CN102875136A - Recovery method of mullite and recovery preparation of mullite - Google Patents
Recovery method of mullite and recovery preparation of mullite Download PDFInfo
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- CN102875136A CN102875136A CN2012104365528A CN201210436552A CN102875136A CN 102875136 A CN102875136 A CN 102875136A CN 2012104365528 A CN2012104365528 A CN 2012104365528A CN 201210436552 A CN201210436552 A CN 201210436552A CN 102875136 A CN102875136 A CN 102875136A
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- mullite
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Abstract
The invention discloses a recovery method of mullite and a recovery preparation of the mullite. The preparation comprises an alkaline agent A and an acid agent B which are not contained in the same component, wherein the alkaline agent A is an aqueous solution with 5 to 27% of NaOH; the acid agent B is an aqueous solution preparation containing 4.5 to 15% of HCl based on mass percentage concentration, 100 to 1000ppm of hydrolytic polymaleic anhydride and 0.5 to 5kg/m<3> of NH4Cl. The recovery method comprises the following steps of: dipping particles made from a waste granular mullite fire resistant material into the alkaline agent A; washing via water; dipping in the acid agent B; and then cleaning; or, dipping the particles made from the waste granular mullite fire resistant material in the acid agent B; washing via the water; dipping into the alkaline agent A; then cleaning. With the adoption of the recovery method disclosed by the invention, the mulltie in waste materials can be directly completely separated so as to obtain clean mullite, and a product can be applied without being limited.
Description
Technical field
The present invention relates to the recovery method that a kind of mullite reclaims preparation and mullite.
Background technology
Along with developing rapidly of the industry such as China's ferrous metallurgy, cement, pottery, the consumption of refractory materials increases greatly.Certificate in 2004 is to 136 refractory materials enterprise statisticses of 30 provinces, cities and autonomous regions in the whole nation, and 1867.51 ten thousand tons of national refractory materials output, crude steel output reach 2.7 hundred million tons, and the consumption of refractory materials has reached 800～9,000,000 tons, and anti-/ steel is than 29～33kg/ ton steel.Iron and Steel Production producer consumes the refractory materials of maximum, its steel melting furnace furnace lining, refining furnace the furnace lining, (recycling of the refractory materials that steelworks was used more than 60% that transmits stove furnace lining and the annual consumption of heat treatment furnace lining refractory materials output, Xu Qingbin, external refractory materials, 1999,10:3).Meanwhile, also caused a large amount of consumption of refractory material resources and refractory materials, the annual waste and old refractory materials that produces therefrom (is brief talked the comprehensive utilization of refractory materials, Sun Jie gem etc., Shandong metallurgy, 2006,28 (1): 48) up to more than 300 ten thousand tons.A large amount of goes out of use with refractory, has caused the serious wasting of resources and environmental pollution.
Existing research shows, these have recycle value with the major part in the refractory.For example steel melting furnace is after full furnace life, and steel melting furnace has just been scrapped, and wherein the mullite-type refractory materials as backup lining brick contains a large amount of mullites, is worth very high.If the mullite that reclaims wherein can produce very high economic benefit, simultaneously also can environmental contamination reduction.Thus, seem more and more important with the recycle work of rear waste refractory materials, yet existing research still is in the starting stage.
Existing report has following several to the recycling with refractory, all be to reprocess after directly waste material being pulverized.
1, the useless brick of steel-making refining furnace of magnesium carbon system and magnalium carbon system, through pulverizing, after whole grain and geometric ratio mix, replace the part light dolomite, uses as the filler of making of 70t refining furnace refined alloy structure iron.(effective utilization of the useless brick of steel-making refining furnace, Cen Yongquan, Shanghai Metals, 1996,01).
2, with the good industrial ceramics of aluminosilicate refractory waste processability, the alumina base porcelain ball (technology and the mechanism research that prepare alumina-based ceramic with aluminosilicate refractory waste that prepare a series of aluminium sesquioxide content from 45% to 85%, Zhong Lianyun, Wuhan University of Technology's Ph D dissertation, 2006).
3, take with rear waste aluminium magnesia carbon brick and waste magnesia carbon bricks as main raw material, add graphite, carry out secondary aluminum magnesia carbon brick and magnesia carbon brick; (with the regeneration of refractory, keep one's word in the field. refractory materials, 2002, (6): 339).
4, take with rear magnesia carbon brick, aluminium ash, aluminium titanium slag and aluminium chromium slag as raw material, add titanium dioxide, the synthetic magnalium point of chromic oxide stone (with the research of refractory synthetic MgAl spinal, Yu Pengpeng, ferrous metallurgy, 2012).
Summary of the invention
Technical problem to be solved by this invention is that the recovery method for refractory materials exists in the prior art: all be directly to use refractory waste to process the preparation reconstituted product, and because waste material forms uncertain kind and performance of having limited to reconstituted product, and the defective that the refractory materials that value wherein is higher is not utilized effectively, can directly the mullite in the waste material thoroughly be separated and provide a kind of, obtain clean mullite, the unrestricted mullite of end-use reclaims the recovery method of preparation and mullite.
The invention provides a kind of mullite recovery preparation and comprise alkaline agent A and sour agent B, alkaline agent A and sour agent B are not present in the same component; Described alkaline agent A is for containing the aqueous solution of 5% ~ 27% NaOH; Acid agent B is aqueous solution preparation, contains the HCl of mass percentage concentration 4.5%～15%, the hydrolytic polymaleic anhydride of 100～1000ppm, and 0.5～5kg/m
3NH
4Cl.
Among the present invention, what described mullite recovery preparation was better is: alkaline agent A is that mass percentage concentration is the aqueous solution of 15%NaOH; It is 7% HCl, 0.5kg/m that acid agent B contains mass percentage concentration
3NH
4Cl, and 500ppm hydrolytic polymaleic anhydride.
The better NaOH by 5% ~ 27% of the solute of alkaline agent A of the present invention forms.
The solute of sour agent B of the present invention better by 4.5%～15% HCl, the hydrolytic polymaleic anhydride of 100～1000ppm, and 0.5～5kg/m
3NH
4Cl forms.
Among the present invention, described NaOH, HCl and NH
4Cl is conventional reagent, all commercially available getting of this area.
Among the present invention, described hydrolytic polymaleic anhydride is that this area routine is said, it is a kind of lower molecular weight polyelectrolyte, general relative molecular weight is 400 ~ 800, and outward appearance is light yellow to the red-brown transparent liquid, meets the index among standard GB/T/T 10535-1997, solid content is generally 50%, such as the hydrolytic polymaleic anhydride of Qingdao TianLan Power Industry Co.,Ltd, its product specification is solid content 〉=48%, molecular-weight average 〉=450.
Also can contain respectively conventional various other additives that add among alkaline agent A of the present invention, the sour agent B, as long as its not remarkably influenced mullite of the present invention reclaims the preparation effect, such as sodium polyphosphate Na
5P
3O
10, Secondary ammonium phosphate, H
3PO
4Deng.
The preparation method that mullite of the present invention reclaims preparation presses respectively separately the composition consumption by this area routine with alkaline agent A and sour agent B and evenly mixes and get final product.
The present invention also provides a kind of recovery method of mullite to comprise the steps:
Mode one is: with the particle of the useless mullite refractory behind pulverizing and iron removal by magnetic separation, soak in the alkaline agent A of aforementioned mullite recovery preparation first, washing is soaked in the sour agent B of aforementioned mullite recovery preparation afterwards, and afterwards cleaning gets final product;
Perhaps, mode two is: with the particle of the useless mullite refractory behind pulverizing and iron removal by magnetic separation, soak in the sour agent B of aforementioned mullite recovery preparation first, washing is soaked in the alkaline agent A of aforementioned mullite recovery preparation afterwards, and afterwards cleaning gets final product.
Among the present invention, described useless mullite refractory is that the conventional said main component in this area is the refractory materials of mullite, generally from discarded blast furnace, steel melting furnace, hot metal ladle or ladle.
Among the present invention, described pulverizing is this area routine operation, and generally by the pulverizer operation, the grain diameter after the better pulverizing is≤2cm.After the pulverizing, clear water is washed Powdered tack coat off routinely.
Among the present invention, described iron removal by magnetic separation is this area routine operation, generally operates by magnetic separator.
Among the present invention, the particle of described useless mullite refractory behind pulverizing and iron removal by magnetic separation is generally removed the powder clay according to conventional cleaning the in this area.
Among the present invention, what the consumption of the alkaline agent A of described mullite recovery preparation was better is the useless mullite refractory of 0.5～5.0kg solution/kg.
Among the present invention, soaking in the alkaline agent A of aforementioned mullite recovery preparation is this area routine operation, and better soaking conditions is 40 ℃～90 ℃ and soaked 2～24 hours.
Among the present invention, what the consumption of the sour agent B of described mullite recovery preparation was better is the useless mullite refractory of 1.8～2.5kg solution/kg.
Among the present invention, soaking in the sour agent B of aforementioned mullite recovery preparation is this area routine operation, and better soaking conditions is for soaking 2～24 hours.General soak at room temperature, described normal temperature is generally 0 ℃～40 ℃.
Among the present invention, described washing, cleaning are this area routine operation, and general washing is stirred and got final product.
Among the present invention, carry out drying according to the ability routine after the described cleaning, obtain dry finished product.
Among the present invention, described alkaline agent A and sour agent B all can reuse, and suitably replenish the component that consumes during recycling and get final product.
Agents useful for same of the present invention and raw material be commercially available getting all.
On the basis that meets this area general knowledge, the optimum condition of each above-mentioned technical characterictic can arbitrary combination obtain preferred embodiments of the present invention among the present invention.
Positive progressive effect of the present invention is: the inventive method can directly thoroughly be separated the mullite in the mullite refractory that gives up, and obtains clean mullite, and end-use is unrestricted, can be used for the producers such as electrolytic aluminum, refractory materials, abrasive material; And its cost recovery is low, and benefit is very considerable.
Embodiment
Mode below by embodiment further specifies the present invention, but does not therefore limit the present invention among the described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example according to ordinary method and condition, or is selected according to catalogue.
Among the following embodiment, used hydrolytic polymaleic anhydride is available from electric power Industrial Co., Ltd., and product specification is solid content 〉=48%, molecular-weight average 〉=450.Acid agent B soaks all at normal temperatures operation.
The pre-treatment of embodiment 1 useless mullite refractory
Get grain diameter≤2cm after the mullite refractory that will give up is pulverized, iron removal by magnetic separation cleans and removes the particle that the powder clay namely gets useless mullite refractory.
Embodiment 2
Mullite reclaims preparation alkaline agent A: mass percentage concentration is the aqueous solution of 15%NaOH
It is aqueous solution preparation that mullite reclaims preparation acid agent B: containing mass percentage concentration is 7%HCl, 0.5kg/m
3NH
4Cl, and 500ppm hydrolytic polymaleic anhydride.
The preparation method evenly mixes and gets final product for alkaline agent A and sour agent B being pressed respectively separately the composition consumption.
The recovery method of mullite: with the particle 100kg of the useless mullite refractory of embodiment 1, be soaked among the above-mentioned alkaline agent A of 200kg, soak 50 ℃ of lower maintenances after 20 hours, after washing is clean, be soaked among the above-mentioned sour agent B of 200kg again, soaked 24 hours, obtain through stirring washing: the tack coat of 3/4 fire resisting material particle is loose to come off again, remaining particle has a small amount of tack coat remaining, obtains mullite 61kg.
Embodiment 3
Mullite reclaims preparation alkaline agent A: mass percentage concentration is the aqueous solution of 27%NaOH
It is aqueous solution preparation that mullite reclaims preparation acid agent B: containing mass percentage concentration is 15%HCl, 5kg/m
3NH
4Cl, and 100ppm hydrolytic polymaleic anhydride.
The recovery method of mullite: with the particle 150kg of the useless mullite refractory of embodiment 1, be soaked among the above-mentioned alkaline agent A of 200kg, soak 90 ℃ of lower maintenances after 2 hours, after washing is clean, be soaked in again among the above-mentioned sour agent B of 200kg, soaked 2 hours, again through stirring washing, approximately the tack coat of 1/2 fire resisting material particle is loose comes off, and approximately 2/3 has the part tack coat remaining in the remaining particle, and other has a small amount of tack coat remaining.
Embodiment 4
Mullite reclaims preparation alkaline agent A: mass percentage concentration is the aqueous solution of 5%NaOH
It is aqueous solution preparation that mullite reclaims preparation acid agent B: containing mass percentage concentration is 10%HCl, 5kg/m
3NH
4Cl, and 1000ppm hydrolytic polymaleic anhydride.
The recovery method of mullite: with the particle 100kg of the useless mullite refractory of embodiment 1, be soaked among the above-mentioned alkaline agent A of 200kg, soak 50 ℃ of lower maintenances after 10 hours, after washing is clean, be soaked in again among the above-mentioned sour agent B of 200kg, soaked 10 hours, again through stirring washing, approximately the tack coat of 4/7 fire resisting material particle is loose comes off, and remaining particle has part or a small amount of tack coat remnants.
Embodiment 5
Mullite reclaims preparation alkaline agent A: mass percentage concentration is the aqueous solution of 15%NaOH
It is aqueous solution preparation that mullite reclaims preparation acid agent B: containing mass percentage concentration is 7%HCl, 0.5kg/m
3NH
4Cl, and 500ppm hydrolytic polymaleic anhydride.
The recovery method of mullite: with the particle 100kg of the useless mullite refractory of embodiment 1, be soaked among the above-mentioned sour agent B of 200kg, soaked 24 hours, after washing is clean, be soaked in again among the above-mentioned alkaline agent A of 200kg, soak 60 ℃ of lower maintenances after 10 hours, obtain through stirring washing: approximately the tack coat of 3/4 fire resisting material particle is loose comes off again, and remaining particle has the part tack coat remaining.
Embodiment 6
Mullite reclaims preparation alkaline agent A: mass percentage concentration is the aqueous solution of 15%NaOH
It is aqueous solution preparation that mullite reclaims preparation acid agent B: containing mass percentage concentration is 4.5%HCl, mass percentage concentration 1%H
3PO
4, 0.5kg/m
3NH
4Cl, and 500ppm hydrolytic polymaleic anhydride.
The preparation method evenly mixes and gets final product for alkaline agent A and sour agent B being pressed respectively separately the composition consumption.
The recovery method of mullite: with the particle 100kg of the useless mullite refractory of embodiment 1, be soaked among the above-mentioned alkaline agent A of 50kg, soak 40 ℃ of lower maintenances after 24 hours, after washing is clean, be soaked in again among the above-mentioned sour agent B of 250kg, soaked 24 hours, obtain through stirring washing: approximately the tack coat of 1/2 fire resisting material particle is loose comes off again, and remaining particle has a small amount of tack coat remaining.
Embodiment 7
Mullite reclaims preparation alkaline agent A: mass percentage concentration is the aqueous solution of 15%NaOH
It is aqueous solution preparation that mullite reclaims preparation acid agent B: containing mass percentage concentration is the sodium polyphosphate Na of 7%HCl, mass percentage concentration 1%
5P
3O
10, 0.5kg/m
3NH
4Cl, and 500ppm hydrolytic polymaleic anhydride.
The preparation method evenly mixes and gets final product for alkaline agent A and sour agent B being pressed respectively separately the composition consumption.
The recovery method of mullite: with the particle 100kg of the useless mullite refractory of embodiment 1, be soaked among the above-mentioned sour agent B of 180kg, soaked 24 hours, after washing is clean, be soaked in again among the above-mentioned alkaline agent A of 500kg, soak 50 ℃ of lower maintenances after 20 hours, obtain through stirring washing: the tack coat of 3/4 fire resisting material particle is loose to come off again, and remaining particle has a small amount of tack coat remaining.
Comparative Examples 1-4
It is 5%, 10%, 15%, 20% sulphuric acid soln that Comparative Examples 1-4 preparation is respectively mass percentage concentration.
Respectively with the particle 100kg of the useless mullite refractory of embodiment 1, be soaked in the preparation of Comparative Examples 1-4 of 200kg, soak 1 time-of-week, various types of tack coats all without breaking away from, can't obtain clean mullite.
Comparative Examples 5
Comparative Examples 5 preparations are that mass percentage concentration is 5% aqueous hydrochloric acid.
With the particle 100kg of the useless mullite refractory of embodiment 1, be soaked in the preparation of Comparative Examples 5 of 200kg, soaked 48 hours, only approximately the tack coat of 1/6 fire resisting material particle is loose comes off, and can't obtain clean mullite.
Comparative Examples 6
Comparative Examples 6 preparations are that mass percentage concentration is 15%HCl, 8.5%H
3PO
4, 1000ppm hydrolytic polymaleic anhydride and 0.5kg/m
3NH
4The aqueous solution of Cl.
With the particle 100kg of the useless mullite refractory of embodiment 1, be soaked in the preparation of Comparative Examples 6 of 200kg, soaked 48 hours, the tack coat of nearly 1/2 fire resisting material particle is loose to come off, obtain clean mullite, yet remaining half particle has more tack coat remaining, effect is relatively poor.
Claims (8)
1. a mullite reclaims preparation, it is characterized in that, it comprises alkaline agent A and sour agent B, and alkaline agent A and sour agent B are not present in the same component; Described alkaline agent A is for containing the aqueous solution of 5% ~ 27% NaOH; Acid agent B is aqueous solution preparation, contains the HCl of mass percentage concentration 4.5%～15%, the hydrolytic polymaleic anhydride of 100～1000ppm, and 0.5～5kg/m
3NH
4Cl.
2. mullite as claimed in claim 1 reclaims preparation, it is characterized in that, described mullite reclaims preparation and is: alkaline agent A is that mass percentage concentration is the aqueous solution of 15%NaOH; It is 7% HCl, 0.5kg/m that acid agent B contains mass percentage concentration
3NH
4Cl, and 500ppm hydrolytic polymaleic anhydride.
3. mullite as claimed in claim 1 reclaims preparation, it is characterized in that, described mullite reclaims preparation and is: the solute of alkaline agent A is comprised of 5% ~ 27% NaOH; The solute of acid agent B is by 4.5%～15% HCl, the hydrolytic polymaleic anhydride of 100～1000ppm, and 0.5～5kg/m
3NH
4Cl forms.
4. reclaim preparation such as each described mullite of claim 1 ~ 3, it is characterized in that, described hydrolytic polymaleic anhydride is the hydrolytic polymaleic anhydride of Qingdao TianLan Power Industry Co.,Ltd.
5. the recovery method of a mullite is characterized in that, it comprises the steps:
Mode one is: with the particle of the useless mullite refractory behind pulverizing and iron removal by magnetic separation, in the alkaline agent A that reclaims preparation such as each described mullite of claim 1-4, soak first, washing, soak in the sour agent B that reclaims preparation such as each described mullite of claim 1-4 afterwards, afterwards cleaning gets final product;
Perhaps, mode two is: with the particle of the useless mullite refractory behind pulverizing and iron removal by magnetic separation, in the sour agent B that reclaims preparation such as each described mullite of claim 1-4, soak first, washing, soak in the alkaline agent A that reclaims preparation such as each described mullite of claim 1-4 afterwards, afterwards cleaning gets final product.
6. the recovery method of mullite as claimed in claim 5 is characterized in that, the grain diameter after the described pulverizing is≤2cm.
7. the recovery method of mullite as claimed in claim 5 is characterized in that, the consumption that described mullite reclaims the alkaline agent A of preparation is the useless mullite refractory of 0.5～5.0kg solution/kg; The condition of soaking in described alkaline agent A is 40 ℃～90 ℃ and soaked 2～24 hours.
8. the recovery method of mullite as claimed in claim 5 is characterized in that, the consumption that described mullite reclaims the sour agent B of preparation is the useless mullite refractory of 1.8～2.5kg solution/kg; The condition of soaking in described sour agent B is for soaking 2～24 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210436552.8A CN102875136B (en) | 2012-11-05 | 2012-11-05 | Recovery method of mullite and recovery preparation of mullite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210436552.8A CN102875136B (en) | 2012-11-05 | 2012-11-05 | Recovery method of mullite and recovery preparation of mullite |
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| Publication Number | Publication Date |
|---|---|
| CN102875136A true CN102875136A (en) | 2013-01-16 |
| CN102875136B CN102875136B (en) | 2014-05-07 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1232803A (en) * | 1998-04-21 | 1999-10-27 | 中国石化兰州炼油化工总厂 | Mullite synthesizing method |
| CN1830908A (en) * | 2006-04-04 | 2006-09-13 | 武汉理工大学 | Method for preparing composite carrier material contg, nanometer porous glass and aluminium oxide ceramic substrate |
-
2012
- 2012-11-05 CN CN201210436552.8A patent/CN102875136B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1232803A (en) * | 1998-04-21 | 1999-10-27 | 中国石化兰州炼油化工总厂 | Mullite synthesizing method |
| CN1830908A (en) * | 2006-04-04 | 2006-09-13 | 武汉理工大学 | Method for preparing composite carrier material contg, nanometer porous glass and aluminium oxide ceramic substrate |
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| CN102875136B (en) | 2014-05-07 |
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