Abstract: Polyoxymethylene dimethyl ethers (PODEn) as clean diesel additive can improve the combustion efficiency and quality of diesel fuel and alleviate the problem of atmospheric pollution. Considering synthetic routes, PODE production from methanol and formaldehyde is regarded as the most economical and promising synthetic route. However, methanol used for synthesizing PODE can produce water, which causes the loss of active center of catalyst and hydrolysis of PODEn in the production process. Macroporous strong acidic cation exchange resin catalyst was prepared, which has comparative advantages over other common solid acid catalysts in terms of stability and catalytic efficiency for synthesizing PODE. Catalytic reactions were carried out under 353 K, 1 MPa and 3mL·gcat-1·h-1 in a fixed bed reactor. Methanol conversion and PODE3-6 selectivity reached 49.91% and 23.43%, respectively. Catalyst lifetime evaluation showed that resin catalyst retained its catalytic activity for 20 days without significant changes and catalytic activity of completely deactivated resin catalyst can basically return to previous level by simple acid regeneration. The acid exchange capacities of original and deactivated catalyst were 2.5191 and 0.0979 mmol·g-1, respectively, while regenerated catalyst reached 2.0430 mmol·g-1, indicating that the main reason for resin catalyst deactivation is that Brønsted acid sites of original resin catalyst were temporarily replaced by non-hydrogen ion cations. A separation process consisting of extraction and distillation for PODE3-6 product was designed for separation of water and unreacted formaldehyde from reactive mixture and purification of PODE3-6, respectively. The concentration of PODE3-6 in final product can reach up to 97%. These results indicate that the scale-up production of PODE3-6 from methanol and formaldehyde solution is feasible.
Abstract: This work studied the isomerization of 1-butene over
hydrotalcite catalyst. The experiments were conducted at various gas
hourly space velocity (GHSV), reaction temperature and feed
concentration. No catalyst deactivation was observed over the
reaction time of 16 hours. Two major reaction products were trans-2-
butene and cis-2-butene. The reaction temperature played an
important role on the reaction selectivity. At high operating
temperatures, the selectivity of trans-2-butene was higher than the
selectivity of cis-2-butene while it was opposite at lower reaction
temperature. In the range of operating condition, the maximum
conversion of 1-butene was found at 74% when T = 673 K and GHSV
= 4 m3/h/kg-cat with trans- and cis-2-butene selectivities of 54% and
46%, respectively. Finally, the kinetic parameters of the reaction
were determined.
Abstract: In industrial scale of Gas to Liquid (GTL) process in
Fischer-Tropsch (FT) synthesis, a part of reactor outlet gases such as
CO2 and CH4 as side reaction products, is usually recycled. In this
study, the influence of CO2 and CH4 on the performance and
selectivity of Co-Ru/Al2O3 catalyst is investigated by injection of
these gases (0-20 vol. % of feed) to the feed stream. The effect of
temperature and feed flow rate, are also inspected. The results show
that low amounts of CO2 in the feed stream, doesn`t change the
catalyst activity significantly but increasing the amount of CO2 (more
than 10 vol. %) cause the CO conversion to decrease and the
selectivity of heavy components to increase. Methane acts as an inert
gas and doesn`t affect the catalyst performance. Increasing feed flow
rate has negative effect on both CO conversion and heavy component
selectivity. By raising the temperature, CO conversion will increase
but there are more volatile components in the product. The effect of
CO2 on the catalyst deactivation is also investigated carefully and a
mechanism is suggested to explain the negative influence of CO2 on
catalyst deactivation.
Abstract: The catalytic dehydroxylation of glycerol to propylene
glycol was investigated over Cu-ZnO/Al2O3 prepared by incipient
wetness impregnation (IWI) method with different purity feedstocks -
refined glycerol and technical grade glycerol. The main purpose is to
investigate the effects of feed impurities that cause the catalyst
deactivation. The prepared catalyst were tested for its catalytic
activity and selectivity in a continuous flow fixed bed reactor at 523
K, 500 psig, H2/feed molar ratio of 4 and WHSV of 3 h-1. The results
showed that conversion of refined glycerol and technical grade
glycerol at time on stream 6 hour are 99% and 71% and selectivity to
propylene glycol are 87% and 56% respectively. The ICP-EOS and
TPO results indicated that the cause of catalyst deactivation was the
amount of impurities in the feedstock. The higher amount of
impurities (especially Na and K) the lower catalytic activity.
Abstract: The paper relates to a catalyst, comprising copperchromium
spinel, coated on carrier γ-Al2O3. The effect of preparation
conditions on the active component composition and activity
behavior of the catalysts is discussed. It was found that the activity of
carbon monoxide, DME, formaldehyde and methanol oxidation
reaches a maximum at an active component content of 20 – 30 wt. %.
Temperature calcination at 500oC seems to be optimal for the γ–
alumina supported CuO-Cr2O3 catalysts for CO, DME, formaldehyde
and methanol oxidation. A three months industrial experiment was
carried out to elucidate the changes in the catalyst composition
during industrial exploitation of the catalyst and the main reasons for
catalyst deactivation.
It was concluded that the CuO–Cr2O3/γ–alumina supported
catalysts have enhanced activity toward CO, DME, formaldehyde
and methanol oxidation and that these catalysts are suitable for
industrial application. The main reason for catalyst deactivation
seems to be the deposition of iron and molybdenum, coming from the
main reactor, on the active component surface.
Abstract: In the present study, a procedure was developed to
determine the optimum reaction rate constants in generalized
Arrhenius form and optimized through the Nelder-Mead method. For
this purpose, a comprehensive mathematical model of a fixed bed
reactor for dehydrogenation of heavy paraffins over Pt–Sn/Al2O3
catalyst was developed. Utilizing appropriate kinetic rate expressions
for the main dehydrogenation reaction as well as side reactions and
catalyst deactivation, a detailed model for the radial flow reactor was
obtained. The reactor model composed of a set of partial differential
equations (PDE), ordinary differential equations (ODE) as well as
algebraic equations all of which were solved numerically to
determine variations in components- concentrations in term of mole
percents as a function of time and reactor radius. It was demonstrated
that most significant variations observed at the entrance of the bed
and the initial olefin production obtained was rather high. The
aforementioned method utilized a direct-search optimization
algorithm along with the numerical solution of the governing
differential equations. The usefulness and validity of the method was
demonstrated by comparing the predicted values of the kinetic
constants using the proposed method with a series of experimental
values reported in the literature for different systems.
Abstract: Palladium-catalyzed hydrodechlorination is a
promising alternative for the treatment of environmentally relevant
water bodies, such as groundwater, contaminated with chlorinated
organic compounds (COCs). In the aqueous phase
hydrodechlorination of COCs, Pd-based catalysts were found to have
a very high catalytic activity. However, the full utilization of the
catalyst-s potential is impeded by the sensitivity of the catalyst to
poisoning and deactivation induced by reduced sulfur compounds
(e.g. sulfides). Several regenerants have been tested before to recover
the performance of sulfide-fouled Pd catalyst. But these only
delivered partial success with respect to re-establishment of the
catalyst activity. In this study, the deactivation behaviour of
Pd/Al2O3 in the presence of sulfide was investigated. Subsequent to
total deactivation the catalyst was regenerated in the aqueous phase
using potassium permanganate. Under neutral pH condition,
oxidative regeneration with permanganate delivered a slow recovery
of catalyst activity. However, changing the pH of the bulk solution to
acidic resulted in the complete recovery of catalyst activity within a
regeneration time of about half an hour. These findings suggest the
superiority of permanganate as regenerant in re-activating Pd/Al2O3
by oxidizing Pd-bound sulfide.
Abstract: Modeling and simulation of fixed bed three-phase
catalytic reactors are considered for wet air catalytic oxidation of
phenol to perform a comparative numerical analysis between tricklebed
and packed-bubble column reactors. The modeling involves
material balances both for the catalyst particle as well as for different
fluid phases. Catalyst deactivation is also considered in a transient
reactor model to investigate the effects of various parameters
including reactor temperature on catalyst deactivation. The
simulation results indicated that packed-bubble columns were
slightly superior in performance than trickle beds. It was also found
that reaction temperature was the most effective parameter in catalyst
deactivation.