CN101219903B

CN101219903B - Advanced silica refractory and manufacturing technique thereof

Info

Publication number: CN101219903B
Application number: CN2007101952524A
Authority: CN
Inventors: 王杰曾; 赵洪亮; 李鹏海; 陈雪峰; 叶亚红
Original assignee: RUITAI TECHNOLOGY Co Ltd
Current assignee: RUITAI TECHNOLOGY Co Ltd
Priority date: 2007-12-05
Filing date: 2007-12-05
Publication date: 2010-09-01
Anticipated expiration: 2027-12-05
Also published as: CN101219903A

Abstract

The invention relates to a silicon refractory material with composition proportions of 30 to 55 percent of natural silica of 3.0-1.0 mm, 0 to 15 percent of waste silica brick particles of 3.0 to 1.0mm, 10 to 25 percent of the natural silica of 1.0 to 0.09mm, 0 to 15 percent of the waste silica brick particles of 3.0 to 1.0 mm, 10 to 25 percent of the natural silica plus waste silica brick powder plus calcinations silica less than 0.09mm, 1 to 5 percent of non-aluminum high C3S cement or calcium hydroxide powder, no less than 98 percent of SiO2, 0 to 5 percent of silica micropowder with medianparticle size D50 no more than 10 Mum, 1 to 5 percent of silica fume with SiO2 no more than 96 percent, 0.05 to 1.0 percent of high-efficiency water reducing agent and 0.03 to 1.0 percent of organic binder, doped with 1 to 2 percent of fluorite, 0 to 6 percent of calcium sulfate and 0 to 4 percent of magnesium sulfate or magnesium oxide as mineralizer. The production process comprises the following process: after weighing, mixing and melting, forming and drying, the raw material is roasted into finished products under 1,350 to 1,460 DEG C for 10 to 36 hours. The silicon refractory material has the advantages of good forming, rapid demoulding speed and excellent high temperature performance, so the silicon refractory material is suitable for silicon refractory material for glass manufacture, and large and specially-shaped silicon dioxide refractory material products.

Description

A kind of siliceous refractory [material and production technique thereof

Technical field

The present invention relates to a kind of advanced silica refractory.This material mainly is made up of natural silica, silica grog, siliceous micro mist, the ultra-fine silicate cement of no aluminium and chemical admixture, the feature that has the high-performance amorphous refractory on the proportioning, have good moulding character, stripping rate, excellent high-temperature behavior faster on the performance, be suitable for being used for making the glass industry advanced silica refractory, particularly large-scale siliceous fire resistive material product.

Background technology

Silica brick is a kind of refractory materials commonly used.Small size silica brick press-molding, large-scale siliceous goods need be used ramming method manual assembly.Manual assembly labour intensity is big, blank density is low, constant product quality is poor.Large-scale clay matter, high alumina matter goods are with reference to the technology of low cement, ultra-low cement deposit material: preparation indefinite form material earlier, with the way moulding of vibration, again through maintenance, the demoulding, drying, operation such as burn till and make large-scale fire resistive material product.But large-scale siliceous goods but can not simply be continued to use this technology.

Cement, phosphoric acid and water glass are the main wedding agents of amorphous refractory.Conventional cement contains aluminate.Because of aluminum oxide is deleterious impurity, the advanced silica material should not use conventional cement as wedding agent.Water glass mainly is water glass.Because of sodium oxide is deleterious impurity equally, advanced silica indefinite form material also should not use water glass as wedding agent.Therefore, some have to select the wedding agent of phosphoric acid as siliceous indefinite form material.In the glass furnace, alkali steam dense.Na2O steam is easy to and the reaction of phosphoric acid bonded siliceous refractory [material, and this material is comparatively fast damaged.So phosphoric acid combining silica indefinite form material is only made repair material, local use of kiln labour later stage.

Summary of the invention

The objective of the invention is to develop a kind of advanced silica refractory and adopt synthetic not have aluminium high C3 S cement as wedding agent, the admixture of selecting to be suitable for this cement is made large-scale, special form height level siliceous refractory [material goods.

The above-mentioned synthetic that is suitable for does not have the high C of aluminium ₃The admixture of S cement the results are shown in Table 1:

Table 1 chemical admixture is to siliceous refractory [material slurry Effect on Performance

Numbering	Ground silica	C3S cement	The silicon ash	Admixture 1	Admixture 2	Water	Flow	Sclerosis
Numbering	Ground silica	C3S cement	The silicon ash	Admixture 1	Admixture 2	Water	Flow	Sclerosis	1	75	10	15	Do not have	Do not have	18	0	5
2	75	10	15	FDN 0.25	Do not have	15	1	5	1	75	10	15	Do not have	Do not have	18	0	5

3	75	10	15	SM 0.25	Do not have	15	1	5
3	75	10	15	SM 0.25	Do not have	15	1	5	4	75	10	15	TC 0.2	Do not have	15	1	5
5	75	10	15	Trimerization 0.25	Do not have	12	4	1	4	75	10	15	TC 0.2	Do not have	15	1	5
5	75	10	15	Trimerization 0.25	Do not have	12	4	1	6	75	10	15	TC 0.2	sPVA 0.7	16	5	3

In the table: the sodium salt high efficiency water reducing agent of FDN-sulfonated naphthalene formaldehyde, the sodium salt high efficiency water reducing agent of SM-sulfonated melamine, TC-high-efficiency water-reducing agent of poly-carboxylic acid, tripoly-tripoly phosphate sodium STPP (high efficiency water reducing agent that refractory materials is commonly used), sPVA-water-soluble poval.Flow or hardened rank: 5-good, 4-is better, 3-is relatively poor, 2-is poor, 1-is very poor, 0-does not have this character at all.

As known from Table 1: add the high C of no aluminium separately ₃During S cement, slurry moulding water requirement is very big, does not still have flowability, but sclerosis is very fast.Use tripoly phosphate sodium STPP, need water minimum, disperse better, but the slurry setting rate is very slow.Use building concrete FDN, SM and high-efficiency water-reducing agent of poly-carboxylic acid commonly used, can significantly reduce water requirement.But it is little to improve liquidity.When while admixture polyvinyl alcohol and polycarboxylate water-reducer, slurry has best need water, flows and Hardenability.On the other hand, poly carboxylic acid or polyvinyl alcohol do not contain the Na that is harmful to high-temperature behavior ₂O.So TC-sPVA is the admixture that is suitable for making the advanced silica amorphous refractory in the table most.The mechanism of action of PVA is: 1) lower molecular weight PVA has certain dispersive ability; 2) the moisture aquation in the cement absorbent solution forms the hardening of cement body, and PVA solution dehydration and condense into emplastic forms the organic-inorganic composite gelled material of PVA and hardening of cement body.

In view of above explanation, the proportioning of siliceous refractory [material of the present invention is:

1) 3.0～1.0mm natural silica 30～55%;

2) the useless silica brick of 3.0～1.0mm (contains SiO ₂Silica brick waste product more than 96%) particle 0～15%;

3) 1.0～0.09mm natural silica 10-25%;

4) the useless silica brick of 3.0～1.0mm (contains SiO ₂Silica brick waste product more than 96%) particle 0～15%;

5)＜0.09mm natural silica+useless silica brick (contains SiO ₂Silica brick waste product more than 96%) powder+calcined silica (cristobalite) 10-25%;

6) the high C of no aluminium ₃S cement or calcium hydroxide powder 1-5%;

7) SiO ₂〉=98%, meta particle diameter D ₅₀The silica micro mist 0～5% of≤10 μ m;

8) SiO ₂〉=96% silicon ash 1～5%;

9) high efficiency water reducing agent (poly carboxylic acid+sulfonated naphthalene yuban+sulfonated melamine polymkeric substance)

0.05-1.0％；

10) organic bond (polyvinyl alcohol+wooden calcium sulfonate+polyacrylic acid or its sodium salt) 0.03-1.0%.

The high C of described no aluminium ₃The mineral composition of S cement is: 95～80%C ₃S, 2～14%C ₂S, 3～10%C ₂F, outer

Mixing 1～2% fluorite, 0～6% calcium sulfate, 0～4% sal epsom or magnesium oxide is mineralizer.

The production technique of refractory materials of the present invention is: according to above proportioning weighing, mix, after the moulding, drying, base substrate sent into 1350-1460 ℃ burnt till 10-36 hour, make sinterable silicon fire resistant materials goods.

Embodiment

Embodiment 1:

Adopt 3.2～1.0mm silica of 45%, 1.5～0.15mm silica of 15%, 21%＜the 0.09mm ground silica, 3.5% silica micro mist, 3.5% silicon ash, 3% the high C of aforementioned no aluminium ₃The S silicate cement, the water that adds 0.1% TC, 0.2 sPVA, 0.1 wooden calcium sulfonate and 9% is made, through mix and stir, cast, maintenance, the demoulding, drying, burnt till through 1400-1440 ℃ * 10 hours again.The ultimate compression strength of goods is 110MPa, and folding strength is 10MPa, has reached predetermined requirement.

Embodiment 2:

Adopt 3.2～1.0mm silica of 35%, 3.2～1.0mm of 10% silica brick that gives up, 1.5～0.15mm silica of 10%, 1.5～0.15mm of 5% silica brick that gives up, 11%＜the 0.09mm ground silica, 10%＜the 0.09mm cristobalite, 3% silica micro mist, 5% silicon ash, 3% calcium hydroxide powder, add 0.2% TC and 8% water and make, through mix and stir, cast, maintenance, the demoulding, drying, burnt till through 1400-1440 ℃ * 10 hours again.The ultimate compression strength of goods is 100MPa, and folding strength is 9MPa, has reached predetermined requirement.

Advantage of the present invention is the feature that has the high-performance amorphous refractory on the proportioning, have good moulding character, faster stripping rate, excellent high-temperature behavior on the performance, be suitable for making the glass industry advanced silica refractory, particularly the siliceous fire resistive material product of large-scale, special shape.

Claims

1. advanced silica refractory.It is characterized in that: described refractory materials is made up of natural silica, silica grog, siliceous micro mist, the ultra-fine silicate cement of no aluminium and chemical admixture, and its proportioning is

● 3.0～1.0mm natural silica 30～55%;

● 3.0～1.0mm silica brick particle 0～15% that gives up;

● 1.0～0.09mm natural silica 10-25%;

●＜0.09mm natural silica+useless silica brick powder+calcined silica (cristobalite) 10-25%;

● the high C of no aluminium ₃S cement or calcium hydroxide powder 1-5%;

● SiO ₂〉=98%, meta particle diameter D ₅₀The silica micro mist 0～5% of 10 μ m;

● SiO ₂〉=96% silicon ash 1～5%;

● poly carboxylic acid+sulfonated naphthalene yuban+sulfonated melamine polymkeric substance is 0.05-1.0%;

● polyvinyl alcohol+wooden calcium sulfonate+polyacrylic acid or its sodium salt are 0.03-1.0%

2. production technique of producing the described refractory materials of claim 1, rise and to be characterised in that: according to the described proportioning weighing of claim 1, mix, after the moulding, drying, base substrate is sent into 1350-1460 ℃ burnt till 10-36 hour, promptly can be made into sinterable silicon fire resistant materials goods.