CN113652139A - Anti-corrosion and anti-bacterial coating for upper surface of bottom plate of crude oil storage tank and preparation method thereof - Google Patents
Anti-corrosion and anti-bacterial coating for upper surface of bottom plate of crude oil storage tank and preparation method thereof Download PDFInfo
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Abstract
An anticorrosion antibacterial coating for the upper surface of a bottom plate of a crude oil storage tank and a preparation method thereof, wherein a main agent in the coating is mainly prepared from 35-45% of epoxy resin, 0.5-1.5% of dispersing agent, 0.5-1.0% of anti-settling agent, 10-15% of diluent, 30-40% of talcum powder, 4-8% of barium sulfate, 0.5-3% of bactericide and 0.1-1% of solid antibacterial filler; the curing agent in the coating is mainly prepared from 85-100% of amine curing agent and 0-15% of curing agent accelerator. Pouring epoxy resin into a stirring kettle, adding a dispersing agent and a diluent, stirring, adding the rest components, and stirring to obtain a main agent; adding the curing accelerator into the amine curing agent and stirring to obtain the curing agent; and adding the curing agent into the main agent, stirring and brushing the mixture on the surface of the workpiece. The coating has higher efficient sterilization performance, lower bacterial drug resistance, better adhesive force and oil resistance, and long-term anticorrosion and antibacterial capacity for the bottom plate of the storage tank.
Description
Technical Field
The invention relates to the technical field of coating materials and preparation thereof, in particular to an anticorrosive antibacterial coating for the upper surface of a bottom plate of a crude oil storage tank and a preparation method thereof.
Background
With the rapid development of economy, the consumption of petroleum in China is increasing day by day, and the petroleum produced by China is far from meeting the consumption demand, and a large amount of crude oil needs to be imported from foreign countries every year. The sulfur content of foreign crude oil is generally higher than that of domestic crude oil, especially middle east crude oil. High-sulfur crude oil also contains a large amount of corrosive substances such as water, inorganic salts and the like while having high sulfur content, and not only can seriously corrode a downstream refining device, but also can seriously corrode an oil pipeline and a crude oil storage tank device. The corrosion of the bottom plate of a crude oil storage tank is particularly severe because water in the crude oil is deposited on the bottom of the tank in the storage tank. So far, the application of anticorrosive coatings is still one of the most widely used means for preventing corrosion inside crude oil storage tanks.
However, with the increasing development of oil and gas resources in China in recent years, the yield increasing process for improving the yield by a water injection mode is widely applied, so that corrosive microorganisms in ground water are introduced into each link of oil and gas exploitation, transportation and storage. Corrosive microorganisms represented by Sulfate Reducing Bacteria (SRB) can not only cause rapid and serious corrosion perforation of metal materials, but also decompose components such as epoxy resin in a coating, cause cracking and falling of the coating and finally lose protection performance. Therefore, the coating has high antibacterial performance, and is one of the problems to be solved in the oil and gas industry.
At present, a coating has certain bactericidal performance by adding a single-component organic bactericide and metal oxide nanoparticles into the coating, but the bactericidal performance of the coating is often difficult to meet the anticorrosion requirements of harsh working conditions such as a crude oil storage tank and the like. And because the cleaning cycle of the accumulated water at the bottom of the crude oil storage tank is long and often longer than 1 year, dead water can be formed in individual areas, and microorganisms in the accumulated water can easily generate drug resistance to the antibacterial components in the coating for a long time in the same environment, thereby reducing or even losing the antibacterial performance. Therefore, aiming at the working condition of water accumulation of the crude oil storage tank, the invention improves the long-term antibacterial property of the coating by improving the antibacterial property of the coating and reducing the drug resistance of bacteria.
Disclosure of Invention
The invention aims to provide an anticorrosive antibacterial coating for the bottom plate surface of a crude oil storage tank and a preparation method thereof.
In order to achieve the aim, the invention provides an anti-corrosion and anti-bacterial coating for the upper surface of a bottom plate of a crude oil storage tank, which is prepared from a main agent and a curing agent; the mass fraction ratio of the main agent to the curing agent is (3.5-7.5): 1; the main agent mainly comprises the following components in percentage by mass: 35-45% of epoxy resin, 0.5-1.5% of dispersing agent, 0.5-1.0% of anti-settling agent, 10-15% of diluent, 30-40% of talcum powder, 4-8% of barium sulfate, 0.5-3% of bactericide and 0.1-1% of solid antibacterial filler; the curing agent mainly comprises the following components in percentage by mass: 85-100% of amine curing agent and 0-15% of curing agent accelerator.
Preferably, the bactericide is two or more than three of p-chloro-m-dimethylphenol, trichloro-hydroxy-diphenyl ether, dodecyl dimethyl benzyl ammonium chloride and tetrakis hydroxymethyl phosphonium sulfate.
Preferably, the solid antibacterial filler is two or more than three of nano silver particles, nano zinc oxide particles, nano cuprous oxide particles and nano titanium oxide particles.
Preferably, the particle size of the solid antibacterial filler is 0.5-50 nm.
Preferably, the anti-settling agent is one or more of polyamide wax, organic bentonite, castor oil derivatives, fumed silica and polyolefin wax.
Preferably, the diluent is one or more of neodecanoic acid glycidyl ester, butanol, methyl isobutyl ketone and amyl acetate.
Further, the coating is used for resisting corrosion microorganisms, and the type of the coating is one or more of sulfate reducing bacteria, thiobacillus, saprophytic bacteria, iron bacteria and nitrate reducing bacteria.
The main agent of the invention adopts epoxy resin as a base material, has good adhesive force on metal, good fluidity before curing and easy coating construction; the oil resistance is good, the water permeability is low, and the anti-corrosion effect is good in the crude oil environment; does not react with the bactericide and does not influence the sterilization effect.
The dispersant in the main agent is used for dispersing solid particles added in the coating and keeping the solid particles in a dispersed state, so that the phenomena of agglomeration, flocculation and the like are prevented; the anti-settling agent in the main agent can enable filler particles to suspend without caking, prevent pigment from settling, improve the performance of the coating and keep excellent leveling property; the diluent is used for reducing the viscosity of the resin and improving the process performance; the talcum powder in the main agent is used as a filler, so that the main agent can play a role of a framework, the manufacturing cost is reduced, and the film hardness of the coating is improved; barium sulfate in the main agent is used as an extender pigment in the coating and is applied to the coating to improve the thickness, the wear resistance, the water resistance, the heat resistance, the surface hardness, the impact resistance and the like of the coating; the bactericide in the main agent is a liquid bactericide, has good intersolubility with epoxy resin, does not react with the epoxy resin, and does not influence the performance of the coating; the antibacterial filler in the main agent is dispersed by the dispersant and then is doped into the coating, thereby playing a role in enhancing the sterilizing effect of the bactericide.
The curing agent in the invention mainly refers to a modified amine curing agent, which has the advantages of low toxicity, long working life, low dosage, good curing performance and good bonding performance with metal.
A preparation method of an anti-corrosion and anti-bacterial coating for the upper surface of a bottom plate of a crude oil storage tank comprises the following steps:
(1) preparation of the main agent: sequentially weighing the preparation components of the main agent according to the mass fraction, then pouring the epoxy resin into a high-speed stirring kettle, and then respectively adding the dispersing agent, the diluent, the bactericide and the solid antibacterial filler for stirring; then adding the anti-settling agent, the talcum powder and the barium sulfate in sequence, and fully and uniformly stirring; finally, fully grinding and dispersing the high-viscosity slurry by using a three-roller grinder to finally obtain a main agent;
(2) preparation of the curing agent: weighing the preparation components of the curing agent in sequence according to the mass fraction, adding the curing accelerator into the amine curing agent, and fully and uniformly stirring to obtain the curing agent;
(3) preparing an antibacterial coating: and (3) weighing the main agent and the curing agent in sequence according to the mass fraction, uniformly stirring, brushing the mixture on the surface of a workpiece, wherein the thickness of the coating is 200-500 mu m, and curing at room temperature for 24-30 h to obtain the anticorrosive antibacterial coating.
Compared with the prior art, the antibacterial and anticorrosive coating prepared by compounding the bactericide and the solid bactericidal filler has more efficient bactericidal performance and lower bacterial drug resistance, and also has excellent mechanical performance, medium resistance, binding performance with a substrate and electrical insulation performance, so that the coating can protect the substrate from being corroded by environmental media and microorganisms under severe working conditions such as the bottom of a crude oil storage tank and the like, the service safety of field equipment is ensured, and long-term anticorrosion and antibacterial capacity is provided for the bottom plate of the storage tank.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The coating in the embodiment detects various performance indexes of the coating according to the requirements of the Q/SHCG 18014 and 2017 standards. Wherein the content of the non-volatile matter is detected according to a method specified in GB/T1725; the drying time (normal temperature) is detected according to the method specified in GB/T1728; the adhesion is detected according to the method specified in GB/T5210; the flexibility is detected according to the method specified in GB/T1731; impact resistance was measured according to the method specified in GB/T1732; the electrical strength is detected according to the method specified in GB/T1408.1; the volume resistivity is detected according to the method specified in GB/T1410; the hot water resistance is detected according to a method specified in GB/T1733; gasoline resistance, alkali resistance, salt water resistance and acid resistance are tested according to the GB 9274A method; the salt spray resistance is detected according to the method specified in GB/T1771; cathodic disbonding was detected according to the method defined in SY/T0037; the sag resistance was measured according to the method specified in GB/T9264.
The method for testing the antibacterial effect of the coating comprises the following steps: and (3) putting the antibacterial coating and the comparative coating into a solution containing bacteria for soaking for 3 days, taking out a sample after soaking, immediately soaking for 30min by using a phosphate buffer solution containing 2.5% vol glutaraldehyde, solidifying the bacteria, then dehydrating by using 30%, 60% and 100% alcohol step by step, spraying gold on the surface of the coating after natural drying, and observing by using an electronic scanning microscope to obtain the number of the bacteria in a unit area.
The method for testing the bacterial drug resistance effect of the coating comprises the following steps: and (3) putting the antibacterial coating and the comparative coating into a solution containing bacteria for soaking for 30 days, taking out a sample after soaking, immediately soaking for 30min by using a phosphate buffer solution containing 2.5% vol glutaraldehyde, solidifying the bacteria, then dehydrating by using 30%, 60% and 100% alcohol step by step, spraying gold on the surface of the coating after natural drying, and observing by using an electronic scanning microscope to obtain the number of the bacteria in a unit area.
Example one
An anti-corrosion and anti-bacterial coating for the upper surface of a bottom plate of a crude oil storage tank is prepared from a main agent and a curing agent; the main agent mainly comprises the following components in percentage by mass: 42% of epoxy resin, 0.5% of dispersant, 0.5% of anti-settling agent, 13% of diluent, 37.5% of talcum powder, 4% of barium sulfate, 2% of bactericide and 0.5% of solid antibacterial filler;
the anti-settling agent is one or more of polyamide wax, organic bentonite, castor oil derivatives, fumed silica and polyolefin wax; the diluent is one or more of neodecanoic acid glycidyl ester, butanol, methyl isobutyl ketone and amyl acetate;
the bactericide is a compound of parachlorometaxylenol and trichlorohydroxydiphenyl ether, and the mass ratio of the parachlorometaxylenol to the trichlorohydroxydiphenyl ether is 0.5-1.5; the solid antibacterial filler is nano silver particles and nano cuprous oxide particles, the mass ratio of the nano silver particles to the nano cuprous oxide particles is 0.3-0.8, and the particle size of the solid antibacterial filler is 100-200 nm;
the curing agent mainly comprises the following components in percentage by mass: 95% of amine curing agent and 5% of curing agent accelerator;
the mass fraction ratio of the main agent to the curing agent is 6: 1.
the type of the coating used for resisting corrosion microorganisms is one or more of sulfate reducing bacteria, thiobacillus, saprophytic bacteria, iron bacteria and nitrate reducing bacteria.
The preparation method of the antibacterial coating comprises the following steps:
(1) preparation of the main agent: sequentially weighing the preparation components of the main agent according to the mass fraction, then pouring the epoxy resin into a high-speed stirring kettle, respectively adding the dispersing agent, the diluent, the bactericide and the solid antibacterial filler, and uniformly stirring; finally, adding the anti-settling agent, the talcum powder and the barium sulfate in sequence, and fully and uniformly stirring; finally, fully grinding and dispersing the high-viscosity slurry by using a three-roller grinder to obtain a main agent;
(2) preparation of the curing agent: weighing the preparation components of the curing agent in sequence according to the mass fraction, adding the curing accelerator into the amine curing agent, and fully and uniformly stirring to obtain the curing agent;
(3) preparing an antibacterial coating: and (3) weighing the main agent and the curing agent in sequence according to the mass fraction, uniformly stirring, brushing the mixture on the surface of a workpiece, wherein the thickness of the coating is 200-500 mu m, and curing at room temperature for 24-30 h to obtain the anticorrosive antibacterial coating.
After the coating is cured for 24 hours, various performance tests are carried out on the coating, the test results are shown in Table 1, and various indexes all meet the requirements of Q/SHCG 18014-2017 standards. The results of the coating antibacterial property tests shown in table 2 show that: after the bactericide (a compound of parachlorometaxylenol and trichlorohydroxydiphenyl ether) and the solid antibacterial filler (a compound of nano-silver particles and nano-cuprous oxide particles) are added, the number of bacteria on the surface of the sample is obviously reduced, and the coating has excellent antibacterial performance. And by comparing with the results of comparative examples 2, 3, 4 and 5, it was shown that the antibacterial property of the coating can be greatly improved by compounding the bactericide and the solid antibacterial filler.
Table 1 results of performance test of antibacterial coatings prepared in examples
Table 2 comparison results of antibacterial properties of antibacterial coatings prepared in example one and comparative examples, respectively
Example two
An anti-corrosion and anti-bacterial coating for the upper surface of a bottom plate of a crude oil storage tank is prepared from a main agent and a curing agent;
the main agent mainly comprises the following components in percentage by mass: 45% of epoxy resin, 1.5% of dispersant, 0.5% of anti-settling agent, 13.9% of diluent, 30% of talcum powder, 6% of barium sulfate, 3% of bactericide and 0.1% of solid antibacterial filler;
the anti-settling agent is one or more of polyamide wax, organic bentonite, castor oil derivatives, fumed silica and polyolefin wax; the diluent is one or more of neodecanoic acid glycidyl ester, butanol, methyl isobutyl ketone and amyl acetate.
The bactericide is a compound of parachlorometaxylenol and dodecyl dimethyl benzyl ammonium chloride, and the mass ratio of the parachlorometaxylenol to the dodecyl dimethyl benzyl ammonium chloride is 0.5-2; the solid antibacterial filler is nano zinc oxide particles and nano cuprous oxide particles, the mass ratio of the nano zinc oxide particles to the nano cuprous oxide particles is 0.3-0.8, and the particle size of the solid antibacterial filler is 100-200 nm;
the type of the coating used for resisting corrosion microorganisms is one or more of sulfate reducing bacteria, thiobacillus, saprophytic bacteria, iron bacteria and nitrate reducing bacteria.
The curing agent mainly comprises the following components in percentage by mass: 90% of amine curing agent and 10% of curing agent accelerator;
the mass fraction ratio of the main agent to the curing agent is 7.5: 1;
the preparation method of the antibacterial coating is the same as that of the first embodiment.
After the coating is cured for 24 hours, various performance tests are carried out on the coating, the test results are shown in Table 1, and various indexes all meet the requirements of Q/SHCG 18014-2017 standards. The results of the coating antibacterial property tests shown in table 3 show that: after a bactericide (a compound of p-chloroxylenol and dodecyl dimethyl benzyl ammonium chloride (1227)) and a solid antibacterial filler (a compound of nano zinc oxide particles and nano cuprous oxide particles) are added, the number of bacteria on the surface of a sample is obviously reduced, and the coating has excellent antibacterial performance. And by comparing with the results of comparative examples 6, 7, 8 and 9, it was shown that the antibacterial property of the coating can be greatly improved by compounding the bactericide and the solid antibacterial filler.
Table 3 comparison of antibacterial performance of antibacterial coatings prepared in example two and comparative example respectively
EXAMPLE III
An anti-corrosion and anti-bacterial coating for the upper surface of a bottom plate of a crude oil storage tank is prepared from a main agent and a curing agent;
the main agent mainly comprises the following components in percentage by mass: 35% of epoxy resin, 1.0% of dispersant, 1.0% of anti-settling agent, 15% of diluent, 38.5% of talcum powder, 8% of barium sulfate, 0.5% of bactericide and 1% of antibacterial filler; the anti-settling agent is one or more of polyamide wax, organic bentonite, castor oil derivatives, fumed silica and polyolefin wax; the diluent is one or more of neodecanoic acid glycidyl ester, butanol, methyl isobutyl ketone and amyl acetate;
the bactericide is a compound of tetrakis (hydroxymethyl) phosphonium sulfate (THPS) and dodecyl dimethyl benzyl ammonium chloride (1227), and the mass ratio of the bactericide to the THPS is 0.5-2; the solid antibacterial filler is a compound of nano zinc oxide particles and nano cuprous oxide particles, the mass ratio of the nano zinc oxide particles to the nano cuprous oxide particles is 0.3-0.8, and the particle size of the solid antibacterial filler is 100-200 nm;
the type of the coating used for resisting corrosion microorganisms is one or more of sulfate reducing bacteria, thiobacillus, saprophytic bacteria, iron bacteria and nitrate reducing bacteria.
The curing agent mainly comprises the following components in percentage by mass: 85% of amine curing agent and 15% of curing agent accelerator;
the mass fraction ratio of the main agent to the curing agent is 3.5: 1;
the preparation method of the antibacterial coating is the same as that of the first embodiment.
After the coating is cured for 24 hours, various performance tests are carried out on the coating, the test results are shown in Table 1, and various indexes all meet the requirements of Q/SHCG 18014-2017 standards. The results of the coating antibacterial performance test shown in table 4 show that the coating has excellent antibacterial performance after the addition of the bactericide (a compound of THPS and 1227) and the solid antibacterial filler (a compound of nano zinc oxide particles and nano cuprous oxide particles). And it is shown that the antibacterial property of the coating layer can be greatly improved by compounding the bactericide and the solid antibacterial filler by comparing with the results of comparative examples 10, 11, 12 and 13.
Table 4 comparison results of antibacterial properties of antibacterial coatings prepared in example three and comparative example respectively
Example four
In the embodiment, only the composition of the solid antibacterial filler is modified on the basis of the third embodiment, and the components comprise nano zinc oxide particles, nano titanium oxide particles and nano cuprous oxide particles. The remaining coating compositions and preparation methods were identical to those of the examples. After the coating is cured for 24 hours, various performance tests are carried out on the coating, the test results are shown in Table 1, and various indexes all meet the requirements of Q/SHCG 18014-2017 standards. Table 5 shows the results of the tests on the antibacterial properties of the coating, and by comparing the results with the test results of the third example, the antibacterial properties of the coating can be further improved by adding the compounded components of the bactericide and the solid bactericidal filler.
Table 5 comparison of antibacterial properties of antibacterial coatings prepared in example four and example three respectively
Table 6 comparison of bacterial resistance of samples prepared in examples one to four and comparative example
Table 6 shows the results of comparing the bacterial resistance of the samples prepared in examples one to four with that of the sample prepared in the comparative example. The results show that when the soaking time was extended from 3 days to 30 days, the bacteria content on the surface of the sample of comparative example 14 increased significantly, from 2.1 ten thousand to 6.7 ten thousand, indicating that the bacteria developed significant resistance to comparative example 14. The number of bacteria on the surfaces of the samples in the first to third examples is not greatly increased, and the bacteria growth is always effectively inhibited, which shows that the anticorrosive antibacterial coating prepared by the invention has low bacterial resistance.
As can be seen from the embodiments, the antibacterial and anticorrosive coating prepared by the invention has good bonding performance with a substrate, mechanical performance and medium resistance, and meets the requirements of the Q/SHCG 18014-2017 standard. Particularly, after the bactericide and the solid antibacterial filler are added in a compounding way, the coating has excellent antibacterial performance and low drug resistance. Therefore, the coating prepared by the invention can be used under severe working conditions such as the bottom of a crude oil storage tank and the like, and the matrix is protected from being corroded by environmental media and microorganisms.
Claims (8)
1. An anti-corrosion and anti-bacterial coating for the upper surface of a bottom plate of a crude oil storage tank is characterized in that the coating is prepared from a main agent and a curing agent; the mass fraction ratio of the main agent to the curing agent is (3.5-7.5): 1;
the main agent mainly comprises the following components in percentage by mass: 35-45% of epoxy resin, 0.5-1.5% of dispersing agent, 0.5-1.0% of anti-settling agent, 10-15% of diluent, 30-40% of talcum powder, 4-8% of barium sulfate, 0.5-3% of bactericide and 0.1-1% of solid antibacterial filler;
the curing agent mainly comprises the following components in percentage by mass: 85-100% of amine curing agent and 0-15% of curing agent accelerator.
2. The anti-corrosive and antibacterial coating for the upper surface of the bottom plate of the crude oil storage tank as claimed in claim 1, wherein the bactericide is two or more of parachlorometaxylenol, trichlorohydroxydiphenyl ether, dodecyl dimethyl benzyl ammonium chloride and tetrakis hydroxymethyl phosphonium sulfate.
3. The anti-corrosion antibacterial coating for the upper surface of the bottom plate of the crude oil storage tank as claimed in claim 1 or 2, wherein the solid antibacterial filler is two or more of nano silver particles, nano zinc oxide particles, nano cuprous oxide particles and nano titanium oxide particles.
4. The anti-corrosion and anti-bacterial coating for the upper surface of the bottom plate of the crude oil storage tank as claimed in claim 3, wherein the particle size of the solid anti-bacterial filler is 50-200 nm.
5. The anti-corrosive and antibacterial coating for the upper surface of the bottom plate of the crude oil storage tank as claimed in claim 1 or 2, wherein the anti-settling agent is one or more of polyamide wax, organic bentonite, castor oil derivatives, fumed silica and polyolefin wax.
6. The anti-corrosive and antibacterial coating for the upper surface of the bottom plate of the crude oil storage tank as claimed in claim 1 or 2, wherein the diluent is one or more of glycidyl neodecanoate, butanol, methyl isobutyl ketone and amyl acetate.
7. An anti-corrosive and antibacterial coating for the upper surface of the bottom plate of a crude oil storage tank according to any one of claims 1 to 6, wherein the species of the anti-corrosive microorganisms used for the coating are one or more of sulfate reducing bacteria, thiobacillus, saprophytic bacteria, iron bacteria and nitrate reducing bacteria.
8. A preparation method of an anti-corrosion and anti-bacterial coating for the upper surface of a bottom plate of a crude oil storage tank is characterized by comprising the following steps:
(1) preparation of the main agent: sequentially weighing the preparation components of the main agent according to the mass fraction, then pouring the epoxy resin into a high-speed stirring kettle, and then respectively adding the dispersing agent, the diluent, the bactericide and the solid antibacterial filler for stirring; then adding the anti-settling agent, the talcum powder and the barium sulfate in sequence, fully and uniformly stirring, and finally fully grinding and dispersing the high-viscosity slurry by using a three-roller grinder to finally obtain a main agent;
(2) preparation of the curing agent: weighing the preparation components of the curing agent in sequence according to the mass fraction, adding the curing accelerator into the amine curing agent, and fully and uniformly stirring to obtain the curing agent;
(3) preparing an antibacterial coating: and (3) weighing the main agent and the curing agent in sequence according to the mass fraction, uniformly stirring, brushing the mixture on the surface of a workpiece, wherein the thickness of the coating is 200-500 mu m, and curing at room temperature for 24-30 h to obtain the anticorrosive antibacterial coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110836867.0A CN113652139A (en) | 2021-07-23 | 2021-07-23 | Anti-corrosion and anti-bacterial coating for upper surface of bottom plate of crude oil storage tank and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110836867.0A CN113652139A (en) | 2021-07-23 | 2021-07-23 | Anti-corrosion and anti-bacterial coating for upper surface of bottom plate of crude oil storage tank and preparation method thereof |
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| CN113652139A true CN113652139A (en) | 2021-11-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114752283A (en) * | 2022-04-06 | 2022-07-15 | 华邦建投集团股份有限公司 | Garbage pool coating and preparation method thereof |
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| CN114752283A (en) * | 2022-04-06 | 2022-07-15 | 华邦建投集团股份有限公司 | Garbage pool coating and preparation method thereof |
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Application publication date: 20211116 |