CN115385433A - Composite silicon removing agent for wastewater in iron and steel industry and preparation and use methods thereof - Google Patents
Composite silicon removing agent for wastewater in iron and steel industry and preparation and use methods thereof Download PDFInfo
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- CN115385433A CN115385433A CN202211012429.3A CN202211012429A CN115385433A CN 115385433 A CN115385433 A CN 115385433A CN 202211012429 A CN202211012429 A CN 202211012429A CN 115385433 A CN115385433 A CN 115385433A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/60—Silicon compounds
Abstract
The invention discloses a composite silicon removing agent for wastewater in steel industry and a preparation and use method thereof, wherein the silicon removing agent comprises an auxiliary agent LGF-1 and a main agent LGF-2 which are respectively prepared; the auxiliary agent LGF-1 comprises the following components in percentage by mass: 0.5-2% of hydroxypropyl methylcellulose phthalate, 1-4% of tetramethyl ammonium oxalate, 2-6% of 4-hydroxybutyl acrylate, 2-5% of acrylic styrene copolymer and the balance of water; the main agent LGF-2 comprises the following components in percentage by mass: 6-8% of sodium metaaluminate, 5-8% of polyaluminum chloride, 1-3% of aluminum hydroxide, 3-6% of ferric aluminum sulfate and the balance of water. The composite silicon removing agent disclosed by the invention has the advantages that the auxiliary agent LGF-1 and the main agent LGF-2 are respectively prepared and used, so that a synergistic effect can be generated among various effective silicon removing components, and the silicon removing efficiency and the stability aiming at circulating water are improved.
Description
Technical Field
The invention relates to the field of industrial water treatment, in particular to a steel industrial wastewater composite silicon removal agent and a preparation and use method thereof.
Background
In recent years, various iron and steel enterprises make and implement a 'wastewater zero discharge work plan' gradually. And the final key step of zero discharge of wastewater in the steel industry is the advanced treatment of circulating water. The current circulating water advanced treatment process comprises RO (reverse osmosis) concentration and NF (nanofiltration) salt separation. However, when the silicon dioxide in the circulating water passes through the membrane concentration system in the treatment process, the membrane module is easy to scale and can cause the blockage of the membrane system when serious, so that the membrane flux is reduced; chemical agents are added into the membrane assembly after scaling for washing, so that a large amount of agents are consumed in the washing process, secondary pollution is formed, meanwhile, the membrane system is short in operation period and frequent in inspection and maintenance, and long-period stable operation of the system is difficult to guarantee.
Therefore, silicon removal treatment needs to be carried out in the steel industry wastewater treatment process, and the conventional method at present is to add a solid magnesium-based silicon removal agent, dissolve and dilute the magnesium-based silicon removal agent and continuously put the magnesium-based silicon removal agent into circulating water. Therefore, the water treatment station needs to be reconstructed and expanded, and devices such as a medicine storage tank and a medicine dissolving tank are added, so that the cost of circulating water treatment chemicals is increased. On the other hand, the magnesium-based silicon removal agent has low solubility and is easy to separate out in the wastewater treatment process, so that the dosing pipe is blocked, and uncertain factors are brought to the silicon removal effect.
In view of the above reasons, the efficient composite silicon remover for the wastewater of the steel industry is especially provided. The method solves the problems of low descaling efficiency, high operation cost and blockage of a dosing pipe, thereby ensuring the stable operation and normal operation in the process of treating circulating water by a rear-section RO membrane.
Disclosure of Invention
The invention aims to solve the problems of low descaling efficiency, high operation cost and blockage of a dosing pipe, and provides an efficient composite silicon remover for steel industrial wastewater, so that stable operation and normal operation in a rear-section RO membrane treatment circulating water process are guaranteed.
The technical scheme of the invention is as follows: the composite silicon removing agent for the wastewater in the steel industry is characterized in that: comprises an auxiliary agent LGF-1 and a main agent LGF-2 which are respectively configured;
the auxiliary agent LGF-1 comprises the following components in percentage by mass: 0.5-2% of hydroxypropyl methylcellulose phthalate, 1-4% of tetramethyl ammonium oxalate, 2-6% of 4-hydroxybutyl acrylate, 2-5% of acrylic styrene copolymer and the balance of water;
the main agent LGF-2 comprises the following components in percentage by mass: 6-8% of sodium metaaluminate, 5-8% of polyaluminum chloride, 1-3% of aluminum hydroxide, 3-6% of ferric aluminum sulfate and the balance of water.
The auxiliary agent LGF-1 of the invention comprises: the sum of the mass percentages of hydroxypropyl methylcellulose phthalate, tetramethyl ammonium oxalate, 4-hydroxybutyl acrylate and water is 100 percent; the main agent LGF-2 comprises: the sum of the mass percentages of the sodium metaaluminate, the polyaluminium chloride, the aluminium hydroxide, the aluminum ferric sulfate and the water is 100 percent.
Preferably, the auxiliary agent LGF-1 comprises the following components in percentage by mass: 1-2% of hydroxypropyl methylcellulose phthalate, 2.5-4% of tetramethyl ammonium oxalate, 4-5% of 4-hydroxybutyl acrylate, 3-4% of acrylic styrene copolymer and the balance of water;
the main agent LGF-2 comprises the following components in percentage by mass: 7-8% of sodium metaaluminate, 6-8% of polyaluminium chloride, 2-3% of aluminium hydroxide, 4-6% of ferric aluminum sulfate and the balance of water.
Preferably, the auxiliary agent LGF-1 comprises the following components in percentage by mass: 1% of hydroxypropyl methylcellulose phthalate, 3% of tetramethyl ammonium oxalate, 4% of 4-hydroxybutyl acrylate, 4% of acrylic styrene copolymer and the balance of water;
the main agent LGF-2 comprises the following components in percentage by mass: 7% of sodium metaaluminate, 6% of polyaluminum chloride, 3% of aluminum hydroxide, 4% of aluminum ferric sulfate and the balance of water.
Preferably, the auxiliary agent LGF-1 is used by 20-40 mL and the main agent LGF-2 is used by 100-150 mL per ton of steel industrial wastewater.
The invention also provides a preparation method of the steel industrial wastewater composite silicon removing agent, which is characterized in that the components except water are mixed according to the component proportion of the auxiliary agent LGF-1 and then dissolved in the water to obtain the auxiliary agent LGF-1; mixing the components except water according to the proportion of the main agent LGF-2, and dissolving the mixture in the water to obtain the main agent LGF-2.
The invention also provides a using method of the steel industry wastewater composite silicon removing agent, which comprises the steps of firstly adding the auxiliary agent LGF-1 into the steel industry wastewater, and then adding the main agent LGF-2 into the steel industry wastewater after a certain time interval.
Preferably, the volume ratio of the auxiliary agent LGF-1 to the main agent LGF-2 is 1: (2.5-5).
Preferably, the adding time interval of the auxiliary agent LGF-1 and the main agent LGF-2 is 10-30 min.
Furthermore, 20-40 mL of auxiliary agent LGF-1 and 100-150 mL of main agent LGF-2 are added into each ton of steel industrial wastewater.
The auxiliary agent LGF-1 of the invention contains a large amount of Ca and Si elements which can promote aluminum salt and wastewater to generate stable precipitation and be separated out, thereby reducing the silicon content in circulating water, such as: hydroxypropyl methylcellulose phthalate, tetramethyl ammonium oxalate, acrylic acid styrene copolymer and the like enable Si and Ca ions in the wastewater to generate precipitates with aluminum salt in the main agent to the maximum extent, substances in the auxiliary agent LGF-1 are macromolecular materials, and can be easily intercepted by a rear-section RO film, so that the pollutant content and COD concentration in the treated wastewater cannot be increased.
The main agent LGF-2 contains a large amount of aluminum salt, forms colloidal calcium aluminosilicate salt under the cooperation of the auxiliary agent, is colloidal, has flocculation adsorption effect on polyaluminium chloride, aluminum ferric sulfate and the like in the main agent, and forms floc sediment under the flocculation adsorption effect to be removed.
The invention has the beneficial effects that:
1) The composite silicon removing agent disclosed by the invention has the beneficial effects that the auxiliary agent LGF-1 and the main agent LGF-2 are respectively configured and used, so that the synergistic effect can be generated among various effective silicon removing components, and the preparation method specifically comprises the following steps: hydroxypropyl methylcellulose phthalate, tetramethyl ammonium oxalate, acrylic acid styrene copolymer and the like in the auxiliary agent LGF-1 enable Si and Ca ions in the wastewater to generate precipitation with aluminum salt in the main agent to the maximum extent, aluminum in LGF-2 can form calcium aluminosilicate salt colloid with silicon in the wastewater under the promotion of LGF1, and the colloid is flocculated and precipitated under the flocculation action of LGF-2 to remove silicon in the permanent. The efficiency and stability of removing silicon in the circulating water are improved.
2) The auxiliary agent LGF-1 needs a certain time to dissolve in water, and the auxiliary agent LGF-1 and the circulating water are separately added, so that the main agent LGF-2 can uniformly act in the circulating water.
3) The auxiliary agent LGF-1 can stabilize the performance of the main agent LGF-2 and react quickly, and can quickly combine the main agent LGF-2 with Si and Ca elements in circulating water to precipitate, so that the desiliconization reaction period of the desiliconization agent is shortened.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The following specific examples further illustrate the invention in detail. The drugs used in the examples are commercially available products unless otherwise specified, and the methods used are conventional in the art without further specification.
Example 1
1) Taking 0.5g of hydroxypropyl methylcellulose phthalate, 1g of tetramethyl ammonium oxalate, 6g of 4-hydroxybutyl acrylate and 3.5g of acrylic styrene copolymer, mixing the above substances, and dissolving in 89g of deionized water to obtain 100g of auxiliary agent LGF-1;
2) Mixing 7g of sodium metaaluminate, 8g of polyaluminium chloride, 3g of aluminium hydroxide and 3g of ferric aluminium sulfate, and dissolving the mixture in 79g of deionized water to obtain 100g of main agent LGF-2;
3) Adding 20ml of LGF-1 into each ton of steel industrial wastewater;
4) After 10 minutes, adding 100ml of LGF-1 into each ton of the circulating water;
5) The experiment shows that the Si content in the circulating water is reduced from 85.7ppm to 8.2ppm, and the Si removal rate is as high as 90.4%. The silicon content was measured by GBT 12149-2017 "measurement of silicon in Industrial circulating Cooling Water and boiler Water", the same as below.
6) The composite silicon removal agent is put into a certain circulating water advanced treatment system according to the adding mode to carry out an actual operation test, the average membrane cleaning period of the system is prolonged to 55 days from 30 days before the test, a stable and efficient silicon removal effect is generated on circulating water, and the maintenance cost of an RO membrane in the circulating water advanced treatment system is reduced.
Example 2
1) Taking 2g of hydroxypropyl methylcellulose phthalate, 2g of tetramethyl ammonium oxalate, 4g of 4-hydroxybutyl acrylate and 3g of acrylic styrene copolymer, mixing the above substances, and dissolving in 89g of deionized water to obtain 100g of auxiliary agent LGF-1;
2) Mixing 6g of sodium metaaluminate, 7g of polyaluminium chloride, 2g of aluminum hydroxide and 4g of ferric aluminum sulfate, and dissolving the mixture in 81g of deionized water to obtain 100g of main agent LGF-2;
3) Adding 30ml of LGF-1 into each ton of steel industrial wastewater;
4) After 30 minutes, adding 120ml of LGF-2 into each ton of the circulating water;
5) The experiment proves that the Si content in the circulating water is reduced from 93.2ppm to 7.6ppm, and the Si removal rate is as high as 91.8 percent. The silicon content was measured by GBT 12149-2017 "measurement of silicon in Industrial circulating Cooling Water and boiler Water", the same as below.
6) The composite silicon removal agent is put into a certain circulating water advanced treatment system according to the adding mode to carry out an actual operation test, the average membrane cleaning period of the system is prolonged to 60 days from 30 days before the test, a stable and efficient silicon removal effect is generated on circulating water, and the maintenance cost of an RO membrane in the circulating water advanced treatment system is reduced.
Example 3
1) Taking 1g of hydroxypropyl methylcellulose phthalate, 3g of tetramethyl ammonium oxalate, 4g of 4-hydroxybutyl acrylate and 4g of acrylic styrene copolymer, mixing the above substances, and dissolving in 88g of deionized water to obtain 100g of auxiliary LGF-1;
2) Mixing 7g of sodium metaaluminate, 6g of polyaluminum chloride, 3g of aluminum hydroxide and 4g of aluminum ferric sulfate, and dissolving the mixture in 80g of deionized water to obtain 100g of LGF-2 serving as a main agent;
3) Adding 40ml of LGF-1 into each ton of industrial wastewater;
4) After 30 minutes, 150ml of LGF-2 is added to each ton of the circulating water;
5) The experiment shows that the Si content in the circulating water is reduced from 90.9ppm to 5.3ppm, and the Si removal rate is as high as 94.2 percent. The silicon content is measured by GBT 12149-2017 determination of silicon in industrial circulating cooling water and boiler water.
6) The composite silicon removal agent is put into a certain circulating water advanced treatment system according to the adding mode to carry out an actual operation test, the average membrane cleaning period of the system is prolonged to 65 days from 30 days before the test, a stable and efficient silicon removal effect is generated on circulating water, and the maintenance cost of an RO membrane in the circulating water advanced treatment system is reduced.
Example 4
1) Taking 1.5g of hydroxypropyl methylcellulose phthalate, 4g of tetramethyl ammonium oxalate, 5g of 4-hydroxybutyl acrylate and 3g of acrylic styrene copolymer, mixing the above substances, and dissolving in 86.5g of deionized water to obtain 100g of auxiliary agent LGF-1;
2) Mixing 8g of sodium metaaluminate, 8g of polyaluminium chloride, 3g of aluminum hydroxide and 5g of ferric aluminum sulfate, and dissolving the mixture in 76g of deionized water to obtain 100g of main agent LGF-2;
3) Adding 30ml of LGF-1 into each ton of steel industrial wastewater;
4) After 30 minutes, adding 100ml of LGF-2 into each ton of the circulating water;
5) The experiment shows that the Si content in the circulating water is reduced from 85.9ppm to 6.1ppm, and the Si removal rate is as high as 92.9%. The silicon content is measured by GBT 12149-2017 "measurement of silicon in industrial circulating cooling water and boiler water".
6) The composite silicon removal agent is put into a certain circulating water advanced treatment system according to the adding mode to carry out an actual operation test, the average membrane cleaning period of the system is prolonged to 60 days from 30 days before the test, a stable and efficient silicon removal effect is generated on circulating water, and the maintenance cost of an RO membrane in the circulating water advanced treatment system is reduced.
Example 5
1) Taking 2g of hydroxypropyl methylcellulose phthalate, 2.5g of tetramethyl ammonium oxalate, 4.5g of 4-hydroxybutyl acrylate and 4g of acrylic styrene copolymer, mixing the above substances, and dissolving in 87g of deionized water to obtain 100g of auxiliary agent LGF-1;
2) Mixing 7g of sodium metaaluminate, 7g of polyaluminum chloride, 3g of aluminum hydroxide and 6g of aluminum ferric sulfate, and dissolving in 77g of deionized water to obtain 100g of LGF-2 as a main agent;
3) Adding 40ml of LGF-1 into each ton of industrial wastewater;
4) After 30 minutes, 100ml of LGF-2 was added to the circulating water;
5) The Si content in the circulating water is experimentally measured to be reduced from 106.8ppm to 8.3ppm. The Si removal rate is as high as 92.2%, and the silicon content is measured by GBT 12149-2017 determination of silicon in industrial circulating cooling water and boiler water.
6) The composite silicon removal agent is put into a certain circulating water advanced treatment system according to the adding mode to carry out an actual operation test, the average membrane cleaning period of the system is prolonged to 50 days from 30 days before the test, a stable and efficient silicon removal effect is generated on circulating water, and the maintenance cost of an RO membrane in the circulating water advanced treatment system is reduced.
Claims (8)
1. The composite silicon removing agent for the wastewater in the steel industry is characterized in that: comprises an auxiliary agent LGF-1 and a main agent LGF-2 which are respectively configured;
the auxiliary agent LGF-1 comprises the following components in percentage by mass: 0.5-2% of hydroxypropyl methylcellulose phthalate, 1-4% of tetramethyl ammonium oxalate, 2-6% of 4-hydroxybutyl acrylate, 2-5% of acrylic styrene copolymer and the balance of water;
the main agent LGF-2 comprises the following components in percentage by mass: 6-8% of sodium metaaluminate, 5-8% of polyaluminium chloride, 1-3% of aluminum hydroxide, 3-6% of ferric aluminum sulfate and the balance of water.
2. The steel industry wastewater composite silicon removing agent as recited in claim 1, characterized in that: the auxiliary agent LGF-1 comprises the following components in percentage by mass: 1-2% of hydroxypropyl methylcellulose phthalate, 2.5-4% of tetramethyl ammonium oxalate, 4-5% of 4-hydroxybutyl acrylate, 3-4% of acrylic styrene copolymer and the balance of water;
the main agent LGF-2 comprises the following components in percentage by mass: 7-8% of sodium metaaluminate, 6-8% of polyaluminum chloride, 2-3% of aluminum hydroxide, 4-6% of ferric aluminum sulfate and the balance of water.
3. The steel industry wastewater composite silicon removing agent as set forth in claim 1 or 2, characterized in that: the auxiliary agent LGF-1 comprises the following components in percentage by mass: 1% of hydroxypropyl methylcellulose phthalate, 3% of tetramethyl ammonium oxalate, 4% of 4-hydroxybutyl acrylate, 4% of acrylic styrene copolymer and the balance of water;
the main agent LGF-2 comprises the following components in percentage by mass: 7% of sodium metaaluminate, 6% of polyaluminum chloride, 3% of aluminum hydroxide, 4% of aluminum ferric sulfate and the balance of water.
4. The preparation method of the composite silicon removing agent for the wastewater in the steel industry according to claim 1, characterized in that the components except water are mixed according to the component proportion of the auxiliary agent LGF-1 and then dissolved in the water to obtain the auxiliary agent LGF-1; mixing the components except water according to the component proportion of the main agent LGF-2, and dissolving the mixture in the water to obtain the main agent LGF-2.
5. The use method of the composite silicon removing agent for the wastewater in the steel industry according to claim 1, characterized in that the auxiliary agent LGF-1 is firstly added into the wastewater in the steel industry, and after a certain time interval, the main agent LGF-2 is added into the wastewater in the steel industry.
6. The method for using the composite silicon removing agent for the wastewater in the steel industry as claimed in claim 5, wherein the volume ratio of the dosage of the auxiliary agent LGF-1 to the dosage of the main agent LGF-2 is 1: (2.5-5).
7. The method for using the composite silicon removing agent for the wastewater in the steel industry according to claim 5, wherein the adding time interval of the auxiliary agent LGF-1 and the main agent LGF-2 is 10-30 min.
8. The use method of the composite silicon removing agent for the steel industrial wastewater as claimed in claim 5 or 6, wherein 20-40 mL of the auxiliary agent LGF-1 and 100-150 mL of the main agent LGF-2 are added to each ton of the steel industrial wastewater.
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