CN110257178B - Descaling cleaning agent for galvanizing equipment - Google Patents

Descaling cleaning agent for galvanizing equipment Download PDF

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Publication number
CN110257178B
CN110257178B CN201910622844.2A CN201910622844A CN110257178B CN 110257178 B CN110257178 B CN 110257178B CN 201910622844 A CN201910622844 A CN 201910622844A CN 110257178 B CN110257178 B CN 110257178B
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corrosion
percent
corrosion inhibitor
acid
cleaning agent
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CN110257178A (en
Inventor
吴晋英
陈敏
黄长山
徐会武
张敏
程玉山
薛冕
张晓光
丁鸣
陈俊强
胡国华
邢乃豪
张强
杨敏芝
张蕾
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Energy Research Institute Co Ltd of Henan Academy of Sciences
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Energy Research Institute Co Ltd of Henan Academy of Sciences
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Abstract

The invention discloses a chemical cleaning agent for galvanizing equipment, and belongs to the technical field of chemical cleaning. The material is prepared from the following raw materials in percentage by weight: 0.3 to 1.2 percent of surfactant; imidazoline corrosion inhibitor 0.1-1.2%; 0.1 to 0.8 percent of dispersant; 0.2 to 0.8 percent of auxiliary agent; 7-8% of oxalic acid; 12-14% of hydrochloric acid and the balance of water. The chemical cleaning agent for the galvanizing equipment is prepared by mixing inorganic acid and organic acid together according to the optimal proportion, has the functions of descaling and corrosion inhibition, and is compounded with dodecyl benzyl ammonium chloride, amphoteric imidazoline corrosion inhibitor and auxiliary agent which have good corrosion inhibition on zinc to prepare the chemical cleaning agent for the galvanizing equipment.

Description

Descaling cleaning agent for galvanizing equipment
Technical Field
The invention relates to a descaling cleaning agent for galvanizing equipment, belonging to the technical field of chemical cleaning.
Background
In industrial production, in novel anticorrosion heat exchange equipment and winter heating equipment, a large number of radiating pipe coolers made of galvanized materials are used for heat exchange, water is used as a cooling medium, cooled process fluid flows in the radiating pipes, water and air flow outside the radiating pipes simultaneously, heat of the fluid in the radiating pipes is transferred to the air through the water outside the radiating pipes, the purpose of cooling is achieved, and in order to save water for the water-cooled coolers, the water is cooled in a cooling tower and recycled. The cooler commonly used in large food factories, liquefied gas filling stations and steel plants is an evaporative cooler, the radiating pipe of which is made of iron matrix galvanized material, the inside of which is provided with a cooling material, and the outside of which is provided with water. Because the used cooling water is raw untreated water, after the cooler is used for a period of time, scales, corrosion or bacteria and algae breeding and the like are often generated on the radiating pipe made of galvanized materials, so that the radiating of the cooler is poor, the high temperature is generated, the refrigeration effect of equipment is seriously influenced, the service life of the equipment is shortened, water and electricity are wasted, and the cooler must be chemically cleaned to recover the original effect. However, since the metal zinc is a very active amphoteric metal, it is difficult to protect the zinc coating from corrosion and corrosion by using a general acidic cleaning agent in the chemical cleaning and descaling process, which causes the corrosion of the radiator pipe of the cooler and the leakage of the coolant. Aiming at the problem, Chinese researchers have carried out a great deal of research on zinc corrosion inhibitors, and have carried out a great deal of research and exploration in this respect by the university of Liaoning teachers, and made a certain progress, but the corrosion inhibitors and the acid for descaling have poor solubility and large smell, so that the corrosion to zinc is not thoroughly solved, and the investment in practical application is limited.
Disclosure of Invention
In order to solve the problems and the defects in the technical field, the invention aims to provide a special cleaning agent for galvanizing equipment, which has low corrosion on zinc and can rapidly remove scale without damaging a galvanized layer.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
the chemical cleaning agent for the galvanizing equipment comprises the following raw materials in percentage by weight: 0.3 to 1.2 percent of surfactant; imidazoline corrosion inhibitor 0.1-1.2%; 0.1 to 0.8 percent of dispersant; 0.2 to 0.8 percent of auxiliary agent; 7-8% of oxalic acid; 12-14% of hydrochloric acid and the balance of water.
The raw materials preferably comprise the following components: 0.3% of surfactant; imidazoline corrosion inhibitor 0.1%; 0.1% of a dispersant; 0.2 percent of auxiliary agent; oxalic acid 8%; 12% of hydrochloric acid and the balance of water.
The surfactant is dodecyl benzyl ammonium chloride.
The imidazoline corrosion inhibitor is an amphoteric imidazoline corrosion inhibitor.
The dispersant is polyacrylic acid (PAA).
The auxiliary agent is hexamethylenetetramine.
Further, the ratio of the oxalic acid to the hydrochloric acid equivalent concentration is 1: 6.
The preparation method comprises the following steps:
(1) preparing a mixed acid solution: hydrochloric acid and oxalic acid are prepared according to the equivalent concentration of 1: 6.
(2) And (2) adding dodecyl benzyl ammonium chloride, A KLSS-A imidazoline corrosion inhibitor, PAA and hexamethylenetetramine into the mixed acid solution obtained in the step (1), and uniformly stirring.
The invention has the advantages that: 1. the invention uses inorganic acid hydrochloric acid and organic acid oxalic acid with a certain proportion, and utilizes the characteristics of high descaling speed, high corrosivity, low cost, low descaling speed of the inorganic acid, low corrosivity to zinc and high cost of the organic acid, and the inorganic acid and the organic acid are mixed together by the optimal proportion, so that the descaling and corrosion-inhibiting effects are achieved. 2. Dodecyl benzyl ammonium chloride, KLSS-A amphoteric imidazoline corrosion inhibitor, polyacrylic acid, hexamethylenetetramine andthe cleaning agent prepared by the mixed acid has good cooperativity, no odor and low corrosion rate to zinc. 3. The corrosion rate to zinc is 200g/m2H is reduced to 6g/m2.h。
Detailed description of the preferred embodiments
The invention is further described with reference to the following examples, wherein the dodecylbenzyl ammonium chloride active material comprises about 50% by weight; the KLSS-A amphoteric imidazoline corrosion inhibitor is produced by Ke Ling chemical Co., Ltd, Dongying city; the mass percentage of the PAA is 38 percent, and the oxalic acid is a commercial product; the hydrochloric acid is industrially pure and has the mass percentage of 32 percent; other reagents were commercially available analytically pure reagents.
Example 1
Adding 2 per mill of single-component corrosion inhibitor monomer into 1 gram equivalent/L HCL and oxalic acid solution respectively, and performing a Zn metal corrosion rotary hanging sheet experiment at 25 ℃ for 2 hours; and (3) performing an electrochemical corrosion test, and observing the surface micro-morphology and the change of element components of the corrosion test piece after the corrosion test by using an electron microscope and an energy spectrometer in a scanning manner, wherein the changes are shown in table 1.
TABLE 1, 1 gram equivalent/L (oxalic acid) solution +2 ‰ monomeric corrosion inhibitor + pure Zn corrosion spin coupon, electrochemistry, energy spectrum experimental data
Figure BDA0002126046410000021
As can be seen from Table 1, the corrosion rate of the corrosion inhibitor monomer except dodecyl benzyl ammonium chloride to the zinc corrosion coupon in the oxalic acid solution is generally lower than that in the hydrochloric acid solution with the same concentration, wherein the corrosion rate to metal zinc is lower in the two acidic solutions of KLSS-A, hexamethylenetetramine and PAA.
Example 2
Adding the single-component corrosion inhibitor monomer into a mixed solution of HCL and oxalic acid with the addition of 2 per mill, and performing a Zn metal corrosion rotary hanging sheet experiment at 25 ℃ for 2 hours; and (3) performing an electrochemical corrosion test, and observing the surface micro-morphology and the change of element components of the corrosion test piece after the corrosion test by using an electron microscope and an energy spectrometer in a scanning manner, wherein the changes are shown in table 2.
TABLE 2 data of 1 g eq/L (oxalic acid: HCL 1: 4; 1: 5; 1: 6; 1:7) +2 ‰ monomeric corrosion inhibitor + pure Zn corrosion spin coupon, electrochemistry, energy spectrum experiments
Figure BDA0002126046410000031
From the corrosion coupon experimental data of each corrosion inhibitor monomer in table 2, the corrosion inhibition effect is good when the corrosion inhibitor monomer is in a mixed solution of HCl and oxalic acid in a ratio of 1:6 by combining the comprehensive judgment of electrochemical analysis and electronic scanning analysis.
Example 3
Adding a plurality of corrosion inhibitor monomers with different amounts into a mixed acid of 1 gram equivalent/LHCL and oxalic acid solution (1:6) for compounding, and performing a Zn metal corrosion rotary hanging sheet experiment at 25 ℃ for 2 hours; and (3) performing an electrochemical corrosion test, and observing the surface micro-morphology and the change of element components of the corrosion test piece after the corrosion test by using an electron microscope and an energy spectrometer through scanning, wherein the changes are shown in table 3.
Table 3: 1 gram equivalent/L mixed acid solution (the equivalent ratio of oxalic acid: HCL is 1:6), different amounts of monomer corrosion inhibitor, pure Zn corrosion rotary hanging piece, electrochemistry and energy spectrum orthogonal experiment result
Figure BDA0002126046410000032
Figure BDA0002126046410000041
K of different corrosion inhibitor monomers in the experiment according to Table 31、K2、K3The optimal combination ratio of the corrosion inhibitor monomer is dodecyl benzyl ammonium chloride 3 per mill, KLSS-A1 per mill, PAA 1 per mill and hexamethylenetetramine 2 per mill.
Example 4
Adding 3 thousandth of dodecyl benzyl ammonium chloride, 1 thousandth of KLSS-A, 1 thousandth of PAA and 2 thousandth of hexamethylenetetramine into mixed acid of 1 gram equivalent/LHCL and oxalic acid solution (1:6) for compounding, and performing corrosion rotary hanging piece experiments on Zn metal at 25 ℃ for 1, 2, 3, 4 and 5 hours; and (3) performing an electrochemical corrosion test, and observing the surface micro-morphology and the change of element components of the corrosion test piece after the corrosion test by using an electron microscope and an energy spectrometer in a scanning manner, wherein the changes are shown in table 4.
TABLE 4 Corrosion rotary hanging piece, electrochemistry and energy spectrum experimental results of zinc plating equipment cleaning agent changing with time
Figure BDA0002126046410000042
As can be seen from the results in Table 4, the zinc corrosion inhibitor of the cleaning agent for the galvanizing equipment shows good corrosion inhibition effect along with the prolonging of the experiment time.
Example 5
1 g of calcium carbonate is added into 200mL of hydrochloric acid, oxalic acid and mixed acid (oxalic acid + hydrochloric acid 1:4, 1:5, 1:6 and 1:7) solution respectively at an equivalent/L of 1 g, and the descaling speed is compared.
TABLE 5 comparison of descaling speed for monoacids and mixed acids of different ratios
Figure BDA0002126046410000043
Example 6
Table 6, 1:6 mixed acid with different corrosion inhibitor monomers added under the same proportion for compounding
Figure BDA0002126046410000051
As can be seen from Table 6, dodecylbenzyl ammonium chloride, KLSS-A, PAA and hexamethynyltetramine showed the lowest corrosion rates and the best cooperativity in the 1:6 mixed acid.

Claims (3)

1. The descaling cleaning agent for the galvanizing equipment is characterized by being prepared by mixing the following raw materials in percentage by weight:
0.3 to 1.2 percent of surfactant; imidazoline corrosion inhibitor 0.1-1.2%; 0.1 to 0.8 percent of dispersant; 0.2 to 0.8 percent of auxiliary agent; 7-8% of oxalic acid; 12-14% of hydrochloric acid and the balance of water;
the surfactant is dodecyl benzyl ammonium chloride; the imidazoline corrosion inhibitor is an amphoteric imidazoline corrosion inhibitor; the dispersant is polyacrylic acid; the auxiliary agent is hexamethylenetetramine.
2. The descaling cleaning agent for galvanizing equipment as claimed in claim 1, wherein the raw material components are as follows: 0.3% of surfactant; imidazoline corrosion inhibitor 0.1%; 0.1% of a dispersant; 0.2 percent of auxiliary agent; oxalic acid 8%; 12% of hydrochloric acid and the balance of water.
3. The descaling cleaner for zinc-plating equipment as claimed in claim 1, wherein the ratio of the equivalent concentration of oxalic acid to hydrochloric acid is 1: 6.
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CN110735144A (en) * 2019-09-30 2020-01-31 上海柯灵展新化工有限公司 acidic cleaning agent for food factory pipelines and preparation method and application thereof
CN113897615B (en) * 2021-09-30 2023-06-02 河南省科学院能源研究所有限公司 Zinc plating corrosion inhibitor in mixed acid medium

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CN102021590A (en) * 2010-12-14 2011-04-20 戴锐 Metal scale remover and using method thereof
CN104277932A (en) * 2014-09-25 2015-01-14 苏州长盛机电有限公司 Scale cleaning agent and preparation method thereof

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CN102021097A (en) * 2009-09-22 2011-04-20 秦亚兵 Cleaning scale-removing agent
CN102071416B (en) * 2011-01-31 2012-04-25 神华集团有限责任公司 Preparation and application of chemical derusting cleaning agent
CN105695169A (en) * 2016-01-19 2016-06-22 马鞍山纽泽科技服务有限公司 Anti-scaling agent for water heater

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Publication number Priority date Publication date Assignee Title
CN102021590A (en) * 2010-12-14 2011-04-20 戴锐 Metal scale remover and using method thereof
CN104277932A (en) * 2014-09-25 2015-01-14 苏州长盛机电有限公司 Scale cleaning agent and preparation method thereof

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