Effect of the support on the coking of nickel catalysts in hydrocarbon steam reforming

Experiments on the coking rates of variously prepared nickel catalysts on TiO₂, Al₂O₃ and MgO in n-butane steam reforming show that changes in the relative coking rate at a rising steam excess in the gas phase depend mainly on the kind of support. The results obtained are accounted for by changes in the electron density at the site of nickel crystallite contact with the surface of various supports.

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, TiO₂, Al₂O₃ MgO, - , , , , , . .

     

Activity of some crystal faces of supported palladium catalysts for benzene hydrogenation

Using known coverages of preadsorbed carbon monoxide as a specific poison on supported polycrystalline Pd, the degree of benzene conversion into cyclohexane was measured and compared with the conversion over a CO-free catalyst surface. Palladium crystal faces adsorbing carbon monoxide in various manners are uniformly active for benzene hydrogenation, which appears to be a structure insensitive reaction.

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. . , , . , .

     

Effect of P2O5 content in phosphogypsum on its thermal decomposition to CaCO and SO2

The effect of P₂O₅ on the thermal decomposition of phosphogypsum to phospholime and sulphur dioxide has been studied.

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Zusammenfassung Es wurde der Einfluß von P₂O₅ auf die thermische Zersetzung von Phosphogips zu Phospholim und Schwefeldioxid untersucht.

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.

     

Kinetic conversion of complex hydrocarbon mixtures in reforming on platinum/alumina catalysts

General forms of the kinetic equations for the conversion of various hydrocarbons in reforming of multicomponent gasoline fractions on platinum/alumina catalysts have been confirmed experimentally by using a gradientless method.

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Enantioface-differentiating transfer hydrogenation of ethyl acetoacetate on modified Raney nickel

Ethyl acetoacetate was hydrogenated on tartaric acid-NaBr-modified Raney nickel in the presence of isopropanol as hydrogen source—the first example concerning the asymmetric transfer hydrogenation using a chiral modified metal catalyst.

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, — NaBr — . , .

     

Studies on thermal stability and knot formation in the TG curves of Co(III) model complexes

TG studies of vitamin B₁₂ coenzyme model complexes, BrCo(diacetylmonoximeiminatodiacetylmonoximatoiminobenzene-1,6)L have been carried out with different heating rates and sample sizes. The trans ligand, L, is bromine, imidazole, methylimidazole, pyridine or triphenylphosphine. The decompositions of the complexes (except for the triphenylphosphine complex) are associated with the formation of a knot at the point of completion of the inflection of the TG curve at a heating rate of 20 deg/min; such a phenomenon is not observed for rates of 10 and 5 deg/min. The formation of a knot with increase in weight and decrease in temperature is attributed to the transition from high-energy six-coordinate Co(III) species to low-energy five-coordinate Co (II) species. The triphenylphosphine complex is found to deviate from these characteristics of decomposition.

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Zusammenfassung TG-Untersuchungen von Vitamin-B₁₂-Coenzymkomplexen — BrCo (Diacetylmonoxim-iminato-diacetylmonoximato-iminobenzol-1,6)L wurden bei verschiedenen Aufheizgeschwindigkeiten und mit unterschiedlichen Probenmengen ausgeführt. Der trans-Ligand L ist mit Brom, Imidazol, Methylimidazol, Pyridin bzw. Triphenylphosphin modifiziert. Mit Ausnahme des Triphenylphosphinkomplexes geht die Zersetzung der Komplexe bei einer Aufheizgeschwindigkeit von 20 °/min mit der Ausbildung einer Schleife an der Stelle des TG Kurve einher, an der die Inflektion beendet ist. Solch ein Effekt ist nicht bei Aufheizgeschwindigkeiten von 10 und 5 °/min zu beobachten. Das eten einer Schleife mit zunehmenden Gewicht und abnehmender Temperatur ist der Umwandlung von 6-fach koordinierten Co(III)-Species hoher Energie in 5-fach koordinierte Co (II) -Species niedriger Energie zuzuschreiben. Der Triphenylphosphinkomplex weicht von dieser Zersetzungscharakteristik ab.

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- ₁₂, r(- - -- -1,6)L, . - L , , , . , , 20°/. 10 5°/. () ((II) . , .

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The author acknowledges the help of Mr. V. Alexander, who provided gift coenzyme model complex samples.     

Some investigations on the photostabilization of polypropylene

The effect of substituted hydroxybenzophenone, benzotriazole and organic metal complexes on the photooxidation of PP films has been studied. It has been established that NiDBTC added in 1.0 wt. % is the most effective photostabilizer.While in the case of other stabilizers there is a slight increase in the Co content even during the induction period, with the application of NiDBTC practically no oxidation can be observed before the stabilizer completely disappears. This means that NiDBTC inhibits the photooxidation of the polymer even in low concentration.

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, - . , Ni, 1,0 . %. . , Ni , . , Ni .

     

Fluctuations and dynamics of chemical reactions near neutral steady-state

The effect of fluctuations on the behavior of a simple kinetic model of catalytic reactions allowing a neutral steady-state, is analyzed.

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, , .

     

Catalytic decomposition of N2O on La2CuO4 in the presence of LaNi5 alloy

Decomposition of N₂O has been studied on pure La₂CuO₄, La₂CuO₄ with 5 and 10 wt. % LaNi₅ and oxidized LaNi₅ in the temperature range of 240–490 °C at 50 and 200 Torr initial pressures of N₂O. The addition of LaNi₅ decreases the energy of activation compared to that of La₂CuO₄ which has been explained based on the dispersity of NiO over La₂CuO₄.

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N₂O La₂CuO₄ La₂CuO₄ LaNi₅ 5–10 .%, 240–490°C N₂O 50 200 . LaNi₅ , . NiO La₂CuO₄.

     

Reaction between the OH group of hydroxyproline and diisocyanate catalyzed by an organotin compound

We have studied the kinetics of the reaction of L-hydroxyproline with OCH(CH₂)₆NCO, catalyzed by organotin, avoiding side reactions by protecting the other active hydrogens of the aminoacid, and comparing it with the MeOH/n-BuNCO system.

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L-- -OCN(CH₂)₆NCO, , . . - .

     

New models of monooxygenase on the basis of Sn(II) compounds

The data on the selectivity of various C–H bonds and the stereochemical course of the reaction in the known chemical systems simulating monooxygenase, do not agree with the oxenoid mechanism postulated for these reactions, but correspond to the interaction of saturated hydrocarbons with the OH radical intermediate. On the basis of organic compounds of Sn(II) in aprotic media, new systems have been developed which selectively oxidize alkanes to alcohols in the presence of O₂ in the coupled process and display many characteristics of the oxenoid reactions.

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C–H , , , , . (II) , .

     

Kinetic equations with a complex balanced stationary point

A class of ordinary differential equations including nonideal nonisothermal kinetics is introduced. The behavior of their solutions for the system with a positive complex-balanced stationary point is studied. Sufficient conditions for this point to exist are described.

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, . . .

     

Simultaneous DTA and DTG measurements on aluminium oxide monohydroxides

Simultaneous DTA and DTG curves (Mettler TA-2) have been measured for one diaspore and four different boehmites at temperatures up to 750° in a flow of dried argon. The crystallographic structures of the materials were assessed by X-ray diffraction and the degree of clustering of the elementary particles by scanning electron microscopy. To get straight base-lines a calibration curve was used to correct the DTA curves. The usefulness of the correction was established by comparison with DTA curves obtained with a Mettler TA-2000.The diaspore contained occluded water. Expulsion of the water at 300–350° brought about fragmentation of the crystals. The DTA and DTG peaks that correspond to the dehydration to alumina both lie at 560°.There is a noticeable spread in the DTA and DTG peaks for the different boehmites in the temperature range 455–530°. All the DTA peaks lie close to the corresponding DTG peaks. One of the boehmites displayed a double peak (470° and 502°). To trace the origin of the variation in peak temperature, the porous structure of the boehmite having its peak at 530° was varied by ball-milling and by dispersion into water, neither of which markedly affected the crystallographic structure and the crystallite size. Whereas ball-milling did not change the peak temperature much, dispersion into water brought about a transition from a single peak at 530° to a double peak at 450° and 490°. Prolonged storage in air led to a shift of the peaks to 480° and 520°. It is concluded that the porous structure of boehmites can profoundly affect the appearance and the temperature of their dehydration peaks.

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Zusammenfassung Simultane DTA- und DTG-Kurven (Mettler TA-2) wurden für ein Diaspor und vier verschiedene Boehmite bei Temperaturen bis zu 750° in einem Strom von getrocknetem Argon aufgenommen. Die kristallographische Struktur der Substanzen wurde mittels Röntgendiffraktion und der Anhäufungsgrad der Elementarpartikel mittels Raster-Elektronenmikroskopie bestimmt. Um gerade Grundlinien zu erhalten wurde eine Eichkurve zur Korrektur der DTA-Kurven verwendet. Die Nützlichkeit der Korrektur wurde durch Vergleiche der in einem Mettler TA-2000 Gerät erhaltenen DTA-Kurven festgestellt.Der Diaspor enthielt eingeschlossenes Wasser. Das bei 300 bis 350° erfolgte Abspalten des Wassers brachte eine Fragmentierung der Kristalle mit sich. Die DTA- und DTG-Peaks, welche der Dehydratisierung zu Aluminiumoxid entsprechen, liegen beide bei 560°.Im Temperaturbereich von 455 bis 530° läßt sich ein Verbreitern der DTA- und DTG-Peaks der verschiedenen Boehmite wahrnehmen. Einer der Boehmite zeigte einen Doppel-peak (470° und 502°). Um dem Ursprung der Änderungen der Peak-Temperaturen festzustellen wurde die poröse Struktur des Boehmits mit einem Peak bei 530° mit Hilfe einer Kugelmühle und durch Dispersion in Wasser verändert. Keine dieser Behandlungen änderte merklich die kristallographische Struktur und die Kristallgröße. Während das Vermählen in der Kugelmühle die Peak-Temperatur nicht wesentlich änderte, erbrachte die Dispergierung in Wasser einen Übergang von einem einzigen Peak bei 530° zu einem Doppelpeak bei 450 und 490°. Längeres Lagern an der Luft führte zu einer Verschiebung der Peaks nach 480° und 520°. Es wird gefolgert, daß die Porösstruktur von Boehmiten das Erscheinen und die Temperatur ihrer Dehydratisierungspeaks stark beeinflussen kann.

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Résumé Les courbes ATD et TGD d'une diaspore et de quatre boehmites différentes ont été enregistrées simultanément (Mettler TA-2) jusqu'à 750°, sous circulation d'argon desséché. La structure cristallographique de ces composés a été examinée par diffraction des rayons X et le degré de compacité a été évalué par microscopie électronique à balayage. Une courbe d'étalonnage a été utilisée pour corriger les courbes ATD et obtenir des lignes de base droites. L'utilité de cette correction est démontrée en comparant avec les courbes ATD obtenues à l'aide d'un appareil Mettler-TA-2000.La diaspore contenait de l'eau d'inclusion. L'élimination de l'eau à 300–350° a entraîné la fragmentation des cristaux. Les pics ATD et TGD qui correspondent à la déshydratation en oxyde d'aluminium se trouvent tous deux à 560°.Un étalement des pics ATD et TGD est perceptible pour les différentes boehmites dans l'intervalle de température 455–530°. Tous les pics ATD sont proches des pics TGD correspondants. L'une des boehmites a donné un pic double (470 et 502°). Afin de trouver l'origine de la différence de température entre les deux pics, la structure poreuse de la boehmite dont le pic se situait à 530° a été modifiée par traitement dans un broyeur à boulets et par dispersion dans de l'eau; ni l'un ni l'autre de ces deux traitements n'influence de façon apparente la structure cristallographique et la taille des cristaux. Alors que le traitement au broyeur à boulets ne change pas beaucoup la température du pic, la dispersion dans de l'eau fait apparaitre le passage d'un pic unique à 530° à un pic double à 450 et 490°. Le stockage prolongé dans l'air provoque un déplacement des pics à 480 et 520°. On en conclut que la structure poreuse des boehmites peut influer profondément sur l'apparition et la température de leurs pics de déshydratation.

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— ( TA-2) 750° . - , — . . , TA-2000. . 300–350°C, . — , , 560°. - 455–530°. . (470° 502°). , 530°C . . , — 530° — 450° 490°. 480° 520°. , , .

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The authors are indebted to Dr. P. F. Elbers for placing the electron microscopic facilities of the University of Utrecht at their disposal. We especially wish to acknowledge the time and energy spent by Mr. J. Pieters in the preparation of samples and the investigation with the scanning electron microscope. The assistance given by Dr. A. Duisenberg in the measurement of the line-broadening is also gratefully acknowledged.     

Investigation of catalytic purification of gases from aromatic hydrocarbons

1,1- (AH) ([AH]=6,9 /, 50°C). AH W_i/W_{O 3}=0,40±0,16.

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The kinetics and oxidation products of 1,1-diethoxyethane (AH) ozonolysis have been investigated at [AH]=6.9 mol/l and 50 °C. The initiation efficiency of radical oxidation by ozone is W_i/W_{O 3}=0.40±0.16.

     

High-temperature pyrolysis of polymers

The experimental results on the pyrolysis of thermoplastic polymers under high-temperature heating and burning conditions are discussed. The reaction of polymer degradation in this case proceeds in the same way as in a low-temperature region.

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Zusammenfassung Die experimentellen Ergebnisse der Pyrolyse von thermoplastischen Polymeren unter Erhitzungs- und Brehnbedingungen hoher Temperatur werden besprochen. Die Reaktion der Polymerzersetzung verläuft in diesem Falle genau so wie in der Niedrigtemperaturzone ab.

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. , .

     

H/D isotope exchange during ethylene adsorption on a clean iridium surface

The H/D isotope exchange of C₂D₄ adsorbed on an Ir surface has been studied by the thermal desorption method. Only deuterium atoms detached from the molecule after its adsorption on the metal surface participate in the exchange with a relatively high rate.

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H/D C₂D₄, Ir, . , , .

     

Thermoanalytical studies of substances liberating aggressive gases

A modification to the derivatograph has been designed that allows thermoanalytical investigations of chemical compounds, including sulphides and acids, that evolve aggressive gases such as CO, SO₂, S, etc. during warming. Application of this modification is exemplified by studies on the thermal dehydrogenation of titanium hydride (TiH_1.85) and on the interaction of rhenium disulphide (ReS₂) with concentrated sulphuric acid.

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Zusammenfassung Es wird über die Modifizierung eines Derivatografen berichtet, die die Thermoanalyse von Stoffen ermöglicht, die wie z. B. Sulfide oder Säuren beim Erhitzen aggressive Gase wie z. B. CO, SO₂, S usw. freisetzen. Als Beispiel für die Anwendung dieser Modifizierung dienten Untersuchungen der thermischen Dehydrogenierung von Titanhydrid (TiH_1.85) und des Einwirkens von konzentrierter Schwefelsäure auf Rheniumsulfid (ReS₂).

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, , , , , SO₂, S . . 2- , - (³_1,85) (ReS₂) (H₂SO₄).

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Presented as a poster at ESTAC-4, Jena, GDR, 1987.     

Catalytic activity of palladium-containing zeolites in the complete oxidation of benzene

The dependence of palladium distribution in zeolites on the temperature of thermal treatment has been established from the data on oxygen chemisorption and the statistical processing of electron micrographs. The influence of palladium distribution in zeolites on their catalytic activity towards the complete oxidation of benzene has been shown.

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Michael addition of nitromethane to 3-buten-2-one catalyzed by potassium fluoride supported on Al2O3, ZnO, SnO2, sepiolite, AlPO4, AlPO4?Al2O3 and AlPO4?ZnO

The Michael addition of nitromethane to 3-buten-2-one has been carried out in the absence of solvent, using potassium fluoride supported on Al₂O₃, ZnO, SnO₂, sepiolite, AlPO₄, AlPO₄–Al₂O₃ and AlPO₄–ZnO catalysts. We found that KF/ZnO easily performed the Michael addition and thus, ZnO is a better support for the basic reagent than Al₂O₃. Besides, the Michael addition was not successful with AlPO₄ or AlPO₄-metal oxide acidic supports.

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3--2- , , Al₂O₃, ZnO, SnO₂, , AlPO₄, AlPO₄–Al₂O₃ AlPO₄–ZnO. , KF/ZnO .. ZnO, , , Al₂O₃. , , AlPO₄ AlPO₄- .