Double reverse flotation process for high-magnesium aluminosilicate medium-phosphorus grade collophanite

Abstract

The present application relates to a kind of high magnesium containing aluminosilicate medium phosphorus grade collophanite double reverse flotation process, which uses different properties reagent combination to carry out beneficiation method as follows: first, the phosphate ore is ground finely;The pulp is thickened;The thickened gravity separation concentrate slurry is de-magnesium, then the adjusting agent / inhibitor and reverse flotation de-magnesium anion collector are added to carry out de-magnesium roughing;De-magnesium concentrate slurry is continued to carry out de-aluminum flotation operation;De-aluminum surfactant is added to the de-aluminum concentrate and tailings of roughing, and one de-aluminum flotation is carried out again, respectively, which is de-aluminum cleaning and scavenging;De-aluminum cleaning tailings and de-aluminum concentrate of scavenging are combined into middlings and returned to de-aluminum roughing section for circulation, and the tank concentrate slurry is the final concentrate.The present application uses the properties of acid and base inhibitors and de-aluminum surfactant, which not only improves the phosphate concentrate product index, but also significantly reduces the foam diameter.

Description

Technical Field

[0001] This invention belongs to the field of phosphate rock beneficiation flotation technology, specifically relating to a combined reagent for double reverse flotation of high-magnesium, aluminum-containing, silicon-containing medium-phosphorus phosphate rock and its application method. Background Technology

[0002] Phosphate ore flotation typically separates phosphate rock from gangue minerals such as dolomite and silicates. Flotation processes include direct flotation, reverse flotation, combined direct and reverse flotation, combined reverse and direct flotation, and combined dual-reverse flotation. Direct flotation inevitably carries gangue minerals such as quartz, making it difficult to obtain high-grade phosphate concentrate. Reverse flotation, on the other hand, enriches gangue minerals like quartz by flotation, yielding high-grade phosphate concentrate and is widely recognized and used.

[0003] Compared with existing technologies, this process addresses the issue from two aspects: desliming pretreatment of the slurry and reagents. The phosphate rock is ground to a fineness of -200 mesh (88%). First, the ground slurry is adjusted to a suitable concentration before gravity separation for desliming, reducing the amount of reagents required in subsequent operations. In the demagnesiation stage, organic acids and organic bases are used as modifiers. These two agents both adjust the pH and inhibit phosphate rock growth. A demagnesiation anionic collector is then added for the demagnesiation step. No modifier is needed in the dealuminization stage; a dealuminizing surfactant is added directly. The demagnesiation stage includes a roughing stage, and the dealuminization stage involves a roughing, cleaning, and scavenging process, resulting in a concentrate grade of over 31% P₂O₅ and a recovery rate greater than 70%.

[0004] The modifier used in this process is a combination of two inhibitors, organic acid and organic base, which enhances the inhibitory effect on phosphate rock during the reverse flotation process.

[0005] The dealuminizing surfactant used in this process can effectively separate useful minerals from gangue minerals, improve foam viscosity, reduce foam diameter, and enhance its flow properties.

[0006] CN109453891A discloses a combined gravity and flotation process for high-density semi-colloidal phosphate rock via a spiral sluice. This invention reduces the influence of mineral particle size on gravity and flotation to some extent, but it cannot eliminate the influence of fine slime on the entire process. Summary of the Invention

[0007] To address the problems of existing technologies, the present invention aims to provide a combined reagent and its application method for the double reverse flotation of high-magnesium, aluminum-containing, silicon-containing, medium-phosphorus phosphate rock. This method reduces flotation reagent consumption through a pre-gravity separation and desliming process, and employs a novel combined modifier that not only enhances the inhibitory effect on the phosphate rock during reverse flotation but also significantly improves the fluidity of the froth through the use of a dealuminizing agent. This invention simplifies the process flow, reduces the types and quantities of flotation reagents, lowers production costs, and enables the effective recovery and utilization of phosphorus resources.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows: a combined reagent for double reverse flotation of high magnesium-aluminum-silica medium-phosphorus phosphate rock and its application method adds a gravity separation and desliming pretreatment stage before the ordinary demagnesiation process, then adds a combined modifier and anionic collector for demagnesiation, and finally directly adds a cationic collector for dealuminization.

[0009] This invention provides a double-reverse flotation process for high-magnesium, aluminum-containing, silicon-containing, medium-phosphorus phosphate rock, comprising the following steps:

[0010] After grinding, slurry preparation, and gravity separation to remove slime, the pH of the raw collophane ore is adjusted to 4.5-5.0. An anionic magnesium collector is added to carry out magnesium removal reverse flotation. The magnesium removal concentrate slurry is collected, and a dealuminizing surfactant is added to the magnesium removal concentrate slurry to carry out a roughing operation of dealuminizing flotation. The concentrate from the roughing and dealuminizing operation is collected, thus realizing the double reverse flotation of medium-phosphorus grade collophane ore.

[0011] In some practical operations, the raw phosphate rock needs to be ground and the pulp concentration adjusted to 20%~23% before entering the sluice box for gravity separation. The adjusted pulp is then fed into a spiral sluice box for gravity separation, completing the desliming process before flotation. The tailings are directly disposed of as tailings. The raw phosphate rock is a high-magnesium, aluminous silica gel phosphate rock with a P2O5 grade of 23%-26%, MgO content of 6%-7%, and Al2O3 content of 3%-5%.

[0012] During the pH adjustment process, both acidic and alkaline inhibitors are added sequentially to the slurry to act as inhibitors for the phosphate rock and to adjust the pH.

[0013] The acidic inhibitor is one or more of citric acid, malic acid, and tartaric acid; the basic inhibitor is a combination of azole compounds and amino alcohol compounds, wherein the azole compound is any one of 1-vinylimidazole, 1-allylimidazole, and 2-ethylimidazole, and the amino alcohol compound is any one of 2-ethylaminoethanol, 4-amino-1-butanol, and 3-aminocyclobutanol.

[0014] The mass ratio of azole compounds to amino alcohol compounds is 3~5:1.

[0015] The organic acid is prepared into a solution with a mass content of about 3-5%, and the organic base is also prepared into a solution with a mass content of about 3-5%. The concentration of the combined agent after mixing is 6-10%, and the dosage of the mixed inhibitor is 8.0 kg / t-10.0 kg / t.

[0016] The magnesium removal collector is selected from the fatty acid soap collector of Hubei Xingfa Chemical Co., Ltd., and the dosage of the magnesium removal collector is 0.8 kg / t - 1.0 kg / t; the anionic magnesium removal collector is mixed with water to prepare a solution with a concentration of 1.0-2.0%, and it needs to be stirred continuously at a high temperature of 80~100℃ during the process.

[0017] The dealuminizing surfactant is one or more of lauryl sulfate ammonium salt, hydroxyethyl sulfonate ammonium salt, and sodium dodecylbenzene sulfonate, and the dosage of the dealuminizing surfactant is 45-55 g / t. The dealuminizing surfactant can be directly dissolved in water, and one or more of them can be prepared into a 0.3-0.5% solution for use.

[0018] When collecting the concentrate from the roughing and dealuminizing operation, tailings are also collected. The concentrate and tailings are then subjected to dealuminizing flotation operations again, which are named dealuminizing cleaning and scavenging respectively. The cleaning concentrate becomes the final concentrate, and the scavenging tailings become the final tailings. The cleaning tailings and scavenging concentrate together become the middlings, which, together with the magnesium-removing concentrate slurry, achieve dealuminizing cycle.

[0019] In the dealumination process, the amount of dealumination surfactant used is 95-105 g / t, while in the scavenging process, the amount of dealumination surfactant used is 70-80 g / t.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] 1) Combining two depressants with different acidity and alkalinity for flotation, both reagents have varying degrees of inhibitory effect on phosphate rock. The organic acid reagent is added first to ensure thorough binding with the phosphate rock, followed by the addition of an organic base reagent to interact with the remaining unbound phosphate rock. This method exhibits a more significant inhibitory effect on phosphate rock than previous single-property depressants, effectively increasing phosphate rock yield and adjusting pulp pH. Furthermore, no additional depressant is needed in the subsequent dealuminization process, thus reducing the overall amount of flotation reagents used. Compared to previous methods, the total amount of depressant can be reduced by 30%-50%.

[0022] 2) The dealuminating surfactant used is one or more of lauryl sulfate ammonium salt, hydroxyethyl sulfonate ammonium salt, and sodium dodecylbenzene sulfonate. Compared with traditional cationic collectors, this agent can effectively reduce the foam diameter in flotation and optimize foam flowability.

[0023] 3) Under this reagent system, better flotation process indicators can be obtained, with a P2O5 grade of ≥31% and a phosphate concentrate recovery rate of ≥70%. Attached Figure Description

[0024] Figure 1 This is a flowchart illustrating the combined reagents and their application method for the double reverse flotation of high-magnesium, aluminum-containing, silicon-grade phosphate rock, as described in this invention. Detailed Implementation

[0025] To enable those skilled in the art to better understand the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following examples.

[0026] Unless otherwise specified, the reagents used in the following implementations are commercially available chemical reagents or industrial products.

[0027] The sample described in this invention is a high-magnesium phosphate rock from Yichang with a P2O5 grade of 24.76%, MgO content of 6.88%, and Al2O3 content of 3.92%, which is then subjected to flotation. First, the ore is ground to a fineness of -0.074mm (mineral particles accounting for 88.23%), and water is added to adjust the concentration to 20% for a slurry. This slurry is then fed into a gravity separation sluice for desliming. The adjusted slurry is then fed into a spiral sluice for gravity separation, completing the desliming process before flotation to obtain a gravity concentrate. The tailings are directly disposed of as tailings.

[0028] Example 1

[0029] Double reverse flotation process for high-magnesium, aluminum-containing, silicon-containing, medium-phosphorus phosphate rock, such as... Figure 1 As shown, it also includes the following steps:

[0030] (1) Adjust the concentration of the obtained gravity concentrate to 30%, and then add 5% citric acid and 5% organic base (a mixture of 1-vinylimidazolium and 2-ethylaminoethanol in a mass ratio of 3:1) to the gravity concentrate with the adjusted concentration. Stir and adjust the pH to 4.8 at a rate of 10 kg / t. Then add 1.0 kg / t of anionic magnesium removal collector XF-01 to carry out magnesium removal reverse flotation. Collect the concentrate slurry at the bottom of the flotation cell for the next flotation operation. The tailings are directly the final tailings.

[0031] (2) Continue to carry out flotation operation on the magnesium-removed concentrate obtained in (1), add 50 g / t of sodium dodecylbenzenesulfonate, a dealuminizing surfactant, directly to the magnesium-removed concentrate slurry for roughing flotation, and collect the concentrate and tailings from the roughing flotation operation respectively.

[0032] (3) Sodium dodecylbenzenesulfonate is added to the concentrate and tailings in step (2) again for dealuminization flotation, with dosages of 100 g / t and 50 g / t respectively. They are named dealuminization cleaning and scavenging respectively. The cleaned concentrate becomes the final concentrate, and the scavenged tailings become the final tailings. The cleaned tailings and scavenged concentrate together become the middlings, which are added to the dealuminization slurry in step (2) for recycling.

[0033] The flotation concentrate obtained by the closed-circuit double-reverse flotation process has a P2O5 grade of 31.78%, MgO content of 0.5%, and Al2O3 content of 1.80%, with a recovery rate of 70.70%. The flotation froth diameter is reduced to more than half that of commonly used reagents, with an average diameter of 2-3 mm. After flotation, the tailings are gently shaken for about 15 seconds, and a defoaming effect of over 80% can be observed. Commonly used reagents, such as those described in CN114011580, require the addition of 4 kg / t of phosphoric acid for slurry conditioning before dealuminization. The dealuminizing collector is an amine collector, whose main components are ether amines and ether polyamines, used at a dosage of 0.5 kg / t. The final concentrate grade is 31.20%, with a recovery rate of 60.45%, a magnesium oxide content of 0.67%, and a sesquioxide content of 2.41%.

[0034] Example 2

[0035] The process steps are the same as in Example 1, except that the organic base is a mixture of 2-ethylimidazole and 4-amino-1-butanol in a mass ratio of 5:1.

[0036] The flotation concentrate obtained by the closed-circuit double reverse flotation process has a P2O5 grade of 31.62%, an MgO content of 0.6%, an Al2O3 content of 1.81%, and a recovery rate of 70.88%. The average diameter of the flotation froth is about 2 mm. The small froth diameter enhances the fluidity of the froth. The froth scraping time is 2 minutes, and no defoamer is required.

[0037] Commonly used dealuminizing collectors, such as etheramine collectors, require a foaming time of 4 minutes for the same amount of agent used in the dealuminizing step, and the foam is sticky, requiring the use of defoamers.

[0038] Example 3

[0039] The process steps are the same as in Example 1, except that the organic base is a mixture of 1-allylimidazol and 3-aminocyclobutanol in a mass ratio of 4:1.

[0040] The flotation concentrate obtained by the closed-circuit double reverse flotation process has a P2O5 grade of 31.77%, an MgO content of 0.58%, an Al2O3 content of 1.82%, and a recovery rate of 70.73%. The average diameter of the flotation froth is about 2 mm. The small froth diameter enhances the fluidity of the froth. The froth scraping time is 2 minutes, and no defoamer is required.

[0041] Commonly used dealuminizing collectors, such as etheramine collectors, require a foaming time of 4 minutes for the same amount of agent used in the dealuminizing step, and the foam is sticky, requiring the use of defoamers.

[0042] Example 4

[0043] The process steps are the same as in Example 1, except that the organic base is 1-vinylimidazole.

[0044] The flotation concentrate obtained by the closed-circuit double reverse flotation process has a P2O5 grade of 31.50%, MgO content of 0.62%, Al2O3 content of 1.90%, and a recovery rate of 70.80%. The flotation froth diameter is about 3 mm, with enhanced fluidity. The skimming time is shortened by 45 seconds compared with the same amount of dodecylamine, and the froth diameter is half that of the dodecylamine flotation dealuminization froth.

[0045] Example 5

[0046] The process steps are the same as in Example 1, except that the organic base is diethylaminoethanol.

[0047] The flotation concentrate obtained by the closed-circuit double reverse flotation process has a P2O5 grade of 31.59%, MgO content of 0.65%, Al2O3 content of 1.86%, and a recovery rate of 70.82%. The flotation froth diameter is about 3 mm, with enhanced fluidity. The froth scraping time is shortened by 40 seconds compared with the same amount of dodecylamine, and the froth diameter is half that of the dodecylamine flotation dealuminization froth.

[0048] Example 6

[0049] The process steps are the same as in Example 1, except that no organic alkali is added and the water is used to adjust the pH to 4.8.

[0050] The flotation concentrate obtained by the closed-circuit double reverse flotation process had a P2O5 grade of 31.16%, an MgO content of 0.7%, an Al2O3 content of 1.97%, and a recovery rate of 70.84%. The foam fluidity was slightly worse and the foam diameter was slightly smaller. Compared with the quaternary ammonium salt dealuminizing collector, the foam scraping time was not much different from that of the quaternary ammonium salt collector under the same dosage, requiring 3 minutes of foam scraping.

[0051] Example 7

[0052] The process steps are the same as in Example 1, except that the mixture is stirred and the pH is adjusted to 5.8.

[0053] The flotation concentrate obtained by the closed-circuit double-reverse flotation process had a P2O5 grade of 29.55%, MgO content of 0.8%, and Al2O3 content of 2.11%, with a recovery rate of 70.85%. Without the addition of depressants, the flotation fluidity was poor, the flotation foam was sticky, and the flotation state and indicators were not significantly different from those using commonly used reagents. In summary, flotation without adjusting the pH to the required level using depressants will affect the subsequent dealuminization stage and lead to a decrease in flotation quality.

[0054] The above examples illustrate the technical solution of the present invention, but the present invention is not limited to the above embodiments. Any equivalent substitutions made by those skilled in the art based on the present invention are within the scope of protection of this patent.

Claims

1. A double-reverse flotation process for high-magnesium, aluminum-containing, silicon-containing, medium-phosphorus grade collophane ore, characterized in that, The following steps are included: After grinding, pulp conditioning, and gravity separation to remove slime, the pH of the raw collophane ore is adjusted to 4.5-5.

0. An anionic magnesium collector is added for magnesium removal reverse flotation, and the magnesium concentrate is collected. A dealuminizing surfactant is added to the magnesium concentrate for roughing flotation, and the concentrate from the roughing flotation is collected. This achieves double reverse flotation of medium-phosphate grade collophane. During the pH adjustment process, both acidic and alkaline inhibitors are added to the pulp sequentially as inhibitors for the phosphate rock and to adjust the pH. The acidic inhibitor is one or more of citric acid, malic acid, and tartaric acid; the alkaline inhibitor is a combination of azole compounds and amino alcohol compounds, wherein the azole compound is any one of 1-vinylimidazole, 1-allylimidazole, and 2-ethylimidazole, and the amino alcohol compound is any one of 2-ethylaminoethanol, 4-amino-1-butanol, and 3-aminocyclobutanol.

2. The double-reverse flotation process for high-magnesium, aluminum-containing, silicon-containing, medium-phosphorus grade phosphate rock according to claim 1, characterized in that, The mass ratio of azole compounds to amino alcohol compounds is 3~5:

1.

3. The double-reverse flotation process for high-magnesium, aluminum-containing, silicon-containing, medium-phosphorus grade phosphate rock according to claim 1, characterized in that, The acidic inhibitor is prepared as a solution with a mass content of 3-5%, the alkaline inhibitor is prepared as a solution with a mass content of 3-5%, the concentration of the combined agent after mixing is 6-10%, and the dosage of the mixed inhibitor is 8.0 kg / t-10.0 kg / t.

4. The double-reverse flotation process for high-magnesium, aluminum-containing, silicon-containing, medium-phosphorus grade phosphate rock according to claim 1, characterized in that, The magnesium removal collector is a fatty acid soap-based collector, and the dosage of the magnesium removal collector is 0.8 kg / t - 1.0 kg / t; The dealuminating surfactant is one or more of lauryl sulfate ammonium salt, hydroxyethyl sulfonate ammonium salt, and sodium dodecylbenzene sulfonate, and the amount of dealuminating surfactant used is 45-55 g / t.

5. The double-reverse flotation process for high-magnesium, aluminum-containing, silicon-containing, medium-phosphorus phosphate rock according to claim 1 or 4, characterized in that, When collecting the concentrate from the roughing and dealuminizing operation, tailings are also collected. The concentrate and tailings are then subjected to dealuminizing flotation operations again, which are named dealuminizing cleaning and scavenging respectively. The cleaning concentrate becomes the final concentrate, and the scavenging tailings become the final tailings. The cleaning tailings and scavenging concentrate together become the middlings, which, together with the magnesium-removing concentrate slurry, achieve dealuminizing cycle.

6. The double-reverse flotation process for high-magnesium, aluminum-containing, silicon-containing, medium-phosphorus phosphate rock according to claim 5, characterized in that, In the dealumination process, the amount of dealumination surfactant used is 95-105 g / t, while in the scavenging process, the amount of dealumination surfactant used is 70-80 g / t.

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