CN116606121A - 一种由劣质煤矸石制备的瓷质材料和制备方法 - Google Patents
一种由劣质煤矸石制备的瓷质材料和制备方法 Download PDFInfo
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- CN116606121A CN116606121A CN202310507294.6A CN202310507294A CN116606121A CN 116606121 A CN116606121 A CN 116606121A CN 202310507294 A CN202310507294 A CN 202310507294A CN 116606121 A CN116606121 A CN 116606121A
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- parts
- oxide
- albite
- porcelain material
- potassium
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- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052656 albite Inorganic materials 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002910 solid waste Substances 0.000 claims abstract description 35
- 239000010881 fly ash Substances 0.000 claims abstract description 30
- 239000003245 coal Substances 0.000 claims abstract description 26
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 22
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 22
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011777 magnesium Substances 0.000 claims abstract description 22
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 22
- 239000010453 quartz Substances 0.000 claims abstract description 22
- 229910001710 laterite Inorganic materials 0.000 claims abstract description 20
- 239000011504 laterite Substances 0.000 claims abstract description 20
- 239000004575 stone Substances 0.000 claims abstract description 20
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011591 potassium Substances 0.000 claims abstract description 19
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 19
- 235000019738 Limestone Nutrition 0.000 claims abstract description 10
- 239000006028 limestone Substances 0.000 claims abstract description 10
- 229910052661 anorthite Inorganic materials 0.000 claims abstract description 4
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 32
- 235000012239 silicon dioxide Nutrition 0.000 claims description 25
- 239000010433 feldspar Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 14
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 14
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 14
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 14
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 229910021532 Calcite Inorganic materials 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 7
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 7
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000464 lead oxide Inorganic materials 0.000 claims description 7
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 7
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 7
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 7
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 238000000748 compression moulding Methods 0.000 claims description 4
- 239000004579 marble Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000010438 heat treatment Methods 0.000 abstract description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 4
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 235000015895 biscuits Nutrition 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 238000012545 processing Methods 0.000 description 13
- 238000005336 cracking Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000010440 gypsum Substances 0.000 description 7
- 229910052602 gypsum Inorganic materials 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000011265 semifinished product Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 238000002386 leaching Methods 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
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- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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- C04B2235/3472—Alkali metal alumino-silicates other than clay, e.g. spodumene, alkali feldspars such as albite or orthoclase, micas such as muscovite, zeolites such as natrolite
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Abstract
本发明属于固废物制备瓷质材料技术领域。本发明提供了一种由劣质煤矸石制备的瓷质材料和制备方法,瓷质材料包含如下质量份的制备原料:劣质煤矸石45~85份、粉煤灰25~45份、钾长石5~38份、钠长石5~28份、锂长石5~18份、钾钠长石5~8份、高岭土5~28份、镁矿石2~8份、红土5~28份、石英石2~28份、钙石2~16份、氧化铝5~28份。本发明通过合理选择各原料,控制各原料的用量以及工艺参数,得到的瓷质材料具有高硬度、高抗压强度和弹性模量,体积密度大,吸水率低,耐酸性能好,急冷急热性能好。本发明的瓷质材料由固废物制备得到,实现了固废物资源化利用,有利于低碳环保、生态平衡。
Description
技术领域
本发明涉及固废物制备瓷质材料技术领域,尤其涉及一种由劣质煤矸石制备的瓷质材料和制备方法。
背景技术
劣质煤矸石、粉煤灰等煤系固废物的排放基本是露天堆存、深埋,堆存或深埋不仅占用了大量土地,而且无任何环保措施,经过风吹雨淋,形成固体颗粒,易对地下水源和土壤等造成极大污染;自然氧化产生的硫化物会破坏臭氧造成环境污染。综合开发利用固废物,在环保前提下实现大宗化、规模化应用劣质煤矸石等固废物,解决固废物占用土地、污染环境等问题,变废为宝,取代其它生产瓷质产品原材料资源过度开发,保护生态环境平衡稳固,具有重要的价值。
目前,用劣质固废物制备瓷质路沿石、路缘石、建筑瓷砖或大理石的技术很少,而且现在用劣质固废物制备材料过程中,由于原料选择不当、原料级配不合理、工艺方法不当等形成了陶质材料,容易导致其力学性能差、密度小、急冷急热性能差、吸水率高等问题,陶质材料建筑产品与瓷质材料建筑产品相比,瓷质材料的质量体系检测数据指标大大高于陶质材料。
因此,研究得到一种由固废物劣质煤矸石制备的瓷质材料,提高其力学性能、急冷急热性能、耐腐蚀性和密度,降低吸水率,充分实现低碳环保、生态平衡,固废物资源化利用,具有重要的意义。
发明内容
本发明的目的是针对现有技术的不足提供一种由劣质煤矸石制备的瓷质材料和制备方法。
为了实现上述发明目的,本发明提供以下技术方案:
本发明提供了一种由劣质煤矸石制备的瓷质材料,所述瓷质材料包含如下质量份的制备原料:
劣质煤矸石45~85份、粉煤灰25~45份、钾长石5~38份、钠长石5~28份、锂长石5~18份、钾钠长石5~8份、高岭土5~28份、镁矿石2~8份、红土5~28份、石英石2~28份、钙石2~16份、氧化铝5~28份。
作为优选,所述瓷质材料为路沿石、路缘石、建筑瓷砖或大理石。
作为优选,所述劣质煤矸石为固废劣质煤矸石,所述粉煤灰为固废粉煤灰。
作为优选,所述劣质煤矸石的粒径≥300目;所述粉煤灰、钾长石、钠长石、锂长石、钾钠长石、高岭土、镁矿石、红土、石英石、钙石和氧化铝的粒径独立的为170~780目。
作为优选,所述粉煤灰、钾长石、钠长石、锂长石、钾钠长石、高岭土、镁矿石、红土、石英石、钙石和氧化铝的粒径独立的为170目、190目、220目、270目、325目、350目、420目、530目、670目或780目。
作为优选,所述瓷质材料包含如下质量分数的成分:
二氧化硅38~68%、三氧化二铝18~38%、三氧化二铁0.01~5%、氧化钙2~18%、氧化镁1~8%、氧化钾0.8~8%、氧化钠0.7~9%、二氧化钛0.01~9%、五氧化二磷0.001~2%、氧化锰0.001~8%、三氧化二铬0.001~3%、氧化锌0.001~3%、氧化铅0.001~2%、二氧化锆0.001~8%、氧化钡0.001~3%、氧化锶0.001~0.8%、氧化镍0.001~0.5%、氧化钴0.001~8%、氧化锂0.001~0.5%、三氧化二锑0.001~0.9%、氮0.001~0.08%、铌0.001~0.003%、硫0.001~0.8%、铜0.001~1%、钨0.001~1%、硼0.001~10%、总碳0.001~10%、氧0.001~0.08%;
所述总碳中包含游离碳,游离碳在瓷质材料中的质量分数为0.001~0.8%。
本发明还提供了所述的瓷质材料的制备方法,包含如下步骤:将原料、减水剂和水混合,得到泥浆,将泥浆注浆成型后顺次进行干燥、预热、煅烧、降温,得到瓷质材料;
所述原料包含劣质煤矸石、粉煤灰、钾长石、钠长石、锂长石、钾钠长石、高岭土、镁矿石、红土、石英石、钙石和氧化铝;
所述减水剂为三聚磷酸钠,减水剂占原料质量的1~5%;
泥浆的水分含量为31~32%。
本发明还提供了所述的瓷质材料的制备方法,包含如下步骤:将原料和水混合,得到粉体料,将粉体料液压成型后顺次进行干燥、预热、煅烧、降温,得到瓷质材料;
所述原料包含劣质煤矸石、粉煤灰、钾长石、钠长石、锂长石、钾钠长石、高岭土、镁矿石、红土、石英石、钙石和氧化铝;
粉体料成型的水分含量为7~10%。
作为优选,所述预热的温度为300~350℃,预热的时间为10~30h;煅烧的温度为1350~1420℃,煅烧的时间为30~50h。
作为优选,室温升温至预热温度的速率为45~55℃/h,预热温度升温至煅烧温度的速率为90~110℃/h,煅烧温度降温至室温的速率为15~40℃/h。
本发明的有益效果包括以下几点:
1)本发明通过合理选择各原料,控制各原料的用量以及工艺参数,得到的瓷质材料具有高硬度、高抗压强度和弹性模量,体积密度大,吸水率低,耐酸性能好,急冷急热性能好。
2)本发明的瓷质材料由大量的固废劣质煤矸石、固废粉煤灰等固废物制备得到,实现了固废物资源化利用,有利于低碳环保、生态平衡。
具体实施方式
本发明提供了一种由劣质煤矸石制备的瓷质材料,所述瓷质材料包含如下质量份的制备原料:
劣质煤矸石45~85份、粉煤灰25~45份、钾长石5~38份、钠长石5~28份、锂长石5~18份、钾钠长石5~8份、高岭土5~28份、镁矿石2~8份、红土5~28份、石英石2~28份、钙石2~16份、氧化铝5~28份。
本发明所述瓷质材料的制备原料中,劣质煤矸石优选为50~80份,进一步优选为55~75份,更优选为60~70份;粉煤灰优选为30~40份,进一步优选为32~38份,更优选为34~36份;钾长石优选为10~35份,进一步优选为15~30份,更优选为20~25份;钠长石优选为10~25份,进一步优选为12~20份,更优选为15~18份;锂长石优选为8~15份,进一步优选为10~13份;钾钠长石优选为6~7份,进一步优选为6.5份;高岭土优选为10~25份,进一步优选为12~20份,更优选为15~18份;镁矿石优选为3~7份,进一步优选为4~6份;红土优选为10~25份,进一步优选为12~20份,更优选为15~18份;石英石优选为5~25份,进一步优选为10~20份,更优选为12~18份;钙石优选为5~14份,进一步优选为8~12份;氧化铝优选为10~25份,进一步优选为12~20份,更优选为15~18份。
本发明中,所述瓷质材料优选为路沿石、路缘石、建筑瓷砖或大理石。
本发明中,所述劣质煤矸石优选为固废劣质煤矸石,所述粉煤灰优选为固废粉煤灰。
本发明中,采用破碎机把劣质煤矸石粗破为20~30mm的颗粒,再经过6~8目的筛网筛分出有热能价值的煤炭用于其它行业,筛分好的块状劣质煤矸石再加工成本发明所需粒径的劣质煤矸石。本发明所述劣质煤矸石的粒径能够提高后续坯体化学成分的稳定性和煅烧温度稳定性,降低次品率,提高产品的平整度、收缩率、抗压强度、抗折强度、耐磨性,改善外观颜色。
本发明中,加工后劣质煤矸石的粒径优选≥300目,进一步优选≥350目;加工后,粉煤灰、钾长石、钠长石、锂长石、钾钠长石、高岭土、镁矿石、红土、石英石、钙石和氧化铝的粒径独立的优选为170~780目,进一步独立的优选为170目、190目、220目、270目、325目、350目、420目、530目、670目或780目。
本发明中,所述瓷质材料优选包含如下质量分数的成分:二氧化硅38~68%、三氧化二铝18~38%、三氧化二铁0.01~5%、氧化钙2~18%、氧化镁1~8%、氧化钾0.8~8%、氧化钠0.7~9%、二氧化钛0.01~9%、五氧化二磷0.001~2%、氧化锰0.001~8%、三氧化二铬0.001~3%、氧化锌0.001~3%、氧化铅0.001~2%、二氧化锆0.001~8%、氧化钡0.001~3%、氧化锶0.001~0.8%、氧化镍0.001~0.5%、氧化钴0.001~8%、氧化锂0.001~0.5%、三氧化二锑0.001~0.9%、氮0.001~0.08%、铌0.001~0.003%、硫0.001~0.8%、铜0.001~1%、钨0.001~1%、硼0.001~10%、总碳0.001~10%、氧0.001~0.08%;进一步优选包含如下质量分数的成分:二氧化硅42~60%、三氧化二铝22~35%、三氧化二铁0.1~3%、氧化钙5~13%、氧化镁2~7%、氧化钾1.5~6%、氧化钠1.5~7%、二氧化钛0.1~7%、五氧化二磷0.01~1%、氧化锰0.01~6%、三氧化二铬0.01~2%、氧化锌0.01~2%、氧化铅0.01~1.5%、二氧化锆0.01~6%、氧化钡0.01~2%、氧化锶0.01~0.6%、氧化镍0.01~0.4%、氧化钴0.01~6%、氧化锂0.01~0.4%、三氧化二锑0.01~0.7%、氮0.01~0.06%、铌0.002%、硫0.01~0.6%、铜0.01~0.8%、钨0.01~0.8%、硼0.1~8%、总碳0.1~8%、氧0.01~0.06%。
本发明中,所述瓷质材料的总碳中包含游离碳,游离碳在瓷质材料中的质量分数优选为0.001~0.8%,进一步优选为0.01~0.6%,更优选为0.1~0.4%。
本发明还提供了所述的瓷质材料的制备方法,包含如下步骤:将原料、减水剂和水混合,得到泥浆,将泥浆注浆成型后顺次进行干燥、预热、煅烧、降温,得到瓷质材料;
所述原料包含劣质煤矸石、粉煤灰、钾长石、钠长石、锂长石、钾钠长石、高岭土、镁矿石、红土、石英石、钙石和氧化铝;
所述减水剂为三聚磷酸钠,减水剂占原料质量的1~5%;
泥浆的水分含量为31~32%。
本发明的注浆成型中,减水剂优选占原料质量的2~4%,进一步优选占原料质量的3~3.5%;泥浆的水分含量优选为31.5%。
本发明中,把泥浆注入石膏模型,在石膏模型内注浆成型,进行自吸水分干燥,干燥的时间优选为12~24h。石膏模型的尺寸根据产品规格尺寸进行定制。配制泥浆过程中加入减水剂能够提高泥浆的流动性和注浆性能。
本发明还提供了所述的瓷质材料的制备方法,包含如下步骤:将原料和水混合,得到粉体料,将粉体料液压成型后顺次进行干燥、预热、煅烧、降温,得到瓷质材料;
所述原料包含劣质煤矸石、粉煤灰、钾长石、钠长石、锂长石、钾钠长石、高岭土、镁矿石、红土、石英石、钙石和氧化铝;
粉体料成型的水分含量为7~10%。
本发明的液压成型中,粉体料的水分含量优选为8~9%。
本发明中,在石膏模型或耐磨高强度钢制模具中成型完成后取出素坯半成品,在隧道窑炉中顺次进行预热更进一步烘干、煅烧、降温,得到瓷质材料;预热在隧道窑炉烘干带,煅烧在隧道窑炉高温区,降温在隧道窑炉降温带,预热到煅烧为逐步升温的过程,煅烧到降温为逐步降温的过程。
本发明的注浆工艺适用于异型产品成型;液压成型工艺有利于提高产品的密度、强度和硬度,尺寸精度更高,满足更高的尺寸要求。
本发明的液压成型工艺中,采用17000吨液压机,将耐磨高强度钢制模具装入液压机中,将粉体料布料加入模具中液压成型,压制成型后粉体料先进行自吸水分干燥,干燥的时间优选为12~24h,耐磨高强度钢制模具的尺寸根据产品规格尺寸进行定制。
本发明中,所述预热的温度优选为300~350℃,进一步优选为310~340℃,更优选为320~330℃;预热的时间优选为10~30h,进一步优选为
15~25h,更优选为18~22h;煅烧的温度优选为1350~1420℃,进一步优选为1370~1410℃,更优选为1380~1400℃,煅烧的时间优选为30~50h,进一步优选为35~45h,更优选为37~42h。
本发明中,室温升温至预热温度的速率优选为45~55℃/h,进一步优选为47~52℃/h,更优选为49~50℃/h;预热温度升温至煅烧温度的速率优选为90~110℃/h,进一步优选为95~105℃/h,更优选为98~102℃/h;煅烧温度降温至室温的速率优选为15~40℃/h,进一步优选为20~35℃/h,更优选为25~30℃/h。
下面结合实施例对本发明提供的技术方案进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。
实施例1
瓷质路沿石由如下质量份的原料制备得到:固废劣质煤矸石50份、固废粉煤灰42份、钾长石8份、钠长石22份、锂长石7份、钾钠长石5份、高岭土24份、镁矿石3份、红土7份、石英石5份、钙石4份、氧化铝6份。固废劣质煤矸石的加工粒径大于等于300目,固废粉煤灰的加工粒径为190目,钾长石、钠长石、锂长石、钾钠长石的加工粒径为325目,高岭土、镁矿石、红土、石英石、钙石和氧化铝的加工粒径为670目。
将上述原料、三聚磷酸钠(三聚磷酸钠的质量为原料总质量的2.5%)和水混合,得到水分含量为31%的泥浆,采用注浆机器,把泥浆注入石膏模型中,在石膏模型内进行自吸水分干燥,干燥时间为15h,将泥浆成型后,取出素坯半成品,在隧道窑炉烘干带由室温以48℃/h的速率升温至预热温度,预热温度为320℃,时间为28h,再以95℃/h的速率逐步升温至煅烧温度,在隧道窑炉高温区进行煅烧,煅烧温度为1380℃,时间为45h,最后在隧道窑炉降温带逐步降温,以20℃/h的速率降温至室温,得到瓷质路沿石。
瓷质路沿石包含如下质量分数的成分:二氧化硅42%、三氧化二铝21.584%、三氧化二铁2.5%、氧化钙5%、氧化镁2%、氧化钾2.2%、氧化钠1.5%、二氧化钛7%、五氧化二磷1.5%、氧化锰0.2%、三氧化二铬0.3%、氧化锌2%、氧化铅0.1%、二氧化锆5.2%、氧化钡0.2%、氧化锶0.1%、氧化镍0.05%、氧化钴5%、氧化锂0.02%、三氧化二锑0.7%、氮0.01%、铌0.001%、硫0.01%、铜0.01%、钨0.7%、硼0.01%、总碳0.1%(游离碳为0.005%)、氧0.005%。
实施例2
瓷质路缘石由如下质量份的原料制备得到:固废劣质煤矸石65份、固废粉煤灰35份、钾长石20份、钠长石15份、锂长石12份、钾钠长石6份、高岭土16份、镁矿石5份、红土16份、石英石15份、钙石8份、氧化铝15份。固废劣质煤矸石的加工粒径大于等于350目,固废粉煤灰的加工粒径为350目,钾长石、钠长石、锂长石、钾钠长石的加工粒径为270目,高岭土、镁矿石、红土、石英石、钙石和氧化铝的加工粒径为530目。
将上述原料和水混合,得到水分含量为8%的粉体料,采用17000吨液压机,将耐磨高强度钢制模具装入压机中,粉体料布料加入模具中压制成型;压制成型后粉体料先进行自吸水分干燥,干燥24h后,在隧道窑炉烘干带由室温以53℃/h的速率升温至预热温度,预热温度为340℃,时间为20h,再以100℃/h的速率逐步升温至煅烧温度,在隧道窑炉高温区进行煅烧,煅烧温度为1400℃,时间为40h,最后在隧道窑炉降温带逐步降温,以30℃/h的速率降温至室温,得到瓷质路缘石。
瓷质路缘石包含如下质量分数的成分:二氧化硅42%、三氧化二铝23%、三氧化二铁0.9%、氧化钙3.3%、氧化镁4%、氧化钾3%、氧化钠4%、二氧化钛0.1%、五氧化二磷0.5%、氧化锰3%、三氧化二铬1%、氧化锌0.3%、氧化铅1.067%、二氧化锆1.5%、氧化钡1.7%、氧化锶0.4%、氧化镍0.2%、氧化钴1.06%、氧化锂0.31%、三氧化二锑0.14%、氮0.07%、铌0.003%、硫0.51%、铜0.8%、钨0.1%、硼4%、总碳3%(游离碳为0.01%)、氧0.04%。
实施例3
瓷质建筑瓷砖由如下质量份的原料制备得到:固废劣质煤矸石78份、固废粉煤灰28份、钾长石35份、钠长石8份、锂长石16份、钾钠长石8份、高岭土10份、镁矿石7份、红土25份、石英石25份、钙石14份、氧化铝25份。固废劣质煤矸石的加工粒径大于等于300目,固废粉煤灰的加工粒径为350目,钾长石、钠长石、锂长石、钾钠长石的加工粒径为420目,高岭土、镁矿石、红土、石英石、钙石和氧化铝的加工粒径为780目。
将上述原料、三聚磷酸钠(三聚磷酸钠的质量为原料总质量的3.5%)和水混合,得到水分含量为32%的泥浆,采用注浆机器,把泥浆注入石膏模型中,在石膏模型内进行自吸水分干燥,干燥时间为18h,将泥浆成型后,取出素坯半成品,在隧道窑炉烘干带由室温以50℃/h的速率升温至预热温度,预热温度为330℃,时间为18h,再以105℃/h的速率逐步升温至煅烧温度,在隧道窑炉高温区进行煅烧,煅烧温度为1370℃,时间为48h,最后在隧道窑炉降温带逐步降温,以36℃/h的速率降温至室温,得到瓷质建筑瓷砖。
瓷质建筑瓷砖包含如下质量分数的成分:二氧化硅48%、三氧化二铝23.7%、三氧化二铁0.2%、氧化钙3%、氧化镁2%、氧化钾2%、氧化钠3%、二氧化钛0.1%、五氧化二磷0.26%、氧化锰3%、三氧化二铬1.3%、氧化锌0.3%、氧化铅1.067%、二氧化锆0.5%、氧化钡2%、氧化锶0.22%、氧化镍0.4%、氧化钴0.1%、氧化锂0.4%、三氧化二锑0.01%、氮0.07%、铌0.003%、硫0.5%、铜0.8%、钨0.01%、硼2%、总碳5%(游离碳为0.6%)、氧0.06%。
对实施例1~3的瓷质材料进行硬度、强度、耐酸性能、体积密度、吸水率、急冷急热性能测试。
耐酸性能测试:将100mm×200mm×1000mm的瓷质材料产品在质量浓度为9%的盐酸中浸泡,密封保持180h后取出,观察瓷质材料的开裂、变色情况。
体积密度测试:实施例1~3的瓷质材料产品各取7块,每块尺寸为100mm×100mm×100mm,称量总质量后取平均值,得到平均质量,再计算平均密度值。
吸水率测试:实施例1~3的瓷质材料产品各取7块,每块尺寸为100mm×100mm×100mm,称重后分别得到实施例1~3的瓷质材料产品总重1,然后再放入水中,保持180h后取出,再分别称量实施例1~3的产品总重2,根据(总重2-总重1)/总重1得到每个实施例的产品平均吸水率。
实施例1的瓷质路沿石的肖氏硬度为73HS,莫氏硬度为9.2,抗压强度为2400kg/cm2,弹性模量为1.4×106kg/cm3。在盐酸中浸泡180h后无开裂、变色现象,产品完整无损;平均密度值为2.68吨/m3;平均吸水率为0.008%。瓷质路沿石在-80℃下保持120h无开裂现象,以120℃/30min的速率升温至380℃,在380℃保持120h后无开裂、变色现象,抗压强度、硬度无变化。
实施例2的瓷质路缘石的肖氏硬度为78HS,莫氏硬度为10,抗压强度为3200kg/cm2,弹性模量为1.58×106kg/cm3。在盐酸中浸泡180h后无开裂、变色现象,产品完整无损;平均密度值为3.02吨/m3;平均吸水率为0.0072%。瓷质路缘石在-80℃下保持120h无开裂现象,以120℃/30min的速率升温至380℃,在380℃保持120h后无开裂、变色现象,抗压强度、硬度无变化。
实施例3的瓷质建筑瓷砖的肖氏硬度为75HS,莫氏硬度为9.6,抗压强度为2800kg/cm2,弹性模量为1.48×106kg/cm3。在盐酸中浸泡180h后无开裂、变色现象,产品完整无损;平均密度值为2.72吨/m3;平均吸水率为0.008%。瓷质建筑瓷砖在-80℃下保持120h无开裂现象,以120℃/30min的速率升温至380℃,在380℃保持120h后无开裂、变色现象,抗压强度、硬度无变化。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种由劣质煤矸石制备的瓷质材料,其特征在于,所述瓷质材料包含如下质量份的制备原料:
劣质煤矸石45~85份、粉煤灰25~45份、钾长石5~38份、钠长石5~28份、锂长石5~18份、钾钠长石5~8份、高岭土5~28份、镁矿石2~8份、红土5~28份、石英石2~28份、钙石2~16份、氧化铝5~28份。
2.根据权利要求1所述的瓷质材料,其特征在于,所述瓷质材料为路沿石、路缘石、建筑瓷砖或大理石。
3.根据权利要求1或2所述的瓷质材料,其特征在于,所述劣质煤矸石为固废劣质煤矸石,所述粉煤灰为固废粉煤灰。
4.根据权利要求3所述的瓷质材料,其特征在于,所述劣质煤矸石的粒径≥300目;所述粉煤灰、钾长石、钠长石、锂长石、钾钠长石、高岭土、镁矿石、红土、石英石、钙石和氧化铝的粒径独立的为170~780目。
5.根据权利要求3所述的瓷质材料,其特征在于,所述粉煤灰、钾长石、钠长石、锂长石、钾钠长石、高岭土、镁矿石、红土、石英石、钙石和氧化铝的粒径独立的为170目、190目、220目、270目、325目、350目、420目、530目、670目或780目。
6.根据权利要求5所述的瓷质材料,其特征在于,所述瓷质材料包含如下质量分数的成分:
二氧化硅38~68%、三氧化二铝18~38%、三氧化二铁0.01~5%、氧化钙2~18%、氧化镁1~8%、氧化钾0.8~8%、氧化钠0.7~9%、二氧化钛0.01~9%、五氧化二磷0.001~2%、氧化锰0.001~8%、三氧化二铬0.001~3%、氧化锌0.001~3%、氧化铅0.001~2%、二氧化锆0.001~8%、氧化钡0.001~3%、氧化锶0.001~0.8%、氧化镍0.001~0.5%、氧化钴0.001~8%、氧化锂0.001~0.5%、三氧化二锑0.001~0.9%、氮0.001~0.08%、铌0.001~0.003%、硫0.001~0.8%、铜0.001~1%、钨0.001~1%、硼0.001~10%、总碳0.001~10%、氧0.001~0.08%;
所述总碳中包含游离碳,游离碳在瓷质材料中的质量分数为0.001~0.8%。
7.权利要求1~6任一项所述的瓷质材料的制备方法,其特征在于,包含如下步骤:将原料、减水剂和水混合,得到泥浆,将泥浆注浆成型后顺次进行干燥、预热、煅烧、降温,得到瓷质材料;
所述原料包含劣质煤矸石、粉煤灰、钾长石、钠长石、锂长石、钾钠长石、高岭土、镁矿石、红土、石英石、钙石和氧化铝;
所述减水剂为三聚磷酸钠,减水剂占原料质量的1~5%;
泥浆的水分含量为31~32%。
8.权利要求1~6任一项所述的瓷质材料的制备方法,其特征在于,包含如下步骤:将原料和水混合,得到粉体料,将粉体料液压成型后顺次进行干燥、预热、煅烧、降温,得到瓷质材料;
所述原料包含劣质煤矸石、粉煤灰、钾长石、钠长石、锂长石、钾钠长石、高岭土、镁矿石、红土、石英石、钙石和氧化铝;
粉体料成型的水分含量为7~10%。
9.根据权利要求7或8所述的制备方法,其特征在于,所述预热的温度为300~350℃,预热的时间为10~30h;煅烧的温度为1350~1420℃,煅烧的时间为30~50h。
10.根据权利要求9所述的制备方法,其特征在于,室温升温至预热温度的速率为45~55℃/h,预热温度升温至煅烧温度的速率为90~110℃/h,煅烧温度降温至室温的速率为15~40℃/h。
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