CN114534925B - Collophanite collecting agent and preparation method thereof - Google Patents
Collophanite collecting agent and preparation method thereof Download PDFInfo
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- CN114534925B CN114534925B CN202210294285.9A CN202210294285A CN114534925B CN 114534925 B CN114534925 B CN 114534925B CN 202210294285 A CN202210294285 A CN 202210294285A CN 114534925 B CN114534925 B CN 114534925B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—Organic compounds containing oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
- B03D2203/06—Phosphate ores
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a collophanite collector and a preparation method thereof. The collophanite collector shown in the formula (1) provided by the invention takes 9,11, 13-octadecenoic acid as a raw material, F atoms are added on a carbon chain to modify the 9,11, 13-octadecenoic acid through an addition reaction, three F atoms are introduced on the carbon chain, the electronegativity of the F atoms on the bubble forest scale is 3.98 as the maximum, the electron arrangement condition on carbon chain molecules can be effectively adjusted, and the molecular property is changed; based on the main chain, F atoms can form hydrogen bonds in water, so that the water solubility and dispersibility of molecules are improved, the hydrophobicity of long carbon chains is reduced, and meanwhile, the CMC concentration is increased, so that the fluidity 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 good separation effect can be still realized under the conditions of low temperature and wide pH, and the grade of the normal concentrate is higher.
Description
Technical Field
The invention relates to the field of beneficiation 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 can be adopted relative to phosphorite with different qualities, such as single reverse flotation, single forward flotation, forward-reverse flotation, double reverse flotation, reverse-forward flotation and the like. Flotation agents are key contributors in the flotation of phosphate ores, with collectors receiving a wide range of attention.
The industrially applied collectors are mainly fatty collectors such as oleic acid, oxidized paraffin soap, taer soap and the like. Although the traditional fat collector has the advantages of wide sources, low price and the like, the collector has poor solubility, poor dispersibility and poor selectivity to collophanite at low temperature, so that the problems of large dosage of flotation agents, low separation efficiency, large viscosity of produced foam, difficult foam elimination and the like are caused.
Fatty acids are a common collector for floating phosphorite, most of the collectors are other industrial byproducts, natural compounds are most common, but the floating effect is poor when the collectors are used for certain minerals, and the pertinence is not strong, so that the fatty acid collector is limited to a certain extent in popularization and application. In recent years, the development trend of phosphorite collectors is toward multi-functional, amphoteric, nonionic or mixed synergistic effect, and the phosphorite collectors are modified by molecules according to the characteristics of collophanite from medicament molecules so as to adapt to the industrial production requirements. Therefore, the development of a collector with a better flotation effect is of great importance.
Disclosure of Invention
In view of the above, the invention aims to provide a collophanite collector and a preparation method thereof. The collophanite collector 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 collector 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 collector 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 formula (a);
b) Reacting 9,11, 13-trichlorostearic acid shown in formula (a) with HF to form 9,11, 13-trifluoro stearic acid shown in formula (b);
c) Reacting 9,11, 13-trichlorooctadecanoic acid shown in the formula (b) with alkaline R metal salt to form a compound shown in the formula (1);
wherein:
r metal in the R metal salt is Na or K;
in the formula (1), R is Na or K.
Preferably, in the step A), the temperature of the reaction is 40 to 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 the 9,11, 13-octadecenoic acid is 2:0.8-1.2.
Preferably, in said step B), said 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, carrying out heating reaction on the mixed powder and HF to obtain a catalyst TCUC.
Preferably, in the step S2, the heating reaction conditions are as follows:
firstly, heating to 200-220 ℃ to react for 1-2 h, and then heating to 650-800 ℃ to react for 1-3 h.
Preferably, the step S2 specifically includes:
placing the mixed powder into a container, heating to 200-220 ℃, introducing HF gas into the container, and reacting for 1-2 h; 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, the calcium chloride powder, the copper oxide powder and the cobalt oxide powder is (1-1.5): (2-3): (1-2): 2.
Preferably, in the step B), the temperature of the reaction is 60 to 90 ℃.
Preferably, in the step C), the R metal salt is selected from NaOH and Na 2 CO 3 、NaHCO 3 、KOH、K 2 CO 3 And KHCO 3 One or more of the following;
the temperature of the reaction is 70-100 ℃.
The collophanite collector shown in the formula (1) provided by the invention takes 9,11, 13-octadecenoic acid as a raw material, F atoms are added on a carbon chain to modify the 9,11, 13-octadecenoic acid through an addition reaction, three F atoms are introduced on the carbon chain, the electronegativity of the F atoms on the bubble forest scale is 3.98 as the maximum, the electron arrangement condition on carbon chain molecules can be effectively adjusted, and the molecular property is changed; based on the main chain, F atoms can form hydrogen bonds in water, so that the water solubility and dispersibility of molecules are improved, the hydrophobicity of long carbon chains is reduced, and meanwhile, the CMC concentration is increased, so that the fluidity 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 special positive separation collector for collophanite is obtained with an auxiliary collecting function, the medicament performance is further improved, and the positive separation concentrate has a better separation effect under the conditions of low temperature and wide pH value.
The test result shows that the compound of the formula (1) provided by the invention is used as a collector, so that the yield of the phosphate concentrate is over 63 percent, the yield of the tailings is reduced to below 38 percent, and the good yield of the phosphate concentrate is obtained. In the obtained phosphate concentrate, P 2 O 5 The grade reaches more than 28.6 percent, al 2 O 3 The quality is reduced to below 1.6 percent, siO 2 The quality is reduced to below 11.2 percent; the aluminum-silicon removal rate is respectively 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 that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of the product obtained in example 1.
Detailed Description
The invention provides a collophanite collector which has a structure shown in a formula (1):
wherein R is Na or K.
In the present invention, preferably, R is Na, namely, the compound of formula (1) is 9,11, 13-sodium trifluorooctadecanoate, and the structure is as follows:
the collophanite collector shown in the formula (1) provided by the invention takes 9,11, 13-octadecenoic acid as a raw material, F atoms are added on a carbon chain to modify the 9,11, 13-octadecenoic acid through an addition reaction, three F atoms are introduced on the carbon chain, the electronegativity of the F atoms on the bubble forest scale is 3.98 as the maximum, the electron arrangement condition on carbon chain molecules can be effectively adjusted, and the molecular property is changed; based on the main chain, F atoms can form hydrogen bonds in water, so that the water solubility and dispersibility of molecules are improved, the hydrophobicity of long carbon chains is reduced, and meanwhile, the CMC concentration is increased, so that the fluidity 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 special positive separation collector for collophanite is obtained with an auxiliary collecting function, the medicament performance is further improved, and the positive separation concentrate has a better separation effect under the conditions of low temperature and wide pH value.
The invention also provides a preparation method of the collophanite collector 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 formula (a);
b) Reacting 9,11, 13-trichlorostearic acid shown in formula (a) with HF to form 9,11, 13-trifluoro stearic acid shown in formula (b);
c) Reacting 9,11, 13-trichlorooctadecanoic acid shown in the formula (b) with alkaline R metal salt to form a compound shown in the formula (1);
wherein:
r metal in the R metal salt is Na or K;
in the formula (1), R is Na or K.
[ regarding step A ]:
the 9,11, 13-octadecenoic acid reacts with HCl to form 9,11, 13-trichlorooctadecanoic acid shown in formula (a).
In the invention, the reaction route of the step A is as follows:
namely HCl and double bond in 9,11, 13-octadecenoic acid undergo addition reaction, thereby forming 9,11, 13-trichlorooctadecenoic acid.
In the present invention, the source of 9,11, 13-octadecenoic acid is not particularly limited, and is commercially available or can be 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. Wherein the organic solvent is preferably one or more of 3, 5-difluoroethylbenzene, 4-difluorocyclohexanone, p-methyltrifluorotoluene and 1, 4-bis (difluoromethyl) benzene, and the solvent is favorable for improving the dissolution and dispersion effects and reducing the occurrence of side reactions. In the invention, the mass ratio of the organic solvent to the 9,11, 13-octadecenoic acid is preferably 2: (0.8-1.2), and can be specifically 2:0.8, 2:0.9, 2:1.0, 2:1.1 and 2:1.2.
In the present invention, the reaction is preferably performed under the protection of a protective gas, i.e., a protective gas is used as an ambient gas and HCl gas is used as a reaction gas. The kind of the protective gas is not particularly limited in the present invention, and may be a conventional protective gas such as nitrogen, helium or argon, which is well known to those skilled in the art.
In the present invention, the reaction temperature is preferably 40 to 90℃and may specifically be 40℃45℃50℃55℃60℃65℃70℃75℃80℃85℃90 ℃. The reaction time is preferably 0.5 to 3 hours, and may specifically be 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours. 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 the liquid phase of the system under stirring to react, thereby forming 9,11, 13-trichlorooctadecanoic acid shown in formula (a).
Wherein:
the above reaction may be carried out in a reaction vessel. The degree of introduction of the protective gas into the system is preferably: until the pressure in the system reaches 2-4 atm, which can be 2atm, 2.5atm, 3atm, 3.5atm, 4atm. The stirring rate of the stirring condition is preferably 300 to 600rpm, and specifically 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm may be used. When the HCl gas is introduced, the flow rate of the HCl gas is preferably 0.5 to 2.5sccm, and more preferably 0.5sccm, 1.0sccm, 1.5sccm, 2.0sccm, or 2.5sccm. And continuously introducing HCl gas to react for 0.5-3 h until the reaction is completed after the full reaction. The mode of ending the reaction is specifically as follows: and stopping introducing HCl gas to replace the mixed gas in the system with protective gas. After the reaction, 9,11, 13-trichlorooctadecanoic acid shown in the formula (a) is formed in the system, and the reaction liquid containing the reaction product is specifically used in the system. In the present invention, it is preferable that after the completion of the reaction in the step A), 9,11, 13-trichlorooctadecanoic acid represented by the formula (a) is not separated from the reaction solution, but the reaction solution containing the same is directly obtained to be subjected to the next reaction.
[ regarding step B ]:
the 9,11, 13-trichlorostearic acid shown in the formula (a) reacts with HF to form 9,11, 13-trifluoro-stearic acid shown in the formula (b).
In the invention, the reaction route of the step B is as follows:
namely, the substitution reaction between 9,11, 13-trichlorostearic acid shown in the formula (a) and HF is carried out, F in the HF substitutes Cl in the 9,11, 13-trichlorostearic acid shown in the formula (a), so that 9,11, 13-trifluoro-stearic acid shown in the formula (b) is formed.
In the present invention, the reaction is preferably performed under the protection of a protective gas, i.e., a protective gas is used as an ambient gas and an HF gas is used as a reaction gas. The kind of the protective gas is not particularly limited in the present invention, and may be a conventional protective gas such as nitrogen, helium or argon, which is well known to those skilled in the art.
In the present invention, the reaction temperature is preferably 60 to 90℃and specifically 60℃65℃70℃75℃80℃85℃90 ℃. The reaction time is preferably 1 to 4 hours, and may be specifically 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 4 hours.
In the present invention, the reaction is preferably carried out under the action of catalyst TCUC. In the present 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 can be 1:100, 2:100, 3:100, 4:100, 5:100, 6:100 and 7:100.
In the present invention, the catalyst TCUC is preferably 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, carrying out heating reaction on the mixed powder and HF to obtain a catalyst TCUC.
Regarding step S1:
the molar ratio of the titanium hydride powder, the calcium chloride powder, the copper oxide powder and the cobalt oxide powder is preferably (1-1.5) to (2-3) to (1-2) to (2), and can be specifically 1:2:1:2, 1:2.5:1.5:2, 1:3:2:2, 1.3:2:1:2.5:1.5:2, 1.3:3:2:2, 1.5:2:1:2, 1.5:2.5:1.5:2, 1.5:3:2. The above 4 kinds of powders (H 2 Ti powder and CaCl 2 Powder, cuO powder, coO powder) is not particularly limited, and the materials can be uniformly mixed by a conventional mixing method well known to those skilled in the art.
Regarding step S2:
the HF is HF gas.
The conditions of the heating reaction are as follows: firstly, heating to 200-220 ℃ to react for 1-2 h, and then heating to 650-800 ℃ to react for 1-3 h. Wherein the 200-220 ℃ can be 200 ℃, 205 ℃, 210 ℃, 215 ℃ and 220 ℃. The reaction time is 1-2 h, and can be 1h, 1.5h and 2h. The 650-800 ℃ can be 650 ℃, 700 ℃, 750 ℃ and 800 ℃. The reaction time for 1 to 3 hours can be specifically 1 hour, 1.5 hours, 2 hours, 2.5 hours and 3 hours. In the reaction process, H 2 Ti+CaCl 2 Reaction of +CuO +CoO with HF to produce M x F y (M is Ti, ca, cu, co), compared with the simple method that the 4 kinds of fluoride are obtained respectively and then the 4 kinds of fluoride powder are mixed, the invention firstly mixes the 4 kinds of powder and then reacts with HF, and M is generated through high-temperature reaction x F y A special physical and chemical structure can be generated in the forming and growing processes, specifically, a water vapor overflow channel generated in the reaction process increases the specific surface area of materials, and part of intergranular doping makes the distance between an active site and a catalytic atom closer, so that the catalytic performance is improved.
The step S2 specifically includes: placing the mixed powder into a container, heating to 200-220 ℃, introducing HF gas into the container, and reacting for 1-2 h; 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 more preferably 1.0sccm, 1.5sccm, 2.0sccm, 2.5sccm, and 3.0sccm. After full reaction, cooling and stopping introducing HF gas to obtain a 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 stirring to react, thereby forming 9,11, 13-trifluoro-octadecanoic 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 gas pressure in the system reaches 2-8 atm, which can be specifically 2atm, 2.5atm, 3atm, 3.5atm, 4atm, 4.5atm, 5atm, 5.5atm, 6atm, 6.5atm, 7atm, 7.5atm and 8atm. The stirring rate of the stirring condition is preferably 300 to 600rpm, and specifically 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm may be used. When the HF gas is supplied, the flow rate of the HF gas is preferably 0.4 to 2.8sccm, and more preferably 0.4sccm, 0.5sccm, 1.0sccm, 1.5sccm, 2.0sccm, 2.5sccm, and 2.8sccm. And continuously introducing HF gas to react for 1-4 h. By the above reaction, 9,11, 13-trifluoro-octadecanoic acid represented by the formula (b) is formed in the system. 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, and is a conventional separation mode well known to those skilled in the art, such as filtration and the like; the catalyst TCUC is removed 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-trifluoro-octadecanoic acid represented by the formula (B) is not separated from the reaction mixture, but the reaction mixture containing the 9,11, 13-trifluoro-octadecanoic acid is directly obtained and subjected to the next reaction.
In the invention, the step A) and the step B) are carried out step by step, namely, HCl is added to Cl, and F in HF is used for replacing Cl instead of HF, so that the smooth reaction can be ensured, the side reaction is greatly reduced, and the yield is improved. If HF is directly used for addition, the olefin is easy to polymerize in the HF environment, the addition reaction is limited, and the olefin with halogen on double bonds is not easy to polymerize; however, as halogen increases, the more difficult the HF addition reaction is, and when an F atom is present on a double bond, the electron cloud density of the double bond is reduced as an electron withdrawing group, making electrophilic addition difficult. The reaction mode of the step A) and the step B) can overcome the problems, ensure that the reaction is carried out smoothly, greatly reduce side reactions and improve the yield.
[ about step C ]:
the 9,11, 13-trichlorooctadecanoic acid shown in the formula (b) reacts with alkaline R metal salt to form the compound shown in the formula (1).
In the invention, the reaction route of the step C is as follows:
namely, the 9,11, 13-trichlorooctadecanoic acid shown in the formula (b) reacts with the alkaline R metal salt to form 9,11, 13-trifluoro octadecanoic acid shown in the formula (1).
In the present invention, in the basic R metal salt, R is Na or K, more preferably Na. The R metal salt is preferably NaOH or Na 2 CO 3 、NaHCO 3 、KOH、K 2 CO 3 And KHCO 3 One or more of the following; more preferably the strongly basic metal salts NaOH and/or KOH, most preferably NaOH.
In the present invention, the molar ratio of 9,11, 13-trichlorooctadecanoic acid to R metal salt represented by the formula (b) is preferably 1: (0.8-1.2), and may be specifically 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.2.
In the present invention, the R metal salt is preferably added in the form of an aqueous R metal salt solution. The mass concentration of the R metal salt aqueous solution is preferably 10% -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 in step B) has ended, the liquid phase obtained is transferred to the still. In the present invention, the reaction temperature is preferably 70 to 100℃and may specifically be 70℃75℃80℃85℃90℃95℃100 ℃. The reaction time is preferably 1 to 3 hours, and may be specifically 1 hour, 1.5 hours, 2 hours, 2.5 hours, or 3 hours. After the reaction, 9,11, 13-trifluoro-octadecanoate shown in the formula (1) is generated in the system, and a reaction mixed solution containing the reaction product is obtained.
In the present invention, after the reaction in step C), the following post-treatment is preferably also 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-trifluoro-octadecanoate shown in the formula (1). Wherein the distillation temperature is preferably 50 to 80 ℃, and more specifically 50 ℃, 60 ℃, 70 ℃ and 80 ℃. The distillation is carried out under vacuum conditions, 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 and 0.09MPa. The distillation time is preferably 1 to 3 hours until the mixed solution is solidified, and the organic solvent is sufficiently removed, thereby obtaining the 9,11, 13-trifluoro-octadecanoate product shown in the formula (1).
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 purity of the product are high, the yield can reach more than 95%, and the purity can reach more than 98%.
The invention also provides application of the 9,11, 13-trifluoro-octadecanoate shown in the formula (1) as a collophanite collector.
And the normal fatty acid collector 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 alkaline flotation solution environment, the specific special-effect collector is mainly used for electric double layer adsorption generated by electrostatic force adsorption and surface chemical adsorption generated by surface chemical reaction on the surface of the collector, and the speed process of electrostatic adsorption is greater than that of surface chemical adsorption. In the process of adhering to the surface of collophanite, fluorine atoms have stronger absorptivity and can generate characteristic adsorption with fluorapatite, the auxiliary collection enhances the selectivity, the electronegativity of the whole hydrophobic group of the collector is reduced, and the electrostatic adsorption can only occur in a smaller range, so that the selectivity of the collector is improved. Due to the effect of surface electrostatic adsorption, the concentration of anions of the mineral surface specific collector is effectively reduced, the probability of irreversible chemical reaction is reduced, the specific range of solubility products of corresponding organic salts is slowed down, a large amount of stable fatty acid salts are prevented from being generated in foam products, and poor foam flowability is further prevented. Electrostatic adsorption can fix to mineral surfaces at a high rate, and when foam products are carried along with rising bubbles, the bubbles tend to crack due to unstable properties. The problems of poor foam fluidity and difficult defoaming are solved through the functions. Therefore, the invention adopts 9,11, 13-trifluoro-octadecanoate as a collector, and can achieve the following effects: the selectivity is strong, the dosage of the agent is low, the flotation foam viscosity is low, the fluidity is good, and the defoaming is easy; solves the problems of large foam quantity and poor fluidity in the forward selection stage of the collophanite forward-reverse flotation; the flotation concentrate has high grade, high phosphorus yield, low grade of tailings phosphorus, little phosphorus loss and high comprehensive economic benefit.
The invention uses the compound of formula (1) as a collector, is suitable for the flotation of high-alumina siliceous collophanite, and compared with the traditional flotation process, the invention effectively improves the separation efficiency of the alumina siliceous collophanite, reduces the dosage of the medicament and improves the quality and recovery rate of concentrate. For the situation that the magnesium content in part of collophanite is higher, magnesium minerals such as dolomite and the like can be removed only by simple reverse flotation; by adopting the flotation method, the treatment difficulty of the subsequent process for positive froth selection 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 combining a simple reverse flotation process under the necessary condition through a short forward separation process, and the process has strong adaptability and can be popularized in the industry.
The 9,11, 13-trifluoro-octadecanoate shown in the formula (1) can be used as a collophanite collector. The existing collector has the defects of unsatisfactory sorting effect, poor foam property, stable foam, high viscosity, difficult breaking and difficult transportation and defoaming. The aqueous solution of the medicament is low, the dispersing effect is poor, the use condition is narrow, the flotation effect in the low-temperature area is poor, the pH condition is strictly controlled, and the industrial application degree is low. Compared with the formula (1), the collector provided by the invention has the following beneficial effects:
1. the octadecanoate is used as a main chain, F atoms are connected at the positions 9,11 and 13, so that the critical micelle concentration is improved, the surface tension is effectively reduced, meanwhile, the difference of hydrophilic and hydrophobic groups is weakened, the fluidity of flotation foam is increased, the foam viscosity is reduced, the foam stabilizing time is short, and foam is easy to foam.
2. The collector has good sorting effect on phosphorite and strong selectivity. Based on the main chain, the addition of fluorine atoms increases the ability of the collector to form hydrogen bonds in part in the aqueous solution, increases the dispersibility and the water solubility, has stronger collecting ability in a low temperature region of 5-25 ℃, and can adapt to the pH range of 10.0-11.7.
3. Calcium fluoride solubility product 2.7x10 -11 After fluorine atoms are added to the specific main chain, the fluorine atoms can react with calcium in the apatite and position the calcium in the apatite, so that the function of increasing the collection performance is achieved, the grade of the normal concentrate is increased, the grade of tailings is decreased, and the separation effect is better.
The test result shows that the compound of the formula (1) provided by the invention is used as a collector, so that the yield of the phosphate concentrate is over 63 percent, the yield of the tailings is reduced to below 38 percent, and the good yield of the phosphate concentrate is obtained. In the obtained phosphate concentrate, P 2 O 5 The grade reaches more than 28.6 percent, al 2 O 3 The quality is reduced to below 1.6 percent, siO 2 The quality is reduced to below 11.2 percent; the aluminum-silicon removal rate is respectively more than 81.5 percent and more than 64.7 percent.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
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 nickel tube 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 raised to 700 ℃ for reaction for 2 hours. After cooling, the introduction of HF gas was stopped to obtain catalyst TCUC.
Example 1: preparation of sodium 9,11, 13-trifluorooctadecanoate
1. Sample preparation
1. Step A:
3, 5-difluoroethylbenzene solvent and 9,11, 13-octadecenoic acid (the mass ratio of the two is 2:1.0) are added into a reaction kettle, and the temperature is raised to 75 ℃. Filling the reaction kettle with argon until the air pressure is increased to 3atm, introducing HCl gas into the liquid phase under continuous stirring, wherein the flow is 2.0sccm, and after the reaction is completed for 2.5 hours, replacing the mixed gas in the reaction kettle with argon. The reaction liquid containing 9,11, 13-trichlorooctadecanoic acid is obtained in the system.
2. And (B) step (B):
adding the catalyst TCUC prepared in the preparation example into a reaction kettle, heating to 80 ℃, and introducing argon gas to ensure that the pressure of the reaction kettle reaches 5.5atm. And (3) introducing HF gas into the reaction kettle under continuous stirring, wherein the flow rate is 2.5sccm, reacting for 3 hours, and filtering to remove the catalyst to obtain a reaction mixed solution containing 9,11, 13-trifluoro-octadecanoic acid.
3. Step C:
transferring the liquid phase obtained in the step B into a distillation kettle, heating to 80 ℃, adding NaOH solution (the mass concentration is 12%, and the mol ratio of 9,11, 13-trifluoro-octadecanoic acid to NaOH is=1:1.1), and carrying out reflux reaction for 2h to obtain a reaction mixed solution containing 9,11, 13-trifluoro-octadecanoic acid sodium.
Distilling the reaction mixture for 2 hours at the temperature of 80 ℃ and the vacuum degree of 0.07MPa, recovering 3, 5-difluoroethylbenzene solvent until the solution is solidified, and obtaining the 9,11, 13-sodium trifluorooctadecanoate product with the yield of 96.8% and the purity of 98.7%.
2. Sample characterization
The obtained 9,11, 13-sodium trifluorooctadecanoate product is subjected to infrared characterization, the result is shown in figure 1, and figure 1 is an infrared spectrogram of the product obtained in example 1; the main functional groups and peak positions are shown in the following table 1. It can be seen that the resulting product is of formula (1) and R is Na.
Table 1 ir 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 test sample adopted is collophanite mined in a certain Guizhou area, the ores belong to high-alumina siliceous collophanite, and the analysis results of the chemical components of the ores by mass percent are shown in Table 2.
TABLE 2 results of chemical multi-element analysis of raw ore
| Composition of the components | P 2 O 5 | CaO | MgO | SiO 2 | Fe 2 O 3 | Al 2 O 3 | F |
| Content/wt% | 22.56 | 35.02 | 2.10 | 20.42 | 1.28 | 5.32 | 2.03 |
Test group:
the collophanite is crushed and ground until the proportion of-0.074 mm is 73.25%, and water is added to adjust the mass concentration of the ore pulp to 30%. Thereafter, an aqueous sodium carbonate solution (concentration 5%) was added to adjust the pH to 9.8. Then adding the positioning inhibitor aluminium trifluoromethylsulfonate aqueous solution (concentration 2%) and stirring for 2 minutes, and adding the 9,11, 13-sodium trifluorooctadecanoate aqueous solution (concentration 2%) and stirring for 2 minutes; then roughing is carried out by an aerated stirring flotation machine: the air charge is set to be 0.35m 3 And/h, stirring speed is 1500rpm, and roughing is carried out for 5min. Then, the 9,11, 13-trifluoro-octadecanoic acid aqueous solution (concentration 2%) is added for scavenging: the air charge is set to 0.15m 3 And/h, stirring speed is 1200rpm, and scavenging is carried out for 3min. The foam product of roughing and scavenging is high-quality phosphorus concentrate with low content of aluminum and siliconThe ore and the product in the flotation machine tank are gangue minerals.
Wherein the dosage of the medicament in the roughing stage is that the mass ratio of collophanite to aluminium triflate to 9,11, 13-sodium trifluorooctadecanoate is 1000:0.2:0.2. The dosage of the medicament in the scavenging stage is collophanite to 9,11, 13-sodium trifluorooctadecanoate with the mass ratio of 1000 to 0.10.
Control group:
the test set was run except that the collector 9,11, 13-sodium trifluorooctadecanoate was replaced with sodium oleate.
The products obtained in the test group and the control group were dried to prepare samples, and chemical component analysis was performed, 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, wt%
As can be seen from the test results in Table 2, the control group adopts the traditional collector sodium oleate, and the aluminum-silicon gangue minerals in the collophanite cannot be removed efficiently. The test group uses the compound of formula (1) as collector, and the P of the obtained product 2 O 5 The grade and the phosphorus recovery rate are obviously improved, and the effect of the silicon-aluminum removal rate is better.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to aid in understanding the method of the invention and its core concept, 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 it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection 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 do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. The collophanite collector 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 as claimed in claim 1, comprising the steps of:
a) Reacting 9,11, 13-octadecenoic acid with HCl to form 9,11, 13-trichlorooctadecanoic acid shown in formula (a);
b) Reacting 9,11, 13-trichlorostearic acid shown in formula (a) with HF to form 9,11, 13-trifluoro stearic acid shown in formula (b);
c) Reacting 9,11, 13-trifluoro-octadecanoic acid shown in the formula (b) with alkaline R metal salt to form a compound shown in the formula (1);
wherein:
r metal in the R metal salt is Na or K;
in the formula (1), R is Na or K.
3. The method according to claim 2, wherein in the step a), the reaction temperature 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 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 the 9,11, 13-octadecenoic acid is 2:0.8-1.2.
5. The process according to claim 2, characterized in that 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, carrying out heating reaction on the mixed powder and HF to obtain a catalyst TCUC.
6. The method according to claim 5, wherein in the step S2, the heating reaction conditions are as follows:
the temperature is raised to 200-220 ℃ to react for 1-2 hours, and then the temperature is raised to 650-800 ℃ to react for 1-3 hours.
7. The method according to claim 5 or 6, wherein the step S2 specifically comprises:
placing the mixed powder into a container, heating to 200-220 ℃, introducing HF gas into the container, and reacting for 1-2 hours; then, the temperature is increased to 650-800 ℃ to react for 1-3 hours, and the catalyst TCUC is formed.
8. The method according to claim 5, wherein in the step S1, the 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.
9. The method according to claim 2, wherein in the step B), the reaction temperature is 60 to 90 ℃.
10. The method according to claim 2, wherein in the step C), the R metal salt is selected from NaOH and Na 2 CO 3 、NaHCO 3 、KOH、K 2 CO 3 And KHCO 3 One or more of the following;
the reaction temperature is 70-100 ℃.
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