CATALYST HANDLING SAFETY

Injuries and fatalities from asphyxiation are often associated with personnel entry into inerted equipment or enclosures. Guidance on safe procedures for confined space access are provided by OSHA (OSHA, 29 CFR 1910.146, Confined Space Entry Standard, 2000), the American National Standards Institute (ANSI, Z117.1, Safety Requirements for Confined Spaces, 2003), Hodson (Hodson, Safe Entry into Confined Spaces, Handbook of Chemical Health and Safety, American Chemical Society, 2001), and BP (BP, Hazards of Nitrogen and Catalyst Handling, 2003). OSHA has established 19.5 vol % as the minimum safe oxygen concentration for confined space entry without supplemental oxygen supply (see Table 23-18). Note that OSHA imposes a safe upper limit on 02 concentration of 23.5 vol % to protect against the enhanced flammability hazards associated with 02-enriched atmospheres. 

Reppe s work also resulted in the high pressure route which was estabUshed by BASF at Ludwigshafen in 1956. In this process, acetylene, carbon monoxide, water, and a nickel catalyst react at about 200°C and 13.9 MPa (2016 psi) to give acryUc acid. Safety problems caused by handling of acetylene are alleviated by the use of tetrahydrofuran as an inert solvent. In this process, the catalyst is a mixture of nickel bromide with a cupric bromide promotor. The hquid reactor effluent is degassed and extracted. The acryUc acid is obtained by distillation of the extract and subsequendy esterified to the desked acryhc ester. The BASF process gives acryhc acid, whereas the Rohm and Haas process provides the esters dkecdy. 

Health and Safety Factors. Animal-feeding studies of DMPPO itself have shown it to be nontoxic on ingestion. The solvents, catalyst, and monomers that are used to prepare the polymers, however, should be handled with caution. Eor example, for the preparation of DMPPO, the amines used as part of the catalyst are flammable toxic on ingestion, absorption, and inhalation and are also severe skin and respiratory irritants (see Amines). Toluene, a solvent for DMPPO, is not a highly toxic material in inhalation testing the TLV (71) is set at 375 mg/m, and the lowest toxic concentration is reported to be 100—200 ppm (72). Toxicity of 2,6-dimethylphenol is typical of alkylphenols (qv), eg, for mice, the acute dermal toxicity is LD q, 4000 mg/kg, whereas the acute oral toxicity is LD q, 980 mg/kg (73). The Noryl blends of DMPPO and polystyrene have PDA approval for reuse food apphcations. 

Most general-purpose release agents have been developed for this market in part because of their low toxicity and chemical inertness and do not usually present health and safety problems. Some of the solvent dispersions require appropriate care in handling volatile solvents, and many supphers are offering water-based alternatives. Some of the sohds, particularly finely divided hydrophobic sohds, can also present inhalation problems. Some of the metallic soaps are toxic, although there is a trend away from the heavier, more toxic metals such as lead. The reactive type of release coating with monomers, prepolymers, and catalysts often presents specific handling difficulties. The potential user with health and safety questions is advised to consult the manufacturer directly. 

Tertiary Amine Catalysts. The Hquid tertiary aHphatic amines used as catalysts in the manufacture of polyurethanes can cause contact dermatitis and severe damage to the eye. Inhalation can produce moderate to severe irritation of the upper respiratory tracts and the lungs. Ventilation, protective clothing, and safety glasses are mandatory when handling these chemicals. 

Reagents were purchased from commercial sources and used without further purification. Product identities were confirmed by comparison of HPLC retention times with authentic samples. The Pd/C catalyst was purchased as a dry, edge-coated, unreduced catalyst with 5 wt% in Pd. HPLC analyses were performed on a HP 1090 (stationary phase C18, 25 cm x 0.46 cm mobile phase CH3CN/H20 1% H3P04, 90% H20 to 100% CH3CN gradient over 25 min, 1 ml/min flow, UV-Vis detection). For safety aspects of handling Pd/C, see ref. 7.7... 

In addition, many other aspects must be considered when developing a catalytic reaction for industrial use these include catalyst separation, stability and poisoning, handling problems, space-time yield, process sensitivity and robustness, toxicity of metals and reagent, and safety aspects, as well as the need for high-pressure equipment. 

Laboratory Handling of Metal Catalysts, in Chem. Safety, 1949, (2), 5... 

Because of safety considerations, 90% hydrogen peroxide, used in most TFPAA oxidations, and 85% MCPBA may soon become commercially unavailable. Possible alternatives are magnesium monoper-oxyphthalate for MCPBA and the easily handled acid catalyst Nafion-H which facilitates oxidations with 30% H2O2. Weaker strength TFPAA acid solutions are effective,gnd the strength of MCPBA is easily increased by washing with buffer solution. ... 

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