Beneficiation reagent containing stearic acid and preparation method of beneficiation reagent
By constructing a molecular framework of stearic acid-sulfur carboxylic acid-nonionic surfactant and a graded emulsification ultrasonic process, the problems of crystallization and flowability imbalance of stearic acid collector at low temperatures were solved, achieving stable application and efficient separation of the agent in low-temperature environments.
Patent Information
- Application Number
- CN202511270773.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-08
- Publication Date
- 2025-12-16
AI Technical Summary
Existing stearic acid collectors are prone to crystallization at low temperatures, resulting in reduced utilization of active ingredients, imbalance of flowability and adsorption, and severe processing loss of heat-sensitive components, making it difficult to use continuously in cold regions.
A molecular framework of stearic acid-sulfur carboxylic acid-nonionic surfactant was constructed, and a stearic acid-containing mineral processing reagent was prepared by combining staged emulsification and pulsed ultrasound processes to ensure that the reagent maintains fluidity at low temperatures and improves mineral recognition ability.
Maintaining the reagent in a completely liquid state at low temperatures prevents pipe blockage, improves the selective separation of scheelite and calcite, and reduces the decomposition rate of heat-sensitive components, ensuring continuous production in cold regions.
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Figure CN121131065A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of pharmaceutical preparation technology, and in particular to a mineral processing reagent containing stearic acid and its preparation method. Background Technology
[0002] Stearic acid-based composite mineral processing collectors achieve selective adsorption on the surface of oxidized minerals through the synergistic effect of polar groups and non-polar hydrocarbon chains. They are widely used in the froth flotation separation process of non-sulfide minerals such as tungsten, tin, and fluorite. With the depletion of mineral resources and the increasing environmental protection requirements, the development of fatty acid collectors with both high selectivity and environmental adaptability has become a key research direction in the industry. In particular, traditional reagent systems face severe challenges in the low-temperature operating environment of high-altitude or cold-region mining areas, and breakthroughs in molecular structure design and formulation processes are urgently needed.
[0003] The current mainstream stearic acid collector has a pure stearic acid melting point of 54-58℃. In a slurry environment below 15℃, it is easy to crystallize and precipitate, which leads to a sharp drop in the utilization rate of effective ingredients by more than 30% and blockage of the dosing pipeline. At the same time, conventional compounding schemes add excessive amounts of unsaturated fatty acids (such as oleic acid ≥40%) to improve fluidity. However, excessive introduction of double bond structures will weaken the directional adsorption capacity of the agent on the mineral surface, resulting in an increase in the flotation rate of gangue minerals such as calcite by 10-15 percentage points. Existing emulsification processes mostly rely on high temperature (>80℃) and strong stirring to achieve component mixing, which is not only energy-intensive, but also leads to the thermal decomposition and deactivation of functional additives (such as sulfur-containing chelating agents).
[0004] Therefore, in view of the problems of low-temperature crystallization inactivation, adsorption-fluidity imbalance and heat-sensitive component processing loss of existing stearic acid collectors, this invention proposes a mineral processing agent containing stearic acid and its preparation method. Summary of the Invention
[0005] To overcome the problems of low-temperature crystallization inactivation, adsorption-flowability imbalance, and processing loss of heat-sensitive components in existing stearic acid collectors, this invention proposes a stearic acid-containing mineral processing agent and its preparation method. By constructing a molecular structure of "stearic acid-sulfur-containing carboxylic acid-nonionic surfactant", the recognition ability of minerals is enhanced while ensuring low-temperature flowability. At the same time, combined with graded emulsification and pulsed ultrasound processes, the efficient integration of heat-sensitive components is achieved, solving the limitation of low-temperature environment on the application of fatty acid agents.
[0006] The technical solution of the present invention is as follows: a mineral processing reagent containing stearic acid, comprising the following components in mass percentage: stearic acid 40-65%, oleic acid 10-30%, mercaptosuccinic acid 5-15%, nonionic surfactant polyoxyethylene sorbitan monooleate 3-8%, and organic solvent diethylene glycol monobutyl ether 10-25%; The mass ratio of stearic acid to oleic acid is (1.5:1) to (4:1).
[0007] Preferably, the stearic acid is a grade III pure industrial stearic acid with a carbon chain length distribution of C16-C18 ≥ 95% and a melting point range of 54-58℃.
[0008] Preferably, the mercaptosuccinic acid forms an intermolecular hydrogen bond with the carboxyl group of stearic acid through sulfur atoms, constituting a "stearic acid-mercaptosuccinic acid binary synergistic structure", and its sulfur content accounts for 0.5-2.5% of the total mass of the composite collector.
[0009] Preferably, the diethylene glycol monobutyl ether has a purity of ≥99%, a moisture content of ≤0.1% by mass, and a mass ratio of (1.2:1) to (3:1) with the nonionic surfactant polyoxyethylene sorbitan monooleate.
[0010] Preferably, the mineral processing reagent has a kinematic viscosity of 35-65 cSt at 25°C, an electrical conductivity of ≤10 μS / cm, and a pH value of 6.5-7.5.
[0011] As a preferred embodiment, a method for preparing a mineral processing reagent containing stearic acid includes the following steps: S1, add stearic acid and oleic acid to the reaction vessel, heat to 70-80℃ to melt and mix, and stir at a constant temperature for 20-40 minutes; S2, cool to 50-60℃, add mercaptosuccinic acid and diethylene glycol monobutyl ether solvent, and shear emulsify at a rate of 300-600 rpm for 15-20 minutes; S3, add polyoxyethylene sorbitan monooleate, maintain the temperature at 45-55℃, and sonicate for 10-20 minutes; S4, cooled to below 25°C, yields a transparent amber liquid product.
[0012] Preferably, the stearic acid in step S1 needs to be pulverized to D90≤20μm, and nitrogen gas is introduced for protection during the melting and mixing stage, with a nitrogen flow rate of 0.5-1.5L / min.
[0013] Preferably, the shear rate of the shear emulsification in step S2 is 10⁴-10⁵ s. -1 This forms microemulsion droplets with a particle size ≤ 5 μm.
[0014] Preferably, during the ultrasonic treatment in step S3, pulsed energy input is applied with a pulse interval of 0.5-2 seconds and a duty cycle of 60-80%.
[0015] Preferably, the cooling process in step S4 is controlled by a program, with a cooling rate of 1-2℃ / min, and 0.05-0.1% of the total amount of defoamer polydimethylsiloxane is added at 30℃.
[0016] The beneficial effects of this invention are: 1. By precisely controlling the mass ratio of stearic acid to oleic acid (1.5:1-4:1) and introducing polyoxyethylene sorbitan monooleate, this invention maintains a completely liquid state in low-temperature slurry at 5-15℃, and no crystallization occurs after 24 hours of standing. Compared with traditional stearic acid reagents, the lower limit of the applicable temperature is reduced by more than 10℃, thereby avoiding pipeline blockage and loss of effective ingredients, and ensuring continuous production throughout the year in cold regions.
[0017] 2. The innovative addition of mercaptosuccinic acid in this invention involves the interaction of sulfur atoms with mineral metal ions (such as Ca). 2+ Zn 2+ It chelates, and at the same time, its carboxyl group forms an intermolecular hydrogen bond network with stearic acid, constructing a "hydrophobic-chelate" bifunctional structure, which improves the selective separation coefficient of scheelite and calcite while maintaining low-temperature fluidity.
[0018] 3. This invention employs a stepped temperature control process: melting at 70-80℃, emulsification at 50-60℃, and ultrasonication at 45-55℃. Combined with nitrogen protection, this significantly reduces the decomposition rate of heat-sensitive mercaptosuccinic acid and greatly reduces the loss of activity compared to conventional high-temperature emulsification processes. At the same time, pulsed ultrasound ensures the integrity of the functional molecular structure and enhances the reactivity of the drug. Attached Figure Description
[0019] Figure 1 The diagram shown illustrates the preparation process of this invention. Detailed Implementation
[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0021] This invention provides an embodiment of a mineral processing reagent containing stearic acid, comprising the following components by mass percentage: stearic acid 40-65%, oleic acid 10-30%, mercaptosuccinic acid 5-15%, nonionic surfactant polyoxyethylene sorbitan monooleate 3-8%, and organic solvent diethylene glycol monobutyl ether 10-25%. The mass ratio of stearic acid to oleic acid is (1.5:1) to (4:1).
[0022] Please see Figure 1 Example 1:
[0023] Raw material preparation: Weigh out 52.0% stearic acid (tertiary purity, C16-C18≥97%), 18.0% oleic acid, 10.0% mercaptosuccinic acid, 5.0% polyoxyethylene sorbitan monooleate (Tween-80), and 15.0% diethylene glycol monobutyl ether, wherein the stearic acid is ultra-finely pulverized to D90=18μm.
[0024] Preparation process: Stearic acid and oleic acid were added to the reaction vessel, sealed, and high-purity nitrogen was continuously introduced at a flow rate of 1.0 liters per minute to replace the air. The stirrer was started and mixed at a speed of 60 revolutions per minute. At the same time, the temperature was increased to 75°C at a rate of 2°C per minute. The temperature was maintained and stirred for 30 minutes until the stearic acid microcrystals were completely melted to form a uniform transparent amber liquid phase. During this period, the nitrogen protection pressure was maintained at 0.05 MPa.
[0025] The reaction system was cooled to 55°C at a rate of 1°C per minute, and mercaptosuccinic acid and diethylene glycol monobutyl ether solvent were added. A high-speed shear press (500 rpm, shear rate 5 × 10⁴ s⁻¹) was then turned on. -1 Continue emulsifying for 15 minutes to obtain a milky white microemulsion.
[0026] Add polyoxyethylene sorbitan monooleate to the reactor, adjust the temperature to 50°C, start a 500-watt ultrasonic generator, set the frequency to 35 kHz, and use pulse working mode to control the ultrasonic energy input. The specific parameters are 1 second working and 1 second intermittent, and the duty cycle is strictly controlled at 70%. After 15 minutes of treatment, the system becomes semi-transparent.
[0027] Turn off the heating and ultrasonic generator, and cool down to 30°C at a rate of 1.5°C per minute. Add 0.08% polydimethylsiloxane defoamer, and continue cooling to 25°C before stopping the stirring. The resulting product is a free-flowing, amber-colored, transparent liquid.
[0028] Example 2: Raw material preparation: Weigh out 63.0% stearic acid (tertiary purity, C16-C18≥97%), 15.0% oleic acid, 6.0% mercaptosuccinic acid, 4.0% polyoxyethylene sorbitan monooleate (Tween-80), and 12.0% diethylene glycol monobutyl ether, wherein the stearic acid is ultra-finely pulverized to D90=15μm.
[0029] Preparation process: Stearic acid and oleic acid were added to the reaction vessel, sealed, and high-purity nitrogen was continuously introduced at a flow rate of 1.2 liters per minute to replace the air. The stirrer was started and mixed at a speed of 60 revolutions per minute. At the same time, the temperature was increased to 80°C at a rate of 2°C per minute. The temperature was maintained and stirred for 40 minutes until the stearic acid microcrystals were completely melted to form a uniform transparent amber liquid phase. During this period, the nitrogen protection pressure was maintained at 0.05 MPa.
[0030] The reaction system was cooled to 60°C at a rate of 1°C per minute, and mercaptosuccinic acid and diethylene glycol monobutyl ether solvent were added. A high-speed shear press (400 rpm, shear rate 5 × 10⁴ s⁻¹) was then turned on. -1 Continue emulsifying for 20 minutes to obtain a milky white microemulsion.
[0031] Add polyoxyethylene sorbitan monooleate to the reactor, adjust the temperature to 50°C, start a 500-watt ultrasonic generator, set the frequency to 28 kHz, and use pulse working mode to control the ultrasonic energy input. The specific parameters are 1 second working and 0.5 seconds intermittent, and the duty cycle is strictly controlled at 80%. After 10 minutes of treatment, the system becomes semi-transparent.
[0032] Turn off the heating and ultrasonic generator, and cool down to 30°C at a rate of 2°C per minute. Add 0.1% polydimethylsiloxane defoamer, and continue cooling to 25°C before stopping the stirring. The resulting product is a free-flowing, amber-colored, transparent liquid.
[0033] Example 3: Raw material preparation: Weigh out 40.0% stearic acid (tertiary purity, C16-C18≥97%), 30.0% oleic acid, 14.0% mercaptosuccinic acid, 8.0% polyoxyethylene sorbitan monooleate (Tween-80), and 8.0% diethylene glycol monobutyl ether, wherein the stearic acid is ultra-finely pulverized to D90=18μm.
[0034] Preparation process: Stearic acid and oleic acid were added to the reaction vessel, sealed, and high-purity nitrogen was continuously introduced at a flow rate of 0.8 liters per minute to replace the air. The stirrer was started and mixed at a speed of 60 revolutions per minute. At the same time, the temperature was increased to 70°C at a rate of 2°C per minute. The temperature was maintained and stirred for 25 minutes until the stearic acid microcrystals were completely melted to form a uniform transparent amber liquid phase. During this period, the nitrogen protection pressure was maintained at 0.05 MPa.
[0035] The reaction system was cooled to 55°C at a rate of 1°C per minute, and mercaptosuccinic acid and diethylene glycol monobutyl ether solvent were added. A high-speed shear press (600 rpm, shear rate 5 × 10⁴ s⁻¹) was then turned on. -1 Continue emulsifying for 15 minutes to obtain a milky white microemulsion.
[0036] Add polyoxyethylene sorbitan monooleate to the reactor, adjust the temperature to 45°C, start a 500-watt ultrasonic generator, set the frequency to 40 kHz, and use pulse working mode to control the ultrasonic energy input. The specific parameters are 1 second working and 1 second intermittent, and the duty cycle is strictly controlled at 60%. After 20 minutes of treatment, the system becomes semi-transparent.
[0037] Turn off the heating and ultrasonic generator, and cool down to 30°C at a rate of 1°C per minute. Add 0.05% polydimethylsiloxane defoamer, and continue cooling to 25°C before stopping the stirring. The resulting product is a free-flowing, amber-colored, transparent liquid.
[0038] Example 4: Raw material preparation: Weigh out 45.0% stearic acid (tertiary purity, C16-C18≥97%), 22.0% oleic acid, 14.0% mercaptosuccinic acid, 4.5% polyoxyethylene sorbitan monooleate (Tween-80), and 14.5% diethylene glycol monobutyl ether, wherein the stearic acid is ultra-finely pulverized to D90=18μm.
[0039] Preparation process: Stearic acid and oleic acid were added to the reaction vessel, sealed, and high-purity nitrogen was continuously introduced at a flow rate of 1.5 liters per minute to replace the air. The stirrer was started and mixed at a speed of 60 revolutions per minute. At the same time, the temperature was increased to 72°C at a rate of 2°C per minute. The temperature was maintained and stirred for 35 minutes until the stearic acid microcrystals were completely melted to form a uniform transparent amber liquid phase. During this period, the nitrogen protection pressure was maintained at 0.05 MPa.
[0040] The reaction system was cooled to 58°C at a rate of 1°C per minute, and mercaptosuccinic acid and diethylene glycol monobutyl ether solvent were added. A high-speed shear press (550 rpm, shear rate 5 × 10⁴ s⁻¹) was then turned on. -1 Continue emulsifying for 18 minutes to obtain a milky white microemulsion.
[0041] Polyoxyethylene sorbitan monooleate was added to the reactor, the temperature was adjusted to 52°C, a 500-watt ultrasonic generator was started, the frequency was set to 38 kHz, and the ultrasonic energy input was controlled in pulse mode. The specific parameters were 1 second operation followed by 0.8 seconds interval, and the duty cycle was strictly controlled at 75%. After 12 minutes of treatment, the system turned into a semi-transparent state.
[0042] Turn off the heating and ultrasonic generator, and cool down to 30°C at a rate of 1.8°C per minute. Add 0.06% polydimethylsiloxane defoamer, and continue cooling to 25°C before stopping the stirring. The resulting product is a free-flowing, amber-colored, transparent liquid.
[0043] Example 5: Raw material preparation: Weigh out 60.0% stearic acid (tertiary purity, C16-C18≥97%), 12.0% oleic acid, 8.0% mercaptosuccinic acid, 7.5% polyoxyethylene sorbitan monooleate (Tween-80), and 12.5% diethylene glycol monobutyl ether, wherein the stearic acid is ultra-finely pulverized to D90=18μm.
[0044] Preparation process: Stearic acid and oleic acid were added to the reaction vessel, sealed, and high-purity nitrogen was continuously introduced at a flow rate of 0.5 liters per minute to replace the air. The stirrer was started and mixed at a speed of 60 revolutions per minute. At the same time, the temperature was increased to 75°C at a rate of 2°C per minute. The temperature was maintained and stirred for 40 minutes until the stearic acid microcrystals were completely melted to form a uniform transparent amber liquid phase. During this period, the nitrogen protection pressure was maintained at 0.05 MPa.
[0045] The reaction system was cooled to 53°C at a rate of 1°C per minute, and mercaptosuccinic acid and diethylene glycol monobutyl ether solvent were added. A high-speed shear press (480 rpm, shear rate 5 × 10⁴ s⁻¹) was then turned on. -1 Continue emulsifying for 22 minutes to obtain a milky white microemulsion.
[0046] Polyoxyethylene sorbitan monooleate was added to the reactor, the temperature was adjusted to 48°C, a 500-watt ultrasonic generator was started, the frequency was set to 22 kHz, and the ultrasonic energy input was controlled in pulse mode. The specific parameters were 1 second operation followed by 1.5 seconds of interval, and the duty cycle was strictly controlled at 6.5%. After 18 minutes of treatment, the system turned into a semi-transparent state.
[0047] Turn off the heating and ultrasonic generator, and cool down to 30°C at a rate of 1.2°C per minute. Add 0.09% polydimethylsiloxane defoamer, and continue cooling to 25°C before stopping the stirring. The resulting product is a free-flowing, amber-colored, transparent liquid.
[0048] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments that can be applied to other fields. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the technical solution of the present invention shall still fall within the protection scope of the technical solution of the present invention.
Claims
1. A stearic acid containing ore beneficiation reagent, characterized in that, Stearic acid 40-65%, oleic acid 10-30%, mercaptosuccinic acid 5-15%, non-ionic surfactant polyoxyethylene sorbitan monooleate 3-8%, organic solvent diethylene glycol monobutyl ether 10-25%, wherein the mass ratio of stearic acid to oleic acid is (1.5:1)-(4:1). The stearic acid is a tertiary pure industrial grade stearic acid with a carbon chain length distribution C16-C18≥95% and a melting point range of 54-58℃.
2. A beneficiation reagent containing stearic acid as claimed in claim 1, characterized in that: The mercaptosuccinic acid forms intermolecular hydrogen bonds with the carboxyl groups of stearic acid through sulfur atoms, forming a "stearic acid-mercaptosuccinic acid binary synergistic structure", and the sulfur element content accounts for 0.5-2.5% of the total mass of the composite collector.
3. A stearic acid containing beneficiation reagent according to claim 1, characterized in that: The diethylene glycol monobutyl ether has a purity of ≥99% and a water content of ≤0.1%, and the mass ratio of diethylene glycol monobutyl ether to non-ionic surfactant polyoxyethylene sorbitan monooleate is (1.2:1)-(3:1).
4. A stearic acid containing beneficiation reagent according to claim 1, characterized in that: The mineral processing reagent has a kinematic viscosity of 35-65 cSt, an electrical conductivity of ≤10 μS / cm, and a pH value of 6.5-7.5 at 25℃.
5. A stearic acid containing beneficiation reagent according to claim 1, characterized in that: The method comprises the following steps:
6. A method for preparing a stearic acid-containing beneficiation reagent using the stearic acid-containing beneficiation reagent according to any one of claims 1 to 5, characterized by, S1, stearic acid and oleic acid are added to a reaction kettle, heated to 70-80℃ for melting and mixing, and constant temperature stirring is performed for 20-40 minutes; S2, cooling to 50-60℃, adding mercaptosuccinic acid and diethylene glycol monobutyl ether solvent, shearing and emulsifying at a speed of 300-600 rpm for 15-20 minutes; S3, adding polyoxyethylene sorbitan monooleate, maintaining the temperature at 45-55℃, and ultrasonic treatment for 10-20 minutes at an ultrasonic frequency of 20-40 kHz and a power of 500 W; S4, cooling to below 25℃ to obtain a transparent amber liquid product. In step S1, the stearic acid needs to be first crushed to D90≤20 μm, and nitrogen gas is introduced for protection during the melting and mixing stage, with a nitrogen gas flow rate of 0.5-1.5 L / min.
7. A process for the preparation of a stearic acid containing beneficiation reagent as claimed in claim 6, wherein: In step S3, pulse energy input is applied during ultrasonic treatment, with a pulse interval of 0.5-2 seconds and a duty cycle of 60-80%.
8. A process for the preparation of a stearic acid containing beneficiation reagent as claimed in claim 6, wherein: The shear rate in the shear emulsification in step S2 is 104-105s -1 , forming microemulsion droplets with a particle size of ≤ 5 μm.
9. A process for the preparation of a stearic acid containing beneficiation reagent as claimed in claim 6, wherein: In step S4, the cooling process adopts programmed temperature control, with a cooling rate of 1-2℃ / min, and 0.05-0.1% of an antifoaming agent polydimethylsiloxane is added at 30℃.
10. A process for the preparation of a beneficiation reagent containing stearic acid as claimed in claim 6, wherein: