CN107226703B - 一种无钙焙烧铬渣致密耐火材料的制备方法 - Google Patents

一种无钙焙烧铬渣致密耐火材料的制备方法 Download PDF

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CN107226703B
CN107226703B CN201710421388.6A CN201710421388A CN107226703B CN 107226703 B CN107226703 B CN 107226703B CN 201710421388 A CN201710421388 A CN 201710421388A CN 107226703 B CN107226703 B CN 107226703B
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chromium slag
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彭熙
李萍
徐亚红
徐中慧
李娜
帅勤
姚正珍
陈筱悦
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Southwest University of Science and Technology
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Abstract

本发明涉及耐火材料制备技术领域，特别涉及无钙焙烧铬渣致密耐火材料的制备方法。无钙焙烧铬渣致密耐火材料，以无钙焙烧铬渣作为主要原料，采用热压烧结的方法制备而成。具体步骤如下：（1）将无钙焙烧铬渣通过物理方法分选成A和B两组分，A组分主要为含铁化合物，B组分为无钙焙烧铬渣分选含铁组分后的残渣；（2）将无钙焙烧铬渣B组分与镁粉均匀混合，置入热压机中热压烧结制备致密耐火材料；（3）A组分可进一步回收利用。本发明提出的无钙焙烧铬渣致密耐火材料制备方法操作简单，成分低，可充分实现无钙焙烧铬渣的高值化利用，废物利用率达100%。

Description

一种无钙焙烧铬渣致密耐火材料的制备方法
技术领域
本发明涉及无钙焙烧铬渣致密耐火材料的制备方法，属于工业固体废物高值化利用技术领域。
背景技术
铬渣是铬盐和铬铁合金生产过程中排放的危险废物。目前我国铬渣堆存量高达七百来万吨，还在以每年7.8～10.4万吨的速率增长，同时铬渣具有三致毒性，对社会环境造成巨大危害。为了减少这些污染和危害，同时废渣中铬与铁含量较高，有一定的冶炼价值。因此，解毒铬渣并将其合理应用成为当务之急。
随着2012年《铬盐行业清洁生产实施计划》的提出，为尽可能减少铬渣产生量和降低铬渣毒性，全国范围内正在全面淘汰有钙焙烧落后生产工艺，在全行业推广无钙焙烧的清洁生产技术。目前专家学者对无钙铬渣的研究较少，我国传统的铬渣无害化处理方法存在如下缺陷，①干法解毒能耗高；②湿法解毒不彻底，成本高，易造成二次污染；③微生物法解毒时间长，工业化应用难度高；④水泥固化增容比高，长期稳定性差，成本高。
中国专利CN 103643040 A《一种无钙铬渣的处理工艺》中：将无钙焙烧所得的铬渣，添加兰炭、黏土、氧化锰混匀，造粒后，投入回转窑中还原。再将窑尾所出物料直接进行水淬，物料自动分散为粉末状，分选，得锰铬铁合金。但此工艺较为复杂，解毒不彻底，且易产生二次污染。
中国专利CN 102796879 A《一种无钙铬渣经直接还原制备含铬铁粉的方法》中：将无钙铬渣与氧化铝、助熔剂混合，制块、还原焙烧、破碎细磨、磁选。以实现无钙铬渣的完全解毒与充分回收利用。但此工艺较为复杂，能耗较高，耗时较长。
中国专利CN 103103346 A《一种无钙铬渣烧结造块循环再利用方法》中将无钙铬渣和焦粉按照一定质量百分比混合，制粒，点火，将铬渣烧结成具有一定强度和粒度的块状物，以便将烧结铬渣与铬铁矿按照一定比例相配，加入资源还原炉中冶炼高碳铬铁合金。使Cr6+的还原产物最终以稳定的Cr2O3形式存在，并实现铬渣的循环再应用。但是在此过程中消耗外部能量，同时烧结产物不能直接使用，需运送至专门的加工产进行后续资源再利用。
寻求一种成本低的，无二次污染的铬渣无害化处理方法是一个亟待解决的涉及环境安全的关键问题。本发明提出了基于热压烧结技术制备致密耐火材料，实现无钙焙烧铬渣的无害化和资源化，为其长期安全有效的处理处置提供了一条新的途径。
发明内容
为实现无钙焙烧铬渣的无害化和资源化问题，本发明提供了一种无钙焙烧铬渣致密耐火材料的制备方法，具体发明内容如下：
（1）本发明通过下述技术方案实现：将无钙焙烧铬渣B组分与镁粉按一定比例均匀混合，在热压烧结炉中热压烧结，即获得本发明所述的耐火材料；
（2）本发明通过热压机加热引发混合物自身强放热反应，进一步提升混合物的反应速度和反应程度，同时在压力作用下可以提高耐火材料的致密程度，制得耐火材料性能好，成本低；
（3）本发明通过对无钙焙烧铬渣进行分选后根据组分性能差异进行再利用，充分实现了无钙焙烧铬渣的高效利用。
本发明的有益效果：
（1）本制备方法涉及的主要生产设备为热压机。工艺设备简单，易于实现工业化生产；
（2）主要制备原料无钙焙烧铬渣成本低廉，可有效降低此类耐火材料生产成本，同时实现了无钙焙烧铬渣的高值化利用,具有显著的经济效益和环境效益；
（3）热压机下制备的耐火材料结构致密，耐火性能好；
（4）本发明所涉及整个制备过程和使用过程无任何有毒有机污染物产生，安全环保。
具体实施方式
本发明以无钙焙烧铬渣为原料制备一种成本低、耐火性能优异、对人体无害的致密耐火材料
实施案例1：
一种无钙焙烧铬渣致密耐火材料的制备方法，将无钙焙烧铬渣破碎磁选成A、B组分。B组分与镁粉按照3:1均匀混合，将其置于真空热压烧结炉中，抽真空到10-3Pa，压力为50Mpa，以6 °C /min 的烧结速率升温到1000 °C，热压40 min。其致密度达到92.1%，室温抗压强度为151 MPa。
实施案例2：
一种无钙焙烧铬渣耐火材料的制备方法，将无钙焙烧铬渣破碎磁选成A、B组分。B组分与镁粉4:1均匀混合，将其置于真空热压烧结炉中，抽真空到10-3 Pa，压力为30 Mpa，以6 °C /min 的烧结速率升温到800 °C，保温20 min。其致密度达到 90.7%，室温抗压强度为104 MPa
最后说明的是，以上优选实施例仅用以说明本发明的技术方案而非限制，尽管通过上述优选实施例已经对本发明进行了详细的描述，但本领域技术人员应当理解，可以在形式上和细节上对其做出各种各样改变，而不偏离本发明权利要求书所限定的范围。

Claims (2)

1.一种无钙焙烧铬渣致密耐火材料的制备方法，以无钙焙烧铬渣作为主要原料，采用热压烧结的方法制备而成，具体步骤如下：
（1）无钙焙烧铬渣的分选：将无钙焙烧铬渣通过物理方法分选成A和B两组分，铁回收率控制在50%以内；A组分主要为含铁化合物，进一步回收利用；B组分为无钙焙烧铬渣分选含铁组分后的残渣；
（2）致密耐火材料的制备：将无钙焙烧铬渣B组分与镁粉按质量比3:1-4:1均匀混合，置入热压机中热压烧结制备致密耐火材料；热压烧结工艺参数为：温度800-1000℃，压力30-50MPa，热压保持20-40min。
2.根据权利要求1中所述的方法，其主要特征在于，无钙焙烧铬渣的化学组分百分比为：Fe2O3 40-60%，Cr2O3 10-20%，MgO 5-15%，Al2O3 5-15%。
CN201710421388.6A 2017-06-07 2017-06-07 一种无钙焙烧铬渣致密耐火材料的制备方法 Expired - Fee Related CN107226703B (zh)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102796879A (zh) * 2012-09-10 2012-11-28 湖北振华化学股份有限公司 一种无钙铬渣经直接还原制备含铬铁粉的方法
CN103643040A (zh) * 2013-08-23 2014-03-19 甘肃锦世化工有限责任公司 一种无钙铬渣的处理工艺
CN103708845A (zh) * 2013-12-25 2014-04-09 魏周 一种连铸中间包工作层涂料
CN104909778A (zh) * 2015-06-24 2015-09-16 周栋 一种耐火浇注料
CN106278333A (zh) * 2016-09-09 2017-01-04 江苏省冶金设计院有限公司 利用铬渣制备致密耐火材料的方法及其专用系统

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007134725A2 (en) * 2006-05-24 2007-11-29 Saudi Basic Industries Corporation Process for recycling of steel industry iron-bearing by-products by treating pellets in direct reduction furnaces

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102796879A (zh) * 2012-09-10 2012-11-28 湖北振华化学股份有限公司 一种无钙铬渣经直接还原制备含铬铁粉的方法
CN103643040A (zh) * 2013-08-23 2014-03-19 甘肃锦世化工有限责任公司 一种无钙铬渣的处理工艺
CN103708845A (zh) * 2013-12-25 2014-04-09 魏周 一种连铸中间包工作层涂料
CN104909778A (zh) * 2015-06-24 2015-09-16 周栋 一种耐火浇注料
CN106278333A (zh) * 2016-09-09 2017-01-04 江苏省冶金设计院有限公司 利用铬渣制备致密耐火材料的方法及其专用系统

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