CN113058607B - 一种利用转炉钢渣转化六价铬并协同固定三价铬的方法 - Google Patents
一种利用转炉钢渣转化六价铬并协同固定三价铬的方法 Download PDFInfo
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Abstract
一种利用转炉钢渣转化六价铬并协同固定三价铬的方法,属于功能材料领域。以大宗工业固废钢渣中转炉渣为主要原料,经湿法提取‑综合利用转炉渣中有价金属元素制备镁掺杂四氧化三铁可见光光催化剂,进而在光照下实现Cr(VI)光催化还原,另一方面,该类光催化剂不稳定,在光催化过程中形成大量二价铁,与还原生成的Cr(III)形成铬铁矿(Fe,Mg)Cr2O4尖晶石,从而实现了三价铬的有效固定。因此,基于转炉钢渣的表面功能化以后可实现还原六价铬与固定三价铬的高效协同,进而为新型Cr处理材料的开发提供新的思路。所得的复合结构在水净化和土壤治理领域具有较好的应用前景。
Description
技术领域
本发明涉及一种利用转炉钢渣转化六价铬(Cr(VI))并协同固定三价铬(Cr(III))的方法,属于功能及环境保护材料领域。
背景技术
当前,寻找新型高效的铬处理材料尤为迫切。转炉钢渣是炼钢过程中产生的固体废物,每年排放大量钢渣(~1亿吨),约占粗钢产量的15~20%。目前,钢渣主要用作建筑材料约占65%,其余的被倾倒在钢铁厂或堆存在钢渣场。因此,由于钢渣大量排放,造成高额的处理成本,严重污染地下水,钢渣的高效管理已成为环境保护中的一个严峻问题。钢渣是一种非均质工业固体废弃物,主要由Fe、Ca、Si、Mg等元素组成,具有很大的潜力利用这些化学成分构建低成本、多功能的水净化和环境修复材料,以促进废弃钢渣资源的回收利用。
铬是人体必需的微量元素之一,能调节人体内糖和胆固醇的代谢。当人体内含量较低时,人体的血管会发生硬化,这也是动脉硬化的一个重要因素。三价铬化合物和氨基酸构成的复合物还可以促进胰岛素的作用,改善胰岛素的敏感性。铬的毒性主要来自于Cr(VI)。Cr(VI)的毒性是Cr(III)的100倍,它对人体呼吸道、消化道等有着强烈的刺激,Cr(VI)还具有诱变作用,环境中的铬化合物可进入人体细胞,引发细胞突变,严重地可诱发癌症。Cr(VI)对其他动植物也有一定程度的危害,当植物土壤环境中Cr(VI)含量超标时,植物的生长和代谢会受到不同程度的抑制。环境中铬的化合价有主要有三价和六价,其他二价、四价和五价的铬化合物性质极其不稳定。Cr(III)易水解,吸附于土壤矿物和有机质而形成沉淀,而Cr(VI)有较强的迁移能力,不易被土壤胶体吸附,且Cr(VI)具有较高的毒性。环境中Cr(III)和Cr(VI)相互转化对铬的生物毒性,迁移性有着重要的影响。
本发明以大宗工业固废钢渣中转炉渣为主要原料,经湿法提取-综合利用转炉渣中有价金属元素制备镁掺杂四氧化三铁可见光光催化剂,进而在光照下实现Cr(VI)光催化还原,另一方面,该类光催化剂不稳定,在光催化过程中形成大量二价铁,与还原生成的Cr(III)形成铬铁矿(Fe,Mg)Cr2O4尖晶石,从而实现了三价铬的有效固定。因此,基于转炉钢渣的表面功能化以后可实现还原六价铬与固定三价铬的高效协同,进而为新型Cr处理材料的开发提供新的思路。所得的复合结构在水净化和土壤治理领域具有较好的应用前景。
发明内容
本发明的目的是提供一种利用转炉钢渣转化六价铬(Cr(VI))并协同固定三价铬(Cr(III))的方法,可将转炉钢渣变废为宝,开发Cr(VI)治理环境修复材料,大大降低修复成本,提高净化效率,实际应用价值重大。
本发明的目的通过以下技术方案予以实现:
一种利用转炉钢渣转化六价铬(Cr(VI))并协同固定三价铬(Cr(III))的方法,其特征在于,包括以下步骤:
(1)水杨酸-甲醇改性的钢渣SAM-RSS的制备:每15-40克的钢渣原料(RSS)对应添加200-800毫升的水杨酸-甲醇(SAM)混合溶液中,其中水杨酸-甲醇(SAM)混合溶液中水杨酸浓度为100-300g/L,搅拌均匀后使用0.45μm滤纸过滤,滤渣干燥,用超纯水反复洗涤,得到水杨酸-甲醇改性的钢渣SAM-RSS;
(2)已处理钢渣(TSS)的制备:将水杨酸-甲醇改性的钢渣SAM-RSS与NaOH混合,钢渣SAM-RSS与NaOH的质量比1:1-2:1,500-600℃加热1.5-3h进行碱焙烧,碱焙烧的目的是通过形成可溶性金属钠盐过滤掉Si、Al、Cr、V等大部分杂质元素,碱性焙烧渣被命名为已处理钢渣(TSS);
(3)复合结构的光催化剂的制备:已处理钢渣添加到浓度1.0-3.0mol/L NH4Cl水溶液中,每0.2-0.5g已处理钢渣对应20-50毫升NH4Cl水溶液,在150-200°C水热反应18-36h,然后所得的表层为镁掺杂四氧化三铁的钢渣(记为MSS),用去离子水洗涤和干燥,保存在干燥器中;
(4)复合结构光催化剂的转化及协同固定,取复合结构光催化剂分散于重铬酸钾溶液中,添加草酸为空穴捕获剂,在太阳光或300W氙灯(模拟太阳光)下光照,即可将Cr(VI)光催化还原为Cr(III),同时以尖晶石(Fe,Mg)Cr2O4的形式实现了Cr(III)的固定。
复合结构的光催化剂质量与重铬酸钾溶液浓度以及草酸质量之间的比例关系为20-50mg:50-150mg/L(总体积为60ML):10-20mg,此范围内的转化-固定实验均可实现溶液中残余总铬浓度低于第一类污染物最高允许排放浓度(GB8978-1996)。
以Cr(VI)光催化还原为探针反应验证复合结构的光催化转化及协同固定效果:取20mg复合结构的光催化分散于60mL 120mg/L的重铬酸钾溶液中,添加20mg草酸为空穴捕获剂,在300W氙灯(模太阳光拟)下光照15分钟,即可完全将Cr(VI)光催化还原为Cr(III),同时以尖晶石(Fe,Mg)Cr2O4的形式实现了Cr(III)的固定,通过原子发射光谱分析溶液中的铬浓度发现为0.08mg/L。
本发明以转炉钢渣为原料,使用转炉钢渣为原料进行表面处理,将钢渣自身包含的Mg、Fe金属元素原位转化为镁掺杂四氧化三铁表层经表面处理,能够实现转化六价铬(Cr(VI))并协同固定三价铬(Cr(III)),证实了钢渣在处理铬污染应用领域的潜力。
本发明的有益效果是:本发明的制备方法所得的产品可重复性好,操作简单,成本低,能够变废为宝。在铬固定领域具有较好的应用前景。
附图说明
图1扫描电镜图片:(A)原钢渣(RSS),(B)改性原钢渣(SAM-RSS),(C)处理后的钢渣(TSS),(D)表层为Mg掺杂Fe3O4钢渣(MFSS),(E)和(F)MSS的透射电镜图片。
图2.原钢渣(RSS)和表层为Mg掺杂Fe3O4钢渣(MSS)以及空白实验(Contrast)在相同条件下对Cr(VI)(60mL 120mg/L)的反应曲线。
图3.表层为Mg掺杂Fe3O4钢渣(MSS)经光催化反应后得到的铬铁矿(Fe,Mg)Cr2O4尖晶石XRD衍射图谱。
具体实施方式
下面结合实施例对本发明作进一步说明,但本发明并不限于以下实施例。
实施例1
1、15克的钢渣原料(RSS)添加在200毫升的水杨酸-甲醇(SAM)混合溶液中(100g/L),在300rpm 30℃磁力搅拌18h后使用0.45μm滤纸过滤。滤渣在60℃干燥24h,用超纯水反复洗涤。将水杨酸-甲醇改性的钢渣(记为SAM-RSS)与NaOH(质量比1:1)混合,500℃加热1.5h,碱焙烧的目的是通过形成可溶性金属钠盐过滤掉Si、Al、Cr、V等大部分杂质元素。碱性焙烧渣被命名为已处理钢渣(TSS)。最后,已处理钢渣(0.2g)添加到20毫升1.0mol/LNH4Cl水溶液中,在150℃水热反应18h。然后所得的表层为镁掺杂四氧化三铁的钢渣(记为MSS)用去离子水洗涤和干燥24小时60℃,保存在干燥器中。
2、取20mg MSS复合结构分散于60mL 120mg/L的重铬酸钾溶液中,添加20mg草酸为空穴捕获剂,在300W氙灯(模太阳光拟)下光照15分钟,即可完全将Cr(VI)光催化还原为Cr(III),通过原子发射光谱分析溶液中的铬浓度发现为0.08mg/L,同时XRD证实了光还原得到的Cr(III)以尖晶石(Fe,Mg)Cr2O4的形式实现了Cr(III)的固定。
实施例2
1、40克的钢渣原料(RSS)添加在800毫升的水杨酸-甲醇(SAM)混合溶液中(300g/L),在300rpm 30℃磁力搅拌18h后使用0.45μm滤纸过滤。滤渣在60℃干燥24h,用超纯水反复洗涤。将水杨酸-甲醇改性的钢渣(记为SAM-RSS)与NaOH(质量比2:1)混合,600℃加热3h,碱焙烧的目的是通过形成可溶性金属钠盐过滤掉Si、Al、Cr、V等大部分杂质元素。碱性焙烧渣被命名为已处理钢渣(TSS)。最后,已处理钢渣(0.5g)添加到50毫升3.0mol/L NH4Cl水溶液中,在200℃水热反应36h。然后所得的表层为镁掺杂四氧化三铁的钢渣(记为MSS)用去离子水洗涤和干燥24小时60℃,保存在干燥器中。
2、取20mg MSS复合结构分散于60mL 120mg/L的重铬酸钾溶液中,添加20mg草酸为空穴捕获剂,在300W氙灯(模太阳光拟)下光照15分钟,即可完全将Cr(VI)光催化还原为Cr(III),通过原子发射光谱分析溶液中的铬浓度发现为0.07mg/L,同时XRD证实了光还原得到的Cr(III)以尖晶石(Fe,Mg)Cr2O4的形式实现了Cr(III)的固定。
实施例3
1、30克的钢渣原料(RSS)添加在500毫升的水杨酸-甲醇(SAM)混合溶液中(200g/L),在300rpm 30℃磁力搅拌18h后使用0.45μm滤纸过滤。滤渣在60℃干燥24h,用超纯水反复洗涤。将水杨酸-甲醇改性的钢渣(记为SAM-RSS)与NaOH(质量比1.5:1)混合,550℃加热2h,碱焙烧的目的是通过形成可溶性金属钠盐过滤掉Si、Al、Cr、V等大部分杂质元素。碱性焙烧渣被命名为已处理钢渣(TSS)。最后,已处理钢渣(0.3g)添加到30毫升2.0mol/L NH4Cl水溶液中,在180℃水热反应24h。然后所得的表层为镁掺杂四氧化三铁的钢渣(记为MSS)用去离子水洗涤和干燥24小时60℃,保存在干燥器中。
2、取20mg MSS复合结构分散于60mL 120mg/L的重铬酸钾溶液中,添加20mg草酸为空穴捕获剂,在300W氙灯(模太阳光拟)下光照15分钟,即可完全将Cr(VI)光催化还原为Cr(III),通过原子发射光谱分析溶液中的铬浓度发现为0.75mg/L,同时XRD证实了光还原得到的Cr(III)以尖晶石(Fe,Mg)Cr2O4的形式实现了Cr(III)的固定。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所做的任何修改,等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (4)
1.一种利用转炉钢渣转化六价铬并协同固定三价铬的方法,其特征在于,包括以下步骤:
(1)水杨酸-甲醇改性的钢渣SAM-RSS的制备:每15-40克的钢渣原料RSS对应添加200-800毫升的水杨酸-甲醇SAM混合溶液中,其中水杨酸-甲醇SAM混合溶液中水杨酸浓度为100-300g/L,搅拌均匀后使用0.45μm滤纸过滤,滤渣干燥,用超纯水反复洗涤,得到水杨酸-甲醇改性的钢渣SAM-RSS;
(2)已处理钢渣TSS的制备:将水杨酸-甲醇改性的钢渣SAM-RSS与NaOH混合,钢渣SAM-RSS与NaOH的质量比1:1-2:1,500-600℃加热1.5-3h进行碱焙烧,碱焙烧的目的是通过形成可溶性金属钠盐过滤掉Si、Al、Cr、V等大部分杂质元素,碱性焙烧渣被命名为已处理钢渣TSS;
(3)复合结构的光催化剂的制备:已处理钢渣添加到浓度1.0-3.0mol/L NH4Cl水溶液中,每0.2-0.5g已处理钢渣对应20-50毫升NH4Cl水溶液,在150-200℃水热反应18-36h,然后所得的表层为镁掺杂四氧化三铁的钢渣,记为MSS,用去离子水洗涤和干燥,保存在干燥器中,得到所述复合结构的光催化剂;
(4)复合结构光催化剂的转化及协同固定,取复合结构的光催化剂分散于重铬酸钾溶液中,添加草酸为空穴捕获剂,在太阳光或300W氙灯下光照,即可将六价铬光催化还原为三价铬,同时以尖晶石(Fe,Mg)Cr2O4的形式实现了三价铬的固定。
2.按照权利要求1所述的一种利用转炉钢渣转化六价铬并协同固定三价铬的方法,其特征在于,复合结构的光催化剂质量与重铬酸钾溶液浓度以及草酸质量之间的比例关系为20-50mg:50-150mg/L:10-20mg,重铬酸钾溶液的总体积为60mL,此范围内的转化-固定实验均可实现溶液中残余总铬浓度低于GB8978-1996第一类污染物最高允许排放浓度。
3.一种利用转炉钢渣转化六价铬并可协同固定三价铬的复合结构的光催化的制备方法,其特征在于,包括以下步骤:
(1)水杨酸-甲醇改性的钢渣SAM-RSS的制备:每15-40克的钢渣原料RSS对应添加200-800毫升的水杨酸-甲醇SAM混合溶液中,其中水杨酸-甲醇SAM混合溶液中水杨酸浓度为100-300g/L,搅拌均匀后使用0.45μm滤纸过滤,滤渣干燥,用超纯水反复洗涤,得到水杨酸-甲醇改性的钢渣SAM-RSS;
(2)已处理钢渣TSS的制备:将水杨酸-甲醇改性的钢渣SAM-RSS与NaOH混合,钢渣SAM-RSS与NaOH的质量比1:1-2:1,500-600℃加热1.5-3h进行碱焙烧,碱焙烧的目的是通过形成可溶性金属钠盐过滤掉Si、Al、Cr、V等大部分杂质元素,碱性焙烧渣被命名为已处理钢渣TSS;
(3)复合结构的光催化剂的制备:已处理钢渣添加到浓度1.0-3.0mol/L NH4Cl水溶液中,每0.2-0.5g已处理钢渣对应20-50毫升NH4Cl水溶液,在150-200℃水热反应18-36h,然后所得的表层为镁掺杂四氧化三铁的钢渣,记为MSS,用去离子水洗涤和干燥,保存在干燥器中。
4.按照权利要求3的方法制备得到的复合结构的光催化剂。
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