CN114075402A - High-temperature-resistant and corrosion-resistant coating for sulfur-containing heat exchanger, preparation method of coating and corrosion-resistant shell-and-tube heat exchanger - Google Patents
High-temperature-resistant and corrosion-resistant coating for sulfur-containing heat exchanger, preparation method of coating and corrosion-resistant shell-and-tube heat exchanger Download PDFInfo
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- 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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- 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
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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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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
- F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
- F28F19/04—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of rubber; of plastics material; of varnish
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to a high-temperature-resistant corrosion-resistant coating for a sulfur-containing heat exchanger, a preparation method thereof and a corrosion-resistant shell-and-tube heat exchanger. The high-temperature-resistant anticorrosive paint mainly comprises a component A and a component B, wherein the component A comprises a paint auxiliary agent, a pigment, a solvent and the following components in parts by weight: 40-75 parts of organic silicon modified epoxy resin, 11-18 parts of nano reinforced anticorrosive filler and 8-20 parts of nano flaky carbon powder; the organic silicon modified epoxy resin is prepared by the reaction of 30-50 parts of linear phenolic epoxy resin and 10-25 parts of organic silicon resin; the nano reinforced anticorrosive filler is prepared by compounding nano titanium dioxide, nano aluminum oxide and nano silicon carbide according to the mass ratio of 1:1: 2; the component B is an organic amine curing agent. The high-temperature-resistant and corrosion-resistant coating has the characteristics of high adhesion, sulfur corrosion resistance, high temperature resistance and high heat conductivity, ensures the long-term safe and stable operation of the sulfur-containing heat exchanger, is cured at normal temperature, is convenient and fast to construct, and has good engineering application value.
Description
Technical Field
The invention belongs to the field of coating compositions with corrosion resistance, and particularly relates to a high-temperature-resistant corrosion-resistant coating for a sulfur-containing heat exchanger, a preparation method thereof, and a corrosion-resistant shell-and-tube heat exchanger.
Background
The heat exchanger is important equipment in the chemical production process of oil and gas fields, accounts for 40% of the total amount of process equipment, and the sulfur-containing heat exchanger mainly exists in a sulfur recovery unit in the purification process of petroleum and natural gas and is an important link in the whole purification process of the natural gas.
The shell-and-tube heat exchanger is generally made of carbon steel, and the tubes (i.e. the heat exchange tube bundle) in the heat exchanger are welded on the tube plate, so that the welding seam has defects of different degrees, such as depression, air holes, slag inclusion and the like, and the stress distribution of the welding seam is not uniform. When the sulfur-containing heat exchanger works, the tube pass is high-temperature process gas (comprising sulfur vapor and H)2S、SO2、CO2、O2And water vapor) with a high shellThe high-temperature process gas brings high-temperature and high-sulfur corrosion working conditions to the boiler water, and the disturbance of the high-pressure boiler water is large during operation. Above-mentioned factor leads to containing sulphur heat exchanger when using, and tube sheet department corrodes often and reveals, and high pressure boiler water gets into the tube side for the liquid sulphur in the tube side solidifies, blocks up the heat exchange tube, causes whole sulphur recovery unit to shut down and overhauls, changes the heat exchanger, and frequent start-stop has increased whole manufacturing cost and operation degree of difficulty, and it more can arouse the damage of other relevant equipment (for example Claus stove) to be in the operation under the corrosion state for a long time. With the improvement of treatment requirements, the specification of the heat exchanger is larger and larger, the requirement of continuous production of equipment is higher and higher, and the existing corrosion prevention design of the heat exchanger cannot meet the requirement.
The Chinese patent with the publication number of CN102964963B discloses an anti-corrosion heat-conducting coating for a heat exchanger and a preparation method thereof, wherein the anti-corrosion heat-conducting coating for the heat exchanger consists of 30-40% of main resin, 40-50% of filler, 0.5-1% of auxiliary agent and 15-25% of diluent, the main resin consists of resin A and resin B according to the mass ratio of 60: 10-80: 10, wherein the resin A is SH-023-7 type organic silicon modified epoxy resin, the resin B is 2130 type phenolic resin, the filler is a mixture of 40-55% of aluminum nitride, 10-15% of glass powder, 15-25% of barium sulfate, 10-15% of titanium dioxide and 15-20%. The heat exchanger coating aims at a conventional heat exchanger, the maximum use temperature is 350 ℃, the adhesive force is required to be grade 1, and the corrosion medium mainly aims at low-concentration acid and alkali (10% sulfuric acid and 10% NaOH).
The working condition of the sulfur-containing heat exchanger is greatly different from that of a conventional heat exchanger, the sulfur-containing heat exchanger requires that the coating still has long-term tolerance to high sulfur-containing gas at the temperature of more than 400 ℃ (even about 800 ℃), can still withstand long-term disturbance of high-pressure boiler water under the condition of ultrahigh temperature, and also provides higher requirements for the coating of the heat exchanger.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant and corrosion-resistant coating for a sulfur-containing heat exchanger, which can be applied to the sulfur-containing heat exchanger, has long-term resistance to high-sulfur-containing gas at the temperature of more than 400 ℃ (even about 800 ℃), and can resist long-term disturbance of high-pressure boiler water.
The second purpose of the invention is to provide a preparation method of the high-temperature-resistant and corrosion-resistant coating for the sulfur-containing heat exchanger.
The third purpose of the invention is to provide an anti-corrosion shell-and-tube heat exchanger, which solves the problem that the existing shell-and-tube heat exchanger has poor corrosion resistance when being applied to a sulfur recovery unit.
In order to achieve the purpose, the technical scheme of the high-temperature-resistant and corrosion-resistant coating for the sulfur-containing heat exchanger is as follows:
a high-temperature-resistant and corrosion-resistant coating for a sulfur-containing heat exchanger mainly comprises a component A and a component B, wherein the component A comprises a coating auxiliary agent, a pigment, a solvent and the following components in parts by weight: 40-75 parts of organic silicon modified epoxy resin, 11-18 parts of nano reinforced anticorrosive filler and 8-20 parts of nano flaky carbon powder;
the organic silicon modified epoxy resin is prepared by the reaction of 30-50 parts of linear phenolic epoxy resin and 10-25 parts of organic silicon resin; the epoxy equivalent of the novolac epoxy resin is 170-190 g/eq;
the nano reinforced anticorrosive filler is prepared by compounding nano titanium dioxide, nano aluminum oxide and nano silicon carbide according to the mass ratio of 0.5-1.5:0.5-1.5: 2-3;
the component B is an organic amine curing agent.
The high-temperature-resistant and corrosion-resistant coating for the sulfur-containing heat exchanger provided by the invention mainly takes cured substances of organic silicon modified epoxy resin and an organic amine curing agent as film-forming substances, takes nano reinforced corrosion-resistant filler and nano flaky carbon powder as functional substances, and the coating prepared by combining the components can resist disturbance of a flowing medium, resist high-temperature and high-sulfur corrosion, has the characteristics of high adhesion, sulfur corrosion resistance, high-temperature resistance and high heat conductivity, ensures long-term safe and stable operation of the sulfur-containing heat exchanger, is cured at normal temperature, is convenient to construct, and has good engineering application value, and the whole heat exchange coefficient is not reduced by more than 5%.
The preparation of the organic silicon modified epoxy resin can refer to the prior art, and the preparation method is mainly characterized in that active groups such as alkoxy, hydroxyl and the like in the organic silicon resin and secondary hydroxyl of the epoxy resin are subjected to condensation reaction to form a graft modified polymer. In order to further optimize the high adhesion and heat resistance of the organosilicon modified epoxy resin, the reaction is preferably completed at the temperature of 150-170 ℃ under the action of a catalyst. The catalyst is dibutyltin dilaurate. When 30-50g of linear phenolic epoxy resin and 10-25g of organic silicon resin are reacted, the dosage of the corresponding catalyst is 0.5 ml.
The linear phenolic epoxy resin is prepared by taking linear phenolic resin and epoxy chloropropane as raw materials and performing polycondensation reaction, and can be classified into phenol type, o-cresol type, bisphenol A type and the like. In order to further improve the sulfur corrosion resistance in consideration of the application scenario of the epoxy linear novolac resin in the sulfur-containing condition, the epoxy linear novolac resin is preferably one or more of F-51, EPN1179 and YDPN-638.
The organic silicon resin is formed by alternately connecting silicon atoms and oxygen atoms to form a framework, and the organic silicon resin is used for modifying the epoxy resin, so that the advantages of the organic silicon resin and the epoxy resin can be integrated, and the adhesive force and the heat resistance of the resin can be further optimized. Preferably, the silicone Resin is one or two of the company rosidi with model numbers of Resin 6405 and Resin 6407.
The organic amine curing agent is a common curing agent of epoxy resin, and is preferably prepared by compounding an aliphatic amine curing agent and a polyamide curing agent according to the mass ratio of 35-50:40-70, and the mass ratio of the organic silicon modified epoxy resin to the organic amine curing agent is 40-75:15-30, in order to improve the heat resistance and the adhesive force of a cured product and meet the requirements of curing at normal temperature. The fatty amine curing agent can be one or two of Basfiaux-1000 and amix-1500. The polyamide curing agent can be selected from one or more of the types of BASF V-125, V-115 and V-140.
In order to further improve the heat resistance of the coating, the pigment is preferably a ceramic pigment, and the addition amount is 5-10 parts. The ceramic pigment is commercially available conventional commercial product, such as one or two of cobalt black-1637 and cobalt black-1612 of Shandong pottery Zheng New Material science and technology Limited.
The selection of the solvent in the coating is not particularly limited, the solvent can have good dissolution or dispersion performance on the raw materials, the volatilization rate is appropriate, for example, xylene and ester solvents can be selected, and in order to further optimize the performance, the solvent is preferably a mixed solvent composed of isobutanol, xylene and diethyl ether according to the mass ratio of 0.5-1.5:2-3: 0.5-1.5. The amount of the solvent in the coating is not particularly limited, and the coating can meet the dispersion requirement, storage requirement and construction requirement of each raw material.
The paint auxiliary agent in the paint component can comprise an anti-settling agent, a dispersing agent, a flatting agent, a defoaming agent, a wetting agent and the like. The amount of each additive in the coating additive can be added according to the recommended amount. The anti-settling agent can be selected from organic bentonite and the like, and in order to facilitate the dispersion of the anti-settling agent, organic bentonite paste can be selected, the organic bentonite paste is prepared from organic bentonite and a solvent, and the mass ratio of the organic bentonite to the solvent can be set to be 1: 3. The addition amount of the organobentonite paste may be set to 5-9 parts.
The total addition amount of the additives such as a dispersant, a leveling agent, a defoaming agent, a wetting agent and the like (except for the anti-settling agent) can be set to 0.5 to 3 parts.
In the high-temperature-resistant and corrosion-resistant coating, components such as a diluent and the like can be added according to the construction method of the coating, so that the construction requirements of brushing and spraying are facilitated, the requirements of various constructions on the diluent and the using amount of the diluent can refer to the related prior art, and detailed description is omitted. In addition, components such as a drier and the like can be added into the coating according to environmental conditions to adjust the curing rate of the coating so as to meet the curing requirements under different conditions.
The preparation method of the high-temperature-resistant and corrosion-resistant coating for the sulfur-containing heat exchanger adopts the technical scheme that:
a preparation method of a high-temperature-resistant and corrosion-resistant coating for a sulfur-containing heat exchanger comprises the following steps: and grinding and dispersing the organic silicon modified epoxy resin, the solvent, the pigment, the nano reinforced anticorrosive filler, the nano flaky carbon powder and the coating auxiliary agent to obtain the paint.
The coating is prepared by mixing, dispersing and packaging corresponding raw materials in the component A and the component B, has the characteristics of normal-temperature curing and easy construction, and is mainly applied to the anticorrosion engineering of sulfur-containing heat exchangers, sulfur-containing storage tanks and equipment in the chemical process of petroleum and natural gas.
The nano reinforced anticorrosive filler is pre-ultrasonically prefabricated, and the ultrasonic prefabrication is an efficient auxiliary dispersion method, and comprises the steps of uniformly mixing the nano reinforced anticorrosive filler with a solvent, adjusting the pH value to 3-5, performing ultrasonic treatment, separating and drying to obtain the nano reinforced anticorrosive filler. Preferably, the nano titanium dioxide, the nano alumina and the nano silicon carbide are respectively treated, and then all nano fillers (the nano titanium dioxide, the nano alumina and the nano silicon carbide) prefabricated by an ultrasonic method are uniformly mixed.
The ultrasonic treatment temperature is 50-70 deg.C, and the treatment time is 90-120 min. The ultrasonic treatment is 90-120W. The solvent can be ethanol water solution, and the volume ratio of water to ethanol in the ethanol water solution is preferably 40-50: 20. The surface of each nano filler can be further activated by adopting ultrasonic treatment, so that the dispersion effect of the nano reinforced anticorrosive filler in the coating is optimized.
When the nano titanium dioxide is prefabricated by an ultrasonic method, the temperature is 50 ℃, and the processing time is 100 min. When the nano alumina is prefabricated, the temperature is 70 ℃, and the treatment time is 90 min. When the nano silicon carbide is prefabricated, the temperature is 60 ℃, and the treatment time is 120 min.
In order to further improve the uniformity of the coating, the coating is ground and dispersed until the fineness is below 50 mu m.
When the paint is prepared, the organosilicon modified epoxy resin, the mixed solvent and various auxiliaries can be uniformly dispersed at the speed of less than 1500rad/min, the dispersion time is 30-40 minutes, cooling circulating water is added to keep the temperature of the system to be not more than 55 ℃, the system is uniformly dispersed and then transferred into a small horizontal grinder, the ceramic pigment, the nano reinforced anticorrosive filler, the nano flaky carbon powder and the organic bentonite paste are respectively added to be mixed and ground, the mixture is ground and dispersed to be less than 50 mu m, and the paint is prepared by filtering, weighing and packaging.
The technical scheme of the corrosion-resistant shell-and-tube heat exchanger is as follows:
an anti-corrosion shell-and-tube heat exchanger comprises a heat exchanger shell, a tube plate and a tube bundle, wherein the tube bundle is welded on the tube plate, a high-temperature-resistant anti-corrosion coating is coated on the welding position of the tube plate and the tube bundle or on the tube plate, and the high-temperature-resistant anti-corrosion coating is obtained by curing the high-temperature-resistant anti-corrosion coating for the sulfur-containing heat exchanger.
The welding positions of the tube plate and the tube bundle often have defects of different degrees, such as pits, air holes, slag inclusion and the like, and the distribution of the welding line stress is not uniform. In addition, the disturbance of the shell-side boiler water causes the greatest corrosion risk at the welding position, and the high-temperature-resistant and corrosion-resistant coating is used for coating and protecting the welding position, so that the tube plate can be prevented from being corroded and damaged, and the long-term safe and stable operation of the sulfur-containing heat exchanger is ensured.
It is easy to understand that for the convenience of construction and the improvement of the overall corrosion resistance of the equipment, the parts of the equipment which are in contact with the sulfur-containing high-temperature process gas can be coated with the coating, thereby enhancing the tolerance of the equipment to sulfur-containing media.
Drawings
FIG. 1 is a photograph of a coated test plate prepared from the high temperature and corrosion resistant coating of example 1 of the present invention, wherein the left side is the test plate before testing, and the right side is the test plate placed at 400 ℃ for 800 hours;
FIG. 2 is a photograph of a test plate prepared from the high temperature and corrosion resistant coating of example 2 according to the present invention;
FIG. 3 is a photograph of a drawdown adhesion test of a coated test plate prepared from the high temperature and corrosion resistant coating of example 2 of the present invention;
FIG. 4 is a microstructure diagram of a coated test plate prepared from the high temperature and corrosion resistant coating of example 3 of the present invention before high temperature treatment at 240 ℃;
FIG. 5 is a microstructure diagram of a coated test plate prepared from the high temperature and corrosion resistant coating of example 3 of the present invention after high temperature treatment at 240 ℃;
FIG. 6 is a microstructure diagram of a coated test plate prepared from the high temperature and corrosion resistant coating of example 3 of the present invention before high temperature treatment at 400 ℃;
FIG. 7 is a microstructure diagram of a coated test plate prepared from the high temperature and corrosion resistant coating of example 3 of the present invention after a high temperature treatment at 400 ℃.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings and specific examples.
In the following examples, the types and manufacturers of the main raw materials are listed in table 1.
TABLE 1 type and manufacturer of the main raw materials
| Serial number | Type (B) | Model number | Manufacturer of the |
| 1 | Epoxy resin | F-51 | Hua |
| 2 | Silicone resin | Resin 6405 | Root of Rodiya |
| 3 | Polyamide curing agent | V125 | Basf-Fr |
| 4 | Aliphatic amine curing agent | amix-1500 | Basf-Fr |
| 5 | Ceramic materialPigment (I) | Cobalt black-1637 | Shandong pottery zheng |
| 6 | Dispersing agent | BYK-940 | German bike |
| 7 | Defoaming agent | BYK-065 | German bike |
| 8 | Wetting agent | BYK-7410ET | German bike |
The organobentonite paste is prepared by dispersing 2g of organobentonite in 6mL of solvent. The solvent is xylene.
The nano reinforced anticorrosive filler is prepared by compounding nano titanium dioxide, nano aluminum oxide and nano silicon carbide according to the mass ratio of 1:1: 2. The particle size of the nano titanium dioxide is 5-20 nm; the grain size of the nano alumina is 10-40 nm; the grain size of the nanometer silicon carbide is 10-40 nm. The specific operation of the ultrasonic prefabrication is a preparation method of the nano titanium dioxide: respectively weighing 50mL of distilled water and 20mL of absolute ethyl alcohol, uniformly mixing in a 250mL beaker, adjusting the pH of the solution to 4 by using dilute hydrochloric acid, putting the solution into an ultrasonic reactor, slowly adding 20g of titanium dioxide powder into the solution, starting ultrasonic treatment, setting the temperature at 50 ℃, treating for 100min, cooling, drying and packaging to obtain the nano TiO2. The ultrasonic preparation method of the nano aluminum oxide and the nano silicon carbide is the same as the steps of the nano titanium dioxide, and the difference is that the ultrasonic temperature of the nano aluminum oxide is set to be 70 ℃, and the processing time is 90 min; nano carbonThe ultrasonic temperature of the silicon is set to be 60 ℃ and the processing time is 120 min.
The mixed solvent is prepared by mixing isobutanol, xylene and diethyl ether according to the mass ratio of 1:2: 1.
First, specific examples of the high temperature and corrosion resistant coating for a sulfur-containing heat exchanger of the present invention
Example 1
The high-temperature-resistant and corrosion-resistant coating for the sulfur-containing heat exchanger in the embodiment comprises a component A and a component B, wherein the proportion of each raw material in the component A is shown in Table 2.
TABLE 2 formulation composition of the A component in the coating of example 1
And B component: 65% of polyamide curing agent and 35% of fatty amine curing agent.
The product of example 1 is a two-component product, which is formulated for use at a specified ratio of a: B to 100: 15.
Example 2
The high-temperature-resistant and corrosion-resistant coating for the sulfur-containing heat exchanger in the embodiment comprises a component A and a component B, wherein the proportion of each raw material in the component A is shown in Table 3.
TABLE 3 formulation composition of A component in the coating of example 2
And B component: 50% of polyamide curing agent and 50% of fatty amine curing agent.
The product of example 2 is a two-component product, which is formulated for use at a specified ratio of a: B to 100: 20.
Example 3
The high-temperature-resistant and corrosion-resistant coating for the sulfur-containing heat exchanger in the embodiment comprises a component A and a component B, wherein the proportion of each raw material in the component A is shown in Table 4.
Table 4 formulation composition of the a component in the coating of example 3
And B component: 50% of polyamide curing agent and 50% of fatty amine curing agent.
The product of example 3 is a two-component product, which is formulated for use at a specified ratio of a: B to 100: 25.
Second, specific examples of the preparation method of the high temperature and corrosion resistant coating for a sulfur-containing heat exchanger of the present invention
Example 4
The preparation method of the high-temperature-resistant and corrosion-resistant coating for the sulfur-containing heat exchanger in this embodiment is described in the preparation of the coating in example 1, and the preparation of the component a specifically includes the following steps:
1) adding 20g of organic silicon resin, 30g of epoxy resin and 8g of mixed solvent into a four-neck flask provided with a stirrer, a thermometer and a condensation reflux device, heating and uniformly stirring, adding a catalyst (specifically dibutyltin dilaurate with the addition of 0.5ml) when the temperature is increased to 80 ℃, stirring and heating to 150 ℃ for reflux reaction, and after the reaction is carried out for 5 hours, cooling, filtering and packaging to obtain the organic silicon modified epoxy resin.
2) Uniformly dispersing the organic silicon modified epoxy resin and various auxiliaries at 1000rad/min for 30 minutes, adding cooling circulating water to keep the temperature of the system not to exceed 55 ℃, uniformly dispersing, transferring into a small horizontal grinder, respectively adding ceramic pigment, nano reinforced anticorrosive filler, nano flaky carbon powder and organic bentonite paste, mixing and grinding together, grinding and dispersing to below 50 micrometers, filtering, weighing and packaging.
Preparation of the component B: adding the aliphatic amine curing agent and the polyamide curing agent into a mixing tank according to the mass ratio of 0.35:0.65, maintaining the dispersion for 10min at 500rad/min, and canning after uniform dispersion.
Example 5
The preparation of the high temperature and corrosion resistant coating for a sulfur-containing heat exchanger of this example is described with reference to the method of example 4 for the preparation of the coating of example 2, except that:
in the step 1), the dosage of the miscible solvent is 8g, the reflux reaction temperature is 160 ℃, and the reaction time is 4 h.
When the component B is prepared, the aliphatic amine curing agent and the polyamide curing agent are added into a mixing tank according to a proportion, the mixture is dispersed for 10min under the condition of keeping 500rad/min, and the mixture is canned after being uniformly dispersed.
Example 6
The preparation of the high temperature and corrosion resistant coating for sulfur-containing heat exchanger of this example is described in example 3 with reference to the method of example 4, except that:
in the step 1), the dosage of the miscible solvent is 11g, the reflux reaction temperature is 170 ℃, and the reaction time is 3.5 h.
When the component B is prepared, the aliphatic amine curing agent and the polyamide curing agent are added into a mixing tank according to a proportion, the mixture is dispersed for 10min under the condition of keeping 500rad/min, and the mixture is canned after being uniformly dispersed.
Third, embodiments of the corrosion-resistant shell-and-tube heat exchanger of the present invention
Example 7
The anti-corrosion shell-and-tube heat exchanger comprises a heat exchanger shell, a tube plate and a tube bundle, wherein the tube plate and the tube bundle are arranged in the heat exchanger shell, the tube bundle is welded on the tube plate, a high-temperature-resistant anti-corrosion coating is coated at the welding position of the tube plate and the tube bundle, and the high-temperature-resistant anti-corrosion coating is obtained by curing the high-temperature-resistant anti-corrosion coating in the embodiment 1. The thickness of the high temperature and corrosion resistant coating is 300 μm.
Example 8
The difference between the corrosion-resistant shell-and-tube heat exchanger of this example and example 7 is that a high temperature and corrosion resistant coating is applied to the tube sheet as a whole, including the welding position of the tube sheet to the tube bundle. The thickness of the high temperature and corrosion resistant coating is 400 μm.
When the shell-and-tube heat exchanger is applied to a plain gas field of a central oil field, the specification of the shell-and-tube heat exchanger is a final-stage sulfur condenser E-307 with the equipment name and the size
(horizontal), the equipment volume tube pass is 60.1m3Shell side 22.9m3The operating pressure tube side is 0.028MPa and the shell side is 5.397MPa, and the device belongs to large-scale sulfur-containing heat exchange equipment, and the temperature of high-temperature process gas of the tube side is 130-140 ℃, and comprises sulfur vapor and H2S、SO2、CO2、O2And steam, the sulfurous acid corrosion is serious, the shell side is high-pressure boiler water, and the disturbance of a flowing medium is large.
Before anticorrosion measures are not taken, the welding part of the tube pass of the sulfur condenser and the tube plate is often seriously corroded and leaked after use, the corrosion part of a base material has problems of pitting corrosion, perforation and the like, and after the base material is used for 2 years, equipment shutdown caused by corrosion does not occur.
Fourth, test example
Test example 1
The test examples tested the performance indexes of the high temperature and corrosion resistant coatings of examples 1-3, and the results are shown in tables 5 and 6.
TABLE 5 table of physico-mechanical properties of the high temperature and corrosion resistant coatings of the examples
TABLE 6 Medium-resistant Property Table
From the test results in tables 5 and 6, the high-temperature-resistant and corrosion-resistant coating of the embodiment has the characteristics of high adhesion, sulfur corrosion resistance, high temperature resistance and high heat conductivity, is convenient and fast to construct, and can achieve the effects of one-time construction and long-acting protection.
The high temperature and corrosion resistant coating of example 1 was prepared into a high temperature and corrosion resistant coating layer having a thickness of 300 μm, and the temperature resistance thereof was measured, and the results are shown in fig. 1. As can be seen from FIG. 1, after being placed at 400 ℃ for 800h, the coating has a smooth appearance and no peeling or peeling phenomenon.
The photographs of the adhesion test by the circling method and the drawing method of the coating prepared from the high temperature resistant and corrosion resistant coating of example 2 after high temperature (400 ℃, 800h) treatment are respectively shown in fig. 2 and fig. 3. As can be seen from FIGS. 2 and 3, the adhesion of the coating is very excellent, and the application requirements of large-size, high-temperature and large-flow medium disturbance sulfur-containing heat exchangers can be met.
The microstructure of the coating prepared by the high-temperature-resistant and corrosion-resistant coating in example 3 is shown in fig. 4-5 before and after the coating is subjected to heat preservation at 240 ℃ for 1200h, and the microstructure of the coating after the coating is subjected to heat preservation at 400 ℃ for 800h is shown in fig. 6-7.
In other embodiments of the high-temperature-resistant and corrosion-resistant coating for the sulfur-containing heat exchanger, F-51 novolac epoxy resin can be replaced by EPN1179 and YDPN-638 resin with similar components and properties according to example 1; resin 6405 can be replaced by Resin 6407 with similar components and properties; the fatty amine curing agent can be selected from amix-1000, and the polyamide curing agent can be selected from V-115, V-140 and the like, which can achieve the temperature resistance and corrosion prevention effects equivalent to those of the embodiment 1.
Claims (10)
1. The high-temperature-resistant and corrosion-resistant coating for the sulfur-containing heat exchanger is characterized by mainly comprising a component A and a component B, wherein the component A comprises a coating auxiliary agent, a pigment, a solvent and the following components in parts by weight: 40-75 parts of organic silicon modified epoxy resin, 11-18 parts of nano reinforced anticorrosive filler and 8-20 parts of nano flaky carbon powder;
the organic silicon modified epoxy resin is prepared by the reaction of 30-50 parts of linear phenolic epoxy resin and 10-25 parts of organic silicon resin; the epoxy equivalent of the novolac epoxy resin is 170-190 g/eq;
the nano reinforced anticorrosive filler is prepared by compounding nano titanium dioxide, nano aluminum oxide and nano silicon carbide according to the mass ratio of 0.5-1.5:0.5-1.5: 2-3;
the component B is an organic amine curing agent.
2. The high temperature and corrosion resistant coating for sulfur-containing heat exchangers of claim 1 wherein the reaction is completed at 150 ℃ and 170 ℃ under the action of a catalyst.
3. The high temperature and corrosion resistant coating for a sulfur containing heat exchanger of claim 1 wherein said novolac epoxy resin is one or more of F-51, EPN1179, YDPN-638.
4. The high temperature and corrosion resistant coating for sulfur-containing heat exchangers of claim 1 wherein the silicone Resin is one or both of Resin 6405 and Resin 6407, manufactured by rolia.
5. The high-temperature-resistant and corrosion-resistant coating for the sulfur-containing heat exchanger as claimed in any one of claims 1 to 4, wherein the organic amine curing agent is prepared by compounding an aliphatic amine curing agent and a polyamide curing agent according to a mass ratio of 35-50:40-70, and the mass ratio of the organosilicon modified epoxy resin to the organic amine curing agent is 40-75: 15-30.
6. The high-temperature-resistant and corrosion-resistant coating for a sulfur-containing heat exchanger as claimed in any one of claims 1 to 4, wherein the pigment is a ceramic pigment and is added in an amount of 5 to 10 parts.
7. The high-temperature-resistant and corrosion-resistant coating for the sulfur-containing heat exchanger as claimed in any one of claims 1 to 4, wherein the solvent is a mixed solvent of isobutanol, xylene and diethyl ether in a mass ratio of 0.5-1.5:2-3: 0.5-1.5.
8. A method for preparing a high-temperature-resistant and corrosion-resistant coating for a sulfur-containing heat exchanger as claimed in any one of claims 1 to 7, comprising the steps of: and grinding and dispersing the organic silicon modified epoxy resin, the solvent, the pigment, the nano reinforced anticorrosive filler, the nano flaky carbon powder and the coating auxiliary agent to obtain the paint.
9. The method for preparing the high-temperature-resistant and corrosion-resistant coating for the sulfur-containing heat exchanger according to claim 8, wherein the nano reinforced corrosion-resistant filler is pre-ultrasonically prefabricated, and the ultrasonic prefabrication comprises the steps of uniformly mixing the nano reinforced corrosion-resistant filler and a solvent, adjusting the pH value to 3-5, ultrasonically treating, separating and drying.
10. An anti-corrosion shell-and-tube heat exchanger comprising a heat exchanger shell, a tube sheet and a tube bundle, the tube bundle being welded to the tube sheet, characterized in that a high temperature and corrosion resistant coating is applied on the tube sheet or on the welding position of the tube sheet and the tube bundle, said high temperature and corrosion resistant coating being obtained by curing a high temperature and corrosion resistant coating for a sour heat exchanger according to any one of claims 1 to 7.
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