CN103880444A - Environment-friendly anhydrous tamping plug and preparation method thereof - Google Patents
Environment-friendly anhydrous tamping plug and preparation method thereof Download PDFInfo
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- CN103880444A CN103880444A CN201410066363.5A CN201410066363A CN103880444A CN 103880444 A CN103880444 A CN 103880444A CN 201410066363 A CN201410066363 A CN 201410066363A CN 103880444 A CN103880444 A CN 103880444A
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Abstract
The invention relates to an environment-friendly anhydrous tamping plug and a preparation method thereof and belongs to the field of fireproof materials. The environment-friendly anhydrous tamping plug comprises the following components by weight: 15-20 parts of coke, 22-43 parts of bauxite, 0-10 parts of brown aluminum oxide, 20-25 parts of silicon carbide, 0-8 parts of silicon nitride, 0-3 parts of silicon metal, 10-15 parts of clay, 3-6 parts of sericite and 15-20 parts of a binding agent, wherein the total parts of all materials, except for the binding agent, is 100 parts; the binding agent is composed of the following raw materials in parts by weight: 20-60 parts of carbon-containing resin, 20-50 parts of vegetable fat, 10-40 parts of linear phenolic resin and 5-10 parts of carbon powder. The environment-friendly anhydrous tamping plug has the following advantages of (1) being low in harmful substance content and harmless to a human body; (2) being free of smoke dust and hardly affecting the environment; (3) meeting the use requirements of flushing and casting operation of a blast furnace.
Description
Technical field
The invention belongs to technical field of refractory materials, be specifically related to a kind of environment-friendly type anhydrous stemming and preparation method thereof.
Background technology
The all right and wrong environment-friendly type anhydrous stemmings truly of anhydrous stemming that use before most domestic State of Blast Furnace at present.And a lot of users only limit to not smolder to the understanding of environment-friendly type anhydrous stemming or flue dust is few, few to harmful substance contents in used stemming, be harmful to human health and do not have concept.Domestic only have minority manufacturer production environment-friendly type anhydrous stemming, and its oxious component containing is also more, and health of human body and environment are caused to certain harm.Therefore should meeting following three aspects, environment-friendly type anhydrous stemming truly requires:
1) harmful substance contents is few, is harmful to human health (solve and in traditional anhydrous stemming, contain the problems that in a large number HUMAN HEALTH had the carcinogenic substance benzopyrene of serious harm);
2) smoke dust, to environmental influence little (solving the problem that traditional anhydrous stemming in use has volume of smoke to produce);
3) meet better the service requirements to anhydrous stemming before State of Blast Furnace (solve tradition without water cannon mud Chao Tiekou often, disconnected iron mouth, shallow iron mouth, puts the iron time inadequate, slag iron goes out unclean, the work of iron mouth worsens, the problem such as at the bottom of iron mouth qualification rate).
Along with expanding economy, ecocrisis has become an extremely important and severe problem of China and even the whole world.Country's Eleventh Five-Year Plan has proposed domestic production of units total value Energy Intensity Reduction 20% left and right, and total emissions of major pollutants reduces by 10% target.Therefore walk low-carbon (LC), EP Road is the inevitable direction of industrial sustainable development.
Present Domestic blast furnace casting is uneven by anhydrous stemming quality product, easily occurs Chao Tiekou, shallow iron mouth, disconnected iron mouth, runs and flow greatly, reduce pressure, leak informaton, burn out the problems such as casthouse equipment, has a strong impact on the normal production of big-and-middle-sized blast furnace.Coal tar and pitch that tradition stemming bonding agent uses all belong to complicated condensed ring arene material, they have good plasticity and durability, but the content that temperature is slightly high will give out acid, peppery, smelly gas and yellow smog, particularly benzopyrene reaches 1%-2.5%.Known from institute, benzopyrene is one of universally acknowledged carcinogenic substance, and it easily causes the major diseases such as cancer of the stomach, lung cancer, tumour.Along with progressively cognitive and to healthy abundant concern to coal tar, pitch toxicity of people, someone proposes to adopt resin to replace coal tar, it is environment friendly and pollution-free that original scheme is considered to, for coal tar and pitch, the stemming of resol combination, smolder few, but phenol and formaldehyde monomers are contained and have also been listed in the ranks of Hazardous substances CMR product in its inside, equally human body and environment are produced to very large harm.
Therefore, meaning and the necessity of enforcement research environment-friendly type anhydrous stemming are self-evident.
Summary of the invention
The object of the invention is for a kind of environment-friendly type anhydrous stemming and preparation method thereof is provided.
Based on above-mentioned purpose, the present invention has taked following technical scheme: a kind of environment-friendly type anhydrous stemming, by weight, consist of: 15～20 parts, coke, 22～43 parts of bauxitic clays, 0～10 part, brown corundum, 20～25 parts, silicon carbide, 0～8 part of silicon nitride, 0～3 part of Pure Silicon Metal, 10～15 parts of clays, 3～6 parts of sericites, 15～20 parts of bonding agents, except bonding agent, total umber of unclassified stores is 100 parts; Described bonding agent is made up of the raw material of following weight parts: containing 20～60 parts of carbon resins, 20～50 parts of Vegetable oil lipoprotein, 10～40 parts of lacquer resinss, 5～10 parts of carbon dusts.
5～10 parts of described coke 3mm >=particle diameter > 1mm, 8～15 parts of 0.1mm≤particle diameter≤1mm; 4～25 parts of 6～10 parts of described bauxitic clay 3mm >=particle diameter > 1mm, 8～15 parts of 0.1mm≤particle diameter≤1mm, particle diameter 180 object.
Particle diameter≤200 order of described brown corundum, silicon carbide, silicon nitride, Pure Silicon Metal and sericite, clay particle diameter≤325 order.
Preferably, by weight, consisting of of described stemming: 8 parts of the bauxitic clays of 7 parts, the coke of 3mm >=particle diameter > 1mm, 10 parts, the coke of 0.1mm≤particle diameter≤1mm, 3mm >=particle diameter > 1mm, 10 parts of the bauxitic clays of 0.1mm≤particle diameter≤1mm, 4 parts of 180 order bauxitic clays, 200 10 parts, order palm fibre corundum, 22 parts, 200 order silicon carbide, 8 parts of 200 order silicon nitrides, 3 parts of 200 order Pure Silicon Metals, 13 parts of 325 order clays, 5 parts of 200 order sericites, 16.5 parts of bonding agents; Consisting of of described bonding agent: containing 40 parts of carbon resins, 32 parts of Vegetable oil lipoprotein, 20 parts of linear phenolic resins, 8 parts of carbon dusts.
The preparation method of described environment-friendly type anhydrous stemming, comprise the following steps: 1) accurately take required various material, mix preparing the required each raw material of bonding agent, be heated to 100～120 DEG C, under 0.5～0.7MPa, stir, dewater, when detecting its viscosity Engler 9～11, when water content is less than 0.5wt%, stop heating, 45～55 DEG C of constant temperature store, for subsequent use;
2) material of particle diameter < 0.1mm is poured in stirrer and stirred and emit for subsequent use in 5～15 minutes;
3) bonding agent of getting step 1) be heated to 80 DEG C-85 DEG C for subsequent use;
4) temperature in anhydrous stemming stirrer is risen to 55 DEG C-60 DEG C, the temperature of squeezing mud mouth is controlled at 75 DEG C-80 DEG C;
5) leftover materials are added in anhydrous stemming stirrer and stir 1～5 minute, then add step 3) gained bonding agent 60～80wt% stir 1～5 minute, then add step 2) gains stir 10～20 minutes; Finally add remaining bonding agent to stir 15～30 minutes, be worth from the thief hole inspection by sampling horse summer, make the horse summer value of stemming be controlled at 0.7-0.73MPa, qualified discharging, Ruo Maxia value is higher, appends bonding agent, the bonding agent weight of at every turn appending, can not exceed total material heavy 0.5%, continue to stir at least 5 minutes, detect the qualified rear discharging of horse summer value and squeeze mud drum dress.
The physical and chemical index of main raw material of the present invention will be asked for an interview to table 1.
Table 1 main raw material requires physical and chemical index (%)
Environment-friendly type anhydrous stemming of the present invention has following advantage:
1. harmful substance contents is few, harmless; 2. smoke dust, little to environmental influence; 3. meet the service requirements of blast furnace flushing and casting, the environment-friendly type anhydrous stemming composition of producing and composition meet following requirement:
Q value is between 0.45 ~ 0.55
Al
2O
3 ≥ 45 % Si
3N
4+SiC≥ 20 %
C ≥ 19% 。
Environment-friendly type anhydrous stemming of the present invention is taking quality refractory raw materials such as corundum, bauxitic clay homogenization material, silicon carbide, silicon nitrides as basis, adds the composite binder of the independent research system of grinding of mixing to form.Not only use properties is good for it, and environment-friendly type anhydrous stemming such as uses also to have good environmental protection and energy saving at the scene at the link, particular embodiment is: materials consumption is few, block up effective, wear resisting property is good, easily boring, smolder few, without unpleasant irritant gas, benzopyrene concentration is extremely low, stable, the bunchy of flowing molten iron, not splash in the process of tapping a blast furnace.
Brief description of the drawings
Fig. 1 is the horse summer value contrast of various sample;
Fig. 2 is the apparent porosity contrast after 1400 DEG C × 3h of different Q value sample burns;
Fig. 3 is the volume density contrast after 1400 DEG C × 3h of different Q value sample burns;
Fig. 4 is compressive strength after 1400 DEG C × 3h of different Q value sample burns, folding strength contrast;
Fig. 5 is the compressive strength of stemming sample after pyroprocessing;
Fig. 6 is the folding strength of stemming sample after pyroprocessing.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but protection scope of the present invention is not limited to this.
Wherein, containing carbon resin, brown liquid, (require: 50 DEG C of viscosity Engler are 10-12 purchased from Tianjin Ke Fulai commerce and trade Development Co., Ltd, carbon residue amount is greater than 36%), Vegetable oil lipoprotein, chocolate liquid, (require: 50 DEG C of viscosity Engler are 7-9 purchased from Zibo Tai Chang lubricating oil company limited, carbon residue amount is greater than 30%), lacquer resins, brown liquid, (require: pH value 6.5-7.5 purchased from Henan Wan Tong Chemical Co., Ltd., 50 DEG C of viscosity Engler are 13-15, carbon residue amount is greater than 42%), carbon dust, (require: granularity is less than 0.088mm purchased from Tianjin Ke Fulai commerce and trade Development Co., Ltd, carbon residue amount is greater than 80%).
embodiment 1
Table 2 sample composition (wt%)
The consisting of of bonding agent in table 2: containing 40 parts of carbon resins, 32 parts of Vegetable oil lipoprotein, 20 parts of linear phenolic resins, 8 parts of carbon dusts.
The preparation method of stemming A and stemming B in upper table, comprise the following steps: 1) accurately take required various material, mix preparing the required each raw material of bonding agent, be heated to 100 DEG C, under 0.5MPa, stir, dewater, when detecting its viscosity Engler 9～11, when water content is less than 0.5wt%, stop heating, 45 DEG C of constant temperature store, for subsequent use;
2) material of particle diameter < 0.1mm is poured in forced mixer and stirred and emit for subsequent use in 5 minutes;
3) bonding agent of getting step 1) be heated to 80 DEG C for subsequent use;
4) temperature in anhydrous stemming special-purpose stirring machine is risen to 55 DEG C, the temperature of squeezing mud mouth is controlled at 75 DEG C;
5) leftover materials are added in anhydrous stemming special-purpose stirring machine and stir 1 minute, then add step 3) gained bonding agent 60wt% stir 1 minute, then add step 2) gains stir 10 minutes; Finally add remaining bonding agent to stir 15 minutes, be worth from the thief hole inspection by sampling horse summer, make the horse summer value of stemming be controlled at 0.7-0.73MPa, qualified discharging, Ruo Maxia value is higher, appends bonding agent, the bonding agent weight of at every turn appending, can not exceed total material heavy 0.5%, continue to stir at least 5 minutes, detect the qualified rear discharging of horse summer value and squeeze mud drum dress.
The preparation method of stemming C and stemming D in upper table, comprise the following steps: 1) accurately take required various material, mix preparing the required each raw material of bonding agent, be heated to 110 DEG C, under 0.6MPa, stir, dewater, when detecting its viscosity Engler 9～11, when water content is less than 0.5wt%, stop heating, 50 DEG C of constant temperature store, for subsequent use;
2) material of particle diameter < 0.1mm is poured in forced mixer and stirred and emit for subsequent use in 10 minutes;
3) bonding agent of getting step 1) be heated to 83 DEG C for subsequent use;
4) temperature in anhydrous stemming special-purpose stirring machine is risen to 58 DEG C, the temperature of squeezing mud mouth is controlled at 80 DEG C;
5) leftover materials are added in anhydrous stemming special-purpose stirring machine and stir 3 minutes, then add step 3) gained bonding agent 70wt% stir 3 minutes, then add step 2) gains stir 15 minutes; Finally add remaining bonding agent to stir 20 minutes, be worth from the thief hole inspection by sampling horse summer, make the horse summer value of stemming be controlled at 0.7-0.73MPa, qualified discharging, Ruo Maxia value is higher, appends bonding agent, the bonding agent weight of at every turn appending, can not exceed total material heavy 0.5%, continue to stir at least 5 minutes, detect the qualified rear discharging of horse summer value and squeeze mud drum dress.
Table 3 sample composition (wt%)
Table 4 bonding agent composition (wt%)
The preparation method of described environment-friendly type anhydrous stemming, comprise the following steps: 1) accurately take required various material, mix preparing the required each raw material of bonding agent, be heated to 120 DEG C, under 0.7MPa, stir, dewater, when detecting its viscosity Engler 9～11, when water content is less than 0.5wt%, stop heating, 55 DEG C of constant temperature store, for subsequent use;
2) material of particle diameter < 0.1mm is poured in forced mixer and stirred and emit for subsequent use in 15 minutes;
3) bonding agent of getting step 1) be heated to 85 DEG C for subsequent use;
4) temperature in anhydrous stemming special-purpose stirring machine is risen to 60 DEG C, the temperature of squeezing mud mouth is controlled at 80 DEG C;
5) leftover materials are added in anhydrous stemming special-purpose stirring machine and stir 5 minutes, then add step 3) gained bonding agent 80wt% stir 5 minutes, then add step 2) gains stir 20 minutes; Finally add remaining bonding agent to stir 30 minutes, be worth from the thief hole inspection by sampling horse summer, make the horse summer value of stemming be controlled at 0.7-0.73MPa, qualified discharging, Ruo Maxia value is higher, appends bonding agent, the bonding agent weight of at every turn appending, can not exceed total material heavy 0.5%, continue to stir at least 5 minutes, detect the qualified rear discharging of horse summer value and squeeze mud drum dress.
the impact of the allocation plan of 1 raw material on environment-friendly type anhydrous stemming performance
1.1 sample preparations
Prepare burden by table 2.
1.2 environment-friendly type anhydrous stemming test methods
1) accurately take required various material, mix preparing the required each raw material of bonding agent, be heated to 110 DEG C, stir, dewater under 0.6MPa, when detecting its viscosity Engler 9～11, when water content is less than 0.5wt%, stop heating, 50 DEG C of constant temperature store, for subsequent use;
2) material of particle diameter < 0.1mm is poured in forced mixer and stirred and emit for subsequent use in 5～15 minutes;
3) bonding agent of getting step 1) be heated to 80 DEG C-85 DEG C for subsequent use;
4) temperature in anhydrous stemming stirrer is risen to 55 DEG C-60 DEG C, the temperature of squeezing mud mouth is controlled at 80 DEG C;
5) in anhydrous stemming special-purpose stirring machine, add particulate material (3mm >=particle diameter > 1mm), stir the 70wt% that adds required bonding agent after 2 minutes, with particulate material mix and blend 3 minutes, add again the fine powder (particle diameter < 0.1mm) being stirred in advance to stir 15 minutes, finally add again appropriate bonding agent to stir 20 minutes, make the horse summer value of stemming be controlled at 0.7-0.73MPa.Make the bar-shaped sample of 160mm × 40mm × 40mm with the pressure of 5MPa.
Sample is imbedded in advance to the thermal treatment of carrying out 1400 DEG C of 3h in the saggar of filling coke granule, then the various performance index of furnace cooling test sample.Separately make crucible by component design ramming, pack blast furnace finishing slag into, in electric furnace after 1400 DEG C of 3h thermal treatment furnace cooling, cut along crucible central shaft, observe sample resistance performance of slag corrosion situation.
1.3 sample test item and results
1) stemming horse summer value (with GDP-500 type stemming detector)
2) 1400 DEG C of high temperature burn till compressive strength (GB/T3001-2007), folding strength (GB/T5072-2004), apparent porosity (GB/T2997-2000), resistance performance of slag corrosion (GB8931-88), oxidation-resistance (GB/T13244-1991), the linear change under high temperature (GB/T5988-1986) after 3h.
After table 5 pyroprocessing, stemming detects index
Can find out with table 5 from table 2: stemming B, compared with stemming A, replaces the bauxitic clay powder of equivalent with the silicon nitride powder of 8wt%, the cold crushing strength after 1400 DEG C of 3h buried charcoals are burnt till and strength at normal temperature have significantly raising, and apparent porosity reduces.Resistance performance of slag corrosion and the linear change under high temperature also improve significantly.Think; Because silicon nitride has that refractoriness is high, hardness high with the difficult feature such as wetting of slag iron, and can and A1
2o
3reflect into Si-Al-O-N ceramic phase, thereby contribute to improve intensity and the resistance performance of slag corrosion of anhydrous stemming.From oxidation-resistance index, silicon nitride add the effect of also having played inhibited oxidation.
Stemming C is compared with stemming B proportioning: replace the bauxitic clay powder of equivalent with the metallic silicon power of 3wt%, after 1400 DEG C of 3h buried charcoals are burnt till, cold crushing strength and the strength at normal temperature of stemming C all improve, and especially antioxidant property improves a lot.Think: because Pure Silicon Metal is the antioxidant that carbon containing refractory is conventional, in sample sintering process, played antioxygenation, in this external sintering process, the metallic silicon power reaction adding generates SiC and SiO
2.SiC particle has enhancement to sample.SiO
2with the A1 in aluminium bauxitic clay
2o
3further reflection generates fibrous 3Al
2o
32SiO
2mullite crystal whisker, equally sample is had to enhancement, in mullite generative process, be attended by volumetric expansion, in addition, Pure Silicon Metal forms liquid phase in sintering process, can promote the sintering of sample.This intensity of burning till rear sample to improving buried charcoal has also played positive effect.Therefore, the compressive strength of sample and folding strength increased along with adding of Pure Silicon Metal.
Stemming D compares with stemming C: divide the bauxitic clay powder that replaces equivalent with the brown corundum of 10wt%, sample cold crushing strength and strength at normal temperature all improve.Think, brown corundum has higher refractoriness (>=1850 DEG C) and higher volume density (>=3.80g/cm
3) and higher Al
2o
3content (>=95%), brown corundum adds the content that more contributes to improve sample matrix part main component with the form of fine powder, thereby the overall performance of sample is promoted to some extent.
In sum, environment-friendly type anhydrous stemming of the present invention various ingredient requirement major ingredient (Al used
2o
3si
3n
4siC C) content is high, impurity (K
2o Na
2o Fe
2o
3deng) content is low.As high in foreign matter content, easily make stemming in use form low melting component, reduce refractoriness and the hot strength of stemming, affect the normal use of stemming.Many producers, in stemming QIP, all treat raising material purity as major subjects, by using high-quality high pure raw material to improve the quality of stemming.Environment-friendly type anhydrous stemming of the present invention suitably improves the major ingredient content in raw material matrix part according to the practical situation of stokehold, add have that refractoriness is high, high silicon nitride and the antioxidant Pure Silicon Metal with the difficult feature such as wetting of slag iron of hardness, make resistance to slag corrosion and anti-oxidant can the significantly improving of stemming, not only extend the time of tapping a blast furnace, and reduced stemming unit consumption.
the impact of the water content of 2 raw materials on environment-friendly type anhydrous stemming performance.
Prepare burden by other raw materials except bonding agent in stemming D in table 2, with reference to 1.2 method sample preparation, thermal treatment, inspection is along with the variation of water content in the raw material impact on anhydrous stemming performance:
The impact of water content on stemming performance in table 6 raw material
As can be seen from Table 6: along with the increase of water content in raw material, ensure that sample horse summer value is in the scope requiring, the add-on of bonding agent must increase thereupon, in raw material, water content 1wt% is compared with raw material water content 0.5wt%, the existing significantly increase of add-on of bonding agent, the intensity of sample is also the trend of reduction along with the increase of water content in raw material.Think: mutually insoluble with bonding agent due to water, the moisture content in raw material has hindered the mobility of bonding agent, the plasticity variation horse summer value of sample is raise, only add excessive bonding agent guarantee sample horse summer value in the scope requiring.In raw material, water content is higher, and its 1400 DEG C intensity after burning till are lower.This is high the causing of tissue looseness, void content of stemming during due to water evaporates.In addition,, if the moisture content of bringing in raw material is not got rid of completely in the time tapping a blast furnace, in opening process, be prone to iron mouth wattenshlick and jeopardize personnel safety.
the optimization of 3 environment-friendly type anhydrous stemming grain compositions
The use properties that unshape refractory will have, the physics and chemistry performance that must have: Gao Timi, spirit hole, good normal temperature and high-temperature anti-corrosion and abrasion resistance etc.To approach the size-grade distribution when tightly packed in order to obtain the best proportioning of good unshape refractory performance, its material particles.
Anhydrous stemming is as the atypical unshape refractory of one.In practical application, not only pursue and have outside the traditional performance of unshape refractory, more will there is good plasticity-, opening and new and old stemming associativity.So the grain composition of anhydrous stemming can not be explained with the maximal unit weight method of unshape refractory.
Be the per-cent of (particle diameter >=0.1mm) weight of particulate material in stemming material and fine powder material (particle diameter < 0.1mm) weight in this definition Q value, current conventional stemming grain composition Q value is all at 1.0-1.2.For development environment-friendly type anhydrous stemming, domestic and international anhydrous stemming is analyzed, research Q value is respectively 1.2 (a), 0.47(b) and various performances of stemming when 1.0 (c).
3.1 sample test items
1) stemming horse summer value (with GDP-500 type stemming detector)
2) 1400 DEG C of high temperature buried charcoals are burnt till apparent porosity, the volume density (GB/T2997-1982) of sample after 3h
3) 1400 DEG C of high temperature buried charcoals are burnt till compressive strength (GB/T3001-2007), the folding strength (GB/T5072-2004) of sample after 3h
3.2 test result
Can find out from Fig. 1 ~ Fig. 4, Q value is larger on the impact of stemming performance.Q value hour, intensity, void content and volume density after stemming high temperature sintering have had obvious improvement.Meanwhile, plasticity-is also that the less plasticity-of Q value is higher.For anhydrous stemming, solid accumulation is unlike unshape refractory, utilizes flowing of material and reach fine and close under shock conditions, and anhydrous stemming is extrusion molding.In extrusion process, material does not have external force not move, and when Q value is maximum, particle is stressed in extrusion process, but it is fine and close that intergranular gap is not easy to fill: Q value hour, in extrusion process, material is all stressed, makes material densification, so little Q value material can make stemming performance reach special requirement.
Grain composition is one of principal element affecting stemming performance as can be seen here, and the fine powder material ratio in stemming composition increases, and can make the plasticity-of stemming improve, and reduces the extrusion pressure of stemming, good work, and after heating, volume density is high, and apparent porosity is low.Fine powder material is conducive to stemming sintering, improves the intensity of stemming.
the improvement of bonding agent for 4 environment-friendly type anhydrous stemmings
Coal tar and pitch that tradition stemming bonding agent uses all belong to complicated condensed ring arene material, they have good plasticity and durability, but temperature is slightly high will give out acid, peppery, smelly gas and yellow smog, particularly benzene reaches 1v%-2.5v% than the content of pyrene.As everyone knows, benzopyrene is one of universally acknowledged carcinogenic substance, and it easily causes the major diseases such as cancer of the stomach, lung cancer, tumour cancer, serious harm Working environment and health of human body.At present, the manufacturer of developed country's anhydrous stemming and user's common concern is the content of benzopyrene in bonding agent, free-phenol and formaldehyde.
This test and Selection 4 kinds of liquid bonding agents with different viscosity and fixed carbon content, wherein M is carbolineum (belonging to alkanes substance), N is coal tar (belonging to coal tar product), O is lacquer resins (belonging to the one of resol), P class bonding agent is composite binder of the present invention, i.e. consisting of of bonding agent: containing 40 parts of carbon resins, 32 parts of Vegetable oil lipoprotein, 20 parts of linear phenolic resins, 8 parts of carbon dusts.
Bonding agent performance is in table 7.
Table 7 bonding agent performance
4.1 sample preparations
First prepare burden by table 8, that stemming M, stemming N in table 8, stemming O, stemming P add respectively is bonding agent M, bonding agent N, bonding agent O, the bonding agent P in table 7, with reference to 1.2 method sample preparation, thermal treatment, check the impact of four kinds of different bonding agents on anhydrous stemming performance:
Table 8 sample composition (wt%)
4.2 sample test items
1) stemming horse summer value (with GDP-500 type stemming detector);
2) shear-stress (draw ring test method(s)) of stemming 300 DEG C time;
3) mode of appearance of stemming while being heated to rapidly 500 DEG C;
4) 1000 DEG C and 1400 DEG C of high temperature buried charcoals are burnt till compressive strength (GB/T3001-2007), folding strength (GB/T5072-2004) and the apparent porosity (GB/T2997-2000) after 3h.
4.3 test result
4.3.1 the relation of liquid bonding agent add-on and viscosity
From table 7 and table 8, can find out: along with bonding agent viscosity becomes large, its add-on also increases.Bonding agent in stemming plays a part dispersion agent and bonding agent, and relative movement frictional force is reduced on the surface that is wrapped in particulate material and fine powder that they form.If the viscosity of bonding agent is large, if will play identical dissemination, makes wrap film thickness increase, thereby increased the consumption of bonding agent.
4.3.2 the shear-stress of stemming 300 DEG C time
In iron mouth, beat in the process of mud, in the scope that is 5 ~ 10mm apart from iron notch inwall, the temperature of stemming is 200 ~ 300 DEG C, at this moment all bonding agents all have minimum viscosity number, therefore, the stemming mobility state air exercise mud pressure influence in this region is larger, can indirectly judge the mobility of stemming and be out of shape complexity with beating mud pressure.For this reason, detected 300 DEG C at the shear-stress of stemming, wherein stemming M is that 19.2N, stemming N are that 9.1N, stemming O are that 16.8N, stemming P are 9.4N.As can be seen here, stemming M, the O shear-stress in the time of 300 DEG C is large, poor fluidity, and stemming N, the P shear-stress in the time of 300 DEG C is little, and flowing property is better.
4.3.3 the mode of appearance of stemming 500 DEG C time
4 kinds of stemmings are heated rapidly to 500 DEG C by the method that coke granule is buried in employing, observes the mode of appearance of stemming.Result shows: stemming M, O, P all show intact mode of appearance, and the surface of stemming N and longitudinally cut after section all there is larger crackle.Think, because the bonding agent N viscosity add-on that causes bigger than normal is many, make the volatile matter in bonding agent just many, and volatile matter was not all evaporated completely before stemming surface hardening, thereby at the larger stress of the inner generation of stemming, cause the cracking of stemming.
4.3.4 the intensity of stemming and apparent porosity after pyroprocessing
Fig. 5 and Fig. 6 are respectively compressive strength and the folding strength of stemming sample after thermal treatment.Can find out from Fig. 5 and Fig. 6: along with the increase of fixed carbon content bonding agent, after thermal treatment, the physical strength of stemming increases gradually, this is due to its at high temperature coking charing, has formed the carbon of greater amt in conjunction with network, therefore can significantly improve the intensity of anhydrous stemming; And along with the raising of thermal treatment temp, it is large that the physical strength of stemming becomes, this is due to physics chemical action occurring between raw mineral materials, has generated new mineral facies, has optimized stemming structure.But N cracks in temperature-rise period due to stemming, thereby affect the intensity after its heating.
1400 DEG C of buried charcoals are burnt till the apparent porosity of sample after 3h and are respectively: stemming M 30.2%, stemming N 28.6%, stemming O 27.3%, stemming P 24.2%.Hence one can see that: the carbon residue amount of liquid bonding agent is higher, and after thermal treatment, the apparent porosity of stemming is lower, and this is because bonding agent adds and filled in more open pore in bunching process being heated.
determining of 5 environment-friendly type anhydrous stemming processing parameters
The design of 5.1 formula for a product
Be based on meeting the requirement of the following three aspects: of environment-friendly type anhydrous stemming: (1) harmful substance contents is few, harmless; (2) smoke dust, little to environmental influence; (3) meet the service requirements of blast furnace flushing and casting.The particular surroundings and the purposes that use according to anhydrous stemming, through lot of experiments, determine add-on and the size composition of various starting material the bests.Environment-friendly type anhydrous stemming composition and the composition produced should meet following requirement:
Q value is between 0.45 ~ 0.55
Al
2O
3 ≥ 45 % Si
3N
4+SiC≥ 20 %
C ≥ 19%
5.2 determine product processes parameter:
Envrionment temperature in process of production of stemming and the technological process of production determine should be to greatest extent round easily the squeezing into of stemming, easy-sintering, resistance to erosion, anti-erosion, easily carry out the aspect such as opening.
5.2.1 determining of temperature of charge
Bonding agent is heated to 80-85 DEG C, stirs temperature while grinding processed and, at 55-60 DEG C, squeezes mud mouth temperature and be advisable at 75-80 DEG C.
5.2.2 determining of the technological process of production
According to formula requirement, accurately take particulate material and add in anhydrous stemming special-purpose stirring machine and stir 2 minutes, adding afterwards formula to require 70% of bonding agent weight, stir 3 minutes, add again the powder stirring 15 minutes that premix gets togather, finally add the bonding agent lefting in, stir 20 minutes.From thief hole sampling, detect horse summer value qualified, discharging.If horse summer value is higher, then add appropriate bonding agent to continue to stir, the combination dosage at every turn appending must not exceed total material heavy 0.5%, continue to stir after 5 minutes, detect horse summer value qualified after, discharging.The pug being stirred is extruded from mud extruder, cut by certain length, packaging, warehouse-in.
6 product detection devices
Product detects horse summer value with GDP-500 type stemming detector, and supporting chemical examination and detecting instrument equipment, in table 9.
Table 9 chemical examination and test experience equipment
7 product pilot scales
1) accurately taking required various powder according to embodiment 1 stemming D pours in forced mixer and stirs and emit for subsequent use in 10 minutes;
2) bonding agent making is heated to 80 DEG C-85 DEG C for subsequent use;
3) by thermal oil, the temperature in anhydrous stemming special-purpose stirring machine is risen to 55 DEG C-60 DEG C, the temperature of squeezing mud mouth is controlled at 80 DEG C, and the temperature of the temperature while normally production in stirrer and crowded mud mouth also will remain within the scope of this;
4) accurately take required various particulate material according to embodiment 1 stemming D, add in anhydrous stemming special-purpose stirring machine and stir 2 minutes, add again the 70wt% of required bonding agent to stir 3 minutes, then add the powder stirring 15 minutes that premix gets togather, finally add remaining bonding agent to stir 20 minutes, be worth from the thief hole inspection by sampling horse summer, qualified discharging, Ruo Maxia value is higher, append appropriate bonding agent, the combination dosage at every turn appending, can not exceed total material heavy 0.5%, continue to stir 5 minutes, detect the qualified rear discharging of horse summer value and squeeze mud drum dress, 10 batches of so continuous productions, detect index in table 10:
Table 10 10 batch products detect index and detected result
Above result shows: by the strict control to temperature in environment-friendly type anhydrous stemming production process, to the optimization of order of addition(of ingredients) and production technique, greatly improve the stability of anhydrous stemming horse summer value, by adding the bonding agent in the present invention, make the carcinogenic substance benzopyrene content in anhydrous stemming be down to extremely low.Be total to the highest 0.727MPa of horse summer value in 10 batches that produce, the horse summer is worth minimum 0.706MPa, average horse summer value 0.716MPa, and the highest 21ppm of carcinogenic substance benzopyrene content, minimum 17 ppm, average 18.8 ppm, can realize suitability for industrialized production.
Claims (5)
1. an environment-friendly type anhydrous stemming, it is characterized in that, by weight, consisting of of described stemming: 15～20 parts, coke, 22～43 parts of bauxitic clays, 0～10 part, brown corundum, 20～25 parts, silicon carbide, 0～8 part of silicon nitride, 0～3 part of Pure Silicon Metal, 10～15 parts of clays, 3～6 parts of sericites, 15～20 parts of bonding agents, wherein, except bonding agent, total umber of unclassified stores is 100 parts; Described bonding agent is made up of the raw material of following weight parts: containing 20～60 parts of carbon resins, 20～50 parts of Vegetable oil lipoprotein, 10～40 parts of lacquer resinss, 5～10 parts of carbon dusts.
2. environment-friendly type anhydrous stemming as claimed in claim 1, is characterized in that, described coke: 5～10 parts of 3mm >=particle diameter > 1mm, 8～15 parts of 0.1mm≤particle diameter≤1mm; Described bauxitic clay: 4～25 parts of 6～10 parts of 3mm >=particle diameter > 1mm, 8～15 parts of 0.1mm≤particle diameter≤1mm, particle diameter 180 object.
3. environment-friendly type anhydrous stemming as claimed in claim 1 or 2, is characterized in that, particle diameter≤200 order of described brown corundum, silicon carbide, silicon nitride, Pure Silicon Metal and sericite, particle diameter≤325 order of clay.
4. environment-friendly type anhydrous stemming as claimed in claim 3, it is characterized in that, by weight, consisting of of described stemming: 8 parts of the bauxitic clays of 7 parts, the coke of 3mm >=particle diameter > 1mm, 10 parts, the coke of 0.1mm≤particle diameter≤1mm, 3mm >=particle diameter > 1mm, 10 parts of the bauxitic clays of 0.1mm≤particle diameter≤1mm, 4 parts of 180 order bauxitic clays, 200 10 parts, order palm fibre corundum, 22 parts, 200 order silicon carbide, 8 parts of 200 order silicon nitrides, 3 parts of 200 order Pure Silicon Metals, 13 parts of 325 order clays, 5 parts of 200 order sericites, 16.5 parts of bonding agents; Consisting of of described bonding agent: containing 40 parts of carbon resins, 32 parts of Vegetable oil lipoprotein, 20 parts of linear phenolic resins, 8 parts of carbon dusts.
5. the preparation method of the environment-friendly type anhydrous stemming as described in any one of claim 1～4, it is characterized in that, comprise the following steps: 1) accurately take required various material, mix preparing the required each raw material of bonding agent, be heated to 100～120 DEG C, under 0.5～0.7MPa, stir, dewater, when detecting its viscosity Engler 9～11, when water content is less than 0.5wt%, stop heating, 45～55 DEG C of constant temperature store, for subsequent use;
2) material of particle diameter < 0.1mm is poured in stirrer and stirred and emit for subsequent use in 5～15 minutes;
3) bonding agent of getting step 1) be heated to 80 DEG C-85 DEG C for subsequent use;
4) temperature in anhydrous stemming stirrer is risen to 55 DEG C-60 DEG C, the temperature of squeezing mud mouth is controlled at 75 DEG C-80 DEG C;
5) leftover materials are added in anhydrous stemming stirrer and stir 1～5 minute, then add step 3) gained bonding agent 60～80wt% stir 1～5 minute, then add step 2) gains stir 10～20 minutes; Finally add remaining bonding agent to stir 15～30 minutes, be worth from the thief hole inspection by sampling horse summer, make the horse summer value of stemming be controlled at 0.7-0.73MPa, qualified discharging, Ruo Maxia value is higher, appends bonding agent, the bonding agent weight of at every turn appending, can not exceed total material heavy 0.5%, continue to stir at least 5 minutes, detect the qualified rear discharging of horse summer value and squeeze mud drum dress.
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| CN105110674A (en) * | 2015-08-20 | 2015-12-02 | 北京联合荣大工程材料有限责任公司 | Bonding agent, stemming including bonding agent and preparation method of stemming |
| CN105218111A (en) * | 2015-09-21 | 2016-01-06 | 绥芬河鑫耐科技发展有限责任公司 | Anhydrous stemming |
| CN105237000A (en) * | 2015-09-21 | 2016-01-13 | 江苏新环美节能技术有限公司 | Blast-furnace anhydrous stemming and production device thereof |
| CN105906359A (en) * | 2016-04-29 | 2016-08-31 | 郑州赛沃科技有限公司 | Environment-friendly stemming and preparation method thereof |
| CN106830952A (en) * | 2016-12-16 | 2017-06-13 | 中冶建筑研究总院有限公司 | Anhydrous stemming and preparation method thereof |
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| CN108794029A (en) * | 2018-07-17 | 2018-11-13 | 北京瑞普同创科技发展有限公司 | Titaniferous environmental-protection furnace stemming |
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| CN108794029A (en) * | 2018-07-17 | 2018-11-13 | 北京瑞普同创科技发展有限公司 | Titaniferous environmental-protection furnace stemming |
| CN108640662B (en) * | 2018-07-17 | 2020-08-25 | 北京瑞普同创科技发展有限公司 | Environment-friendly anhydrous stemming |
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