METHOD FOR OPTIMIZING LIQUID INJECTION PROCESS OF IONIC RARE EARTH ORE

Abstract

The present disclosure provides a method for optimizing a liquid injection process of ionic rare earth ore, including the following steps of: 1) testing the hydraulic properties of an ore body; 2) determining the diffusion degree of the ore body; 3) determining the spatial distribution of the rare earth grade and the impurity grade of the ore body prior to leaching; 4) determining model parameters of competitive exchange of rare earth ions and impurity ions with ammonium ions; 5) obtaining distribution of rare earth ion concentration within the ore body after completion of leaching; 6) obtaining a profile plot of a rare earth leaching rate as a function of the concentration and dosage of an injected leaching agent; and 7) determining a minimum leaching agent dosage to achieve a target leaching rate according to the profile plot, and then determining the ammonium sulfate concentration according to the minimum leaching agent dosage.

Claims

1. A method for optimizing a liquid injection process of ionic rare earth ore, comprising the following steps of: step 1: testing the hydraulic properties of an ore body: arranging a plurality of moisture sensors within the ore body, performing an in situ water injection test, analyzing moisture content data by using a hydraulic property inverse analysis method, and determining the hydraulic properties of the ore body; step 2: determining the diffusion degree of the ore body; step 3: forming prospecting holes in the ore body and sampling to determine the spatial distribution of the rare earth grade and the impurity grade of the ore body prior to leaching; step 4: establishing a mathematical model for competitive exchange of rare earth ions and impurity ions with ammonium ions, sampling in situ, performing a leaching-in-tube test, and determining model parameters of the competitive exchange of the rare earth ions and impurity ions with ammonium ions; step 5: substituting the hydraulic properties obtained in the step 1 into a mathematical equation of an existing percolation process within the ore body, determining a moisture content distribution within the ore body, substituting the obtained moisture content distribution and the diffusion degree of the ore body obtained in the step 2 into a convection-diffusion equation to obtain distribution of ions within the ore body at any time under the action of convection and diffusion, and modifying the distribution of the ions within the ore body at any time by taking into account the grade distribution of the step 3 and the competitive exchange model of the step 4) to obtain distribution of rare earth ion concentration within the ore body after completion of leaching; step 6: determining a rare earth leaching rate of the ore body according to the ion concentration distribution within the ore body before and after leaching, and varying the concentration and the dosage of an injected leaching agent to obtain a profile plot of the rare earth leaching rate as a function of the concentration and the dosage of the injected leaching agent; and step 7: setting a target leaching rate, determining a minimum leaching agent dosage to achieve the target leaching rate according to the profile plot obtained in the step 6, and determining the ammonium sulfate concentration according to the minimum leaching agent dosage for the purpose of optimizing the liquid injection process.

2. The method for optimizing the liquid injection process of the ionic rare earth ore according to claim 1, wherein specific steps for determining the dispersion degree of the ore body in the step 2 comprise: establishing a fractal model of a soil-water characteristic curve and a fractal model of a non-reactive ion penetration curve by fractal theory, fitting the soil-water characteristic curve obtained in the step 1 by adopting the fractal model of the soil-water characteristic curve to obtain fractal parameters in the fractal model, substituting the fractal parameters into the fractal model of the penetration curve to obtain the penetration curve, and fitting the penetration curve by adopting an analytical solution to a convection-diffusion model of non-reactive ions to determine the diffusion degree of the ore body.

3. The method for optimizing the liquid injection process of the ionic rare earth ore according to claim 1, wherein the hydraulic properties of the ore body comprise the soil-water characteristic curve and an unsaturated permeability coefficient.

4. The method for optimizing the liquid injection process of the ionic rare earth ore according to claim 1, wherein during the prospecting process in the step 3, it is necessary to test simultaneously the amount of rare earth ions and impurity ions adsorbed on a mineral earth sample, the impurity ions comprise all non-rare earth cations adsorbed on the surfaces of mineral earth particles, and the average valence state of the impurity ions is determined by using a weighted average method.

5. The method for optimizing the liquid injection process of the ionic rare earth ore according to claim 1, wherein the process of exchange of the ammonium ions and rare earth ions and the process of exchange of the ammonium ions and impurity ions in the step 4 are described by using a two-parameter model, and the competitive exchange characteristics of the rare earth ions and impurity ions are taken into account by conservation of adsorption sites on the surfaces of the mineral earth particles in the exchange processes.

6. The method for optimizing the liquid injection process of the ionic rare earth ore according to claim 1, wherein in the step 1, a liquid injection hole having an ore discovery depth of 0.50-1.00 m and a diameter of 0.10-0.20 m is dug first, then at least 3 sensor burying holes penetrating through an ore bed are dug in a same plane with the central axis of the liquid injection hole, and at least 3 moisture sensors are buried in each sensor burying hole.

7. The method for optimizing the liquid injection process of the ionic rare earth ore according to claim 6, wherein the vertical spacing of adjacent moisture sensors is 0.50-1.50 m.

8. The method for optimizing the liquid injection process of the ionic rare earth ore according to claim 1, wherein a van Genuchten-Mualem model is used to describe the hydraulic properties of the ore body in the step 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0023] FIG. 1 is a schematic diagram of arrangement of moisture sensors.

[0024] FIG. 2 shows test values of the moisture content.

[0025] FIG. 3 is a test result of hydraulic properties.

[0026] FIG. 4 shows the test values and fitted values of rare earth and impurity ion concentrations.

[0027] FIG. 5 is a profile plot for determining a liquid injection scheme.

DESCRIPTION OF THE EMBODIMENTS

[0028] The present disclosure is described in further detail below with reference to the accompanying drawings and specific embodiments.

[0029] A first step, the hydraulic properties of an ore body are tested.

[0030] An ore body having a cross-sectional area of 953.20 m.sup.2 and an ore bed thickness of 7.54 m is selected from a certain ionic rare earth mining area in Changting, Fujian province, a location is selected to dig a liquid injection hole having an ore discovery depth of 0.50 m and a diameter of 0.15 m, undisturbed soil is sampled by using a soil sampling drill in the digging process, the initial mass moisture content measured by a drying method is 16.87%, and the dry density is 1.35 g/cm.sup.3; 3 sensor burying holes penetrating through an ore bed are dug in a same plane with the central axis of the liquid injection hole, the horizontal spacing of adjacent burying holes is 1.00 m, 3 moisture sensors are buried in each sensor burying hole, the vertical spacing of adjacent moisture sensors is 1.00 m, the schematic diagram of arrangement of the moisture sensors is shown in FIG. 1, wherein a topsoil layer 1, an ore bed 2, a liquid injection hole 3, sensor burying holes 4, and moisture sensors 5 are illustrated, the locations where the moisture sensors 5 are located are also referred to as measuring points, deionized water is injected into the liquid injection hole 3, the change of the moisture content at each location is recorded by the moisture sensors 5, i.e. to obtain test values of the moisture content at the measuring points, the results are shown in FIG. 2, the hydraulic properties of the ore body are described by using the van Genuchten-Mualem model, the soil-water characteristic curve and the unsaturated permeability coefficient in the hydraulic properties are a relational expression (1) and a relational expression (2), respectively, the percolation process of moisture within the ore body is described by an Richards equation (a relational expression (3)), by taking peripheral measuring points as boundary conditions of an intermediate measuring point, a difference method is used to solve the relational expression (3) to obtain a calculated value of the moisture content at the intermediate measuring point p.sub.5 as a function of time, by taking a relational expression (4) as an objective function, and taking hydraulic parameters (θ.sub.r, n, α and K.sub.s) as basic unknowns, an interior point algorithm is used to obtain the hydraulic parameters corresponding to the minimized objective function, the result is (0.0665 m.sup.3/m.sup.3, 1.778, 1.198 m.sup.4, 0.3203 m/d), the hydraulic properties of the ore body can be obtained through a test by substituting the calculation result of the hydraulic parameters into the relational expression (1) and the relational expression (2), respectively, the results are as shown in FIG. 3, and this method of determining the hydraulic properties of the ore body is referred to as a hydraulic property inverse analysis method.

[00001]$\begin{array}{cc}\theta ={\theta }_r+{\left({\theta }_s-{\theta }_r\right)\left[\frac{1}{1+{.Math.\alpha h.Math.}^n}\right]}^m,& \left(1\right)\\ K={{K_s\left(\frac{\theta -{\theta }_r}{{\theta }_s-{\theta }_r}\right)}^{1/2}\left[1-\frac{\theta -{\theta }_r}{{\theta }_s-{\theta }_r}{\left({\left(\frac{\theta -{\theta }_r}{{\theta }_s-{\theta }_r}\right)}^{-\frac{1}{m}}-1\right)}^{\frac{n-1}{n}}\right]}^2,& \left(2\right)\\ \frac{\partial \theta }{\partial t}=\frac{1}{r}\frac{\partial }{\partial r}\left(rD\frac{\partial \theta }{\partial r}\right)+\frac{\partial }{\partial z}\left(D\frac{\partial \theta }{\partial z}\right)-\frac{\partial K}{\partial z},& \left(3\right)\\ \mathrm{OF}={.Math.\tilde{\theta }-{\theta }_b.Math.}_2.& \left(4\right)\end{array}$

[0031] In the relational expressions (1)-(4), θ is volumetric moisture content, abbreviated as moisture content, θ.sub.r and θ.sub.s are residual moisture content and saturated moisture content, respectively, α, n and m are parameters related to pore distribution, m=1−1/n, h is a suction head, K.sub.s and K are a saturated permeability coefficient and a non-saturated permeability coefficient, respectively, D is a diffusion coefficient, D=−Kdθ/dh, t is time, z is a vertical coordinate, r is a radial coordinate, OF is an objective function, b is hydraulic parameters, b=b (θ.sub.r, n, α, K.sub.s), ∥ ∥.sub.2 is a 2-norm operation, {tilde over (θ)} is a test value of the moisture content at the intermediate measuring point, and θ.sub.b is the calculated value of the moisture content at the corresponding intermediate measuring point p.sub.5 when the hydraulic parameters adopt b.

[0032] A second step, the diffusion degree of the ore body is tested.

[0033] The soil-water characteristic curve tested in the first step is fitted by using a fractal model of the soil-water characteristic curve shown in a relational expression (5) with h.sub.max and D.sub.f as the basic unknowns to obtain h.sub.max and D.sub.f, 0.4837 m and 2.510, respectively; the h.sub.max and D.sub.f are substituted into a relational expression (6) to obtain a penetration curve of non-reactive ions under fractal theory and the penetration curve is fitted by using a relational expression (7) with the diffusion degree a.sub.L and true pore flow rate u.sub.L as basic unknowns to obtain α.sub.L and u.sub.L, 4.61×10.sup.−2 m/d and 0.2314 m/d, respectively.

[00002]$\begin{array}{cc}\frac{\theta }{{\theta }_s}={\left(\frac{h_{\max }}{h}\right)}^{3-D_f},& \left(5\right)\\ C_f=\frac{{\int }_{r_{\min }}^{r_{\max }}2Q_r{r}_L^{-D_f}d{r}_L}{{\int }_{r_{\min }}^{r_{\max }}\pi J{r}_L^{4-D_f}d{r}_L},& \left(6\right)\\ C_{\mathrm{CDE}}=\frac{1}{2}\mathrm{erfc}\left(\frac{L_z-u_{L}t}{2\sqrt{D_{L}t}}\right).& \left(7\right)\end{array}$

[0034] In the relational expressions (5)-(7), h.sub.max is a suction head corresponding to the maximum pore size, D.sub.f is a fractal dimension, C.sub.f is the outflow concentration of non-reactive ions of the fractal model, r.sub.min and r.sub.max are taken to be 0.53×10.sup.−6 m and 1.23×10.sup.−6 m, respectively, r.sub.L is a pore radius within the ore body, J=2.43×10.sup.6, L.sub.z is a thickness of an ore bed, Q.sub.r=0 when t<2L.sub.z/Jr.sub.L.sup.2, Q.sub.r=Jπr.sub.L.sup.4/2 when t≥2L.sub.z/Jr.sub.L.sup.2, C.sub.CDE is the outflow concentration of the convection-diffusion equation, u.sub.L is a true pore flow rate, D.sub.L is a hydrodynamic diffusion coefficient, D.sub.L=α.sub.Lu.sub.L, and α.sub.L is the diffusion degree.

[0035] A third step, the spatial distribution of the rare earth grade and the impurity grade of the ore body prior to leaching is determined.

[0036] Prospecting holes with a diameter of 0.12 m penetrating through the ore bed are formed in the ore body every other 15.00 m, samples are taken once every other 1.50 m, continuous leaching is performed with 20 g/L of ammonium sulfate, the concentrations of rare earth and all impurity ions in the leachate are tested by using an ICP-MS instrument, the average valence state of the impurity ions is determined by a weighted average method of dividing the product of the valence state and concentration of various impurity ions by the total concentration, the result is +2.31, the mass of the oxides corresponding to the rare earth and impurities in the leachate is divided by the mass of the mineral earth to obtain the grades of the rare earth and impurities in the mineral earth, the spatial distribution of the grades of the rare earth and impurities at each coordinate (x, y, z, ERE, EIM) (x, y and z are coordinates, and ε.sub.RE and ε.sub.IM are the grades of the rare earth and impurities, respectively) is (7.5, 7.5, 1.5, 0.26‰, 0.40‰), (7.5, 7.5, 3.0, 0.65‰, 0.12‰), (7.5, 7.5, 4.5, 0.80‰, 0.13‰), (7.5, 7.5, 6.0, 0.51‰, 0.32‰), (7.5, 22.5, 1.5, 0.25‰, 0.36‰), (7.5, 22.5, 3.0, 0.55‰, 0.23‰), (7.5, 22.5, 4.5, 0.85‰, 0.10‰), (7.5, 22.5, 6.0, 0.43‰, 0.30‰), (22.5, 7.5, 1.5, 0.22‰, 0.41‰), (22.5, 7.5, 3.0, 0.70‰, 0.26‰), (22.5, 7.5, 4.5, 0.65‰, 0.29‰), (22.5, 7.5, 6.0, 0.47‰, 0.33‰), (22.5, 22.5, 1.5, 0.24‰, 0.43‰), (22.5, 22.5, 3.0, 0.47‰, 0.32‰), (22.5, 22.5, 4.5, 0.85‰, 0.09‰), and (22.5, 22.5, 6.0, 0.28‰, 0.51‰), respectively.

[0037] A fourth step, model parameters of exchange of rare earth ions and impurity ions with ammonium ions are determined.

[0038] 10 centrifuge cartridges of 100 mL are taken, 10-50 g (20 g for this embodiment) of mineral earths are added, respectively, 80 mL of an ammonium sulfate solution of 1.0-20.0 g/L is added sequentially, stirring is performed with a magnetic stirrer for 2 h, and the concentrations of rare earth ions and impurity ions in the leachate are tested by using an ICP-MS instrument, the results are as shown in FIG. 4, and the process of exchange for ammonium ions and rare earth ions and the process of exchange for ammonium ions and impurity ions are described by using a two-parameter model, as shown in a relational expression (8) and a relational expression (9).

[00003]$\begin{array}{cc}\frac{C_{s0}^{RE}-\frac{V_L}{m_s}{C}_{aq}^{RE}}{C_{\mathrm{aq}}^{RE}}=\exp \left(p_1\ln \left(\frac{\frac{3M_N{V}_L}{M_{RE}{m}_s}{C}_{aq}^{RE}+\frac{2.31M_N{V}_L}{M_{\mathrm{IM}}{m}_s}{C}_{aq}^{\mathrm{IM}}}{C_{aq0}^N-\frac{3M_N}{M_{RE}}{C}_{aq}^{RE}-\frac{2.31M_N}{M_{\mathrm{IM}}}{C}_{aq}^{\mathrm{IM}}}\right)+p_2\right),& \left(8\right)\\ \frac{C_{s0}^{\mathrm{IM}}-\frac{V_L}{m_s}{C}_{aq}^{\mathrm{IM}}}{C_{aq}^{\mathrm{IM}}}=\exp \left(p_3\ln \left(\frac{\frac{3M_N{V}_L}{M_{RE}{m}_s}{C}_{aq}^{RE}+\frac{2.31M_N{V}_L}{M_{\mathrm{IM}}{m}_s}{C}_{aq}^{\mathrm{IM}}}{C_{aq0}^N-\frac{3M_N}{M_{RE}}{C}_{aq}^{RE}-\frac{2.31M_N}{M_{\mathrm{IM}}}{C}_{aq}^{\mathrm{IM}}}\right)+p_4\right).& \left(9\right)\end{array}$

[0039] In the relational expression (8) and the relational expression (9), V.sub.L, and m.sub.s are the volume of the added ammonium sulfate solution and the mass of the added mineral earth, respectively, p.sub.1, p.sub.2, p.sub.3 and p.sub.4 are model parameters of the two-parameter model, C.sub.s0.sup.RE and C.sub.s0.sup.IM are the concentrations of rare earth ions and impurity ions on the ore sample prior to leaching, respectively, C.sub.s0.sup.REε.sub.REM.sub.RE/M.sub.REO, C.sub.s0.sup.IM=ε.sub.IMM.sub.IM/M.sub.IMO, ε.sub.RE and ε.sub.IM are the rare earth grade and the impurity grade, respectively, M.sub.RE and M.sub.REO are the relative molecular masses of the rare earth ions and the rare earth oxides, respectively, M.sub.IM and M.sub.IMO are the relative molecular masses of the impurity ions and the corresponding oxides, respectively, MN is the relative molecular mass of the ammonium ions, CR.sub.aq.sup.RE and C.sub.aq.sup.IM are the concentrations of the rare earth ions and the impurity ions in the leachate, respectively, and C.sub.aq0.sup.N is the concentration of the added ammonium sulfate solution.

[0040] The model parameters (p.sub.1, p.sub.2, p.sub.3, p.sub.4) of exchange for the rare earth ions and impurity ions with ammonium ions are determined to be (3.82, 24.57, 3.96, 27.23) by fitting the experimental data in FIG. 4 by using the relational expression (8) and the relational expression (9) to yield the fitted value curve in FIG. 4.

[0041] A fifth step, the liquid injection process is optimized.

[0042] A relational expression (10) is used to describe the percolation process of moisture within the ore body, and a relational expression (11) is used to describe the transport process of the ammonium ions, rare earth ions and impurity ions within the ore body.

[00004]$\begin{array}{cc}\frac{\partial \theta }{\partial t}=\frac{\partial }{\partial x}\left(K_x\frac{\partial h}{\partial x}\right)+\frac{\partial }{\partial y}\left(K_y\frac{\partial h}{\partial y}\right)+\frac{\partial }{\partial z}\left(K_z\frac{\partial h}{\partial z}\right)-\frac{\partial K_z}{\partial z},& \left(10\right)\\ \frac{\partial \left(\theta C_x\right)}{\partial t}=\frac{\partial }{\partial x}\left(\theta D_x\frac{\partial C_X}{\partial x}\right)+\frac{\partial }{\partial y}\left(\theta D_y\frac{\partial C_X}{\partial y}\right)+\frac{\partial }{\partial z}\left(\theta D_z\frac{\partial C_X}{\partial z}\right)-\frac{\partial \left(\theta u_x{C}_X\right)}{\partial x}-\frac{\partial \left(\theta u_y{C}_X\right)}{\partial y}-\frac{\partial \left(\theta u_z{C}_X\right)}{\partial z}.& \left(11\right)\end{array}$

[0043] In the relational expression (10) and the relational expression (11), X═NH for the ammonium ions, X=RE for the rare earth ions, X=IM for the impurity ions, K.sub.x, K.sub.y and K.sub.z are the non-saturated permeability coefficients in x, y and z directions, respectively, u.sub.x, u.sub.y and u.sub.z are the true pore flow rates in x, y and z directions, respectively, D.sub.x, D.sub.y and D.sub.z are the hydrodynamic diffusion coefficients in x, y and z directions, respectively, D.sub.x=α.sub.xu.sub.x, D.sub.y=α.sub.yu.sub.y, D.sub.z=α.sub.zu.sub.z, α.sub.x, α.sub.y and α.sub.z are the diffusion degrees in x, y and z directions, respectively, and the mineral earth isotropy problem is assumed, u.sub.x=u.sub.y=u.sub.z=u.sub.L, α.sub.x=α.sub.y=α.sub.z=α, and K.sub.x=K.sub.y=K.sub.z=K.

[0044] The leaching process is equivalent to a uniform liquid injection situation, the moisture content is constant to be 0.4500 m.sup.3/m.sup.3 at the boundary between the ore bed and the topsoil layer, the ammonium sulfate concentration injected first is 20 g/L, then underscreen water is injected, the moisture content distribution within the ore body is calculated by using the relational expression (10), the distribution of the ammonium ions, rare earth ions and impurity ions under the action of convection and diffusion is calculated by using the relational expression (11), finally the distribution of the ammonium ions, rare earth ions and impurity ions within the ore body is modified by the relational expression (8) and the relational expression (9), during which the penetration curve of the rare earth ions can be obtained, leaching is ended when the rare earth ion concentration is less than 0.1 g/L, the rare earth ion distribution within the tailings is calculated, and the rare earth leaching rate is calculated by using a relational expression (12).

[00005]$\begin{array}{cc}{\eta }_{RE}=\frac{{\int }_0^{L_x}{\int }_0^{L_y}{\int }_0^{L_z}{C}_{s0}^{RE}\mathrm{dxdydz}-{\int }_0^{L_x}{\int }_0^{L_y}{\int }_0^{L_z}{C}_{s,\mathrm{end}}^{RE}\mathrm{dxdydz}}{{\int }_0^{L_x}{\int }_0^{L_y}{\int }_0^{L_z}{C}_{s0}^{RE}\mathrm{dxdydz}}.& \left(12\right)\end{array}$

[0045] In the relational expression (12), η.sub.RE is the rare earth leaching rate, L.sub.x, L.sub.y, and L.sub.z are the length, and width of the ore body, and the thickness of the ore bed, respectively, and C.sub.s,end.sup.RE is the distribution of rare earth ion concentration within the ore body after leaching.

[0046] The concentration and total amount of the injected ammonium sulfate solution are changed, the relationship between the rare earth leaching rate and the concentration and dosage of the injected ammonium sulfate solution can be obtained, the results are shown in FIG. 5, the target leaching rate is set to 0.95, a vertical line is drawn in the figure, and moves horizontally to the right, the coordinates of the first intersection of the vertical line with the profile line of the leaching rate of 0.95 are the concentration and dosage of the injected ammonium sulfate, results are 134.63 t and 35.16 g/L, respectively, liquid injection meshes of 1.50 m×1.50 m are formed in the ore body, a liquid collection project is arranged at the mountain foot with a rare earth grade of 0.25‰ as a boundary grade, an ammonium sulfate solution having a concentration of 35.16 g/L is injected into the liquid injection meshes, after 134.63 t of ammonium sulfate is completely injected, then the underscreen water is injected, after the rare earth ion concentration in the mother liquor is less than 0.01 g/L, the leaching is completed, tailings are taken to test the rare earth grade of the tailings in the ore body, and the actual leaching rate of the leaching process is calculated to be 0.93, and thus it can be seen that the method presented in this patent can better determine the liquid injection scheme (the concentration and dosage of the injected ammonium sulfate).

[0047] The above are only the preferred embodiments of the present disclosure, and the protection scope of the present disclosure is not limited to the above-mentioned embodiments. All technical solutions under the idea of the present disclosure belong to the protection scope of the present disclosure. It should be noted that for those of ordinary skill in the art, several improvements and modifications without departing from the principle of the present disclosure should also be regarded as the protection scope of the present disclosure.