CN117023753A - 一种鸟粪石结构除铊剂及高效稳定重金属铊的方法 - Google Patents
一种鸟粪石结构除铊剂及高效稳定重金属铊的方法 Download PDFInfo
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- 229910052716 thallium Inorganic materials 0.000 title claims abstract description 88
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims abstract description 75
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical group [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 10
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 13
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 13
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 12
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- 229910052567 struvite Inorganic materials 0.000 claims description 16
- -1 ammonium ions Chemical class 0.000 claims description 15
- 239000002351 wastewater Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 10
- 239000001103 potassium chloride Substances 0.000 claims description 9
- 235000011164 potassium chloride Nutrition 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 238000005342 ion exchange Methods 0.000 abstract description 10
- 239000007791 liquid phase Substances 0.000 abstract description 3
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- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
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- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000031404 Chromosome Aberrations Diseases 0.000 description 1
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 1
- 230000006820 DNA synthesis Effects 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
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- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明涉及一种鸟粪石结构除铊剂及高效稳定重金属铊的方法,所述鸟粪石结构除铊剂以钾盐或铵盐与可溶性镁盐、可溶性磷酸盐为原料,经化学反应或机械力球磨制备得到,其有效成分化学式为KMgPO4·6H2O或NH4MgPO4·6H2O。本发明提供的鸟粪石结构除铊剂与TI+进行离子交换反应速率快,能达到摩尔当量的交换量,除铊过程中不释放有害物质,离子交换后的产物稳定性好,除铊效率高,为液相中高浓度Tl+的固定化提供了一种简便方法。
Description
技术领域
本发明属于采用离子交换法对水、废水或污水的处理技术领域,具体涉及一种鸟粪石结构除铊剂及高效稳定重金属铊的方法。
背景技术
铊(Tl)是一种典型的分散型剧毒元素,其毒性远远超过常见的铜(Cu2+)、铅(Pb2 +)、锌(Zn2+),甚至高于砷(As3+)以及有机汞(C-Hg)。Tl元素具有亲硫性与亲石性两种特性,因此常伴生于含Cu/Pb/Zn的硫化物矿床或者含钾/锂元素的伟晶岩矿床中。其元素特性具体表现为Ag+与K+两种特性。因此在两种矿床的开采及冶炼过程中均会将含Tl废弃物排入环境中,最终在雨水浸淋、地质风化以及人类其它工业活动作用下排放到水环境中。人体通过消化道、呼吸系统或者皮肤触碰等方式摄取含Tl废水后,Tl+通过与半径相似的K+竞争,最终与体内巯基蛋白或者核黄素结合,干扰DNA合成,导致染色体畸变,甚至会直接对人体器官造成损伤。而水相中的Tl主要有+1和+3两种氧化态,其中以6s2排布的+1价态最为稳定,因此水相中高迁移性、难固定的Tl+是目前需要处理的重中之重。
目前对Tl+的处理有吸附法、沉淀法、离子交换法为主。吸附法主要是利用碳基、合成有机类材料等对含Tl+的废水进行处理,处理方法简单方便、速率快。但是这类材料面临的最大问题是对Tl+的吸附往往不够稳定,且吸附材料使用前需要对其进行硫化改性或者有机负载等,这会导致药剂的浪费甚至会带来二次污染。沉淀法主要是以硫化沉淀以及氧化沉淀为主,硫化沉淀主要是利用Tl+的亲硫性质并最终以Tl2S形式沉淀,处理工艺与传统的重金属处理工艺相似,但是该过程所涉及大量Na2S的投加以及H2S的产生会带来成本的升高,且具有安全隐患。而氧化沉淀主要是利用铁锰型氧化物对迁移性较强的Tl+进行氧化处理,使其转化为较为稳定的Tl3+,然后再进行沉淀处置,该方法通过降低Tl+的迁移性来缓解饮用水中铊威胁,但是氧化效率不够理想,引入的锰元素也是一个危险因素,使其在工业上推广具备难度。目前离子交换法是对含Tl+废水处理的一个热点研究,通过交换材料中可交换离子与废水中Tl+理论上可以达到摩尔当量上的交换,最终对废水中Tl+进行稳定,该法具有绿色环保、无二次污染等优势。常见的研究是通过合成一价的离子交换材料如普鲁士蓝、水钠锰矿等,通过结构中的NH4 +/K+/Na+等离子与Tl+进行交换,最终Tl+以稳定配体的形式固定在结构中。但是目前这些材料实际应用中交换量较小,未达到摩尔级别的置换。
基于上述背景,本发明以KCl、NH4Cl、MgCl2·6H2O、Na3PO4等常见化合物为原材料,通过控制合适的反应条件,无需外加碱源或晶体生长辅助,制备得到鸟粪石结构除铊剂,利用该除铊剂对废水中的Tl+可以达到Tl+-K+/NH4 +之间摩尔当量上的交换去除,最终铊以TlMgPO4·6H2O的形式沉淀。
发明内容
本发明所要解决的技术问题是针对现有技术中存在的上述不足,提供一种鸟粪石结构除铊剂及高效稳定重金属铊的方法,该除铊剂对铊离子具有优异的选择性,有望解决目前有色矿产或含锂矿石开采过程中带来的铊污染问题。
为解决上述技术问题,本发明提供的技术方案是:
提供一种鸟粪石结构除铊剂,其以钾盐或铵盐与可溶性镁盐、可溶性磷酸盐为原料,经化学反应或机械力球磨制备得到,其有效成分化学式为KMgPO4·6H2O或NH4MgPO4·6H2O。
按上述方案,所述钾盐为氯化钾、硝酸钾、硫酸钾中的一种,所述铵盐为氯化铵或硫酸铵,所述可溶性镁盐为氯化镁、硫酸镁、硝酸镁中的一种,所述可溶性磷酸盐为磷酸三钠。
按上述方案,所述钾盐中的钾离子或铵盐中的铵根离子与可溶性镁盐中镁离子、可溶性磷酸盐中磷酸根离子的摩尔比为1:1~5:1~5。
本发明还包括上述鸟粪石结构除铊剂的制备方法,具体步骤如下:将钾盐或铵盐与可溶性镁盐、可溶性磷酸盐溶于水中,常温(15~35℃)搅拌反应得到鸟粪石结构除铊剂;或
将钾盐或铵盐与可溶性镁盐、可溶性磷酸盐置于球磨机中球磨,然后将得到的粉末用清水进行清洗,再阴干得到鸟粪石结构除铊剂。
按上述方案,所述钾盐或铵盐与可溶性镁盐、可溶性磷酸盐的总质量与水的体积比为0.01~0.02g/mL,常温搅拌反应时间为1~4h。
按上述方案,所述球磨工艺条件为:以水为溶剂,在200~400r转速下球磨1~4h。
本发明还包括利用上述鸟粪石结构除铊剂高效稳定重金属铊的方法,具体步骤如下:调节含TI+废水的pH值为5~11,然后将所述鸟粪石结构除铊剂加入到含TI+废水中进行搅拌反应,鸟粪石结构除铊剂的掺入量为1~2g/L,搅拌反应时间为0.5~6h。
按上述方案,所述含TI+废水中TI+浓度为1~200mg/L。
本发明合成鸟粪石结构除铊剂,涉及的化学反应方程式如下:
KCl+MgCl2·6H2O+Na3PO4·12H2O→KMgPO4·6H2O+3NaCl+12H2O(1)
NH4Cl+MgCl2·6H2O+Na3PO4·12H2O→NH4MgPO4·6H2O+3NaCl+12H2O(2)
使用上述鸟粪石结构除铊剂除去废水中TI+的原理是基于鸟粪石结构除铊剂中的K+/NH4 +与废水中的Tl+发生离子交换反应生成稳定的沉淀从而被固定,反应
方程式如下:
KMgPO4 ·6H2O + Tl+ → TlMgPO4·6H2O + K+ (3)
NH4MgPO4 ·6H2O + Tl+ → TlMgPO4 ·6H2O + NH4 + (4)
本发明使用常见的无毒化合物为原料通过简单化学反应或球磨法一步合成钾-鸟粪石与氨-鸟粪石,钾-鸟粪石或氨-鸟粪石能够与TI+进行离子交换,在适当的反应条件下,Tl+可以在摩尔浓度水平上被NH4MgPO4·6H2O或KMgPO4·6H2O中的NH4 +/K+取代,最终TI+以TlMgPO4·6H2O固溶体的形式存在于结构中。
本发明的有益效果在于:1、本发明提供的鸟粪石结构除铊剂与TI+进行离子交换反应速率快,能达到摩尔当量的交换量,除铊过程中不释放有害物质,离子交换后的产物稳定性好,除铊效率高,为液相中高浓度Tl+的固定化提供了一种简便方法。2、本发明以常见无毒化合物为原材料通过调控适当反应条件合成钾/氨型鸟粪石,合成过程中不需要外加碱源,反应步骤简单,反应条件温和,成本低,具有工业化应用前景。3、与传统除铊方法相比,本发明稳定重金属铊的方法不需要将Tl+氧化为Tl3+,成本低廉,且反应速率快,离子交换后的产物稳定性好,除铊效率高,绿色无二次污染,Tl+的固定量高,反应步骤简单,反应条件温和。
附图说明
图1为本发明实施例1以及实施列2所制备的鸟粪石结构除铊剂的XRD图;
图2为实施例1、实施例4和实施例5所制备的鸟粪石结构除铊剂的XRD图;
图3为实施例1、实施例4和实施例5所制备的鸟粪石结构除铊剂的铊去除率对比图;
图4为实施例1和实施例4所制备的鸟粪石结构除铊剂对不同浓度的铊离子溶液的铊去除率对比图;
图5为实施例1所制备的鸟粪石结构除铊剂处理不同浓度的铊离子溶液后Tl+固定率与NH4 +溶出率对比图;
图6为实施例1所制备的鸟粪石结构除铊剂处理不同浓度的铊离子溶液前后XRD对比图;
图7为实施例1所制备的鸟粪石结构除铊剂的SEM-EDS扫描图;
图8为实施例1所制备的鸟粪石结构除铊剂处理浓度为1000mg/L的铊离子溶液后的SEM-EDS扫描图。
具体实施方式
为使本领域技术人员更好地理解本发明的技术方案,下面结合附图对本发明作进一步详细描述。
本发明实施例所用KCl、NH4Cl、MgCl2·6H2O、Na3PO4·12H2O购自国药集团,为分析纯。所用硝酸铊(TlNO3)标准母液为西格玛奥德里奇公司提供,浓度为1000mg/L。
实施例1
一种鸟粪石结构除铊剂,其制备方法如下:将总质量为2g的NH4Cl与MgCl2·6H2O、Na3PO4·12H2O溶于100mL水中,其中NH4Cl与MgCl2·6H2O、Na3PO4·12H2O的摩尔比为1:1:1,常温搅拌反应1h得到鸟粪石结构除铊剂(NH4MgPO4·6H2O)。
实施例2
一种鸟粪石结构除铊剂,其制备方法如下:将总质量为2g的KCl与MgCl2·6H2O、Na3PO4·12H2O溶于100mL水中,其中KCl与MgCl2·6H2O、Na3PO4·12H2O的摩尔比为1:1:1,常温搅拌反应1h得到鸟粪石结构除铊剂(KMgPO4·6H2O)。
如图1所示为实施例1和本实施例制备的产品的XRD图,显示得到的产物具有鸟粪石结构,可以看出,得到的产物分别为氨-鸟粪石和钾-鸟粪石,纯度较高。
量取1mL浓度为1000mg/L的硝酸铊母液定容到100mL烧杯中进行稀释,配制成初始浓度为10mg/L的铊离子溶液,然后将实施例1和本实施例制备的两种鸟粪石结构除铊剂按2g/L的投加量加入,进行固铊试验,震荡时长为4h,反应后静置10min,取上清液用火焰原子吸收分光光度计测量溶液中TI离子浓度,钾-鸟粪石和氨-鸟粪石对铊去除率分别为68.37%与67.07%。
实施例3
一种鸟粪石结构除铊剂,其制备方法如下:称取总质量为2g的原料粉体(KCl与MgCl2·6H2O、Na3PO4·12H2O)加入配备7颗直径为15mm锆球的二氧化锆材质的研磨罐中,球料比为35:1,KCl与MgCl2·6H2O、Na3PO4·12H2O的摩尔比为1:1:1,并加入去离子水为溶剂,原料粉体与去离子水质量比为1:1,设定球磨机转数为400rpm,球磨时间为1h,球磨结束后将物料取出用100mL去离子水进行清洗,然后过滤并阴干,将粉末收集,得到鸟粪石结构除铊剂,为钾-鸟粪石(KMgPO4·6H2O)。
实施例4
一种鸟粪石结构除铊剂,其制备方法如下:称取总质量为2g的原料粉体(NH4Cl与MgCl2·6H2O、Na3PO4·12H2O)加入配备7颗直径为15mm锆球的二氧化锆材质的研磨罐中,球料比为35:1,NH4Cl与MgCl2·6H2O、Na3PO4·12H2O的摩尔比为1:1:1,并加入去离子水为溶剂,原料粉体与去离子水质量比为1:1,设定球磨机转数为400rpm,球磨时间为1h,球磨结束后将物料取出用100mL去离子水进行清洗,然后过滤并阴干,将粉末收集,得到鸟粪石结构除铊剂,为氨-鸟粪石(NH4MgPO4·6H2O)。
实施例5
一种鸟粪石结构除铊剂,其制备方法与实施例4相似,不同之处在于设定球磨机转数为200rpm/h。
实施例1、实施例4和本实施例制备的氨-鸟粪石的XRD图如图2所示,可以看出,三个实施例得到的产品均为氨-鸟粪石结构,但各产物之间的晶体结晶相有所不同,实施例1合成的结晶度相明显好于实施例4和本实施例采用球磨法制备的产物。实施例4和本实施例相比可以看出,随着球磨转速的增加会导致其结晶度降低。
使用1000mg/L的硝酸铊母液进行稀释配制成10mg/L的铊离子溶液,各取25mL Tl+溶液,分别与实施例1、实施例4和本实施例合成的NH4MgPO4·6H2O样品(投加量2g/L)同置于具塞容器中进行震荡反应,震荡时长为4h,反应后静置10min,取上清液运行火焰原子吸收分光光度计测量溶液中Tl+浓度,据此计算铊去除率,测试结果如图3所示,可以看出,实施例1合成的NH4MgPO4·6H2O样品对TI+的去除率可以达到91.32%,实施例4和实施例5样品对TI+的去除率分别为67.07%,87.17%。与图2中合成样品的XRD图进行对照,说明合成样品的结晶度越高,越有利于TI+的固定。
使用1000mg/L的硝酸铊母液进行稀释配制得到不同浓度的铊离子溶液(1mg/L,10mg/L,50mg/L,100mg/L,200mg/L,1000mg/L),各取25mL Tl+溶液与上述实施例1和实施例4合成的NH4MgPO4·6H2O样品同置于具塞容器中进行震荡反应,样品投加量为2g/L,震荡时长为4h,反应后静置10min,测定液相中残余Tl+浓度,并计算铊去除率,测试结果如图4所示,其中左边纵坐标代表反应后Tl+的残余浓度,右边的纵坐标代表Tl+去除率,横坐标代表Tl+的初始浓度,蓝色的线对应实施例1样品,黄色的线代表实施例4样品,可以看出实施例1合成的NH4MgPO4·6H2O在1~200mg/L的Tl+溶液中对Tl+的固定率均在80%以上,优于实施例4球磨合成的样品。对实施例1合成样品在不同浓度的铊离子溶液中反应后溶液中NH4 +的浸出量进行测定,并与被固定的Tl+进行对比,结果如图5所示,可以看出,随着Tl+交换量的增加,NH4 +的浸出量也随之增加,这说明随着Tl+被不断固定,NH4 +也在按比例不断溶出,表示以接近1:1摩尔当量的形式进行了NH4 +-Tl+交换。
对实施例1制备的NH4MgPO4·6H2O在上述不同浓度的铊离子溶液(100mg/L,200mg/L,1000mg/L)中进行固定之后的残渣进行XRD分析,并与未参与反应的产品进行对比,结果如图6所示,可以看出,与未参与反应的产品进行对比,随着Tl+浓度的增加,残渣的峰逐渐减弱,且逐渐发生偏移,因为固定了投加量,所以随着Tl+初始浓度不断增加,可以进入鸟粪石结构中的铊的含量也随着增加,表现在图6中就是与未参与反应的样品相比,进行固定反应后样品的XRD的峰的位置和强度随着铊离子溶液浓度的增加而逐渐变化,NH4MgPO4·6H2O逐渐转变为TlMgPO4·6H2O。
对实施例1制备的样品在Tl+固定反应前后进行了SEM-EDS测试,研究了不同放大倍数条件下NH4MgPO4·6H2O的形貌,图7为实施例1合成的样品的SEM-EDS图片,结合之前图1和图2的XRD分析,表明所合成的NH4MgPO4·6H2O是鸟粪石的纯相,不含其他杂质,可以看出,样品呈现长棒状形貌(图7a-c),进一步放大棒状材料(图7d-f)显示合成的NH4MgPO4·6H2O表面相对光滑。图7中g为全元素扫描图,h为样品原图,i-l分别为测试的O、P、Mg、Tl四种元素的分布图,m为元素含量分布图,n为元素含量分布表,可知,合成样品由71.62wt%的O、13.51wt%的Mg和13.82wt%的P组成,不含Tl(m中Tl含量为1.04%为测试误差),符合理论预期值。
图8为实施例1合成的鸟粪石结构除铊剂处理上述浓度为1000mg/L的铊离子溶液后的样品的SEM-EDS扫描图,与图7对比可以看出,经Tl+处理后,NH4MgPO4·6H2O的形貌和元素分布发生了显著变化,其中图8a-b显示了样品放大倍数为500倍的形貌,并且可以看到棒变粗,证明Tl+粘附在鸟粪石的表面,通过进一步放大到10000倍,可以清楚地观察到混沌态物质附着在棒状鸟粪石表面,如图8c-f所示。图8中g为全元素扫描图,h为样品原图,i-l分别为测试的O、P、Mg、Tl四种元素的分布图,m为元素含量分布图,n为元素含量分布表,从图中可以看出,Tl的分布与O、Mg、P的分布相关,在O、Mg、P集中的地方Tl分布也较密集,且Tl呈均匀分布,与图7对比,表明Tl+在NH4MgPO4·6H2O表面的吸附是均匀的。
Claims (8)
1.一种鸟粪石结构除铊剂,其特征在于,其以钾盐或铵盐与可溶性镁盐、可溶性磷酸盐为原料,经化学反应或机械力球磨制备得到,其有效成分化学式为KMgPO4·6H2O或NH4MgPO4·6H2O。
2.根据权利要求1所述的鸟粪石结构除铊剂,其特征在于,所述钾盐为氯化钾、硝酸钾、硫酸钾中的一种,所述铵盐为氯化铵或硫酸铵,所述可溶性镁盐为氯化镁、硫酸镁、硝酸镁中的一种,所述可溶性磷酸盐为磷酸三钠。
3.根据权利要求1所述的鸟粪石结构除铊剂,其特征在于,所述钾盐中的钾离子或铵盐中的铵根离子与可溶性镁盐中镁离子、可溶性磷酸盐中磷酸根离子的摩尔比为1:1~5:1~5。
4.一种权利要求1-3任一项所述的鸟粪石结构除铊剂的制备方法,其特征在于,具体步骤如下:将钾盐或铵盐与可溶性镁盐、可溶性磷酸盐溶于水中,常温搅拌反应得到鸟粪石结构除铊剂;或
将钾盐或铵盐与可溶性镁盐、可溶性磷酸盐置于球磨机中球磨,然后将得到的粉末用清水进行清洗,再阴干得到鸟粪石结构除铊剂。
5.根据权利要求4所述的鸟粪石结构除铊剂的制备方法,其特征在于,所述钾盐或铵盐与可溶性镁盐、可溶性磷酸盐的总质量与水的体积比为0.01~0.02g/mL,常温搅拌反应时间为1~4h。
6.根据权利要求4所述的鸟粪石结构除铊剂的制备方法,其特征在于,所述球磨工艺条件为:以水为溶剂,在200~400r转速下球磨1~4h。
7.一种利用权利要求1-3任一项所述的鸟粪石结构除铊剂高效稳定重金属铊的方法,其特征在于,具体步骤如下:调节含TI+废水的pH值为5~11,然后将所述鸟粪石结构除铊剂加入到含TI+废水中进行搅拌反应,鸟粪石结构除铊剂的掺入量为1~2g/L,搅拌反应时间为0.5~6h。
8.根据权利要求7所述的利用鸟粪石结构除铊剂高效稳定重金属铊的方法,其特征在于,所述含TI+废水中TI+浓度为1~200mg/L。
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