Steel corrosion inhibitor material, preparation method thereof, steel corrosion inhibitor and application thereof

Abstract

The invention relates to the technical field of corrosion protection, in particular to a steel corrosion inhibitor material, a preparation method thereof, a steel corrosion inhibitor and application thereof. The steel corrosion inhibitor material provided by the invention is prepared from water and the following components: 82.0-97.0 parts by mass of a trehalose lipid surfactant; 3.0 to 18.0 parts by mass of zinc phosphate; the mass ratio of the trehalose lipid surfactant in the water is 0.8%-2%. According to the steel corrosion inhibitor material provided by the invention, through the co-component action of the trehalose lipid surfactant and the zinc phosphate, compared with the co-component action of other biological surface active substances and the zinc phosphate, the prepared corrosion inhibitor can more effectively protect steel from being corroded in a highly mineralized corrosive environment; the corrosion inhibitor is especially suitable for protecting steel in a high-mineralization corrosive environment, can also be used for circulating water supply systems and energy industries of enterprises such as chemical industry and petrochemical industry, and does not contain toxic synthetic organic substances in the components.

Description

Technical Field

[0001] The invention relates to the technical field of anti-corrosion protection, in particular to a steel corrosion inhibitor material and a preparation method thereof, a steel corrosion inhibitor and an application thereof. Background Art

[0002] Analysis of the scope and composition of corrosion inhibitors in the oil and gas complex shows that mainly amines, complex esters, synthetic organic compounds of oxyethylation and nitration products are used, as well as phosphates, dialkyl and diaryl phosphates, pyrophosphoric acids, sulfonates and other compounds. In general, there is a steady trend towards the sophistication of corrosion inhibitor production technology and the use of chemical synthesis industrial waste products as raw materials. At the same time, organic corrosion inhibitors synthesized on the basis of mineral raw materials are toxic products that are harmful to the environment and accumulate in the environment.

[0003] The prior art also has steel corrosion inhibitor products synthesized from non-toxic raw materials, such as steel corrosion inhibitor products containing biological surfactants and synergists obtained by microbial synthesis methods, especially using rhamnolipids (biological surfactants) and potassium iodide (synergist). This inhibitor is safe for the environment and biodegradable. However, it is not effective enough in protecting steel from corrosion in highly mineralized reservoir water environments. Summary of the invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide a steel corrosion inhibitor material and a preparation method thereof, a steel corrosion inhibitor and an application thereof. The steel corrosion inhibitor material provided by the present invention can effectively protect steel from corrosion in a highly mineralized corrosive environment and does not contain toxic synthetic organic substances.

[0005] The present invention provides a steel corrosion inhibitor material, which is prepared from water and the following components:

[0006] Trehalose lipid surfactant: 82.0-97.0 parts by weight;

[0007] Zinc phosphate: 3.0-18.0 parts by mass;

[0008] The mass proportion of the trehalose lipid surfactant in the water is 0.8% to 2%, preferably 0.8% to 1.5%.

[0009] The steel corrosion inhibitor material provided by the present invention is a steel corrosion inhibitor material prepared by mixing a biosurfactant and a synergist co-component with water, and specifically uses trehalose lipid surfactant (TPAR) as a biosurfactant and zinc phosphate as a synergist. The inventors of the present application creatively discovered that compared with other co-components of biological surfactants and zinc phosphate, the co-component of trehalose lipid surfactant and zinc phosphate has a better corrosion inhibition effect, and the prepared corrosion inhibitor is more suitable for the application scenario of steel in a highly mineralized corrosive environment.

[0010] The steel corrosion inhibitor material provided by the present invention is prepared from water, trehalose lipid surfactant and zinc phosphate. Specifically, the particle size of the zinc phosphate in the present invention is 5 μm to 6 μm; the trehalose lipid surfactant in the present invention includes trehalose-6,6'-dimycolate, and the structural formula is as follows:

[0011]

[0012] The trehalose lipid surfactant of the present invention further comprises trehalose lipid, trehalose fatty acid ester, other fatty acids and alcohol; wherein the trehalose lipid comprises trehalose mycolate and trehalose dimicolate.

[0013] The trehalose lipid surfactant of the present invention is produced by Rhodococcus erythropolis, and specifically comprises the following steps: growing the Rhodococcus erythropolis on a culture medium, and then inoculating it into a nutrient solution for continued growth to obtain a culture solution; separating cells from the obtained culture solution, and extracting the separated cells with a mixture of chloroform and methanol to obtain the trehalose lipid surfactant.

[0014] The present invention first grows Rhodococcus erythropolis on a culture medium, and then inoculates it into a nutrient solution to continue growing, thereby obtaining a culture solution. Specifically, Rhodococcus erythropolis is grown on a culture medium for 42 hours to 54 hours, and then inoculated into a culture medium to continue growing at 25° C. to 35° C. for 4 to 6 days, thereby obtaining a culture solution. The inoculation amount of the inoculation of the present invention is 8% to 12% of the volume of the nutrient solution, and the cell titer is (4.8×10 8 ~5.2×10 8 )CFU / cm 3 The culture medium of the present invention contains (25-35) g / dm 3 The composition of the nutrient solution of the present invention is as follows: (2.5-3.5) g / dm 3 NaNO3; (1.5~2.5) g / dm 3 K2HPO4; (1.5~2.5) g / dm 3 KH2PO4; (0.4~0.6) g / dm 3 MgSO4×7H2O; (0.8~1.2)g / dm 3 Na3C6H5O7×2H2O; (0.8~1.2)g / dm 3 Yeast extract; (18.0~22.0)g / dm 3 Carbon source; up to 1dm 3 of distilled water and hexadecane was used as the carbon source.

[0015] After obtaining the culture fluid, the present invention separates cells from the obtained culture fluid, extracts the separated cells with a mixture of chloroform and methanol, and obtains a trehalose lipid surfactant. Specifically, the obtained culture fluid is centrifuged at 5500rpm to 6500rpm for 12min to 18min to separate cells, and the separated cells are dissolved in a mixture of chloroform and methanol, and then chloroform, a mixture of chloroform and methanol with a volume ratio of (85 to 95):10, (45 to 55):10, (35 to 40):10, (25 to 30):10, (15 to 20):10, (5 to 10):10, and methanol are used to elute fractions, and the eluate obtained by eluting the fractions is crystallized to obtain a trehalose lipid surfactant.

[0016] The present invention also provides a method for preparing the steel corrosion inhibitor material described in any of the above technical solutions, comprising the following steps:

[0017] Water, trehalose lipid surfactant and zinc phosphate are ball-milled to obtain a steel corrosion inhibitor.

[0018] Specifically, the present invention dissolves a trehalose lipid surfactant in water to obtain a trehalose lipid surfactant aqueous solution; zinc phosphate and the trehalose lipid surfactant aqueous solution are mixed and ball-milled to obtain the steel corrosion inhibitor material. In certain embodiments of the present invention, zinc phosphate is added to the trehalose lipid surfactant aqueous solution, ball-milled, and the material obtained after ball milling is allowed to stand, and then decanted to separate to obtain a colloidal solution, which is the above-mentioned steel corrosion inhibitor material; the standing time is 1.5h to 2.5h.

[0019] The invention uses a ball mill to prepare a steel corrosion inhibitor material, which has the advantage that zinc phosphate powder can be ground to a nanometer size, resulting in an increase in its specific surface area and an increase in the interaction between zinc phosphate and the functional groups of the trehalose lipid surfactant. At the same time, mechanical grinding and the solubilization of biological surfactants help to increase the solubility of zinc phosphate. The frequency of the ball milling in the invention is 80 rpm to 150 rpm; and the time of the ball milling is 0.8 h to 2 h.

[0020] The present invention also provides a steel corrosion inhibitor, which is the steel corrosion inhibitor material described in any of the above technical solutions; or, it includes an additive and the steel corrosion inhibitor material described in any of the above technical solutions. In the present invention, the steel corrosion inhibitor material described in any of the above technical solutions can be used alone as a steel corrosion inhibitor, or it can be used in combination with conventional additives in the art as a steel corrosion inhibitor.

[0021] The present invention also provides the use of the above-mentioned steel corrosion inhibitor to protect steel in a high-mineral water environment. The high-mineral water environment of the present invention includes one or more of a high-mineralized reservoir water environment, a high-mineralized water environment of petroleum development geology, or a high-mineralized water environment of natural gas development geology, and the water environment includes a formation water environment or a surface water environment. In certain embodiments of the present invention, the use of the above-mentioned steel corrosion inhibitor to protect steel in a high-mineral water environment includes: putting the above-mentioned steel corrosion inhibitor into a high-mineral water environment, and the high-mineral water environment includes 150g / L to 200g / L of NaCl; 20g / L to 40g / L of CaCl2; 10g / L to 30g / L of MgCl2; 0.1g / L to 0.5g / L of Na2SO4·10H2O, wherein the content of the steel corrosion inhibitor in the high-mineral water environment is 0.2g / L to 0.5g / L.

[0022] The present invention provides a steel corrosion inhibitor material and a preparation method thereof, a steel corrosion inhibitor and an application thereof. The steel corrosion inhibitor material provided by the present invention is prepared from water and the following components: trehalose lipid surfactant: 82.0-97.0 parts by mass; zinc phosphate: 3.0-18.0 parts by mass; the mass proportion of the trehalose lipid surfactant in the water is 0.8%-2%. The steel corrosion inhibitor material provided by the present invention is made into a corrosion inhibitor through the co-component action of trehalose lipid surfactant and zinc phosphate, which is more effective in protecting steel from corrosion in a highly mineralized corrosive environment than the co-component action of other biological surfactants and zinc phosphate, that is, it is particularly suitable for the protection of steel in a highly mineralized corrosive environment, especially in reservoir water, and can also be used in the circulating water supply system and energy industry of chemical, petrochemical and other enterprises, and the components do not contain toxic synthetic organic substances. DETAILED DESCRIPTION

[0023] The present invention discloses a steel corrosion inhibitor material and a preparation method thereof, a steel corrosion inhibitor and an application thereof. Those skilled in the art can refer to the content of this article and appropriately improve the process parameters to achieve it. It is particularly important to point out that all similar substitutions and modifications are obvious to those skilled in the art, and they are all considered to be included in the present invention. The method and application of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the method and application of this article without departing from the content, spirit and scope of the present invention to realize and apply the technology of the present invention.

[0024] The steel corrosion inhibitor material of the invention is prepared from water, trehalose lipid surfactant (TPAR) and zinc phosphate.

[0025] Wherein, the zinc phosphate is Actirox 106 (manufacturer-Nubiola Pigmentos, SL (Spain));

[0026] The trehalose lipid surfactant is produced by using Rhodococcus erythropolis synthesized in the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, and the specific steps are as follows:

[0027] 1. Strain culture

[0028] The Rhodococcus erythropolis strain was grown in a sucrose (30 g / dm 3 ) medium for 48 hours, and then the culture was inoculated into liquid nutrient medium for growth. The inoculation volume was 10% of the nutrient solution volume and the cell titer was 5×10 8 CFU / cm 3 The composition of the liquid nutrient medium is as follows: 3.0 g / dm 3 NaNO3; 2.0g / dm 3 K2HPO4; 2.0g / dm 3 KH2PO4; 0.5g / dm 3 MgSO4×7H2O; 1.0g / dm 3 Na3C6H5O7×2H2O; 1.0g / dm 3 Yeast extract; 20.0g / dm 3 Hexadecane; up to 1dm 3 The microorganisms were cultured in a conical flask (750 mL) with a working volume of 150 mL at 30° C. on a rotary shaker (220 rpm) for 5 days to obtain a culture solution.

[0029] 2. Extraction of Trehalose Lipid Surfactant

[0030] The cells were separated from the culture medium by centrifugation at 6000 rpm for 15 minutes. Trehalose lipid surfactant was extracted from the cells using Folch's mixture (chloroform-methanol with a volume ratio of 2:1). Specifically, the separated cells were used as trehalose lipid surfactant samples to separate the trehalose lipid surfactant therefrom. The separation of the trehalose lipid surfactant was performed by column chromatography on a 220×15 mm column using silica gel 60 (0.06-0.20 mm, ROSS, Belgium). The silica gel was activated by heating at a temperature of 120°C. 0.5 g of the trehalose lipid surfactant sample was dissolved in 15 cm 3 Folch's mixture and then coated on silica gel. To remove residual hexadecane, nonpolar lipids and pigments, the column is washed with hexane. The fractions are then eluted with a solvent system of increasing polarity: chloroform, chloroform: methanol (volume ratios of 90:10, 50:10, 40:10, 30:10, 20:10, 10:10, respectively), methanol. The composition of each fraction is controlled by thin layer chromatography (TLC).

[0031] TLC was performed using Merck 25 Chromatofollhas AL TLC plates 20 × 20 cm silica gel 60 (Germany). Chloroform-methanol-water (volume ratio 65:15:2) mobile phase was used for qualitative analysis. Glycolipids were identified by visualizing the plate using anise reagent. The presence of green spots on the plate indicated the presence of glycolipids. The extracted trehalose lipid surfactant, the main component of which was trehalose-6,6'-dimycolate (TDM), also included trehalose lipids (trehalose mycolate and trehalose dimycolate), a small amount of trehalose fatty acid esters, and other fatty acids and alcohols.

[0032] The present invention will be further described below in conjunction with embodiments:

[0033] Example 1

[0034] 0.03 g of zinc phosphate powder was added to a 1% aqueous solution of trehalose lipid surfactant (100 mL), and the resulting mixture was then placed in a PM 100 ball mill (Retsch), and the zinc phosphate was dispersed by rotating the cylinder at a frequency of 100 rpm for 1 hour. After grinding, a suspension of zinc phosphate in a 1% TPAR aqueous solution was obtained. After mechanical processing, the suspension was allowed to stand for 2 hours, and its colloidal solution was separated by decantation, and the resulting colloidal solution was used as a corrosion inhibitor.

[0035] Example 2

[0036] 0.06 g of zinc phosphate powder was added to a 1% aqueous solution of trehalose lipid surfactant (100 mL), and the resulting mixture was then placed in a PM 100 ball mill (Retsch), and the zinc phosphate was dispersed by rotating the cylinder at a frequency of 100 rpm for 1 hour. After grinding, a suspension of zinc phosphate in a 1% TPAR aqueous solution was obtained. After mechanical processing, the suspension was allowed to stand for 2 hours, and its colloidal solution was separated by decantation, and the resulting colloidal solution was used as a corrosion inhibitor.

[0037] Example 3

[0038] 0.09 g of zinc phosphate powder was added to a 1% aqueous solution of trehalose lipid surfactant (100 mL), and the resulting mixture was then placed in a PM 100 ball mill (Retsch), and the zinc phosphate was dispersed by rotating the cylinder at a frequency of 100 rpm for 1 hour. After grinding, a suspension of zinc phosphate in a 1% TPAR aqueous solution was obtained. After mechanical processing, the suspension was allowed to stand for 2 hours, and its colloidal solution was separated by decantation, and the resulting colloidal solution was used as a corrosion inhibitor.

[0039] Example 4

[0040] 0.16 g of zinc phosphate powder was added to a 1% aqueous solution of trehalose lipid surfactant (100 mL), and the resulting mixture was then placed in a PM 100 ball mill (Retsch), and the zinc phosphate was dispersed by rotating the cylinder at a frequency of 100 rpm for 1 hour. After grinding, a suspension of zinc phosphate in a 1% TPAR aqueous solution was obtained. After mechanical processing, the suspension was allowed to stand for 2 hours, and its colloidal solution was separated by decantation, and the resulting colloidal solution was used as a corrosion inhibitor.

[0041] Example 5

[0042] 0.21 g of zinc phosphate powder was added to a 1% aqueous solution of trehalose lipid surfactant (100 mL), and the resulting mixture was then placed in a PM 100 ball mill (Retsch), and the zinc phosphate was dispersed by rotating the cylinder at a frequency of 100 rpm for 1 hour. After grinding, a suspension of zinc phosphate in a 1% TPAR aqueous solution was obtained. After mechanical processing, the suspension was allowed to stand for 2 hours, and its colloidal solution was separated by decantation, and the resulting colloidal solution was used as a corrosion inhibitor.

[0043] Comparative Example 1

[0044] 1 g of 100% rhamnolipid was dissolved in 100 mL of water, and the resulting solution was used as an inhibitor.

[0045] Comparative Example 2

[0046] 0.06 g of zinc phosphate powder was added to a 1% rhamnolipid aqueous solution (100 mL), and the resulting mixture was then placed in a PM 100 ball mill (Retsch), and the zinc phosphate was dispersed by rotating the cylinder at a frequency of 100 rpm for 1 hour. After grinding, a suspension of zinc phosphate in a 1% rhamnolipid aqueous solution was obtained. After mechanical processing, the suspension was allowed to stand for 2 hours, and its colloidal solution was separated by decantation, and the resulting colloidal solution was used as a corrosion inhibitor.

[0047] The present invention uses formation water as a corrosive medium to evaluate the corrosion protection effect of the corrosion inhibitor of the present invention on steel. Formation water is groundwater flowing in rock formations. Homogeneous sedimentary rock deposits that are distributed over a large area in the earth's crust and bounded by two approximately parallel surfaces are generally referred to as formations. The corrosion inhibitors of Examples 1 to 5 and Comparative Examples 1 to 2 are added to the model formation water (corrosive medium) of the following composition: NaCl - 163 g / L; CaCl2 - 34 g / L; MgCl2 - 17 g / L; Na2SO4·10H2O - 0.32 g / L. Among them, the content of the corrosion inhibitor in the corrosive medium is 0.3 g / L.

[0048] The corrosion of 20 carbon steel (No. 20 steel) disc samples was investigated by gravimetric method in model formation water at temperatures of 80°C, 90°C and 107°C, and the corrosion protection effect of the corrosion inhibitors of Examples 1 to 5 and Comparative Examples 1 to 2 on steel was evaluated.

[0049] The corrosion rate of steel is K(g / cm 2 h) Calculate according to formula 1:

[0050] К = [(m1–m2) / S] · τ Formula 1;

[0051] Among them, К represents the corrosion rate, the unit is g / cm 2 ·h;

[0052] m1 represents the initial weight of the sample, in g;

[0053] m2 represents the weight of the sample after exposure to the corrosive environment and removal, in g;

[0054] S represents the total sample area, in см 2 ;

[0055] τ represents the exposure time of the sample in the corrosive environment, in h.

[0056] The steel protection grade Z (%) is determined according to formula 2:

[0057] Z = [(K o –K i ) / К o ] · 100% Formula 2;

[0058] Among them, K ο Represents the corrosion rate of steel in an environment without corrosion inhibitors, in g / см 2 ·h;

[0059] K i Represents the corrosion rate of steel in an environment containing corrosion inhibitors, in g / см 2 ·h.

[0060] The evaluation results are shown in Table 1, which shows the corrosion rate of 20# steel in model formation water at different temperatures with corrosion inhibitor added (g / cm) 2 h) and protection level Z (%), the test time is 175h:

[0061] Table 1

[0062]

[0063] No corrosion inhibitor: that is, the corrosion rate of No. 20 steel in the model formation water without adding corrosion inhibitor.

[0064] As can be seen from Table 1, the corrosion inhibitor of the present invention can more effectively protect carbon steel from corrosion in formation water than known corrosion inhibitors. Specifically, when the corrosion inhibitor component of the present invention is added to the model formation water, at all research temperatures, compared with the corrosion inhibitor component of the comparative example, the corrosion rate of the steel is significantly reduced, and the protection degree of the steel is significantly improved; for example, the corrosion inhibitor of Example 2 at 80°C in the test is the best, compared with Comparative Example 1, the steel corrosion rate is reduced by 3.20 times, and the steel protection degree is increased from 80.2% to 93.8%; the corrosion inhibitor of Example 4 at 93°C in the test is the best, compared with Comparative Example 1, the steel corrosion rate is reduced by 3.47 times, and the steel protection degree is increased from 77.4% to 91.7%; the corrosion inhibitor of Example 4 at 107°C in the test is also the best, compared with Comparative Example 1, the steel corrosion rate is reduced by 3.09 times, and the steel protection degree is increased from 71.5% to 86.7%;. The specific anti-corrosion effect is achieved by combining biological surfactants (trehalose lipid surfactants) and inorganic components (dispersed zinc phosphate) in the steel corrosion inhibitor material. According to working data, Rhodococcus erythropolis is one of the strains that can produce trehalose lipid surfactants that can effectively dissolve zinc phosphate. Zinc phosphate interacts with the trehalose lipid surfactants produced by Rhodococcus erythropolis, synergistically enhancing the anti-corrosion effect of the steel corrosion inhibitor material.

[0065] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. Steel corrosion inhibitor material, characterized in that: It is prepared from water and the following ingredients: Trehalose lipid surfactant: 82.0-97.0 parts by weight; Zinc phosphate: 3.0-18.0 parts by mass; The mass percentage of the trehalose lipid surfactant in the water is 0.8% to 2%.

2. The steel corrosion inhibitor material according to claim 1, characterized in that: The trehalose lipid surfactant includes trehalose-6,6'-dimycolate.

3. The steel corrosion inhibitor material according to claim 2, characterized in that: The trehalose lipid surfactant also includes trehalose mycolate, trehalose dimicolate, trehalose fatty acid esters, other fatty acids and alcohols.

4. The steel corrosion inhibitor material according to claim 1, characterized in that: The trehalose lipid surfactant is produced by Rhodococcus erythropolis.

5. The steel corrosion inhibitor material according to claim 1, characterized in that: The particle size of the zinc phosphate is 5 μm to 6 μm.

6. The method for preparing the steel corrosion inhibitor material according to any one of claims 1 to 5, characterized in that: The following steps are involved: Water, trehalose lipid surfactant and zinc phosphate are ball-milled to obtain a steel corrosion inhibitor.

7. The method for preparing a steel corrosion inhibitor according to claim 6, characterized in that: The frequency of the ball milling is 80 rpm to 150 rpm; The ball milling time is 0.8h to 2h.

8. A steel corrosion inhibitor, characterized in that: It is the steel corrosion inhibitor material as claimed in any one of claims 1 to 5; or, it comprises an additive and the steel corrosion inhibitor material as claimed in any one of claims 1 to 5.

9. Use of the steel corrosion inhibitor according to claim 8 for protecting steel in a high mineral water environment.

10. The use according to claim 9, characterized in that: The high mineral water environment includes 150g / L to 200g / L NaCl; 20g / L to 40g / L CaCl2; 10g / L~30g / L MgCl2; 0.1g / L~0.5g / L Na2SO4·10H2O; The content of the steel corrosion inhibitor in the high mineral water environment is 0.2 g / L to 0.5 g / L.

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