γ辐照30%三烷基氧化膦—煤油体系萃取乳化的研究

研究了γ辐射三烷基氧化膦（TRPO）的乳化性能。实验表明，萃取水相酸度的增加，有利于去乳化作用。γ辐射对30?RPO-煤油-硝酸体系的乳化作用有显著影响，不同厂家生产的TRPO具有不同的乳化性能。γ辐照的磷酸三丁酯（TBP）-煤油-硝酸体系较RTPO-煤油-HNO3体系分相和去乳化速度较快。但当用5?a2CO3溶液洗涤上述两个体系时，TBP-煤油体系有机相去乳化速度较慢，其平衡水相有乳化现象，面TRPO-煤油体系虽分相慢，但分相后有机相的去乳化速度较快，其平衡水相无乳化现象。     

γ辐照对TRP0流程萃取体系乳化性能的影响

研究了处理高放废液的TRPO流程的萃取剂TRPO经γ辐照后的乳化情况。提出了在所研究的体系中对乳化程度的衡量方法。研究了平衡水相PH值和吸收剂量对萃取体系乳化的影响,结果表明：乳化与水相PH密切相关,且随着有机相吸收剂量的增加,乳化程度加剧。考察了TRPO辐解产生的辐解产物对乳化的影响,结果表明：TRPO和稀释剂辐照生成的聚合产物是引起乳化的主要原因。体系的乳化可以通过酸化、碱洗或采用离心萃取器等方法减轻甚至消除。     

γ辐照对TRPO流程萃取体系乳化性能的影响

研究了处理高放废液的TRPO流程的萃取剂TRPO经γ辐照后的乳化情况.提出了在所研究的体系中对乳化程度的衡量方法.研究了平衡水相pH值和吸收剂量对萃取体系乳化的影响,结果表明:乳化与水相pH密切相关,且随着有机相吸收剂量的增加,乳化程度加剧.考察了TRPO辐解产生的辐解产物对乳化的影响,结果表明:TRPO和稀释剂辐照生成的聚合产物是引起乳化的主要原因.体系的乳化可以通过酸化、碱洗或采用离心萃取器等方法减轻甚至消除.     

TRPO中Am3+,Pu(Ⅳ),UO2+2,TcO-4的反萃及其红外光谱和裂解色谱分析

研究了硝酸、草酸、碳酸钠和碳酸铵对4种不同来源的TRPO/煤油中Am^3 ,Pu(Ⅳ),UO2^2 和TcO4^-的反萃，观察了碳酸钠溶液反萃铀时的乳化现象，比较了上述4种TRPO的红外光谱、裂解色谱。结果表明，不同来源的TRPO具有相似的基团，但组成有差别。     

TRPO-TBP/煤油体系对高放废液中镅、铀、钚和锝等的萃取和反萃

比较研究了混合三烷基氧膦（TRPO）－磷酸三丁酯（TBP）／煤油混合体系和TRPO／煤油体系对铀和硝酸的萃取含量,结果表明,混合体系的萃取容量比TRPO／煤油体系高。测定了20％TRPO－20％TBP／煤油混合体系对二十余种离子的萃取分配比,结果表明在较宽的NHO3浓度范围（0.5-5mol/L)内,该混合体系对低浓度UO2^2 、低浓度U^4 ,Pu^4 ,Pu^3 ,NpO2^2 ,Np^4 都有较高的萃取能力;低酸条件（＜1.0mol/L)下,混合体系对TcO4^-1,Am^3 ,Eu^3 ,Y^3 有较高的分配比;混合体系对NpO2^ ,Sr^2 ,Cs^ 等的萃取能力较弱。TRPO－TBP／煤油有机相中萃取的镅、铀、钚和锝可以分别用高浓度硝酸、碳权铵溶液、羟基乙酸和高浓度硝酸（或碳酸盐）反萃下来。     

φ70mm核用离心萃取器Ⅱ．传质性能

研究了φ70mm核用离心萃取器的传质.性能以30％TRPO－煤油－HNO3为体系,在转速3000r/min、总流量40－100L/h、流比1／3．0－3．0／1的操作条件下,硝酸的传质级效率达85％以上。以含Nd^3 的30％TRPO－煤油－HNO3为体系,在转速1500r/min、流比1．3／4．1／1、总流量29．4－46．3L／h的操作条件下,Nd^3 的平均反萃级效率达87％以上。     

三烷基氧膦对硝酸介质中钌的萃取行为

研究了三烷基氧膦(TRPO)对硝酸介质中钌的萃取行为。使用TRPO为萃取剂,煤油(OK)为稀释剂,重点考察了萃取平衡时间、水相硝酸浓度、温度、萃取剂浓度、亚硝酸盐浓度等因素对钌的萃取影响,并进行了钌的三级错流萃取实验。另外,还研究了硝酸浓度、温度等因素对钌的反萃过程影响。结果表明,由于钌在水相和有机相中存在着多个种态的平衡和转化过程,热力学和动力学作用相互影响,使得TRPO对钌的萃取行为以及有机相中钌的反萃行为均十分复杂。为进一步了解TRPO对高放废液中钌的萃取行为,进行了TRPO/煤油对不同酸度、浓缩倍数的模拟高放废液中钌的萃取和反萃实验,相关结果为进一步优化TRPO流程工艺提供了重要参考。     

Φ70核用离心萃取器传质性能研究

用单级φ70核用离萃取器在硝酸溶液中进行了30％TRPO／煤油体系萃取 Nd^3 的传质性能实验。结果表明：在流比为2：1和1：1,转速为1760－2650r/min,总流量为40－200L／h的条件下,Nd^3 的传质级效率达90％以上。在模拟料液和30％TRPO／煤油体系中的传质性能实验结果表明:在流比为2：1,转速为1760－2650r/min,总流量为30－150L／h的条件下,传质级效率达90％以上。用5．5mol/L HNO3反萃有机相中Nd^3 的实验结果表明：反萃级效率随总量增加而减小,在同一总流量下随转速的增加而增大,在实验条件范围内,Nd^3 的反萃级效率在83％－93％之间。实验结果证明：φ70核用离萃取器具有良好的水力学性能和传质性能。     

三烷基(混合)氧膦(TRPO)对Fe(Ⅲ)萃取性能的研究

研究了TRPO萃取剂对Fe(Ⅲ)的萃取性能,测定了在该实验条件下Fe(Ⅲ)的萃取随萃取平衡时间、水相中HNO_3的浓度、Fe~(3 )离子浓度、温度的变化。计算了TRPO萃取Fe(Ⅲ)的反应焓变ΔH°,熵变ΔS°及表观平衡常数K。结果表明,30％TRPO-煤油萃取体系萃取高放废液的模拟料液时,三相的产生是与水溶液中Fe~(3 )离子的浓度紧密相关的。当水溶液中[H~ ]=1.5mol/L,[Fe~(3 )]_(初始)>8.0g/L时,30％TRPO-煤油的萃取体系即出现三相。同时测定了分相后,轻、重两个有机相的体积比和Fe含量比随水相Fe~(3 )离子初始浓度的变化。     

三烷基(混合)氧膦(TRPO)对Fe(Ⅲ)萃取性能的研究

研究了TRPO萃取剂对Fe(Ⅲ)的萃取性能,测定了在该实验条件下Fe(Ⅲ)的萃取随萃取平衡时间、水相中HNO_3的浓度、Fe~(3-)离子浓度、温度的变化。计算了TRPO萃取Fe(Ⅲ)的反应焓变ΔH,熵变ΔS及表观平衡常数K。结果表明,30％TRPO-煤油萃取体系萃取高放废液的模拟料液时,三相的产生是与水溶液中Fe~(3 )离子的浓度紧密相关的。当水溶液中[H~ ]=1.5 mol/L,[Fe~(3 )]_初始>8.0g/L时,30％TRPO-煤油的萃取体系即出现三相。同时测定了分相后,轻、重两个有机相的体积比和Fe含量比随水相Fe~(3 )离子初始浓度的变化。     

核燃料循环中所用含磷萃取剂的辐照稳定性研究

对核燃料后处理以及高放废液处理中所用的含磷萃取剂的辐照稳定性已经进行了广泛的研究。对正辛基苯基-N，N’-二异丁基胺甲酰甲基氧化膦(CMPO)、二(2-乙基己基)磷酸(DEHPA)以及混合三烷基氧化膦(TRPO)等的辐照稳定性的研究进行了综述。主要介绍了CMPO、DEHPA和TRPO的辐解产物；辐照对萃取和保留的影响以及辐照后溶剂的净化方法。     

Changes to Plutonium Extraction Behavior of TBP and Alkylamines through Irradiation

Changes to plutonium extraction properties brought about through irradiation of 30v/o TBP (Tri-n-butyl phosphate)/kerosene and 5v/o alkylamines/kerosene modified with lauryl alcohol were studied in such respects as extraction, scrubbing and stripping characteristics in nitrate media.

The alkylamines examined were tri-n-octyl amine (TOA), N-cyclohexyl dilauryl amine (N-CHDLA) and Amberlite LA-2 (LA-2). These extractante were irradiated to the extent of 10⁸R by ⁶⁰Co γ-ray, prior to extraction.

Marked changes with irradiation were observed in plutonium extraction performance with the TBP system tending to bring losses of plutonium, but very little change was found to occur with amine systems.

Calculation of the single stage decontamination factors of fission products from plutonium proved that separation deteriorated with irradiation in the TBP system but hardly changed in the amine systems. From these findings, tertiary amines, especially N-CHDLA, can be judged superior to TBP for the direct recovery of plutonium from irradiated fuels, a process that has to be carried out under high irradiation.

The phase separation time after mixing in the extraction stage varied very little with irradiation, and no formation of emulsion occurred in the extraction of tracer plutonium with either irradiated TBP or amines.     

TRPO—稀释剂萃取硝酸过程中三相形成机理的研究

研究了ＴＲＰＯ－正辛烷萃取硝酸过程中三相形成的机理。测定了３０％ＴＲＰＯ－正十二烷、３０％ＴＲＰＯ－正辛烷、１５％ＴＲＰＯ－正辛烷萃取硝酸过程中水相酸度及有机相酸度、密度、组成及稀释剂对形成第三相的影响。提出了第三相形成是由于有机相中各组分形成了一个部分互溶体系，在一定条件下发生相分裂，从而导致第三相的形成。给出了ＴＲＰＯ－正辛烷萃取硝酸过程中有机相各组分的液－液平衡相图。     

TRPO流程中U的反萃Ⅰ.反萃剂的选择

研究了ＴＲＰＯ萃取流程中的Ｈ２Ｃ２Ｏ４反萃Ｎｐ、Ｐｕ段,在含Ｕ的ＴＲＰＯ相中出现沉淀的条件及消除办法。结果表明,提高洗涤段硝酸浓度,使ＴＲＰＯ相中Ｈ２Ｃ２Ｏ４与ＨＮＯ３的浓度比小于３,在该相中就不会出现沉淀。当用０．２ｍｏｌ／Ｌ或０．８ｍｏｌ／ＬＨＮＯ３洗涤ＴＲＰＯ相２次后,再用（ＮＨ４）２ＣＯ３或Ｎａ２ＣＯ３溶液反萃Ｕ时,水相也不会产生（ＮＨ４）２Ｃ２Ｏ４或Ｎａ２Ｃ２Ｏ４沉淀,保证萃取过程正常进行     

Radiation-chemical stability of TBP in solutions of hydrocarbons

The radiolysis of binary mixtures containing tributyl phosphate (TBP) and ali-phatic or aromatic hydrocarbons is discussed. The radiation-chemical stability of the irradiated systems was measured according to the yields of the acid esters (di- and monobutyl phosphate) and gaseous products, as welI as according to the change in the distribution coef ficients of plutonium and zirconium between the irradiated organic phase and an aqueous solution containing 2M nitric acid and the nitrates of these metals.The concentration dependence of the radiation chemical yields of gaseous and acid radiolysis products gives evidence of a deviation from the additivity rule and of a transfer of energy from the aliphatic hydrocarbon to TBP. As a result of replacement of the aliphatic hydrocarbon by an aromatic hydrocarbon, the yields of the radiolysis products are sharply reduced. The influence of aromatic hydrocarbons upon the radiation-chemical stability of TBP is confirmed by data on the distribution coefficients of plutonium and zirconium, the values of which are determined to a considerable degree by the content of dibutyl phosphate-the basic product of the radiolysis of TBP.Translated from Atomnaya Énergiya, Vol. 21, No. 4, pp. 281–285, 1966.     

TRPO流程中U的反萃：Ⅱ.（NH4）2CO3对U的反萃

研究了用 ５０ ｇ／ Ｌ（ Ｎ Ｈ４ ）２ Ｃ Ｏ３ 溶液从含 Ｕ 的 Ｔ Ｒ Ｐ Ｏ 相中反萃 Ｕ 的条件。测定了反萃平衡时间、相比、反萃次数、温度及有机相中 Ｕ 的质量浓度对反萃率的影响。用（ Ｎ Ｈ４）２ Ｃ Ｏ３ 反萃 Ｕ 比原流程的 Ｎａ２ Ｃ Ｏ３ 可减少 ２ 级,反萃液中不会析出（ Ｎ Ｈ４）２ Ｃ２ Ｏ４ 结晶。（ Ｎ Ｈ４）４［ Ｕ Ｏ２（ Ｃ Ｏ３）３ ］在加热转型时, Ｎ Ｈ＋４ 、 Ｃ Ｏ２－３ 及少量 Ｃ２ Ｏ２－４ 、 Ｎ Ｏ－３ 均可挥发除去。     

Uranium (IV)-(VI) Electron Exchange Reactions in Anion Exchange Resin,Tri-n-Octyl Amine and Tri-Butyl Phosphate

A study has been made of the U(IV)-U(VI) electron exchange reactions taking place between natural U(IV) and depleted U(VI) in anion exchange resin, as well as in TnOA/benzene and TBP/benzene systems.

The exchange rate in the anion exchange resin was smaller than the corresponding rates in 8–10 M HCl, which might be explained by considering that the diffusion of the exchangeable species is much slower in the anion exchange resin than in 8–10 M HCl.

The exchange rates in TnOA/benzene and in TBP/benzene were accelerated by decreasing the concentration of TnOA or TBP in benzene. The reason may be that TnOA and TBP, including the exchangeable species, is more easily diffused in dilute than in concentrated solution.

Based on activation energy values, the mechanism of exchange in the anion exchange resin was estimated to be similar to that in 8–10 M HCl solution, and the corresponding mechanism for TBP/benzene similar to that for the cation exchange resin. In the case of TnOA/benzene, the exchange process was presumed to resemble that of the anion exchange resin, judging from the similarity of ionic species extracted thereinto.     

软X射线对血液有形成分表面电荷的影响——2、淋巴细胞和血小板膜电荷的变化

软X射线不仅能引起红细胞表面电荷的变化,同时也能导致淋巴细胞和血小板表面电荷下降,表现为照射后它们的电泳率下降。低剂量范围内,这种电荷的变化是暂时性的,照后4小时降到最低点,24小时后恢复到对照的水平。细胞电泳率的下降与辐射剂量相关。淋巴细胞是一个复杂的细胞群,正常状态下,按细胞在电场中泳动速度的快慢,可分为两个组分:快峰为T细胞,慢峰为B细胞。软X射线照射以后,T和B细胞的电泳率皆减慢,频数分布峰值下降,离散度加大。血小板成分单一,电泳率较一致。 从照射浓集的血小板再加回自身血浆中电泳率的下降较照射血浆再加到血小板中的电泳率下降大得多;受照射的血小板在磷酸缓冲液中电泳率下降较在血浆悬液中严重得多;2000 rad照后,悬浮于血浆中的血小板电泳率能恢复,而悬浮于磷酸缓冲液中则不能恢复,三个方面来看,血浆中可能存在抗辐射因子。超氧化物岐化酶能有效地预防血小板电泳率的下降,从而可阻止血小板的凝聚。     

用于锕系元素提取分离的萃取剂——TiAP

对磷酸三异戊酯(TiAP)和磷酸三丁酯(TBP)萃取体系的物理性质、萃取能力、耐辐照等方面进行了比较,结果表明,TiAP作为萃取剂在物理性质、萃取Pu(Ⅳ)和Np(Ⅳ)的能力以及辐照稳定性能等方面明显好于TBP。提出TiAP是一种很好的并有可能用于锕系元素提取分离的萃取剂。