CN104119081B - Coke oven high thermal conductive silicon brick - Google Patents
Coke oven high thermal conductive silicon brick Download PDFInfo
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- CN104119081B CN104119081B CN201310146445.6A CN201310146445A CN104119081B CN 104119081 B CN104119081 B CN 104119081B CN 201310146445 A CN201310146445 A CN 201310146445A CN 104119081 B CN104119081 B CN 104119081B
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Abstract
The present invention relates to a kind of coke oven high thermal conductive silicon brick and preparation method thereof.A kind of coke oven high thermal conductive silicon brick, its composition is by weight percentage: natural silica particle 68.0% ~ 82.0%, natural silica fine powder 13.0% ~ 26.0%, containing dispersion agent 0.5% ~ 2.0% in additive, containing siliceous non-oxidized substance 1.5% ~ 5.0%; Mineralizer 1.0% ~ 3.0%; Bonding agent is+1.5% ~ 3.0% of additional above material gross weight.Described additive comprises dispersion agent carboxymethyl cellulose (CMC), carboxymethyl cellulose granularity < 0.088mm; Siliceous non-oxidized substance Si granularity < 0.043mm, wherein Si content > 96wt%.Silica brick of the present invention has high thermal conductivity and keeps silica brick other comprehensive premium properties, can meet the needs of coke oven's long campaign, energy-conservation and High-efficient Production simultaneously.
Description
Technical field
The present invention relates to a kind of siliceous refractory [material in coke oven field, particularly relate to a kind of coke oven high thermal conductive silicon brick.
Background technology
Silica brick is that modern capacity coke oven builds topmost refractory materials by laying bricks or stones, and the design direction of advanced coke oven is efficient, long-lived, energy saving standard, and the properties of silica brick directly affects the advance of coke oven technology.For a long time, the fire performance such as intensity, thermal shock, loading softening of people's many concerns silica brick, in the hope of the coke oven long lifetime as much as possible.But along with energy-conservation with the increasingly stringent of environmental requirement, enterprise requirements coke oven saves gas consumption in process of coking, reduce the discharge of COx and NOx simultaneously.The energy-conservation of coke oven mainly contains two kinds of methods: (1) reduces coking chamber wall thickness; (2) thermal conductivity of coking chamber wall refractory materials is improved.But thinning furnace wall thickness will certainly reduce the intensity of structural unit, cause the reduction of overall construction intensity, finally cause the decline in furnace wall life-span.So in the conservation measures of coke oven, coking chamber wall selects the material with high heat conductance to be selection most suitable in conservation measures.Therefore, as the Main Refractory that coke oven is applied---silica brick, the raising of its heat conductivility seems particularly important.
Along with the development of silica brick manufacturing technology, the various novel silica brick with specific demand arises at the historic moment, and such as Chinese patent 200810049567.2 discloses a kind of nanometer composite silicon brick and preparation method thereof, and the feature of this patented technology is to have employed Nano-meter CaCO3
3, nano-sized iron oxide, Nano-meter SiO_2
2raw material, puts into water and is beneficial to dispersion.The advantage of its silica brick is that compressive strength is high, can reduce firing temperature 20 DEG C to save the energy simultaneously.Chinese patent 200510048575.1 discloses a kind of composite silicon brick, and the hotblast stove of this patent and silica brick for coke oven emphasize the feature that good thermal shock stability, load softening point are high, compressive strength is high, have employed SiC raw material in manufacture, additive Na
2cO
3with iron scale powder, mineralizer CaO.Chinese patent 20071006241.5 discloses a kind of 7.63m silica brick for coke oven, and its silica brick has that compressive strength is high, void content is low, refractoriness is high, Fe
2o
3low feature, the feature of manufacturing technology is additive manganese powder and potassium felspar sand, and mineralizer adopts milk of lime.Above prior art is all to highlight the Typical physical performance improving silica brick, to meet the needs of coke oven's long campaign; Manufacturing technology have employed some special source materials, to reach technical indicator more better than common silica brick.
In existing silica brick manufacturing technology, also there is the problem that silica brick internal structure performance is relatively uneven.Mix in operation because silica brick is manufactured on, adding of traditional mineralizer-milk of lime adds in edge runner-wet mill by pipeline, wrapped up rapidly by part silica granule and fine powder, and can not be evenly distributed in pug well, this makes the skewness of CaO in adobe.SiO between particle and matrix is at the same temperature made in sintering process
2crystal conversion is uneven, and some local conversion are too fast, and some local conversion are excessively slow again, the expansion stress that such brick body inside produces due to crystal conversion is very uneven, be easy to the generation causing gross blow hole, even crackle, so not only affect yield rate, also affect the stability of silica brick quality.So want that making mineralizer homogenizing distribute has limitation, can affect the homogeneity of silica brick internal structure like this, thus can affect silica brick performance only by the mechanical agitation methods of physics.
Existing common silica brick is due to its traditional mineralizer remineralization efficacy and the limitation adding form, and make silica brick work in-process make moisture distribution in base process even not, pug moisture is also higher.Silica brick is after burning till, and it is also very uneven that moisture gets rid of the gas cell distribution stayed, and pore bunch group's concentration of local situation is given prominence to, and this all seriously have impact on the raising of silica brick thermal conductivity.
Summary of the invention
The object of the present invention is to provide a kind of coke oven high thermal conductive silicon brick, this silica brick has high thermal conductivity and keeps silica brick other comprehensive premium properties, can meet the needs of coke oven's long campaign, energy-conservation and High-efficient Production simultaneously.
In order to realize above-mentioned technical purpose, the present invention adopts following technical scheme:
A kind of coke oven high thermal conductive silicon brick, its composition is by weight percentage: natural silica particle 68.0% ~ 82.0%, natural silica fine powder 13.0% ~ 26.0%, containing dispersion agent 0.5% ~ 2.0% in additive, containing siliceous non-oxidized substance 1.5% ~ 5.0%; Mineralizer 1.0% ~ 3.0%; Bonding agent is+1.5% ~ 3.0% of additional above material gross weight.
Described natural silica particle is 3-0mm, and fine powder is < 0.074mm, SiO in natural silica
2content>=98.5%.
Described bonding agent is lignosulfite, proportion 1.1 ~ 1.3.
Described additive comprises dispersion agent carboxymethyl cellulose (CMC), carboxymethyl cellulose granularity < 0.088mm; Siliceous non-oxidized substance Si granularity < 0.043mm, wherein Si content > 96%.
Described mineralizer is aluminous cement, its granularity < 0.043mm, wherein Al
2o
3content > 65%.
A kind of coke oven high thermal conductive silicon brick preparation method, silica raw material and additive, mineralizer, additional bonding agent are sent in edge runner-wet mill according to a certain ratio and mixes, by mixed material through brick pressing machine mechanical pressing, adobe after shaping is admitted in moisture eliminator, the temperature of moisture eliminator is between 100 ~ 150 DEG C, and time of drying is 24 ~ 48 hours; Dried adobe is put into tunnel furnace and is sintered, and firing temperature is 1420 ~ 1450 DEG C, is incubated 48 ~ 60 hours, namely obtains described high thermal conductive silicon brick after burning till.
Special additive is introduced in high thermal conductive silicon brick of the present invention, decrease pug moisture content, and being uniformly distributed of glassy phase is facilitated by chemical reaction in sintering process, and be filled with the hole of particle surface and matrix preferably, make the densification more of silica brick internal microstructure, this is that the raising of silica brick thermal conductivity provides the foundation.
High thermal conductive silicon brick of the present invention is on the basis keeping silica brick good physical behavior, and be have adjusted the microtexture of silica brick inside by chemical reaction, heat conductivility is significantly improved, the energy-conservation and High-efficient Production for the current special concern of coke oven has extraordinary effect.
High thermal conductive silicon brick of the present invention is used on coking chamber wall, and the heat that each quirk in combustion chamber is delivered in coking chamber in the same time can be made more, and like this when not changing technique, coking time can shorten; If do not change coking cycle, then the flame temperature in quirk can have and reduces to a certain extent, so just serves the effect reducing the burnt thermal losses of ton.Calculate for JNX-70-2 Formed Coke Furnace (2 groups × 60 hole): 31840.8t can be saved every year according to coke-oven gas heating and mark coal; 35833.7t can be saved every year according to blast furnace (BF) gas heating and mark coal.Therefore under the condition not changing existing production system, not only can reduce the fuel quantity in the unit time, the exhaust gas volumn produced due to unit of fuel is certain, the exhaust gas volumn then produced in the unit time reduces, flue gas is by ensureing the heat-exchange time more grown during regenerator lattice brick, the temperature out of final reduction flue gas, also can reach energy-saving effect.If do not change supply fuel quantity and heating cycle, then can increase production 22.6%, the target of High-efficient Production can be reached.Therefore coke oven industry adopts high thermal conductive silicon brick significant.
Silica brick internal void of the present invention is evenly distributed, and the common silica brick of aperture ratio is little, and silica brick structure is more even, makes silica brick thermal conductivity ratio of the present invention tradition silica brick improve more than 20%.
Accompanying drawing explanation
Fig. 1 is existing common coke oven silica brick 15 times of scanning electron microscopic picture;
Fig. 2 is high thermal conductive silicon brick of the present invention 15 times of scanning electron microscopic picture.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
A kind of coke oven high thermal conductive silicon brick, with natural silica particle and silica fine powder, according to certain ratio fused mineralizer, additive and additional bonding agent.The weight percent (wt%) of starting material is natural silica particle 68.0% ~ 82.0%, and natural silica fine powder is 13.0% ~ 26.0%, containing dispersion agent 0.5% ~ 2.0% in additive, containing siliceous non-oxidized substance 1.5% ~ 5.0%; Mineralizer 1.0% ~ 3.0%; Bonding agent is+1.5% ~ 3.0% of additional above material gross weight.The particle of natural silica described in raw material is 3-0mm, and fine powder is < 0.074mm, SiO in natural silica
2content>=98.5wt%; Described bonding agent is lignosulfite, proportion 1.1 ~ 1.3; Described additive comprises dispersion agent carboxymethyl cellulose (CMC), carboxymethyl cellulose granularity < 0.088mm, siliceous non-oxidized substance Si granularity < 0.043mm, wherein Si content > 96wt%.Described mineralizer is aluminous cement, its granularity < 0.043mm, wherein Al
2o
3content > 65wt%.
A kind of coke oven high thermal conductive silicon brick preparation method, silica raw material and additive, mineralizer, additional bonding agent are sent in edge runner-wet mill according to a certain ratio mix, by mixed material through brick pressing machine mechanical pressing, adobe after shaping is admitted in moisture eliminator, the temperature of moisture eliminator is between 100 ~ 150 DEG C, and time of drying is 24 ~ 48 hours; Dried adobe is put into tunnel furnace and is sintered, and firing temperature is 1420 ~ 1450 DEG C, is incubated 48 ~ 60 hours, namely obtains high thermal conductive silicon brick of the present invention after burning till.
The principle of coke oven high thermal conductive silicon brick of the present invention and preparation method thereof is: by adding dispersion agent, and the better mineralizer of remineralization efficacy, make the synchronism of crystal conversion between silica brick particle and matrix in sintering process better, at high temperature due to crystal formation change and produce expansion evenly, improve originally because the hole of the uneven generation of expanding is concentrated largely, aperture more greatly, even crackle situation about being formed.The siliceous non-oxidized substance Si of additive first produces liquid phase in temperature-rise period, alleviate the expansion stress of silica brick in sintering process well, avoid the larger space because stress relieve causes not in time, crack and other defect, the oxidation of this material can pore between filler particles simultaneously.In addition, the introducing of dispersion agent, moisture is disperseed in pug evenly, and half-finished moisture obtains effective reduction, for being uniformly distributed of final finished pore provides the foundation.Can clearly be seen (as shown in Figure 1, 2) by scanning electron microscopic picture, silica brick internal void of the present invention is evenly distributed, and the common silica brick of aperture ratio is little, and structure is even compact more, and the thermal conductivity of silica brick of the present invention is greatly increased.Tradition silica brick thermal conductivity range is at 1.80-2.05w/mk, and product thermal conductivity range of the present invention can reach 2.30-2.50w/mk.
Embodiment 1: with weight percentage, adds natural silica particulate material 82.0%, fine powder material 13.0%, Si1.5%, CMC0.5%, calcium aluminate 3.0%, additional lignosulfite+1.5%.After being weighed up by above-mentioned raw materials, put into edge runner-wet mill, mix 30 minutes, be pressed into base with brick pressing machine machine, then base substrate is sent into temperature is in the moisture eliminator of 120 DEG C dry 36 hours.Enter kiln high temperature sintering after oven dry, temperature rise rate is about 15 DEG C/h, and firing temperature is 1435 DEG C, and soaking time is 54 hours, and rate of cooling is 20 DEG C/h, is cooled to normal temperature, product kiln discharge.
Embodiment 2: with weight percentage, adds natural silica particulate material 78.0%, fine powder material 17.0%, Si1.0%, CMC1.5%, calcium aluminate 2.5%, additional lignosulfite+2.0%.After being weighed up by above-mentioned raw materials, put into edge runner-wet mill, mix 30 minutes, be pressed into base with brick pressing machine machine, then base substrate is sent into temperature is in the moisture eliminator of 130 DEG C dry 32 hours.Enter kiln high temperature sintering after oven dry, temperature rise rate is about 15 DEG C/h, and firing temperature is 1450 DEG C, and soaking time is 48 hours, and rate of cooling is 20 DEG C/h, is cooled to normal temperature, product kiln discharge.
Embodiment 3: with weight percentage, adds natural silica particulate material 74.0%, fine powder material 18.0%, Si5.0%, CMC1.0%, calcium aluminate 2.0%, additional lignosulfite+2.2%.After being weighed up by above-mentioned raw materials, put into edge runner-wet mill, mix 30 minutes, be pressed into base with brick pressing machine machine, then base substrate is sent into temperature is in the moisture eliminator of 150 DEG C dry 24 hours.Enter kiln high temperature sintering after oven dry, temperature rise rate is about 15 DEG C/h, and firing temperature is 1420 DEG C, and soaking time is 60 hours, and rate of cooling is 20 DEG C/h, is cooled to normal temperature, product kiln discharge.
Embodiment 4: with weight percentage, adds natural silica particulate material 72.0%, fine powder material 24.0%, Si2.0%, CMC0.5%, calcium aluminate 1.5%, additional lignosulfite+2.5%.After being weighed up by above-mentioned raw materials, put into edge runner-wet mill, mix 30 minutes, be pressed into base with brick pressing machine machine, then base substrate is sent into temperature is in the moisture eliminator of 110 DEG C dry 40 hours.Enter kiln high temperature sintering after oven dry, temperature rise rate is about 15 DEG C/h, and firing temperature is 1440 DEG C, and soaking time is 50 hours, and rate of cooling is 20 DEG C/h, is cooled to normal temperature, product kiln discharge.
Embodiment 5: with weight percentage, adds natural silica particulate material 68.0%, fine powder material 26.0%, Si3.0%, CMC2.0%, calcium aluminate 1.0%, additional lignosulfite+3.0%.After being weighed up by above-mentioned raw materials, put into edge runner-wet mill, mix 30 minutes, be pressed into base with brick pressing machine machine, then base substrate is sent into temperature is in the moisture eliminator of 100 DEG C dry 48 hours.Enter kiln high temperature sintering after oven dry, temperature rise rate is about 15 DEG C/h, and firing temperature is 1430 DEG C, and soaking time is 56 hours, and rate of cooling is 20 DEG C/h, is cooled to normal temperature, product kiln discharge.
The common silica brick of table 1 and high thermal conductive silicon brick Performance comparision of the present invention
More known by table 1: high thermal conductive silicon brick of the present invention improves thermal conductivity on the basis that ensure that the physical and chemical performance that common silica brick is excellent, brick body consistent internal structure, excellent combination property.
Along with the whole society's increasing substantially degrees of awareness such as green, low-carbon (LC), environmental protection, promote and the common recognition using green refractory materials to become fire-resistant industry and high temperature industry.Silica brick is as the Main Refractory that coke oven is applied, and the raising of its heat conductivility seems particularly important.The heat of coke oven combustion chamber is transmitted in coking chamber by silica brick furnace wall, at identical tactile coal face area, in the identical time, flame combustion chamber temperature-resistant, the heat transmitted by high thermal conductive silicon brick is compared common silica brick and is wanted many, the fuel quantity be so smelt needed for ton Jiao must reduce, and serves energy-conservation effect.While energy-conservation, NOx, COx gas be discharged in air will inevitably reduce, and therefore, high thermal conductive silicon brick also serves the effect of environmental protection while energy-conservation.Adopt high silica brick of leading also can subtract burning coking time simultaneously, improve coke output, for enterprise brings huge economic benefit.
High thermal conductive silicon brick of the present invention improves thermal conductivity on the basis that ensure that traditional silica brick high-temperature physics chemical property, so this product is structural and functional balanced excellent, a kind of effective power-economizing method is provided, for the energy-saving and emission-reduction of enterprise, clean and effective are produced and provided new technology approach to coke oven.
Claims (5)
1. a coke oven high thermal conductive silicon brick, it is characterized in that: the composition of described high thermal conductive silicon brick is by weight percentage: natural silica particle 68.0% ~ 82.0%, natural silica fine powder 13.0% ~ 26.0%, containing dispersion agent 0.5% ~ 2.0% in additive, containing siliceous non-oxidized substance 1.5% ~ 5.0%; Mineralizer 1.0% ~ 3.0%; Bonding agent is+1.5% ~ 3.0% of additional above material gross weight; Si content > 96%, Si granularity < 0.043mm in described siliceous non-oxidized substance.
2. coke oven high thermal conductive silicon brick according to claim 1, is characterized in that: described natural silica particle is 3-0mm, and fine powder is < 0.074mm, SiO in natural silica
2content>=98.5%.
3. coke oven high thermal conductive silicon brick according to claim 1, is characterized in that: described bonding agent is lignosulfite, proportion 1.1 ~ 1.3.
4. coke oven high thermal conductive silicon brick according to claim 1, is characterized in that: the dispersion agent in described additive is carboxymethyl cellulose (CMC), carboxymethyl cellulose granularity < 0.088mm.
5. coke oven high thermal conductive silicon brick according to claim 1, is characterized in that: described mineralizer is aluminous cement, its granularity < 0.043mm, wherein Al
2o
3content > 65%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104591749B (en) * | 2014-11-12 | 2016-06-08 | 中钢集团耐火材料有限公司 | A kind of super-high heat-conductive silica brick and preparation method thereof for oven wall of coke oven carbonization chamber |
| CN106278297A (en) * | 2015-06-26 | 2017-01-04 | 沈阳铝镁设计研究院有限公司 | Petroleum coke can-type calcine furnace silica brick of resistance to sulphur corrosion and preparation method thereof |
| CN107805077B (en) * | 2017-11-08 | 2020-08-04 | 济源市耐火炉业有限公司 | Composite low-aluminum checker brick and production method thereof |
| CN107867868B (en) * | 2017-12-02 | 2020-10-13 | 山东鲁桥新材料股份有限公司 | Ultra-compact high-thermal-conductivity silica brick and preparation method thereof |
| CN109574641A (en) * | 2018-12-27 | 2019-04-05 | 中钢集团耐火材料有限公司 | A kind of energy-saving hot-air stove high thermal conductivity silica brick |
| CN113087504A (en) * | 2021-04-16 | 2021-07-09 | 郑州东豫新材料科技有限公司 | High-thermal-conductivity compact silica brick and preparation method thereof |
| CN113416081A (en) * | 2021-06-30 | 2021-09-21 | 南京钢铁股份有限公司 | Preparation method of fired ultrathin siliceous plate for pouring large high-quality steel ingot |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597175A (en) * | 2009-06-29 | 2009-12-09 | 河北理工大学 | A kind of silica refractory material with high tridymite content and preparation method thereof |
| CN102126866A (en) * | 2011-04-06 | 2011-07-20 | 瑞泰科技股份有限公司 | High-purity silica refractory material and production process thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597175A (en) * | 2009-06-29 | 2009-12-09 | 河北理工大学 | A kind of silica refractory material with high tridymite content and preparation method thereof |
| CN102126866A (en) * | 2011-04-06 | 2011-07-20 | 瑞泰科技股份有限公司 | High-purity silica refractory material and production process thereof |
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