Water gas shift reaction catalyst

The National Technical University of Athens (NTUA) works on hydrogen production from waste gases, production of hydrogen from solid fuels, water-gas-shift reaction catalysts, membrane separation, gasification of solid fuels, simulation of advanced power systems based on fuel cells, and hydrogen production and infrastructure. 

X. Lin, C. Chen, J. Ma, X. Fang, Y. Zhan, Q. Zheng, Promotion effect of Nb for Cu/Ce02 water gas shift reaction catalyst by generating mobile electronic carriers, Int. J. Hydrogen Energy 38 (2013) 11841-11852. 

Nishida K, Atake 1, Li D, Shishido T, Oumi Y, Sano T, Takeira K (2008) Effects of noble metal-doping on Cu/ZnO/Al203 catalysts for water-gas shift reaction. Catalyst preparation by adopting memory effect of hydrotalcite. Appl Catal A 337 48-57... 

Hydroformylation can be performed with cobalt and rhodium catalysts. The latter are extremely expensive, but their use is justified because they usually show much higher efficiency and selectivity, with respect to both regioselectivity (the ratio of normal to branched aldehydes in hydroformylation of terminal olefins) and the absence of side-reactions, e.g. the reduction of aldehydes to alcohols. The selectivity of catalyst is particularly important for aqueous methods to avoid the concurrent processes triggered by the water-gas shift reaction. Catalyst recycling is a vital task only for rhodium-catalyzed processes, and that is clearly reflected by research efforts. 

M.V. Twigg, 1989, The Water-gas Shift Reaction, Catalyst Handbook, 2"... 

The mixture of carbon monoxide and hydrogen is enriched with hydrogen from the water gas catalytic (Bosch) process, ie, water gas shift reaction, and passed over a cobalt—thoria catalyst to form straight-chain, ie, linear, paraffins, olefins, and alcohols in what is known as the Fisher-Tropsch synthesis. 

This reaction is first conducted on a chromium-promoted iron oxide catalyst in the high temperature shift (HTS) reactor at about 370°C at the inlet. This catalyst is usually in the form of 6 x 6-mm or 9.5 x 9.5-mm tablets, SV about 4000 h . Converted gases are cooled outside of the HTS by producing steam or heating boiler feed water and are sent to the low temperature shift (LTS) converter at about 200—215°C to complete the water gas shift reaction. The LTS catalyst is a copper—zinc oxide catalyst supported on alumina. CO content of the effluent gas is usually 0.1—0.25% on a dry gas basis and has a 14°C approach to equihbrium, ie, an equihbrium temperature 14°C higher than actual, and SV about 4000 h . Operating at as low a temperature as possible is advantageous because of the more favorable equihbrium constants. The product gas from this section contains about 77% H2, 18% CO2, 0.30% CO, and 4.7% CH. ... 

Shift Conversion. Carbon oxides deactivate the ammonia synthesis catalyst and must be removed prior to the synthesis loop. The exothermic water-gas shift reaction (eq. 23) provides a convenient mechanism to maximize hydrogen production while converting CO to the more easily removable CO2. A two-stage adiabatic reactor sequence is normally employed to maximize this conversion. The bulk of the CO is shifted to CO2 in a high... 

HTS catalyst consists mainly of magnetite crystals stabilized using chromium oxide. Phosphoms, arsenic, and sulfur are poisons to the catalyst. Low reformer steam to carbon ratios give rise to conditions favoring the formation of iron carbides which catalyze the synthesis of hydrocarbons by the Fisher-Tropsch reaction. Modified iron and iron-free HTS catalysts have been developed to avoid these problems (49,50) and allow operation at steam to carbon ratios as low as 2.7. Kinetic and equiUbrium data for the water gas shift reaction are available in reference 51. 

Tubular Fixed-Bed Reactors. Bundles of downflow reactor tubes filled with catalyst and surrounded by heat-transfer media are tubular fixed-bed reactors. Such reactors are used most notably in steam reforming and phthaUc anhydride manufacture. Steam reforming is the reaction of light hydrocarbons, preferably natural gas or naphthas, with steam over a nickel-supported catalyst to form synthesis gas, which is primarily and CO with some CO2 and CH. Additional conversion to the primary products can be obtained by iron oxide-catalyzed water gas shift reactions, but these are carried out ia large-diameter, fixed-bed reactors rather than ia small-diameter tubes (65). The physical arrangement of a multitubular steam reformer ia a box-shaped furnace has been described (1). 

Conversion to Hydrogen (Water Gas Shift Reaction). Carbon monoxide reacts with water over a catalyst to produce hydrogen and carbon monoxide (25). This reaction is used to prepare high purity hydrogen or synthesis gas with a higher hydrogen-to-carbon monoxide ratio than the feed (eq. 3). 

Metal coordination compounds may also provide alternatives to the heterogeneous catalysts used for the water gas shift reaction. In fact, Ru, Rh, Ir, and Pt coordination compounds have all shown some promise (27). 

This is the so-called water-gas shift reaction (—AG29gl9.9kJmoP ) and it can also be effected by low-temperature homogeneous catalysts in aqueous acid solutions. The extent of subsequent purification of the hydrogen depends on the use to which it will be put. 

Research is also being conducted in Japan to aromatize propane in presence of carhon dioxide using a Zn-loaded HZSM-5 catalyst/ The effect of CO2 is thought to improve the equilibrium formation of aromatics by the consumption of product hydrogen (from dehydrogenation of propane) through the reverse water gas shift reaction. 

The carbonyl complex [Ru(EDTAH)(CO)] has been reported to be a very good catalyst for reactions like hydroformylation of alkenes, carbonylation of ammonia and ammines as well as a very active catalyst for the water gas shift reaction. The nitrosyl [Ru(EDTA)(NO)] is an oxygen-transfer agent for the oxidation of hex-l-ene to hexan-2-one, and cyclohexane to the corresponding epoxide. 

An examination of some laboratory runs with diluted C150-1-02 catalyst can illustrate this problem. In one run with 304°C at inlet, 314 °C at exit, and 97,297 outlet dry gas space velocity, the following results were obtained after minor corrections for analytical errors. Of the CO present (out of an inlet 2.04 mole % ), 99.9885% disappeared in reaction while the C02 present (from an initial 1.96%) increased by over 30%. Equilibrium carbon oxides for both methanation reactions were essentially zero whereas the equilibrium CO based on the water-gas shift reaction at the exit composition was about one-third the actual CO exit of 0.03 mole %. From these data, activities for the various reactions may be estimated on the basis of various assumptions (see Table XIX for the effect of two different assumptions). 

The attention given to the causes and control of catalyst die-off in industry is well illustrated by the behavior of different formulations of Cu-ZnO-AhOs catalysts for the low temperature water gas shift reaction. 

Figure 8.56. Effect of catalyst potential and work function on the rate of CO2 hydrogenation on Pd/YSZ (reverse water-gas shift reaction). pC02=22.5 kPa pH2=73 kPa , T= 546°C , T= 559°C , T= 573°C.59 Open symbols correspond to open-circuit.

The reaction is endothermic, but large amounts of steam are used to minimize the temperature drop and, by way of the water-gas shift reaction, to prevent accumulation of coke on the catalyst. Ignore the reverse and competitive... 

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