an m
u
n
i
t Processes Review
Nuclear Technology by W. R. Tomlinson, Jr., The Johns Hopkins University, Operations Research Ofice, Bethesda, M d .
Research and Development effort has reached a stage promising early breakthroughs in
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economics shielding
UST a few short months ago the nuclear industry was an infant one with a tremendous potential for the participation of the chemical industry. Today, the atomic energy program represents a national investment of some $20 billion, an amount which increases every year although many would prefer a more rapid increase. On this score, the Government is admittedly making more progress than industry. T h e Atomic Energy Commission has issued 6100 licenses for nuclear facilities and materials-by-product, source, and special materials. Licensees operate in every state or the union in some 1500 cities, some handling substantial amounts of radioactive materials. In the medical field over 800,000 persons per year are treated or diagnosed with radioisotopes, and industrial applications are being made in a variety of fields-rubber, paper, plastics, steel, food, construction, electric power, instruments, and agriculture. Estimates of savings from the use of radioisotopes run u p to $500 million a year, and the U.S.S.R. claims $350 million per year. Recent surveys of business statistics pertaining to the atomic energy industry for the past four or five years are most satisfying. There are 350 reactors of various kinds in operation or in definite planning stages in the U. S. ; 25 of these are power reactors. Eight reactors are now producing power, several provide electricity for commercial distribution, and others being constructed will start operating in the next year or two. Many of our leading universities operate research reactors, and most of the larger consulting research organizations in the country have one or more. There is little doubt that the future will bring many important space uses, Deboth radioisotope and reactor. velopment of high temperature reactor sources for metallurgical and chemical uses, application of fission product energy to production of chemicals, peaceful uses of underground explosions for excavation, geologic exploration, oil, mineral, and water resources exploitation, and the direct production of electricity all hold exciting prospects.
1030
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properties of materials conceptual approaches to utilizing fission
Chemical Processing of Ores
Uranium. iMining and early processing in the production of uranium involve practices and techniques familiar in the handling of other nonferrous ores. While flotation (73A) and physical beneficiation would be valuable, not much success has been achieved. T h e first step in chemical treatment is digestion. the choice between acid ( 7 A ) and alkaline (&I77A) , processes depending on the type of mineralization concerned and the amount and type of other material in the ore. I n primary ores, where uranium exists in reduced states, considerable advantage can often be realized by the use of a n oxidizing agent such as air, MnOz ( 7 6 A ) , or KMnO4. Secondary ores containing uranium in either partially or almost completely oxidized states do not generally require oxidants. Oxidants are helpful in the case of refractory and sulfide-containing ores. Certain primary ores, such as pitchblende and all the secondary ores, are amenable to both acid and alkaline processing. Refractory primary ores require strong acid leaching. When large amounts of acid-consuming matter like lime are present, alkaline agents are generally employed to extract uranium. Carbonates (77A), which attack few other ore components in uranium minerals. are attractive from this standpoint, yielding relatively pure uranium solutions. However, the ores generally require more grinding to expose the uranium when well protected by gangue minerals. Further, carbonates make thickening and filtering difficult. Recent work with shale-type, lowgrade ores, such as Chattanooga shale, indicates that treatment with chlorinating agents (CC14, phosgene, Clz, and SCl) during roasting effectively removes the volatile uranium chloride (70A. 17A) which can be recovered by contacting with aqueous metal chlorides or adsorption on granular A1,0,. T h e problems of effecting the liquidsolid separations necessary to permit further processing of uranium after its solution are unique, difficult, and quite specific to the ore involved and its
INDUSTRIALAND ENGINEERINGCHEMISTRY
treatment ( 1 8 A ) . An unusual method is the absorption of the uranium solution on particles of anion exchange resin which can later be screened out (75A). Uranium is usually removed froni solution by precipitation, solvent extraction, or ion exchange. Removal from leach solutions by precipitation requires complete clarification. The method is straightforward and simple, but in the case of acid digestions it is demanding in reagent to neutralize to the proper p H ; the barren leach liquors are generally not suitable for recycle. Precipitation is more generally used for alkaline digestions, and the barren leach is regenerated by alkali using COS. Another possibility showing some promise, but not yet developed to large scale, is precipitation with reduction. Hydrogen, sodium amalgam, and electrolytic reduction have been studied, and one of the more promising approaches is hydrogen reduction in the presence of a nickel catalyst. Bailes recommends reducing uranium in phosphate fertilizer solutions to U(IV) and precipitating as the fluoride ( Z A ) . Ion exchange is a very attractive method for removal of uranium from clarified leach liquors. Resins used are generally of the anion exchange type, and quaternary ammonium salts seem best suited to the purpose. This kind of process increases uranium concentration from about a gram per liter IO the order of 20 grams perliterwhilesimultaneously reducing the concentrations of impurities. Modified water-softening equipment is normally used, although fluidized and semifluidized resins have been used in the pulsed column technique (7A), and resin particles, in a modification of the fluidized bed technique referred to above (75A), have been used. Permutit SK resin is claimed to be quite effective in column operations and Permutit SKB in the modified technique, referred to as resin-in-pulp (9-4). T h e resin-in-pulp process might eliminate a nasty liquid-solid separation. T h e application of solvent extraction to uranium ore processing has led to the most promising and widely used methods to date ( 4 A ) . Solvent methods have
a
-l
been applied to clarified solutions, slurries, and on a limited scale to treated, dry ores. Solvents such as tributyl phosphate (5y0 in kerosine) (8A), alkyl pyrophosphates, long chain derivatives of HgP04, H4P207, phosphonic, and phosphitic acids ( 7 4 A ) , and selected mixed primary, secondary, ternary, and quaternary complex amines (5A) have given very promising results. Extraction with alkylamines is similar to resin sorption but more versatile. Thorium is usually obtained from monazite sand by H2S04 digestion to destroy the sand structure, decantation after dissolution in water, dilution, and pH adjustment to 1.O (which precipitates most of the thorium with a small amount of the rare earths). This is followed by dissolution of the thorium concentrate in H N 0 3 and extraction with tributyl phosphate (2OA). Thorium and the rare earths can also be precipitated as oxalates a t p H 0.4 to 3.0, leaving the uranium in solution; solution of the precipitate by caustic, followed by extraction with dibutyl phthalate, removes thorium and cerium, and the thorium can be stripped with water or 2y0 H z S 0 4 ( 3 A ) . Solution of the thoand extracrium precipitate in " 0 3 tion with tributyl phosphate is also feasible (224). Dowex 50 cation exchange resin has a high affinity for thorium, which is not eluted by relatively concentrated HCl (27A). Bastnaesite is a source of the lighter rare earths. Digestion of a flotation concentrate with HzS04, calcining a t 1200" F., and water leaching yields them in pure form (79A). Protoactinium can be obtained from initial acid leaches of pitchblende by treatment with alkali carbonate, which precipitates it; silica is removed by hydroxide treatment, and the palladium residue is dissolved in "OB, concentrated by cyclic precipitations with MnO2, and separated from T i and Zr by ion exchange (72A). Chemical Processing of Nuclear Fuels Separations may be classified as precipitation, sorption, extraction, or volatilization processes. Precipitation processes (4B, 9B, 77B)are the most interesting to the chemist and chemical engineer because of their familiarity and simplicity. However, as very low concentrations of plutonium and fission products are often involved, they are not too suitable for use in the classical sense. Rather, the wanted element must be "carried" (ZOB,I C , QC, I I C , I4C, 16C, d6C, SOC) in many cases by finding another material which will form a solid solution with it or absorb it. Although such methods may have been invaluable in the early days, making possible the isolation of plutonium
and uranium-235 urgently needed in the defense program, they seem outmoded for the high throughput and mass production methods of the new nuclear industry. Separations by sorption appear much more attractive, as do extraction and volatilization. Two main types of sorption are possible-molecular or surface sorption (78B, 2OB, 26B) and ionic sorption (8B, 72B, 22B, 2523). T h e molecular type, which is characterized by the use of such materials as activated charcoal, silica gel, and certain types of soils, has not been too successful to date-it is not so specific as ionic sorption. Ion exchange can be either of the anionic or cationic type. I n the latter case, among the active groupings may be carboxylic, phenolic, or sulfonic. Anion exchange resins contain active groups such as amino, imino, or quaternary ammonium. T h e resin involved is usually weakly cross linked. Dowex-50 (72B) and Amberlite I R 120, containing the strongly acidic sulfonic acid group, are examples of the cationic type, which has found more use to date than the anionic. These resins are easier to make and more stable under conditions of use than those of the anionic variety. T h e different affinities of resins for ions may be used in their separation. After fixing the desired ions on the resin, they may be eluted using solutions of various materials, often buffered (8B, 2223, 25B). Generally, ion exchange permits rapid, easy separation with good decontamination factors and allows
Table I. Agent or Treatment
n
v
d Unit Processes Review
considerable concentration, but most resins are susceptible to radiation damage. Inorganic ion exchangers, such as the hydrous oxides of aluminum and iron or zirconium phosphate, do not suffer as much from this defect. Solvent extraction ( I B , 3B, 5B, 6B, 73B, 76B, 79B) needs no introduction or explanation; in this field, methods to date involve solubilization effected by salt formation with organics (79B), chelation with them (7B, 24B, 27B, 29B), or the advantageous tendency of inorganic salts to form additive products (23B) or solvates with organic solvents. T h e advantages and disadvantages of solvent extraction are also well known. Extraction can also be carried out using salts, oxides (75B), and metals' (77B, 30B) as the extractants. For example, in extracting lanthanum from the metal phase by LiCI, it is replaced by lithium. T h e latter methodshigh temperature metallurgical processes-are of considerable promise for the future, but although they are well established in the metallurgical industry, to date none has reached full scale development. I n the same category are the distillation of plutonium and certain fission products and the use of fluorination to provide the volatile UFG (7OB). Considerable work has already been done in these fields, and some of the less well developed methods will find extensive use in the future. Other interesting processes are outlined in Tables I, 11, and 111.
Chemical Processing of Uranium Nuclear Fuels Rcf.
Details Solvent Extraction
Recovery improved if soln. reduced before extr. Alkyl phosphates, phosphonates, phosphites Amine, heterocyclic U recovered by strippin with HzO and pptn. as diuranate ( N a 4 ) Diethyl dithiocarbonate used as complexing agent Amyl acetate to facilitate extr. sym-Dithiocarbonates used as complexing agents 2-Heptanone Ketone plus hydrazine ( a ketazine formed) extr. Hexone U from acid s o h . Alkali thiocyanate added to uranyl salt s o h . Ketone, methyl is0bu t yl Antipyrine, bromoantipyrine, pyramidon used as Organic solvent complexing agents for U Diamines, used to chelate U, are sol. in Organic solvent pyridine, CH3N02 Benzene soln. used to extr. U from acid sulfate soln. Trioctvlamine sulfite Volatilization
Heat Fluoride BrF,
Irrad. U ; bubble A and Ns through molten U to remove Te, Ce, rare earths Treat with KHFz in Hz atm., 150' C., followed by HF at 120" C.; treat with Fz at 700° C. Addn. of SbFb, NbFb, or SnF4 increases halogenation rate
VOL. 52, NO. 12
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DECEMBER 1960
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Unit Processes Review
an1d -
Stable Isotopes Table Agent or Treatment
It.
Chemical Processing of Plutonium Nuclear Fuels
Ref.
Details Precipitation
Sulfate, potassium plutonyl Redox Redox Redox
Heat 10 min. at 95' C., pH 7.1 ; 95y0 recovery Sodium bismuthate and HNO, for oxidation of Pu(1V) to higher valence state Bismuthate and Ce(1V) ions oxidize Pu from Pu(1V) and lower valence to valence above Pu(1V) Dithionate at 75' C. reduces to Pu(II1) even in alk. medium Solvent Extraction
Electron donor 2-Hexylpyridine Organic solvent Organic solvent Organic solvent Tribu tyl phosphate Triglycol dichloride
Pu(1V) or higher valence extr. by 0-, h?, S - electron donor solvent, acid soln. Extr. from acid soln. by amine 10% excess cupferron used to complex; extr. from 2'M oxalate soln. Fluorinated P-diketones as chelating agents for extr. Pu(1V) chelates with subst. ethylenediimines Extr. in Pu(II1) valence state by reduction with hydroxylamine or Fe(I1) ion Extr. improved by addn. of saturated aliphatic aldehydes, benzaldehyde, phenols Sorption
Ale( SiO, ), Anion exchange CaFz Cation exchange Cation exchange General Ton exchange
Oxid. to Pu(V1) in HNO, soln., then contact with Alz(SiOl)n which adsorbs fission products Amberlite LRA-401 (16-50 mesh) or Permutit SK (20-50 mesh) Pu(V1) passes through, fission products held; Pu reduced to Pu(IV), held by CaFz New elutriant-NH4 lactate and (NHd)&O?; no gas evolved Phenol-formaldehyde resin ; complexing with Na salt of ferron allows Pu to pass through Pu sorbed by diatomaceous earth, silica, fuller's earth, A1203, MgSiO3, adsorbent C Pu(I11) held on cationic resin, eluted with 4-6.44
Radioisotopes
"08
NbO Phenol-formaidehyde resin, sulfonated Permutit SK Super Cel, Hyflo
Sorbent for Pu selectively reduced by FeS04, U( S O ~ ) Z , or SO2 Adsorbs Pu and fission products; Zr(P04)2then adsorbs Pu but not fission products Best combination of characteristics for Pu sorbent Adsorbs Pu with Nb and Zr from " 0 8 soln. of UOQINO, -, - ") Q, " Sorbent for Pu(1V); does not carry rare earths, Rb, Sr, Y , Cs, Ba, Kr, Xe, U U compd. solubilized by oxid. with " 0 3 , leaving insol. Pu( IV) Sorbs Pu(1V) in I-6N HCl, " 0 3 , or HzSO4, but not iodates of Cs, Rb, La, trivalent rare earths, and UO?(11) ~
ThPzOj U(P2Os) 'C;(IOda
Volatilization
Hydriding, treatment with HF and fluorination, followed by two-step fluorination Removal of Pu from irrad. U by treat. with H F at 600' C., Fz at 300' C., Fz at 500' C. UF6 and PuF6 passed over c u surface at 100'450' C., Pu deposits Fluorination at 250'-300' C. removes Np and Mo; heating to 500' C. volatilizes Pu fluoride
Fluoride Fluoride Fluoride Fluoride
Salt Extraction
extr. at 45j0 C.
ZnCla. NaCl
ZnCl2:NaCl = 60-90:40-10;
Mg
Pu and fission products extr. from irrad. Ll ( 7 2 4 9 % extr.) Pu exir. from irrad. U Fission products extr. Pu selectively extr. from U by Sn, Cu, Bi, Ag, Au, or rare earth metals Extr. above m.p. of Pu-A1 for Pu-A1 fuel rods
Pyrometallurgy
Sn Bi General Bi
1032
INDUSTRIAL AND ENGINEERING CHEMISTRY
While the isotopes of a given element have similar chemical a n d physical properties, their behavior is different in many nuclear reactions. Thus, their separation, difficult because of similar physical properties: is important. For instance, U2j5 (6E) is the only natural; fissionable isotope of uranium. Deuterium (27E) has a very low cross section for capture of thermal neutrons compared with hydrogen and, therefore, makes a very good moderator. Lithium-6, with a low neutron-capture cross section, is a n excellent coolant, while lithium-7, with a high neutroncapture cross section would be useful as a neutron attenuator (75E). Boron10 (76.73) has such a high slow-neutroncapture cross section (3990 barns) that it is valuable for shielding and in neutron counters and reactor controls. Most of the methods used for isotope separation have been physical-e.g., gaseous ( 6 E ) and thermal diffusion ( 79E), electromagnetic, and distillation, but some chemical methods such as ion exchange have found application (73E). Isotope exchange reactions are a general source of these isotopes ( 78E). Some recent activity in this field is shown in Table I V .
( 34C (37C) (39Cj
(47C)
Production. Just as atoms and/or molecules react to form new species, nuclei and/or particles also react to form new nuclei. I n reacting, atoms or molecules approach each other, and at some close distance in certain orientations a so-called activated complex can be said to form. This leads to the new chemical species tvhose nature is determined by the strengths of the bonds involved. including the potentials involved in the activated complex. I n the nuclear analogy the particle and/or nucleus form a so-called "compound nucleus" from which the new nuclear species is derived. Thus nuclei react with protons (24F); deuterons (24F), alpha particles (78F), and so on with a probability related to both reactants via the forces exerted. I n this analogy, the nuclear "conditions" under which the reaction occurs-e.g., temperature and pressure-are then represented by particle velocity and nuclear reactant concentration. respectively. Generally such reactions require quite eratures, or velocities, and the reactants to intermingle i s - n n t t s u & i e n ~ . The particle must be "fired" a t the nucleus, and accelerators are often used for the purpose. Another procedure is the use of a particle emitted with high velocity from another nuclear reaction, such as the alpha particle from radium, Exceptions are neutron re-
a n v d Unit Processes Review
7
actions. Here the uncharged neutron, generally experiencing no strong interactions with nuclei (except on very close approach), reacts a t low velocity, generally even more readily than a t high velocities. Thus, neutrons (33F), particularly thermal ones, are a good choice for half the reactant species. I n utilizing a reactor for the production of isotopes one can then utilize neutrons (16F, 39F) to irradiate a n element and obtain a radioactive element from it. O n the other hand, many neutron reactions yield a compound nucleus which emits a desirable particle. This reaction can then be used as the basis for another reaction. T h e fission process which produces energy in the reactor, however, not only produces neutrons but fission products as well. These include a number of radioisotopes of great practical value. Uranium-235, for instance, undergoes fission in more than 40 different ways, yielding over 80 radioisotopes. This provides an excellent source ( 9 F ) of radioisotopes to be derived from the used fuel by extensions of the fuel reprocessing techniques ( 4 4 F ) . Fission products represent the most likely source of radioisotopes for the future. O n e gram of U '35 leads to almost 1 gram of fission product, from which most of the radioelements can be recovered. O n the other hand, as 1 gram of uranium is equivalent to 1 megawatt-day of energy, this source obviously must be associated with the prime purpose of power production. Table V indicates some of work accomplished recently in connection with both nuclear reactions and extensions of fuel reprocessing ( Q F ) . Application. There has been a considerable amount of fine material published recently (76G, 78G, 20G) summarizing work in this field. A brief indication of the basis for radioisotope application is in order here, in addition to some interesting studies published recently (Table VI). T h e most interesting classification method for radioisotope applications, from the standpoint of the future development of radioisotope technology, is based on the scale of use-the amount of radioisotope required for a particular technique of utilization (elementary use process). This can vary from a trace (5G) to a more substantial amount (77G), such as a gram or pound. Generally, because even a very large number of applications on a trace scale requires only a small amount of material, the same compariSon still holds when amounts for a year's utilization of a technique are considered. T h e small-scale class includes the familiar utilizations as tracers (77G), in activation analysis, in process con-
Table 111. Agent or Treatment
Chemical Processing of Plutonium and Uranium Nuclear Fuels Details
Ref.
Precipitation
Ppt. containing Pu, U, fission products washed with NH3-HF (1 :4-1 :2 ) to remove U and fission products Form uranous hydroxide ppt. at p H > 5 , redissolve in acid, and at pH 2.5 U ppts., leaves Pu in soln.
BiP04 Hydroxide
( 700) (20)
Solvent Extraction
Reduce to Pu(I11) with NHzOH in neutral soln. and extr. U, then oxid. to Pu(V1) and extr. ; dibutyl carbitol used in both cases U and Pu extr. from HNO, soln. ( 3 N in acid) with bis(2-dibutoxyethyl) ether of dibutyl carbitol (others); reduce to 1.8N "0,; Pu is reduced and extr. Removes Pu(IV) from Zr, U(VI\, others in 0.25-0.57M
Dibutyl carbitol Oxygenated organics Thenoyl trifluoroacetone in benzene Tributyl phosphate
(90) (70)
(5D)
"03
Pu(IV) or higher valence and U(V1) extr. from 2-7N " 0 3 at room temp.; Pu(II1) extr. back into 3N HNO, using Fe(I1) sulfamate to reduce Pu
(77D)
Sorption
Cation exchangephenoLforma1dehyde
Separate U from Pu sorbed on resin by eluting U with 0.2-0.3M HzS04; elute Pu with 0.8M HqP04, 1M in
Bromination
Brz, HBr, A1Br3,BrzS less corrosive than fluorination (6D) (table of volatilities of bromides of Pu, U, fission products) Irrad. U chlorinated at 450' C., volatile chlorides re(30) moved, temp. raised to 700" C . to volatilize Pu as separate fraction; Clz pressure in reactor = 1 atm. Irrad. U chlorinated in presence of holdback metal oxide (80) (La or T h oxide) to give chloride of U(V) or higher valence; latter is volatilized below temp. for Pu chloride Fluorination at 250' C. with Fz; U fluoride distills off (40,7 7 0 ) but not Pu fluoride
(70)
"03
Volatilization
Chlorination Chlorination
Fluorination
Table IV.
Isotope B
B"J, 99% B, 0 2 C'4 C isotopes
Production of Stable Isotopes Process n-Butyl sulfide-BFB complex BFa,HzO SOJF? BF3 H & 0 4 (220' C., 100 mm. Hg) General General-method for concentrating in COZ Thecmal diffusion, using glass columns and Pt wire ( C O us.
+
GH4)
Ce Dz Dz Dz Dz Li isotopes Li
+
Ref. ( IlE,74E)
(16E) ( 72E)
(5E) ( 79E)
+
Ignition of nitrates to CeO rare earth nitrates, leach Two temp. Hz-HzO exchange on Pt or Pd catalyst Atm. press. distr. of dissociable Dz compounds High temp. and press. reduction of steam with Fe or FeO Exceptionally large isotope separations from study of 0-p H Z Lia, Li7 by fractional pptn. or cryst. Ion exchange chromatography; degree of cross link us. sep. factor HNOJ-NZoxides, N 1 6 conc. in HNOa Cation exchange resin-NH4+ band sharp, NIJ at front edge Sep. factors studied as function of "0, conc. Sep. tube used with 0 2 provides sep. factor of 106 Study of CaCOa-HZO water system NO'B(g) Hz0'*(1) NO'*(g) HzO'e(1) UFB-study of light isotope removal
+
+
Table V.
Isotope
Production of Radioisotopes Details Radiochemical sep. techniques (review) Fission product pilot plant at ORNL Isotope prod. with electron linear accelerator Prod. of threshold reactions in graphite reactor (cross section given) Short-lived radioisotopes-rapid radiochemical procedures for isolation
VOL. 52, NO. 12
Ref. ( QF) (26F) ( 29F) (36F) (469 ( Continued)
DECEMBER 1960
1033
a n b y a Unit Processes Review
Table Isotope
Actinides Actinides
/I126
AmZ41 Ba Bk Cs Cs
Cm2", Cm246 Cm2'i. Hg Kr8j
IW Pb2I2 NP (Am)
Np T\JP Np
Np237 P32 p32
P33 Pa Pa Pa Pa Pa Po s35
Ra-Ba Ru RL~
R LI RU
RU Ru Tc99
Xe (Kr) Zr Zr Zr (Nb)
1034
Production o f Radioisotopes (continued) Details Amalgam exchange sep.-rapid selective method for short lives Carrier-free radioisotopes by adsorption on ~ X l a 0j . ~ "?OH elution Sep. of long-lived radioisotopes from a mixture of fission products and corrosion elements Extr. from wastes-ThZ30, Pa231,NpZ37,Am2" Sep. by anion exchange-Dowex-I resin, elution by H N 0 . 3(HC1) Dowex 1 , elution with HC1-Y, C e , Pm, Zr, Nb, Ru-Rh Bombard. of Mg tvith 15 m.c.v. deuterons and 21 m.e.v. protons (NaZ2also formed) Sep. from Pm"; with fluosilicic acid; cyclic process Sep. from U and fission prodl ct:; Ba absorbed on cation exchange resin From alpha bomhard. of Am; extr. with tributyl phosphate as B i ( 1 V ) in Hh'O:{ soln. From waste fission product solutions; Cs ppt. with ferrocyanide carrier Dev. of continuous ion exchange process for recovery from alkaline waste Amz4] neutron -+ AmU2-+ Cm2'2 (separate on ion exchange column) Pu239 irrad. in high neutron flux, oxid. to Pu(1V) ; ion exchanoe sep. Cm24*(al;ha, n ) Cf245 4 Bk2'5 + CrnZ45(sep. described) Photochemical separation of Hg isotopes Sep. KrRj at multicurie level ; chromatographic sep. from Xe CCl, extr. from dissolver waste gases; recovery over 99% by vol. Obtained from thoron (Rn220) which decays to Po216, then Pb212 Solvent extr. with tributyl phosphate; purif. by ion exchange Isolation as mono-octyl phosphoric acid complex by liquid-liquid extr. Sep. from Pu by chlorination on mixed oxides and vaporization of NpCl, Sep. from Pu by carrying on LaF, in Np(IV) state, with Pu in ( > I V ) Sep. from irrad. U by chelation in nonpolar solvent Recovery by Neptex solvent extr. process From irrad. of S with neutrons in organic solvcnt and acid extr. S32(n> p)P32; P36 also formed; prep. and purif. in 2 days: 50% yield Best prod. method: use enriched S33and expose in reactor Pa recovered from irrad. T h by MnOs-carrying . - and ion exchange Purif. bv chlorination with AlCL at 100'-600' C. Pa complexed in acid s o h , complex broken by m a terial complexipg more strongly; Pa extr. with specific organic solvent. From pitchblende ; MnOg-carrying followed by solvent extr. Pa from irrad. T h by ion exchange Sep. from Bi and Pb and decay products by tributyl phosphate extr. Extr. from irrad. KCI using anion exchange column Sep. via continuous removal by cation exchange resin From irrad. U by solvent extr. with tetrachloroethane Passing O3through aqueous 0.01-0.05.44 NaNO? soln. oxidizes and volatilizes Ru Removal from organic UO2(NOJ)2 soln. by aqueous stripping Removal from U, Th, fission products by complexing with SO9-- or HS0,- and extr. with organic solvent; Ru stays in aqueous phase Sep. from aqueous s o h . by oxidation to RuO, and volatilization From "0,-air mixtures by adsorption on silica gel Mo irrad. in thermal neutron flux; T c ppt. with low sol. phosphate Sep. by gas chromatography Sep. from aqueous solns. of Nb, rare earths, and alkaline earths From irrad. U ; chelation with fluorinated p-diketone and solvent extr. From actinides and irrad. U ; adsorption on glassy material; actinides in valence state > 4 stay in soln.
+
Cm242
Sp
V.
INDUSTRIAL AND ENGINEERING CHEMISTRY
trol instrumentation, as markers (73Gj, and for time scales (22G). I n the largescale use class are applications in the sterilization of food, as ionizing agents. and power (ZG) and heat sources (3G).
Radioactive Waste I t is difficult to become interested in the problem of \vaste disposal when one considers that radioactive wastes are potentially useful. A t the present time, however, it is necessary to take care of current problems. A good account of the status of the problem has been and interesting data on the given (ZH), volume and heat evolution of wastes from a few reactors have been presented ( 7H). T h e treatment of radioactive \\rater has been discussed ( 3 H ) in a general and thorough manner. So far as the interest of the chemical industry is concerned, this lies mainly in the future and consists of extensions of the chemical and physical treatments discussed earlier under chemical processing of nuclear fuels. Table VI1 shows that there has been some activity in the direction of recovering valuable radioisotopes from wastes. Miscellaneous Until recently there has been a rather pessimistic attitude toward the possibility of directly utilizing the energy of fission fragments in a reactor, thus using the reactor effectively for, say, chemical reactions. Although researchers had recognized the feasibility of such processes, the economic possibilities were not so attractive. Recent developments are the consideration, by the Hercules Powder Co., of a dust reactor to produce ethylene glycol from methyl alcohol by free radical dimerization. T h e process seems attractive economically and is claimed to produce ethylene glycol in better than 65% yield with a n energy requirement of only 10 thermal kw.-hr. per pound. .4 second promising achievement in this area was the production of 7 molecules of hT02 per 100 e.v. from nitrogen and oxygen ( 7 J ) . This indicates hope for world-wide availability of cheap nitrate fertilizers. A detailed study of the industrial applications of ionizing radiations was completed by Arthur D. Little, Inc. (ZJ). They concluded that ionizing radiation is not yet a processing tool of major import to industry, generally. T h e field is young, and skillfully oriented research and development can lead to promising applications. They also concluded that the earliest major application of radionuclide fission products, in millions of curies, will be novel power sources for government projects-e.g., space applications.
a n ) T K ( i ; J Unit Processes Review Congr., Stockholm, 1957, pp. 61 1-44 (1958). (14A) Long, R. L. (to U. S. Atomic Energy Commission), U. S. Patent 2,882,123 (April 14, 1959). (15A) McQuiston, F. W., Jr. (to U. K. Atomic Energy Authority), Brit. Patent 809,327 (Feb. 25, 1959). (16A) Michal, E. J., Porter, R. R. (to U. S. Atomic Energy Commission , U. S. Patent 2,890,933 (June 16, 1959j. (17A) Rhodes, H. B., Pesold, W. F., Hirshon, J. M. (to U. S. Atomic Energy Commission), Jbid., 2,890,099 (June 5, 1959). (18A) Rosenbaum, J. B., Borrowman, S. R . , Clemmer, J. B., Proc. U. N. Intern. Conf. Peaceful Uses At. Energy, 2nd, 1958 3, pp. 505-9. (19A) Shaw, V. E., U. S. Bur. Mines ReDt. Invest. BM-RI-5474 (1959). (20Aj Smutz, M., Bridger, G. L.: others, Chem. Eng. Progr. Symtosium Ser., No. 13, 50, 167-70 (1954). (21A) Strelow, F. W. E., Anal. Chem. 31, 1201-3 (1959). (22A) Welt, M. A., Smutz, M. (to U. S. Atomic Energy Commission), U. S. Patent 2,849,286 (Aug. 26, 1958).
Table VI.
Subject Nuclear batteries Clathrates Engine studv Flow Atmos.
Blood M'ater
General Lighting Neutron source Power Radioassay Space power Surface study
Radioisotope Applications Details General discussion Kr*6 in hydroquinone; high specific activity rare gas sources of low biological hazard Deposit formation; CI4 to establish source of deposit Atmospheric Ra-C as tracer in geophysical circulation problems Meteorological aspects of peaceful uses of atomic energy Cosmic ray-produced isotopes in study of large scale circulation Measure cardiac output by vein injection and artery sampling Tritium as a tracer for HzO in nature Trace elements and transport rates in the ocean Ground water studies using tritium as tracer Residence times in sewage plants; flow patterns (dilutions) in rivers Ionium, Th, and Pb isotope ratios as indicators for water masses Natural R a as tracer in ocean Mixing rates in oceans and atmospheres by radiocarbon techniques Book AEC special report National Industrial Conference Board report KrsK gas, no high energy gammas, low toxicity, long life Po2'0-B, less gammas and more alpha energy than Ra-Be source SrQopower source; 100-watt electrical generator, land and sea use Measurements on inactive gas by passage through solid bed of radioactive material which yields active gas for monitoring SNAP-111, Poz10thermocouple elements, 8-1 0 % efficiency, 5 watts Glow discharges used to label surfaces with about 1 pg./sq. cm. of radioactive inert gas (e.g., R n ) ; adsorption changes permit surface study, topography, chemical changes, presence of waxes, etc.
'
Table VII.
Subject Cs (Sr, rare earths) Cs (Sr) I 2
Ion exchange Ru
Radioactive Wastes Details Sep. from wastes in kilocurie amounts-Cs by cocryst. with NH4A1(S04)2;Sr, Ru, rare earths by ppt. as hydroxides and carbonates in Fe( OH), as carrier Cs removed by adding K,Fe(CN)a to solution; Sr removed by addn. of inactive Sr and ppt. with Pod--Removal from gas streams by Ag-packed tower (NH4)3[ P ( M O ~ O ~is~effective )~] Removal by oxidation and volatilization
Other studies (3J, 4J-70J) concerned the peaceful applications of nuclear explosions. O n the basis of work done to date and planning and theoretical evaluation, underground explosions offer considerable promise in the fields of excavation, development of mineral resources, oil field development, and isotope production. literature Cited Chemical Processing of Ores (1A) Atomic Energy Commission, Brit. Patent 811,890 (April 15, 1959). (2A) Bailes, K. H., Long, R. S. (to U. S. Atomic Energy Commission), U. S. Patent 2,873,165 (Feb. 10, 1959). (3A) Bargusen, J., Jr., Smutz, M., IND. END.CHEM.50, 1754-5 (1958). (4A) Clemmer, J. B., Progr. in Mineral Dressing, Trans. Intern. Mineral Dressing Congr., Stockholm, 1957, pp. 650-67 (1958).
Chemical Processing of Uranium Nuclear Fuels (1B) Aktiebolaget Atomenergi, Brit. Patcnt 816.628 (.Tulv 15. 1959). (2B) hien,'-K,' A:,7 U.- S. Atomic Energy Comm. ORNL-2709 (June 4, 1959). (3B) Bailes, R. H . , Long, R. S. (to U. S. Atomic Energy Commission),' U. S. Patent 2,859,092 (Nov. 4, 1959). (4B) Ballard, A. E. (to U. S. Atomic Energy Commission), Ibid., 2,779,637 (Jan. 27, 1957). (5B) Blake, C. F., Jr., Brown, K. E., IND.ENG.CHEM.50, 1763-7 (1958). (6B) Brown, K. B., Crouse, D. B., Jr. ( t o U. S. Atomic Energy Commission), U. S. Patent 2,877,250 (March 10, 1959). (7B) Brown, H. D., Wolter, F. J. (to U. S. . Atomic Energy Commission); Ibid., 2,778,843 (Jan. 22, 1957). (8B) Calkins, G. D. (to U. S. Atomic gnergy Commission)', Ihid., 2,?38,370 (June 10, 1958). (9B) Carter. J. M.. Larson. C. E. (to ' U. S. Atomic Energy CommissioA), Zbid., 2,855,270 (Oct. 7, 1958). (10B) Cathers, G. I., Nucleat Sri. and Eng. 2, 768-77 (1957). (11B) Chiotti, P., Shoemaker, H. E., IND.ENG.CHEM.50, 137-40 (1958). (12B) Crespi, M. B., Suner, A. A., Macchiaverna, E. G., Proc. U. N. Intern. Conf. Peaceful Uses At. Enerev. 2nd. Geneva, 1958 18, pp. 146-9. (13B) Cronan, C. S., Chem. Eng. 6 6 , 108- I1 (1959). (14B) Dess, H. M. (to Union Carbide Corp.), Brit. Patent 824,413 (Dec. 2, 1959). (15B) Feder, H. M . , Chellew, N. R. (to U. S. Atomic Energy Commission), U. S. Patent 2,822,260 (April 2, 1958). (16B) Fletcher, J. M. (to U. K. Atomic Energy Authority), Brit. Patent 811,772 (April 15, 1959). (17B) Gooch, L. F. (to U. S. Atomic Energy Commission), U. S. Patent 2,894,808 (July 14, 1959). (18B) Gruen, D. M. (to U. S. Atomic Energy Commission), Ibid., 2,869,989 (Jan. 20. 1959). (IGB) Hyman, H . H. (to W. S. Atomic Energy Commission), Ibid., 2,893,822 (July 7, 1959). (20B) Hyman, H. H., Dreher, J. L. (to U. S. Atomic Energy Commission), Zbid., 2,893,824 (July 7, 1959).
Ref.
(6H)
(7H) (5 H ) (8H)
(4H)
(5A) Coleman, C. F., Brown K. B., others, IND.ENG. CHEM. 50, 1756-62 (1958). (6A) Commissariat a 1'Energie Atomique, Brit. Patent 802,453; Platinum Metals Rev. 3, 34 (January 1959). (7A) Commonwealth Scientific and Industrial Research Organization, Brit. Patent 813,269 (May 13, 1959). (8A) Galvanek, P., Jr. (to U. S. Atomic Energy Commission), U. S. Patent 2,875,023 (Feb. 24, 1959). (9A) Greer, A. H., Mindler, A. B., Termini, J. P., IND. ENG. CHEM. 50, 166-70 (1958). (10A) Hanley, W. K. (to U. S. Atomic Energy Commission), U. S. Patent 2,867,501 (Jan. 6 1959). (11A) Karcher, J. C., Allen, F. J. (to Concho Petroleum Co.), Jbid., 2,885,270 (May 5, 1959). (12A) Katzin, L. I., Larson, R. G., others (to U. S. Atomic Energy Commission), Zbid.,2,887,355 (May 19, 1959). (13A) Levin, J., Progr. in Mineral Dressing, Trans. Intern. Mineral Dressing
~
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VOL. 52, NO. 12
0
DECEMBER 1960
1035
a n ) f l d Unit Processes Review
W:'H., Reas, W. H. (to S. Atomic Energy Commission), Ibid.,2,877,087 (March 10,1959). (24B) Neville. 0. K. (to U. S. Atomic ' Eiergy Commission): Ibid., 2,899,451 (Aiig.. 11. 1959). (25'B) 3 0 l a n . J. D. (to Permutit Co., Ltd.), Brit. Patent 805,745 (Dec. 10, 1958). (26B) Paqny, P., Proc. U. N. Intern. Conf. ' Peacefd Uses At. Energy, 2nd, Gencva, 1958 18, pp. 138-45. (27BI Reas. W. H. (to U . S. Atomic ' Energy 'Commission), U. S. Patent 2,877,092 (March 10, 1959). (28B) Spedding, F. H., Butler, T. A., Johns, I. B. (to U. S. Atomic Energy Commission), Ibid., 2,877,109 (March 10. 1959). (29Bj U. 'K. Atomic Energy Authority, Brit. Patent 809,282 (Feb. 18, 1959). (30B) Watson, C. W., Beyer, G. H., U. S. Atomic Energy Comm. ISC-696 (March 1956). '
U.'
Chemical Processing of Plutonium Nuclear Fuels (1C) hngermann, A. A . (to U. S. Atomic Energy Commission), U. S. Patent 2,857,241 (Oct. 21, 1958). (2C) Atomic Energy of Canada, Ltd., Brit. Patent 820,660 (Sept. 23: 1959). (3C) Bonner, 0. D., Burney, G. A,, Tober, F. W., U. S. Atomic Energy Comm. DP-192 (December 1956). H., Maddock, A. G., Can. (4C) Booth, -4. Patent 654,467 (Oct. 14, 1958). (5C) Boyd, G. E., Adamson, A. W., Schubert, J. (to U. S. Atomic Energy Commission), U. S. Patent 2,855,269 (Oct. 7, 1958). (6C) Brown, H. S., Hill, 0. F. (to U. S. Atomic Energy Commission) Ibid., 2,822,239 (Feb. 4: 1958). (7C) Butler, T. A4.(to Atomic Energy of Canada, Ltd.), Can. Patent 549,312 ANov. 26, 1957). (8 ) Calvin, M . (to U. S. Atomic Energy Commission), U. S. Patent 2,853,418 (Oct. 14, 1958). (9C) Davies, T. H. (to U . S. Atomic Energy Commission), Ibid., 2,917,359 (Dec. 15, 1959). (1OC) Duffield, D. B. (to U. S. Atomic Energy Commission), Ibid., 2,875,026 (Feb. 24, 1959). (11C) Faris, B. F. (to U. S. Atomic Energy Commission)! Zbid., 2,892,676 (Jan. 30, 1959). (12C) Feder, H . M., Nuttal, R . 1,. (to U. S. Atomic Energy Commission), Zbid.,2,917,382 (Dec. 15, 1958). (13C) Fitch, F. T.: Russell, D. S. (to U. S. Atomic Energy Commission), Ibid.,2,852,338 (Sept. 16, 1958). (14C) Garner, C. S. (to U. S. Atomic Energy Commission), Zbid., 2,917,362 (Dec. 15, 1959). (15C) Kaplan, L. (to U. S. Atomic Energy Commission), Zbid., 2,910,442 (Oct. 27, 1959). (16C) King, E. L. (to U. S. Atomic Energy Commission), Ibid., 2,884,305 (April 28, 1959). (17C) Lowe, C. S. (to U. S. Atomic Energy Commission), Ibbid., 2,890,932 (June 16, 1959). (18C) Maddock, ,4. G., Booth, A. H. (to Honorary Advisory Council for Scientific & Industrial Research of Canada), Can. Patent 586,100 (Dec. 30, 1958). (19C) McKenzie, D. E. (to Atomic Energy ~
1 036
Ltd. of Canada), Zbid., 552,481 (Sept. 28, 1958). (20C) Miller, D. R., Seaborg, G. T., Thompson, S. G. (to U. S. Atomic Energy Commission). U. S. Patent 2,916358 (Dec. 15, 1959). 121C) Morgan. W. W..Mather. W. G.. ' Hart, R."G: (to Atdmic Energy Ltd.; of Canada), Can. Patent 557,561 (June 12. 19591. (22C) Ovirholt, D. C., Tober, F. W. (to U. S. Atomic Energy Commission), U. S. Patent, 2,863,718 (Dec. 9, 1958). (23C) Potratz, H . A . (to U. S. Atomic ' Energy Commission),' Jbid., 2,868,817 (Jan. 13, 1959). (24C) Reavis, J . G., Leary, J. A., Walsh, K . A. (to U. S. Atomic Enewv Commission)', Zbid., 2,886,410 (May 12, 1959). (25C) Ritter, D. M., Black, R. P. E. (to U. S. Atomic Energy Commission), Zbid.,2,906,597 (Sept. 29, 1959). (26C) Russell, E. R . , Adamson, A. W., Schubert, J. (to U. S. Atomic Energy Commission), Zbid., 2,859,093 (Nov. 4, 1958). (27C) Ryan, J. L., Wheelwright, E. J., IND.ENG.CHEW51, 60-5 (1959). (28C) Ryan, J. L., Wheelwright, E. J., U. N. Intern. Conf. Peaceful Uses At. Energy, 2nd, Geneva, 1958, paper 1915 USA. (29C) Seaborg, G. T. (to U. S. Atomic Energy Commission), U. S. Patent 2,882,124 (April 14, 1959). (30C) Seaborg, G. T., James, R. A. (to U. S. Atomic Energy Commission), Zbid.! 2,917,361 (Dec. 15, 1959). (31C) Seaborg, G. T., Willard, J. E. (to E.S. Atomic Energy Commission), Zbid.,2,819,144 (Jan. 7, 1958). (32C) Spedding. F. H., Ayres, J. A. (to U. S. Atomic Energy Commission), Ibid.,2,837,548 (June 3, 1958). (33C) Spedding, F. H., Butler, T. A. (to U. S. Atomic Energy Commission), Zbid.,2,778,730 (Jan. 22; 1957). (34C) Spedding, F. H., Newton, A. S. (to U. S. Atomic Energy Commission), Ibid.,2,882,125 (April 14, 1959). ~(35C)Thompson, S. G., Miller, D. R . (to U. S. Atomic Energv Commission), Zbid., 2,892,678 (June 36, 1959). (36C) U. K . Atomic Energy Authority, Brit. Patent, 783,601 (Sept. 25, 1957). (37C) Zbid.,800,377 (Aug. 27, 1958). {38C) Itid.,801,379 (Sept. 10, 1958). (39C) Ibid., 804,999 (Nov. 26, 1958). (40C) Zbid.,805,000 (Sept. 17, 1958). (41'2) Werner, L. B., Hill, 0. F. (to U. S. Atomic Energy Commission), U. S. Patent 2,815,265 (Dec. 3, 1957). (42C) Wolter, F. J., Diehl, H . C., Jr. (to U. S. Atomic Energy Commission), Jbid., 2,819,280 (Jan. 7,1958). Chemical Processing of Uranium a n d Plutonium Nuclear Fuels (ID) Boyd, G. E. (to U. S. Atomic Energy Commission), U. S. Patent 2,849,282 .~ (Aug. 26, 1958). (2D) Brown, H. S., Hill, 0. F. (to U. S. Atomic Energy Commission), Ibid., 2,851,333 (Sept. 9, 1958). (3D) Brown, H. S., Seaborg, G. T. (U. S. Atomic Energv Commission), Zbid.. 2,875,021 (Feby'24, 1959). (4D) Brown, H. S., Webster, D. S. (to U. S. Atomic Energy Commission), Zbid.,2,869,982 (Jan. 20, 1959). (5D) Crandall, H. W., Hicks, T. E., others (to U. S. Atomic Energy Commission), Ibid.:2,916,349 (Dec. 8,1959). (6D) Jaffey, A. H., Seaborg, G. T. (to U. S. Atomic Energy Commission)? Ibid.,2,865,704 (Dec. 23, 1958).
INDUSTRIAL AND ENGINEERING CHEMISTRY
"
(7D) Nicholls, C. M., Wells, I., Spence, R. (to U. S. Atomic Energy Commission) Ibid.,2,908,547 (Oct. 13, 1959). (8D) Seaborg, G. T., Brown, H. S. (to U. S. Atomic Energy Commission), Zbid.,2,875,021 (Feb. 24, 1959). (9D) Spence, R., Lister, M . W. (to U. S. Atomic Energy Commission), Ibid.> 2,864,664 (Dec. 16, 1958). (10D) Stahl, G. W. (to U. S. Atomic Energy Commission), Zbid., 2,867,500 (Jan. 6, 1959). (11D) U. K. Atomic Energy Authority, Brit. Patent 801,743 (Sept. 17, 1958). Stable Isotope Production (1E) Becker, E. W. A., Brit. Patent 803,274; iVucZear Eng. 4, 284 (1959). (2E) Brown, L. L., Begun, G. M . , J . Chem. Phys. 30, 1206-9 (1959). (3E) Clayton, R . N., Itid., 30, 1246-50 (1 959). (4E) Clusius, K., Dickel, G.: U. S. Atomic Energy Comm. AEC-tr-3692 (1959). (5E) Denman, J., New Zealand Dept. Sci. & Ind. Research, Div. Nuclear Sci. NS-3 (May 9, 1958). (6E) Hoffman, J. D., Ballou, J. K., U. S. Patent 2,813,598 (Nov. 19, 1957). (7E) Holmberg, K. E., U. N. Intern. Conf. Peaceful Uses At. Energy, 2nd, Geneva, 1958, Paper 180, Sweden. (8E) Hoogschagen, J. (to Stamicarbon N. V.), U. S. Patent 2,908,554 (Oct. 13, 1959). (9E) Johnson, R . W., Olson. E. H., U. S. Atomic Energy Comm. 1%-1069 (September 1958). (1OE) Kander, L. N., Taylor, T. I., Spindel, N., J . Chem. Phys. 31, 232-5 (1959). (11E) Kilpatrick, M., Hutchinson, C. A , , Jr., U. S. Atomic Energy Comm. TID-5227 (1952). (12E) Kirshenbaum, I., Christ: R. H. (to U. S. Atomic Energy Commission), U. S. Patents 2,795,303, 2,796,330 (June 18, 1957). (13E) Lee, D. A,, Begun, G. M., J A m . Chem. Ssc. 81, 2332- 5 (1959). (14E) Palko, A. A,, J. Chem. Phys. 30, 1187-9 (1959). (15E) Peters, K., Austrian Patent 204,052 (June 25, 1959). (16E) Ribniker, S. V., Knezevic? A. V.: Bull. Inst. iVu'utlear Sci. "Boris Kidrich" (Belgrade)9, 111-3 (1959). (17E) Spedding: F. H., Powell, J. E. (to Iowa State College Research Foundation). U. S. Patent 2,889,205 (June 2, 1959). (18E) Taylor, T. I., Clarke, J. C., J . Chem. Phys. 31, 277-8 (1959). (19E) Tunitskii, K. N., Devyatykh, G. G., others, Soviet Phjs.-?'ech. Pllys. 3, 822- 6 119581. (2dE) U, K. Atomic Energy Authority, Brit. Patent 795,920 (Sept. 25. 1957); Nuclear Eng. 4, 48 (1959). (21E) White, D., Haubach, W.J., J . Chem. Phys. 30, 1368-9 (1959). Radioisotope Production (1F) Beederman, M., Vogler, S., Hyman, H. H. (to U. S. Atomic Energy Commission), U. S. Patent 2,894,818 (July . . 14, i959j. (2F) Blanco, R. E. (to U. S. Atomic Enerrrv Commission), 2.895.798 ~, . , . Zbid., (Julf21, 1959). (3F) Burgus, W. H. (to U. S. Atomic Energy Commission), Zbid., 2,892,680 (June 30, 1959 . (4F) Callis, C. F!, Moore, R. L. (to U. S. Atomic Energy Commission), Ibid., 2,903,332 (Sept. 8, 1959). ~,
an(5F) Crandall, H. W., Thomas, J. R. (to U. S. Atomic Energy Commission), /bid., 2,892,681 (June 30, 1959). (6F) Deshpande, R. G., J . Chromatog. 2, 117-18 (1959). (7F) DeVoe, J. R., Kim, C. K., Meinke, W. W., Talanta 3, 298-9 (1960). (8F) Elson, R. E. (to U. S. Atomic Energy Commission), U. S. Patent 2,894,806 (July 14, 1959). (9F) Finston, H. L., Miskel, H. L., Ann. Rev. Nuclear Sri. 5 , 269-96 (1955). (10F) Flanary, J. R., Goode, J . H., others, U. S. Atomic Energy Comm. ORNL2235 (April 3, 1957). (11F) Fried, S. M. (to U. S. Atomic Energy Commission), U. S. Patent 2,860,948 (Nov. 18, 1958). (12F) Fuenteville, M. E. (to U. S. Atomic Energy Commission), Zbid., 2,892,679 (June 30, 1959). (13F) Grimley, S. S., Wells, I. (to U. K. Atomic Energy Authority), Brit. Patent 811,771 (April 15, 1959). (14F) Grummitt, W. E., Hardwick, W. H., Zbid., 812,682 (April 29, 1959). (15F) Hanson, D. A., Newby, B. J., Rohde, K. L., U. S. Atomic Energy Comm. IDO-14458 (June 8, 1959). (16F) Higgins, G. H., Crane, W. W. T. (to U. S. Atomic Energy Commission), U. S. Patent 2,887,358 (May 19: 1959). (17F) Higgins, I. R., Messing, A. F., U. S. Atomic Energy Comm. ORNL-2491 (1958). (18F) Hulet, E. K. (to U. S. Atomic Energy Commission), U. S. Patent 2,909,405 (Oct. 20, 1959). (19F) Hulet, E. K., Thompson, S. G. (to U. S. Atomic Energy Commission), Zbid., 2,891,839 (June 23, 1959). (20F) Institute for Atomenergi, Brit. Patent 812,701 (April 29, 1959). (21F) Karraker, D. G. (to U. S. Atomic Energy Commission), U. S. Patent 2,894,817 (July 14, 1959). (22F) Katzin, L. I., Larson, R. G., others (to U. S. Atomic Energy Commission), Zbid., 2,887,355 (May 19, 1959). (23F) Koch, R. C., Grandy, G. L., Nucleonics 18, 76-80 (July 1960). (24F) Kohman, T. P., Rightmire, R. A., others, Radioisotopes Sci. Research, Proc. Intern. Conf. Paris, 1957 1, 1-18 (1958). (25F) Kraus, K . A., Moore, G. E. (to U. S. Atomic Energy Commission), U. S. Patent 2,872,284 (Feb. 3, 1959). (26F) Lamb, E., Seagren, H. E., Beauchamp; E. E., t!, N. Intern. Conf. Peaceful Uses At. Energy, 2nd, Geneva, 1958, Paper 831 USA. (27F) Lewis, W. H., Ibid., Paper 1771 USA. (28F) Love, C. S., McVey, W. H. (to U. S. Atomic Energy Commission), U. S. Patent 2,903,333 (Sept. 8, 1959). (29F) MacGregor, M. H., Proc. U. N. Intern. Conf. Peaceful Uses At. Energy, I 2nd, Geneva, 1958 14, 109-15. (30F) Magnusson, L. B. (to U. S. Atomic Energy commission), 1,. S. Patent 2,830,066 (April 8. 1958). (31F) Ibid., 2,841,464 (July 1, 1958). (32F) Malm, J. G., Fried, S. (to U. S. Atomic Energy Commission), Ibid., 2,893,829 (July 7, 1959). (33F) Manning, W. M.; Studier, M. H., others, (to U. S. Atomic Energy Commission), Zbid., 2,859,095 (Nov. 4, 1958). (34F) McDonald, C. C., McDowell, J. R., Gunning, H. E., Can. J. Chem. 37, 930-9 (1 959). (35F) McIlroy, R. W., Glueckauf, E., others, Proc. U. N. Intern. Conf. Peaceful Uses At. Energy, 2nd, Geneva, 1958 18, pp. 27-32.
(36F) Mellish, C. E., Payne, J. A., Outlet, R. L., Radioisotopes Sci. Research, Proc. Intern. Conf. Paris, 1957 1, 35-49 (1958). (37F) Meservey, A. B., Rainey, R. H. (to U . S. Atomic Energy Commission), U. S. Patent 2,909,406 (Oct. 20, 1959). (38F) Morimoto, E. M., Kahn, M., J . Chem. Educ. 36, 296 (1959). (39F) Morris, E. T., Jr., Schultz, M. A., U. N. Conf. Peaceful Uses At. Energy, Znd, Geneva, 1958, Paper 1873 USA. (40F) Nairn, J. S., Co!lina, D. A,, others, Ibid., Paper 1485UK. (41F) Peppard, D. F., Mason, G. W., Sironen, R. J., J . Jnn~rg. &? Nuclear Chem. 10,117-27 (1959). (42F) Pczynajlo, A., Campbell, I. G., U. S. Atomic Energy Comm. NP-7641 (March 1958). (43F) Pressly, R. S. (to U. S. Atomic Energy Commission), U. S. Patent 2,893,827 (July 7, 1959). (44F) Roberts, F. P., Brauer, F. P., LJ. S. Atomic Energy Comm. HW-60552 (June 1, 1959). (45F) Spitsyn, V. I., Kuzina, A. F., Soviet. J . A t . Energy 5 , 975-81 (1959) (English transl.) : Atomnaya Fnercg. 5 , NO. 2, 141-6 (1959). (46F) Stang, L. G., Jr., Tucker, W. D., others, Radioisotopes Sci. Research, Proc. Intern. Conf. Paris, 1957 1, 50-70 (1 958). (47F) Susic, M., Selenic, T. S., Proc. U. N. Intern. Conf. Peaceful Uses at Energy, Znd, Geneva, 1958 18, pp. 82-5. (48F) Tompkins, E. R. (to U. S. Atomic Energy Commission), U. S. Patent 2,875,024 (Feb. 24, 1959). (49F) U. K. Atomic Energy Authority, Brit. Patent 810,542 (March 18, 1959). (50F) Veljkovic, S. R., Milenkovic, S. M., U. N. Intern. Conf. Peaceful Uses At. Energy, 2nd, Geneva, 1958, Paper 467 Yugoslavia. (51F) Westermark, E. G. T., FogelstromFineman, I. G. A,, Forsberg, S. R., Radioisotopes Sci. Research, Proc. Intern. Conf. Paris, 1957 1, 19-34 (1958). (52F) Wilson, E. J., Taylor, K. J., Atomic Energy Research Establishment I / R 2693 (1958). (53F) Yajima’, S., Shikata, F., Yamaguchi, C., bunseki Kagaku 7, 721 (1958). Radioisotope Applications (1G) Arnold, J. R., U. N. Intern. Conf. Peaceful Uses At. Energy, Znd, Genrva, 1958, Paper 411, USA. (2G) Bauks, H. O., Jr., U. S. Atomic Energy Comm. MND-SR-1673 (April 1959). (3G) Barnett, M., Anderson, G. M., Bollmeier, E. W., Nucleonics 17, 166-75 (1 959). (4G) Birdcn, J. h. (to U. S. Atomic Energy commission), U. S. Patent 2,870,339 (May 20, 1959). (5G) Bolin, B., U. N. Intern. Conf. Peaceful Uses At. Energy, 2nd, Geneva, 1958, Paper 176, Sweden. (6G) Chleck, D. J., Bronsoides, F. J., others, U. S. Atomic Energy Comm. AECU 4493 (July 1959). (7G) Chleck, D. J. Ziegler, C. A., Chem. ProcessEng. 40, 287 (1959). (8G) Craig, H., U. N. Intern. Conf. Peaceful Uses At. Energy, Znd, Geneva, 1958, Paper 1979 USA. (9G) Eastwood, W. S., Mullett, L. B., Putman, J. L., Nature 183, 643-4 (1959). (10G) Ellis, R. H., Jr., Nucleonics 17, 56-9 (1959).
Unit Processes Review
(11G) Garrett, A. B., J . Chem. Educ. 33, 446 (1956). (12G) Goldberg, E. D., Patterson, C., Chow, T., U. N. Intern. Conf. Peaceful Uses At. Energv, Znd, Geneva, 1958, Patxr 1980 USA. 3Gj Jech, C., Radioisotopes Sci. Research, Proc. Intern. Conf. Paris, 1957 2, 491-501 (1958). 4G) Koczy, F. F., U. N. Intern. Conf. Peaceful Uses At. Energy, 2nd, Geneva, 1958, Paper 2370 USA. 5G) Lal, D., Peters, B., Ibid., Paper 1626, India. 6G) Natl. Ind. Conf. Board, “Radioisotopes in Industry,” Off. Tech Services, Washington, D. C., 1959. 7G) Rafter, T. A., Fergusson, G. I., Proc. U. N. Intern. Conf. Peaceful Uses At. Energy, Znd, Geneva, 1958, 1 8 , pp. 526-32. (18G) Rochlin. R. S.. Schultz. W. W.. ’ “Radioisotopes for Industry,” ’Reinhold;. New York, 1959. (19G) Sechrist: C. N., Hammen, H. H., IND.END.CHEM.50, 341-2 (1958). (20G) U. S. Atomic Energy Comm., “Radioisotopes in Science and Industry,” Govt. Printing Office, Washington, D. C., 1960. (21G) von Buttlar, H., Wendt, I., U. N. Intern. Conf. Peaceful Uses At. Enerm. Znd, Geneva, 1958, Paper 1954, Germgny (Fed. Rep.). (22G) Westermark, T., Ljunggren, K., Erwall, L. G., Intern. J . AFpl. Radiation and IsotoFes 5 , 204-12 (1959). (23G) Wilson, F. J., Atomwirtshaft 4, 191-4 (1959). (24G) World Meteorological Organization, U. N. Intern. Conf. Peaceful Uses At. Energy, 2nd, Geneva, 1958, Paper 1536 WMO. Radioactive Wastes (IH) Conger, W. L., U. S. Atomic Energy Comm. ORNL-CF-59-6-73 (June 19, 1959). (2H) George, W. J., Chem. Eng. 66, 151-60 (Dec. 14, 1959). (3H) Health Physics Division, Oak Ridge Natl. Lab., and Robert A. Taft Sanit. Eng. Center, U. S. Atomic Energy Comm. ORNL-2257 (Feb. 11, 1959). (4H) Lowe, C. S. (to U. S. Atomic Energy Commission), U. S. Patent 2,766,204 (Nov. 27, 1956). (5H) McNabney, R., Lyon, A. M., U. S. Atomic Energy Comm. ARSC-28 (del.) (Aug. 26, 1949) (declass. March 24, 1959). (6H) Rimshaw, S. J., U. S.Atomic Energy Comm. TID-7517 (seminar, December 1955). (7H) Schulz, W. W., McKenzie, T. R., Ibid. (8H) Smit, J. V. R., Robb. W., Jacobs, J. J., Nucleonics 17, 116-23 (1959). Miscellaneous (1J) Aerojet-General Nucleonics, U. S. Atomic Energy Comm. TID-5693 (Novemiber 1959). (23) Arth ur D. Little, Inc., Zbid., ALI-52 (January 1959). (3J) Bacigalupi, C. M., Ibid., UCRL-5457 nuary 1959). Johnson, G . W., Ibid., UCRL-5458 (January 1960). 65) Lawrence Radiation Laboratory, Ibid., UCRL-5253 (Sept. 8 , 1958). (75) Jbid., UCRL-5676 (May 15, 1959). Zbtd., UCRL-5677 (May 15, 1959). Ztid., UCRL-5678 (May 15, 1959). Ibzd., UCRL-5679 (May 15, 1959). VOL. 52, NO. 12
DECEMBER 1960
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