CN115992355A - Compound corrosion inhibitor for marine environment and preparation method thereof - Google Patents
Compound corrosion inhibitor for marine environment and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a compound corrosion inhibitor for marine environment and a preparation method thereof, belonging to the technical field of corrosion inhibition of marine metal materials. The corrosion inhibitor disclosed by the invention is prepared from the following raw materials in parts by weight: 20-30 parts of organic corrosion inhibitor, 30-50 parts of sodium metasilicate, 1-3 parts of zinc dihydrogen phosphate, 30-40 parts of corrosion inhibitor carrier and 1-3 parts of synergist. The invention uses ion liquid gradient concentration modification to prepare porous material as carrier, and forms corrosion inhibition functional component with organic corrosion inhibitor, sodium metasilicate, zinc dihydrogen phosphate, etc., which can realize timely and effective release of corrosion inhibition functional component in practical application, and presents certain self-repairing function; the compound corrosion inhibitor provided by the invention takes the corrosion inhibitor such as amino acid as a main material, has low price and is environment-friendly, and particularly under the harsher ocean conditions, a compact film can be formed on the surface of ocean machinery, so that the compound corrosion inhibitor has long service life, low maintenance cost and obvious corrosion inhibition effect.
Description
Technical Field
The invention belongs to the technical field of corrosion inhibition of marine metal materials, and particularly relates to a compound corrosion inhibitor for marine environments and a preparation method thereof.
Background
Rust on metal is a problem frequently encountered in production, and the rust on metal not only causes the metal workpiece to be damaged in the aspects of appearance, color, mechanical property and the like, but also causes the product quality to be reduced, and particularly causes the product to be scrapped.
With the rapid development and great adoption of offshore facilities such as oil and gas development platforms, tidal power stations, mineral resource exploration, coastal equipment and the like, related metal components need to face the marine atmospheric corrosion test. As the marine environment is a very severe natural corrosion environment, seawater has very strong corrosiveness and high conductivity, so that corrosion problems of metal components, marine steel structures and the like are increasingly highlighted, the reliability and the service life of marine equipment are seriously influenced, and effective corrosion protection measures are urgently needed.
The protection of the ocean metal matrix is mainly carried out by using methods such as corrosion resistant materials, metal surface modification, coating of anti-corrosion paint, electrochemical protection and the like.
At present, corrosion inhibition of marine steel structures is mostly carried out by adopting a method of coating anti-corrosion paint. Such as publication (bulletin) numbers: CN112934639a discloses a method for preparing an anti-corrosion steel, comprising the following steps: s1, cooling rolled steel on a factory production line; s2, cleaning the surface of the steel; s3, coating anti-corrosion paint on the surface of the steel, and drying; s4, inspecting finished products of the steel and the coating thereof, packaging, warehousing and leaving the factory.
However, the existing paint or coating has poor permeation resistance and photo aging resistance in the marine atmospheric environment, has poor strength performance, single function and easy bubble peeling, so that the in-use platform steel structure needs to be subjected to corrosion prevention maintenance regularly, the personnel cost is greatly increased, and meanwhile, the paint uses organic solvents as main raw materials, so that the paint has certain negative influence on the marine ecological environment.
Therefore, how to develop a novel corrosion inhibitor for marine environment, reduce environmental pollution and improve corrosion inhibition efficiency is a technical problem to be solved urgently at present.
Disclosure of Invention
Aiming at the problems of the corrosion inhibitor in the prior art, the invention provides a high-efficiency stable composite corrosion inhibitor, and aims to realize continuous and high-efficiency corrosion inhibition of a metal steel structure in a marine environment, reduce the treatment frequency, improve the corrosion prevention efficiency, adapt to the marine complex climate conditions and prolong the service life of components.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the compound corrosion inhibitor for the marine environment is prepared from the following raw materials in parts by weight: 20-30 parts of organic corrosion inhibitor, 30-50 parts of sodium metasilicate, 1-3 parts of zinc dihydrogen phosphate, 30-40 parts of corrosion inhibitor carrier and 1-3 parts of synergist.
Further, the organic corrosion inhibitor is one or more of polyethylenimine, L-serine, L-arginine, cystine and methionine.
Further, the sodium metasilicate is sodium metasilicate pentahydrate.
Further, the corrosion inhibitor carrier is an ionic liquid modified porous material, and the specific preparation method comprises the following steps:
(1) Weighing 10mmol of cobalt nitrate hexahydrate and 5mmol of 2-amino terephthalic acid, dissolving in 75 mM of an LDMF solvent, placing in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic treatment, reacting for 48 hours at 130 ℃, slowly cooling to room temperature, washing the product with DMF and absolute methanol respectively, and drying overnight to obtain a nano porous material;
(2) Mixing the ionic liquid with absolute ethyl alcohol to prepare a mixed solution A, B, C with ionic liquid concentration of 1-5mmol/L, 10-15mmol/L and 20-25mmol/L respectively;
(3) And (2) sequentially soaking the nano porous material prepared in the step (1) in a mixed solution A, B, C for gradient concentration treatment, wherein the soaking time is 1h, and finally, vacuum drying the mixture to obtain the ionic liquid modified porous material.
Further, the ionic liquid is any one of 1-methylimidazole, 1-ethylimidazole and 1-heptadecylimidazole.
Further, the synergistic agent is sodium citrate or sodium gluconate.
The preparation method of the compound corrosion inhibitor for the marine environment comprises the following preparation steps:
(1) Preparing a corrosion inhibitor carrier;
(2) Uniformly mixing the raw materials according to the parts by weight, and mixing the raw materials according to the solid-liquid ratio of 1g: dispersing 10mL in deionized water, placing into a closed vacuum drying oven, reducing the air pressure of the vacuum oven to below 0.1MPa, standing for 30-60min, and taking out to obtain the final product, wherein the final product can be sprayed or soaked for use.
The raw materials used in the invention are all commercially available.
The imidazole ionic liquid is a good corrosion inhibitor component and has the characteristics of high efficiency, low toxicity and easy degradation. The high activity of two nitrogen atoms at 1-position and 3-position in imidazole ionic liquid molecules determines that the imidazole ionic liquid is easy to adsorb on a metal surface, particularly derivatives with different substituent groups have strong adsorption capacity and large coverage area on the metal surface, however, when the imidazole ionic liquid is applied to corrosion prevention and inhibition under marine environment, the problems of insufficient corrosion resistance and short service life exist in the face of complex marine climate environment.
Therefore, the nano porous material is prepared by taking the metal organic framework as a basic carrier, carrying out gradient concentration treatment from low concentration to high concentration by using the imidazole ionic liquid, wherein the soaking time is 1h, so that the ionic liquid is fully adsorbed on the surface and the inner pores of the porous material, a compact film layer is gradually formed in the carrier and on the surface, and meanwhile, the components such as an organic corrosion inhibitor, sodium metasilicate, zinc dihydrogen phosphate, a synergist and the like are fully adsorbed. In practical application, when the membrane layer is damaged such as cracks, the carrier of the nano porous material can timely and effectively release corrosion inhibition components stored in the nano porous material, so that timely filling of the cracks is realized, the corrosion inhibition effect is fully exerted, the service life of the corrosion inhibitor is greatly prolonged, and a certain self-repairing effect of the membrane layer is realized.
In summary, the beneficial effects of the invention are as follows:
1. the invention uses ion liquid gradient concentration modification to prepare porous material as carrier, and forms corrosion inhibition functional component with organic corrosion inhibitor, sodium metasilicate, zinc dihydrogen phosphate, etc., which can realize timely and effective release of corrosion inhibition functional component in practical application, and presents certain self-repairing function;
2. sodium citrate or sodium gluconate is used as a synergistic agent, and contains a large amount of hydroxyl or carboxyl, so that the synergistic agent has good metal cation complexing capacity, and can play a role in scale inhibition in marine environment;
3. the compound corrosion inhibitor provided by the invention takes the corrosion inhibitor such as amino acid as a main material, is low in price and environment-friendly, and particularly can form a compact film on the surface of ocean machinery under the severe ocean condition, and has the advantages of long service life, low maintenance cost and remarkable corrosion inhibition effect.
Drawings
FIG. 1 is a Nyquist plot of Q235 steel in the corrosion inhibitor solution of inventive example 5, comparative examples 1-4;
FIG. 2 is a microscopic morphology electron microscope image of the corrosion inhibitor carrier prepared in example 5 of the present invention, wherein A is an overall morphology image, and a is a partial enlargement image of A; b is an internal structure diagram, and B is a partial enlarged view of B.
Detailed Description
The technical scheme of the present invention is further described below with reference to specific examples, but is not limited thereto.
Example 1
The compound corrosion inhibitor for the marine environment is prepared from the following raw materials in parts by weight: 20 parts of organic corrosion inhibitor, 30 parts of sodium metasilicate, 1 part of zinc dihydrogen phosphate, 30 parts of corrosion inhibitor carrier and 1 part of synergist.
The organic corrosion inhibitor is polyethyleneimine.
The sodium metasilicate is sodium metasilicate pentahydrate.
The corrosion inhibitor carrier is an ionic liquid modified porous material, and the specific preparation method comprises the following steps:
(1) Weighing 10mmol of cobalt nitrate hexahydrate and 5mmol of 2-amino terephthalic acid, dissolving in 75 mM of an LDMF solvent, placing in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic treatment, reacting for 48 hours at 130 ℃, slowly cooling to room temperature, washing the product with DMF and absolute methanol respectively, and drying overnight to obtain a nano porous material;
(2) Mixing the ionic liquid with absolute ethyl alcohol to prepare a mixed solution A, B, C with ionic liquid concentration of 1-5mmol/L, 10-15mmol/L and 20-25mmol/L respectively;
(3) And (2) sequentially soaking the nano porous material prepared in the step (1) in a mixed solution A, B, C for gradient concentration treatment, wherein the soaking time is 1h, and finally, vacuum drying the mixture to obtain the ionic liquid modified porous material.
The ionic liquid is 1-methylimidazole.
The synergistic agent is sodium citrate.
The preparation method of the compound corrosion inhibitor for the marine environment comprises the following preparation steps:
(1) Preparing a corrosion inhibitor carrier;
(2) Uniformly mixing the raw materials according to the parts by weight, and mixing the raw materials according to the solid-liquid ratio of 1g: dispersing 10mL in deionized water, placing into a closed vacuum drying oven, reducing the air pressure of the vacuum oven to below 0.1MPa, standing for 30min, and taking out to obtain the final product, wherein the final product can be sprayed or soaked for use.
Example 2
The compound corrosion inhibitor for the marine environment is prepared from the following raw materials in parts by weight: 24 parts of organic corrosion inhibitor, 40 parts of sodium metasilicate, 2 parts of zinc dihydrogen phosphate, 35 parts of corrosion inhibitor carrier and 2 parts of synergist.
The organic corrosion inhibitor is L-serine.
The sodium metasilicate is sodium metasilicate pentahydrate.
The corrosion inhibitor carrier is an ionic liquid modified porous material, and the specific preparation method comprises the following steps:
(1) Weighing 10mmol of cobalt nitrate hexahydrate and 5mmol of 2-amino terephthalic acid, dissolving in 75 mM of an LDMF solvent, placing in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic treatment, reacting for 48 hours at 130 ℃, slowly cooling to room temperature, washing the product with DMF and absolute methanol respectively, and drying overnight to obtain a nano porous material;
(2) Mixing the ionic liquid with absolute ethyl alcohol to prepare a mixed solution A, B, C with ionic liquid concentration of 1-5mmol/L, 10-15mmol/L and 20-25mmol/L respectively;
(3) And (2) sequentially soaking the nano porous material prepared in the step (1) in a mixed solution A, B, C for gradient concentration treatment, wherein the soaking time is 1h, and finally, vacuum drying the mixture to obtain the ionic liquid modified porous material.
The ionic liquid is 1-ethylimidazole.
The synergistic agent is sodium gluconate.
The preparation method of the compound corrosion inhibitor for the marine environment comprises the following preparation steps:
(1) Preparing a corrosion inhibitor carrier;
(2) Uniformly mixing the raw materials according to the parts by weight, and mixing the raw materials according to the solid-liquid ratio of 1g: dispersing 10mL in deionized water, placing into a closed vacuum drying oven, reducing the air pressure of the vacuum oven to below 0.1MPa, standing for 40min, and taking out to obtain the final product, wherein the final product can be sprayed or soaked for use.
Example 3
The compound corrosion inhibitor for the marine environment is prepared from the following raw materials in parts by weight: 30 parts of organic corrosion inhibitor, 42 parts of sodium metasilicate, 3 parts of zinc dihydrogen phosphate, 40 parts of corrosion inhibitor carrier and 3 parts of synergist.
The organic corrosion inhibitor is L-arginine.
The sodium metasilicate is sodium metasilicate pentahydrate.
The corrosion inhibitor carrier is an ionic liquid modified porous material, and the specific preparation method comprises the following steps:
(1) Weighing 10mmol of cobalt nitrate hexahydrate and 5mmol of 2-amino terephthalic acid, dissolving in 75 mM of an LDMF solvent, placing in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic treatment, reacting for 48 hours at 130 ℃, slowly cooling to room temperature, washing the product with DMF and absolute methanol respectively, and drying overnight to obtain a nano porous material;
(2) Mixing the ionic liquid with absolute ethyl alcohol to prepare a mixed solution A, B, C with ionic liquid concentration of 1-5mmol/L, 10-15mmol/L and 20-25mmol/L respectively;
(3) And (2) sequentially soaking the nano porous material prepared in the step (1) in a mixed solution A, B, C for gradient concentration treatment, wherein the soaking time is 1h, and finally, vacuum drying the mixture to obtain the ionic liquid modified porous material.
The ionic liquid is 1-heptadecyl imidazole.
The synergistic agent is sodium citrate.
The preparation method of the compound corrosion inhibitor for the marine environment comprises the following preparation steps:
(1) Preparing a corrosion inhibitor carrier;
(2) Uniformly mixing the raw materials according to the parts by weight, and mixing the raw materials according to the solid-liquid ratio of 1g: dispersing 10mL in deionized water, placing into a closed vacuum drying oven, reducing the air pressure of the vacuum oven to below 0.1MPa, standing for 50min, and taking out to obtain the final product, wherein the final product can be sprayed or soaked for use.
Example 4
The compound corrosion inhibitor for the marine environment is prepared from the following raw materials in parts by weight: 24 parts of organic corrosion inhibitor, 45 parts of sodium metasilicate, 2 parts of zinc dihydrogen phosphate, 35 parts of corrosion inhibitor carrier and 2 parts of synergist.
The organic corrosion inhibitor is cystine.
The sodium metasilicate is sodium metasilicate pentahydrate.
The corrosion inhibitor carrier is an ionic liquid modified porous material, and the specific preparation method comprises the following steps:
(1) Weighing 10mmol of cobalt nitrate hexahydrate and 5mmol of 2-amino terephthalic acid, dissolving in 75 mM of an LDMF solvent, placing in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic treatment, reacting for 48 hours at 130 ℃, slowly cooling to room temperature, washing the product with DMF and absolute methanol respectively, and drying overnight to obtain a nano porous material;
(2) Mixing the ionic liquid with absolute ethyl alcohol to prepare a mixed solution A, B, C with ionic liquid concentration of 1-5mmol/L, 10-15mmol/L and 20-25mmol/L respectively;
(3) And (2) sequentially soaking the nano porous material prepared in the step (1) in a mixed solution A, B, C for gradient concentration treatment, wherein the soaking time is 1h, and finally, vacuum drying the mixture to obtain the ionic liquid modified porous material.
The ionic liquid is 1-methylimidazole.
The synergistic agent is sodium citrate.
The preparation method of the compound corrosion inhibitor for the marine environment comprises the following preparation steps:
(1) Preparing a corrosion inhibitor carrier;
(2) Uniformly mixing the raw materials according to the parts by weight, and mixing the raw materials according to the solid-liquid ratio of 1g: dispersing 10mL in deionized water, placing into a closed vacuum drying oven, reducing the air pressure of the vacuum oven to below 0.1MPa, standing for 60min, and taking out to obtain the final product, wherein the final product can be sprayed or soaked for use.
Example 5
The compound corrosion inhibitor for the marine environment is prepared from the following raw materials in parts by weight: 30 parts of organic corrosion inhibitor, 50 parts of sodium metasilicate, 2 parts of zinc dihydrogen phosphate, 38 parts of corrosion inhibitor carrier and 3 parts of synergist.
The organic corrosion inhibitor is methionine.
The sodium metasilicate is sodium metasilicate pentahydrate.
The corrosion inhibitor carrier is an ionic liquid modified porous material, and the specific preparation method comprises the following steps:
(1) Weighing 10mmol of cobalt nitrate hexahydrate and 5mmol of 2-amino terephthalic acid, dissolving in 75 mM of an LDMF solvent, placing in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic treatment, reacting for 48 hours at 130 ℃, slowly cooling to room temperature, washing the product with DMF and absolute methanol respectively, and drying overnight to obtain a nano porous material;
(2) Mixing the ionic liquid with absolute ethyl alcohol to prepare a mixed solution A, B, C with ionic liquid concentration of 1-5mmol/L, 10-15mmol/L and 20-25mmol/L respectively;
(3) And (2) sequentially soaking the nano porous material prepared in the step (1) in a mixed solution A, B, C for gradient concentration treatment, wherein the soaking time is 1h, and finally, vacuum drying the mixture to obtain the ionic liquid modified porous material.
The ionic liquid is 1-ethylimidazole.
The synergistic agent is sodium gluconate.
The preparation method of the compound corrosion inhibitor for the marine environment comprises the following preparation steps:
(1) Preparing a corrosion inhibitor carrier;
(2) Uniformly mixing the raw materials according to the parts by weight, and mixing the raw materials according to the solid-liquid ratio of 1g: dispersing 10mL in deionized water, placing into a closed vacuum drying oven, reducing the air pressure of the vacuum oven to below 0.1MPa, standing for 60min, and taking out to obtain the final product, wherein the final product can be sprayed or soaked for use.
Comparative example 1
The compound corrosion inhibitor for the marine environment is prepared from the following raw materials in parts by weight: 30 parts of organic corrosion inhibitor, 50 parts of sodium metasilicate, 2 parts of zinc dihydrogen phosphate, 38 parts of corrosion inhibitor carrier and 3 parts of synergist.
The organic corrosion inhibitor is methionine.
The sodium metasilicate is sodium metasilicate pentahydrate.
The corrosion inhibitor carrier is an ionic liquid modified porous material, and the specific preparation method comprises the following steps:
(1) Weighing 10mmol of cobalt nitrate hexahydrate and 5mmol of 2-amino terephthalic acid, dissolving in 75 mM of an LDMF solvent, placing in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic treatment, reacting for 48 hours at 130 ℃, slowly cooling to room temperature, washing the product with DMF and absolute methanol respectively, and drying overnight to obtain a nano porous material;
(2) Mixing the ionic liquid with absolute ethyl alcohol to prepare a mixed solution A with the ionic liquid concentration of 1-5 mmol/L;
(3) And (2) soaking the nano porous material prepared in the step (1) in the mixed solution A for 1h, and finally drying the mixture in vacuum to obtain the ionic liquid modified porous material.
The ionic liquid is 1-ethylimidazole.
The synergistic agent is sodium gluconate.
The preparation method of the compound corrosion inhibitor for the marine environment comprises the following preparation steps:
(1) Preparing a corrosion inhibitor carrier;
(2) Uniformly mixing the raw materials according to the parts by weight, and mixing the raw materials according to the solid-liquid ratio of 1g: dispersing 10mL in deionized water, placing into a closed vacuum drying oven, reducing the air pressure of the vacuum oven to below 0.1MPa, standing for 60min, and taking out to obtain the final product, wherein the final product can be sprayed or soaked for use.
In this comparative example, the raw materials and the process were the same as in example 5 except that in the preparation of the corrosion inhibition carrier, only 1 to 5mmol/L of the mixed solution A was used for the treatment.
Comparative example 2
The compound corrosion inhibitor for the marine environment is prepared from the following raw materials in parts by weight: 30 parts of organic corrosion inhibitor, 50 parts of sodium metasilicate, 2 parts of zinc dihydrogen phosphate, 38 parts of corrosion inhibitor carrier and 3 parts of synergist.
The organic corrosion inhibitor is methionine.
The sodium metasilicate is sodium metasilicate pentahydrate.
The corrosion inhibitor carrier is an ionic liquid modified porous material, and the specific preparation method comprises the following steps:
(1) Weighing 10mmol of cobalt nitrate hexahydrate and 5mmol of 2-amino terephthalic acid, dissolving in 75 mM of an LDMF solvent, placing in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic treatment, reacting for 48 hours at 130 ℃, slowly cooling to room temperature, washing the product with DMF and absolute methanol respectively, and drying overnight to obtain a nano porous material;
(2) Mixing the ionic liquid with absolute ethyl alcohol to prepare a mixed solution B with the ionic liquid concentration of 10-15 mmol/L;
(3) And (2) soaking the nano porous material prepared in the step (1) in the mixed solution B for 1h, and finally drying the mixture in vacuum to obtain the ionic liquid modified porous material.
The ionic liquid is 1-ethylimidazole.
The synergistic agent is sodium gluconate.
The preparation method of the compound corrosion inhibitor for the marine environment comprises the following preparation steps:
(1) Preparing a corrosion inhibitor carrier;
(2) Uniformly mixing the raw materials according to the parts by weight, and mixing the raw materials according to the solid-liquid ratio of 1g: dispersing 10mL in deionized water, placing into a closed vacuum drying oven, reducing the air pressure of the vacuum oven to below 0.1MPa, standing for 60min, and taking out to obtain the final product, wherein the final product can be sprayed or soaked for use.
In this comparative example, the raw materials and the process were the same as in example 5 except that in the preparation of the corrosion inhibition carrier, only 10-15mmol/L of the mixed solution B was used for the treatment.
Comparative example 3
The compound corrosion inhibitor for the marine environment is prepared from the following raw materials in parts by weight: 30 parts of organic corrosion inhibitor, 50 parts of sodium metasilicate, 2 parts of zinc dihydrogen phosphate, 38 parts of corrosion inhibitor carrier and 3 parts of synergist.
The organic corrosion inhibitor is methionine.
The sodium metasilicate is sodium metasilicate pentahydrate.
The corrosion inhibitor carrier is an ionic liquid modified porous material, and the specific preparation method comprises the following steps:
(1) Weighing 10mmol of cobalt nitrate hexahydrate and 5mmol of 2-amino terephthalic acid, dissolving in 75 mM of an LDMF solvent, placing in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic treatment, reacting for 48 hours at 130 ℃, slowly cooling to room temperature, washing the product with DMF and absolute methanol respectively, and drying overnight to obtain a nano porous material;
(2) Mixing the ionic liquid with absolute ethyl alcohol to prepare a mixed solution C with the ionic liquid concentration of 20-25 mmol/L;
(3) And (2) soaking the nano porous material prepared in the step (1) in the mixed solution C for 1h, and finally drying the mixture in vacuum to obtain the ionic liquid modified porous material.
The ionic liquid is 1-ethylimidazole.
The synergistic agent is sodium gluconate.
The preparation method of the compound corrosion inhibitor for the marine environment comprises the following preparation steps:
(1) Preparing a corrosion inhibitor carrier;
(2) Uniformly mixing the raw materials according to the parts by weight, and mixing the raw materials according to the solid-liquid ratio of 1g: dispersing 10mL in deionized water, placing into a closed vacuum drying oven, reducing the air pressure of the vacuum oven to below 0.1MPa, standing for 60min, and taking out to obtain the final product, wherein the final product can be sprayed or soaked for use.
In this comparative example, the raw materials and the process were the same as in example 5 except that in the preparation of the corrosion-inhibiting carrier, only 20-25mmol/L of the mixed solution C was used for the treatment.
Comparative example 4
The compound corrosion inhibitor for the marine environment is prepared from the following raw materials in parts by weight: 30 parts of organic corrosion inhibitor, 50 parts of sodium metasilicate, 2 parts of zinc dihydrogen phosphate, 38 parts of corrosion inhibitor carrier and 3 parts of synergist.
The organic corrosion inhibitor is methionine.
The sodium metasilicate is sodium metasilicate pentahydrate.
The corrosion inhibitor carrier is a porous material, and the specific preparation method comprises the following steps:
(1) 10mmol of cobalt nitrate hexahydrate and 5mmol of 2-amino terephthalic acid are weighed and dissolved in 75 mM of LDMF solvent, the solution is placed in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic treatment, the reaction is carried out for 48 hours at 130 ℃, the solution is slowly cooled to room temperature, and the product is respectively washed by DMF and absolute methanol and dried overnight, so that the nano-porous material is obtained.
The synergistic agent is sodium gluconate.
The preparation method of the compound corrosion inhibitor for the marine environment comprises the following preparation steps:
(1) Uniformly mixing the raw materials according to the parts by weight, and mixing the raw materials according to the solid-liquid ratio of 1g: dispersing 10mL in deionized water, placing into a closed vacuum drying oven, reducing the air pressure of the vacuum oven to below 0.1MPa, standing for 60min, and taking out to obtain the final product, wherein the final product can be sprayed or soaked for use.
In this comparative example, the materials and processes were the same as in example 5 except that no immersing treatment with ionic liquid was performed in the preparation of the corrosion inhibition carrier.
Performance testing
Weight loss test
Experiments are carried out according to national standard GB10124-88, Q235 steel is processed into 50mm multiplied by 20mm multiplied by 5mm samples, all sides of the samples are polished to be bright by using 280# metallographic sand paper, 480# metallographic sand paper and 800# metallographic sand paper in sequence, the samples are ultrasonically cleaned by absolute ethyl alcohol and dried, and the samples are weighed to be 0.1mg after being placed in a dryer for 24 hours. The corrosion inhibitors obtained in examples 1-5 and comparative documents 1-4 of the present invention were uniformly sprayed on the Q235 steel samples to be used, respectively, and after drying, they were immersed in seawater, and a blank control was set, i.e., no treatment was performed and direct immersion was performed. The seawater volume was 500mL and the corrosion time was 10 cycles, with a constant temperature water bath to control the temperature to 25 ℃.
According to the method for cleaning corrosion products after steel corrosion in GB/T16545-1996, Q235 steel is subjected to 10 dry-wet cycle corrosion experiments, soaked in a cleaning solution for ten minutes under 298K, cleaned twice with distilled water, ultrasonically treated in absolute ethyl alcohol for 10 minutes, dehydrated, dried in a drying oven for 24 hours and then weighed. Wherein the cleaning solution is prepared by adding distilled water into 500ml of concentrated hydrochloric acid and 3.5g of hexamethylenetetramine to prepare 1000ml of solution. The average was determined in triplicate for each solution. The corrosion inhibition rate eta% of the weightlessness experiment is obtained by the following formula:
wherein v is the corrosion rate, mg (cm) 2 ·d） -1 The method comprises the steps of carrying out a first treatment on the surface of the Δw is the difference in weight before and after corrosion, mg; s is the surface area of the sample, cm 2 The method comprises the steps of carrying out a first treatment on the surface of the t is the etching time, d.
The test was performed after 10 cycles of three replicates each.
The test results are shown in table 1:
TABLE 1 Corrosion test results
To verify the experimental results, an electrochemical impedance test was further performed:
using a Gemary electrochemical test system, performing electrochemical impedance spectrum test in a standard three-electrode system, and setting experimental parameters as follows: the measured excitation signal amplitude is a sine wave of 10 mV, the test frequency range is 0.01 to 100000 Hz, and the corrosion rate is analyzed according to the experimentally measured change of the sheet surface resistance.
At 1cm 2 The Q235 steel sheet is used as a working electrode, the platinum sheet is used as a counter electrode and the calomel electrode is used as a reference electrode, and a simulated seawater solution added with the corrosion inhibitors (the addition amount of the corrosive agent is 200 mg/L) in the embodiment 5 and the comparative examples 1-4 of the invention is used as a test system. The experimental parameters were set as follows: the scanning range is 0.15V relative to the open circuit potential of-0.15, and the scanning speed is 10 mV/s. As shown in fig. 1, it can be seen from the graph that as the concentration of the ionic liquid treatment increases, the impedance spectrum gradually increases, and the reaction rate of the hanging piece in the corrosive medium is reduced, but the impedance values of the test groups of comparative examples 1-3 are smaller than those of the test group of example 5 of gradient concentration treatment, because the porous carrier of gradient concentration treatment has more continuous and compact internal film forming property than single concentration treatment, and the corrosion inhibition effect is more stable.
It should be noted that the above-mentioned embodiments are merely some, but not all embodiments of the preferred mode of carrying out the invention. It is evident that all other embodiments obtained by a person skilled in the art without making any inventive effort, based on the above-described embodiments of the invention, shall fall within the scope of protection of the invention.
Claims (7)
1. The compound corrosion inhibitor for the marine environment is characterized by comprising the following raw materials in parts by weight: 20-30 parts of organic corrosion inhibitor, 30-50 parts of sodium metasilicate, 1-3 parts of zinc dihydrogen phosphate, 30-40 parts of corrosion inhibitor carrier and 1-3 parts of synergist.
2. The compound corrosion inhibitor for marine environment according to claim 1, wherein the organic corrosion inhibitor is one or more of polyethylenimine, L-serine, L-arginine, cystine and methionine.
3. The marine environmental use compound corrosion inhibitor according to claim 1, wherein the sodium metasilicate is sodium metasilicate pentahydrate.
4. The compound corrosion inhibitor for marine environment according to claim 1, wherein the corrosion inhibitor carrier is an ionic liquid modified porous material, and the specific preparation method comprises the following steps:
(1) Weighing 10mmol of cobalt nitrate hexahydrate and 5mmol of 2-amino terephthalic acid, dissolving in 75 mM of an LDMF solvent, placing in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic treatment, reacting for 48 hours at 130 ℃, slowly cooling to room temperature, washing the product with DMF and absolute methanol respectively, and drying overnight to obtain a nano porous material;
(2) Mixing the ionic liquid with absolute ethyl alcohol to prepare a mixed solution A, B, C with ionic liquid concentration of 1-5mmol/L, 10-15mmol/L and 20-25mmol/L respectively;
(3) And (2) sequentially soaking the nano porous material prepared in the step (1) in a mixed solution A, B, C for gradient concentration treatment, wherein the soaking time is 1h, and finally, vacuum drying the mixture to obtain the ionic liquid modified porous material.
5. The compound corrosion inhibitor for marine environments according to claim 4, wherein the ionic liquid is any one of 1-methylimidazole, 1-ethylimidazole and 1-heptadecylimidazole.
6. The compound corrosion inhibitor for marine environments according to claim 1, wherein the synergist is sodium citrate or sodium gluconate.
7. A method for preparing the compound corrosion inhibitor for marine environments according to any one of claims 1 to 6, which is characterized by comprising the following preparation steps:
(1) Preparing a corrosion inhibitor carrier;
(2) Uniformly mixing the raw materials according to the parts by weight, and mixing the raw materials according to the solid-liquid ratio of 1g: dispersing 10mL in deionized water, placing into a closed vacuum drying oven, reducing the air pressure of the vacuum oven to below 0.1MPa, standing for 30-60min, and taking out to obtain the final product, wherein the final product can be sprayed or soaked for use.
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