In Part I (Tsonopoulos and Wilson, 1983), the mutual solubilities of three Ca hydrocarbons (benzene, cyclohexane, n-hexane) and water were experimentally investigated and, together with critically selected literature data, were correlated up to the three-phase critical end point. The present paper extends this analysis to the mutual solubilities of three Cs hydrocarbons (ethylbenzene, ethylcyclohexane, n-octane) and water, which have been measured at the threephase equilibrium pressure up to the critical temperatures (568,561 and 539 K, respectively), A thermodynamic analysis of these new measurements and of available literature data has been performed up to the three-phase critical end point. Information is also provided on vapor-phase equilibrium compositions. The solubility of hydrocarbons in water has been used to calculate Henry's constants, while the solubility and volatility of water in hydrocarbons has been successfully correlated with several modifications of the Redlich-Kwong equation of state. SCOPEThe importance of hydrocarbon/water mutual solubilities to the design and operation of process equipment in refineries and petrochemical pIants was discussed by Tsonopoulos and Wilson (1983) [this reference will be cited as TW (1983)J The same reference also discussed the correlation and prediction of mutual solubilities, Henry's constants for hydrocarbons in water, and the use of equations of slate. All these were applied to Ce hydrocarbons, for which much more is known than for other hydrocarbons.Our work continues with CS hydrocarbons to study the effect of carbon number on mutual solubilities. But we have also expanded the scope of our study by including experimental data for the vapor composition and the three-phase critical end point, the highest temperature at which the vapor and the two liquid phases coexist.

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Liquid products from the SRC-II processing of a high volatile bituminous coal were distilled into narrow boiling range fractions with average boiling points ranging up to 800 K. Liquid density, thermal conductivity, and viscosity were measured at temperatures to 505 K, and specific heat was determined to 600 K. Other property determinations included molecular weight, pour point, elemental analyses, water content and solubility, and hydrocarbon types. Both organic oxygen content and water solubility showed a pronounced maximum for the fraction having an average boiling point of 470 K and significantly Influenced density. A secondary distillation on six different fractions spaced over the entire boiling range yielded heart cuts spanning 4-26 K that were used for measurement of surface tension, heat of vaporization, and vapor pressure at temperatures to 755 K. Property data for all the fractions are compared with other published data and existing property correlations.

H-ZSM-5 zeolite-supported Ga (Ga/H-ZSM-5) has been considered as a selective catalyst for nonoxidative propane dehydrogenation (PDH) for decades; however, the reaction mechanism remains a topic of considerable discussion. In particular, the correlation between various Ga species present on the catalyst at the reaction conditions and the PDH activity has yet to be established. In this work, intrinsic PDH rates and activation energies were determined on Ga + −H + pair sites and isolated Ga + sites on Ga/H-ZSM-5 samples with a wide range of Si/Al and Ga/Al ratios. The turnover frequency on Ga + −H + pair sites in the PDH is higher than that of isolated Ga + sites by a factor of ∼15. Experimental measurements combined with a dual-site model show the activation energy in the PDH on the Ga + −H + pair sites and isolated Ga + sites to be 90.8 ± 1.5 and 117 ± 4.7 kJ•mol −1 , respectively. These results demonstrate that Ga + −H + pair sites are much more active in the PDH than isolated Ga + sites. The activation energy of GaH x decomposition to form H 2 was determined to be 40−60 kJ•mol −1 higher than that of the PDH on Ga species, suggesting that the GaH x decomposition is unlikely to be part of the PDH mechanism. Although both Brønsted acid and Ga sites interact with propane, Fourier transform infrared spectroscopy results provide strong evidence suggesting that the alkyl mechanism is more likely in the PDH on Ga/H-ZSM-5 catalysts.

Enzymatic hydrolysis of triglycerides has been studied as a low energy‐consuming alternative to the present steam (Colgate‐Emery) process. Cost analysis of the enzymatic process indicates that use of immobilized lipase compares favorably with the present steam process. This paper discusses the search for an adsorbent to use as the support material for the lipase. Hydrophobic microporous powders, membranes and fibers were found to give the best performance, as little of the lipase's activity was lost upon immobilization. Lipase immobilized on Accurel powder has been studied in various reactor configurations for the hydrolysis of triglycerides. Reactor designs studied include cocurrent and counter‐current fixed beds, continuous stirred tank reactors, and the diaphragm reactor. Productivities of the latter two reactor types were 1100 and 1700 kg fatty acid per kg immobilized lipase.

Amines are widely used in the manufacture of pharmaceuticals, agricultural chemicals, polymers, and surfactants. However, amines are mostly produced via petrochemical means, which motivates amine production from renewable resources, such as biomass. However, biomass compounds present added challenges involving poor carbon balances. We show that furfural reacts homogeneously with ammonia to produce reactive primary imines, which form large side products and leads to significant carbon losses. The carbon balance is improved by mixing furfural with furfurylamine prior to reaction to form a secondary imine for use as the reaction substrate. While controlling the primary to secondary amine selectivity is a common challenge in reductive amination, supported metal catalysts, including Ni/SiO2, Co/SiO2, and Ru/SiO2 optimize the primary amine yield to 90 to 94 % by using the secondary imine as the reaction substrate. A qualitative correlation between the primary to secondary amine selectivity with the nitrogen binding energy of metals is identified.

Methane dehydroaromatization (DHA) is a desirable process for the conversion of methane in stranded natural gas to valuable and easy-to-transport liquid aromatic compounds. However, the reaction is severely limited by thermodynamics. We present a method to circumvent the thermodynamic limitation by coupling DHA with chemical looping to achieve reactive separation of H2 from the products of DHA. The proposed strategy involves a four-step cycle, i.e., DHA on the Mo/H-ZSM-5 catalyst, hydrogen removal, and regeneration on the Fe3O4/FeO redox pair, and water removal on Zeolite 5A. The feasibility of this process is validated by investigating each step individually. The results indicate that an aromatics yield up to >40% is possible with the proposed process.

This paper reports on the catalyst stability of the hydrotreatment of HTL (Hydrothermal Liquefaction) biocrudes to produce finished liquid transportation fuel blendstocks. We report the stable hydrotreating of HTL biocrude derived from sewage sludge and food waste over industrially relevant hydrotreating CoMo and NiMo catalysts at relevant catalyst activities. The use of wet-wastederived HTL biocrudes derived from both food waste and sewage sludge in the hydrotreater campaign strengthens the case that HTL biocrudes derived from a variety of wet-waste feedstocks can be upgraded without significant catalyst instability over industrially relevant hydrotreater time-periods. Stable hydrotreating performance was obtained with each feedstock. The overall yield was approximately 85% with all HTL biocrudes. Over 1500 h of steady-state operation, minimal deactivation was observed. These results indicate that a hydrotreatment process to upgrade can be stable for industrially relevant times, a critical roadblock to derisking commercialization. The upgraded product produces a diesel-rich (∼70% in the 150−350 °C range) fuel blendstock, with high cetane due to the high fraction of alkanes. Further, we report the impact of process levers on hydrotreating performance on a fully broken-in catalyst (following 1500 h of steady-state operation). The long-term catalyst stability presented here is an important demonstration to derisk HTL commercialization.