CN115323386A - High-temperature-resistant corrosion-inhibition-descaling integrated agent for carbon steel equipment and preparation method thereof - Google Patents
High-temperature-resistant corrosion-inhibition-descaling 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 and scale inhibition 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 to 5 percent of compound corrosion inhibitor; 0.1 to 30 percent of hydrochloric acid; 0.1 to 3 percent of hydrofluoric acid; 0.5 to 5 percent of surfactant; 0.0005 to 0.002 percent of scale inhibitor; 60-88% of water; wherein, the compound corrosion inhibitor comprises 5-10% of ethanol, 15-35% of imidazoline, 15-30% of didodecyldimethylammonium chloride, 3-10% of diamide podand 5-10% of molybdate and 5-57% of water by mass percentage. The corrosion inhibition-descaling integrated agent provided by the invention can ensure the descaling effect, has good corrosion inhibition effect on carbon steel equipment, can keep the double effects of corrosion inhibition and descaling, and is particularly suitable for removing scaling substances in the carbon steel equipment.
Description
Technical Field
The invention relates to a corrosion inhibition-descaling integrated agent, in particular to a high-temperature resistance corrosion inhibition-descaling integrated agent for carbon steel equipment and a preparation method thereof.
Background
In a petrochemical plant, more than 80 percent of water 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 oxide generated by corrosion and the like can deposit and scale in the circulating system, and particularly, the scaling process is accelerated due to the complex structure, more dead zones, high surface temperature and the like on the shell side of a heat exchanger. If the scale deposit that produces if the clearance is not timely, not only can influence the heat exchange efficiency of heat exchanger, increase the energy consumption, still will further aggravate under the dirt corruption to damage equipment, lead to the material to leak etc. not only influence production stability, bring the safety risk even.
At present, two modes of physical cleaning and chemical cleaning are mainly used for treating scaling substances of carbon steel equipment such as a heat exchanger. The physical cleaning is only suitable for cleaning the pipe side with a simple scaling layer and a loose structure, but the water side of the heat exchanger is more, the physical cleaning mainly comprises calcium sulfate, magnesium sulfate, ferric oxide, ferroferric oxide, silicate and the like, the scaling layer is compact and has high bonding strength with a matrix, and a dispersing agent for physical cleaning cannot permeate and cannot achieve a good scaling effect. For the chemical cleaning mode, if only organic acid such as citric acid, sulfamic acid and the like is adopted for treatment, the problem of unmatched corrosivity of acid liquor and scaling components exists, the descaling effect is poor, high-concentration inorganic acid is usually added and the temperature is increased to carry out enhanced dissolution on the scaling, but a heat exchanger made of carbon steel has no resistance to the inorganic acid, and particularly the high-temperature and high-concentration inorganic acid can cause serious corrosion problem. At present, most of formulas ensure a certain corrosion inhibition effect under normal temperature operation conditions by regulating and controlling the pH value to be neutral or alkalescent in an inorganic acid solution, but greatly reduce the acid corrosivity of the formulas and sacrifice the descaling effect of the descaling agent.
Patent CN101186395A discloses a composite acid descaling agent which integrates organic acid and inorganic acid, and uses citric acid, propionic acid, sulfamic acid, phosphoric acid and other acids to mix for descaling, but the formula has strong corrosivity to carbon steel equipment, and the descaling effect on silicate is not obvious, and the purpose of one agent for multiple purposes cannot be realized at normal temperature.
Patent CN111807528a discloses a descaling agent with sulfuric acid, acrylic acid and the like as main components, but the formula is obviously not beneficial to descaling of calcium sulfate and magnesium sulfate with compact structure, and is easy to form precipitation with magnesium ions and calcium ions; meanwhile, the patent controls pH =8-12, and controls corrosivity to equipment, but cannot dissolve and remove iron oxides, silicates and the like.
Patent CN109264879a discloses a descaling agent mainly for barium and strontium scales in water wells and bottom layers in oil fields, which utilizes the dispersing, neoplasms and action of hydrofluoric acid, hydrochloric acid, neoplasms and scale inhibitor to dissolve the scales of strontium sulfate, barium sulfate, strontium carbonate and barium carbonate, but has no solubility for iron oxide, silicate, etc.
Therefore, the problems of poor descaling effect and incapability of simultaneously descaling and inhibiting corrosion still exist in the existing descaling agent formula and need to be solved urgently.
Disclosure of Invention
The invention provides a high-temperature-resistant corrosion and scale inhibition integrated agent for carbon steel equipment and a preparation method thereof, aiming at solving the problems that a scale formation layer is difficult to be compact and scales containing various mixed components such as calcium sulfate, magnesium sulfate, ferric oxide, ferroferric oxide, silicate and the like are difficult to be effectively cleaned in the prior art and the corrosion inhibition of the carbon steel equipment is difficult to be ensured under the condition of ensuring the scale inhibition effect.
The carbon steel equipment high-temperature-resistant corrosion-inhibition-descaling integrated agent provided by the invention has good high-temperature resistance and acid resistance, excellent corrosion inhibition performance and scale layer dissolution performance, good wetting effect and penetration capacity, ensures that the scale layer contacted with cleaning fluid is fully contacted and permeates into the interior through the scale pores, and can accelerate the reaction and dissolution of scale substances.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the high-temperature-resistant corrosion and scale inhibition integrated agent for the carbon steel equipment is prepared from the following components in percentage by mass:
0.1 to 5 percent of compound corrosion inhibitor;
0.1 to 30 percent of hydrochloric acid;
0.1 to 3 percent of hydrofluoric acid;
0.5 to 5 percent of surfactant;
0.0005 to 0.002 percent of scale inhibitor;
60-88% of water;
wherein, the compound corrosion inhibitor comprises 5-10% of ethanol, 15-35% of imidazoline, 15-30% of didodecyldimethylammonium chloride, 3-10% of diamide podand 5-10% of molybdate and 5-57% of water by mass percentage.
The corrosion inhibition-descaling integrated agent is prepared by mixing a corrosion inhibitor, hydrochloric acid and hydrofluoric acid in proportion, and matching with a surfactant and a scale inhibitor for use together, so that the aim of preventing carbon steel equipment from being corroded while descaling is achieved by dissolving high-temperature and high-concentration inorganic acid. The synergistic mixture of hydrochloric acid and hydrofluoric acid has high-efficiency solubility to calcium salt, magnesium salt, silicate and iron oxide, especially ferroferric oxide. The surfactant can promote the integrating agent to wet and permeate a scaling layer, a scaling object and the acidic integrating agent are fully contacted and reacted and then dissolved and stripped, and meanwhile, the scale inhibitor and corroded metal ions are complexed to form a water-soluble complex compound, so that the continuous effectiveness of the integrating agent is ensured.
Particularly, in the compound corrosion inhibitor, due to the special molecular structure and the electron cloud arrangement mode, the diamido podioether is beneficial to the uniform and ordered adsorption of molecules on the metal surface, and participates in the bonding of the metal matrix together with the amide oxygen symmetrical at two ends under the coordination of the middle ether oxygen to form a triangular plane bonding mode, so that the stability of chemical bonds is enhanced. In addition, the special structure and bonding mode of the diamide podosol are favorable for locking imidazolines on the surface of the carbon steel substrate to form an oxidation film with molybdenum at the bottom layer, the middle layer is an adsorption layer formed by alternately adsorbing and crosslinking diamide podosol molecules and imidazoline molecules, so that the adsorption integrity of the imidazolines is increased, and the corrosion and the scouring of the carbon steel substrate, the oxidation film and the imidazoline adsorption layer by the high-temperature acid solution are efficiently resisted by utilizing the synergistic effect of the diamide podosol, the imidazoline and molybdate, so that the corrosion and scale removal integrated agent has the effect of one agent with multiple purposes.
In a preferable 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, tetradecyltrimethyl ammonium chloride and hexadecyltrimethyl ammonium chloride.
In a preferred technical scheme of the invention, the scale inhibitor is 2-phosphonic acid butane-1,2,4-tricarboxylic acid.
In a preferred embodiment of the present invention, the diamide podethers are selected from at least one compound having the structural formula shown in formula I;
in the formula I, R, R' are all selected from C 1 -C 6 The alkyl group of (1).
In a preferred embodiment of the present invention, the diamide pod ether is one or more of N, N '-tetramethyl-3-oxoglutaramide, N' -tetraethyl-3-oxoglutaramide, N '-tetra-N-propyl-3-oxoglutaramide, N' -tetraisobutyl-3-oxoglutaramide, N-dimethyl-N ', N' -diethyl-3-oxoglutaramide, and N, N '-dimethyl-N, N' -dihexyl-3-oxoglutaramide.
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 carbon steel equipment high temperature resistant corrosion and scale inhibition integrated agent comprises the following steps:
1) Mixing and stirring 5-10% of ethanol, 15-35% of imidazolines, 15-30% of didodecyldimethylammonium chloride, 3-10% of diamide podand ether, 5-10% of molybdate and 5-57% of water uniformly to obtain a compound corrosion inhibitor;
2) Preparing the following raw materials in percentage by mass:
0.1 to 5 percent of compound corrosion inhibitor;
0.1 to 30 percent of hydrochloric acid;
0.1 to 3 percent of hydrofluoric acid;
0.5 to 5 percent of surfactant;
0.0005 to 0.002 percent of scale inhibitor;
60-88% of water;
firstly, mixing the compound corrosion inhibitor and water, uniformly stirring, adding the surfactant and the scale inhibitor while stirring, adding the hydrochloric acid and the hydrofluoric acid while stirring, uniformly mixing and discharging to obtain the high-temperature-resistant corrosion and scale inhibition integrated agent for the carbon steel equipment.
The corrosion inhibition-descaling integrated agent can be used for cleaning a scale formation layer of a carbon steel heat exchanger of a circulating water system, so that the carbon steel equipment can be cleaned without dead angles, the corrosion of the equipment under the scale is avoided, the operation period of the equipment is prolonged, and the high efficiency and stability of the heat exchanger are ensured.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The raw material sources in the following examples and comparative examples of the present invention were obtained commercially, 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 descaling effect of the corrosion/scale inhibition integrated agent is characterized by a descaling rate (N) and a cleaning rate (B).
(1)N＝(M/M 0 )*100％
Wherein:
N-Scale removal Rate,%;
m-amount of scale washed, g;
M 0 the original amount of scale before cleaning, g.
(2)B＝(S/S 0 )*100％
Wherein:
b-cleaning efficiency,%;
s-area of dirt cleaned, m 2 ；
S 0 Area of dirt before cleaning, m 2 。
In the chemical cleaning process, the relative rate of corrosion of the surface of the cleaned equipment is expressed by corrosion rate (K) and is expressed in g/m 2 H, corrosion inhibitorThe corrosion inhibition effect is expressed by corrosion inhibition efficiency (eta) and the unit is%.
(3)K＝△m/(t*s)*100％
Wherein:
k-corrosion rate, g/m 2 /h；
Δ 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 the corrosion rate under the action of the scale remover without the corrosion inhibitor is g/m 2 /h；
K 1 Is corrosion rate under the action of a scale remover containing a corrosion inhibitor, g/m 2 /h。
The raw material sources in the following examples and comparative examples of the present invention were obtained commercially, unless otherwise specified.
Examples 1-3 various diamide podethers were prepared according to the method disclosed in patent CN 102993042B.
[ PREPARATION EXAMPLE 1 ]
Preparation of N, N' -tetraethyl-3-oxoglutaramide:
(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 while stirring at the water bath temperature of 5 ℃, and reacting for 2.5h; followed by reaction at 25 ℃ for 4h. And then removing 1,4 dioxane by rotary evaporation, adding a hydrochloric acid aqueous solution with the volume fraction of 50%, precipitating white crystals, performing suction filtration, recrystallizing by using a water-methanol system with the volume ratio of 1:2, and performing vacuum drying to obtain 85.2g of N, N-diethyl-3-oxoglutaramic acid.
(2) Uniformly stirring 0.3mol of N, N-diethyl-3-oxoglutaramic acid, 0.3mol of N-methylmorpholine and 250ml of ethyl acetate, cooling to-10 ℃, dropwise adding 0.3mol of isobutyl chloroformate, stirring for 2min, dropwise adding 0.3mol of diethylamine, continuing to react for 2h, and then reacting for 2h at the room temperature of 25 ℃ to obtain a crude product. And washing the crude product with water, 1% of sodium hydroxide and 0.1mol/L hydrochloric acid in sequence, finally washing the crude product with water to be neutral, collecting an organic phase, drying the organic phase with anhydrous sodium sulfate, and performing rotary evaporation to obtain 66g of a product, namely the N, N' -tetraethyl-3-oxoglutaramide.
The nuclear magnetic hydrogen spectrum analysis data of the obtained product is 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 ]
Preparing N, N' -tetra-N-propyl-3-oxoglutaramide:
(1) 0.5mol of diglycolic anhydride is added into 5mol of 1, 4-dioxane, and under the condition that the water bath temperature is 5 ℃, the mixed solution of 0.5mol of di-n-propylamine and 0.6mol of pyridine is added under stirring, and the reaction lasts for 2.5 hours. Reacting for 4 hours at 25 ℃, removing 1,4 dioxane by rotary evaporation, adding hydrochloric acid aqueous solution with volume fraction of 50%, precipitating white crystals, performing suction filtration, performing recrystallization by a water-methanol system with volume ratio of 1:2, and performing vacuum drying to obtain 85.2g of N, N-di-N-propyl-3-oxoglutaramic acid.
(2) Uniformly stirring 0.3mol of N, N-di-N-propyl-3-oxoglutaramide acid, 0.3mol of N-methylmorpholine and 250ml of ethyl acetate, cooling to-10 ℃, dropwise adding 0.3mol of isobutyl chloroformate, stirring for 2min, dropwise adding 0.3mol of di-N-propylamine, continuing to react for 2h, reacting for 2h at room temperature and 25 ℃ to obtain a crude product, washing the crude product by sequentially using water, 1% of sodium hydroxide and 0.1mol/L of hydrochloric acid, finally washing to be neutral by using water, collecting an organic phase, drying by using anhydrous sodium sulfate, and performing rotary evaporation to obtain 105g of a product, namely N, N' -tetra-N-propyl-3-oxoglutaramide.
The nuclear magnetic hydrogen spectrum analysis data of the obtained product is 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-oxoglutaramide:
(1) Adding 0.5mol of dinucleotide anhydride into 5mol of 1, 4-dioxane, and adding a mixed solution of 0.5mol of diisobutylamine and 0.6mol of pyridine while stirring at the water bath temperature of 5 ℃ to react for 2.5 hours; followed by reaction at 25 ℃ for 4h. Then removing 1,4 dioxane by rotary evaporation, adding hydrochloric acid aqueous solution with volume fraction of 50%, precipitating white crystals, performing suction filtration, recrystallizing by using a water-methanol system with volume ratio of 1:2, and performing vacuum drying to obtain 90.2g N, N-diisobutyl-3-oxoglutaramic acid.
(2) Uniformly stirring 0.3mol of N, N-diisobutyl-3-oxoglutaramic acid, 0.3mol of N-methylmorpholine and 250ml of ethyl acetate, cooling to-10 ℃, dropwise adding 0.3mol of isobutyl chloroformate, stirring for 2min, dropwise adding 0.3mol of diisobutylamine, continuously reacting for 2h, and then reacting for 2h at room temperature of 25 ℃ to obtain a crude product. And washing the crude product with water, 1% sodium hydroxide and 0.1mol/L hydrochloric acid in sequence, finally washing with water to neutrality, collecting an organic phase, drying with anhydrous sodium sulfate, and performing rotary evaporation to obtain 120g of a product, namely the N, N' -tetraisobutyl-3-oxoglutaramide.
The nuclear magnetic hydrogen spectrum analysis data of the obtained product is 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 inhibitor-remover integrators of different formulations:
[ example 1 ] A method for producing a polycarbonate
(1) Preparing a compound corrosion inhibitor:
at normal temperature, 20% of water, 5% of ethanol, 35% of lauryl amphoteric imidazoline, 20% of didodecyl dimethyl ammonium chloride, 10% of N, N' -tetraethyl-3-oxoglutaramide and 10% of potassium molybdate are sequentially added into a dry reaction kettle by taking the total mass as 100%, and the mixture is uniformly stirred to obtain a compound corrosion inhibitor which is stored for later use.
(2) Preparing a corrosion inhibition-descaling integrated agent:
0.5% of a built corrosion inhibitor, 0.001% of 2-phosphonobutane-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 were prepared, respectively, based on 100% of the total mass. Firstly, mixing a compound corrosion inhibitor and water, uniformly stirring, adding 2-phosphonic acid butane-1,2,4, -tricarboxylic acid and tetrabutylammonium chloride while stirring, adding industrial hydrochloric acid and industrial hydrofluoric acid while stirring, completely mixing uniformly, and discharging to obtain the corrosion and scale removal integrated agent.
[ example 2 ]
(1) Preparing a compound corrosion inhibitor:
at normal temperature, 20% of water, 10% of ethanol, 30% of lauryl amphoteric imidazoline, 25% of didodecyl dimethyl ammonium chloride, 8% of N, N' -tetraethyl-3-oxoglutaramide and 7% of sodium molybdate are sequentially added into a dry reaction kettle by taking the total mass as 100%, and the mixture is uniformly stirred to obtain a compound corrosion inhibitor which is stored for later use.
(2) Preparing a corrosion inhibition-descaling integrated agent:
0.3% of a built corrosion inhibitor, 0.0015% of 2-phosphonobutane-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 were prepared, respectively, based on 100% of the total mass. Firstly, mixing a compound corrosion inhibitor and water, uniformly stirring, adding 2-phosphonic acid butane-1,2,4, -tricarboxylic acid and tetrabutylammonium chloride while stirring, adding industrial hydrochloric acid and industrial hydrofluoric acid while stirring, completely mixing uniformly, and discharging to obtain the corrosion and 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-oxoglutaramide and 8% of potassium molybdate are sequentially added into a dry reaction kettle by taking the total mass as 100%, and the mixture is uniformly stirred to obtain a compound corrosion inhibitor which is stored for later use.
(2) Preparing a corrosion inhibition-descaling integrated agent:
based on 100% of the total mass, 1% of a built corrosion inhibitor, 0.002% of 2-phosphonobutane-1,2,4, tricarboxylic acid, 3% of cetyltrimethylammonium chloride, 10% of industrial hydrochloric acid, 1% of industrial hydrofluoric acid, and 85% of water were prepared, respectively. Firstly, mixing a compound corrosion inhibitor and water, uniformly stirring, adding 2-phosphonic acid butane-1,2,4, -tricarboxylic acid and tetrabutylammonium chloride while stirring, adding industrial hydrochloric acid and industrial hydrofluoric acid while stirring, completely mixing uniformly, and discharging to obtain the corrosion and scale removal integrated agent.
[ example 4 ]
(1) Preparing a compound corrosion inhibitor:
at normal temperature, 32% of water, 8% of ethanol, 25% of lauryl amphoteric imidazoline, 15% of didodecyl dimethyl ammonium chloride, 10% of N, N' -tetra-N-propyl-3-oxoglutaramide and 10% of potassium molybdate are sequentially added into a dry reaction kettle by taking the total mass as 100%, and the mixture is uniformly stirred to obtain a compound corrosion inhibitor and stored for later use.
(2) Preparing a corrosion inhibition-descaling integrated agent:
2% of a built corrosion inhibitor, 0.0015% of 2-phosphonobutane-1,2,4, -tricarboxylic acid, 3.5% of tetradecyltrimethylammonium chloride, 8% of industrial hydrochloric acid, 2% of industrial hydrofluoric acid, and 84.5% of water, respectively, were prepared, based on 100% of the total mass. Firstly, mixing a compound corrosion inhibitor and water, uniformly stirring, adding 2-phosphonic acid butane-1,2,4, -tricarboxylic acid and tetradecyltrimethyl ammonium chloride while stirring, adding industrial hydrochloric acid and industrial hydrofluoric acid while stirring, completely mixing uniformly, and discharging to obtain the corrosion and scale removal integrated agent.
[ example 5 ]
(1) Preparing a compound corrosion inhibitor:
at normal temperature, 27% of water, 8% of ethanol, 15% of lauryl bisoxazoline, 30% of didodecyl dimethyl ammonium chloride, 10% of N, N' -tetraisobutyl-3-oxoglutaramide and 10% of sodium molybdate are sequentially added into a dry reaction kettle by taking the total mass as 100%, and are uniformly stirred to obtain a compound corrosion inhibitor which is stored for later use.
(2) Preparing a corrosion inhibition and descaling integrated agent:
based on 100% of the total mass, 5% of a built corrosion inhibitor, 0.0015% of 2-phosphonobutane-1,2,4, -tricarboxylic acid, 2.0% of tetradecyltrimethylammonium chloride, 8% of industrial hydrochloric acid, 3% of industrial hydrofluoric acid, and 82% of water were prepared, respectively. Firstly, mixing a compound corrosion inhibitor and water, uniformly stirring, adding 2-phosphonic acid butane-1,2,4, -tricarboxylic acid and tetradecyltrimethyl ammonium chloride while stirring, adding industrial hydrochloric acid and industrial hydrofluoric acid while stirring, completely mixing uniformly, and discharging to obtain the corrosion and 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-oxoglutaramide and 10% of sodium molybdate are sequentially added into a dry reaction kettle by taking the total mass as 100%, and the mixture is uniformly stirred to obtain a compound corrosion inhibitor which is stored for later use.
(2) Preparing a corrosion inhibition-descaling integrated agent:
0.5% of a built corrosion inhibitor, 0.001% of 2-phosphonobutane-1,2,4, -tricarboxylic acid, 5.0% of tetradecyltrimethylammonium chloride, 10% of industrial hydrochloric acid, 1% of industrial hydrofluoric acid, and 83.5% of water were prepared, respectively, based on 100% of the total mass. Firstly, mixing the compound corrosion inhibitor and water, uniformly stirring, adding 2-phosphonic butane-1,2,4, -tricarboxylic acid and tetradecyl trimethyl ammonium chloride while stirring, adding industrial hydrochloric acid and industrial hydrofluoric acid while stirring, completely mixing uniformly, and discharging to obtain the corrosion inhibition-descaling integrated agent.
Comparative example 1
A corrosion and scale inhibition integrated agent is prepared according to the method which is basically the same as the embodiment, and the difference is that: when preparing the compound corrosion inhibitor, N' -tetraethyl-3-oxoglutaramide is not added.
Comparative example 2
A corrosion and scale inhibition integrated agent is prepared according to the method which is basically the same as the embodiment, and the difference is that: when the corrosion inhibition-descaling integrated agent is prepared, industrial hydrofluoric acid is not processed.
The following application examples 1-2 were used for the corrosion and scale inhibition effect tests on different fouling compositions:
[ application example 1 ]
The corrosion inhibition and descaling integrated agent prepared by the embodiment and the comparative example has the composition of 58 percent of iron oxide (Fe) on the shell side of the carbon steel heat exchanger 2 O 3 Calculated) 26% 4 11% silicate (in SiO) 2 The content of the scale and the scale A with 5 percent of other components are respectively tested for descaling effect and corrosion inhibition effect, and the test method is as follows:
taking an on-site scaling substance sample, checking the scaling area, placing the sample in a reaction vessel, adding 500ml of the prepared corrosion inhibition-scale removal integrated agent to completely immerse the sample, controlling the temperature to be 60 ℃, soaking and dissolving for 7 hours, sampling and analyzing, calculating the effective scale removal area, and determining the cleaning rate. And (3) putting 30g of on-site scaling substances into another reaction container, adding 500ml of the prepared corrosion and scale inhibition integrated agent, putting a 20# carbon steel standard hanging piece with the size of 50 multiplied by 25 multiplied by 2mm, controlling the temperature to be 60 ℃, soaking and dissolving for 7 hours, taking the hanging piece, analyzing, 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 of the monoliths on the foulant A
[ application example 2 ]
The corrosion inhibition and descaling integrated agent prepared by the embodiment and the comparative example has the composition of 65 percent of iron oxide (Fe) on the shell side of the carbon steel heat exchanger 2 O 3 Calculated by (b) 12% by weight CaSO 4 、10％CaCO 3 9% silicate (in SiO) 2 Content of (1) and 4% of other scaling substances B, respectively carrying out the tests of descaling effect and corrosion inhibition effect, wherein the test method comprises the following steps:
taking an on-site scaling substance sample, checking the scaling area, placing the sample in a reaction vessel, adding 500ml of the prepared corrosion inhibition-scale removal integrated agent to completely immerse the sample, controlling the temperature to be 60 ℃, soaking and dissolving for 7 hours, sampling and analyzing, calculating the effective scale removal area, and determining the cleaning rate. And (3) putting 30g of on-site scaling substances into another reaction container, adding 500ml of the prepared corrosion and scale inhibition integrated agent, putting a 20# carbon steel standard hanging piece with the size of 50 multiplied by 25 multiplied by 2mm, controlling the temperature to be 60 ℃, soaking and dissolving for 7 hours, taking the hanging piece, analyzing, 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 of the monoliths on the foulant B
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (8)
1. The high-temperature-resistant corrosion and scale inhibition integrated agent for the carbon steel equipment is characterized by being prepared from the following components in percentage by mass:
0.1 to 5 percent of compound corrosion inhibitor;
0.1 to 30 percent of hydrochloric acid;
0.1 to 3 percent of hydrofluoric acid;
0.5 to 5 percent of surfactant;
0.0005 to 0.002 percent of scale inhibitor;
60-88% of water;
wherein, the compound corrosion inhibitor comprises 5-10% of ethanol, 15-35% of imidazoline, 15-30% of didodecyldimethylammonium chloride, 3-10% of diamide podand 5-10% of molybdate and 5-57% of water by mass percentage.
2. The carbon steel equipment high-temperature-resistant corrosion and scale inhibition-removal integrated agent as claimed in claim 1, wherein the hydrochloric acid is industrial hydrochloric acid with a mass concentration of 30-38%;
preferably, the hydrofluoric acid is industrial hydrofluoric acid with a mass concentration of 40%.
3. A carbon steel equipment high temperature corrosion and scale inhibition-removal integrated agent as claimed in claim 1, wherein said imidazolines are lauryl amphoteric imidazoline;
preferably, the surfactant is one or more of tetrabutylammonium chloride, tetradecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride.
4. The carbon steel equipment high temperature corrosion and scale inhibition-removal integrated agent as claimed in any one of claims 1 to 3, wherein the scale inhibitor is 2-phosphonobutane-1,2,4, -tricarboxylic acid.
5. The carbon steel equipment high temperature corrosion and scale inhibition-removal integrated agent as claimed in claim 4, wherein the diamide podosol is selected from at least one compound having a structural expression shown in formula I;
in the formula I, R, R' are all selected from C 1 -C 6 Alkyl group of (1).
6. The carbon steel equipment high temperature corrosion and scale inhibition integrated agent as claimed in claim 5, wherein the diamide pod ether is one or more of N, N '-tetramethyl-3-oxoglutaramide, N' -tetraethyl-3-oxoglutaramide, N '-tetra-N-propyl-3-oxoglutaramide, N' -tetraisobutyl-3-oxoglutaramide, N-dimethyl-N ', N' diethyl-3-oxoglutaramide, N '-dimethyl-N, N' -dihexyl-3-oxoglutaramide.
7. A carbon steel equipment high temperature resistant corrosion and scale inhibition integrated agent as claimed in any one of claims 1 to 3, wherein the molybdate is at least one of sodium molybdate and potassium molybdate.
8. A method for preparing the carbon steel equipment high temperature resistant corrosion and scale inhibition-removing integrated agent as defined in any one of claims 1-7, comprising the following steps:
1) Mixing and stirring 5-10% of ethanol, 15-35% of imidazolines, 15-30% of didodecyldimethylammonium chloride, 3-10% of diamide podand ether, 5-10% of molybdate and 5-57% of water uniformly to obtain a compound corrosion inhibitor;
2) Preparing the following raw materials in percentage by mass:
0.1 to 5 percent of compound corrosion inhibitor;
0.1 to 30 percent of hydrochloric acid;
0.1 to 3 percent of hydrofluoric acid;
0.5 to 5 percent of surfactant;
0.0005 to 0.002 percent of scale inhibitor;
60-88% of water;
firstly, mixing the compound corrosion inhibitor and water, uniformly stirring, adding the surfactant and the scale inhibitor while stirring, adding the hydrochloric acid and the hydrofluoric acid while stirring, uniformly mixing and discharging to obtain the high-temperature-resistant corrosion and scale inhibition 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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