BRIEFS RECYCLING PROCESS FOR THE COMMERCIAL PREPARATION OF I-METHYLPYRIDINIUM-2-ALDOXIME CHLORIDE
A process has been developed for the preparation of l-methylpyridinium-2-aldoxime chloride (2-PAM-Cl) by simply heating the corresponding iodide salt (2-PAM-I) with methanolic hydrogen chloride. The yields are high, and the resulting product is white and does not require recrystallization. Methyl iodide, recovered as a by-product in 80% yields, may be made to react with pyridine-2-aldoxime to prepare additional starting product for the reaction.
Robert I. Ellin, Physiological Chemistry Branch, Physiology Division, Edgewood Arsenal, M d .
IND.END.CHEM.PROD.RES.DEVELOP. 3, 20-21 (1964) XANTHATION OF STARCH BY A CONTINUOUS PROCESS
catalyst; however. the carbided catalyst required about twice as much sulfur as the reduced sample for poisoning to the same extent. For catalysts converted to epsilon iron nitride, the activity decreased less rapidly with sulfur fed to the catalyst than with reduced or carbided catalysts. When temperature was increased to compensate for loss in activity, moderately long tests at constant productivity were possible. Catalysts used in tests in which operating temperatures exceeded 300" C . were less oxidized than the same catalysts in synthesis tests at 250" to 260' C. In the high temperature poisoning tests, nitrided catalysts were partly converted to Hagg carbide.
F. S. Karn, J . F. Shultz, R. E. Kelly, and R. B. Anderson, Pittsburgh Coal Research Center, Bureau of Mines, U. S. Department of the Interior, Pittsburgh, Pa. IND.ENG.CHEM.PROD.RES.DEVELOP. 3, 33-38 (1964)
A rapid, continuous procedure for making starch xanthates was developed to make additives suitable for improving strength properties of pulp and paper products. Starch xanthates having degrees of substitution from 0.07 to 0.47 have been made in a smallscale continuous mixer-reactor system. Data were developed on the effect of mole ratios of starch, CS1, and aqueous NaOH, order of addition, temperature, and discharge pressure on degree of substitution, reaction efficiency, and power consumption. Starch xanthates were discharged as viscous pastes of 53 to 61% solids following 2-minute mixing. Conversion of CS2 to xanthate was 87 and 80% complete, respectively, for starch xanthates of D.S. 0.07 and 0.17 analyzed within 10 minutes after discharge. For products of D.S. 0.10 to 0.29, conversion was 90 to 9370 upon standing 1 hour after discharge. In general, maximum efficiency is favored by increasing the temperature, adding CS2 to starch before NaOH, increasing the NaOH/CS2 ratio, and decreasing discharge orifice size.
Four fluids were pumped in a simulated aircraft hydraulic circuit at 3000 p.s.i.g. and at temperatures as high as 700' F.: bis(phenoxyphenoxy)benzene, phenyl methyl silicone, deep dewaxed mineral oil, and an ester of trimethylolpropane. Bis(phenoxyphenoxy)benzene exhibited good reistance to degradation but phenyl methyl silicone deteriorated during 100-hour experiments at 700' F. The deep dewaxed mineral oil degraded rapidly at 700' F., so the run was terminated after 27 hours. The ester of trimethylolpropane experienced rapid degradation at 650' F. after it had been pumped for 25 hours at 550" F. and 25 hours at 600' F. Only the bis(phenoxyphenoxy)benzene warrants further investigation at 700" F. and above.
C. L. Swanson, T. R . Naffziger, C. R. Russell, B. T. Hofreiter, and C. E. Rist, Northern Regional Research Laboratory, Peoria, Ill.
IND.ENG.CHEM.PROD.RES.DEVELOP. 3, 38-43 (1964)
IND.ENG.CHEM.PROD.RES.DEVELOP. 3, 22-27 (1964) RECLAMATION OF DAMAGED NUCLEAR REACTOR COOLANT BY CATALYTIC HYDROCRACKING
Organic liquids such as terphenyls have been proposed for use as neutron moderators and heat transfer media in production of electrical power from nuclear reactors. Theory and experience have shown that thermal and radiolytic effects produce higher molecular weight materials which are detrimental to heat transfer. Catalytic hydrocracking is recommended for reconstituting this undesirable high boiling waste into usable coolant. Active metal oxides and metals on low surface alumina are effective catalysts for selective hydrocracking of polyphenyls into smaller aromatic molecules. Among the better catalysts are NiO-Al203, CoMoOa-Al203, Pt-Al203, and CoO-Vz06-AlzC03. Polyphenyls become more susceptible to hydrocracking with increasing chain length. Because of elimination of a vacuum distillation step, hydrocracking of total coolant is more efficient than that of undiluted high boiler. Reclaimed coolants from both methods were similar to terphenyl in viscosity, density, and vapor pressure. Although these products contained some alkylated aromatics, they are radiolytically stable at 650' F. and dosages of 1010 rads and thermally stable up to 750' F. Conservative economic evaluations indicated that hydrocracking coolant was commercially feasible for power plants producing 1000 megawatts (thermal).
L. E. Gardner and W . M . Hutchinson, Phillips Petroleum Go., Bartlesuille, Okla. IND. ENG.CHEM.PROD.RES. DEVELOP. 3, 28-33 (1964) HYDROGEN SULFIDE POISONING OF NITRIDED AND CARBIDED IRON CATALYSTS IN THE FISCHER-TROPSCHSYNTHESIS
Sulfur poisoning of iron Fischer-Tropsch catalysts was investigated because synthesis gas prepared by gasification of coal contains sulfur compounds. The poisoning of fused iron oxide catalysts 1CO feed gas was converted to Hagg carbide by H2S in 1H? qualitatively similar to the poisoning of the corresponding reduced
+
EVALUATION OF POTENTIAL 700' I N A PUMP LOOP
F. HYDRAULIC FLUIDS
Vern Hopkins and Donnell R. Wilson, Midwest Research Institute, Kansas City, Mo.
DESTRUCTION OF THE CAKING QUALITY OF BITUMINOUS COAL IN A FIXED BED
Bituminous coal heated through its plastic range in fixed, fluidized, or falling beds will generally agglomerate, resulting in inefficient operation. A pretreatment process was developed in which a caking coal was converted into a free-flowing char in a fixed bed. (All pretreated coals with a free swelling index of 1.5 or less are referred to as char.) Heating coal through its plastic range under controlled temperature and atmosphere is the basis of successful pretreatment. High-volatile A (hvab) and B and lowto 1 inches were pretreated in volatile coals in the size range of bed depths of 6 and 18 inches and at pressures from 0 to 300 p.s.i.g. Preliminary bench-scale tests indicate that char produced from a hvab coal can be gasified without caking, with steam in a fixed bed at 800' C. and atmospheric pressure, and with hydrogen in a dilute-phase free-falling bed at 750 O C. and 3000 p.s.i.g.
Stanley J . Gasior, Albert J. Forney, and Joseph H . Field, Bureau of Mines, U.S.Department of the Interior, Pittsburgh, Pa.
IND.ENG.CHEM.PROD.RES.DEVELOP. 3, 43-47 (1964) DESTRUCTION OF CAKING PROPERTIES OF COAL BY PRETREATMENT IN A FLUIDIZED BED
Treating fine coals at 400' to 425' C. with a fluidizing gas composed of either inert gas or steam containing at least 0.2Oj, oxygen destroys the caking properties of the coal. The minimum time required to produce a completely nonagglomerating char is about 5 minutes. The chars made may be used as a feed for a fluidizedbed gasification or a hydrogasification process.
Albert J. Forney, Richard I;: Kenny, Stanley J. Gasior, and Joseph H . Field, Bureau of Mines, U. S. Department of the Interior, Pittsburgh, Pa. IND.ENG.CHEM.PROD.RES.DEVELOP, 3,48-53 (1964).
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M A R C H 1964
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