Preparation method of carboxylic acid collector, carboxylic acid collector prepared by the method and application of the carboxylic acid collector

Abstract

The application discloses a preparation method of a carboxylic acid collector, the carboxylic acid collector prepared by the method and application thereof, and belongs to the technical field of flotation in mineral processing engineering. The preparation method is as follows: uniformly mixing fatty acid raw materials and non-fatty acid raw materials to form mixed raw materials, adding sodium percarbonate after microwave pre-irradiation of the mixed raw materials, stirring and reacting under microwave irradiation, and performing microwave curing irradiation treatment after the reaction is completed to obtain the carboxylic acid collector. The fatty acid raw materials include a mixture of any one or more of plant-based fatty acids or animal-based fatty acids, and the non-fatty acid raw materials include a short carbon chain alcohol and an anionic cellulose ether. The preparation method is simple, convenient to operate, low in requirement for related equipment, and favorable for reducing production cost. The prepared carboxylic acid collector is good in selectivity, strong in collecting capacity, good in solubility and dispersibility in water, and capable of adapting to efficient flotation under normal temperature or low temperature conditions of minerals, and is suitable for application in flotation of oxidized ores.

Description

TECHNICAL FIELD

[0001] The application relates to a preparation method of a carboxylic acid collector, the prepared carboxylic acid collector and application, and belongs to the technical field of mineral processing engineering flotation. BACKGROUND

[0002] The mineral processing process mainly separates useful minerals and gangue minerals, and is a key link for obtaining qualified mineral raw material products, wherein flotation is one of the most widely used mineral processing methods. In the flotation process, the performance of the collector used directly relates to the flotation index. At present, the flotation collectors used in the oxidation ore industry are mainly fatty acids, and relatively widely used are oleic acid collectors and compound products thereof, for example, compound collectors taking soybean oil, rapeseed oil, cottonseed oil and the like as raw materials.

[0003] In the prior art, the main development trend of the compound collector in recent years is multifunctionalization, heteropolarity, non-ionization and mixed synergistic effect and the like. The mineral processing engineering practitioners have carried out a large amount of work in aspects such as mixing and compounding of different types of raw materials, functional group reaction and improvement of molecular polarity, and the performance of the flotation collector has been greatly improved since the end of the last century. However, due to the factors such as the weak selectivity of the source of the collector itself and the insufficient collecting capacity, the collectors used in the industrial production are still difficult to take into account the selectivity, collecting capacity and production cost and the like. Based on this situation, it is necessary to propose a preparation method of a collector taking into account the selectivity, collecting capacity and production cost, so as to obtain a collector with excellent performance. SUMMARY

[0004] The application aims at overcoming the defects of the prior art, and provides a preparation method of a carboxylic acid collector with low freezing point, good solubility and dispersibility in water, good flotation selectivity for specific minerals, strong collecting capacity, simple reaction preparation process and the like, and the application also provides the carboxylic acid collector prepared by the preparation method and application.

[0005] The application aims at overcoming the defects of the prior art, and provides a preparation method of a carboxylic acid collector with low freezing point, good solubility and dispersibility in water, good flotation selectivity for specific minerals, strong collecting capacity, simple reaction preparation process and the like, and the application also provides the carboxylic acid collector prepared by the preparation method and application.

[0006] Further, the mixed raw material comprises 70-90% of the fatty acid raw material and 10-30% of the non-fatty acid raw material in percentage by mass.

[0007] Further, the short carbon chain alcohol accounts for 5-15% of the mixed raw materials by mass percentage, and the anionic cellulose ether accounts for 5-15% of the mixed raw materials by mass percentage.

[0008] Further, the fatty acid raw material includes 5-10% of C8-C16 carboxylic acid, 5-15% of linoleic acid, 20-50% of oleic acid, 5-10% of stearic acid and 15-25% of ester compound by mass percentage.

[0009] Further, the mass ratio of the mixed raw material to sodium percarbonate is 8-9:1-2.

[0010] Further, the sodium percarbonate is a mixture of powdered sodium percarbonate and granular sodium percarbonate, and the ratio of the powdered sodium percarbonate to the granular sodium percarbonate is 0.6-2:1.

[0011] Further, heating and stirring are performed during the mixing of the fatty acid raw material and the non-fatty acid raw material, and the temperature of the mixed raw material is heated to 120-150°C.

[0012] Further, the microwave pre-irradiation is an irradiation reaction under stirring at 120-150°C, the microwave pre-irradiation frequency is 1-10GHz, the microwave pre-irradiation microwave power is 0.5-5KW, and the microwave pre-irradiation time is 0.5-2h.

[0013] Further, the microwave irradiation under stirring reaction temperature is 120-150°C, the microwave irradiation frequency is 10-50GHz, the microwave irradiation microwave power is 4-10KW, and the microwave irradiation time is 3-6h.

[0014] Further, the microwave curing irradiation treatment reduces the temperature to 60-100°C, the microwave curing irradiation frequency is 1-20GHz, the microwave curing irradiation microwave power is 0.5-6KW, and the microwave curing irradiation time is 1-2h.

[0015] The application also provides a carboxylic acid collector prepared by the preparation method of the carboxylic acid collector.

[0016] Further, the component includes the following structural formula:

[0017] Or ;

[0018] In the formula, R is a C5-C 30 hydrocarbon group.

[0019] The application also provides the use of the carboxylic acid collector for floating oxide ore.

[0020] The beneficial effects of the present application are:

[0021] 1) The present application is based on the microwave mechanism to prepare carboxylic acid collector. The carboxylic acid collector product is prepared by the oxidation reaction of the mixed raw material containing fatty acid under microwave irradiation and sodium percarbonate. The high frequency vibration effect of molecules under microwave irradiation promotes the reaction of oxidation addition peroxide group between the phase interface, thereby improving the performance of the collector, increasing the selectivity and collecting ability of the collector, and improving and increasing the flotation recovery and flotation concentrate grade. At the same time, the sodium ions after the dissolution of sodium carbonate and the carboxyl groups of the organic phase interact, greatly improving the solubility and low temperature resistance of the collector, so as to reduce the requirements for application conditions and application environment in application.

[0022] 2) The sodium percarbonate used in the present application is a strong oxidant. By using a mixture of powdered sodium percarbonate and granular sodium percarbonate, it can be slowly dissolved and reacted in the organic phase after adding the mixed raw material, which is beneficial to improve the safety of the preparation process and reduce the requirements for related equipment in the preparation process, thereby reducing the production cost.

[0023] 3) The carboxylic acid collector prepared by the present application has low freezing point, good solubility and dispersibility in water, good selectivity for specific mineral flotation, strong collecting ability, and can adapt to high-efficiency flotation under normal temperature (about 25℃) and low temperature (about 10℃) conditions of minerals. DETAILED DESCRIPTION

[0024] The technical solutions of the present application will be described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0025] The application provides a technical scheme: a preparation method of a carboxylic acid collector, which comprises the following steps: uniformly mixing fatty acid raw materials and non-fatty acid raw materials to form mixed raw materials. The fatty acid raw materials include any one or a mixture of multiple of plant-based fatty acids or animal-based fatty acids. For example, the plant-based fatty acids can be any one or multiple of palm oil fatty acids, cottonseed oil fatty acids, rice bran oil fatty acids, coconut oil fatty acids or tall oil fatty acids, and the animal-based fatty acids can be any one or multiple of ox and sheep oil fatty acids or hogwash oil fatty acids. In a preferred embodiment, the fatty acid raw materials include 5-10% of C8-C16 carboxylic acids, 5-15% of linoleic acid, 20-50% of oleic acid, 5-10% of stearic acid and 15-25% of ester compounds in terms of mass percentage. The non-fatty acid raw materials include short-chain alcohol and anionic cellulose ether. The short-chain alcohol can increase the molecular polarity of the mixed raw materials, and the short-chain alcohol refers to alcohol with a carbon chain length of 1-6 carbon atoms, such as glycerol. The anionic cellulose ether can improve the sol emulsion capacity of the fatty acid, and the anionic cellulose ether is sodium carboxymethyl cellulose. The plant-based fatty acids or animal-based fatty acids used in the embodiments of the application are all derived from industrial products, and the product purity (effective content of carboxylic acid) is greater than or equal to 50%. The non-carboxylic acid raw materials used are industrial products, and the product purity is greater than or equal to 90%.

[0026] In a preferred embodiment, the mixed raw materials include 70-90% of the fatty acid raw materials and 10-30% of the non-fatty acid raw materials in terms of mass percentage, the short-chain alcohol accounts for 5-15% of the mixed raw materials, and the anionic cellulose ether accounts for 5-15% of the mixed raw materials. The process of mixing the fatty acid raw materials and the non-fatty acid raw materials to form the mixed raw materials comprises the following steps: adding the fatty acid raw materials and the non-fatty acid raw materials into a reaction container, starting stirring and heating, maintaining the stirring speed at 5-15 revolutions per minute, maintaining the temperature rising rate at 1-3 ℃ / min until the material temperature rises to 120-150 ℃, and obtaining the mixed raw materials. The reaction container used in the embodiment is a closed container that can only discharge outward in one direction, and the reaction container has non-contact heating and insulation functions and stirring functions. The stirring speed of the stirrer is 0-50 revolutions per minute, and the reaction container is provided with a microwave generating device.

[0027] The process of microwave pre-irradiation of the mixed raw materials comprises the following steps: stirring and irradiation reaction at 120-150 ℃, the stirring speed is 5-15 revolutions per minute, the microwave pre-irradiation frequency is 1-10 GHz, the microwave pre-irradiation power is 0.5-5 KW, and the microwave pre-irradiation time is 0.5-2 h.

[0028] Then add sodium percarbonate, here the mass ratio of the mixed raw materials to sodium percarbonate is 8-9:1-2. And the added sodium percarbonate is a mixture of powdered sodium percarbonate and granular sodium percarbonate, and the ratio of powdered sodium percarbonate to granular sodium percarbonate is 0.6-2:1. After adding, stirring and reaction under microwave irradiation, the specific process is: the material temperature is maintained at 120-150℃, the stirring speed is 20-50 revolutions / minute, the microwave irradiation frequency is 10-50GHz, the microwave irradiation power is 4-10KW, and the microwave irradiation time is 3-6h.

[0029] After the reaction is completed, microwave aging irradiation treatment is carried out, and the specific process is: the material temperature is lowered to 60-100℃ at a cooling rate of 1-3℃ / min, the stirring speed is maintained at 10-30 revolutions / minute, the microwave aging irradiation frequency is 1-20GHz, the microwave aging irradiation power is 0.5-6KW, and the microwave aging irradiation time is 1-2h.

[0030] The application also provides a carboxylic acid collector prepared by the preparation method of the carboxylic acid collector.

[0031] Or ;

[0032] In the formula, R is a C5-C 30 hydrocarbon group.

[0033] The carboxylic acid collector prepared by the application is used for floating various oxide ores, such as scheelite, spodumene, cassiterite and phosphate rock.

[0034] Example one

[0035] The application provides a preparation method of a carboxylic acid collector, which comprises the following steps.

[0036] Preparation of mixed raw materials: 70 parts of industrial animal and plant-based fatty acid raw materials and 10 parts of non-fatty acid raw materials are weighed according to the mass fraction. The industrial animal and plant-based fatty acid raw materials used in this example include 30 parts of gutter oil fatty acid, 20 parts of tar oil fatty acid and 20 parts of cottonseed oil fatty acid. The non-fatty acid raw materials used in this example include 5 parts of glycerol and 5 parts of hydroxyethyl cellulose sodium. The industrial animal and plant-based fatty acid raw materials and the non-fatty acid raw materials are added together into a reaction container, and stirring and heating are started. The stirring speed is 10 revolutions / minute, the temperature rising rate is 3℃ / min, and the temperature is raised to 120℃.

[0037] Microwave pre-irradiation: after the material temperature reaches 120℃, microwave pre-irradiation is started. The pre-irradiation frequency in this example is 5GHz, the microwave power is 1KW, and the irradiation time is 2h. During the pre-irradiation process, the stirring speed is maintained at 10 revolutions / minute.

[0038] Irradiation reaction: 20 parts of sodium percarbonate were weighed into the reaction vessel. The sodium percarbonate used in this example was a mixture of powdered and granular products, with a mixing ratio of 1:1 between the powdered and granular sodium percarbonate. After addition, the material temperature was maintained at 120°C, the stirring speed was 50 rpm, the microwave irradiation frequency was 30 GHz, the microwave power was 10 KW, and the irradiation time was 6 h.

[0039] Microwave maturation irradiation treatment: After the irradiation reaction, the microwave irradiation frequency was reduced to 10 GHz, the microwave power was reduced to 2 KW, and the irradiation time was 2 h. During this process, the stirring speed was 20 rpm, and the material temperature was reduced to 60°C at a rate of 2°C / min. After the reaction was completed, the carboxylic acid collector product was obtained.

[0040] Example Two

[0041] The main difference between this example and Example One is that the mixed raw materials of this example include 75 parts of industrial-grade animal and plant-based fatty acid raw materials and 10 parts of non-fatty acid raw materials, wherein the industrial-grade animal and plant-based fatty acid raw materials use cottonseed oil fatty acids, and the non-fatty acid raw materials include 3 parts of ethylene glycol and 7 parts of sodium hydroxymethyl cellulose. The stirring speed of the mixture of industrial-grade animal and plant-based fatty acid raw materials and non-fatty acid raw materials was 12 rpm, the temperature was raised at a rate of 2°C / min, and the temperature was raised to 130°C. The pre-irradiation frequency in the microwave pre-irradiation stage was 8 GHz, the microwave power was 3 KW, the irradiation time was 1.5 h, and during the pre-irradiation process, the stirring speed was maintained at 15 rpm. The sodium percarbonate added in the irradiation reaction stage was 15 parts, wherein the mixing ratio of powdered sodium percarbonate to granular sodium percarbonate was 1.5:1. After addition, the material temperature was maintained at 150°C, the microwave irradiation frequency was 40 GHz, the microwave power was 10 KW, and the irradiation time was 6 h. In the microwave maturation irradiation stage, the microwave irradiation frequency was reduced to 15 GHz, the microwave power was reduced to 2 KW, and the irradiation time was 2 h. During this process, the stirring speed was 25 rpm.

[0042] Example Three

[0043] The difference between this embodiment and embodiment one is mainly that the mixed raw materials of this embodiment include 80 parts of industrial grade animal and plant based fatty acid raw materials and 20 parts of non-fatty acid raw materials, wherein the industrial grade animal and plant based fatty acid raw materials include 65 parts of coconut oil fatty acids and 15 parts of ox and sheep oil fatty acids, and the non-fatty acid raw materials include 12 parts of n-butanol and 8 parts of sodium hydroxymethyl cellulose. The stirring speed of the mixture of the industrial grade animal and plant based fatty acid raw materials and the non-fatty acid raw materials is 7 revolutions per minute, the temperature rising rate is 3 ℃ per minute, and the temperature is raised to 120 ℃. The pre-irradiation frequency in the microwave pre-irradiation stage is 3 GHz, the microwave power is 3 KW, and the irradiation time is 2 h. During the pre-irradiation process, the stirring speed is maintained at 15 revolutions per minute. The sodium percarbonate added in the irradiation reaction stage is 15 parts, wherein the mixing ratio of the powdery sodium percarbonate to the granular sodium percarbonate is 0.6:1. After the addition, the material temperature is maintained at 150 ℃, the microwave irradiation frequency is 50 GHz, the microwave power is 10 KW, and the irradiation time is 6 h. In the microwave aging irradiation stage, the microwave irradiation frequency is reduced to 5 GHz, the microwave power is reduced to 1 KW, and the irradiation time is 2 h. During this process, the stirring speed is 10 revolutions per minute, and the material temperature is reduced to 60 ℃ at a rate of 3 ℃ per minute.

[0044] Embodiment four

[0045] The difference between this embodiment and embodiment one is mainly that the mixed raw materials of this embodiment include 80 parts of industrial grade animal and plant based fatty acid raw materials and 20 parts of non-fatty acid raw materials, wherein the industrial grade animal and plant based fatty acid raw materials include 65 parts of coconut oil fatty acids and 15 parts of ox and sheep oil fatty acids, and the non-fatty acid raw materials include 12 parts of n-butanol and 8 parts of sodium hydroxymethyl cellulose. The stirring speed of the mixture of the industrial grade animal and plant based fatty acid raw materials and the non-fatty acid raw materials is 7 revolutions per minute, the temperature rising rate is 3 ℃ per minute, and the temperature is raised to 120 ℃. The pre-irradiation frequency in the microwave pre-irradiation stage is 3 GHz, the microwave power is 3 KW, and the irradiation time is 2 h. During the pre-irradiation process, the stirring speed is maintained at 15 revolutions per minute. The sodium percarbonate added in the irradiation reaction stage is 15 parts, wherein the mixing ratio of the powdery sodium percarbonate to the granular sodium percarbonate is 0.6:1. After the addition, the material temperature is maintained at 150 ℃, the microwave irradiation frequency is 50 GHz, the microwave power is 10 KW, and the irradiation time is 6 h. In the microwave aging irradiation stage, the microwave irradiation frequency is reduced to 5 GHz, the microwave power is reduced to 1 KW, and the irradiation time is 2 h. During this process, the stirring speed is 10 revolutions per minute, and the material temperature is reduced to 60 ℃ at a rate of 3 ℃ per minute.

[0046] Embodiment five

[0047] This embodiment provides an application of the carboxylic acid collector. The carboxylic acid collector of this embodiment is the carboxylic acid collector prepared in embodiment one, which is used for floating spodumene ore, and the sodium oleate collector (C 17 H 33NaOH as a comparison. The raw ore used in the test of the present example is a certain pegmatite type spodumene ore from Ganzi, Sichuan. The raw ore is subjected to a process of crushing-grinding-flotation (one-stage roughing), and the material fed into the flotation has a fineness of 70% passing 0.074 mm. The flotation is carried out under the condition that the pulp is adjusted to a pH value of 10-11 by sodium carbonate and sodium hydroxide, and the flotation results are shown in Table 1.

[0048] Table 1 Flotation results of spodumene ore by collector

[0049]

[0050] As shown in Table 1, the carboxylic acid collector prepared in Example 1 has good selectivity and strong collecting ability for minerals, greatly improves the concentrate Li2O grade and recovery rate, and has good implementation effect.

[0051] Example 6

[0052] The present example provides an application of a carboxylic acid collector. The carboxylic acid collector used in the present example is the carboxylic acid collector prepared in Example 2, which is used for flotation of phosphate ore, and sodium oleate (C 17 H 33 NaOH as a comparison. The raw ore used in the test of the present example is a certain pegmatite type spodumene ore from Ganzi, Sichuan. The raw ore is subjected to a process of crushing-grinding-flotation (one-stage roughing), and the material fed into the flotation has a fineness of 70% passing 0.074 mm. The flotation is carried out under the condition that the pulp is adjusted to a pH value of 10-11 by sodium carbonate and sodium hydroxide, and the flotation results are shown in Table 1.

[0053] Table 2 Flotation results of phosphate ore by collector

[0054]

[0055] As shown in Table 2, the carboxylic acid collector prepared in Example 2 can greatly reduce the MgO content in the concentrate, improve the P2O5 grade and recovery rate of the concentrate, compared with the traditional collector sodium oleate (C

[0056] Example 7

[0057] The present example provides an application of a carboxylic acid collector. The carboxylic acid collector used in the present example is the carboxylic acid collector prepared in Example 3, which is used for flotation of scheelite, and sodium oleate (C 17 H 33As a comparative example. The raw ore of the test example is a scheelite from Yunnan, and after crushing, grinding, desulfurization and decarbonization flotation, the raw ore is used as the feed ore of the example, and the material fed into the flotation has a fineness of 85% of -0.074 mm. After the slurry is treated by sodium carbonate and water glass to a pH value of 9-10, a closed circuit process of one roughing, three cleaning and two scavenging is used to obtain the flotation results shown in Table 3.

[0058] Table 3 Flotation results of scheelite flotation by collector

[0059]

[0060] As shown in Table 3, the carboxylic acid collector prepared in Example 3 has good selectivity and strong collecting ability for minerals, greatly improves the concentrate WO3 grade and recovery rate, and has good implementation effect.

[0061] The above is only the preferred embodiment of the present application, and it should be understood that the present application is not limited to the form disclosed herein, and should not be considered as excluding other embodiments, but can be used in various other combinations, modifications and environments, and can be modified within the scope of the present application by the above teachings or related art or knowledge. Any modification and change made by those skilled in the art without departing from the spirit and scope of the present application shall be within the protection scope of the appended claims of the present application.

Claims

1. A process for the preparation of a carboxylic acid collector characterised in that: The fatty acid raw material and the non-fatty acid raw material are mixed uniformly to form a mixed raw material, the mixed raw material is subjected to microwave pre-irradiation, then sodium percarbonate is added, and the mixed raw material is subjected to stirring reaction under microwave irradiation, and then microwave curing irradiation treatment is performed to obtain the carboxylic acid collector.

2. A process for the preparation of a carboxylic acid collector as claimed in claim 1, wherein: The mixed raw material contains 70-90% of the fatty acid raw material and 10-30% of the non-fatty acid raw material by mass percentage; the fatty acid raw material and the non-fatty acid raw material are mixed while being heated and stirred, and the temperature of the mixed raw material is heated to 120-150°C.

3. A process for the preparation of a carboxylic acid collector as claimed in claim 2, wherein: The short carbon chain alcohol accounts for 5-15% of the mixed raw material by mass percentage, and the anionic cellulose ether accounts for 5-15% of the mixed raw material by mass percentage.

4. The process for the preparation of a carboxylic acid collector as claimed in claim 1, wherein: The mass ratio of the mixed raw material to sodium percarbonate is 8-9:1-2.

5. The process for the preparation of a carboxylic acid collector as claimed in claim 1, wherein: The sodium percarbonate is a mixture of powdered sodium percarbonate and granular sodium percarbonate, and the ratio of the powdered sodium percarbonate to the granular sodium percarbonate is 0.6-2:

1.

6. A process for the preparation of a carboxylic acid collector as claimed in claim 1, wherein: The microwave pre-irradiation is stirring irradiation reaction at 120-150°C, the microwave pre-irradiation frequency is 1-10 GHz, the microwave pre-irradiation power is 0.5-5 KW, and the microwave pre-irradiation time is 0.5-2 h.

7. A process for the preparation of a carboxylic acid collector as claimed in claim 1, wherein: The temperature of the stirring reaction under microwave irradiation is 120-150°C, the microwave irradiation frequency is 10-50 GHz, the microwave irradiation power is 4-10 KW, and the microwave irradiation time is 3-6 h; the material temperature is reduced to 60-100°C by the microwave curing irradiation treatment, the microwave curing irradiation frequency is 1-20 GHz, the microwave curing irradiation power is 0.5-6 KW, and the microwave curing irradiation time is 1-2 h.

8. A carboxylic acid collector characterized by: The carboxylic acid collector is prepared by the preparation method of any one of claims 1-7.

9. A carboxylic acid collector according to claim 8, characterised in that: The component comprises the following structural formula: or ; wherein R is a C5to C 30 hydrocarbon group.

10. Use of a carboxylic acid collector according to claim 8 or 9, characterized in that: The component is used for floating oxide ore.

Images