Production Process for Diesel Fuel Components Polyoxymethylene Dimethyl Ethers from Methanol and Formaldehyde Solution

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.

Kinetic Study of 1-Butene Isomerization over Hydrotalcite Catalyst

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.

Effect of Recycle Gas on Activity and Selectivity of Co-Ru/Al2O3 Catalyst in Fischer- Tropsch Synthesis

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.

Dehydroxylation of Glycerol to Propylene Glycol over Cu-ZnO/Al2O3 Catalyst: Effect of Feed Purity

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.

Deactivation of Cu - Cr/γ-alumina Catalysts for Combustion of Exhaust Gases

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.

Optimization of Reaction Rate Parameters in Modeling of Heavy Paraffins Dehydrogenation

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.

Palladium-Catalyzed Hydrodechlorination for Water Remediation: Catalyst Deactivation and Regeneration

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.

Modeling of Catalyst Deactivation in Catalytic Wet Air Oxidation of Phenol in Fixed Bed Three-Phase Reactor

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.