CN104043409B - A synchronous phosphorus and iron enrichment fixing film and its production method - Google Patents

A synchronous phosphorus and iron enrichment fixing film and its production method Download PDF

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CN104043409B
CN104043409B CN 201310076971 CN201310076971A CN104043409B CN 104043409 B CN104043409 B CN 104043409B CN 201310076971 CN201310076971 CN 201310076971 CN 201310076971 A CN201310076971 A CN 201310076971A CN 104043409 B CN104043409 B CN 104043409B
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CN104043409A (en )
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丁士明
许笛
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中国科学院南京地理与湖泊研究所
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一种同步富集磷和铁的固定膜,是由包含水合氢氧化锆粉末、Chelex‑100阳离子交换树脂和聚丙烯酰胺的成膜液胶凝制成的凝胶薄膜。 Phosphorus and iron a synchronous fixed film enrichment, by containing a hydrated zirconium hydroxide powders, Chelex-100 cation exchange resin forming a liquid gel and polyacrylamide gel film formed. 其制作方法是,将水合氢氧化锆粉末和Chelex树脂及聚丙烯酰胺水溶液充分混合,制成均匀的膜液,加入适量四甲基二乙胺和过硫酸铵后,将该膜液注入玻璃模具中,在2‑4℃低温下水平放置,使得氢氧化锆和Chelex自由沉降后,再升温至45±5℃放置,直到膜液胶凝成膜。 Its production method, the mixed powder of hydrated zirconium hydroxide and an aqueous solution of polyacrylamide and Chelex resin, a film made of a uniform solution, adding an appropriate amount of diethylamine and tetramethyl ammonium persulfate, the mixture was poured into a glass mold the film allowed to stand at a low temperature level of 2-4 deg.] C, such that the zirconium hydroxide and the free settling Chelex, then warmed to place 45 ± 5 ℃, until the membrane was gelled film. 本发明的固定膜能够同步富集磷酸根和二价铁离子,富集容量高,可进行环境样品中磷和铁离子的高分辨同步分析。 Film of the present invention is capable of fixing phosphate and divalent iron ions synchronization enrichment, highly enriched capacity, environmental samples may be phosphorus and high resolution analysis of iron ions synchronization.

Description

一种同步富集磷和铁的固定膜及其制作方法 A synchronous phosphorus and iron enrichment fixing film and its production method

技术领域 FIELD

[0001 ] 本发明涉及一种薄膜扩散梯度技术(Diffusive gradients in thin films,DGT)中的固定膜及其制备方法,适用于环境介质中磷和铁的富集和分析,尤其涉及一种环境分析中同步富集磷和铁的固定膜及其制作方法。 [0001] The present invention relates to a thin film diffusion gradient technique (Diffusive gradients in thin films, DGT) a fixed film and method, environmental media suitable for enrichment and analysis of phosphorus and iron, in particular, relates to an environmental analysis Simultaneous phosphorus and iron enrichment of the fixed film and its production method.

背景技术 Background technique

[0002]磷和铁均是水体环境中重要的生源要素。 [0002] phosphorus and iron are important biogenic elements in the aquatic environment. 磷是造成水体富营养化的关键限制性元素,水体磷含量的升高,是造成蓝藻过度生长和藻华形成的主要原因。 Phosphorus is a critical limiting element causing eutrophication, the phosphorus content of water increases, the main cause algal blooms of cyanobacteria overgrowth and formation. 铁结合态磷是沉积物和淹水土壤中磷的主要赋存形态之一。 Phosphorus is one of the iron-bound sediment and the main Forms flooded soil phosphorus. 这些磷被吸附到(氢)氧化铁表面,当氧化铁在缺氧条件下被还原成二价铁时,吸附到氧化铁上的磷将释放出来,造成沉积物磷对水体的二次污染。 These phosphorus is adsorbed to the (hydro) surface of iron oxide, when the iron oxide is reduced to ferrous iron under anaerobic conditions, phosphorous adsorbed to the iron oxide will be released, causing secondary sediment phosphorus polluted water. 因此,研究磷和铁两者耦合关系,是揭示沉积物磷污染过程和机制的核心内容之一,同步高分辨获取两者的空间分布信息,则为开展相关研究提供重要的技术支撑。 Therefore, the study of the relationship between the two coupling phosphorus and iron, is one of the core processes and mechanisms of sediment pollution revealed phosphorus, both synchronous high-resolution spatial distribution of information acquisition, research was conducted to provide important technical support.

[0003]对水体沉积物中活性磷和铁的测定主要采取主动方式,将沉积物从水体中取出后,送回实验室进行分析。 [0003] Determination of the activity of phosphorus and iron sediments mainly proactive manner, the sediment from the water removed and returned to the laboratory for analysis. 由于沉积物在水体的自然条件下处于还原环境,取出后极易发生变化,造成分析误差。 Since deposits in a reducing environment under natural conditions in the body of water, easily removed after the change, resulting in analysis error. 目前发展的被动采样技术,如薄膜扩散梯度技术,将能吸收磷或铁等元素的固定膜插入沉积物中,原位富集磷或铁,再将固定膜取出后,通过分析固定膜上的磷或铁,间接获取沉积物中活性磷或铁的信息。 Currently passive sampling development, diffusion gradient thin film techniques, the film can absorb a fixed element such as phosphorus or iron sediments insertion, phosphorus or iron enrichment in situ, and then removed after the film is fixed, by analyzing the fixing film phosphorus or iron, the information obtained indirectly sediments active phosphorus or iron.

[0004]薄膜扩散梯度技术(Diffusive gradients in thin films,DGT)是一种非破坏性、原位获取沉积物中污染物分布和活性的技术,能够利用固定膜富集并测定沉积物活性磷或铁,但目前DGT测定中所用的固定膜绝大部分为单一吸收功能的固定膜,即只能吸收磷或铁,不能同步吸收和富集磷和铁,造成分析测定效率低下,同时运行成本高。 [0004] The diffusion gradient thin film technology (Diffusive gradients in thin films, DGT) is a non-destructive, in-situ contaminant acquisition and distribution of active technique sediments, and can be measured using the fixed membrane-enriched sediment or reactive phosphorus iron, but most of the current fixed-film DGT assay used a single fixed absorbing function film, i.e. iron or phosphorus absorption only, and not synchronize absorb phosphorus and iron-rich, resulting in low Determination efficiency, high operating costs .

[0005] 201210208540X公开了一种同步富集磷(P043—)和硫(S2—)的固定膜及其制作方法,采用水合氢氧化锆(ZrO)和碘化银为固定剂,分别对磷和硫离子产生吸附和沉淀作用,由于这两种不同作用不会产生干扰,因此该固定膜可同步富集磷和硫,且单一富集量不受两种固定剂叠加的影响。 [0005] 201210208540X discloses a synchronous enrichment phosphorus (P043-) and sulfur (S2-) in the fixed film and a manufacturing method using hydrated zirconium hydroxide (of ZrO) and silver iodide as the fixing agent, and sulfide ions are phosphorus generating adsorption and precipitation, since this does not interfere with the two different effect, so that the fixing film may be synchronized enriched phosphorus and sulfur, and is not affected by a single enrichment superposed two kinds of fixing agents. 目前,尚没有见到同步固定磷和铁(Fe2+)的固定膜及其制作方法。 Currently, there is no synchronization see the fixed film fixed phosphorus and iron (Fe2 +) and its manufacturing method. 单一功能的磷固定膜主要采用水合氢氧化错、氢氧化铁和Metsorb作为磷的固定剂,单一吸收功能的铁固定膜通常采用Chelex-100为固定剂。 Phosphorus fixed film single function mainly wrong hydroxide hydrate, iron hydroxide and a phosphorus Metsorb fixatives, film single fixed iron absorption is usually used as a fixing agent Chelex-100. 由于上述固定剂对磷或铁离子的固定原理均是吸附作用,且吸附对象分别是阴离子和阳离子,将它们叠加用于制作磷铁同步固定膜时,有可能产生相互干扰,达不到同步固定的效果。 Since the fixing agent to phosphorus fixation principle or iron ions are adsorption, and the adsorption is the object anions and cations respectively, superimposing them for the production of iron phosphate film is fixed synchronization, mutual interference may occur, reach the fixed synchronization Effect.

发明内容 SUMMARY

[0006]本发明旨在提供一种能同步富集磷和铁的固定膜及其制作方法,提高DGT技术应用于水体环境分析中活性磷和铁的测定效率,同时降低测定成本。 [0006] The present invention is intended to provide a method for manufacturing a fixing film and a phosphorus and iron enrichment can be synchronized to improve the water environment DGT technology to assay the activity of iron phosphorus and measurement efficiency, while reducing measurement costs.

[0007]本发明的上述目的是通过以下技术方案实现的: [0007] The object of the present invention is achieved by the following technical solution:

[0008] —种同步富集磷和铁的固定膜,其特征在于,该固定膜是由包含水合氢氧化锆、Chelex-100阳离子交换树脂和聚丙烯酰胺的成膜液,胶凝后制成的凝胶薄膜。 [0008] - the latter synchronization enriched phosphorus and iron fixed film, wherein the fixing film is formed containing a hydrated zirconium hydroxide, Chelex-100 cation exchange resin and a film-forming solution polyacrylamide gel formed gel film.

[0009]所述的固定膜表面沉积氢氧化锆和Chelex-100阳离子交换树脂。 [0009] The fixing film surface, and depositing a zirconium hydroxide Chelex-100 cation exchange resin.

[0010]所述的固定膜中,水合氢氧化锆与chelex-100阳离子交换树脂的重量比为1:0.6〜I: I ο [0010] The fixed film, a hydrated zirconium hydroxide by weight with chelex-100 cation exchange resin ratio is 1: 0.6~I: I ο

[0011]所述的同步富集磷和铁的固定膜采用以下方法制作:将Ig水合氢氧化锆粉末和0.6〜Ig Chelex-100阳离子交换树脂及聚丙烯酰胺水溶液充分混合,制成均匀的成膜液,加入适量过硫酸铵和四甲基二乙胺后,将该成膜液注入玻璃模具中,在2-4°C低温下水平放置,使得氢氧化锆和Chelex-100自由沉降后,再升温至45 土5°C放置,直到成膜液胶凝成膜。 Synchronization enrichment of phosphorus and iron fixed film [0011] prepared according to the following method: The mixed resin and an aqueous solution of polyacrylamide Ig hydrated zirconium hydroxide powder and 0.6~Ig Chelex-100 cation exchange, to form a uniform film solution, after addition of an appropriate amount of ammonium persulfate and tetramethyl diethylamine, the solution was poured into a glass forming mold, placed horizontally at 2-4 ° C temperature, so that the zirconium hydroxide and the free settling Chelex-100, then warmed to 45 [deg.] C soil is placed. 5, until the film-forming solution gelled film.

[0012]更具体和优化地,所述的方法包括以下步骤: [0012] More specifically and optimally, said method comprising the steps of:

[0013] I)将Ig含水率50土5%的水合氢氧化锆粉末和3〜5mL 30%聚丙烯酰胺水溶液混合后研磨,加入0.6〜Ig Chelex-100阳离子交换树脂混合均勾得到成膜液; [0013] I) mixing the milled Ig moisture 50 ± 5% of the hydrated zirconium hydroxide powder and 3~5mL 30% aqueous solution of polyacrylamide was added 0.6~Ig Chelex-100 cation exchange resin were mixed to give film-forming solution hook ;

[0014] 2)再向步骤I)所得的成膜液中加入12〜16yL 10% (wt)的过硫酸铵和4〜8yL四甲基二乙胺(TEMED),混匀后注入玻璃模具的两片玻璃板间厚度均匀的空隙中,将气泡赶尽; [0014] 2) again in step I) forming the resultant solution was added 12~16yL 10% (wt) ammonium persulfate and tetramethyl 4~8yL diethylamine (TEMED), injected into a glass mold after mixing between two glass plates of uniform thickness in the gap, the time to make the bubbles;

[0015] 3)玻璃模具在2-4°C低温下水平放置半小时以上,使水合氢氧化锆和Chelex-100颗粒自由沉降到底部(则向下一面为固定膜的正面),然后升温至45 ± 5°C,放置半小时以上,直至成膜液胶凝成膜; [0015] 3) horizontally placed glass mold at 2-4 ° C for half an hour more than the low temperature, zirconium hydroxide and hydrated Chelex-100 free settling particles in the end portion (toward the lower side is a front fixing film), then warmed to 45 ± 5 ° C, standing for at least half an hour, until the gel forming solution deposition;

[0016] 4)取出凝胶薄膜后,放入去离子水中浸泡24小时以上,制得所述的同步富集磷和铁的固定膜。 [0016] 4) After removing the gel film into deionized water soak for 24 hours or more, phosphorus and iron fixed film prepared according to the synchronization enrichment.

[0017]所述的水合氢氧化锆粉末可按以下方法制备,用25%氨水调节0.1M的氧氯化锆水溶液的PH至7.0±0.2,所产生的沉淀用去离子水洗至无氯离子,沉淀经离心分离后,干燥并控制其含水率为50 ± 5%之间,再研磨成粉末。 The hydration of the [0017] Preparation of the zirconium hydroxide powders according to a method of, PH was adjusted with 25% aqueous ammonia 0.1M aqueous solution of zirconium oxychloride to 7.0 ± 0.2, the precipitate generated with deionized water until no more chloride ions, the precipitate was centrifuged, dried and controls between 50 ± 5% of its water content, and then ground to a powder.

[0018]本发明的优点及有益效果包括: [0018] The advantages and beneficial effects of the present invention comprises:

[0019] I)本发明的固定膜制作过程优化,固定膜在吸附性能和物理强度方面均有着优异的性能。 [0019] I) of the present invention the fixed film production process optimization, the membrane is fixed in both adsorption and physical strength with excellent performance. 复合功能的固定膜包含两种不同的固定剂,其制作程序与包含单一固定剂的固定膜不同,各种参数需要进行探索和优化。 Fixed film composite functions comprise two different fixatives which the fixing film production process comprising a single different fixatives, various parameters need to be explored and optimized. 氢氧化锆和Chelex-100加入量和配比,过硫酸铵和四甲基二乙胺加入量、膜液沉降和胶凝的温度与时间等,对于膜的形成与性能,特别是两种吸附剂在膜表面的分布有显著影响。 Zirconium hydroxide and Chelex-100 and an amount ratio, tetramethyl ammonium persulfate and the amount of diethylamine was added, and the film was left to decant the gelling temperature and time, with respect to the properties of the film formed, in particular, are two adsorption agents have a significant effect on the distribution of the film surface. 对上述参数优化后,本发明固定膜的制备过程中,氢氧化锆和Chelex-100能够充分沉降到表面,并在表面形成合理的分布,使得两种吸附剂对磷或铁的吸附能力达到最优,同时固定膜能够保持稳定的形状,不易变形,吸附剂颗粒不脱落。 After the above-described parameter optimization, the manufacturing process of the fixing film of the present invention, zirconium hydroxide and Chelex-100 can be sufficiently settle to the surface and form a reasonable distribution of the surface, so that the two adsorbents for phosphorus or iron reaches the maximum adsorption capacity preferably, the film can be secured while maintaining a dimensionally stable, easily deformed, the adsorbent particles do not fall off.

[0020] 2)与报道的单一功能磷固定膜相比,本发明的同步富集磷和铁的固定膜两种吸附剂具有协同作用,对于磷和铁均具有非常高的富集容量。 Fixed-film single-function P [0020] 2) with the reported compared to fixed-film two adsorbents synchronization phosphorus and iron enrichment of the present invention has a synergistic effect for the phosphorus and iron enrichment has a very high capacity. 在Chelex-100优先在膜表面分布,保证铁富集容量的同时,Chelex-100的添加量对磷吸附性能没有显著的不利影响(参见图3B),磷富集容量(>83此P cm-2)分别是传统FeO膜、改进型FeO膜和Metsorb膜的20倍、6倍和3.5倍以上。 Preferentially distributed in the film surface Chelex-100, while the capacity to ensure the enrichment of iron, the addition amount of Chelex-100 no significant adverse effects (see FIG. 3B) Adsorption of phosphorus, phosphorus enrichment capacity (> 83 This P cm- 2) are the conventional film FeO, FeO film and a 20-fold improved Metsorb film, more than 6 times and 3.5 times. 由于这一优势,可以将本发明的固定膜用于分析高磷背景的富营养化湖泊。 Because of this advantage, the fixing film of the present invention may be used to analyze the high phosphorus eutrophic lake background. 另一方面,令人意想不到的是,本发明的固定膜对于铁的吸附容量显著高于单一功能的铁固定膜(参见图3A)。 On the other hand, it is unexpected that the film of the present invention is fixed to the iron adsorption capacity is significantly higher than the fixed iron film single function (see FIG. 3A). 已有铁固定膜在胶凝泡水后膨胀1.6倍,固定膜沉降面的Chelex-100分布密度也随之降低1.6倍,造成对铁的吸附能力下降。 After the film has gelled fixed iron soaked expanded 1.6 times, Chelex 100-settling distribution density of the fixed film surface also decreases 1.6 times, resulting in a decline in adsorption capacity for iron. 本发明的固定膜胶凝泡水后不膨胀,沉降面Chelex-1OO分布密度比已有铁固定膜高,因此吸附能力相应提高。 Gelled film of the present invention is fixed is not soaked in water after the expansion, settling surface Chelex-1OO iron distribution has a higher density than the fixed film, and therefore a corresponding increase in the adsorption capacity. 此外,我们发现水合氢氧化锆具有两性特征,在PH 5.0以上环境中同时带正电荷和负电荷,可以同时吸附磷和铁离子,促使本发明的固定膜对铁的吸附能力大幅度上升。 Furthermore, we found a hydrated zirconium hydroxide having amphoteric character, PH 5.0 in the above environment while positively and negatively charged, phosphorus and iron ions can be adsorbed at the same time, the fixed film of the present invention causes significant increase in the adsorption capacity of iron.

[0021] 3)本发明固定膜两种固定剂的搭配合理。 [0021] 3) with a reasonable fixed film of the present invention, two kinds of fixing agents. 固定膜对目标物的吸附性能取决于吸附剂在膜表面的分布;分布密度越大,则吸附性能越强。 Adsorption of the fixed target membrane is dependent on the distribution of the film surface of the adsorbent; greater distribution density, the stronger the adsorption performance. 要实现一种固定膜同步富集两种目标物的功能,所采用的两种吸附剂均需要在固定膜表面形成合理的分布,使得吸附剂能够产生吸附作用并具有一定的吸附容量。 To realize a function of two kinds of the fixed film synchronization enriched target object, two adsorbents used are required to form a reasonable distribution of the fixing film surface, so that the adsorbent can be generated with a certain adsorption and adsorption capacity. 本发明固定膜分别采用氢氧化锆和Chelex-1OO作为磷和铁的吸附剂,其中Chelex-1OO颗粒粒径较大(200-400目),将优先沉降到表面,无定型水合氢氧化锆比重轻,随后沉降并分布于没有被Chelex-1OO占据的其余表面部分,使得固定膜表面同时分布氢氧化锆和Chelex-1OO,能够同时吸附磷和铁离子。 The fixed film of the present invention were used, and zirconium hydroxide Chelex-1OO phosphorus and iron as an adsorbent, wherein the Chelex-1OO large particle size (200-400 mesh), preferentially settle to the surface of amorphous hydrated zirconium hydroxide gravity light, and then distributed to settle the remaining surface portion is not occupied by the Chelex-1OO, so that the fixing film surface while the distribution of zirconium hydroxide and Chelex-1OO, capable of simultaneously adsorbing phosphorus and iron ions. 对水合氢氧化锆和Chelex-1OO添加量的优化,可使得本发明的固定膜氢氧化锆和Chelex-1OO在固定膜表面的分布密度合理,吸附容量大,达到同步高效富集磷和铁的功能。 Hydrated zirconium hydroxide was added, and the amount of Chelex-1OO optimized such that the fixed film of the present invention, zirconium hydroxide and Chelex-1OO reasonable distribution density in the fixed film surface, a large adsorption capacity, to achieve synchronization efficient enrichment of phosphorus and iron Features.

[0022]下面结合具体实施例对本发明进行详细描述。 Specific embodiments of the present invention will be described in detail [0022] below in conjunction. 本发明的保护范围并不以具体实施方式为限,而是由权利要求加以限定。 The scope of the present invention is not limited to particular embodiments, but be defined by the claims.

附图说明 BRIEF DESCRIPTION

[0023]图1本发明的同步富集磷和铁固定膜表面的电镜扫描图像(放大50倍),可以看到固定膜表面Chelex-1OO颗粒的分布,周围为氢氧化错。 [0023] FIG synchronization phosphorus enrichment of the present invention and the fixed iron SEM image of the film surface (50X), the film surface can be seen that the distribution of the fixed particles Chelex-1OO, around hydroxide wrong. 扫描前固定膜经过高猛酸钾染色。 Before scanning the fixed film through the high potassium permanganate staining.

[0024]图2A本发明固定膜Chelex-1OO树脂添加量对铁吸附性能的影响。 [0024] Effect of the addition amount FIGS Chelex-1OO 2A fixing resin film of the present invention Adsorption of iron. 当Chelex-1OO树脂添加量从0.6g变化到Ig时,固定膜对铁的吸附性能与目前商用Chelex-1OO树脂固定膜相比,吸附性能明显增强,120分钟时对二价铁的吸附率由40%提高到100%。 When the added amount of the resin Chelex-1OO to change from an Ig 0.6g, fixed film Adsorption of Fe as compared with current commercial film fixing resin Chelex-1OO, significantly enhanced adsorption performance, the adsorption rate of ferrous iron at 120 minutes 40% to 100%.

[°°25]图2B本发明固定膜Chelex-1OO树脂添加量对磷吸附性能的影响。 [°° 25] Effect of the addition amount FIGS Chelex-1OO 2B fixing resin film of the present invention phosphorus adsorption performance. 当Chelex-1OO树脂添加量从0.6g变化到Ig时,固定膜对磷的吸附性能与未添加Chelex-1OO树脂相比没有明显差异。 When the added amount of the resin Chelex-1OO changed from 0.6g to Ig, no significant difference in the fixed film on the adsorption of phosphorus with resin Chelex-1OO No comparison.

[0026]图3A本发明固定膜DGT装置与目前商用Chelex-1OO树脂固定膜DGT装置对二价铁离子的吸附容量对比。 [0026] FIG. 3A fixing film according to the present invention means DGT contrast with current commercial film fixing resin Chelex-1OO DGT means for divalent iron ions adsorption capacity. 本发明固定膜二价铁固定容量70±2 yg cnf2,明显高于商用Chelex-100树脂固定膜对二价铁固定容量(45±5 yg cm—2)。 Fixed film divalent iron present invention is a fixed displacement 70 ± 2 yg cnf2, significantly higher than the commercial Chelex-100 resin fixing film divalent iron fixed capacity (45 ± 5 yg cm-2).

[0027]图3B本发明固定膜DGT装置与氢氧化锆固定膜DGT装置对磷酸根磷的吸附容量对比。 [0027] Comparative absorption capacity fixed film of the present invention FIG. 3B DGT fixing means and the zirconium hydroxide of the phosphate film DGT means of phosphorus. 本发明固定膜对磷酸根磷的固定容量为83±2 yg cm—2,比单一的氢氧化锆固定膜对磷酸根磷的固定容量(100 yg cm—2)略低,但比其他固定膜的固定容量高至少3.5倍。 Fixed film fixed volume of phosphate phosphor of the present invention is 83 ± 2 yg cm-2, (100 yg cm-2) fixed slightly lower capacity than a single phosphorus phosphate zirconium hydroxide fixing film, but a film other than the fixed fixing capacity of at least 3.5 times higher.

具体实施方式 detailed description

[0028] 实施例1 [0028] Example 1

[0029] —种同步富集磷和铁的固定膜,其制作方法如下: [0029] - the fixed film synchronization species enrichment of phosphorus and iron, its production method is as follows:

[0030]用25%氨水调节0.1M的氧氯化锆水溶液pH达到并稳定在7.0±0.2,所产生的沉淀用去离子水洗至没有氯离子,沉淀经离心去除上清液后,用吹风机干燥,至其含水率为50 ±5%,再用研钵磨成粉末,得到含水率50 ± 5%的水合氢氧化锆粉末。 [0030] with 25% ammonia to adjust pH of the aqueous zirconyl chloride 0.1M precipitate washed with deionized water to reach and stabilize at 7.0 ± 0.2, produced no chloride ions to precipitate the supernatant was removed by centrifugation, and dried with a hair dryer , to which water was 50 ± 5%, and then pulverized in a mortar to give a water content of 50 ± 5% hydrated zirconium hydroxide powders.

[0031 ]将Ig含水率50 ±5%的水合氢氧化锆粉末和5mL 30%聚丙烯酰胺水溶液混合于研钵中,研磨lOmin,转移至1ml离心管中,加入Ig Chelex-1OO阳离子交换树脂混合均勾得到成膜液,再向成膜液中加入16yL 10% (wt)的过硫酸铵和8yL TEMED,快速混匀后将其缓慢注入夹有0.4_、厚度均匀的U形塑料薄片的两片玻璃板组成的模具的空隙中;将气泡赶尽后,玻璃板在2-4°C低温下水平放置半小时,使水合氢氧化锆和Chelex-100颗粒自由沉降到底部,则向下一面为固定膜的正面;然后升温至45± 5°C,放置半小时以上,使得成膜液胶凝成膜。 [0031] The Ig moisture 50 ± 5% hydrated zirconium hydroxide powder and 5mL 30% aqueous solution of polyacrylamide were mixed in a mortar, triturated lOmin, 1ml is transferred to a centrifuge tube, was added Ig Chelex-1OO cation exchange resin are mixed were obtained hook forming solution, was added again forming 16yL 10% (wt) ammonium persulfate and 8yL TEMED, after rapid mixing slowly injected interposed 0.4_, a uniform thickness of the two U-shaped plastic sheet void mold consisting of glass plates; time to make the bubbles, the glass plate was left at 2-4 ° C for half an hour a low temperature level, zirconium hydroxide and hydrated Chelex-100 in the end portion free settling particles, down one side of the It is a front of the fixed film; then warmed to 45 ± 5 ° C, standing for at least half an hour, so that the gel forming solution deposition. 然后将玻璃板撬开,取出凝胶薄膜,放入去离子水中浸泡24小时,期间换水3次。 The glass plate is then prized open, the gel was removed film, into deionized water soak for 24 hours, changing the water 3 times during.

[0032]所制得的固定膜以及已有铁固定膜(Chelex膜)和磷固定膜(ZrO膜)的显微镜放大图像见图1,其表面氢氧化锆和Chelex-100颗粒分布均匀致密。 [0032] The fixing film, and the resulting film has a fixed iron (the Chelex film) and the fixed film phosphorus (ZrO film) enlarged microscopic image shown in Figure 1, the surface of zirconium hydroxide and Chelex-100 particle distribution is uniform and compact.

[0033]将制得的上述同步富集磷和铁的固定膜切成直径1.1cm的圆片,放入同时含有 [0033] The synchronization of the fixing film of phosphorus and iron enrichment obtained wafer was cut into 1.1cm diameter, placed contain both

0.2mg L—1的磷和二价铁的溶液中,室温下振荡120分钟,固定膜对磷和铁的富集效率曲线如图2所示。 Phosphorus and ferrous iron solution of 0.2mg L-1 and shaken for 120 minutes at room temperature, fixed film phosphorus and iron enrichment efficiency curve shown in FIG. 固定膜对磷和铁的富集量均随着振荡时间而增加,且两者的增加趋势非常类似,富集120分钟后,固定膜对磷和铁的富集效率均达到98%以上。 Phosphorus and fixed film with the iron-rich volume increases and the oscillation time, and the increasing tendency of both are very similar, enriched after 120 minutes and the fixed film phosphorus iron enrichment efficiency reached 98%.

[0034] 实施例2 [0034] Example 2

[0035] —种同步富集磷和铁的固定膜,其制作方法如下: [0035] - the fixed film synchronization species enrichment of phosphorus and iron, its production method is as follows:

[0036]按照实施例1的方法制备含水率50 土5%的水合氢氧化锆粉末。 [0036] Following the procedure of Example 1 was prepared moisture content of 50 ± 5% of the hydrated zirconium hydroxide powders.

[0037]将Ig含水率50 土5%的水合氢氧化锆粉末和5mL 30%聚丙烯酰胺水溶液混合于研钵中,研磨1min,转移至1ml离心管中,加入0.8g Chelex-100阳离子交换树脂混合均勾得到成膜液,再向成膜液中加入16yL 10% (wt)的过硫酸铵和8yL TEMED,快速混匀后将其缓慢注入夹有0.4mm、厚度均匀的U形塑料薄片的两片玻璃板组成的模具的空隙中;将气泡赶尽后,玻璃板在2-4 °C低温下水平放置半小时,使水合氢氧化锆和Chelex-100颗粒自由沉降到底部,则向下一面为固定膜的正面;然后升温至45± 5°C,放置半小时以上,使得成膜液胶凝成膜。 [0037] The Ig moisture 50 ± 5% of the hydrated zirconium hydroxide powder and 5mL 30% aqueous solution of polyacrylamide were mixed in a mortar, triturated 1min, 1ml is transferred to a centrifuge tube, was added 0.8g Chelex-100 cation exchange resin were mixed to give hook forming solution, was added again forming 16yL 10% (wt) ammonium persulfate and 8yL TEMED, after rapid mixing slowly 0.4mm interposed injection, a uniform thickness of the U-shaped plastic sheet the void of the mold consisting of two glass plates; time to make the bubbles, the glass plate was left at 2-4 ° C for half an hour a low temperature level, zirconium hydroxide and hydrated Chelex-100 in the end portion free settling particles, the downward positive side of the fixed film; then warmed to 45 ± 5 ° C, standing for at least half an hour, so that the gel forming solution deposition. 然后将玻璃板撬开,取出凝胶薄膜,放入去离子水中浸泡24小时,期间换水3次。 The glass plate is then prized open, the gel was removed film, into deionized water soak for 24 hours, changing the water 3 times during.

[0038]所制得的固定膜其表面氢氧化错和Chelex-100颗粒分布均勾致密。 [0038] The fixed film prepared on its surface dislocation hydroxide and Chelex-100 particles are distributed densely hook. 固定膜对磷和铁的富集效率曲线如图2所示。 Phosphorus fixed film and iron enrichment efficiency curve shown in FIG.

[0039] 实施例3 [0039] Example 3

[0040] —种同步富集磷和铁的固定膜,其制作方法如下: [0040] - the fixed film synchronization species enrichment of phosphorus and iron, its production method is as follows:

[0041 ]按照实施例1的方法制备含水率55%的水合氢氧化锆粉末。 [0041] Following the procedure of Example 1 of preparing an aqueous 55% hydrated zirconium hydroxide powders.

[0042]将Ig含水率50 土5%的水合氢氧化锆粉末和5mL 30%聚丙烯酰胺水溶液混合于研钵中,研磨1min,转移至1ml离心管中,加入0.6g Chelex-100阳离子交换树脂混合均勾得到成膜液,再向成膜液中加入16yL 10% (wt)的过硫酸铵和8yL TEMED,快速混匀后将其缓慢注入夹有0.4mm、厚度均匀的U形塑料薄片的两片玻璃板组成的模具的空隙中;将气泡赶尽后,玻璃板在2-4 °C低温下水平放置半小时,使水合氢氧化锆和Chelex-100颗粒自由沉降到底部,则向下一面为固定膜的正面,然后升温至45±5°C,放置半小时以上,使得成膜液胶凝成膜。 [0042] The Ig moisture 50 ± 5% of the hydrated zirconium hydroxide powder and 5mL 30% aqueous solution of polyacrylamide were mixed in a mortar, triturated 1min, 1ml is transferred to a centrifuge tube, was added 0.6g Chelex-100 cation exchange resin were mixed to give hook forming solution, was added again forming 16yL 10% (wt) ammonium persulfate and 8yL TEMED, after rapid mixing slowly 0.4mm interposed injection, a uniform thickness of the U-shaped plastic sheet the void of the mold consisting of two glass plates; time to make the bubbles, the glass plate was left at 2-4 ° C for half an hour a low temperature level, zirconium hydroxide and hydrated Chelex-100 in the end portion free settling particles, the downward positive side of the fixed film, and then warmed to 45 ± 5 ° C, standing for at least half an hour, so that the gel forming solution deposition. 然后将玻璃板撬开,取出凝胶薄膜,放入去离子水中浸泡24小时,期间换水3次。 The glass plate is then prized open, the gel was removed film, into deionized water soak for 24 hours, changing the water 3 times during.

[0043]所制得的固定膜其表面氢氧化错和Chelex-100颗粒分布均勾致密。 [0043] The fixed film prepared on its surface dislocation hydroxide and Chelex-100 particles are distributed densely hook. 固定膜对磷和铁的富集效率曲线如图2所示。 Phosphorus fixed film and iron enrichment efficiency curve shown in FIG.

Claims (4)

  1. 1.一种同步富集磷和铁的固定膜,其特征在于:该固定膜是由包含水合氢氧化锆、Chelex-1OO阳离子交换树脂和聚丙烯酰胺的成膜液,胶凝后制成的凝胶薄膜;所述的固定膜表面沉积氢氧化锆和Che I ex-100阳离子交换树脂; 所述的固定膜采用以下方法制得,将Ig水合氢氧化锆粉末和0.6〜Ig Chelex-1OO阳离子交换树脂及聚丙烯酰胺水溶液混合,制成均匀的成膜液,加入4〜SyL四甲基二乙胺和12〜16yL 10 wt %的过硫酸铵后,将该成膜液注入玻璃模具中,在2-4°C低温下水平放置,使得氢氧化锆和Chelex-1OO自由沉降后,再升温至45土5°C放置,直到成膜液胶凝成膜。 1. A synchronous enrichment of phosphorus and iron fixed film, wherein: the fixing film by the film-forming solution containing a hydrated zirconium hydroxide, Chelex-1OO cation exchange resin and a polyacrylamide gel formed after the gel film; the zirconium hydroxide and the fixed film surface deposition Che I ex-100 cation exchange resin; the fixed film prepared by the following method, the Ig hydrated zirconium hydroxide powders and cation 0.6~Ig Chelex-1OO after exchange resin and mixing an aqueous solution of polyacrylamide, a homogeneous film-forming solution, was added diethylamine and 4~SyL tetramethyl 12~16yL 10 wt% of ammonium persulfate, and the film-forming solution was poured into a glass mold, placed horizontally at 2-4 ° C temperature, so that the zirconium hydroxide and the free settling Chelex-1OO, then heated to 45 [deg.] C soil is placed. 5, until the film-forming solution gelled film.
  2. 2.—种权利要求1所述的同步富集磷和铁的固定膜的制作方法,其特征在于,所述的固定膜采用以下方法制得,将Ig水合氢氧化锆粉末和0.6〜Ig Chelex-1OO阳离子交换树脂及聚丙烯酰胺水溶液混合,制成均匀的成膜液,加入4〜8yL四甲基二乙胺和12〜16yL 10 wt%的过硫酸铵后,将该成膜液注入玻璃模具中,在2〜4°C低温下水平放置,使得氢氧化锆和Chelex-1OO自由沉降后,再升温至45土5°C放置,直到成膜液胶凝成膜。 Synchronization phosphorus enrichment and the fixed film manufacturing method according to a kind of iron 2.- claim, wherein said fixed film prepared by the following method, the Ig hydrated zirconium hydroxide powders and 0.6~Ig Chelex after -1OO cation exchange resin and mixing an aqueous solution of polyacrylamide, a homogeneous film-forming solution, was added diethylamine and 4~8yL tetramethyl 12~16yL 10 wt% of ammonium persulfate, the mixture was poured into a glass forming mold, placed horizontally at 2~4 ° C low temperature, so that the zirconium hydroxide and the free settling Chelex-1OO, then heated to 45 [deg.] C soil is placed. 5, until the film-forming solution gelled film.
  3. 3.根据权利要求2所述的固定膜的制作方法,其特征在于,所述的方法包括以下步骤: 1)将Ig含水率50±5%的水合氢氧化锆粉末和3〜5mL 30%聚丙烯酰胺水溶液混合后研磨,加入0.6〜Ig Chelex-1OO阳离子交换树脂混合均勾得到成膜液; 2)再向步骤I)所得的成膜液中加入12〜16yL 10 wt %的过硫酸铵和4〜8yL四甲基二乙胺,混匀后注入玻璃模具的两片玻璃板间厚度均匀的空隙中,将气泡赶尽; 3)玻璃模具在2〜4°C低温下水平放置30min以上,使水合氢氧化锆和Chelex-100颗粒自由沉降到底部,然后升温至45 土1°C,放置半小时以上,直至成膜液胶凝成膜; 4)取出凝胶薄膜后,放入去离子水中浸泡24小时以上,制得所述的同步富集磷和铁的固定膜。 The fixing film manufacturing method according to claim 2, characterized in that the method comprises the following steps: 1) the Ig moisture content of 50 ± 5% hydrated zirconium hydroxide powder and poly 3~5mL 30% after grinding the mixed aqueous solution of acrylamide was added 0.6~Ig Chelex-1OO cation exchange resin are mixed to obtain each hook forming solution; 2) again in step I) forming the resultant solution was added 12~16yL 10 wt% of ammonium persulfate and 4~8yL tetramethyl diethylamine, injected between two glass plates of a glass mold after mixing a uniform gap thickness, the time to make the bubbles; 3) glass mold was placed over 30min at 2~4 ° C low temperature level, hydrated zirconium hydroxide and Chelex-100 in the end portion free settling particles, and then warmed to 45 soil 1 ° C, standing for at least half an hour, until the gel forming solution deposition; 4) remove the gel film into deionized water for 24 hours or more, phosphorus and iron fixed film prepared according to the synchronization enrichment.
  4. 4.根据权利要求2或3所述的固定膜的制作方法,其特征在于:所述的水合氢氧化锆粉末按以下方法制备,用25%氨水调节0.1M的氧氯化锆水溶液至pH为7.0 ± 0.2,所产生的沉淀用去离子水洗至无氯离子,沉淀经离心分离后,干燥并控制其含水率为50±5%之间,再研磨成粉末。 The manufacturing method of the fixing film 2 or claim 3, wherein: said hydrated zirconium hydroxide powder prepared by the following method, to an aqueous solution of zirconium oxychloride with a pH of 25% aqueous ammonia to adjust 0.1M 7.0 ± 0.2, the precipitate generated with deionized water until no more chloride ions, precipitate was centrifuged, dried and its water content was controlled between 50 ± 5%, and then ground to a powder.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101629881A (en) * 2009-08-05 2010-01-20 中国科学院南京地理与湖泊研究所 Phosphorus fixing film applied to diffusive gradients in thin-films measurement technology
CN102507388A (en) * 2011-10-24 2012-06-20 河海大学 Improved phosphorus fixing film used in DGT (diffusive gradients in thin films) measurement and preparation method thereof
CN102698715A (en) * 2012-06-25 2012-10-03 中国科学院南京地理与湖泊研究所 Fixed film for synchronously enriching phosphorus and sulphur and manufacturing method for fixed film

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CN101629881A (en) * 2009-08-05 2010-01-20 中国科学院南京地理与湖泊研究所 Phosphorus fixing film applied to diffusive gradients in thin-films measurement technology
CN102507388A (en) * 2011-10-24 2012-06-20 河海大学 Improved phosphorus fixing film used in DGT (diffusive gradients in thin films) measurement and preparation method thereof
CN102698715A (en) * 2012-06-25 2012-10-03 中国科学院南京地理与湖泊研究所 Fixed film for synchronously enriching phosphorus and sulphur and manufacturing method for fixed film

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