110.
Respectively collecting 29 water samples of 22 coal goafs, 31 coal mining working faces and 31 coal driving tunnels, detecting the concentration of the fluorine ions, and calculating the average concentration and the maximum concentration of the fluorine ions in mine water from different sources according to a formula. And (3) calculating the average concentration and the maximum concentration of the fluorine ions in the mine water from different sources according to the formulas (1), (2) and (3).
TABLE 1-1 analysis results of mine water fluoride ion concentration
The method for predicting the water inflow of the four working faces comprises the following steps:
in the determination of the water inflow of the mining working face, the key point of the calculation of the dynamic replenishment lies in determining the permeability coefficient (K), the thickness (M) of an aquifer, the height (H) of an average water head and the water level depreciation (S) in the hydrogeology replenishment period; query for face strike length (B) from mining plan 0 ) Wide working face inclination (b); and (4) inquiring and determining the pit shape influence coefficient (eta) according to a coal mine control water manual. Specific values of the above acquisition parameters are shown in Table 1-1.
TABLE 1-2 Hara ditch coal mine hydrogeological parameters
Calculating the working face according to the parameters obtainedDynamic replenishment quantity, taking 31101 working surface as an example, takes the above parameters into formula to calculate
R o ＝965+67.53＝1032.53、
The dynamic replenishment amounts for the respective work planes 31101 to 31110 were calculated, and the results are shown in Table 1-2.
TABLE 1-3 Hara gully coal mine 31107-31110 face dynamic replenishment calculation
Calculating static reserves of the mining working face, substituting parameters such as mu d, F, M, t (obtained according to mining plan) and the like into formula (3), and calculating static reserves Q of the mining working face 2 Also, taking 31107 as an example of a work surface,
TABLE 1-4 Hara gully coal mine 31107-31110 working face static reserve calculation
Predicting the total water inflow in the stoping process of the continuous working face by using a dynamic-static reserve method, wherein the total water inflow of the mining working face is equal to the superposition of the dynamic supply amount and the static reserve amount, and the water inflow of the mining working face is obtained by Q = Q 1 +Q 2 The calculation results are shown in tables 1 to 5.
TABLE 1-5 Hara ditch coal mine 31107-31110 working face water inflow
| Working surface | Dynamic replenishment quantity Q 1 (m 3 /h) | Static reserve Q 2 (m 3 /h) | Water inflow of mining working face (m 3/h) |
| 31101 | 59.94 | 10.15 | 70.09 |
| 31102 | 59.16 | 3.94 | 63.1 |
| 31103 | 59.34 | 3.02 | 62.36 |
| 31104 | 59.61 | 5.88 | 65.49 |
| 31105 | 59.77 | 7.55 | 67.32 |
| 31106 | 48.28 | 7.92 | 56.2 |
| 31107 | 45.66 | 7.00 | 52.66 |
| 31108 | 43.64 | 7.00 | 50.64 |
| 31109 | 43.58 | 17.86 | 61.44 |
| 31110 | 43.59 | 10.96 | 54.55 |
Water inflow Q of goaf and tunneling roadway Air conditioner And Q Digging machine The method comprises the steps of collecting and counting data of water inflow of 12 years of a driving working face and a goaf mine in 2010-2021 of a 22-coal mined coal seam (the past water inflow of the mined coal seam can be generally regarded as historical water inflow, and the change of the future water inflow can be predicted according to the change rule of the historical water inflow), and drawing a curve graph of the water inflow along with the change of time. FIG. 2 (a) is a time-varying curve of water inflow of the goaf, and FIG. 2 (b) is a time-varying curve of the heading faceFigure (a). According to the change data of the water inflow amount of the goaf, the total water inflow amount of the goaf basically presents a dynamic and stable state, and the water inflow amount is 220m 3 Fluctuating around/h. As can be seen from the water inflow change curve of the tunneling working face, after 2014, the water inflow of the tunneling working face is basically in a dynamic stable state, and the stable value is 20.85m 3 H is the ratio of the total weight of the catalyst to the total weight of the catalyst. Therefore, the water inflow Q of the goaf is predicted according to the prediction Air conditioner Is 220m 3 Per, water inflow quantity Q of driving tunnel Digging machine Is 20.85m 3 /h。
Calculating the proportion of the water inflow of the mining working face to the total water inflow according to the water inflow of the mining working face, the goaf and the mine of the driving working face
Proportion of water inflow to total water inflow in goaf
The ratio of water inflow to total water inflow of the excavation roadway
The results are shown in tables 1-6.
TABLE 1-6 proportionality coefficients of water burst from mines of different sources
| Working surface | 22 coal goaf K Air conditioner | 31 coal mining working face K | 31 coal driving tunnel K Digging machine |
| 31101 | 0.44 | 0.25 | 0.31 |
| 31102 | 0.45 | 0.23 | 0.32 |
| 31103 | 0.45 | 0.235 | 0.315 |
| 31104 | 0.45 | 0.24 | 0.31 |
| 31105 | 0.44 | 0.25 | 0.31 |
| 31106 | 0.46 | 0.22 | 0.32 |
| 31107 | 0.47 | 0.21 | 0.32 |
| 31108 | 0.47 | 0.2 | 0.33 |
| 31109 | 0.45 | 0.23 | 0.32 |
| 31110 | 0.46 | 0.21 | 0.33 |
The fluorine ion concentrations in the mixed mine water of the non-mined working surfaces 31101 to 31110 were calculated according to the formula (9), and the fluorine concentrations in the mine water ranged from 2.94 to 6.27mg/L as shown in tables 1 to 7.
TABLE 1-7 31101-31110 Normal and maximum concentrations of fluoride ions in mine water at working face
| Working face numbering | Normal concentration of fluoride ion | Maximum concentration of fluoride ion |
| 31101 | 3.18 | 6.27 |
| 31102 | 3.10 | 6.21 |
| 31103 | 3.09 | 6.20 |
| 31104 | 3.13 | 6.23 |
| 31105 | 3.15 | 6.25 |
| 31106 | 3.01 | 6.14 |
| 31107 | 2.96 | 6.11 |
| 31108 | 2.94 | 6.09 |
| 31109 | 3.08 | 6.19 |
| 31110 | 2.99 | 6.13 |
Example 2:
a fluorine removal method adopts a dosing method and an adsorption method to cooperatively remove fluorine, the dosing method adopts a membrane chemical reactor to remove fluorine, and the dosing concentration of the membrane chemical reactor is determined according to the fluorine ion concentration obtained by the prediction method of the fluorine ion concentration in example 1.
As a preferable solution of this embodiment, when the fluoride ion concentration is greater than 2.5mg/L, the dosing concentration of the membrane chemical reactor is:
C＝100+(C1-2.5)×50
wherein, C is the addition concentration of the membrane chemical reactor medicament, unit: mg/L; c1 is the concentration of fluorine ions in the inlet water, and the unit is as follows: mg/L.
Fluoride concentrations in ten face mine waters of Hara gully mines 31101-31110 were predicted to be between 2.94mg/L and 6.27mg/L, as predicted by fluoride concentrations in example 1. Taking the fluoride ion concentration of the inlet water as 5.20mg/L as an example, the PAC dosage is 235mg/L. Wherein the added PAC is 30 mass percent of Al 2 O 3 Commercial PAC products.
By adding different dosages of the defluorination reagent PAC (polyaluminium chloride), the concentration of the fluorine ions in the produced water of the membrane chemical reactor is changed along with the concentration of the added reagent, and the curve is shown in figure 3. When the dosage is 235mg/L, the concentration of the fluorine ions generated by the water is 2.4mg/L. In addition, as is apparent from fig. 3, as the amount of the chemical increases, the concentration of the fluoride ions in the produced water gradually decreases, and as is apparent from fig. 4, the removal rate of the fluoride ions in the produced water changes gradually with the concentration of the chemical, which means that as the amount of the chemical added increases, the removal rate of the fluoride ions increases first and then becomes gentle. Both FIGS. 3 and 4 show that the removal effect of fluoride ion is not obvious with the increase of the dosage, and at this time, the concentration of fluoride ion in the produced water is still higher than 1mg/L, and the fluoride removal needs to be continued in combination with another process. In the defluorination process, the removal rate is considered, and the economic cost is considered, so that a curve of the change of the mine water treatment cost per ton (water cost per ton) along with the concentration of the added chemicals is drawn as shown in fig. 5. Obviously, the treatment cost per ton of water increases linearly with the increase of the medicament, and the treatment cost per ton of water is 0.125 yuan when the medicament is added at 235mg/L. Therefore, when the concentration of the fluorine ions in the inlet water is 5.2mg/L, the method is economical and reliable while the method selects to firstly add the medicament to remove the fluorine ions to achieve a certain removal effect.
After the treatment of the membrane chemical reactor, the concentration of the fluoride ions in the mine aquatic water is 2.4mg/L, in order to further reduce the concentration of the fluoride ions in the mine water, the adsorption method fluorine removal process is continuously utilized, hydroxyapatite is selected as an adsorption material for the adsorption material, and finally the concentration of the fluoride ions in the mine water is controlled to be less than 1mg/L.
Hydroxyl fluorapatite is selected as an adsorbing material, indoor simulation is carried out in a laboratory, and fluoride ions in mine water are further removed. The height of the adsorption column of the adsorption material is 70cm, the inner diameter is 5cm, the upper end and the lower end of the adsorption column are respectively filled with 10cm of quartz sand, and the middle of the adsorption column is filled with 50cm of hydroxyapatite. When the fluoride concentration of the raw water of the fluorine-containing mine water is 5.20mg/L, the fluorine ion concentration of the produced water is 2.4mg/L after the raw water is filtered by a membrane chemical reactor. Under the condition, when the flow rate of the inlet water is 2.0BV/h, the concentration of the fluorine ions in the produced water changes along with the time as shown in the following figure 6. Over time, fluoride ion concentrations tend to increase and then stabilize. When the adsorption time is 20min, the water production concentration can be controlled at 1mg/L. Therefore, after 20min, the hydroxyapatite with saturated adsorption is regenerated by adding 1.5% of sodium hydroxide, and the test result shows that the adsorbent still has good capability of removing the fluoride ions after regeneration 6. Therefore, the hydroxyapatite defluorination process and system are stable and reliable.
Example 3:
a fluorine removal device, the device comprising: the membrane chemical reactor 1 and the adsorption tank 2 according to embodiment 2 further include:
the first water inlet pump 3, the first water inlet pump 3 is connected with the inlet of the membrane chemical reactor 1;
an inlet of the middle water tank 4 is connected with an outlet of the membrane chemical reactor 1, an outlet of the middle water tank 4 is connected with an inlet of the adsorption tank 2 through a second water pump 5, the second water pump 5 is also connected with a regeneration liquid 6, an outlet of the adsorption tank 2 is respectively connected with a waste liquid 7 and a filtering liquid 8,
the two ends of the reflux pump 9 are respectively connected with the outlet of the intermediate water tank 4 and the inlet of the membrane chemical reactor 1, the outlet of the intermediate water tank 4 is also connected with a sludge tank 10, the connections are all connected through a pipeline, and the pipeline is provided with a valve 11;
in the adsorption method, an adsorption tank 2 is adopted, and hydroxyapatite is placed in the adsorption tank to serve as an adsorption material.
Fluoride ion's getting rid of in carrying out the membrane chemical reactor through first intake pump with fluorine mine water in this embodiment, water after the reaction gets into after the middle water tank and in carrying to adsorption tank 2 through second water pump 5, more deepening in adsorption tank 2 get rid of the fluoride ion in the water, and valve 11 is used for controlling the intercommunication that each pipeline carried.
The method for removing the fluoride ions in the water by the hydroxyapatite mainly comprises two ways, one way is through adsorption, the other way is through replacement with hydroxyl on the surface of the hydroxyapatite, the regeneration liquid is mainly NaOH solution with the mass concentration of 1% -2%, OH-ions and F-ions in the solution are in a competitive adsorption relation, when the OH-concentration in the solution is very high, the fluoride ions in the hydroxyapatite with saturated adsorption can be replaced again, and in addition, the negative charge effect of the adsorption filter material under a strong alkaline environment is obviously increased, so that the fluoride adsorbed on the surface of the filter material can be desorbed into the solution again.
The waste liquid is mainly strong alkali solution generated after the regenerated liquid elutes the filter material, in particular NaOH solution containing high-concentration fluorine ions.
The filtrate is mainly low-fluorine water obtained by purifying mine water by hydroxyapatite;
the main principle of the adsorption tank 2 for removing fluoride ions is that the adsorption effect and the ion replacement effect of hydroxyapatite remove fluoride in water.
The fluorine removal device provided by the embodiment of the invention combines the membrane chemical reactor and adsorption method combined process, so that the advantages of a medicament method in removing fluorine in a medium-high fluorine ion concentration range and the advantages of an adsorption method in removing fluorine in a low-concentration fluorine ion concentration range can be fully exerted, the fluorine removal efficiency is improved, and the fluorine removal cost is saved.
Claims (10)
1. A method for predicting the concentration of fluorine ions, comprising the steps of:
s10, collecting water samples of a mining working face, a goaf and a driving roadway mine respectively, detecting the concentration of fluorine ions, and calculating the average concentration of the fluorine ions in the water samples of the mining working face, the goaf and the driving roadway mine;
s20, respectively determining the water inflow Q of the mining working face and the water inflow Q of the goaf Air conditioner And the water inflow Q of the excavation roadway Digging machine ；
S30, determining the water inflow Q of the mining working face according to the S20, and miningWater inflow Q in dead zone Air conditioner And water inflow amount Q of tunneling roadway Digging machine And S10, determining the concentration of the fluorine ions in the mine water from all sources, and calculating the concentration of the fluorine ions in the mixed mine water of the unexplored coal seam.
2. The method for predicting a fluoride ion concentration according to claim 1,
the average concentration C of the fluorine ions on the mining working face in the S10 Mining A ：
Average concentration C of fluorinion in goaf Empty F ：
Average fluorine ion concentration C of excavation roadway Digging F ：
Wherein, C F1 The average concentration of fluoride ions in the mining face sample 1, unit: mg/L; c F2 Average concentration of fluoride ions in the mining face sample 2, unit: mg/L; c F3 The average concentration of fluoride ions in the mining face sample 3, unit: mg/L; c Fn The average concentration of the fluorine ions in the mining working face sample n is as follows: mg/L; c Fn1 The average concentration of fluorine ions in n samples in the goaf is as follows: mg/L; c Fn2 The average concentration of fluorine ions in n samples of a driving roadway is as follows: mg/L; and n is the number of water samples of the mining working face, the goaf and the tunneling roadway.
3. The method for predicting a fluoride ion concentration according to claim 2,
and in S20, adopting the water inflow amount of the working face:
Q＝Q 1 +Q 2 (4)
wherein, Q is the water inflow of mining working face, unit: m is 3 /d；Q 1 Dynamic replenishment quantity for mining working face, unit: m is 3 /d；Q 2 Is the static reserve of the mining working face, unit: m is 3 D; k is the permeability coefficient, unit: m/d; m is the aquifer thickness, unit: m; h is the average head height, in units: m; s is a drainage head reduction value in units: m; r 0 To influence the radius, the unit: m; r is 0 For reference to radius, unit: m; b is 0 For adopting the working face trend length, unit: m; b is the working face inclination width, unit: m; eta is the pit shape influence coefficient.
4. The method for predicting a fluoride ion concentration according to claim 3,
and in the step S20, determining the water inflow Q of the goaf Air conditioner Water inflow Q of tunneling roadway Digging machine Collecting water inflow data of the mined goaf and the tunneling roadway in history, acquiring the water inflow change rule of the goaf and the tunneling roadway, and predicting the unexplored area according to the water inflow increase or attenuation ruleGoaf water inflow Q Air conditioner And the water inflow Q of the driving tunnel Digging machine 。
5. The method for predicting a fluoride ion concentration according to claim 4,
the proportion K of the water inflow of the mining working face to the total water inflow is as follows:
ratio K of water inflow to total water inflow in goaf Air conditioner ：
Ratio K of water inflow to total water inflow of excavation roadway Digging machine ：
Wherein Q Air conditioner The unit of water inflow of the goaf is as follows: m is 3 /d；Q Digging machine The unit is the water inflow amount of the tunneling roadway: m is 3 /d。
6. The method for predicting a fluoride ion concentration according to claim 5,
in the step S30, the concentration of typical ions a in the mixed mine water of the unexplored coal seam:
C A ＝K·C mining of F +K Air conditioner ·C Empty F +K Digging machine ·C Digging F (9)
Wherein K is the proportion of the water inflow of the mining working face to the total water inflow, and K is Air conditioner The ratio of the water inflow to the total water inflow in the goaf, K Digging machine The ratio of water inflow to total water inflow for the driving tunnel, C Mining A The average concentration of ions in the mining working face A is shown as unit: mg/L; c Null A The average concentration of ions in the goaf A is shown in unit: mg/L; c Digging A Average concentration of ions A in the excavation roadway, unit: mg/L.
7. A defluorination method is characterized in that the defluorination method is cooperated with an adsorption method, the dosing method adopts a membrane chemical reactor to defluorinate, the dosing concentration of the membrane chemical reactor is determined according to the fluoride ion concentration obtained by the prediction method of the fluoride ion concentration according to any one of claims 1 to 6, and the adsorption method adopts an adsorption tank to defluorinate.
8. The fluorine removal method of claim 7, wherein when the fluoride ion concentration is greater than 2.5mg/L, the dosing concentration of the membrane chemical reactor is:
C＝100+(C1-2.5)×50
wherein, C is the addition concentration of the membrane chemical reactor medicament, unit: mg/L; c1 is the concentration of fluorine ions in the inlet water, and the unit is as follows: mg/L.
9. The defluorination method according to claim 7, wherein in the defluorination process by adsorption, hydroxyapatite is selected and placed as the adsorbing material in the adsorption tank.
10. A fluorine removal device, the device comprising: the membrane chemical reactor (1) and the sorption tank (2) according to any of claims 7 to 9, further comprising:
the first water inlet pump (3), the first water inlet pump (3) is connected with the inlet of the membrane chemical reactor (1);
an inlet of the middle water tank (4) is connected with an outlet of the membrane chemical reactor (1), an outlet of the middle water tank (4) is connected with an inlet of the adsorption tank (2) through a second water pump (5), the second water pump (5) is also connected with a regenerated liquid (6), an outlet of the adsorption tank (2) is respectively connected with a waste liquid (7) and a filtrate (8),
the two ends of the reflux pump (9) are respectively connected with the outlet of the middle water tank (4) and the inlet of the membrane chemical reactor (1), the connections are all connected through a pipeline, and valves (11) are arranged on the pipelines;
and the ion concentration detector (10) is connected with the filtrate (8), an adsorption tank (2) is adopted in the adsorption method, and hydroxyapatite is placed in the adsorption tank to serve as an adsorption material.
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| CN116754735A (en) * | 2023-06-20 | 2023-09-15 | 北京低碳清洁能源研究院 | Method for predicting water quality components and concentration content of mine water of coal mine |
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| CN116754735B (en) * | 2023-06-20 | 2024-01-09 | 北京低碳清洁能源研究院 | Method for predicting water quality components and concentration content of mine water of coal mine |
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