Iron ore room temperature flotation ester carboxylic acid collector and application thereof
By using an ester-based carboxylic acid collector with the structure CnH2n+1-O-CO-R1-COOH in iron ore flotation, the problems of traditional collectors requiring heating and high reagent consumption are solved, achieving a high-efficiency separation effect with low reagent dosage at room temperature.
Patent Information
- Application Number
- CN202611087331.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-21
- Publication Date
- 2026-08-25
AI Technical Summary
In existing iron ore flotation processes, traditional anionic collectors require heating and have high reagent consumption, resulting in insufficient selectivity and difficulty in achieving efficient separation with low reagent dosage at room temperature.
An ester-based carboxylic acid collector for room-temperature flotation of iron ore with the structural formula CnH2n+1-O-CO-R1-COOH is synthesized by reacting it with diacids or anhydrides and alkyl alcohols in dichloromethane, achieving efficient separation with low reagent dosage.
Under room temperature conditions, it reduces reagent consumption by 5% to 20%, increases concentrate iron grade by 0.05% to 0.18%, reduces tailings iron grade by 0.10% to 0.28%, and maintains good harvesting and selectivity.
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Figure CN122625324A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to an ester-based carboxylic acid collector for room temperature flotation of iron ore and its application, belonging to the field of mineral processing reagents technology. Background Technology
[0002] Iron ore is an extremely important mineral, a basic raw material for the steel industry, and plays a prominent role in national economic development. With the increasing depletion of readily beneficiated rich iron ore resources, the efficient mining and utilization of iron ore faces enormous challenges. At the same time, improving iron ore beneficiation efficiency has received increasing attention. Foam flotation is one of the most important technologies for recovering useful minerals in mineral processing. For many years, reverse flotation technology has developed into an important process for separating low-grade iron ore. In iron ore reverse flotation, the collector is the core reagent for effectively separating iron minerals from gangue minerals. Among them, anionic collectors have long dominated due to their strong collecting ability and good separation indicators. However, traditional anionic collectors such as sodium oleate have drawbacks in practical applications, such as the need for pulp heating, high reagent consumption, and insufficient selectivity. Therefore, developing an anionic collector that can achieve low reagent dosage and high selective flotation separation at room temperature is the key to overcoming the current bottleneck in iron ore flotation reagents. Most of the iron ore anionic collectors of this invention are simple to synthesize, and can achieve efficient separation of iron ore with low reagent dosage at room temperature, which is of great significance for reducing mineral processing costs and saving energy consumption. Summary of the Invention
[0003] The purpose of this invention is to provide an ester-based carboxylic acid collector for room temperature flotation of iron ore and its application, which achieves good collection and selectivity for iron ore flotation at room temperature while reducing reagent dosage.
[0004] To achieve the objectives of this invention, the following technical solution is adopted: This invention provides a low-reagent-consumption anionic collector for room-temperature flotation of iron ore, the collector containing the structural formula: C n H 2n+1 The iron ore room temperature flotation ester carboxylic acid collector with the structure shown in -O-CO-R1-COOH, where R1 is C4H8, CH=CH or a benzene ring, and n is 8~12; Another aspect of the present invention provides a method for synthesizing an ester-based carboxylic acid collector for room temperature flotation of iron ore, the method comprising the following steps: A diacid or anhydride compound is placed in dichloromethane, and a catalyst and an alkyl alcohol compound are added. The alkyl alcohol compound reacts with the diacid or anhydride compound in the presence of the catalyst to produce a product as shown in formula C. n H 2n+1 Iron ore room temperature flotation ester carboxylic acid collector with the structure shown in -O-CO-R1-COOH.
[0005] In the above technical solution, further, the molar ratio of the alkyl alcohol to the diacid or anhydride compound in the step is 1:1.0 ~ 5.0, the reaction temperature is 20 ℃ ~ 40 ℃, and the reaction time is 2 h ~ 12 h.
[0006] The diacid or anhydride compound mentioned is adipic acid, maleic anhydride, or phthalic anhydride.
[0007] The room temperature mentioned refers to the slurry temperature of 5 ℃ to 40 ℃.
[0008] The aforementioned low drug consumption refers to a 5% to 20% reduction in the unit consumption of traditional fatty acid collectors compared to using this anionic collector alone or in combination with fatty acid collectors.
[0009] The iron ore room temperature flotation collector can be used alone or in combination with fatty acid collectors.
[0010] The present invention has the following advantages and beneficial effects: The preparation methods for most of the organic ester-based carboxylic acid compounds provided by this invention are simple. When the prepared organic ester-based carboxylic acid compounds are floated at room temperature, they exhibit collecting properties and selectivity for the target minerals comparable to or better than those of traditional fatty acids, requiring low reagent dosages. Using the organic ester-based carboxylic acid compounds described in this invention alone as collectors or in combination with fatty acids can reduce reagent consumption and achieve the separation of target iron minerals from gangue. Attached Figure Description
[0011] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the following description of the embodiments taken in conjunction with the accompanying drawings, wherein: Figure 1 The 1H NMR spectrum of 6-octyloxycarbonylhexanoic acid in Example 1; Figure 2 The 1H NMR spectrum of 4-octyloxycarbonylbutyric acid in Example 2; Figure 3 The 1H NMR spectrum of 4-dodecyloxycarbonylbutyric acid in Example 3; Figure 4 The 1H NMR spectrum of 2-octyloxycarbonylbenzoic acid in Example 4; Figure 5 The image shows the 1H NMR spectrum of 2-dodecyloxycarbonylbenzoic acid from Example 5. Detailed Implementation
[0012] The technical solutions in the embodiments of the present invention will be clearly and completely described below. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.
[0013] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.
[0014] Unless otherwise specified, the reagents and other materials used in the following examples can be prepared commercially or according to methods published in the literature.
[0015] In this document, unless otherwise defined, all technical and scientific terms used herein have the meanings commonly understood by one of ordinary skill in the art to which this invention pertains. Example
[0016] A method for synthesizing an ester-based carboxylic acid collector for room temperature flotation of iron ore, comprising the following steps: 0.03 mol EDC, 0.01 mol DMAP, and 0.06 mol DIPEA were added to a stirred solution of 0.10 mol adipic acid and 200 mL dichloromethane. The reaction mixture was stirred at 25 °C for 30 min, followed by the addition of 0.02 mol n-octanol. The mixture was then stirred at 25 °C for 10 h. 50 mL of water was added, and the mixture was extracted two to three times with dichloromethane. The organic layer was dried over anhydrous sodium sulfate and rotary evaporated to obtain the crude product. Elution with a petroleum ether / ethyl acetate gradient yielded the 6-octyloxycarbonylhexanoic acid anion collector. 1 ¹H NMR (600MHz, DMSO-d⁶) δ 0.85 (t, 3H), 1.24–1.26 (m, 10H), 1.49–1.55 (m, 6H), 2.19 (t, 2H), 2.27 (t, 2H), 4.00 (m, 2H), 11.97 (s, 1H). Its ¹H NMR spectrum is shown in the appendix. Figure 1 .
[0017] The structure of the synthesized compound is as follows:
[0018] Product performance: The laboratory used a flotation process with one rougher, one cleaner, and three scavengers to evaluate the reagents. Under the condition that the beneficiation indicators are qualified, compared with the iron ore collector used in the Dongshao beneficiation plant, the flotation temperature was 20 ℃, the iron grade of the concentrate increased by 0.10%, the iron grade of the tailings decreased by 0.13%, and the reagent consumption per unit decreased by 6%.
[0019] The laboratory used a flotation process with one rougher, one cleaner, and three scavengers to evaluate the reagents. Under the condition that the beneficiation indicators are qualified, compared with the iron ore collector used in the industrial beneficiation plant, the flotation temperature is 30 ℃, the iron grade of the concentrate is increased by 0.08%, the iron grade of the tailings is increased by 0.22%, and the reagent consumption is reduced by 5%. Example
[0020] A method for synthesizing an ester-based carboxylic acid collector for room temperature flotation of iron ore, comprising the following steps: 0.12 mol maleic anhydride and 120 mL dichloromethane were added to a round-bottom flask, followed by the sequential addition of 0.10 mol n-octanol, 0.01 mol DMAP, and 0.20 mol TEA. The mixture was stirred at 25 °C for 3 hours. After the reaction was stopped, the mixture was acidified with 1M hydrochloric acid and extracted with dichloromethane. The organic layer was washed three times with saturated brine, dried over anhydrous sodium sulfate, and rotary evaporated to obtain the crude product. The crude product was eluted with a petroleum ether / ethyl acetate gradient to obtain the 4-octyloxycarbonylbutyrate anion collector. 1 ¹H NMR (600MHz, DMSO-d⁶) δ 0.84 (t, 3H), 1.24–1.26 (m, 10H), 1.58 (p, 2H), 4.06 (t, 2H), 6.28–6.35 (dd, 2H). Its ¹H NMR spectrum is shown in the appendix. Figure 2 .
[0021] The structure of the synthesized compound is as follows:
[0022] Product performance: The laboratory used a flotation process with one rougher, one cleaner, and three scavengers to evaluate the reagents. Under the condition that the beneficiation indicators are qualified, compared with the iron ore collector used in the Dongshao beneficiation plant, the flotation temperature was 20 ℃, the iron grade of the concentrate increased by 0.12%, the iron grade of the tailings decreased by 0.15%, and the reagent consumption per unit decreased by 10%.
[0023] The laboratory used a flotation process with one rougher, one cleaner, and three scavengers to evaluate the reagents. Under the condition that the beneficiation indicators are qualified, compared with the iron ore collector used in the industrial beneficiation plant, the flotation temperature is 30 ℃, the iron grade of the concentrate is increased by 0.11%, the iron grade of the tailings is decreased by 0.17%, and the reagent consumption is reduced by 7%. Example
[0024] A method for synthesizing an ester-based carboxylic acid collector for room temperature flotation of iron ore, comprising the following steps: 0.12 mol maleic anhydride and 120 mL dichloromethane were added to a round-bottom flask, followed by the sequential addition of 0.10 mol dodecanol, 0.01 mol DMAP, and 0.20 mol TEA. The mixture was stirred at 25 °C for 3 hours. After the reaction was stopped, the mixture was acidified with 1M hydrochloric acid and extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate and rotary evaporated to obtain the crude product. Purification by pulping with petroleum ether yielded the 4-dodecyloxycarbonylbutyrate anion collector. 1¹H NMR (600MHz, CHCl³-d⁶) δ 0.87 (t, 3H), 1.25–1.37 (m, 18H), 1.71 (p, 2H), 4.27 (t, 2H), 6.36–6.47 (dd, 2H). Its ¹H NMR spectrum is shown in the appendix. Figure 3 .
[0025] The structure of the synthesized compound is as follows:
[0026] Product performance: The laboratory used a flotation process with one rougher, one cleaner, and three scavengers to evaluate the reagents. Under the condition that the beneficiation indicators were qualified, compared with the iron ore collector used in the Dongshao beneficiation plant, the flotation temperature was 20 ℃, the iron grade of the concentrate increased by 0.18%, the iron grade of the tailings decreased by 0.28%, and the reagent consumption per unit decreased by 16.5%.
[0027] The laboratory used a flotation process with one rougher, one cleaner, and three scavengers to evaluate the reagents. Under the condition that the beneficiation indicators are qualified, compared with the iron ore collector used in the industrial process at Anshan Qianxi Mineral Processing Plant, the flotation temperature was 30 ℃, the iron grade of the concentrate increased by 0.13%, the iron grade of the tailings decreased by 0.19%, and the reagent consumption per unit decreased by 9%.
[0028] A method for synthesizing an ester-based carboxylic acid collector for room temperature flotation of iron ore, comprising the following steps: 0.12 mol phthalic anhydride and 120 mL dichloromethane were added to a round-bottom flask, followed by 0.10 mol n-octanol, 0.01 mol DMAP, and 0.20 mol TEA. The mixture was stirred at 25 °C for 3 hours. After the reaction was stopped, 1 M hydrochloric acid was added to the mixture for acidification, followed by extraction with dichloromethane. The organic phase was then washed three times with saturated brine to obtain the crude product. The organic layer was washed three times with 5% sodium hydroxide solution and water, respectively. The organic layer was dried with anhydrous sodium sulfate and rotary evaporated to obtain the 2-octyloxycarbonylbenzoic acid anion collector. 1 ¹H NMR (600MHz, CHCl³⁻d⁶) δ 0.83 (t, 3H), 1.22–1.41 (m, 10H), 1.73 (p, 2H), 4.32 (t, 2H), 7.52–7.61 (m, 2H), 7.67 (d, 1H), 7.89 (d, 1H), 11.94 (s, 1H). Its ¹H NMR spectrum is shown in the appendix. Figure 4 .
[0029] The structure of the synthesized compound is as follows:
[0030] Product performance: The laboratory used a flotation process with one rougher, one cleaner, and three scavengers to evaluate the reagents. Under the condition that the beneficiation indicators are qualified, compared with the iron ore collector used in the Dongshao beneficiation plant, the flotation temperature was 20 ℃, the iron grade of the concentrate increased by 0.08%, the iron grade of the tailings decreased by 0.17%, and the reagent consumption per unit decreased by 5%.
[0031] The laboratory used a flotation process with one rougher, one cleaner, and three scavengers to evaluate the reagents. Under the condition that the beneficiation indicators are qualified, compared with the iron ore collector used in the industrial beneficiation plant, the flotation temperature is 30 ℃, the iron grade of the concentrate increases by 0.05%, the iron grade of the tailings decreases by 0.23%, and the reagent consumption per unit decreases by 5.5%.
[0032] A method for synthesizing an ester-based carboxylic acid collector for room temperature flotation of iron ore, comprising the following steps: 0.12 mol phthalic anhydride and 120 mL dichloromethane were added to a round-bottom flask, followed by 0.10 mol dodecanol, 0.01 mol DMAP, and 0.20 mol TEA. The mixture was stirred at 25 °C for 3 hours. After the reaction was stopped, the mixture was acidified with 1M hydrochloric acid and extracted with dichloromethane. The organic phase was then washed three times with saturated brine to obtain the crude product. The organic layer was washed three times with 5% sodium hydroxide solution and water, respectively. The organic layer was dried with anhydrous sodium sulfate and rotary evaporated to obtain the 2-dodecyloxycarbonylbenzoic acid anion collector. 1 ¹H NMR (600MHz, CHCl₃-d₆) δ 0.88 (t, 3H), 1.20–1.33 (m, 18H), 1.53–1.59 (m, 2H), 4.13 (t, 2H), 7.39–7.40 (m, 2H), 7.61–7.66 (m, 2H), 12.26 (s, 1H). Its ¹H NMR spectrum is shown in the appendix. Figure 5 .
[0033] The structure of the synthesized compound is as follows:
[0034] Product performance: The laboratory used a flotation process with one rougher, one cleaner, and three scavengers to evaluate the reagents. Under the condition that the beneficiation indicators are qualified, compared with the iron ore collector used in the Dongshao beneficiation plant, the flotation temperature was 20 ℃, the iron grade of the concentrate increased by 0.12%, the iron grade of the tailings decreased by 0.10%, and the reagent consumption per unit decreased by 8%.
[0035] The laboratory used a flotation process with one rougher, one cleaner, and three scavengers to evaluate the reagents. Under the condition that the beneficiation indicators are qualified, compared with the iron ore collector used in the industrial beneficiation plant, the flotation temperature is 20 ℃, the iron grade of the concentrate is increased by 0.09%, the iron grade of the tailings is decreased by 0.15%, and the reagent consumption is reduced by 6.5%.
[0036] In this invention, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.
[0037] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.
Claims
1. An ester-based carboxylic acid collector for room temperature flotation of iron ore and its application, characterized in that, The collector contains C. n H 2n+1 The iron ore room temperature flotation low-consumption collector with the structure shown in -O-CO-R1-COOH, where R1 is C4H8, CH=CH or a benzene ring, and n is 8~12; The preparation method of the ester-based carboxylic acid collector includes the following steps: A diacid or anhydride compound is placed in dichloromethane, and a catalyst and an alkyl alcohol compound are added. The alkyl alcohol compound reacts with the diacid or anhydride compound under the action of the catalyst to produce a product as shown in formula C. n H 2n+1 An anionic collector for room temperature flotation of iron ore with the structure shown in -O-CO-R1-COOH.
2. The iron ore room temperature flotation ester-based carboxylic acid collector according to claim 1 and its application, characterized in that, The molar ratio of the alkyl alcohol to the diacid or anhydride is 1:1.0 ~ 5.0, the reaction temperature is 20 ℃ ~ 40 ℃, and the reaction time is 2 h ~ 12 h.
3. The iron ore room temperature flotation ester-based carboxylic acid collector according to claim 1 and its application, characterized in that, The diacid or anhydride compound mentioned is any one of adipic acid, maleic anhydride, or phthalic anhydride.
4. The iron ore room temperature flotation ester-based carboxylic acid collector according to claim 1 and its application, characterized in that, The room temperature flotation is defined as a pulp temperature of 5 ℃ ~ 40 ℃.
5. The iron ore room temperature flotation ester-based carboxylic acid collector according to claim 1 and its application, characterized in that, The aforementioned low drug consumption refers to a 5% to 20% reduction in the single-agent consumption of traditional fatty acid collectors compared to using this anionic collector alone or in combination with fatty acid collectors.
6. The anionic collector for room temperature flotation of iron ore according to claim 1, its synthesis method and application, characterized in that, The iron ore room temperature flotation ester carboxylic acid collector can be used alone or in combination with fatty acid collectors.