A method for reducing the viscosity of barite concentrate

Abstract

The present invention belongs to the field of mineral processing, and particularly relates to a method for reducing the viscosity of barite concentrate. The barite concentrate is first subjected to a first-stage modification treatment with an organic modifier to obtain first-stage modified barite; subsequently, the first-stage modified barite is subjected to a second-stage modification treatment with an inorganic modifier to obtain barite with reduced viscosity. The organic modifier includes compounds of formula 1 (#imgabs0#) and formula 2 (#imgabs1#) in a weight ratio of 7-9:1-3; the inorganic modifier includes sodium salt and magnesium salt in a molar ratio of 5-8:2-5. The present invention innovatively uses a composite organic modifier of formula 1 and formula 2 for the first-stage modification treatment, and then uses the sodium-magnesium combined inorganic modifier for the second-stage modification treatment, further combined with the control of the composition and ratio of the modifier, so as to achieve synergy, effectively reduce the viscosity of barite, and effectively reduce the deterioration of the physical and chemical properties of barite.

Description

Technical Field

[0001] The present invention belongs to the technical field of mineral processing, and specifically relates to the field of barite mineral treatment. Background Art

[0002] Barite (BaSO4) is an important industrial mineral and is widely used in fields such as petroleum and chemical industry. However, the quality of current barite ores is generally low, and flotation technology is usually used to improve the grade and specific gravity of concentrates. Although the concentrate after flotation purification has a relatively high specific gravity, it often has too high viscosity due to surface adsorption of impurities, flotation reagents (mainly organic collectors) or particle aggregation, which affects subsequent processing (such as drilling fluid formulation).

[0003] In the prior art, the viscosity is often improved by physical grinding or calcination methods. For example, a Chinese patent with publication number CN118218125A discloses a means of crushing barite to reduce viscosity. A Chinese patent document with publication number CN108452952A discloses a method of reducing the viscosity of flotation barite concentrate by high-temperature calcination at 200 - 800 °C. Although the existing means can reduce the viscosity of flotation barite to a certain extent, the energy consumption is high, and it is difficult to achieve large-scale utilization.

[0004] In summary, there are still few simple and efficient methods in the prior art to reduce the viscosity of barite flotation concentrate. Summary of the Invention

[0005] Aiming at the problem that the existing process means for reducing the viscosity of barite flotation concentrate are relatively scarce, the present invention proposes a method for reducing the viscosity of barite concentrate, aiming to provide a method that can gently and efficiently reduce the viscosity of barite concentrate.

[0006] A method for reducing the viscosity of barite concentrate, wherein the barite concentrate is first subjected to a first-stage modification treatment with an organic modifier to obtain first-stage modified barite; then the first-stage modified barite is subjected to a second-stage modification treatment with an inorganic modifier to obtain barite with reduced viscosity;

[0007] The organic modifier includes compounds of formula 1 and formula 2 with a weight ratio of 7 - 9:1 - 3; the inorganic modifier includes sodium salts and water-soluble magnesium salts with a molar ratio of 5 - 8:2 - 5;

[0008] Formula 1

[0009] Formula 2

[0010] The R is at least one of H, C1 - C4 alkyl, C1 - C4 alkoxy, halogen, trifluoromethyl, nitro, carboxyl, amide group;

[0011] The M is H, Na, K or NH4.

[0012] Aiming at the problem that it is difficult to remove the collector on the surface of barite concentrate and the viscosity is difficult to meet the requirement of below 100 mPa·s, the present invention innovatively adopts an organic modifier compounded by Formula 1 and Formula 2 for the first-stage modification treatment, and then adopts the combined sodium-magnesium inorganic modifier for the second-stage modification treatment. Further cooperating with the combined control of the composition and proportion of the modifier, synergism can be achieved, the viscosity of barite can be effectively reduced, and the deterioration problem of the physical and chemical properties of barite can be effectively reduced.

[0013] In the present invention, the barite concentrate is a barite mineral with a collector surface-targetedly adsorbed thereon; it can be obtained based on a conventional flotation method.

[0014] For example, in the present invention, the collector can be any collector known in the industry that can be used to collect barite. For example, the collector is at least one of fatty acids and their salts with C6~C 20 and sulfuric acid and its salts with C6~C 20 .

[0015] In the present invention, the barite concentrate can be dispersed in a solution containing an organic modifier such as an aqueous solution for the first-stage modification treatment to obtain a first-stage modified material. Subsequently, the first-stage modified material is placed in a solution containing an inorganic modifier such as an aqueous solution for the second-stage modification treatment to obtain barite with reduced viscosity.

[0016] In the present invention, the combined control of the composition of the organic modifier, inorganic modifier and the treatment sequence is the key to synergistically improving the viscosity reduction effect of barite concentrate. Research also shows that further optimizing the control of the composition of the organic modifier, inorganic modifier and the treatment conditions is expected to further optimize the synergism of the process.

[0017] Preferably, in the organic modifier, R can be H.

[0018] Preferably, in the organic modifier, the weight ratio of Formula 1 to Formula 2 is 8~9:1~2.

[0019] Preferably, in the starting solution system of the first-stage modification treatment, the mass concentration of the organic modifier is 15~30%, preferably 15~20%.

[0020] Preferably, the weight ratio of barite concentrate to organic modifier is 1:0.5~1.5; further, it can be 1:0.6~1.2. In addition, in the present invention, the liquid-solid ratio of the organic modifier to barite concentrate is 1~10 mL / g; 3~5 mL / g.

[0021] In the present invention, the first-stage modification treatment process is carried out under stirring, and there is no special requirement for the stirring speed. For example, it can be 200 - 2000 rpm.

[0022] In the present invention, there is no special requirement for the temperature of the first-stage modification treatment. For example, it can be 0 - 40 °C, and further can be room temperature (15 - 35 °C);

[0023] In the present invention, the time of the first-stage modification treatment is 1 - 3 h.

[0024] In the present invention, among the inorganic modifiers, the sodium salt is at least one of sodium chloride, carbonate, bicarbonate, nitrate, sulfate, and acetate.

[0025] The magnesium salt is a water-soluble salt of magnesium ion. For example, it can be at least one of magnesium chloride, magnesium nitrate, and magnesium acetate.

[0026] In the present invention, the molar ratio of the sodium salt to the magnesium salt in the inorganic modifier is 6 - 8:2 - 4.

[0027] Preferably, in the starting solution system of the second-stage modification treatment, the concentration of the inorganic modifier is 0.15 - 0.75 mol / L; preferably 0.25 - 0.65 mol / L, and further can be 0.4 - 0.5 mol / L.

[0028] Preferably, the weight ratio of the first-stage modified barite to the inorganic modifier is 1:0.05 - 0.5.

[0029] In the present invention, the liquid-solid ratio in the second-stage modification treatment stage is 1 - 10 mL / g; further can be 3 - 5 mL / g.

[0030] Preferably, the temperature of the second-stage modification treatment is 60 - 100 °C, and further is 70 - 80 °C.

[0031] Preferably, the time of the second-stage modification treatment is 1 - 3 h.

[0032] Beneficial effects

[0033] 1. In the present invention, innovatively, the barite concentrate and the organic modifier are subjected to the first-stage modification treatment, and then the inorganic modifier is used for the second-stage modification treatment. Based on the combined control of the components, ratios, and treatment sequences of the organic modifier and the inorganic modifier, synergy can be achieved, effectively reducing the adsorption of organic components on the surface of barite, reducing its viscosity, and moreover, reducing the deteriorating effect on the intrinsic physical and chemical structure of barite.

[0034] 2. The chemical treatment method for barite concentrate provided by the present invention is simple, with a high removal rate of agents on the surface of barite concentrate, no pollution in the process and low cost. The viscosity of the treated barite concentrate is not higher than 100 mPa·s, and the index is far lower than the national standard requirement of 130 mPa·s. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is the process flow diagram of the barite concentrate treatment process of the present invention.

[0036] Figure 2 They are the infrared spectrograms of the barite concentrate before and after chemical treatment in Example 1.

[0037] Figure 3 They are the scanning electron micrographs of the barite concentrate before and after chemical treatment in Example 1. Among them, (a) is the scanning electron micrograph before treatment, and (b) is the SEM image of the barite after treatment in Example 1B. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0038] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below in conjunction with specific embodiments and the drawings.

[0039] In the present invention, as an exemplary scheme, the compound of Formula 1 takes Formula 1A as a typical case, and the compound of Formula 1A is a compound of Formula 1 where R is H and M is H.

[0040] In addition, the compound of Formula 2 takes Formula 2A as a typical case, and the compound of Formula 2A is a compound of Formula 2 where M is H.

[0041] In the present invention, the barite concentrate is the barite concentrate obtained by a conventional flotation process (the grade of barite can be, for example, 85-95%). For example, as an exemplary scheme, in the following cases, the collector used in the barite flotation in Example 1 is oxidized paraffin soap, and the main component is a fatty acid containing a carboxyl group; the dosage of the collector in the flotation process can be 450-550 g / t.

[0042] In Example 2, the collectors used in the barite flotation are sodium oleate and sodium dodecyl sulfate, and their dosage ratio in the flotation is 4:1. Among them, the dosage of the collector used in the flotation is, for example, 450-550 g / t.

[0043] In the following cases, the Na + all comes from sodium chloride. The Mg 2+ all comes from magnesium chloride.

[0044] In the present invention, the solution system in the first-stage modification treatment and the second-stage modification treatment can be water.

[0045] In the present invention, the test scheme for viscosity can be well-known and can be determined according to the relevant regulations and operation steps in Sections 3.12 and 3.13 of GB / T 5005-2010.

[0046] Example 1

[0047] The detailed steps for the present invention to reduce the viscosity effect of barite concentrate are as follows:

[0048] 1. Step 1: Barite concentrate

[0049] Select the flotation concentrate of barite from a certain place in Gansu. The grade of BaSO4 in the concentrate is 92%, and the measured viscosity value of the concentrate is 220.0 mPa·s.

[0050] 2. First-stage modification treatment:

[0051] For a single experiment, 2000 g of barite flotation concentrate is stirred with an organic modifier solution. The composition and proportion of the organic modifier are shown in Table 1. The solute mass fraction of the organic modifier solution in each group is 20%. During the stirring process, the solid-liquid ratio is set to 1:3 (g / mL), the stirring speed is 750 rpm, the solution temperature is 25°C, and the stirring time is 2 h.

[0052] Filter to obtain the first-stage modified barite, dry it, and measure its viscosity.

[0053] 3. Second-stage modification treatment:

[0054] Take 1000 g of the first-stage modified barite sample prepared in Step 2 and mix it with an inorganic modifier solution containing NaCl and MgCl2, where the concentration of Na + is 0.3 mol / L, and the concentration of Mg 2+ is 0.15 mol / L. During the stirring process, the solution temperature is kept constant at 80°C, the solid-liquid ratio is set to 1:3 (g / mL), the stirring speed is 750 rpm, and the stirring time is 2 h;

[0055] Filter and dry the barite sample after treatment with the inorganic modifier solution, and measure its viscosity.

[0056] The relevant experimental results are shown in Table 1 below.

[0057]

[0058] Note: The total amount of the organic modifier in each group is the same.

[0059] In Table 1, Comparative Formula A is: ;

[0060] Comparative Formula B is: ;

[0061] Comparative Formula C is: ;

[0062] Among them, as can be seen from Groups A, B, and C, when the organic modifiers of Formula 1A and Formula 2A are mixed in proportion in the organic modifier solution, it can effectively desorb the collector adsorbed on the surface of the barite flotation concentrate, reduce the viscosity of the barite powder. After being treated with the combined inorganic modifier solution, the viscosity of the barite powder is reduced to below 100 mPa·s.

[0063] As can be seen from the results of Groups A, B, C and Comparative Groups 1-3, the combined Formula 1A and Formula 2A need to be mixed in proportion. Among them, the weight content of Formula 1A is 70-90%, preferably 80-90%; the weight content of Formula 2A is 10-30%, preferably 10-20%.

[0064] As can be seen from Group B and Comparative Groups 4-7, the combination of Formula 1 and Formula 2 of the present invention can unexpectedly achieve synergy, and can significantly enhance the desorption effect of barite at the same dosage, and has a better effect on reducing the viscosity of barite concentrate powder.

[0065] Example 2

[0066] 1. Select barite flotation concentrate from a certain place in Guizhou. The grade of BaSO4 in the concentrate is 90%, and the measured viscosity value of the concentrate is 238.5 mPa·s;

[0067] 2. For each single experiment, 2000 g of barite flotation concentrate is stirred and treated with the organic modifier solution. The mass fraction of the organic modifier solution is 30%. Among them, in the organic modifier, the weight content of Formula 1A is 70%, and the weight content of Formula 2A is 30%. During the stirring process, the solid-liquid ratio is set to 1:3 (g / mL), the stirring speed is 800 rpm, the solution temperature is 20 °C, and the stirring time is 3 h.

[0068] 3. Mix 1000 g of the barite sample in Step 2 with the inorganic modifier solution containing Na + and Mg 2+ . The concentration of the inorganic modifier solution is 0.60 mol / L. Change the configuration method of the combined inorganic modifier solution. During the stirring process, the solution temperature is kept constant at 70 °C, the solid-liquid ratio is set to 1:3 (g / mL), the stirring speed is 800 rpm, and the stirring time is 3 h;

[0069] 4. Filter and dry the barite sample after being treated with the inorganic modifier solution to measure the viscosity. The relevant experimental results are shown in Table 2.

[0070]

[0071] Note: Na + , K + , Mg 2+ , Ca2+ All are chloride salts of their respective ions, and the total molar amount of metal cations in each group is the same, all being 0.6 M.

[0072] Among them, from groups D, E, and F, it can be seen that by using the combined inorganic modifiers described in the present invention and controlling the combined control of the proportions, unexpectedly, synergy can be achieved, which can be combined with the organic components, and can synergistically reduce the viscosity of barite, and the viscosity of barite concentrate can be reduced to below 100 mPa·s.

[0073] From the results of groups D, E, F and comparative groups 8 - 11, it can be seen that in the combined inorganic modifier, Na + and Mg 2+ need to be mixed in proportion. Among them, the molar content ratio of Na + is 60 - 80%; the molar content of Mg 2+ is 20 - 40%. In this way, it is beneficial to achieve synergy, and the viscosity of barite concentrate can be reduced to below 100 mPa·s.

[0074] From the results of group E and comparative groups 12 and 13, it can be seen that the combined inorganic modifier of Na + and Mg 2+ can unexpectedly obtain better performance compared with similar inorganic ion combinations, which helps to reduce the viscosity of the treated barite concentrate to below 100 mPa·s.

[0075] Example 3

[0076] Compared with group E in Example 2, the difference is only that the conditions of the first modification in step 2 and the second modification in step 3 are changed (see Table 3), and other operations and parameters are the same as those in Example 2. The relevant research results are shown in Table 3.

[0077]

[0078] It can be seen from Table 3 that the process described in the present invention, based on the combination of the first - stage modification treatment with the organic modifier and the second - stage modification treatment with the inorganic modifier, can achieve a reduction in the viscosity of barite concentrate, and can make it reach below 100 mPa·s.

[0079] Comparative Example 1

[0080] Compared with Group E in Example 2, the difference is only that the organic modifier and the inorganic modifier are treated jointly in one pot. That is to say, the barite concentrate is placed in a mixed solution containing the organic modifier and the inorganic modifier, and the contents of the organic modifier and the inorganic modifier are the same as those in Group E of Example 2. After being treated jointly in one pot for 6 h, the viscosity of the barite concentrate decreases from 238.5 mPa·s to 197.8 mPa·s. The results show that the patent needs to be processed according to Step 2 and Step 3, and the effect of viscosity reduction of the concentrate by the one-pot joint treatment is poor.

[0081] Comparative Example 2

[0082] Compared with Group E in Example 2, the difference is only that the barite concentrate in Step 1 is first subjected to the second-stage modification treatment of Step 3, and then the first-stage modification treatment of Step 2. After the second-stage modification treatment of Step 3, the viscosity of the barite concentrate decreases from 238.5 mPa·s to 187.6 mPa·s. After the first-stage modification treatment of Step 2, the viscosity of the barite concentrate decreases from 187.6 mPa·s to 161.8 mPa·s.

[0083] It can be seen from Example 2 and Comparative Example 2 that by first performing the organic modification treatment described in the present invention and then performing the inorganic modification treatment, synergism can be unexpectedly achieved, and the viscosity of the barite concentrate can be effectively reduced.

[0084] Figure 2 The infrared spectra of the barite concentrate before the treatment in Example 1 and the barite after the treatment in Example 1B show that, before and after the treatment, the intensities of the characteristic peaks of the collector (the characteristic peaks at the positions of —CH2 and —CH3) are significantly reduced. -1 The characteristic peaks of —CH2 and —CH3) are significantly reduced.

[0085] Figure 3 Shown are the scanning electron microscope images of the barite concentrate before the treatment in Example 1 and the barite after the treatment in Example 1B. It can be seen that the viscosity of the concentrate decreases, the cohesive adsorption between the barite concentrates decreases, and the particle surface becomes significantly smoother.

[0086] The above examples are only used to illustrate the technical solutions of the present invention and are not intended to limit them. It should be noted that the above preferred embodiments should not be regarded as limitations of the present invention, and the protection scope of the present invention should be defined by the scope of the claims. For those of ordinary skill in the art, without departing from the spirit and scope of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as within the protection scope of the present invention.

Claims

1. A method for reducing the viscosity of barite concentrate, characterized in that, The barite concentrate is first subjected to a first-stage modification treatment with an organic modifier to obtain first-stage modified barite; Subsequently, the first-stage modified barite is subjected to a second-stage modification treatment with an inorganic modifier to obtain barite with reduced viscosity; The organic modifier includes compounds of Formula 1 and Formula 2 in a weight ratio of 7-9:1-3; the inorganic modifier includes a sodium salt and a water-soluble magnesium salt in a molar ratio of 5-8:2-5; Formula 1; Formula 2; R is at least one of H, C1-C4 alkyl, C1-C4 alkoxy, halogen, trifluoromethyl, nitro, carboxyl, amide; M is H, Na, K or NH4.

2. The method for reducing the viscosity of barite concentrate according to claim 1, characterized in that, The barite concentrate is a barite mineral with a collector surface-targetedly adsorbed thereon; The collector is at least one of fatty acids and their salts with C6~C 20 and sulfuric acid and their salts with C6~C 20 .

3. The method for reducing the viscosity of barite concentrate according to claim 1, characterized in that, In the starting solution system of the first-stage modification treatment, the mass concentration of the organic modifier is 15-30%.

4. The method for reducing the viscosity of barite concentrate according to claim 1, characterized in that, The weight ratio of the barite concentrate to the organic modifier is 1:0.5-1.

5.

5. The method for reducing the viscosity of barite concentrate as claimed in claim 1, wherein, The temperature of the first-stage modification treatment is 0-40 °C; The time of the first-stage modification treatment is 1-3 h.

6. The method for reducing the viscosity of barite concentrate according to claim 1, characterized in that, Among the inorganic modifiers, the sodium salt is at least one of sodium chloride, carbonate, bicarbonate, nitrate, sulfate, acetate; The magnesium salt is at least one of magnesium chloride, magnesium nitrate, magnesium acetate.

7. The method for reducing the viscosity of barite concentrate according to claim 1, wherein In the starting solution system of the second-stage modification treatment, the concentration of the inorganic modifier is 0.15-0.75 mol / L.

8. The method for reducing the viscosity of barite concentrate according to claim 7, wherein The liquid-solid ratio of the second-stage modification treatment is 1-10 mL / g.

9. The method for reducing the viscosity of barite concentrate according to claim 1, characterized in that, The temperature of the second-stage modification treatment is 60-100 °C.

10. The method for reducing the viscosity of barite concentrate as described in claim 1, characterized in that, The time of the second-stage modification treatment is 1-3 h.

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