Method for reducing viscosity of barite concentrate

Abstract

The invention belongs to the field of mineral treatment, and particularly relates to a method for reducing the viscosity of barite concentrate, which comprises the following steps: carrying out first-stage modification treatment on the barite concentrate through an organic modifier in advance to obtain first-stage modified barite; performing second-stage modification treatment on the first-stage modified barite through an inorganic modifier to obtain viscosity-reduced barite; the organic modifier comprises a compound shown as a formula 1 (# imgabs 0 #) and a compound shown as a formula 2 (# imgabs 1 #) in a weight ratio of (7-9): (1-3); the inorganic modifier comprises sodium salt and magnesium salt in a molar ratio of (5-8): (2-5). According to the invention, the organic modifier compounded by the formula 1 and the formula 2 is innovatively adopted to carry out first-stage modification treatment, then the sodium-magnesium combined inorganic modifier is adopted to carry out second-stage modification treatment, and combined control of the components and proportion of the modifier is further matched, so that synergism can be realized, the viscosity of the barite can be effectively reduced, and the performance of the barite is improved. And the physical and chemical property degradation of the barite can be effectively reduced.

Description

Technical Field

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

[0002] Barite (BaSO 4 ) is an important industrial mineral, widely used in the fields of petroleum, chemical industry, etc. However, the quality of barite ore is currently low, and flotation technology is usually used to improve the grade and specific gravity of the concentrate. Although the concentrate after flotation purification has a high specific gravity, it is often too viscous due to surface adsorption of impurities, flotation reagents (mainly organic collectors) or particle agglomeration, which affects subsequent processing (such as drilling fluid ratio).

[0003] In the prior art, viscosity is often improved by physical grinding or roasting. For example, Chinese patent publication number CN118218125A discloses a method for crushing barite to reduce viscosity. Chinese patent publication number CN108452952A discloses a method for reducing the viscosity of flotation barite concentrate by high-temperature roasting 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 few methods in the prior art that can simply and efficiently reduce the viscosity of barite flotation concentrate. Summary of the invention

[0005] In view of 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 subjected to a first-stage modification treatment with an organic modifier in advance to obtain a first-stage modified barite; and 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 in a weight ratio of 7-9:1-3; the inorganic modifier includes sodium salt and water-soluble magnesium salt in a molar ratio of 5-8:2-5;

[0008] Formula 1

[0009] Formula 2

[0010] The R is H, C 1 ~C 4 Alkyl, C 1 ~C 4At least one of alkoxy, halogen, trifluoromethyl, nitro, carboxyl, and amide;

[0011] The M is H, Na, K or NH 4 .

[0012] In view of the difficulty in removing the collecting agent on the surface of barite concentrate and the difficulty in meeting the viscosity requirement of less than 100 mPa·s, the present invention innovatively adopts a composite organic modifier of Formula 1 and Formula 2 for the first stage of modification treatment, and then adopts the sodium-magnesium combined inorganic modifier for the second stage of modification treatment, and further cooperates with the combined control of the composition and proportion of the modifier, so that synergy can be achieved, the viscosity of the barite can be effectively reduced, and the deterioration of the physical and chemical properties of the barite can be effectively reduced.

[0013] In the present invention, the barite concentrate is a barite mineral with a collector adsorbed on the surface in a targeted manner; 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 capture barite. 6 ~C 20 Fatty acids and their salts, C 6 ~C 20 At least one of sulfuric acid and its salts.

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

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

[0017] Preferably, in the organic modifier, the R may 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 organic modifier to barite concentrate is 1-10 mL / g; 3-5 mL / g.

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

[0022] In the present invention, there is no particular 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 of modification treatment is 1 to 3 hours.

[0024] In the present invention, in the inorganic modifier, 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 ions, 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-to-solid ratio in the second modification treatment stage is 1-10 mL / g; further, it can be 3-5 mL / g.

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

[0031] Preferably, the second modification treatment lasts for 1 to 3 hours.

[0032] Beneficial Effects

[0033] 1. The present invention innovatively subjects the barite concentrate and an organic modifier to a first modification treatment, and then subjects the barite concentrate to a second modification treatment with an inorganic modifier, and based on the combined control of the composition, proportion and treatment sequence of the organic modifier and the inorganic modifier, synergy can be achieved, which can effectively reduce the adsorption of organic components on the surface of the barite and reduce its viscosity. In addition, the degradation effect on the intrinsic physicochemical structure of the barite can also be reduced.

[0034] 2. The chemical treatment method of barite concentrate provided by the present invention is simple, the removal rate of reagents on the surface of barite concentrate is high, the process is pollution-free and the cost is low, and the viscosity of the treated barite concentrate is not higher than 100 mPa·s, which is far lower than the national standard requirement of 130 mPa·s. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 The present invention is a process flow chart of barite concentrate treatment.

[0036] Figure 2 These are infrared spectra of the barite concentrate of Example 1 before and after chemical treatment.

[0037] Figure 3 The following are scanning electron microscope images of the barite concentrate before and after chemical treatment of Example 1, wherein (a) is the SEM image before treatment, and (b) is the SEM image of the barite after treatment of Example 1B. DETAILED DESCRIPTION

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

[0039] In the present invention, as an illustrative scheme, the Formula 1 is represented by Formula 1A as a typical example, and the Formula 1A is a compound of Formula 1 in which R is H and M is H.

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

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

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

[0043] In the following cases, the Na + All are derived from sodium chloride. 2+ All derived from magnesium chloride.

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

[0045] In the present invention, the viscosity test scheme may be a known one, and may be measured according to the relevant provisions and operating procedures of Sections 3.12 and 3.13 of GB / T 5005-2010.

[0046] Example 1

[0047] The detailed steps of reducing the viscosity effect of barite concentrate in the present invention are:

[0048] 1. Step 1: Barite Concentrate

[0049] Select barite flotation concentrate from Gansu, concentrate BaSO 4 The grade is 92%, and the viscosity of the concentrate is 220.0 mPa·s;

[0050] 2. The first stage of modification:

[0051] In a single experiment, 2000 g of barite flotation concentrate was 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 was 20%. During the stirring process, the solid-liquid ratio was set to 1:3 (g / mL), the stirring speed was 750 rpm, the solution temperature was 25 °C, and the stirring time was 2 h.

[0052] A section of modified barite is obtained by filtration and its viscosity is measured after drying.

[0053] 3. The second stage of modification:

[0054] Take 1000g of the modified barite sample prepared in step 2 and mix it with NaCl and MgCl 2 of inorganic modifier solution, wherein Na + The concentration is 0.3 mol / L, Mg 2+ The concentration was 0.15 mol / L, the solution temperature was kept constant at 80°C during stirring, the solid-liquid ratio was set at 1:3 (g / mL), the stirring speed was 750 rpm, and the stirring time was 2 h;

[0055] The barite sample treated with inorganic modifier solution was filtered, dried and the viscosity was measured.

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

[0057]

[0058] Note: The total amount of organic modifier used 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, it can be seen from groups A, B and C that the organic modifier solution of formula 1A and formula 2A mixed in proportion can effectively desorb the collector adsorbed on the surface of the barite flotation concentrate and 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] From the results of groups A, B, C and comparative groups 1 to 3, it can be seen that the combination of formula 1A and formula 2A needs to be mixed in proportion. 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] It can be seen from group B and comparison groups 4 to 7 that the combination of formula 1 and formula 2 described in the present invention can unexpectedly achieve synergy, 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 Guizhou, concentrate BaSO 4 The grade is 90%, and the viscosity of the concentrate is 238.5 mPa·s;

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

[0068] 3. Mix 1000g of the barite sample from step 2 with + and Mg 2+ The inorganic modifier solution was mixed with the inorganic modifier solution, the concentration of the inorganic modifier solution was 0.60 mol / L, the configuration of the combined inorganic modifier solution was changed, the solution temperature was kept constant at 70°C during the stirring process, the solid-liquid ratio was set to 1:3 (g / mL), the stirring speed was 800 rpm, and the stirring time was 3 h;

[0069] 4. The barite sample treated with the inorganic modifier solution was filtered, dried and the viscosity was measured. The relevant experimental results are shown in Table 2.

[0070]

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

[0072] Among them, it can be seen from groups D, E and F that the combined inorganic modifiers described in the present invention are used and the proportions are controlled jointly, so that unexpected synergy can be achieved, and can be combined with the organic components to synergistically reduce the viscosity of barite, and the viscosity of the barite concentrate can be reduced to below 100 mPa·s.

[0073] The results of groups D, E, F and comparison groups 8 to 11 show that the Na + and Mg 2+ Need to be mixed in proportion. + The molar content ratio of Mg is 60~80%; 2+ The molar content of barite is 20-40%. This is conducive to achieving synergy and can reduce the viscosity of barite concentrate to below 100mPa·s.

[0074] The results of group E and comparison groups 12 and 13 show that the use of Na + and Mg 2+ The combination of inorganic modifiers unexpectedly achieves superior performance compared to similar inorganic ion combinations, helping 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 only difference is that the conditions of the first modification in step 2 and the second modification in step 3 are changed (see Table 3), and the 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 of the present invention, based on the combination of the first stage modification treatment of the organic modifier and the second stage modification treatment of the inorganic modifier, can reduce the viscosity of the barite concentrate to below 100 mPa·s.

[0079] Comparative Example 1

[0080] Compared with Group E in Example 2, the only difference is that the organic modifier and the inorganic modifier are treated in one pot. That is, the barite concentrate is placed in a mixed solution containing the organic modifier and the inorganic modifier, wherein the content of the organic modifier and the inorganic modifier is the same as that of Group E in Example 2. After 6 hours of one-pot combined treatment, the viscosity of the barite concentrate was reduced from 238.5 mPa·s to 197.8 mPa·s. The results show that the patent needs to be processed according to steps 2 and 3, and the one-pot combined treatment concentrate has a poor viscosity reduction effect.

[0081] Comparative Example 2

[0082] Compared with Group E in Example 2, the only difference is that the barite concentrate of step 1 is pre-modified by the second stage of step 3, and then the first stage of step 2 is modified. After the second stage of step 3, the viscosity of the barite concentrate is reduced from 238.5 mPa·s to 187.6 mPa·s. After the first stage of step 2, the viscosity of the barite concentrate is reduced from 187.6 mPa·s to 161.8 mPa·s.

[0083] It can be seen from Example 2 and Comparative Example 2 that the organic modification treatment described in the present invention is performed in advance and then the inorganic modification treatment is performed, which can unexpectedly achieve synergy and effectively reduce the viscosity of the barite concentrate.

[0084] Figure 2 The infrared images of the barite concentrate before treatment in Example 1 and the barite after treatment in Example 1B show that the characteristic peak of the collector (2900 cm -1 Location—CH 2 and—CH 3 The intensity of the characteristic peak of

[0085] Figure 3 The scanning electron microscope images of the barite concentrate before the treatment in Example 1 and the barite after the treatment in Example 1B show that the viscosity of the concentrate is reduced, the agglomeration and adsorption between the barite concentrates is reduced, and the particle surface becomes obviously smooth.

[0086] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. It should be noted that the above preferred embodiments should not be regarded as limiting the present invention, and the protection scope of the present invention should be based on the scope defined by the claims. For those skilled in the art, several improvements and modifications can be made without departing from the spirit and scope of the present invention, and these improvements and modifications should also be regarded as 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 pre-modified with an organic modifier to obtain a 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 sodium salt and water-soluble magnesium salt in a molar ratio of 5-8:2-5; Formula 1; Formula 2; The R is at least one of H, C1-C4 alkyl, C1-C4 alkoxy, halogen, trifluoromethyl, nitro, carboxyl, and amide; The 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 adsorbed on the surface in a targeted manner; The collector is C6~C 20 Fatty acids and their salts, C6~C 20 At least one of sulfuric acid and its salts.

3. The method for reducing the viscosity of barite concentrate according to claim 1, characterized in that, In the initial 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 barite concentrate to organic modifier is 1:0.5~1.

5.

5. The method for reducing the viscosity of barite concentrate according to claim 1, characterized in that: The temperature of the first stage of modification treatment is 0~40℃; The first modification treatment time is 1~3h.

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

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

9. The method for reducing the viscosity of barite concentrate according to claim 1, characterized in that: The temperature of the second modification treatment is 60~100℃.

10. The method for reducing the viscosity of barite concentrate according to claim 1, characterized in that: The second modification treatment time is 1~3h.

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