阅读说明：本技术 一种多功能环保酸洗添加剂及其制备方法 (Multifunctional environment-friendly acid pickling additive and preparation method thereof ) 是由 卢宝阳 谢孝文 吴荣方 郅西敬 徐景坤 于 2021-08-17 设计创作，主要内容包括：本发明公开了一种多功能环保酸洗添加剂及其制备方法,是将阴离子表面活性剂、非离子表面活性剂溶解后,再加入缓蚀剂、促进剂,混合而成。本发明制备的多功能环保酸洗添加剂,可以抑制传统酸洗工艺中酸雾的大量产生,同时可以实现清除金属表面油脂、减少酸洗用量、加快酸洗速度和高效缓蚀的目的。本发明适用于制备多功能环保酸洗添加剂,所制产品进一步用作酸洗工艺的添加剂。(The invention discloses a multifunctional environment-friendly acid pickling additive and a preparation method thereof. The multifunctional environment-friendly pickling additive prepared by the invention can inhibit a large amount of acid mist generated in the traditional pickling process, and can simultaneously realize the purposes of removing grease on the surface of metal, reducing the pickling dosage, accelerating the pickling speed and efficiently inhibiting corrosion. The invention is suitable for preparing the multifunctional environment-friendly acid pickling additive, and the prepared product is further used as the additive of the acid pickling process.)

1. A multifunctional environment-friendly acid pickling additive is characterized in that: the raw materials for preparing the effective components of the medicine comprise the following components in parts by weight: 2-15 parts of anionic surfactant, 1-10 parts of nonionic surfactant, 3-8 parts of corrosion inhibitor, 2-8 parts of accelerator and 63-82 parts of water.

2. The multifunctional environment-friendly pickling additive as claimed in claim 1, wherein: the multifunctional environment-friendly acid washing additive also comprises 2-7 parts of auxiliary materials;

the auxiliary material is urea, sodium chloride, potassium iodide or sodium tartrate.

3. The multifunctional environment-friendly pickling additive as claimed in claim 1 or 2, wherein: the anionic surfactant is at least one of carboxylate, sulfonate, sulfate and phosphate.

4. The multifunctional environment-friendly pickling additive as claimed in claim 3, wherein: the carboxylate is a compound corresponding to any one of the general formulas I-III:

R₁₁COOM――――――――――――――(Ⅰ)

R₁₂-CONH(CONHR₁₂')_nCOOM――――――(Ⅱ)

R₁₃-(OC₂H₄)_nOCH₂COOM――――――――(Ⅲ)

wherein R is₁₁、R₁₂、R₁₃Are each an alkyl group having 1 to 30 carbon atoms; r₁₂' is a compound containing 1 to 30 carbon atomsAlkyl groups of (a); n is a positive integer of 1-20; m is sodium ion, potassium ion, magnesium ion or ammonium ion.

5. The multifunctional environment-friendly pickling additive as claimed in claim 3, wherein: the sulfonate is a compound conforming to any one of the general formulas IV-VI:

R₂₂SO₃M――――――――――――――(Ⅴ)

R₂₃HC＝CHCH₂SO₃M――――――――――(Ⅵ)

wherein R is₂₁、R₂₂、R₂₃Are each an alkyl group having 1 to 40 carbon atoms; m is sodium ion, potassium ion, magnesium ion or ammonium ion.

6. The multifunctional environment-friendly pickling additive as claimed in claim 3, wherein: the sulfate is at least one of fatty alcohol sulfate, sulfated olefin and sulfated oil;

the structural general formula of the fatty alcohol sulfate is R₃OSO₃M；

Wherein R is₃Is an alkyl group having 1 to 30 carbon atoms; m is sodium ion, potassium ion, magnesium ion or ammonium ion.

7. The multifunctional environment-friendly pickling additive as claimed in claim 3, wherein: the phosphate is a compound conforming to any one of the general formulas VII-XII:

wherein R is₄₁、R₄₂、R₄₃、R₄₄、R₄₅、R₄₆Are each an alkyl group having 1 to 30 carbon atoms; m is sodium ion, potassium ion, magnesium ion or ammonium ion.

8. The multifunctional environment-friendly pickling additive as claimed in claim 1 or 2, wherein: the nonionic surfactant is a compound corresponding to the general formulae i, ii:

wherein R is₅₁、R₅₂Are each an alkyl group having 1 to 20 carbon atoms; n is a positive integer from 2 to 80;

the corrosion inhibitor is at least one of acetylene alcohol, butynediol, propiolic alcohol, hexynol, octynol, benzyl pyridine chloride, dodecyl pyridine bromide, dodecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, diphenylthiourea, dibenzyl sulfoxide, 2-mercaptobenzotriazole and 1-chloro-3- (beta-hydroxy-ethoxy) -3-methyl-1-butyne;

the accelerant is at least one of triethylamine, benzyl dimethylamine, pyridine, trimethylamine, triethanolamine, N-dimethylaniline, N-dimethylethanolamine, ethylene triamine, triethylene tetramine, polyethylene polyamine, chlorourea, dimethyl imidazole urea, benzyl triethyl ammonium chloride, phenol, o-cresol, m-cresol, resorcinol, quebrachol, bisphenol A, thiourea, tetramethyl guanidine, peroxide, 2-Thiosylbenzothiazole and triphenylphosphine.

9. The method for preparing the multifunctional environment-friendly acid pickling additive as claimed in claim 1, wherein the multifunctional environment-friendly acid pickling additive comprises the following steps: the preparation method comprises the following steps of:

s1, obtaining a solution X by using an anionic surfactant, a nonionic surfactant and water;

s2, adding a corrosion inhibitor and an accelerant into the solution X, and mixing to obtain the multifunctional environment-friendly acid pickling additive Y.

10. A method of preparing the multifunctional environmental friendly pickling additive according to any one of claims 2-8, characterized in that: the preparation method comprises the following steps of:

s1', mixing an anionic surfactant, a nonionic surfactant and water to obtain a solution X;

s2', adding a corrosion inhibitor, an accelerant and auxiliary materials into the solution X, and uniformly mixing to obtain the multifunctional environment-friendly acid pickling additive Y'.

Technical Field

The invention belongs to the technical field of metal surface treatment, relates to metal rust removal, and particularly relates to a multifunctional environment-friendly acid pickling additive and a preparation method thereof.

Background

With the continuous progress of social economy, China comprehensively enters a mechanized era, the demand of steel increases year by year, the corrosion phenomenon of the steel is more serious with the change of the environment, and a large amount of steel is corroded to directly cause great economic loss in China.

The corrosion prevention of steel in the traditional process is mainly divided into two aspects: 1. the environment of the steel is changed, however, the purpose of realizing the environmental adaptation to the protection condition of the steel is not practical in the technology at the present stage, and more economic consumption can be brought; 2. the surface treatment protection of steel is one of the most effective means for delaying the corrosion of steel materials at present. The acid pickling rust removal is the most important surface treatment process in the industries of metal processing, mechanical manufacturing and the like, and therefore, a large amount of inorganic acids such as sulfuric acid, hydrochloric acid and the like and organic acids such as citric acid, tartaric acid and the like are consumed each year. However, in the conventional pickling process, the pickling solution needs to be heated, and meanwhile, in the pickling process, metal and metal oxide can have severe chemical reaction with the pickling solution to generate a large amount of acid gas, and the acid gas can form acid mist in the rising process, so that the surrounding environment is seriously polluted, the steel structure of a factory building is corroded, mechanical equipment and instruments are corroded, and the physical health of operators is threatened. In addition, in order to achieve the purpose of thoroughly cleaning the metal surface, the pickling time is generally longer, which not only causes the generation of hydrogen embrittlement and over-corrosion phenomena to affect the mechanical strength of steel, but also increases the labor intensity and the production cost of workers, and meanwhile, the residual oil stains on the surface after the steel is pickled can also affect the subsequent process to affect the anticorrosion effect.

In order to solve the problems, some acid mist inhibitors appear on the market successively, and traditional patents such as Chinese patent CN101818352A (strong acid mist inhibitor and preparation method thereof), CN103628077A (environment-friendly steel acid pickling acid mist inhibitor), CN102286750A (acid mist inhibitor) and the like all improve the acid mist inhibition effect, can effectively inhibit the generation of acid mist, but have low attention on the aspects such as acid pickling speed, acid pickling dosage, metal corrosion inhibition and the like, so that the cost is high, the working efficiency is low, and the performance of metal materials is influenced.

Disclosure of Invention

The invention aims to provide a multifunctional environment-friendly acid pickling additive, which is used for inhibiting the generation of acid mist in the traditional metal acid pickling process and simultaneously achieving the purposes of reducing the consumption of acid pickling solution, accelerating the acid pickling speed, efficiently inhibiting corrosion and removing grease on the surface of metal;

the invention also aims to provide a preparation method of the multifunctional environment-friendly pickling additive.

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

the multifunctional environment-friendly acid pickling additive comprises the following raw materials of effective components in parts by weight: 2-15 parts of anionic surfactant, 1-10 parts of nonionic surfactant, 3-8 parts of corrosion inhibitor, 2-8 parts of accelerator and 63-82 parts of water.

As a limitation, the multifunctional environment-friendly acid washing additive also comprises 2-7 parts of auxiliary materials;

the auxiliary material is urea, sodium chloride, potassium iodide or sodium tartrate.

As another limitation, the anionic surfactant is at least one of carboxylate, sulfonate, sulfate, and phosphate.

By way of further limitation, the carboxylate is a compound according to any one of formulas I-III:

R₁₁COOM――――――――――――――(Ⅰ)

R₁₂-CONH(CONHR₁₂')_nCOOM――――――(Ⅱ)

R₁₃-(OC₂H₄)_nOCH₂COOM――――――――(Ⅲ)

wherein R is₁₁、R₁₂、R₁₃Are each an alkyl group having 1 to 30 carbon atoms; r₁₂' is an alkyl group having 1 to 30 carbon atoms; n is a positive integer of 1-20; m is sodium ion, potassium ion, magnesium ion or ammonium ion.

By way of further limitation, the sulfonate is a compound conforming to any one of formulas IV-VI:

R₂₂SO₃M――――――――――――――(Ⅴ)

R₂₃HC＝CHCH₂SO₃M――――――――――(Ⅵ)

wherein R is₂₁、R₂₂、R₂₃Are each an alkyl group having 1 to 40 carbon atoms; m is sodium ion, potassium ion, magnesium ion or ammonium ion.

As a further limitation, the sulfate is at least one of a fatty alcohol sulfate, a sulfated olefin, and a sulfated oil;

the structural general formula of the fatty alcohol sulfate is R₃OSO₃M；

Wherein R is₃Is an alkyl group having 1 to 30 carbon atoms; m is sodium ion, potassium ion, magnesium ion or ammonium ion.

By way of further limitation, the phosphate is a compound corresponding to any one of formulae VII to XII:

wherein R is₄₁、R₄₂、R₄₃、R₄₄、R₄₅、R₄₆Are each an alkyl group having 1 to 30 carbon atoms; m is sodium ion, potassium ion, magnesium ion or ammonium ion.

As a third limitation, the nonionic surfactant is a compound according to formulas i, ii:

wherein R is₅₁、R₅₂Are each an alkyl group having 1 to 20 carbon atoms; n is a positive integer from 2 to 80;

the corrosion inhibitor is at least one of acetylene alcohol, butynediol, propiolic alcohol, hexynol, octynol, benzyl pyridine chloride, dodecyl pyridine bromide, dodecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, diphenylthiourea, dibenzyl sulfoxide, 2-mercaptobenzotriazole and 1-chloro-3- (beta-hydroxy-ethoxy) -3-methyl-1-butyne;

the accelerant is at least one of triethylamine, benzyl dimethylamine, pyridine, trimethylamine, triethanolamine, N-dimethylaniline, N-dimethylethanolamine, ethylene triamine, triethylene tetramine, polyethylene polyamine, chlorourea, dimethyl imidazole urea, benzyl triethyl ammonium chloride, phenol, o-cresol, m-cresol, resorcinol, quebrachol, bisphenol A, thiourea, tetramethyl guanidine, peroxide, 2-Thiosylbenzothiazole and triphenylphosphine.

The invention also provides a preparation method of the multifunctional environment-friendly acid pickling additive, which comprises the following steps of:

s1, obtaining a solution X by using an anionic surfactant, a nonionic surfactant and water;

s2, adding a corrosion inhibitor and an accelerant into the solution X, and mixing to obtain the multifunctional environment-friendly acid pickling additive Y.

The invention also provides another preparation method of the multifunctional environment-friendly acid pickling additive, which comprises the following steps of:

s1', mixing an anionic surfactant, a nonionic surfactant and water to obtain a solution X;

s2', adding a corrosion inhibitor, an accelerant and auxiliary materials into the solution X, and uniformly mixing to obtain the multifunctional environment-friendly acid pickling additive Y'.

Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:

firstly, the added anionic surfactant can quickly generate a layer of fine bubbles on the surface of the pickling solution, so that the escape of acid mist is inhibited, the operating environment is improved, the consumption of the pickling solution is reduced, the harm to the human body is reduced, meanwhile, the residual oil stain on the surface can be removed in the pickling process, and the pickling quality of steel is improved;

the added nonionic surfactant can enable pickling solution to quickly reach the surface of a basic oxide film of steel, the basic oxide film is removed, a hydrogen evolution reaction is carried out at the same time, the purpose of further removing the oxide film is achieved by utilizing the stripping effect of hydrogen, the pickling speed is increased, and the nonionic surfactant and the anionic surfactant are jointly used, so that the pickling speed is further accelerated, and the pickling effect is improved;

the corrosion inhibitor added in the invention has the function of selective adsorption, can not be adsorbed on the surface of an oxide film in the pickling process, and only is adsorbed on the surface of the metal matrix with oxide skin removed, thereby forming a layer of protective film to isolate the metal matrix from acid liquor, effectively reducing the over-corrosion and hydrogen embrittlement of metal while accelerating the pickling speed, and simultaneously reducing the consumption of pickling liquor;

the addition of the accelerator can accelerate the falling of oxide skin and further accelerate the pickling speed, and the addition of the sodium tartrate can neutralize iron ions generated in the pickling process;

the multifunctional environment-friendly pickling additive is an environment-friendly product, does not contain toxic and harmful substances, does not generate toxic and harmful substances in the pickling process, can recycle the pickling waste liquid after pickling, and reduces the pollution problem of waste liquid discharge to the environment;

after the multifunctional environment-friendly pickling additive is added into the pickling solution, the multifunctional environment-friendly pickling additive can play a role when used at normal temperature, so that the using condition of the pickling solution is reduced, the labor intensity of workers is reduced, and the labor cost is saved;

the preparation method of the multifunctional environment-friendly acid washing additive provided by the invention has no special requirements on equipment, is simple to operate, and adds the ionic surfactant, the corrosion inhibitor and the accelerator in batches, so that the influence of the addition of the corrosion inhibitor and the accelerator on the dissolution rate of the ionic surfactant is avoided.

The invention is suitable for preparing the multifunctional environment-friendly acid pickling additive, and the prepared product is further used as the additive of the acid pickling process.

Detailed Description

The present invention will be described in further detail with reference to specific examples. It should be understood that the described embodiments are only for illustrating the present invention and do not limit the present invention.

Example 1 preparation method of multifunctional environment-friendly acid pickling additive

The embodiment comprises the following steps which are carried out in sequence:

s1, respectively weighing 20kg of sodium octadecyl sulfate as an anionic surfactant, 50kg of polyoxyethylene lauryl ether as a nonionic surfactant and 200kg of water, and uniformly mixing the three to obtain a solution X₁；

S2, adding the solution X₁Adding 70kg of butynediol as a slow release agent, 80kg of triethylamine as an accelerant, adding 580kg of water, and uniformly mixing to obtain the multifunctional environment-friendly acid washing additive Y₁。

The preparation method comprises the following steps:

sodium octadecyl sulfate is sulfate as anionic surfactant, and has a general formula of R₃OSO₃M, is a fatty alcohol sulfate salt, wherein R₃Is (CH)₂)₁₇CH₃；

The polyoxyethylene lauryl ether is a nonionic surfactant and has a structural formulaAccording to the general formula i, wherein R₅₁Is (CH)₂)₁₁CH₃N is 12;

butynediol is a slow release agent;

triethylamine is used as an accelerant;

the weight ratio of the anionic surfactant to the nonionic surfactant to the slow release agent to the accelerator to the water is 2:5:7:8: 78.

Example 2-5 preparation of multifunctional Environment-friendly Pickling additive

Examples 2 to 5 are methods for preparing multifunctional environmentally friendly pickling additives, respectively, and the steps are substantially the same as those of example 1, except for the amount of each raw material and the mixing time of all raw materials, which are specifically shown in table 1:

TABLE 1 summary of the parameters of examples 2-5

Example 6 a method for preparing a multifunctional environmentally friendly pickling additive this example comprises the following steps performed in order:

s1, respectively weighing 150kg of potassium dodecyl monophosphate serving as an anionic surfactant, 70kg of lauryl alcohol polyoxyethylene ether serving as a nonionic surfactant and 200kg of water, and uniformly mixing the potassium dodecyl monophosphate, the anionic surfactant, the lauryl alcohol polyoxyethylene ether and the water to obtain a solution X₆；

S2, adding the solution X₆Adding 60kg of butynediol as a slow release agent, 60kg of triethylamine as an accelerating agent and 580kg of water, and uniformly mixing to obtain a solution X₆'；

S2, adding the solution X₆Adding 30kg of urea as an auxiliary material, adding 430kg of water, and uniformly mixing to obtain the multifunctional environment-friendly acid pickling additive Y₆；

The preparation method comprises the following steps:

the potassium dodecyl monophosphate is phosphate and is used as an anionic surfactant, and the structural general formula of the potassium dodecyl monophosphate isBelonging to fatty alcohol phosphate ester salts, in which R₃Is (CH)₂)₁₁CH₃；

The polyoxyethylene lauryl ether is a nonionic surfactant and has a structural formulaAccording to the general formula i, wherein R₅₁Is (CH)₂)₁₁CH₃N is 12;

butynediol is a slow release agent;

triethylamine is used as an accelerant;

urea is taken as an auxiliary material;

the weight ratio of the anionic surfactant to the nonionic surfactant to the sustained-release agent to the accelerator to the auxiliary material to the water is 15:7:6:6:3: 63.

Example 7 Performance testing of the multifunctional Environment-friendly Pickling additive

Control group one: acid pickling additive W was prepared according to the method in patent CN 101818352A: weighing 1kg of thiourea, and dissolving at 45 ℃ to obtain thiourea solution; weighing 2kg of Ruditapella chinensis, and dissolving at 30 deg.C to obtain Folum Ilicis solution; weighing 2kg of urea, and dissolving at 35 ℃ to obtain a urea solution; weighing 3kg of triethanolamine, and dissolving at 60 ℃ to obtain a triethanolamine solution; weighing 3kg of AEO-9 emulsifier, and dissolving at 60 ℃ to obtain AEO-9 emulsifier solution; weighing 2kg of oxalic acid, and dissolving at 30 ℃ to obtain an oxalic acid solution; weighing 3kgDX penetrant, and dissolving at 30 ℃ to obtain DX penetrant solution; weighing 1kg of sodium dodecyl benzene sulfonate, and dissolving at 30 ℃ to obtain a sodium dodecyl benzene sulfonate solution; mixing the prepared solutions uniformly to obtain an acid pickling additive W;

control group two: acid wash additive V was prepared according to the method in patent CN 103628077A: weighing 2kg of glycerol monostearate, 3kg of solid extract of rice straws, 500g of glycerol, 400g of 4-sulfophthalic acid, 100g of heptadecyl hydroxyethyl carboxymethyl imidazoline and 4kg of water, and uniformly mixing to obtain an acid pickling additive V;

control group three: pickling additive U was prepared according to the method in patent CN 102286750A: weighing 1kg of corrosion inhibitor, 800g of mist inhibitor, 2kg of surfactant and 6.2kg of water, and uniformly mixing to obtain an acid pickling additive U;

the acid washing method comprises the following steps: 700g of control acid pickling additive W, V, U and acid pickling additive Y prepared in examples 1-6 were used₁-Y₆Respectively adding into acid pickling solution composed of 10kg hydrochloric acid, 5kg sulfuric acid, 1kg hydrofluoric acid and 84kg water, mixing well to obtain multifunctional acid pickling solution T1-T9, and adding 10kg water into acid pickling solution composed of 10kg hydrochloric acid, 5kg sulfuric acid, 1kg hydrofluoric acid and 84kg water84kg of water to prepare multifunctional pickling solution T10 as a blank group;

under the condition of 25 ℃, different parts of the steel structure under the same environment are respectively treated by multifunctional pickling solution T1-T10, and the treatment results are shown in table 1:

TABLE 1 acid washing results of multifunctional acid washing solution T1-T10

Multifunctional pickling solution

Surface condition of the surface

Acid pickling time

Corrosion inhibition rate

Size of smoke

Acid saving

Surface condition after treatment

T1

Is smooth and smooth

7min

85％

Is smaller

15.5％

Is smooth and smooth

T2

Is smooth and smooth

10min

90％

Is smaller

22.0％

Is smooth and smooth

T3

Is smooth and smooth

11min

87％

Is smaller

19.5％

Is slightly rough

T4

Is smooth and smooth

6min

95％

Is basically free of

34.5％

Is smooth and smooth

T5

Is smooth and smooth

8min

98％

Is basically free of

34.0％

Is smooth and smooth

T6

Is smooth and smooth

6min

97％

Is basically free of

35.0％

Is smooth and smooth

T7

Is smooth and smooth

8min

98％

Is basically free of

33.5％

Is smooth and smooth

T8

Is smooth and smooth

7min

96％

Is basically free of

35.5.0％

Is smooth and smooth

T9

Is smooth and smooth

7min

97％

Is basically free of

36.0％

Is smooth and smooth

T10

Roughness of

8min

——

Is larger

——

Roughness of

As can be seen from Table 1, the pickling additive Y prepared in accordance with the invention₁-Y₆The stripping and dissolving speed of the oxide skin or the rust can be accelerated, and the cleaning speed is improved; reducing darkening of workpieces after picklingA phenomenon that a bright pickled surface is formed; the corrosion of the acid liquor to the steel matrix is inhibited, the over-corrosion phenomenon is effectively avoided, the concentration of iron ions in the acid liquor is reduced, and the corrosion of the matrix is reduced; the excessive acid consumption caused by the corrosion of the matrix is reduced, and the acid liquor is saved by about 35 percent; the fog inhibiting rate reaches 90 percent, thereby reducing the corrosion of acid fog to surrounding equipment in the production process and preventing operators from being hurt due to the generation of the acid fog.