CN114534925A

CN114534925A - Collophanite collecting agent and preparation method thereof

Info

Publication number: CN114534925A
Application number: CN202210294285.9A
Authority: CN
Inventors: 段湛健; 吴海斌; 石建华; 居荣梅; 龙辉; 浦绍广
Original assignee: Guizhou Chuan Heng Chemical Co ltd
Current assignee: Guizhou Chuan Heng Chemical Co ltd
Priority date: 2022-03-24
Filing date: 2022-03-24
Publication date: 2022-05-27
Anticipated expiration: 2042-03-24
Also published as: CN114534925B

Abstract

The invention provides a collophanite collecting agent and a preparation method thereof. The collophanite collecting agent shown in the formula (1) takes 9,11, 13-octadecenoic acid as a raw material, and adds F atoms on a carbon chain through addition reaction to modify the 9,11, 13-octadecenoic acid, and introduces three F atoms on the carbon chain, wherein the electrical negativity of the F atoms on the kyrine scale is 3.98 at the maximum, so that the electronic arrangement condition on the carbon chain molecules can be effectively adjusted, and the molecular properties can be changed; based on the main chain, F atoms can form hydrogen bonds in water, so that the water solubility and the dispersity of molecules are increased, the hydrophobicity of long carbon chains is reduced, and the CMC concentration is increased, so that the flowability of flotation foam is improved, the viscosity is reduced, and the foam is easy to break; meanwhile, F atoms can be adsorbed with positioning atomic calcium, so that the auxiliary collecting function is realized, the medicament performance is further improved, a better separation effect can be still realized under the conditions of low temperature and wide pH value, and the grade of the concentrate being separated is higher.

Description

Collophanite collecting agent and preparation method thereof

Technical Field

The invention relates to the field of mineral separation materials, in particular to a collophanite collecting agent and a preparation method thereof.

Background

At present, the domestic method for separating phosphorite and gangue minerals is mainly a flotation method, and different flotation methods such as single reverse flotation, single direct flotation, forward-reverse flotation, double reverse flotation, reverse-forward flotation and the like can be adopted for phosphorite with different qualities. Flotation reagents are key influencing factors in phosphorite flotation, and collecting agents are paid extensive attention to.

The collectors which are already applied in industry are mainly fatty collectors such as oleic acid, oxidized paraffin soap, tall soap and the like. Although the traditional fat collecting agent has the advantages of wide source, low price and the like, the collecting agent has poor solubility, poor dispersibility and poor selectivity to collophanite at low temperature, so that the problems of large dosage of flotation reagents, low separation efficiency, large viscosity of generated foam, difficult foam elimination and the like are caused.

The fatty acid is a collecting agent commonly used for flotation of phosphorite, most of the fatty acid is other industrial byproducts, natural compounds are abundant, the universality is good, but the flotation effect on certain minerals is poor, and the pertinence is not strong, so that the popularization and the application of the fatty acid collecting agent are limited to a certain extent. In recent years, the development trend of the phosphorite collecting agent is towards multi-functionalization, amphoteric, non-ionization or mixed synergistic action, and the collophanite collecting agent starts from medicament molecules and modifies the molecules according to the characteristics of the collophanite so as to adapt to the industrialized production requirement. Therefore, the development of the collecting agent with better flotation effect is of great significance.

Disclosure of Invention

In view of the above, the present invention aims to provide a collophanite collecting agent and a preparation method thereof. The collophanite collecting agent provided by the invention has the advantages of good collecting performance, good water solubility, good low temperature resistance, strong selectivity, good foam fluidity, easy foam elimination and the like.

The invention provides a collophanite collecting agent, which has a structure shown in a formula (1):

wherein R is Na or K.

The invention also provides a preparation method of the collophanite collecting agent in the technical scheme, which comprises the following steps:

A) reacting 9,11, 13-octadecenoic acid with HCl to form 9,11, 13-trichlorooctadecanoic acid shown in a formula (a);

B) reacting 9,11, 13-trichlorooctadecanoic acid shown in the formula (a) with HF to form 9,11, 13-trifluorooctadecanoic acid shown in the formula (b);

C) reacting 9,11, 13-trichlorooctadecanoic acid shown in the formula (b) with basic R metal salt to form a compound shown in the formula (1);

wherein:

the metal R in the metal R salt is Na or K;

in the formula (1), R is Na or K.

Preferably, in the step A), the reaction temperature is 40-90 ℃.

Preferably, in said step a), the reaction is carried out in an organic solvent medium;

the organic solvent is selected from one or more of 3, 5-difluoroethylbenzene, 4-difluorocyclohexanone, p-methyltrifluorotoluene and 1, 4-bis (difluoromethyl) benzene;

the mass ratio of the organic solvent to 9,11, 13-octadecenoic acid is 2: 0.8-1.2.

Preferably, in step B), the reaction is carried out under the action of a catalyst TCUC;

the catalyst TCUC is prepared by the following method:

s1, mixing titanium hydride powder, calcium chloride powder, copper oxide powder and cobalt oxide powder to obtain mixed powder;

s2, heating and reacting the mixed powder with HF to obtain the catalyst TCUC.

Preferably, in step S2, the heating reaction conditions are:

the temperature is increased to 200-220 ℃ for reaction for 1-2 h, and then the temperature is increased to 650-800 ℃ for reaction for 1-3 h.

Preferably, the step S2 specifically includes:

placing the mixed powder in a container, heating to 200-220 ℃, introducing HF gas into the container, and reacting for 1-2 hours; and then heating to 650-800 ℃ to react for 1-3 h to form the catalyst TCUC.

Preferably, in the step S1, the molar ratio of the titanium hydride powder to the calcium chloride powder to the copper oxide powder to the cobalt oxide powder is (1-1.5) to (2-3) to (1-2) to 2.

Preferably, in the step B), the reaction temperature is 60-90 ℃.

Preferably, in the step C), the R metal salt is selected from NaOH and Na₂CO₃、NaHCO₃、KOH、K₂CO₃And KHCO₃One or more of the above;

the reaction temperature is 70-100 ℃.

The collophanite collecting agent shown in the formula (1) takes 9,11, 13-octadecenoic acid as a raw material, and adds F atoms on a carbon chain through addition reaction to modify the 9,11, 13-octadecenoic acid, and introduces three F atoms on the carbon chain, wherein the electrical negativity of the F atoms on the kyrine scale is 3.98 at the maximum, so that the electronic arrangement condition on the carbon chain molecules can be effectively adjusted, and the molecular properties can be changed; based on the main chain, F atoms can form hydrogen bonds in water, so that the water solubility and the dispersity of molecules are increased, the hydrophobicity of long carbon chains is reduced, and the CMC concentration is increased, so that the flowability of flotation foam is improved, the viscosity is reduced, and the foam is easy to break; meanwhile, F atoms can be adsorbed with positioning atomic calcium, so that the collecting agent has an auxiliary collecting function, a special type direct separation collecting agent suitable for collophanite is obtained, the performance of the collecting agent is further improved, a good separation effect can be still achieved under the conditions of low temperature and wide pH, and the grade of direct separation concentrate is higher.

Test results show that the compound of the formula (1) provided by the invention is used as the collecting agent, so that the yield of the phosphate concentrate is more than 63%, the yield of tailings is reduced to be less than 38%, and good phosphate concentrate yield is obtained. The obtained phosphorus extractIn the mine, P₂O₅The grade reaches more than 28.6 percent, and Al₂O₃The grade is reduced to below 1.6 percent, SiO₂The grade is reduced to below 11.2 percent; the removal rate of the aluminum and silicon materials respectively reaches more than 81.5 percent and more than 64.7 percent.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.

FIG. 1 is an IR spectrum of the product obtained in example 1.

Detailed Description

wherein R is Na or K.

In the present invention, preferably, R is Na, that is, the compound of formula (1) is sodium 9,11, 13-trifluorooctadecanoate, and the structure is as follows:

wherein:

the metal R in the metal R salt is Na or K;

in the formula (1), R is Na or K.

[ with respect to step A ]:

reacting 9,11, 13-octadecenoic acid with HCl to form 9,11, 13-trichlorooctadecanoic acid shown in formula (a).

In the present invention, the reaction route of step a is as follows:

that is, HCl reacts with the double bond in 9,11, 13-octadecenoic acid to form 9,11, 13-trichlorooctadecanoic acid.

In the present invention, the source of the 9,11, 13-octadecenoic acid is not particularly limited, and it may be commercially available or prepared according to a conventional preparation method well known to those skilled in the art.

In the invention, the HCl is HCl gas.

In the present invention, the reaction is preferably carried out in an organic solvent medium. The organic solvent is preferably one or more of 3, 5-difluoroethylbenzene, 4-difluorocyclohexanone, p-methyltrifluorotoluene and 1, 4-bis (difluoromethyl) benzene, and the adoption of the solvent is favorable for improving the dissolving and dispersing effects and reducing the occurrence of side reactions. In the invention, the mass ratio of the organic solvent to 9,11, 13-octadecenoic acid is preferably 2: 0.8-1.2, and specifically can be 2: 0.8, 2: 0.9, 2: 1.0, 2: 1.1, 2: 1.2.

In the present invention, the reaction is preferably carried out under the protection of a protective gas, that is, the protective gas is used as an ambient gas, and the HCl gas is used as a reaction gas. The type of the protective gas is not particularly limited in the present invention, and may be a conventional protective gas known to those skilled in the art, such as nitrogen, helium, argon, or the like.

In the present invention, the reaction temperature is preferably 40 to 90 ℃, and specifically 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ and 90 ℃. The reaction time is preferably 0.5-3 h, and specifically can be 0.5h, 1h, 1.5h, 2h, 2.5h and 3 h. After the reaction, 9,11, 13-trichlorooctadecanoic acid shown in the formula (a) is generated in the system.

In the present invention, preferably, the step a) specifically includes the following steps:

mixing 9,11, 13-octadecenoic acid with an organic solvent, heating the system to a target reaction temperature, introducing protective gas into the system, and introducing HCl gas into a liquid phase of the system under a stirring condition to react to form 9,11, 13-trichlorooctadecanoic acid shown in a formula (a).

Wherein:

the above reaction can be carried out in a reaction vessel. The degree of introduction of the protective gas into the system is preferably: until the air pressure in the system reaches 2-4 atm, specifically 2atm, 2.5atm, 3atm, 3.5atm, 4 atm. The stirring rate under the stirring condition is preferably 300 to 600rpm, and specifically may be 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600 rpm. When introducing HCl gas, the flow rate of the HCl gas is preferably 0.5 to 2.5sccm, and specifically may be 0.5sccm, 1.0sccm, 1.5sccm, 2.0sccm, or 2.5 sccm. And (4) continuously introducing HCl gas for reacting for 0.5-3 h until the reaction is fully performed, and finishing the reaction. The reaction is terminated in a specific manner: and stopping introducing the HCl gas, and replacing the mixed gas in the system with protective gas. After the reaction is finished, 9,11, 13-trichlorooctadecanoic acid shown in the formula (a) is formed in the system, and the reaction solution containing the reaction product is specifically formed in the system. In the present invention, it is preferable that the 9,11, 13-trichlorooctadecanoic acid represented by the formula (a) is not separated from the reaction solution after the completion of the reaction in the step A), but the reaction solution containing the substance is directly obtained and subjected to the next reaction.

[ with respect to step B ]:

and (b) reacting the 9,11, 13-trichlorooctadecanoic acid shown in the formula (a) with HF to form the 9,11, 13-trifluorooctadecanoic acid shown in the formula (b).

In the invention, the reaction route of the step B is as follows:

that is, a substitution reaction occurs between 9,11, 13-trichlorooctadecanoic acid represented by the formula (a) and HF, and F in HF substitutes for Cl in 9,11, 13-trichlorooctadecanoic acid represented by the formula (a), thereby forming 9,11, 13-trifluorooctadecanoic acid represented by the formula (b).

In the present invention, the reaction is preferably carried out under the protection of a protective gas, that is, the protective gas is used as an ambient gas, and the HF gas is used as a reaction gas. The type of the protective gas is not particularly limited in the present invention, and may be a conventional protective gas known to those skilled in the art, such as nitrogen, helium, argon, or the like.

In the invention, the reaction temperature is preferably 60-90 ℃, and specifically 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ and 90 ℃. The reaction time is preferably 1-4 h, and specifically can be 1h, 1.5h, 2h, 2.5h, 3h and 4 h.

In the present invention, the reaction is preferably carried out under the action of the catalyst TCUC. In the invention, the mass ratio of the catalyst TCUC to the 9,11, 13-octadecenoic acid in the step A) is preferably (1-7) to 100, and specifically can be 1: 100, 2: 100, 3: 100, 4: 100, 5: 100, 6: 100, 7: 100.

In the present invention, the catalyst TCUC is preferably prepared by the following method:

s2, heating and reacting the mixed powder with HF to obtain the catalyst TCUC.

Regarding step S1:

the preferred molar ratio of the titanium hydride powder, the calcium chloride powder, the copper oxide powder and the cobalt oxide powder is (1-1.5): (2-3): (1-2): 2, and the specific ratio can be 1: 2: 1: 2, 1: 2.5: 1.5: 2, 1: 3: 2, 1.3: 2: 1: 2, 1.3: 2.5: 1.5: 2, 1.3: 3: 2, 1.5: 2: 1: 2, 1.5: 2.5: 1.5: 2, and 1.5: 3: 2. Mixing the above 4 powders (H)₂Ti powder and CaCl₂Powder, CuO powder, CoO powder) is not particularly limited, and the materials can be mixed by a conventional mixing method well known to those skilled in the art.

Regarding step S2:

the HF is HF gas.

The heating reaction conditions are as follows: the temperature is increased to 200-220 ℃ for reaction for 1-2 h, and then the temperature is increased to 650-800 ℃ for reaction for 1-3 h. Wherein the temperature of 200-220 ℃ can be 200 ℃, 205 ℃, 210 ℃, 215 ℃ and 220 ℃. The reaction is carried out for 1-2 h, specifically 1h, 1.5h and 2 h. The temperature of 650-800 ℃ can be 650 ℃, 700 ℃, 750 ℃ and 800 ℃. The reaction time of 1-3 h can be 1h, 1.5h, 2h, 2.5h and 3 h. In the above reaction process, H₂Ti+CaCl₂+ CuO + CoO reaction with HF to produce M_xF_y(M is Ti, Ca, Cu, Co), compared with the simple method of respectively obtaining the above 4 fluoride substances and then mixing the 4 fluoride powders, the invention firstly mixes the above 4 powders, then reacts with HF, and generates M through high temperature reaction_xF_yThe method can generate a special physical and chemical structure in the forming and growing processes, specifically, the specific surface area of the material is increased due to the overflow channel of water vapor generated in the reaction process, and the active sites are closer to catalytic atoms due to partial intercrystalline doping, so that the catalytic performance is improved.

The step S2 specifically includes: placing the mixed powder in a container, heating to 200-220 ℃, introducing HF gas into the container, and reacting for 1-2 hours; and then heating to 650-800 ℃ to react for 1-3 h to form the catalyst TCUC. Wherein the container may be a nickel tube. The flow rate of the HF gas is preferably 1.0 to 3.0sccm, and specifically may be 1.0sccm, 1.5sccm, 2.0sccm, 2.5sccm, or 3.0 sccm. After full reaction, cooling and stopping introducing HF gas to obtain the catalyst TCUC product.

In the present invention, preferably, the step B) specifically includes the following steps:

adding a catalyst into the reaction liquid obtained in the step A), heating the system to a target reaction temperature, introducing protective gas into the system, and introducing HCl gas into the system under a stirring condition to react to form 9,11, 13-trifluorooctadecanoic acid shown in the formula (b).

Wherein:

the above reaction is still carried out in the reaction vessel of step A). The degree of introduction of the protective gas into the system is preferably: until the air pressure in the system reaches 2-8 atm, specifically 2atm, 2.5atm, 3atm, 3.5atm, 4atm, 4.5atm, 5atm, 5.5atm, 6atm, 6.5atm, 7atm, 7.5atm, 8 atm. The stirring rate under the stirring condition is preferably 300 to 600rpm, and specifically may be 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600 rpm. When the HF gas is introduced, the flow rate of the HF gas is preferably 0.4 to 2.8sccm, and specifically may be 0.4sccm, 0.5sccm, 1.0sccm, 1.5sccm, 2.0sccm, 2.5sccm, or 2.8 sccm. And continuously introducing HF gas for reaction for 1-4 h. The 9,11, 13-trifluoro octadecanoic acid shown in the formula (b) is formed in the system through the reaction. In the present invention, it is preferable to further perform solid-liquid separation after the above reaction. The solid-liquid separation mode is not particularly limited in the invention, and the solid-liquid separation mode can be a conventional separation mode well known to those skilled in the art, such as filtration and the like; removing catalyst TCUC by solid-liquid separation to obtain a mixed solution containing 9,11, 13-trifluoro octadecanoic acid shown in the formula (b). In the present invention, it is preferable that, after the completion of the reaction in the step B), the 9,11, 13-trifluorooctadecanoic acid represented by the formula (B) is not separated from the reaction mixture, but the reaction mixture containing the substance obtained as it is subjected to the next reaction.

According to the method, the step A) and the step B) are carried out step by step, Cl is added by HCl, and then F in HF replaces Cl instead of HF directly, so that smooth reaction can be ensured, side reactions are greatly reduced, and the yield is improved. If HF is directly used for addition, olefin is easy to polymerize in an HF environment, the addition reaction is limited to be carried out, and the olefin with halogen on a double bond is difficult to polymerize; however, the addition reaction of HF becomes more difficult as the halogen content increases, and if there is an F atom in the double bond, the electron-withdrawing group decreases the electron cloud density of the double bond, making electrophilic addition difficult. The invention is divided into the reaction modes of the step A) and the step B), which can overcome the problems, ensure the smooth reaction, greatly reduce the side reaction and improve the yield.

[ with respect to step C ]:

and (b) reacting the 9,11, 13-trichlorooctadecanoic acid shown in the formula (b) with basic R metal salt to form the compound shown in the formula (1).

In the present invention, the reaction scheme of step C is as follows:

namely, 9,11, 13-trichlorooctadecanoic acid shown in the formula (b) and basic R metal salt are subjected to acid-base reaction to form 9,11, 13-trifluorooctadecanoic acid salt shown in the formula (1).

In the present invention, in the basic R metal salt, R is Na or K, and more preferably Na. The metal salt of R is preferably NaOH or Na₂CO₃、NaHCO₃、KOH、K₂CO₃And KHCO₃One or more of the above; more preferably the strongly basic metal salts NaOH and/or KOH, most preferably NaOH.

In the invention, the molar ratio of the 9,11, 13-trichlorooctadecanoic acid shown in the formula (b) to the R metal salt is preferably 1: 0.8-1.2, and specifically can be 1: 0.8, 1: 0.9, 1: 1.0, 1: 1.1 and 1: 1.2.

In the present invention, the R metal salt is preferably added in the form of an aqueous solution of the R metal salt. The mass concentration of the aqueous solution of the R metal salt is preferably 10% to 15%, and specifically may be 10%, 11%, 12%, 13%, 14%, 15%.

In the present invention, the reaction is preferably carried out in a still, i.e., after the reaction of step B) is completed, the resulting liquid phase is transferred to a still. In the invention, the reaction temperature is preferably 70-100 ℃, and specifically 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ and 100 ℃. The reaction time is preferably 1-3 h, and specifically can be 1h, 1.5h, 2h, 2.5h and 3 h. After the reaction, 9,11, 13-trifluoro octadecanoic acid salt shown in the formula (1) is generated in the system, and reaction mixed liquid containing the reaction product is obtained.

In the present invention, after the reaction of step C), the following post-treatment is preferably further carried out: distilling the reaction mixture obtained in the step C) to recover the organic solvent added in the step A), thereby obtaining the 9,11, 13-trifluorooctadecanoic acid salt shown in the formula (1). Wherein the distillation temperature is preferably 50-80 ℃, and specifically can be 50 ℃, 60 ℃, 70 ℃ and 80 ℃. The distillation is carried out under vacuum condition, and the vacuum degree is 0.01-0.09 MPa, specifically 0.01MPa, 0.02MPa, 0.03MPa, 0.04MPa, 0.05MPa, 0.06MPa, 0.07MPa, 0.08MPa, 0.09 MPa. The distillation time is preferably 1-3 h until the mixed solution is solidified, and the organic solvent is sufficiently removed, so that the 9,11, 13-trifluorooctadecanoic acid salt product shown in the formula (1) is obtained.

The preparation method provided by the invention is simple and feasible, mild in condition, simple in equipment and convenient for industrial production and application. Moreover, the yield and the purity of the product are high, the yield can reach more than 95 percent, and the purity can reach more than 98 percent.

The invention also provides an application of the 9,11, 13-trifluoro-octadecanoic acid salt shown in the formula (1) as a collophanite collecting agent.

The conventional fatty acid collecting agent is adopted to carry out forward-reverse flotation on the collophanite, and the foam yield and viscosity in the forward flotation stage are high, the fluidity is poor, and the defoaming is difficult. In the invention, the specific special collecting agent is adopted, in an alkaline flotation solution environment, the collecting agent and the mineral surface are mainly electric double layer adsorption generated by electrostatic force adsorption and surface chemical adsorption generated by surface chemical reaction, and the speed process of electrostatic adsorption is greater than that of surface chemical adsorption. In the process of surface attachment with collophanite, fluorine atoms have stronger electricity absorption property and can generate characteristic adsorption with fluorapatite, the selectivity is enhanced by auxiliary collection, the overall electronegativity of the hydrophobic group of the collecting agent is reduced, and electrostatic adsorption can only occur in a smaller range, so that the selectivity of the collecting agent is improved. Due to the action of surface electrostatic adsorption, the concentration of anions of the mineral surface special-effect collecting agent is effectively reduced, the probability of irreversible chemical reaction is reduced, the specific range of the solubility product corresponding to organic salt is slowed down, a large amount of stable fatty acid salt is prevented from being generated in foam products, and the poor foam fluidity is avoided. Electrostatic adsorption can fix on mineral surface at a high speed, and when foam product is taken out along with rising bubbles, the property is unstable, so that the foam is easy to break. The problems of poor foam fluidity and difficult defoaming are solved through the above effects. Therefore, the invention adopts 9,11, 13-trifluoro octadecanoic acid salt as the collecting agent, and can achieve the following effects: the selectivity is strong, the dosage of the medicament is low, the viscosity of flotation foam is low, the fluidity is good, and defoaming is easy; the problems of large foam amount and poor fluidity in the forward flotation stage in the direct-reverse flotation of the collophanite are solved; the flotation concentrate has high grade, high phosphorus yield, low phosphorus grade of tailings, less phosphorus loss and high comprehensive economic benefit.

The invention uses the compound of formula (1) as the collecting agent, is suitable for the flotation of high-aluminum silicon collophanite, effectively improves the separation efficiency of the aluminum silicon collophanite compared with the traditional flotation process, reduces the dosage of the medicament, and improves the quality and the recovery rate of the concentrate. For the condition that the magnesium content in part of collophanite is higher, the magnesium minerals such as dolomite can be removed by simple reverse flotation; by adopting the flotation method, the treatment difficulty of the selected foam in the subsequent process can be reduced, the medicament cost and the energy consumption are further reduced, and the comprehensive economic benefit is improved; the high-quality phosphate concentrate can be obtained by a short forward flotation process and a simple reverse flotation process in necessary combination, and the process has strong adaptability and can be popularized in the industry.

The 9,11, 13-trifluoro-octadecanoic acid salt shown in the formula (1) can be used as a collophanite collecting agent. The existing collecting agent has the defects of unsatisfactory separation effect, poor foam property, stable foam, high viscosity, difficult breakage and difficulty in transmission and defoaming. The reagent aqueous solution is low, the dispersion effect is poor, the use condition is narrow, the low-temperature zone flotation effect is not good, and the pH condition is strictly controlled, so that the industrial application degree is not high. Compared with the collector with the formula (1), the collector has the following beneficial effects:

1. the octadecanoic acid salt is used as a main chain, F atoms are connected at 3 positions of 9,11 and 13, the critical micelle concentration is improved, the surface tension is effectively reduced, and the hydrophilic/hydrophobic group difference is weakened at the same time, so that the mobility of flotation foam is increased, the foam viscosity is reduced, the foam stabilizing time is short, and the defoaming is easy.

2. The collecting agent has good separation effect on phosphorite and strong selectivity. Based on the main chain, the addition of fluorine atoms increases the partial formation of hydrogen bonds of the collecting agent in an aqueous solution, improves the dispersibility and water solubility, has stronger collecting property at a low temperature of 5-25 ℃, and can adapt to the pH range of 10.0-11.7.

3. Calcium fluoride solubility product 2.7x10^-11After the fluorine atoms are added to the specific main chain, the fluorine atoms can react with calcium in apatite and be positioned, so that the effect of increasing the collecting performance is achieved, the grade of the concentrate to be sorted is high, the grade of the tailings is low, and the sorting effect is better.

Test results show that the compound of the formula (1) provided by the invention is used as the collecting agent, so that the yield of the phosphate concentrate is more than 63%, the yield of tailings is reduced to be less than 38%, and good phosphate concentrate yield is obtained. In the obtained phosphate concentrate, P₂O₅The grade reaches more than 28.6 percent, and Al₂O₃The grade is reduced to below 1.6 percent, SiO₂The grade is reduced to below 11.2 percent; the removal rate of the aluminum and silicon materials respectively reaches more than 81.5 percent and more than 64.7 percent.

For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.

Preparation example: preparation of catalyst TCUC

Uniformly mixing titanium hydride powder, calcium chloride powder, copper oxide powder and cobalt oxide powder according to the mol ratio of 1: 2.5: 1.5: 2, placing the mixture in a nickel tube, heating the mixture to 210 ℃, introducing HF gas into the nickel tube at the flow of 2.0sccm, and reacting for 1.5 hours; then the temperature is increased to 700 ℃ for reaction for 2 h. And stopping introducing HF gas after cooling to obtain the catalyst TCUC.

Example 1: preparation of sodium 9,11, 13-trifluorooctadecanoate

First, sample preparation

1. Step A:

adding 3, 5-difluoroethylbenzene solvent and 9,11, 13-octadecenoic acid (the mass ratio of the two is 2: 1.0) into a reaction kettle, and heating to 75 ℃. Filling the reaction kettle with argon until the pressure is raised to 3atm, introducing HCl gas into the liquid phase under continuous stirring, wherein the flow rate is 2.0sccm, and after the reaction is finished for 2.5h, replacing the mixed gas in the reaction kettle with argon. The reaction solution containing 9,11, 13-trichlorooctadecanoic acid is obtained in the system.

2. And B:

adding the prepared catalyst TCUC into a reaction kettle, heating to 80 ℃, and introducing argon to make the pressure of the reaction kettle reach 5.5 atm. Introducing HF gas into the reaction kettle under the condition of continuous stirring, wherein the flow rate is 2.5sccm, finishing the reaction after 3 hours, and filtering to remove the catalyst to obtain a reaction mixed solution containing 9,11, 13-trifluoro octadecanoic acid.

3. And C:

and C, transferring the liquid phase obtained in the step B into a distillation still, heating to 80 ℃, adding a NaOH solution (the mass concentration is 12%, and the molar ratio of the 9,11, 13-trifluorooctadecanoic acid to the NaOH is 1: 1.1), and carrying out reflux reaction for 2 hours to obtain a reaction mixed solution containing the 9,11, 13-trifluorooctadecanoic acid sodium.

Distilling the reaction mixed solution at the temperature of 80 ℃ and the vacuum degree of 0.07MPa for 2h, recovering the 3, 5-difluoroethylbenzene solvent until the solution is solidified to obtain the 9,11, 13-trifluoro-sodium octadecanoate product, wherein the yield is 96.8 percent, and the purity is 98.7 percent.

Second, sample characterization

Performing infrared characterization on the obtained sodium 9,11, 13-trifluorooctadecanoate product, wherein the result is shown in figure 1, and figure 1 is an infrared spectrum of the product obtained in example 1; the main functional groups and the peak positions are shown in table 1 below. It can be seen that the product obtained is of formula (1) and R is Na.

Table 1 infrared spectral characteristics of the product of example 1

Functional group	Peak position cm^-1
		C-F	1543、2749
COOH(υ_C＝O)	1705

Example 2: effect testing

The adopted test sample is collophanite mined in a certain place in Guizhou, the ore belongs to high-alumina siliceous collophanite, and the analysis results of the chemical components of the ore according to the mass percentage are shown in Table 2.

TABLE 2 Multi-element analysis of raw ore chemistry

Composition (I)	P₂O₅	CaO	MgO	SiO₂	Fe₂O₃	Al₂O₃	F
								Content/wt%	22.56	35.02	2.10	20.42	1.28	5.32	2.03

Test groups:

crushing collophanite, grinding to reach-0.074 mm proportion of 73.25%, and regulating with waterThe mass concentration of the ore pulp is 30 percent. Thereafter, an aqueous sodium carbonate solution (concentration 5%) was added to adjust the pH to 9.8. Then, adding an aluminum trifluoromethanesulfonate aqueous solution (with the concentration of 2%) as a positioning inhibitor, stirring for 2 minutes, adding a 9,11, 13-sodium trifluorooctadecanoate aqueous solution (with the concentration of 2%) and stirring for 2 minutes; then roughing is carried out by using an air agitation flotation machine: the air inflation amount was set to 0.35m³The stirring speed is 1500rpm, and the roughing time is 5 min. Then, 9,11, 13-trifluorooctadecanoic acid aqueous solution (concentration 2%) is supplemented for scavenging: the air inflation amount was set to 0.15m³The stirring speed is 1200rpm, and the scavenging time is 3 min. The foam products of roughing and scavenging are high-quality phosphate concentrate with low aluminum-silicon content, and the products in the flotation machine tank are gangue minerals.

Wherein, the dosage of the medicament in the roughing stage is that the mass ratio of the collophanite to the aluminum trifluoromethanesulfonate to the 9 and the 11, 13-sodium trifluorooctadecanoate is 1000: 0.2. The adding amount of the chemical agent in the scavenging stage is that the mass ratio of collophanite to 9 to 11, 13-sodium trifluorooctadecanoate is 1000 to 0.10.

Control group:

performed according to the experimental group except that the collector sodium 9,11, 13-trifluorooctadecanoate was replaced by sodium oleate.

The products obtained from the test group and the control group were dried and sampled for chemical composition analysis, and the results are shown in table 3.

TABLE 3 chemical analysis results of the products obtained in the test group and the control group,% by weight

As can be seen from the test results in Table 2, the control group adopts the traditional collecting agent sodium oleate, and the aluminum-silicon gangue minerals in the collophanite cannot be efficiently removed. The test group adopts the compound of the formula (1) provided by the invention as a collecting agent, and the P of the obtained product is obtained as a result₂O₅The grade and the phosphorus recovery rate are obviously improved, and the silicon-aluminum removal rate effect is better.

The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims

1. The collophanite collecting agent is characterized by having a structure shown in a formula (1):

wherein R is Na or K.

2. A method for preparing a collophanite collector of claim 1, which is characterized by comprising the following steps:

wherein:

the metal R in the metal R salt is Na or K;

in the formula (1), R is Na or K.

3. The method according to claim 2, wherein the reaction temperature in step A) is 40 to 90 ℃.

4. The process according to claim 2, wherein in step a), the reaction is carried out in an organic solvent medium;

the organic solvent is: the mass ratio of the 9,11, 13-octadecenoic acid is 2: 0.8-1.2.

5. The preparation method according to claim 2, wherein in step B), the reaction is carried out under the action of a catalyst TCUC;

the catalyst TCUC is prepared by the following method:

s2, heating and reacting the mixed powder with HF to obtain the catalyst TCUC.

6. The method according to claim 5, wherein in the step S2, the heating reaction conditions are as follows:

7. The preparation method according to claim 5 or 6, wherein the step S2 specifically comprises:

8. The method according to claim 5, wherein in step S1, the molar ratio of the titanium hydride powder to the calcium chloride powder to the copper oxide powder to the cobalt oxide powder is (1-1.5) to (2-3) to (1-2) to 2.

9. The method according to claim 2, wherein the reaction temperature in step B) is 60 to 90 ℃.

10. The method according to claim 2, wherein in step C), the R metal salt is selected from NaOH and Na₂CO₃、NaHCO₃、KOH、K₂CO₃And KHCO₃One or more of the above;

the reaction temperature is 70-100 ℃.