CN105541351B - Glass melter regenerator top specific complex spinelle zirconia block and its manufacture method - Google Patents

Glass melter regenerator top specific complex spinelle zirconia block and its manufacture method Download PDF

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CN105541351B
CN105541351B CN201510959494.0A CN201510959494A CN105541351B CN 105541351 B CN105541351 B CN 105541351B CN 201510959494 A CN201510959494 A CN 201510959494A CN 105541351 B CN105541351 B CN 105541351B
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zirconia
granularity
spinelle
glass melter
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CN105541351A (en
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董跃
慕松林
董梅花
张方浩
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ZHENGZHOU HUITE REFRACTORY MATERIALS CO Ltd
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ZHENGZHOU HUITE REFRACTORY MATERIALS CO Ltd
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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Abstract

It is by 35~62 parts of dense alumina, 12~18 parts of plate diamond spar, 8~14 parts of fused zirconia-mullite, 5~11 parts of chrome ore, 10~13 parts of chrome green, 1~4 part of electric-melting zirconia, β Al the invention discloses a kind of glass melter regenerator top specific complex spinelle zirconia block2O3 2~5 parts and appropriate bonding agent are prepared from：Above-mentioned raw materials are put into strength puddle mixer and carried out after batch mixing and ageing mixture 48h, adobe is pressed on a hydraulic press, send into drying kiln for drying more than 60 hours, it is sent at a temperature of 1600~1650 DEG C of hyperthermia tunnel Kiln and burns till again, 120~150 minutes stroller time, obtain composite spinelle zirconia block finished product.The composite spinelle zirconia block that the present invention is produced substitutes other refractory brick for being applied to glass melter regenerator top at present, substantially increases the service life of glass melter.Simultaneously manufacture method of the present invention simply, the characteristics of with short production cycle, efficiency high.

Description

Glass melter regenerator top specific complex spinelle zirconia block and its manufacture method
Technical field
The present invention relates to refractory material, more particularly, to a kind of glass melter regenerator top specific complex Zirconium spinel Brick, the invention further relates to the manufacture method of the composite spinelle zirconia block.
Background technology
In recent years, the metallurgy industry of China's glass is developed rapidly, refractory material manufacture and the raising of use level, is The safe operation of glass melter provides reliable guarantee.So far, using high-grade basic refractory as glass melter regenerator The supporting mode of the resistance to material of checker is still occupied an leading position in China's glass industry.With the structural adjustment of glass industries, some Technique falls behind, pollutes larger kiln and be gradually eliminated, and is replaced by large-scale environmentally friendly kiln.But many manufacturers are Glass throughput is pursued, efficiency is improved, the granularity of raw material can be reduced as possible, causes the winged doses into regenerator to increase, together When increasingly sharpen due to market competition, many manufacturers are reduction production cost, are increased economic efficiency, fuel by heavy oil, Natural gas or coal gas are changed to after petroleum coke powder, petroleum coke powder combustion that substantial amounts of SO can be produced2And V2O5, this flue gas is molten into glass After kiln regenerator, exacerbate the Corrosion rate of refractory material, cause be for the content of MgO of glass melter regenerator top 97.5% or so electrically fused magnesite brick, advanced magnesite-chrome brick and magnesium zirconia block is serious due to corroding, and usage cycles are greatly shortened, service life It was reduced to 2 ~ 3 years by original 5 ~ 7 years.
The main Erosion Mechanism of the resistance to material of glass melter regenerator top is：Periclase recrystallizes growth in the basic conditions, Produce bulk effect.While MgO and SO2Reaction generation Mg SO4, so as to cause cracking and the efflorescence of refractory product.Inside resistance to material C2S and CaO and V2O5And SO2The CMS of the volatile calcium vanadate of contact generation and low melting point（1495 DEG C of fusing point）And C3MS2（It is molten 1575 DEG C of point）.Regenerator top is high due to temperature, and the erosion that temperature fluctuation is frequent and various winged material are to refractory material is serious, because This regenerator top just turns into the key factor for determining overall regenerator service life from suitable refractory material.So, grind Fixture has good resistance SO3, V2O5、SO2、Na2O、K2The erosion performances such as O, and the new resistance to material with good thermal shock resistance Product just seems particularly urgent for glass melter regenerator top.
The content of the invention
It is molten there is provided a kind of glass of high thermal shock corrosion resistance it is an object of the invention to the defect for above-mentioned prior art Kiln regenerator top specific complex spinelle zirconia block.
To achieve the above object, the present invention can take following technical proposals：
Glass melter regenerator top specific complex spinelle zirconia block of the present invention, is by raw material dense alumina, plate Shape corundum, fused zirconia-mullite, chrome ore, chrome green, electric-melting zirconia, β-Al2O3And auxiliary material bonding agent presses following weights It is prepared from：
Formula：35~62 parts of 0.1~5mm of granularity dense alumina, 12~18 parts of 1~5mm of granularity plate diamond spar, grain Spend 8~14 parts of 1 ~ 4mm fused zirconia-mullites, 5~11 parts of 0.1~1mm of granularity chrome ore, granularity≤0.045mm chrome green 10~ 13 parts, 1~4 part of granularity≤0.045mm electric-melting zirconia, granularity≤0.045mm β-Al2O3 2~5 parts；Bonding agent consumption For the 5~11% of above-mentioned raw materials gross weight.
Bonding agent used in the present invention is by aluminium dihydrogen phosphate and diesel oil in mass ratio 8:2 mixed solutions prepared.
The manufacture method of glass melter regenerator top specific complex spinelle zirconia block of the present invention is：
The first step, each raw material is weighed by above-mentioned weight；
Second step, all raw materials and bonding agent are put into strength puddle mixer together and carry out batch mixing；
3rd step, by mixed pug ageing mixture 48h（Ageing mixture in the jumbo bag with film lining can be placed on）；
4th step, shaping adobe is pressed into by the pug after ageing mixture on Full Automatic Liquid press；
5th step, will be dried, dry kiln hot blast temperature is 90~110 DEG C, is dried in shaping adobe feeding dry kiln Time is not less than 60 hours；
6th step, sends dried adobe into hyperthermia tunnel Kiln（111 meters）In, burnt at a temperature of 1600~1650 DEG C Into the stroller time is 120~150 minutes, obtains composite spinelle zirconia block finished product.
Raw materials used chemical composition requires as follows：
。
The advantage of the invention is that the composite spinelle zirconia block produced can be substituted is applied to glass melter accumulation of heat at present The Cr in ceiling portion2O3The advanced magnesite-chrome brick of content 24%, the electrically fused magnesite brick and ZrO of content of MgO 97.5%2The magnesium zirconia block of content 13%, Greatly improve the service life of glass melter regenerator top（Brought up to 5 ~ 6 years by original 2 ~ 3 years）.The hyperpyrexia of the present invention Corrosion resistance composite spinelle zirconia block is shaken using aluminium chromium eutectic, corundum, mullite, monocline zirconium as principal crystalline phase, is introduced in particle Zirconium mullite, hole is produced using the decomposition of zirconium mullite under high temperature, and introduces electric-melting zirconia in base portion, utilizes oxidation Zirconium crystal transfer in sintering process produces micro-crack etc. to improve the thermal shock resistance of product.Simultaneously base portion introduce β- Al2O3Improve product resistance K2O、Na2The performance that the alkaline matters such as O corrode, to solving glass melter regenerator top refractory material Cracking in use and deteriorate serious significant, greatly enhance the efficiency of glass melter.
Simultaneously manufacture method of the present invention simply, be molded using hydraulic press, hyperthermia tunnel Kiln is burnt till, with it is with short production cycle, The characteristics of efficiency high.
Thing between composite spinelle zirconia block and electric smelting recombined magnesia-chrome brick produced by the present invention, electrically fused magnesite brick, magnesium zirconia block Manage index contrast（Representative value）It see the table below 1.
Table 1
。
To verify the performance of composite spinelle zirconia block produced by the present invention, glass melting raw material is fetched in glass factory, and A large amount of SO are produced according to petroleum coke powder combustion3And V2O5The characteristics of, prepare a certain amount of slag specimen.High thermal shock corrosion resistance is combined Spinelle zirconia block and Cr2O3Advanced magnesite-chrome brick, content of MgO electrically fused magnesite brick and ZrO 97.5% of the content 24%2Content is 13% High temperature magnesium zirconia block carry out resistance to slag contrast experiment.
Experiment uses Static crucible method, and 120 grams of preparations are placed in 50 × 50mm of Φ unlike material refractory crucible Good slag specimen, 1460 DEG C × 6h is sintered in electric furnace, after so circulating 6 times, and crucible is splitted along crucible center, measures slag corrosion Depth, while observing the crackle degree of each crucible specimen surface to judge that the thermal shock resistance of unlike material refractory material can be excellent Bad, anti-slag experiment slag specimen composition used is shown in Table 2.Anti-slag experimental result is shown in Table 3.
The chemical composition of the anti-slag of table 2 experiment slag specimen used（%）
。
The erosion comparing result of the anti-slag of table 3 experiment
。
From the experimental result of table 3, composite spinelle zirconia block resistance glass melter produced by the present invention flies what material corroded Performance and thermal shock resistance can all be better than the Cr used at present2O3The electric smelting recombined magnesia-chrome brick of content 24%, content of MgO 97.5% Electrically fused magnesite brick and ZrO2The magnesium zirconia block of content 13%.
Embodiment
More detailed explanation is done to the present invention below by specific embodiment.
Embodiment 1
Composite spinelle zirconia block of the present invention, is by raw material dense alumina, plate diamond spar, fused zirconia-mullite, chromium Ore deposit, chrome green, electric-melting zirconia, β-Al2O3And bonding agent（By aluminium dihydrogen phosphate and diesel oil in mass ratio 8:2 mixing prepared are molten Liquid）By following weights（Match somebody with somebody including level）It is prepared from method：
The first step, 35 parts of 0.1~5mm of precise granularity dense alumina, 18 parts of 1~5mm of granularity plate diamond spar, 14 parts of 1 ~ 4mm of granularity fused zirconia-mullites, 11 parts of 0.1~1mm of granularity chrome ore, 13 parts of granularity≤0.045mm chrome green, grain 4 parts of degree≤0.045mm electric-melting zirconia, granularity≤0.045mm β-Al2O35 parts；Bonding agent consumption is above-mentioned raw materials gross weight The 5% of amount；
Second step, all raw materials and bonding agent are put into strength puddle mixer together and carry out batch mixing；
3rd step, by mixed pug in the jumbo bag with film lining ageing mixture 48h；
4th step, shaping adobe is pressed into by the pug after ageing mixture on Full Automatic Liquid press；
5th step, will be dried, dry kiln hot blast temperature is 90~110 DEG C, is dried in shaping adobe feeding dry kiln Time is not less than 60 hours；
6th step, dried adobe is sent into 111 meters of hyperthermia tunnel Kilns, burnt till at a temperature of 1600~1650 DEG C, The stroller time is 120~150 minutes, obtains composite spinelle zirconia block finished product, the testing result of finished product brick body see the table below 4.
Embodiment 2
Composite spinelle zirconia block of the present invention, is by raw material dense alumina, plate diamond spar, fused zirconia-mullite, chromium Ore deposit, chrome green, electric-melting zirconia, β-Al2O3And bonding agent（By aluminium dihydrogen phosphate and diesel oil in mass ratio 8:2 mixing prepared are molten Liquid）By following weights（Match somebody with somebody including level）It is prepared from method：
The first step, 44 parts of 0.1~5mm of precise granularity dense alumina, 16 parts of 1~5mm of granularity plate diamond spar, 12 parts of 1 ~ 4mm of granularity fused zirconia-mullites, 9 parts of 0.1~1mm of granularity chrome ore, 12 parts of granularity≤0.045mm chrome green, granularity 3 parts of≤0.045mm electric-melting zirconia, granularity≤0.045mm β-Al2O34 parts；Bonding agent consumption is above-mentioned raw materials gross weight 7%；
Second step is to the 6th step be the same as Example 1；The testing result of obtained finished product brick body see the table below 4.
Embodiment 3
Composite spinelle zirconia block of the present invention, is by raw material dense alumina, plate diamond spar, fused zirconia-mullite, chromium Ore deposit, chrome green, electric-melting zirconia, β-Al2O3And bonding agent（By aluminium dihydrogen phosphate and diesel oil in mass ratio 8:2 mixing prepared are molten Liquid）By following weights（Match somebody with somebody including level）It is prepared from method：
The first step, 53 parts of 0.1~5mm of precise granularity dense alumina, 14 parts of 1~5mm of granularity plate diamond spar, 10 parts of 1 ~ 4mm of granularity fused zirconia-mullites, 7 parts of 0.1~1mm of granularity chrome ore, 11 parts of granularity≤0.045mm chrome green, granularity 2 parts of≤0.045mm electric-melting zirconia, granularity≤0.045mm β-Al2O33 parts；Bonding agent consumption is above-mentioned raw materials gross weight 9%；
Second step is to the 6th step be the same as Example 1；The testing result of obtained finished product brick body see the table below 4.
Embodiment 4
Composite spinelle zirconia block of the present invention, is by raw material dense alumina, plate diamond spar, fused zirconia-mullite, chromium Ore deposit, chrome green, electric-melting zirconia, β-Al2O3And bonding agent（By aluminium dihydrogen phosphate and diesel oil in mass ratio 8:2 mixing prepared are molten Liquid）By following weights（Match somebody with somebody including level）It is prepared from method：
The first step, 62 parts of 0.1~5mm of precise granularity dense alumina, 12 parts of 1~5mm of granularity plate diamond spar, 8 parts of 1 ~ 4mm of granularity fused zirconia-mullites, 5 parts of 0.1~1mm of granularity chrome ore, 10 parts of granularity≤0.045mm chrome green, granularity 1 part of≤0.045mm electric-melting zirconia, granularity≤0.045mm β-Al2O32 parts；Bonding agent consumption is above-mentioned raw materials gross weight 11%；
Second step is to the 6th step be the same as Example 1；The testing result of obtained finished product brick body see the table below 4.
The testing result of the finished product brick body of the embodiment 1 ~ 4 of table 4 manufacture
。

Claims (3)

1. a kind of glass melter regenerator top specific complex spinelle zirconia block, it is characterised in that：It is by raw material dense alumina, Plate diamond spar, fused zirconia-mullite, chrome ore, chrome green, electric-melting zirconia, β-Al2O3And auxiliary material bonding agent is matched somebody with somebody by following weight parts Than being prepared from：
Formula：35~62 parts of 0.1~5mm of granularity dense alumina, 12~18 parts of 1~5mm of granularity plate diamond spar, granularity 1 ~ 8~14 parts of 4mm fused zirconia-mullites, 5~11 parts of 0.1~1mm of granularity chrome ore, 10~13 parts of granularity≤0.045mm chrome green, 1~4 part of granularity≤0.045mm electric-melting zirconia, granularity≤0.045mm β-Al2O32~5 parts；Bonding agent consumption is above-mentioned The 5~11% of raw material gross weight.
2. glass melter regenerator top specific complex spinelle zirconia block according to claim 1, it is characterised in that：It is described Bonding agent is by aluminium dihydrogen phosphate and diesel oil in mass ratio 8:2 mixed solutions prepared.
3. the manufacture method of the glass melter regenerator top specific complex spinelle zirconia block of claim 1 is：
The first step, each raw material is weighed by above-mentioned weight；
Second step, all raw materials and bonding agent are put into strength puddle mixer together and carry out batch mixing；
3rd step, by mixed pug ageing mixture 48h；
4th step, shaping adobe is pressed into by the pug after ageing mixture on a hydraulic press；
5th step, will be dried, dry kiln hot blast temperature is 90~110 DEG C, drying time in shaping adobe feeding dry kiln Not less than 60 hours；
6th step, dried adobe is sent into 111 meters of hyperthermia tunnel Kilns, burnt till at a temperature of 1600~1650 DEG C, stroller Time is 120~150 minutes, obtains composite spinelle zirconia block finished product.
CN201510959494.0A 2015-12-21 2015-12-21 Glass melter regenerator top specific complex spinelle zirconia block and its manufacture method Expired - Fee Related CN105541351B (en)

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CN111689780A (en) * 2020-06-04 2020-09-22 宁夏众城新能源科技有限公司 Refractory material for Acheson closed resistance furnace and preparation method thereof
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CN102731126A (en) * 2012-07-25 2012-10-17 营口青花耐火材料股份有限公司 Composite spinel-zirconium refractory material for smelting colored heavy metal
CN104355633A (en) * 2014-10-28 2015-02-18 郑州汇特耐火材料有限公司 Flexible composite spinel tin refractory material for pyrometallurgical noble metal smelting and preparation method of flexible composite spinel tin refractory material

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