CN114177879B - 一种纳米硒等离子体改性的陶瓷纳米汞吸附材料的制备方法 - Google Patents
一种纳米硒等离子体改性的陶瓷纳米汞吸附材料的制备方法 Download PDFInfo
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 61
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 59
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 32
- 239000011669 selenium Substances 0.000 title claims abstract description 32
- 239000000919 ceramic Substances 0.000 title claims abstract description 31
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims description 24
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 230000004888 barrier function Effects 0.000 claims abstract description 16
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 229940091258 selenium supplement Drugs 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000010802 sludge Substances 0.000 claims description 8
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229960001471 sodium selenite Drugs 0.000 claims description 3
- 235000015921 sodium selenite Nutrition 0.000 claims description 3
- 239000011781 sodium selenite Substances 0.000 claims description 3
- 150000002730 mercury Chemical class 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 230000008929 regeneration Effects 0.000 abstract description 6
- 238000011069 regeneration method Methods 0.000 abstract description 6
- 239000002912 waste gas Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 208000028659 discharge Diseases 0.000 description 15
- 229920006395 saturated elastomer Polymers 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 12
- 239000003546 flue gas Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
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- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
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- 150000003254 radicals Chemical group 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- 229910010293 ceramic material Inorganic materials 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 2
- 238000012163 sequencing technique Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000005495 cold plasma Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 230000016615 flocculation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
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- 238000004062 sedimentation Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
本发明公开了一种纳米硒等离子体改性的陶瓷纳米汞吸附材料的制备方法,在常温常压下,将陶瓷纳米汞吸附材料采用介质阻挡放电的方式对多层吸附材料层进行等离子体改性,制得纳米硒等离子体改性的陶瓷纳米汞吸附材料。本发明改性后材料的吸附容量增大,比表面积增大,汞吸附位点增加,进一步提升含汞废气、含汞废水的深度处理,材料的再生能力增加,可实现多次再生,相应降低材料成本。
Description
技术领域
本发明属于汞吸附材料技术领域,尤其涉及一种纳米硒等离子体改性的陶瓷纳米汞吸附材料的制备方法。
背景技术
目前含汞废气主要以吸附、吸收为主。吸附剂主要包括活性炭、载银活性炭等,一般活性炭存在吸附效果差、吸附饱和后仍属于危险废物等问题,载银活性炭成本高,不能大规模使用;吸收方法主要以高锰酸钾溶液吸收、碘络合吸收法、硫化钠+氯络合法等,但都不用于实现达标排放。含汞废水主要以沉降/絮凝法、吸附法、膜过滤法、离子交换法、生物方法等为主,普遍存在处理效果不佳、成本较高等问题。等离子体可起到高热源和化学活性粒子的双重作用,可以在没有催化剂的存在下就可以直接加速开始反应,以及给予反应提供足够的能量,是一种高效率、低能耗的对天然气的裂解的方法。并且与传统的工艺相比,等离子体技术具有生产规模灵活,没有污染,催化剂可用可不用,投资少,转化率高,反应迅速等特点。因此需要一种纳米硒等离子体改性的陶瓷纳米汞吸附材料的制备方法。
发明内容
本发明提供一种操作简单的纳米硒等离子体改性的陶瓷纳米汞吸附材料的制备方法。
本发明一种纳米硒等离子体改性的陶瓷纳米汞吸附材料的制备方法,在常温常压下,将陶瓷纳米汞吸附材料采用介质阻挡放电的方式对多层吸附材料层进行等离子体改性,制得纳米硒等离子体改性的陶瓷纳米汞吸附材料。
作为优选,所述介质阻挡放电的参数为电压为3-5kV、频率为20kHz的脉冲电流。
作为优先,所述纳米硒在是在好氧颗粒污泥反应器内以亚硒酸钠为硒源还原得到的,反应器内污泥浓度为3000mg/L,污泥体积指数为33.6mL/g。序批式颗粒污泥反应器在22-25℃和近中性pH下运行。
作为优选,在介质阻挡放电等离子体反应器的密闭内腔中通入由氦气和甲烷气按照体积比为7:13混合而成的混合气体,混合气体的流量为2L/min,然后通过脉冲电源装置对介质阻挡放电等离子体反应器内施加电流,并保持5-30分钟,
一种纳米硒等离子体改性的陶瓷纳米汞吸附材料,包括第一吸附材料层、第二吸附材料层和第三吸附材料层,所述第一吸附材料层、第二吸附材料层和第三吸附材料层依次堆叠设置,所述所述第一吸附材料层的Hg2+的饱和吸附容量为3.6mg/g,比表面积128m2/g,烟气中汞排放浓度<0.01mg/m3,所述第二吸附材料层:Hg0的饱和吸附容量为6mg/g,比表面积120m2/g,,烟气中汞排放浓度<0.01mg/m3,所述第三吸附材料层:Hg2+的饱和吸附容量为5mg/g,比表面积180m2/g,可至少再生5次。烟气中汞排放浓度<0.01mg/m3。
一种纳米硒等离子体改性的陶瓷纳米汞吸附材料脱除汞中的应用,包括以下步骤:将含有汞的气体通入装有纳米硒等离子体改性的陶瓷纳米汞吸附材料的反应器中,在60~90℃下实现汞的脱除;
本发明的有益效果为:
本发明改性后材料的吸附容量增大,比表面积增大,汞吸附位点增加,进一步提升含汞废气、含汞废水的深度处理,材料的再生能力增加,可实现多次再生,相应降低材料成本。
具体实施方式
以下对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
在本实施例子中:
一种纳米硒等离子体改性的陶瓷纳米汞吸附材料的制备方法,在常温常压下,将陶瓷纳米汞吸附材料采用介质阻挡放电的方式对多层吸附材料层进行等离子体改性,制得纳米硒等离子体改性的陶瓷纳米汞吸附材料,所述介质阻挡放电的参数为电压为4kV、频率为20kHz的脉冲电流,在介质阻挡放电等离子体反应器的密闭内腔中通入由氦气和甲烷气按照体积比为7:13混合而成的混合气体,混合气体的流量为2L/min,然后通过脉冲电源装置对介质阻挡放电等离子体反应器内施加电流,并保持5-30分钟。
所述纳米硒在是在好氧颗粒污泥反应器内以亚硒酸钠为硒源还原得到的,反应器内污泥浓度为3000mg/L,污泥体积指数为33.6mL/g。序批式颗粒污泥反应器在22-25℃和近中性pH下运行。
等离子体可实现材料改性。对于汞离子印迹材料,汞吸附容量可达到36579μg/g,陶瓷纳米吸附材料Hg2+的饱和吸附容量为5mg/g,可至少再生5次。为进一步提高汞的吸附效果,实现含汞废气、含汞废水中汞的深度净化及达标排放,调节等离子体电压、电流、频率等关键参数,实现材料的纳米硒修饰,充分利用汞与硒的高亲和性,提高材料对汞的吸附容量。
低温等离子体对材料进行改性,电子和离子的能量可达10eV以上,处理温度为常温,可应用于表面聚合、表面接枝、冶金、表面催化、化学合成及各种粉、粒、片材料的表面改性。
低温等离子体参数
实施例子1选用陶瓷纳米管作为催化载体:吸附材料层:Hg2+的饱和吸附容量为3.6mg/g,比表面积128m2/g,可至少再生3次。烟气中汞排放浓度<0.01mg/m3,也可应用于水体中Hg2+的吸附。
实施例子2选用碳纳米管作为催化载体吸附材料层:Hg0的饱和吸附容量为6mg/g,比表面积120m2/g,可至少再生4次。烟气中汞排放浓度<0.01mg/m3。
实施例子3选用纳米硒管作为催化载体吸附材料层:Hg2+的饱和吸附容量为5mg/g,比表面积180m2/g,可至少再生5次。烟气中汞排放浓度<0.01mg/m3,也可应用于水体中Hg2+的吸附。
通过实施例子1-3在吸附反应的前两个小时纳米硒的吸附速率非常快,吸附容量迅速增加而且大约有一半的镉离子在15min内被吸附去除。在随后的6h内,吸附容量还是在逐步增加,但是增加速率远远小于前两个小时。整个吸附反应在8h时达到吸附平衡,这时的吸附容量为32.2mg/g。为确保反应达到吸附平衡,将后续开展的吸附实验的反应时间定为10h。反应开始阶段吸附速率非常快是因为溶液中镉离子浓度高,纳米硒上有充足的活性位点,镉离子可以被迅速吸附到位点上;随着反应的进行,吸附剂上的活性位点越来越少,导致镉离子不容易吸附结合。另外,在反应进行到最后,整个体系达到吸附-解析平衡,镉离子含量在固液两相达到平衡。
根据吸附等温线数据,我们可以得到吸附过程的焓变(△Ho)、熵变(Aso)以及吉布斯自由能变(AGo)。。当AGo<0,表明u(vI)在PTFG.4上的吸附过程是自发的,并且其值随着温度升高,其值是逐渐变小的,这表明温度升高有利于U(VI)吸附。此外,AHo>0,表明了PTFG.4对u(v1)的去除过程是吸热的,温度的上升可以增加吸热反应的程度,这和等温线实验结果是吻合的。这可能是因为u(vI)以水合离子形式达到
吸附剂表面时,u(vI)需要能量才能够脱去这些结合的水分子,而这些所需的能量又远高于u(vI)与材料表面官能团反应所释放的能量,所以PTFG一4对u(vI)的去除过程是吸热的。另外,△So>0,这表明吸附过程是熵驱动的,这表明u(vI)
吸附到PTFG.4表面上时,固一液界面的自由度有所提高,因此吸附过程是一个自发的吸热过程。
纳米硒具有强烈的亲汞特性,其与硫相比硒与汞亲和能力更高,其平衡常数为1045,是硫汞亲和力的百万倍,同时红硒具有纳米结构的强活性特征,因此,将其应用于汞污染防治领域具有较大的应用前景。
冷等离子体装置,在密封容器中设置特定的电极形成电场,分子间距及分子或离子的自由运动距离也愈来愈长﹐它们在电场作用下发生碰撞而形成等离子体;因这时会发出辉光.故称为辉光放电。辉光放电时的气压大小对材料处理效果有很大影响﹐其他影响因素还有放电功率、气体成分.材料类型等。电源作为等离子体发生装置的主要部件﹐功率范围一般在50~500W之间﹐根据电源频率的不同可分为直流.低频(50Hz.~50kHz),射频(指定频率13.56MHz)微波(常用2450MHz)。
纳米改性陶瓷汞吸附的粒子具有比表面积效应和小尺寸效应,可以作为常用的催化载体。陶瓷长径比巨大且独特的中空管状结构,表现出特殊的表面效应和电子效应,都是良好的催化剂载体的有利方面。选用陶瓷纳米管作为催化载体l61',能大幅度的提高催化剂的活性和选择性,大多数气体通过陶瓷纳米管的扩散速度很快,是常规催化剂颗粒的上千倍。
等离子体是部分电离的气体,系统主要由带电粒子(电子、正离子、负离子等)组成,在外部电场、磁场、电磁场的影响,等离子体放电过程中受存在多种基元反应,具有独特的电、光、热等物理性质,可以对材料进行表面改性。这些粒子能量的参数范围如下:电子0-20ev,亚稳态粒子0-2ev,离子0.03-0.05ev,光子3-40ev。等离子体在处理材料表面的过程中,高速电子可以使反应的分子电离、激发或者断裂成自由基碎片。正离子和一些能与材料表面的一些分子结合的中性原子对材料的表面有一定的刻蚀作用,还有一些中性原子和自由基会在材料表面沉积形成沉积层。
在介质阻挡放电等离子体反应器上,氢气在氩气氛围下受到高能电子及电场的激发而转化为激发态,成为电子供体,陶瓷在等离子体的作用下接受激发态的氢气所提供的电子,从而价态降低转化为Magneli态(低价态的氧化钛即TiOx)。与正常态的陶瓷不同,经过介质阻挡放电处理后而形成的Magneli态氧化钛由于价态更低,因而具有更小的禁带宽度(2.6eV),因而具有吸收可见光的性能。此外,介质阻挡放电所产生的的高能电子可以净化陶瓷材料中的杂质,修饰其表面结构,最终导致纳米陶瓷具有更多的孔隙结构和更大的比表面积,从而有利于改性后的陶瓷实现高效的光催化作用。料的表面有一定的刻蚀作用,还有一些中性原子和自由基会在材料表面沉积形成沉积层。
本发明改性后材料的吸附容量增大,比表面积增大,汞吸附位点增加,进一步提升含汞废气、含汞废水的深度处理,材料的再生能力增加,可实现再生8次,相应降低材料成本。
改性前,对于陶瓷纳米材料:Hg2+的饱和吸附容量为3.6mg/g,比表面积128m2/g,可至少再生5次。可用于烟气、水体中汞的去除;对于陶瓷纳米材料:Hg0的饱和吸附容量为6.0mg/g,比表面积120m2/g,可至少再生4次。可用于烟气中汞的去除;对于活性炭吸附材料:Hg的饱和吸附容量为1.0mg/g,比表面积180m2/g。可用于烟气、水体中汞的去除。
改性前,对于陶瓷纳米材料:Hg2+的饱和吸附容量为4.8mg/g,比表面积140m2/g,可至少再生5次。可用于烟气、水体中汞的去除;对于陶瓷纳米材料:Hg0的饱和吸附容量为7.2mg/g,比表面积130m2/g,可至少再生5次。可用于烟气中汞的去除;对于活性炭吸附材料:Hg的饱和吸附容量为1.3mg/g,比表面积210m2/g。可用于烟气、水体中汞的去除。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都涵盖在本发明的保护范围之内。
Claims (2)
1.一种纳米硒等离子体改性的陶瓷纳米汞吸附材料在脱除汞中的应用,其特征在于:将含有汞的气体通入装有纳米硒等离子体改性的汞吸附材料的反应器中,在60~90℃下实现汞的脱除,所述纳米硒等离子体改性的陶瓷纳米汞吸附材料是在常温常压下,将陶瓷纳米汞吸附材料采用介质阻挡放电的方式进行等离子体改性制得,所述介质阻挡放电的参数为电压为3-5kV、频率为20kHz的脉冲电流,在介质阻挡放电等离子体反应器的密闭内腔中通入由氦气和甲烷气按照体积比为7:13混合而成的混合气体,混合气体的流量为2L/min,然后通过脉冲电源装置对介质阻挡放电等离子体反应器内施加电流,并保持5-30分钟。
2.根据权利要求1所述的应用,其特征在于,所述纳米硒是在好氧颗粒污泥反应器内以亚硒酸钠为硒源还原得到的,反应器内污泥浓度为3000mg。
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