CN114368961B - 一种铁尾矿陶瓷滤料的制备方法及其新应用 - Google Patents
一种铁尾矿陶瓷滤料的制备方法及其新应用 Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title claims abstract description 61
- 239000000919 ceramic Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 75
- 239000002351 wastewater Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 10
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010840 domestic wastewater Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000002028 Biomass Substances 0.000 claims abstract description 6
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 12
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004927 clay Substances 0.000 claims description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims description 8
- 238000005453 pelletization Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000019738 Limestone Nutrition 0.000 claims description 5
- 239000010459 dolomite Substances 0.000 claims description 5
- 229910000514 dolomite Inorganic materials 0.000 claims description 5
- 239000006028 limestone Substances 0.000 claims description 5
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
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- 240000007594 Oryza sativa Species 0.000 claims description 2
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- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
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- 235000009566 rice Nutrition 0.000 claims description 2
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- 229910001720 Åkermanite Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
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- 238000000034 method Methods 0.000 abstract description 10
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- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
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Abstract
本发明公开了一种铁尾矿陶瓷滤料的制备方法及其新应用,原料配比为:铁尾矿50~75%、硅铝原料10~20%、钙镁原料15~40%,生物质原料0~7%;将原料分别进行烘干/干燥后各自采用磨机碎磨至过100目筛,然后在混料机中混合得到坯料,备用;将坯料放入造球机进行造球成型,将造球成型的滤料在回转窑中于1150~1250℃烧制,得到铁尾矿陶瓷滤料产品,制备出铁尾矿陶瓷滤料完全满足CJ/T299‑2009技术指标要求,可用于矿山废水、化工废水、生活废水处理,为铁尾矿大宗利用开辟一条新的途径,达到以废治废的成效。其中处理矿山废水上,更是就地取材,就地生产,就地应用,节约时序和空间序的环节,具有显著的经济、环境和社会效益。
Description
技术领域
本发明属于固体废弃物资源综合利用领域,具体涉及一种铁尾矿陶瓷滤料产品,可在矿山废水处理、化工废水、生活废水处理等领域广泛应用,特别适合含镉重金属矿山废水的处理。
背景技术
陶瓷滤料属于一种新型的过滤材料,其相对于传统的石英砂、核桃壳、无烟粉等,具有孔隙率高、吸附性好、机械强度高、耐磨损、化学性能稳定、过滤周期长、耐反冲洗、不易造成二次污染等优点。因此,陶瓷滤料现已成为水处理行业的新一代滤料,其需求量逐年增加。
尾矿作为我国最大的工业固体废物之一,每年产量高达11亿余吨,现堆积总量约190亿余吨,其中铁尾矿占比最大。2020年八部委联合印发《防范化解尾矿库安全风险方案》明确:自2020年起,在保证紧缺和战略性矿产矿山正常建设开发的前提下,全国尾矿库数量原则上只减不增,不再产生新的“头顶库”。故此,如何处理处置后续新生成的铁尾矿,已成为相关部门和企业可持续发展的重点课题。此外,现有铁尾矿的大量堆存会带来经济、环境和安全等诸多方面的问题,例如占用大量土地面积,环境污染和安全隐患等风险。如何有效实现大宗利用铁尾矿,达到减量化、无害化和资源化的目的,成为国内外研究的热点和难点。
国外文献《Thermal Conductivity and Impact Properties of Iron OreTailings Filled Epoxy Composites》一文介绍利用铁尾矿作为环氧树脂复合材料的填充,这种方法虽然具备高值利用的特性,但是从去存量上很难做到有效缓解。
中国专利ZL201510279164公布一种全部以固体废物为原料制备的超轻陶粒,是以粘土性含铁尾矿、煤矸石和城镇污水处理厂脱水污泥为原料,经过预处理、配料及混料、造球,经预热和焙烧,其中预热温度500-600℃、焙烧温度1250-1350℃、升温速率10-15℃/min,制备出的超轻陶瓷堆积密度为390kg/m3、筒压强度为1.2MPa、吸水率为3.8%,达到GB/T 17431.1-2010的要求。但是这种方法,烧制温度高达1350℃,且烧制时间长,能耗高,不宜推广和应用。
中国专利ZL20121031498.8公布一种低硅铁尾矿制备多孔陶粒及其制备方法,将低硅铁尾矿、造孔剂和粘土粉混合后,造粒成生球,生球干燥后,在1100-1180℃条件下焙烧40-60min,得到烧成的铁尾矿陶粒。该方法主要适用于低硅铁尾矿,随着选矿技术与装备的提升,高硅铁尾矿越来越成为主导的铁尾矿类别,故此对于铁尾矿减量化的能力存在不足。此外,铁尾矿的造粒过程中涉及喷洒水玻璃,增加成本。
本发明以铁尾矿为主要原料制备陶瓷滤料,实现铁尾矿的大宗高效利用,处理包括矿山在内的废水,达到以废治废的成效,其中在矿山废水的治理上,更是就地取材,就地生产,原位就地应用,节约时序和空间序的环节。
发明内容
本发明的目的就是针对现有尾矿陶粒制备存在的烧制温度高、能耗高、成本高以及适应性窄等问题,而提供一种生产成本低、原料普遍且来源广泛、易就地取材进行制备且产品性能优良的铁尾矿陶瓷滤料的制备方法,从而为铁尾矿综合利用提供了新的途径。
本发明的另一目的是提供一种铁尾矿陶瓷滤料的新应用。
为实现本发明的上述目的,本发明一种铁尾矿陶瓷滤料的制备方法,采用以下工艺、步骤实施:
(1)将原料按以下干重质量百分比称量配比:铁尾矿50~75%、硅铝原料10~20%、钙镁原料15~40%,生物质原料0~7%;其中以以下配比为优:铁尾矿51~71%、硅铝原料11~20%、钙镁原料15~35%,生物质原料3~7%。
(2)将上述原料分别进行烘干/干燥,使其含水率均低于5%,随后各自采用磨机碎磨至过100目筛,然后在混料机中混合得到坯料,备用。
(3)将上述坯料放入造球机进行造球成型,造球机出料粒度应控制在0.5~15mm范围;其中造球机出料粒度控制在1~5mm范围为优。
(4)将造球成型的滤料在70~110℃进行干燥至含水率低于1%,然后放入回转窑中,于1150~1250℃烧制,得到铁尾矿陶瓷滤料产品。
为了提高铁尾矿陶瓷滤料的性能,所述铁尾矿的化学组分按质量百分比较佳为:32%<SiO2<65%,2%<CaO<25%,5%<(Al2O3+MgO)<25%。
进一步地,所述的硅铝原料为普通粘土、石英、长石或渣土中的一种或多种;所述的钙镁原料为石灰石、白云石、大理石或钢渣中的一种或多种;
进一步地,所述钙镁原料经950~1050℃煅烧26~35min,且煅烧后产品中40%<(CaO+MgO)<100%,其中以在1000℃下煅烧30min为佳。
上述步骤(4)中,回转窑的转速为1~5r/min,全过程烧制时间为30min-120min。
经过试验研究,制备的铁尾矿陶瓷滤料用于矿山废水、化工废水、生活废水的处理时,去污效率效果明显,浊度去除率达75%~85%,COD去除率82~90%,特别在处理含镉重金属的矿山废水表现出优良的技术效果,镉去除率高达85-97%。
与现有技术相比,本发明一种铁尾矿陶瓷滤料的制备方法及其新应用具有如下优点:
(1)以铁尾矿为主要原料,其它原料较为普遍,分布广泛,受原料区域性影响较小,具有较好的可实施性,可就地为铁尾矿综合利用提供新的途径,具有显著的经济、环境和社会效益。
(2)所制备的环保陶瓷滤料,可广泛应用于废水处理,甚至包括铁尾矿所在的矿山废水,真正做到以废治废。
(3)生产工艺简易、成本低,所得产品在市场上具有较好竞争力。
附图说明
图1为本发明一种铁尾矿陶瓷滤料的制备方法原则工艺流程图;
图2为本发明实施例3制得的铁尾矿陶瓷滤料烧结后的XRD图。
具体实施方式
为描述本发明,下面结合附图和实施例对本发明一种铁尾矿陶瓷滤料的制备方法及其新应用做进一步详细说明。
由图1所示的本发明一种铁尾矿陶瓷滤料的制备方法原则工艺流程图看出,本发明一种铁尾矿陶瓷滤料的制备方法按照以下步骤实施:
(1)将原料按以下干重质量百分比称量配比:铁尾矿50~75%、硅铝原料10~20%、钙镁原料15~40%,生物质原料0~7%;
(2)将上述原料分别进行烘干/干燥,使其含水率均低于5%,随后各自采用磨机碎磨至过100目筛,然后在混料机中混合得到坯料,备用;
(3)将上述坯料放入造球机进行造球成型,造球机出料粒度应控制在0.5~15mm范围;
(4)将造球成型的滤料在70~110℃进行干燥至含水率低于1%,然后放入回转窑中,于1150~1250℃烧制,得到铁尾矿陶瓷滤料产品。
下面是5个具体的实施例。
实施例1
(1)将原料按以下干重质量百分比称量配比:铁尾矿55%、普通粘土10%、白云石30%、木屑粉5%;
(2)将上述原料分别烘干3小时,其含水率均低于5%,随后各自在球磨机中球磨至过100目筛,然后在混料机中混合得到坯料,备用;
(3)将上述坯料放入造球机进行造球,造球机出料粒度在3-5mm范围;
(4)将成型的滤料在100℃进行干燥至含水率低于1%,然后放入回转窑中,于1170℃烧制,得到铁尾矿陶瓷滤料产品。
实施例2
(1)将原料按以下干重质量百分比称量配比:铁尾矿65%、渣土10%、石英2%、白云石20%、稻壳粉3%;
(2)将上述原料分别烘干4小时,其含水率均低于5%,随后各自在球磨机中球磨至过100目筛,然后在混料机中混合得到坯料,备用;
(3)将上述坯料放入造球机进行造球,造球机出料粒度在5-8mm范围;
(4)将成型的滤料在100℃进行干燥至含水率低于1%,然后放入回转窑中,于1200℃烧制,得到铁尾矿陶瓷滤料产品。
实施例3
(1)将原料按以下干重质量百分比称量配比:铁尾矿50%、普通粘土10%、长石10%、石灰石10%、白云石10%、钢渣7%、木屑粉3%;
(2)将上述原料分别烘干2.5小时,其含水率均低于5%,随后各自在球磨机中球磨至过100目筛,然后在混料机中混合得到坯料,备用;
(3)将上述坯料放入造球机进行造球,造球机出料粒度在0.5-3mm范围;
(4)将成型的滤料在100℃进行干燥至含水率低于1%,然后放入回转窑中,于1150℃烧制,得到铁尾矿陶瓷滤料产品。
实施例4
(1)将原料按以下干重质量百分比称量配比:铁尾矿75%、普通粘土10%、石灰石10%、大理石5%。
(2)将上述原料分别烘干5小时,其含水率均低于5%,随后各自在球磨机中球磨至过100目筛,然后在混料机中混合得到坯料,备用;
(3)将上述坯料放入造球机进行造球,造球机出料粒度在1-3mm范围;
(4)将成型的滤料在100℃进行干燥至含水率低于1%,然后放入回转窑中,于1250℃烧制,得到铁尾矿陶瓷滤料产品。
实施例5
(1)将原料按以下干重质量百分比称量配比:铁尾矿60%、普通粘土10%、长石5%、石灰石13%、大理石5%、秸秆粉3%、木屑粉4%。
(2)将上述原料分别烘干4.5小时,其含水率均低于5%,随后各自在球磨机中球磨至过100目筛,然后在混料机中混合得到坯料,备用;
(3)将上述坯料放入造球机进行造球,造球机出料粒度在8-15mm范围;
(4)将成型的滤料在100℃进行干燥至含水率低于1%,然后放入回转窑中,于1230℃烧制,得到铁尾矿陶瓷滤料产品。
本发明实施例1、2、3、4、5所制备的铁尾矿陶瓷滤料产品-环保陶瓷滤球,其物理化学性能符合要求,破碎率与磨碎率之和、孔隙率、盐酸可溶性、含泥量、比表面积,完全满足CJ/T 299-2009指标要求,并在处理含镉重金属的矿山酸性废水表现出优良效果,具体如下表:
表1制备的铁尾矿陶瓷滤料产品性能
项目 | 测量值 | 指标 |
破碎率与磨碎率之和,% | 2.15-4.85 | ≤6 |
含泥量,% | 0.12-0.69 | ≤1 |
盐酸可溶性,% | 0.35-1.27 | ≤2 |
孔隙率,% | 54-76 | ≥40 |
比表面积cm<sup>2</sup>/g | 6734-9628 | ≥0.5Х10<sup>4</sup> |
矿山废水Cd去除率 | 85-97% | —— |
由图2所示的本发明实施例3制得的铁尾矿陶瓷滤料烧结后的XRD图看出,所述铁尾矿陶瓷滤料的物相组成主要含有镁黄长石、辉石、石英、尖晶石中的一种或多种。
Claims (5)
1.一种用于矿山废水、化工废水、生活废水的COD与含镉重金属处理的铁尾矿陶瓷滤料的制备方法,其特征在于采用以下步骤:
(1)将原料按以下干重质量百分比称量配比:铁尾矿51~71%、硅铝原料11~20%、钙镁原料15~35%,生物质原料3~7%;
硅铝原料中SiO2+Al2O3含量满足:70.0%<(SiO2+Al2O3)<100%;钙镁原料经950~1050℃煅烧26~35min,且煅烧后产品中 40%<(CaO+MgO)<100%;
(2)将上述原料分别进行干燥,使其含水率均低于5%,随后各自采用磨机碎磨至过100目筛, 然后在混料机中混合得到坯料,备用;
(3)将上述坯料放入造球机进行造球成型,造球机出料粒度应控制在0.5~15mm;
(4)将造球成型的滤料在70~100℃进行干燥至含水率低于1%,然后放入回转窑中,于1150~1250℃烧制,得到物相组成主要含有镁黄长石、辉石、石英、尖晶石中的一种或多种的铁尾矿陶瓷滤料产品,其产品性能为:破碎率与磨碎率之和2.15~4.85%,含泥量0.12~0.69%,盐酸可溶性0.35~1.27%,孔隙率54~76%,比表面积6734~9628cm2/g。
2.如权利要求1所述的一种用于矿山废水、化工废水、生活废水的COD与含镉重金属处理的铁尾矿陶瓷滤料的制备方法,其特征在于:步骤(3)中,造球机出料粒度控制在1~5mm。
3.如权利要求1或2所述的一种用于矿山废水、化工废水、生活废水的COD与含镉重金属处理的铁尾矿陶瓷滤料的制备方法,其特征在于:所述的硅铝原料为普通粘土、石英、长石或渣土中的一种或多种。
4.如权利要求3所述的一种用于矿山废水、化工废水、生活废水的COD与含镉重金属处理的铁尾矿陶瓷滤料的制备方法,其特征在于:所述的钙镁原料为石灰石、白云石、大理石或钢渣中的一种或多种。
5.如权利要求4所述的一种用于矿山废水、化工废水、生活废水的COD与含镉重金属处理的铁尾矿陶瓷滤料的制备方法,其特征在于:所述生物质原料包括秸秆粉、稻壳粉或木屑粉中的一种或多种。
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