CN111606614A - A filling material containing lepidolite slag and preparation method and application thereof - Google Patents
A filling material containing lepidolite slag and preparation method and application thereof Download PDFInfo
- Publication number
- CN111606614A CN111606614A CN202010370784.2A CN202010370784A CN111606614A CN 111606614 A CN111606614 A CN 111606614A CN 202010370784 A CN202010370784 A CN 202010370784A CN 111606614 A CN111606614 A CN 111606614A
- Authority
- CN
- China
- Prior art keywords
- filling material
- sodium
- filling
- lepidolite
- air entraining
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 79
- 238000011049 filling Methods 0.000 title claims abstract description 78
- 239000002893 slag Substances 0.000 title claims abstract description 36
- 229910052629 lepidolite Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 238000005086 pumping Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 239000004568 cement Substances 0.000 claims description 22
- 239000006260 foam Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000004281 calcium formate Substances 0.000 claims description 8
- 229940044172 calcium formate Drugs 0.000 claims description 8
- 235000019255 calcium formate Nutrition 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- 239000000701 coagulant Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000010881 fly ash Substances 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- -1 fatty alcohol sulfonate Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 4
- 235000021120 animal protein Nutrition 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 235000013877 carbamide Nutrition 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 235000010981 methylcellulose Nutrition 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims description 4
- 229930182490 saponin Natural products 0.000 claims description 4
- 150000007949 saponins Chemical class 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 108010082495 Dietary Plant Proteins Proteins 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 235000011148 calcium chloride Nutrition 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 239000005913 Maltodextrin Substances 0.000 claims description 2
- 229920002774 Maltodextrin Polymers 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 239000010440 gypsum Substances 0.000 claims description 2
- 229910052602 gypsum Inorganic materials 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- 229940035034 maltodextrin Drugs 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229920001184 polypeptide Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 2
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 2
- 235000018102 proteins Nutrition 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- 235000019794 sodium silicate Nutrition 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 2
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims 1
- 108010064851 Plant Proteins Proteins 0.000 claims 1
- 239000011398 Portland cement Substances 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 235000021118 plant-derived protein Nutrition 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 238000007596 consolidation process Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000005429 filling process Methods 0.000 abstract description 3
- 238000009415 formwork Methods 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/021—Ash cements, e.g. fly ash cements ; Cements based on incineration residues, e.g. alkali-activated slags from waste incineration ; Kiln dust cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
- C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/08—Slag cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
- E21F15/00—Methods or devices for placing filling-up materials in underground workings
- E21F15/005—Methods or devices for placing filling-up materials in underground workings characterised by the kind or composition of the backfilling material
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
- E21F15/00—Methods or devices for placing filling-up materials in underground workings
- E21F15/08—Filling-up hydraulically or pneumatically
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00146—Sprayable or pumpable mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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Abstract
本发明涉及一种用于锂云母矿渣的充填材料及其制备方法和应用，属于锂云母矿渣的充填技术领域。本发明制备的充填材料，与水混合后形成的浆料，具有接近水的粘度，易于泵送（泵送距离可达100m‑500m）、优异的触变性和快速的初凝时间（小于60s），解决了现有专利技术产品初凝时间长，浆料易流淌，堆积效果差的不足；本发明制备的充填材料，100%固结，抗压强度最高可达到5MPa，解决了现有技术产品固结性能差，抗压强度低的问题。本发明制备的高水充填材料，施工过程中无需充填模板支护等复杂辅助处理，充填工艺简单，尤其适用于矿井中紧急情况下快速充填需求。The invention relates to a filling material for lepidolite slag, a preparation method and application thereof, and belongs to the technical field of lepidolite slag filling. The filling material prepared by the invention, the slurry formed after mixing with water, has a viscosity close to water, is easy to pump (the pumping distance can reach 100m-500m), excellent thixotropy and fast initial setting time (less than 60s) , solves the problems of long initial setting time, easy flow of slurry and poor stacking effect of the existing patented technology products; the filling material prepared by the invention is 100% consolidated, and the maximum compressive strength can reach 5MPa, which solves the problem of the existing technology products. The problem of poor consolidation performance and low compressive strength. The high-water filling material prepared by the invention does not need complicated auxiliary treatment such as filling formwork support in the construction process, and the filling process is simple, and is especially suitable for the rapid filling requirement in the emergency situation in the mine.
Description
技术领域technical field
本发明涉及一种含锂云母矿渣的充填材料及其制备方法和在矿山充填中的应用，属于应用锂云母矿渣的充填技术领域。The invention relates to a filling material containing lepidolite slag, a preparation method thereof and an application in mine filling, belonging to the technical field of filling using lepidolite slag.
背景技术Background technique
我国锂资源种类丰富，储藏量大，其中江西省锂资源主要为锂云母矿石，保有储量为71.03万吨，为我国开采利用最大的锂资源之一。随着新兴产业的迅猛发展，中国对锂盐的需求量逐年快速增加，锂矿渣的排放量也与日俱增。据统计，每生产1t锂盐，约产生8～10t锂云母矿渣，大量堆积的锂云母矿渣一方面占用土地，另一方面也会对环境造成二次污染，并且随着锂云母大量的开采，锂云母矿井上覆岩层垮落造成地表大范围塌陷，致使地面建筑、铁路、公路、河流等遭到严重破坏。矿山充填开采是我国现代化矿井开采效率高、安全、绿色建设的一个重要技术手段，能够起到综合解决矿山固体废料有效利用问题、提高矿石资源采出率问题和保护地表生态环境问题的多重作用。my country is rich in types of lithium resources and has a large amount of reserves. Among them, the lithium resources in Jiangxi Province are mainly lepidolite ore, with a reserve of 710,300 tons, which is one of the most exploited and utilized lithium resources in my country. With the rapid development of emerging industries, China's demand for lithium salts is increasing rapidly year by year, and the discharge of lithium slag is also increasing day by day. According to statistics, about 8-10t of lepidolite slag is produced for every 1t of lithium salt produced. On the one hand, a large amount of accumulated lepidolite slag occupies land, and on the other hand, it will cause secondary pollution to the environment. The collapse of the overlying strata in the lepidolite mine caused extensive subsidence of the ground surface, resulting in serious damage to ground buildings, railways, highways, and rivers. Mine filling mining is an important technical means for the efficient, safe and green construction of modern mines in my country. It can play multiple roles in comprehensively solving the problem of effective utilization of mine solid waste, improving the recovery rate of ore resources and protecting the surface ecological environment.
目前用作矿井充填的材料主要有高分子发泡充填材料，无机粉末发泡类充填材料，水泥、粉煤灰为主的发泡水泥浆体充填材料，高水充填材料等。高分子发泡充填材料反应迅速、材料发泡倍数大、施工简单快捷、单方用料少，但存在不能远距离泵送、固化温度高，存在安全隐患、含有毒害的甲醛、苯酚等物质以及抗压强度低等问题。无机粉体发泡类充填材料具有泵送性能好，可实现远距离泵送、操作简便、密封性优异的特点，但前期投入成本高、发泡时间长、抗压强度低，不能满足矿井充填实际使用需求。水泥、粉煤灰为主的发泡水泥浆体充填材料大量使用水泥、粉煤灰等材料，材料来源广、成本低、远距离泵送性能优异，浆体抗压强度可以达到1MPa左右，但设备投资大、粉尘污染严重、且对废旧巷道充填需要预埋注浆管路，设计分段充填、分段止浆墙，机动灵活性不够，不适合小范围充填。高水充填材料具有泵送性能好、速凝时间短及可利用矿渣作为原料等优点，既能充分满足分层采矿技术的要求，快速充填处理大采空区，又能利用废弃矿渣，减少对土地环境污染、降低材料成本，在矿山充填领域得到广泛的应用。发明专利CN107417228A和CN105152612A分别公开了一种粉煤灰掺杂的高水充填材料和一种碎石掺杂的高水充填材料，降低了充填材料的成本，但终凝强度有待进一步提高(前者28d终凝强度仅达到540kPa；后者终凝强度仅达到755～1140kPa)。发明专利CN108706922A和CN101792291A分别公开了一种高水膨胀充填材料，具有流动性好，终凝强度高的特点，但初凝时间长(前者初凝时间67min～187min；后者初凝时间90min～120min)，浆料堆积能力差。目前，中国关于高水充填材料的研究开展较少，现有高水充填材料普遍存在初凝时间长，浆料粘度低，在充填过程中易流淌的问题，因此难以实现在规定区域内精准固结，为充填施工以及后续开采带来不便。使用矿渣掺杂制备高水材料时，也存在固结性能变差，材料力学性能降低的质量问题。At present, the materials used for mine filling mainly include polymer foamed filling materials, inorganic powder foamed filling materials, foamed cement slurry filling materials mainly composed of cement and fly ash, and high-water filling materials. The polymer foam filling material reacts quickly, the material foaming ratio is large, the construction is simple and fast, and the unilateral material is small, but it cannot be pumped over a long distance, the curing temperature is high, there are potential safety hazards, toxic formaldehyde, phenol and other substances and anti- problems such as low compressive strength. Inorganic powder foam filling materials have the characteristics of good pumping performance, long-distance pumping, easy operation, and excellent sealing, but high initial investment cost, long foaming time, and low compressive strength, which cannot meet mine filling. actual use requirements. Cement and fly ash-based foamed cement slurry filling materials use a large number of materials such as cement and fly ash, which have wide material sources, low cost, and excellent long-distance pumping performance. The compressive strength of the slurry can reach about 1MPa, but The equipment investment is large, the dust pollution is serious, and the filling of the waste roadway needs to be pre-buried grouting pipelines, and the segmented filling and segmented grouting walls are designed, and the maneuverability is not enough, so it is not suitable for small-scale filling. The high-water backfill material has the advantages of good pumping performance, short quick-setting time, and can use slag as raw material. It has been widely used in the field of mine filling due to the pollution of the land environment and the reduction of material costs. Invention patents CN107417228A and CN105152612A respectively disclose a high-water filling material doped with fly ash and a high-water filling material doped with gravel, which reduces the cost of the filling material, but the final setting strength needs to be further improved (the former 28d). The final setting strength only reaches 540kPa; the final setting strength of the latter only reaches 755-1140kPa). Invention patents CN108706922A and CN101792291A respectively disclose a high water expansion filling material, which has the characteristics of good fluidity and high final setting strength, but the initial setting time is long (the former initial setting time is 67min～187min; the latter initial setting time is 90min～120min ), the slurry accumulation capacity is poor. At present, there are few researches on high-water filling materials in China. The existing high-water filling materials generally have the problems of long initial setting time, low slurry viscosity, and easy flow during the filling process. Therefore, it is difficult to achieve precise solidification in the specified area. It will bring inconvenience to the filling construction and subsequent mining. When slag doping is used to prepare high-water materials, there are also quality problems that the consolidation performance is deteriorated and the mechanical properties of the material are reduced.
发明内容SUMMARY OF THE INVENTION
本发明的目的是为了克服现有技术的不足，提出一种含锂云母矿渣的充填材料及其制备方法和应用。The purpose of the present invention is to provide a filling material containing lepidolite slag and its preparation method and application in order to overcome the deficiencies of the prior art.
本发明的目的是通过以下技术方案实现的。The object of the present invention is achieved through the following technical solutions.
一种含锂云母矿渣的充填材料，该充填材料的原料包括水泥基胶凝材料、引气剂、早强剂、增稠剂、稳泡剂和促凝剂；A filling material containing lepidolite slag, the raw materials of the filling material include cement-based cementitious material, air-entraining agent, early strength agent, thickener, foam stabilizer and coagulant;
以该充填材料的原料的总质量为100％计算，各组分的质量百分含量如下：Taking the total mass of the raw materials of the filling material as 100%, the mass percentage of each component is as follows:
锂云母矿渣的质量为充填材料的原料的总质量的15％-30％。The mass of the lepidolite slag is 15%-30% of the total mass of the raw materials of the filling material.
所述的水泥基胶凝材料具有调控充填材料胶凝时间，增加充填材料抗压强度的作用，水泥基胶凝材料为硫铝酸盐水泥、铝酸盐水泥、铁铝酸盐水泥、硅酸盐水泥、矿渣水泥、粉煤灰水泥、石膏中的至少一种；The cement-based cementitious material has the functions of regulating the gelling time of the filling material and increasing the compressive strength of the filling material, and the cement-based cementitious material is sulfoaluminate cement, aluminate cement, ferric aluminate cement, silicate At least one of salt cement, slag cement, fly ash cement, and gypsum;
所述的引气剂可以促使充填材料与水混合反应产生气泡，改善浆料的流动性和粘聚性，引气剂为动物蛋白质引气剂、植物蛋白质引气剂、皂苷引气剂、松香树脂引气剂、脂肪醇磺酸盐引气剂中的至少两种，优选选自动物蛋白质引气剂、植物蛋白质引气剂和皂苷引气剂的两种或三种复配所得；The air-entraining agent can promote the mixing reaction of filling material and water to generate bubbles, and improve the fluidity and cohesion of the slurry. The air-entraining agent is animal protein air-entraining agent, vegetable protein air-entraining agent, saponin air-entraining agent, rosin. At least two kinds of resin air-entraining agent and fatty alcohol sulfonate air-entraining agent, preferably selected from animal protein air-entraining agent, vegetable protein air-entraining agent and saponin air-entraining agent two or three kinds of compound obtained;
所述的早强剂具有加速充填材料水化反应速度和促进早期抗压强度增长的作用，早强剂为氟化钠、氯化钠、氯化钾、氯化钙、亚硝酸钠、尿素、水玻璃、乙二醇、三异丙醇胺、三乙醇胺、甲酸、甲酸钙中的至少两种，优选选自氟化钠、亚硝酸钠、尿素、三乙醇胺和甲酸钙中的两种或两种以上复合使用；The early strength agent has the effect of accelerating the hydration reaction speed of the filling material and promoting the growth of the early compressive strength, and the early strength agent is sodium fluoride, sodium chloride, potassium chloride, calcium chloride, sodium nitrite, urea, At least two of water glass, ethylene glycol, triisopropanolamine, triethanolamine, formic acid, calcium formate, preferably two or two selected from sodium fluoride, sodium nitrite, urea, triethanolamine and calcium formate More than one compound use;
所述的增稠剂主要是调节充填材料与水混合后浆料的流动性以及促进浆料与充填空穴接触面的粘结性，增稠剂为淀粉、明胶、天然橡胶、麦芽糊精、有机膨润土、硅藻土、硅凝胶、甲基纤维素、羧甲基纤维素、羧甲基羟乙基纤维素、羟乙基纤维素中的至少一种，优选选自淀粉、甲基纤维素、羧甲基纤维素的一种或多种；The thickener mainly adjusts the fluidity of the slurry after mixing the filling material with water and promotes the cohesion between the slurry and the contact surface of the filling cavity, and the thickener is starch, gelatin, natural rubber, maltodextrin, At least one of organic bentonite, diatomaceous earth, silica gel, methyl cellulose, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, and hydroxyethyl cellulose, preferably selected from starch, methyl cellulose One or more of carboxymethyl cellulose and carboxymethyl cellulose;
所述的稳泡剂可以提高充填材料与水混合反应产生气泡的稳定性，使得充填材料内部气孔分布均匀，改善气孔结构，提高力学性能，降低材料用量，稳泡剂为十二烷基硫酸钠、脂肪醇聚氧乙烯醚硫酸钠(AES)、α-烯基磺酸钠(AOS)、聚丙烯酰胺、聚乙烯醇、蛋白、多肽、淀粉、羟丙基甲基纤维素、羟乙基甲基纤维素醚中的至少一种，优选选自AES、AOS和聚丙烯酰胺中的一种或多种；The foam stabilizer can improve the stability of the bubbles generated by the mixing reaction between the filling material and water, make the internal pores of the filling material evenly distributed, improve the pore structure, improve the mechanical properties, and reduce the amount of materials. The foam stabilizer is sodium lauryl sulfate. , Sodium Fatty Alcohol Polyoxyethylene Ether Sulfate (AES), Sodium α-Alkenyl Sulfonate (AOS), Polyacrylamide, Polyvinyl Alcohol, Protein, Polypeptide, Starch, Hydroxypropyl Methyl Cellulose, Hydroxyethyl Methyl At least one of cellulose ethers, preferably one or more selected from AES, AOS and polyacrylamide;
所述的促凝剂可以提高充填材料与水混合后浆料的稠度，促进胶凝的作用，促凝剂为硅酸钠、硅酸钾、碳酸钠、碳酸氢钠、碳酸锂、碳酸钙、氯化钠、氯化钙、硫酸钠、硫酸铝、铝酸钠、铝酸钙、氟铝酸钙、甲酸钙、三乙醇胺、聚丙烯酸、聚甲基丙烯酸和丙烯酸盐中的至少两种，优选选自硅酸钠、碳酸钙、碳酸锂、甲酸钙和铝酸钠的两种或两种以上复合使用；The coagulant can improve the consistency of the slurry after mixing the filling material and water, and promote the effect of gelation. The coagulant is sodium silicate, potassium silicate, sodium carbonate, sodium bicarbonate, lithium carbonate, calcium carbonate, At least two of sodium chloride, calcium chloride, sodium sulfate, aluminum sulfate, sodium aluminate, calcium aluminate, calcium fluoroaluminate, calcium formate, triethanolamine, polyacrylic acid, polymethacrylic acid and acrylate, preferably Two or more kinds selected from sodium silicate, calcium carbonate, lithium carbonate, calcium formate and sodium aluminate are used in combination;
所述的锂云母矿渣为锂云母矿冶炼过程中产生的具有活性的固体废料，在本发明中具有促进水化反应的作用，同时可以降低材料成本，锂云母矿渣，细度选为500～2000目，优选800-1500目。The lepidolite slag is an active solid waste generated during the smelting process of lepidolite ore, and in the present invention, it has the effect of promoting the hydration reaction and can reduce the material cost. The lepidolite slag has a fineness of 500-2000 mesh, preferably 800-1500 mesh.
一种用于锂云母矿渣的高水充填材料的制备方法，将锂云母矿渣的高水充填材料的原料按照质量比加入搅拌釜内，搅拌混合15-30min，得到高水填充材料。A method for preparing a high-water filling material for lepidolite slag. The raw materials of the high-water filling material for lepidolite slag are added into a stirring kettle according to the mass ratio, and are stirred and mixed for 15-30 minutes to obtain the high-water filling material.
一种用于锂云母矿渣的高水充填材料的应用，将高水填充材料与水按照质量比为1：1-5进行混合，通过注浆泵高速搅拌和快速输出，泵送距离长度100m-500m，在管口出料处形成泡沫浆料，将泡沫浆料置于空穴处即可堆积充填。An application of high-water filling material for lepidolite slag, the high-water filling material and water are mixed according to the mass ratio of 1:1-5, and the high-speed stirring and fast output are carried out by a grouting pump, and the pumping distance is 100m- 500m, foam slurry is formed at the outlet of the nozzle, and the foam slurry can be stacked and filled by placing it in the cavity.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明制备的充填材料，与水混合后形成的浆料，具有接近水的粘度，易于泵送(泵送距离可达100m-500m)、优异的触变性和快速的初凝时间(小于60s)，解决了现有专利技术产品初凝时间长，浆料易流淌，堆积效果差的不足；(1) The filling material prepared by the present invention, the slurry formed after mixing with water, has a viscosity close to water, is easy to pump (the pumping distance can reach 100m-500m), excellent thixotropy and fast initial setting time ( less than 60s), which solves the problems of long initial setting time, easy flow of slurry and poor accumulation effect of existing patented technology products;
(2)本发明制备的充填材料，100％固结，抗压强度最高可达到5MPa，解决了现有技术产品固结性能差，抗压强度低的问题；(2) The filling material prepared by the present invention is 100% consolidated and has a maximum compressive strength of 5 MPa, which solves the problems of poor consolidation performance and low compressive strength of the prior art products;
(3)本发明制备的高水充填材料，发泡倍数大(最高可达20倍)，固化后不收缩，能有效充填不规则的空穴空间，实现优异的密实性，防止矿井下瓦斯积聚，充填质量稳定；(3) The high-water filling material prepared by the present invention has a large foaming ratio (up to 20 times), does not shrink after curing, can effectively fill irregular cavity spaces, achieve excellent compactness, and prevent gas accumulation in underground mines , the filling quality is stable;
(4)本发明制备的充填材料，利用冶金厂锂云母固体废料作为原料，减少了二次污染，降低了材料成本；(4) The filling material prepared by the present invention utilizes the lepidolite solid waste from the metallurgical plant as a raw material, thereby reducing secondary pollution and material cost;
(5)本发明制备的高水充填材料，施工过程中无需充填模板支护等复杂辅助处理，充填工艺简单，尤其适用于矿井中紧急情况下快速充填需求。(5) The high-water filling material prepared by the present invention does not require complicated auxiliary treatment such as filling formwork support during construction, and the filling process is simple, and is especially suitable for rapid filling in emergency situations in mines.
具体实施方式Detailed ways
为了进一步理解本发明，下面结合具体的实施方式对本发明优选实施方案作进行描述。In order to further understand the present invention, the preferred embodiments of the present invention will be described below with reference to specific embodiments.
实施例1-5Examples 1-5
按照下表1所列水泥基胶凝材料、锂云母矿渣、引气剂、早强剂、增稠剂、稳泡剂和促凝剂的质量份数，经搅拌30min制得锂云母矿渣基高水充填材料备用。According to the mass fraction of cement-based cementitious material, lepidolite slag, air-entraining agent, early strength agent, thickener, foam stabilizer and coagulant listed in Table 1 below, the lepidolite slag-based high Water filling material is available for use.
表1Table 1
将表1制得的锂云母矿渣基高水充填材料与水按照下表2所列质量比例在注浆泵搅拌仓内混合和快速输出，产品性能指标如表2所列。The lepidolite slag-based high-water filling material prepared in Table 1 was mixed with water according to the mass ratio listed in Table 2 in the grouting pump stirring chamber, and the product performance indicators were listed in Table 2.
表2Table 2
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| CN115872695A (en) * | 2022-10-25 | 2023-03-31 | 江西省建材科研设计院有限公司 | Lepidolite slag concrete |
| CN116535153A (en) * | 2023-01-06 | 2023-08-04 | 武汉三源特种建材有限责任公司 | A kind of lepidolite slag road water stable mixture and preparation method thereof |
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| CN116535153A (en) * | 2023-01-06 | 2023-08-04 | 武汉三源特种建材有限责任公司 | A kind of lepidolite slag road water stable mixture and preparation method thereof |
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