CN111253858A - Nano hybrid heavy-duty anticorrosive material and preparation method and application thereof - Google Patents
Nano hybrid heavy-duty anticorrosive material and preparation method and application 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
- 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
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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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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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a nano hybrid heavy-duty anticorrosive material and a preparation method and application thereof, wherein the nano hybrid heavy-duty anticorrosive material is prepared from the following raw materials in parts by weight: 1-2 parts of organic silicon resin; 1-2 parts of fluororesin; 2-4 parts of inorganic nano ceramic material; 0.01-0.05 part of graphene material. The preparation method comprises the steps of mixing fluororesin and organic silicon resin for reaction to prepare modified nano organic silicon fluororesin base material, fusing the inorganic nano ceramic material and the graphene material to form a nano hybrid composite material, and then uniformly mixing the nano organic silicon fluororesin base material and the nano hybrid composite material for reaction to prepare the nano hybrid heavy anti-corrosion material. The nano hybrid heavy-duty anticorrosive material prepared by the invention has good performances of high temperature resistance, wear resistance, corrosion resistance and the like, is convenient to construct, can effectively replace the traditional ceramic tile masonry anticorrosive method, and can be widely applied to high-temperature concentrated sulfuric acid tower equipment.
Description
Technical Field
The invention relates to an anticorrosive material, in particular to a nano hybrid heavy anticorrosive material, a preparation method of the nano hybrid heavy anticorrosive material, and application of the nano hybrid heavy anticorrosive material.
Background
The drying tower and the absorption tower in the production process of sulfuric acid are important equipment of a dry absorption working section, the daub jointing of the acid-resistant ceramic tiles lined in the carbon steel shell is traditionally adopted, the structure is very heavy, a huge foundation is needed, the construction is complex, the manufacturing working period is long, the cost is high, the dry absorption tower adopting special stainless steel to replace the acid-resistant ceramic tiles lined in the steel shell is small and exquisite, the huge and heavy foundation is not needed, the manufacturing working period is short, the installation is simple and convenient, the operation is reliable, the service life is long, and the dry absorption tower is an important technology for updating and transforming the sulfuric acid industrial equipment.
At present, the corrosion prevention of the acid tower is mainly two methods of traditional ceramic tile masonry or foreign acid-resistant alloy, and the development and application of the foreign high-temperature concentrated sulfuric acid high-silicon austenitic stainless steel begin in the 80 th generation of the 20 th century. The research and development of domestic high-silicon austenitic stainless steel for high-temperature concentrated sulfuric acid starts from the end of 80 years in the 20 th century, plates for the high-temperature concentrated sulfuric acid are successfully developed in 2002, XDS-1 pipes of various specifications are successfully developed in the near future, and the high-silicon austenitic stainless steel is successfully used for manufacturing sulfuric acid production equipment such as a dry absorption tower, an acid tank, a valve, a pipeline, a pipe-tank type acid distributor, a filler support grate plate in the tower and the like.
In the prior art, due to the characteristics of molecular structures, the compatibility of a plurality of organic synthetic resins and silicone resin is poor, the common physical blending method cannot achieve the expected modification effect, and the organic polymer has the advantages of good film forming property, good flexibility, high air permeability and the like, but has poor mechanical strength, solvent resistance, corrosion resistance and heat resistance; the inorganic material has the advantages of high mechanical strength, wear resistance, corrosion resistance, solvent resistance, high temperature resistance and the like, but is brittle, difficult to process and poor in film forming property.
In the construction of foreign projects, the construction quality and the construction period have great influence on the engineering, and the anticorrosion masonry in the construction of sulfuric acid production equipment is a link which is not easy to control the construction quality and has a long period.
Disclosure of Invention
The invention mainly aims to overcome the technical defects, provides a nano hybrid heavy-duty anticorrosive material, also provides a preparation method of the nano hybrid heavy-duty anticorrosive material, and also provides application of the nano hybrid heavy-duty anticorrosive material in sulfuric acid production equipment.
In order to realize the purpose of the invention, the following technical scheme is adopted:
the invention provides a nano hybrid heavy-duty anticorrosive material which is prepared from the following raw materials in parts by weight:
silicone resin: 1-2 parts;
fluorine resin: 1-2 parts;
inorganic nano-ceramic material: 2-4 parts;
graphene material: 0.01-0.05 part;
wherein, the organic silicon resin and the fluororesin are prepared into a modified organic silicon fluororesin base material; the inorganic nano ceramic material and the graphene material are fused to form a nano hybrid composite material, and the nano organic silicon fluororesin base material and the nano hybrid composite material are mixed and reacted to prepare the nano hybrid heavy anti-corrosion material.
Inorganic nanoceramic materials (also called "nanoceramic powders") have the following characteristics: the rigidity is good, the hardness is high, and the compressive strength is high; (2) has a high melting point (mostly above 2000 ℃) and excellent chemical stability at high temperatures; (3) is not easy to oxidize at high temperature and has good corrosion resistance to acid, alkali and salt.
Graphene is one of the materials with the highest known strength, has good toughness and can be bent, the theoretical Young modulus of the graphene reaches 1.0TPa, and the inherent tensile strength is 130 GPa. The chemical property of the graphene is similar to that of graphite, and the graphene can adsorb and desorb various atoms and molecules, so that the graphene can be fused with an inorganic nano ceramic material to form a nano hybrid composite material.
The organic silicon resin can be selected from 1053 organic silicon resin of Shenzhen Jipeng silicon fluorine material Co. The fluororesin may be fluororesin (CAS No.9010-75-7) from Hebei Hengjing chemical Co., Ltd.
The organic silicon resin is polyorganosiloxane with a highly cross-linked network structure, so the organic silicon resin is also called polysiloxane, and preferably the organic silicon resin is at least one of methyl trichlorosilane, dimethyl dichlorosilane, phenyl trichlorosilane, diphenyl dichlorosilane and methyl phenyl dichlorosilane. When the organic silicon resin is a mixture of two or more substances, the proportion of each substance can be randomly matched.
Preferably, the fluororesin is at least one of Polytetrafluoroethylene (PTFE), Polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF). When the fluororesin is a mixture of two or more substances, the proportions of the substances can be freely matched.
The invention also provides a preparation method of the nano hybrid heavy anti-corrosion material, which comprises the steps of mixing fluorine resin and organic silicon resin for reaction to prepare a modified nano organic silicon fluororesin base material, fusing an inorganic nano ceramic material and a graphene material to form a nano hybrid composite material, and then uniformly mixing the nano organic silicon fluororesin base material and the nano hybrid composite material for reaction to prepare the nano hybrid heavy anti-corrosion material.
Firstly, the organic silicon resin is modified by the fluororesin, the C-F bond energy in the fluororesin is higher, the fluorine-containing polymer molecules are rod-shaped carbon-carbon bonds and are easy to converge on the molecular level, and fluorine atoms can generate a molecular rearrangement phenomenon when forming a film on the polymer and are distributed on the surface of the resin, so that the surface energy of the coating is obviously reduced, and the coating can be endowed with excellent stability, weather resistance and acid and alkali resistance; the excellent solvent resistance of the fluororesin is combined with the high temperature resistance of the organic silicon resin to prepare an anticorrosive base material-nano organic silicon fluororesin base material with good performance; then adding a nano hybrid composite material obtained by fusing an inorganic nano ceramic material and a graphene material, and connecting organic molecules and inorganic molecules by adopting an organic-inorganic hybrid reaction to prepare a nano hybrid heavy-duty anticorrosive material with good high temperature resistance, wear resistance, corrosion resistance and other properties;
preferably, the preparation method of the nano hybrid heavy anti-corrosion material comprises the following steps:
a: adding the organic silicon resin and the fluororesin into a reaction kettle, and continuously stirring;
b: the temperature of the reaction kettle is increased to 80-120 ℃, the reaction time is 6-10h, and the modified nano organic silicon fluororesin base material is prepared after the reaction is finished;
c: fusing an inorganic nano ceramic material and a graphene material in a melting mode to form a nano hybrid composite material;
d: adding the nano hybrid composite material into a reaction kettle, and continuously stirring;
e: the temperature of the reaction kettle is increased to 100 ℃ and 150 ℃, the reaction time is 6-12h, and the nano organic silicon fluororesin base material in the reaction kettle is fully reacted with the nano hybrid composite material;
f: and cooling to room temperature, and filtering to remove impurities to obtain the nano hybrid heavy anticorrosive material.
The invention also provides application of the nano hybrid heavy anti-corrosion material, wherein the nano hybrid heavy anti-corrosion material is applied to high-temperature concentrated sulfuric acid tower equipment, and the nano hybrid heavy anti-corrosion material is sprayed in the high-temperature concentrated sulfuric acid tower equipment in a spraying and microwave high-temperature curing mode.
The invention has the beneficial technical effects that:
according to the nano hybrid heavy-duty anticorrosive material provided by the invention, the nano hybrid heavy-duty anticorrosive material is sprayed in corresponding equipment in a spraying, baking and curing mode, the construction operation is simple, the control is easy, the construction period is short, the nano organic silicon fluorine resin base material obtained by modifying organic silicon resin by fluorine resin combines the advantages of fluorine resin and organic silicon resin, the performance is stable, and then the nano hybrid composite material is added, organic molecules and inorganic molecules are connected by adopting organic-inorganic hybrid reaction, so that the nano hybrid heavy-duty anticorrosive material prepared from the high-temperature-resistant and corrosion-resistant nano anticorrosive material has the characteristics of stable quality, wear resistance and long service life.
The nano hybrid heavy-duty anticorrosive material provided by the invention has good performances of high temperature resistance, wear resistance, corrosion resistance and the like, can be sprayed, baked and cured, is convenient to construct, can effectively replace the traditional tile building anticorrosive method, and can be widely applied to high-temperature concentrated sulfuric acid tower equipment.
Detailed Description
In order to make the technical solutions of the present invention more clear and definite for those skilled in the art, the present invention is further described in detail with reference to the following examples, but the embodiments of the present invention are not limited thereto.
Example one
A nanometer hybrid heavy-duty anticorrosive material is prepared from the following raw materials in parts by weight:
silicone resin: 1 part;
fluorine resin: 1 part;
inorganic nano-ceramic material: 2 parts of (1);
graphene material: 0.01 part;
wherein, the organic silicon resin and the fluororesin are prepared into a modified organic silicon fluororesin base material; the inorganic nano ceramic material and the graphene material are fused to form a nano hybrid composite material, and the nano organic silicon fluororesin base material and the nano hybrid composite material are mixed and reacted to prepare the nano hybrid heavy anti-corrosion material.
The organic silicon resin is at least one of methyl trichlorosilane, dimethyl dichlorosilane, phenyl trichlorosilane, diphenyl dichlorosilane and methyl phenyl dichlorosilane. When the organic silicon resin is a mixture of two or more substances, the proportion of each substance can be freely matched. The fluororesin is at least one of Polytetrafluoroethylene (PTFE), Polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF). When the fluororesin is a mixture of two or more substances, the proportions of the substances can be freely matched.
Example two:
a nanometer hybrid heavy-duty anticorrosive material is prepared from the following raw materials in parts by weight:
silicone resin: 1.2 parts;
fluorine resin: 1.5 parts;
inorganic nano-ceramic material: 2.6 parts;
graphene material: 0.01-0.03 part;
wherein, the organic silicon resin and the fluororesin are prepared into a modified organic silicon fluororesin base material; the inorganic nano ceramic material and the graphene material are fused to form a nano hybrid composite material, and the nano organic silicon fluororesin base material and the nano hybrid composite material are mixed and reacted to prepare the nano hybrid heavy anti-corrosion material.
The organic silicon resin is at least one of methyl trichlorosilane, dimethyl dichlorosilane, phenyl trichlorosilane, diphenyl dichlorosilane and methyl phenyl dichlorosilane. When the organic silicon resin is a mixture of two or more substances, the proportion of each substance can be freely matched. The fluororesin is at least one of Polytetrafluoroethylene (PTFE), Polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF). When the fluororesin is a mixture of two or more substances, the proportions of the substances can be freely matched.
EXAMPLE III
A nanometer hybrid heavy-duty anticorrosive material is prepared from the following raw materials in parts by weight:
silicone resin: 1.8 parts;
fluorine resin: 2 parts of (1);
inorganic nano-ceramic material: 3.7 parts;
graphene material: 0.04 parts;
wherein, the organic silicon resin and the fluororesin are prepared into a modified organic silicon fluororesin base material; the inorganic nano ceramic material and the graphene material are fused to form a nano hybrid composite material, and the nano organic silicon fluororesin base material and the nano hybrid composite material are mixed and reacted to prepare the nano hybrid heavy anti-corrosion material.
The organic silicon resin is at least one of methyl trichlorosilane, dimethyl dichlorosilane, phenyl trichlorosilane, diphenyl dichlorosilane and methyl phenyl dichlorosilane. When the organic silicon resin is a mixture of two or more substances, the proportion of each substance can be freely matched. The fluororesin is at least one of Polytetrafluoroethylene (PTFE), Polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF). When the fluororesin is a mixture of two or more substances, the proportions of the substances can be freely matched.
Example four:
a nanometer hybrid heavy-duty anticorrosive material is prepared from the following raw materials in parts by weight:
silicone resin: 2 parts of (1);
fluorine resin: 2 parts of (1);
inorganic nano-ceramic material: 4 parts of a mixture;
graphene material: 0.05 part;
wherein, the organic silicon resin and the fluororesin are prepared into a modified organic silicon fluororesin base material; the inorganic nano ceramic material and the graphene material are fused to form a nano hybrid composite material, and the nano organic silicon fluororesin base material and the nano hybrid composite material are mixed and reacted to prepare the nano hybrid heavy anti-corrosion material.
The organic silicon resin is at least one of methyl trichlorosilane, dimethyl dichlorosilane, phenyl trichlorosilane, diphenyl dichlorosilane and methyl phenyl dichlorosilane. When the organic silicon resin is a mixture of two or more substances, the proportion of each substance can be freely matched. The fluororesin is at least one of Polytetrafluoroethylene (PTFE), Polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF). When the fluororesin is a mixture of two or more substances, the proportions of the substances can be freely matched.
The performance of the nano hybrid heavy anti-corrosion material of the above four groups of embodiments is detected to obtain the following detection results:
1. adhesion (cross-hatch method): grade 1;
2. coating impact strength (GB/T1732-93): not less than 3;
3. ultraviolet accelerated aging (ISO11507-2007)2000 h: no change is made;
4. the chemical resistance of the coating film (GB/T1763-79) is 10 percent of H2SO 4500 d; 10% NaOH 500 d; 5% NaCl500 d: the film coating is complete and unchanged;
5. salt spray resistance (GB/T1771-91) 15% NaCl 4000 h: there was no change.
In addition, the detection result of the application of the nano hybrid heavy anti-corrosion material on the experimental sample plate is as follows:
1. the temperature of 500 ℃ in a muffle furnace is kept for 12 hours, and the surface of the material is unchanged;
2. the mixture is boiled at the acid temperature of 110 ℃ for 24 hours, and the surface of the mixture is not changed;
3. the concentration of H2SO4 is 90-99% at 80-120 deg.C in sulfuric acid absorption tower, and the sample is hung without change for one month.
A preparation method of a nanometer hybrid heavy-duty anticorrosive material comprises the steps of mixing fluororesin and organic silicon resin for reaction to obtain a modified nanometer organic silicon fluororesin base material, fusing an inorganic nanometer ceramic material and a graphene material to form a nanometer hybrid composite material, and then uniformly mixing the nanometer organic silicon fluororesin base material and the nanometer hybrid composite material for reaction to obtain the nanometer hybrid heavy-duty anticorrosive material.
As a preferable scheme, the preparation method of the nano hybrid heavy anti-corrosion material comprises the following steps:
a: adding the organic silicon resin and the fluororesin into a reaction kettle, and continuously stirring;
b: the temperature of the reaction kettle is increased to 80-120 ℃, the reaction time is 6-10h, and the modified nano organic silicon fluororesin base material is prepared after the reaction is finished;
C. fusing an inorganic nano ceramic material and a graphene material in a melting mode to form a nano hybrid composite material;
d: adding the nano hybrid composite material into a reaction kettle, and continuously stirring;
e: the temperature of the reaction kettle is increased to 100 ℃ and 150 ℃, the reaction time is 6-12h, and the nano organic silicon fluororesin base material in the reaction kettle is fully reacted with the nano hybrid composite material;
f: and cooling to room temperature, and filtering to remove impurities to obtain the nano hybrid heavy anticorrosive material.
As a preferential scheme, the preparation method of the nano hybrid heavy anti-corrosion material comprises the following steps:
a: adding the organic silicon resin and the fluororesin into a reaction kettle, and continuously stirring;
b: the temperature of the reaction kettle is raised to 110 ℃, the reaction time is 8 hours, and the modified nano organic silicon fluororesin base material is prepared after the reaction is finished;
C. fusing an inorganic nano ceramic material and a graphene material in a melting mode to form a nano hybrid composite material;
d: adding the nano hybrid composite material into a reaction kettle, and continuously stirring;
e: the temperature of the reaction kettle is raised to 140 ℃, the reaction time is 10 hours, and the nano organic silicon fluororesin base material in the reaction kettle is fully reacted with the nano hybrid composite material;
f: and cooling to room temperature, and filtering to remove impurities to obtain the nano hybrid heavy anticorrosive material.
The application of the nano hybrid heavy anti-corrosion material is characterized in that the nano hybrid heavy anti-corrosion material is applied to high-temperature concentrated sulfuric acid tower equipment, and the nano hybrid heavy anti-corrosion material is sprayed in the high-temperature concentrated sulfuric acid tower equipment in a spraying and microwave high-temperature curing mode.
The above description is only for the purpose of illustrating the present invention and is not intended to limit the scope of the present invention, and any person skilled in the art can substitute or change the technical solution of the present invention and its conception within the scope of the present invention.
Claims (6)
1. The nanometer hybrid heavy-duty anticorrosive material is characterized by being prepared from the following raw materials in parts by weight:
silicone resin: 1-2 parts;
fluorine resin: 1-2 parts;
inorganic nano-ceramic material: 2-4 parts;
graphene material: 0.01-0.05 part;
wherein, the organic silicon resin and the fluororesin are prepared into a modified organic silicon fluororesin base material; the inorganic nano ceramic material and the graphene material are fused to form a nano hybrid composite material, and the nano organic silicon fluororesin base material and the nano hybrid composite material are mixed and reacted to prepare the nano hybrid heavy anti-corrosion material.
2. The nano-hybrid heavy duty anticorrosive material according to claim 1, characterized in that: the organic silicon resin is at least one of methyl trichlorosilane, dimethyl dichlorosilane, phenyl trichlorosilane, diphenyl dichlorosilane and methyl phenyl dichlorosilane.
3. The nano-hybrid heavy duty anticorrosive material according to claim 1, characterized in that: the fluororesin is at least one of Polytetrafluoroethylene (PTFE), Polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF).
4. The preparation method of the nano hybrid heavy anti-corrosion material according to any one of claims 1 to 3, characterized in that fluororesin and organic silicon resin are mixed and reacted to prepare modified nano organic silicon fluororesin base material, then the inorganic nano ceramic material and graphene material are fused to form nano hybrid composite material, and then the nano organic silicon fluororesin base material and the nano hybrid composite material are uniformly mixed and reacted to prepare the nano hybrid heavy anti-corrosion material.
5. The preparation method of the nano hybrid heavy anticorrosive material according to claim 4, characterized by comprising the following steps:
a: adding the organic silicon resin and the fluororesin into a reaction kettle, and continuously stirring;
b: the temperature of the reaction kettle is increased to 80-120 ℃, the reaction time is 6-10h, and the modified nano organic silicon fluororesin base material is prepared after the reaction is finished;
c: fusing an inorganic nano ceramic material and a graphene material in a melting mode to form a nano hybrid composite material;
d: adding the nano hybrid composite material into a reaction kettle, and continuously stirring;
e: the temperature of the reaction kettle is increased to 100 ℃ and 150 ℃, the reaction time is 6-12h, and the nano organic silicon fluororesin base material in the reaction kettle is fully reacted with the nano hybrid composite material;
f: and cooling to room temperature, and filtering to remove impurities to obtain the nano hybrid heavy anticorrosive material.
6. The use of the nano-hybrid heavy duty material according to any one of claims 1 to 5, characterized in that: the nano hybrid heavy anti-corrosion material is applied to high-temperature concentrated sulfuric acid tower equipment, and is sprayed in the high-temperature concentrated sulfuric acid tower equipment in a spraying and microwave high-temperature curing mode.
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