Uranium gaseous diffusion

The first S5m.thetic ventures into actinide and lanthanide organometalhc chemistry were attempted during World War II and were motivated by the need for stable, volatile uranium complexes in the uranium gaseous diffusion process. It soon became apparent that the homoalkyl complexes (MR4) of uranium were extremely unstable and at best could exist only as transient intermediates at low temperatures [128). With the isolation of the tricyclopentadienides of the lanthanides in 1954, the focus of /-transition metal organometaUic chemistry shifted to the n-carbocychc complexes and has remained unchanged until the recent isolation of stable alkyls and aryls of both the lanthanides and actinides. 

Uranium-235 can be concentrated by gaseous diffusion and other physical processes, if desired, and used directly as a nuclear fuel, instead of natural uranium, or used as an explosive. 

Uranium hexafluoride is used in the gaseous diffusion process for the separation and enrichment of uranium-235, which exists in low concentration in natural uranium. The enriched UF is converted back into an oxide and used as fuel for the nuclear power industry. 

To convert naturally occurring uranium oxide, yellow cake or U Og, to the gaseous UF, hydrofluoric acid is first used to convert the U Og to UF. Further fluorination using fluorine (generated from more HF) is employed to convert the UF to UF. The UF is then processed at gaseous diffusion enrichment plants. 

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). 

Gaseous diffusion cascades for uranium enrichment have also been built in the United Kingdom, France, the former USSR, China, and, more recendy, in Argentina. 

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. 

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. 

Natural uranium consists mostly of and 0.711 wt % plus an inconsequential amount of The United States was the first country to employ the gaseous diffusion process for the enrichment of the fissionable natural uranium isotope. During the 1940s and 1950s, this enrichment appHcation led to the investment of several bUHon dollars in process faciHties. The original plants were built in 1943—1945 in Oak Ridge, Teimessee, as part of the Manhattan Project of World War II. 

The need for a large number of stages and for the special equipment makes gaseous diffusion an expensive process. The three United States gaseous diffusion plants represent a capital expenditure of close to 2.5 x 10 dollars (17). However, the gaseous diffusion process is one of the more economical processes yet devised for the separation of uranium isotopes on a large scale. 

In 1985, owiag to the declining demand by the nuclear power industry for enriched uranium, the Oak Ridge gaseous diffusion plant was taken out of operation and, subsequently, was shut down. The U.S. gaseous diffusion plants at Portsmouth, Ohio and Paducah, Kentucky remain ia operation and have a separative capacity of 19.6 million SWU (separative work unit) per year which as of this writing is not fully utilized. 

From equation 60 one can obtain a theoretical power requirement of about 900 kWh/SWU for uranium isotope separation assuming a reasonable operating temperature. A comparison of this number with the specific power requirements of the United States (2433 kWh/SWU) or Eurodif plants (2538 kWh/SWU) indicates that real gaseous diffusion plants have an efficiency of about 37%. This represents not only the barrier efficiency, the value of which has not been reported, but also electrical distribution losses, motor and compressor efficiencies, and frictional losses in the process gas flow. 

The cost of enriched material from a gaseous diffusion plant depends both on the cost of separative work and of feed material. It can be seen from equation 15 that if the optimum tails concentration from a gaseous diffusion plant is 0.25%, the ratio of the cost of a kg of normal uranium to the cost of a kg of separative work equal to 0.80 is impfled. Because the cost of separative work in new gaseous diffusion plants is expected to be about 100/SWU, equation 16 gives the cost per kg of uranium containing 4% as about 1,240. 

It should be noted that the separation factor for the centrifuge process is a function of the difference in the mol wts of the components being separated rather than, as is the case in gaseous diffusion, a function of their ratio. The gas centrifuge process would therefore be expected to be relatively more suitable for the separation of heavy molecules. As an example of the equiUbrium separation factor of a gas centrifuge, consider the Zippe centrifuge, operating at 60°C with a peripheral velocity of 350 m/s. From equation 68, OC is calculated to be 1.0686 for uranium isotopes in the form of UF. ... 

UFe is important in the separation of uranium isotopes by gaseous diffusion (p. 1259). 

Enrichment, Isotopic—An isotopic separation process by which the relative abundances of the isotopes of a given element are altered, thus producing a form of the element that has been enriched in one or more isotopes and depleted in others. In uranium enrichment, the percentage of uranium-235 in natural uranium can be increased from 0.7% to >90% in a gaseous diffusion process based on the different thermal velocities of the constituents of natural uranium (234U, 235U, 238U) in the molecular form UF6. 

Fig. 8.2 Gaseous diffusion cell for uranium enrichment, schematic (http //www.globalsecuiity.

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