CN110510882B - Pyroxene-based cast stone and preparation method thereof - Google Patents

Pyroxene-based cast stone and preparation method thereof Download PDF

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CN110510882B
CN110510882B CN201910907935.0A CN201910907935A CN110510882B CN 110510882 B CN110510882 B CN 110510882B CN 201910907935 A CN201910907935 A CN 201910907935A CN 110510882 B CN110510882 B CN 110510882B
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pyroxene
cast stone
based cast
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stainless steel
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CN110510882A (en
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张延玲
张帅
屈振民
梁益玮
余阚
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University of Science and Technology Beijing USTB
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of waste materials, e.g. slags
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0063—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing waste materials, e.g. slags

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

The invention discloses a pyroxene-based cast stone and a preparation method thereof, wherein the pyroxene-based cast stone is prepared by utilizing stainless steel slag, acid-washed sludge, quartz sand and certain magnesite, Cr element in the pyroxene-based cast stone is sealed in a magnesium-chromium spinel mineral phase by controlling process parameters, the magnesium-chromium spinel is an excellent nucleating agent, and meanwhile, in view of the oriented attachment phenomenon of the pyroxene phase on the surface of spinel, a mineral phase structure which takes the spinel phase as an inner core and is wrapped with the pyroxene phase is finally formed, and the mineral phase structure effectively controls Cr leaching and has high safety performance.

Description

Pyroxene-based cast stone and preparation method thereof
Technical Field
The invention relates to the technical field of cast stone processing, in particular to a pyroxene-based cast stone and a preparation method thereof.
Background
The stainless steel industry in China is rapidly developed to generate a large amount of chromium-containing solid waste, wherein the pickling sludge is definitely classified as dangerous solid waste in 2018. In addition, the yield of stainless steel of more than 3000 ten thousand tons per year brings about 1000 ten thousand tons of chromium-containing smelting slag. The chromium content in the chromium-containing slag fluctuates within the range of 0.5 to 3 percent, and the separation and recovery value is not large. On one hand, land resources are wasted due to long-term stockpiling, and on the other hand, huge potential safety hazards are caused due to the harm of Cr leaching to human bodies and the environment. At present, the resource treatment of the chromium-containing solid waste becomes a key factor for limiting the sustainable development of the stainless steel industry.
Chemical stabilization/solidification of chromium is an effective way to limit leaching of the Cr element. On the basis of realizing chemical stabilization/solidification of Cr element, the stainless steel slag and the acid-washing sludge are prepared into green and safe building materials and realize industrial application, thus being undoubtedly an ideal way for recycling the chromium-containing solid waste. At present, related patents for preparing the microcrystalline glass by using chromium-containing solid wastes exist at home and abroad. For example: the microcrystalline glass and the preparation method thereof (application No. 201810856304.6), the green microcrystalline glass and the preparation method thereof (application No. 201711260307.5), the method for preparing the microcrystalline glass by using stainless steel slag and fluorite tailings (application No. 201710631368.1), and the method for preparing the microcrystalline glass by using all wastes in a short flow (application No. 201610426057.7). The common problems of the above technologies are: (1) the preparation process is a two-step method, firstly, chromium-containing solid waste (added with a certain proportion of modifier) is heated to a molten state, the temperature is kept for a period of time, then, the cooled mother glass is cooled to obtain mother glass, and then, the cooled mother glass is heated to a certain temperature for heat treatment, and finally, a microcrystalline glass product is obtained. The method needs two steps of heating, melting, heat preservation, cooling and reheating, heat preservation and cooling, and has relatively complex process, high energy consumption and high cost; (2) the mineral phase structure of the Cr element in the final product is not clearly given, and the long-term leaching behavior of Cr is difficult to scientifically evaluate.
The cast stone is an inorganic material with excellent performance, and the use performance of the high-quality cast stone is far superior to that of metal materials such as stainless steel and the like under the condition of extremely severe environment in view of the excellent wear-resisting and corrosion-resisting characteristics of the cast stone. Cast stone is currently prepared mainly using natural stone. The solid wastes of the stainless steel chromium-containing slag and the like contain abundant CaO and Al2O3、MgO、SiO2The components can be completely prepared into the artificial cast stone from the chemical composition. However, the cast stone with different crystal phase structures has great property difference, and the prepared artificial cast stone may have leaching phenomena of toxic and harmful heavy metal elements in contact with the environment. Therefore, the curing of the hazardous elements and the properties are considered together during the preparation.
The most important is that the Cr element in the magnesium-chromium spinel can be sealed in the magnesium-chromium spinel ore phase by controlling the process parameters (the research of the prior art shows that Cr is most stable in the magnesium-chromium spinel phase and the leaching safety performance is optimal), the magnesium-chromium spinel is an excellent nucleating agent, and meanwhile, in view of the oriented attachment phenomenon of a pyroxene phase on the surface of the spinel, an ore phase structure which takes the spinel phase as an inner core and is wrapped by the pyroxene phase is finally formed, and the ore phase structure is undoubtedly the best guarantee of effective control of Cr leaching and excellent safety performance. In addition, in the aspect of preparation process, only one step of heating, melting, heat preservation and cooling is needed, and compared with the prior art, the method has the advantages of simple steps, easiness in operation, reduction in cost and energy consumption and wide application prospect.
Disclosure of Invention
The invention aims to provide a pyroxene-based cast stone. Another object of the present invention is to provide a process for producing the pyroxene-based cast stone. The magnesium-chromium spinel crystal phase is prepared by using stainless steel slag, acid-washing sludge, quartz sand and magnesite, wherein Cr element is sealed in a magnesium-chromium spinel mineral phase by controlling process parameters, the magnesium-chromium spinel is an excellent crystal nucleating agent, and meanwhile, in view of the oriented attachment phenomenon of a pyroxene phase on the surface of spinel, a mineral phase structure which takes the spinel phase as a core and is externally wrapped by the pyroxene phase is finally formed, and the mineral phase structure effectively controls Cr leaching and has high safety performance.
The pyroxene-based cast stone comprises the following raw materials in percentage by weight: 3 parts of stainless steel slag, 1 part of acid-washing sludge, 4 parts of quartz sand and 2 parts of magnesite, wherein the acid-washing sludge comprises 5-12wt% of Cr2O3,17-25wt％Fe2O3，34-48wt％CaF2And the balance of water.
Preferably, the stainless steel slag comprises 48-67wt% of CaO and SiO2:26-29wt％,MgO:4-8wt％,Al2O3:1-5wt％,Cr2O31-5wt%, the balance being iron and unavoidable impurities.
Preferably, the quartz sand comprises 90-99wt% SiO2And the balance of inevitable impurities.
Preferably, the content of magnesium oxide in the magnesite is 44-47 wt%.
Preferably, the pyroxene-based cast stone comprises, by weight, 14-20% CaO, 10-15% MgO, and 45-50% SiO2，1.3-3.0％Cr2O3，3.0-5.0％CaF2The balance of iron and inevitable impurities.
Preferably, the pyroxene-based cast stone has a crystal phase structure in which a magnesium chromium spinel phase is used as an inner core and a pyroxene phase is wrapped outside.
The preparation method of the pyroxene-based cast stone comprises the following steps:
s1, mixing the stainless steel slag, the acid-washing sludge and the fly ash according to a proportion, crushing, and sieving with a 100-mesh and 200-mesh sieve;
s2, placing the mixed material sieved in the step S1 in an alumina crucible and melting in a tubular furnace, wherein the melting temperature is 1450 and 1550 ℃, and the temperature is kept for 1-3h, so that the mixed material is fully and uniformly melted;
s3, pouring the mixed material melted in the step S2 into a graphite mold, placing the mold in a muffle furnace, performing heat treatment at 800-;
and S4, grinding and polishing the solidified cast stone to obtain the pyroxene-based cast stone.
Preferably, the heat treatment temperature in the step S3 is 900 ℃ and the heat treatment crystallization time is 3 hours.
Compared with the prior art, the invention has the following beneficial effects: (1) the preparation of the prior cast stone mainly takes natural stone as main material, such as basalt, diabase, limestone, dolomite, hornblende and the like, the technology mainly utilizes solid wastes such as stainless steel slag, acid-washing sludge, fly ash and the like, saves the natural stone, and simultaneously promotes the comprehensive utilization of secondary resources, particularly chromium-containing hazardous waste solid wastes; (2) compared with the prior art for preparing the microcrystalline glass by utilizing chromium-containing solid wastes such as stainless steel slag, the method has the following three advantages: firstly, in the aspect of preparation process, the preparation of the microcrystalline glass needs two steps of heating melting/heat preservation/cooling and reheating/heat preservation/cooling, the technology only needs one step of heating melting/heat preservation/cooling, and the technology is simple, easy to operate, low in energy consumption and low in cost; secondly, the product developed by the technology has an ore phase structure with a magnesium-chromium spinel phase as an inner core and a pyroxene phase wrapped outside, and the product has a microstructure with spinel as a core and the pyroxene phase growing around the spinel phase. The spinel phase is dispersed in the product, and the formed pyroxene phases are mutually interwoven, so that the physical properties of the product are greatly improved. Meanwhile, in the process of growing the pyroxene phase, the glass phase is fully transformed, so that the structure of the pyroxene phase is more compact. The method is a dual guarantee for effectively controlling Cr leaching and ensuring the safety performance; thirdly, the cast stone product developed by the technology has the Mohs hardness of 7 and the breaking strength of 140Mpa, and has more excellent wear resistance and chemical corrosion resistance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is an SEM image of a pyroxene-based cast stone prepared in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples and figures.
Example 1
A preparation method of pyroxene-based cast stone comprises the following steps:
s1, selecting stainless steel slag containing the following components in percentage by weight: 55 wt% CaO, 28 wt% SiO2，5wt％MgO，5wt％Al2O3，5wt％Cr2O3The balance of iron and inevitable impurities; the acid pickling sludge comprises the following components in percentage by weight: 10 wt% Cr2O3，20wt％Fe2O3，40wt％CaF2The balance of water; the quartz sand contains 95 wt% SiO2(ii) a The content of magnesium oxide in the magnesite is 45 wt%.
Weighing 3 parts of the stainless steel slag, 1 part of acid-washing sludge, 4 parts of quartz sand and 2 parts of magnesite, fully mixing, crushing, and sieving by a 100-mesh sieve;
s2, placing the mixed material sieved in the step S1 into an alumina crucible to be melted in a tubular furnace, wherein the melting temperature is 1500 ℃, and keeping the temperature for 2 hours to ensure that the mixed material is fully melted and uniform;
s3, pouring the mixed material melted in the step S2 into a graphite mold, placing the mold in a muffle furnace, performing heat treatment crystallization at 900 ℃ for 3 hours, and cooling along with the furnace to obtain solidified cast stone;
and S4, grinding and polishing the solidified cast stone to obtain the pyroxene-based cast stone, as shown in figure 1. The pyroxene-based cast stone prepared in this example has the following components in mass fraction: 16.5 wt% CaO, 46.4 wt% SiO2，10.5wt％MgO，1.5wt％Al2O3，2.5wt％Cr2O3，2wt％Fe2O3，4wt％CaF2And the balance impurities.
Example 2
A preparation method of pyroxene-based cast stone comprises the following steps:
s1, selecting stainless steel slag containing the following components in percentage by weight: 48 wt% CaO, 26 wt% SiO2，8wt％MgO，5wt％Al2O3，5wt％Cr2O3The balance of iron and inevitable impurities; the acid pickling sludge comprises the following components in percentage by weight: 12wt% Cr2O3，20wt％Fe2O3，45wt％CaF2(ii) a The quartz sand contains 95 wt% SiO2(ii) a The content of magnesium oxide in the magnesite is 45 wt%.
Weighing 3 parts of the stainless steel slag, 1 part of acid-washing sludge, 4 parts of quartz sand and 2 parts of magnesite, fully mixing, crushing, and sieving by a 100-mesh sieve;
s2, placing the mixed material sieved in the step S1 into an alumina crucible to be melted in a tubular furnace, wherein the melting temperature is 1450 ℃, and the temperature is kept for 3 hours to ensure that the mixed material is fully melted and uniform;
s3, pouring the mixed material melted in the step S2 into a graphite mold, placing the mold in a muffle furnace, performing heat treatment crystallization at 1000 ℃ for 2 hours, and cooling along with the furnace to obtain solidified cast stone;
and S4, grinding and polishing the solidified cast stone to obtain the pyroxene-based cast stone. The pyroxene-based cast stone prepared in this example has the following components in mass fraction: 14.4 wt% CaO, 45.8 wt% SiO2，11.4wt％MgO，1.5wt％Al2O3，2.7wt％Cr2O3，2wt％Fe2O3，4.5wt％CaF2And the balance impurities.
Example 3
S1, selecting stainless steel slag containing the following components in percentage by weight: 67wt% CaO, 27 wt% SiO2，5wt％MgO，1wt％Al2O3，1wt％Cr2O3The balance of iron and inevitable impurities; the acid pickling sludge comprises the following components in percentage by weight: 10 wt% Cr2O3，17wt％Fe2O3，34wt％CaF2(ii) a The quartz sand contains 99wt% SiO2(ii) a The content of magnesium oxide in the magnesite is 45 wt%.
Weighing 3 parts of the stainless steel slag, 1 part of acid-washing sludge, 4 parts of quartz sand and 2 parts of magnesite, fully mixing, crushing, and sieving by a 100-mesh sieve;
s2, placing the mixed material sieved in the step S1 into an alumina crucible to be melted in a tubular furnace, wherein the melting temperature is 1550 ℃, and the heat is preserved for 1 hour to ensure that the mixed material is fully melted and uniform;
s3, pouring the mixed material melted in the step S2 into a graphite mold, placing the mold in a muffle furnace, performing heat treatment at 1200 ℃ for crystallization for 1h, and cooling along with the furnace to obtain solidified cast stone;
and S4, grinding and polishing the solidified cast stone to obtain the pyroxene-based cast stone. The pyroxene-based cast stone prepared in this example has the following components in mass fraction: 20.0 wt% CaO, 47.7 wt% SiO2，10.5wt％MgO，0.3wt％Al2O3，1.3wt％Cr2O3，1.7wt％Fe2O3，3.4wt％CaF2And the balance impurities.
According to examples 1 to 3 of the present invention, the pyroxene-based cast stone of the present invention has a crystal phase structure in which a spinel phase is a core and a pyroxene phase grows around the spinel phase. The prepared cast stone material has excellent wear resistance and chemical corrosion resistance, Mohs hardness of 7, breaking strength of 140MPa, and acid and alkali resistance of over 99.5%.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.

Claims (6)

1. A pyroxene-based cast stone is characterized by comprising the following raw materials in parts by weight:
3 parts of stainless steel slag, 1 part of acid-washing sludge, 4 parts of quartz sand and 2 parts of magnesite, wherein the acid-washing sludge comprises 5-12wt% of Cr2O3, 17-25wt%Fe2O3，34-48wt%CaF2The balance of water;
the stainless steel slag comprises 48-67wt% of CaO and SiO2:26-29wt%, MgO:4-8wt%, Al2O3:1-5wt%, Cr2O31-5wt%, the balance being iron and unavoidable impurities;
the crystal phase structure of the flint-based cast stone is an ore phase structure with a magnesium-chromium spinel phase as an inner core and a pyroxene phase wrapped outside.
2. Pyroxene-based cast stone according to claim 1, characterized in that the quartz sand comprises 90-99wt% SiO2And the balance of inevitable impurities.
3. Pyroxene based cast stone according to claim 1, characterized in that the mass fraction of magnesium oxide in the magnesite is 44-47 wt%.
4. The pyroxene-based cast stone according to claim 1, characterized in that the pyroxene-based cast stone comprises the following components in weight percent: 14-20% of CaO, 10-15% of MgO and 45-50% of SiO2，1.3-3.0% Cr2O3，3.0-5.0% CaF2The balance of iron and inevitable impurities.
5. The method for producing pyroxene based cast stone according to any one of claims 1 to 4, characterized by comprising the steps of:
s1, mixing the stainless steel slag, the acid-washing sludge and the fly ash according to a proportion, crushing, and sieving with a 100-mesh and 200-mesh sieve;
s2, placing the mixed material sieved in the step S1 in an alumina crucible and melting in a tubular furnace, wherein the melting temperature is 1450 and 1550 ℃, and the temperature is kept for 1-3h, so that the mixed material is fully and uniformly melted;
s3, pouring the mixed material melted in the step S2 into a graphite mold, placing the mold in a muffle furnace, performing heat treatment at 800-;
and S4, grinding and polishing the solidified cast stone to obtain the pyroxene-based cast stone.
6. The method for producing pyroxene-based cast stone according to claim 5, wherein the heat treatment crystallization temperature in the step S3 is 900 ℃ and the heat treatment crystallization time is 3 hours.
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