THERMAL STABILITY ANALYSIS OF THE LIQUID PHASE METHANOL SYNTHESIS REACTOR

The effect of addition of an inert liquid phase on the rate of heat generation in the catalytic synthesis of methanol from syngas has been studied. Gas compositions typical of product gases from Lurgi and Koppers-Totzek gasifiers, represented by H₂-rich and CO-rich syngas respectively, were used to experimentally verify the “slope” and “dynamic” critria in a three-phase fixed bed recycle reactor. The liquid medium, witco-40 oil, has been effective in controlling the rate of heat generation and in preventing catalyst overheating, signifying that the liquid phase synthesis is thermally far more stable than the vapor phase synthesis. The experimental thermal stability study provides crucial and valuable information in commercializing the liquid phase methanol synthesis process. The current approach of thermal stability analysis does not require any a priori assumption or predetermined reaction kinetics.     

The desorption of O2 during NO and N2O decomposition on Cu- and Fe-zeolites

The decomposition of NO and of N₂O over a CuZSM-5 zeolite and a Fe-mordenite, respectively, has been studied using tracer techniques. The results demonstrate the high mobility of the lattice oxygen ions in self-diffusion. They afford a possible explanation for the problem of how two extralattice oxygens located at positions remote from each other may combine to form the O₂ molecules which are spontaneously desorbed in these redox reactions. They show that a portion of the lattice oxygen mixes into the O₂ released on decomposition. The data also show that N¹⁸O and N₂ ¹⁸O undergo exchange with the catalyst oxygen under reaction conditions.On leave from Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1525 Budapest, Hungary.     

THE “UCKRON-1” TEST PROBLEM FOR REACTION ENGINEERING MODELING

Testing kinetic models against a “true” and detailed kinetic expression was the aim of the Workshop on Kinetic Model Development at the Denver AIChE Meeting in August, 1983. For this purpose an artificial reaction mechanism was created, based on the known thermodynamics of the methanol synthesis as a framework. The kinetic rate laws, that were derived from this mechanism, were made thermodynamically consistent by achieving agreement between equilibrium constants calculated at various temperatures from the given, real original thermodynamic relationship and those calculated from the detailed reversible kinetic expressions.

Using the artificial kinetics as the "true" one, CSTR experiments were simulated. The results of a statistically designed set of experiments were published after 5% random error was added to the data. Participation was invited for all interested to correlate the data, develop kinetic models and to calculate the performance of the specified reactor.

The results of 19 submitted entries are summarized with the conclusion that the models had more differences than were expected, but their predictive values were not as different as was anticipated, if the extreme high production rates due to thermal runaways are not considered. This in turn points out the necessity to check models experimentally, in pilot plant, not only for predicted optimum, but also for calculated runaway conditions. Models which did not capture the true character of this reaction failed to predict the onset of runaway reactions.     

On the preparation and properties of CuZSM-5 catalysts for NO decomposition

Equilibrium exchange isotherms were determined for the exchange of Cu²⁺ with NaZSM-5 at varying Cu(Ac)₂ concentrations in solutions of constant volume and zeolite weight. At low Cu²⁺ levels the solid scavenged all the copper ions. When copper could be detected in the equilibrated solutions, overexchange was observed. The extent of overexchange was higher at pH 6 than at pH 4. These results were analyzed in relation to catalytic activity.On leave from the Central Institute for Chemistry, Hungarian Academy of Sciences, H1525 Budapest, Hungary.     

N-Aminierung von Isochinolinbasen

N-Amination of Isoquinoline Bases 3, 3-Pentamethylene oxaziridine 1 forms an N N-bond with secondary isoquinoline bases 2a – f to give the cyclohexylidene hydrazines 3a – f . In some cases nitrogen elimination yielding indane derivatives 13b, 13e competes with hydrazone formation. The cyclic Schiff'base 14 and the β-carboline derivative 16 can also be aminated.     

Hydroisomerization of Fischer�CTropsch Wax on Pt/AlSBA-15 and Pt/SAPO-11 Catalysts

A Pt/AlSBA-15 catalyst was investigated in the selective isomerisation of Fischer?CTropsch wax, which type of catalyst have not been studied in detail in this reaction system yet. Its hydroconversion activity was compared with that of the Pt/SAPO-11 catalyst. Based on the results it was concluded that the selective isomerization of the Fischer?CTropsch wax can be a new application of the Pt/AlSBA-15 catalyst.     

Tobacco etch virus protease: mechanism of autolysis and rational design of stable mutants with wild-type catalytic proficiency

Because of its stringent sequence specificity, the catalyticdomain of the nuclear inclusion protease from tobacco etch virus(TEV) is a useful reagent for cleaving genetically engineeredfusion proteins. However, a serious drawback of TEV proteaseis that it readily cleaves itself at a specific site to generatea truncated enzyme with greatly diminished activity. The rateof autoinactivation is proportional to the concentration ofTEV protease, implying a bimolecular reaction mechanism. Yet,a catalytically active protease was unable to convert a catalyticallyinactive protease into the truncated form. Adding increasingconcentrations of the catalytically inactive protease to a fixedamount of the wild-type enzyme accelerated its rate of autoinactivation.Taken together, these results suggest that autoinactivationof TEV protease may be an intramolecular reaction that is facilitatedby an allosteric interaction between protease molecules. Inan effort to create a more stable protease, we made amino acidsubstitutions in the P2 and P1' positions of the internal cleavagesite and assessed their impact on the enzyme's stability andcatalytic activity. One of the P1' mutants, S219V, was not onlyfar more stable than the wild-type protease (~100-fold), butalso a more efficient catalyst.     

Building Budapest's new reservoir

Nearing completion on Gellert Hill overlooking the Danube at Budapest is an enclosed pianoshaped water reservoir of 80 000 m³ capacity. The complexities of this waterproof, stressed concrete structure, which entailed placing 2 000 m² of base slab in 41 hours and erecting walls in situ in 20 m sections 350 mm thick and 10 m high, presented several technical challenges.

They are discussed here by the department head of the Civil Engineering Design Enterprise, Mélyépterv.     

Mechanism of NO decomposition over Cu-ZSM-5

In the preceding Letter Shelef [1] has proposed a mechanism for NO decomposition involving coordinatively unsaturated Cu²⁺ sites on which NO molecules are chemisorbed in the gem-dinitrosyl form. At reaction temperature this complex is supposed to decompose into N₂ and O₂ without involving a redox process. That such a process is feasible has been pointed out by Moser [2]. Shelef cited several reasons in support of this view and others that have led him to think that a cyclic redox mechanism is not operative. These arguments are countered herein and some new data are presented showing the infrared spectra of surface species recorded under in situ reaction conditions.On leave from Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1525 Budapest, Hungary.     

PERFORMANCE COMPARISON OF LABORATORY AND COMMERCIAL REACTORS USING THE UCKRON-I REACTION SYSTEM

A reactor model which includes axial and radial mass and heat dispersion was developed to compare the performance of laboratory and commercial reactors for the UCKRON-I reaction system. The program for the model allowed selection of either the ideal gas assumption or the real gas assumption for estimating physical properties and fugacities of each component. The two dimensional model using ideal gas assumptions gave essentially the same coolant temperature, 485.5 K, for the onset of thermal instability for commercial reactors as published values obtained using one dimensional models. Use of real gas assumptions reduced the coolant temperature at which thermal instability occurred for the commercial reactor by about 3 K. The coolant temperature at which thermal instability occurred for the laboratory reactor was about 50 K lower for both ideal and real gases assumptions.