CN110813257B - 同步去除水中硝酸盐和高氯酸盐的磁性吸附催化材料的制备及使用方法 - Google Patents
同步去除水中硝酸盐和高氯酸盐的磁性吸附催化材料的制备及使用方法 Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 42
- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 39
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 39
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 title claims abstract description 39
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 title claims abstract description 38
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 40
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000007885 magnetic separation Methods 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 13
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- 150000002940 palladium Chemical class 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims 1
- 239000010941 cobalt Substances 0.000 abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052763 palladium Inorganic materials 0.000 abstract description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 6
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
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- 239000003651 drinking water Substances 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
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- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
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- 210000002249 digestive system Anatomy 0.000 description 1
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- 230000009939 endogenous nitrosation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
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- 235000013305 food Nutrition 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
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- 235000013336 milk Nutrition 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
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- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid 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 physical properties
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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Abstract
本发明涉及一种同步去除水中硝酸盐和高氯酸盐的磁性吸附催化材料的制备及使用方法。该材料的制备方法是首先制备具有超顺磁性能的铁氧化物基体,然后采用共沉淀法将镁盐和铁盐,以及能够起到催化作用的钴和钯金属盐溶液与碱液同步滴加到磁性基体溶液中沉淀形成钴和钯修饰的具有磁性的吸附材料。负载于基体上的Pd/Co经过还原为零价态后,能够促使通入水体的氢气放出电子,同时为吸附于材料上的硝酸盐和高氯酸盐提供电子从而促使硝酸盐和高氯酸盐的降解。该材料对水中硝酸盐和高氯酸盐有吸附和催化降解双重作用,有极高的吸附催化活性,同时具有可磁分离循环使用特征、且在宽pH值范围内有高效催化性能,反应过程友好清洁,无二次污染的发生。
Description
技术领域
本发明属于水体污染控制技术领域和无机功能材料制备技术领域,涉及一种用钴和钯修饰的磁性镁铁基吸附催化剂的制备及去除水中硝酸盐和高氯酸盐污染物的使用方法,具有反应效率高,成本低廉,过程绿色清洁,无二次污染物等优点。
背景技术
我国由于农业生产中氮素化肥的广泛使用以及含氮工业废水的大量排放,导致地下水中硝酸盐污染日趋严重。2017年10月27日,世界卫生组织国际癌症研究机构(IARC)整理公布了致癌物清单,其中在导致内源性亚硝化条件下摄入的硝酸盐或亚硝酸盐在2A类致癌物清单中。当人体摄入大量硝酸盐时,其在人体中由硝酸盐还原酶作用转化为亚硝酸盐,致使人体极易患上高铁血红蛋白症,还有极大的可能发生消化系统癌变,对人体健康造成严重威胁。欧盟规定的地下水硝酸盐氮质量浓度的最大饮用标准为11.3mg/L,而我国环境保护部对地表水源生活饮用水的最大限制为10mg/L,并规定集中式饮用水水源地下水的硝酸盐氮最大质量浓度为20mg/L。
高氯酸盐是一种有毒的无机化学物质,水溶性极高,在地表水或地下水系统中流动性非常强,很难在有氧条件下进行生物降解,由于其性质稳定和不易分解,可能会在正常环境条件下存在几年或几十年,是具有高扩散性和持久性的有毒污染物质。在世界各地的水环境、饮用水和牛奶、蔬菜等食品中均检测到不同程度的高氯酸盐污染。较低浓度的高氯酸盐即可干扰人体的甲状腺功能,从而影响人体正常的代谢,危害人体健康。据美国环保署(EPA)报道,高氯酸盐已于1998年初被列入饮用水候选污染物名单(CCL),且在2005年规定高氯酸盐在饮用水中的标准为24.5μg/L。
由于硝酸盐和高氯酸盐在水环境中存在较为广泛,对人体危害较大,且通过自来水厂常规的混凝,沉淀,过滤和消毒的处理工艺难以有效的去除,所以制备一种能够将其有效去除的吸附材料是十分必要的。根据现有研究结果表明,能够将硝酸盐和高氯酸盐有效吸附去除的材料少之又少且吸附效率低下。此外,在吸附过程中为了加强吸附材料与污染物的接触面积,往往把吸附材料研磨成粉末态,因而在吸附完成后很难将其取出,导致二次污染问题,所以找到一种不仅对硝酸盐和高氯酸盐有着较大吸附容量,且较容易在吸附完成之后将其取出的材料是研究的重点。
发明内容
本发明针对上述需求,制备出一种能够同步去除水中硝酸盐和高氯酸盐的磁性吸附催化剂及其使用方法。该催化剂通过外加磁场吸附,能够快速进行固液分离,具有良好的应用价值。
本发明采用共沉淀法制备镁铁基阴离子吸附材料,引入具有超顺磁性能的铁氧化物,以达到快捷磁分离回收和循环使用的目的;同时,本发明在形成稳定的铁氧化物之后,通过共沉淀技术引入优选的钴和钯金属盐,使之与镁盐和铁盐共沉淀,通过空气煅烧和氢气下还原得到钴和钯修饰的具有磁性的材料。负载于基体上的Pd/Co经过还原为零价态后,能够促使通入水体的氢气放出电子,同时为吸附于材料上的硝酸盐和高氯酸盐提供电子从而促使含氧酸盐的降解。该催化剂对水中硝酸盐和高氯酸盐进行了吸附和化学催化降解两个过程,有高的催化活性,同时具有可磁分离循环使用特征、且在宽pH值范围内有高效催化性能。
为实现如上所述目的,本发明所述的吸附催化材料,由含Mg2+、Fe2+、Fe3+、Pd2+和Co2 +盐溶液(所述的Mg2+、Fe2+、Fe3+、Pd2+和Co2+盐为氯盐,硝酸盐,硫酸盐中的至少一种),含NaOH或KOH、Na2CO3或K2CO3的碱溶液经如下步骤制备而成:
(1)按Fe2+/Fe3+的摩尔比为1:2称取Fe2+,Fe3+盐配制成的盐溶液,亚铁盐浓度范围为0.16~800mmol/L,在温度为20~60℃下将5~40%的氨水逐滴加入上述溶液,剧烈搅拌,调节pH为9~13。将生成的沉淀物在上述温度下陈化10~720min,然后利用磁分离装置将上述得到的油黑色沉淀用去离子水反复洗涤至中性,置于盛有去离子水的瓶中为待用液A。
(2)按照Mg2+与Fe3+的摩尔比为5:1~2:1称取镁盐和铁盐,铁盐浓度范围为4 ~1600mmol/L。称取少量Co2+与Pd2+盐与上述溶液混合,Co2+与Pd2+的摩尔比为1:1~9:1,钯盐浓度范围为0.25~100mmol/L,该混合盐溶液为B溶液。
(3)称取NaOH和KOH的一种或两种,Na2CO3和K2CO3的一种或两种,其中OH-浓度范围为32mmol/L~12.8mol/L,CO3 2-浓度范围为2~800mmol/L,混合配置成碱溶液C。
(4)将上述B,C两种溶液逐滴加入A中,控制温度30~90℃,控制pH为9~13,剧烈搅拌,滴定完成之后继续搅拌1~4h。将上述沉淀产物于水浴中晶化12~24h,控制水浴温度为15~95℃。利用磁分离装置将晶化产物用去离子水反复洗涤至其电导率于2ms以下,产品在50~105℃下干燥。
(5)上述干燥产物置于马弗炉中,在350~800℃条件下煅烧,冷却后将煅烧产物研磨至粉末状;然后放入管式炉中,在H2气氛、100~400℃条件下还原煅烧产物60~300min,取出后冷却至室温,待用。
制备出的磁性吸附催化材料去除水中硝酸盐和高氯酸盐的应用方法如下:
(1)将该材料以1g/L~10g/L的投加量加入待处理的含硝酸盐和高氯酸盐的溶液中,反应体系密闭,通入氢气,H2流量为10~1000ml/min,保持溶液混合均匀,充分反应后,采用磁分离装置将混合液固液分离,回收材料。对于硝酸盐和高氯酸盐污染程度较严重的水体,可采用加大材料投加量及氢气流量或采取二次或者二次以上催化反应进行处理。
与现有技术相比,本发明的有益效果如下:
(1)本发明涉及的一种用于去除水中硝酸盐和高氯酸盐的磁性吸附催化材料,采用共沉淀法制备而成,既可以对水中硝酸盐和高氯酸盐进行吸附去除和催化转化,同时其本身又具备磁性,从而能够通过磁分离装置在反应完成之后较为简便的从水体中分离出来;
(2)本发明涉及的一种用于去除水中硝酸盐和高氯酸盐的磁性吸附催化材料在水环境中通过结构重建可吸附大量阴离子,从而有利于硝酸盐和高氯酸盐的吸附去除;
(3)本发明涉及的一种用于去除水中硝酸盐和高氯酸盐的磁性吸附催化材料在水环境中通过其吸附性能将硝酸盐和高氯酸盐污染物吸附于材料表面,同时依靠钴、钯催化位点促使通入的氢气放出电子而已被吸附的污染物在催化位点得到电子,从而实现硝酸盐和高氯酸盐的降解。上述过程中氢气作为电子供体,无二次污染物产生,过程绿色清洁。
具体实施方式
下面通过具体的实施方案叙述本发明,应理解这些实施例仅用于说明本发明而不用于限制本发明的范围,在阅读了本发明之后,本领域技术人员对本发明的各种等价形式的修改均落入本申请所附权利要求所限定的范围内。
实施例1
一种吸附与催化去除水中硝酸盐和高氯酸盐污染物的制备方法如下:
(1)制备磁性基质,氯化亚铁与氯化铁摩尔比为1:2,其中氯化亚铁浓度为30mmol/L,逐滴滴加10%的氨水并调节pH为9±1,陈化30min后用去离子水反复洗涤至中性;配制盐溶液A,氯化镁与氯化铁的摩尔比为3:1,其中氯化铁浓度为100mmol/L,氯化钴与氯化钯的摩尔比为1:2,其中氯化钯浓度为6.3mmol/L,分别溶解后混合;再配制碱溶液B,氢氧化钠浓度为0.8mol/L,碳酸钠浓度为50mmol/L,完全混合;
(2)在充分搅拌并控制温度为30±1℃的条件下,将盐溶液A与碱溶液B逐滴加入磁性基质中,并调节pH值为10±1,共沉淀完成之后继续搅拌2h;将上述产物于恒温水浴锅中晶化24h,并控制水浴温度为45±1℃;
(3)晶化完成后,将上述沉淀物冷却至室温,然后利用磁分离装置对晶化产物进行处理,同时用去离子水反复洗涤至其电导率在300μs以下,随后在50℃的环境下干燥完全;
(4)将上述干燥产物置于马弗炉中,在500℃条件下煅烧5h,冷却后将煅烧产物研磨并过100目筛,得到粉末状材料;将上述粉末状材料放入管式炉中,通入H2和N2的流速分别为50mL/min和150mL/min,并在200℃条件下保持120min,取出后冷却至室温,即获得磁性吸附催化材料。
将上述磁性吸附催化材料应用于去除硝酸盐和高氯酸盐:
对于初始浓度为20mg N/L的NaNO3和20mg/L的NaClO4受污溶液,投加上述磁性吸附催化材料1g/L,使用磁力搅拌器不断搅拌使其混合均匀,并控制温度为25℃,120min后,对硝酸盐和高氯酸盐单独吸附去除率分别为58%和67%。
对于初始浓度为20mg N/L的NaNO3和20mg/L的NaClO4受污溶液,投加上述磁性吸附催化材料1g/L,使用磁力搅拌器不断搅拌使其混合均匀,并控制温度为25℃,以50mL/min的产氢流量通入氢气,混合反应时间为180min,之后通过磁分离装置系统进行固液分离,两种污染物去除率分别为95%和90%。
实施例2
一种吸附与催化去除水中硝酸盐和高氯酸盐污染物的制备方法如下:
(1)制备磁性基质,氯化亚铁与氯化铁摩尔比为1:2,其中氯化亚铁浓度为240mmol/L,逐滴滴加40%的氨水并调节pH为12±1,陈化60min后用去离子水反复洗涤至中性;配制盐溶液A,硝酸镁与硝酸铁的摩尔比为3:1,其中硝酸铁浓度为800mmol/L,氯化钴与氯化钯的摩尔比为1:2,其中氯化钯浓度为50mmol/L,分别溶解后混合;再配制碱溶液B,氢氧化钾浓度为6.4mol/L,碳酸钾浓度为400mmol/L,完全混合;
(2)在充分搅拌并控制温度为50±1℃的条件下,将盐溶液A与碱溶液B逐滴加入磁性基质中,并调节pH值为12±1,共沉淀完成之后继续搅拌4h;将上述产物于恒温水浴锅中晶化18h,并控制水浴温度为65±1℃;
(3)晶化完成后,将上述沉淀物冷却至室温,然后利用磁分离装置对晶化产物进行处理,同时用去离子水反复洗涤至其电导率在300μs以下,随后在70℃的环境下干燥完全;
(4)将上述干燥产物置于马弗炉中,在500℃条件下煅烧5h,冷却后将煅烧产物研磨至粉末状并过100目筛,得到粉末状材料;将上述粉末状材料放入管式炉中,通入H2和N2的流速分别为50mL/min和150mL/min,并在200℃条件下保持120min,取出后冷却至室温,即获得磁性吸附催化材料。
将上述磁性吸附催化材料应用于去除硝酸盐和高氯酸盐:
对于浓度为40mg N/L的NaNO3和30mg/L的NaClO4溶液,投加上述磁性吸附催化材料5g/L,使用磁力搅拌器不断搅拌使其混合均匀,并控制温度为25℃,120min后,对硝酸盐和高氯酸盐单独吸附去除率分别为75%和86%。
对于浓度为40mg N/L的NaNO3和30mg/L的NaClO4溶液,投加上述磁性吸附催化材料5g/L,使用磁力搅拌器不断搅拌使其混合均匀,并控制温度为25℃,用氢气发生器以100mL/min的产氢流量通入氢气,改变混合反应时间为240min,之后通过磁分离装置系统进行固液分离,两种污染物去除率分别为96%和92%。
Claims (3)
1.一种用于去除水中硝酸盐和高氯酸盐的磁性吸附催化材料的制备方法,其特征在于:由含Mg2+、Fe2+、Fe3+、Pd2+和Co2+的盐溶液,含NaOH或KOH、Na2CO3或K2CO3的碱溶液经如下步骤制备而成:
(1)按Fe2+/Fe3+的摩尔比为1:2称取Fe2+、Fe3+盐配制成的盐溶液,亚铁盐浓度范围为0.16~800mmol/L,在温度为20~60℃下将5~40%的氨水逐滴加入上述溶液,剧烈搅拌,调节pH为9~13,将生成的沉淀物在上述温度下陈化10~720min,然后利用磁分离装置将上述得到的油黑色沉淀用去离子水反复洗涤至中性,置于盛有去离子水的瓶中为待用液A;
(2)按照Mg2+与Fe3+的摩尔比为5:1~2:1称取镁盐和铁盐,铁盐浓度范围为4~1600mmol/L,称取少量Co2+与Pd2+盐与上述溶液混合,Co2+与Pd2+的摩尔比为1:1~9:1,钯盐浓度范围为0.25~100mmol/L,该混合盐溶液为B溶液;
(3)称取NaOH和KOH的一种或两种,Na2CO3和K2CO3的一种或两种,其中OH-浓度范围为32mmol/L~12.8mol/L,CO3 2-浓度范围为2~800mmol/L,混合配置成碱溶液C;
(4)将上述B,C两种溶液逐滴加入A中,控制温度为30~90℃,控制pH为9~13,剧烈搅拌,滴定完成之后继续搅拌1~4h;将上述沉淀产物于水浴中晶化12~24h,控制水浴温度为15~95℃;然后利用磁分离装置将晶化产物用去离子水反复洗涤至其电导率于2ms以下,产物在50~105℃下干燥;
(5)上述干燥产物置于马弗炉中,在350~800℃条件下煅烧,冷却后将煅烧产物研磨至粉末状;然后放入管式炉中,在H2气氛、100~400℃条件下还原煅烧产物60~300min,取出后冷却至室温,待用。
2.根据权利要求1中所述的一种用于去除水中硝酸盐和高氯酸盐的磁性吸附催化材料的制备方法,其特征在于,所述的Mg2+、Fe2+、Fe3+、Pd2+和Co2+盐为氯盐,硝酸盐,硫酸盐中的至少一种。
3.根据权利要求1所述制备方法制备得到的用于去除水中硝酸盐和高氯酸盐的磁性吸附催化材料的应用,其特征在于:将材料以1g/L~10g/L的投加量加入待处理的含硝酸盐和高氯酸盐的溶液中,反应体系密闭,通入氢气,H2流量为10~1000mL/min,保持溶液混合均匀,充分反应后,采用磁分离装置将混合液固液分离,回收材料。
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