Diffusion separation

The wastes from uranium and plutonium processing of the reactor fuel usually contain the neptunium. Precipitation, solvent extraction, ion exchange, and volatihty procedures (see Diffusion separation methods) can be used to isolate and purify the neptunium. 

Another impetus to expansion of this field was the advent of World War 11 and the development of the atomic bomb. The desired isotope of uranium, in the form of UF was prepared by a gaseous diffusion separation process of the mixed isotopes (see Fluorine). UF is extremely reactive and required contact with inert organic materials as process seals and greases. The wartime Manhattan Project successfully developed a family of stable materials for UF service. These early materials later evolved into the current fluorochemical and fluoropolymer materials industry. A detailed description of the fluorine research performed on the Manhattan Project has been pubUshed (2). 

Many challenging industrial and military applications utilize polychlorotriduoroethylene [9002-83-9] (PCTFE) where, ia addition to thermal and chemical resistance, other unique properties are requited ia a thermoplastic polymer. Such has been the destiny of the polymer siace PCTFE was initially synthesized and disclosed ia 1937 (1). The synthesis and characterization of this high molecular weight thermoplastic were researched and utilized duting the Manhattan Project (2). The unique comhination of chemical iaertness, radiation resistance, low vapor permeabiUty, electrical iasulation properties, and thermal stabiUty of this polymer filled an urgent need for a thermoplastic material for use ia the gaseous UF diffusion process for the separation of uranium isotopes (see Diffusion separation methods). 

Different combinations of stable xenon isotopes have been sealed into each of the fuel elements in fission reactors as tags so that should one of the elements later develop a leak, it could be identified by analyzing the xenon isotope pattern in the reactor s cover gas (4). Historically, the sensitive helium mass spectrometer devices for leak detection were developed as a cmcial part of building the gas-diffusion plant for uranium isotope separation at Oak Ridge, Tennessee (129), and heHum leak detection equipment is stiU an essential tool ia auclear technology (see Diffusion separation methods). 

Uranium oxide [1344-57-6] from mills is converted into uranium hexafluoride [7783-81-5] FJF, for use in gaseous diffusion isotope separation plants (see Diffusion separation methods). The wastes from these operations are only slightly radioactive. Both uranium-235 and uranium-238 have long half-Hves, 7.08 x 10 and 4.46 x 10 yr, respectively. Uranium enriched to around 3 wt % is shipped to a reactor fuel fabrication plant (see Nuclear REACTORS, NUCLEAR FUEL reserves). There conversion to uranium dioxide is foUowed by peUet formation, sintering, and placement in tubes to form fuel rods. The rods are put in bundles to form fuel assembHes. Despite active recycling (qv), some low activity wastes are produced. 

The individual membrane filtration processes are defined chiefly by pore size although there is some overlap. The smallest membrane pore size is used in reverse osmosis (0.0005—0.002 microns), followed by nanofiltration (0.001—0.01 microns), ultrafHtration (0.002—0.1 microns), and microfiltration (0.1—1.0 microns). Electro dialysis uses electric current to transport ionic species across a membrane. Micro- and ultrafHtration rely on pore size for material separation, reverse osmosis on pore size and diffusion, and electro dialysis on diffusion. Separation efficiency does not reach 100% for any of these membrane processes. For example, when used to desalinate—soften water for industrial processes, the concentrated salt stream (reject) from reverse osmosis can be 20% of the total flow. These concentrated, yet stiH dilute streams, may require additional treatment or special disposal methods. 

A number of special processes have been developed for difficult separations, such as the separation of the stable isotopes of uranium and those of other elements (see Nuclear reactors Uraniumand uranium compounds). Two of these processes, gaseous diffusion and gas centrifugation, are used by several nations on a multibillion doUar scale to separate partially the uranium isotopes and to produce a much more valuable fuel for nuclear power reactors. Because separation in these special processes depends upon the different rates of diffusion of the components, the processes are often referred to collectively as diffusion separation methods. There is also a thermal diffusion process used on a modest scale for the separation of heflum-group gases (qv) and on a laboratory scale for the separation of various other materials. Thermal diffusion is not discussed herein. 

The most important industrial appHcation of the diffusion separation methods has been for the enrichment of uranium-235 [5117-96-17,... 

Reversible Processes. Distillation is an example of a theoretically reversible separation process. In fractional distillation, heat is introduced at the bottom stiUpot to produce the column upflow in the form of vapor which is then condensed and turned back down as Hquid reflux or column downflow. This system is fed at some intermediate point, and product and waste are withdrawn at the ends. Except for losses through the column wall, etc, the heat energy spent at the bottom vaporizer can be recovered at the top condenser, but at a lower temperature. Ideally, the energy input of such a process is dependent only on the properties of feed, product, and waste. Among the diffusion separation methods discussed herein, the centrifuge process (pressure diffusion) constitutes a theoretically reversible separation process. 

Irreversible processes are mainly appHed for the separation of heavy stable isotopes, where the separation factors of the more reversible methods, eg, distillation, absorption, or chemical exchange, are so low that the diffusion separation methods become economically more attractive. Although appHcation of these processes is presented in terms of isotope separation, the results are equally vaUd for the description of separation processes for any ideal mixture of very similar constituents such as close-cut petroleum fractions, members of a homologous series of organic compounds, isomeric chemical compounds, or biological materials. 

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