Quartz sand reverse flotation collector and preparation method thereof

Abstract

The present application relates to the technical field of quartz sand purification, and particularly relates to a quartz sand reverse flotation collector and a preparation method thereof, the collector is composed of the following components in mass percentage: Gemini type quaternary ammonium salt cationic surfactant 15-35%, alkyl polyglycoside nonionic surfactant 10-25%, N,N-dimethyl-N-alkylaminopropane sulfonate 20-40%, modified vegetable oil acid 5-15%, cosolvent 3-10% and water in remainder. The preparation method comprises mixing, dissolving and melting the components at a specific temperature and then compounding. The collector can realize efficient reverse flotation purification of quartz sand under weak acidic conditions (pH 3.0-5.0), has the advantages of good selectivity, strong collecting ability, high micro-fine particle recovery rate, no fluorine and no phosphorus, environmental friendliness and the like, is suitable for purification of quartz sand containing impurities such as feldspar, mica and iron minerals, and has a wide application prospect.

Description

Technical Field

[0001] This invention relates to the field of quartz sand purification technology, and in particular to a quartz sand reverse flotation collector and its preparation method. Background Technology

[0002] Quartz sand, as an important non-metallic mineral raw material, is widely used in glass manufacturing, photovoltaic materials, electronic packaging, and high-purity quartz products. With the increasing demands for purity in high-end applications, efficiently removing impurities such as feldspar, mica, and iron-bearing minerals from quartz sand has become a key research focus in mineral processing. Reverse flotation is a crucial technology in quartz sand purification. Its basic principle is to use a collector to cause hydrophobic impurities (such as feldspar, mica, and iron-bearing minerals) to float to the surface, while the quartz remains at the bottom of the tank as concentrate. Currently, commonly used collectors for quartz sand reverse flotation mainly include the following categories:

[0003] Cationic collectors, represented by amine compounds such as dodecylamine, coconut alkyl amine, and ether amine, act on the surface of negatively charged silicate minerals through electrostatic adsorption under acidic conditions. However, traditional amine collectors have problems such as poor water solubility, high foam viscosity, insufficient selectivity, and poor dispersibility at low temperatures.

[0004] Anionic collectors: represented by fatty acids (oleic acid, oxidized paraffin soap, etc.) and sulfonates (sodium dodecyl sulfonate, etc.). Anionic collectors are usually used under alkaline conditions and have a certain collecting effect on iron-containing minerals, but their collecting ability on silicate impurities such as feldspar and mica is relatively weak.

[0005] Combined collectors: In recent years, the combined use of cationic and anionic collectors has gradually become a trend. For example, Chinese patent CN119327623B discloses a collector for quartz forward and reverse flotation, which is composed of a cationic collector, anionic collector and emulsifier; Chinese patent CN121016962A discloses a mixed collector composed of C12-C14 alkyl sulfonate, isotridecyl alcohol polyoxyethylene ether, organic chelating agent and foam regulator.

[0006] However, existing combined collectors still have the following shortcomings: most combined collectors need to be used under strong acid (pH 1.5-3) or strong alkali (pH 9-12) conditions, which causes severe corrosion to equipment and high wastewater treatment costs; some collectors rely on fluorine-containing activators (such as hydrofluoric acid), which poses a serious risk of environmental pollution; existing collectors have low recovery rates for fine-grained (-0.045mm) quartz; the selectivity of collectors needs to be improved, as they are prone to causing quartz loss while collecting impurity minerals.

[0007] Therefore, based on the relevant technologies mentioned above, there is an urgent need to develop a quartz sand reverse flotation collector and its preparation method. Summary of the Invention

[0008] In view of this, the purpose of this invention is to provide a quartz sand reverse flotation collector and its preparation method. This collector can achieve efficient reverse flotation under weakly acidic conditions and has the advantages of good selectivity, strong collection ability, high recovery rate of fine particles, and environmental friendliness.

[0009] To achieve the above objectives, the present invention provides a quartz sand reverse flotation collector and its preparation method.

[0010] A quartz sand reverse flotation collector is composed of the following components by mass percentage: 15%-35% Gemini-type quaternary ammonium salt cationic surfactant, 10%-25% alkyl glycoside nonionic surfactant, 20%-40% N,N-dimethyl-N-alkylaminopropane sulfonate, 5%-15% modified vegetable oleic acid, 3%-10% cosolvent, and the balance being water.

[0011] Preferably, the structural formula of the Gemini-type quaternary ammonium salt cationic surfactant is as follows:

[0012] [RN + (CH3)2-(CH2) n -N + [(CH3)2-R]·2X - Where R is one of alkyl and alkenyl groups with 8-18 carbon atoms, n is an integer from 2 to 6, and X is a C1 group. - ,Br - and CH3SO4 - One of them.

[0013] Preferably, the Gemini-type quaternary ammonium salt cationic surfactant is at least one selected from ethylidene-1,2-bis(dodecyl dimethyl ammonium bromide), ethylidene-1,2-bis(tetradecyl dimethyl ammonium bromide), ethylidene-1,2-bis(hexadecyl dimethyl ammonium bromide), propylene-1,3-bis(dodecyl dimethyl ammonium chloride), propylene-1,3-bis(tetradecyl dimethyl ammonium chloride), propylene-1,3-bis(hexadecyl dimethyl ammonium chloride), butylidene-1,4-bis(dodecyl dimethyl ammonium chloride), butylidene-1,4-bis(tetradecyl dimethyl ammonium chloride), and butylidene-1,4-bis(hexadecyl dimethyl ammonium chloride).

[0014] Preferably, the alkyl glycoside nonionic surfactant is an alkyl glycoside with 8-14 carbon atoms and a degree of polymerization of 1.2-2.0.

[0015] Preferably, in the N,N-dimethyl-N-alkylaminopropane sulfonate, the alkyl group is one of a straight-chain alkyl group and a branched alkyl group having 12-18 carbon atoms.

[0016] Preferably, the modified vegetable oleic acid is any one of the following: ricinoleic acid modified with maleic anhydride, soybean oleic acid modified with maleic anhydride, and palm oleic acid modified with maleic anhydride, with a degree of modification of 30%-70%.

[0017] Preferably, the co-solvent is at least one selected from ethanol, isopropanol, ethylene glycol, n-butanol, isooctanol, n-octanol, and polyethylene glycol.

[0018] Preferably, the quartz sand reverse flotation collector is composed of the following components by mass percentage: 20%-30% Gemini-type quaternary ammonium cationic surfactant, 15%-20% alkyl glycoside nonionic surfactant, 25%-35% N,N-dimethyl-N-alkylaminopropane sulfonate, 8%-12% modified vegetable oleic acid, 5%-8% cosolvent, and the balance being water.

[0019] The present invention also provides a method for preparing the above-mentioned quartz sand reverse flotation collector, comprising the following steps:

[0020] Step S1. Add the Gemini-type quaternary ammonium salt cationic surfactant, alkyl glycoside nonionic surfactant and cosolvent to the reaction vessel according to the ratio, and stir and mix at 40-60℃ for 10-30 min to obtain mixture A;

[0021] Step S2. Dissolve N,N-dimethyl-N-alkylaminopropane sulfonate in water and stir at 50-70°C until completely dissolved to obtain solution B;

[0022] Step S3. The modified vegetable oleic acid is heated and melted at 60-80℃ to obtain molten liquid C;

[0023] Step S4. Under stirring conditions, slowly add solution B to mixture A, stir for 20-40 minutes, then add molten liquid C, continue stirring for 30-60 minutes, and cool to room temperature to obtain the quartz sand reverse flotation collector.

[0024] Preferably, the stirring temperature in step S1 is 45-55℃ and the stirring time is 15-25 min.

[0025] Preferably, the dissolution temperature in step S2 is 55-65℃.

[0026] Preferably, the total stirring time in step S4 is 60-120 min.

[0027] Preferably, the application process of the quartz sand reverse flotation collector is as follows: After grinding the raw quartz sand ore, the slurry concentration is adjusted to 25%-40%, the pH of the slurry is adjusted to 3.0-5.0 with a pH adjuster, the collector of the present invention is added, and the proportion of the collector is 100-500g / t based on the dry weight of the raw ore. After stirring and activating for 3-8 minutes, reverse flotation roughing, cleaning and scavenging operations are carried out to obtain quartz concentrate.

[0028] The beneficial effects of this invention are:

[0029] This invention provides a quartz sand reverse flotation collector and its preparation method. Compared with the prior art, this invention has the following advantages:

[0030] Wide pH adaptability and environmentally friendly: The collector of this invention can achieve efficient reverse flotation under weakly acidic conditions (pH 3.0-5.0), avoiding the severe corrosion of equipment caused by strong acid (pH<3) or strong alkali (pH>10) conditions in traditional processes, and reducing the difficulty and cost of wastewater treatment;

[0031] High selectivity and high concentrate grade: Gemini-type quaternary ammonium salt cationic surfactants have a double quaternary ammonium salt structure, which has a stronger electrostatic adsorption capacity and higher selectivity on the surface of negatively charged silicate minerals; at the same time, N,N-dimethyl-N-alkylaminopropane sulfonate has both sulfonate and tertiary amine structures, which can selectively adsorb onto the surface of impurity minerals such as feldspar and mica through electrostatic and hydrogen bonding synergistic effects under different pH conditions, while the adsorption on quartz is weak, thus achieving efficient and selective collection of impurity minerals;

[0032] High recovery rate of fine particles: Alkyl glycoside nonionic surfactants have good dispersing properties and foam control capabilities, which can effectively improve the dispersion state of fine mineral particles in the slurry and reduce fine mud covering and foam entrainment; Gemini-type surfactants have a unique double hydrophobic chain structure that enables them to form a denser hydrophobic adsorption layer on the mineral surface, enhancing the ability to capture fine impurity minerals.

[0033] Good low-temperature performance: The alkyl glycosides and Gemini-type surfactants in the components of this invention have good low-temperature solubility and dispersibility. With the addition of appropriate co-solvents, the collector can maintain good flotation performance in the temperature range of 5-40℃.

[0034] Fluorine-free and phosphorus-free, green and environmentally friendly: This invention does not add any fluorine-containing or phosphorus-containing compounds, avoiding the harm to the environment and human body caused by the traditional hydrofluoric acid method, and conforming to the development direction of green mineral processing. Attached Figure Description

[0035] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only for this invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0036] Figure 1 This is a flow chart of the flotation process in Example 1. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments.

[0038] Example 1:

[0039] A quartz sand reverse flotation collector is composed of the following components by mass percentage: 25% ethylene-1,2-bis(dodecyldimethylammonium bromide) (Gemini-type quaternary ammonium salt), 18% decyl glycoside (alkyl glycoside, degree of polymerization 1.5), 30% N,N-dimethyl-N-dodecylaminopropane sulfonate, 10% maleic anhydride-modified ricinoleic acid (modification degree 50%), 7% n-butanol, and 10% water.

[0040] A method for preparing a quartz sand reverse flotation collector includes the following steps:

[0041] S1. Add 25 parts of ethylene-1,2-bis(dodecyldimethylammonium bromide), 18 parts of decyl glycoside and 7 parts of ethanol to a reaction vessel, and stir and mix at 50°C for 20 min to obtain mixture A;

[0042] S2. Dissolve 30 parts of N,N-dimethyl-N-dodecylaminopropane sulfonate in 10 parts of water, and stir at 60°C until completely dissolved to obtain solution B;

[0043] S3. Ten parts of maleic anhydride-modified ricinoleic acid were heated and melted at 70°C to obtain molten liquid C;

[0044] S4. Under stirring conditions, slowly add solution B to mixture A, stir for 30 minutes, then add molten liquid C, continue stirring for 45 minutes, and cool to room temperature to obtain the collector.

[0045] The raw quartz sand processed in this embodiment contains SiO2: 95.52%, Al2O3: 2.4%, Fe2O3: 0.013%, K2O: 0.84%, and Na2O: 0.08%.

[0046] Processing technology such as Figure 1As shown: A process of "one roughing, one cleaning, one scavenging, with the scavenged concentrate returned to the original ore" was adopted. Sulfuric acid was added as a modifier to an 80-140 mesh slurry with a 30% concentration to adjust the pH to 4. 400 g / t of the collector used in this example was added, and the mixture was stirred and activated for 6 minutes before reverse flotation. The resulting quartz concentrate yield was 86.53%, SiO2 content was 99.85%, Fe2O3 content was 0.0069%, Al2O3 content was 0.042%, feldspar concentrate yield was 11.87%, and open-circuit quartz recovery rate was 91.51% (based on Al), as detailed in Table 1 below.

[0047] Table 1 Reverse flotation results of Example 1

[0048]

[0049] Example 2

[0050] A quartz sand reverse flotation collector is composed of the following components by mass percentage: propylene-1,3-bis(tetradecyl dimethyl ammonium chloride) (Gemini-type quaternary ammonium salt) 20%, octyl glycoside (alkyl glycoside, degree of polymerization 1.3) 20%, N,N-dimethyl-N-hexadecylaminopropane sulfonate 35%, maleic anhydride modified soybean oleic acid (modification degree 40%) 8%, isopropanol 5%, and water 12%.

[0051] A method for preparing a quartz sand reverse flotation collector includes the following steps:

[0052] S1. Add 25 parts of ethylene-1,2-bis(dodecyldimethylammonium bromide), 18 parts of decyl glycoside and 7 parts of ethanol to a reaction vessel, and stir and mix at 45°C for 20 min to obtain mixture A;

[0053] S2. Dissolve 30 parts of N,N-dimethyl-N-dodecylaminopropane sulfonate in 10 parts of water, and stir at 55°C until completely dissolved to obtain solution B;

[0054] S3. Ten parts of maleic anhydride-modified ricinoleic acid were heated and melted at 65°C to obtain molten liquid C;

[0055] S4. Under stirring conditions, slowly add solution B to mixture A, stir for 30 minutes, then add molten liquid C, continue stirring for 45 minutes, and cool to room temperature to obtain the collector.

[0056] The raw quartz sand processed in this embodiment contains SiO2: 92.17%, Al2O3: 5.02%, Fe2O3: 0.043%, K2O: 1.17%, and Na2O: 1.41%.

[0057] The processing technology adopts a "roughing, cleaning, and scavenging, with the scavenged concentrate returned to the original ore" process. Sulfuric acid is added as a modifier to a 70-200 mesh slurry with a concentration of 28% to adjust the pH to 3.2. Collector is added at a rate of 500 g / t, and the mixture is stirred and activated for 6 minutes before reverse flotation. The resulting quartz concentrate yield is 76.29%, with SiO2 content of 99.87%, Fe2O3 content of 0.009%, and Al2O3 content of 0.046%. The feldspar concentrate yield is 23.7%, and the open-circuit quartz recovery rate is 92.3% (based on Al). Details are shown in Table 2 below.

[0058] Table 2 Reverse flotation results of Example 2

[0059]

[0060] Example 3

[0061] A quartz sand reverse flotation collector is composed of the following components by mass percentage: 30% butylide-1,4-bis(hexadecyldimethylammonium chloride) (Gemini-type quaternary ammonium salt), 15% dodecyl glycoside (alkyl glycoside, degree of polymerization 1.8), 25% N,N-dimethyl-N-tetradecylaminopropane sulfonate, 12% maleic anhydride-modified palmitoleic acid (60% modification), 8% polyethylene glycol, and 10% water.

[0062] A method for preparing a quartz sand reverse flotation collector includes the following steps:

[0063] S1. Add 25 parts of ethylene-1,2-bis(dodecyldimethylammonium bromide), 18 parts of decyl glycoside and 7 parts of ethanol to a reaction vessel, and stir and mix at 55°C for 20 min to obtain mixture A;

[0064] S2. Dissolve 30 parts of N,N-dimethyl-N-dodecylaminopropane sulfonate in 10 parts of water, and stir at 65°C until completely dissolved to obtain solution B;

[0065] S3. Ten parts of maleic anhydride-modified ricinoleic acid were heated and melted at 75°C to obtain molten liquid C;

[0066] S4. Under stirring conditions, slowly add solution B to mixture A, stir for 30 minutes, then add molten liquid C, continue stirring for 45 minutes, and cool to room temperature to obtain the collector.

[0067] The raw quartz sand processed in this embodiment contains 86.85% SiO2, 8.52% Al2O3, 0.045% Fe2O3, 2.25% K2O, and 2.11% Na2O.

[0068] The processing technology adopts the process of "one roughing, two cleaning, and one scavenging; the cleaned concentrate is scavenged, and the scavenged concentrate is returned to the original ore". Sulfuric acid is added as an adjuster to the 80-200 mesh slurry with a concentration of 33% to adjust the pH to 3.8. 600 g / t of the collector in this example is added, and the mixture is stirred and activated for 6 min. Reverse flotation is then carried out. The quartz concentrate yield is 62.69%, the SiO2 content is 99.52%, the Fe2O3 content is 0.011%, and the Al2O3 content is 0.243%. The feldspar concentrate yield is 37.31%, and the open-circuit quartz recovery rate is 89.55% (calculated as Al). The details are shown in Table 3 below.

[0069] Table 3 Reverse flotation results of Example 2

[0070]

[0071] Those skilled in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the invention is limited to these examples; within the framework of the invention, the technical features of the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.

[0072] This invention is intended to cover all such substitutions, modifications, and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this invention should be included within the scope of protection of this invention.

Claims

1. A quartz sand reverse flotation collector, characterized in that, Composed of the following components by mass percentage Composition: 15%-35% Gemini-type quaternary ammonium cationic surfactant, 10%-25% alkyl glycoside nonionic surfactant, 20%-40% N,N-dimethyl-N-alkylaminopropane sulfonate, 5%-15% modified vegetable oleic acid, 3%-10% cosolvent, and the balance is water.

2. The quartz sand reverse flotation collector according to claim 1, characterized in that, The structural formula of the Gemini-type quaternary ammonium salt cationic surfactant is as follows: [RN + (CH3)2-(CH2) n -N + (CH3)2-R]·2X - , Where R is one of alkyl and alkenyl groups with 8-18 carbon atoms, n is an integer from 2 to 6, and X is a C1 group. - ,Br - and CH3SO4 - One of them.

3. The quartz sand reverse flotation collector according to claim 2, characterized in that, The Gemini-type quaternary ammonium salt cationic surfactant is at least one selected from ethylidene-1,2-bis(dodecyl dimethyl ammonium bromide), ethylidene-1,2-bis(tetradecyl dimethyl ammonium bromide), ethylidene-1,2-bis(hexadecyl dimethyl ammonium bromide), propylene-1,3-bis(dodecyl dimethyl ammonium chloride), propylene-1,3-bis(tetradecyl dimethyl ammonium chloride), propylene-1,3-bis(hexadecyl dimethyl ammonium chloride), butylidene-1,4-bis(dodecyl dimethyl ammonium chloride), butylidene-1,4-bis(tetradecyl dimethyl ammonium chloride), and butylidene-1,4-bis(hexadecyl dimethyl ammonium chloride).

4. The quartz sand reverse flotation collector according to claim 1, characterized in that, The alkyl glycoside nonionic surfactant is an alkyl glycoside with 8-14 carbon atoms and a degree of polymerization of 1.2-2.0; In the N,N-dimethyl-N-alkylaminopropane sulfonate, the alkyl group is one of a straight-chain alkyl group or a branched alkyl group with 12-18 carbon atoms.

5. The quartz sand reverse flotation collector according to claim 1, characterized in that, The modified vegetable oleic acid is one of the following: castor oil acid modified with maleic anhydride, soybean oleic acid modified with maleic anhydride, and palm oil acid modified with maleic anhydride, with a modification degree of 30%-70%.

6. The quartz sand reverse flotation collector according to claim 1, characterized in that, The co-solvent is at least one selected from ethanol, isopropanol, ethylene glycol, n-butanol, isooctyl alcohol, n-octanol, and polyethylene glycol.

7. The quartz sand reverse flotation collector according to claim 1, characterized in that, Composed of the following components by mass percentage Composition: 20%-30% Gemini-type quaternary ammonium salt cationic surfactant, 15%-20% alkyl glycoside nonionic surfactant, 25%-35% N,N-dimethyl-N-alkylaminopropane sulfonate, 8%-12% modified vegetable oleic acid, 5%-8% cosolvent, and the balance is water.

8. The method for preparing the quartz sand reverse flotation collector according to any one of claims 1-7, characterized in that, Includes the following steps: Step S1. Add the Gemini-type quaternary ammonium salt cationic surfactant, alkyl glycoside nonionic surfactant and cosolvent to the reaction vessel according to the ratio, and stir and mix at 40-60℃ for 10-30 min to obtain mixture A; Step S2. Dissolve N,N-dimethyl-N-alkylaminopropane sulfonate in water and stir at 50-70°C until completely dissolved to obtain solution B; Step S3. The modified vegetable oleic acid is heated and melted at 60-80℃ to obtain molten liquid C; Step S4. Under stirring conditions, slowly add solution B to the mixture A and stir for 20-40 minutes. Then add solution C and continue stirring for 30-60 minutes. Cool to room temperature to obtain the quartz sand reverse flotation collector.

9. The method for preparing the quartz sand reverse flotation collector according to claim 8, characterized in that, In step S1, the stirring temperature is 45-55℃ and the stirring time is 15-25 min; in step S2, the dissolution temperature is 55-65℃; and in step S4, the total stirring time is 60-120 min.

10. The method for preparing the quartz sand reverse flotation collector according to claim 8, characterized in that, The application process of the quartz sand reverse flotation collector is as follows: After grinding the raw quartz sand ore, adjust the slurry concentration to 25%-40%, adjust the pH of the slurry to 3.0-5.0 with a pH adjuster, add the collector, and the proportion of the collector based on the dry weight of the raw ore is 100-500g / t. Stir and activate for 3-8 minutes, and then carry out reverse flotation operation.

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