CN111205012B

CN111205012B - Concrete accelerator taking waste aluminum ring-pull cans as raw materials and preparation method thereof

Info

Publication number: CN111205012B
Application number: CN202010068780.9A
Authority: CN
Inventors: 董耀武; 代柱端; 陈健; 周晓阳
Original assignee: Wuhan Youcheng Technology Co ltd
Current assignee: Wuhan Youcheng Technology Co ltd
Priority date: 2020-01-21
Filing date: 2020-01-21
Publication date: 2021-12-24
Anticipated expiration: 2040-01-21
Also published as: CN111205012A

Abstract

The invention belongs to the field of accelerator preparation, and particularly relates to a concrete accelerator prepared from waste aluminum pop cans as a raw material and a preparation method thereof, wherein the concrete accelerator comprises the following components in percentage by weight: 70-75% of self-made aluminum sulfate solution, 3-8% of active aluminum hydroxide, 0.2-0.6% of methylene dinaphthalene sodium sulfonate, 3-6% of organic alcohol amine, 0.1-0.3% of sulfobetaine and the balance of deionized water; the self-made aluminum sulfate solution is prepared by filtering aluminum slag powder obtained by grinding waste pop cans and a 50% sulfuric acid solution in a mass ratio of 1: 13-16. The invention takes the aluminum sulfate solution obtained by filtering after the aluminum slag powder obtained by grinding the waste pop can reacts with the sulfuric acid solution as the main raw material, and micron-sized carbonized particles can be used as crystal seeds to promote the generation of hydration products besides the conventional coagulation promoting component aluminum sulfate, thereby accelerating the thickening of cement slurry, filling the pores among the particles and improving the early strength.

Description

Concrete accelerator taking waste aluminum ring-pull cans as raw materials and preparation method thereof

Technical Field

The invention relates to the field of accelerator preparation, in particular to a concrete accelerator prepared from waste aluminum ring-pull cans and a preparation method thereof.

Background

In the field of construction, the concrete accelerator is widely applied, and is a chemical additive capable of accelerating the setting and hardening speed of concrete. The early accelerating agent mainly comprises aluminate, carbonate and the like, has high alkali content and has the defects of large loss of the hardening strength of the slurry in the later period; therefore, in recent years, alkali-free liquid accelerators have become the main stream.

At present, an alkali-free liquid accelerator with more excellent performance is developed at home and abroad by adopting an organic-inorganic composite method, wherein organic components mainly comprise various alcohol amines, amides, organic alcohols, carboxylic acids and the like, and inorganic components mainly comprise aluminum sulfate and aluminate. For example, Chinese patent No. CN201910659832.7 discloses an early high-strength composite alkali-free liquid accelerator, a preparation method and sprayed concrete; the alkali-free liquid accelerator comprises the following components: aluminum sulfate: 45% -55%; activated aluminum hydroxide: 5% -10%; fluoride salt: 5% -10%; alcohol amine: 1.5% -4%; polyacrylamide: 0.5 to 1 percent; organic water reducing agent: 1% -3%; a stabilizer: 0.8% -1%; water: 25 to 35 percent. However, the fluoride salt content in the formula is too high, so that the fluoride ion content is too high, if the fluoride ion flows out of the concrete, underground water resources can be polluted, and great negative effects can be generated on the health of human bodies, and the alkali-free liquid accelerator has the problems of low early strength and poor long-term stability of the concrete. In addition, chinese patent No. CN201611119241.3 discloses a cement accelerator and a preparation method thereof, wherein the liquid accelerator comprises the following raw materials: aluminum sulfate: 50-70%, phosphoric acid: 1-7%, amide: 1-5%, aluminum hydroxide: 1-10%, alcohol amine: 1-8%, silicate: 1-5% and the balance of water. However, the addition amount of the cement accelerator exceeds 7%, when the addition amount reaches 9%, the initial setting time and the final setting time are still longer, which exceed 2min20s and 7min20s respectively, and the initial setting time and the final setting time, the early strength and the later strength have large fluctuation range along with the content change of main components such as aluminum sulfate, silicate, phosphoric acid, aluminum hydroxide and the like, so that the product performance is unstable. Secondly, the main raw material of the accelerator, namely aluminum sulfate, is a commercial industrial grade raw material, and the industrial production aluminum sulfate is prepared by pressure reaction of bauxite and sulfuric acid, filtration of insoluble substances and recrystallization.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a concrete accelerator taking waste aluminum ring-pull cans as raw materials and a preparation method of the concrete accelerator; the invention takes the aluminum sulfate solution obtained by filtering after the aluminum slag powder obtained by grinding the waste pop can reacts with the sulfuric acid solution as the main raw material, and micron-sized carbonized particles can be used as crystal seeds to promote the generation of hydration products besides the conventional coagulation promoting component aluminum sulfate, thereby accelerating the thickening of cement slurry, filling the pores among the particles and improving the early strength.

In order to achieve the purpose, the invention adopts the technical scheme that:

a concrete accelerator taking waste aluminum ring-pull cans as raw materials comprises the following raw materials in parts by mass: 70-75% of self-made aluminum sulfate solution, 3-8% of active aluminum hydroxide, 0.2-0.6% of methylene dinaphthalene sodium sulfonate, 3-6% of organic alcohol amine, 0.1-0.3% of sulfobetaine and the balance of deionized water;

the self-made aluminum sulfate solution is prepared by filtering aluminum slag powder obtained by grinding waste pop cans and a 50% sulfuric acid solution in a mass ratio of 1: 13-16.

Adopt above-mentioned technical scheme: firstly, crushing and grinding waste aluminum ring-pull cans into aluminum slag powder with certain fineness by adopting pretreatment, wherein the grinding action can damage organic paint layers on the surfaces and increase the specific surface area of particles, so that the chemical reaction activity of subsequent acid dissolution treatment is improved; reacting aluminum slag powder with an excessive high-concentration sulfuric acid solution (mass concentration, wt) at a high temperature, and gradually carbonizing an organic paint layer on the surface layer to form tiny carbonized particles suspended in the sulfuric acid solution; and then gradually dissolving the metal aluminum in the organic paint layer, simultaneously discharging hydrogen, finally filtering larger waste residues to obtain a self-made aluminum sulfate solution, and repeating the acid dissolving step on the filtered waste residues to improve the dissolution rate of the metal aluminum. The self-made aluminum sulfate solution is used in the accelerator, and contains a certain amount of micron-sized carbonized particles besides the high-concentration accelerating component aluminum sulfate, so that the specific surface area of solid particles can be increased, more water molecules can be adsorbed, and the self-made aluminum sulfate solution can also be used as a crystal seed to promote the generation of hydration products, thereby accelerating the thickening of cement slurry, filling the pores among the particles and improving the early strength.

The active aluminum hydroxide in the accelerator is used for neutralizing excessive sulfuric acid and adjusting the pH value of the system to 1.8-2.3; on the other hand, the percentage of the aluminum oxide in the accelerator can be increased, and the percentage of the aluminum oxide is positively correlated with the accelerating effect of the accelerator.

The methylene dinaphthalene sodium sulfonate in the accelerator is an anionic surfactant, is stable to strong acid and strong base, has good wetting performance, can increase the breakage probability and degree of a hydration membrane in a hydration reaction system, promotes the dissolution rate of calcium ions and aluminum ions to be accelerated, contains a sulfonic group with strong electronegativity, can complex metal cations, increases the solubility and the dispersibility of the aluminum ions and the calcium ions, increases effective amount of the aluminum ions and the calcium ions in the reaction system, and promotes the generation of early hydration products due to chemical imbalance caused by high content of the aluminum ions and the calcium ions, thereby enhancing the effect of accelerating coagulation.

The sulfobetaine in the accelerator is a zwitterionic surfactant, is stable to strong acid and strong alkali, contains a large amount of hydroxyl, sulfonic acid groups, quaternary ammonium salt cations and the like in a molecular structure, can form hydrogen bonds with water, has a good thickening effect, and is favorable for improving the stability of the accelerator.

The methylene dinaphthalene sodium sulfonate and the sulfobetaine are compounded, a hydrophobic chain of the methylene dinaphthalene sodium sulfonate is easily inserted into a carbon chain of the sulfobetaine to form a stable three-dimensional network space structure, so that the dispersibility of metal cations is improved, a good thickening effect is achieved, the system viscosity can be improved under the condition of a low addition amount, the resistance of aluminum sulfate crystallization is increased, and the rebound loss is favorably reduced when the methylene dinaphthalene sodium sulfonate and the sulfobetaine are applied to sprayed concrete. Therefore, the proper amount of the methylene dinaphthalene sodium sulfonate and the sulfobetaine are added, so that the long-term standing and low-temperature stability of the accelerator are improved, the thickening of cement paste can be accelerated, and the setting time is shortened; however, it was found that excessive addition significantly affected the 1d strength development of the cement.

Further, the reaction temperature of the aluminum slag powder and a 50% sulfuric acid solution is 60 +/-2 ℃. The high-temperature reaction is beneficial to the generation of the carbonized particles and improves the generation amount of the carbonized particles.

Further, after the aluminum slag powder and a 50% sulfuric acid solution are reacted, the reaction solution is subjected to high-speed shearing and dispersion, and then the self-made aluminum sulfate solution is prepared by filtering. Under the high-speed shearing and stirring, the carbonized particles become micron-sized particles suspended in the solution, which is beneficial to improving the specific surface area and the nucleation effect of the particles.

Further, the mass ratio of the sodium methylene dinaphthalene sulfonate to the sulfobetaine is 2: 1.

further, the sulfobetaine is one or more of dodecyl sulfopropyl betaine, hydroxypropyl sulfobetaine and alkylamide propyl hydroxypropyl sulfobetaine.

Furthermore, the organic alcohol amine is one of triethanolamine, diethanolamine and ethylene glycol monoisopropanolamine, and the content is more than or equal to 85%. When the alcohol amine is applied to the accelerator, the pH value can be adjusted, and the solubility and low-temperature stability of aluminum sulfate are improved; when the calcium silicate is used in cement, the ion dissolution rate and hydration reaction of tricalcium aluminate in the cement can be accelerated, the rapid coagulation of the cement is promoted, the hydration induction period of tricalcium silicate can be shortened, and the calcium silicate has a certain effect of promoting the development of early strength.

Further, the aluminum content in the waste aluminum ring-pull can is more than or equal to 95%.

Furthermore, the mesh number of the aluminum slag powder is 50-100.

Furthermore, the active aluminum hydroxide is amorphous aluminum hydroxide, namely, is prepared by drying hydrated alumina and is easy to dissolve in acid.

Furthermore, the sodium methylene dinaphthalenesulfonate is of industrial grade, the content is more than or equal to 98 percent, the sulfobetaine is of industrial grade, and the solid content is more than or equal to 50 percent.

The invention also discloses a preparation method of the concrete accelerator by taking the waste aluminum ring-pull can as a raw material, which comprises the following steps:

s1, preprocessing: grinding and crushing the recovered waste aluminum ring-pull cans into aluminum slag powder with the mesh number of 50-100; the inner and outer surfaces of the waste aluminum ring-pull cans are provided with surface layers such as organic matter spray paint and oxide passivation layers, the chemical reaction activity is obviously blocked and reduced, if the reaction activity and the recovery efficiency are improved, the waste aluminum ring-pull cans are subjected to crushing and grinding pretreatment, the specific surface area is increased, the spray paint or the passivation layers on the surface layers are damaged, and the aluminum slag powder with certain fineness is prepared;

s2, acid dissolution: heating a 50% sulfuric acid solution to 60 +/-2 ℃, then adding aluminum slag powder, reacting for 2-4h at normal pressure until no air bubbles are generated on the residual aluminum slag powder at the mass ratio of the aluminum slag powder to the 50% sulfuric acid solution of 1: 13-16, then shearing and dispersing the reaction liquid at high speed, and filtering the reaction liquid to obtain a self-made aluminum sulfate solution;

s3, pH adjustment: adding active aluminum hydroxide into the self-made aluminum sulfate solution, and reacting for 0.5-1h at the rotation speed of 300-;

s4, modification and adjustment: adding sodium methylene dinaphthalene sulfonate, performing heat preservation curing for 0.2-0.5h under the conditions that the rotation speed is 100-.

The composite material comprises the following raw materials in percentage by mass: 70-75% of self-made aluminum sulfate solution, 3-8% of active aluminum hydroxide, 0.2-0.6% of methylene dinaphthalene sodium sulfonate, 3-6% of organic alcohol amine, 0.1-0.3% of sulfobetaine and the balance of deionized water.

Compared with the prior art, the invention has the advantages that:

1. the method comprises the steps of crushing and grinding waste aluminum ring-pull cans by adopting pretreatment to destroy organic paint layers on the surfaces and increase the chemical reaction activity, and then dissolving aluminum slag powder under the conditions of excessive strong acid and high temperature to dissolve out metal aluminum and form micron-sized carbonized particles to be suspended in a solution, so as to obtain a self-made aluminum sulfate solution; besides the conventional coagulation accelerating component aluminum sulfate, the micron-sized carbonized particles can be used as seed crystals to promote the generation of hydration products, so that the thickening of cement paste is accelerated, the pores among the particles are filled, and the early strength is improved. On the other hand, the method avoids high energy consumption caused by the conventional smelting and paint removing process for treating the waste aluminum pop cans, and simultaneously ensures higher aluminum conversion rate.

2. The addition of the sodium methylene dinaphthalene sulfonate and the sulfobetaine improves the solubility and the dispersibility of aluminum ions and calcium ions, and the synergistic effect of the sodium methylene dinaphthalene sulfonate and the sulfobetaine improves the low-temperature and long-standing stability of the concrete accelerator, and obvious crystallization and precipitation are not generated after the concrete accelerator is placed at normal temperature for one year; and the rebound rate of the sprayed concrete is reduced, and the early strength of the concrete is improved.

3. The invention has the advantages of easily obtained raw materials, low cost, simple preparation method and production process, easy industrialization, capability of meeting the technical requirements of relevant national standards, long-term storage and good low-temperature stability.

Detailed Description

The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the following examples, the raw materials except the self-made aluminum sulfate solution are all technical grade, for example, the sulfuric acid is technical grade sulfuric acid, and the concentration is 50%; the sulfobetaine is of industrial grade, and the solid content is more than or equal to 50 percent; many sulfobetaines have little influence on the product performance of the invention, and the sulfobetaine in the following examples is only exemplified by hydroxypropyl sulfobetaine and is not used as a limitation to the protection scope of the invention; the sodium methylene dinaphthalenesulfonate is of industrial grade, and the content is more than or equal to 98 percent.

Experiments show that when the stirring speed and the reaction time in the steps S2-S4 and the mesh number of the aluminum slag in the step S1 are selected within the protection range of the invention, the product performance is not greatly influenced, when the reaction temperature is lower than the protection range of the invention, carbonized particles cannot be formed, the dissolution speed of the aluminum sulfate is slow, the temperature is further increased, and the dissolution speed of the aluminum sulfate is not obviously increased, so that the temperature is preferably about 60 ℃; therefore, in the following examples and comparative examples, the preparation method is as follows, without specific description:

s1, preprocessing: putting the recovered waste aluminum ring-pull cans into a crusher, and crushing the cans into small granular aluminum slag powder with the mesh number of 100;

s2, acid dissolution: adding a certain amount of deionized water into a three-neck flask with a mechanical stirring and reflux condenser pipe and a thermometer, stirring at the rotating speed of 400r/min, slowly adding sulfuric acid with the same mass, uniformly mixing, heating to raise the temperature to 60 +/-2 ℃, then adding a certain amount of aluminum slag powder, reacting for 3 hours under normal pressure until no bubbles are generated on the residual slag, shearing and dispersing the reaction liquid at high speed, and filtering the reaction liquid to obtain an aluminum sulfate solution;

s3, pH adjustment: weighing the self-made aluminum sulfate solution obtained in the step S2 into a three-neck flask, adding a certain amount of active aluminum hydroxide, reacting for 1h at the rotation speed of 500r/min and the temperature of 60 +/-2 ℃ until the active aluminum hydroxide solid is completely dissolved, and neutralizing excessive sulfuric acid to adjust the pH to 2-3;

s4, modification and adjustment: adding sodium methylene dinaphthalene sulfonate, performing heat preservation curing for 0.5h at the rotation speed of 150r/min and the temperature of 60 +/-2 ℃, then adding organic alcohol amine and sulfobetaine, continuing to perform heat preservation curing for 0.5h, and adjusting the pH value to be 2.0-2.5 to obtain a semi-transparent concrete accelerator finished product.

Examples 1 to 12 and comparative examples 1 to 7

The concrete accelerator taking waste aluminum ring-pull cans as raw materials provided in the embodiments 1 to 12 and the comparative examples 1 to 8 comprises the following components in percentage by weight as shown in table 1.

TABLE 1 concrete accelerators of examples 1 to 12 and comparative examples 1 to 8

Application example Performance detection

Preparing concrete accelerators of examples 1-12 and comparative examples 1-8 according to the raw materials and mass percentages in the table 1; according to relevant regulations in GB/T35159-2017 accelerating agent for sprayed concrete, two indexes of net slurry setting time and mortar compressive strength are respectively detected when the concrete accelerating agent of each group is used, and the stability of the concrete accelerating agent of each group is measured. Blank groups are also provided for comparison of test results. The type of the used cement is P.O 42.5.5, and the mixing amount of the concrete accelerator in each group accounts for 5 percent of the mass of the cement. The results of the measurements are shown in Table 2.

TABLE 2 Performance test results of concrete accelerator made of waste aluminum cans

Analyzing the data of the examples 1-3 and the comparative examples 1-2, it can be seen that the setting time of the accelerator is obviously shortened and the compressive strength is obviously increased along with the increase of the content of the self-made aluminum sulfate solution, when the content of the self-made aluminum sulfate solution exceeds 70%, enough aluminum sulfate serving as a set accelerating component and enough carbonized particles serving as a nucleation component can be provided, the content is increased again, the setting time and the compressive strength of the accelerator are not obviously changed, the initial setting of the examples 1-3 is not more than 3min, the final setting time is not more than 10min, the compressive strength of 1d is not less than 16MPa, the strength ratio of 28d is not less than 90%, and the volume of the 28d standing crystal is not more than 5mL, which all meet the standard requirements; however, when the content of the self-made aluminum sulfate solution is increased to the content of the comparative example 2, although the initial setting time and the final setting time meet the standard requirements, precipitation is obvious due to precipitation of aluminum sulfate and increase of carbonized particles, the pH value and 28d crystal do not meet the standard requirements, and the long-term stability is poor. Moreover, the inventors found in experiments that when the self-made aluminum sulfate solution in example 2 was replaced with a conventional technical grade aluminum sulfate solution (in terms of aluminum sulfate content) in equal amount, the initial setting time was extended to 2min33s due to lack of nucleation of carbonized particles, the 1d strength was 16.3MPa, and the 28d compressive strength ratio was only 96.5%; therefore, the invention not only provides a recovery way of the waste gas pop can, but also expands the application of the waste gas pop can in the accelerating agent, and has good social prospect.

As is apparent from the analysis of the data of examples 2, 4 to 5 and comparative examples 3 to 4, the amount of active aluminum hydroxide used is preferably 6% because the pH is significantly reduced and the initial setting and final setting times are prolonged by reducing the amount of active aluminum hydroxide used, and the long-term stability of 28 days is deteriorated by an excessive amount.

Analyzing the data of examples 2, 6-7 and comparative examples 5-6, it can be seen that as the appropriate content of sodium methylenedinaphthalene sulfonate increases, the setting time is significantly improved, and as the content of sodium methylenedinaphthalene sulfonate increases, the amount of crystals precipitated when the sodium methylenedinaphthalene sulfonate is kept standing for 28 days is reduced, that is, the stability is also improved, but the strength is significantly reduced by 1 day when the content is too high; the sodium methylene dinaphthalene sulfonate has negative influence on the early strength, and the proper mixing amount is selected.

Analyzing the data of the examples 2, 8-9 and the comparative example 7 shows that the three kinds of alcohol amines with the same dosage can obviously reduce the setting time and improve the strength of 1 d; however, in the absence of the alcohol amine, the stability at 28d still was poor and the pH was low.

The data of examples 2, 11-12 and comparative example 8 show that as the amount of sulfobetaine is reduced, the indexes such as pH value, setting time and strength are not changed much, but the crystallization generated by standing the system 28d is increased, which is not favorable for long-term storage of the finished product.

The results of examples 2, 6 to 7 and 11 to 12 show that the accelerator has good static stability, low rebound resilience and high after strength retention when the mass ratio of sodium methylenedinaphthalenesulfonate to sulfobetaine is 2: 1. When the mass ratio of sodium methylenedinaphthalene sulfonate to sulfobetaine is lower than (example 6, example 12) or higher than (example 7, example 11), the static stability of the accelerator is lowered to some extent, because when the mass ratio of sodium methylenedinaphthalene sulfonate to sulfobetaine is low, most of sodium methylenedinaphthalene sulfonate is bound by sulfobetaine, the wetting ability is lowered, so that the hydration reaction speed of metal cations is slowed to some extent, and when the mass ratio of sodium methylenedinaphthalene sulfonate to sulfobetaine is high, sodium methylenedinaphthalene sulfonate which does not form a network structure with sulfobetaine is increased, and the effect of lowering the compressive strength is remarkable. Meanwhile, the inventors found in experiments that when sulfobetaine is equivalently replaced with polyacrylamide which is commonly used in the market, since the sulfonic acid group of sodium methylenedinaphthalene sulfonate and the free ammonium group of polyacrylamide can be covalently bound, the dispersibility of sodium methylenedinaphthalene sulfonate is reduced, the stability of the accelerator is very poor, and the volume of 28d crystal is 28.3 mL.

In conclusion, the concrete accelerator can achieve good accelerating effect and early and later strength requirements only if the raw materials and the proportion are in the reasonable range of the invention, and the concrete accelerator is stable for a long time in normal-temperature storage.

Claims

1. The concrete accelerator taking waste aluminum ring-pull cans as raw materials is characterized by comprising the following raw materials in percentage by mass: 70-75% of self-made aluminum sulfate solution, 3-8% of active aluminum hydroxide, 0.2-0.6% of methylene dinaphthalene sodium sulfonate, 3-6% of organic alcohol amine, 0.1-0.3% of sulfobetaine and the balance of deionized water;

the self-made aluminum sulfate solution is prepared by filtering aluminum slag powder obtained by grinding waste pop cans and a 50% sulfuric acid solution in a mass ratio of 1: 13-16;

the mass ratio of the sodium methylene dinaphthalene sulfonate to the sulfobetaine is 2: 1.

2. the concrete accelerator using waste aluminum cans as raw materials according to claim 1, wherein the reaction temperature of the aluminum slag powder and a 50% sulfuric acid solution is 60 ± 2 ℃.

3. The concrete accelerator using waste aluminum cans as raw materials according to claim 1, wherein the self-made aluminum sulfate solution is prepared by high-speed shearing and dispersion of the reaction liquid after the aluminum slag powder reacts with 50% sulfuric acid solution, and then filtering.

4. The concrete accelerator using waste aluminum cans as raw materials according to claim 1, wherein the sulfobetaine is one or more of dodecyl sulfopropyl betaine, hydroxypropyl sulfobetaine, and alkylamidopropyl hydroxypropyl sulfobetaine.

5. The concrete accelerator using waste aluminum cans as raw materials according to claim 1, wherein the organic alcohol amine is one of triethanolamine, diethanolamine and ethylene glycol monoisopropanolamine, and the content is not less than 85%.

6. The concrete accelerator using the waste aluminum cans as raw materials according to claim 1, wherein the aluminum content in the waste aluminum cans is not less than 95%.

7. The concrete accelerator using waste aluminum cans as raw materials according to claim 1, wherein the mesh number of the aluminum slag powder is 50-100.

8. The concrete accelerator using waste aluminum cans as raw materials according to claim 1, wherein the activated aluminum hydroxide is amorphous aluminum hydroxide.

9. A preparation method of a concrete accelerator taking waste aluminum ring-pull cans as raw materials is characterized by comprising the following steps:

s1, preprocessing: grinding and crushing the recovered waste aluminum ring-pull cans into aluminum slag powder with the mesh number of 50-100;

s4, modification and adjustment: adding sodium methylene dinaphthalene sulfonate, performing heat preservation curing for 0.2-0.5h under the conditions that the rotation speed is 100-;

the concrete accelerator comprises the following raw materials in percentage by mass: 70-75% of self-made aluminum sulfate solution, 3-8% of active aluminum hydroxide, 0.2-0.6% of methylene dinaphthalene sodium sulfonate, 3-6% of organic alcohol amine, 0.1-0.3% of sulfobetaine and the balance of deionized water; the mass ratio of the sodium methylene dinaphthalene sulfonate to the sulfobetaine is 2: 1.