A red ore composite soil for pellets

Abstract

The application relates to the technical field of iron-making pellet, and discloses a red ore composite soil for pellets, which is prepared from triallylamine and 3-chloropropene as raw materials, through a quaternary amination reaction to obtain a tetraallyl quaternary ammonium salt, through catalytic oxidation of sodium periodate and ruthenium trichloride to obtain a tetracarboxy quaternary ammonium salt, through an amidation reaction of the tetracarboxy quaternary ammonium salt and aminotri-sodium phosphate under catalysis of EDC and NHS to obtain a tetra(tri-sodium phosphate) quaternary ammonium salt, and finally adding bentonite into the red soil nickel ore and mixing to prepare the red ore composite soil. The prepared red ore composite soil is applied to the pellets, can improve the pelletizing performance of the pellets, improves the green ball falling strength and green ball compressive strength, and has good pellet grade.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of iron ore pellets, in particular to a red ore composite soil for pellets. BACKGROUND

[0002] At present, in the field of pellet production, the mixture of iron concentrate powder and bentonite is often used as raw material for producing pellets. The bentonite does not contain iron and mainly plays a role in improving the green ball strength, adjusting the moisture content of the raw material, improving the nucleation rate of the material, and reducing the growth speed of the green ball, so that the green ball size is small and uniform. However, the bentonite contains harmful elements, which will reduce the pellet grade and affect the product performance and the production efficiency of the blast furnace when added to the iron concentrate.

[0003] At present, technological innovation, cost reduction and efficiency improvement, and high-quality development play a crucial role in the survival and development of enterprises. Therefore, a material containing iron and having the characteristics of bentonite is crucial to the pellet production industry. SUMMARY

[0004] (I) Technical problems solved

[0005] In view of the deficiencies of the prior art, the present application provides a red ore composite soil for pellets, which contains lateritic nickel ore, bentonite and organic binder. When applied to pellets, it can improve the pelletizing performance of the material, increase the green ball drop strength and green ball compression strength, and has a good pellet grade.

[0006] (II) Technical scheme

[0007] A red ore composite soil for pellets, which is composed of the following weight components:

[0008] 100 parts by weight of lateritic nickel ore, 10-30 parts by weight of bentonite, and 1-5 parts by weight of tetra(trisodium tripolyphosphate) quaternary ammonium salt.

[0009] The red ore composite soil for pellets is prepared by the following method:

[0010] Add bentonite and tetra(trisodium tripolyphosphate) quaternary ammonium salt to the lateritic nickel ore and mix evenly to obtain the red ore composite soil for pellets.

[0011] Preferably, the preparation method of the tetra(trisodium tripolyphosphate) quaternary ammonium salt is as follows:

[0012] (1) Under nitrogen conditions, add triallylamine and 3-chloropropene to dichloromethane solvent, heat and react, after the reaction is completed, remove the solvent by rotary evaporation, wash with deionized water, and dry to obtain tetraalkenyl quaternary ammonium salt.

[0013] (2) under the condition of nitrogen, dissolving the tetraenyl quaternary ammonium salt in dichloromethane, stirring and dispersing, then adding sodium periodate and ruthenium trichloride into it, stirring and reacting at room temperature for 4-8 hours, after the reaction, washing with dichloromethane, drying, and concentrating under reduced pressure to obtain the tetra-carboxyl quaternary ammonium salt.

[0014] (3) adding the tetra-carboxyl quaternary ammonium salt into deionized water, stirring and dispersing, then adding amino-tripolyphosphate sodium, 15-30 mmol / L of EDC and 5-15 mmol / L of NHS into it, heating and reacting, washing, and drying to obtain the tetra-tripolyphosphate quaternary ammonium salt.

[0015] Preferably, in the step (1), the molar ratio of the triallylamine and 3-chloropropene is 1:3-5.

[0016] Preferably, in the step (1), the heating and reacting is performed for 12-26 hours at 45-60 DEG C.

[0017] Preferably, in the step (2), the molar ratio of the tetraenyl quaternary ammonium salt, sodium periodate and ruthenium trichloride is 1:10-15:3-5.

[0018] Preferably, in the step (3), the molar ratio of the tetra-carboxyl quaternary ammonium salt and amino-tripolyphosphate sodium is 1:4-6.

[0019] Preferably, in the step (3), the heating and reacting is performed for 5-10 hours at 40-50 DEG C.

[0020] (Three) beneficial technical effects

[0021] The present application uses triallylamine and 3-chloropropene as raw materials, and obtains the tetraenyl quaternary ammonium salt through quaternary amination, then obtains the tetra-carboxyl quaternary ammonium salt through catalytic oxidation of sodium periodate and ruthenium trichloride, then obtains the tetra-tripolyphosphate quaternary ammonium salt through amidation reaction of the tetra-carboxyl quaternary ammonium salt and amino-tripolyphosphate sodium under the catalysis of EDC and NHS, and finally adds the bentonite into the laterite nickel ore to make the red ore composite soil.

[0022] The tetra-tripolyphosphate quaternary ammonium salt contained in the red ore composite soil prepared by the present application contains the tripolyphosphate sodium structure which can be attached to the bentonite through chemical adsorption, the sodium ion contained therein can exchange with the calcium ion and magnesium ion on the surface of the bentonite to make the double electric layer thicker and improve the hydrophilicity of the bentonite, the phosphoric acid group and quaternary ammonium salt group contained therein can interact with the aluminum ion and hydroxyl group on the surface of the bentonite to form complex ions, so that the negative potential on the surface of the bentonite is further enhanced, the flocculation effect of the calcium ion in the bentonite is weakened, the structure of the bentonite is changed from "agglomeration-flocculation" to "agglomeration-anti-flocculation", and the hydrophilicity of the bentonite and the quality of the green ball are improved.

[0023] In addition, the affinity of the processed red ore composite soil and the iron concentrate powder is improved, the total iron content is about 40%, which is beneficial to improve the influence of bentonite on the pellet grade, can optimize the ore matching cost, and no other adverse factors are found in the subsequent preheating, roasting and cooling process, and the stable production target can be reached in the pellet production process.

[0024] The red ore composite soil prepared in the application can improve the balling performance of the pellets, improve the green ball drop strength and green ball compression strength, and has good pellet grade. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 It is a preparation route of a quaternary carboxyl salt. DETAILED DESCRIPTION

[0026] In order to make the purpose, implementation and advantages of the present application clearer, the following will combine the drawings in the exemplary embodiments of the present application to clearly and completely describe the exemplary embodiments of the present application. Obviously, the described exemplary embodiments are only a part of the embodiments of the present application, not all the embodiments of the present application.

[0027] It should be noted that the brief description of the terms in the present application is only for the convenience of understanding the following described embodiments, and is not intended to limit the embodiments of the present application. Unless otherwise specified, these terms should be understood according to their ordinary and general meanings.

[0028] The preparation method of the aminated sodium tripolyphosphate is as follows: 4g of sodium tripolyphosphate and 6mL of gamma-aminopropyl triethoxysilane are dissolved in a toluene solvent, stirred and dispersed, heated to 70℃, and reacted for 6h. After the reaction is completed, the toluene is washed and dried to obtain aminated sodium tripolyphosphate.

[0029] Example 1

[0030] (1) Under the condition of nitrogen, 0.2mol of triallylamine and 0.8mol of 3-chloropropene are added to dichloromethane solvent, heated to 50℃, reacted for 18h, after the reaction is completed, the solvent is removed by rotary evaporation, washed with deionized water, and dried to obtain a tetraalkenyl quaternary ammonium salt.

[0031] (2) Under the condition of nitrogen, 0.4mol of tetraalkenyl quaternary ammonium salt is dissolved in dichloromethane solvent, stirred and dispersed, 5mol of sodium periodate and 2mol of ruthenium trichloride are added thereto, stirred at room temperature for 6h, after the reaction is completed, dichloromethane is washed, dried, and concentrated under reduced pressure to obtain a tetraalkyl quaternary ammonium salt.

[0032] (3) 0.5 mol of the tetracarboxy quaternary ammonium salt was added to deionized water, stirred and dispersed, 2.5 mol of aminated sodium tripolyphosphate, 20 mmol / L of an EDC solution, and 5 mmol / L of an NHS solution were added thereto, the temperature was raised to 45°C, and reaction was performed for 8 h, followed by washing and drying to obtain a tetrakis (sodium tripolyphosphate) quaternary ammonium salt.

[0033] (4) 10 g of bentonite and 1 g of the tetrakis (sodium tripolyphosphate) quaternary ammonium salt were added to 100 g of laterite nickel ore, and mixed uniformly to obtain a pellet composite red ore soil.

[0034] Example 2

[0035] (1) 0.2 mol of triallylamine and 0.6 mol of 3-chloropropene were added to a dichloromethane solvent under nitrogen, the temperature was raised to 60°C, and reaction was performed for 24 h. After the reaction was completed, the solvent was removed by rotary evaporation, washed with deionized water, and dried to obtain a tetraalkenyl quaternary ammonium salt.

[0036] (2) 0.4 mol of the tetraalkenyl quaternary ammonium salt was dissolved in a dichloromethane solvent under nitrogen, stirred and dispersed, 5 mol of sodium periodate and 2 mol of ruthenium trichloride were added thereto, and stirred at room temperature for 6 h. After the reaction was completed, the reaction mixture was washed with dichloromethane and dried under reduced pressure to obtain a tetracarboxy quaternary ammonium salt.

[0037] (3) 0.5 mol of the tetracarboxy quaternary ammonium salt was added to deionized water, stirred and dispersed, 3 mol of aminated sodium tripolyphosphate, 20 mmol / L of an EDC solution, and 10 mmol / L of an NHS solution were added thereto, the temperature was raised to 50°C, and reaction was performed for 6 h, followed by washing and drying to obtain a tetrakis (sodium tripolyphosphate) quaternary ammonium salt.

[0038] (4) 15 g of bentonite and 2 g of the tetrakis (sodium tripolyphosphate) quaternary ammonium salt were added to 100 g of laterite nickel ore, and mixed uniformly to obtain a pellet composite red ore soil.

[0039] Example 3

[0040] (1) 0.2 mol of triallylamine and 0.8 mol of 3-chloropropene were added to a dichloromethane solvent under nitrogen, the temperature was raised to 60°C, and reaction was performed for 12 h. After the reaction was completed, the solvent was removed by rotary evaporation, washed with deionized water, and dried to obtain a tetraalkenyl quaternary ammonium salt.

[0041] (2) 0.4 mol of the tetraalkenyl quaternary ammonium salt was dissolved in a dichloromethane solvent under nitrogen, stirred and dispersed, 5 mol of sodium periodate and 2 mol of ruthenium trichloride were added thereto, and stirred at room temperature for 4 h. After the reaction was completed, the reaction mixture was washed with dichloromethane and dried under reduced pressure to obtain a tetracarboxy quaternary ammonium salt.

[0042] (3) Add 0.5 mol of tetracarboxylic quaternary ammonium salt to deionized water, stir and disperse, then add 3 mol of aminated sodium tripolyphosphate, 30 mmol / L EDC solution and 8 mmol / L NHS solution, heat to 50℃, react for 8 h, wash and dry to obtain tetra(sodium tripolyphosphate) quaternary ammonium salt.

[0043] (4) Add 20g of bentonite and 3g of tetra(sodium tripolyphosphate) quaternary ammonium salt to 100g of laterite nickel ore and mix evenly to obtain laterite composite soil for pelletizing.

[0044] Example 4

[0045] (1) Under nitrogen conditions, 0.2 mol of triallylamine and 0.9 mol of 3-chloropropene were added to dichloromethane solvent, heated to 50°C, and reacted for 26 h. After the reaction was completed, the solvent was removed by rotary evaporation, washed with deionized water, and dried to obtain tetraenyl quaternary ammonium salt.

[0046] (2) Under nitrogen conditions, 0.4 mol of tetraenyl quaternary ammonium salt was dissolved in dichloromethane solvent, stirred and dispersed, and then 5 mol of sodium periodate and 2 mol of ruthenium trichloride were added. The mixture was stirred and reacted at room temperature for 6 h. After the reaction was completed, the mixture was washed with dichloromethane, dried, and concentrated under reduced pressure to obtain tetracarboxylic quaternary ammonium salt.

[0047] (3) Add 0.5 mol of tetracarboxylic quaternary ammonium salt to deionized water, stir and disperse, then add 3 mol of aminated sodium tripolyphosphate, 30 mmol / L EDC solution and 15 mmol / L NHS solution, heat to 45℃, react for 10 h, wash and dry to obtain tetra(sodium tripolyphosphate) quaternary ammonium salt.

[0048] (4) Add 25g of bentonite and 4g of tetra(sodium tripolyphosphate) quaternary ammonium salt to 100g of laterite nickel ore and mix evenly to obtain laterite composite soil for pelletizing.

[0049] Example 5

[0050] (1) Under nitrogen conditions, 0.2 mol of triallylamine and 0.6 mol of 3-chloropropene were added to dichloromethane solvent, heated to 50°C, and reacted for 26 h. After the reaction was completed, the solvent was removed by rotary evaporation, washed with deionized water, and dried to obtain tetraenyl quaternary ammonium salt.

[0051] (2) Under nitrogen conditions, 0.4 mol of tetraenyl quaternary ammonium salt was dissolved in dichloromethane solvent, stirred and dispersed, and then 6 mol of sodium periodate and 2 mol of ruthenium trichloride were added. The mixture was stirred and reacted at room temperature for 8 h. After the reaction was completed, the mixture was washed with dichloromethane, dried, and concentrated under reduced pressure to obtain tetracarboxylic quaternary ammonium salt.

[0052] (3) Add 0.5 mol of tetracarboxylic quaternary ammonium salt to deionized water, stir and disperse, then add 2 mol of aminated sodium tripolyphosphate, 20 mmol / L EDC solution and 15 mmol / L NHS solution, heat to 40℃, react for 8 h, wash and dry to obtain tetra(sodium tripolyphosphate) quaternary ammonium salt.

[0053] (4) Add 30g of bentonite and 5g of tetra(sodium tripolyphosphate) quaternary ammonium salt to 100g of laterite nickel ore and mix evenly to obtain laterite composite soil for pelletizing.

[0054] Comparative Example 1

[0055] Add 10g of bentonite to 100g of laterite nickel ore and mix well to obtain laterite composite soil for pelletizing.

[0056] Weigh 4 kg of magnetite concentrate, add 20 g of red mineral composite clay and deionized water to it, adjust the moisture content to 7%, and add it to a grinding mill for grinding at 400 r / min for 10 min. After grinding, use a disc pelletizer to pelletize the pellets for 15 min, and then compact the pellets for 2 min.

[0057] The prepared pellets were placed at a height of 50 cm and allowed to fall freely onto a steel plate. The number of falls until the green pellets broke was recorded. The green pellets were then placed in a drying oven for drying, and their compressive strength was tested using a pressure gauge.

[0058]

[0059]

[0060] As shown in the table, the red mineral composite soil prepared by this invention, when applied to pellets, can improve the drop strength and compressive strength of green pellets.

[0061] Preheating and calcination experiments were conducted on dried pellets using two horizontal tubular electric furnaces in an air atmosphere. The preheating / calcination regime was set as follows: preheating temperature was 950℃ for 20 min, and calcination temperature was 1250℃ for 25 min. The compressive strength of the pellets was tested using a compressive strength tester.

[0062] Compressive strength (N / ball -1 )]]> Example 1 2785 Example 2 2850 Example 3 2991 Example 4 3210 Example 5 3116 Comparative Example 1 2659

[0063] As shown in the table, the prepared pellets have good compressive strength.

[0064] The above embodiments are for illustrative purposes only and are not intended to limit the invention. Those skilled in the art can make various changes or modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions should also fall within the scope of the invention and should be defined by the claims.

Claims

1. A red mineral composite soil for pelletizing, characterized in that, The red mineral composite soil for pelletizing is composed of the following weight components: 100 parts by weight of laterite nickel ore, 10-30 parts by weight of bentonite, and 1-5 parts by weight of tetra(sodium tripolyphosphate) quaternary ammonium salt; The pellets are prepared using the red mineral composite clay according to the following method: Bentonite and tetra(sodium tripolyphosphate) quaternary ammonium salt were added to laterite nickel ore and mixed evenly to obtain laterite composite soil for pelletizing. The preparation method of the tetra(sodium tripolyphosphate) quaternary ammonium salt is as follows: (1) Under nitrogen conditions, triallylamine and 3-chloropropene were added to dichloromethane solvent and the temperature was raised to react. After the reaction was completed, the solvent was removed by rotary evaporation, washed with deionized water, and dried to obtain tetraenyl quaternary ammonium salt. (2) Under nitrogen conditions, the tetraenyl quaternary ammonium salt was dissolved in dichloromethane solvent, stirred and dispersed, and then sodium periodate and ruthenium trichloride were added. The reaction was stirred at room temperature for 4-8 hours. After the reaction was completed, the mixture was washed with dichloromethane, dried, and concentrated under reduced pressure to obtain tetracarboxylic quaternary ammonium salt. (3) Add tetracarboxylic quaternary ammonium salt to deionized water, stir to disperse, then add amino-modified sodium tripolyphosphate, 15-30 mmol / L EDC, and 5-15 mmol / L NHS, heat to react, wash, and dry to obtain tetra(sodium tripolyphosphate) quaternary ammonium salt.

2. The red mineral composite soil for pelletizing according to claim 1, characterized in that, In step (1), the molar ratio of triallylamine to 3-chloropropene is 1:3-5.

3. The red mineral composite soil for pelletizing according to claim 1, characterized in that, In step (1), the heating reaction time is 12-26 hours and the temperature is 45-60℃.

4. The red mineral composite soil for pelletizing according to claim 1, characterized in that, In step (2), the molar ratio of tetraenyl quaternary ammonium salt, sodium periodate, and ruthenium trichloride is 1:10-15:3-5.

5. The red mineral composite soil for pelletizing according to claim 1, characterized in that, In step (3), the molar ratio of tetracarboxylated quaternary ammonium salt and aminolated sodium tripolyphosphate is 1:4-6.

6. The red mineral composite soil for pelletizing according to claim 1, characterized in that, In step (3), the heating reaction time is 5-10 hours and the temperature is 40-50℃.

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