CN107267033B - Graphene-doped heat exchanger tube bundle coating and preparation method thereof - Google Patents
Graphene-doped heat exchanger tube bundle coating and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/04—Epoxynovolacs
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/103—Anti-corrosive paints containing metal dust containing Al
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C08K2003/0812—Aluminium
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Abstract
The invention provides a graphene-doped heat exchanger tube bundle coating and a preparation method thereof, and the graphene-doped heat exchanger tube bundle coating has the advantages of corrosion resistance, hydrophobicity, high-temperature and high-pressure steam blowing resistance and the like through the synergistic effect of novolac epoxy resin, epoxy modified organic silicon resin and a graphene dispersion. The graphene-doped heat exchanger tube bundle coating provided by the invention is coated in a heat exchanger tube bundle, can increase the corrosion resistance of the heat exchanger tube bundle, reduce the generation of scale in a pipeline, greatly improve the heat transfer performance, and meanwhile, under the condition of high-temperature and high-pressure steam blowing, the graphene-doped heat exchanger tube bundle coating still has excellent adhesive force, does not bubble or fall off, prolongs the service life of a heat exchanger, and reduces the maintenance cost of enterprises. The graphene-doped heat exchanger tube bundle coating prepared by the preparation method provided by the invention has the advantages of corrosion resistance, hydrophobicity, high-temperature and high-pressure steam blowing resistance and the like.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a graphene-doped heat exchanger tube bundle coating and a preparation method thereof.
Background
In the production processes of chemical industry, petroleum industry, metallurgical industry and the like, a hot process medium is often required to be cooled by industrial cooling water, a heat exchanger is one of key devices in the cooling step, and the industrial cooling water indirectly exchanges heat with the process medium through the heat exchanger so as to achieve the purpose of cooling the hot process medium.
The heat exchanger is easy to have the problems of high-temperature corrosion, acid corrosion, abrasion and the like in the using process; and as the industrial cooling water contains a large amount of calcium and magnesium inorganic salts, microorganisms and mould fungi, the tube bundle of the heat exchanger is corroded and scaled, so that the heat exchange efficiency of the heat exchanger is influenced, the service life of the heat exchanger is shortened, production accidents caused by the corrosion and scaling problems of the heat exchanger are countless every year, and huge economic loss is caused.
At present, the heat exchanger is made of carbon steel which is the most widely used and has higher cost performance, so that the heat exchanger tube bundle corrosion prevention made of carbon steel is of great importance; in the cleaning period of the heat exchanger, the tube bundle of the heat exchanger needs to be purged for a long time by using high-temperature high-pressure steam, the working temperature of purging is usually 200-300 ℃, and the steam pressure is 4-8 KG; common epoxy resin can not meet the requirement when the temperature resistance is less than 100 ℃, and Chinese patent with application number of 201410598636.0 discloses an epoxy resin-graphene oxide composite coating and a use method thereof, wherein the main raw materials comprise epoxy resin and graphene oxide; however, the paint in the patent has poor hydrophobicity and temperature resistance, and cannot meet the requirement of 200-300 ℃ high-temperature blowing of a heat exchanger, and a paint which has high-temperature and high-pressure steam blowing resistance, good resistance-reducing and scale-preventing properties and good heat-conducting property is urgently needed in the market.
Disclosure of Invention
In order to solve the problems mentioned in the background art, the invention provides a graphene-doped heat exchanger tube bundle coating and a preparation method thereof, wherein the graphene-doped heat exchanger tube bundle coating is prepared from the following raw materials in parts by mass:
the component A comprises: 35-50 parts of mixed resin, 1.2-8 parts of graphene dispersoid, 30-50 parts of filler, 0.2-2 parts of coupling agent, 0.5-3 parts of thixotropic agent, 0.1-0.5 part of defoaming agent and 10-30 parts of solvent;
the component B comprises: mixing a curing agent;
the mixed resin is mixed resin of novolac epoxy resin and epoxy modified organic silicon resin; (ii) a
The total mass of the component B accounts for 5 to 15 percent of the total mass of the component A.
Further, the coating is prepared from the following raw materials in parts by mass:
the component A comprises: 37-45 parts of mixed resin, 2-6 parts of graphene dispersoid, 35-45 parts of filler, 0.8-1.5 parts of coupling agent, 1-2 parts of thixotropic agent, 0.2-0.4 part of defoaming agent and 15-25 parts of solvent;
the component B comprises: mixing and curing;
the mixed resin is mixed resin of novolac epoxy resin and epoxy modified organic silicon resin;
the total mass of the component B accounts for 8 to 12 percent of the total mass of the component A.
Further, the solid content ratio of the novolac epoxy resin to the epoxy modified organic silicon resin is 1:1-3: 1.
Further, the total mass of the graphene dispersion accounts for 5-20% of the solid content of the mixed resin.
Further, the mixed curing agent is formed by mixing a modified alicyclic amine curing agent and a phenolic aldehyde amine curing agent; the mass ratio of the modified alicyclic amine curing agent to the phenolic aldehyde amine curing agent is 1:1-5: 1.
Further, the thixotropic agent is at least one of polyamide wax, polyethylene wax, organic bentonite and fumed silica.
Further, the filler is at least one of talcum powder, aluminum tripolyphosphate, ferrophosphorus powder, barite powder, sericite and aluminum powder slurry; the coupling agent is a silane coupling agent.
Further, the solvent is at least one of xylene, n-butanol, butyrolactone and epichlorohydrin.
The graphene-doped heat exchanger tube bundle coating provided by the invention has the advantages that the coating has corrosion resistance, hydrophobicity, high-temperature and high-pressure steam blowing resistance and the like under the synergistic effect of the novolac epoxy resin, the epoxy modified organic silicon resin and the graphene dispersoid, the coating can be coated in the heat exchanger tube bundle, the corrosion resistance of the heat exchanger tube bundle can be improved, the generation of scale in a pipeline is reduced, the heat transfer performance is greatly improved, and meanwhile, the coating still has excellent adhesive force under the high-temperature and high-pressure steam blowing condition, is not foamed or fallen off, prolongs the service life of the heat exchanger, and reduces the maintenance cost of enterprises.
The invention also provides a preparation method of the graphene-doped heat exchanger tube bundle coating, which specifically comprises the following steps:
step one, adding the mixed resin, the graphene dispersoid and the coupling agent into a stirrer, and stirring at the rotating speed of 500-1000rpm for 0.5-1 h;
step two, adding the dispersing agent, the filler, the thixotropic agent and the solvent into a stirrer, and stirring at the rotating speed of 2000-3000rpm for 0.5-1.5 h;
step three, adding the filler, the defoaming agent, the solvent and the mixed curing agent into the stirrer, and stirring at the rotating speed of 500-1000rpm for 0.5-1 h;
and step four, curing at room temperature after uniformly stirring to obtain the coating.
Further, the dispersant is a copolymer with an acid group.
The preparation method of the graphene doped heat exchanger tube bundle coating provided by the invention is simple in process, and the graphene doped heat exchanger tube bundle coating prepared by the preparation method has corrosion resistance, hydrophobicity and high temperature resistance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic view of a coating contact angle of a graphene-doped heat exchanger tube bundle coating after 8KG steam purging;
fig. 2 is a schematic illustration of the contact angle of the coating without steam purging.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention more clear and fully described, it is obvious that the described embodiments are a part of the embodiments of the present invention, not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention is further illustrated by the following examples, and Table 1 provides the component A and component B of 5 preferred examples of the invention:
TABLE 1
The technical indexes and the effects of the graphene-doped heat exchanger tube bundle coating tested by each embodiment are shown in table 2:
TABLE 2
The invention provides comparative example 1, the phenolic epoxy resin is used as the coating for testing, and the adhesive force of the coating is 6.5 Mpa; the flexibility test result is 2 mm; the impact resistance test result was 48 cm; the surface drying time is 6h, and the actual drying time is 27 h; the test results of acid resistance and alkali resistance are both 30d foaming and dropping; the water resistance test result shows that the foam and the fall-off are generated at 3 m; after 4-8kg of steam purging, the steel wire falls off and cracks appear for 6 hours; the contact angle test result is 80 degrees; the thermal conductivity was 33W/(mK).
The performance indexes and the standards of the coating provided by the invention are shown in a table 3:
TABLE 3
Note: 30d is 30 days; 3m is 3 months; 6h is 6 hours.
The embodiments are all prepared by the preparation method of the graphene doped heat exchanger tube bundle coating provided by the invention;
the raw materials of each comparative example and each example are the same brand and the same series of products, and have the same experimental environment and experimental conditions;
in each of the above embodiments:
the epoxy value of the novolac epoxy resin is 0.56-0.58mol/100 g, and the solid content is 100%;
the epoxy value of the epoxy modified organic silicon resin is 0.03-0.08mol/100 g, and the solid content is 50%;
the size of the graphene dispersoid is 1-100 mu m, the thickness is 1-2nm, and the solid content is 10%;
the viscosity of the modified alicyclic amine curing agent is 100-600mPa & s, and the amine value is 300-400 mgKOH/g;
the viscosity of the phenolic aldehyde amine curing agent is 800-2000 mPa.s, and the amine value is 400-600 mgKOH/g;
the coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane coupling agent with the trade name of KH 560.
As shown in table 1, the mass ratios of the novolac epoxy resin to the epoxy-modified silicone resin in example 1, example 2, and example 3 are 10:20, 20:20, and 30:20, respectively; the solid content of the novolac epoxy resin is 100%, and the solid content of the epoxy modified organic silicon resin is 50%, and the solid content ratio of the novolac epoxy resin to the epoxy modified organic silicon resin is 1:1, 2:1 and 3:1 respectively; the total mass of the graphene dispersoid accounts for 6.5 percent, 10 percent and 20 percent of the solid content of the mixed resin respectively; the mass ratio of the modified alicyclic amine curing agent to the phenolic aldehyde amine curing agent is 2:1, 3:1 and 4.8:1 respectively.
As shown in Table 2, the performance indexes of the coatings in the examples 1, 2 and 3 reach the standard, and the coatings have good corrosion resistance, hydrophobicity and high-temperature and high-pressure steam blowing resistance.
Comparing example 1 with comparative example 1, the coating in example 1 has good corrosion resistance, hydrophobicity and high temperature and high pressure steam blowing resistance, and all the test indexes of the coating in comparative example 1 can not reach the test standards. Therefore, in order to ensure that the coating has good corrosion resistance, temperature resistance and scale resistance and excellent adhesive force under high-temperature and high-pressure conditions, and the single novolac epoxy resin can not completely meet the use conditions, the invention adopts the technical scheme of mixing and matching the novolac epoxy resin, the epoxy modified organic silicon resin and the graphene dispersoid.
The novolac epoxy resin is cured to form a three-dimensional network structure, so that the crosslinking density of the coating is greatly improved, and the solvent resistance and the water resistance of the coating are enhanced, so that the coating has corrosion resistance; the heat-resistant temperature of the novolac epoxy resin can reach about 200 ℃, but the heat-resistant requirement of a heat exchanger can not be met, and the glass transition temperature and the heat-resistant temperature of the mixed resin are improved through the synergistic effect of the epoxy modified organic silicon resin and the novolac epoxy resin; in addition, the epoxy modified organic silicon resin has the characteristic of surface energy, can play a role in dewatering and prevents scale deposit;
the graphene dispersion has excellent heat dissipation performance and temperature resistance, low expansion coefficient and stable performance under high temperature conditions, and can improve the heat resistance and heat conduction performance of the coating; the graphene dispersoid has a special two-dimensional sheet layered structure, low density and high aspect ratio, has good stability and physical shielding property on water molecules, oxygen and ions, can increase the permeation path of a corrosive medium in a coating like sheet-shaped filler when being used as the filler in a coating, and ensures that the physical shielding property of an organic coating is better, particularly the shielding property on water molecules is extremely strong; and because the surface of the graphene dispersion body is provided with a large number of functional groups such as hydroxyl, carboxyl and the like, the graphene dispersion body can be chemically bonded with a carbon steel substrate, so that the coating still has excellent adhesive force to the carbon steel substrate at high temperature and high pressure without foaming and falling off; in addition, the contact angle of a paint film of the coating is improved by the graphene dispersoid, so that the penetration of water vapor to the interior of the coating is effectively prevented, and the coating has excellent hydrophobic property. The synergistic effect of the novolac epoxy resin, the epoxy modified organic silicon resin and the graphene dispersoid enables the coating to have corrosion resistance, temperature resistance and hydrophobic property.
The mechanical property of a phenolic epoxy resin and epoxy modified organic silicon resin mixed system is poor, the mechanical property of a paint film of the paint can be improved by adopting low-molecular-weight modified alicyclic amine as a curing agent, the crosslinking density is improved, but the drying time is slow, the curing time can be accelerated by adopting phenolic amine curing agent to be compounded with the phenolic amine curing agent, the overall temperature resistance of the paint film of the paint is improved, and the reasonable ratio of the modified alicyclic amine curing agent to the phenolic amine curing agent is 1:1-5: 1; furthermore, the optimal mixing ratio range of the modified alicyclic amine curing agent to the phenolic amine curing agent is 2:1-4:1, the mixed curing agent can ensure that the mechanical property and the temperature resistance of a paint film are optimal by adopting the mixing ratio range, and as can be seen from table 2, the drying time of the examples 1, 2 and 3 which adopt the modified alicyclic amine curing agent and the phenolic amine curing agent provided by the invention as the mixed curing agent is obviously shorter than the 4h and 24h of the test standard, so that the curing efficiency is greatly accelerated.
As shown in table 1, the total mass of the graphene dispersion in examples 4 and 5 accounts for 4% (less than 5%), 25% (more than 20%) of the solid content of the mixed resin, and as shown in table 2, the results of the acid resistance, alkali resistance and water resistance tests of the coatings in examples 4 and 5 do not meet the test standards; therefore, the contact angle of a paint film of the coating can be improved and the surface hydrophobicity of the coating can be increased by adding the graphene dispersion, so that the cooling water in the tube bundle of the heat exchanger can achieve the effect of no residue on the surface of the coating, the generation probability of scale in the tube bundle is effectively reduced, the heat conduction efficiency of the coating is increased, and the heat transfer performance of the heat exchanger is kept excellent. But the addition amount of the graphene dispersoid in the coating and the mixing proportion of the resin are critical, the addition amount of the graphene dispersoid is small, the application effect cannot be reflected, the overall performance of a coating with more addition amount is reduced, the optimal proportion range of the mass of the novolac epoxy resin and the epoxy modified organic silicon resin is 1:1-3:1 by integrating various use conditions of the heat exchanger coating, and the total mass addition range of the graphene dispersoid is 5-20% of the solid content of the mixed resin.
In comparative example 1, the contact angle of the coating without steam blowing (as shown in fig. 2) and the contact angle of the coating after 8KG steam blowing (as shown in fig. 1) are 110.7 degrees, the contact angle of the coating after 8KG steam blowing is 101.5 degrees, the contact angle after blowing is still larger than 100 degrees, and it can be seen that the surface deformation of the coating after high-temperature blowing is small, good hydrophobicity is maintained, and the high-temperature blowing resistance is stable.
The graphene-doped heat exchanger tube bundle coating has the advantages that the coating has corrosion resistance, hydrophobicity, high-temperature and high-pressure steam blowing resistance and the like under the synergistic effect of the novolac epoxy resin, the epoxy modified organic silicon resin and the graphene dispersoid. The graphene-doped heat exchanger tube bundle coating provided by the invention can be applied to a heat exchanger tube bundle, the corrosion resistance of the heat exchanger tube bundle is improved, the generation of scale in a pipeline is reduced, the heat transfer performance is greatly improved, and meanwhile, the graphene-doped heat exchanger tube bundle coating still has excellent adhesive force under the condition of high-temperature and high-pressure steam blowing, does not bubble or fall off, prolongs the service life of a heat exchanger, and reduces the maintenance cost of enterprises.
The prepared graphene-doped heat exchanger tube bundle coating has corrosion resistance, hydrophobicity, high-temperature and high-pressure steam blowing resistance and the like, is used for corrosion prevention in a heat exchanger tube bundle, greatly improves the heat transfer performance of a heat exchanger, reduces the generation of scale in a pipeline, has excellent adhesive force under the condition of high-temperature and high-pressure steam blowing, is not foamed or dropped, prolongs the service life of the heat exchanger, and reduces the maintenance cost of enterprises.
Although terms such as graphene dispersion, novolac epoxy, epoxy modified silicone resin, coupling agent, thixotropic agent, antifoaming agent, modified alicyclic amine curing agent, and phenolic amine curing agent are used more often herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The graphene-doped heat exchanger tube bundle coating is characterized by being prepared from the following raw materials in parts by mass:
the component A comprises: 35-50 parts of mixed resin, 1.2-8 parts of graphene dispersoid, 30-50 parts of filler, 0.2-2 parts of coupling agent, 0.5-3 parts of thixotropic agent, 0.1-0.5 part of defoaming agent and 10-30 parts of solvent;
the component B comprises: mixing a curing agent;
the mixed resin is mixed resin of novolac epoxy resin and epoxy modified organic silicon resin;
the total mass of the component B accounts for 5 to 15 percent of the total mass of the component A;
the mixed curing agent is formed by mixing a modified alicyclic amine curing agent and a phenolic aldehyde amine curing agent; the mass ratio of the modified alicyclic amine curing agent to the phenolic aldehyde amine curing agent is 1:1-5: 1.
2. The graphene doped heat exchanger tube bundle coating according to claim 1, characterized in that: the coating is prepared from the following raw materials in parts by mass:
the component A comprises: 37-45 parts of mixed resin, 2-6 parts of graphene dispersoid, 35-45 parts of filler, 0.8-1.5 parts of coupling agent, 1-2 parts of thixotropic agent, 0.2-0.4 part of defoaming agent and 15-25 parts of solvent;
the component B comprises: mixing a curing agent;
the mixed resin is mixed resin of novolac epoxy resin and epoxy modified organic silicon resin;
the total mass of the component B accounts for 8 to 12 percent of the total mass of the component A.
3. The graphene doped heat exchanger tube bundle coating according to claim 1, characterized in that: the solid content ratio of the novolac epoxy resin to the epoxy modified organic silicon resin is 1:1-3: 1.
4. The graphene doped heat exchanger tube bundle coating according to claim 1, characterized in that: the total mass of the graphene dispersoid accounts for 5-20% of the solid content of the mixed resin.
5. The graphene doped heat exchanger tube bundle coating according to claim 1, characterized in that: the thixotropic agent is at least one of polyamide wax, polyethylene wax, organic bentonite and fumed silica.
6. The graphene doped heat exchanger tube bundle coating according to claim 1, characterized in that: the filler is at least one of talcum powder, aluminum tripolyphosphate, ferrophosphorus powder, barite powder, sericite and aluminum powder slurry; the coupling agent is a silane coupling agent.
7. The graphene doped heat exchanger tube bundle coating according to claim 1, characterized in that: the solvent is at least one of dimethylbenzene, n-butyl alcohol, butyrolactone and epichlorohydrin.
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