海水中微量元素无机离子交换动力学研究 Ⅳ.海水中铀(Ⅵ)与水合氧化钛离子交换反应的级数和活化能的测定

关于海水中铀(Ⅵ)与水合氧化钛的作用、国内外已有许多报导,内容包括水合氧化钛制备方法的不同对交换铀量的影响,水合氧化钛和海水中铀的基本物理—化学性质的研究及它们在反应过程中物理—化学性质变化规律的研究,海水中铀与水合氧化钛作用机理的研究等等。但对这一反应的动力学研究文献上报导极少,除了在本研究Ⅰ、Ⅱ和Ⅲ中报导的反应机理的研究[1,2]证明反应过程的速率由液膜扩散所控制之外,关于这一离子交换过程的反应级数和活化能的研究却至今未见有文献报导。     

海水中铀与锌型吸附剂离子交换的液膜扩散机理

我们根据Boya等人的扩散理论,由试验结果证实:当海水中的铀浓度为10μg U/ml及20μg U/ml时,海水中的铀与碱式碳酸锌吸附剂的离子交换速率主要为液膜扩散所控制[1],本文用天然海水直接进行实验,也获得了与上述相同的结果.由此可见,在含10-20μg U/ml的加浓铀海水中及天然海水中,铀与锌型离子交换速率主要为液膜扩散所控制.     

偕胺肟树脂的吸铀机理

通过对偕胺肟树脂对铀的吸附等温线和吸附速率测定,研究了偕胺肟树脂在海水中的吸铀机理,实验表明树脂吸铀量随温度上升而增加,亦随pH值不同而变,由热力学计算的吸附焓变为ΔH=42.4千焦尔/摩尔,由动力学计算的吸附表观活化能为41.2千焦尔/摩尔,结果表明吸附过程是通过树脂的偕胺肟基对铀酰离子的化学吸附,而树脂对铀酰离子吸附能力的次序为:UO₂2+>[UO₂(OH)₃]->[UO₂(CO₃)₃]4-。     

厦门西港表层沉积物对铅的吸附作用

在海水介质中,模拟研究了厦门西港沉积物对Pb吸附过程的热力学和动力学性质,提出相应的定量模式,测定饱和吸附量、吸附速率常数和表观活化能等重要物化参数。结果表明,沉积物-Pb的吸附以化学作用为主,静电作用为辅。其吸附性质与水合氧化铁-Pb的吸附类似。     

碱式碳酸锌吸附剂对天然海水中铀的吸附

本文实验结果表明:1.吸附剂中的铀浓度与所使用的天然海水的含铀量存在如下关系:C=8.51×10-1(u*)0.49.2.当吸附剂的用量基本保持不变时,随着通过吸附柱海水量的增加,吸附剂的吸铀量、吸附剂中的铀浓度以及吸铀后天然海水中剩余的铀浓度不断增加;而铀的回收率不断减少;分配系数随着通过吸附柱海水量的增加而减少至一定值之后,又稍有回升.     

海水中铜与针铁矿离子交换的动力学研究

本文较系统地研究了海水体系中Cu(Ⅱ)与α-FeOOH间的离子/配位子交换动力学。实验测定反应级数n=1;速率常数k(25℃)=6.12、k(35℃)=8.40;活化能E_a=2.43×10~4J/mol。反应第一阶段的速率由固有液膜扩散所控制;反应第二阶段的速率由递进液膜扩散所控制。反应全过程可统一地用固有液膜扩散和递进液膜扩散的复合模型、描述,理论计算与实验测定相吻合。     

水合氧化钛对海水中一些元素的富集

从海水中富集铀有多种方法,其中,水合氧化钛对铀的吸附容量大且选择性好,认为是最好的吸附剂。 水合氧化钛的制备方法和吸附条件不同,其富集的元素及富集系数也有差异,这是正常的现象。本文所用水合氧化钛是在本实验条件下制备和通水的,测定了两组水合氧化钛吸附     

具有偕胺肟基的螯合树脂从海水中提取铀

海水中蕴藏着总量为42亿吨的铀,海水提铀的研究是人们普遍关注的一个课题,海水提铀的关键是从铀含量3.34微克/升的海水中富集铀,使用吸附法富集铀时,首要的问题是吸附剂的研制,由于螯合树脂(或纤维)类有机吸附剂的选择性强,容易成形,物理机械性能好等优点,正日益受到人们的重视。     

偕胺肟基聚丙烯腈/蒙脱土纳米复合材料海水铀的吸附规律研究

采用偕胺肟化聚丙烯腈/蒙脱土(APAN/MMT)复合纳米吸附材料对海水中的铀进行吸附,考察了吸附条件对APAN/MMT吸附铀量的影响,并对APAN/MMT吸附铀的动力学和热力学进行了探讨.结果表明:铀初始浓度、溶液温度较高、采用磁力搅拌吸附方式有利于吸附速率的提高,溶液pH对吸附性能有一定的影响,在pH为5时,平衡吸附...     

日本的海水化学资源提取技术研究

海水化学资源例如铀、锂提取技术已进入海水现场小规模试验。以纤维状偕胺肟类化合物为吸附材料 ,每公斤吸附剂的提铀量为 1 g。添加质量分数为 2 0 %聚氯乙烯的尖晶石型锰氧化物粒状海水提锂吸附剂 ,每克吸附剂的提铀量为 1 8mg。浮体式吸铀装置可用于深海作业。流动床或船舶提锂系统 ,可规模化海水提锂。吸锂剂的脱附以及脱锂液的浓缩分离已初步达到小型生产的程度。用吸附法从海水中提取的碳酸锂纯度达 99%以上 ,海水锂回收率为 2 7%。     

DETERMINATION FO URANIUM IN SEAWATER

This article deals with a new method of analysing in seawater, i. e. the uranium is concentrated with an aqueous suspension of basic zinc carbonate, subsequently isolated and determined by extraction-photometric method. In concentrating uranium such factors as stirring time, amount of adsorbent used, acidity of seawater were studied and conditions suitable for analysis were found. This method is simple, accurate and good in reproducibility. It is not necessary to adjust the pH of seawater before analysis. This technique can also be applied to determination of uranium in river or lake.     

ADSORPTION ACTION OF BASIC ZINC CARBONATE ADSORBENT ON URANIUM IN NATURAL SEAWATER

1. The adsorption action of basic zinc carbonate adsorbent on uranium in natural seawater can be expressed with the following formula of adsorption isotherm:C=k(U*)n = 8.51× 10-1(U*)0.49,where C is the concentration of uranium on adsorbent; U* is content of uranium in natural seawater employed.2. when the quantity of basic zinc carbonate adsorbent (T) is constant, with the increase of natural seawater quantity through the adsorption column (G), also increased are the adsorption content of uranium of the adsorbent (U), the concentration of uranium on the adsorbent (C) and the concentration of residual uranium (C0*) in natural seawater after adsorbing uranium, while the rate of recovery of uranium (R) is decreased. With the increase of (G) the coefficient of distribution (Kd) decreases to a certain value and then a little rises again.     

MECHANISM OF URANIUM ADSORPTION ON AMIDOXIME RESIN

The mechanism of uranium adsorption from seawater by polyacrylamidoxime resin is investigated by means of the experiments of adsorption isotherm and adsorption rate. The uranium uptake increases with the adsorption temperature and varies with the pH of seawater. Thermochemical and kinetic calculation show that the enthalpy change (△H) and the activation energy (E) of the uranium adsorption are 42.4 42.4 kJ mol-1 and 41.2 kJ mol-1 respectively, indicating that the uranium adsorption on the resin proceeds via a certain complex chemical reaction in which the amidoxime group in the resin chelates uranyl ions.     

Coprecipitation of zinc with silica in seawater and in distilled water

Dissolved silica can coprecipitate with zinc from seawater or distilled water that has been enriched with both elements. More than 2 ppm Si are necessary for the reaction to begin. The coprecipitation shows pH dependence. The addition of pulverized illite or natural sediment as suspended particulate material does not enhance the reaction in seawater. The organic material present in the nearshore seawater samples decreases the rate and extent of reaction, as indicated by comparisons of results of experiments using natural seawater with results obtained using UV-irradiated seawater. In unbuffered distilled water the reaction must compete with hydrolysis of zinc; however, reaction does occur, which indicates that the seawater matrix is not essential for the reaction. The coprecipitation can limit the concentration of zinc in seawater to less than the solubility concentration assumed for ZnCO₃ or Zn(OH)₂. The results suggest that a zinc silicate can precipitate directly from seawater or interstitial water as an authigenic mineral.     

ON CHELATING RESINS FOR EXTRACTING URANIUM FROM SEAWATER

A number of dictating resins have been synthesized for extracting uranium from scawatcr. The feasibilities of extracting uranium directly from seawater by synthesizing chelating resins have been investigated by studying three factors:(1) the chelating ability of the resins for uranyl ion;(2) the competitive complex of calcium, magnesium and other cations with uranyl ion;(3) the competitive complex of carbonate ion with uranyl ion.It is suggested that the competitive complex of carbonate ion with uranyl ion should be the most important factor.     

悬浮泥沙在长江口铀非保守行为中的重要作用

利用高精度的电感耦合等离子体质谱仪对2014年1月长江口表层水中溶解铀浓度及其234U/238U比值、2013年3月长江口表层沉积物中各矿物组分的铀含量及其234U/238U比值进行了测定,研究了其空间分布特征和影响因素。结果表明:除了长江径流和海水之外,长江口还有其他的溶解铀来源。水体中过剩铀与悬浮颗粒物浓度呈现显著相关性（r2=0.96）。对长江口表层沉积物进行的序列提取实验进一步表明,水体中悬浮颗粒物或沉积物中可解吸态和碳酸钙结合态铀可以在河口区域释放进入水体,而铁锰氧化物和有机物结合铀比较稳定,不受河口区混合过程的影响。每千克颗粒物或沉积物能够释放约2 μmol颗粒态铀,使其转化为溶解态。然而,铁氢氧化物和细颗粒物的絮凝吸附作用也可使溶解铀同时从河口水体中清除。在低盐度区,铀的清除和添加过程速率相近,使溶解铀呈现暂时的"伪保守"现象:颗粒态释放的铀具有明显低的234U/238U比值,导致水体的234U/238U低于保守混合值。在中高盐度区域,溶解铀呈现明显的富集现象。但是由于水相和颗粒相中的铀交换,可释放颗粒态铀的234U/238U接近溶解铀的234U/238U比值,从而导致水体的234U/238U比值呈现出保守性。长江口颗粒物的铀释放通量为（3.48±0.41）×105 mol/a,约占输入的总颗粒态铀通量（1.80±0.17）×106 mol/a的19.3%。长江口输入东海的溶解铀总通量（河流溶解态铀与河口添加铀之和）为（2.68±0.13）×106 mol/a,约为世界河流入海铀通量的11.7%。     

EXTRACTION OF URANIUM FROM SEAWATER BY AMIDOXIME RESINS

The adsorption behaviour for uranium of four kinds of amidoxime resinst RNH, RCH, RAH and RPH in seawater has been investigated. It has been found that all these resins are capable of adsorbing rapidly uranium from U-cnriched seawater with a high uranium uptake.RNH was able to adsorb uranium satisfactorily from natural seawater, and the uranium uptake of RNH with a degree of cross-linking of 3-5 mol % was above 200 μg/g-R (adsorption for 15 days). The uranium uptakes of RCH, RAH and RPH from natural seawater were much lower than the uranium uptake of RNH. The factors which caused the difference between resins RCH, RAH, RPH and resin RNH are discussed.     

莱州湾海水中U的不均匀分布规律及地球化学研究

本文报道了1984年和1987年莱州湾海水中U分布规律的调查研究结果。发现莱州湾海水中U存在着不均匀分布规律,其不均匀分布主要受黄河水高浓度U入海扩散、稀释的影响和控制;雨季,也受到附近河流输入的一定影响。调查结果说明,莱州湾海水中U浓度普遍较高,但尚未构成对海洋生物污染的影响。初步论证了莱州湾海水中U对形成沿岸地下浓缩海水高U浓度的影响。     

Dissolved uranyl complexed species in artificial seawater

The distribution of dissolved uranyl species was calculated on the basis of the stability constants published elsewhere and compared with the results obtained from the experiments performed in artificial seawater. According to the distributions calculated and electrochemical and spectrophoto-metrical measurements performed in model electrolytes and artificial seawater (pH=8.2) in the presence of sufficient hydrogen peroxide, uranium most probably predominates in the form of a mixed uranyl-dicarbonato-hydrogenperoxo complex. The results obtained could be applied to the natural marine photic zone.The mixed complex has to be taken into account as an additional form of dissolved uranium species influencing their cycle in natural water systems. Recent discovery of the presence of hydrogen peroxide in the surface waters of seas has challenged a long-held notion of the prevalence of uranyl-carbonato complexes in seawater.