Pretreatment of catalyst

Pretreatment of Catalysts. Acidity. Dilute acids—hydrochloric, sulfuric, and phosphoric acids—were deposited by soaking Chromosorb-A in the dilute acid solution and decanting and drying the granules at 100 °C. For the acid-loaded Chromosorb-A, no activity increase for Claus reaction was detected. The acid-loaded Chromosorb-A ( 2% ) at the end of the reaction was still acidic a slurry of the catalyst in distilled water had a pH about 5. 

Scheme 10.24 Pretreatment of catalyst 11 with ethylene, generated by the RCM of diallyl...

Rhodium was about three times the price of gold through 1988—1989 until skyrocketing to 74/g ( 2300/troy oz) in early 1990. Thus precious metal catalyst costs requite an absolute minimum level of use and maximum number of catalyst recycle uses when batch processing is employed. Starting material contaminants may effect catalyst poisoning, though process routes to overcome this by feed stream pretreatment may be devised (37,60). 

A vapor-phase process primarily for ECC off-gas feeds was developed by Sinopec Technology Company based on a 2eoHte catalyst of the Pentasd type (24,25). It reHes on frequent regeneration of the catalyst to minimi2e pretreatment of the ECC off-gas and allows the impurities in the feed gas to react with ben2ene to form by-products. Consequently, the product yield and purity are low. Joint licensing by ABB Lummus Crest and Sinopec was announced in 1994. 

As was found in Ref. [13], the method of catalytic decomposition of acetylene on graphite-supported catalysts provides the formation of very long (50 fim) tubes. We also observed the formation of filaments up to 60 fim length on Fe- and Co-graphite. In all cases these long tubules were rather thick. The thickness varied from 40 to 100 nm. Note that the dispersion of metal particles varied in the same range. Some metal aggregates of around 500 nm in diameter were also found after the procedure of catalyst pretreatment (Fig. 2). Only a very small amount of thin (20-40 nm diameter) tubules was observed. 

A similar reaction was studied by Kowaka Jfi) who investigated the catalytic activity of palladium and its alloys with silver in the hydrogenation of ethylene. The author alluded to the poisoning effect of hydrogen pretreatment of the palladium catalyst. 

Experimental evidence illustrating the effect that hydrides of nickel or its alloys with copper have on the catalytic activity of the respective metals is to be found in papers which discuss catalytic consequences of the special pretreatment of these metal catalysts with hydrogen during their preparation. One must also look very carefully into cases where self-poisoning has been reported as appearing in reactions of hydrogen with other reactants. 

J. Nicole, D. Tsiplakides, S. Wodiunig, and C. Comninellis, Activation of catalyst for gas-phase combustion by electrochemical pretreatment, J. Electrochem. Soc. 144(12), L312-L314 (1997). 

Design parameters of the anode catalyst for the polymer electrolyte membrane fiiel cells were investigated in the aspect of active metal size and inter-metal distances. Various kinds of catalysts were prepared by using pretreated Ketjenblacks as support materials. The prepared electro-catalysts have the morphology such as the sizes of active metal are in the range from 2.0 to 2.8nm and the inter-metal distances are 5.0 to 14.2nm. The electro-catalysts were evaluated as an electrode of PEMFC. In Fig. 1, it looked as if there was a correlation between inter-metal distances and cell performance, i.e. the larger inter-metal distances are related to the inferior cell performance. 

Pretreatment of the samples was performed in the prechamber of the spectrometer, except for the sulfiding described previously. Catalysts were calcined in air at 500 C for one hour, or reduced in hydrogen at 310 C or 350 C for up to four hours. The prechamber was then evacuated and the sample Introduced into the spectrometer without exposure to the atmosphere. 

Determination of Metal Precursor Mobilities During Pretreatment. Relative precursor mobilities were obtained by premixing the sllica-or alumina-supported metal catalysts with pure silica (Cab-O-Sll, grade M-5, Cabot Corp.) or pure alumina (Alon C, Cabot Corp.) In a 1 2 ratio prior to pretreatment. The catalyst and silica were ground together using a mortar and pestle for at least 0.5 hr. before they were placed in the Pyrex microreactor for pretreatment. 

The reactions were carried out in the steady state flow mode as described previously [11]. Differential kinetics were determined from plots of conversion vs. W/F. Three catalysts CoZSM-5, HZSM-5 and NaZSM-5 (Si/AI = 11) were studied in this work. The catalyst preparation and the standard pretreatment used prior to reaction have been described previously [11]. It involved dehydration in flowing dried 0 as the temperature was raised slowly to 500°C. The feed comprised CH4 (0.28%), NO (0.21 %) or NOj (0.21 %). and/or Oj (2.6%) in He. The flow rate was 75 ml/min and the gas hour space velocity (GHSV) was varied between 4,500 and 250,000 h by changing the weight of catalyst samples. 

P 17] In order to have a catalyst with a sufficiently high specific surface area, pretreatment of the micro channels made of aluminum was necessary [17], Following a cleaning procedure, an oxide layer with a regular system of nanopores was generated by anodic oxidation (1.5% oxalic acid 25 °C 50 V DC 2 h exposure using an aluminum plate cathode followed by calcination). 

Barometric chemisorption. Chemisorption on catalysts is measured routinely by the barometric method. The equipment is very similar to that commonly used in texture determination by physical adsorption (see Section 3.6.2), except that for chemisorption measurements facilities for pretreatment of the samples should be present. In particular for metal catalysts often the catalyst is received in a partly or fully oxidized form and, as a consequence, reduction is required when one wants to measure the amount of active sites. Moreover, during storage adsorption of various molecules might occur and evacuation is... 

Alternatively, data points can be collected in the decreasing pressure mode . This procedure is usually applied for the quantification of activated adsorption processes (Reuel and Bartholomew, 1984), such as the adsorption of H2. After the pretreatment of the sample (usually after reduction or reaction, and evacuation for a certain period to remove all the adsorbed surface species) the temperature is lowered to the temperature of measurement. First, a known amount of adsorbate gas is added to the reactor. Subsequently, the pressure in the catalyst compartment is lowered stepwise by expansion of the gas into the repeatedly evacuated reference volume. The adsorbed amount of gas can be calculated for each step. From this procedure, the monolayer capacity of the catalyst can be evaluated. 

As always in chemisorption measurements, pretreatment of the samples should be done with care. For metal catalysts prepared from oxides in particular this is experimentally troublesome because a reduction step is always needed in the preparation of the metal catalyst. Hydrogen or hydrogen diluted with an inert gas is usually used for the reduction but it is difficult to remove adsorbed H2 from the surface completely. So, after reduction the metal surfaces contains (unknown) amounts of H atoms, which are strongly retained by the surface and, as a consequence, it is not easy to find reliable values for the dispersion from H2 chemisorption data. 

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