Application of pullulan as calcite inhibitor in fluorite flotation and application method

Abstract

The invention provides application of pullulan as a calcite inhibitor in fluorite flotation and an application method, and relates to the technical field of fluorite mine flotation, the pullulan is used as the calcite inhibitor in the fluorite mine flotation, and the application method comprises the steps of ore pulp preparation, pH adjustment and addition of the pullulan inhibitor and a collecting agent. And fluorite flotation operation is conducted, and fluorite concentrate products and tailings are obtained. Compared with inhibitor water glass and modified products thereof which are most widely used in fluorite mine flotation at present, the pullulan is small in dosage, only needs to be added once in rough flotation, is higher in selectivity and better in flotation effect, is good in solubility, is easy to prepare and degrade, and is free of pollution to the environment.

Description

Technical Field

[0001] The invention relates to the technical field of fluorite ore flotation, and in particular to an application of pullulan as a calcite inhibitor in fluorite flotation and an application method. Background Art

[0002] Fluorite is mainly composed of CaF2. It is the only mineral that can provide a large amount of fluorine in industrial production. It is mainly used to extract or prepare fluorine and its compounds. It is widely used in traditional and emerging industries such as metallurgy, chemical industry, building materials, ceramics, aviation, refrigeration, medicine, atomic energy industry, fluorine chemical industry, etc. According to the National Mineral Resources Planning, fluorite is included in my country's "Strategic Mineral Catalogue" and is a "world-class scarce resource similar to rare earths". According to the different types of deposits, my country's fluorite deposits can be divided into two categories: single-type fluorite deposits and associated fluorite deposits. According to the main mineral composition, fluorite deposits can be divided into quartz-type fluorite, calcite-type fluorite, barite-type associated fluorite, and polymetallic associated fluorite. Most of the associated fluorite ores are poor ores with complex ore properties. Among them, the main associated mineral of calcite-type fluorite is calcite, which is a calcium-containing mineral like fluorite, and the active sites are all calcium ions. This makes the collector limited in its selectivity, so it is necessary to use a selective inhibitor to selectively inhibit calcite.

[0003] In the field of fluorite flotation, the depressant water glass currently used in industry has a large amount of water glass in actual production and poor selectivity. A large amount of water glass not only inhibits the floating of fluorite and reduces the quality of fluorite concentrate, but also in order to improve the selectivity of water glass, Cu is usually added. 2+ , Pb 2+ Heavy metal ions such as polyacrylic acid and starch are used to assist in the separation of fluorite. The heavy metal ions pollute the environment. The high molecular weight inhibitors such as polypropylene carboxylic acid and starch have high solution viscosity, which will make the flotation foam difficult to break and cause mineral entrainment in production. Therefore, finding a more efficient and environmentally friendly inhibitor is of great significance for the selection of fluorite.

[0004] Pullulan is a colorless, odorless white powder. It is safe, non-toxic, stable, biodegradable, widely found in nature, easy to prepare and inexpensive. Due to its unique structure and properties, it has broad application prospects in the pharmaceutical, food, petroleum, chemical and other industries. Because it can be degraded and utilized by microorganisms in nature and does not cause environmental pollution, it is known as a pollution-free plastic. Currently, there are few reports on its application in the field of mineral processing engineering.

[0005] Background

[0006] In view of the above shortcomings, the present invention provides an application of pullulan as a calcite inhibitor in fluorite flotation and an application method. For the first time, the pullulan inhibitor is applied to the flotation of calcite-type fluorite ore (i.e., the main associated mineral in the main fluorite ore is calcite). Compared with water glass and its modified products, which are currently the most widely used inhibitors in fluorite flotation, the pullulan of the present invention has a small dosage and only needs to be added once in the rough selection. It has stronger selectivity, better flotation effect, is easy to configure, and is easy to degrade and has no pollution to the environment. The specific technical scheme is as follows:

[0007] The application of pullulan as a calcite inhibitor in fluorite flotation of the present invention is: in the flotation process of fluorite ore, pullulan is added as a calcite inhibitor.

[0008] In the present invention, the application of pullulan as a calcite inhibitor in fluorite flotation uses a calcite-type fluorite ore. The method for applying pullulan as a calcite inhibitor in fluorite flotation of the present invention comprises the following steps:

[0009] S1. dissolving pullulan in water to obtain an inhibitor solution with a mass concentration of 1-5%;

[0010] S2. Use a ball mill or rod mill to grind the fluorite ore to a fineness of -72 to -77 microns, accounting for 65% to 90%;

[0011] S3, adding water to slurry the fluorite ore ground in step S2 to a slurry mass concentration of 30%-50%, and adjusting the pH to 8-10;

[0012] S4, flotation, adding inhibitors and collectors to the slurry obtained in step S3 in sequence to perform roughing operation first, and obtaining roughing concentrate and roughing tailings after roughing; performing concentrating operation on the roughing concentrate, adding collectors to the roughing concentrate again for the first concentrating, obtaining primary concentrating concentrate and primary concentrating tailings; adding collectors to the primary concentrating concentrate again, and continuing the second concentrating, obtaining secondary concentrating concentrate and secondary concentrating tailings; the secondary concentrating tailings are returned to the previous concentrating operation; the foam product of the last concentrating operation is the final fluorite concentrate product;

[0013] The roughing tailings are subjected to scavenging operation, and primary scavenging concentrate and primary scavenging tailings are obtained after one scavenging operation; the primary scavenging tailings are subjected to secondary scavenging operation, and secondary scavenging concentrate and secondary scavenging tailings are obtained after the secondary scavenging operation; the secondary scavenging concentrate is returned to the previous scavenging operation; the bottom product of the last scavenging operation is the final tailings; no reagents need to be added in the scavenging operation.

[0014] Preferably, in step S2, the fluorite is finely ground to -74 microns using a ball mill or a rod mill, and the fluorite content accounts for 65%-90%;

[0015] Preferably, in step S4, the number of selections of the selection operation is 4-7 times.

[0016] Preferably, in step S4, the scanning operation is performed 1-3 times.

[0017] Preferably, in step S4, the collector is one or more of sodium oleate, oxidized paraffin soap, and hydroxamic acid.

[0018] More preferably, in step S4, the collector is sodium oleate.

[0019] Preferably, the amount of pullulan is 500-1800 g / t; wherein g (gram) in g / t refers to the mass of pullulan, and t (ton) refers to the dry weight of fluorite ore.

[0020] Preferably, the total amount of collector is 2000-3000g / t; wherein g (gram) in g / t is based on the mass of collector; t (ton) is based on the dry weight of fluorite sample; the amount of collector used in the first selection is 1 / 3-2 / 3 of the amount used in the rough selection, and the amount of collector used in the second selection is 1 / 3-2 / 3 of the amount used in the first selection.

[0021] In the field of fluorite flotation, the depressant water glass currently used in industry has a large amount of water glass in actual production and poor selectivity. A large amount of water glass not only inhibits the floating of fluorite and reduces the quality of fluorite concentrate, but also in order to improve the selectivity of water glass, Cu is usually added. 2+ , Pb 2+ Heavy metal ions such as polypropylene carboxylic acid and starch are used to assist separation, and heavy metal ions pollute the environment. The high molecular weight inhibitors such as polypropylene carboxylic acid and starch have high solution viscosity, which will make the flotation foam difficult to break during production and cause mineral entrainment.

[0022] The present invention provides for the first time an application and application method of pullulan as an inhibitor of calcite, a gangue mineral in fluorite flotation, in the field of mineral processing. The pullulan molecule in the pullulan contains a large number of hydroxyl functional groups, which are both hydrophilic groups and polar groups. Hydroxyl and carboxyl groups can chemically adsorb calcium ions on the surface of calcium-containing gangue, and the distribution of its hydroxyl functional groups is easier to adsorb with calcite, which can enhance its selectivity. The hydrophilicity of this selective adsorption of calcite becomes larger, and does not affect the effect of the collector on fluorite, thereby achieving the separation of the two. Compared with water glass and its modified products, which are the most widely used inhibitors in industry, the pullulan of the present invention has a small dosage and only needs to be added once in the rough selection, with stronger selectivity and better flotation effect. In addition, pullulan has good solubility and is easy to configure, easy to degrade and has no pollution to the environment. DETAILED DESCRIPTION

[0023] The specific embodiments of the present invention are described in detail below, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.

[0024] An application of pullulan as a calcite inhibitor in fluorite flotation according to an embodiment of the present invention is: in the flotation process of fluorite ore, pullulan is added as a calcite inhibitor.

[0025] The fluorite ore used in the embodiment of the present invention is a calcite-type fluorite ore.

[0026] The method for using pullulan as a calcite inhibitor in fluorite flotation according to an embodiment of the present invention comprises the following steps:

[0027] S1. dissolving pullulan in water to obtain an inhibitor solution with a mass concentration of 1-5%;

[0028] S2. Use a ball mill or rod mill to grind the fluorite ore to a fineness of -74 microns, accounting for 65%-90%;

[0029] S3, adding water to slurry the fluorite ore ground in step S2 to a slurry mass concentration of 30%-50%, and adjusting the pH to 8-10 with an alkaline solution;

[0030] S4, flotation, adding inhibitors and collectors to the slurry obtained in step S3 in sequence to carry out roughing operation first, and obtaining roughing concentrate and roughing tailings after roughing; carrying out concentrating operation on the roughing concentrate, adding collectors to the roughing concentrate again for the first concentrating, obtaining primary concentrating concentrate and primary concentrating tailings; adding collectors to the primary concentrating concentrate again, and continuing the second concentrating, obtaining secondary concentrating concentrate and secondary concentrating tailings; returning the secondary concentrating tailings to the previous concentrating operation; the foam product of the last concentrating operation is the final fluorite concentrate product; the number of concentrating operations is 4-7 times.

[0031] The roughing tailings are subjected to scavenging operation, and primary scavenging concentrate and primary scavenging tailings are obtained after one scavenging operation; the primary scavenging tailings are subjected to secondary scavenging operation, and secondary scavenging concentrate and secondary scavenging tailings are obtained after the secondary scavenging operation; the secondary scavenging concentrate is returned to the previous scavenging operation; the bottom product of the trough of the last scavenging operation is the final tailings; the scavenging times of the scavenging operation are 1-3 times, and no reagents need to be added in the scavenging operation.

[0032] The collector in the embodiment of the present invention is sodium oleate, and the total dosage is 2000-3000g / t, wherein g (gram) in g / t is based on the mass of the collector, and t (ton) is based on the dry weight of the fluorite sample. The amount of collector used in the first selection is 1 / 3-2 / 3 of the amount used in the rough selection, and the amount of collector used in the second selection is 1 / 3-2 / 3 of the amount used in the first selection; the dosage of pullulan is 500-1800g / t, wherein g (gram) in g / t is based on the mass of pullulan, and t (ton) is based on the dry weight of fluorite ore.

[0033] Example 1

[0034] In this embodiment, pullulan is dissolved in water to obtain an inhibitor solution with a mass fraction of 2% for later use;

[0035] The fluorite ore used in this embodiment is a calcite-type fluorite ore, and the components and mass percentages of the components are: CaF2 is 18.5%, CaCO3 is 9.1%, and SiO2 is 50.21%. The specific operation steps are as follows:

[0036] First, 250g of fluorite ore was ground to a fineness of -74μm and a content of 80%, and added to a 0.5L flotation tank. The pH of the pulp was adjusted to 10 with sodium hydroxide. An inhibitor solution was added to the pulp according to the addition amount of 650g / t of pullulan. After stirring for 5 minutes, 1200g / t of sodium oleate was added to start roughing. After roughing, a roughing concentrate and a roughing tailing were obtained. After the roughing concentrate was again added with 600g / t of sodium oleate for the first concentration, a primary concentrated concentrate and a primary concentrated tailing were obtained. 300g / t sodium oleate is added to the concentrated concentrate again to continue the second concentration to obtain secondary concentrate and secondary concentrated tailings; the secondary concentrated tailings are returned to the previous concentration operation; the amount of collector used in the first concentration is 1 / 3-2 / 3 of the amount used in the roughing concentration, and the amount of collector used in the second concentration is 1 / 3-2 / 3 of the amount used in the first concentration. The concentration operation is repeated 4 times in total, with a total amount of sodium oleate of 2200g / t to obtain the final fluorite concentrate product; the roughing tailings are scavenged once, and no reagents are added in the scavenging operation.

[0037] Example 2

[0038] The inhibitor used in this example is the same as that in Example 1.

[0039] The fluorite ore used in this embodiment is a calcite-type fluorite ore, and the components and mass percentages of the components are: CaF2 is 19.87%, CaCO3 is 8.56%, and SiO2 is 49.65%; the specific operation steps are:

[0040] 200g of fluorite ore was ground to -74μm with a content of 85%, and added to a 0.5L flotation tank, and the pH of the pulp was adjusted to 9; the prepared inhibitor solution was added to the pulp according to the addition amount of 600g / t of pullulan, and after stirring for 5 minutes, 1100g / t of sodium oleate was added to start roughing, and roughing concentrate and roughing tailings were obtained after roughing; 600g / t of sodium oleate was added to the roughing concentrate again for the first concentration, and a primary concentrated concentrate and a primary concentrated tailings were obtained; 300g / t sodium oleate is added to the primary concentrated concentrate again to continue the second concentration to obtain secondary concentrate and secondary concentrated tailings; the secondary concentrated tailings are returned to the previous concentration operation; the amount of collector used in the first concentration is 1 / 3-2 / 3 of the rough selection amount, and the amount of collector used in the second concentration is 1 / 3-2 / 3 of the first concentration amount. The concentration operation is repeated 4 times in total, and the total amount of sodium oleate is 2500g / t to obtain the final fluorite concentrate product; no reagent is added in the scavenging operation.

[0041] Example 3

[0042] The inhibitor used in this example is the same as that in Example 1.

[0043] The fluorite ore used in this embodiment is a calcite-type fluorite ore, and the components and mass percentages of the components are: CaF2 is 18.12%, CaCO3 is 12.36%, and SiO2 is 49.89%. The specific operation steps are as follows:

[0044] First, 300g of fluorite ore was ground to -74μm with a content of 70%, and added to a 0.75L flotation tank, and the pH of the pulp was adjusted to 9; an inhibitor solution was added to the pulp according to the addition amount of 680g / t of pullulan, and after stirring for 5 minutes, 1600g / t of sodium oleate was added to start roughing, and roughing concentrate and roughing tailings were obtained after roughing; 500g / t of sodium oleate was added to the roughing concentrate for the first concentration, and a primary concentrated concentrate and a primary concentrated tailings were obtained; the primary concentrated concentrate 200g / t sodium oleate is added again to continue the second concentration to obtain secondary concentrate and secondary concentrated tailings; the secondary concentrated tailings are returned to the previous concentration operation; the amount of collector used in the first concentration is 1 / 3-2 / 3 of the amount used in the roughing concentration, and the amount of collector used in the second concentration is 1 / 3-2 / 3 of the amount used in the first concentration. The concentration operation is repeated 5 times in total, and the total amount of sodium oleate is 2800g / t to obtain the final fluorite concentrate product; the roughing tailings are scavenged once, and no reagents are added in the scavenging operation.

[0045] Example 4

[0046] The inhibitor used in this example is the same as that in Example 1.

[0047] The fluorite ore used in this embodiment is a calcite-type fluorite ore, and the components and mass percentages of the components are: CaF2 is 18.5%, CaCO3 is 9.1%, and SiO2 is 50.21%. The specific operation steps are as follows:

[0048] First, 250g of fluorite ore was ground to -74μm with a content of 80%, and added to a 0.5L flotation tank. The pH of the pulp was adjusted to 10 with sodium hydroxide. An inhibitor solution was added to the pulp according to the addition amount of 650g / t of pullulan. After stirring for 5 minutes, 1200g / t of sodium oleate was added to start roughing. After roughing, roughing concentrate and roughing tailings were obtained. After the roughing concentrate was added with 600g / t of sodium oleate for the first concentration, a primary concentrate and a primary concentrate tailings were obtained. 300g / t sodium oleate is added to the concentrate again to continue the second concentration to obtain the final concentrate and secondary concentrated tailings; the secondary concentrated tailings are returned to the previous concentration operation; the amount of collector used in the first concentration is 1 / 3-2 / 3 of the amount used in the roughing concentration, and the amount of collector used in the second concentration is 1 / 3-2 / 3 of the amount used in the first concentration. The concentration operation is repeated 6 times in total, with a total amount of sodium oleate of 2800g / t to obtain the final fluorite concentrate product; the roughing tailings are scavenged once, and no reagents are added in the scavenging operation.

[0049] Example 5

[0050] The inhibitor used in this example is the same as that in Example 1.

[0051] The fluorite ore used in this embodiment is a calcite-type fluorite ore, and the components and mass percentages of each component are: CaF2 is 18.59%, CaCO3 is 12.31%, and SiO2 is 49.12%. The specific operation steps are as follows:

[0052] First, 200g of fluorite ore was ground to -74μm with a content of 75%, and added to a 0.5L flotation tank. The pH of the pulp was adjusted to 8.2 with sodium hydroxide. An inhibitor solution was added to the pulp according to the addition amount of 700g / t of pullulan. After stirring for 3 minutes, 1300g / t of sodium oleate was added to start roughing. Roughing concentrate and roughing tailings were obtained after roughing. 600g / t of sodium oleate was added to the roughing concentrate for the first concentration to obtain a primary concentrate and a primary concentrate tailings. 150g / t sodium oleate is added to the concentrate again to continue the second concentration to obtain the final concentrate and secondary concentrated tailings; the secondary concentrated tailings are returned to the previous concentration operation; the amount of collector used in the first concentration is 1 / 3-2 / 3 of the amount used in the roughing concentration, and the amount of collector used in the second concentration is 1 / 3-2 / 3 of the amount used in the first concentration. The concentration operation is repeated 4 times in total, and the total amount of sodium oleate is 2400g / t to obtain the final fluorite concentrate product; the roughing tailings are scavenged once, and no reagents are added in the scavenging operation.

[0053] Example 6

[0054] In this embodiment, pullulan is dissolved in water to obtain an inhibitor solution with a mass fraction of 2% for standby use;

[0055] The fluorite ore used in this embodiment is a calcite-type fluorite ore, and the components and mass percentages of each component are: CaF2 is 17.25%, CaCO3 is 13.20%, and SiO2 is 48.54%. The specific operation steps are as follows:

[0056] First, 250g of fluorite ore was ground to a fineness of -74μm and a content of 60%, and then added to a 0.5L flotation tank. The pH of the pulp was adjusted to 8 with sodium hydroxide. An inhibitor solution was added to the pulp according to an addition amount of 500g / t of pullulan. After stirring for 5 minutes, 1200g / t of sodium oleate was added to start roughing. After roughing, a roughing concentrate and a roughing tailing were obtained. After the roughing concentrate was again added with 600g / t of sodium oleate for the first concentration, a primary concentrate and a primary concentrate tailing were obtained. 300g / t sodium oleate is added to the concentrate again to continue the second concentration to obtain secondary concentrate and secondary concentrated tailings; the secondary concentrated tailings are returned to the previous concentration operation; the amount of collector used in the first concentration is 1 / 3-2 / 3 of the amount used in the roughing concentration, and the amount of collector used in the second concentration is 1 / 3-2 / 3 of the amount used in the first concentration. The concentration operation is repeated 5 times in total, with a total amount of sodium oleate of 2600g / t to obtain the final fluorite concentrate product; the roughing tailings are scavenged once, and no reagents are added in the scavenging operation.

[0057] Example 7

[0058] In this embodiment, pullulan is dissolved in water to obtain an inhibitor solution with a mass fraction of 2% for standby use;

[0059] The fluorite ore used in this embodiment is a calcite-type fluorite ore, and the components and mass percentages of each component are: CaF2 is 18.02%, CaCO3 is 20.10%, and SiO2 is 48.21%. The specific operation steps are as follows:

[0060] First, 250g of fluorite ore was ground to a fineness of -74μm and a content of 85%, and then added to a 0.5L flotation tank. The pH of the pulp was adjusted to 10 with sodium hydroxide. An inhibitor solution was added to the pulp according to the addition amount of pullulan of 1800g / t. After stirring for 5 minutes, 1200g / t of sodium oleate was added to start roughing. After roughing, a roughing concentrate and a roughing tailing were obtained. After the roughing concentrate was again added with 600g / t of sodium oleate for the first concentration, a primary concentrated concentrate and a primary concentrated tailing were obtained. 300g / t sodium oleate is added to the concentrated concentrate again to continue the second concentration to obtain secondary concentrate and secondary concentrated tailings; the secondary concentrated tailings are returned to the previous concentration operation; the amount of collector used in the first concentration is 1 / 3-2 / 3 of the amount used in the roughing concentration, and the amount of collector used in the second concentration is 1 / 3-2 / 3 of the amount used in the first concentration. The concentration operation is repeated 5 times in total, with a total amount of sodium oleate of 3000g / t to obtain the final fluorite concentrate product; the roughing tailings are scavenged once, and no reagents are added in the scavenging operation.

[0061] Comparative Example 1

[0062] The difference between Comparative Example 1 and Example 1 is that the 500 g / t pullulan inhibitor used in Example 1 is replaced with 1700 g / t water glass, and the implementation is the same as Example 1.

[0063] Comparative Example 2

[0064] The difference between Comparative Example 2 and Example 2 is that the 600 g / t pullulan inhibitor used in Example 2 is replaced by 2000 g / t water glass, and the rest is implemented in the same way as Example 2. The flotation effect is shown in Table 1.

[0065] Comparative Example 3

[0066] The difference between Comparative Example 3 and Example 3 is that the 680 g / t pullulan inhibitor used in Example 3 is replaced by 2000 g / t water glass, and the rest is the same as Example 3.

[0067] Comparative Example 4

[0068] The difference between Comparative Example 4 and Example 4 is that 650 g / t of pullulan is replaced by 1800 g / t of water glass, and the rest is the same as Example 4.

[0069] Comparative Example 5

[0070] The difference between Comparative Example 5 and Example 1 is that 500 g / t of pullulan is replaced by 2000 g / t of water glass, and the rest is the same as Example 5.

[0071] Comparative Example 6

[0072] The difference between Comparative Example 6 and Example 6 is that 500 g / t of pullulan in Example 6 is replaced by 500 g / t of water glass, and the rest is the same as Example 6.

[0073] Comparative Example 7

[0074] The difference between Comparative Example 7 and Example 7 is that 1800 g / t pullulan in Example 7 is replaced by 1800 g / t water glass, and the rest is the same as Example 7.

[0075] The flotation effects of Examples 1-7 and Comparative Examples 1-7 are shown in Table 1.

[0076] Table 1 Flotation effect of flotation method of embodiment and comparative example

[0077]

[0078] As can be seen from the above embodiments, the present invention uses pullulan as an inhibitor of calcite, a gangue mineral in fluorite flotation, and its flotation effect is better than water glass. The pullulan molecule in the pullulan contains a large number of hydroxyl functional groups, which are both hydrophilic groups and polar groups. Hydroxyl and carboxyl can chemically adsorb with calcium ions on the surface of calcium-containing gangue, and the distribution of its hydroxyl functional groups is easier to adsorb with calcite, which can enhance its selectivity. The hydrophilicity of this selective adsorption calcite becomes larger, and does not affect the effect of the collector on fluorite, thereby achieving the separation of the two. Compared with water glass and its modified products, which are the most widely used inhibitors in industry, the pullulan of the present invention only needs to be added once in the rough selection, with a small amount, stronger selectivity, better flotation effect, and pullulan has good solubility and is easy to configure, and is easy to degrade and has no pollution to the environment.

[0079] The foregoing description of specific exemplary embodiments of the present invention is for the purpose of illustration and demonstration. These descriptions are not intended to limit the present invention to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can realize and utilize various different exemplary embodiments of the present invention and various different selections and changes. The scope of the present invention is intended to be limited by the claims and their equivalents.

Claims

1. An application of pullulan as a calcite inhibitor in fluorite flotation, characterized in that: During the flotation of fluorite ore, pullulan is added as a calcite depressant.

2. The use of pullulan as a calcite inhibitor in fluorite flotation according to claim 1, characterized in that: The fluorite is a calcite-type fluorite ore.

3. A method for using pullulan as a calcite inhibitor in fluorite flotation, characterized in that: The steps include: S1. dissolving pullulan in water to obtain an inhibitor solution with a mass concentration of 1-5%; S2. Use a ball mill or rod mill to grind the fluorite ore to a fineness of -72 microns to -77 microns, accounting for 65%-90%; S3, adding water to slurry the fluorite ore ground in step S2 to a slurry mass concentration of 30%-50%, and adjusting the pH to 8-10; S4, flotation, adding inhibitors and collectors to the slurry obtained in step S3 in sequence to perform roughing operation first, and obtaining roughing concentrate and roughing tailings after roughing; performing concentrating operation on the roughing concentrate, adding collectors to the roughing concentrate again for the first concentrating, obtaining primary concentrating concentrate and primary concentrating tailings; adding collectors to the primary concentrating concentrate again, and continuing the second concentrating, obtaining secondary concentrating concentrate and secondary concentrating tailings; the secondary concentrating tailings are returned to the previous concentrating operation; the foam product of the last concentrating operation is the final fluorite concentrate product; The roughing tailings are subjected to scavenging operation to obtain primary scavenging concentrate and primary scavenging tailings after one scavenging operation; the primary scavenging tailings are subjected to secondary scavenging operation to obtain secondary scavenging concentrate and secondary scavenging tailings; the secondary scavenging concentrate is returned to the previous scavenging operation; the bottom product of the last scavenging operation is the final tailings.

4. The use of pullulan as a calcite inhibitor in fluorite flotation according to claim 3, characterized in that: In the step S2, the fluorite is finely ground to a fineness of -74 microns and a proportion of 65%-90% using a ball mill or a rod mill.

5. The use of pullulan as a calcite inhibitor in fluorite flotation according to claim 3, characterized in that: In the step S4, the number of selections in the selection operation is 4-7 times.

6. The use of pullulan as a calcite depressant in fluorite flotation according to claim 3, characterized in that: In the step S4, the scanning operation is performed 1-3 times.

7. The use of pullulan as a calcite depressant in fluorite flotation according to claim 3, characterized in that: In step S4, the collector is one or more of sodium oleate, oxidized paraffin soap, and hydroxamic acid.

8. The use of pullulan as a calcite depressant in fluorite flotation according to claim 7, characterized in that: In the step S4, the collector is sodium oleate.

9. The use of pullulan as a calcite depressant in fluorite flotation according to claim 3, characterized in that: The dosage of the pullulan is 500-1800 g / t; wherein g in g / t is based on the mass of the pullulan, and t is based on the dry weight of the fluorite ore.

10. The use of pullulan as a calcite depressant in fluorite flotation according to claim 3, characterized in that: The total dosage of the collector is 2000-3000 g / t, wherein g in g / t is based on the mass of the collector, and t is based on the dry weight of the fluorite sample.

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