A scale and fouling removal composition for smelting wastewater softening equipment and methods of use thereof

Abstract

The present application belongs to the technical field of tungsten smelting plant wastewater treatment, and particularly relates to a smelting wastewater softening equipment anti-blocking and descaling composition and a use method thereof. The method comprises: mixing the smelting wastewater softening equipment anti-blocking and descaling composition with water to form an anti-blocking and descaling composition water dispersion, and then using the anti-blocking and descaling composition water dispersion for blocking and / or fouling, adjusting the pH value to neutral or weakly acidic after the anti-blocking and descaling composition water dispersion completely immerse the blocking and / or fouling, and then reacting and flushing. The technical scheme of the present application adopts a composition that takes effect in a neutral or weakly acidic system, can avoid using a large amount of acid and alkali solution to clean the equipment, and can achieve highly effective descaling and decontamination, has low cleaning cost, and has a green and environmentally-friendly cleaning method and long service life of the equipment.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of tungsten smelting plant wastewater treatment, and particularly relates to a smelting wastewater softening equipment anti-blocking and descaling composition and a use method thereof. BACKGROUND

[0002] Tungsten is a high-melting-point rare metal or refractory rare metal in the field of metallurgy and metal materials. Tungsten and its alloys are one of the most important functional materials in modern industry, national defense and high-tech applications, and are widely used in aerospace, atomic energy, shipbuilding, automobile industry, electrical industry, electronic industry, chemical industry and many other fields. Tungsten mainly comes from scheelite and wolframite, and is often associated with other gangue minerals, so it is often separated by flotation to obtain tungsten concentrate. The "alkali digestion-ion exchange method" is the most commonly used and efficient method in the wet smelting of tungsten concentrate. However, this can lead to a high content of calcium ions in the wastewater, thereby causing the wastewater to be severely hardened, so softening is urgently needed. China has strengthened the wastewater discharge standard, and in order to achieve zero discharge of tungsten smelting wastewater, a regenerated acid and alkali process can be carried out, which includes a "softening-nanofiltration-reverse osmosis-dipolar membrane electrodialysis" regenerated acid and alkali, and the softening process generally adds "lime-sodium carbonate" or "caustic soda-sodium carbonate" to remove calcium and magnesium ions, but a large amount of scale can occur during equipment connection, which needs to be cleaned.

[0003] Patent CN112139133A discloses a descaling-wastewater integrated treatment method for an evaporation system for producing tannin, when the evaporation system is scaled and needs to be shut down for treatment, first adjust the pH value of the tannin aqueous solution to 8-9 with alkali, then increase the temperature to 60-80℃, slowly add hydrogen peroxide or ozone, and circulate and stir for 10-100h until the scale is completely removed; then adjust the pH value to 5-6 with acid, and then add a softening agent for stirring, the softening agent being a phosphate and / or a polyphosphate, the aqueous solution obtained by the treatment is discharged into a recovery tank, the supernatant is recovered to the tannin production line for use, and the remaining scale residue is treated harmlessly. The method can effectively dissolve the scale and react with calcium and magnesium ions in the wastewater to generate a complex that dissolves in water, thereby achieving descaling, the dark tannin aqueous solution becomes a light-colored or colorless solution, and the descaling-wastewater integrated treatment effect is achieved by reusing the tannin production system after softening. However, a large amount of acid and alkali solution is often added to clean the equipment in the industry, which inevitably damages the equipment, causes faults, affects work efficiency, and brings huge economic losses. Therefore, a new smelting wastewater softening equipment anti-blocking and descaling method is needed to solve the above problems. SUMMARY

[0004] Based on the above, in order to solve the problems of the existing sewage treatment process, such as the deposition of a large amount of dirt in the treatment equipment, and the limited effect or harm to the equipment of the current anti-blocking and descaling agent, the present application provides a smelting wastewater softening equipment anti-blocking and descaling composition and a use method thereof.

[0005] The present application aims at:

[0006] I. Softening dirt and completely removing caked dirt;

[0007] II. Reducing the impact and damage to the equipment and ensuring the normal operation of the equipment.

[0008] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions.

[0009] A smelting wastewater softening equipment anti-blocking and descaling composition,

[0010] The composition is obtained by mixing the agent 1 and the agent 2;

[0011] The agent 1 has at least one compound with the structural formula of formula 1, and the formula 1 is as follows:

[0012] Formula 1:

[0013] R1-R4 in the formula 1 contains at least two substituents, the substituents are formula a substituents, and the remaining substituents are H and / or C1-C5 alkyl, and the formula a is as follows:

[0014] Formula a:

[0015] X in the formula 1 and formula a is C2-C10 alkylene, Y is C1-C2 alkylene, and M is H and / or Na and / or K and / or NH4;

[0016] The agent 2 is one of the agents such as acetic acid and oxalic acid.

[0017] As a preferred,

[0018] The structural formula of the agent 1 is formula 1-A, and the formula 1-A is as follows:

[0019] Formula 1-A:

[0020] In the formula 1-A, PO3M is a phosphoric acid group.

[0021] As a preferred,

[0022] The agent 1 and the agent 2 are uniformly mixed in a mass ratio of (0.3-3):1.

[0023] A use method of a smelting wastewater softening equipment anti-blocking and descaling composition,

[0024] The method comprises:

[0025] The smelting wastewater softening equipment anti-blocking and descaling composition is mixed with water to form an anti-blocking and descaling composition water dispersion, and then is used for blocking and / or fouling, and reacts after the pH value is adjusted to neutral or weakly acidic after the blocking and / or fouling is completely immersed, and is flushed.

[0026] Preferably,

[0027] The concentration of the smelting wastewater softening equipment anti-blocking and descaling composition in the anti-blocking and descaling composition water dispersion is 10-20 mg / L.

[0028] Preferably,

[0029] The amount of the smelting wastewater softening equipment anti-blocking and descaling composition is 0.01-0.1 mg / g of the blocking and / or fouling.

[0030] Preferably,

[0031] The pH value is adjusted to 6-7;

[0032] The reaction time is 2-5 min.

[0033] In the anti-blocking and descaling composition of the present application, Y is preferably methylene (-CH2-). Methylene is often used to represent a secondary carbon atom, that is, a carbon atom having two bonds substituted. The two hydrogen atoms on the methylene are located on both sides of the carbon atom, and it can be connected to other atom groups, such as dichloromethane. Methylene is often a constituent unit of a carbon chain, which increases the lipophilicity of the compound. When the anti-blocking and descaling composition is used, a “:CH2” electrically neutral molecule is formed, which is called “carbene” or “methylene”, and is a highly active reaction intermediate.

[0034] The active components of the material tend to bind to the fouling, and after binding to the fouling, no foam is generated, and no secondary pollution is caused. The medicament 1 and the medicament 2 have good killing effects on bacteria such as iron bacteria, sulfate-reducing bacteria, and saprophytic bacteria. In particular, the long chain of the medicament 1 is easily adsorbed on the tiny calcium carbonate crystal grains, and at the same time, does not displace the anions of the fouling, avoiding the precipitation of calcium carbonate, hydrated iron oxide, calcium sulfate and other substances. The medicament 1 is used in combination with the medicament 2, and the anti-blocking and descaling composition is not easily hydrolyzed after being combined with the fouling.

[0035] The application provides a simple method of combining water and chemical methods to remove dirt, which can solve the problem of dirt accumulation and prolong the service life of related equipment. The water dispersion of the anti-blocking and dirt-removing composition of the application can reduce the viscosity of dirt, quickly penetrate into dirt, and disperse oil components, further penetrate to destroy and separate oil components, and finally completely remove microorganisms and grease. In an alkaline environment, the dirt removal rate of the anti-blocking and dirt-removing composition is low, and when the pH value of the system is more than 11 or less than 5, there is a problem of equipment corrosion. However, the composition of the application can achieve efficient dirt removal and decontamination under neutral and weakly acidic conditions, thereby protecting the equipment.

[0036] The application has the following beneficial effects:

[0037] The technical scheme of the application adopts a composition that takes effect under a neutral or weakly acidic system, which can avoid using a large amount of acid or alkali solution to clean the equipment while achieving highly effective decontamination and dirt removal, has low cleaning cost, and is green and environmentally friendly, and the service life of the equipment is long. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 It is a schematic diagram of the operation steps of the dirt removal method in the application. DETAILED DESCRIPTION

[0039] The application will be further described and illustrated in detail in combination with specific embodiments and the accompanying drawings of the specification. Those skilled in the art will be able to implement the application based on these descriptions. In addition, the embodiments of the application involved in the following description are generally only a part of the embodiments of the application, not all the embodiments. Therefore, based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor should be within the scope of protection of the application.

[0040] Unless otherwise specified, the raw materials used in the embodiments of the application are commercially available or can be obtained by those skilled in the art; unless otherwise specified, the methods used in the embodiments of the application are methods mastered by those skilled in the art.

[0041] Unless otherwise specified, the calcium scale used in the embodiments of the application comes from a tungsten smelting softening equipment in Jiangxi.

[0042] Unless otherwise specified, the simulation equipment used in the embodiments of the application is equipment that has not yet been corroded.

[0043] Embodiment 1

[0044] A method for using a smelting wastewater softening equipment anti-blocking and dirt-removing composition, the method comprising:

[0045] 1) Take the medicament 1 and the medicament 2 and mix them uniformly according to a mass ratio of 1:1 to obtain an anti-blocking and dirt-removing composition;

[0046] wherein the formula of the medicament 1 is as follows:

[0047]

[0048] The medicament 2 is acetic acid

[0049] 2) 5 mg of the anti-blocking and descaling composition is taken and mixed uniformly with 500 mL of water to obtain an aqueous dispersion of the anti-blocking and descaling composition;

[0050] 3) The aqueous dispersion of the anti-blocking and descaling composition is added to a simulated device containing 100 g of calcium scale, the pH value of the system is adjusted to 6, and after 2 min of reaction, the device is rinsed.

[0051] The system after the reaction is filtered and dried to obtain residual calcium scale, the calcium scale is weighed, and the descaling rate is calculated. As a result, 26.6 g of calcium scale is obtained, and the descaling rate of the anti-blocking and descaling composition in this example is 73.4%.

[0052] Further, 5 mg of the anti-blocking and descaling composition is added again and reacted for 2 min, and the above filtering, drying, and weighing steps are repeated. It is found that the calcium scale is only 0.9 g, which indicates that the anti-blocking and descaling composition has good descaling effect. In addition, observation and array electrode characterization of the device show that no obvious corrosion occurs at the treated site, so it can also be seen that the composition and the use method of the composition can effectively avoid corrosion damage to the device.

[0053] Example 2

[0054] A use method of a smelting wastewater softening device anti-blocking and descaling composition, the method comprises:

[0055] 1) Medicament 1 and medicament 2 are mixed uniformly according to a mass ratio of 0.3:1 to obtain an anti-blocking and descaling composition;

[0056] wherein the formula of the medicament 1 is as follows:

[0057]

[0058] The medicament 2 is acetic acid

[0059] 2) 5 mg of the anti-blocking and descaling composition is taken and mixed uniformly with 500 mL of water to obtain an aqueous dispersion of the anti-blocking and descaling composition;

[0060] 3) The aqueous dispersion of the anti-blocking and descaling composition is added to a simulated device containing 100 g of calcium scale, the pH value of the system is adjusted to 6, and after 2 min of reaction, the device is rinsed.

[0061] The reacted system was filtered and dried to obtain residual calcium scale, the calcium scale was weighed, and the scale removal rate was calculated. As a result, 30.9 g of calcium scale was obtained, and the scale removal rate of the anti-blocking scale removal composition in this example was 69.1%.

[0062] Further, 5 mg of the anti-blocking scale removal composition was added again and reacted for 2 min, and the above filtering, drying, and weighing steps were repeated. It was found that the calcium scale was only 1.1 g.

[0063] Compared with Example 1, the initial scale removal rate of Example 2 was relatively reduced, because the medicament 1 was the main scale removal efficiency component, and the reduction of the amount would also be accompanied by the weakening of the effect. However, the amount of medicament 2 was increased, which actually made the scale removal more moderate. When the initial scale removal reaction time was extended to 5 min, a great improvement was achieved, and the scale removal rate reached 77.2%, close to that of Example 1. When the initial scale removal reaction time of Example 1 was extended to 5 min, the scale removal rate reached 79.6%, without a great improvement, indicating that the medicament 1 was quickly consumed, and the medicament 2 had the effect of stabilizing the medicament 1. Therefore, by controlling the relative amounts of the medicaments 1 and 2, the efficiency and mildness of the scale removal composition can be adjusted. For the equipment that has been corroded to a certain extent, the composition with a higher proportion of medicament 2 can produce a more moderate and effective scale removal effect.

[0064] Example 3

[0065] A method for using a smelting wastewater softening equipment anti-blocking scale removal composition, the method comprising:

[0066] 1) mixing medicament 1 and medicament 2 uniformly according to a mass ratio of 3:1 to obtain an anti-blocking scale removal composition;

[0067] The structural formula of the medicament 1 is as follows:

[0068]

[0069] The medicament 2 is acetic acid

[0070] 2) mixing 5 mg of the anti-blocking scale removal composition and 500 mL of water uniformly to obtain an anti-blocking scale removal composition water dispersion;

[0071] 3) adding the anti-blocking scale removal composition water dispersion to a simulated equipment containing 100 g of calcium scale, adjusting the pH value of the system to 6, and rinsing after reacting for 2 min.

[0072] The reacted system was filtered and dried to obtain residual calcium scale, the calcium scale was weighed, and the scale removal rate was calculated. As a result, 30.9 g of calcium scale was obtained, and the scale removal rate of the anti-blocking scale removal composition in this example was 69.1%.

[0073] Further, 5 mg of the anti-blocking and descaling composition was added again and reacted for 2 min, and the above filtration, drying, and weighing steps were repeated, and it was found that the calcium scale was only 0.6 g.

[0074] As explained in Example 2, the ratio of the use of the medicament 1 and the medicament 2 determines the treatment property of the medicament, whether it is efficient treatment or mild treatment. In this example, the treatment efficiency is higher and the effect is better.

[0075] However, as mentioned above, when the initial descaling test of step 3) of the present application is carried out, when the simulation test is carried out using the old equipment that has been corroded as the simulation equipment, the medicament composition of Example 1 causes slight corrosion to the equipment that is not visible to the naked eye, and the array electrode characterization can characterize that it causes extremely slight corrosion aggravation, while the medicament composition of Example 2 does not cause any corrosion aggravation, but when the medicament composition of Example 3 is used, a small amount of bubbles appears, indicating that it may cause slight corrosion, but it is still not visible to the naked eye and needs to be characterized by the array electrode. From this experiment, it can be seen that the composition of the present application has good descaling effect and mildness, but the descaling efficiency and mildness can be adjusted by the ratio of the medicament 1 and the medicament 2, so as to be used in different scenarios.

[0076] Comparative Example 1

[0077] A method for using the anti-blocking and descaling composition for a smelting wastewater softening equipment, the method comprising:

[0078] 1) 5 mg of the medicament 1 was taken and mixed uniformly with 500 mL of water to obtain an anti-blocking and descaling composition aqueous dispersion; the structural formula of the medicament 1 is as follows:

[0079]

[0080] 2) The anti-blocking and descaling composition aqueous dispersion was added to the simulation equipment containing 100 g of calcium scale, the pH value of the system was adjusted to 6, and the reaction was carried out for 2 min and then rinsed.

[0081] The system after the reaction was filtered and dried to obtain the remaining calcium scale, the calcium scale was weighed, the descaling rate was calculated, and 39.3 g of calcium scale was obtained, and the descaling rate of the anti-blocking and descaling composition in this example was 60.7%. This shows that the anti-blocking and descaling composition cannot achieve the descaling effect in the example when the medicament 1 is used alone.

[0082] Comparative Example 2

[0083] A method for using the anti-blocking and descaling composition for a smelting wastewater softening equipment, the method comprising:

[0084] 1) 5 mg of the medicament 2 was taken and mixed uniformly with 500 mL of water to obtain an anti-blocking and descaling composition aqueous dispersion;

[0085] Medicament 2 is acetic acid;

[0086] 2) Add the water dispersion of the anti-clogging and scale removal composition to the simulated equipment containing 100 g of calcium scale, adjust the pH value of the system to 6, and rinse after 2 min of reaction.

[0087] The reacted system is filtered and dried to obtain residual calcium scale, the calcium scale is weighed, and the scale removal rate is calculated. The result is 62.3 g of calcium scale, and the scale removal rate of the anti-clogging and scale removal composition in this example is 37.7%. This shows that the anti-clogging and scale removal composition cannot achieve the scale removal effect in the example when used alone with medicament 2, and the scale removal effect is worse than that of Comparative Example 1.

[0088] Comparative Example 3

[0089] A method for using a smelting wastewater softening equipment anti-clogging and scale removal composition, the method comprising:

[0090] 1) Mix medicament 1 and medicament 2 uniformly at a mass ratio of 1:1 to obtain an anti-clogging and scale removal composition;

[0091] The structural formula of medicament 1 is as follows:

[0092]

[0093] Medicament 2 is acetic acid;

[0094] 2) Mix 5 mg of the anti-clogging and scale removal composition with 500 mL of water to obtain a water dispersion of the anti-clogging and scale removal composition;

[0095] 3) Add the water dispersion of the anti-clogging and scale removal composition to the simulated equipment containing 100 g of calcium scale, adjust the pH value of the system to 8, and rinse after 2 min of reaction.

[0096] The reacted system is filtered and dried to obtain residual calcium scale, the calcium scale is weighed, and the scale removal rate is calculated. The result is 36.2 g of calcium scale, and the scale removal rate of the anti-clogging and scale removal composition in this example is 63.8%. This shows that the scale removal effect of the anti-clogging and scale removal composition is not as good in a weak alkaline environment as in an alkaline environment. In addition, it is found through array electrode characterization that slight corrosion occurs at the treatment site during the scale removal process.

[0097] Comparative Example 4

[0098] A method for using a smelting wastewater softening equipment anti-clogging and scale removal composition, the method comprising:

[0099] 1) Mix medicament 1 and medicament 2 uniformly at a mass ratio of 1:1 to obtain an anti-clogging and scale removal composition;

[0100] The structural formula of medicament 1 is as follows:

[0101]

[0102] The medicament 2 is acetic acid;

[0103] 2) 5 mg of the anti-blocking and descaling composition is taken and mixed with 500 mL of water to obtain an aqueous dispersion of the anti-blocking and descaling composition;

[0104] 3) The aqueous dispersion of the anti-blocking and descaling composition is added to a simulated device containing 100 g of calcium scale, and the pH of the system is adjusted to 12, and the system is rinsed after 2 min of reaction.

[0105] The reacted system is filtered and dried to obtain residual calcium scale, and the calcium scale is weighed to calculate the descaling rate. As a result, 78.4 g of calcium scale is obtained, and the descaling rate of the anti-blocking and descaling composition in this example is 21.6%. The excessively strong alkaline environment causes the medicament to fail, and the descaling effect is extremely poor. And there is also slight corrosion at the treatment site.

[0106] Comparative Example 5

[0107] A method for using a descaling composition for preventing blockage of a smelting wastewater softening device, the method comprising:

[0108] 1) The medicament 1 and the medicament 2 are mixed in a mass ratio of 1:1 to obtain an anti-blocking and descaling composition;

[0109] The structural formula of the medicament 1 is as follows:

[0110]

[0111] The medicament 2 is acetic acid;

[0112] 2) 4 mg of the anti-blocking and descaling composition is taken and mixed with 500 mL of water to obtain an aqueous dispersion of the anti-blocking and descaling composition;

[0113] 3) The aqueous dispersion of the anti-blocking and descaling composition is added to a simulated device containing 100 g of calcium scale, and the pH of the system is adjusted to 8, and the system is rinsed after 2 min of reaction.

[0114] The reacted system is filtered and dried to obtain residual calcium scale, and the calcium scale is weighed to calculate the descaling rate. As a result, 26.8 g of calcium scale is obtained, and the descaling rate of the anti-blocking and descaling composition in this example is 70.2%. Compared with Example 1, the descaling rate is reduced by 3.2%.

[0115] It can be seen from the results of Examples 1-3 and Comparative Examples 1-5 that, in order to achieve good descaling effect, the combination mode, dosage, and pH environment of the medicament should be controlled.

Claims

1. A method of using an anti-clogging and descaling composition for a smelting wastewater softening equipment, characterized in that, The composition is obtained by mixing reagent 1 and reagent 2; The structural formula of the drug 1 is Formula 1-A, and Formula 1-A is as follows: Formula 1-A: ; In Formula 1-A, PO3M is a phosphate group, X is a C2 to C10 alkylene group, and M is H and / or Na and / or K and / or NH4; The reagent 2 is acetic acid and / or oxalic acid; The reagent 1 and reagent 2 are mixed evenly at a mass ratio of (0.3-3):1; The method of use includes: The anti-clogging and descaling composition of the smelting wastewater softening equipment is mixed with water to form an aqueous dispersion of the anti-clogging and descaling composition. Then, it is applied to the blockages and / or dirt, and after the blockages and / or dirt are completely submerged, the pH value is adjusted to 6-7, the reaction is carried out for 2-5 minutes, and then rinsed. The concentration of the anti-clogging and descaling composition in the aqueous dispersion of the smelting wastewater softening equipment is 10-20 mg / L.

2. The method of using the anti-clogging and descaling composition for a smelting wastewater softening equipment according to claim 1, characterized in that, The dosage of the anti-clogging and descaling composition for the smelting wastewater softening equipment is 0.01–0.1 mg / g of blockages and / or dirt.

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