CN108927292B - Aminophosphonic acid compound and preparation method and application thereof - Google Patents
Aminophosphonic acid compound and preparation method and application thereof Download PDFInfo
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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
- B03D1/014—Organic compounds containing phosphorus
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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
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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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Abstract
The invention discloses an aminophosphonic acid compound which has a general formula of (A)
) As shown. The invention also discloses a preparation method of the aminophosphonic acid compound, wherein the aminophosphonic acid compound is prepared by carrying out Mannich reaction on 3, 7-dimethyl-2, 6-octadienal, aniline or substituted aniline and phosphorous acid under the action of an acid catalyst. The aminophosphonic acid compound can be used as a flotation collector of ilmenite, bauxite, fluorite ore, rare earth ore or collophanite, has the characteristics of good selectivity, strong water solubility, good dispersibility and the like, and can improve the flotation recovery rate by 2-16%. The preparation method adopts a one-pot synthesis method, is easy to control the operation, has high product yield and is easy for industrial production.
Description
Technical Field
The invention belongs to the field of mineral flotation, relates to an aminophosphonic acid compound, and also relates to a preparation method and application thereof in the flotation of ilmenite, bauxite, rare earth ore, fluorite ore or phosphorite.
Background
Oleic acid and modified products thereof are the most common mineral separation collecting agent in the flotation process of oxidized ores, and oleic acid is used as the collecting agent in the flotation agent, the flotation method and the flotation system for limonite in Chinese published patent literature (publication number: CN 102921537A), so that the grade of iron ore concentrate can be effectively improved; in the Chinese published patent literature (publication number: CN 101585016), in the flotation separation method of the low-grade fluorite barite, oleic acid is used as a collecting agent, and water glass is used as siliceous and calcareous mineral inhibitors to carry out flotation separation; in the Chinese published patent literature (publication number: CN 101712014A), the single fluorite ore of various impurities is separated by alkaline oleic acid, neutral oleic acid and acidic oleic acid in the beneficiation method of the single fluorite ore of various impurities; chinese published patent literature (publication number: CN 101648157B) discloses a beneficiation method of black and white tungsten minerals, which uses sulfated oleate soap as a collecting agent for flotation; chinese published patent literature (publication number: CN 102962144A) a high-efficiency selective collector for bauxite and a preparation method thereof, wherein oleic acid with saponification degree of 50% is used as the collector for bauxite flotation; in the Chinese published patent literature (publication number: CN 102716811A), the weathered phosphorite is separated by using the mixed flotation of the gossypoleic acid and the erucic acid in the water-soluble weathered phosphorite foam flotation collector.
Oleic acid has the advantages of strong collecting capability, lower price and the like as a flotation collecting agent, but has the obvious defects of low selectivity, lower freezing resistance, layering after long-term storage, and poor water solubility and dispersibility at normal temperature, so the collecting agent needs to be emulsified or flotation pulp needs to be heated, and the heating flotation not only increases the energy consumption, but also brings inconvenience to production operation and management. Aiming at the defects of oleic acid, the development of the efficient flotation collector has important significance for the development and utilization of the mining industry.
The phosphonic acid group in the organic phosphonic acid compound has stronger polarity, so the organic phosphonic acid compound is a high-efficiency mineral separation collector, has good separation performance, and can successfully separate useful minerals from gangue minerals by matching with an effective inhibitor. In the preferred flotation of zircon in seashore placer of Chinese published patent literature (publication number: CN 1047462A), 1-hydroxy-alkyl-1, 1-diphosphonic acid is used as a zircon collecting agent; chinese published patent literature (publication number: CN 1063627A) discloses the use of α -nitrosophosphonates as pyrite collectors; the rutile roughing technology of selective ore grinding, coarse grain gravity separation and fine grain flotation of Chinese published patent literature (publication number: CN 102500462A) uses styrene phosphonic acid and hydroximic acid as rutile collecting agent; chinese published patent literature (publication number: CN 103613614A) discloses a novel organic phosphonic acid compound used for various mineral collectors, and an alpha-hydroxy unsaturated alkyl phosphonic acid compound and a preparation and application method thereof. The organic phosphonic acid compounds are used as flotation collectors and are well sorted, but the preparation processes of the compounds are complex, the synthesis yield is low, the environmental pollution is large in the preparation process, and the organic phosphonic acid compounds are also used as collectors in ilmenite, bauxite, phosphorite and other ores, so that the effect is not obvious and the selectivity is poor.
Disclosure of Invention
The invention aims to provide a novel aminophosphonic acid compound which can be used as a flotation collector of ilmenite, bauxite, rare earth ore, fluorite ore or phosphorite, can improve the separation property of minerals and realize the effective separation of target minerals and gangue minerals aiming at the defects of the prior art.
Another object of the present invention is to provide a process for the preparation of the above aminophosphonic acid compounds.
Still another object of the invention is to provide the application of the aminophosphonic acid compound as the flotation collector.
The object of the present invention is achieved by the following means. The invention relates to an aminophosphonic acid compound, which is characterized in that the structure is shown as the formula (A)
) Shown in the figure:
wherein: r is H, F, Cl, Br or C1~6A hydrocarbyl group;
in a preferred embodiment, the substituent R is H.
The application method of the aminophosphonic acid compound can be used as a flotation collector for ilmenite, bauxite, rare earth ore, fluorite ore or phosphorite.
The aminophosphonic acid compound of the invention can be prepared by the following method: adding aniline or aniline containing substituent groups, phosphorous acid solution and an acid catalyst into a reaction kettle, raising the temperature of a reaction system to 80-100 ℃ (preferably 85-95 ℃, most preferably 90 ℃), slowly dropwise adding 3, 7-dimethyl-2, 6-octadienal at the temperature, raising the temperature of the reaction system to 110-160 ℃ (preferably 120-150 ℃, most preferably 130 ℃) after dropwise adding, reacting for 1-4 hours (preferably reacting for 1-2 hours, most preferably reacting for 1.5 hours) at the temperature, and cooling to obtain a white solid.
The acidic catalyst used in the synthesis reaction of the present invention may be an inorganic acid compound or an organic acid compound. Preferred inorganic acid compound catalysts are hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid or phosphoric acid; the most preferred acidic catalyst is phthalic acid. Preferred organic acid compound catalysts are oxalic acid, citric acid, tartaric acid, glycolic acid, phthalic acid, sulfamic acid, p-toluenesulfonic acid. In the synthesis reaction, the molar ratio of the raw materials of 3, 7-dimethyl-2, 6-octadienal, aniline or substituted aniline, phosphorous acid and the acid catalyst is 1: 1-2: 1-3: 0.02-0.08. Most preferred is a molar ratio of 3, 7-dimethyl-2, 6-octadienal, aniline or substituted aniline, phosphorous acid and acidic catalyst of 1:1:1: 0.05.
The aminophosphonic acid compound provided by the invention has a benzene ring structure, an amino structure, a branched chain structure and a plurality of carbon-carbon double bonds, and is a brand new organic phosphonic acid compound. The organic phosphonic acid compound is also used as a flotation collector for ilmenite, bauxite, rare earth ore, fluorite ore or phosphorite for the first time, and has phosphonic acid groups and amino groups, so that the organic phosphonic acid compound can chelate various metal ions, has high separation performance on useful minerals and does not need heating operation during flotation. The aminophosphonic acid compound can be used as a flotation collector for ilmenite, bauxite, rare earth ore, fluorite ore or phosphorite.
Compared with the prior art, the invention has the beneficial effects that: the organic phosphonic acid containing a benzene ring structure, an amino structure, a branched chain structure and a plurality of carbon-carbon double bond structures is obtained for the first time. The organic phosphonic acid group in the compound has a chelating effect on metal ions, and amino groups in the structure can play a synergistic effect with phosphonic acid groups, so that the collecting capacity on target minerals is improved; multiple carbon-carbon double bonds in the structure can improve the hydrophilicity and the dispersibility in the flotation process. The compound is used as a flotation collector, has good water solubility and strong dispersibility, and is convenient to use; meanwhile, the catalyst has good selectivity and collecting property. The preparation method of the compound can adopt a one-pot synthesis method, is easy to control the operation, has high product yield, is easy for industrial production, has lower cost and does not produce environmental pollution.
Drawings
FIG. 1 is an infrared spectrum of 1-anilino-2, 7-methyl-2, 6-octadienyl-1-phosphonic acid.
FIG. 2 shows the mass spectrum of 1-anilino-2, 7-methyl-2, 6-octadienyl-1-phosphonic acid.
FIG. 3 is a flow chart of the flotation process for flotation of ilmenite ore by 1-anilino-2, 7-methyl-2, 6-octadienyl-1-phosphonic acid.
FIG. 4 is a flow chart of the flotation process for flotation of fluorite ore by 1-anilino-2, 7-methyl-2, 6-octadienyl-1-phosphonic acid.
Detailed Description
The invention is further illustrated by, but is not limited to, the following examples. All parts and percentages in the examples are by mass unless otherwise specified.
Example 1 an aminophosphonic acid compound of the formula
) Shown in the figure:
wherein: r is H, F, Cl or Br.
The preparation method comprises the following steps: adding aniline or aniline containing substituent groups, phosphorous acid solution and an acid catalyst into a reaction kettle, raising the temperature of a reaction system to 80 ℃, slowly dropwise adding 3, 7-dimethyl-2, 6-octadienal at the temperature, raising the temperature of the reaction system to 110 ℃ after dropwise adding, reacting at the temperature, and cooling to obtain a white solid. The reaction time was 1 hour. The acid catalyst used in the reaction is selected from one of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid or phosphoric acid; the molar ratio of the reaction raw materials of 3, 7-dimethyl-2, 6-octadienal, aniline or substituted aniline, phosphorous acid and the acid catalyst is 1:1:1: 0.02. In the flotation process of ilmenite, bauxite, rare earth ore, fluorite ore or phosphorite, an aminophosphonic acid compound is used as a flotation collector.
Example 2 an aminophosphonic acid compound of the formula
) Shown in the figure:
wherein: r is C1~6A hydrocarbyl group.
The preparation method comprises the following steps: adding aniline or aniline containing substituent groups, phosphorous acid solution and an acid catalyst into a reaction kettle, raising the temperature of a reaction system to 100 ℃, slowly dropwise adding 3, 7-dimethyl-2, 6-octadienal at the temperature, raising the temperature of the reaction system to 160 ℃ after dropwise adding, reacting at the temperature, and cooling to obtain a white solid. The reaction time was 4 hours. The acidic catalyst used in the reaction is selected from oxalic acid, citric acid, tartaric acid, glycolic acid, phthalic acid, sulfamic acid or p-toluenesulfonic acid. The molar ratio of the reaction raw materials of 3, 7-dimethyl-2, 6-octadienal, aniline or substituted aniline, phosphorous acid and the acid catalyst is 1: 2: 3: 0.08. In the flotation process of ilmenite, bauxite, rare earth ore, fluorite ore or phosphorite, an aminophosphonic acid compound is used as a flotation collector.
Example 3 an aminophosphonic acid compound of the formula
) Shown in the figure:
wherein: r is H.
The preparation method comprises the following steps: adding aniline or aniline containing substituent groups, phosphorous acid solution and an acid catalyst into a reaction kettle, raising the temperature of a reaction system to 90 ℃, slowly dropwise adding 3, 7-dimethyl-2, 6-octadienal at the temperature, raising the temperature of the reaction system to 130 ℃ after dropwise adding, reacting at the temperature, and cooling to obtain a white solid. The reaction time was 1.5 hours. The acidic catalyst used in the reaction is selected from oxalic acid, citric acid, tartaric acid, glycolic acid, phthalic acid, sulfamic acid or p-toluenesulfonic acid. The molar ratio of the reaction raw materials of 3, 7-dimethyl-2, 6-octadienal, aniline or substituted aniline, phosphorous acid and the acid catalyst is 1:1:1: 0.05. In the flotation process of ilmenite, bauxite, rare earth ore, fluorite ore or phosphorite, an aminophosphonic acid compound is used as a flotation collector.
Example 3: preparation of 1-anilino-2, 7-methyl-2, 6-octadienyl-1-phosphonic acid
Adding 93 parts of aniline, 166 parts of phosphorous acid solution (with the concentration of 50%) and 8.3 parts of phthalic acid into a reaction kettle with a stirrer, raising the temperature of a reaction system to 90 ℃, adding 152 parts of 3, 7-dimethyl-2, 6-octadienal into the reaction kettle at the temperature, raising the temperature of the reaction system to 130 ℃ after the addition is finished, and reacting at the temperature for 1.5 hours to obtain a white solid, namely the required collector OP, wherein the yield is 83%. The maps are shown in figures 1 and 2.
Example 4: preparation of 1-anilino-2, 7-methyl-2, 6-octadienyl-1-phosphonic acid
Adding 93 parts of aniline, 166 parts of phosphorous acid solution (with the concentration of 50%) and 4 parts of hydrochloric acid into a reaction kettle with a stirrer, raising the temperature of a reaction system to 90 ℃, adding 152 parts of 3, 7-dimethyl-2, 6-octadienal into the reaction kettle at the temperature, raising the temperature of the reaction system to 130 ℃ after the addition is finished, and reacting at the temperature for 1.5 hours to obtain a white solid, namely the required collecting agent OP, wherein the yield is 73%.
Example 5: application of collecting agent in ilmenite flotation
The ilmenite sample comes from Sichuan Pan Steel group titanium-selecting factory, and the raw ore grade TiO218.56 percent and-200 meshes account for-33 percent, water is added for pulp mixing until the concentration of the ore pulp is 30 percent, 1kg/t sulfuric acid, 0.3kg/t xanthate and 0.05kg/t98# oil are added for flotation and desulfurization, 0.8 kg/t sulfuric acid and a collecting agent OP2.8kg/t are added for ilmenite roughing, 0.3kg/t sulfuric acid is added for primary concentration, and 0.2kg/t sulfuric acid is added for secondary concentration. The flotation process flow diagram is shown in figure 3. The results of the flotation comparative experiment of the collector OP of the invention and the industrial collector MOH are shown in Table 1. As can be seen from table 1, the flotation recovery rate of the collector OP of the present invention to ilmenite was improved by 9.43% over the existing collector MOH.
TABLE 1 comparative results of collector flotation ilmenite
| Species of collector | Titanium concentrate yield/% | TiO2Grade/% | TiO2Percent recovery% |
| OP | 32.21 | 48.12 | 83.30 |
| MOH | 28.52 | 48.07 | 73.87 |
Example 6: application of collecting agent in fluorite ore flotation
CaF in raw ore of fluorite ore in Zhejiang2The grade is 36.20%, the fluorite ore is ground by an ore grinding machine to-200 meshes accounting for-65%, water is added for size mixing until the concentration of ore pulp is 30%, 1.5kg/t of sodium carbonate, 0.5kg/t of water glass and 0.6kg/t of collecting agent OP are added, the flotation test is carried out at the room temperature of about 10 ℃, and the flow chart of the flotation process is shown in figure 4. The results of the flotation tests of the collector OP of the present invention with the conventional collector oleic acid are shown in table 2. As can be seen from Table 2, the flotation recovery rate of the fluorite ore by the collector OP is 15.37 percent higher than that of the conventional collector oleic acid
TABLE 2 comparative results of collector flotation fluorite ore
| Species of collector | Yield of coarse concentrate/%) | CaF2Grade/% | CaF2Percent recovery% |
| Sodium oleate | 30.12 | 81.69 | 67.97 |
| Collector OP | 37.10 | 81.32 | 83.34 |
Claims (13)
1. An aminophosphonic acid compound, wherein the compound has the general formula (I):
wherein: r is H, F, Cl, Br or C alkyl.
2. A process for the preparation of an aminophosphonic acid compound as claimed in claim 1, comprising the steps of: adding aniline or aniline containing substituent groups, phosphorous acid solution and an acid catalyst into a reaction kettle, raising the temperature of a reaction system to 80-100 ℃, slowly dropwise adding 3, 7-dimethyl-2, 6-octadienal at the temperature, raising the temperature of the reaction system to 110-160 ℃ after dropwise adding, reacting at the temperature, and cooling to obtain a white solid.
3. The method of claim 2, wherein the reaction time is 1 to 4 hours.
4. The method of claim 2, wherein the acidic catalyst used in the reaction is an inorganic acid compound or an organic acid compound.
5. The method of claim 4, wherein the inorganic acid compound is selected from hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and phosphoric acid; the organic acid compound is selected from oxalic acid, citric acid, tartaric acid, glycolic acid, phthalic acid, sulfamic acid or p-toluenesulfonic acid.
6. The method for preparing aminophosphonic acid compounds as claimed in claim 2, wherein the molar ratio of the reaction raw materials 3, 7-dimethyl-2, 6-octadienal, aniline or substituted aniline, phosphorous acid and acidic catalyst is 1: 1-2: 1-3: 0.02-0.08.
7. The method of claim 6, wherein the molar ratio of the reaction raw materials 3, 7-dimethyl-2, 6-octadienal, aniline or substituted aniline, phosphorous acid and acidic catalyst is 1:1:1: 0.05.
8. The method of claim 2, wherein the temperature of the reaction system is increased to 120 ℃ to 150 ℃ after the 3, 7-dimethyl-2, 6-octadienal is added dropwise.
9. The process according to claim 8, wherein the temperature of the reaction system is increased to 130 ℃ after the addition of 3, 7-dimethyl-2, 6-octadienal is completed.
10. The method of claim 2 or 3, wherein the reaction time is 1 to 2 hours.
11. The method of claim 10, wherein the reaction time is 1.5 hours.
12. Use of an aminophosphonic acid compound as claimed in claim 1 or an aminophosphonic acid compound as prepared by a process as claimed in any one of claims 2 to 11 as a collector for flotation.
13. Use according to claim 12, characterized in that: the application is that the aminophosphonic acid compound is used as a flotation collector in the flotation process of ilmenite, bauxite, rare earth ore, fluorite ore or phosphorite.
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| CN111068926B (en) * | 2019-11-12 | 2021-06-29 | 中南大学 | Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent and preparation method and application thereof |
| CN111468306A (en) * | 2020-05-26 | 2020-07-31 | 河南天鸿选矿科技有限公司 | Fluorite ore flotation collecting agent |
| CN111482278B (en) * | 2020-06-03 | 2022-03-22 | 广东省资源综合利用研究所 | Copper oxide ore flotation method |
| CN112791859B (en) * | 2020-12-21 | 2022-07-19 | 湖南新田岭钨业有限公司 | Application of phosphoric acid amino acid compound |
| CN112808463B (en) * | 2020-12-30 | 2022-06-21 | 中南大学 | Medicament and method for flotation separation of iron-titanium ore and iron-containing gangue |
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