A method for producing phosphorus ore powder pellets by using phosphating waste liquid

Abstract

The application discloses a method for producing phosphorus ore powder pellets by using phosphating waste liquid, which comprises the following steps: uniformly mixing 80-100 parts by weight of phosphorus ore powder, 5-20 parts by weight of heat-treated copper slag powder, 4.8-8.0 parts by weight of water and 8.0-11.2 parts by weight of phosphating waste liquid, pressing the mixture into balls, drying and calcining the balls, and obtaining the phosphorus ore powder pellets; in the method, the acidic components in the phosphating waste liquid are reacted with the aluminum and calcium system substances in the phosphorus ore powder, the iron system components in the smelting copper slag are used as a ball strength enhancer, the P2O5 in the phosphating waste liquid participates in the phosphorus production reaction, the P grade in the powder ball is improved, the comprehensive utilization of the waste liquid and solid waste is realized, and the method has the significance of treating waste with waste and treating pollution with waste.

Description

Technical Field

[0001] This invention belongs to the field of mineral processing and chemical technology, and in particular relates to a method for preparing phosphate rock powder pellets using phosphate rock powder and phosphating waste liquid. Background Technology

[0002] High-grade lumpy phosphate rock is the main raw material for the traditional electric arc furnace (EAF) process in the production of yellow phosphorus. However, with the continuous depletion of high-grade phosphate rock resources, the availability of lumpy raw materials that meet the requirements for furnace feeding is decreasing. To effectively address the raw material source problem in yellow phosphorus production, the rational application of the large amount of phosphate rock powder generated during phosphate rock mining or crushing to yellow phosphorus production has attracted industry attention. Pressing this phosphate rock powder into pellets for use in yellow phosphorus chemical processing can not only reduce the waste of phosphorus resources but also solve the problems of phosphate rock powder storage and environmental protection.

[0003] Briquetting technology has garnered widespread attention in the industry due to its simple operation and the ability to achieve high strength in pellets without calcination. However, this process places high demands on the binder. Current technologies using sodium humate or sodium silicate as binders lead to the introduction of excessive sodium salts, causing instability in yellow phosphorus production and severely impacting its quality. Using phosphoric acid and sulfuric acid as composite binders in phosphate rock powder briquetting can improve the phosphorus content in the pellets, but this method suffers from drawbacks such as high manufacturing costs.

[0004] In the electric furnace process for producing yellow phosphorus, there are certain requirements for the compressive strength of phosphate rock pellets. Low-strength pellets are easily broken, resulting in large variations in the voids inside the furnace, which affects the airflow distribution and heat transfer, and is not conducive to the uniformity of the reaction. It can also cause instability in the material layer structure inside the furnace, requiring frequent adjustments to operating parameters to maintain normal production. Therefore, excellent mechanical properties of the pellets are a standard for entering the furnace. Summary of the Invention

[0005] This invention provides a method for producing phosphate rock powder pellets using phosphate ore powder through a pelletizing process, with phosphate ore waste liquid and copper smelting slag as composite binders. The method of this invention has the advantages of inexpensive and readily available raw materials, low pellet production cost, and high strength.

[0006] The present invention describes a method for producing phosphate rock powder pellets using phosphate leaching waste liquid. This method involves mixing 80-100 parts by weight of phosphate rock powder, 5-20 parts by weight of heat-treated copper slag powder, 4.8-8.0 parts by weight of water, and 8.0-11.2 parts by weight of phosphate leaching waste liquid evenly, pressing the mixture into pellets, drying and calcining it, and then cooling it to obtain calcined phosphate rock powder pellets.

[0007] The phosphate rock powder mentioned is raw phosphate rock powder or waste residue generated during the mining or crushing of phosphate rock, with a particle size of 40-100 mesh.

[0008] The heat-treated copper slag powder is obtained by grinding smelting copper slag and then heat-treating it at 350-450℃ for 1-3 hours. The main components of the smelting copper slag are: Fe2O3 55-60wt%, SiO2 20-23wt%, MgO 4-5wt%, Al2O3 3-4wt%, CaO 3-4wt%, ZnO 1-2wt%, and other components 5-6wt%.

[0009] The phosphating waste liquid is the waste liquid generated after phosphating the metal surface with phosphating solution.

[0010] The calcination is performed at 200-400℃ for 0.5-2 hours.

[0011] Advantages and technical effects of the present invention:

[0012] 1. This invention uses phosphate rock powder, waste generated during phosphate rock mining or crushing, phosphating waste liquid after metal surface treatment, and copper smelting slag as raw materials to prepare phosphate rock powder pellets. It treats waste with waste and provides an effective way for the comprehensive utilization of industrial waste resources, which has economic and environmental value.

[0013] 2. The phosphate rock powder pellets prepared by the method of the present invention have the advantages of excellent mechanical properties and low cost. The present invention uses the acidic components in the phosphating waste liquid to react with the silicon, aluminum and calcium-based substances in the phosphate rock powder, and uses the ferrosilicon-based components in the copper smelting slag as the pellet strength strengthening agent. The product obtained meets the furnace feed standard for the production of yellow phosphorus by electric furnace method.

[0014] 3. P2O5 in phosphating waste liquid participates in the phosphorus production reaction, increases the P grade in the powder pellets, and realizes the comprehensive utilization of waste liquid and solid waste;

[0015] 4. The preparation process of this invention is simple, easy to operate, and the raw materials are readily available, making it suitable for industrial production and market application. Attached Figure Description

[0016] Figure 1 The image shows the XRD pattern of phosphate rock powder.

[0017] Figure 2 The image shows the XRD pattern of phosphate rock powder pellets. Detailed Implementation

[0018] To better understand the specific content of this invention, the following specific examples will be used to illustrate the invention in detail, but the scope of protection of this invention is not limited to the following content;

[0019] The main components of the copper smelting slag in the following examples are: Fe2O3 58.09wt%, SiO2 22.84wt%, MgO 4.99wt%, Al2O3 3.4wt%, CaO 3.28wt%, ZnO 1.67wt%, and others 5.73wt%; the phosphating waste liquid is the waste liquid generated after phosphating the surface of metals such as aluminum and iron with phosphating solution. Example 1

[0020] 1. Heat-treated copper slag powder is obtained by grinding smelting copper slag powder to a particle size of 100 mesh and heat-treating it at 400℃ for 2 hours.

[0021] 2. Phosphate rock powder with a particle size of 40-60 mesh, heat-treated copper slag powder, water, and phosphating waste liquid were mixed according to the experimental group below. After stirring for 1 minute, the mixture was placed in a mold and extruded (pressure 40t). The pellets were dried in a 60℃ oven for 5 hours to obtain raw phosphate rock powder pellets. These pellets were then calcined in a muffle furnace at 200℃ for 1.5 hours. After cooling, cooked phosphate rock powder pellets with a particle size of 3.6-3.9cm were obtained. At the same time, phosphate rock powder pellets without the addition of heat-treated copper slag powder were used as a control (100g phosphate rock powder, 4.8g phosphating waste liquid, 11.2g water).

[0022] Experimental Group 1: 95g phosphate rock powder, 5g calcined copper slag, 4.8g phosphating waste liquid, 11.2g water;

[0023] Experimental Group 2: 90g phosphate rock powder, 10g calcined copper slag, 4.8g phosphating waste liquid, 11.2g water;

[0024] Experimental Group 3: 85g phosphate rock powder, 15g calcined copper slag, 4.8g phosphating waste liquid, 11.2g water;

[0025] Experimental Group 4: 80g phosphate rock powder, 20g calcined copper slag, 4.8g phosphating waste liquid, 11.2g water;

[0026] 3. The mechanical properties of green and cooked phosphate rock pellets were tested, and the results are shown in Table 1.

[0027] Table 1

[0028] . Example 2

[0029] 1. Heat-treated copper slag powder is prepared by grinding copper slag powder from powder metallurgy to a particle size of 100 mesh and then heat-treating it at 400℃ for 2 hours.

[0030] 2. Phosphate rock powder with a particle size of 60-80 mesh, heat-treated copper slag powder, water, and phosphating waste liquid were mixed according to the experimental group below. After stirring for 1 minute, the mixture was placed in a mold and extruded (pressure 40t). The pellets were dried in a 60℃ oven for 5 hours to obtain raw phosphate rock powder pellets. Then, they were calcined in a muffle furnace at 200℃ for 1.5 hours. After cooling, calcined phosphate rock powder pellets with a particle size of 3.6-3.9cm were obtained. At the same time, phosphate rock powder pellets without the addition of heat-treated copper slag powder were used as a control (100g phosphate rock powder, 6.4g phosphating waste liquid, 9.6g water).

[0031] Experimental Group 1: 95g phosphate rock powder, 5g calcined copper slag, 6.4g phosphating waste liquid, and 9.6g water;

[0032] Experimental Group 2: 90g phosphate rock powder, 10g calcined copper slag, 6.4g phosphating waste liquid, and 9.6g water;

[0033] Experimental Group 3: 85g phosphate rock powder, 15g calcined copper slag, 6.4g phosphating waste liquid, and 9.6g water;

[0034] Experimental Group 4: 80g phosphate rock powder, 20g calcined copper slag, 6.4g phosphating waste liquid, and 9.6g water;

[0035] 3. The mechanical properties of green and cooked phosphate rock pellets were tested, and the results are shown in Table 2.

[0036] Table 2

[0037] . Example 3

[0038] 1. Heat-treated copper slag powder is prepared by grinding copper slag powder from powder metallurgy to a particle size of 100 mesh and then heat-treating it at 400℃ for 2 hours.

[0039] 2. Phosphate rock powder with a particle size of 80-100 mesh, heat-treated copper slag powder, water, and phosphating waste liquid were mixed according to the experimental group below. After stirring for 1 minute, the mixture was placed in a mold and extruded (pressure 40t). The pellets were dried in a 60℃ oven for 5 hours to obtain raw phosphate rock powder pellets. These pellets were then calcined in a muffle furnace at 200℃ for 1.5 hours. After cooling, calcined phosphate rock powder pellets with a particle size of 3.6-3.9cm were obtained. At the same time, phosphate rock powder pellets without the addition of heat-treated copper slag powder were used as a control (100g phosphate rock powder, 8g phosphating waste liquid, 8g water).

[0040] The test blocks were removed from the muffle furnace and cooled to room temperature before their compressive strength was measured. The specific experimental groups are as follows:

[0041] Experimental Group 1: 95g phosphate rock powder, 5g calcined copper slag, 8g phosphating waste liquid, 8g water;

[0042] Experimental Group 2: 90g phosphate rock powder, 10g calcined copper slag, 8g phosphating waste liquid, and 8g water;

[0043] Experimental Group 3: 85g phosphate rock powder, 15g calcined copper slag, 8g phosphating waste liquid, and 8g water;

[0044] Experimental Group 4: 80g phosphate rock powder, 20g calcined copper slag, 8g phosphating waste liquid, 8g water;

[0045] 3. The mechanical properties of green and cooked phosphate rock pellets were tested, and the results are shown in Table 3.

[0046] Table 3

[0047] . Example 4

[0048] 1. Heat-treated copper slag powder is prepared by grinding copper slag powder from powder metallurgy to a particle size of 100 mesh and then heat-treating it at 400℃ for 2 hours.

[0049] 2. Phosphate rock powder with a particle size of 50-60 mesh, heat-treated copper slag powder, water, and phosphating waste liquid, after being ground by a vibratory mill, are mixed according to the experimental group described below. After stirring and mixing for 1 minute, the mixture is placed in a mold and extruded (pressure 40t). The pellets are then dried in a 60℃ oven for 5 hours to obtain green phosphate rock powder pellets (XRD see...). Figure 1 Then, it is placed in a muffle furnace and calcined at 200℃ for 1.5 hours. After cooling, calcined phosphate rock powder pellets with a particle size of 3.6-3.9 cm are obtained (see XRD). Figure 2 Meanwhile, phosphate rock pellets prepared without the addition of heat-treated copper slag powder were used as a control (100g phosphate rock powder, 9.6g phosphating waste liquid, 6.4g water).

[0050] Experimental Group 1: 95g phosphate rock powder, 5g calcined copper slag, 9.6g phosphating waste liquid, and 6.4g water;

[0051] Experimental Group 2: 90g phosphate rock powder, 10g calcined copper slag, 9.6g phosphating waste liquid, and 6.4g water;

[0052] Experimental Group 3: 85g phosphate rock powder, 15g calcined copper slag, 9.6g phosphating waste liquid, and 6.4g water;

[0053] Experimental Group 4: 80g phosphate rock powder, 20g calcined copper slag, 9.6g phosphating waste liquid, and 6.4g water;

[0054] 3. The mechanical properties of green and cooked phosphate rock pellets were tested, and the results are shown in Table 4.

[0055] Table 4

[0056] ;

[0057] 4. Using the phosphate rock powder pellets obtained by the above method as raw materials, yellow phosphorus was produced by electric furnace method. The reduction rate of Comparative Example 4 was 88.2% at 1450℃, while the reduction rates of Experimental Groups 1, 2, 3, and 4 were 89.5%, 90.3%, 91.5%, and 91.7% at 1400℃, respectively.

[0058] Compared to Comparative Example 4, in experimental groups 1, 2, 3, and 4, the reduction rate of the pellets continuously increased at the same temperature with the increase of the amount of heat-treated copper slag added. Therefore, heat-treated copper slag powder can act as a strength enhancer and also replace silica as a flux. In addition, the rich iron content in copper slag can also improve the quality of the by-product phosphite slag while reducing and producing yellow phosphorus. Example 5

[0059] 1. Heat-treated copper slag powder is prepared by grinding copper slag powder from powder metallurgy to a particle size of 100 mesh and then heat-treating it at 400℃ for 2 hours.

[0060] 2. Phosphate rock powder with a particle size of 60-70 mesh, heat-treated copper slag powder, water, and phosphating waste liquid were mixed according to the experimental group described below. After stirring for 1 minute, the mixture was placed in a mold and extruded (pressure 40t). The pellets were dried in a 60℃ oven for 5 hours to obtain raw phosphate rock powder pellets. These pellets were then calcined in a muffle furnace at 200℃ for 1.5 hours. After cooling, calcined phosphate rock powder pellets with a particle size of 3.6-3.9cm were obtained. At the same time, phosphate rock powder pellets without the addition of heat-treated copper slag powder were used as a control (100g phosphate rock powder, 11.2g phosphating waste liquid, 4.8g water).

[0061] Experimental Group 1: 95g phosphate rock powder, 5g calcined copper slag, 11.2g phosphating waste liquid, and 4.8g water;

[0062] Experimental Group 2: 90g phosphate rock powder, 10g calcined copper slag, 11.2g phosphating waste liquid, and 4.8g water;

[0063] Experimental Group 3: 85g phosphate rock powder, 15g calcined copper slag, 11.2g phosphating waste liquid, and 4.8g water;

[0064] Experimental Group 4: 80g phosphate rock powder, 20g calcined copper slag, 11.2g phosphating waste liquid, and 4.8g water;

[0065] 3. The mechanical properties of green and cooked phosphate rock pellets were tested, and the results are shown in Table 5.

[0066] Table 5

[0067] .

[0068] As shown in Table 1-2, when the phosphating waste liquid is 4.8 parts and water is 11.2 parts, the addition of heat-treated copper slag has a negative effect on improving the strength of phosphate rock powder granules, reducing their strength. This indicates that the amount of phosphating waste liquid is too small to react with the heat-treated copper slag and thus exert its strengthening effect. When the phosphating waste liquid is 6.4 parts and water is 9.6 parts, the heat-treated copper slag has no effect on improving the strength of phosphate rock powder granules, and the strength remains almost unchanged.

[0069] As can be seen from Table 3-5, when the phosphating waste liquid is 8.0-11.2 parts and the water is 4.8-8.0 parts, the strength of the phosphate rock powder pellets after being mixed with heat-treated copper slag is higher than that of the control group. Sufficient phosphating waste liquid can react with heat-treated copper slag powder, exert its reinforcing agent effect, and significantly improve the strength of phosphate rock powder pellets.

Claims

1. A method for producing phosphate rock powder pellets using phosphate leaching waste liquid, characterized in that, Mix 80-100 parts by weight of phosphate rock powder, 5-20 parts by weight of heat-treated copper slag powder, 4.8-8.0 parts by weight of water, and 8.0-11.2 parts by weight of phosphating waste liquid evenly, press into pellets, dry and calcine to obtain phosphate rock powder pellets.

2. The method for producing phosphate rock pellets from phosphating waste liquid according to claim 1, characterized in that: The particle size of phosphate rock powder is 40-100 mesh.

3. The method for producing phosphate rock pellets from phosphating waste liquid according to claim 1, characterized in that: The heat-treated copper slag is obtained by grinding smelting copper slag and then heat-treating it at 350-450℃ for 1-3 hours.

4. The method for producing phosphate rock pellets from phosphating waste liquid according to claim 1, characterized in that: Phosphating waste liquid is the waste liquid generated after phosphating metal surfaces with phosphating solution.

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