CN101591541A - The rotproofing material and the anticorrosion construction method of a kind of chimney and flue - Google Patents
The rotproofing material and the anticorrosion construction method of a kind of chimney and flue Download PDFInfo
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- CN101591541A CN101591541A CNA2009101034682A CN200910103468A CN101591541A CN 101591541 A CN101591541 A CN 101591541A CN A2009101034682 A CNA2009101034682 A CN A2009101034682A CN 200910103468 A CN200910103468 A CN 200910103468A CN 101591541 A CN101591541 A CN 101591541A
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Abstract
The present invention proposes the rotproofing material and the anticorrosive construction technology of a kind of chimney and flue, the rotproofing material adopts modified silicon rubber (M50) as bottom bonding material, surface modification tetrafluoroethylene (DS1) is bonded in the inwall of chimney and flue as the surface layer impregnating material.Modified silicon rubber (M50) passes through additive nanometer SiO for room temperature vulcanized silicone rubber
xAnd TiO
2Modification forms, and surface modification tetrafluoroethylene (DS1) is to adopt earlier machinery, physical method that tetrafluoroethylene is carried out surface roughening to handle, and then carries out sodium one naphthalene chemical treatment, imports polar group and obtain on its surface molecular chain.The present invention has solved the normal temperature bonding of PTFE, the technical problem that high temperature uses well, can use in the hot environment more than 200 ℃, for the later chimney anticorrosion of desulfurization searched out a kind of economic and practical, and heatproof, the superpower corrosion-resistant lining material of comprehensive anticorrosive performance such as acidproof.
Description
Technical field
The present invention relates to high-temperature resistant anti-corrosive inner lining material and application art, be mainly used in later chimney of fuel-burning power plant desulfurization and flue anticorrosion on, belong to the organic polymer material field.
Background technology
Present anticorrosive measure at the desulfurization after-funnel, no matter design at chimney, standard specifications aspects such as construction, still on the engineering practical application, all exist blank or do not have enough experiences, because investment and technical problem, headed by China's five big Power Group, each tame genco is since the second half year in 2006,80% startup project has all taked to remove GGH (smoke heat replacing device), so, the minimum exhaust temperature of flue gas is between 40~50 ℃, and the FGD device when stopping transport in line temperature reach more than 130 ℃, so chimney must carry out rotproofing.
At present, the chimney anticorrosion technology mainly contains foam glass brick technology, VP technology, glass flake and improved technique, acid resistant adhesive mortar, alloy lining technology etc.And Chinese quality product and technology that is that all right is ripe, comparatively ripe and good market prospect all be foreign technology, but this series products price is higher, exceeds user's ability to bear.
Polytetrafluoroethylene (PTFE) is extensive use of in the chemical anticorrosion field as lining material, but its surface treatment and normal temperature bonding never have big breakthrough.More as the argumentation of lining material to tetrafluoroethylene on the existing document, its bonding mode is normally undertaken by thermo-welding, and it is bigger influenced by substrate material and surface roughness, and in order to reduce the difference of PTFE and base material, what have has also introduced transition layer.The thermo-welding mode is normally carried out on metal and plastic-substrates, does not see the report that carries out thermo-welding PTFE in inorganic materials such as concrete and brick substrate up to now.And the lining that these weld is generally used for pipeline, pipe fitting and various chemical industry with in the tower, is lower than 80 ℃ in temperature and uses down.Because this class liner big, yielding, anti-negative pressure poor performance of expanding with heat and contract with cold 180 ℃ of high-temperature flue gas may occur at chimney and flue, and exist cold and heat succeed each other and the working condition of long-term negative pressure under can't use at all.
Summary of the invention
The objective of the invention is to the problems referred to above, propose the rotproofing material and the anticorrosion construction method of a kind of chimney and flue at existing prior art existence.
The technical solution used in the present invention is as follows:
The chimney that the present invention proposes and the rotproofing material of flue adopt modified silicon rubber (M50) as bottom bonding material, and surface modification tetrafluoroethylene (DS1) is bonded in the inwall of chimney and flue as the surface layer impregnating material.
Wherein modified silicon rubber M50 forms for the room temperature vulcanized silicone rubber modification, and additive is nanometer SiO
xAnd TiO
2, it is as follows to fill a prescription:
Table 1:M50 formula table
Title material | Room temperature vulcanized silicone rubber | Nanometer SiO x | TiO 2 | White carbon black | Remarks |
Ratio of weight and number | 100 | 2-6 | 1-3 | 3-7 |
Above-mentioned modified silicon rubber M50 has adopted nano-material modified, because nanoparticle has quantum size effect, small-size effect, surface effects and macro quanta tunnel effect, has huge development space aspect the modification of macromolecular material performance.Utilizing nano material that room temperature vulcanized silicone rubber is carried out study on the modification is a kind of first and then effective means, nanometer SiO
xSize of particles is at 10-15nm, and specific surface area is 580-700m
2/ g, the surface atom number is many, has higher surface energy and Surface binding energy; Simultaneously, nanometer SiOx (X=1.2-1.6) particle surface Sauerstoffatom runs off in a large number, has unsettled silica structure; Also there is great amount of hydroxy group in its surface simultaneously, thereby utilizes nanometer SiO
xTo produce special effect during to the room temperature vulcanized silicone rubber modification, intensity and toughness are improved.And TiO
2Effect be thermostability and the anti-uv-ray that improves silicon rubber, but the adding of its amount must strict control, just can reach the high temperature bonding performance that improves silicon rubber, the present invention has selected suitable consumption, the too low effect that do not reach, too Gao Zehui runs counter to desire.
In addition, also add as white carbon black as weighting agent, also have enhancement (improving toughness and intensity) simultaneously.
The preparation process of above-mentioned modified silicon rubber M50 is as follows:
(1) prescription by table 1 at first adds nanometer SiO in the vacuum stirring device
xAnd white carbon black, stirred 1 hour with 200-500 rev/min of (best 300-400 rev/min) rotating speed;
(2) will add TiO in proportion again
2
(3) vacuumize, arrive-0.01MPa-0.5 in vacuum degree control;
(4) under vacuum tightness meets the requirements of condition, stirred 2 hours with 300-600 rev/min of (best 400-500 rev/min) rotating speed;
(5) detect the packing warehouse-in.
The surface material DS1 that the present invention adopts is the tetrafluoroethylene of surface modification.Polytetrafluoroethylene (PTFE) is commonly called as the plastics king, is a kind of plastics of high comprehensive performance, and fabulous heatproof and chemical resistance are arranged, be commonly used for the lining of resistant to corrosive media, but the PTFE surface energy is extremely low, the surface wettability performance is poor, be unfavorable for bonding and application etc., biocompatibility is poor.For this reason, must carry out modification to the PTFE surface and handle, mainly contain following several thinking at present:
(1) on the molecular chain of PTFE material surface, leads people's polar group;
(2) surface energy of raising PTFE material;
(3) roughness of raising PTFE product surface;
(4) weak interface layer of elimination PTFE product surface.
A kind of in above four kinds of thinkings normally adopted in the modification of PTFE at present, and the comprehensive above advantage of modification mode of the present invention, adopt machinery, physics and chemical process simultaneously, method by machinery, physics improves its surperficial roughness earlier, on its surface molecular chain, import polar group with chemical process again, eliminate weak interface layer and improve surface energy.Concrete treating processes is as follows:
(1) successively on 120# and 220# oilstone with PTFE film plucking, improve its surfaceness.Surfaceness requires: Ra=2-6 micron, Rz=8-30 micron (surfaceness is Ra=2.5-5 micron, Rz=10-20 micron the best);
(2) in acetone or alcohol, clean, and oven dry under 70-90 ℃ of (78-83 ℃ of the best) temperature condition
(3) carry out sodium one naphthalene chemical treatment, time 10-40 minute (15-30 minute the best).
Sodium one naphthalene method of chemical treatment is one of PTFE surface modification effective means, it mainly is by corrosive fluid and PTFE plastics generation chemical reaction, tear off lip-deep part fluorine atom, stayed carburization zone on the surface and introduced some as hydroxyl, carbonyl and unsaturated link(age) isopolarity group.These polar groups make surface energy polymer increase, contact angle diminishes, wetting property improves, thereby become and can glue by difficulty is sticking.
The preparation of sodium one naphthalene chemical pretreatment solution is to carry out in the reactor that is equipped with water cooling plant and gas shield device, and shielding gas is N
2Go into (through the pyrogallol deoxygenation, using vitriol oil drying), prescription for the treatment of liquid is as follows:
Title material | Essence how | Tetrahydrofuran (THF) | Sodium Metal 99.5 | Active additive A | Active additive B |
Ratio of weight and number | 8-9 | 90-100 | 1-2 | 0-2.5 | 0-1.5 |
(4) after the PTFE film that will handle cleans in acetone or alcohol,, and under 70-90 ℃ of (78-83 ℃ of the best) temperature, dry with the de-mineralized water flushing;
(5) after oven dry finishes, use the black PVC film wrapped immediately, sealing is kept in Dark Place.
By using above-mentioned machinery, physics and chemical process modification is carried out on the PTFE surface, can be realized boning at normal temperatures, at high temperature (be higher than 200 ℃) and use.
The construction technology that above material is applied on the chimney anticorrosion after the desulfurization is as follows:
(1) goes out matrix material M50 by production standard and explained hereafter and surface material DS1 is standby in factory;
(2) after finishing the installation of preparation of construction and operation platform, at first inner wall of stack is carried out base treatment (high pressure water washing or mechanical ashing);
(3) levelling is handled, and carries out levelling more than the concavo-convex 6-8mm of reaching and handles, and brick chimney uses my VP-24G of company (blade coating type) proprietary material;
(4) agent M50 at the bottom of the blade coating VP-5, wet-film thickness is controlled at 2-3mm, and the surface is smooth substantially, and temperature is more than 10 ℃, and humidity is below 85%;
(5) finish in the 5-40min (10-30min is best) scraping primer coating, by design paving VP-5 surface material from top to bottom, action is wanted slowly drive air in the interlayer out of as far as possible during paving.
The chimney that the present invention proposes and the rotproofing material of flue are a kind of at the desulfurization after-funnel and carry out the special liner system of rot-resistant, the numerous chimney lining impregnating material of this inner lining body assembly advantage can satisfy the requirement of desulfurization after-funnel working condition operation fully.This impregnating material adopts special bilayer structure, end agent is elasticity and the strong M50 of cohesiveness, surface layer is the strong DS1 of temperature tolerance and erosion resistance (a surface modification polytetrafluoroethylene sheet material), two kinds of materials are by the construct inwall of chimney of special sticking lining mode, the singularity of material and construction has determined it to have the following advantages: heat resistance is good, strong adhesion, superpower acid resistance, resistance to heat shocks is good, weather resistance is good, anti-permeability performance is strong, antifouling property is strong, abrasion resistance can be good, construction is simple, duration is short, Quality Process is easy to control, non-Equipment of Flammable and Explosive Materials, construction safety, in light weight, load to chimney requires low, applied range is fit to metal, the brick substrate is used.
Below be concrete analysis to two kinds of composition materials:
End agent M50 is a kind of two-pack, and macromolecule modified multipolymer has shockproof, ageing-resistant and characteristics such as cohesive strength height.It recommends to be used for acid resisting brick plate or other chimney lining material bonding and protection metal or concrete substrate as sealing and matrix material usually.By knife-coat application, form a kind of pliable and tough coating with of the corrosion of media such as the acid of the matrix motion that prevents to be accompanied by the flue gas environment and cause owing to temperature variation or other reason, salt to matrix.M50 is to keep below 180 ℃ concrete or fabulous elasticity and the adhesive power of steel matrix in temperature, and to be adapted at temperature be 180 ℃ medium-term and long-term use of environment, can be fit to higher temperature under the exsiccant condition of sevice.
The M50 performance perameter:
Tensile strength 〉=1.5Mpa
Unit elongation 〉=140%
Do solid work time 〉=1h
250 ℃ of temperature tolerances
Density 〉=1
Surface layer DS1 (surface modification polytetrafluoroethylene sheet material) is a kind of special modified high-molecular engineering materials, it has superpower high temperature resistant, corrosion-resistant, ageing-resistant performance, especially acid resistance excellence, sulfuric acid, nitric acid, hydrochloric acid and the hydrofluoric acid of all concentration of ability under 65 ℃ of conditions.Surperficial autohension and the mutual viscosity of DS1 are stronger.
The DS1 performance perameter:
Heat resistance>240 ℃;
Proportion (kg/m
3) 2-2.3
Tensile strength>13Mpa
Ultimate compression strength>8Mpa
Elongation>100%
The sulfuric acid of all concentration of acid resistance, nitric acid, hydrochloric acid and hydrofluoric acid
(65℃)
Normal temperature bonding, high temperature that the present invention has solved PTFE well use the art problem of skill to use, in the hot environment more than 200 ℃, for the later chimney anticorrosion of desulfurization searched out a kind of economic and practical, and heatproof, the superpower corrosion-resistant lining material of comprehensive anticorrosive performance such as acidproof.
Embodiment
Embodiment 1
1, the preparation of modified silicon rubber M50:
In 100L vacuum stirring device, at first add 100kg room temperature vulcanized silicone rubber, 3kg nanometer SiO
xWith the 3kg white carbon black, stirred 1 hour with best 300-400 rev/min rotating speed; To add the TiO of 2kg in proportion again
2After vacuumize, stirred 2 hours at vacuum degree control rotating speed with 400-500 rev/min under-0.5 to-0.01MPa condition, after the assay was approved the M50 finished product;
2, the preparation of surface modification polytetrafluoroethyl-ne DS1:
At first with PTFE film plucking on 120# and 220# oilstone successively, surfaceness is Ra=2.5-5 micron, Rz=10-20 micron;
In acetone or alcohol, clean again, and carrying out sodium one naphthalene chemical treatment, time 20-30 minute after the oven dry under the 78-83 ℃ of temperature condition;
Sodium one naphthalene chemical pretreatment solution process for preparation is as follows: feeding shielding gas in the reactor that is equipped with water cooling plant and gas shield device is N
2By essence how, (through the pyrogallol deoxygenation, using vitriol oil drying): tetrahydrofuran (THF): sodium: tetrahydrochysene boric acid magnesium salts: KH-550's is 8.4: 90: 1.6: (unit: mixed kg) evenly got final product in 2: 1;
After the PTFE film that will handle at last cleans with acetone or alcohol, with the de-mineralized water flushing, and also use the black PVC film wrapped immediately under 78-83 ℃ of temperature, sealing is kept in Dark Place.
3, the construction process of above-mentioned impregnating material:
At first after preparation of construction and operation platform installation, at first the brick chimney inwall is carried out high pressure water (pressure 5Mpa) flushing, remove dust stratification and unconsolidated formation; De-mineralized water is brushed the brickwork joint and the rough zone of repairing at needs again, uses the acid resistant adhesive mortar material to repair with levelling immediately and handles; Wait to solidify back (about 48h), blade coating adhesives modified silicon rubber M50, wet-film thickness is controlled at 2-3mm, and the surface is smooth substantially, and temperature is more than 10 ℃, and humidity is below 85%; M50 finishes in the 30min at the blade coating modified silicon rubber, paving surface material surface modification polytetrafluoroethyl-ne DS1 from top to bottom, action is wanted slowly during paving, drive air in the interlayer out of as far as possible, earlier overlapping back, handing-over position is fixed with holdfast, and behind the blade coating M50, the upset left-hand thread serves as a contrast subsides downwards again, holdfast is wrapped in its inside, keeps its globality to greatest extent.
Embodiment 2:
This example is that modified silicon rubber M50, surface modification polytetrafluoroethyl-ne DS1 are different with the concrete prescription of sodium one naphthalene chemical pretreatment solution, and all the other preparations, processing and constructional method are all identical.
1, modified silicon rubber M50
In 100L vacuum stirring device, at first add 100kg room temperature vulcanized silicone rubber, 2kg nanometer SiO
xWith the 4kg white carbon black, stirred 1 hour with best 300-400 rev/min rotating speed; To add the TiO of 2kg in proportion again
2After vacuumize, stirred 2 hours at vacuum degree control rotating speed with 400-500 rev/min under-0.5 to-0.01MPa condition, after the assay was approved the M50 finished product;
2, surface modification tetrafluoroethylene DS1
At first with PTFE film plucking on 120# and 220# oilstone successively, surfaceness is Ra=2.5-4 micron, Rz=10-15 micron;
In acetone or alcohol, clean again, and carrying out sodium one naphthalene chemical treatment, time 15-25 minute after the oven dry under the 80-85 ℃ of temperature condition
3, sodium one naphthalene chemical pretreatment solution
Feeding shielding gas in the reactor that is equipped with water cooling plant and gas shield device is N
2By essence how, (through the pyrogallol deoxygenation, using vitriol oil drying): tetrahydrofuran (THF): sodium: tetrahydrochysene boric acid magnesium salts is 8.4: 90: 1.6: 1.9 (unit: mixed kg) evenly gets final product;
Clean with acetone or alcohol at last, and dry under 80-85 ℃ of temperature condition, sealing is preserved standby.
Construction process is identical with example 1.
Embodiment 3:
This example is that modified silicon rubber M50, surface modification polytetrafluoroethyl-ne DS1 are different with the concrete prescription of sodium one naphthalene chemical pretreatment solution, and all the other preparations, processing and constructional method are all identical.
Modified silicon rubber M50
In 100L vacuum stirring device, at first add 100kg room temperature vulcanized silicone rubber, 2kg nanometer SiO
xWith the 6kg white carbon black, stirred 1 hour with best 300-400 rev/min rotating speed; To add the TiO of 1kg in proportion again
2After vacuumize, stirred 2 hours at vacuum degree control rotating speed with 450-550 rev/min under-0.5 to-0.01MPa condition, after the assay was approved the M50 finished product;
Surface modification tetrafluoroethylene DS1
At first with PTFE film plucking on 120# and 220# oilstone successively, surfaceness is Ra=3-6 micron, Rz=15-20 micron;
In acetone or alcohol, clean again, and carrying out sodium one naphthalene chemical treatment, time 20-30 minute after the oven dry under the 85-90 ℃ of temperature condition
Sodium one naphthalene chemical pretreatment solution
Feeding shielding gas in the reactor that is equipped with water cooling plant and gas shield device is N
2By essence how, (through the pyrogallol deoxygenation, using vitriol oil drying): tetrahydrofuran (THF): sodium: KH-550 is 8.4: 90: 1.6: 1 (unit: mixed kg) evenly gets final product;
Clean with acetone or alcohol at last, and dry under 85-90 ℃ of temperature condition, sealing is preserved standby.
Construction process is identical with example 1.
Embodiment 4:
This example is that modified silicon rubber M50, surface modification polytetrafluoroethyl-ne DS1 are different with the concrete prescription of sodium one naphthalene chemical pretreatment solution, and all the other preparations, processing and constructional method are all identical.
Modified silicon rubber M50
In 100L vacuum stirring device, at first add 100kg room temperature vulcanized silicone rubber, 2kg nanometer SiO
xWith the 6kg white carbon black, stirred 1 hour with best 300-400 rev/min rotating speed; To add the TiO of 1.5kg in proportion again
2After vacuumize, stirred 2 hours at vacuum degree control rotating speed with 450-550 rev/min under-0.5 to-0.01MPa condition, after the assay was approved the M50 finished product;
Surface modification tetrafluoroethylene DS1
At first with PTFE film plucking on 120# and 220# oilstone successively, surfaceness is Ra=3-6 micron, Rz=15-20 micron;
In acetone or alcohol, clean again, and carrying out sodium one naphthalene chemical treatment, time 20-30 minute after the oven dry under the 70-78 ℃ of temperature condition
Sodium one naphthalene chemical pretreatment solution
Feeding shielding gas in the reactor that is equipped with water cooling plant and gas shield device is N
2By essence how, (through the pyrogallol deoxygenation, using vitriol oil drying): tetrahydrofuran (THF): sodium is that (unit: mixed kg) evenly got final product in 8.4: 90: 1.6;
Clean with acetone or alcohol at last, and dry under 70-78 ℃ of temperature condition, sealing is preserved standby.
Construction process is identical with example 1.
Claims (10)
1, the rotproofing material of a kind of chimney and flue, it is characterized in that: it is made up of modified silicon rubber (M50) and surface modification tetrafluoroethylene (DS1), by modified silicon rubber (M50) as bottom bonding material, surface modification tetrafluoroethylene (DS1) is bonded in the inwall of chimney and flue as the surface layer impregnating material.
2, the rotproofing material of chimney according to claim 1 and flue is characterized in that, described modified silicon rubber (M50) passes through additive nanometer SiO for room temperature vulcanized silicone rubber
xAnd TiO
2Modification forms, and three's weight ratio is room temperature vulcanized silicone rubber: nanometer SiO
x: TiO
2=100: 2-6: 1-3; Described nanometer SiO
xX=1.2-1.6.
3, the rotproofing material of chimney according to claim 2 and flue is characterized in that, also adding in described modified silicon rubber M50 has white carbon black as weighting agent, and the weight ratio of room temperature vulcanized silicone rubber and white carbon black is 100: 3-7.
4, the rotproofing material of chimney according to claim 3 and flue is characterized in that, described modified silicon rubber M50 at first adds nanometer SiO in the vacuum stirring device
xAnd white carbon black, after stirring with 200-500 rev/min of rotating speed, add TiO again
2, vacuumize, vacuum degree control is arrived-0.01MPa-0.5, stir i.e. acquisition with 300-600 rev/min of rotating speed.
5, the rotproofing material of chimney according to claim 3 and flue is characterized in that, adds nanometer SiO in the vacuum stirring device
xThe rotating speed that stirs with white carbon black is 300-400 rev/min; Add TiO again
2The rotating speed that stirs is at 400-500 rev/min.
6, according to the rotproofing material of claim 1,2,3,4 or 5 described chimneys and flue, it is characterized in that, described surface modification tetrafluoroethylene (DS1) is to adopt machinery, physical method that tetrafluoroethylene is carried out surface roughening earlier to handle, and then carry out sodium one naphthalene chemical treatment, on its surface molecular chain, import polar group and obtain.
7, the rotproofing material of chimney according to claim 6 and flue, it is characterized in that, the surface roughening of described surface modification tetrafluoroethylene (DS1) handle be on oilstone with PTFE film plucking, surfaceness requires Ra=2-6 micron, Rz=8-30 micron.
8, the rotproofing material of chimney according to claim 7 and flue is characterized in that, described plucking adopts is followed successively by 120# and 220# oilstone, and surfaceness is Ra=2.5-5 micron, Rz=10-20 micron.
9, the rotproofing material of chimney according to claim 8 and flue, it is characterized in that, the weight ratio of chemically treated each component of treatment solution of sodium one naphthalene of described surface modification tetrafluoroethylene (DS1) be essence how: tetrahydrofuran (THF): sodium Metal 99.5: active additive A: active additive B=8-9: 90-100: 1-2: 0-2.5: 0-1.5; Described active additive A selects tetrahydrochysene boric acid magnesium salts for use, and active additive B selects KH-55 for use; Described sodium one naphthalene chemically treated time 10-40 minute.
10, chimney and the flue of the rotproofing material that utilizes claim 1,2,3,4 or 5 described chimneys and flue after for desulfurization carries out antiseptic constructional method, and step is as follows:
(1) chimney and flue inwall are carried out base treatment, adopt with high pressure water washing or mechanical ashing;
(2) levelling being carried out in substrate handles: carry out the levelling processing at the position that concave-convex surface reaches more than the 6-8mm;
(3) blade coating bottom bonding material modified silicon rubber (M50), wet-film thickness is controlled at 2-3mm, surfacing, temperature is more than 10 ℃, and humidity is below 85%;
(4) finish in the 5-40min at the blade coating bottom bonding material, the paving surface material moves during paving and wants slowly drive air in the interlayer out of as far as possible from top to bottom.
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CN103388827B (en) * | 2013-07-26 | 2015-10-28 | 西安华捷奥海新材料有限公司 | The application of nanofiber heavy-duty anticorrosive composite material in wet desulfurization concrete chimney |
CN110961063A (en) * | 2019-12-16 | 2020-04-07 | 石狮华宝新材料工程有限公司 | Photocuring nano anticorrosive material for desulfurization system and construction process thereof |
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