CN110156481A - 利用熔模铸造废砂制备的耐火材料及耐火材料的制备方法 - Google Patents
利用熔模铸造废砂制备的耐火材料及耐火材料的制备方法 Download PDFInfo
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- CN110156481A CN110156481A CN201910276783.9A CN201910276783A CN110156481A CN 110156481 A CN110156481 A CN 110156481A CN 201910276783 A CN201910276783 A CN 201910276783A CN 110156481 A CN110156481 A CN 110156481A
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical class [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 19
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开一种利用熔模铸造废砂制备的耐火材料及耐火材料的制备方法,制备方法包括以下步骤:(1)将熔模铸造废砂破碎并磁选;(2)将经步骤(1)上述处理后的熔模铸造废砂与镁铝尖晶石混合,并以无水乙醇作为介质,球磨机中混合形成浆料;(3)于浆料中加入碳纳米管、聚乙烯醇,超声分散;然后干燥,热处理,得到第一混合料;(3)将第一混合料加入改性水玻璃搅拌,形成第二混合料;(4)于第二混合料中加入结合剂、外加剂以及氧化剂,出料后成型,干燥10~15;(5)干燥后的成型料升温至1450℃高温处理,获得该耐火材料。本发明可以解决现有技术中的熔模铸造废砂的再生利用问题。
Description
技术领域
本发明属于耐火材料制造技术领域,尤其涉及一种利用熔模铸造废砂制备的耐火材料及耐火材料的制备方法。
背景技术
熔模铸造的模壳材料是耐火材料,在熔模铸造中,模壳要具有耐高温、热化学稳定、热膨胀性能适合,透气性及脱壳性能需要符合对铸件的性能要求。 而这些对模壳的要求均需要由制造模壳的耐火材料来实现。
现有技术中,熔模铸造过程中排除大量的废砂,直接影响铸造生产的能源消耗、环境污染以及铸件的质量、生产效率和成本。而现阶段,国家环保政策的日趋严格,对企业的环境、资源循环利用度提出了越来越高的要求,而现阶段并没有一套铸造工业废砂再利用的成熟方案。因而非常有必要就铸造废砂的再循环利用进行深入挖掘,以促进行业的转型和可持续发展。
发明内容
因此,本发明的目的之一在于提供一种利用熔模铸造废砂制备的耐火材料及耐火材料的制备方法,以解决现有技术中的熔模铸造废砂的再生利用问题。
为达上述目的,本发明提供一种耐火材料的制备方法,该制备方法包括以下步骤:
(1)将60~70重量份熔模铸造废砂破碎为5~10mm,并磁选后再经筛分分选处理;
(2)将经步骤(1)上述处理后的熔模铸造废砂与粒度≤3mm的14~20重量份的镁铝尖晶石混合,并以无水乙醇作为介质,在行星式球磨机中混合3.5~4.5小时,转速为300r/min,形成浆料,其中该镁铝尖晶石的组成为MgO+Al2O3≥90%;
(3)于该浆料中加入5~6重量份的碳纳米管、2~3重量份聚乙烯醇,并在质量浓度为8~10%的乙醇溶液中超声分散1.5~2小时;然后在循环热风条件下干燥,然后在温度为450~550 ℃的条件下热处理3~4小时,得到第一混合料;
(3)将该第一混合料经冷却、除尘后,在搅拌机中混料1~3分钟,并加入4~7重量份的改性水玻璃,继续搅拌3~5分钟,形成第二混合料;
(4)于该第二混合料中加入7~9重量份的结合剂、0.5~1重量份的外加剂以及1~3重量份的氧化剂,并进行均化,出料后成型,在180~260℃下干燥10~15小时;
(5)干燥后的成型料升温至1450 ℃高温处理,其中,升温过程中在450℃时保温 30min 以便结合剂的烧失,升至最高温度后保温 3 h,然后随炉冷却至室温,获得该耐火材料。
作为可选的技术方案,该改性水玻璃制备方法为:将改性剂聚丙烯酰胺或三聚磷酸钠,常温下按照重量比1:7~10的比例加入到水玻璃溶液中,静置24小时后即成,且改性后的水玻璃模数为2.4~3.0。
作为可选的技术方案,该碳纳米管为石墨化羟基多壁碳纳米管,长度为30-50nm。
作为可选的技术方案,该抗氧化剂为由碳化硅、碳化硼、镁铝合金粉、氮化硅粉组成的混合物,且该碳化硼的质量百分比大于15%。
作为可选的技术方案,该结合剂为纯铝酸钙水泥、硅酸盐水泥、β 晶型三氧化二铝、硅溶胶或水玻璃的至少一种。
作为可选的技术方案,该外加剂为木质素磺酸钠、三聚磷酸钠、聚乙烯二醇或六偏磷酸钠的至少一种。
作为可选的技术方案,该熔模铸造废砂的化学组成为:SiO2 53.39%,Al2O336.84%,Fe2O3 1.56%,CaO 0.3%,MgO 0.23%,K2O 0.27%,Na2O 0.02%,TiO2 1.06%,ZrO26.17%。
作为可选的技术方案,步骤(5)中的高温处理的升温制度为:室温升到180℃,升温速度为5℃/min,于180℃保温30 min;180~250℃,升温速度为3℃/min,于250℃保温10min; 250~500℃,升温速度为0.5℃/min,于500℃保温30min;500~800℃,升温速度为6℃/min,于800℃保温10min;800~1450℃,升温速度为3℃/min,于1450℃保温3小时。
本发明还提供一种利用熔模铸造废砂制备的耐火材料,该耐火材料采用如上所述的耐火材料的制备方法制备。
与现有技术相比,本发明针对现有的废弃的精密铸造废砂污染环境的问题,通过合适的处理工艺,对精密铸造废砂资源化应用,变废为宝,制备出生产成本较低的耐火材料浇注料。从根本上解决了精密铸造废砂堆放、填埋所带来的环境污染问题,使其从原先铸造行业的经济环保包袱成为企业绿色制造的盈利点,促进铸造行业的循环低碳经济化。 另外,由于采用固体废弃物为主要原料,减少了耐火材料生产对天然矿物的消耗,节约了我国的矿产资源,促进了耐火材料行业的健康发展。而且,制造出来的耐火材料性能优异。
关于本发明的优点与精神可以藉由以下的发明详述得到进一步的了解。
具体实施方式
本发明提供一种耐火材料的制备方法,该制备方法包括以下步骤:
(1)将60~70重量份熔模铸造废砂破碎为5~10mm,并磁选后再经筛分分选处理;其中,该熔模铸造废砂的化学组成为:SiO2 53.39%,Al2O3 36.84%,Fe2O3 1.56%,CaO 0.3%,MgO0.23%,K2O 0.27%,Na2O 0.02%,TiO2 1.06%,ZrO2 6.17%;
(2)将经步骤(1)上述处理后的熔模铸造废砂与粒度≤3mm的14~20重量份的镁铝尖晶石混合,并以无水乙醇作为介质,在行星式球磨机中混合3.5~4.5小时,转速为300r/min,形成浆料,其中该镁铝尖晶石的组成为MgO+Al2O3≥90%;
(3)于该浆料中加入5~6重量份的碳纳米管、2~3重量份聚乙烯醇,并在质量浓度为8~10%的乙醇溶液中超声分散1.5~2小时;然后在循环热风条件下干燥,然后在温度为450~550 ℃的条件下热处理3~4小时,得到第一混合料;其中,上述碳纳米管为石墨化羟基多壁碳纳米管,较佳地,长度为30~50nm;
(3)将该第一混合料经冷却、除尘后,在搅拌机中混料1~3分钟,并加入4~7重量份的改性水玻璃,继续搅拌3~5分钟,形成第二混合料;
(4)于该第二混合料中加入7~9重量份的结合剂、0.5~1重量份的外加剂以及1~3重量份的氧化剂,并进行均化,出料后成型,在180~260℃下干燥10~15小时;
(5)干燥后的成型料升温至1450 ℃高温处理,其中,升温过程中在450℃时保温 30min 以便结合剂的烧失,升至最高温度后保温 3 h,然后随炉冷却至室温,获得该耐火材料。且较佳地,步骤(5)中的高温处理的升温制度为:室温升到180℃,升温速度为5℃/min,于180℃保温30 min;180~250℃,升温速度为3℃/min,于250℃保温10min; 250~500℃,升温速度为0.5℃/min,于500℃保温30min;500~800℃,升温速度为6℃/min,于800℃保温10min;800~1450℃,升温速度为3℃/min,于1450℃保温3小时。
本发明从烧结工艺上进行了优化,进行了多步保温成型,可大幅度提高成品的质量。而且,本发明将温度设定在1450℃,是因为熔模铸造废砂在1450℃液相生成量明显增加,温度升至1500℃时,锆英石引起的方英石的熔融,液相量会进一步上升,所以此温度设定可以避免高温处理中材料间的相互粘黏和控制耐火材料自身的收缩。
上述步骤(3)中于磁选且磨浆后的熔模铸造废砂加入碳纳米管和聚乙烯醇混合,使有机成分进入碳纳米管内部,在经过高温焙烧后能够去除,再重新加入适应量的新砂或其他配料,可使得再生型砂具有较好的通气性、紧实度和可塑性,其耐火性和退让性较好。
其中,上述改性水玻璃制备方法为:将改性剂聚丙烯酰胺或三聚磷酸钠,常温下按照重量比1:7~10的比例加入到水玻璃溶液中,静置24小时后即成,且改性后的水玻璃模数为2.4~3.0。镁铝尖晶石具有良好的耐高温、良好的化学稳定性,机械性能优良 ,高的熔点(>2000℃)等优点,可以用作熔铸氧化铝耐火材料砂型的优质原料;同时改性水玻璃结合镁铝尖晶石砂型耐火度高,高温性能好,抗热冲击性能强,不污染铸件,显著改善砂型的溃散性和表面稳定性,可以实现砂型的重复利用。
上述抗氧化剂为由碳化硅、碳化硼、镁铝合金粉、氮化硅粉组成的混合物,且该碳化硼的质量百分比大于15%。碳化硼为最合适的耐火材料的抗氧化剂,得到既能保证含碳耐火材料的抗氧化性且不降低抗熔蚀性能的抗氧化剂,加入本发明的耐火材料中,提高了耐火材料的抗氧化性。
上述结合剂为纯铝酸钙水泥、硅酸盐水泥、β 晶型三氧化二铝、硅溶胶或水玻璃的至少一种。
上述外加剂为木质素磺酸钠、三聚磷酸钠、聚乙烯二醇或六偏磷酸钠的至少一种。
此外,本发明还提供一种利用熔模铸造废砂制备的耐火材料,该耐火材料采用如上所述的耐火材料的制备方法制备。
下面通过具体实施例对本发明的利用熔模铸造废砂制备的耐火材料的制备方法进行进一步的说明。
实施例1
本实施例中,耐火材料采用如下方法步骤制备:
(1)将65重量份熔模铸造废砂破碎为5~10mm,并磁选后再经筛分分选处理;
(2)将经步骤(1)上述处理后的熔模铸造废砂与粒度≤3mm的15重量份的镁铝尖晶石混合,并以无水乙醇作为介质,在行星式球磨机中混合3.5~4.5小时,转速为300r/min,形成浆料;
(3)于该浆料中加入5重量份的碳纳米管、3重量份聚乙烯醇,并在质量浓度为8~10%的乙醇溶液中超声分散1.5~2小时;然后在循环热风条件下干燥,然后在温度为450~550 ℃的条件下热处理3~4小时,得到第一混合料;
(3)将该第一混合料经冷却、除尘后,在搅拌机中混料1~3分钟,并加入5重量份的改性水玻璃,继续搅拌3~5分钟,形成第二混合料;
(4)于该第二混合料中加入8重量份的结合剂、1重量份的外加剂以及3重量份的氧化剂,并进行均化,出料后成型,在180~260℃下干燥10~15小时;
(5)干燥后的成型料升温至1450 ℃高温处理,升温制度为:室温升到180℃,升温速度为5℃/min,于180℃保温30 min;180~250℃,升温速度为3℃/min,于250℃保温10min;250~500℃,升温速度为0.5℃/min,于500℃保温30min;500~800℃,升温速度为6℃/min,于800℃保温10min;800~1450℃,升温速度为3℃/min,于1450℃保温3小时。
实施例1
本实施例中,耐火材料采用如下方法步骤制备:
(1)将70重量份熔模铸造废砂破碎为5~10mm,并磁选后再经筛分分选处理;
(2)将经步骤(1)上述处理后的熔模铸造废砂与粒度≤3mm的14重量份的镁铝尖晶石混合,并以无水乙醇作为介质,在行星式球磨机中混合3.5~4.5小时,转速为300r/min,形成浆料;
(3)于该浆料中加入5重量份的碳纳米管、2重量份聚乙烯醇,并在质量浓度为8~10%的乙醇溶液中超声分散1.5~2小时;然后在循环热风条件下干燥,然后在温度为450~550 ℃的条件下热处理3~4小时,得到第一混合料;
(3)将该第一混合料经冷却、除尘后,在搅拌机中混料1~3分钟,并加入4重量份的改性水玻璃,继续搅拌3~5分钟,形成第二混合料;
(4)于该第二混合料中加入7重量份的结合剂、0.5重量份的外加剂以及1.5重量份的氧化剂,并进行均化,出料后成型,在180~260℃下干燥10~15小时;
(5)干燥后的成型料升温至1450 ℃高温处理,升温制度为:室温升到180℃,升温速度为5℃/min,于180℃保温30 min;180~250℃,升温速度为3℃/min,于250℃保温10min;250~500℃,升温速度为0.5℃/min,于500℃保温30min;500~800℃,升温速度为6℃/min,于800℃保温10min;800~1450℃,升温速度为3℃/min,于1450℃保温3小时。
实施例3
本实施例中,耐火材料采用如下方法步骤制备:
(1)将60重量份熔模铸造废砂破碎为5~10mm,并磁选后再经筛分分选处理;
(2)将经步骤(1)上述处理后的熔模铸造废砂与粒度≤3mm的20重量份的镁铝尖晶石混合,并以无水乙醇作为介质,在行星式球磨机中混合3.5~4.5小时,转速为300r/min,形成浆料;
(3)于该浆料中加入6重量份的碳纳米管、2重量份聚乙烯醇,并在质量浓度为8~10%的乙醇溶液中超声分散1.5~2小时;然后在循环热风条件下干燥,然后在温度为450~550 ℃的条件下热处理3~4小时,得到第一混合料;
(3)将该第一混合料经冷却、除尘后,在搅拌机中混料1~3分钟,并加入7重量份的改性水玻璃,继续搅拌3~5分钟,形成第二混合料;
(4)于该第二混合料中加入9重量份的结合剂、1重量份的外加剂以及2重量份的氧化剂,并进行均化,出料后成型,在180~260℃下干燥10~15小时;
(5)干燥后的成型料升温至1450 ℃高温处理,升温制度为:室温升到180℃,升温速度为5℃/min,于180℃保温30 min;180~250℃,升温速度为3℃/min,于250℃保温10min;250~500℃,升温速度为0.5℃/min,于500℃保温30min;500~800℃,升温速度为6℃/min,于800℃保温10min;800~1450℃,升温速度为3℃/min,于1450℃保温3小时。
性能检测:
将上述实施例1-3的耐火材料置于感应炉中测试,上述耐火材料在密度、钱弯曲强度、气孔率等方面均超过性能要求,且耐火度均能达到1900℃以上。
综上所述,本发明针对现有的废弃的精密铸造废砂污染环境的问题,通过合适的处理工艺,对精密铸造废砂资源化应用,变废为宝,制备出生产成本较低的耐火材料浇注料。从根本上解决了精密铸造废砂堆放、填埋所带来的环境污染问题,使其从原先铸造行业的经济环保包袱成为企业绿色制造的盈利点,促进铸造行业的循环低碳经济化。 另外,由于采用固体废弃物为主要原料,减少了耐火材料生产对天然矿物的消耗,节约了我国的矿产资源,促进了耐火材料行业的健康发展。而且,制造出来的耐火材料性能优异。
藉由以上较佳具体实施例的详述,是希望能更加清楚描述本发明的特征与精神,而并非以上述所揭露的较佳具体实施例来对本发明的保护范围加以限制。相反地,其目的是希望能涵盖各种改变及具相等性的安排于本发明所欲申请的权利要求的保护范围内。因此,本发明所申请的权利要求的保护范围应该根据上述的说明作最宽广的解释,以致使其涵盖所有可能的改变以及具相等性的安排。
Claims (9)
1.一种耐火材料的制备方法,其特征在于,该制备方法包括以下步骤:
(1)将60~70重量份熔模铸造废砂破碎为5~10mm,并磁选后再经筛分分选处理;
(2)将经步骤(1)上述处理后的熔模铸造废砂与粒度≤3mm的14~20重量份的镁铝尖晶石混合,并以无水乙醇作为介质,在行星式球磨机中混合3.5~4.5小时,转速为300r/min,形成浆料,其中该镁铝尖晶石的组成为MgO+Al2O3≥90%;
(3)于该浆料中加入5~6重量份的碳纳米管、2~3重量份聚乙烯醇,并在质量浓度为8~10%的乙醇溶液中超声分散1.5~2小时;然后在循环热风条件下干燥,然后在温度为450~550 ℃的条件下热处理3~4小时,得到第一混合料;
(3)将该第一混合料经冷却、除尘后,在搅拌机中混料1~3分钟,并加入4~7重量份的改性水玻璃,继续搅拌3~5分钟,形成第二混合料;
(4)于该第二混合料中加入7~9重量份的结合剂、0.5~1重量份的外加剂以及1~3重量份的氧化剂,并进行均化,出料后成型,在180~260℃下干燥10~15小时;
(5)干燥后的成型料升温至1450 ℃高温处理,其中,升温过程中在450℃时保温 30min 以便结合剂的烧失,升至最高温度后保温 3 h,然后随炉冷却至室温,获得该耐火材料。
2.如权利要求1所述的耐火材料的制备方法,其特征在于,该改性水玻璃制备方法为:将改性剂聚丙烯酰胺或三聚磷酸钠,常温下按照重量比1:7~10的比例加入到水玻璃溶液中,静置24小时后即成,且改性后的水玻璃模数为2.4~3.0。
3.如权利要求1所述的耐火材料的制备方法,其特征在于,该碳纳米管为石墨化羟基多壁碳纳米管,长度为30-50nm。
4.如权利要求1所述的耐火材料的制备方法,其特征在于,该抗氧化剂为由碳化硅、碳化硼、镁铝合金粉、氮化硅粉组成的混合物,且该碳化硼的质量百分比大于15%。
5.如权利要求1所述的耐火材料的制备方法,其特征在于,该结合剂为纯铝酸钙水泥、硅酸盐水泥、β 晶型三氧化二铝、硅溶胶或水玻璃的至少一种。
6.如权利要求1所述的耐火材料的制备方法,其特征在于,该外加剂为木质素磺酸钠、三聚磷酸钠、聚乙烯二醇或六偏磷酸钠的至少一种。
7.如权利要求1所述的耐火材料的制备方法,其特征在于,该熔模铸造废砂的化学组成为:SiO2 53.39%,Al2O3 36.84%,Fe2O3 1.56%,CaO 0.3%,MgO 0.23%,K2O 0.27%,Na2O0.02%,TiO2 1.06%,ZrO2 6.17%。
8.如权利要求1所述的耐火材料的制备方法,其特征在于,步骤(5)中的高温处理的升温制度为:室温升到180℃,升温速度为5℃/min,于180℃保温30 min;180~250℃,升温速度为3℃/min,于250℃保温10min; 250~500℃,升温速度为0.5℃/min,于500℃保温30min;500~800℃,升温速度为6℃/min,于800℃保温10min;800~1450℃,升温速度为3℃/min,于1450℃保温3小时。
9.一种利用熔模铸造废砂制备的耐火材料,其特征在于,该耐火材料采用如权利要求1-8中任意一项所述的耐火材料的制备方法制备。
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