CN115323386B - High-temperature-resistant corrosion-inhibition and scale-removal integrated agent for carbon steel equipment and preparation method thereof - Google Patents
High-temperature-resistant corrosion-inhibition and scale-removal integrated agent for carbon steel equipment and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/086—Iron or steel solutions containing HF
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
Abstract
The invention discloses a high-temperature-resistant corrosion-inhibition and scale-removal integrated agent for carbon steel equipment and a preparation method thereof. The integrated agent is prepared from the following components in percentage by mass: 0.1-5% of compound corrosion inhibitor; hydrochloric acid 0.1-30%; 0.1-3% of hydrofluoric acid; 0.5-5% of surfactant; 0.0005-0.002% of scale inhibitor; 60-88% of water; wherein the compound corrosion inhibitor consists of 5-10% of ethanol, 15-35% of imidazolines, 15-30% of didodecyl dimethyl ammonium chloride, 3-10% of diamide capsular ether, 5-10% of molybdate and 5-57% of water by mass percent. The corrosion inhibition and scale removal integrated agent provided by the invention can ensure the scale removal effect and simultaneously has good corrosion inhibition effect on carbon steel equipment, can keep the dual effects of corrosion inhibition and scale removal, and is especially suitable for removing scale matters in the carbon steel equipment.
Description
Technical Field
The invention relates to a corrosion inhibition and scale removal integrated agent, in particular to a high-temperature resistant corrosion inhibition and scale removal integrated agent for carbon steel equipment and a preparation method thereof.
Background
In petrochemical plants, more than 80% of water consumption is used as circulating cooling water, wherein most circulating water systems adopt open circulating cooling systems, dust in the environment, calcium and magnesium ions in the circulating water, inorganic silicate, iron oxides generated by corrosion and the like can deposit and scale in the circulating systems, and particularly, the scale is accelerated due to the fact that the shell side of a heat exchanger has complex structure, more dead zones, high surface temperature and the like. If the generated scale is not cleaned timely, the heat exchange efficiency of the heat exchanger can be affected, the energy consumption is increased, the under-scale corrosion is further aggravated, equipment is damaged, material leakage and the like are caused, the production stability is affected, and even the safety risk is brought.
Aiming at the treatment method of the scaling substances of carbon steel equipment such as a heat exchanger and the like, two modes of physical cleaning and chemical cleaning exist at present. The physical cleaning is only suitable for cleaning the tube side with a simple scale formation layer and a loose structure, but when the water side of the heat exchanger is more, the heat exchanger mainly comprises components such as calcium sulfate, magnesium sulfate, ferric oxide, ferroferric oxide, silicate and the like, the scale formation layer is compact, the bonding strength with a matrix is high, and a dispersing agent for physical cleaning cannot permeate, so that a better descaling effect cannot be achieved. For the chemical cleaning mode, if only organic acids such as citric acid and sulfamic acid are adopted for treatment, the problem of unmatched corrosivity of acid liquor and scale formation components exists, the descaling effect is poor, high-concentration inorganic acid is generally required to be added and the temperature is increased to strengthen dissolution of the scale, but the carbon steel heat exchanger is not resistant to the inorganic acid at all, and particularly the high-temperature and high-concentration inorganic acid can cause serious corrosion problems. At present, most of formulas have a certain corrosion inhibition effect under normal temperature operation conditions by regulating and controlling pH to be neutral or slightly alkaline in an inorganic acid solution, but the acid corrosiveness of the formulas is greatly reduced, and the descaling effect of the descaling agent is sacrificed.
Patent CN101186395a discloses a compound acid type scale remover which combines organic acid and inorganic acid into a whole, and uses a plurality of acids such as citric acid, propionic acid, sulfamic acid, phosphoric acid and the like to mix for scale removal, but the scale remover has strong corrosiveness to carbon steel equipment under the formula, has no obvious scale removal effect to silicate, and cannot realize the purpose of one dose for multiple purposes at normal temperature.
Patent CN111807528A discloses a detergent containing sulfuric acid, acrylic acid and the like as main components, but the formula is obviously unfavorable for the descaling of calcium sulfate and magnesium sulfate with compact structures, and is easy to form precipitation with magnesium ions and calcium ions; while this patent controls ph=8-12, although controlling the corrosiveness to the equipment, it is also insoluble in iron oxides, silicates, etc.
Patent CN109264879a discloses a scale remover mainly aiming at barium-strontium scale in water wells and bottom layers in oil fields, which dissolves the scale of strontium sulfate, barium sulfate, strontium carbonate, barium carbonate by utilizing dispersion, addition and action of hydrofluoric acid, hydrochloric acid, addition agent, scale inhibitor and the like, but does not have solubility to iron oxides, silicate and the like.
Therefore, the existing detergent formula still has the problems that the descaling effect is poor and the descaling and corrosion inhibition cannot be achieved simultaneously.
Disclosure of Invention
Aiming at the problems that in the prior art, the scale formation layer is compact and the scale formation material containing various mixed components such as calcium sulfate, magnesium sulfate, ferric oxide, ferroferric oxide, silicate and the like is difficult to effectively clean, and the corrosion inhibition of carbon steel equipment is difficult to ensure under the condition of ensuring the descaling effect, the invention provides a high-temperature corrosion inhibition and descaling integrated agent for the carbon steel equipment and a preparation method thereof, and aims to solve the problems.
The high-temperature-resistant corrosion-scale-removing integrated agent for carbon steel equipment provided by the invention has good high-temperature resistance, acid resistance, corrosion inhibition performance and scale layer dissolution performance, and good wetting effect and penetration capability, ensures that the scale layer contacted by cleaning liquid is fully contacted and is permeated into the interior through scale pores, and can accelerate the reaction dissolution of scale matters.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a high-temperature corrosion inhibition and scale removal integrated agent for carbon steel equipment is prepared from the following components in percentage by mass:
0.1-5% of compound corrosion inhibitor;
hydrochloric acid 0.1-30%;
0.1-3% of hydrofluoric acid;
0.5-5% of surfactant;
0.0005-0.002% of scale inhibitor;
60-88% of water;
wherein the compound corrosion inhibitor consists of 5-10% of ethanol, 15-35% of imidazolines, 15-30% of didodecyl dimethyl ammonium chloride, 3-10% of diamide capsular ether, 5-10% of molybdate and 5-57% of water by mass percent.
The corrosion inhibition and scale removal integrated agent provided by the invention is prepared by mixing the corrosion inhibitor, hydrochloric acid and hydrofluoric acid in proportion, and combining the surfactant and the scale inhibitor for use together, so that the aims of dissolving and removing scale at high temperature and high concentration of inorganic acid and protecting carbon steel equipment from corrosion are fulfilled. Wherein the synergistic ratio of hydrochloric acid and hydrofluoric acid has high-efficiency solubility for calcium salt, magnesium salt, silicate and iron oxide, especially for ferroferric oxide. The surfactant can promote the integral agent to wet and permeate the scaling layer, the scaling substance is dissolved and stripped after fully contacting and reacting with the acid integral agent, and meanwhile, the scale inhibitor and corroded metal ions are used for complexing to form a water-soluble complex, so that the continuous effectiveness of the integral agent is ensured.
In particular, in the compound corrosion inhibitor, the diamide capsular ether is favorable for uniform and orderly adsorption of molecules on the metal surface due to a special molecular structure and an electron cloud arrangement mode, and the diamide capsular ether and the symmetrical amide oxygen at two ends participate in metal matrix bonding together under the cooperation of intermediate ether oxygen to form a triangular plane bonding form, so that the stability of chemical bonds is enhanced. In addition, the special structure and bonding mode of the diamide capsular ether are favorable for locking the imidazolines on the surface of the carbon steel substrate, the oxide film with the bottom layer of molybdenum is formed, the adsorption layer with the alternate adsorption and cross-linking of the diamide capsular ether molecules and the imidazoline molecules is adopted as the middle layer, the adsorption integrity of the imidazolines is improved, and the corrosion and the scouring of the high-temperature acid solution on the carbon steel substrate, the oxide film and the imidazoline adsorption layer are effectively resisted by utilizing the synergistic effect of the diamide capsular ether, the imidazolines and the molybdate, so that the corrosion inhibition and scale removal integrated agent has the effect of one agent with multiple purposes.
In a preferred technical scheme of the invention, the hydrochloric acid is industrial hydrochloric acid with the mass concentration of 30-38%;
preferably, the hydrofluoric acid is industrial hydrofluoric acid with a mass concentration of 40%.
In a preferred embodiment of the present invention, the surfactant is one or more of tetrabutylammonium chloride, tetradecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride.
In a preferred embodiment of the invention, the scale inhibitor is butane-2-phosphonate-1, 2,4, -tricarboxylic acid.
In a preferred embodiment of the present invention, the diamide capsular ether is selected from at least one compound having a structural formula shown in formula I;
in the formula I, R, R' are all selected from C 1 -C 6 Is a hydrocarbon group.
In a preferred embodiment of the present invention, the diamide capsular ether is one or more of N, N '-tetramethyl-3-oxaglutaramide, N' -tetraethyl-3-oxaglutaramide, N '-tetra-N-propyl-3-oxaglutaramide, N' -tetraisobutyl-3-oxaglutaramide, N-dimethyl-N ', N' -diethyl-3-oxaglutaramide, N '-dimethyl-N, N' -dihexyl-3-oxaglutaramide.
In a preferred embodiment of the present invention, the molybdate is at least one of sodium molybdate and potassium molybdate.
The preparation method of the high-temperature corrosion inhibition and scale removal integrated agent for the carbon steel equipment comprises the following steps of:
1) Mixing and stirring 5-10% of ethanol, 15-35% of imidazolines, 15-30% of didodecyl dimethyl ammonium chloride, 3-10% of diamide pod ether, 5-10% of molybdate and 5-57% of water uniformly to obtain a compound corrosion inhibitor;
2) The preparation method comprises the following steps of:
0.1-5% of compound corrosion inhibitor;
hydrochloric acid 0.1-30%;
0.1-3% of hydrofluoric acid;
0.5-5% of surfactant;
0.0005-0.002% of scale inhibitor;
60-88% of water;
firstly, mixing the compound corrosion inhibitor and water, uniformly stirring, then adding the surfactant and the scale inhibitor while stirring, then adding hydrochloric acid and hydrofluoric acid while stirring, and discharging after all the components are uniformly mixed, thus obtaining the high-temperature corrosion inhibition and scale removal integrated agent for the carbon steel equipment.
The corrosion inhibition and scale removal integrated agent can be used for removing the scale formation layer of the carbon steel heat exchanger of the circulating water system, so that dead angle-free cleaning of carbon steel equipment is realized, corrosion of the equipment under scale is avoided, the running period of the equipment is prolonged, and the high efficiency and stability of the heat exchanger are ensured.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The raw material source information in the following examples and comparative examples of the present invention are commercially available, unless otherwise specified. Wherein, the mass concentration of the industrial hydrochloric acid is 36 percent, and the mass concentration of the industrial hydrofluoric acid is 40 percent.
In the following embodiments of the present invention, the scale removal effect of the corrosion and scale removal integrated agent is characterized by a scale removal rate (N) and a cleaning rate (B).
(1)N＝(M/M 0 )*100％
Wherein:
n-descaling rate,%;
m-the amount of the cleaned scale, g;
M 0 the original amount of scale, g, before cleaning.
(2)B＝(S/S 0 )*100％
Wherein:
b-washing rate,%;
s-area of dirt washed off, m 2 ；
S 0 Area of soil before cleaning, m 2 。
In the chemical cleaning process, the relative corrosion rate of the surface of the cleaned equipment is expressed as corrosion rate (K) in g/m 2 And (h) the corrosion inhibition effect of the corrosion inhibitor is expressed by corrosion inhibition efficiency (eta), and the unit is percent.
(3)K＝△m/(t*s)*100％
Wherein:
K-Corrosion Rate, g/m 2 /h；
Delta m-weight of metal corroded, g;
t-time of metal corrosion, h;
s-area of contact of metal with detergent, m 2 ；
(4)η＝(K 0 -K 1 )/K 0 *100％；
Wherein eta is corrosion inhibition efficiency and has no unit;
K 0 for corrosion rate under the action of scale remover without corrosion inhibitor, g/m 2 /h；
K 1 Is corrosion speed under the action of scale remover containing corrosion inhibitorRate, g/m 2 /h。
The raw material source information in the following examples and comparative examples of the present invention are commercially available, unless otherwise specified.
The following preparation examples 1-3 prepare different diamide capsular ethers by the method disclosed in patent CN 102993042B.
[ preparation example 1 ]
Preparation of N, N' -tetraethyl-3-oxaglutaramide:
(1) Adding 0.5mol of diglycolic anhydride into 5mol of 1,4 dioxane, adding a mixed solution of 0.5mol of diethylamine and 0.6mol of pyridine under stirring at the water bath temperature of 5 ℃ for 2.5 hours; the reaction was followed at 25℃for 4h. Then removing 1,4 dioxane by rotary evaporation, adding hydrochloric acid aqueous solution with the volume fraction of 50%, precipitating white crystals, carrying out suction filtration, recrystallizing by using a water-methanol system with the volume ratio of 1:2, and carrying out vacuum drying to obtain 85.2g of N, N-diethyl-3-oxaglutarimide.
(2) 0.3mol of N, N-diethyl-3-oxaglutarimide, 0.3mol of N-methylmorpholine and 250ml of ethyl acetate are stirred uniformly, cooled to-10 ℃,0.3mol of isobutyl chloroformate is added dropwise, stirred for 2min, 0.3mol of diethylamine is added dropwise for continuous reaction for 2h, and then the crude product is obtained after reaction for 2h at room temperature of 25 ℃. The crude product was washed successively with water, 1% sodium hydroxide, 0.1mol/L hydrochloric acid, finally with water to neutrality, the organic phase was collected and dried over anhydrous sodium sulfate, and rotary evaporation gave 66g of the product, N' -tetraethyl-3-oxaglutaramide.
The nuclear magnetic hydrogen spectrum analysis data of the obtained product are as follows:
1 HNMR(CCLD 3 ，400MHz)δ＝4.30(s，4H；OCH 2 ),3.41-3.30(2m，8H；CH 2 )，1.21-1.09(m，12H；CH 3 )。
[ preparation example 2 ]
Preparation of N, N' -tetra-N-propyl-3-oxoglutarate:
(1) 0.5mol of diglycolic anhydride is added into 5mol of 1,4 dioxane, and a mixture of 0.5mol of di-n-propylamine and 0.6mol of pyridine is added under stirring at the water bath temperature of 5 ℃ for 2.5 hours. Then reacting for 4 hours at 25 ℃, then removing 1,4 dioxane by rotary evaporation, adding hydrochloric acid aqueous solution with the volume fraction of 50%, precipitating white crystals, carrying out suction filtration, recrystallizing by using an aqueous methanol system with the volume ratio of 1:2, and carrying out vacuum drying to obtain 85.2g of N, N-di-N-propyl-3-oxaglutarimide.
(2) Stirring 0.3mol of N, N-di-N-propyl-3-oxoglutarate, 0.3mol of N-methylmorpholine and 250ml of ethyl acetate uniformly, cooling to-10 ℃, dropwise adding 0.3mol of isobutyl chloroformate, stirring for 2min, dropwise adding 0.3mol of di-N-propylamine to continue to react for 2h, and then reacting at room temperature of 25 ℃ for 2h to obtain a crude product, washing the crude product with water, 1% sodium hydroxide and 0.1mol/L of hydrochloric acid in sequence, washing with water to neutrality, collecting an organic phase, drying with anhydrous sodium sulfate, and performing rotary evaporation to obtain 105g of the product, namely N, N' -tetra-N-propyl-3-oxoglutarate.
The nuclear magnetic hydrogen spectrum analysis data of the obtained product are as follows:
1 HNMR(CCLD 3 ，400MHz)δ＝4.31(s，4H；OCH 2 ),3.29-3.313(2m，8H；CH 2 )，1.59-1.52(2m，8H；CH 2 ),0.92-0.86(m，12H；CH 3 )。
[ preparation example 3 ]
Preparation of N, N' -tetraisobutyl-3-oxoglutarate:
(1) Adding 0.5mol of diglycosidic anhydride into 5mol of 1,4 dioxane, adding a mixed solution of 0.5mol of diisobutylamine and 0.6mol of pyridine under stirring at the water bath temperature of 5 ℃ for 2.5h; the reaction was followed at 25℃for 4h. Then removing 1,4 dioxane by rotary evaporation, adding hydrochloric acid aqueous solution with the volume fraction of 50%, precipitating white crystals, carrying out suction filtration, recrystallizing by using a water-methanol system with the volume ratio of 1:2, and carrying out vacuum drying to obtain 90.2g of N, N-diisobutyl-3-oxaglutarimide.
(2) 0.3mol of N, N-diisobutyl-3-oxaglutarimide, 0.3mol of N-methylmorpholine and 250ml of ethyl acetate are stirred uniformly, cooled to-10 ℃,0.3mol of isobutyl chloroformate is added dropwise, stirred for 2min, 0.3mol of diisobutylamine is added dropwise for continuous reaction for 2h, and then the crude product is obtained after reaction for 2h at room temperature of 25 ℃. The crude product was washed successively with water, 1% sodium hydroxide, 0.1mol/L hydrochloric acid, finally with water to neutrality, the organic phase was collected and dried over anhydrous sodium sulfate, and rotary evaporation gave 120g of the product, N' -tetraisobutyl-3-oxoglutarate.
The nuclear magnetic hydrogen spectrum analysis data of the obtained product are as follows:
1 HNMR(CCLD 3 ，400MHz)δ＝4.35(s，4H；OCH 2 ),3.20-3.03(2d，8H；NCH 2 )，2.03-1.87(2m，4H；CH)，0.89-0.85(t，24H；CH 3 )。
the following examples 1-7 were used to prepare corrosion and scale inhibition integrated agents of different formulations:
[ example 1 ]
(1) Preparing a compound corrosion inhibitor:
at normal temperature, water accounting for 100% of the total mass, ethanol accounting for 5% of the total mass, lauryl amphoteric imidazoline accounting for 35% of the total mass, didodecyl dimethyl ammonium chloride accounting for 20% of the total mass, N' -tetraethyl-3-oxaglutaramide accounting for 10% of the total mass and potassium molybdate are sequentially added into a dry reaction kettle, and uniformly stirred to obtain the compound corrosion inhibitor, and the compound corrosion inhibitor is stored for standby.
(2) Preparing an integrated agent for corrosion inhibition and scale removal:
based on 100% of total mass, 0.5% of compound corrosion inhibitor, 0.001% of 2-phosphonic butane-1, 2, 4-tricarboxylic acid, 2.5% of tetrabutylammonium chloride, 8% of industrial hydrochloric acid, 0.5% of industrial hydrofluoric acid and 88.5% of water are respectively prepared. Firstly, mixing a compound corrosion inhibitor and water, uniformly stirring, then adding 2-phosphonic butane-1, 2, 4-tricarboxylic acid and tetrabutylammonium chloride while stirring, adding industrial hydrochloric acid and industrial hydrofluoric acid while stirring, uniformly mixing all the materials, and discharging to obtain the corrosion inhibition-scale removal integrated agent.
[ example 2 ]
(1) Preparing a compound corrosion inhibitor:
at normal temperature, water accounting for 100% of the total mass, 10% of ethanol, 30% of lauryl amphoteric imidazoline, 25% of didodecyl dimethyl ammonium chloride, 8% of N, N' -tetraethyl-3-oxaglutaramide and 7% of sodium molybdate are sequentially added into a dry reaction kettle, and uniformly stirred to obtain the compound corrosion inhibitor for standby.
(2) Preparing an integrated agent for corrosion inhibition and scale removal:
based on 100% of total mass, 0.3% of compound corrosion inhibitor, 0.0015% of 2-phosphonic butane-1, 2, 4-tricarboxylic acid, 2.5% of tetrabutylammonium chloride, 10% of industrial hydrochloric acid, 0.5% of industrial hydrofluoric acid and 86.7% of water are respectively prepared. Firstly, mixing a compound corrosion inhibitor and water, uniformly stirring, then adding 2-phosphonic butane-1, 2, 4-tricarboxylic acid and tetrabutylammonium chloride while stirring, adding industrial hydrochloric acid and industrial hydrofluoric acid while stirring, uniformly mixing all the materials, and discharging to obtain the corrosion inhibition-scale removal integrated agent.
[ example 3 ]
(1) Preparing a compound corrosion inhibitor:
at normal temperature, 17% of water, 5% of ethanol, 35% of lauryl amphoteric imidazoline, 25% of didodecyl dimethyl ammonium chloride, 10% of N, N' -tetra-N-propyl-3-oxaglutaramide and 8% of potassium molybdate are sequentially added into a dry reaction kettle, and uniformly stirred to obtain the compound corrosion inhibitor for standby.
(2) Preparing an integrated agent for corrosion inhibition and scale removal:
according to the total mass of 100%, preparing 1% of compound corrosion inhibitor, 0.002% of 2-phosphonic acid butane-1, 2, 4-tricarboxylic acid, 3% of hexadecyl trimethyl ammonium chloride, 10% of industrial hydrochloric acid, 1% of industrial hydrofluoric acid and 85% of water respectively. Firstly, mixing a compound corrosion inhibitor and water, uniformly stirring, then adding 2-phosphonic butane-1, 2, 4-tricarboxylic acid and tetrabutylammonium chloride while stirring, adding industrial hydrochloric acid and industrial hydrofluoric acid while stirring, uniformly mixing all the materials, and discharging to obtain the corrosion inhibition-scale removal integrated agent.
[ example 4 ]
(1) Preparing a compound corrosion inhibitor:
at normal temperature, adding water accounting for 100% of the total mass, ethanol accounting for 8% of the total mass, lauryl amphoteric imidazoline accounting for 25% of the total mass, didodecyl dimethyl ammonium chloride accounting for 15% of the total mass, N' -tetra-N-propyl-3-oxaglutaramide accounting for 10% of the total mass and potassium molybdate into a dry reaction kettle in sequence, stirring uniformly to obtain a compound corrosion inhibitor, and storing for later use.
(2) Preparing an integrated agent for corrosion inhibition and scale removal:
according to the total mass of 100%, 2% of compound corrosion inhibitor, 0.0015% of 2-phosphonic butane-1, 2, 4-tricarboxylic acid, 3.5% of tetradecyl trimethyl ammonium chloride, 8% of industrial hydrochloric acid, 2% of industrial hydrofluoric acid and 84.5% of water are respectively prepared. Firstly, mixing a compound corrosion inhibitor and water, uniformly stirring, then adding 2-phosphonic butane-1, 2, 4-tricarboxylic acid and tetradecyltrimethylammonium chloride while stirring, then adding industrial hydrochloric acid and industrial hydrofluoric acid while stirring, and discharging after all the materials are uniformly mixed, thus obtaining the corrosion inhibition-scale removal integrated agent.
[ example 5 ]
(1) Preparing a compound corrosion inhibitor:
at normal temperature, 27% of water, 8% of ethanol, 15% of lauryl ampholytic azoline, 30% of didodecyl dimethyl ammonium chloride, 10% of N, N' -tetraisobutyl-3-oxa-diamide and 10% of sodium molybdate are sequentially added into a dry reaction kettle, and uniformly stirred to obtain the compound corrosion inhibitor for standby.
(2) Preparing an integrated agent for corrosion inhibition and scale removal:
according to the total mass of 100%, 5% of compound corrosion inhibitor, 0.0015% of 2-phosphonic butane-1, 2, 4-tricarboxylic acid, 2.0% of tetradecyl trimethyl ammonium chloride, 8% of industrial hydrochloric acid, 3% of industrial hydrofluoric acid and 82% of water are respectively prepared. Firstly, mixing a compound corrosion inhibitor and water, uniformly stirring, then adding 2-phosphonic butane-1, 2, 4-tricarboxylic acid and tetradecyltrimethylammonium chloride while stirring, then adding industrial hydrochloric acid and industrial hydrofluoric acid while stirring, and discharging after all the materials are uniformly mixed, thus obtaining the corrosion inhibition-scale removal integrated agent.
[ example 6 ]
(1) Preparing a compound corrosion inhibitor:
at normal temperature, 15% of water, 10% of ethanol, 25% of lauryl amphoteric imidazoline, 30% of didodecyl dimethyl ammonium chloride, 10% of N, N' -tetraethyl-3-oxaglutaramide and 10% of sodium molybdate are sequentially added into a dry reaction kettle, and uniformly stirred to obtain a compound corrosion inhibitor for standby.
(2) Preparing an integrated agent for corrosion inhibition and scale removal:
based on 100% of total mass, 0.5% of compound corrosion inhibitor, 0.001% of 2-phosphonic butane-1, 2, 4-tricarboxylic acid, 5.0% of tetradecyl trimethyl ammonium chloride, 10% of industrial hydrochloric acid, 1% of industrial hydrofluoric acid and 83.5% of water are respectively prepared. Firstly, mixing a compound corrosion inhibitor and water, uniformly stirring, then adding 2-phosphonic butane-1, 2, 4-tricarboxylic acid and tetradecyltrimethylammonium chloride while stirring, then adding industrial hydrochloric acid and industrial hydrofluoric acid while stirring, and discharging after all the materials are uniformly mixed, thus obtaining the corrosion inhibition-scale removal integrated agent.
Comparative example 1
A corrosion inhibition-scale removal integrated agent was prepared in substantially the same manner as in example except that: when preparing the compound corrosion inhibitor, N' -tetraethyl-3-oxaglutaramide is not added.
Comparative example 2
A corrosion inhibition-scale removal integrated agent was prepared in substantially the same manner as in example except that: when preparing the corrosion inhibition and scale removal integrated agent, hydrofluoric acid in the non-processing industry is not used.
The following application examples 1-2 were used to test corrosion inhibition-scale removal effects for different foulants compositions:
[ application example 1 ]
The corrosion inhibition and scale removal integrated agent prepared by the above examples and comparative examples has a composition of 58% iron oxide (in Fe on the shell side of a carbon steel heat exchanger 2 O 3 Content meter of (c), 26% CaSO 4 11% silicate (in SiO) 2 The content meter) of the scale deposit A with 5 percent of other components, and respectively testing the descaling effect and the corrosion inhibition effect, wherein the testing method comprises the following steps:
taking a sample of a scaling substance in a field, accounting the scaling area, placing the sample in a reaction vessel, adding 500ml of the prepared corrosion inhibition and scale removal integrated agent to completely submerge the sample, controlling the temperature to be 60 ℃, soaking and dissolving for 7 hours, sampling and analyzing the sample, calculating the effective scaling area, and determining the cleaning rate. And (3) taking 30g of the scaling substances in the field, placing the scaling substances in another reaction container, adding 500ml of the prepared corrosion inhibition and scale removal integrated agent, placing 20# carbon steel standard hanging pieces with the size of 50 multiplied by 25 multiplied by 2mm into the reaction container, controlling the temperature to be 60 ℃, soaking and dissolving for 7 hours, taking the hanging pieces for analysis, filtering residues, weighing, and respectively calculating the scale removal rate, the corrosion rate and the corrosion inhibition efficiency. The test results are shown in table 1:
TABLE 1 dissolution test results of each Integrated agent on fouling agent A
[ application example 2 ]
The corrosion inhibition and scale removal integrated agent prepared by the above examples and comparative examples has a composition of 65% iron oxide (in Fe on the shell side of a carbon steel heat exchanger 2 O 3 Content meter of (2), 12% CaSO 4 、10％CaCO 3 9% silicate (in SiO) 2 The content meter) and 4% of other scaling substances B, respectively performing scale removal effect and corrosion inhibition effect tests, wherein the test method comprises the following steps:
taking a sample of a scaling substance in a field, accounting the scaling area, placing the sample in a reaction vessel, adding 500ml of the prepared corrosion inhibition and scale removal integrated agent to completely submerge the sample, controlling the temperature to be 60 ℃, soaking and dissolving for 7 hours, sampling and analyzing the sample, calculating the effective scaling area, and determining the cleaning rate. And (3) taking 30g of the scaling substances in the field, placing the scaling substances in another reaction container, adding 500ml of the prepared corrosion inhibition and scale removal integrated agent, placing 20# carbon steel standard hanging pieces with the size of 50 multiplied by 25 multiplied by 2mm into the reaction container, controlling the temperature to be 60 ℃, soaking and dissolving for 7 hours, taking the hanging pieces for analysis, filtering residues, weighing, and respectively calculating the scale removal rate, the corrosion rate and the corrosion inhibition efficiency. The test results are shown in table 2:
TABLE 2 dissolution test results of each Integrated agent on Scale inhibitor B
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (6)
1. The high-temperature corrosion inhibition and scale removal integrated agent for the carbon steel equipment is characterized by being prepared from the following components in percentage by mass:
0.1-5% of compound corrosion inhibitor;
hydrochloric acid 0.1-30%;
0.1-3% of hydrofluoric acid;
0.5-5% of surfactant;
0.0005-0.002% of scale inhibitor;
60-88% of water;
wherein the compound corrosion inhibitor consists of 5-10% of ethanol, 15-35% of imidazolines, 15-30% of didodecyl dimethyl ammonium chloride, 3-10% of diamide capsular ether, 5-10% of molybdate and 5-57% of water by mass percent;
the imidazolines are lauryl amphoteric imidazolines;
the surfactant is one or more of tetrabutylammonium chloride, tetradecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride;
the diamide pod ether is selected from at least one compound with a structural expression shown in a formula I;
in the formula I, R, R' are all selected from C 1 -C 6 Is a hydrocarbon group.
2. The high-temperature corrosion inhibition and scale removal integrated agent for carbon steel equipment according to claim 1, wherein the hydrochloric acid is industrial hydrochloric acid with the mass concentration of 30-38%;
the hydrofluoric acid is industrial hydrofluoric acid with the mass concentration of 40%.
3. The high temperature corrosion and scale inhibitor for carbon steel equipment as claimed in claim 1, wherein the scale inhibitor is 2-butane-phosphonate-1, 2,4, -tricarboxylic acid.
4. The high temperature corrosion and scale inhibitor for carbon steel equipment according to claim 1, wherein the diamide capsular ether is one or more of N, N '-tetramethyl-3-oxaglutaramide, N' -tetraethyl-3-oxaglutaramide, N '-tetra-N-propyl-3-oxaglutaramide, N' -tetraisobutyl-3-oxaglutaramide, N-dimethyl-N ', N' -diethyl-3-oxaglutaramide, N '-dimethyl-N, N' -dihexyl-3-oxaglutaramide.
5. The high temperature resistant corrosion and scale inhibitor for carbon steel equipment according to any one of claims 1 to 4, wherein the molybdate is at least one of sodium molybdate and potassium molybdate.
6. A method for preparing the high temperature corrosion inhibition and scale removal integrated agent for carbon steel equipment according to any one of claims 1 to 5, comprising the following steps:
1) Mixing and stirring 5-10% of ethanol, 15-35% of imidazolines, 15-30% of didodecyl dimethyl ammonium chloride, 3-10% of diamide pod ether, 5-10% of molybdate and 5-57% of water uniformly to obtain a compound corrosion inhibitor;
2) The preparation method comprises the following steps of:
0.1-5% of compound corrosion inhibitor;
hydrochloric acid 0.1-30%;
0.1-3% of hydrofluoric acid;
0.5-5% of surfactant;
0.0005-0.002% of scale inhibitor;
60-88% of water;
firstly, mixing the compound corrosion inhibitor and water, uniformly stirring, then adding the surfactant and the scale inhibitor while stirring, then adding hydrochloric acid and hydrofluoric acid while stirring, and discharging after all the components are uniformly mixed, thus obtaining the high-temperature corrosion inhibition and scale removal integrated agent for the carbon steel equipment.
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| CN202210876616.XA CN115323386B (en) | 2022-07-25 | 2022-07-25 | High-temperature-resistant corrosion-inhibition and scale-removal integrated agent for carbon steel equipment and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011772A1 (en) * | 2002-07-31 | 2004-02-05 | Champion Technologies, Inc. | Method of controlling scale formation |
| JP2006045608A (en) * | 2004-08-03 | 2006-02-16 | Ito Seiyu Kk | Corrosion inhibitor for pickling and corrosion-inhibiting pickling liquid using it |
| CN111334272A (en) * | 2020-04-09 | 2020-06-26 | 克拉玛依翎昊科技有限责任公司 | Scale remover for water injection system of oil and gas field and preparation and application methods thereof |
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2022
- 2022-07-25 CN CN202210876616.XA patent/CN115323386B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011772A1 (en) * | 2002-07-31 | 2004-02-05 | Champion Technologies, Inc. | Method of controlling scale formation |
| JP2006045608A (en) * | 2004-08-03 | 2006-02-16 | Ito Seiyu Kk | Corrosion inhibitor for pickling and corrosion-inhibiting pickling liquid using it |
| CN111334272A (en) * | 2020-04-09 | 2020-06-26 | 克拉玛依翎昊科技有限责任公司 | Scale remover for water injection system of oil and gas field and preparation and application methods thereof |
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