CN101607821B - Method for utilizing gasifier slag to synthesize Ca-alpha-Sialon - Google Patents
Method for utilizing gasifier slag to synthesize Ca-alpha-Sialon Download PDFInfo
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- CN101607821B CN101607821B CN200910023302XA CN200910023302A CN101607821B CN 101607821 B CN101607821 B CN 101607821B CN 200910023302X A CN200910023302X A CN 200910023302XA CN 200910023302 A CN200910023302 A CN 200910023302A CN 101607821 B CN101607821 B CN 101607821B
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Abstract
The invention discloses a method for utilizing gasifier slag to prepare Ca-alpha-Sialon. In the method, the gasifier slag is taken as main raw materials to prepare Ca-alpha-Sialon materials through carbon thermal reduction nitridation method, and the Ca-alpha-Sialon materials with higher purity can be obtained by controlling process parameters of burden, sintering temperature, thermal insulation time, nitrogen flow and the like in a preparation process. The invention has the advantage that regular hexagonal prism-shaped Ca-alpha-Sialon ceramic powders with higher purity (the quality percentage is 60 percent to 90 percent) can be obtained through lower cost to reasonably and fully utilize the gasifier slag.
Description
Technical field
The present invention relates to pottery, technical field of refractory materials, a kind of method of utilizing gasifier slag to prepare Ca-α-Sialon material particularly is provided, have stronger feasibility.
Background technology
Sialon has kept Si
3N
4Premium propertiess such as high strength, high rigidity, high heat resistance, and be better than Si at aspects such as toughness, chemical stability and oxidation-resistances
3N
4, therefore be considered to one of most promising high-temperature structural ceramics.Ca-α-Sialon is that five yuan of solid solution alkaline-earth metal are Sai Long family material, because its crystal morphology is a long column shape, make with Ca-α-Sialon powder to be that the stupalith that raw material is made improves a lot aspect the toughness, this has opened up new approaches for the development of toughness pottery.Now on equipment such as blast furnace lining, hot metal mixer (car) liner, hot metal ladle, slide gate nozzle and heat exchanger member, be used widely.
Usually, Ca-α-Sialon utilizes nitride (α-Si
3N
4, AlN) and CaO be that raw material is prepared under the hot pressed condition of high temperature, synthesis temperature height (1700～1800 ℃), technology is numerous and diverse, the preparation cost height has limited the large-scale commercial production of Ca-α-Sialon.
Less at the gasifier slag report at present, very few especially to the applied research of gasifier slag.Acosta (A.Acosta, I.Iglesias, M.Aineto, et al, Utilisation of IGCC slag andclay steriles in soft mud bricks (by pressing) for use in building bricksmanufacturing, Waste Management, 2002,22:887-89) utilize gasifier slag and clay to prepare building brick, clay and gasifier slag are mixed the back according to a certain percentage under 900 ℃ of conditions, carry out sintering, studies show that when sample gasifier slag content reaches 50% to make the building brick that satisfies service requirements.Yet the achievement in research that gasifier slag is applied to synthetic preparation Ca-α-Sialon does not have related.Therefore, utilize gasifier slag to prepare Ca-α-Sialon material, have very strong researching value and technical meaning for satisfying the Sustainable utilization of resources requirement.
Summary of the invention
At the defective that exists in the above-mentioned background technology, the object of the present invention is to provide a kind of method from the gasifier slag to synthesize Ca-alpha-Sialon material, the one, realized the comprehensive utilization of gasifier slag; The 2nd, designed a kind of preparation Ca-α-Sialon material inexpensive process, reduced cost.
In order to realize above-mentioned technical assignment, the present invention takes following technical scheme:
A kind of method of utilizing gasifier slag to prepare Ca-α-Sialon material is characterized in that, may further comprise the steps:
A. prepare burden: as raw material, carbon black is as reductive agent, according to 6C+3SiO with gasifier slag
2+ 2N
2→ Si
3N
4+ 6CO is configured to compound, and wherein the carbon black add-on should surpass the 7%-10% of theoretical add-on, and it is more abundant that this carbon black add-on is convenient to the carbothermal reduction-nitridation reaction.
B. ball milling mixes: the material that will prepare is put into ball grinder, adds 10% white dextrin as wedding agent, and dry ball milling 10-20 hour, to reach the purpose that mixes with the refinement powder.
C. compression moulding: compound is pressed into cylindric sample under the pressure of 120MPa.
E. dry: as forming blocks to be put into baking oven dried 10-20 hour down at 70 ℃.
F. carbothermal reduction-nitridation is synthetic: sample is put into the controlled tubular type atmosphere furnace of high temperature, with 5～7 the degree/minute heat-up rate be heated to 800 ℃, rise to 1200 ℃ behind 2～3h, 1～3h is warmed up to 1300～1500 ℃, the feeding nitrogen flow is 0.5L/min, top temperature insulation 9 hours, to realize the abundant sintering of sample.
G. carbon elimination deironing: sintered specimen is incubated 6-7h under 700-800 ℃ of condition, to remove the carbon in the sample; Sample behind the de-carbon is clayed into power, be positioned over and carry out deironing in the magnetic separator de-ironing, finally obtain Ca-α-Sialon ceramic powder.
Described gasifier slag composition is: SiO
235～40%, Al
2O
37～12%, CaO 7～9%, and MgO 0.5～1%, and C 20～25%, and Fe 3～5%, K
2O 1.2～1.8%, Na
2O 1～1.5%, other: surplus.
The invention has the advantages that:, make gasifier slag obtain rationally utilizing fully by lower cost obtain the having higher degree regular hexa-prism Ca-α-Sialon ceramic powder of (mass percent is 60～90%).
Description of drawings
Fig. 1 composes for the XRD figure of the gasifier slag that the present invention selects for use.
The XRD figure spectrum of Fig. 2 embodiment 1,2,3,4 products.
The phase composite content figure of Fig. 3 embodiment 1,2,3,4 products.
The microscopic appearance figure of Ca-α-Sialon among Fig. 4 embodiment 4, wherein the magnification of Fig. 4 (a) is 50,000 times, the magnification of Fig. 4 (b) is 200,000 times.
The embodiment that provides below in conjunction with accompanying drawing and contriver is described in further detail the present invention.
Embodiment
The present invention is main raw material with the gasifier slag, be equipped with Ca-α-Sialon material by the carbothermal reduction-nitridation legal system, in preparation process,, can obtain having the Ca-α-Sialon material of higher degree by processing parameters such as control sintering temperature, soaking time, nitrogen flows.Wherein: the formation reaction principle of Ca-α-sialon is as follows:
mCaO+(24-2(m+n))SiO
2+(m+n)Al
2O
3+(16-n)N
2+(48-3n)C
→2Ca
(m/2)Si
(12-(m+n))Al
m+nO
nN
16-n+(48-3n)CO
Follow above-mentioned reaction principle, the present invention takes following steps:
A. prepare burden: as raw material, carbon black is as reductive agent, according to 6C+3SiO with gasifier slag
2+ 2N
2→ Si
3N
4+ 6CO is configured to compound, and wherein the carbon black add-on should surpass the 7%-10% of theoretical add-on, and it is more abundant that this carbon black add-on is convenient to the carbothermal reduction-nitridation reaction.
B. ball milling mixes: the material that will prepare is put into ball grinder, adds 10% white dextrin as wedding agent, and dry ball milling 10-20 hour, to reach the purpose that mixes with the refinement powder.
C. compression moulding: compound is pressed into cylindric sample under the pressure of 120MPa.
E. dry: as forming blocks to be put into baking oven dried 10-20 hour down at 70 ℃.
F. carbothermal reduction-nitridation is synthetic: sample is put into the controlled tubular type atmosphere furnace of high temperature, with 5～7 the degree/minute heat-up rate be heated to 800 ℃, rise to 1200 ℃ behind 2～3h, 1～3h is warmed up to 1300～1500 ℃, the feeding nitrogen flow is 0.5L/min, top temperature insulation 9 hours, to realize the abundant sintering of sample.
G. carbon elimination deironing: sintered specimen is incubated 6-7h under 700-800 ℃ of condition, to remove the carbon in the sample; Sample behind the de-carbon is clayed into power, be positioned over and carry out deironing in the magnetic separator de-ironing, finally obtain Ca-α-Sialon ceramic powder.
The invention has the advantages that:, make gasifier slag obtain rationally utilizing fully by lower cost obtain the having higher degree regular hexa-prism Ca-α-Sialon ceramic powder of (mass percent is 60～90%).
Below be the embodiment that the contriver provides, the invention is not restricted to these embodiment, in the scope that the present invention provides, all can utilize gasifier slag to prepare qualified Ca-α-Sialon material through experiment showed, of applicant.The gasifier slag that is provided in following examples is all selected the Texaco of chemical industry company limited of Shenmu County, Shaanxi vapourizing furnace slag for use, and the main chemical constitution of related gasifier slag is SiO
2, Al
2O
3And CaO, and containing higher remaining carbon, the gasifier slag composition is: SiO
2: 35～40%, Al
2O
3: 7～12%, CaO:7～9%, MgO:0.5～1%, C:20～25%, Fe:3～5%, K
2O:1.2～1.8%, Na
2O:1～1.5%, other: surplus.The X-ray diffracting spectrum of gasifier slag as shown in Figure 1.Gasifier slag glassy phase, unsetting substances content are very high as seen from the figure, reach more than 90%, and crystalline phase is mainly quartz and calcite.Wherein quartz is got by glassy phase crystallization in the high-temperature liquid-phase process of cooling, calcite is the solubility promoter of introducing for the fusing point of adjusting ash content and melt property, and is big owing to grain diameter, remain in the gasification slag short the decomposition fully of the residence time in vapourizing furnace.
Embodiment 1:
Gasifier slag, carbon black are prepared burden, wherein the carbon black add-on surpasses 7% of theoretical value, with mixture ball milling 14 hours, the compression moulding under 120MPa pressure of compound behind the ball milling was dried 10-20 hour down at 70-80 ℃, and dry back sample was 1300 ℃ of calcinings 9 hours, and the control nitrogen flow is 0.5L/min, principal crystalline phase is β-sialon in the end article that obtains, only contain a spot of Ca-α-Sialon mutually with mullite mutually, referring to Fig. 2 and shown in Figure 3.
Embodiment 2:
Gasifier slag, carbon black are prepared burden, wherein the carbon black add-on surpasses 8% of theoretical value, with mixture ball milling 15 hours, the compression moulding under 120MPa pressure of compound behind the ball milling, dried 10-20 hour down at 70-80 ℃, dry back sample was 1400 ℃ of calcinings 9 hours, and the control nitrogen flow is 0.5L/min, principal crystalline phase still is β-sialon phase in the end article that obtains, but the content with respect to embodiment 1 decreases, Ca-α-Sialon contains to some extent mutually to be increased, referring to Fig. 2 and shown in Figure 3.
Embodiment 3:
Gasifier slag, carbon black are prepared burden, wherein the carbon black add-on surpasses 9% of theoretical value, with mixture ball milling 18 hours, the compression moulding under 120MPa pressure of compound behind the ball milling was dried 10-20 hour down at 70-80 ℃, and dry back sample was 1450 ℃ of calcinings 9 hours, and the control nitrogen flow is 0.5L/min, principal crystalline phase is Ca-α-Sialon phase in the end article that obtains, contain a spot of β-sialon mutually with mullite mutually, referring to Fig. 2 and shown in Figure 3.
Embodiment 4:
Gasifier slag, carbon black are prepared burden, wherein the carbon black add-on surpasses 10% of theoretical value, with mixture ball milling 20 hours, the compression moulding under 120MPa pressure of compound behind the ball milling was dried 10-20 hour down at 70-80 ℃, and dry back sample was 1500 ℃ of calcinings 9 hours, and the control nitrogen flow is 0.5L/min, principal crystalline phase is Ca-α-Sialon in the end article that obtains, and its massfraction reaches more than 80%, referring to Fig. 2 and Fig. 3.This principal crystalline phase Ca-α-Sialon is regular hexa-prism, and radical length is 3.5-5 μ m, referring to shown in Figure 4.
Claims (2)
1. a method of utilizing gasifier slag to prepare Ca-α-Sialon material is characterized in that, may further comprise the steps:
A. prepare burden: as raw material, carbon black is as reductive agent, according to 6C+3SiO with gasifier slag
2+ 2N
2→ Si
3N
4+ 6CO is configured to compound, and wherein the carbon black add-on should surpass the 7%-10% of theoretical add-on, and it is more abundant that this carbon black add-on is convenient to the carbothermal reduction-nitridation reaction;
B. ball milling mixes: the material that will prepare is put into ball grinder, adds 10% white dextrin as wedding agent, and dry ball milling 10-20 hour, to reach the purpose that mixes with the refinement powder;
C. compression moulding: compound is pressed into cylindric sample under the pressure of 120MPa;
E. dry: as the moulding sample to be put into baking oven dried 10-20 hour down at 70 ℃;
F. carbothermal reduction-nitridation is synthetic: sample is put into the controlled tubular type atmosphere furnace of high temperature, with 5～7 the degree/minute heat-up rate be heated to 800 ℃, rise to 1200 ℃ behind 2～3h, 1～3h is warmed up to 1300～1500 ℃, the feeding nitrogen flow is 0.5L/min, top temperature insulation 9 hours, to realize the abundant sintering of sample;
G. carbon elimination deironing: sintered specimen is incubated 6-7h under 700-800 ℃ of condition, to remove the carbon in the sample; Sample behind the de-carbon is clayed into power, be positioned over and carry out deironing in the magnetic separator de-ironing, finally obtain Ca-α-Sialon ceramic powder.
2. the method for utilizing gasifier slag to prepare Ca-α-Sialon material as claimed in claim 1 is characterized in that described gasifier slag composition is: SiO
2: 35～40%, Al
2O
3: 7～12%, CaO:7～9%, MgO:0.5～1%, C:20～25%, Fe:3～5%, K
2O:1.2～1.8%, Na
2O:1～1.5%, other: surplus.
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| CN101607821B true CN101607821B (en) | 2011-11-09 |
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| CN103626499B (en) * | 2013-12-16 | 2015-04-15 | 武汉科技大学 | Method for preparing Ca-alpha-Sialon-Si3N4-SiC composite ceramic powder |
| CN106497559B (en) * | 2016-09-08 | 2018-12-14 | 西安建筑科技大学 | A method of white light LEDs Ca- α-SiAlON:Eu fluorescent powder is synthesized using slag of coal gasification |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1521141A (en) * | 2003-02-14 | 2004-08-18 | 中国科学院上海硅酸盐研究所 | Process for preparation of self-spread high-temperature synthesizing low cost alpha-sialon powder |
| CN101234902A (en) * | 2008-02-21 | 2008-08-06 | 上海交通大学 | Method for synthesizing alpha-Sialon ceramic material by using aluminum ash and blast furnace slag |
-
2009
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1521141A (en) * | 2003-02-14 | 2004-08-18 | 中国科学院上海硅酸盐研究所 | Process for preparation of self-spread high-temperature synthesizing low cost alpha-sialon powder |
| CN101234902A (en) * | 2008-02-21 | 2008-08-06 | 上海交通大学 | Method for synthesizing alpha-Sialon ceramic material by using aluminum ash and blast furnace slag |
Non-Patent Citations (3)
| Title |
|---|
| JP昭58-49666A 1983.03.23 |
| 张作泰等.高炉渣合成Ca-a-Sialon-SiC热力学分析与实验验证.《中国稀土学报》.2002,第20卷第77-80页. * |
| 蒋久信等.炉渣α-Sialon粉的高温自蔓延燃烧合成及炉渣α-Sialon陶瓷性能的研究.《无机材料学报》.2004,第19卷(第4期),第953-957页. * |
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