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 PDF

Info

Publication number
CN114177879B
CN114177879B CN202111539210.4A CN202111539210A CN114177879B CN 114177879 B CN114177879 B CN 114177879B CN 202111539210 A CN202111539210 A CN 202111539210A CN 114177879 B CN114177879 B CN 114177879B
Authority
CN
China
Prior art keywords
mercury
nano
adsorption
selenium
adsorption material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111539210.4A
Other languages
English (en)
Other versions
CN114177879A (zh
Inventor
陈扬
冯钦忠
刘俐媛
杨世童
郭剑波
王通哲
张秀锦
崔皓
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Chinese Academy of Sciences
Original Assignee
University of Chinese Academy of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Chinese Academy of Sciences filed Critical University of Chinese Academy of Sciences
Priority to CN202111539210.4A priority Critical patent/CN114177879B/zh
Publication of CN114177879A publication Critical patent/CN114177879A/zh
Priority to NL2033523A priority patent/NL2033523B1/en
Application granted granted Critical
Publication of CN114177879B publication Critical patent/CN114177879B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/288Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033Membrane, sheet, cloth, pad, lamellar or mat
    • B01J20/28035Membrane, sheet, cloth, pad, lamellar or mat with more than one layer, e.g. laminates, separated sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057Surface area, e.g. B.E.T specific surface area
    • B01J20/28061Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3085Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204Inorganic carriers, supports or substrates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3295Coatings made of particles, nanoparticles, fibers, nanofibers
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10Inorganic adsorbents
    • B01D2253/102Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25Coated, impregnated or composite adsorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30Physical properties of adsorbents
    • B01D2253/302Dimensions
    • B01D2253/306Surface area, e.g. BET-specific surface
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/60Heavy metals or heavy metal compounds
    • B01D2257/602Mercury or mercury compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/08Nanoparticles or nanotubes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Nanotechnology (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

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

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
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。
CN202111539210.4A 2021-12-15 2021-12-15 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 Active CN114177879B (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202111539210.4A CN114177879B (zh) 2021-12-15 2021-12-15 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
NL2033523A NL2033523B1 (en) 2021-12-15 2022-11-14 Method for preparing ceramic nano-mercury adsorption material modified by nano-selenium plasma

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111539210.4A CN114177879B (zh) 2021-12-15 2021-12-15 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

Publications (2)

Publication Number Publication Date
CN114177879A CN114177879A (zh) 2022-03-15
CN114177879B true CN114177879B (zh) 2023-11-21

Family

ID=80605227

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111539210.4A Active CN114177879B (zh) 2021-12-15 2021-12-15 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

Country Status (2)

Country Link
CN (1) CN114177879B (zh)
NL (1) NL2033523B1 (zh)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003093518A1 (en) * 2002-05-06 2003-11-13 Nelson Sidney G Jr Sorbents and methods for the removal of mercury from combustion gases
CN102553527A (zh) * 2011-12-20 2012-07-11 华北电力大学(保定) 一种改性碳纳米管材料、用于吸附气态元素汞的方法及其再生方法
CN106984269A (zh) * 2017-05-13 2017-07-28 重庆工商大学 自组装低温等离子体改性提高活性炭性能的方法
CN109200742A (zh) * 2018-11-27 2019-01-15 中国科学院北京综合研究中心 一种生活垃圾焚烧烟气的处理系统及处理方法
CN109569551A (zh) * 2018-11-27 2019-04-05 中国科学院北京综合研究中心 一种负载纳米硒的纳米陶瓷材料的制备方法与再生方法
CN109831867A (zh) * 2019-01-31 2019-05-31 中国农业科学院农业质量标准与检测技术研究所 一种介质阻挡放电装置及其汞分析方法
CN110170301A (zh) * 2019-05-31 2019-08-27 贵州重力科技环保有限公司 原位级纳米硒非炭基脱汞吸附材料制备方法及材料和应用
CN112169757A (zh) * 2020-09-29 2021-01-05 上海交通大学 一种低温等离子体改性碳纳米管及其在水处理中的应用
CN112191226A (zh) * 2020-08-31 2021-01-08 山东大学 一种低温等离子体改性制备脱汞吸附剂的方法及应用

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003093518A1 (en) * 2002-05-06 2003-11-13 Nelson Sidney G Jr Sorbents and methods for the removal of mercury from combustion gases
CN102553527A (zh) * 2011-12-20 2012-07-11 华北电力大学(保定) 一种改性碳纳米管材料、用于吸附气态元素汞的方法及其再生方法
CN106984269A (zh) * 2017-05-13 2017-07-28 重庆工商大学 自组装低温等离子体改性提高活性炭性能的方法
CN109200742A (zh) * 2018-11-27 2019-01-15 中国科学院北京综合研究中心 一种生活垃圾焚烧烟气的处理系统及处理方法
CN109569551A (zh) * 2018-11-27 2019-04-05 中国科学院北京综合研究中心 一种负载纳米硒的纳米陶瓷材料的制备方法与再生方法
CN109831867A (zh) * 2019-01-31 2019-05-31 中国农业科学院农业质量标准与检测技术研究所 一种介质阻挡放电装置及其汞分析方法
CN110170301A (zh) * 2019-05-31 2019-08-27 贵州重力科技环保有限公司 原位级纳米硒非炭基脱汞吸附材料制备方法及材料和应用
CN112191226A (zh) * 2020-08-31 2021-01-08 山东大学 一种低温等离子体改性制备脱汞吸附剂的方法及应用
CN112169757A (zh) * 2020-09-29 2021-01-05 上海交通大学 一种低温等离子体改性碳纳米管及其在水处理中的应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Plasma Induced Addition of Active Functional Groups to Biochar for Elemental Mercury Removal;Huicong Zhang et al.;Plasma Chemistry and Plasma Processing;第39卷;第1449-1468页 *
低温等离子体--陶瓷纳米材料集成系统烟气脱汞研究;魏石豪 等;环境工程;第35卷(第11期);第94-98、154页 *

Also Published As

Publication number Publication date
NL2033523A (en) 2023-06-27
CN114177879A (zh) 2022-03-15
NL2033523B1 (en) 2024-01-08

Similar Documents

Publication Publication Date Title
Zhang et al. Carbothermal reduction for preparing nZVI/BC to extract uranium: insight into the iron species dependent uranium adsorption behavior
Babaei et al. Comparative treatment of textile wastewater by adsorption, Fenton, UV-Fenton and US-Fenton using magnetic nanoparticles-functionalized carbon (MNPs@ C)
Sheth et al. Prospects of titanium carbide-based MXene in heavy metal ion and radionuclide adsorption for wastewater remediation: a review
Zhang et al. Removal of nickel ions from wastewater by Mg (OH) 2/MgO nanostructures embedded in Al2O3 membranes
WO2021258515A1 (zh) 柚子皮生物碳应用于催化臭氧氧化降解废水中的有机污染物
CN111921536B (zh) 一种基于天然矿物和生物质制备的新型催化吸附材料
CN111151304A (zh) 三维MXene/MOF水凝胶的制备及其在水处理方面的应用
CN112169757A (zh) 一种低温等离子体改性碳纳米管及其在水处理中的应用
CN112808233A (zh) 一种Fe3O4-生物炭复合纳米材料的制备方法及降解水体有机污染物的方法
Wei et al. Efficient photocatalytic oxidation of methane over β-Ga 2 O 3/activated carbon composites
CN112978983B (zh) 基于铁基生物炭的重金属络合废水处理及其资源化工艺
Wang et al. Highly efficient adsorptive removal of persistent organic pollutants using NPD-acid combined modified NaY zeolites
Dong et al. Physicochemical and porosity characteristics of thermally regenerated activated carbon polluted with biological activated carbon process
Ji et al. Adsorption of cerium (III) by zeolites synthesized from kaolinite after rare earth elements (REEs) recovery
CN112340830A (zh) 以吸附-解析后的废弃吸附剂为原料的催化剂在活化过硫酸盐处理高盐有机废水中应用
Han et al. Efficient activation of persulfate by calcium sulfate whisker supported nanoscale zero-valent iron for methyl orange removal
CN111729654A (zh) 一种改性槐树叶生物炭的制备方法及其应用
CN114177879B (zh) 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
CN114835477B (zh) 一种多功能净水陶瓷材料
Guo et al. Highly dispersed FeN-CNTs heterogeneous electro-Fenton catalyst for carbamazepine removal with low Fe leaching at wide pH
Wang et al. Efficient removal of sulfamethoxazole by biomass phosphorus-derived Cu3P/biochar catalyst combined with persulfate
Ren et al. The study on adsorption behavior of 2, 4-DCP in solution by biomass carbon modified with CTAB-KOH
CN111701602B (zh) 一种复合催化剂及制备方法和其应用
Zhao et al. Adsorptive behavior of prepared metal-organic framework composites on phosphates in aqueous solutions
CN114054027A (zh) 一种具有磁分离性能的石墨类材料改性赤泥基类芬顿催化剂及其制备方法和应用

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant