CN116003000A - Chlorine-containing mineral six-element system cementing material prepared from waste incineration fly ash, and preparation and application thereof - Google Patents
Chlorine-containing mineral six-element system cementing material prepared from waste incineration fly ash, and preparation and application thereof Download PDFInfo
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- 239000000460 chlorine Substances 0.000 title claims abstract description 217
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 195
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 133
- 239000011707 mineral Substances 0.000 title claims abstract description 133
- 239000000463 material Substances 0.000 title claims abstract description 119
- 239000010881 fly ash Substances 0.000 title claims abstract description 93
- 238000004056 waste incineration Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 235000019738 Limestone Nutrition 0.000 claims abstract description 17
- 239000006028 limestone Substances 0.000 claims abstract description 17
- 229910004283 SiO 4 Inorganic materials 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 4
- 235000012241 calcium silicate Nutrition 0.000 claims abstract description 4
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000292 calcium oxide Substances 0.000 claims description 27
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 27
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- 239000011398 Portland cement Substances 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000004568 cement Substances 0.000 abstract description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 11
- 239000003469 silicate cement Substances 0.000 abstract description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 description 115
- 239000002131 composite material Substances 0.000 description 13
- 239000004567 concrete Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- -1 chlorine ions Chemical class 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 6
- 238000004255 ion exchange chromatography Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 3
- 150000001804 chlorine Chemical class 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 238000011278 co-treatment Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 229910052604 silicate mineral Inorganic materials 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010053567 Coagulopathies Diseases 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 230000035602 clotting Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Images
Classifications
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of cement materials, and provides a chlorine-containing mineral six-element system cementing material prepared from waste incineration fly ash, and preparation and application thereof, wherein the cementing material comprises the following components in percentage by mass: dicalcium silicate 16.44-71.23%, ca 2 SiO 3 Cl 2 0.6～2.6％、Ca 3 SiO 4 Cl 2 1.42 to 2.46 percent, 4.93 to 9.66 percent of dodecacalcium heptaluminate, 1.21 to 8.41 percent of calcium chloroaluminate and 2.47 to 5.90 percent of tricalcium aluminate. The cementing material is obtained by using waste incineration fly ash, limestone, sandstone and fly ash as main raw materials, compacting, calcining at 1025-1250 ℃ and then quenching to room temperature, and the method not only can stabilize water-soluble chloride in the waste incineration fly ash, but also can prepare chlorine-containing ore by mixing the cementing material with silicate cementThe compound silicate cement has the characteristics of shortened setting time and improved strength.
Description
Technical Field
The invention relates to the technical field of cement materials, in particular to a chlorine-containing mineral six-element system cementing material prepared from waste incineration fly ash, and preparation and application thereof.
Background
The chlorine-containing components in the solid waste of the waste incineration fly ash are high, mainly derived from waste plastics, waste rubber products, kitchen garbage and the like, and are calculated according to the mass of 5% of the incineration fly ash, 730 ten thousand tons of the waste incineration fly ash are probably produced each year, and a large amount of the waste incineration fly ash is accumulated to influence the environment. The cement kiln has the advantages of wide treatment objects, low treatment cost, large treatment amount and the like, and harmful substances in the solid waste can be stably solidified by adopting the rotary kiln and the secondary combustion chamber for high-temperature incineration. The high-temperature environment of the cement kiln can decompose organic pollutants such as dioxin and the like and prevent secondary synthesis, heavy metals can be well dissolved into cement clinker and hydration products, chlorine in fly ash serves as a mineralizer in the cement firing process, so that the decomposition of carbonate is promoted, the solid-phase reaction is accelerated, the firing temperature is reduced, the energy consumption is saved, but high-concentration chlorine can cause unqualified cement products, and the phenomena of skinning and blockage of the cement kiln can be caused by evaporation of the chlorine. The most mature technology for cooperatively disposing the waste incineration fly ash by using a cement kiln at present is to wash the fly ash, almost all heavy metals and chlorine in the fly ash can be removed by water washing, for example, patent application CN105478438A discloses a method for cooperatively disposing the waste fly ash by using the cement kiln and recycling harmless resources.
In view of this, the present invention has been proposed.
Disclosure of Invention
The invention provides a chlorine-containing mineral six-element system cementing material prepared by waste incineration fly ash, and preparation and application thereof, which are used for solving the defect of complex dechlorination process of water washing fly ash in the prior art, and the chlorine-containing mineral six-element system cementing material formed by designing specific mineral compositions can utilize harmful substances chlorine and useful substances CaO and Al in the waste incineration fly ash 2 O 3 、SiO 2 And the like, chlorine in the fly ash is converted into minerals, two chlorine atoms occupy the position of one oxygen atom, calcium chloroaluminate and calcium chloroaluminate minerals are formed, the water-soluble chlorine salt in the waste incineration fly ash is stabilized, and the chlorine-containing mineral-silicate composite cement prepared by mixing the six-element system cementing material of the chlorine-containing minerals with silicate cement has the characteristics of shortening the setting time and improving the strength.
The invention provides a chlorine-containing mineral six-element system cementing material, which comprises the following components in percentage by mass: dicalcium silicate (2 CaO. SiO) 2 Abbreviated as C 2 S)：16.44～71.23％、Ca 2 SiO 3 Cl 2 ：0.6～2.6％、Ca 3 SiO 4 Cl 2 :1.42 to 2.46 percent of dodecacalcium heptaluminate (12 CaO.7Al) 2 O 3 Abbreviated as C 12 A 7 ): 4.93 to 9.66 percent, and calcium chloroaluminate (12 CaO.7Al) 2 O 3 ·CaCl 2 Abbreviated as C 11 A 7 ·CaCl 2 ): 1.21 to 8.41 percent, tricalcium aluminate (3CaO.Al) 2 O 3 Abbreviated as C 3 A)：2.47～5.90％。
The mineral composition range of the chlorine-containing mineral six-element system cementing material provided by the invention is as follows in percentage by mass: dicalcium silicate (2 CaO. SiO) 2 Abbreviated as C 2 S)：16.44～71.23％、Ca 2 SiO 3 Cl 2 ：0.6～2.6％、Ca 3 SiO 4 Cl 2 :1.42 to 2.46 percent of dodecacalcium heptaluminate (12 CaO.7Al) 2 O 3 Abbreviated as C 12 A 7 ): 4.93 to 9.66 percent, and calcium chloroaluminate (12 CaO.7Al) 2 O 3 ·CaCl 2 Abbreviated as C 11 A 7 ·CaCl 2 ): 1.21 to 8.41 percent, tricalcium aluminate (3CaO.Al) 2 O 3 Abbreviated as C 3 A) The method comprises the following steps 2.47 to 5.90 percent, wherein two chlorine atoms occupy the position of one oxygen atom, and the chlorine ions are combined with aluminate and silicate minerals to form Ca 2 SiO 3 Cl 2 、Ca 3 SiO 4 Cl 2 、C 11 A 7 ·CaCl 2 The mineral stabilizes the water soluble chloride in the fly ash of the garbage incineration, and the chlorine-containing mineral-silicate composite cement prepared by mixing the cementing material of the six-element system of the chlorine-containing mineral with silicate cement has the characteristics of shortening the setting time and improving the strength.
According to the chlorine-containing mineral six-membered system cementing material provided by the invention, chlorine in the chlorine-containing mineral six-membered system cementing material is derived from the waste incineration fly ash.
The main component of the waste incineration fly ash is CaO-SiO 2 -Al 2 O 3 -Fe 2 O 3 The chlorine-containing six-element mineral system cementing material prepared by adopting the waste incineration fly ash has the same chemical components as those of silicate cement raw materials, the existence form of chlorine in the waste incineration fly ash in the chlorine-containing mineral six-element system cementing material is combined with aluminate minerals and silicate minerals, and two chlorine atoms occupy the position of one oxygen atom, so that the chlorine in the waste incineration fly ash can be effectively utilized, the chlorine in the fly ash serves as a mineralizer in the cement firing process, the decomposition of carbonate is promoted, the solid phase reaction is accelerated, the firing temperature is reduced, the energy consumption is saved, and the chlorine-containing six-element mineral system cementing material has important significance in the aspect of the co-treatment of the waste incineration fly ash in a cement kiln.
The chlorine-containing mineral six-element system cementing material is prepared by calcining waste incineration fly ash, limestone, sandstone and fly ash serving as main raw materials;
calcination according to the invention may be co-processed using a cement kiln.
When the utilization condition of chlorine in the waste incineration fly ash in the calcination of the cement kiln is explored, the invention discovers that the utilization effect of the waste incineration fly ash is better by taking the waste incineration fly ash as a chlorine source and combining cement raw materials such as limestone, sandstone, fly ash and the like to obtain the chlorine-containing mineral six-element system cementing material through calcination.
Preferably, the chemical composition of the chlorine-containing mineral six-membered system cementing material comprises the following components in percentage by mass: caO: 46.27-59.64%, siO 2 ：15.67～22.35％，Al 2 O 3 ：3.49～4.98％，Fe 2 O 3 ：1.46～1.95％，Cl - ：3.31～9.27％；
More preferably, the chemical composition of the chlorine-containing mineral six-membered system cementitious material comprises, in mass percent: caO: 46.27-59.64%, siO 2 ：15.67～22.35％，Al 2 O 3 ：3.49～4.98％，Fe 2 O 3 ：1.46～1.95％，MgO：1.38～2.0％，Cl - ：3.31～9.27％。
Through researches, the MgO content in the system can influence the utilization rate of chlorine to a certain extent and the Ca which is an inactive component 7 Mg(SiO 4 ) 4 Therefore, the MgO content is preferably 1.38 to 2.0%.
According to the chlorine-containing mineral six-membered system cementing material provided by the invention, the utilization rate of chlorine in the waste incineration fly ash is 32.11-67.13%.
The invention uses industrial raw materials and solid wastes, and uses waste incineration fly ash as a chlorine source, and designs a six-element system cementing material for chlorine-containing minerals prepared from the waste incineration fly ash, wherein the chlorine-containing minerals are prepared by firing water-soluble chloride salts and calcium carbonate in the fly ash, and the utilization rate of chlorine in the waste incineration fly ash can reach 32.11-67.13%.
The chlorine-containing mineral six-membered system cementing material provided by the invention has the free calcium oxide content of less than 0.1 percent, and is a low-calcium cement system.
The invention also provides a preparation method of the chlorine-containing mineral six-element system cementing material, which comprises the steps of taking waste incineration fly ash, limestone, sandstone and fly ash as main raw materials, performing compression molding (mixing, ball milling and compression molding), calcining at 1025-1250 ℃, preserving heat for 1h, and then quenching to room temperature.
The invention omits a fly ash washing process in the calcination process, reduces the cost, effectively utilizes chemical components harmful to the environment in the waste incineration fly ash, namely chloride ions in the fly ash, and has important significance on the recycling of the fly ash in the cement kiln co-treatment. In particular, the calcination temperature is critical to the quality of the cementitious material of the six-membered system of chlorine-containing minerals, and it has been found in experiments that as the temperature increases, the inactive component Ca in the cementitious material of the six-membered system of chlorine-containing minerals 7 Mg(SiO 4 ) 4 If the content of the free calcium oxide in the cementitious material of the chlorine-containing mineral six-element system is lower than 1025 ℃, the content of the free calcium oxide in the cementitious material of the chlorine-containing mineral six-element system is higher; if the temperature is too high, when the temperature reaches 1300 ℃, a large amount of chlorine volatilizes, and the utilization rate of the chlorine is obviously reduced.
According to the preparation method of the chlorine-containing mineral six-element system cementing material, the addition amounts of the waste incineration fly ash, the limestone, the sandstone and the fly ash are as follows in sequence according to mass percent: 10 to 30 percent, 47.26 to 72.01 percent, 10.29 to 13.78 percent and 2.76 to 3.29 percent.
According to the invention, the ideal chlorine-containing mineral six-element system cementing material can be obtained by adding raw materials such as limestone, sandstone, fly ash and the like and adjusting the calcination temperature and the raw material proportion.
According to the preparation method of the chlorine-containing mineral six-membered system cementing material provided by the invention, the main raw materials also comprise: ca (OH) 2 ；
Preferably, the Ca (OH) is expressed in mass percent 2 The addition amount of the catalyst is 5.96-6.05%.
By exploring the reaction process of chlorine in the waste incineration fly ash in the calcination of a cement kiln, it is found that CaO in the limestone is CaCO 3 In the presence of a chlorine source, caCO 3 The decomposition temperature of (C) is reduced to between 700 and 800 DEG CAt this temperature, some of the chlorine is already volatilized due to insufficient calcium source being combined with the chlorine, by adding an appropriate amount of Ca (OH) to the feedstock 2 The decomposition temperature is 400-500 ℃, and Ca (OH) is adopted 2 Providing enough CaO to combine with chlorine to form CaCl 2 Thereby greatly improving the utilization rate of chlorine, such as Ca (OH) 2 When the addition amount of the catalyst accounts for 5.96-6.05% of the total raw material amount, the utilization rate of chlorine is improved by 20.26-23.11%. In addition, it was found in experiments that Ca (OH) was not added 2 When the method is used, although the chlorine-containing mineral six-membered system cementing material can be obtained, the content of inactive components in the chlorine-containing mineral six-membered system cementing material is higher, the strength of the cementing material is lower, the 28d net paste strength is only 1.46MPa, and the application performance is limited.
According to the preparation method of the chlorine-containing mineral six-membered system cementing material provided by the invention, the mass percentage of chlorine in the waste incineration fly ash is 20-30%, and the existence form of chlorine is mainly NaCl, KCl and CaClOH.
It is found that when the content of the fly ash is higher than 30%, the alkali (sodium oxide and potassium oxide) content in the system is higher, and adverse effects such as skinning blockage and the like can be caused to the cement kiln.
The invention also provides application of the chlorine-containing mineral six-element system cementing material, and the chlorine-containing mineral six-element system cementing material is mixed with silicate cement to prepare chlorine-containing mineral-silicate composite cement;
preferably, the mass ratio of the chlorine-containing mineral six-membered system cementing material to the Portland cement during the mixing is 5-30:95-70, preferably 5:95.
The initial setting time of the chlorine-containing mineral-silicate composite cement is 48-60 min earlier than that of the silicate cement, and the final setting time is 76-95 min earlier than that of the silicate cement;
the 1d strength of the chlorine-containing mineral-silicate composite cement is improved by 0.11-2.82 MPa, the 3d strength is improved by 3.52-5.52 MPa, the 7d strength is improved by 1.14-5.95 MPa, and the 28d strength is improved by 3.27-5.58 MPa.
The addition of the cementing material of the chlorine-containing mineral six-element system shortens the setting time of the silicate cement, improves the early strength and has no collapse in the later strength.
The chlorine-containing mineral six-element system cementing material prepared by the waste incineration fly ash provided by the invention is characterized in that the water-soluble chlorine salt is stabilized by designing the specific composition of the chlorine-containing mineral six-element system cementing material, and the chlorine-containing mineral-silicate composite cement prepared by mixing the chlorine-containing mineral six-element system cementing material with silicate cement has the characteristics of shortening the setting time and improving the strength.
The chlorine-containing mineral six-membered system cementing material prepared by the waste incineration fly ash provided by the invention is prepared by taking the waste incineration fly ash as a chlorine source, and taking solid waste of fly ash, limestone and other industrial raw materials, so that the problems of increased process cost, complex process for subsequent treatment of water washing liquid and the like caused by the water washing of the fly ash can be effectively avoided, chlorine in the fly ash can be effectively utilized to calcine the chlorine-containing mineral six-membered system cementing material, the calcination temperature is reduced by chlorine, the baked chlorine-containing mineral six-membered system cementing material is soft and is easy to break, and the energy consumption of the chlorine-containing mineral six-membered system cementing material prepared by the waste incineration fly ash is reduced in both the firing process and the grinding process, so that the chlorine-containing mineral six-membered system cementing material is an effective way for recycling the cement kiln and utilizing chlorine ions in the waste incineration fly ash.
The chlorine-containing mineral-silicate composite cement prepared from the chlorine-containing mineral six-element system cementing material provided by the invention has the advantages of higher chloride ion concentration, early setting time and high strength, is not suitable for concrete engineering under the action of seawater and other corrosive media, and is suitable for the application of rapid repair of cement concrete pavement breaking, concrete engineering under a dry environment and the like.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow diagram of a chlorine-containing mineral six-membered system cementitious material and preparation and application thereof;
FIG. 2 is an XRD pattern of a chlorine-containing mineral six-membered system cementitious material provided by the invention;
FIG. 3 shows topas quantitative results of the six-membered system cementing material containing chlorine minerals, wherein a blue line is a raw data graph, a red line is a quantitative fitting graph, and a blue and red graph can be fitted to each other to show that the quantitative results are reliable.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
The chlorine-containing mineral six-membered system cementitious material of the invention and its preparation and use are described below in connection with fig. 1-3.
As shown in figure 1, in the preparation process of the chlorine-containing mineral six-membered system cementing material, the calcination system and the clinker proportion are mainly changed to fire the chlorine-containing mineral six-membered system cementing material, so that chlorine is combined with silicate and aluminate to form chlorine-containing minerals, and the water-soluble chlorine salt in the fly ash is used for firing Ca 2 SiO 3 Cl 2 、Ca 3 SiO 4 Cl 2 、C 11 A 7 ·CaCl 2 Mineral, further made into compositeAnd (3) cement.
In the invention, the calculation formula of the utilization rate of chlorine is as follows:
chlorine utilization rate= (chlorine content in chlorine-containing mineral six-element system cementing material/theoretical chlorine content in burning raw material) ×100%;
wherein, the chlorine content in the cementing material of the chlorine-containing mineral six-element system is detected by adopting an ion chromatography in GB-T176-2017 cement chemistry analysis method, and the step of measuring the chlorine content by the ion chromatography is as follows: decomposing the chlorine-containing mineral six-element system cementing material with nitric acid, allowing the sample solution to enter an ion chromatographic column, eluting with carbonate eluent to obtain a chromatogram, and obtaining the chloride ion content according to the peak area or peak height of the chromatogram. The theoretical chlorine content in the burnt raw material is obtained according to the mixing amount of the fly ash.
The mass percentage of chlorine in the waste incineration fly ash is 20-30%, and the existence forms of the chlorine mainly comprise NaCl, KCl and CaClOH.
Examples 1 to 3
The method for preparing the chlorine-containing mineral six-element system cementing material from the waste incineration fly ash comprises the following specific steps:
taking waste incineration fly ash as a chlorine source, selecting cement raw materials such as limestone, sandstone, fly ash and the like, mixing and ball milling according to the mass percentages of the raw materials in table 1, then compacting, calcining at 1200 ℃, preserving heat for 1h, and then quenching to room temperature to obtain a chlorine-containing mineral six-membered system cementing material, measuring the content of chloride ions in the chlorine-containing mineral six-membered system cementing material by utilizing an ion chromatography, wherein table 2 shows that the chlorine-containing mineral six-membered system cementing material is subjected to Topas quantitative analysis, table 3 shows that the quantitative data of each mineral in the chlorine-containing mineral six-membered system cementing material shows that the free calcium oxide content of the chlorine-containing mineral six-membered system cementing material is shown in table 4.
TABLE 1 Main chemical Components (wt.%) of the raw materials mass percent and chlorine-containing mineral six-membered system cementing Material
TABLE 2 utilization of chlorine in fly ash at different fly ash loadings (%)
Table 3 mineral composition content (wt.%) in the six-membered system cementitious material containing chlorine minerals
| Example 1 | Example 2 | Example 3 | |
| Fly ash mass percent/ |
10 | 20 | 30 |
| C 2 S/wt.％ | 28.78 | 24.62 | 18.34 |
| Ca 7 Mg(SiO 4 ) 4 /wt.％ | 45.66 | 50.01 | 51.98 |
| C 3 A/wt.％ | 4.08 | 3.98 | 3.69 |
| C 12 A 7 /wt.％ | 4.93 | 6.51 | 8.05 |
| Ca 11 A 7 ·CaCl 2 /wt.％ | 1.21 | 4.06 | 5.02 |
| Ca 2 SiO 3 Cl 2 /wt.％ | 0.60 | 1.53 | 1.38 |
| Ca 3 SiO 4 Cl 2 /wt.％ | 2.27 | 2.46 | 2.25 |
TABLE 4 free calcium oxide content of cementitious materials of six-membered systems containing chlorine minerals (%)
| Example 1 | Example 2 | Example 3 | |
| Free calcium oxide content | 0.082 | 0.076 | 0.074 |
Examples 4 to 6
The method for preparing the chlorine-containing mineral six-element system cementing material from the waste incineration fly ash comprises the following specific steps:
limestone, sandstone, fly ash and waste incineration fly ash according to mass percent: mixing 52.53% of limestone, 12.84% of sandstone, 3.61% of fly ash and 30% of fly ash, ball milling, pressing and forming, heating to 1025-1200 ℃ at the speed of 10 ℃/min, calcining, preserving heat for 1h, quenching to room temperature to obtain a chlorine-containing mineral six-element system cementing material, measuring the chloride ion content in the chlorine-containing mineral six-element system cementing material by utilizing an ion chromatography, and carrying out Topas quantitative analysis on the chlorine-containing mineral six-element system cementing material, wherein the quantitative data of each mineral in the chlorine-containing mineral six-element system cementing material are shown in table 6, and the free calcium oxide content of the chlorine-containing mineral six-element system cementing material is shown in table 7.
TABLE 5 utilization of chlorine at different calcination temperatures (%)
Table 6 mineral composition content (wt.%) in the six-membered system cementitious material containing chlorine minerals
| Example 4 | Example 5 | Example 6 | Example 3 | |
| Calcination temperature/. Degree.C | 1025 | 1100 | 1150 | 1200 |
| C 2 S/wt.％ | 55.72 | 22.45 | 20.43 | 18.34 |
| Ca 7 Mg(SiO 4 ) 4 /wt.％ | 3.94 | 49.15 | 50.11 | 51.98 |
| C 3 A/wt.％ | 5.90 | 2.47 | 3.04 | 3.69 |
| C 12 A 7 /wt.％ | 4.99 | 9.66 | 5.93 | 8.05 |
| Ca 11 A 7 ·CaCl 2 /wt.％ | 8.41 | 5.03 | 4.28 | 5.02 |
| Ca 2 SiO 3 Cl 2 /wt.％ | 1.85 | 1.37 | 1.13 | 1.38 |
| Ca 3 SiO 4 Cl 2 /wt.％ | 2.05 | 2.04 | 2.02 | 2.25 |
TABLE 7 free calcium oxide content of cementitious materials of six-membered systems containing chlorine minerals (%)
| Example 4 | Example 5 | Example 6 | Example 3 | |
| Free calcium oxide content | 0.067 | 0.069 | 0.068 | 0.074 |
Examples 7 to 10
The method for preparing the chlorine-containing mineral six-element system cementing material by using the waste incineration fly ash specifically comprises the following steps:
taking waste incineration fly ash as a chlorine source, selecting cement raw materials such as limestone, sandstone, fly ash and the like, mixing and ball-milling the raw materials and main chemical components of a chlorine-containing mineral six-element system cementing material as shown in tables 8-1 and 8-2, pressing the mixture to form, calcining the mixture at 1025 ℃ and keeping the mixture
Quenching to room temperature after 1h to obtain chlorine-containing mineral six-membered system cementing material, measuring the chloride ion content in the chlorine-containing mineral six-membered system cementing material by utilizing an ion chromatography 0 method, and performing the following steps of
The Topas quantitative analysis is carried out on the chlorine-containing mineral six-membered system cementing material, the quantitative data of each mineral in the chlorine-containing mineral six-membered system cementing material are shown in table 10, and the free calcium oxide content of the chlorine-containing mineral six-membered system cementing material is shown in table 11.
Table 8-1. Raw materials mass percent (wt.)
| Limestone powder | Sandstone | Fly ash | Ca(OH) 2 | Fly ash | |
| Example 7 | 47.26 | 12.04 | 3.42 | 5.96 | 30 |
| Example 8 | 48.13 | 11.41 | 3.18 | 5.98 | 30 |
| Example 9 | 48.98 | 10.83 | 2.93 | 6.00 | 30 |
| Example 10 | 49.70 | 10.29 | 2.76 | 6.01 | 30 |
Table 8-2. Main chemical Components (wt.%) of the six-membered System cementitious Material for chlorine-containing minerals
| CaO | Al 2 O 3 | SiO 2 | Fe 2 O 3 | MgO | Cl- | |
| Example 7 | 46.27 | 3.85 | 17.35 | 1.46 | 2.00 | 9.02 |
| Example 8 | 46.91 | 3.72 | 16.74 | 1.47 | 2.00 | 9.05 |
| Example 9 | 47.53 | 3.59 | 16.19 | 1.47 | 2.00 | 9.08 |
| Example 10 | 48.05 | 3.49 | 15.67 | 1.48 | 2.00 | 9.10 |
TABLE 9 utilization of chlorine by cementitious materials of chlorine-containing mineral six-membered System (%)
As can be seen from the above table, ca (OH) 2 The utilization rate of chlorine by the cementing material of the chlorine-containing mineral six-element system is improved by 20.26 to 23.11 percent by adding the cementing material.
Table 10 mineral composition content (wt/. -%) in cementitious materials of six-membered systems containing chlorine minerals
| Example 7 | Example 8 | Example 9 | Example 10 | |
| C 2 S/wt.％ | 66.67 | 71.23 | 67.08 | 63.81 |
| Ca 7 Mg(SiO 4 ) 4 /wt.％ | 2.34 | 1.91 | 0.65 | - |
| C 3 A/wt.％ | 5.40 | 3.18 | 3.62 | 5.07 |
| C 12 A 7 /wt.％ | 7.44 | 7.12 | 7.40 | 6.38 |
| Ca 11 A 7 ·CaCl 2 /wt.％ | 3.96 | 5.41 | 5.90 | 5.59 |
| Ca 2 SiO 3 Cl 2 /wt.％ | 1.45 | 1.87 | 2.28 | 2.29 |
| Ca 3 SiO 4 Cl 2 /wt.％ | 2.07 | 2.18 | 2.43 | 1.58 |
TABLE 11 free calcium oxide content of cementitious materials of six-membered systems containing chlorine minerals (%)
| Example 7 | Example 8 | Example 9 | Example 10 | |
| Free calcium oxide content | 0.065 | 0.069 | 0.071 | 0.073 |
Examples 11 to 13
The concrete steps of the chlorine-containing mineral six-element system cementing material prepared by the waste incineration fly ash are the same as those of the example 10, and the difference is that: the MgO content in the chlorine-containing mineral six-membered system cement was varied to be 1.38wt.%, 1.59wt.% and 1.80wt.%. The mass percentages of the raw materials and the main chemical components of the chlorine-containing mineral six-element system cementing material are shown in tables 12-1 and 12-2, the content of chloride ions in the chlorine-containing mineral six-element system cementing material is measured by utilizing an ion chromatography, the Topas quantitative analysis is carried out on the chlorine-containing mineral six-element system cementing material, the quantitative data of each mineral in the chlorine-containing mineral six-element system cementing material are shown in table 14, and the content of free calcium oxide in the chlorine-containing mineral six-element system cementing material is shown in table 15.
Table 12-1 raw materials mass percent (wt.%) at different MgO contents
| Limestone powder | Sandstone | Fly ash | Ca(OH)2 | Fly ash | |
| Example 11 | 50.74 | 10.46 | 2.75 | 6.05 | 30 |
| Example 12 | 50.36 | 10.40 | 2.78 | 6.04 | 30 |
| Example 13 | 50.05 | 10.35 | 2.76 | 6.02 | 30 |
| Example 10 | 49.70 | 10.29 | 2.76 | 6.01 | 30 |
Table 12-2 Main chemical Components (wt.%) of six-membered System cementing Material containing chlorine minerals with different MgO contents
| CaO | Al 2 O 3 | SiO 2 | Fe 2 O 3 | MgO | Cl- | |
| Example 11 | 49.05 | 3.54 | 15.99 | 1.50 | 1.38 | 9.15 |
| Example 12 | 48.69 | 3.53 | 15.88 | 1.50 | 1.59 | 9.13 |
| Example 13 | 48.39 | 3.51 | 15.79 | 1.48 | 1.80 | 9.12 |
| Example 10 | 48.05 | 3.49 | 15.67 | 1.48 | 2.00 | 9.10 |
TABLE 13 utilization of chlorine by chlorine-containing mineral six-membered System gel materials with different MgO contents (%)
Table 14 mineral composition content (wt.%) in the six-membered system cement containing chlorine minerals
| Example 11 | Example 12 | Example 13 | Example 10 | |
| MgO content/wt.% | 1.4 | 1.6 | 1.8 | 2 |
| C 2 S/wt.％ | 66.43 | 66.09 | 67.97 | 63.81 |
| C 3 A/wt.％ | 4.18 | 4.07 | 4.03 | 5.07 |
| C 12 A 7 /wt.％ | 5.74 | 6.62 | 8.00 | 6.38 |
| Ca 11 A 7 ·CaCl 2 /wt.％ | 2.39 | 2.59 | 4.07 | 5.59 |
| Ca 2 SiO 3 Cl 2 /wt.％ | 1.48 | 2.46 | 2.60 | 2.29 |
| Ca 3 SiO 4 Cl 2 /wt.％ | 1.57 | 1.67 | 1.79 | 1.58 |
TABLE 15 free calcium oxide content of cementitious materials of six-membered systems containing chlorine minerals (%)
| Example 11 | Example 12 | Example 13 | Example 10 | |
| Free calcium oxide content | 0.068 | 0.072 | 0.074 | 0.073 |
Example 10 XRD patterns of a chlorine-containing mineral six-membered system binder are shown in FIG. 2, wherein 2θ= 32.230,32.649,34.371 is C 2 Characteristic peak of S, ca at 2θ= 32.621 2 SiO 3 Cl 2 Characteristic peaks of 2θ= 32.053 corresponds to Ca 3 SiO 4 Cl 2 Is C at 2θ= 57.166 12 A 7 Characteristic peak of 2θ= 18.071 corresponds to C 11 A 7 ·CaCl 2 Characteristic peak of 2θ= 32.951 corresponds to C 3 Characteristic peaks of A.
The Topas quantification is shown in FIG. 3, in which corundum (. Alpha. -Al) 2 O 3 ) To analyze the sample for a reference, corundum was incorporated in an amount of 10% by mass of the sample being tested. In the figure, the composition contains alpha-Al 2 O 3 The final quantitative result was to remove 10% corundum content, i.e. the quantitative data of example 10 of table 14.
Examples 14 to 17
The application of the chlorine-containing mineral six-element system cementing material prepared by the waste incineration fly ash is that the chlorine-containing mineral six-element system cementing material prepared in the example 10 and ordinary Portland cement are mixed according to the mass ratio: 5:95, 10:90, 20:80 and 30:70 are mixed to prepare chlorine-containing mineral-silicate composite cement, and the gelation activity is tested.
The test method of the coagulation time comprises the following steps: the chlorine-containing mineral-silicate composite cement and the ordinary silicate cement adopted are tested for setting time by adopting a water cement ratio of 0.26 according to GB/T1346-2001 method for testing water consumption, setting time and stability of cement standard consistence. The results of the clotting time test are shown in Table 16.
The mechanical property testing method comprises the following steps: the chlorine-containing mineral-silicate composite cement and the ordinary silicate cement adopted are tested for mechanical properties at different ages according to GB/T17671-2021 cement mortar strength test method, water is selected from tap water, and the cement ratio is selected to be 0.5. The test results for the different ages are shown in table 17.
TABLE 16 setting time of chlorine-containing mineral-silicate composite cements
| Cementing material/wt.% | Portland cement/wt.% | Initial setting/min | Final setting/ | |
| Portland cement | ||||
| 0 | 100 | 121 | 173 | |
| Example 14 | 5 | 95 | 73 | 97 |
| Example 15 | 10 | 90 | 62 | 79 |
| Example 16 | 20 | 80 | 61 | 79 |
| Example 17 | 30 | 70 | 61 | 78 |
TABLE 17 mechanical Properties of chlorine-containing mineral-silicate composite Cement
The chlorine-containing mineral-silicate composite cement is not suitable for concrete engineering under the action of seawater and other corrosive media due to higher chloride ion concentration, but can be considered for the rapid repair of broken cement concrete pavement and the concrete engineering under the dry environment due to the characteristics of early setting time, high strength and the like.
Comparative example 1
The concrete steps of the chlorine-containing mineral six-element system cementing material prepared by the waste incineration fly ash are the same as those of the example 4, and the specific differences are that: the calcination temperature is 1300 ℃, the test result shows that the chlorine content in the chlorine-containing mixture is 9.27%, the acid-soluble chlorine content in the chlorine-containing mineral six-component system cementing material is 0.06%, only 0.6% of chloride ions are dissolved in a solid solution, and a large amount of chlorine volatilizes.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A chlorine-containing mineral six-membered system cementitious material, characterized by comprising, in mass percent: dicalcium silicate: 16.44 to 71.23 percent of Ca 2 SiO 3 Cl 2 ：0.6～2.6％、Ca 3 SiO 4 Cl 2 :1.42 to 2.46 percent of dodecacalcium heptaluminate: 4.93 to 9.66 percent of calcium chloroaluminate: 1.21-8.41 percent of tricalcium aluminate: 2.47 to 5.90 percent.
2. The chlorine-containing mineral six-membered system binder according to claim 1, wherein the chlorine in the chlorine-containing mineral six-membered system binder is derived from the waste incineration fly ash.
3. The chlorine-containing mineral six-membered system cementing material according to claim 1, wherein the chlorine-containing mineral six-membered system cementing material is prepared by calcining waste incineration fly ash, limestone, sandstone and fly ash as main raw materials;
preferably, the chemical composition of the chlorine-containing mineral six-membered system cementing material comprises the following components in percentage by mass: caO: 46.27-59.64%, siO 2 ：15.67～22.35％，Al 2 O 3 ：3.49～4.98％，Fe 2 O 3 ：1.46～1.95％，Cl - ：3.31～9.27％；
More preferably, the chemical composition of the chlorine-containing mineral six-membered system cementitious material comprises, in mass percent: caO: 46.27-59.64%, siO 2 ：15.67～22.35％，Al 2 O 3 ：3.49～4.98％，Fe 2 O 3 ：1.46～1.95％，MgO：1.38～2.0％，Cl-：3.31～9.27％。
4. A chlorine-containing mineral six-membered system cementitious material according to any one of claims 1 to 3, wherein the utilization of chlorine in the waste incineration fly ash is 32.11 to 67.13%.
5. The chlorine-containing mineral six-membered system binder according to any of claims 1 to 4, characterized in that the content of free calcium oxide in the chlorine-containing mineral six-membered system binder is below 0.1%.
6. The method for preparing the six-membered system cementing material containing chlorine minerals as claimed in any one of claims 1 to 5, which is characterized in that the cementing material is obtained by taking waste incineration fly ash, limestone, sandstone and fly ash as main raw materials, performing compression molding, calcining at 1025 to 1250 ℃, and then quenching to room temperature.
7. The method for preparing the chlorine-containing mineral six-membered system cementing material according to claim 6, wherein the addition amounts of the waste incineration fly ash, the limestone, the sandstone and the fly ash are as follows in percentage by mass: 10 to 30 percent, 47.26 to 72.01 percent, 10.29 to 13.78 percent and 2.76 to 3.29 percent.
8. The method for preparing a chlorine-containing mineral six-membered system cementitious material according to claim 6 or 7, wherein the main raw materials further comprise: ca (OH) 2 ；
Preferably, the Ca (OH) is expressed in mass percent 2 The addition amount of the catalyst is 5.96-6.05%.
9. The method for preparing a six-membered system cementing material containing chlorine according to any one of claims 6 to 8, wherein the mass percentage of chlorine in the waste incineration fly ash is 20 to 30%, and the existence forms of chlorine are mainly NaCl, KCl and caclioh.
10. Use of a chlorine-containing mineral six-membered system cementitious material as defined in any one of claims 1 to 4, wherein said chlorine-containing mineral six-membered system cementitious material is mixed with portland cement to produce a chlorine-containing mineral-portland cement;
preferably, the mass ratio of the chlorine-containing mineral six-membered system cementing material to the Portland cement during the mixing is 5-30:95-70, preferably 5:95.
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| CN116947342A (en) * | 2023-09-18 | 2023-10-27 | 常熟理工学院 | Method for preparing cement by utilizing lithium magnesium slag extracted from salt lake and waste incineration fly ash and product thereof |
| CN116947342B (en) * | 2023-09-18 | 2024-02-23 | 常熟理工学院 | Method for preparing cement by utilizing lithium magnesium slag extracted from salt lake and waste incineration fly ash and product thereof |
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