Nickel Oxide-Alumina Catalysts

The production of nickel oxide/kieselguhr catalysts illustrates that not only the composition but also the method of preparation of catalyst precursors determines 

TABLE 3.10. Composition of Nickel Oxide Kieselguhr Catalysts. 

Wt % Typical catalyst Catalyst plus 5% copper oxide 

Zelinsky, the Russian chemist, woiked with nickel oxide/alumina catalysts for a number of hydrogenation reactions and was probably one of the first to describe co-precipitation of nickel oxide and alumina in 1924. Since then many other nickel catalysts with alumina supports have been co-precipitated and used successfully in the production of synthesis gas, hydrogen, and town gas. 

In the 1940 s Feitknecht and others recognized that a particular form of blue-green basic nickel/aluminum carbonate could be prepared from mixed nickel and aluminum solutions under specific conditions. The solid, as with the nickel oxide/ kieselguhr catalyst had the magnesia bracite structore, with part of the nickel layer replaced by aluminum and some of the hydroxyl groups replaced by carbonate.  

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The alkali free catalyst used in this study was a commercial nickel oxide/ -alumina steam reforming catalyst. The total nickel content of the catalyst was 10 % w/w. An alkali promoted catalyst was prepared by dipping the nickel oxide/< -alumina catalyst in a 12% v/v potassium hydroxide solution and then drying the catalyst, at lOD C, for a period of 16 hours The... 

Li C, Chen YW. Temperature-programmed-reduction studies of nickel oxide/alumina catalysts effects of the preparation method. Thermochim Acta. 1995 256 457. 

Isomerization of olefins can be accomplished also in the gas phase m a flow reactor with alumina or nickel oxide as catalyst Thus perfluoro 2-butene can be prepared by passing perfluoro-1 butene over these catalysts at 150-400 °C [79] Similar results may be obtained in an autoclave with the same catalysts Perfluoro-1 butene isomenzes almost quantitatively at 250 °C after 100 h to perfluoro-2-butene [20]... 

Several other important commercial processes need to be mentioned. They are (not necessarily in the order of importance) the low pressure methanol process, using a copper-containing catalyst which was introduced in 1972 the production of acetic add from methanol over RhI catalysts, which has cornered the market the methanol-to-gasoline processes (MTG) over ZSM-5 zeolite, which opened a new route to gasoline from syngas and ammoxidation of propene over mixed-oxide catalysts. In 1962, catalytic steam reforming for the production of synthesis gas and/or hydrogen over nickel potassium alumina catalysts was commercialized. 

B. Scheffer, I.I. Heijeinga, and J.A. MouUjn, An electron spectroscopy and X-ray diffraction study of nickel oxide/alumina and nickel oxide/tungsten trioxide/alumina catalysts, J. Phys. Chem. 91, 4752 759 (1987). 

S. Abou Arnadasse, G. M. Pajonk, J. E. Germain and S. J. Teichner, Catalytic nitroxidation of Toluene into Benzonitrile over Nickel oxide Alumina Xero or Aero-gels catalysts, Applied Catalysis, Vol. 9, 1984 pp 119-128. 

The first suitable activated-alumina catalyst contained 10% M0O3 activated by addition of 3% nickel oxide. This catalyst was superseded by a more active tungsten catalyst containing 70% activated alumina, 27% tungsten sulfide, and 3% nickel sulfide. This catalyst is used in commercial plants for the prehydrogenation of middle oils and also for the direct hydrogenation of shale oil and lignite tar (TTH process). 

L.M. Knijff, P.H. Bolt, R. van Yperen, A.J. van Dillen, J.W. Geus, Production of nickel-on-alumina catalysts from preshaped bodies K.P. de Jong, Deposition-precipitation onto preshaped carrier bodies — possibilities and limitations P.J. van den Brink, A. Scholten, A. van Wageningen, M.D.A. Lamers, A.J. van Dillen, J.W. Geus, The use of chelating agents for the preparation of iron oxide catalysts for the selective oxidation of hydrogen sulfide, all in Preparation of Catalysts V, Elsevier, Amsterdam, 1991. 

Reactions with Ammonia and Amines. Acetaldehyde readily adds ammonia to form acetaldehyde—ammonia. Diethyl amine [109-87-7] is obtained when acetaldehyde is added to a saturated aqueous or alcohoHc solution of ammonia and the mixture is heated to 50—75°C in the presence of a nickel catalyst and hydrogen at 1.2 MPa (12 atm). Pyridine [110-86-1] and pyridine derivatives are made from paraldehyde and aqueous ammonia in the presence of a catalyst at elevated temperatures (62) acetaldehyde may also be used but the yields of pyridine are generally lower than when paraldehyde is the starting material. The vapor-phase reaction of formaldehyde, acetaldehyde, and ammonia at 360°C over oxide catalyst was studied a 49% yield of pyridine and picolines was obtained using an activated siHca—alumina catalyst (63). Brown polymers result when acetaldehyde reacts with ammonia or amines at a pH of 6—7 and temperature of 3—25°C (64). Primary amines and acetaldehyde condense to give Schiff bases CH2CH=NR. The Schiff base reverts to the starting materials in the presence of acids. 

Fuel sulfur is also responsible for a phenomena known as storage and release of sulfur compounds. Sulfur oxides (S02,S02) easily react with ceria, an oxygen storage compound incorporated into most TWC catalysts, and also with alumina. When the air/fuel mixture temporarily goes rich and the catalyst temperature is in a certain range, the stored sulfur is released as H2S yielding a rotten egg odor to the exhaust. A small amount of nickel oxide incorporated into the TWC removes the H2S and releases it later as SO2 (75—79). 

The catalysts used in the process are essentially nickel metal dispersed on a support material consisting of various oxide mixtures such as alumina, silica, lime, magnesia, and compounds such as calcium aluminate cements. When the catalyst is made, the nickel is present as nickel oxide which is reduced in the plant converter with hydrogen, usually the 3 1 H2 N2 synthesis gas ... 

There is little data available to quantify these factors. The loss of catalyst surface area with high temperatures is well-known (136). One hundred hours of dry heat at 900°C are usually sufficient to reduce alumina surface area from 120 to 40 m2/g. Platinum crystallites can grow from 30 A to 600 A in diameter, and metal surface area declines from 20 m2/g to 1 m2/g. Crystal growth and microstructure changes are thermodynamically favored (137). Alumina can react with copper oxide and nickel oxide to form aluminates, with great loss of surface area and catalytic activity. The loss of metals by carbonyl formation and the loss of ruthenium by oxide formation have been mentioned before. 

The catalyst was prepared by impregnating porous alumina particles with a solution of nickel and lanthanum nitrates. The metal loading was 20 w1% for nickel and 10 wt% for lanthanum oxide. The catalyst particles were A group particles [8], whereas they were not classified as the AA oup [9]. The average particle diameter was 120 pm, and the bed density was 1.09 kg m . The minimum fluidization velocity was 9.6 mm s. The settled bed height was around 400 mm. The superficial gas velocity was 40-60 mm s. The reaction rate was controlled by changing the reaction temperature. 

Other metal oxide catalysts studied for the SCR-NH3 reaction include iron, copper, chromium and manganese oxides supported on various oxides, introduced into zeolite cavities or added to pillared-type clays. Copper catalysts and copper-nickel catalysts, in particular, show some advantages when NO—N02 mixtures are present in the feed and S02 is absent [31b], such as in the case of nitric acid plant tail emissions. The mechanism of NO reduction over copper- and manganese-based catalysts is different from that over vanadia—titania based catalysts. Scheme 1.1 reports the proposed mechanism of SCR-NH3 over Cu-alumina catalysts [31b],... 

With nickel/alumina catalysts (cf. 4 ) preparation by coprecipitation or by the decomposition of a high dispersion of nickel hydroxide on fresh alumina hydrogel, yields nickel aluminate exclusively. On the other hand, when, as in impregnation, larger particles of nickel compound are deposited, the calcination product is a mixture of nickel oxide and nickel aluminate. The proportion of nickel oxide increases when occlusion of the impregnation solution leads to a very nonuniform distribution (49). 

Morikawa et al. (42) suggest that nickel aluminate itself undergoes hydrogen reduction only to a superficial extent, and then produces extremely small nickel particles as the reduction product. In this circumstance, the nickel particle size distribution in a reduced nickel/alumina catalyst will obviously be much dependent on the preparative details that control the proportions nickel oxide and nickel aluminate and the size of the particles in which these substances exist before reduction. 

Standard Oil A process for polymerizing ethylene and other linear olefins and di-olefins to make linear polymers. This is a liquid-phase process, operated in a hydrocarbon solvent at an intermediate pressure, using a heterogeneous catalyst such as nickel oxide on carbon, or vanadia or molybdena on alumina. Licensed to Furukawa Chemical Industry Company at Kawasaki, Japan. 

The catalyst used is a promoted nickel oxide on an alumina support [4], manufactured in cylindrical form. Because of the highly oxidised state of the nickel, the catalyst is resistant to classic poisons and extended lifetimes have been observed in industrial installations. 

Ermakova and co-workers manipulated the Ni particle size to achieve large CF yields from methane decomposition. The Ni-based catalysts employed for the process were synthesized by impregnation of nickel oxide with a solution of the precursor of a textural promoter (silica, alumina, titanium dioxide, zirconium oxide and magnesia). The optimum particle size (10 0 nm) was obtained by varying the calcination temperature of NiO. The 90% Ni-10% silica catalyst was found to be the most effective catalyst with a total CF yield of 375 gcp/gcat- XRD studies by the same group on high loaded Ni-silica... 

The exchange of a number of compounds in this category with deuterium has been examined by Burwell and his colleagues. n-Heptane has been exchanged over nickel-keiselguhr (43), reduced nickel oxide (29), a series of nickel catalysts of varying crystallite size (37), and over palladium supported on 7-alumina (43). Less extensive studies were also made with 2,3-dimethylbutane (29, 43) and n-hexane (42). 

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