Fluorite collector and preparation and application thereof

Abstract

The present application relates to the technical field of mineral processing, and particularly relates to a fluorite collecting agent, which is a compound with the formula: wherein n is an integer of 5-10; R1 is C3-C15 alkyl; R2 and R3 are hydroxyl or are cyclically combined to form an epoxy group. 12 The present application also relates to a preparation method and application in fluorite flotation. The present application provides a collecting agent with a novel structure, and the collecting agent has excellent collecting capacity and selectivity for fluorite.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of mineral processing, in particular to the field of fluorite flotation. BACKGROUND

[0002] Fluoride chemical products are widely used in materials, metallurgy, chemical industry, biology and other fields. Fluorite is the main mineral raw material for preparing fluoride chemical products. Fluorite is often associated with gangue minerals such as calcite, dolomite and quartz, and its embedded particle size is relatively fine, so it often needs to be finely ground to completely dissociate the fine particle size embedded fluorite. Flotation is the most effective method for separating fluorite and gangue minerals and recovering fine particle size fluorite. In flotation, a flotation collector needs to be added to expand the difference in surface hydrophilicity and hydrophobicity between minerals. Developing a high selectivity flotation collector is the key to obtaining high-quality fluorite flotation concentrate. At present, the most commonly used collector for fluorite flotation is oleic acid.

[0003] As a fluorite flotation collector, oleic acid has the advantages of strong collecting ability and low cost. Oleic acid reacts with the active sites of mineral surface metal ions through its carboxylic acid group to form carboxylate, thereby adsorbing on the mineral surface. The solubility product of different metal ion carboxylates is different, so the adsorption strength of oleic acid on different mineral surfaces is different, which reflects the selectivity of the oleic acid collector. However, since the active sites on the surfaces of fluorite and its associated gangue minerals calcite and dolomite are all Ca 2+ , the poor selectivity of oleic acid will be highlighted, so the oleic acid collector often needs to be used in combination with inhibitors such as water glass, starch, tannin and sodium hexametaphosphate. In order to enhance the selectivity of the oleic acid collector, a large amount of inhibitors such as water glass needs to be added, which has two negative effects: 1. Inhibiting fluorite flotation, resulting in low concentrate recovery, 2. Causing difficulty in subsequent solid-liquid separation processes such as sedimentation and filtration, increasing the difficulty of mineral processing wastewater treatment and wastewater reuse. Oleic acid also has another disadvantage, poor solubility at low temperatures. In environments with low temperatures caused by seasonal changes, high altitudes and other factors, the recovery rate of fluorite flotation concentrate is not high. SUMMARY

[0004] In view of the poor selectivity of fluorite flotation, the first object of the present application is to provide a fluorite collector, which aims to improve the flotation recovery rate and selectivity of fluorite.

[0005] The second object of the present application is to provide a preparation method of the fluorite collector, which aims to obtain a new reagent with excellent flotation performance based on a simple reagent and method.

[0006] The third object of the present application is to provide the application of the fluorite collector in fluorite flotation.

[0007] The fourth object of the present application is to provide a flotation reagent comprising the fluorite collector.

[0008] Fluorite and calcium-containing gangue (such as common calcite) are often embedded and associated, and both have good natural floatability, and the separation difficulty is huge, aiming at the problem, the application provides the following improved scheme:

[0009] A fluorite collecting agent is a compound with a formula 1 structure:

[0010]

[0011] Said n is an integer of 5-10;

[0012] Said R1 is C3-C 12 alkyl;

[0013] Said R2, R3 is hydroxyl or both are cyclic to form an epoxy group.

[0014] The application provides a fatty CONOH collecting agent with ortho-dihydroxy or an epoxy group. Research finds that the collecting agent with the novel structure can solve the problem that the solubility and carbon chain hydrophobicity of the long carbon chain fatty collecting agent are difficult to be considered, can improve the flotation activity of the fatty collecting agent, can improve the fluorite flotation selectivity, and can effectively improve the low-temperature flotation performance and anti-interference capacity and improve the flotation selectivity.

[0015] The application researches and finds that the synergistic effect of the ortho-dihydroxy (epoxy) and the fatty CONOH is the key to improve the fluorite flotation recovery rate and selectivity. Research also finds that further controlling the one-dimensional position relationship of the fatty carbon chain and the ortho-dihydroxy (epoxy) and the fatty CONOH is helpful to further improve the flotation selectivity of the compound to fluorite.

[0016] As preferred, said n is an integer of 6-9, and further preferably an integer of 7-8;

[0017] Preferably, said R1 is a linear alkyl, preferably a linear alkyl with a carbon number of C7-C 10 ;

[0018] Preferably, in formula 1, the total carbon number is 16-20.

[0019] As preferred, said fluorite collecting agent is at least one of formula 1-A and formula 1-B;

[0020]

[0021] The application also provides a preparation method of the fluorite collecting agent, which reacts a compound of formula 2 with NH3OH to obtain;

[0022]

[0023] R1, R2, R3 in formula 2 are selected from the same range as formula 1; R4 is C1-C6 alkyl;

[0024] Preferably, the molar ratio of the compound of formula 2 and NH3OH is 1:(1.2-2), and the reaction temperature is 30-60℃.

[0025] Preferably, the compound of formula 2 is prepared by hydroxylation or epoxidation reaction of the unsaturated bond of the compound of formula 3:

[0026]

[0027] R1, R4 in formula 3 are selected from the same range as formula 2.

[0028] Preferably, formula 3, glacial acetic acid are mixed, and then hydrogen peroxide, concentrated sulfuric acid in acetic acid solution is added dropwise to perform hydroxylation reaction on the unsaturated bond to obtain the product of formula 2 with R2 and R3 being hydroxyl;

[0029] Preferably, the molar ratio of formula 3, glacial acetic acid, hydrogen peroxide and concentrated sulfuric acid is 1:(14-16):(6-8):(0.02-0.05);

[0030] Preferably, the temperature of the hydroxylation reaction is 30-60℃;

[0031] Alternatively, formula 3 and peroxide are mixed to react to obtain the product of formula 2 with R2 and R3 being epoxidized to form a ring;

[0032] Preferably, the peroxide is meta-chloroperoxybenzoic acid;

[0033] Preferably, the molar ratio of formula 3 and peroxide is 1:(1-2);

[0034] Preferably, the temperature of the epoxidation reaction is 15-40℃.

[0035] Preferably, formula 3 is obtained by esterification reaction of formula 4 and R4OH in concentrated sulfuric acid:

[0036]

[0037] R1, R4 in formula 4 are selected from the same range as formula 3;

[0038] Preferably, the molar ratio of formula 4, concentrated sulfuric acid and R4OH is 1:(0.02-0.05):(45-55);

[0039] Preferably, the temperature of the esterification reaction is 60-90℃.

[0040] Preferably, the preparation reaction formula of formula 1-A is:

[0041]

[0042] The preparation of Formula 1-A is as follows:

[0043] (1) Esterification

[0044] Formula 4-A (CH3(CH2)7CH=CH(CH2)7COOH) is added to a three-necked round bottom flask using a glass funnel, and an amount of methanol is added to dissolve Formula 4-A, followed by dropwise addition of a concentrated sulfuric acid (98%, H2SO4) solution in methanol using a constant pressure funnel. The molar ratio of Formula 4-A, concentrated sulfuric acid, and methanol is 1 : (0.02-0.05) : (45-55). The reaction mixture is heated in a water bath, and the temperature is maintained at 70°C. A reflux condenser is used to condense and evaporate the methanol that is heated. The reaction time is 24 hours.

[0045] After the reaction is complete, the reaction mixture is washed with saturated sodium bicarbonate (NaHCO3) solution to adjust the pH of the mixture to about 7, followed by extraction of the reaction product using ethyl acetate (CH3COOCH2CH3). The upper organic layer is collected using a separatory funnel, and anhydrous sodium sulfate is added to the organic layer to dry the water. The anhydrous sodium sulfate is left to dry for 12 hours, and then the organic layer is filtered to remove the solid sodium sulfate. The ethyl acetate and methanol are removed from the organic layer by rotary evaporation to obtain Formula 3-A (CH3(CH2)7CH=CH(CH2)7COOCH3).

[0046] (2) Hydroxylation

[0047] Formula 3-A is added to a three-necked round bottom flask using a glass funnel, and an amount of glacial acetic acid (CH3COOH) is added to dissolve Formula 3-A, followed by dropwise addition of hydrogen peroxide (30%, H2O2) and concentrated sulfuric acid in glacial acetic acid. The molar ratio of Formula 3-A, glacial acetic acid, hydrogen peroxide, and concentrated sulfuric acid is 1 : (14-16) : (6-8) : (0.02-0.05). The reaction mixture is heated in a water bath, and the temperature is maintained at 40°C. The reaction time is 12 hours.

[0048] After the reaction is complete, the reaction mixture is washed with saturated sodium sulfite (Na2SO3) solution to quench the excess hydrogen peroxide until the starch-iodine test paper does not change color. The mixture is then washed with saturated sodium bicarbonate solution to adjust the pH of the mixture to about 7. The upper organic layer is collected using a separatory funnel, and anhydrous sodium sulfate is added to the organic layer to dry the water. The anhydrous sodium sulfate is left to dry for 12 hours, and then the organic layer is filtered to remove the solid sodium sulfate. The ethyl acetate and methanol are removed from the organic layer by rotary evaporation to obtain Formula 2-A (9,10-dihydroxyoctadecanoic acid methyl ester).

[0049] (3) Preparation of free hydroxylamine

[0050] Hydroxylamine hydrochloride (NH2OH-HCl) was added to a single-necked round bottom flask, followed by the addition of a certain amount of methanol using a glass funnel, followed by the addition of sodium hydroxide (NaOH) solid in batches, the molar ratio of hydroxylamine hydrochloride to sodium hydroxide being 1:(1.2-2), and the reaction was carried out in an ice bath for 2 hours.

[0051] After the reaction was completed, the product sodium chloride (NaCl) and unreacted hydroxylamine hydrochloride and sodium hydroxide solid were filtered out to obtain a methanol solution of free hydroxylamine.

[0052] (4) Amide formation

[0053] First, formula 2-A was added to a three-necked round bottom flask using a glass funnel, followed by the addition of a certain amount of methanol to dissolve formula 2-A in the three-necked round bottom flask using a glass funnel, and then a methanol solution of free hydroxylamine was added dropwise using a constant pressure funnel, the molar ratio of formula 2-A to hydroxylamine being 1:(1.2-2), the reaction mixture was heated in a water bath, the reaction temperature was maintained at 40°C, and the reaction time was 12 hours to prepare formula 1-A.

[0054] After the reaction was completed, the reaction mixture was rotary evaporated to obtain the crude product of formula 1-A. The crude product was dissolved in a mixed solution of water, acetone, and ethyl acetate, the volume ratio of water, acetone, and ethyl acetate being 1:(1-2):(2-4). The organic layer solution was collected using a separatory funnel. The organic solution was rotary evaporated to remove acetone and ethyl acetate to obtain formula 1-A with higher purity.

[0055] Another preferred preparation scheme of formula 1-B of the present application is as follows:

[0056]

[0057] The step is to:

[0058] (1) Esterification

[0059] Formula 3-A was prepared according to the same step (1) as that for formula 1-A.

[0060] (2) Epoxidation

[0061] First, formula 3-A was added to a single-necked round bottom flask using a glass funnel, followed by the dropwise addition of a dichloromethane (CH2Cl2) solution of meta-chloroperoxybenzoic acid (Cl-(C6H4)-C(=O)-OOH) using a constant pressure funnel, the molar ratio of formula 3-A to meta-chloroperoxybenzoic acid being 1:(1-2), and the reaction was carried out at room temperature for 12 hours to prepare formula 2-B.

[0062] After the reaction, the reaction mixture is washed with saturated sodium sulfite solution to quench the unreacted m-chloroperbenzoic acid until the starch-iodide paper does not change color, then the reaction product is extracted with dichloromethane, the lower organic solution is collected in a separatory funnel, anhydrous sodium sulfate is added to the organic solution to dry it, the anhydrous sodium sulfate is left to dry for 12 hours, after drying, the sodium sulfate solid is filtered out, the organic solution is rotary evaporated to remove the dichloromethane, and methyl 9,10-epoxyoctadecanoate (2-B) is obtained.

[0063] (3) Preparation of free hydroxylamine

[0064] The same as the preparation step (3) of formula 1-A.

[0065] (4) Amide

[0066] Formula 2-B is added to a three-necked round bottom flask using a glass funnel, then a certain amount of methanol is added to dissolve formula 2-B using a glass funnel, then a free hydroxylamine methanol solution is added dropwise using a constant pressure funnel, the molar ratio of formula 2-B to hydroxylamine is 1: (1.2-2), the reaction mixture is heated in a water bath, the reaction temperature is maintained at 40°C, and the reaction time is 12 hours.

[0067] After the reaction, the reaction mixture is rotary evaporated to obtain the crude product of formula 1-B. The crude product is dissolved in a mixed solution of water, acetone and ethyl acetate. The volume ratio of water, acetone and ethyl acetate is 1: (1-2): (2-4). The organic layer solution is collected using a separatory funnel. The organic solution is rotary evaporated to remove acetone and ethyl acetate, and formula 1-B (N-hydroxy-9,10-epoxyoctadecanamide) with higher purity is obtained.

[0068] The application also provides a use of the fluorite collector as a collector for the flotation of fluorite.

[0069] As preferred, the use as a collector is for the selective flotation separation of fluorite and other calcium-containing gangues:

[0070] Preferably, the other calcium-containing gangues are at least one of calcite, dolomite and scheelite;

[0071] Preferably, the amount of formula 1 collector used in the flotation stage is 50-300 g / t;

[0072] Preferably, the pH in the flotation stage is 8-10;

[0073] Preferably, an inhibitor is also added in the flotation stage;

[0074] Preferably, the inhibitor is water glass;

[0075] Preferably, the amount of the depressant used in the flotation stage is 50-1300 g / t;

[0076] For the preferred fluorite flotation application, the steps include:

[0077] (1) In the fluorite flotation roughing stage, the pulp concentration (i.e. mass fraction) is about 30%, the pH of the pulp is adjusted to 8-10 using a pH regulator, and then the depressant and the collector are added in sequence. After the addition of the depressant, the pulp is stirred for 3 minutes, and after the addition of the collector, the pulp is stirred for 20-30 minutes. Formula 1-A and Formula 1-B are used as the collector, and the amount of Formula 1-A and Formula 1-B used is 200-300 g (expressed as 200-300 g / t) per ton of raw ore feed sample.

[0078] (2) In the fluorite flotation cleaning stage, the pH of the pulp is adjusted to 8-10 using a pH regulator, and then the depressant and the collector are added in sequence. After the addition of the depressant, the pulp is stirred for 3 minutes, and after the addition of the collector, the pulp is stirred for 20-30 minutes. Formula 1-A and Formula 1-B are used as the collector, and the amount of Formula 1-A and Formula 1-B used is 50-200 g (expressed as 50-200 g / t) per ton of raw ore feed sample.

[0079] (3) In the fluorite flotation scavenging stage, the pH of the pulp is adjusted to 8-10 using a pH regulator, and then the collector is added. After the addition of the collector, the pulp is stirred for 20-30 minutes. Formula 1-A and Formula 1-B are used as the collector, and the amount of Formula 1-A and Formula 1-B used is 50-200 g (expressed as 50-200 g / t) per ton of raw ore feed sample.

[0080] In the technical solution of the present application, the cleaning tailings are sequentially returned to the previous flotation operation, and the scavenging concentrate is sequentially returned to the previous flotation operation.

[0081] The present application also provides a fluorite flotation reagent comprising a depressant and the fluorite collector described above.

[0082] Preferably, the fluorite flotation reagent is a flotation reagent for separating fluorite and other calcium-containing gangues.

[0083] Compared with the prior art, the collector of the present application has the following advantages.

[0084] (1) The present application provides a new fatty CONOH collector containing ortho-dihydroxy (epoxy), which has a synergistic effect based on the combination of fatty chains and ortho-dihydroxy (epoxy), CONOH, can effectively solve the problem that the solubility and carbon chain hydrophobicity of long carbon chain fatty collectors are difficult to balance, can improve the flotation activity of fatty collectors, can improve the selectivity of fluorite flotation, and in addition, can effectively improve the low-temperature flotation performance, anti-interference and flotation selectivity.

[0085] (2) The present application has good universality, and does not need to be saponified or heated. It is less affected by temperature, and can obtain good flotation effect at low temperature. It is less affected by soluble cations in solution, and can obtain good flotation result at high concentration of soluble cations. BRIEF DESCRIPTION OF DRAWINGS

[0086] Figure 1 is a 1H-NMR chart of formula 1-A;

[0087] Figure 2 is a C-NMR chart of formula 1-A;

[0088] Figure 3 is a 1H-NMR chart of formula 1-B;

[0089] Figure 4 is a C-NMR chart of formula 1-B;

[0090] Figure 5 is a flotation flow chart of fluorite in Inner Mongolia in Example 1;

[0091] Figure 6 is a flotation flow chart of fluorite in Henan in Example 8; DETAILED DESCRIPTION

[0092] The following examples are intended to further illustrate the present application, but the scope of the protection of the present application is not limited by these examples.

[0093] Preparation Example 1 - Preparation of formula 1-A:

[0094] (1) Esterification to prepare formula 3-A

[0095] Formula 4-A (CH3(CH2)7CH=CH(CH2)7COOH) is added to a three-necked round bottom flask using a glass funnel, and a certain amount of methanol is added to dissolve formula 4-A, followed by dropwise addition of a concentrated sulfuric acid (98%, H2SO4) methanol solution using a constant pressure funnel. The molar ratio of formula 4-A, concentrated sulfuric acid, and methanol is 1:0.03:50. The reaction mixture is heated in a water bath, and the temperature is maintained at 70°C. A serpentine condenser is used to condense the refluxed evaporated methanol. The reaction time is 24 hours.

[0096] After the reaction, the reaction mixture was washed with saturated sodium bicarbonate (NaHCO3) solution to adjust the pH of the mixture to about 7, and then the reaction product was extracted with ethyl acetate (CH3COOCH2CH3) using a separatory funnel. The upper organic layer was collected and dried over anhydrous sodium sulfate. The anhydrous sodium sulfate was left to dry for 12 hours. The organic layer was then filtered to remove the solid sodium sulfate. The ethyl acetate and methanol were removed from the organic layer by rotary evaporation to obtain formula 3-A (CH3(CH2)7CH=CH(CH2)7COOCH3).

[0097] (2) Preparation of 9,10-dihydroxyoctadecanoic acid methyl ester (formula 2-A) by hydroxylation

[0098] Formula 3-A was added to a three-necked round bottom flask using a glass funnel. A certain amount of glacial acetic acid (CH3COOH) was added to dissolve 3-A. Then, hydrogen peroxide (30%, H2O2) and concentrated sulfuric acid in glacial acetic acid were added dropwise. The molar ratio of formula 3-A, glacial acetic acid, hydrogen peroxide, and concentrated sulfuric acid was 1:15:7:0.03. The reaction mixture was heated in a water bath, and the reaction temperature was maintained at 40°C. The reaction time was 12 hours.

[0099] After the reaction, the reaction mixture was washed with saturated sodium sulfite (Na2SO3) solution to quench the excess hydrogen peroxide until the starch-iodine paper did not change color. Then, the mixture was washed with saturated sodium bicarbonate solution to adjust the pH of the mixture to about 7. The upper organic layer was collected using a separatory funnel. The organic layer was dried over anhydrous sodium sulfate. The anhydrous sodium sulfate was left to dry for 12 hours. The organic layer was then filtered to remove the solid sodium sulfate. The ethyl acetate and methanol were removed from the organic layer by rotary evaporation to obtain formula 2-A.

[0100] (3) Preparation of free hydroxylamine

[0101] Hydroxylamine hydrochloride (NH2OH·HCl) was added to a single-necked round bottom flask. A certain amount of methanol was added using a glass funnel. Then, sodium hydroxide (NaOH) solid was added in portions. The molar ratio of hydroxylamine hydrochloride to sodium hydroxide was 1:2. The reaction was carried out in an ice bath for 2 hours.

[0102] After the reaction, the product sodium chloride (NaCl) and unreacted hydroxylamine hydrochloride and sodium hydroxide solids were filtered out to obtain a methanol solution of free hydroxylamine.

[0103] (4) Preparation of N,9,10-trihydroxyoctadecanamide (formula 1-A) by amidation

[0104] First, add Formula 2-A into a three-necked round bottom flask using a glass funnel, then add a certain amount of methanol into the three-necked round bottom flask to dissolve Formula 2-A using a glass funnel, and then add a methanol solution of free hydroxylamine drop by drop using a constant pressure funnel, with a molar ratio of Formula 2-A to hydroxylamine being 1:2, water bath heating of the reaction mixture, reaction temperature maintained at 40°C, and reaction time of 12 hours to prepare Formula 1-A.

[0105] After the reaction is completed, the reaction mixture is rotary evaporated to obtain the crude product of Formula 1-A. The crude product is dissolved in a mixed solution of water, acetone and ethyl acetate. The volume ratio of water, acetone and ethyl acetate is 1:2:4. The organic layer solution is collected using a separatory funnel. The organic solution is rotary evaporated to remove acetone and ethyl acetate to obtain Formula 1-A with higher purity.

[0106] Preparation Example 2 - Preparation of Formula 1-B:

[0107] (1) Esterification to prepare Formula 3-A

[0108] The same as Step (1) of Example 1.

[0109] (2) Epoxidation to prepare 9, 10-epoxy octadecanoic acid methyl ester (Formula 2-B)

[0110] First, add Formula 3-A into a single-necked round bottom flask using a glass funnel, then add a dichloromethane (CH2Cl2) solution of meta-chloroperoxybenzoic acid (Cl-(C6H4)-C(=O)-OOH) drop by drop using a constant pressure funnel, with a molar ratio of Formula 3-A to meta-chloroperoxybenzoic acid being 1:2, and reaction at room temperature for 12 hours to prepare Formula 2-B.

[0111] After the reaction is completed, the reaction mixture is washed with a saturated sodium sulfite solution to quench the unreacted meta-chloroperoxybenzoic acid until the starch-iodine paper does not change color, then the reaction product is extracted with dichloromethane, the lower organic layer is collected in a separatory funnel, anhydrous sodium sulfate is added to the organic solution to dry, the anhydrous sodium sulfate is placed to dry for 12 hours, after drying, the sodium sulfate solid is filtered out, and the organic solution is rotary evaporated to remove dichloromethane to obtain Formula 2-B.

[0112] (3) Preparation of free hydroxylamine

[0113] Add hydroxylamine hydrochloride into a single-necked round bottom flask, then add a certain amount of methanol using a glass funnel, and then add sodium hydroxide (NaOH) solid in batches, with a molar ratio of hydroxylamine hydrochloride to sodium hydroxide being 1:2, and reaction in an ice bath for 2 hours.

[0114] After the reaction is completed, the generated sodium chloride and unreacted hydroxylamine hydrochloride and sodium hydroxide solid are filtered out to obtain a methanol solution of free hydroxylamine.

[0115] (4) amidation to prepare N-hydroxy-9,10-epoxyoctadecanamide (Formula 1-B)

[0116] Formula 2-B was added to a three-necked round bottom flask using a glass funnel, then an amount of methanol was added to dissolve Formula 2-B using a glass funnel, and then a solution of free hydroxylamine in methanol was added dropwise using a constant pressure funnel, the molar ratio of Formula 2-B to hydroxylamine being 1:2, the reaction mixture was heated in a water bath, the reaction temperature was maintained at 40°C, and the reaction time was 12 hours.

[0117] After the reaction was completed, the reaction mixture was rotary evaporated to obtain a crude product of Formula 1-B. The crude product was dissolved in a mixed solution of water, acetone and ethyl acetate. The volume ratio of water, acetone and ethyl acetate was 1:2:4. The organic layer solution was collected using a separatory funnel. The organic solution was rotary evaporated to remove acetone and ethyl acetate, thereby obtaining Formula 1-B with higher purity.

[0118] Example 1:

[0119] This example describes the application of the collector of Formula 1-A in fluorite flotation. The experimental sample was obtained from a certain place in Inner Mongolia. The experimental temperature (flotation temperature) was 25°C. The flotation flow chart is shown in Figure 5 and specifically includes the following steps:

[0120] (1) Preparation of the sample: the fluorite ore sample was crushed to a particle size of less than 2 mm by an eccentric crusher and a pair roller crusher. The sample was mixed and divided by the heap shifting method.

[0121] (2) Preparation of the roughing slurry: the sample was ground to a particle size of -0.074 mm by a conical ball mill, and the roughing was performed. The mass concentration of the flotation slurry was 30%, and the slurry was stirred at a speed of 1992 r / min to obtain the fluorite roughing slurry.

[0122] (3) Roughing process: sodium carbonate was used as the pH regulator, and the pH of the fluorite roughing slurry was adjusted to 9. Then, the depressant and the collector were added in sequence. In the roughing stage, the dosage of the depressant sodium silicate was 1300 g / t, and the dosage of the collector of Formula 1-A was 300 g / t. After the addition of the depressant, the slurry was stirred for 3 minutes, and after the addition of the collector, the slurry was stirred for 25 minutes. After the addition of all the reagents, the slurry was aerated for 1 minute, and then the froth product was collected by a scraper for 5 minutes at a speed of 20 r / min. The froth product collected by the scraper was the fluorite roughing concentrate.

[0123] (4) Preparation of the cleaning slurry: the fluorite roughing concentrate was ground to a particle size of -0.038 mm by a conical ball mill, and the cleaning was performed. The flotation slurry was stirred at a speed of 1992 r / min to obtain the fluorite cleaning slurry.

[0124] (5) Concentration process: The feed of concentration stage I is the regrinding product of rough fluorite concentrate. The feed of concentration stages (II-VII) is the fluorite concentrate product of the previous concentration stage. In all concentration stages, sodium carbonate is used as the pH regulator, and after adjusting the pH of fluorite concentration slurry to 9, the depressant and collector are added in turn. In concentration stage I, the dosage of water glass is 350 g / t, and the dosage of formula 1-A is 200 g / t. In concentration stages (II-IV), the dosage of water glass is 250 g / t. In concentration stages (V-VII), the dosage of water glass is 150 g / t. After adding the depressant, the slurry is stirred for 3 minutes, and after adding the collector, the slurry is stirred for 25 minutes. After all reagents are added, the slurry is aerated for 1 minute, and then the froth product is collected by scraper for 5 minutes at a speed of 20 r / min. The froth product scraped out is the flotation concentrate.

[0125] (6) Scavenging process: The feed of scavenging stage I is the rough fluorite tailings, and the feed of scavenging stage II is the tailings of fluorite scavenging stage I. In all scavenging stages, sodium carbonate is used as the pH regulator, and after adjusting the pH of fluorite scavenging slurry to 9, the collector is added. In scavenging stage I, the dosage of formula 1-A is 200 g / t. In scavenging stage II, the dosage of formula 1-A is 100 g / t. After adding the collector, the slurry is stirred for 25 minutes. After all reagents are added, the slurry is aerated for 1 minute, and then the froth product is collected by scraper for 5 minutes at a speed of 20 r / min. The product at the bottom of the tank is the flotation tailings.

[0126] Example 2:

[0127] Compared with Example 1, the only difference is that formula 1-B is used instead of formula 1-A in Example 1, and other parameters are the same as in Example 1. The flotation results are shown in Table 1.

[0128] Example 3:

[0129] Compared with Example 1, the only difference is that low-temperature flotation is used, and the flotation temperature is 10°C, and other parameters are the same as in Example 1. The flotation results are shown in Table 1.

[0130] Example 4:

[0131] Compared with Example 2, the only difference is that low-temperature flotation is used, and the flotation temperature is 10°C, and other parameters are the same as in Example 2. The flotation results are shown in Table 2.

[0132] Example 5:

[0133] Compared with Example 1, the only difference is that the concentration of Ca 2+ and Mg2+ The concentration was 100 mg / L, respectively, and other parameters were the same as in Example 1. The flotation results are shown in Table 1.

[0134] Example 6:

[0135] Compared with Example 2, the only difference was that the concentration of Ca 2+ and Mg 2+ The concentration was 100 mg / L, respectively, and other parameters were the same as in Example 1. The flotation results are shown in Table 1.

[0136] Example 7:

[0137] Compared with Example 1, the only difference was that the collector of Formula 1-C was used instead of Formula 1-A in Example 1, and other parameters were the same as in Example 1. The flotation results are shown in Table 1.

[0138]

[0139] Comparative Example 1:

[0140] Compared with Example 1, the only difference was that the collector of Formula 4-A was used instead of Formula 1-A in Example 1, and other parameters were the same as in Example 1. The flotation results are shown in Table 1.

[0141] Comparative Example 2:

[0142] Compared with Example 1, the only difference was that the collector of Comparative Formula a was used instead of Formula 1-A in Example 1, and other parameters were the same as in Example 1. The flotation results are shown in Table 1.

[0143]

[0144] Comparative Example 3:

[0145] Compared with Example 1, the only difference was that the collector of Comparative Formula b was used instead of Formula 1-A in Example 1, and other parameters were the same as in Example 1. The flotation results are shown in Table 1.

[0146]

[0147] Comparative Example 4:

[0148] Compared with Example 1, the only difference was that the collector of Comparative Formula c was used instead of Formula 1-A in Example 1, and other parameters were the same as in Example 1. The flotation results are shown in Table 1.

[0149]

[0150] Comparative Example 5:

[0151] The difference between the example 1 and the comparative example 1 is that the collector of formula 1-A in the example 1 is replaced by the collector of formula 1-B, and other parameters are the same as the example 1. The flotation results are shown in Table 1.

[0152]

[0153] Comparative example 6

[0154] Comparative example 6:

[0155] The difference between the example 1 and the comparative example 1 is that the collector of formula 1-A in the example 1 is replaced by the collector of formula 1-B, and other parameters are the same as the example 1. The flotation results are shown in Table 1.

[0156] Table 1. Flotation results of different examples of fluorite in Inner Mongolia

[0157]

[0158]

[0159] The results of Table 1 show that for fluorite flotation, formula 1-A and formula 1-B have good selection effect (example 1 and 2). As a collector, formula 1-A and formula 1-B have the advantages of low temperature resistance and good solubility (example 3 and 4), and are less affected by soluble cations in the solution (example 5 and 6). As a collector, the collecting ability of formula 1-A and formula 1-B is affected by the one-dimensional position of hydroxyl or epoxy group and CONON (example 7). The comparison of example 1 and 2 with comparative example 1 shows that compared with oleic acid, formula 1-A and formula 1-B as a collector have the advantages of high selectivity and strong collecting ability. The comparison of example 1 and 2 with comparative example 2 shows that formula 1-A and formula 1-B respectively contain hydroxyl and epoxy groups, and the collecting ability is enhanced. The comparison of example 1 with comparative example 3 shows that formula 1-A contains CONOH, and the selectivity is improved. The comparison of example 1 with comparative example 4 shows that the hydroxyl group in formula 1-A and CONOH synergistically act, enhancing the collecting ability and improving the selectivity. The comparison of example 1 and 2 with comparative example 5 shows that the one-dimensional position of hydroxyl or epoxy group is close to CONON, and the collecting ability of aliphatic amide is reduced. The comparison of example 1 and 2 with comparative example 6 shows that the collecting ability of aliphatic amide (formula 1-A and formula 1-B) on fluorite is stronger than that of aromatic amide (salicylhydroxylamine).

[0160] Example 8

[0161] This example is the application of formula 1-A collector in fluorite flotation. The ore sample used in the experiment is from a certain place in Henan. The experimental temperature is 25℃. The flotation flow chart is shown in Figure 6 , which specifically includes the following steps:

[0162] (1) Preparation of the ore sample: The grade of the raw fluorite ore is 49.25%. The ore sample is crushed to a particle size of less than 2 mm by an eccentric crusher and a pair-roller crusher. The ore sample is mixed and divided by the moving heap method.

[0163] (2) Preparation of the roughing slurry: The ore sample is ground to 85.6% of -0.074 mm mineral particles by a conical ball mill, and roughing is performed. The mass concentration of the flotation slurry is 30%, and the slurry is stirred and adjusted at a speed of 1992 r / min to obtain the fluorite roughing slurry.

[0164] (3) Roughing process: Sodium carbonate is used as the pH adjuster, and the pH of the fluorite roughing slurry is adjusted to 9. Then, the depressant and the collector are added in sequence. In the roughing stage, the dosage of the depressant sodium silicate is 500 g / t, and the dosage of the collector Formula 1-A is 300 g / t. After the addition of the depressant, the slurry is stirred for 3 minutes, and after the addition of the collector, the slurry is stirred for 25 minutes. After all the reagents are added, the slurry is aerated for 1 minute, and then the froth product is collected by a scraper for 5 minutes at a speed of 20 r / min. The scraped froth product is the fluorite roughing concentrate.

[0165] (4) Cleaning process: The feed of the cleaning stage I is the fluorite roughing concentrate. The feed of the cleaning stages (II-VI) is the fluorite cleaning concentrate of the previous cleaning stage. In all the cleaning stages, sodium carbonate is used as the pH adjuster, and the pH of the fluorite cleaning slurry is adjusted to 9. Then, the depressant and the collector are added in sequence. In the cleaning stage I, the dosage of sodium silicate is 200 g / t, and the dosage of Formula 1-A is 200 g / t. In the cleaning stages (II-IV), the dosage of sodium silicate is 100 g / t. In the cleaning stages (V-VI), the dosage of sodium silicate is 50 g / t. After the addition of the depressant, the slurry is stirred for 3 minutes, and after the addition of the collector, the slurry is stirred for 25 minutes. After all the reagents are added, the slurry is aerated for 1 minute, and then the froth product is collected by a scraper for 5 minutes at a speed of 20 r / min. The scraped froth product is the flotation concentrate.

[0166] (5) Scavenging process: The feed of the scavenging stage I is the fluorite roughing tailings, and the feed of the scavenging stage II is the fluorite scavenging stage I tailings. In all the scavenging stages, sodium carbonate is used as the pH adjuster, and the pH of the fluorite scavenging slurry is adjusted to 9. Then, the collector is added. In the scavenging stage I, the dosage of Formula 1-A is 200 g / t. In the scavenging stage II, the dosage of Formula 1-A is 100 g / t. After the addition of the collector, the slurry is stirred for 25 minutes. After all the reagents are added, the slurry is aerated for 1 minute, and then the froth product is collected by a scraper for 5 minutes at a speed of 20 r / min. The product at the bottom of the tank is the flotation tailings.

[0167] (6) Analysis and detection: The flotation concentrate and tailings are dried and weighed, the grade of fluorite in the flotation concentrate and tailings is tested, the yield of the flotation concentrate and tailings is calculated, and the recovery rate of fluorite is calculated. The fluorite flotation results are shown in Table 2. As can be seen from the results, the use of Formula 1-A can obtain a fluorite flotation concentrate with a high grade and a high recovery rate.

[0168] Example 9

[0169] Compared with Example 8, the only difference is that the collector of Formula 1-B is used instead of Formula 1-A in Example 8, and other parameters are the same as those in Example 8. The flotation results are shown in Table 2. According to the results, the use of Formula 1-B can obtain a fluorite flotation concentrate with high grade and high recovery rate.

[0170] Table 2. Flotation results of fluorite in different examples in a certain place in Henan

[0171]

[0172]

[0173] The results in Table 2 show that Formula 1-A and Formula 1-B have good separation effect for fluorite flotation.

Claims

1. A fluorite collector, characterized by, A compound having the structural formula of Formula 1: Formula 1 The n is an integer of 5-10; R1 is C3~C 12 Alkyl groups; The R2 and R3 are hydroxyl or are cyclically combined to form an epoxy group.

2. The fluorite collector according to claim 1, characterized in that, The n is an integer of 6-9.

3. The fluorite collector according to claim 1, characterized in that, The R1 is a linear alkyl.

4. The fluorite collector according to claim 3, characterized in that, R1is a linear alkyl group of C7-C 10 linear alkyl group of C7-C 5. The fluorite collector according to claim 1, characterized in that, In the Formula 1, the total carbon number is 16-20.

6. The fluorite collector according to claim 1, wherein The fluorite collector is at least one of Formula 1-A and Formula 1-B; Formula 1-A Formula 1-B.

7. A process for the preparation of the fluorite collector according to any one of claims 1 to 6, characterized in that, The compound of Formula 2 is reacted with NH2OH to obtain; Formula 2 The R1, R2 and R3 in Formula 2 are selected in the same range as in Formula 1; and the R4 is a C1-C6 alkyl. The molar ratio of the compound of Formula 2 to NH2OH is 1:(1.2-2), and the reaction temperature is 30-60°C.

8. The method of preparing a fluorite collector according to claim 7, wherein The compound of Formula 2 is prepared by subjecting a compound of Formula 3 to a hydroxylation or epoxidation reaction at an unsaturated bond: Formula 3 The R1 and R4 in Formula 3 are selected in the same range as in Formula 2.

9. The method of preparing a fluorite collector according to claim 8, characterized in that, The compound of Formula 3 is mixed with glacial acetic acid, and then a solution of hydrogen peroxide and concentrated sulfuric acid in acetic acid is added dropwise to subject the unsaturated bond to a hydroxylation reaction, thereby obtaining a product of Formula 2 in which R2 and R3 are hydroxyl.

10. The method of preparing a fluorite collector according to claim 9, wherein The molar ratio of the compound of Formula 3 to glacial acetic acid, hydrogen peroxide and concentrated sulfuric acid is 1:(14-16):(6-8):(0.02-0.05), and the hydroxylation reaction temperature is 30-60°C.

11. The method of preparing a fluorite collector according to claim 8, wherein The compound of Formula 3 is mixed with a peroxide to subject the unsaturated bond to an epoxidation reaction, thereby obtaining a product of Formula 2 in which R2 and R3 are cyclically combined to form an epoxy group. The peroxide is meta-chloroperoxybenzoic acid. The molar ratio of the compound of Formula 3 to the peroxide is 1:(1-2). The epoxidation reaction temperature is 15-40°C.

12. The method of preparing a fluorite collector according to claim 8, wherein The compound of Formula 3 is obtained by subjecting a compound of Formula 4 to an esterification reaction in concentrated sulfuric acid: Formula 4 The R4 in Formula 4 is selected in the same range as in Formula 3.

13. The method for preparing the fluorite collector as described in claim 12, characterized in that, The molar ratio of the compound of Formula 4 to concentrated sulfuric acid and R4OH is 1:(0.02-0.05):(45-55). The esterification reaction temperature is 60-90°C.

14. Use of a fluorite collector according to any one of claims 1 to 6 or a fluorite collector prepared according to the method of any one of claims 7 to 13, characterized in that, It is used as a collector for the flotation of fluorite.

15. The use according to claim 14, wherein the compound is ###0002### It is used as a collector for the selective flotation separation of fluorite and other calcium-containing gangues: The other calcium-containing gangues are at least one of calcite, dolomite and scheelite.

16. The use of claim 15, wherein, In the flotation stage, the amount of the collector of Formula 1 used is 50-300 g / t. The pH in the flotation stage is 8-10.

17. The use according to claim 16, wherein An inhibitor is further added in the flotation stage. The inhibitor is water glass. The amount of the inhibitor used in the flotation stage is 50-1300 g / t.

18. A fluorite flotation reagent characterised in that, The inhibitor and the fluorite collector of any one of claims 1-6 or prepared by the preparation method of any one of claims 7-13.

19. The fluorite flotation reagent according to claim 18, c h a r a c t e r i z e d in that The fluorite flotation reagent is a flotation reagent for separating fluorite and other calcium-containing gangues.

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