CN114873919B - TiO 2 Method for strengthening mass harmless and high-value utilization of stainless steel slag - Google Patents
TiO 2 Method for strengthening mass harmless and high-value utilization of stainless steel slag Download PDFInfo
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 72
- 239000010935 stainless steel Substances 0.000 title claims abstract description 72
- 239000002893 slag Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000005728 strengthening Methods 0.000 title claims abstract description 14
- 229910010413 TiO 2 Inorganic materials 0.000 title abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 59
- 239000000919 ceramic Substances 0.000 claims abstract description 54
- 239000011521 glass Substances 0.000 claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000006121 base glass Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000010899 nucleation Methods 0.000 claims abstract description 19
- 230000006911 nucleation Effects 0.000 claims abstract description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 239000006004 Quartz sand Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000010881 fly ash Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000006060 molten glass Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 239000011651 chromium Substances 0.000 abstract description 55
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 21
- 239000013078 crystal Substances 0.000 abstract description 19
- 238000002386 leaching Methods 0.000 abstract description 17
- 229910052804 chromium Inorganic materials 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 9
- 239000002241 glass-ceramic Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 230000001737 promoting effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 15
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 13
- 229910052637 diopside Inorganic materials 0.000 description 13
- 239000011029 spinel Substances 0.000 description 12
- 229910052596 spinel Inorganic materials 0.000 description 12
- 238000001514 detection method Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- NACUKFIFISCLOQ-UHFFFAOYSA-N [Mg].[Cr] Chemical compound [Mg].[Cr] NACUKFIFISCLOQ-UHFFFAOYSA-N 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910001430 chromium ion Inorganic materials 0.000 description 5
- 239000000156 glass melt Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000004568 cement Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001038 titanium pigment Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to a TiO 2 A method for strengthening the harmless and high-value utilization of large quantities of stainless steel slag. According to the invention, stainless steel slag, titanium dioxide and other raw materials are melted and prepared into base glass, the base glass is subjected to nucleation heat treatment to obtain nucleated glass, the content of titanium dioxide in the glass is regulated, a large number of fine nano magnesia-chromite crystal grains with low leaching rate are formed in the process of the nucleation heat treatment by promoting Cr in the base glass, the effect of strengthening chromium fixation is achieved, and the nucleated glass is subjected to crystallization heat treatment to finally obtain high-value microcrystalline ceramic. The invention has good harmless treatment effect on the stainless steel slag and large treatment capacity, and when TiO 2 At a content of 3.4wt%, the glass ceramic has an acidity resistance (20 wt% H) 2 SO 4 ) 99.95%, alkali resistance (20 wt% NaOH) 99.96%, water absorption 0.01%, compressive strength 267.4MPa, and Vickers hardness 1211.8HV.
Description
Technical Field
The invention relates to a harmless treatment technology of metallurgical secondary resources, in particular to a TiO (titanium dioxide) 2 A method for strengthening the harmless and high-value utilization of large quantities of stainless steel slag.
Background
Stainless steel is used as an important production material and is widely applied in the fields of metallurgy, construction, transportation, food, medical treatment and the like. The crude stainless steel yield of the whole country in 2020 is 3013.9 ten thousand tons, and the generated stainless steel slag exceeds 900 ten thousand tons. Chromium in stainless steel slag is usually Cr 3+ A small amount of Cr 6+ The state exists. Researches show that the stainless steel slag is piled up for a long time under natural environment, cr 3+ Can be oxidized into Cr 6+ ，Cr 6+ Has high toxicity, is easy to dissolve in water, and can be infiltrated into the environmentAnd causes harm to the environment and human body. Therefore, the production of a large amount of stacked stainless steel slag in the stainless steel industry is severely restricted, and whether harmless treatment can be obtained becomes a bottleneck for sustainable development of the stainless steel manufacturing industry. At present, the harmless and high-value utilization of large quantities of stainless steel slag is an important problem which needs to be solved in industry.
Microcrystalline ceramics are a type of polycrystalline solid material containing a large number of microcrystalline phases and glass phases, which is produced by nucleation and crystallization of a base glass of a specific composition during heating. Compared with common glass, the microcrystalline ceramic has the advantages of high mechanical strength, good wear resistance, stable chemical property and the like, and is widely applied to a plurality of fields of construction, chemical industry, medical treatment and the like. The main chemical components of the stainless steel slag are similar to those of the microcrystalline ceramic, and the chromium oxide in the slag can be used as a main nucleating agent for preparing the microcrystalline ceramic, so that the chromium in the slag can be solidified by preparing the microcrystalline ceramic from the stainless steel slag, and the method is an effective way for realizing harmless and high-value utilization of the stainless steel slag.
The traditional harmless treatment of the stainless steel slag adopts a curing method. The cement solidification method is to add cement into the fusion of stainless steel slag and other solid wastes to wrap the fusion by cement. The method has the advantages of large treatment capacity for stainless steel slag and convenient operation, and the defect that the solidification degree of Cr is not high enough. The invention discloses a method for high-temperature harmless treatment of stainless steel slag by using molten blast furnace slag (patent number 201611053294X), which comprises the steps of adding the stainless steel slag into the molten blast furnace slag, electrifying, heating, stirring, and water quenching to obtain a mixed slag glass body, so that heavy metal Cr is fixed in the mixed slag glass body. When the addition amount of the stainless steel slag in the patent is 40wt%, the leaching concentration of Cr in glassy slag is 0.03mg/L, and the effect of solidifying Cr is achieved to a certain extent, but the obtained product has low added value and cannot be directly applied as a building material.
Ouyang, "preparation of glass ceramics from stainless steel slag: crystal structure and solidification of heavy metal chromium "(" science report ", 2019,9 (1): 1-9): [ Preparation of Glass-ceramics Using Chromium-containing stainless steel slag: crystal structure and Solidification of Heavy Metal Chromium ] ("Scientific Reports", 2019,9 (1): 1-9) ] discloses that glass ceramics are prepared from 0-20wt% stainless steel slag, and the compressive strength of the prepared glass ceramics is 222.9MPa, and the Vickers hardness is 729.27HV. The utilization rate of the stainless steel slag in the article is low by about 20%, and the mechanical property of the prepared glass ceramics is not high enough.
Disclosure of Invention
The invention aims to provide TiO 2 A method for strengthening the harmless and high-value utilization of large quantities of stainless steel slag. The stainless steel slag, titanium dioxide and other raw materials are melted to prepare base glass, the base glass is subjected to nucleation heat treatment, and the added titanium dioxide (titanium dioxide) can promote Cr in the base glass to form nano magnesia-chromite spinel grains with low leaching rate in the nucleation heat treatment process, so that the nucleated glass is obtained and the purpose of primarily strengthening chromium fixation is realized (as shown in figure 1); then the nucleated glass is subjected to crystallization heat treatment, nano-scale magnesium-chromium spinel crystal grains are used as heterogeneous nuclei to induce precipitation of diopside crystal phases (as shown in figure 2), cr in the nano-scale magnesium-chromium spinel crystal grains is diffused into the diopside, and meanwhile Cr in the glass phase is gradually diffused into the diopside crystal lattice along with the generation of the diopside, so that more Cr is solidified, further strengthening of Cr is achieved, and the harmless effect of the stainless steel slag is greatly improved. With the addition of a proper amount of titanium dioxide, the number of nano-scale magnesia-chromite spinel crystal grains can be obviously increased, and a large number of fine nano-scale magnesia-chromite spinel crystal grains are used as heterogeneous nuclei in the crystallization heat treatment process to induce and separate out a large number of fine diopside crystals, so that the compressive strength of the glass ceramic is greatly improved, and the high-value utilization of the stainless steel slag is realized. Thus, the microcrystalline ceramics are prepared by using stainless steel slag, and TiO is adjusted 2 The addition amount can solve the difficult problems of mass innocuity and high-value utilization of the stainless steel slag.
The technical scheme of the invention is as follows:
TiO (titanium dioxide) 2 The method for strengthening the harmless and high-value utilization of a large amount of stainless steel slag comprises the following steps:
(1) Pulverizing the raw materials, drying, and sieving;
(2) Placing the raw materials screened in the step (1) into a ball mill for ball milling and mixing uniformly,TiO in the mixed raw material 2 The content of (2) is 1-6wt%;
(3) Loading the mixed raw materials subjected to ball milling in the step (2) into an alumina crucible, heating the alumina crucible in a tube furnace to 1450-1650 ℃, then preserving heat for 0.5-1.5 h to obtain molten glass solution, and simultaneously, putting a stainless steel mold into a muffle furnace to heat the stainless steel mold to 550 ℃;
(4) Taking out the stainless steel mold from the muffle furnace, pouring the molten glass solution obtained in the step (3) into the stainless steel mold, putting the stainless steel mold into the muffle furnace again, preserving heat for 0.5-1.5 h at 550 ℃ for annealing, and cooling along with the furnace to obtain basic glass;
(5) Respectively carrying out nucleation heat treatment and crystallization heat treatment on the base glass obtained in the step (4) in an isothermal gradient furnace, obtaining nucleated glass after the nucleation heat treatment, and finally obtaining microcrystalline ceramic after the crystallization heat treatment of the nucleated glass;
the raw materials in the step (1) comprise 50-70wt% of stainless steel slag, 10-30wt% of fly ash, 5-15wt% of quartz sand, 0-8wt% of light magnesium oxide, 0-5wt% of titanium dioxide, 0-4wt% of industrial ferric oxide and 0-3wt% of sodium carbonate.
The heating system of the tube furnace in the step (3) is that the temperature is increased to 1000 ℃ from room temperature at a heating rate of 10 ℃/min, the temperature is increased to 1300 ℃ from 1000 ℃ at a heating rate of 7 ℃/min, and the temperature is increased to 1450-1650 ℃ from 1300 ℃ at a heating rate of 5 ℃/min.
And (3) the nucleation heat treatment system of the base glass in the step (5) is 670-780 ℃ for heat preservation for 1.5-2.5 h, and the crystallization heat treatment system of the nucleation glass is 830-900 ℃ for heat preservation for 2-3 h.
TiO in the mixed raw material of the step (2) 2 The content is preferably 3.4% by weight.
The starting material in step (1) was dried at 100℃for 24 hours and sieved through a 200 mesh sieve.
The ball milling time in the step (2) is 3 hours.
The invention has the beneficial effects that:
(1) The invention has good harmless treatment effect on the stainless steel slag, and the TiO is adjusted 2 The content of the heavy metal element Cr in the stainless steel slag is promoted to be endowed in the nucleation stage of the microcrystalline ceramicIn the chromium spinel crystal lattice, spinel is wrapped and fused by diopside crystal after crystallization, so that the solidification degree of Cr is further improved. When TiO 2 When the content is 3.4wt%, 97.4wt% of Cr in the stainless steel slag is added in diopside crystal of the microcrystalline ceramic, and the leaching concentration of Cr is only 0.009mg/L.
(2) The invention has large treatment capacity for the stainless steel slag, the utilization rate of the stainless steel slag reaches more than 60wt percent, the use amount of the stainless steel slag is greatly improved (40 percent is improved), and the mass harmless effect of the invention is far better than that of the prior art.
(3) The invention strengthens the bulk innocuous treatment of the stainless steel slag, and the obtained product microcrystalline ceramic has better chemical stability and mechanical property, thereby realizing the high-value utilization of solid wastes. When TiO 2 At a content of 3.4wt%, the glass ceramic has an acidity resistance (20 wt% H) 2 SO 4 ) 99.95%, alkali resistance (20 wt% NaOH) 99.96%, water absorption 0.01%, compressive strength 267.4MPa, vickers hardness 1211.8HV, far higher than the prior art.
Drawings
FIG. 1 is an SEM image (a) and XRD pattern (b) of nucleated glass according to the present invention;
FIG. 2 is an SEM image (a) and XRD pattern (b) of crystallized glass (microcrystalline ceramic) according to the present invention;
FIG. 3 shows the results of the compressive strength and the Vickers hardness test of the microcrystalline ceramics according to examples T1 to T5 of the present invention.
Detailed Description
The invention prepares the microcrystalline ceramics by utilizing stainless steel slag and adjusts TiO 2 The addition amount ensures that more Cr in slag migrates to be added into diopside crystals in the microcrystalline ceramic, achieves the effects of strengthening chromium fixation and reducing Cr leaching amount, and simultaneously obtains high-strength microcrystalline ceramic, thereby providing technical support for realizing the harmless and high-value utilization of large quantities of stainless steel slag.
The following 5 examples were selected from 120 experiments.
Example 1 (T1)
60wt% of stainless steel slag, 20wt% of fly ash, 10wt% of quartz sand, 0wt% of titanium dioxide, 6wt% of light magnesium oxide,2% by weight of technical iron oxide and 2% by weight of soda ash are crushed and dried at 100℃for 24 hours, and sieved through a 200-mesh sieve. Ball milling for 3h by a ball mill to uniformly mix the raw materials. The mixture, as analyzed, contained CaO25.1wt%, mgO 12.5wt%, al 2 O 3 10wt％、SiO 2 45wt％、Cr 2 O 3 1.3wt％、Fe 2 O 3 2.9wt％、TiO 2 1.4wt％、Na 2 O 1.6wt％、K 2 O 0.1wt％；
The obtained mixture was charged into a 200ml alumina crucible, placed in a tube furnace, heated from room temperature to 1000℃at a heating rate of 10℃per minute, heated from 1000℃to 1300℃at a heating rate of 7℃per minute, heated from 1300℃to 1550℃at a heating rate of 5℃per minute, and incubated at 1550℃for 1 hour. Simultaneously, placing the stainless steel die into a muffle furnace to be heated to 550 ℃;
pouring the melted glass melt into a mould for annealing, preserving heat for 1h, and cooling along with a furnace to obtain the base glass. And (3) carrying out nucleation heat treatment on the obtained base glass in an isothermal gradient furnace under the condition of preserving heat for 2 hours at 730 ℃ to obtain the nucleated glass. The obtained nucleated glass is subjected to crystallization heat treatment in an isothermal gradient furnace under the condition of heat preservation at 860 ℃ for 2.5 hours to obtain microcrystalline ceramic;
and (3) performing XPS detection on the prepared microcrystalline ceramic by using Cr elements, taking XPS electron combination energy spectrum of chromium ions in magnesium-chromium spinel and base glass as a reference, and fitting and peak separation on detection results to obtain the microcrystalline ceramic, wherein 93.13wt% of Cr is endowed in diopside crystal lattices. The results of Cr leaching test and chemical stability test on the microcrystalline ceramics are shown in Table 1, wherein the leaching concentration of Cr in the microcrystalline ceramics is 0.018mg/L, and the acid resistance (20 wt% H) 2 SO 4 ) 99.84%, alkali resistance (20 wt% NaOH) 99.81%, water absorption 0.07%. The results of mechanical property test on the microcrystalline ceramics are shown in fig. 3, wherein the compressive strength of the microcrystalline ceramics is 248MPa, and the Vickers hardness of the microcrystalline ceramics is 1082.5HV.
Example 2 (T2)
60wt% stainless steel slag, 19wt% fly ash, 10wt% quartz sand, 1wt% titanium pigment, 6wt% light magnesium oxide, 2wt% industrial iron oxide and 2wt% sodium carbonate are crushed and dried at 100 ℃ for 24 hours, and pass through 200 meshesThe sieve is used for sieving. Ball milling for 3h by a ball mill to uniformly mix the raw materials. The mixture contains 25.1wt% of CaO, 12.5wt% of MgO and Al by analysis 2 O 3 9.7wt％、SiO 2 44.5wt％、Cr 2 O 3 1.3wt％、Fe 2 O 3 2.9wt％、TiO 2 2.4wt％、Na 2 O 1.6wt％、K 2 O 0.1wt％；
The obtained mixture was charged into a 200ml alumina crucible, placed in a tube furnace, heated from room temperature to 1000℃at a heating rate of 10℃per minute, heated from 1000℃to 1300℃at a heating rate of 7℃per minute, heated from 1300℃to 1550℃at a heating rate of 5℃per minute, and incubated at 1550℃for 1 hour. Simultaneously, placing the stainless steel die into a muffle furnace to be heated to 550 ℃;
pouring the melted glass melt into a mould for annealing, preserving heat for 1h, and cooling along with a furnace to obtain the base glass. And (3) carrying out nucleation heat treatment on the obtained base glass in an isothermal gradient furnace under the condition of preserving heat for 2 hours at 730 ℃ to obtain the nucleated glass. The obtained nucleated glass is subjected to crystallization heat treatment in an isothermal gradient furnace under the condition of heat preservation at 860 ℃ for 2.5 hours to obtain microcrystalline ceramic;
and (3) performing XPS detection on the prepared microcrystalline glass by using Cr elements, taking XPS electron combination energy spectrum of chromium ions in the magnesium-chromium spinel and the base glass as a reference, and fitting and peak separation on detection results to obtain the microcrystalline glass, wherein 95.15wt% of Cr is added in a diopside crystal lattice. The microcrystalline ceramics were subjected to Cr leaching test and chemical stability test, and the results are shown in Table 1, wherein the microcrystalline ceramics had a Cr leaching concentration of 0.013mg/L and an acid resistance (20 wt% H) 2 SO 4 ) 99.90%, alkali resistance (20 wt% NaOH) 99.91%, water absorption 0.03%. The results of mechanical property test on the microcrystalline ceramics are shown in fig. 3, wherein the compressive strength of the microcrystalline ceramics is 255.3MPa, and the vickers hardness of the microcrystalline ceramics is 1132.5HV.
Example 3 (T3)
60wt% of stainless steel slag, 19wt% of fly ash, 9wt% of quartz sand, 2wt% of titanium pigment, 6wt% of light magnesium oxide, 2wt% of industrial iron oxide and 2wt% of sodium carbonate are crushed, dried for 24 hours at 100 ℃ and screened through a 200-mesh screen. Ball milling for 3 hours by using a ball mill to uniformly mix the raw materials; through analysis, the mixture isThe material contains 25.1wt% of CaO, 12.5wt% of MgO and Al 2 O 3 9.7wt％、SiO 2 43.4wt％、Cr 2 O 3 1.3wt％、Fe 2 O 3 2.9wt％、TiO 2 3.4wt％、Na 2 O 1.6wt％、K 2 O 0.1wt％；
The obtained mixed raw material was charged into a 200ml alumina crucible, placed in a tube furnace, heated from room temperature to 1000 ℃ at a heating rate of 10 ℃/min, heated from 1000 ℃ to 1300 ℃ at a heating rate of 7 ℃/min, heated from 1300 ℃ to 1550 ℃ at a heating rate of 5 ℃/min, and incubated for 1h at 1550 ℃. Simultaneously, placing the stainless steel die into a muffle furnace to be heated to 550 ℃;
pouring the melted glass melt into a stainless steel mold for annealing, preserving heat for 1h, and cooling along with a furnace to obtain base glass; performing nucleation heat treatment on the obtained base glass in an isothermal gradient furnace under the condition of preserving heat for 2 hours at 730 ℃ to obtain nucleated glass; the obtained nucleated glass is subjected to crystallization heat treatment in an isothermal gradient furnace under the condition of heat preservation at 860 ℃ for 2.5 hours to obtain microcrystalline ceramic;
performing XPS detection on the prepared microcrystalline ceramic by using Cr elements, taking XPS electron combination energy spectrum of chromium ions in magnesium-chromium spinel and base glass as a reference, fitting and peaking the detection result to obtain 97.4wt% of Cr which is assigned in diopside crystal lattices; the microcrystalline ceramics were subjected to Cr leaching test and chemical stability test, and the results are shown in Table 1, wherein the microcrystalline ceramics had a Cr leaching concentration of 0.009mg/L and an acid resistance (20 wt% H) 2 SO 4 ) 99.95%, alkali resistance (20 wt% NaOH) 99.88%, water absorption 0.02%; the results of mechanical property test on the microcrystalline ceramics are shown in fig. 3, wherein the compressive strength of the microcrystalline ceramics is 267.4MPa, and the Vickers hardness of the microcrystalline ceramics is 1211.8HV.
Example 4 (T4)
60 weight percent of stainless steel slag, 18 weight percent of fly ash, 9 weight percent of quartz sand, 3 weight percent of titanium dioxide, 6 weight percent of light magnesium oxide, 2 weight percent of industrial iron oxide and 2 weight percent of sodium carbonate are crushed and dried for 24 hours at 100 ℃, and are sieved by a 200-mesh sieve; ball milling for 3 hours by using a ball mill to uniformly mix the raw materials; the mixture contains 25wt% of CaO, 12.5wt% of MgO and Al by analysis 2 O 3 9.3wt％、SiO 2 42.9wt％、Cr 2 O 3 1.3wt％、Fe 2 O 3 2.9wt％、TiO 2 4.4wt％、Na 2 O 1.6wt％、K 2 O 0.1wt％；
Placing the obtained mixture into a 200ml alumina crucible, placing the crucible into a tube furnace, heating the crucible from room temperature to 1000 ℃ at a heating rate of 10 ℃/min, heating the crucible from 1000 ℃ to 1300 ℃ at a heating rate of 7 ℃/min, heating the crucible from 1300 ℃ to 1550 ℃ at a heating rate of 5 ℃/min, and preserving the heat for 1h at 1550 ℃ to obtain molten glass; simultaneously, placing the stainless steel die into a muffle furnace to be heated to 550 ℃;
pouring the melted glass melt into a stainless steel mold for annealing, preserving heat at 550 ℃ for 1h, and cooling along with a furnace to obtain base glass; performing nucleation heat treatment on the obtained base glass in an isothermal gradient furnace under the condition of preserving heat for 2 hours at 730 ℃ to obtain nucleated glass; the obtained nucleated glass is subjected to crystallization heat treatment in an isothermal gradient furnace under the condition of heat preservation at 860 ℃ for 2.5 hours to obtain microcrystalline ceramic;
and (3) performing XPS detection on the prepared microcrystalline ceramic by using Cr elements, wherein XPS electron combination energy spectrum of chromium ions in magnesium-chromium spinel and base glass is used as a reference, and the detection result is fitted and subjected to peak separation to obtain 96.15wt% of Cr which is assigned in a diopside crystal lattice. The microcrystalline ceramics were subjected to Cr leaching test and chemical stability test, and the results are shown in Table 1, wherein the microcrystalline ceramics had a Cr leaching concentration of 0.011mg/L and an acid resistance (20 wt% H) 2 SO 4 ) 99.92%, alkali resistance (20 wt% NaOH) 99.92%, water absorption 0.01%. The results of mechanical property test on the microcrystalline ceramics are shown in fig. 3, wherein the compressive strength of the microcrystalline ceramics is 258.6MPa, and the vickers hardness of the microcrystalline ceramics is 1182.6HV.
Example 5 (T5)
60wt% of stainless steel slag, 18wt% of fly ash, 8wt% of quartz sand, 4wt% of titanium pigment, 6wt% of light magnesium oxide, 2wt% of industrial iron oxide and 2wt% of sodium carbonate are crushed and dried at 100 ℃ for 24 hours, and are screened through a 200-mesh screen. Ball milling for 3h by a ball mill to uniformly mix the raw materials. The mixture contains 25wt% of CaO, 12.5wt% of MgO and Al by analysis 2 O 3 9.3wt％、SiO 2 41.9wt％、Cr 2 O 3 1.3wt％、Fe 2 O 3 2.9wt％、TiO 2 5.4wt％、Na 2 O 1.6wt％、K 2 O 0.1wt％；
The obtained mixture was charged into a 200ml alumina crucible, placed in a tube furnace, heated from room temperature to 1000℃at a heating rate of 10℃per minute, heated from 1000℃to 1300℃at a heating rate of 7℃per minute, heated from 1300℃to 1550℃at a heating rate of 5℃per minute, and incubated at 1550℃for 1 hour. Simultaneously, placing the stainless steel die into a muffle furnace to be heated to 550 ℃;
pouring the melted glass melt into a mould for annealing, preserving heat for 1h, and cooling along with a furnace to obtain the base glass. And (3) carrying out nucleation heat treatment on the obtained base glass in an isothermal gradient furnace under the condition of preserving heat for 2 hours at 730 ℃ to obtain the nucleated glass. The obtained nucleated glass is subjected to crystallization heat treatment in an isothermal gradient furnace under the condition of heat preservation at 860 ℃ for 2.5 hours to obtain microcrystalline ceramic;
and (3) performing XPS detection on the prepared microcrystalline ceramic by using Cr elements, wherein XPS electron combination energy spectrum of chromium ions in magnesium-chromium spinel and base glass is used as a reference, and the obtained detection result is fitted and subjected to peak separation, so that 95.33wt% of Cr is added into diopside crystal lattices. The microcrystalline ceramics were subjected to Cr leaching test and chemical stability test, and the results are shown in Table 1, wherein the microcrystalline ceramics had a Cr leaching concentration of 0.011mg/L and an acid resistance (20 wt% H) 2 SO 4 ) 99.87%, alkali resistance (20 wt% NaOH) 99.88%, water absorption 0.04%. The results of mechanical property test on the microcrystalline ceramics are shown in fig. 3, wherein the compressive strength of the microcrystalline ceramics is 249.1MPa, and the Vickers hardness of the microcrystalline ceramics is 1093.4HV.
TABLE 1 detection of Cr leaching, acidity and alkali resistance and water absorption of microcrystalline ceramics prepared by the invention
| Examples | Cr leaching concentration (mg/L) | Acidity resistance (%) | Alkali resistance (%) | Water absorption (%) |
| 1 | 0.018 | 99.84 | 99.81 | 0.07 |
| 2 | 0.013 | 99.90 | 99.91 | 0.03 |
| 3 | 0.009 | 99.95 | 99.96 | 0.01 |
| 4 | 0.011 | 99.92 | 99.92 | 0.01 |
| 5 | 0.011 | 99.87 | 99.88 | 0.04 |
The microcrystalline ceramic prepared by the invention is compared with the microcrystalline glass prepared by Ouyang smoothly and the like in mechanical properties, and the results are shown in Table 2.
TABLE 2 comparison of mechanical properties of microcrystalline ceramics prepared by the invention and microcrystalline glass prepared by Ouyang
| Examples | Intensity (MPa) | Vickers Hardness (HV) |
| 1 | 248 | 1082.5 |
| 2 | 255.3 | 1132.5 |
| 3 | 267.4 | 1211.8 |
| 4 | 258.6 | 1182.6 |
| 5 | 249.1 | 1093.4 |
| Ouyang smooth waiting | 222.9 | 729.27 |
。
Claims (4)
1. TiO (titanium dioxide) 2 The method for strengthening the harmless and high-value utilization of a large amount of stainless steel slag is characterized by comprising the following steps of:
(1) Pulverizing the raw materials, drying, and sieving;
(2) Placing the raw materials screened in the step (1) into a ball mill for ball milling and mixing uniformly, and mixing TiO in the raw materials 2 The content of (2) is 1-6wt%;
(3) Loading the mixed raw materials subjected to ball milling in the step (2) into an alumina crucible, heating the alumina crucible in a tube furnace to 1450-1650 ℃, then preserving heat for 0.5-1.5 h to obtain molten glass solution, and simultaneously, putting a stainless steel mold into a muffle furnace to heat the stainless steel mold to 550 ℃;
(4) Taking out the stainless steel mold from the muffle furnace, pouring the molten glass solution obtained in the step (3) into the stainless steel mold, putting the stainless steel mold into the muffle furnace again, preserving heat for 0.5-1.5 h at 550 ℃ for annealing, and cooling along with the furnace to obtain basic glass;
(5) Respectively carrying out nucleation heat treatment and crystallization heat treatment on the base glass obtained in the step (4) in an isothermal gradient furnace, obtaining nucleated glass after the nucleation heat treatment, and finally obtaining microcrystalline ceramic after the crystallization heat treatment of the nucleated glass;
the raw materials in the step (1) comprise 50-70wt% of stainless steel slag, 10-30wt% of fly ash, 5-15wt% of quartz sand, 0-8wt% of light magnesium oxide, 0-5wt% of titanium dioxide, 0-4wt% of industrial ferric oxide and 0-3wt% of sodium carbonate;
the heating system of the tube furnace in the step (3) is that the temperature is increased to 1000 ℃ from room temperature at a heating rate of 10 ℃/min, the temperature is increased to 1300 ℃ from 1000 ℃ at a heating rate of 7 ℃/min, and the temperature is increased to 1450-1650 ℃ from 1300 ℃ at a heating rate of 5 ℃/min;
and (3) the nucleation heat treatment system of the base glass in the step (5) is 670-780 ℃ for heat preservation for 1.5-2.5 h, and the crystallization heat treatment system of the nucleation glass is 830-900 ℃ for heat preservation for 2-3 h.
2. A TiO according to claim 1 2 The method for strengthening the harmless and high-value utilization of a large amount of stainless steel slag is characterized by comprising the following steps of: tiO in the mixed raw material of the step (2) 2 The content was 3.4wt%.
3. A TiO according to claim 1 2 The method for strengthening the harmless and high-value utilization of a large amount of stainless steel slag is characterized by comprising the following steps of: the starting material in step (1) was dried at 100℃for 24 hours and sieved through a 200 mesh sieve.
4. A TiO according to claim 1 2 The method for strengthening the harmless and high-value utilization of a large amount of stainless steel slag is characterized by comprising the following steps of: the ball milling time in the step (2) is 3 hours.
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| CN102211874A (en) * | 2011-05-10 | 2011-10-12 | 北京科技大学 | Microcrystalline glass and preparation method thereof |
| CN105347684A (en) * | 2015-11-26 | 2016-02-24 | 上海宝田新型建材有限公司 | Blast-furnace-slag glass ceramics and preparation method therefor |
| CN106082679A (en) * | 2016-06-15 | 2016-11-09 | 北京科技大学 | A kind of method that full waste material short route prepares devitrified glass |
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| CN102211874A (en) * | 2011-05-10 | 2011-10-12 | 北京科技大学 | Microcrystalline glass and preparation method thereof |
| CN105347684A (en) * | 2015-11-26 | 2016-02-24 | 上海宝田新型建材有限公司 | Blast-furnace-slag glass ceramics and preparation method therefor |
| CN106082679A (en) * | 2016-06-15 | 2016-11-09 | 北京科技大学 | A kind of method that full waste material short route prepares devitrified glass |
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