CN108774003B - Microcrystalline glass and preparation method thereof - Google Patents
Microcrystalline glass and preparation method thereof Download PDFInfo
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- CN108774003B CN108774003B CN201810862715.6A CN201810862715A CN108774003B CN 108774003 B CN108774003 B CN 108774003B CN 201810862715 A CN201810862715 A CN 201810862715A CN 108774003 B CN108774003 B CN 108774003B
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- 239000011521 glass Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000010802 sludge Substances 0.000 claims abstract description 149
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 28
- 229910052745 lead Inorganic materials 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims description 30
- 239000002699 waste material Substances 0.000 claims description 29
- 238000009713 electroplating Methods 0.000 claims description 20
- 238000003723 Smelting Methods 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011505 plaster Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 34
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000011133 lead Substances 0.000 description 36
- 239000010949 copper Substances 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 235000011837 pasties Nutrition 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052924 anglesite Inorganic materials 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
Images
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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
- Glass Compositions (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention provides microcrystalline glass which is formed by mixing municipal sludge ash and industrial sludge raw materials, wherein the molar ratio of elements in a mixture of the municipal sludge ash and the industrial sludge is as follows: (Al + Fe): Pb: Cu: Zn ═ 2-18:1-2:1-2: 1-2. The preparation method comprises the following steps: mixing the raw materials according to the proportion; grinding the mixture evenly and pressing the mixture into slices by a tablet press; and then the sheet is kept at 850-950 ℃ for a period of time in a high temperature furnace, and the microcrystalline glass is prepared after cooling. The invention takes solid waste as raw material to prepare the glass ceramics, which not only can achieve the purposes of resource recycling and environmental protection, but also can realize the stability of three heavy metals Zn, Pb and Cu with serious harm at lower sintering temperature because industrial sludge polluted by heavy metals Pb, Cu and Zn is doped, and the doped elements destroy the regular system of a pure phase system.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to microcrystalline glass constructed by using sludge as a raw material and a preparation method of the microcrystalline glass.
Background
The microcrystalline glass is a polycrystalline solid material which is generated by controlling crystallization or inducing crystallization of base glass with a specific material ratio in a heat treatment process and contains a large number of microcrystalline phases and a certain number of glass phases. The coexistence characteristic of the crystal phase and the glass phase determines the diversity of the microcrystalline glass on the microstructure and the chemical composition, thereby leading the microcrystalline glass to integrate various excellent performances.
In the existing method for preparing the microcrystalline glass, pure chemical substances (pure phase Al) are generally used2O3,SiO2MgO, CaO, etc.) or mineral clay, which is a limited resource. The microcrystalline glass is usually prepared under the condition of high-temperature sintering, so the preparation of the microcrystalline glass has the problems of high price of raw materials, high energy consumption and high economic cost.
In recent years, the use of municipal sludge as a raw material for preparing glass ceramics has become a new way for resource utilization of sludge. The urban sludge ash contains a large amount of basic elements such as Si, Al, Ca and the like which form a microcrystalline glass matrix, but the temperature of the existing microcrystalline glass preparation technology needs to be controlled at about 1300 ℃, and the existing microcrystalline glass preparation technology needs to be kept at a high temperature for several hours, so that a large amount of energy is consumed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and firstly provides the microcrystalline glass which takes municipal sludge and industrial sludge as raw materials, has simple preparation process and low energy consumption, and can stabilize three heavy metals of Zn, Pb and Cu with serious harm.
The microcrystalline glass provided by the invention is prepared by mixing municipal sludge ash and industrial sludge as raw materials, wherein the molar ratio of elements in a mixture of the municipal sludge ash and the industrial sludge is as follows: (Al + Fe): Pb: Cu: Zn ═ 2-18:1-2:1-2: 1-2.
As the industrial sludge raw material, the industrial sludge can be electroplating industrial sludge and smelting industrial sludge polluted by Pb, Zn and Cu or/and waste lead-acid storage battery lead plaster.
Wherein, the electroplating industrial sludge can be sludge generated in the process of treating electroplating wastewater, and is formed by dehydration, heating, drying, crushing and sieving.
Wherein, the smelting industrial sludge can be formed by dehydrating, heating, drying, crushing and sieving sludge treated by lead-zinc smelting wastewater.
The lead plaster of the waste lead-acid battery can be a slurry substance formed after the active substance on the two electrode plates of the waste lead-acid battery is used through charging and discharging for many times.
The microcrystalline glass provided by the invention is prepared by taking solid wastes, namely municipal sludge and industrial sludge, as the adopted raw materials are all waste materials, the manufacturing cost of the microcrystalline glass can be reduced, waste can be changed into valuable, and the purpose of resource recycling is achieved.
The invention also provides a preparation method of the microcrystalline glass, which comprises the following steps:
the method comprises the following steps of mixing municipal sludge ash and industrial sludge according to the molar ratio of elements in the mixture: (Al + Fe) Pb, Cu: Zn: 2-18:1-2:1-2: 1-2;
uniformly grinding the mixture of the municipal sludge ash and the industrial sludge, and then pressing the mixture into slices by using a tablet press;
and (3) keeping the temperature of the sheet in a high-temperature furnace at 850-950 ℃ for a period of time, and then cooling the sheet to room temperature along with the furnace to obtain the glass ceramics.
In the steps, ethanol can be added into the mixture of the municipal sludge ash and the industrial sludge, and then the mixture is ground to be uniform.
In the above steps, the mixture can be pressed into the sheet under the pressure of 12-15MPa after being uniformly ground.
In the steps, the slice is placed in a high temperature furnace, and then is kept for 3-4h at the temperature of 850 ℃ and 850 ℃ at the heating rate of 5 ℃/min, and then is cooled to the room temperature along with the furnace.
The preparation method of the microcrystalline glass provided by the invention has the advantages that the preparation temperature is lower, and the stability of three heavy metals can be realized at the lower temperature. Therefore, on one hand, the energy consumption is greatly saved in the aspect of energy, on the other hand, the treatment and disposal of the current urban dewatered sludge and industrial sludge are very difficult (the quantity of land for landfill is limited, and the secondary pollution problem is possibly generated), and the microcrystalline glass prepared by the method can be used in a plurality of industries such as building, aviation and the like, so that the aim of resource recycling is fulfilled; in addition, the current heavy metal pollution problem is very serious, and the invention can be used for solidifying a plurality of heavy metals (which are easy to migrate and convert because the actual heavy metal pollution is usually that a plurality of heavy metals exist at the same time) in a toxic form into the microcrystalline glass, so that the harm of the heavy metals to the environment and human bodies can be reduced, and the invention has very important significance for the treatment of the environment.
Drawings
FIG. 1 is an SEM photograph of a sheet heated to 750 ℃ in a high temperature furnace during preparation of example 1 of the present invention;
FIG. 2 is an SEM photograph of a sheet heated to 850 ℃ in a high temperature furnace during preparation of example 1 of the present invention;
FIG. 3 is an SEM photograph of a sheet heated to 950 ℃ in a high temperature furnace during the preparation of example 1 of the present invention;
FIG. 4 is a graph showing the effect of stabilizing heavy metals (Pb, Zn, Cu) in the crystallized glass prepared in example 1 of the present invention;
FIG. 5 is an SEM photograph of a sheet heated to 750 ℃ in a high temperature furnace during the preparation of example 2 of the present invention;
FIG. 6 is an SEM photograph of a sheet heated to 850 ℃ in a high temperature furnace during preparation of example 2 of the present invention;
FIG. 7 is an SEM photograph of a sheet heated to 950 ℃ in a high temperature furnace during the preparation of example 2 of the present invention;
FIG. 8 is a graph showing the effect of stabilizing heavy metals (Pb, Zn, Cu) in the glass-ceramic prepared in example 2 of the present invention.
Fig. 9 is a picture of microcrystalline glass prepared in example 3 of the present invention.
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, 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 that other drawings can be obtained according to these drawings without creative efforts.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The microcrystalline glass provided by the invention is prepared by mixing municipal sludge ash and industrial sludge as raw materials, wherein the molar ratio of elements in a mixture of the municipal sludge ash and the industrial sludge is as follows: (Al + Fe): Pb: Cu: Zn ═ 2-18:1-2:1-2: 1-2. The preferred ratio is (Al + Fe), Pb, Cu, Zn, 8-14:1:1: 1.
In one of the raw materials for constructing the microcrystalline glass, the municipal sludge is used for sewage treatment plants and sewage treatmentThe inevitable product contains a large amount of basic elements such as Si, Al and Ca for constructing the microcrystalline glass matrix, and also contains a small amount of metal elements such as Fe, Mg and K. The current treatment method is to remove water from the fluid primary, concentrated or digested sludge, and convert the fluid primary, concentrated or digested sludge into semi-solid or solid sludge blocks for landfill, incineration and land utilization. The invention can select municipal sludge with water content of less than 20% after dehydration, and has main components capable of constructing microcrystalline glass, such as SiO2、Al2O3、MgO、CaO、Fe2O3And the municipal dewatered sludge can be dried for 24-30h at the temperature of 100-110 ℃, then sintered into ash at the temperature of 800-900 ℃ to remove organic matter components in the sludge, and ground and sieved (300-400 meshes) to form municipal sludge ash which is used as a raw material for preparing the glass ceramics.
In the other raw material for constructing the microcrystalline glass, the industrial sludge not only contains components participating in the construction of the microcrystalline glass, but also contains polluted heavy metal components, and can be electroplating industrial sludge and smelting industrial sludge polluted by Pb, Zn and Cu or/and waste lead-acid storage battery lead plaster.
The electroplating sludge is mainly from various electroplating waste liquids and electrolytic bath liquids of industrial electroplating plants, solid waste generated after wastewater treatment mainly contains heavy metal compounds such as chromium, iron, nickel, lead, copper, zinc and the like and soluble salts, is dried by heating after dehydration, and is crushed and sieved (300 meshes and 400 meshes).
The smelting industrial sludge is sludge from wastewater treatment of a lead-zinc smelting plant, is dehydrated, heated, dried, crushed and sieved (300-400 meshes). Mainly contains heavy metal compounds of zinc, lead, cadmium and the like, CaO and Fe2O3MgO, and soluble salts.
The waste lead-acid battery lead plaster is a pasty substance formed by using the active substances on the two polar plates of the recovered waste lead-acid battery through repeated charging and discharging. Mainly contains PbSO4、PbO2PbO and small amount of metals such as iron, copper and cadmium.
The microcrystalline glass provided by the invention takes solid wastes, namely municipal sludge and industrial sludge as raw materials, and comprises most components for constructing the microcrystalline glass, particularly the municipal sludge, Al and Si in the sludge can form a grid structure (such as an aluminosilicate crystal structure) at a high temperature, non-bridge oxygen possibly exists among grids and some cations (such as Ca, Na and the like) are combined, heavy metals in a mixture can be subjected to phase change at the high temperature, heavy metal elements can be inlaid in a stable crystal structure in order to balance the charge of the grid structure, feasibility is provided for preparing the microcrystalline glass by the sludge, and a high-performance glass matrix and a stable crystalline phase of the microcrystalline glass can provide double guarantee for fixing the heavy metals.
Under the condition that the treatment and disposal of the municipal dewatered sludge and the industrial sludge are very difficult (the quantity of land for landfill is limited, and secondary pollution is possibly generated in the landfill) at present, the microcrystalline glass is prepared, so that the waste can be changed into valuable, the purpose of resource recycling is achieved, and the microcrystalline glass can be widely applied as structural materials, technical materials and optical materials in the fields of national defense, aviation, construction, production and life and the like. The heavy metal elements can be fixed together when the microcrystalline glass is prepared, and the doped elements destroy a regular system prepared by pure phases, so that the melting point of the system is reduced, the stability of the three heavy metals Zn, Pb and Cu with serious harm can be realized at a lower sintering temperature, the activity of the system is improved, and the system can react at a relatively lower temperature to generate a product. Meanwhile, other components in the raw materials are CaO and Fe2O3MgO, and the like, which can be sintered at high temperature with SiO2And Al2O3The reaction generates various minerals which are retained in the glass ceramics, and the density and the strength of the glass ceramics can be enhanced.
The microcrystalline glass provided by the invention uses wastes formed after urban life and production processing as raw materials, so that the manufacturing cost of the microcrystalline glass is greatly reduced, waste can be changed into valuables, the microcrystalline glass is more beneficial to environmental management, the pollution to the ecological environment is reduced, and a better way is provided for the treatment of industrial sludge processed by manufacturers.
The invention also provides a preparation method of the microcrystalline glass, which comprises the following steps:
s1, mixing municipal sludge ash and industrial sludge according to the molar ratio of elements in the mixture: (Al + Fe): Pb: Cu: Zn ═ 2-18:1-2:1-2: 1-2.
The preferred ratio is (Al + Fe), Pb, Cu, Zn, 8-14:1:1: 1.
The selection and the matching of the industrial sludge in the step can be selected and combined according to the contents of heavy metals in the electroplating industrial sludge, smelting industrial sludge and waste lead-acid battery lead plaster.
S2 grinding the mixture of municipal sludge ash and industrial sludge uniformly, and then pressing the mixture into slices by a tablet press.
Before grinding, a proper amount of ethanol can be added into the mixture to make the mixture powder into a paste, so that the mixture is more uniform in the subsequent grinding process.
After the mixing is completed, the mixture can be pressed into slices with the thickness of about 2 mm by a tablet machine under the pressure of 12-15 MPa.
S3, the sheet is put in a high temperature furnace and is kept at 850-850 ℃ for a period of time, and then is cooled along with the furnace, thus obtaining the glass ceramics.
In the step, the slice is kept at the temperature of 750-850 ℃ for 3-4h in a muffle furnace at the heating rate of 5 ℃/min, and then cooled to room temperature along with the furnace.
Under the high temperature state, Al and Si form a grid structure (such as an aluminosilicate crystal structure), non-bridge oxygen possibly exists among grids to be combined with cations (such as Ca, Na and the like), and heavy metal elements are dissolved in the grid structure in a solid mode in order to balance the charge of the grid structure, so that the heavy metal is stabilized, and meanwhile, certain impurities in the mixture can be volatilized through gasification after calcination.
In the preparation, SiO is generated due to the existence of various impurities2And Al2O3Compared with a pure phase system, the method has the advantages that the crystallinity is poor, the defects are more, the constraint of potential barriers is easier to overcome in the reaction, the migration diffusion occurs, and the conditions (namely, sintering temperature) required for the reaction to occur are lower.
In the preparation method, the sintering temperature is far lower than that of the microcrystalline glass prepared in the prior art, and the stability of the three heavy metals is realized at the lower sintering temperature, so that on one hand, in the aspect of energy, the energy consumption is greatly saved (in the industry, the influence on the energy consumption is huge when every 50 ℃ is reduced in an attempt); in addition, the current heavy metal pollution problem is very serious, and multiple heavy metals (which are easy to migrate and convert due to actual heavy metal pollution) in toxic forms can be solidified in the glass ceramics by using the technology, so that the harm of the heavy metals to the environment and human bodies is reduced. Therefore, on one hand, municipal sludge with huge yield and difficult disposal can be effectively consumed, and on the other hand, the problem of heavy metal pollution in the environment can be reduced; and the product microcrystalline glass is used as a material with excellent performance, so that the sludge resource is effectively utilized, waste is changed into valuable, the manufacturing cost is reduced, positive contributions are made to the treatment of the sludge waste and the environmental protection, and the microcrystalline glass is an important way for fully utilizing the waste, saving the cost and utilizing the waste.
The present invention will be described in further detail with reference to examples.
Example 1:
s1, 29.01g of municipal sludge ash, 35.05g of electroplating industrial sludge, 64.52g of smelting industrial sludge and 24.68g of waste lead paste are mixed uniformly.
In the step, the municipal sludge is dried sludge of a Shenzhen Luo aromatic sewage treatment plant, and the main components and the contents of the dried sludge are as follows:
SiO2 42.69%;Al2O3 18.6%;Fe2O3 6.09%;CaO 0.9%;MgO 1.0%;K2O 2.47%,NaO 0.4%。
drying the municipal sludge at 110 ℃, sintering the sludge at 900 ℃ to sludge ash, and sieving the sludge ash with a 300-mesh sieve for later use.
In the step, the electroplating industrial sludge selected from electroplating plant sludge mainly contains Fe2O3、CuO、Cr2O3And part of insoluble impurities, heating and drying by adopting dewatering equipment and an industrial sludge dryer, grinding and sieving by using a 300-mesh sieve for later use.
The smelting industrial sludge is sludge of a lead-zinc smelting plant, mainly contains Zn, Pb, MgO, CaO and other impurities, is heated, dried and ground by adopting a dewatering device and an industrial sludge dryer, and is sieved by a 300-mesh sieve for later use.
The waste lead-acid battery lead plaster is a pasty substance formed by using the active substances on the two polar plates of the recovered waste lead-acid battery through repeated charging and discharging.
S2, detecting the contents of Al, Fe, Pb, Cu and Zn in the sludge, and basically meeting the proportioning requirement of (Al + Fe) that Pb, Cu and Zn are 2.2:1.3:1.6:1.1, then placing the municipal sludge and the industrial sludge into a container for mixing, gradually adding ethanol with the total amount of 150ml, grinding for about 30min to form paste, then placing the paste into a tablet press, and preparing into a plurality of slices with the diameter of about 2 cm and the thickness of about 2 mm under the condition that the forming pressure is 12 MPa;
s3, placing the prepared slice into a muffle furnace, heating the temperature in the furnace from room temperature to 750 ℃, 850 ℃ and 950 ℃ respectively at a heating rate of 5 ℃/min, preserving the heat for 3 hours, and then cooling along with the furnace to room temperature.
As can be seen from FIGS. 1 to 3, the temperature in the furnace is 750 ℃ and is in the process of reaction; at 850 ℃, there is already a significant grain formation (a regular block of darker color); when the temperature reaches 950 ℃, the microcrystalline glass with better quality can be obtained. The leaching amounts of heavy metals in the sludge and the microcrystalline glass are compared by using a TCLP detection method, and the stabilizing effect of the microcrystalline glass on the heavy metals (Pb, Zn and Cu) is evaluated. The microcrystalline glass prepared from the luo-arene sludge is found to have the best effect of fixing three heavy metals at 900 ℃ at the same time (see figure 4).
Example 2:
s1, 26.07g of municipal sludge ash, 38.34g of electroplating industrial sludge, 70.64g of smelting industrial dry sludge and 25.88g of waste lead-acid battery lead plaster are uniformly mixed.
In the step, the municipal sludge is dried sludge of a Shenzhen sand well sewage treatment plant, and the main components and the contents of the dried sludge are as follows:
SiO2 34.89%;Al2O3 21.92%;Fe2O3 8.27%;CaO 2.07%;MgO 0.59%;K2O 1.51%。
drying the municipal sludge at 110 ℃, sintering the sludge at 900 ℃ to sludge ash, and sieving the sludge ash with a 300-mesh sieve for later use.
In the step, the electroplating industrial sludge is electroplating plant sludge mainly containing Fe2O3、CuO、Cr2O3And part of insoluble impurities are heated, dried and ground to 300 meshes by adopting a dewatering device and an industrial sludge dryer.
The smelting industrial sludge is sludge of a lead-zinc smelting plant, mainly contains Zn, Pb, MgO, CaO and other impurities, is heated, dried and ground by adopting a dewatering device and an industrial sludge dryer, and is sieved by a 300-mesh sieve for later use.
The waste lead-acid battery lead plaster is a pasty substance formed by using the active substances on the two polar plates of the recovered waste lead-acid battery through repeated charging and discharging.
S2, detecting the contents of Al, Fe, Pb, Cu and Zn in the sludge, and basically meeting the proportioning requirement of (Al + Fe) Pb, Cu and Zn (8.0: 1.3:1.2: 1.2), then placing the municipal sludge and the industrial sludge into a container for mixing, gradually adding ethanol with the total amount of 150ml, grinding for about 30min to form paste, then placing the paste into a tablet press, and preparing into a plurality of slices with the diameter of about 2 cm and the thickness of about 2 mm under the condition that the forming pressure is 15 MPa;
s3, placing the prepared slice into a muffle furnace, heating the temperature in the furnace from room temperature to 750 ℃, 850 ℃ and 950 ℃ respectively at a heating rate of 5 ℃/min, preserving the heat for 3 hours, and then cooling along with the furnace to room temperature.
As can be seen from FIGS. 5 to 7, the temperature in the furnace is 750 ℃ and is in the process of reaction; at 850 ℃, there is already a significant grain formation (a regular block of darker color); when the temperature reaches 950 ℃, the microcrystalline glass with better quality can be obtained. The leaching amounts of heavy metals in the sludge and the microcrystalline glass are compared by using a TCLP detection method, and the stabilizing effect of the microcrystalline glass on the heavy metals (Pb, Zn and Cu) is evaluated. The microcrystalline glass prepared from sand well sludge was found to have the best effect of fixing three heavy metals at the temperature of 800-850 ℃ (see figure 8).
Example 3:
s1 municipal sludge ash 72.53g, electroplating industrial sludge 17.525g, lead-zinc smelting dry sludge 32.26g and waste lead-acid battery lead plaster 12.34g are mixed evenly.
In the step, the municipal sludge is dried sludge of a Shenzhen Luo aromatic sewage treatment plant, and the main components and the contents of the dried sludge are as follows:
SiO2 42.69%;Al2O3 18.6%;Fe2O3 6.09%;CaO 0.9%;MgO 1.0%;K2O 2.47%,NaO 0.4%。
drying the municipal sludge at 110 ℃, sintering the sludge at 900 ℃ to sludge ash, and sieving the sludge ash with a 300-mesh sieve for later use.
The smelting industrial sludge is sludge of a lead-zinc smelting plant, mainly contains Zn, Pb, MgO, CaO and other impurities, is heated, dried and ground by adopting a dewatering device and an industrial sludge dryer, and is sieved by a 300-mesh sieve for later use.
In the step, the electroplating industrial sludge is electroplating plant sludge mainly containing Fe2O3、CuO、Cr2O3And part of insoluble impurities are heated, dried and ground to 300 meshes by adopting a dewatering device and an industrial sludge dryer.
The waste lead-acid battery lead plaster is a pasty substance formed by using the active substances on the two polar plates of the recovered waste lead-acid battery through repeated charging and discharging.
S2, detecting the contents of Al, Fe, Pb, Cu and Zn in the sludge, and basically meeting the proportioning requirement of (Al + Fe) Pb, Cu and Zn (18: 1.5:1.8: 1.3), then placing the municipal sludge and the industrial sludge into a container for mixing, gradually adding 150ml of ethanol, grinding for about 30min to form paste, then placing the paste into a tablet press, and preparing a plurality of slices with the diameter of about 2 cm and the thickness of about 2 mm under the condition that the forming pressure is 14 MPa;
s3, placing the prepared sheet into a muffle furnace, heating the temperature in the furnace from room temperature to about 900 ℃ at a heating rate of 5 ℃/min, preserving the heat for 3.5 hours, and then cooling along with the furnace to room temperature to obtain the microcrystalline glass (see figure 9).
The above-mentioned embodiments of the present invention and the accompanying drawings are only part of the preferred embodiments of the present invention, and are not intended to limit the present invention, and those skilled in the art may make modifications, equivalents and improvements without departing from the spirit of the present invention.
Claims (9)
1. The microcrystalline glass is characterized by being formed by mixing municipal sludge ash and industrial sludge serving as raw materials, wherein a mixture of the municipal sludge ash and the industrial sludge comprises elements Al, Fe, Pb, Cu and Zn, and the element molar ratios of the elements Al, Fe, Pb, Cu and Zn are as follows: and (Al + Fe) Pb, Cu, Zn, 2-18:1-2:1-2:1-2, wherein the municipal sludge ash is formed by drying municipal dewatered sludge at the temperature of 100 ℃ and 110 ℃ for 24-30h, sintering at the high temperature of 800 ℃ and 900 ℃, grinding and sieving.
2. The microcrystalline glass according to claim 1, wherein the industrial sludge is electroplating industrial sludge and smelting industrial sludge polluted by Pb, Zn and Cu or/and waste lead-acid storage battery lead plaster.
3. The microcrystalline glass according to claim 2, wherein the electroplating industrial sludge is sludge produced in an electroplating wastewater treatment process, and is formed by dehydration, drying, crushing and sieving.
4. The microcrystalline glass according to claim 2, wherein the smelting industrial sludge is sludge produced by lead-zinc smelting wastewater treatment, and is formed by drying, crushing and sieving.
5. The microcrystalline glass according to claim 2, wherein the waste lead-acid storage battery lead plaster is a slurry substance formed after an active material on a waste lead-acid storage battery bipolar plate is used for multiple times of charging and discharging.
6. The method for producing a crystallized glass according to any one of claims 1 to 5, comprising the steps of:
the method comprises the following steps of mixing municipal sludge ash and industrial sludge according to the molar ratio of elements in the mixture: (Al + Fe) Pb, Cu, Zn, 2-18, 1-2;
uniformly grinding the mixture of the municipal sludge ash and the industrial sludge, and pressing the mixture into slices with the diameter of 2 cm and the thickness of 2 mm by using a tablet press;
and (3) keeping the temperature of the sheet in a high-temperature furnace at 850-950 ℃ for 3-4h, and then cooling the sheet to room temperature along with the furnace to obtain the glass ceramics.
7. The method for preparing glass-ceramic according to claim 6, wherein ethanol is added to the mixture of municipal sludge ash and industrial sludge, and then the mixture is ground to be uniform.
8. The method for producing a glass ceramic according to claim 6, wherein the mixture is uniformly ground and then pressed into the sheet under a pressure of 12 to 15 MPa.
9. The method for preparing the microcrystalline glass as claimed in claim 6, wherein the thin sheet is placed in a high temperature furnace, and then is kept at 850-950 ℃ for 3-4h at a heating rate of 5 ℃/min, and then is cooled to room temperature along with the furnace.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5580735A (en) * | 1978-12-07 | 1980-06-18 | Nippon Electric Glass Co Ltd | Solidification treating method for high level radioactive waste |
IL104438A (en) * | 1993-01-19 | 1995-07-31 | Kaminsky Friedrich | Decorative multicolored glass and method of its manufacture |
CN101700959A (en) * | 2009-11-12 | 2010-05-05 | 君达(凤县)环保资源无害化过程科技有限公司 | Black micro-crystal glass plate manufactured from lead-zinc-copper tailings and manufacturing method thereof |
CN101759368A (en) * | 2010-03-18 | 2010-06-30 | 凤县三联建材有限责任公司 | Green glass-ceramic plate made from lead-zinc smelting slag and manufacturing method thereof |
CN108264233A (en) * | 2018-02-05 | 2018-07-10 | 北京工业大学 | The method that electrolytic manganese residues comprehensively utilize and prepare devitrified glass |
-
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5580735A (en) * | 1978-12-07 | 1980-06-18 | Nippon Electric Glass Co Ltd | Solidification treating method for high level radioactive waste |
IL104438A (en) * | 1993-01-19 | 1995-07-31 | Kaminsky Friedrich | Decorative multicolored glass and method of its manufacture |
CN101700959A (en) * | 2009-11-12 | 2010-05-05 | 君达(凤县)环保资源无害化过程科技有限公司 | Black micro-crystal glass plate manufactured from lead-zinc-copper tailings and manufacturing method thereof |
CN101759368A (en) * | 2010-03-18 | 2010-06-30 | 凤县三联建材有限责任公司 | Green glass-ceramic plate made from lead-zinc smelting slag and manufacturing method thereof |
CN108264233A (en) * | 2018-02-05 | 2018-07-10 | 北京工业大学 | The method that electrolytic manganese residues comprehensively utilize and prepare devitrified glass |
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