Aerosol-resistant butyl rubber anticorrosion lining and preparation method thereof

Abstract

The invention provides an aqua regia-resistant butyl rubber anticorrosive lining and a preparation method thereof. The aqua regia-resistant butyl rubber anticorrosive lining is prepared from the following raw materials in parts by weight: 100 parts of butyl rubber, 50 to 80 parts of terpene phenolic resin, 55 to 70 parts of silane modified SiO2 / porous carbon black composite material, 1.5 to 3 parts of vulcanizing agent, 0.5 to 2 parts of vulcanization accelerator, 1 to 3 parts of activating agent and 1 to 3 parts of anti-aging agent. The aqua regia-resistant butyl rubber anticorrosive lining disclosed by the invention has excellent aqua regia resistance and relatively high mechanical strength.

Description

Technical Field

[0001] The invention relates to the technical field of butyl rubber materials, and in particular to an aqua regia-resistant butyl rubber anti-corrosion lining and a preparation method thereof. Background Art

[0002] Butyl rubber anti-corrosion linings are corrosion-resistant insulation layers made primarily from butyl rubber and are widely used in the chemical, electric power, and metallurgical industries. Butyl rubber is a copolymer of isobutylene and a small amount of isoprene. Its dense molecular chain structure, containing a large number of isobutylene units, offers extremely low gas permeability, excellent air tightness, and chemical resistance. It effectively resists corrosion from acids, alkalis, salts, and various organic media. It is also heat-stable, resistant to ozone aging, and has a long service life.

[0003] In industries like chemical engineering, metallurgy, and electroplating, aqua regia is commonly used in metal purification and equipment cleaning processes. Aqua regia-resistant linings protect equipment like storage tanks and reactors from corrosion, reducing maintenance costs and extending service life. In the photovoltaic and semiconductor industries, aqua regia is used to clean silicon wafers and metal components. Aqua regia-resistant linings ensure stable operation of cleaning equipment in highly corrosive environments, improving product quality. However, while current butyl rubbers have good resistance to non-oxidizing acids like dilute nitric acid, hydrochloric acid, and phosphoric acid, as well as some alkaline solutions, their resistance to strongly oxidizing mixed acids like aqua regia is less robust. Long-term immersion in aqua regia can lead to performance degradation. Summary of the Invention

[0004] The purpose of the present invention is to provide an aqua regia-resistant butyl rubber anti-corrosion lining and a preparation method thereof. The aqua regia-resistant butyl rubber anti-corrosion lining of the present invention has excellent aqua regia resistance and high mechanical strength.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solutions: The invention discloses an aqua regia resistant butyl rubber anticorrosive lining, comprising the following raw materials in parts by weight: 100 parts of butyl rubber, 50-80 parts of terpene phenolic resin, 55-70 parts of silane modified SiO2 / porous carbon black composite material, 1.5-3 parts of vulcanizing agent, 0.5-2 parts of vulcanization accelerator, 1-3 parts of activator and 1-3 parts of antioxidant.

[0006] Preferably, the preparation method of the silane-modified SiO2 / porous carbon black composite material comprises the following steps: S1: Preparation of porous carbon black; S2: placing the porous carbon black in silica sol A, ultrasonically treating for 5-20 hours, filtering, drying, and then calcining at 600-650°C under a nitrogen atmosphere for 1-2 hours. After cooling to room temperature, grinding and dispersing to obtain SiO2 / porous carbon black composite material A; the average particle size of silicon dioxide in the silica sol A is 5-7 nm; S3: placing SiO2 / porous carbon black composite material A in silica sol B, ultrasonically treating for 5-20 hours, filtering, drying, and then heating to 600-650°C under a nitrogen atmosphere for 1-2 hours. After cooling to room temperature, grinding and dispersing to obtain SiO2 / porous carbon black composite material B; the average particle size of silicon dioxide in the silica sol B is 20-25 nm; S4: Modifying the SiO2 / porous carbon black composite material B with a silane coupling agent to obtain the silane-modified SiO2 / porous carbon black composite material.

[0007] In preparing the silane-modified SiO2 / porous carbon black composite material, the porous carbon black is first prepared. Then, nano-silica with a smaller particle size (average particle size of 5-7 nm) is loaded. This smaller nano-silica is primarily loaded into the mesopores of the porous carbon black, thereby building a silica skeleton within the porous carbon black. Subsequently, nano-silica with a larger particle size (average particle size of 20-25 nm) is loaded onto the porous carbon black. This larger nano-silica is primarily loaded onto the surface of the porous carbon black, thereby altering the surface properties of the porous carbon black, increasing the roughness of the porous carbon black structure, and further enhancing the mechanical properties of the porous carbon black.

[0008] Preferably, in step S1, the method for preparing porous carbon black comprises the following steps: The carbon black is placed in an activation furnace and activated with water vapor at 820-880° C. for 1-2 hours to obtain water vapor-activated carbon black; the water vapor-activated carbon black is then placed in a potassium hydroxide solution with a mass fraction of 15-20%, heated to 60-80° C., and ultrasonically stirred for 2-3 hours, then filtered, washed with dilute hydrochloric acid and then washed with water, and then dried to obtain the porous carbon black.

[0009] The present invention first performs water vapor activation on carbon black and then uses potassium hydroxide solution to treat it, so that the obtained porous carbon black has more mesoporous structures.

[0010] Preferably, the carbon black is N700 series carbon black; During the ultrasonic and stirring treatment, the ultrasonic power is 1000-1600W, and the stirring speed is 300-500r / min.

[0011] Preferably, in step S2, the solid content of silica sol A is 10-15%; in step S3, the solid content of silica sol B is 10-15%.

[0012] Preferably, step S4 includes the following steps: placing the SiO2 / porous carbon black composite material B in anhydrous ethanol, heating it to 60-70°C while stirring, adding a silane coupling agent, continuing to stir at a constant temperature for 2-4 hours, and then filtering and drying to obtain a silane-modified SiO2 / porous carbon black composite material.

[0013] Preferably, the silane coupling agent is KH550, KH560 or KH570.

[0014] Preferably, the vulcanizing agent is sulfur; and the vulcanization accelerator is any one or more of a thiazole vulcanization accelerator and a thiuram vulcanization accelerator.

[0015] Preferably, the activator is composed of stearic acid and zinc oxide in a mass ratio of 1-2:5; and the antioxidant is antioxidant RD or antioxidant 4020.

[0016] As a general inventive concept, the present invention provides a method for preparing an aqua regia resistant butyl rubber anticorrosive lining, comprising the following steps: Add butyl rubber and terpene phenolic resin into an internal mixer and mix for 1-1.5 minutes, then add silane-modified SiO2 / porous carbon black composite material and antioxidant and mix for 2-3 minutes, then add vulcanizing agent, vulcanization accelerator and activator and mix for 2-3 minutes to obtain a rubber mixture; The mixed rubber is placed in a mold, and the mold filled with the mixed rubber is vulcanized using a flat vulcanizing machine at a vulcanizing pressure of 12-15 MPa, a vulcanizing temperature of 160-170°C, and a vulcanizing time of 25-35 minutes. After demolding, the aqua regia resistant butyl rubber anti-corrosion lining material is obtained; The aqua regia butyl rubber anti-corrosion lining material is fixed on the inner wall of the equipment through adhesive vulcanization to obtain the aqua regia butyl rubber anti-corrosion lining.

[0017] The beneficial effects of the present invention are: The aqua regia-resistant butyl rubber anti-corrosion lining of the present invention uses a silane-modified SiO2 / porous carbon black composite material as the main reinforcing filler. The composite material uses porous carbon black as the matrix material, and its pores are mainly loaded with small-particle nano-silica, while the outer surface is mainly loaded with larger-particle nano-silica. The porous carbon black has a higher specific surface area and pore structure than carbon black, and can adsorb plasma in aqua regia, forming a physical barrier, reducing its direct attack on the rubber molecular chains, and thus can slow the diffusion rate of the corrosive medium into the rubber. In addition, because the porous carbon black has a higher roughness, combined with the nano-silica loaded on its outer surface, it can enhance the physical entanglement and chemical bonding with the molecular chains of the butyl rubber, thereby strengthening the interfacial adhesion between the rubber and the carbon black, reducing the penetration path of the corrosive medium, and at the same time having a strong reinforcing effect on the rubber, which can effectively improve the tensile strength of the butyl rubber lining. The pores of porous carbon black are loaded with small-particle nano-silica, whose surface silanol groups can form chemical bonds with rubber molecular chains, thereby enhancing the bonding force between the porous carbon black pores and the rubber, and forming a denser barrier layer as a whole, thereby enhancing the aqua regia resistance of the anti-corrosion lining. At the same time, the loading of nano-silica in the pores of porous carbon black also forms a silica skeleton in the porous carbon black, thereby enhancing the mechanical properties of the porous carbon black itself, and further improving the mechanical strength of the anti-corrosion lining, making it less prone to cracking.

[0018] In addition, the silane-modified SiO2 / porous carbon black composite material of the present invention has nano-silica loaded on the outer surface of the porous carbon black and is modified with a silane coupling agent, so that the composite material has excellent dispersion properties in butyl rubber and fully exerts its reinforcing effect.

[0019] The aqua regia-resistant butyl rubber anti-corrosion lining prepared by the present invention has excellent aqua regia resistance and high mechanical strength. DETAILED DESCRIPTION

[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0021] Example 1: The invention discloses an aqua regia-resistant butyl rubber anticorrosive lining, comprising the following raw materials in parts by weight: 100 parts of butyl rubber, 70 parts of terpene phenolic resin, 60 parts of silane-modified SiO2 / porous carbon black composite material, 2 parts of sulfur, 1 part of vulcanization accelerator DM, 2 parts of activator, and 2 parts of antioxidant RD; the activator is composed of stearic acid and zinc oxide in a mass ratio of 1:5.

[0022] The preparation method of the silane-modified SiO2 / porous carbon black composite material in this embodiment includes the following steps: S1: Preparation of porous carbon black: N700 series carbon black was placed in an activation furnace and activated with steam at 850°C for 2 hours to obtain steam-activated carbon black; the steam-activated carbon black was then placed in a 15% by mass potassium hydroxide solution, heated to 70°C, and ultrasonically stirred for 3 hours at a power of 1600W and a stirring speed of 400 r / min; the carbon black was then filtered, washed with 10% by mass hydrochloric acid, then washed with water, and then dried to obtain porous carbon black; S2: Porous carbon black was placed in silica sol A and ultrasonically treated for 10 h. The mixture was then filtered and dried. The mixture was then heated to 650°C and calcined for 1 h under a nitrogen atmosphere. After cooling to room temperature, the mixture was ground and dispersed to obtain SiO2 / porous carbon black composite material A. The average particle size of silica in silica sol A was 7 nm, and the solid content of silica sol A was 15%. S3: SiO2 / porous carbon black composite material A was placed in silica sol B, ultrasonically treated for 10 hours, filtered, dried, and then calcined at 650°C for 1 hour under a nitrogen atmosphere. After cooling to room temperature, the SiO2 / porous carbon black composite material B was obtained by grinding and dispersion. The average particle size of silica in silica sol B was 20 nm, and the solid content of silica sol B was 15%. S4: Place the SiO2 / porous carbon black composite material B in anhydrous ethanol, raise the temperature to 70°C while stirring, then add the silane coupling agent KH560, continue stirring at a constant temperature for 3 hours, then filter and dry to obtain the silane-modified SiO2 / porous carbon black composite material.

[0023] The preparation method of the aqua regia resistant butyl rubber anti-corrosion lining in this embodiment includes the following steps: Butyl rubber and terpene phenolic resin were added to an internal mixer and mixed for 1.5 minutes, and then silane-modified SiO2 / porous carbon black composite material and antioxidant RD were added and mixed for 3 minutes, and then sulfur, vulcanization accelerator DM and activator were added and mixed for 2 minutes to obtain a rubber mixture; The mixed rubber is placed in a mold, and the mold filled with the mixed rubber is vulcanized using a flat vulcanizing machine at a vulcanizing pressure of 15 MPa, a vulcanizing temperature of 170°C, and a vulcanizing time of 30 minutes. After demolding, a material for aqua regia-resistant butyl rubber anti-corrosion lining is obtained; The aqua regia butyl rubber anti-corrosion lining material is fixed on the inner wall of the equipment through adhesive vulcanization to obtain the aqua regia butyl rubber anti-corrosion lining.

[0024] Example 2: The invention discloses an aqua regia-resistant butyl rubber anti-corrosion lining, comprising the following raw materials in parts by weight: 100 parts of butyl rubber, 65 parts of terpene phenolic resin, 65 parts of silane-modified SiO2 / porous carbon black composite material, 2 parts of sulfur, 2 parts of vulcanization accelerator DM, 3 parts of activator, and 2 parts of antioxidant RD; the activator is composed of stearic acid and zinc oxide in a mass ratio of 2:5.

[0025] The preparation method of the silane-modified SiO2 / porous carbon black composite material in this embodiment includes the following steps: S1: Preparation of porous carbon black: N700 series carbon black was placed in an activation furnace and activated with steam at 880°C for 2 hours to obtain steam-activated carbon black; the steam-activated carbon black was then placed in a 20% by mass potassium hydroxide solution, heated to 80°C, and ultrasonically stirred for 3 hours at a power of 1500W and a stirring speed of 300 r / min; the carbon black was then filtered, washed with 10% by mass hydrochloric acid, then washed with water, and then dried to obtain porous carbon black; S2: Porous carbon black was placed in silica sol A and ultrasonically treated for 20 h. The mixture was then filtered and dried. The mixture was then heated to 630°C and calcined for 2 h under a nitrogen atmosphere. After cooling to room temperature, the mixture was ground and dispersed to obtain SiO2 / porous carbon black composite material A. The average particle size of silica in silica sol A was 5 nm, and the solid content of silica sol A was 15%. S3: SiO2 / porous carbon black composite material A was placed in silica sol B, ultrasonically treated for 20 hours, filtered, dried, and then calcined at 630°C for 2 hours under a nitrogen atmosphere. After cooling to room temperature, the SiO2 / porous carbon black composite material B was obtained by grinding and dispersion. The average particle size of silica in silica sol B was 25 nm, and the solid content of silica sol B was 15%. S4: Place the SiO2 / porous carbon black composite material B in anhydrous ethanol, raise the temperature to 70°C while stirring, then add the silane coupling agent KH560, continue stirring at a constant temperature for 2 hours, then filter and dry to obtain the silane-modified SiO2 / porous carbon black composite material.

[0026] The preparation method of the aqua regia resistant butyl rubber anti-corrosion lining in this embodiment includes the following steps: Butyl rubber and terpene phenolic resin were added to an internal mixer and mixed for 1.5 minutes, and then silane-modified SiO2 / porous carbon black composite material and antioxidant RD were added and mixed for 3 minutes, and then sulfur, vulcanization accelerator DM and activator were added and mixed for 2.5 minutes to obtain a rubber mixture; The mixed rubber is placed in a mold, and the mold filled with the mixed rubber is vulcanized using a flat vulcanizing machine at a vulcanizing pressure of 15 MPa, a vulcanizing temperature of 165°C, and a vulcanizing time of 32 minutes. After demolding, a material for aqua regia-resistant butyl rubber anti-corrosion lining is obtained; The aqua regia butyl rubber anti-corrosion lining material is fixed on the inner wall of the equipment through adhesive vulcanization to obtain the aqua regia butyl rubber anti-corrosion lining.

[0027] Example 3: The invention discloses an aqua regia-resistant butyl rubber anti-corrosion lining, comprising the following raw materials in parts by weight: 100 parts of butyl rubber, 50 parts of terpene phenolic resin, 55 parts of silane-modified SiO2 / porous carbon black composite material, 1.5 parts of sulfur, 2 parts of vulcanization accelerator DM, 2 parts of activator, and 1 part of antioxidant RD; the activator is composed of stearic acid and zinc oxide in a mass ratio of 1:5.

[0028] The preparation method of the silane-modified SiO2 / porous carbon black composite material in this embodiment includes the following steps: S1: Preparation of porous carbon black: N700 series carbon black was placed in an activation furnace and activated with steam at 820°C for 1 hour to obtain steam-activated carbon black; the steam-activated carbon black was then placed in a 15% by mass potassium hydroxide solution, heated to 60°C, and ultrasonically stirred for 2 hours, with an ultrasonic power of 1000W and a stirring speed of 500 r / min; the carbon black was then filtered, washed with 10% by mass hydrochloric acid, then washed with water, and then dried to obtain porous carbon black; S2: Porous carbon black was placed in silica sol A, ultrasonically treated for 5 h, filtered, dried, and then calcined at 600°C for 1 h under a nitrogen atmosphere. After cooling to room temperature, the SiO2 / porous carbon black composite material A was obtained by grinding and dispersion. The average particle size of silica in silica sol A was 5 nm, and the solid content of silica sol A was 10%. S3: SiO2 / porous carbon black composite material A was placed in silica sol B, ultrasonically treated for 5 hours, filtered, dried, and then calcined at 600°C for 1 hour under a nitrogen atmosphere. After cooling to room temperature, the SiO2 / porous carbon black composite material B was obtained by grinding and dispersion. The average particle size of silicon dioxide in silica sol B was 20 nm, and the solid content of silica sol B was 10%. S4: Place the SiO2 / porous carbon black composite material B in anhydrous ethanol, raise the temperature to 60°C while stirring, then add the silane coupling agent KH560, continue stirring at a constant temperature for 4 hours, then filter and dry to obtain the silane-modified SiO2 / porous carbon black composite material.

[0029] The preparation method of the aqua regia resistant butyl rubber anti-corrosion lining in this embodiment includes the following steps: Butyl rubber and terpene phenolic resin were added to an internal mixer and mixed for 1 minute, and then silane-modified SiO2 / porous carbon black composite material and antioxidant RD were added and mixed for 3 minutes, and then sulfur, vulcanization accelerator DM and activator were added and mixed for 2 minutes to obtain a rubber mixture; The mixed rubber is placed in a mold, and the mold filled with the mixed rubber is vulcanized using a flat vulcanizing machine at a vulcanizing pressure of 12 MPa, a vulcanizing temperature of 160°C, and a vulcanizing time of 35 minutes. After demolding, a material for aqua regia-resistant butyl rubber anti-corrosion lining is obtained; The aqua regia butyl rubber anti-corrosion lining material is fixed on the inner wall of the equipment through adhesive vulcanization to obtain the aqua regia butyl rubber anti-corrosion lining.

[0030] Example 4: The invention discloses an aqua regia-resistant butyl rubber anti-corrosion lining, comprising the following raw materials in parts by weight: 100 parts of butyl rubber, 80 parts of terpene phenolic resin, 70 parts of silane-modified SiO2 / porous carbon black composite material, 3 parts of sulfur, 1 part of vulcanization accelerator DM, 3 parts of activator, and 2 parts of antioxidant RD; the activator is composed of stearic acid and zinc oxide in a mass ratio of 2:5.

[0031] The preparation method of the silane-modified SiO2 / porous carbon black composite material in this embodiment is the same as that in Example 1.

[0032] The preparation method of the aqua regia resistant butyl rubber anti-corrosion lining in this embodiment includes the following steps: Butyl rubber and terpene phenolic resin were added to an internal mixer and mixed for 1.5 minutes, and then silane-modified SiO2 / porous carbon black composite material and antioxidant RD were added and mixed for 2.5 minutes, and then sulfur, vulcanization accelerator DM and activator were added and mixed for 3 minutes to obtain a rubber mixture; The mixed rubber is placed in a mold, and the mold filled with the mixed rubber is vulcanized using a flat vulcanizing machine at a vulcanizing pressure of 15 MPa, a vulcanizing temperature of 170°C, and a vulcanizing time of 25 minutes. After demolding, a material for aqua regia-resistant butyl rubber anti-corrosion lining is obtained; The aqua regia butyl rubber anti-corrosion lining material is fixed on the inner wall of the equipment through adhesive vulcanization to obtain the aqua regia butyl rubber anti-corrosion lining.

[0033] Example 5: The invention discloses an aqua regia-resistant butyl rubber anticorrosive lining, comprising the following raw materials in parts by weight: 100 parts of butyl rubber, 65 parts of terpene phenolic resin, 60 parts of silane-modified SiO2 / porous carbon black composite material, 2 parts of sulfur, 0.5 parts of vulcanization accelerator DM, 1 part of activator, and 3 parts of antioxidant RD; the activator is composed of stearic acid and zinc oxide in a mass ratio of 2:5.

[0034] The preparation method of the silane-modified SiO2 / porous carbon black composite material in this embodiment is the same as that in Example 2.

[0035] The preparation method of the aqua regia resistant butyl rubber anti-corrosion lining in this embodiment includes the following steps: Butyl rubber and terpene phenolic resin were added to an internal mixer and mixed for 1.5 minutes, and then silane-modified SiO2 / porous carbon black composite material and antioxidant RD were added and mixed for 3 minutes, and then sulfur, vulcanization accelerator DM and activator were added and mixed for 2.5 minutes to obtain a rubber mixture; The mixed rubber is placed in a mold, and the mold filled with the mixed rubber is vulcanized using a flat vulcanizing machine at a vulcanizing pressure of 13 MPa, a vulcanizing temperature of 165° C., and a vulcanizing time of 30 min. After demolding, a material for aqua regia-resistant butyl rubber anticorrosive lining is obtained; The aqua regia butyl rubber anti-corrosion lining material is fixed on the inner wall of the equipment through adhesive vulcanization to obtain the aqua regia butyl rubber anti-corrosion lining.

[0036] Comparative Example 1: An aqua regia resistant butyl rubber anti-corrosion lining, which differs from Example 1 in that the silane-modified SiO2 / porous carbon black composite material is replaced by silane-modified carbon black.

[0037] The preparation method of silane-modified carbon black in this comparative example comprises the following steps: N700 series carbon black was placed in anhydrous ethanol, heated to 70°C while stirring, and then silane coupling agent KH560 was added. The mixture was stirred at a constant temperature for 3 hours, and then filtered and dried to obtain silane-modified carbon black.

[0038] Comparative Example 2: An aqua regia resistant butyl rubber anti-corrosion lining, which differs from Example 1 in that the silane-modified SiO2 / porous carbon black composite material is replaced by silane-modified porous carbon black.

[0039] The preparation method of silane-modified porous carbon black in this comparative example comprises the following steps: S1: Preparation of porous carbon black: N700 series carbon black was placed in an activation furnace and activated with water vapor at 850°C for 2 hours to obtain water vapor-activated carbon black; the water vapor-activated carbon black was then placed in a 15% by mass potassium hydroxide solution, heated to 70°C, and ultrasonically stirred for 3 hours, with an ultrasonic power of 1600W and a stirring speed of 1000 r / min; the carbon black was then filtered, washed with 10% by mass hydrochloric acid, then washed with water, and then dried to obtain porous carbon black; S2: Place the porous carbon black in anhydrous ethanol, raise the temperature to 70°C while stirring, then add the silane coupling agent KH560, continue stirring at a constant temperature for 3 hours, and then filter and dry to obtain the silane-modified porous carbon black.

[0040] Comparative Example 3: A butyl rubber anti-corrosion lining resistant to aqua regia is provided. Different from Example 1, the preparation method of the silane-modified SiO2 / porous carbon black composite material in this comparative example comprises the following steps: S1: Preparation of porous carbon black: N700 series carbon black was placed in an activation furnace and activated with water vapor at 850°C for 2 hours to obtain water vapor-activated carbon black; the water vapor-activated carbon black was then placed in a 15% by mass potassium hydroxide solution, heated to 70°C, and ultrasonically stirred for 3 hours, with an ultrasonic power of 1600W and a stirring speed of 1000 r / min; the carbon black was then filtered, washed with 10% by mass hydrochloric acid, then washed with water, and then dried to obtain porous carbon black; S2: Porous carbon black was placed in silica sol and ultrasonically treated for 10 hours, then filtered and dried. The mixture was then heated to 650°C and calcined for 1 hour under a nitrogen atmosphere. After cooling to room temperature, the mixture was ground and dispersed to obtain a SiO2 / porous carbon black composite material. The average particle size of silicon dioxide in the silica sol was 7 nm, and the solid content of the silica sol was 15%. S3: Place the SiO2 / porous carbon black composite material in anhydrous ethanol, raise the temperature to 70°C while stirring, then add silane coupling agent KH560, continue stirring at a constant temperature for 3 hours, then filter and dry to obtain a silane-modified SiO2 / porous carbon black composite material.

[0041] Comparative Example 4: A butyl rubber anti-corrosion lining resistant to aqua regia is provided. Different from Example 1, the preparation method of the silane-modified SiO2 / porous carbon black composite material in this comparative example comprises the following steps: S1: Preparation of porous carbon black: N700 series carbon black was placed in an activation furnace and activated with water vapor at 850°C for 2 hours to obtain water vapor-activated carbon black; the water vapor-activated carbon black was then placed in a 15% by mass potassium hydroxide solution, heated to 70°C, and ultrasonically stirred for 3 hours, with an ultrasonic power of 1600W and a stirring speed of 1000 r / min; the carbon black was then filtered, washed with 10% by mass hydrochloric acid, then washed with water, and then dried to obtain porous carbon black; S2: Porous carbon black was placed in silica sol and ultrasonically treated for 10 hours, then filtered and dried. The mixture was then heated to 650°C and calcined for 1 hour under a nitrogen atmosphere. After cooling to room temperature, the mixture was ground and dispersed to obtain a SiO2 / porous carbon black composite material. The average particle size of silicon dioxide in the silica sol was 20 nm, and the solid content of silica sol B was 15%. S3: Place the SiO2 / porous carbon black composite material in anhydrous ethanol, raise the temperature to 70°C while stirring, then add silane coupling agent KH560, continue stirring at a constant temperature for 3 hours, then filter and dry to obtain a silane-modified SiO2 / porous carbon black composite material.

[0042] Performance testing: 1. Test method for aqua regia resistance: prepare rectangular specimens of aqua regia resistant butyl rubber anti-corrosion lining materials with dimensions of 100 mm × 50 mm × 25 mm. Completely immerse the specimens in aqua regia to ensure that the aqua regia covers the surface of the specimens. The immersion temperature is 50 ± 1 ° C and the immersion time is 72 h. Observe the changes in the appearance of the specimens and calculate the mass loss rate. The specific results are shown in Table 1.

[0043] Table 1:

[0044] 2. According to GB / T 528-2009, samples of aqua regia-resistant butyl rubber anticorrosion lining material were prepared and their tensile strength was tested before and after immersion in aqua regia. The immersion temperature was 50±1°C and the immersion time was 72 hours. The specific test results are shown in Table 2.

[0045] Table 2:

[0046] It can be seen from Tables 1 and 2 that the aqua regia-resistant butyl rubber anti-corrosion lining material obtained in the embodiment of the present invention has excellent aqua regia resistance, a small mass loss rate after immersion in aqua regia, almost no change in appearance, and very little change in tensile strength.

[0047] It can be seen from Example 1 and Comparative Examples 1-2 that when the silane-modified SiO2 / porous carbon black composite material is replaced with silane-modified carbon black or silane-modified porous carbon black, the aqua regia resistance and tensile strength of the butyl rubber anti-corrosion lining material are significantly reduced.

[0048] From the comparison between Example 1 and Comparative Examples 3-4, it can be seen that when preparing the silane-modified SiO2 / porous carbon black composite material, if only nano-silica with small particle size (average particle size of 5-7nm) or large particle size (average particle size of 20-25nm) is loaded, the aqua regia resistance and tensile strength of the butyl rubber anti-corrosion lining material will also be reduced.

[0049] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A butyl rubber anti-corrosion lining resistant to aqua regia, characterized in that: The invention comprises the following raw materials in parts by weight: 100 parts of butyl rubber, 50-80 parts of terpene phenolic resin, 55-70 parts of silane-modified SiO2 / porous carbon black composite material, 1.5-3 parts of vulcanizing agent, 0.5-2 parts of vulcanization accelerator, 1-3 parts of activator and 1-3 parts of antioxidant.

2. The aqua regia resistant butyl rubber anti-corrosion lining according to claim 1, characterized in that: The preparation method of the silane-modified SiO2 / porous carbon black composite material comprises the following steps: S1: Preparation of porous carbon black; S2: placing the porous carbon black in silica sol A, ultrasonically treating for 5-20 hours, filtering, drying, and then calcining at 600-650°C under a nitrogen atmosphere for 1-2 hours. After cooling to room temperature, grinding and dispersing to obtain SiO2 / porous carbon black composite material A; the average particle size of silicon dioxide in the silica sol A is 5-7 nm; S3: placing SiO2 / porous carbon black composite material A in silica sol B, ultrasonically treating for 5-20 hours, filtering, drying, and then heating to 600-650°C under a nitrogen atmosphere for 1-2 hours. After cooling to room temperature, grinding and dispersing to obtain SiO2 / porous carbon black composite material B; the average particle size of silicon dioxide in the silica sol B is 20-25 nm; S4: Modifying the SiO2 / porous carbon black composite material B with a silane coupling agent to obtain the silane-modified SiO2 / porous carbon black composite material.

3. The aqua regia resistant butyl rubber anti-corrosion lining according to claim 2, characterized in that: In step S1, the method for preparing porous carbon black comprises the following steps: The carbon black is placed in an activation furnace and activated with water vapor at 820-880° C. for 1-2 hours to obtain water vapor-activated carbon black; the water vapor-activated carbon black is then placed in a potassium hydroxide solution with a mass fraction of 15-20%, heated to 60-80° C., and ultrasonically stirred for 2-3 hours, then filtered, washed with dilute hydrochloric acid and then washed with water, and then dried to obtain the porous carbon black.

4. The aqua regia resistant butyl rubber anti-corrosion lining according to claim 3, characterized in that: The carbon black is N700 series carbon black; During the ultrasonic and stirring treatment, the ultrasonic power is 1000-1600W, and the stirring speed is 300-500r / min.

5. The aqua regia resistant butyl rubber anti-corrosion lining according to claim 2, characterized in that: In step S2, the solid content of silica sol A is 10-15%; in step S3, the solid content of silica sol B is 10-15%.

6. The aqua regia resistant butyl rubber anti-corrosion lining according to claim 2, characterized in that: Step S4 includes the following steps: placing the SiO2 / porous carbon black composite material B in anhydrous ethanol, heating it to 60-70°C while stirring, adding a silane coupling agent, continuing to stir at a constant temperature for 2-4 hours, and then filtering and drying to obtain a silane-modified SiO2 / porous carbon black composite material.

7. The aqua regia resistant butyl rubber anti-corrosion lining according to claim 6, characterized in that: The silane coupling agent is KH550, KH560 or KH570.

8. The aqua regia resistant butyl rubber anti-corrosion lining according to claim 1, characterized in that: The vulcanizing agent is sulfur; the vulcanization accelerator is one or more of a thiazole vulcanization accelerator and a thiuram vulcanization accelerator.

9. The aqua regia resistant butyl rubber anti-corrosion lining according to claim 1, characterized in that: The activator is composed of stearic acid and zinc oxide in a mass ratio of 1-2:5; the antioxidant is antioxidant RD or antioxidant 4020.

10. A method for preparing aqua regia resistant butyl rubber anticorrosive lining according to any one of claims 1 to 9, characterized in that: The following steps are involved: Add butyl rubber and terpene phenolic resin into an internal mixer and mix for 1-1.5 minutes, then add silane-modified SiO2 / porous carbon black composite material and antioxidant and mix for 2-3 minutes, then add vulcanizing agent, vulcanization accelerator and activator and mix for 2-3 minutes to obtain a rubber mixture; The mixed rubber is placed in a mold, and the mold filled with the mixed rubber is vulcanized using a flat vulcanizing machine at a vulcanizing pressure of 12-15 MPa, a vulcanizing temperature of 160-170°C, and a vulcanizing time of 25-35 minutes. After demolding, the aqua regia resistant butyl rubber anti-corrosion lining material is obtained; The aqua regia butyl rubber anti-corrosion lining material is fixed on the inner wall of the equipment through adhesive vulcanization to obtain the aqua regia butyl rubber anti-corrosion lining.

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