Preparation method and application of flotation reagent for collophanite

Abstract

The invention relates to a preparation method and application of a collophanite flotation reagent, illegal cooking oil is used as a raw material, filtration and impurity removal are performed, the filtered illegal cooking oil is saponified to prepare fatty acid soap, and the saponified fatty acid soap is mixed with a surfactant to prepare a collophanite flotation collector. The swill-cooked dirty oil is turned into wealth, the environment is protected, the prepared flotation reagent and the surface active agent are mixed to be applied to the flotation process, the selectivity and the collecting performance of phosphorite in flotation can be obviously enhanced, efficient recovery of phosphorite is achieved, the technological process is simple and efficient, the sorting index is excellent, and good application prospects are achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral processing, and in particular relates to a method for preparing a flotation agent for collophanite and application thereof. Background Art

[0002] my country has large reserves of phosphate resources, but there are few high-quality phosphate ores that can be truly utilized. With the increase in demand for phosphate, rich and easy-to-select phosphate resources are becoming increasingly depleted, making the development and utilization of phosphate resources increasingly urgent. In order to meet the requirements of national sustainable development, it is urgent to strengthen the optimization of the beneficiation process and the development of collectors for large reserves of difficult-to-select phosphate ores. At present, fatty acid collectors are mostly used in phosphate flotation. Fossil raw materials and edible oils are used as the main flotation collectors at home and abroad, but the consumption of these collectors is generally large. In recent years, with the increase in raw material costs, the selection of waste oils for the preparation of fatty acids has also received increasing attention. It is very important to find a low-cost, safe and reliable raw material research and development of a new flotation agent with excellent performance.

[0003] Patent CN103555430A discloses a flotation collector prepared by simple filtration, saponification and salting out of waste oil or swill, which can reduce the ash content of clean coal and increase the calorific value of coal when used in coal preparation, but the flotation collector prepared by this method has certain requirements on the pulp temperature when applied in phosphate ore. Patent CN102240602B discloses a mixed fatty acid collector prepared by using waste oil as raw material, which is used for flotation desiliconization of iron ore at room temperature, can achieve good technical indicators and reduce the loss of concentrate. However, the collector prepared by this method has the disadvantages of poor dispersion in water, needing emulsification and poor tolerance to hard water, and needs to be floated at room temperature. Patent CN103394414A discloses a pretreatment of waste oil such as heating, filtering, precipitation, dehydration, etc., and then adding specific components to carry out saponification reaction to obtain a carbonate mineral collector for reverse flotation of collophanite. By adding 300-500 g / t of waste oil saponification product to the reverse flotation carbonate minerals with a MgO content of 3-7% in low-grade collophanite, high-quality phosphate concentrate with a MgO content of less than 1% can be obtained, and the MgO removal rate is greater than 80%. However, it is difficult to produce industrially due to the limitations of separation technology.

[0004] In addition to the above patents, there are still the following problems in the preparation of flotation reagents for waste oil: (1) The sources of waste cooking oil are complex and diverse, and there are large differences in composition and properties, which brings difficulties to the design and application of collectors.

[0005] (2) Waste cooking oil often contains a large amount of impurities and toxic and harmful substances, which places higher requirements on the selectivity and stability of the collector.

[0006] (3) The low efficiency of separation technology in the waste cooking oil recovery process also restricts the application effect of collectors.

[0007] At present, there are many types of collectors and compounding technologies in the flotation reagents of collophosphate, but the collectors that are truly successfully applied in production are still limited. Due to the insufficient selectivity and collection capacity of the collectors, as well as the high cost, it is economically unreasonable and not conducive to large-scale application. Among them, waste cooking oil, as a waste resource, has the characteristics of low price, wide source of raw materials, and easy processing and purification, but the current utilization rate is not high and needs further research and utilization. Summary of the invention In order to solve the above problems, the present invention aims to provide a method for preparing a flotation agent for collophosphite and its application. The present invention uses waste oil, which is a cheap raw material, to prepare a flotation agent, promotes the pollution control and comprehensive utilization of waste oil, improves the properties of the agent, improves the technical and economic indicators of flotation, and has broad practical significance for the comprehensive utilization of phosphate resources.

[0008] The technical solution of the present invention is as follows: In view of the difficulties existing in the prior art, the purpose of the present invention is to provide a method for preparing a flotation agent for collophanite and its application, which has solved the problems raised in the above background.

[0009] In order to solve the above technical problems, the present invention provides the following technical solutions: A method for preparing a flotation agent for collophanite and a collector for use therein, the method comprising the following steps: Step 1: remove impurities, separate and purify waste cooking oil; Step 2: Take 30 parts by weight of filtered waste oil and 15-30 parts by weight of 95% ethanol, pour them into a 100 ml three-necked flask, stir and heat; after rising to a certain temperature, add the prepared sodium hydroxide solution dropwise, heat and saponify at a constant temperature of 85°C for a certain period of time, cool the liquid, and obtain the desired collector.

[0010] In the step 1, a filter with a mesh diameter of 25 to 50 meshes is first used to preliminarily remove large particle impurities of the waste oil; then the waste oil is placed in a steam preheating tank for heating to separate the heavy components, and the heating temperature is maintained between 40° C. and 50° C.; the remaining light phase and impurities are removed by a filter with a particle size of 100 to 150 meshes; finally, the filtered waste oil is separated from oil and water by an oil-water separator to obtain purified waste oil.

[0011] Preferably, the stirring rate in the preparation step 2 is 300 r / min.

[0012] Preferably, the heating method in the preparation step 2 is water heating and the temperature is 85°C.

[0013] Preferably, the concentration of the sodium hydroxide solution in the preparation step 2 is 40%, and the dropping time is 20 minutes.

[0014] Preferably, the constant temperature in the preparation step 2 is 85°C.

[0015] Preferably, the saponification time in the preparation step 2 is 30 min.

[0016] The anionic surfactant is at least one of sodium sulfonate, palmitic acid, sodium linoleate, sodium stearate, stearic acid, sodium oleate, acetic acid, and dodecyl phosphate.

[0017] Preferably, the weight ratio of the waste oil to ethanol and polyoxyethylene ether is 30:18:12.

[0018] Furthermore, a method for preparing a flotation agent for collophanite and an application method thereof are provided, comprising the following steps: S1. Grinding a single portion of 400 g of apatite ore; S2. The pulp is introduced into a 1L single tank flotation machine, water is added, stirred, and the pH is adjusted; S3. Adding a composite flotation agent aqueous solution to the pH-adjusted slurry; S4. Aeration is used for reverse flotation roughing to obtain concentrate and tailings.

[0019] Preferably, the grinding particle size of the collophanite ore is -0.074 mm, accounting for 59% to 63%.

[0020] Preferably, the pH range is 7 to 10.

[0021] The additive adjusting agent is at least one of sulfuric acid and phosphoric acid.

[0022] Preferably, the mass ratio of the homemade fatty acid soap from waste oil to the surfactant is 4:6-8:2 Preferably, the concentration of the collector aqueous solution is 600 g / t, and the concentration of the ore pulp is 20% to 40%.

[0023] Compared with the prior art, the present invention has the following beneficial effects: 1. Compared with the existing collector, the fatty acid soap new agent prepared from waste cooking oil as raw material has good solubility, strong selectivity, and certain low temperature resistance, which can effectively improve the flotation effect; it has a wide pH range, small dosage, low cost, and is also easy to promote on a large scale. The present invention provides a solution for realizing the recycling of waste cooking oil.

[0024] 2. Adding a small amount of other types of surfactants to the fatty acid collector for flotation of phosphate ore, the surfactant effect of the resulting composite system is better than the performance of each component; at the same time, the problem of poor flotation effect of a single fatty acid collector is solved.

[0025] 3. The raw materials of homemade flotation agents are widely available and low in cost. When used in combination with other types of surfactants, it can further improve the flotation effect and reduce the cost of agents. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is the flotation reagent system and flow chart.

[0027] Figure 2 This is the experimental result of implementation case 1 in the present invention.

[0028] Figure 3 This is the experimental result of implementation case 2 in the present invention. DETAILED DESCRIPTION

[0029] The following will be combined with the specific embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. The embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work belong to the protection scope of the present invention.

[0030] In the context of this specification, except for the contents explicitly described, any matters or items not mentioned directly use the technology known in the art. Moreover, any embodiment described in this patent can be freely combined with one or more other embodiments described in this patent, and the technical solutions or technical ideas formed thereby are regarded as part of the original disclosure or original record of the present invention, and should not be regarded as new content not disclosed in this patent, unless a person skilled in the art considers that the combination is obviously unreasonable.

[0031] The data points disclosed in the present invention include not only the specifically disclosed numerical points, but also the endpoints of each numerical range. Any combination of these data points should be regarded as the disclosed or recorded range of the present invention, regardless of whether these numerical points are disclosed one by one in this article.

[0032] A carbonate-type collophanite in Hubei was selected, and the original ore P2O5 content was 21.37%, SiO2 content was 27.81, and MgO content was 5.26%. According to the liquid-solid ratio of 1:2, the ore sample and water were put into a ball mill for grinding until the grinding fineness of -0.074mm accounted for 60%. Example The standard method for determining the content of phosphorus pentoxide (P2O5) in phosphate ore is GB / T223.3-1988 ammonium phosphomolybdate volumetric method, and the content of magnesium oxide (MgO) in phosphate ore is determined by GB / T1871.5-2022 volumetric method.

[0033] The preparation method of the medicament in the embodiment comprises the following steps: The method for preparing homemade fatty acid soap comprises the following steps: Step 1: remove impurities, separate and purify waste cooking oil; Step 2: Stir and heat the waste oil treated in step 1; add the prepared sodium hydroxide solution dropwise to the waste oil until it rises, heat and saponify at a constant temperature, cool the liquid to obtain a homemade fatty acid soap, and compound the fatty acid soap obtained by saponification with a surfactant to obtain a flotation collector.

[0034] In the step 1, a filter with a mesh diameter of 40 meshes is used to preliminarily remove large particle impurities of the waste oil; then the waste oil is placed in a steam preheating tank for heating to separate the heavy components, and the heating temperature is maintained at 45° C.; the remaining light phase and impurities are removed by a filter with a particle size of 100 meshes; finally, the filtered waste oil is separated from the oil by an oil-water separator to obtain purified waste oil.

[0035] In step 2, ethanol and polyoxyethylene ether are further added to the waste oil treated in step 1, and the weight ratio of waste oil to ethanol and polyoxyethylene ether is 30:18:12; preferably, the concentration of ethanol is 95%.

[0036] In step 2, the stirring rate is 250 r / min; the heating method is water bath heating, and sodium hydroxide solution is added dropwise after the temperature rises to 80°C.

[0037] In step 2, the concentration of the sodium hydroxide solution is 25%, and the dropping time is 20 min.

[0038] In step 2, the constant temperature is 85° C. and the saponification time is 40 min. Preparation of comparative fatty acid soap 1: The preparation method is based on the above-mentioned homemade fatty acid soap method 1, except that in step 1, ethanol and polyoxyethylene ether are not added, and the rest is the same as example 1 to obtain comparative fatty acid soap 1.

[0039] Preparation of comparative fatty acid soap 2: The preparation method is based on the above-mentioned homemade fatty acid soap method 1, except that in step 1, no polyoxyethylene ether is added, and the rest is the same as example 1 to obtain comparative fatty acid soap 2.

[0040] Preparation of comparative fatty acid soap 3: The preparation method is based on the above-mentioned homemade fatty acid soap method 1, except that in step 1, ethanol is not added. The rest is the same as example 1, and a comparative fatty acid soap 3 is obtained. Example 1 The slurry is subjected to reverse flotation roughing, specifically: the above slurry is fed into the flotation machine, the slurry temperature is 25°C, dilute sulfuric acid is added, stirred for 1 minute, phosphoric acid is added and stirred for 1 minute, and collector is added and stirred for 3 minutes for flotation roughing. Relative to the original collophanite ore, the amount of dilute sulfuric acid is 900g / t, the amount of phosphoric acid is 500g / t, and the amount of single self-made agent (not used in proportion with surfactant) is 100g / t, 250g / t, 400g / t, 500g / t, 600g / t, 700g / t, 950 g / t, respectively, to obtain roughing concentrate and roughing tailings. The test flow chart is as follows Figure 1 The test results are as follows Figure 2 shown.

[0041] It can be seen from Example 1 that as the concentration of the synthetic agent increases, the increase in the apatite recovery rate gradually tends to be flat, and the phosphorus grade first increases and then decreases. When the collector concentration is 600 mg / L, the apatite recovery rate is as high as 90.74%, and the concentrate grade is 26.86%, indicating that the homemade agent has good sorting properties, and the recovery rate and mineral processing efficiency are ideal.

[0042] Example 2 The ore pulp is subjected to reverse flotation roughing, specifically: the above ore pulp is fed into the flotation machine, the ore pulp temperature is 25°C, dilute sulfuric acid is added, stirred for 1 minute, phosphoric acid is added and stirred for 1 minute, and collector is added and stirred for 3 minutes for flotation roughing. Relative to the original collophanite ore, the dosage of the self-made agent (not used in proportion with surfactant) is 600g / t, and the ore pulp pH is set to 2, 4, 6, 8, 9, 10, 11, 12, and roughing concentrate and roughing tailings are obtained. The test flow chart is as follows Figure 1 The test results are as follows Figure 3 shown.

[0043] It can be seen from Example 2 that when the inhibitor is in the pH range of 4 to 10, the apatite recovery rate is basically maintained at about 90%, indicating that the homemade agent has a good separation effect on collophanite and dolomite in a wider pH range and is highly practical.

[0044] Example 3 Under the optimal conditions, the pulp is subjected to reverse flotation roughing, specifically: the above pulp is fed into the flotation machine, the pulp temperature is 25°C, dilute sulfuric acid is added, stirred for 1 min, phosphoric acid is added and stirred for 1 min, and collector is added and stirred for 3 min for flotation roughing. Relative to the original collophanite ore, the amount of dilute sulfuric acid is 950g / t, the amount of phosphoric acid is 500g / t, the composite collector is used at an amount of 500g / t, the mass ratio of the selected fatty acid soap (obtained by the above fatty acid soap preparation method) and the surfactant sodium linoleate is 7:3, and the amount of the agent used when sodium linoleate is used alone is 500g / t, and roughing concentrate and roughing tailings are obtained. The test results are shown in Table 2.

[0045] Table 1 Comparative test results of reagent flotation

[0046] The test results show that the final P2O5 grade in the above embodiment is 27.39%, the MgO content is 0.97%, the overall phosphorus recovery rate is 89.81%, and the sorting index is relatively ideal. As shown in Table 1, the mixed use of the homemade fatty acid soap and sodium linoleate in the present invention not only saves costs compared with the single use of sodium linoleate, but also has better capture capacity and practicality, and has a higher application value.

[0047] Example 4 Under the optimal conditions, the pulp is subjected to reverse flotation roughing, specifically: the above pulp is fed into the flotation machine, the pulp temperature is 25°C, dilute sulfuric acid is added, stirred for 1 min, phosphoric acid is added and stirred for 1 min, and collector is added and stirred for 3 min for flotation roughing. Wherein, relative to the original collophanite ore, the amount of dilute sulfuric acid is 1.0 kg / t, the amount of phosphoric acid is 550 g / t, the composite collector is used at an amount of 550 g / t, the mass ratio of the selected fatty acid soap (obtained by the above fatty acid soap preparation method) and the surfactant sodium oleate is 6:4, and the amount of the agent used when sodium oleate is used alone is 550 g / t, and the roughing concentrate and roughing tailings are obtained. The test results are shown in Table 3. Table 3 Comparative test results of reagent flotation

[0048] After compounding with homemade fatty acid soap, the phosphorus grade in the concentrate and the concentrate recovery rate were significantly improved, and the magnesium removal rate was also improved.

[0049] Example 5 Under the optimal conditions, the pulp is subjected to reverse flotation roughing, specifically: the above pulp is fed into the flotation machine, dilute sulfuric acid is added, the pulp temperature is 25°C, stirred for 1 min, phosphoric acid is added and stirred for 1 min, and collector is added and stirred for 3 min for flotation roughing. Relative to the original collophanite ore, the amount of dilute sulfuric acid is 850g / t, the amount of phosphoric acid is 500g / t, the composite collector is used at an amount of 600g / t, the mass ratio of the selected fatty acid soap (obtained by the above fatty acid soap preparation method) and the surfactant sodium stearate is 6:4, and the dosage of the agent when sodium stearate is used alone is 600g / t, and the roughing concentrate and roughing tailings are obtained. The test results are shown in Table 4. Table 4 Comparative test results of reagent flotation

[0050] It can be seen from Table 4 that the self-made fatty acid soap and sodium stearate compound of the present invention has a stronger capture ability and better solubility and dispersibility than the single use of sodium stearate under the same drug system. It proves that the capture ability and practicality of the drug of the present invention are better when mixed with anionic surfactants, and it has a higher application value.

[0051] Example 6 Under the optimal conditions, the pulp was subjected to reverse flotation roughing, specifically: the above pulp was fed into the flotation machine, the pulp temperature was 20°C, dilute sulfuric acid was added, stirred for 1 min, phosphoric acid was added and stirred for 1 min, and collector was added and stirred for 3 min for flotation roughing. Relative to the original collophanite ore, the amount of dilute sulfuric acid was 950g / t, the amount of phosphoric acid was 400g / t, the composite collector was used at an amount of 630g / t, the mass ratio of the selected fatty acid soap (obtained by the above fatty acid soap preparation method) and the surfactant palmitic acid was 8:2, and the amount of the agent used when palmitic acid was used alone was 630g / t, and roughing concentrate and roughing tailings were obtained. The test results are shown in Table 5.

[0052] Table 5 Comparative test results of reagent flotation

[0053] Compared with palmitic acid alone, the use of homemade fatty acid soap mixed with palmitic acid has a higher MgO removal effect, improved capture performance, increased selectivity, while reducing the amount of reagents used and saving costs.

[0054] Example 7 Under the optimal conditions, the pulp is subjected to reverse flotation roughing, specifically: the above pulp is fed into the flotation machine, dilute sulfuric acid is added and stirred for 1 min, phosphoric acid is added and stirred for 1 min, and collector is added and stirred for 3 min for flotation roughing. Relative to the original collophanite ore, the amount of dilute sulfuric acid is 1.0 g / t, the amount of phosphoric acid is 550 g / t, the collector is used at 550 g / t, the collector is selected from the prepared fatty acid soap (obtained by the above fatty acid soap preparation method) and the surfactant in a mass ratio of 6:4, and in the comparative collector: the mass ratio of the comparative fatty acid soap 1-3 and the surfactant (sodium oleate) is 6:4, and the dosage of the surfactant when used alone is 550 g / t, and the roughing concentrate and roughing tailings are obtained. The test results are shown in Table 5.

[0055] Table 6 Comparative test results of reagent flotation temperature

[0056] From the data in Table 6, it can be seen that under low temperature conditions, the self-made fatty acid soap compound agent is better than the comparative fatty acid soap compound agent and the single use. This is because ethanol and polyoxyethylene ether are added in the synthesis of the self-made fatty acid soap, which accelerates the saponification reaction and improves the reaction efficiency in the synthetic fatty acid soap of grease, reduces the interfacial tension, and enables the grease to be better dispersed in water. It is unexpectedly found that the above scheme can make the agent of the present invention have a low melting point, dissolve in water at low temperature, and the prepared aqueous solution is not easy to gel during long-term storage at low temperature, which is suitable for use under low temperature conditions. In addition, by using it in combination with a surfactant, the co-toxicity coefficient can be further improved, and the low temperature resistance of the flotation agent can be effectively improved, so that a good flotation effect can be maintained under low temperature conditions.

[0057] The technical solution of the present invention is explained through the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above specific embodiments to be implemented. Any improvements made by technicians in the relevant field based on the present invention, or equivalent replacement of the materials selected by the present invention, etc., fall within the scope of protection of the patent.

Claims

1. A method for preparing a flotation agent, characterized in that: The method comprises the following steps: Step 1: remove impurities, separate and purify waste cooking oil; Step 2: Stir and heat the waste oil treated in step 1, add sodium hydroxide solution dropwise when it rises, heat and saponify at a constant temperature, cool the liquid to obtain fatty acid soap, and compound the fatty acid soap obtained by saponification with a surfactant to prepare a flotation collector.

2. The method for preparing a flotation agent for collophanite according to claim 1, characterized in that: In the step 1, a filter with a mesh diameter of 25-50 mesh is used to preliminarily remove large particle impurities of the waste oil; then the waste oil is placed in a steam preheating tank for heating to separate the heavy components, and the heating temperature is maintained at 40° C.-50° C.; the remaining light phase and impurities are removed by a filter with a particle size of 100-150 mesh; finally, the filtered waste oil is separated from oil and water by an oil-water separator to obtain purified waste oil.

3. The method for preparing a flotation agent for collophanite according to claim 1, characterized in that: In the preparation step 2, ethanol is added to the waste oil treated in step 1, and then stirred and heated, and the weight ratio of waste oil to ethanol and polyoxyethylene ether is 30: (15-32); preferably, the concentration of ethanol is 75-95%; Preferably, polyoxyethylene ether should also be added to the waste cooking oil after treatment in step 1, and the weight ratio of waste cooking oil to polyoxyethylene ether is 30: (10-20).

4. The method for preparing a flotation agent for collophanite according to claim 1, characterized in that: In the preparation step 2, the stirring rate is 100 r / min-350 r / min; the heating method is water bath heating, and sodium hydroxide solution is added dropwise after the temperature rises to 75° C.-85° C.

5. The method for preparing a flotation agent for collophanite according to claim 1, characterized in that: In the step 2, the concentration of the sodium hydroxide solution is 20% to 45%, and the dropping time is 10 min to 30 min.

6. The method for preparing a flotation agent for collophanite according to claim 1, characterized in that: In the step 2, the constant temperature is 85° C. and the saponification time is 10 min to 60 min.

7. The method for preparing a flotation agent for collophanite according to claim 1, characterized in that: The surfactant is at least one of sodium sulfonate, palmitic acid, sodium linoleate, sodium stearate, stearic acid, sodium oleate, acetic acid, and dodecyl phosphate; preferably, the mass ratio of fatty acid soap to surfactant is (6-9): (1-4).

8. A flotation agent obtained by the flotation agent preparation method as claimed in any one of claims 1 to 7, which is used in the flotation of collophanite.

9. The use according to claim 8, characterized in that: The following steps are involved: S1: grinding the apatite ore; S2. The pulp is introduced into a single tank flotation machine, water is added, stirred, and the pH is adjusted; S3. Adding a composite flotation agent aqueous solution to the pH-adjusted slurry; S4. Aeration is used for reverse flotation roughing to obtain concentrate and tailings.

10. The use according to claim 9, characterized in that: The S1 collophanite ore grinding fine particle size -0.074mm accounts for 59%~63%; The pH range of S2 is 6-12, and the type of adjusting agent added is at least one of sulfuric acid and phosphoric acid; The concentration of S3 collector aqueous solution is 100~950g / t.

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