CN106552507A - 利用电解铝灰铝渣同时脱除电解铝烟气中hf、so2的方法 - Google Patents
利用电解铝灰铝渣同时脱除电解铝烟气中hf、so2的方法 Download PDFInfo
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Abstract
本发明公开一种利用电解铝灰铝渣同时脱除电解铝烟气中HF、SO2的方法，该方法以电解铝灰铝渣制成的浆液作为吸收剂，在常温常压下对电解铝烟气中的HF、SO2进行液相催化氧化，达到同时脱除电解铝烟气中HF、SO2的目的；本发明方法是通过铝灰铝渣所含的金属氧化物及过渡金属离子的催化氧化作用实现烟气中HF、SO2的脱除；本发明制备方法简单，原材料储量极大、易得、成本低廉、易实现工业化应用、脱除效果好，副产品氟化铝能回收利用，实现以废治废，清洁生产。
Description
技术领域
本发明涉及一种利用电解铝灰铝渣同时脱氟脱硫的方法，属工业废气处理领域。
背景技术
近几年我国铝工业迅猛发展，产量持续增加，已成为世界上第一大铝生产国和铝消费国。电解铝生产过程中SO2排放污染也日益突出，同时排放的废气中含有HF。电解铝烟气具有“大烟气量、低SO2浓度、含氟等特点”。治理和回收电解铝烟气中的SO2和氟化物，并实现资源化利用，是当今世界铝工业的一个难题。此外，炼铝时产生的铝灰铝渣是一种产量大、污染严重的工业废渣。铝灰铝渣是在氧化铝熔盐电解生产的过程中产生，含有大量的金属铝，其中只有部分铝能得到回收，剩余的废铝灰铝渣堆积在厂区或填埋，不仅造成资源的浪费，同时也带来环境的污染。因此，对于铝灰铝渣的经济效益、环境污染的迫切要求等使得其回收显得额外重要。
近年来，电解铝烟气脱氟脱硫一体化技术受到了各方的重视，期望能找到一种空间利用率高、运行管理成本低、脱除效率高、能回收副产物提高经济性的脱氟脱硫一体化技术。中国发明CN102080235A公开了一种电解铝SO2、CO2及含氟烟气循环利用生产冰晶石的方法，利用含NaOH 5-60％的水溶液密闭循环吸收电解铝生产过程中产生的含SO2、CO2、HF及Al2O3粉尘的烟气，吸收后液中的NaF与Al(OH)3在20-90℃反应1-8小时，然后经常规方式冷却结晶、沉降、过滤、干燥后得到电解铝生产用冰晶石。这种方法由于采用了大量的碱性吸收液，易造成设备腐蚀，投资成本高。
中国发明CN102228775A公开了一种电解铝烟气脱硫脱氟一体化方法，即：在氨法脱硫过程中，洗涤吸收塔吸收SO2的同时将F-离子吸收溶解在系统内硫酸铵溶液中，形成氟化铵；在硫酸铵晶粒分离时，氟化铵仍溶解在硫酸铵溶液中，将硫酸铵晶体分离的液体进行脱氟处理，将脱氟产物冰晶石及氧化铝粉尘过滤回收，并循环利用。该方法存在工艺流程复杂、吸收剂成分复杂，产生的废液难以处理等问题。
发明内容
本发明的目的在于提供一种新型、更加环保的同时脱氟、脱硫的方法，即以铝灰铝渣浆作为吸收剂，在常温常压下对HF、SO2催化氧化，用于脱除有色冶炼烟气中SO2、HF；所述铝灰铝渣浆是将铝灰铝渣烘干、粉碎、筛分后与水混合制得，铝灰铝渣浆含固量为质量百分比10%~60%。
所述烘干温度为80~100℃。
所述筛分至100~400目。
所述铝灰铝渣为电解铝灰铝渣，电解铝灰铝渣是铝电解过程中产生的一种浮渣，在电解过程中漂浮于电解槽铝液的上表面，由电解过程中未参加反应的氧化铝、冰晶石等原料及混合物组成，也包括与添加剂进行化学反应产生的少量其他杂质及阴阳极材料的脱落，其与其他重金属熔炼产生的炉渣不同，呈松散的灰渣状，因此又被称为铝灰铝渣。由于电解过程是连续进行的，因此铝灰铝渣的产生量较大，电解铝灰铝渣的成分比较复杂。成分如表1所示：
表1：电解铝灰铝渣组分
铝灰铝渣中的Al2O3、CaO、MgO、FeO、SiO2等金属氧化物，使得铝灰铝渣具有很好的吸附能力，且其中的碱性氧化物能与尾气中的SO2发生中和反应。反应如下：
Na2O + SO2 → Na2SO3
Al(OH)3 + SO2 → Al(SO4)3
CaO + SO2 + 2H2O = CaSO3·2H2O
Al2O3能和尾气中的HF反应生成AlF3，AlF3在工业上有多种用途，例如在铝电解工业中用以降低电解质的熔化温度和提高导电率，用作非铁金属的熔剂，陶瓷釉和搪瓷釉的助熔剂和釉药的组分，以及精油生产中副发酵作用的抑止剂。在金属焊接中用于焊接液，用于制造光学透镜等。Al2O3和HF反应方式如下：
Al2O3+6HF=2AlF3+3H2O
除此之外，铝灰铝渣中含有多种有色金属，如Al、Fe、Mn、Zn等，具有液相催化氧化的特性，本发明利用其中的金属氧化物和过渡金属离子对冶炼烟气中的HF、SO2催化氧化，该方法理论上不消耗催化剂，不产生固体废物，无二次污染，是一种更为环保的工业废气处理工艺，不仅能实现多种污染物联合脱除，还能达到以废治废，实现清洁生产，具有明显的社会与经济效益。
本发明的有益效果：
相较于现有的技术，本发明原材料来源广，制备方法简单；材料的制备和应用都易实现工业化；应用过程中能耗低；在常温常压下即可实现对HF、SO2的有效吸收；液相催化氧化效果好，不易中毒；不需要添加任何化学试剂，直接利用铝灰铝渣中所含的Al、Fe等过渡金属离子与及金属氧化物就可以达到较为理想的脱除效果，且在电解铝生产的过程中，直接利用生产废料对生产废气进行处理，生产、治废一体化，实现清洁生产。
附图说明
图1为实施例1所述铝灰铝渣同时脱氟、脱硫效果图；
图2为实施例2所述铝灰铝渣同时脱氟、脱硫效果图；
图3为实施例3所述铝灰铝渣同时脱氟、脱硫效果图；
图4为实施例4所述铝灰铝渣同时脱氟、脱硫效果图。
具体实施方式
下面结合具体实施例及附图对本发明进一步的详细说明，但本发明保护范围不限于此。
实施例1
将取自云南铝业的铝灰铝渣，在80℃下烘干，然后研磨并筛分成200~400目；将所得粉末与自来水按一定比例混合，混合后铝灰铝渣浆含固量为质量百分比15%；将气体通过含铝灰铝渣浆的气体吸收瓶；吸收剂用量为56mL；进气SO2浓度为500mg/L，HF浓度为10mg/L。两种污染物同时脱除效果见图1所示，当选用云南铝业的铝灰铝渣，制成含固量为15%的浆液后，测得吸收90min内，烟气中SO2浓度<20mg/L，HF浓度<2.5mg/L。SO2平均去除率>96%，HF平均去除率>75%。
实施例2
将取自云南铝业的铝灰铝渣，在90℃下烘干，然后研磨并筛分成300~400目；将所得粉末与自来水按一定比例混合，混合后铝灰铝渣浆含固量为质量百分比45%；将气体通过含铝灰铝渣浆的气体吸收瓶；浆液用量为56mL；进气SO2浓度为200mg/L，HF浓度为20mg/L。两种污染物同时脱除效果见图2所示，当选用云南铝业的铝灰铝渣，制成含固量为45%的浆液后，测得吸收90min内，烟气中SO2浓度<10mg/L，HF浓度<4mg/L。SO2平均去除率>90%，HF平均去除率>80%。
实施例3
将取自云南铝业的铝灰铝渣，在100℃下烘干，然后研磨并筛分成200~300目；将所得粉末与自来水按一定比例混合，混合后铝灰铝渣浆含固量为质量百分比60%；将气体通过含铝灰铝渣浆的气体吸收瓶；浆液用量为56mL；进气SO2浓度为300mg/L，HF浓度为30mg/L。两种污染物同时脱除效果见图3所示，当选用云南铝业的铝灰铝渣，制成含固量为60%的浆液后，测得吸收90min内，烟气中SO2浓度<10mg/L，HF浓度<4.5mg/L。SO2平均去除率>90%，HF平均去除率>85%。
实施例4
将取自云南文山铝业的铝灰铝渣，在80℃下烘干，然后研磨并筛分成100~300目；将所得粉末与自来水按一定比例混合，混合后铝灰铝渣浆含固量为质量百分比45%；将气体通过含铝灰铝渣浆的气体吸收瓶；浆液用量为56mL；进气SO2浓度为300mg/L，HF浓度为30mg/L。两种污染物同时脱除效果见图4所示，当选用云南文山铝业的铝灰铝渣，制成含固量为45%的浆液后，测得吸收90min内，烟气中SO2浓度<6mg/L，HF浓度<2mg/L。SO2平均去除率>98%，HF平均去除率>87%。
Claims (4)
1.一种利用电解铝灰铝渣同时脱除电解铝烟气中HF、SO2的方法，其特征在于：以电解铝灰铝渣制成的浆液作为吸收剂，在常温常压下对电解铝烟气中的HF、SO2进行液相催化氧化。
2.根据权利要求1所述的利用电解铝灰铝渣同时脱除电解铝烟气中HF、SO2的方法，其特征在于：吸收剂是将电解铝灰铝渣烘干、粉碎、筛分后与水混合制得，吸收剂含固量为质量百分比10%~60%。
3.根据权利要求2所述的利用电解铝灰铝渣同时脱除电解铝烟气中的HF、SO2方法，其特征在于：烘干温度为80~100℃。
4.根据权利要求2所述的利用电解铝灰铝渣同时脱除电解铝烟气中HF、SO2的方法，其特征在于：筛分至100~400目。
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