CN113684483B - Zinc chloride compound corrosion inhibitor for circulating cooling water and preparation method thereof - Google Patents
Zinc chloride compound corrosion inhibitor for circulating cooling water and preparation method thereof Download PDFInfo
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Abstract
The application relates to the field of corrosion inhibitor materials, and particularly discloses a zinc chloride compound corrosion inhibitor for circulating cooling water and a preparation method thereof, wherein the zinc chloride compound corrosion inhibitor for circulating cooling water comprises a slow-release pre-filming liquid and a slow-release confining liquid, and the mass ratio of the slow-release pre-filming liquid to the slow-release confining liquid is 1: 2-3, wherein the slow-release pre-membrane liquid comprises the following substances in parts by weight: 0.5-1.0 part of zinc chloride, 6-8 parts of chitosan, 80-100 parts of deionized water, wherein the slow-release confining liquid comprises a silicon-containing compound aqueous solution, and the concentration of a silicon-containing compound in the silicon-containing compound aqueous solution is 10-15%. The preparation method comprises the following preparation steps: s1, preparing a slow-release pre-film solution; s2, preparing a slow-release confining liquid; s3, compounding the corrosion inhibitor. The zinc chloride compound corrosion inhibitor for circulating cooling water effectively overcomes the defects of poor corrosion inhibition effect and poor corrosion inhibition durability of the existing zinc chloride corrosion inhibitor material.
Description
Technical Field
The application relates to the field of corrosion inhibitor materials, in particular to a zinc chloride compound corrosion inhibitor for circulating cooling water and a preparation method thereof.
Background
The circulating water system has a very important status in industrial production, and is mainly used for cooling in the production process so as to cool process media, meet the process requirements, have more important significance in circulating water control, and when the circulating water system has the problems of deposition, scaling and the like, the circulating water system is like hardening or blocking of agglomeration, and cannot be unblocked; if the circulating water system has corrosion problems, such as the blood vessel is damaged, the circulating water system is easy to break. These obstacles are sufficient to bring a plant to a complete standstill and even to suffer serious losses. Therefore, the circulating water system is a life line in industrial production and is a key control point, and because the circulating water is a key control point for production and operation of companies, corrosion inhibition treatment by adopting a corrosion inhibitor is necessary.
The corrosion inhibitor is a chemical substance capable of effectively preventing metal corrosion, and is a chemical substance capable of achieving the effect of resisting metal corrosion only by adding a very small amount of the corrosion inhibitor. Its advantages are low consumption (only 0.1-1%), and high corrosion-retarding effect. Moreover, it does not change the properties of the metal and does not affect the corrosion system. In cooling water systems, zinc salts are the most commonly used corrosion inhibitors of the cathodic type, and zinc ions play a role. Zinc ions in the cathode site can rapidly form Zn (OH) due to the increase of pH 2 Deposited on the surface of the cathode and acts as a protective film.
However, in the use process of the existing zinc chloride corrosion inhibitor material, although the film formation of zinc salt is relatively rapid, the film is not durable, and the zinc ion tends to precipitate when the pH value of circulating water is more than 8.3, so the concentration addition amount of the zinc ion is not too high, thereby influencing the corrosion inhibition effect of the zinc ion zinc chloride corrosion inhibitor material.
Disclosure of Invention
In order to overcome the defects of poor corrosion inhibition effect and poor corrosion inhibition durability of the conventional zinc chloride corrosion inhibitor material, the application provides a zinc chloride compound corrosion inhibitor for circulating cooling water and a preparation method thereof, and the following technical scheme is adopted:
in a first aspect, the application provides a zinc chloride compound corrosion inhibitor for circulating cooling water, which adopts the following technical scheme:
a zinc chloride compound corrosion inhibitor for circulating cooling water comprises a corrosion inhibition pre-filming liquid and a corrosion inhibition confining liquid, wherein the mass ratio of the corrosion inhibition pre-filming liquid to the corrosion inhibition confining liquid is 1: 2-3, wherein the corrosion inhibition pre-film liquid comprises the following substances in parts by weight: 0.5-1.0 part of zinc chloride, 6-8 parts of chitosan, 80-100 parts of deionized water and the corrosion inhibition confining liquid comprise a silicon-containing compound aqueous solution, wherein the concentration of a silicon-containing compound in the silicon-containing compound aqueous solution is 10-15%.
By adopting the technical scheme, the corrosion inhibition pre-membrane solution and the corrosion inhibition confining liquid are adopted to carry out synergistic action, and as zinc ions in zinc chloride are at the cathode part, when the pH value of cooling water is increased, the zinc ions are combined with hydroxyl ions and form Zn (OH) rapidly 2 The corrosion inhibition pre-membrane solution is deposited on the surface of a cathode, so that the chitosan loaded with zinc chloride in the corrosion inhibition pre-membrane solution is quickly released, after the corrosion inhibition pre-membrane solution acts, a silicon-containing compound in a silicon-containing compound aqueous solution in the corrosion inhibition sealing solution is used as an anode inhibition type corrosion inhibitor, and the formation of a protective membrane is promoted through divalent ions, so that the corrosion resistance of a corrosion inhibition membrane formed by the corrosion inhibition pre-membrane solution is further improved, and the defects of poor corrosion inhibition effect and poor corrosion inhibition durability of a zinc chloride corrosion inhibitor material are effectively overcome.
Further, the corrosion inhibition pre-membrane solution also comprises 3-5 parts by weight of dibasic acid.
By adopting the technical scheme, the binary acid is added into the corrosion inhibition pre-membrane solution for modification treatment, and the binary acid is combined with zinc ions and generates a complexing effect, so that the corrosion inhibition synergistic effect in the corrosion inhibition pre-membrane solution is improved, at the moment, the zinc ions mainly exist in a complexing ion form, so that the formed complexing film stably exists in cooling water, the quality of a formed film in the corrosion inhibition pre-membrane solution is effectively ensured, the adverse effect of ions in low pH (potential of hydrogen) in water on the formation of the corrosion inhibition film is avoided, the problem that the stability of the corrosion inhibition film is reduced due to the existence of high-hardness water bicarbonate ions is solved, and the corrosion inhibition durability of the zinc chloride corrosion inhibitor material is further improved.
Further, the dibasic acid includes any one of oxalic acid and selenic acid.
By adopting the technical scheme, the type of the used binary acid is optimized, and the corrosion inhibition synergistic effect between the binary acid and zinc ions is further improved, so that the corrosion inhibition durability of the zinc chloride corrosion inhibitor material is further improved.
Further, the corrosion inhibition pre-filming liquid also comprises 8-10 parts by weight of organic phosphate compound.
By adopting the technical scheme, the corrosion inhibition pre-membrane solution is also added with an organic phosphate compound, and the organic phosphate compound is an ester derivative of phosphoric acid and belongs to a class of phosphoric acid derivatives. The phosphate ester molecule has the advantages of low toxicity, low irritation, good biodegradability, good electrochemical stability, lower surface tension, good wettability, good emulsifying dispersibility and the like, particularly, hetero atoms in the phosphate ester molecule can be used as an adsorption center to be adsorbed on the metal surface, so that a good corrosion inhibition effect is achieved, and when the phosphate ester compound is used, hydrocarbon groups of the phosphate ester compound can promote the compactness and stability of a film formed by the corrosion inhibition pre-film liquid through the interaction of van der Waals forces among molecules, so that the defects of poor corrosion inhibition effect and poor durability of a zinc chloride corrosion inhibitor material are further overcome.
Further, the organic phosphate compound comprises chitosan phosphate.
By adopting the technical scheme, the chitosan phosphate molecules prepared by performing phosphorylation modification on the chitosan molecules contain ammoniaRadical (-NH) 2 ) Hydroxyl (-OH) and phosphate (-H) 2 PO 4 ) And the structural strength of a protective film formed by the corrosion inhibition pre-film liquid can be improved. Meanwhile, the chitosan phosphate ester molecules have good corrosion inhibition effect, so that the defects of poor corrosion inhibition effect and poor corrosion inhibition durability of the zinc chloride corrosion inhibitor material are further improved.
Further, the chitosan phosphate is prepared by adopting the following scheme:
(1) Taking chitosan and deionized water, stirring and mixing to prepare a chitosan solution with the mass fraction of 10%, adding a phosphoric acid solution and a formaldehyde solution into the chitosan solution according to the mass ratio of 1;
(2) Adding the mixed solution into absolute ethyl alcohol according to the mass ratio of 1.
By adopting the technical scheme, chitosan is used as a matrix and is subjected to phosphorylation treatment, free amino groups in the chitosan structure are easily combined with hydrogen ions in a medium under an acidic condition, molecules become colloid macromolecules with positive charges, chitin colloid molecules absorb and block a cathode process under the electrostatic action to form a cathode type corrosion inhibitor, and after the phosphorylation modification, a phosphate ester compound has a good corrosion inhibition effect, so that the defects of poor corrosion inhibition effect and poor corrosion inhibition durability of a zinc chloride corrosion inhibitor material are further improved.
Further, the aqueous solution of the silicon-containing compound is an aqueous sodium silicate solution.
By adopting the technical scheme, the sodium silicate aqueous solution is preferably used as the aqueous solution of the silicon-containing compound, and NA in the sodium silicate is dissolved by the sodium silicate in water 2 O in water to form sodium hydroxide, OH - With Zn 2+ The combination inhibits the proceeding of cathode reaction, thereby further improving the corrosion inhibition durability of the zinc chloride corrosion inhibitor material.
In a second aspect, the application provides a preparation method of a zinc chloride compound corrosion inhibitor for circulating cooling water, which adopts the following technical scheme:
a preparation method of a zinc chloride compound corrosion inhibitor for circulating cooling water comprises the following specific preparation steps:
s1, preparing a corrosion inhibition pre-filming liquid: stirring and mixing zinc chloride, chitosan, deionized water, dibasic acid and chitosan phosphate according to a formula, standing at room temperature for 6-8 hours, homogenizing and filtering, and collecting filtrate to obtain a corrosion inhibition pre-membrane solution;
s2, preparing a corrosion inhibition confining liquid: adding sodium silicate into deionized water according to a formula, stirring, mixing, and performing rotary evaporation until the mass fraction of the corrosion inhibition pre-filming liquid is 10-15%, so as to prepare a corrosion inhibition confining liquid;
s3, inhibitor compounding: adding the corrosion inhibition confining liquid into the corrosion inhibition pre-film liquid, stirring, mixing, performing ultrasonic dispersion, standing at room temperature for swelling, homogenizing, and screening with a screen of 500-1000 meshes to obtain the zinc chloride compound corrosion inhibitor for circulating cooling water.
By adopting the technical scheme, the corrosion inhibition pre-filming liquid and the corrosion inhibition confining liquid are respectively prepared, and finally, the gel material is uniformly and stably formed through swelling treatment after mixing, the prepared gel corrosion inhibitor material has more excellent corrosion inhibition effect, and the formed corrosion inhibition coating film can further improve the corrosion inhibition durability of the zinc chloride corrosion inhibitor material.
In summary, the present application includes at least one of the following beneficial technical effects:
firstly, the application adopts the synergistic effect of the corrosion inhibition pre-membrane solution and the corrosion inhibition confining solution, as zinc ions in zinc chloride are at the cathode part, and as the pH value is increased, zn (OH) 2 is quickly formed and deposited on the surface of the cathode, so that the chitosan loaded with the zinc chloride in the corrosion inhibition pre-membrane solution is quickly released, after the action of the corrosion inhibition pre-membrane solution, a silicon-containing compound in a silicon-containing compound aqueous solution in the corrosion inhibition confining solution is used as an anode inhibition type corrosion inhibitor, and the formation of a protective membrane is promoted through divalent ions, so that the corrosion resistance of a corrosion inhibition membrane formed by the corrosion inhibition pre-membrane solution is further improved, and the defects of poor corrosion inhibition effect and poor corrosion inhibition durability of a zinc chloride corrosion inhibitor material are effectively overcome.
Secondly, the binary acid is added into the corrosion inhibition pre-membrane solution for modification treatment, and the binary acid is combined with zinc ions and generates a complexing effect, so that the corrosion inhibition synergistic effect in the corrosion inhibition pre-membrane solution is improved, at the moment, the zinc ions mainly exist in a complexing ion form, so that the formed complexing film stably exists in cooling water, the quality of a formed film in the corrosion inhibition pre-membrane solution is effectively ensured, the adverse effect of ions in low pH (potential of hydrogen) in water on the formation of the corrosion inhibition film is avoided, the problem that the stability of the corrosion inhibition film is reduced due to the existence of high-hardness bicarbonate ions is solved, and the corrosion inhibition durability of the zinc chloride corrosion inhibitor material is further improved.
Thirdly, an organic phosphate compound is added into the corrosion inhibition pre-filming liquid, and the organic phosphate compound is an ester derivative of phosphoric acid and belongs to the class of phosphoric acid derivatives. The phosphate ester molecule has the advantages of low toxicity, low irritation, good biodegradability, good electrochemical stability, lower surface tension, good wettability, good emulsifying dispersibility and the like, particularly, hetero atoms in the phosphate ester molecule can be used as an adsorption center to be adsorbed on the metal surface, so that a good corrosion inhibition effect is achieved, and when the phosphate ester compound is used, hydrocarbon groups of the phosphate ester compound can promote the compactness and stability of a film formed by the corrosion inhibition pre-film liquid through the interaction of van der Waals forces among molecules, so that the defects of poor corrosion inhibition effect and poor durability of a zinc chloride corrosion inhibitor material are further overcome.
Fourthly, the corrosion inhibition pre-filming liquid and the corrosion inhibition confining liquid are prepared respectively, and finally are subjected to swelling treatment after mixing to form a uniform and stable gel material.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples.
The starting materials for the preparation examples, examples and comparative examples of the present application are commercially available unless otherwise specified.
Preparation of chitosan phosphate
Preparation example 1
(1) Taking 0.1kg of chitosan and 10kg of deionized water, stirring and mixing to prepare a chitosan solution with the mass fraction of 10%, adding 0.1kg of phosphoric acid solution with the mass fraction of 10% and 0.2kg of formaldehyde solution with the mass fraction of 10% into 0.3kg of chitosan solution with the mass fraction of 10%, stirring and mixing, and then carrying out heat preservation reaction for 3 hours at 55 ℃ to obtain a mixed solution;
(2) Adding 0.3kg of mixed solution into 1.5kg of absolute ethyl alcohol, stirring and mixing at 250r/min, standing and aging for 6h, filtering to obtain a filter cake, respectively and sequentially washing the filter cake for 3 times by respectively adopting the absolute ethyl alcohol, acetone and diethyl ether, drying and grinding in a 55 ℃ drying oven after washing is finished, and sieving by a 1000-mesh sieve to obtain the chitosan phosphate particles 1.
Preparation example 2
(1) Taking 0.1kg of chitosan and 10kg of deionized water, stirring and mixing to prepare a chitosan solution with the mass fraction of 10%, adding 0.1kg of phosphoric acid solution with the mass fraction of 10% and 0.25kg of formaldehyde solution with the mass fraction of 10% into 0.4kg of chitosan solution with the mass fraction of 10%, stirring and mixing, and carrying out heat preservation reaction at 57 ℃ for 4 hours to obtain a mixed solution;
(2) Adding 0.3kg of mixed solution into 1.5kg of absolute ethyl alcohol, stirring and mixing at 275r/min, standing and aging for 7h, filtering to obtain a filter cake, washing the filter cake respectively and sequentially with absolute ethyl alcohol, acetone and diethyl ether for 3 times, drying and grinding in a 55 ℃ drying oven after washing is completed, and sieving with a 1000-mesh sieve to obtain the chitosan phosphate particles 2.
Preparation example 3
(1) Taking 0.1kg of chitosan and 10kg of deionized water, stirring and mixing to prepare a chitosan solution with the mass fraction of 10%, adding 0.1kg of phosphoric acid solution with the mass fraction of 10% and 0.3kg of formaldehyde solution with the mass fraction of 10% into 0.5kg of chitosan solution with the mass fraction of 10%, stirring and mixing, and then carrying out heat preservation reaction for 5 hours at the temperature of 60 ℃ to obtain a mixed solution;
(2) Adding 0.3kg of mixed solution into 1.5kg of absolute ethyl alcohol, stirring and mixing at 300r/min, standing and aging for 8h, filtering to obtain a filter cake, respectively and sequentially washing the filter cake for 3 times by respectively adopting the absolute ethyl alcohol, acetone and diethyl ether, drying and grinding in an oven at 55 ℃ after washing is finished, and sieving by a 1000-mesh sieve to obtain the chitosan phosphate particles 3.
Examples
Example 1
S1, preparing a corrosion inhibition pre-filming liquid: taking 0.5kg of zinc chloride, 6kg of chitosan and 80kg of deionized water, stirring and mixing, standing at room temperature for 6 hours, homogenizing at 4500r/min, filtering, and collecting filtrate to obtain a corrosion inhibition pre-membrane solution;
s2, preparing a corrosion inhibition confining liquid: adding 1kg of sodium silicate into 10kg of deionized water, stirring and mixing, placing the mixture for rotary evaporation at 45 ℃, and preparing a corrosion inhibition confining liquid after the rotary evaporation until the mass fraction of the sodium silicate in the rotary evaporation liquid is 10%;
s3, inhibitor compounding: adding 1kg of corrosion inhibition confining liquid into 2kg of corrosion inhibition pre-membrane liquid, stirring and mixing, placing under 200W for ultrasonic dispersion for 10min, standing and swelling at room temperature for 24h, homogenizing at 4500r/min, and sieving with a 500-mesh sieve to obtain the zinc chloride compound corrosion inhibitor for circulating cooling water.
Example 2
S1, preparing a corrosion inhibition pre-filming liquid: taking 0.75kg of zinc chloride, 7kg of chitosan and 90kg of deionized water, stirring and mixing, standing for 7 hours at room temperature, homogenizing at 5200r/min, filtering, and collecting filtrate to obtain a corrosion inhibition pre-membrane solution;
s2, preparing a corrosion inhibition confining liquid: adding 1.5kg of sodium silicate into 10kg of deionized water, stirring and mixing, placing at 47 ℃ for rotary evaporation, and preparing a corrosion inhibition confining liquid after the rotary evaporation until the mass fraction of sodium silicate in the rotary evaporation liquid is 12%;
s3, inhibitor compounding: adding 1kg of corrosion inhibition confining liquid into 2.5kg of corrosion inhibition pre-membrane liquid, stirring and mixing, placing under 250W for ultrasonic dispersion for 12min, standing and swelling at room temperature for 24h, homogenizing at 5200r/min, and screening with a 750-mesh screen to obtain the zinc chloride compound corrosion inhibitor for circulating cooling water.
Example 3
S1, preparing a corrosion inhibition pre-filming liquid: taking 1.0kg of zinc chloride, 8kg of chitosan and 100kg of deionized water, stirring and mixing, standing at room temperature for 8 hours, homogenizing at 6000r/min, filtering, and collecting filtrate to obtain a corrosion inhibition pre-membrane solution;
s2, preparing a corrosion inhibition confining liquid: adding 2kg of sodium silicate into 10kg of deionized water, stirring and mixing, placing the mixture for rotary evaporation at 50 ℃, and preparing a corrosion inhibition confining liquid after the rotary evaporation till the mass fraction of the sodium silicate in the rotary evaporation liquid is 15%;
s3, compounding of a corrosion inhibitor: adding 1kg of corrosion inhibition confining liquid into 3kg of corrosion inhibition pre-membrane liquid, stirring, mixing, placing under 300W for ultrasonic dispersion for 15min, standing at room temperature for swelling for 24h, homogenizing at 6000r/min, and sieving with a 1000-mesh sieve to obtain the zinc chloride compound corrosion inhibitor for circulating cooling water.
Example 4: the preparation method of the zinc chloride compound corrosion inhibitor for circulating cooling water is different from that in the embodiment 1 in that 3kg of oxalic acid solution with the mass fraction of 1% is added into a corrosion inhibition pre-membrane solution, and the rest preparation steps and preparation environment are the same as those in the embodiment 1.
Example 5: the preparation method of the zinc chloride compound corrosion inhibitor for circulating cooling water is different from that in the embodiment 1 in that 4kg of oxalic acid solution with the mass fraction of 1% is added into a corrosion inhibition pre-membrane solution, and the rest preparation steps and preparation environment are the same as those in the embodiment 1.
Example 6: the preparation method of the zinc chloride compound corrosion inhibitor for circulating cooling water is different from the preparation method of the embodiment 1 in that 5kg of oxalic acid solution with the mass fraction of 1% is added into a corrosion inhibition pre-membrane solution, and the rest preparation steps and preparation environment are the same as those of the embodiment 1.
Example 7: the preparation method of the zinc chloride compound corrosion inhibitor for circulating cooling water is different from that of the embodiment 1 in that 3kg of selenic acid solution with the mass fraction of 1% is added into a corrosion inhibition pre-membrane solution, and the rest preparation steps and preparation environment are the same as those of the embodiment 1.
Example 8: the preparation method of the zinc chloride compound corrosion inhibitor for circulating cooling water is different from the preparation method of the example 4 in that 8kg of chitosan phosphate ester 1 is also added into a corrosion inhibition pre-membrane solution, and the other preparation steps and preparation environment are the same as those of the example 1.
Example 9: the preparation method of the zinc chloride compound corrosion inhibitor for circulating cooling water is different from the preparation method of the example 4 in that 9kg of chitosan phosphate 2 is also added into a corrosion inhibition pre-membrane solution, and the other preparation steps and preparation environment are the same as those of the example 1.
Example 10: the preparation method of the zinc chloride compound corrosion inhibitor for circulating cooling water is different from the preparation method of the example 4 in that 10kg of chitosan phosphate 3 is also added into a corrosion inhibition pre-membrane solution, and the other preparation steps and preparation environment are the same as those of the example 1.
Comparative example
Comparative example 1: the preparation method of the zinc chloride compound corrosion inhibitor for circulating cooling water is different from that of the example 1 in that no corrosion inhibition confining liquid is arranged in the comparative example 1, and the other preparation schemes and material compositions are the same as those in the example 1.
Comparative example 2: a preparation method of a zinc chloride compound corrosion inhibitor for circulating cooling water is different from that of example 1 in that 0.5kg of aluminum chloride is adopted to replace the zinc chloride in example 1 in comparative example 2, and the other preparation schemes and material compositions are the same as those in example 1.
Comparative example 3: a preparation method of a zinc chloride compound corrosion inhibitor for circulating cooling water is different from that of example 4 in that 3kg of hydrochloric acid with the mass fraction of 1% is adopted in comparative example 3 to replace oxalic acid in example 4, and the rest preparation schemes and material compositions are the same as those in example 4.
Comparative example 4: a preparation method of a zinc chloride compound corrosion inhibitor for circulating cooling water is different from that of example 8 in that 8kg of carboxymethyl chitosan is adopted to replace chitosan phosphate in example 8 in comparative example 4, and the other preparation schemes and material compositions are the same as those in example 8.
Performance test
The performance tests were performed on the zinc chloride compound corrosion inhibitors for circulating cooling water prepared in examples 1 to 10 and comparative examples 1 to 4, respectively.
Detection method/test method
(1) Adding 200mL of calcium chloride standard solution into 2.5L of water to enable the amount of calcium ions to be 1.2g, adding 50mL of zinc chloride compound corrosion inhibitor for circulating cooling water and 200mL of borax buffer solution, and finally slowly adding 200mL of sodium bicarbonate standard solution to enable the amount of bicarbonate ions to be 3.66g and simultaneously using the solution as a blank test solution;
(2) And (3) placing the sample solution and the blank test solution prepared by the method into a constant-temperature water bath kettle at the temperature of 80 ℃, and heating at the constant temperature for 10 hours. Cooling to room temperature, filtering, transferring 250mL of filtrate, adding water to about 800mL, adding 50mL of potassium hydroxide and 1g of calcium-carboxylic acid indicator, finally measuring the calcium ion concentration by using an EDTA standard solution, and titrating until the solution is changed from purple red to bright blue, namely the end point. The scale inhibition performance of the water treatment agent is expressed by a scale inhibition rate \3311, and a calculation formula is as follows: 3, = (ρ 2 — ρ 1)/(ρ 0 — ρ 1). In the formula, rho 2 is the numerical value of the calcium ion concentration after the test of the test solution added with the water treatment agent, mg/mL; rho 1 is the numerical value of the calcium ion concentration after the test of the blank test solution without the water treatment agent, mg/mL; rho 0 is the value of the concentration of calcium ions in the prepared test solution before the experiment, mg/mL.
The specific detection results are shown in the following table 1:
TABLE 1 Corrosion inhibition performance test of zinc chloride compound corrosion inhibitor for circulating cooling water
Performance analysis was performed from table 1 above:
(1) It can be seen from table 1 in combination with examples 1 to 3, and from the experimental results of examples 1 to 3 in combination with comparative example 1, that in examples 1 to 3, the synergistic effect of the corrosion inhibition pre-membrane solution and the corrosion inhibition confining liquid is adopted to realize the rapid release of chitosan loaded with zinc chloride in the corrosion inhibition pre-membrane solution, and after the action of the corrosion inhibition pre-membrane solution, the silicon-containing compound in the aqueous solution of the silicon-containing compound in the corrosion inhibition confining liquid is used as an anode inhibition type corrosion inhibitor, and the formation of the protective membrane is promoted by divalent ions, so that the corrosion resistance of the corrosion inhibition membrane formed by the corrosion inhibition pre-membrane solution is further improved.
And comparing examples 1-3 with comparative example 2, the comparison between the zinc chloride material adopted by the application and aluminum chloride shows that the corrosion resistance of the corrosion inhibition film formed by the corrosion inhibition pre-filming liquid can be further improved by the zinc chloride.
(2) The embodiment 4-6 is combined and compared with the comparative example 3, and it can be seen that the technical scheme of the application adds the binary acid into the corrosion inhibition pre-membrane solution for modification treatment, and the binary acid is combined with the zinc ions and generates a complexing effect, so that the corrosion inhibition synergistic effect in the corrosion inhibition pre-membrane solution is improved, at the moment, the zinc ions mainly exist in a complex ion form, so that the formed complex film stably exists in cooling water, the quality of the formed film in the corrosion inhibition pre-membrane solution is effectively ensured, the adverse effect of ions on the formed corrosion inhibition film in low pH water is avoided, the problem that the existence of high-hardness bicarbonate ions reduces the stability of the corrosion inhibition film is also solved, and the corrosion inhibition durability of the zinc chloride corrosion inhibitor material is further improved.
(3) Combining examples 8-10 with comparative example 4 and finding from experimental data, the chitosan phosphate prepared by the present application through the phosphate esterification modification treatment of chitosan molecules contains amino groups (-NH) 2 ) Hydroxyl (-OH) and phosphate (-H) 2 PO 4 ) And the structural strength of a protective film formed by the corrosion inhibition pre-film liquid can be improved. Meanwhile, the chitosan phosphate ester molecules have good corrosion inhibition effect, so that the defects of poor corrosion inhibition effect and poor corrosion inhibition durability of the zinc chloride corrosion inhibitor material are further improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (2)
1. The zinc chloride compound corrosion inhibitor for circulating cooling water is characterized by comprising a corrosion inhibition pre-filming liquid and a corrosion inhibition confining liquid, wherein the mass ratio of the corrosion inhibition pre-filming liquid to the corrosion inhibition confining liquid is 1: 2-3, wherein the corrosion inhibition pre-membrane solution consists of the following substances in parts by weight:
0.5 to 1.0 portion of zinc chloride;
6-8 parts of chitosan;
80-100 parts of deionized water;
3-5 parts of dibasic acid;
8-10 parts of chitosan phosphate;
the dibasic acid comprises any one of oxalic acid and selenic acid;
the corrosion inhibition sealing liquid is prepared from a sodium silicate aqueous solution, and the concentration of sodium silicate in the sodium silicate aqueous solution is 10-15%;
the chitosan phosphate is prepared by adopting the following scheme:
(1) Taking chitosan and deionized water, stirring and mixing to prepare a chitosan solution with the mass fraction of 10%, adding a phosphoric acid solution and a formaldehyde solution into the chitosan solution according to the mass ratio of 1;
(2) And (2) adding the mixed solution into absolute ethyl alcohol according to the mass ratio of 1.
2. The preparation method of the zinc chloride compound corrosion inhibitor for circulating cooling water according to claim 1 is characterized by comprising the following specific preparation steps:
s1, preparing a corrosion inhibition pre-filming liquid: stirring and mixing zinc chloride, chitosan, deionized water, dibasic acid and chitosan phosphate according to a formula, standing at room temperature for 6-8 hours, homogenizing and filtering, and collecting filtrate to obtain a corrosion inhibition pre-membrane solution;
s2, preparing a corrosion inhibition confining liquid: adding sodium silicate into deionized water according to a formula, stirring, mixing, and performing rotary evaporation until the mass fraction of the corrosion inhibition pre-filming liquid is 10-15%, so as to prepare a corrosion inhibition confining liquid;
s3, inhibitor compounding: adding the corrosion inhibition confining liquid into the corrosion inhibition pre-film liquid, stirring, mixing, performing ultrasonic dispersion, standing at room temperature for swelling, homogenizing, and screening with a screen of 500-1000 meshes to obtain the zinc chloride compound corrosion inhibitor for circulating cooling water.
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| CN104843880A (en) * | 2015-05-13 | 2015-08-19 | 扬州大学 | Compound corrosion inhibitor and application of compound corrosion inhibitor in carbon steel material circulating cooling water system |
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| CN109110933B (en) * | 2018-08-22 | 2021-05-04 | 江苏科利恩净水科技有限公司 | Low-phosphorus scale and corrosion inhibitor and preparation method thereof |
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| CN102603086A (en) * | 2012-04-19 | 2012-07-25 | 山东京博控股股份有限公司 | Corrosion and scale inhibitor for cooling water in petrochemical industry |
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