Method for determining molecular composition of associate on surface of mineral

Abstract

The invention relates to the technical field of mineral separation, in particular to a method for determining molecular composition of an associate on the surface of a mineral. According to the method, a combination of a first reagent and a second reagent is used as a flotation combination reagent, and the flotation combination reagents with different molar ratios are subjected to mineral flotation; obtaining the mineral recovery rate of the flotation combined reagents with different molar ratios after mineral flotation; establishing a mineral recovery rate change curve by taking the molar ratio of the flotation combined reagent as an abscissa and the mineral recovery rate as an ordinate; according to the mineral recovery rate change curve, horizontal coordinates corresponding to extreme points of the curve are obtained and serve as molar ratios of different reagent molecules in the associates generated by the flotation combined reagent on the surface of the mineral, and molecular composition and spatial conformation of the associates are obtained. By means of the method, the molar ratio and the spatial orientation of different agent molecules in the associate generated on the surface of the mineral when the combined collecting agent is located at the flotation extreme point can be rapidly judged.

Description

Technical Field

[0001] The present invention relates to the technical field of mineral processing, and in particular to a method for determining the molecular composition of mineral surface associates. Background Art

[0002] Flotation is one of the most promising mineral separation technologies in the current mineral processing industry. Its core lies in the use of flotation reagents to achieve efficient mineral separation. However, with the increasing complexity of mineral resources, the performance of traditional flotation reagents can no longer meet the needs of modern mineral processing. Therefore, the development of high-efficiency flotation collectors has become a key link in promoting the upgrading of flotation technology.

[0003] Currently, there are two main research and development directions in flotation collectors. While synthesizing new flotation collectors is a viable approach, this approach has significant limitations, including a long R&D cycle and high costs, making it difficult for companies to accept. On the other hand, combining two or more traditional collectors is more common. For example, some collectors have strong mineral collection capabilities but weak selectivity, while others have strong selectivity but weak collection capabilities. Combining these two types of collectors to create a new collector significantly improves both its mineral collection capability and selectivity. Due to these advantages, combined collectors have been widely used in mineral processing practices.

[0004] While combination reagents have demonstrated promising results in practical applications, their mechanism of action remains largely unresolved. It is generally believed that the synergistic effect of combined collectors on mineral flotation results from the formation of complexes between two or more collectors on the mineral surface due to intermolecular interactions. However, current technologies are unable to accurately determine the molecular composition and spatial conformation of these complexes, hindering progress in theoretical research on combination reagents and the development of novel, highly efficient combined flotation reagent systems. Summary of the Invention

[0005] In order to solve the problem that the existing technology cannot accurately determine the molecular composition and spatial conformation of the associated complex, the present invention provides a method for determining the molecular composition of the associated complex on the surface of a mineral.

[0006] The method of the present invention can rapidly determine the molar ratio and spatial orientation of different reagent molecules within the association complex formed on the mineral surface when the combined collector is at the flotation extreme point. This method has important practical significance and promotes the advancement of basic theoretical research on combined flotation reagents, shortens R&D cycles, and develops new, highly efficient combined reagents.

[0007] To achieve the above objectives, the technical solutions of the present invention are as follows.

[0008] The present invention provides a method for determining the molecular composition of mineral surface association compounds, comprising the following steps: A combination of a first reagent and a second reagent is used as a flotation combination reagent, and by changing the molar ratio of the first reagent and the second reagent, flotation combination reagents with different molar ratios are used for mineral flotation; both the first reagent and the second reagent have a polar group and a non-polar group; the mineral recovery rate after the flotation combination reagents with different molar ratios are used for mineral flotation is obtained; a mineral recovery rate change curve is established with the molar ratio of the flotation combination reagents as the horizontal coordinate and the mineral recovery rate as the vertical coordinate; based on the mineral recovery rate change curve, the horizontal coordinate corresponding to the extreme value point of the curve is obtained as the molar ratio of different reagent molecules in the associated complex generated by the flotation combination reagent on the mineral surface, and the molecular composition and spatial conformation of the associated complex are obtained.

[0009] Preferably, the method for obtaining the horizontal coordinate corresponding to the extreme point of the curve is: All data points of the mineral recovery rate variation curve are fitted to obtain a fitting curve; and according to the fitting curve, the abscissa corresponding to the extreme value point of the fitting curve is obtained.

[0010] Preferably, the method for obtaining the spatial conformation of the associated complex is: The data points at both ends of the mineral recovery rate change curve are connected to obtain a straight line; the synergistic effect of the flotation combination reagent on the mineral flotation is determined based on the positional relationship between all data points and the straight line; and the spatial conformation of the association complex is obtained based on the synergistic effect of the flotation combination reagent on the mineral flotation.

[0011] Preferably, the conditions for determining the synergistic relationship of the flotation combination reagents on mineral flotation are: When all data points are above the straight line, the flotation combination reagents have a positive synergistic effect on mineral flotation; or, when all data points are below the straight line, the flotation combination reagents have a negative synergistic effect on mineral flotation.

[0012] Preferably, the conditions for determining the spatial conformation of the associated complex are: When the flotation combination reagents have a positive synergistic effect on mineral flotation, the first reagent and the second reagent are both adsorbed on the mineral surface with the polar groups facing the mineral surface to form a first pattern associate; or, when the flotation combination reagents have a negative synergistic effect on mineral flotation, at least one of the first reagent and the second reagent is adsorbed on the mineral surface with the non-polar groups facing the mineral surface to form a second pattern associate; and the molar number of the non-polar groups facing the mineral surface is less than the molar number of the non-polar groups facing the slurry.

[0013] Preferably, when the flotation combination reagents have a negative synergistic effect on mineral flotation, and the molar number of the first reagent adsorbed on the mineral surface is greater than the molar number of the second reagent, the molecules of the first reagent are adsorbed on the mineral surface with the polar base facing the mineral surface, and the molecules of the second reagent are adsorbed on the mineral surface with the non-polar base facing the mineral surface to form a second pattern association complex.

[0014] Preferably, the first agent and the second agent are independently selected from any one of fatty acid collectors, alkyl sulfonic acid collectors, alkyl sulfate collectors, alkyl hydroxamic acid collectors and alkyl phosphonic acid collectors.

[0015] Preferably, the first agent and the second agent are independently selected from any one of sodium oleate, benzohydroxamic acid, sodium ricinoleate, salicylic hydroxamic acid, linoleic acid, nonylphosphonic acid, dodecylsulfonic acid, benzaldehyde oxime, hexadecylsulfuric acid and heptylphosphonic acid; and the ingredients of the first agent and the second agent are different.

[0016] Preferably, the method for obtaining the molecular composition of the associated complex is: Assuming the first reagent is A, the second reagent is B, the molar ratio of different reagent molecules in the complex formed by the flotation combination reagent on the mineral surface is x : y , then the molecular composition of the association complex is A x B y .

[0017] Preferably, during mineral flotation, the mineral particle size in the slurry is less than 0.074 mm and the mineral purity is greater than 98%.

[0018] Preferably, the method for flotation of minerals using flotation composition reagents of different molar ratios is: The total molar concentration of the first reagent and the second reagent is set to C, and the concentration of the first reagent is changed from 0 to C by changing the molar ratio of the first reagent and the second reagent; the flotation composition reagents with different molar ratios are used for mineral flotation.

[0019] Beneficial effects of the present invention: 1. The method of the present invention can quickly and accurately determine the molecular composition and spatial conformation of the complex formed by two combined agents on a mineral surface. In particular, when the two agents have a negative synergistic effect, it can also determine the orientation of the two agent molecules on the mineral surface. The method of the present invention has important practical significance and promotes the basic theoretical research of combined agents and the development of new and highly effective combined agents. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a curve showing the change in mineral recovery rate and reagent concentration in one embodiment of the present invention.

[0021] Figure 2 The spatial conformations of the complex in two modes: (a) is the spatial conformation of the complex in the "shoulder-to-shoulder" mode; (b) is the spatial conformation of the complex in the "sandwich" mode.

[0022] Figure 3 The recovery rate curve is an "inverted V-shaped" curve with global extreme points and local extreme points.

[0023] Figure 4 The recovery rate curve is "V-shaped" with global extreme points and local extreme points.

[0024] Figure 5 The recovery rate curve is an "inverted L-shaped" curve with global extreme points and local extreme points.

[0025] Figure 6 The recovery rate curve is an "L-shaped" curve with global extreme points and local extreme points.

[0026] Figure 7 The recovery rate curve is an “M-type” curve with global and local extreme points.

[0027] Figure 8 The recovery rate curve is an "inverted M-shaped" curve with global extreme points and local extreme points.

[0028] Figure 9 The curve of the mineral recovery rate and the change of the reagent concentration in Example 1 is shown.

[0029] Figure 10 This is a curve showing the change in mineral recovery rate and reagent concentration in Example 2.

[0030] Figure 11 This is a curve showing the change in mineral recovery rate and reagent concentration in Example 3.

[0031] Figure 12 This is a curve showing the change in mineral recovery rate and reagent concentration in Example 4.

[0032] Figure 13 This is a curve showing the change in mineral recovery rate and reagent concentration in Example 5. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0034] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative work shall fall within the scope of protection of the present invention.

[0035] The present invention provides a method for determining the molecular composition of mineral surface association compounds, comprising the following steps: Step 1: Using a combination of a first reagent and a second reagent as a flotation combination reagent, and performing mineral flotation on the flotation combination reagents with different molar ratios by changing the molar ratio of the first reagent and the second reagent; both the first reagent and the second reagent have polar groups and non-polar groups.

[0036] In the present invention, the flotation reagent combination is composed of two reagents, both of which are flotation collectors. The first reagent and the second reagent are independently selected from any one of a fatty acid collector, an alkyl sulfonic acid collector, an alkyl sulfate collector, an alkyl hydroxamic acid collector, and an alkyl phosphonic acid collector. For example, the first reagent and the second reagent are independently selected from any one of sodium oleate, benzohydroxamic acid, sodium ricinoleate, salicylic hydroxamic acid, linoleic acid, nonylphosphonic acid, dodecylsulfonic acid, benzaldehyde oxime, hexadecylsulfuric acid, and heptylphosphonic acid; and the first and second reagents have different ingredients.

[0037] During mineral flotation, the mineral particle size in the slurry is less than 0.074 mm and the mineral purity is greater than 98%. In the following examples, the ore samples used in the experiments are single minerals with a purity greater than 98% and a particle size less than 0.074 mm.

[0038] The method for using flotation composition reagents with different molar ratios to carry out mineral flotation is as follows: setting the total molar concentration of the first reagent and the second reagent to C, by changing the molar ratio of the first reagent and the second reagent, the concentration of the first reagent changes from 0 to C; and using the flotation composition reagents with different molar ratios to carry out mineral flotation.

[0039] In the following examples, during the flotation experiments, the total molar concentration of the two reagents in the flotation system remained unchanged, and the molar ratio of the two reagents was 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1 or 10:0. Flotation experiments of minerals were carried out under the above 11 molar ratios.

[0040] During the flotation process, there are three options for the order of adding the combined reagents: one is to add the first reagent to the flotation pulp first, and then add the second reagent after a few minutes; the second is to add the second reagent to the flotation pulp first, and then add the first reagent after a few minutes; the third is to pre-mix the two reagents before adding them to the flotation pulp.

[0041] Step 2: Obtain the mineral recovery rate after mineral flotation using flotation combination reagents with different molar ratios.

[0042] Step 3: Establish a mineral recovery rate curve with the molar ratio of the flotation combination reagent as the horizontal axis and the mineral recovery rate as the vertical axis.

[0043] The mineral recovery rate curve was drawn using Origin software. The mineral recovery rate curve is plotted with the mineral recovery rate as the y-axis and the 11 molar ratio data points as the abscissa, yielding a curve showing the mineral recovery rate versus the concentration of the two reagents.

[0044] For example, assuming that the first reagent is A, the second reagent is B, the total concentration of the two reagents is C, and the molar ratio of the two reagents is [A]:[B]=0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1 or 10:0, the curve of the mineral recovery rate and the change of reagent concentration in the experiment is as follows: Figure 1 shown.

[0045] Step 4: According to the mineral recovery rate change curve, obtain the horizontal coordinate corresponding to the extreme point of the curve as the molar ratio of different reagent molecules in the complex generated by the flotation combination reagent on the mineral surface, and obtain the molecular composition and spatial conformation of the complex.

[0046] The method for obtaining the abscissa corresponding to the extreme point of the curve is: fitting all data points of the mineral recovery rate variation curve to obtain a fitting curve; and obtaining the abscissa corresponding to the extreme point of the fitting curve according to the fitting curve.

[0047] All data points of the mineral recovery rate change curve are fitted mainly using the B-Spline mode. The horizontal coordinate corresponding to the extreme point of the curve is the molar ratio of different reagent molecules in the complex generated by the two reagent molecules on the mineral surface, which ultimately determines the molecular composition of the complex.

[0048] The method for obtaining the molecular composition of the association complex is as follows: the first reagent is set as A, the second reagent is set as B, and the molar ratio of different reagent molecules in the association complex generated by the flotation combination reagent on the mineral surface is x : y , then the molecular composition of the association complex is A x B y .

[0049] Assume that the two reagents generate A on the mineral surface x B y The chemical reaction of the reagent in the flotation system can be expressed as: xA+yB=A x B y .

[0050] Assume that the concentration of free A in the flotation pulp is m , moL / L; the concentration of free B is n , moL / L; free A x B y The concentration is q, moL / L; the equilibrium constant of the reaction is k ;but .

[0051] Taking the logarithm of both sides, we get: .

[0052] By fully differentiating both sides of Equation 3, we can obtain: .

[0053] When the mineral recovery rate reaches a maximum or minimum value, dq=0, so at this time: .

[0054] Assume that the total concentration of the first reagent in the slurry is [A], and the total concentration of the first reagent in the slurry is [B], then [A]= m+ xq ; [B] = n+yq ; we can get: m+xq+n+yq=W;m+n+ ( x+y ) q=W .

[0055] General m+n+ ( x+y ) q=W Differentiate, and we get ( x+y )d q=-dm-dn.

[0056] At the extreme point, d q= 0, then dm=-dn.

[0057] General dm=-dn Substitution We can get: .

[0058] Because the molar ratio of the first agent and the second agent ; General Relational Substitution We can get: .in, represents the molar ratio of the first drug to the second drug.

[0059] From the above deduction, we can know that A x B y The ratio of x and y in the type association complex is equal to the ratio of the total concentrations of A and B in the pulp at the extreme point of the curve, that is, A x B y molecular composition.

[0060] The method for obtaining the spatial conformation of the association complex is: connecting the data points at both ends of the mineral recovery rate change curve to obtain a straight line; determining the synergistic effect of the flotation combination reagent on the mineral flotation based on the positional relationship between all the data points and the straight line; and obtaining the spatial conformation of the association complex based on the synergistic effect of the flotation combination reagent on the mineral flotation.

[0061] Among them, the conditions for determining the synergistic relationship between flotation combination reagents and mineral flotation are: When all data points are above the straight line, the flotation combination reagents have a positive synergistic effect on mineral flotation; or, when all data points are below the straight line, the flotation combination reagents have a negative synergistic effect on mineral flotation.

[0062] Connect the points at both ends of the experimental curve to form a straight line. If the experimental data points are above the straight line, the combined reagents have a positive synergistic effect on mineral flotation, such as Figure 2 As shown in Figure (a), it can be called the "shoulder-to-shoulder" model. On the contrary, the two reagents have a negative synergistic effect on mineral flotation, such as Figure 2 As shown in Figure (b), it can be called the "sandwich" model. Figure 2 In the Chinese language, polar means polar; -polar or -polar- represents a polar group. M represents the mineral surface, which is the area where the flotation reagent is adsorbed on the mineral surface.

[0063] The first agent and the second agent both have polar groups and non-polar groups. The general structural formula of the flotation collector is as follows: ; Among them, the part framed on the left is the non-polar group; the part framed on the right is the polar group.

[0064] The non-polar group is a hydrocarbon chain composed of carbon atoms, which may have branches or double bonds, and n is generally a value between 6 and 17; the polar group is generally a carboxyl group, sulfonic acid group, sulfate group, oxime group and other solid-philic groups.

[0065] The conditions for determining the spatial conformation of the association complex are: when the flotation combination reagents have a positive synergistic effect on mineral flotation, the first reagent and the second reagent are both adsorbed on the mineral surface in a manner that the polar groups face the mineral surface to form a first pattern association complex; or, when the flotation combination reagents have a negative synergistic effect on mineral flotation, at least one of the first reagent and the second reagent is adsorbed on the mineral surface in a manner that the non-polar groups face the mineral surface to form a second pattern association complex; and the molar number of the non-polar groups facing the mineral surface is less than the molar number of the non-polar groups facing the slurry.

[0066] For example, when the flotation combination reagents have a negative synergistic effect on mineral flotation, and the molar number of the first reagent adsorbed on the mineral surface is greater than the molar number of the second reagent, the molecules of the first reagent are adsorbed on the mineral surface with the polar base facing the mineral surface, and the molecules of the second reagent are adsorbed on the mineral surface with the non-polar base facing the mineral surface to form a second pattern complex.

[0067] Only when the polar groups of the collector molecules face the mineral surface and the non-polar groups face the pulp, the mineral surface will be hydrophobic and the flotation process can proceed. Therefore, only when the two reagents are adsorbed on the mineral surface with their polar groups facing the mineral surface and non-polar groups facing the pulp will they have a positive synergistic effect, which can be called a "shoulder-to-shoulder" mode. Figure 2 As shown in Figure (a); negative synergistic effect will only occur when at least one of the two reagent molecules is combined on the mineral surface in the form of a non-polar group facing the mineral surface and a polar group facing the mineral slurry, which can be called a "sandwich" model, such as Figure 2 As shown in Figure (b).

[0068] Assume that the molecular structure of the complex formed by the two reagents on the mineral surface is A x B y , x and y are the molar numbers of A and B in the association molecules respectively; when the reagent combination has a negative synergistic effect on mineral flotation, the spatial conformation of the association is: the reagent molecules with a small molar number in the association form an association in the form of polar groups facing the slurry, while the reagent molecules with a large molar number form an association in the form of non-polar groups facing the slurry.

[0069] When two reagents have a negative synergistic effect on mineral flotation, at least one of the two reagent molecules associates on the mineral surface with its non-polar group facing the mineral surface and its polar group facing the pulp. If the molecules with a higher molar number face the pulp with their polar group, the mineral surface becomes completely hydrophilic, and flotation cannot occur. Therefore, only when the molecules with a higher molar number face the pulp with their non-polar group and the molecules with a lower molar number face the pulp with their polar group, will the mineral surface still have a certain degree of hydrophobicity, allowing flotation to occur, and the recovery rate will definitely be lower than the theoretical recovery rate when there is no synergistic effect between the two reagents.

[0070] The method of the present invention has strong universality and is suitable for Figure 3 The "inverted V shape", Figure 4 "V-shaped", Figure 5 The "inverted L-shaped" Figure 6 "L-shaped", Figure 7 "M-type", Figure 8 The "inverted M-shaped" recovery rate curve with global extreme points and local extreme points is applicable.

[0071] The technical solution of the present invention is further described below through specific embodiments.

[0072] In the following examples, the methods described are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0073] Example 1 2 g of a fluorite single mineral sample with a fineness of -0.074 mm was mixed with 35 mL of water to prepare a slurry. The purity of the fluorite single mineral was greater than 98%.

[0074] The mineral flotation method is as follows: first, sodium oleate is added, stirred for 2 minutes, benzohydroxamic acid is added, stirring is continued for 3 minutes, and then flotation is performed for 3 minutes to obtain concentrate and tailings. The concentrate yield is the mineral recovery rate of the flotation process.

[0075] The total concentration of reagents in the flotation system is 1×10 -4 moL / L, the molar concentration ratio of sodium oleate and benzohydroxamic acid was selected as 0:10, 1:9, 2:8, 3:7, 9:1, 10:0, a total of 11 points, the experimental results are as follows Figure 9 shown.

[0076] Depend on Figure 9 It can be seen that when the total concentrations of the two reagent molecules A and B in the flotation system are 0.6×10 -5 moL / L and 0.4×10 -5 moL / L, that is, when the molar concentration ratio is 6:4, the mineral recovery rate reaches the maximum. After the pulp is centrifuged, the concentrations of the remaining A and B are measured using a spectrophotometer and a total organic carbon (TOC) meter, and the concentrations are 0.27×10 -5 moL / L and 0.18×10 - 5 moL / L. Therefore, the molar ratio of A and B adsorbed on the mineral surface is (0.6-0.27)×10 -5 / (0.4-0.19)×10 -5 =1.57≈6 / 4. The experimental data points are all above the line connecting the two points [A]:[B]=0:10 and [A]:[B]=10:0, indicating that the two reagents form an A6B4 type complex, and A and B associate on the mineral surface in a "shoulder-to-shoulder" mode.

[0077] Example 2 2 g of a single mineral sample of scheelite with a fineness of -0.074 mm was mixed with 35 mL of water to prepare a slurry. The purity of the single mineral scheelite was greater than 98%.

[0078] The mineral flotation method is: first add sodium ricinoleate, stir for 2 minutes, add salicylic acid and continue stirring for 2 minutes, then float for 3 minutes to obtain concentrate and tailings. The concentrate yield is the mineral recovery rate of the flotation process.

[0079] The total concentration of reagents in the flotation system is 1.2×10 -4 moL / L, the molar concentration ratio of sodium ricinoleate and salicylic acid was selected as 0:10, 1:9, 2:8, 3:7, 9:1, 10:0, a total of 11 points, the experimental results are as follows Figure 10 shown.

[0080] Depend on Figure 10 It can be seen that when the initial concentrations of the two reagent molecules A and B in the flotation system are 0.84×10 - 5 moL / L and 0.36×10 -5 moL / L, that is, the mineral recovery rate reaches the lowest value when the molar concentration ratio is 7:3. After the pulp is centrifuged, the concentrations of the remaining A and B are measured using a spectrophotometer and a total organic carbon (TOC) meter, and the concentrations are 0.54×10 -5 moL / L and 0.23×10 -5 moL / L. Therefore, the molar ratio of A and B adsorbed on the mineral surface is (0.84-0.54)×10 -5 / (0.36-0.23)×10 -5 =2.31≈7 / 3. The experimental data points are all below the line connecting the two points [A]:[B]=0:10 and [A]:[B]=10:0, indicating that the two agents form an A7B3-type "sandwich" complex, with the non-polar group of the A molecule and the polar group of the B molecule oriented toward the slurry on the mineral surface.

[0081] Example 3 2 g of a rutile single mineral sample with a fineness of -0.074 mm was mixed with 35 mL of water to prepare a slurry. The purity of the rutile single mineral was greater than 98%.

[0082] The mineral flotation method is as follows: first add linoleic acid, then add nonylphosphonic acid 3 minutes later, continue stirring for 3 minutes, and then float for 3 minutes to obtain concentrate and tailings. The concentrate yield is the mineral recovery rate of the flotation process. The total concentration of reagents in the flotation system is 2.0×10 -4 moL / L, the molar concentration ratio of linoleic acid and nonylphosphonic acid in the experiment was selected as 0:10, 1:9:2:8, 3:7...........9:1, 10:0, a total of 11 points, the experimental results are as follows Figure 11 shown.

[0083] Depend on Figure 11 It can be seen that when the initial concentrations of the two reagent molecules A and B in the flotation system are 0.6×10 -5 moL / L and 1.4×10 -5moL / L, that is, the mineral recovery rate reaches the highest value when the molar concentration ratio is 3:7. After the pulp is centrifuged, the concentrations of the remaining A and B are measured using a spectrophotometer and a total organic carbon (TOC) meter, and the concentrations are 0.31×10 -5 moL / L and 0.72×10 -5 moL / L. Therefore, the molar ratio of A and B adsorbed on the mineral surface is (0.6-0.31)×10 -5 / (1.4-0.72)×10 -5 =0.426≈3 / 7. The experimental data points are all below the line connecting the two points [A]:[B]=0:10 and [A]:[B]=10:0, indicating that the two reagents form an A3B7 type association complex, and A and B associate on the mineral surface in a "shoulder-to-shoulder" mode.

[0084] Example 4 2 g of a barite single mineral sample with a fineness of -0.074 mm was mixed with 35 mL of water to prepare a slurry. The purity of the barite single mineral was greater than 98%.

[0085] The mineral flotation method is: first add dodecyl sulfonic acid, then add benzaldehyde oxime 2 minutes later, continue stirring for 3 minutes, and then float for 4 minutes to obtain concentrate and tailings. The concentrate yield is the mineral recovery rate of the flotation process.

[0086] The total concentration of reagents in the flotation system is 2.0×10 -4 moL / L, the molar concentration ratio of dodecylsulfonic acid and benzaldehyde oxime was selected as 0:10, 1:9:2:8, 3:7...........9:1, 10:0, a total of 11 points, the experimental results are as follows Figure 12 shown.

[0087] Depend on Figure 12 It can be seen that when the initial total concentrations of the two reagent molecules A and B in the flotation system are 1.0×10 - 5 moL / L and 1.0×10 -5 moL / L, that is, the mineral recovery rate reaches the highest value when the molar concentration ratio is 1:1. After the pulp is centrifuged, the concentrations of the remaining A and B are measured using a spectrophotometer and a total organic carbon (TOC) meter, and the concentrations are 0.59×10 -5 moL / L and 0.58×10 -5 moL / L. Therefore, the molar ratio of A and B adsorbed on the mineral surface is (1.0-0.58)×10 -5 / (1.0-0.59)×10 -5=1.02≈1. The experimental data points are all below the line connecting the two points [A]:[B]=0:10 and [A]:[B]=10:0, indicating that the two reagents form an AB-type "sandwich" complex, and the ratio of the polar groups of the A and B molecules facing the slurry and the polar groups facing the mineral surface is close to 1.

[0088] Example 5 2 g of a cassiterite mineral sample with a fineness of -0.074 mm was mixed with 35 mL of water to prepare a slurry, and the purity of the cassiterite mineral was greater than 98%.

[0089] The mineral flotation method is: hexadecyl sulfuric acid and heptylphosphonic acid are pre-mixed and added to the flotation pulp, stirred for 3 minutes and then floated for 4 minutes to obtain concentrate and tailings. The concentrate yield is the mineral recovery rate of the flotation process.

[0090] The total concentration of reagents in the flotation system is 1.8×10 -4 moL / L, the molar concentration ratio of hexadecylsulfuric acid to heptylphosphonic acid was selected as 0:10, 1:9:2:8, 3:7...9:1, 10:0, a total of 11 points, the experimental results are as follows Figure 13 shown.

[0091] Depend on Figure 13 It can be seen that the curve is an "M-type" curve with two extreme points within the test range. The total concentration ratio of the two reagent molecules A and B is 4:6 and 8:2, respectively. The slurry was filtered when the recovery rate reached the extreme value, and the filtrate was measured for the free concentrations of the remaining A and B using a spectrophotometer and a total organic carbon (TOC) meter. When the total concentration ratio of A and B was 4:6, the free concentrations of A and B in the filtrate were 0.35×10 -4 moL / L and 0.525×10 -4 moL / L, so the molar ratio of A and B adsorbed on the mineral surface is (0.72-0.35) / (1.08-0.525)=0.67≈2 / 3. When the total concentration ratio of A and B is 8:2, the free concentrations of A and B in the filtrate are 0.48×10 -4 moL / L and 0.12×10 -4 moL / L, the molar ratio of A and B adsorbed on the mineral surface is (1.44-0.48) / (0.36-0.12)=4=8 / 2

[0092] In summary, the methods provided by the embodiments of the present invention can quickly and accurately determine the molecular composition and spatial conformation of the complex formed by two combined agents on a mineral surface. In particular, when the two agents exhibit a negative synergistic effect, the orientation of the two agent molecules on the mineral surface can also be determined. The methods of the embodiments of the present invention have important practical significance and promote the basic theoretical research of combined agents and the development of new and highly effective combined agents.

[0093] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for determining the molecular composition of mineral surface association compounds, characterized in that: The following steps are involved: A combination of a first reagent and a second reagent is used as a flotation combination reagent, and the flotation combination reagents with different molar ratios are used for mineral flotation by changing the molar ratio of the first reagent and the second reagent; both the first reagent and the second reagent have a polar group and a non-polar group; Obtaining the mineral recovery rate after mineral flotation using flotation reagent combinations with different molar ratios; The mineral recovery rate curve is established with the molar ratio of the flotation reagent combination as the horizontal axis and the mineral recovery rate as the vertical axis; According to the mineral recovery rate change curve, the horizontal coordinate corresponding to the extreme point of the curve is obtained as the molar ratio of different reagent molecules in the association complex generated by the flotation combination reagent on the mineral surface, and the molecular composition and spatial conformation of the association complex are obtained.

2. The method for determining the molecular composition of mineral surface association compounds according to claim 1, characterized in that: The method to obtain the horizontal coordinate corresponding to the extreme point of the curve is: All data points of the mineral recovery rate variation curve are fitted to obtain a fitting curve; and according to the fitting curve, the abscissa corresponding to the extreme value point of the fitting curve is obtained.

3. The method for determining the molecular composition of mineral surface association compounds according to claim 1, characterized in that: The method for obtaining the spatial conformation of the complex is: Connect the data points at both ends of the mineral recovery rate change curve to obtain a straight line; According to the positional relationship between all data points and the straight line, the synergistic effect of the flotation combination reagents on the mineral flotation is determined; According to the synergistic effect of the flotation combination reagents on the mineral flotation, the spatial conformation of the association complex is obtained.

4. The method for determining the molecular composition of mineral surface association compounds according to claim 3, characterized in that: The conditions for determining the synergistic relationship between flotation combination reagents and mineral flotation are: When all data points are above the straight line, the flotation combination reagents have a positive synergistic effect on mineral flotation; Alternatively, when all data points are below the straight line, the flotation combination reagents have a negative synergistic effect on mineral flotation.

5. The method for determining the molecular composition of mineral surface association compounds according to claim 4, characterized in that: The conditions for determining the spatial conformation of the complex are: When the flotation combination reagents have a positive synergistic effect on the mineral flotation, the first reagent and the second reagent are both adsorbed on the mineral surface in a manner that the polar groups face the mineral surface to form a first mode association complex; Alternatively, when the flotation combination reagents have a negative synergistic effect on mineral flotation, at least one of the first reagent and the second reagent is adsorbed on the mineral surface in a manner such that the non-polar group faces the mineral surface to form a second mode association complex; Moreover, the molar number of the non-polar groups facing the mineral surface is less than the molar number of the non-polar groups facing the pulp.

6. The method for determining the molecular composition of mineral surface association compounds according to claim 5, characterized in that: When the flotation combination reagents have a negative synergistic effect on mineral flotation, and the molar number of the first reagent adsorbed on the mineral surface is greater than the molar number of the second reagent, the molecules of the first reagent are adsorbed on the mineral surface with the polar base facing the mineral surface, and the molecules of the second reagent are adsorbed on the mineral surface with the non-polar base facing the mineral surface to form a second pattern complex.

7. The method for determining the molecular composition of mineral surface association compounds according to claim 1, characterized in that: The first agent and the second agent are independently selected from any one of fatty acid collectors, alkyl sulfonic acid collectors, alkyl sulfate collectors, alkyl hydroxamic acid collectors and alkyl phosphonic acid collectors.

8. The method for determining the molecular composition of mineral surface association compounds according to claim 1, characterized in that: The method of using flotation composition reagents of different molar ratios for mineral flotation is as follows: The total molar concentration of the first agent and the second agent is set to C, and the concentration of the first agent is varied from 0 to C by changing the molar ratio of the first agent to the second agent; The flotation composition reagents with different molar ratios are used for mineral flotation.

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