A harmless purification agent for industrial solid waste and its preparation method and application

Abstract

The present invention provides a harmless purification agent for industrial solid waste, a preparation method and an application thereof, and belongs to the technical field of industrial solid waste treatment. The harmless purification agent for industrial solid waste is composed of the following components by mass: 8 to 11 parts of polyaluminium chloride, 4 to 7 parts of calcium hydroxide, 0.5 to 2 parts of polyacrylamide, 5 to 8 parts of calcium carbonate, 20 to 50 parts of sodium silicate, 3 to 6 parts of ferrous sulfate, 1 to 4 parts of potassium permanganate, 6 to 9 parts of polyferric sulfate, and 100 to 175 parts of water. When the harmless purification agent for industrial solid waste is used to treat industrial solid waste, it does not require a large amount of water and a large amount of energy consumption. Only a small amount of admixture is required to efficiently remove harmful substances in industrial solid waste, so that the industrial solid waste can meet the requirements of harmlessness.

Description

Technical Field

[0001] The invention belongs to the technical field of industrial solid waste treatment, and specifically relates to an industrial solid waste harmless purification agent and a preparation method and application thereof. Background Art

[0002] The long-term accumulation of industrial solid wastes such as phosphogypsum, tailings, and coal gangue has not only caused a large amount of land resources to be wasted, but also caused serious pollution to the environment, soil, water quality, and air. Take phosphogypsum as an example. As the main by-product of the phosphate fertilizer industry, phosphogypsum produces about 5 tons of phosphogypsum for every ton of wet phosphoric acid (measured in P2O5); its main component is calcium sulfate, and it also contains residual phosphoric acid, sulfuric acid, soluble fluorine, insoluble fluorine and other harmful components. When phosphogypsum is piled up in large quantities for a long time and soaked in rainwater, the soluble phosphorus and soluble fluorine it contains will diffuse into the surrounding environment through water bodies, causing comprehensive environmental pollution problems in the soil, water bodies, and atmosphere.

[0003] Traditional methods for harmless treatment of phosphogypsum mainly use three methods: water washing, calcination, and lime neutralization. The water washing method is suitable for batch treatment of phosphogypsum, but it will cause a large waste of water resources, and washing wastewater will also cause secondary pollution. The calcination method is suitable for areas with scarce water resources but abundant energy. However, when phosphogypsum is harmlessly treated as building gypsum by calcination, its calcination temperature needs to be maintained above 800°C, and the energy consumption is too large. The lime neutralization method first removes organic matter from phosphogypsum through flotation treatment, and then adds quicklime, which precipitates the soluble phosphorus and fluorine in the phosphogypsum. The lime neutralization method is simple and easy, but it is difficult to completely solidify the pollutants in the phosphogypsum. Summary of the invention

[0004] In order to solve the above problems, the present invention provides a harmless purification agent for industrial solid waste, which does not require a large amount of water or energy consumption, and can achieve the purpose of efficiently removing soluble phosphorus and soluble fluorine with a small amount of doping.

[0005] In order to achieve the above object, the present invention specifically adopts the following technical solutions:

[0006] A harmless purification agent for industrial solid waste is composed of the following components in parts by mass: 8 to 11 parts of polyaluminium chloride, 4 to 7 parts of calcium hydroxide, 0.5 to 2 parts of polyacrylamide, 5 to 8 parts of calcium carbonate, 20 to 50 parts of sodium silicate, 3 to 6 parts of ferrous sulfate, 1 to 4 parts of potassium permanganate, 6 to 9 parts of polyferric sulfate and 100 to 175 parts of water.

[0007] In a preferred embodiment, the industrial solid waste harmless purification agent is composed of the following components in parts by mass: 9 to 11 parts of polyaluminium chloride, 5 to 7 parts of calcium hydroxide, 1 to 2 parts of polyacrylamide, 6 to 8 parts of calcium carbonate, 30 to 50 parts of sodium silicate, 4 to 6 parts of ferrous sulfate, 2 to 4 parts of potassium permanganate, 7 to 9 parts of polyferric sulfate, and 125 to 175 parts of water.

[0008] In a further preferred embodiment, the industrial solid waste harmless purification agent is composed of the following components in parts by mass: 10 to 11 parts of polyaluminium chloride, 6 to 7 parts of calcium hydroxide, 1.5 to 2 parts of polyacrylamide, 7 to 8 parts of calcium carbonate, 40 to 50 parts of sodium silicate, 5 to 6 parts of ferrous sulfate, 3 to 4 parts of potassium permanganate, 8 to 9 parts of polyferric sulfate, and 150 to 175 parts of water.

[0009] In a preferred embodiment, the mass ratio of the polyaluminium chloride, the ferrous sulfate and the polyacrylamide is (5.5:3:1) to (16:6:1).

[0010] In a further preferred embodiment, the mass ratio of the polyaluminium chloride, the ferrous sulfate and the polyacrylamide is (5.5:3:1) to (9:4:1).

[0011] In a further preferred embodiment, the mass ratio of the polyaluminium chloride, the ferrous sulfate and the polyacrylamide is (5.5:3:1) to (20:3:10).

[0012] The present invention also provides a method for preparing the harmless purification agent for industrial solid waste, comprising the following steps:

[0013] S1. Add water to a reactor, heat to a first temperature, add calcium hydroxide, and stir evenly; add ferrous sulfate and potassium permanganate, and continue to stir and mix evenly;

[0014] S2. When the temperature in the reactor drops to the second temperature, add calcium carbonate and stir evenly;

[0015] S3, when the temperature in the reactor drops to the third temperature, add polyferric sulfate, stir evenly, then add polyaluminium chloride, and continue to stir evenly;

[0016] S4. When the temperature in the reaction kettle drops to the fourth temperature, add polyacrylamide and stir evenly; then add sodium silicate and continue to stir evenly; let the mixture in the reaction kettle cool to room temperature to obtain the industrial solid waste harmless purification agent.

[0017] In a preferred embodiment, the first temperature is 100-120°C.

[0018] In a preferred embodiment, the second temperature is 70-90°C.

[0019] In a preferred embodiment, the third temperature is 60-70°C.

[0020] In a preferred embodiment, the fourth temperature is 40-50°C.

[0021] In a further preferred embodiment, the first temperature is 100-120°C, the second temperature is 70-90°C, the third temperature is 60-70°C, and the fourth temperature is 40-50°C.

[0022] In a preferred embodiment, the stirring speed in each step is 1000-1500 rpm, and the stirring time is 5-15 min.

[0023] Controlling the appropriate stirring speed and stirring time can make the prepared industrial solid waste harmless purification agent have a higher concentration, better uniformity, purer color, and no precipitation.

[0024] When the harmless industrial solid waste purification agent provided in the present invention is used to treat industrial solid waste, only 0.5% to 1% of the mass of the industrial solid waste is needed to render the industrial solid waste harmless.

[0025] In a preferred embodiment, the industrial solid waste is phosphogypsum.

[0026] Compared with the prior art, the beneficial effect of the present invention is that the combined use of polyacrylamide, polyaluminium chloride, ferrous sulfate and polyferric sulfate in the harmless purification agent for industrial solid waste in the present invention can significantly improve the removal effect of fluoride and phosphorus. When the harmless purification agent for industrial solid waste in the present invention is used to treat industrial solid waste (such as phosphogypsum), it does not require a large amount of water and a large amount of energy consumption, and only a small amount of admixture is required to efficiently remove harmful substances in industrial solid waste, so that the industrial solid waste can meet the requirements of harmlessness. DETAILED DESCRIPTION

[0027] The following content is combined with the embodiments to clearly and completely describe the technical solution of the present invention so that those skilled in the art can fully understand the present invention. Obviously, the described embodiments are only some preferred embodiments of the present invention, rather than all embodiments. Any equivalent transformation or substitution made by ordinary technicians in this field to the following implementation methods without creative work belongs to the protection scope of the present invention.

[0028] Example 1

[0029] This embodiment provides an industrial solid waste harmless purification agent, which is composed of the following components in parts by weight:

[0030] 8 parts of polyaluminium chloride, 4 parts of calcium hydroxide, 0.5 parts of polyacrylamide, 5 parts of calcium carbonate, 20 parts of sodium silicate, 3 parts of ferrous sulfate, 1 part of potassium permanganate, 6 parts of polyferric sulfate, and 100 parts of water.

[0031] The preparation method of the harmless purification agent for industrial solid waste comprises the following steps:

[0032] S1. Add 100 parts of water to the reactor, heat to 110±3°C under stirring, add 4 parts of calcium hydroxide, and stir at 1500rpm for 5 minutes. Keep the temperature at 110±3°C, add 3 parts of ferrous sulfate and 1 part of potassium permanganate, and continue stirring at 1500rpm for 15 minutes.

[0033] S2. When the water temperature in the reactor drops to 80±2°C, add 5 parts of calcium carbonate and stir at 1000 rpm for 10 minutes.

[0034] S3. When the water temperature in the reactor drops to 65±2°C, add 6 parts of polyferric sulfate and stir at 1500 rpm for 5 minutes. Then add 8 parts of polyaluminium chloride and continue stirring at 1500 rpm for 5 minutes.

[0035] S4. When the water temperature in the reactor drops to 45±2°C, add 0.5 parts of polyacrylamide and stir at 1500rpm for 5 minutes. Then add 20 parts of sodium silicate and stir at 1000rpm for 10 minutes. Then let the mixture in the reactor cool down naturally to room temperature to obtain the harmless purification agent for industrial solid waste.

[0036] Example 2

[0037] This embodiment provides an industrial solid waste harmless purification agent, which is composed of the following components in parts by weight:

[0038] 10 parts of polyaluminium chloride, 6 parts of calcium hydroxide, 1.5 parts of polyacrylamide, 7 parts of calcium carbonate, 40 parts of sodium silicate, 5 parts of ferrous sulfate, 3 parts of potassium permanganate, 8 parts of polyferric sulfate, and 150 parts of water.

[0039] The preparation method of the harmless purification agent for industrial solid waste is basically the same as that in Example 1, except that: the amount of each component is different; the temperature in step S1 is 100°C, the temperature in step S2 is 70°C, the temperature in step S3 is 60°C, and the temperature in step S4 is 40°C.

[0040] Example 3

[0041] This embodiment provides an industrial solid waste harmless purification agent, which is composed of the following components in parts by weight:

[0042] 11 parts of polyaluminium chloride, 7 parts of calcium hydroxide, 2 parts of polyacrylamide, 8 parts of calcium carbonate, 50 parts of sodium silicate, 6 parts of ferrous sulfate, 4 parts of potassium permanganate, 9 parts of polyferric sulfate, and 175 parts of water.

[0043] The preparation method of the harmless purification agent for industrial solid waste is basically the same as that in Example 1, except that: the amount of each component is different; the temperature in step S1 is 120°C, the temperature in step S2 is 90°C, the temperature in step S3 is 70°C, and the temperature in step S4 is 50°C.

[0044] Example 4

[0045] This embodiment provides an industrial solid waste harmless purification agent, which is composed of the following components in parts by weight:

[0046] 9 parts of polyaluminium chloride, 5 parts of calcium hydroxide, 1 part of polyacrylamide, 6 parts of calcium carbonate, 30 parts of sodium silicate, 4 parts of ferrous sulfate, 2 parts of potassium permanganate, 7 parts of polyferric sulfate, and 125 parts of water.

[0047] Except for the different amounts of each component, the preparation method of the industrial solid waste harmless purification agent is the same as that in Example 1.

[0048] Comparative Example 1

[0049] The harmless industrial solid waste purification agent in this comparative example is composed of the following components by mass: 4 parts of calcium hydroxide, 0.5 parts of polyacrylamide, 5 parts of calcium carbonate, 20 parts of sodium silicate, 1 part of potassium permanganate, 6 parts of polyferric sulfate, and 100 parts of water. That is, the difference between this comparative example and Example 1 is that polyaluminium chloride and ferrous sulfate are not included.

[0050] Comparative Example 2

[0051] The harmless industrial solid waste purification agent in this comparative example is composed of the following components by mass: 8 parts of polyaluminium chloride, 4 parts of calcium hydroxide, 5 parts of calcium carbonate, 20 parts of sodium silicate, 3 parts of ferrous sulfate, 1 part of potassium permanganate, and 100 parts of water. That is, the difference between this comparative example and Example 1 is that polyacrylamide and polyferric sulfate are not included.

[0052] Comparative Example 3

[0053] The composition of the harmless purification agent for industrial solid waste in this comparative example is the same as that in Example 1, and its preparation method is as follows:

[0054] S1. Add 100 parts of water into the reactor, heat to 110±3°C under stirring, add 0.5 parts of polyacrylamide, stir at 1500 rpm for 5 minutes, maintain the temperature at 110±3°C, add 8 parts of polyaluminium chloride, and continue stirring at 1500 rpm for 15 minutes.

[0055] S2. When the water temperature in the reactor drops to 80±2°C, add 6 parts of polyferric sulfate and stir at 1500 rpm for 5 minutes.

[0056] S3. When the water temperature in the reactor drops to 65±2°C, add 4 parts of calcium hydroxide and stir at 1500 rpm for 5 minutes. Then add 1 part of potassium permanganate and continue stirring at 1500 rpm for 15 minutes.

[0057] S4. When the water temperature in the reactor drops to 45±2°C, add 3 parts of ferrous sulfate and 5 parts of calcium carbonate, and stir at a speed of 1500rpm for 5 minutes. Then add 20 parts of sodium silicate and stir at a speed of 1000rpm for 10 minutes. Then let the mixture in the reactor cool naturally to room temperature to obtain the harmless purification agent for industrial solid waste.

[0058] Test on the effect of harmless treatment of industrial solid waste

[0059] The harmless purification agents for industrial solid waste prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were used to treat phosphogypsum, and the contents of various harmful substances in the phosphogypsum before and after the treatment were detected. The test results are shown in Table 1. Phosphogypsum was obtained from Hubei Yihua Chuxing Chemical Co., Ltd. The dosage of the harmless purification agent for industrial solid waste was 1% of the mass of the phosphogypsum. The phosphogypsum was first crushed and then mixed evenly with the harmless purification agent for industrial solid waste. The detection method for heavy metals refers to the method in GB / T 23349-2020 "Determination of arsenic, cadmium, chromium, lead and mercury content in fertilizers". The detection methods for the remaining test items refer to the methods in GB / T 5484-2012 "Chemical Analysis Method for Gypsum".

[0060] Table 1 Test results of industrial solid waste harmless purification agent treating phosphogypsum

[0061]

[0062] It can be calculated from Table 1 that when the harmless industrial solid waste purification agent of the present invention is used to treat phosphogypsum, only 1% of the dosage is needed to remove more than 99.8% of phosphorus pentoxide and more than 93.0% of water-soluble fluorine. When the composition of the harmless industrial solid waste purification agent is 10-11 parts of polyaluminium chloride, 6-7 parts of calcium hydroxide, 1.5-2 parts of polyacrylamide, 7-8 parts of calcium carbonate, 40-50 parts of sodium silicate, 5-6 parts of ferrous sulfate, 3-4 parts of potassium permanganate, 8-9 parts of polyferric sulfate, and 150-175 parts of water, only 1% of the dosage is needed to remove more than 99.9% of phosphorus pentoxide and more than 95.5% of water-soluble fluorine. When the harmless purification agent for industrial solid waste prepared in Comparative Examples 1 and 2 is used to treat phosphogypsum, the removal rate of phosphorus and water-soluble fluorine is significantly reduced, which shows that the polyaluminium chloride, polyacrylamide, ferrous sulfate and polyferric sulfate in the harmless purification agent for industrial solid waste of the present invention can significantly improve the removal efficiency of phosphorus and water-soluble fluorine when used in combination with each other. The composition of the harmless purification agent for industrial solid waste in Comparative Example 3 is the same as that in Example 1, but the preparation method is different from that in Example 1, and its removal efficiency of phosphorus and water-soluble fluorine is worse than that in Comparative Examples 1 and 2, which shows that the preparation method of the harmless purification agent for industrial solid waste in the present invention is different and also affects its performance.

[0063] The above description is only a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. For any person skilled in the art, the present invention may have various changes and modifications. Any simple equivalent changes and modifications made according to the scope of protection of the present invention and the contents of the specification should be included in the scope of protection of the present invention.

Claims

1. A harmless purification agent for industrial solid waste, characterized in that: The invention is composed of the following components in parts by mass: 8 to 11 parts of polyaluminium chloride, 4 to 7 parts of calcium hydroxide, 0.5 to 2 parts of polyacrylamide, 5 to 8 parts of calcium carbonate, 20 to 50 parts of sodium silicate, 3 to 6 parts of ferrous sulfate, 1 to 4 parts of potassium permanganate, 6 to 9 parts of polyferric sulfate, and 100 to 175 parts of water; the preparation method of the harmless purification agent for industrial solid waste comprises the following steps: S1. Add water to the reactor, heat to 100-120°C, add calcium hydroxide, and stir evenly; add ferrous sulfate and potassium permanganate, and continue to stir and mix evenly; S2. When the temperature in the reactor drops to 70-90°C, add calcium carbonate and stir evenly; S3. When the temperature in the reactor drops to 60-70°C, add polyferric sulfate, stir evenly, then add polyaluminium chloride, and continue stirring evenly; S4. When the temperature in the reactor drops to 40-50°C, add polyacrylamide and stir evenly; then add sodium silicate and continue to stir evenly; let the mixture in the reactor cool to room temperature to obtain the industrial solid waste harmless purification agent.

2. The harmless purification agent for industrial solid waste according to claim 1, characterized in that: It is composed of the following components in parts by mass: 9-11 parts of polyaluminium chloride, 5-7 parts of calcium hydroxide, 1-2 parts of polyacrylamide, 6-8 parts of calcium carbonate, 30-50 parts of sodium silicate, 4-6 parts of ferrous sulfate, 2-4 parts of potassium permanganate, 7-9 parts of polyferric sulfate, and 125-175 parts of water.

3. The harmless purification agent for industrial solid waste according to claim 1, characterized in that: The mass ratio of the polyaluminium chloride, the ferrous sulfate and the polyacrylamide is (5.5:3:1) to (16:6:1).

4. The harmless purification agent for industrial solid waste according to claim 3, characterized in that: The mass ratio of the polyaluminium chloride, the ferrous sulfate and the polyacrylamide is (5.5:3:1) to (9:4:1).

5. The harmless purification agent for industrial solid waste according to claim 1, characterized in that: The stirring speed in each step is 1000~1500rpm, and the stirring time is 5~15min.

6. The use of the harmless industrial solid waste purification agent according to any one of claims 1 to 5, characterized in that: The harmless purification agent for industrial solid waste is used to treat industrial solid waste, and the mass of the harmless purification agent for industrial solid waste accounts for 0.5% to 1% of the mass of the industrial solid waste.

7. The use according to claim 6, characterized in that: The industrial solid waste is phosphogypsum.

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