CN101591541B - Anticorrosive treatment material for chimney and flue and anticorrosive construction method - Google Patents
Anticorrosive treatment material for chimney and flue and anticorrosive construction method Download PDFInfo
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Abstract
本发明提出一种烟囱及烟道的防腐处理材料及防腐施工工艺，防腐处理材料采用改性硅橡胶(M50)作为底层粘结材料，表面改性聚四氟乙烯(DS1)作为面层防腐材料，粘接在烟囱及烟道的内壁。改性硅橡胶(M50)为室温硫化硅橡胶通过添加剂纳米SiOx和TiO2改性而成，表面改性聚四氟乙烯(DS1)是先采用机械、物理方法对聚四氟乙烯进行表面粗糙化处理，然后再进行钠一萘化学处理，在其表面分子链上导入极性基团而获得。本发明很好地解决了PTFE的常温粘结、高温使用的技术问题，能使用在200℃以上的高温环境，为脱硫以后的烟囱防腐寻找到了一种经济适用，且耐温、耐酸等综合防腐性能超强的防腐内衬材料。The invention proposes an anti-corrosion treatment material and anti-corrosion construction process for chimneys and flues. The anti-corrosion treatment material uses modified silicone rubber (M50) as the bottom bonding material, and surface-modified polytetrafluoroethylene (DS1) as the surface anti-corrosion material. , bonded to the inner wall of the chimney and flue. Modified silicone rubber (M50) is room temperature vulcanized silicone rubber modified by additives such as nano-SiO x and TiO 2. The surface-modified polytetrafluoroethylene (DS1) is first roughened by mechanical and physical methods. chemical treatment, and then sodium-naphthalene chemical treatment to introduce polar groups into its surface molecular chains. The invention well solves the technical problems of PTFE bonding at room temperature and high temperature use, can be used in a high temperature environment above 200°C, and finds an economical and applicable anti-corrosion method for chimneys after desulfurization, and is temperature-resistant, acid-resistant and other comprehensive anti-corrosion High-performance anti-corrosion lining material.
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
At present to the anticorrosive measure of desulfurization after-funnel, no matter aspect standard specificationss such as chimney design, construction, still be 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, and 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.That is that all right is ripe and Chinese quality product is with technology, 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 widely used 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 normally carries out through 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 in inorganic materials such as concrete and brick substrate, carries out thermo-welding PTFE up to now.And the lining that these welding are good 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 type liner big, yielding, anti-negative pressure poor performance of expanding with heat and contract with cold 180 ℃ of high-temperature flue gas possibly occur at chimney and flue, and exist under the working condition that colds and heat succeed each other with negative pressure for a long time and 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 to existing prior art existence.
The technical scheme that the present invention adopts is following:
The chimney that the present invention proposes and the rotproofing material of flue adopt modified silicon rubber (M50) as bottom bonding material, and surface-treated 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, fill a prescription as follows:
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, aspect the modification of macromolecular material performance, has huge development space.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 Zylox, but the adding of its amount must strict control, just can reach the high temperature bonding performance that improves Zylox, 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 like 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 following:
(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-treated.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; The lining of making resistant to corrosive media commonly used, but the PTFE surface energy is extremely low, and 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 kinds of thinkings 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 through machinery, physics improves its surperficial roughness earlier, on its surface molecular chain, imports polar group with chemical process again, eliminates weak interface layer and improves surface energy.Concrete treating processes is following:
(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 that Ra=2.5-5 micron, Rz=10-20 micron are 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-treated effective means; It mainly is through corrosive fluid and PTFE plastics generation chemical reaction; Tear off lip-deep part fluorine atom, stayed carburization zone on the surface and introduced some like hydroxyl, carbonyl and unsaturated link(age) isopolarity group.These polar groups make surface energy polymer increase, contact angle diminishes, wellability improves, thereby become and can glue by difficulty is sticking.
The preparation of sodium one naphthalene chemical pretreatment solution is in the reaction kettle that is equipped with water cooling plant and gas shield device, to carry out, and shielding gas is N
2Go into (through the pyrogallol deoxygenation, dry with the vitriol oil), prescription of treating liquid is following:
| Title material | Essence how | 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.
Through 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 following:
(1) goes out matrix material M50 by production standard and explained hereafter and surface material DS1 is subsequent use in factory;
(2) after accomplishing 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 basically, and temperature is more than 10 ℃, and humidity is below 85%;
(5) in scraping primer coating completion 5-40min (10-30min is best), press plan 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 to 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-treated polytetrafluoroethylene sheet material); Two kinds of materials are through 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 good, anti-permeability performance is strong, antifouling property is strong, abrasion resistance can be good, construction is simple, the duration is short, Quality Process is easy to control, non-Equipment of Flammable and Explosive Materials; Construction safety, in light weight, the load of chimney is required low, applied range, be 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.Through 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, under the exsiccant condition of sevice, can be fit to higher temperature.
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-treated 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 is excellent, 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; The TiO that will add 2kg more in proportion
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-treated 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 following: in the reaction kettle that is equipped with water cooling plant and gas shield device, feeding shielding gas is N
2By essence how, (through the pyrogallol deoxygenation, with vitriol oil drying): 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 under 78-83 ℃ of temperature, also use the black PVC film wrapped immediately, 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 basically, and temperature is more than 10 ℃, and humidity is below 85%; In blade coating modified silicon rubber M50 accomplished 30min, paving surface material surface-treated polytetrafluoroethyl-ne DS1 moved during paving and wants slowly from top to bottom; 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-treated 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; The TiO that will add 2kg more in proportion
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-treated 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
In the reaction kettle that is equipped with water cooling plant and gas shield device, feeding shielding gas is N
2By essence how, (through the pyrogallol deoxygenation, with vitriol oil drying): 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 oven dry under 80-85 ℃ of temperature condition, sealing is preserved subsequent use.
Construction process is identical with instance 1.
Embodiment 3:
This example is that modified silicon rubber M50, surface-treated 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; The TiO that will add 1kg more in proportion
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-treated 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
In the reaction kettle that is equipped with water cooling plant and gas shield device, feeding shielding gas is N
2By essence how, (through the pyrogallol deoxygenation, with vitriol oil drying): 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 oven dry under 85-90 ℃ of temperature condition, sealing is preserved subsequent use.
Construction process is identical with instance 1.
Embodiment 4:
This example is that modified silicon rubber M50, surface-treated 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; The TiO that will add 1.5kg more in proportion
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-treated 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
In the reaction kettle that is equipped with water cooling plant and gas shield device, feeding shielding gas is N
2By essence how, (through the pyrogallol deoxygenation, with vitriol oil drying): 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 oven dry under 70-78 ℃ of temperature condition, sealing is preserved subsequent use.
Construction process is identical with instance 1.
Claims (8)
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891993B (en) * | 2010-07-06 | 2012-10-24 | 重庆大众防腐有限公司 | Fluoropolymer organic lining anticorrosive material for chimney, flue and other pipelines and containers and construction method thereof |
| CN102168501A (en) * | 2010-11-26 | 2011-08-31 | 重庆大众防腐有限公司 | Anticorrosion structure and anticorrosion processing method for dust deposition platform with slope and internal corner in brick lining chimney |
| CN102168500A (en) * | 2010-11-26 | 2011-08-31 | 重庆大众防腐有限公司 | Antiseptic processing method for capping part of brick lining chimney |
| CN102168502B (en) * | 2010-11-26 | 2013-11-13 | 重庆大众防腐股份有限公司 | Anticorrosion structure and anticorrosion method for dust deposition platform and internal corner in brick lining chimney |
| CN102192518A (en) * | 2011-03-09 | 2011-09-21 | 重庆大众防腐有限公司 | Method for making anticorrosive glass reinforced plastic layer of chimney |
| CN102269268B (en) * | 2011-07-15 | 2016-06-08 | 中国中轻国际工程有限公司 | The sealing technology of furnace burning producer gas shape of a hoof glass melting kiln waste flue |
| 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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| WO2005121402A1 (en) * | 2004-06-08 | 2005-12-22 | Pinter Istvan | Method and composition of materials for making wear resistant surface coating |
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| JPH1135912A (en) | 1997-07-24 | 1999-02-09 | Sekisui Chem Co Ltd | Preparation of adhesive composition |
| WO2005121402A1 (en) * | 2004-06-08 | 2005-12-22 | Pinter Istvan | Method and composition of materials for making wear resistant surface coating |
| CN1963057A (en) * | 2006-05-30 | 2007-05-16 | 吴淑环 | Use of plastic film and plastic board as construction member, mechanical device protection layer, and reinforced layer |
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