Hydrogen deactivation

Fukase, S. and Suzuka, T., Residual oil cracking with generation of hydrogen Deactivation of iron oxide catalyst in the steam-iron reaction, Appl. Catal. A General, 100,1,1993. 

Other phosphorus ligands used include PCy3 and diphos. The complex [Ir(cod)py(PPr )3]+ was also active. After the cessation of hydrogenation, deactivation of the catalyst occurs rapidly.160 This was caused by the formation of the dinuclear hydride [Ir2(H)5L4]+. The PPh3 complex has the structure (39). 

Figure 3-19. Photodissociation of HI monomers and clusters. The solid traces indicate the substantial discrimination available when using polarized photolysis radiation note the high S/N. Under conditions of such minimal clustering, it is reasonable to assume that most of the clusters are binary. Peaks labeled v = 1 and v = 2 are due to inelastic H + HI collisions within the cluster. The superelastic peak ft is assigned tentatively to secondary photolysis of I HI complexes, in which the escaping hydrogen deactivates the nearby I, (a) Vertical and (b) horizontal polarization of the photolysis radiation relative to the molecular beam. The plenum pressure is 1900 torr.

S. Zmcevic, Z. Gomzi and E. Kotur, Thiophene poisoning of Ni-Si02-Al203 in benzene hydrogenation. Deactivation Kinetics, Ind.Eng.Chem.Res. 29(1990)774. 

A more detailed study of the nitration of quinolinium (l) in 80-05 % sulphuric acid at 25 °C, using isotopic dilution analysis, has shown that 3-) 5-) 6-, 7- and 8-nitroquinoline are formed (table 10.3). Combining these results with the kinetic ones, and assuming that no 2- and 4-nitration occurs, gives the partial rate factors listed in table 10.4. Isoquinolinium is 14 times more reactive than quinolinium. The strong deactivation of the 3-position is in accord with an estimated partial rate factor of io for hydrogen isotope exchange at the 3-position in the pyridinium ion. It has been estimated that the reactivity of this ion is at least 10 less than that of the quinolinium ion. Based on this estimate, the partial rate factor for 3-nitration of the pyridinium ion would be less than 5 x io . 

Both objectives have been met by designing special hydrogenation catalysts The most frequently used one is the Lindlar catalyst, a palladium on calcium carbonate combi nation to which lead acetate and quinoline have been added Lead acetate and quinoline partially deactivate ( poison ) the catalyst making it a poor catalyst for alkene hydro genation while retaining its ability to catalyze the addition of H2 to the triple bond... 

Activating Standard of comparison Deactivating —R —Ar —CH=CR —H —X (X = F Cl —CH2X (alkyl) (aryl) 2 (alkenyl) (hydrogen) (halogen) Br 1) (halomethyl) Ortho para directing Ortho para directing... 

Deactivating substituent (Sections 12 11 and 12 13) A group that when present in place of hydrogen causes a particular reaction to occur more slowly The term is most often ap plied to the effect of substituents on the rate of electrophilic aromatic substitution... 

This was a Hquid-phase process which used what was described as siUceous zeoUtic catalysts. Hydrogen was not required in the process. Reactor pressure was 4.5 MPa and WHSV of 0.68 kg oil/h kg catalyst. The initial reactor temperature was 127°C and was raised as the catalyst deactivated to maintain toluene conversion. The catalyst was regenerated after the temperature reached about 315°C. Regeneration consisted of conventional controlled burning of the coke deposit. The catalyst life was reported to be at least 1.5 yr. 

Amorphous Silica—Alumina Based Processes. Amorphous siHca—alumina catalysts had been used for many years for xylene isomerization. Examples ate the Chevron (130), Mamzen (131), and ICI (132—135). The primary advantage of these processes was their simpHcity. No hydrogen was requited and the only side reaction of significance was disproportionation. However, in the absence of H2, catalyst deactivation via coking... 

Conditions of hydrogenation also determine the composition of the product. The rate of reaction is increased by increases in temperature, pressure, agitation, and catalyst concentration. Selectivity is increased by increasing temperature and negatively affected by increases in pressure, agitation, and catalyst. Double-bond isomerization is enhanced by a temperature increase but decreased with increasing pressure, agitation, and catalyst. Trans isomers may also be favored by use of reused (deactivated) catalyst or sulfur-poisoned catalyst. 

The fine antimony mist formed from the decomposition of the trichloride also participates in the flame-inhibiting process, deactivating oxygen, hydrogen, and hydroxyl radicals. 

Hydrogenation of the oxides of carbon to methane according to the above reactions is sometimes referred to as the Sabatier reactions. Because of the high exothermicity of the methanization reactions, adequate and precise cooling is necessary in order to avoid catalyst deactivation, sintering, and carbon deposition by thermal cracking. 

The carboxyl group of acids appears to deactivate the hydrogens on the alpha carbon atom toward attack by the free-radical flux in oxidation reactions. Acetic acid, therefore, is particularly inert toward further oxidation (hydrogens are both primary and deactivated) (48). For this reason, it is feasible to produce acetic acid by the oxidation of butane (in the Hquid phase), even under rather severe oxidation conditions under which most other products are further oxidized to a significant extent (22). 

Chromium (ITT) can be analy2ed to a lower limit of 5 x 10 ° M by luminol—hydrogen peroxide without separating from other metals. Ethylenediaminetetraacetic acid (EDTA) is added to deactivate most interferences. Chromium (ITT) itself is deactivated slowly by complexation with EDTA measurement of the sample after Cr(III) deactivation is complete provides a blank which can be subtracted to eliminate interference from such ions as iron(II), inon(III), and cobalt(II), which are not sufficiently deactivated by EDTA (275). 

Propylene, butylenes, or amylenes are combiaed with isobutane ia the presence of an acid catalyst, eg, sulfuric acid or hydrofluoric acid, at low temperatures (1—40°C) and pressures, 102—1035 kPa (1—10 atm). Sulfuric acid or hydrogen fluoride are the catalysts used commercially ia refineries. The acid is pumped through the reactor and forms an emulsion with reactants, and the emulsion is maintained at 50% acid. The rate of deactivation varies with the feed and isobutane charge rate. Butene feeds cause less acid consumption than the propylene feeds. 

In Method 2, hydrogen is also passed over the catalyst to prevent it from deactivating (6). The mole ratio of hydrogen is typically in the range of 1 to 2.5 1 with respect to the alcohol. Operating conditions are maintained in the range 130—250°C. As in Method 1, yields are usually in the 90% range. 

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... 

C, 0.356—1.069 m H2/L (2000—6000 fU/bbl) of Hquid feed, and a space velocity (wt feed per wt catalyst) of 1—5 h. Operation of reformers at low pressure, high temperature, and low hydrogen recycle rates favors the kinetics and the thermodynamics for aromatics production and reduces operating costs. However, all three of these factors, which tend to increase coking, increase the deactivation rate of the catalyst therefore, operating conditions are a compromise. More detailed treatment of the catalysis and chemistry of catalytic reforming is available (33—35). Typical reformate compositions are shown in Table 6. 

The presence of other functional groups ia an acetylenic molecule frequendy does not affect partial hydrogenation because many groups such as olefins are less strongly adsorbed on the catalytic site. Supported palladium catalysts deactivated with lead (such as the Liadlar catalyst), sulfur, or quinoline have been used for hydrogenation of acetylenic compound to (predominantiy) cis-olefins. 

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