Upgrading of solid recovered fuel (SRF) by dechlorination and catalytic pyrolysis over nanocrystalline ZSM-5 zeolite.

Globally increasing concern related to municipal solid waste generation is encouraging research efforts on developing alternative routes to valorize mixed refused wastes. In this way, catalytic pyrolysis is emerging as an interesting and efficient technology due to its great flexibility in terms of feedstock. In the current work, upgrading of a Solid Recovered Fuel (SRF) has been investigated by catalytic pyrolysis over nanocrystalline ZSM-5 zeolite (n-ZSM-5), paying special attention to dechlorination effects due to the high Cl content of the raw waste. Thus, pretreatment of the SRF by water washing and mild thermal processing allows for a significant reduction of the Cl concentration. Regarding the catalytic pyrolysis step, the best conditions correspond with a temperature of 400 °C in the catalyst bed and 0.50 catalyst/SRF mass ratio, which lead to ca. 30 wt% oil yield (rich in aromatic hydrocarbons) together with about 40 wt% gas yield (rich in C3-C4 olefins). Accordingly, these products could find use as raw chemicals or for the production of advanced fuels. In addition, zeolite reutilization has been tested for several cycles, denoting a progressive modification of the products distribution because of coke deposition. However, an almost total recovery of the n-ZSM-5 zeolite catalytic performance is achieved after regeneration by air calcination, affording the production of an oil fraction with a Cl content as low as 40 ppm.

From 3D to 2D zeolite catalytic materials.

Research activities and recent developments in the area of three-dimensional zeolites and their two-dimensional analogues are reviewed. Zeolites are the most important industrial heterogeneous catalysts with numerous applications. However, they suffer from limited pore sizes not allowing penetration of sterically demanding molecules to their channel systems and to active sites. We briefly highlight here the synthesis, properties and catalytic potential of three-dimensional zeolites followed by a discussion of hierarchical zeolites combining micro- and mesoporosity. The final part is devoted to two-dimensional analogues developed recently. Novel bottom-up and top-down synthetic approaches for two-dimensional zeolites, their properties, and catalytic performances are thoroughly discussed in this review.

CO2 reduction over NaNbO3 and NaTaO3 perovskite photocatalysts.

The activity of NaNbO3 and NaTaO3 perovskites for the photocatalytic reduction of CO2 is studied in this work. For this purpose, sodium niobate and tantalate have been prepared using solid-state reactions, extensively characterised by means of powder X-ray diffraction, UV-vis, photoluminescence and Raman spectroscopies and N2 adsorption isotherms, and tested in the gas-phase reduction of CO2 under UV light in a continuous flow photoreactor. NaNbO3 is constituted of an orthorhombically distorted perovskite structure, while a ca. 4.5 : 1 combination of the orthorhombic and monoclinic modifications is found in the tantalate. Both catalysts exhibit interesting intrinsic activities, with the tantalate material giving rise to a slightly higher performance. This is attributed to a compromise situation between electron-hole recombination and the reducing potential of conduction band electrons. In addition, a decrease in the competition of water protons for photogenerated electrons is observed with both catalysts with respect to TiO2.

Revisiting the BaO2/BaO redox cycle for solar thermochemical energy storage.

The barium peroxide-based redox cycle was proposed in the late 1970s as a thermochemical energy storage system. Since then, very little attention has been paid to such redox couples. In this paper, we have revisited the use of reduction-oxidation reactions of the BaO2/BaO system for thermochemical heat storage at high temperatures. Using thermogravimetric analysis, reduction and oxidation reactions were studied in order to find the main limitations associated with each process. Furthermore, the system was evaluated through several charge-discharge stages in order to analyse its possible degradation after repeated cycling. Through differential scanning calorimetry the heat stored and released were also determined. Oxidation reaction, which was found to be slower than reduction, was studied in more detail using isothermal tests. It was observed that the rate-controlling step of BaO oxidation follows zero-order kinetics, although at high temperatures a deviation from Arrhenius behaviour was observed probably due to hindrances to anionic oxygen diffusion caused by the formation of an external layer of BaO2. This redox couple was able to withstand several redox cycles without deactivation, showing reaction conversions close to 100% provided that impurities are previously eliminated through thermal pre-treatment, demonstrating the feasibility of this system for solar thermochemical heat storage.

Transportation fuel production by combination of LDPE thermal cracking and catalytic hydroreforming.

Fuel production from plastics is a promising way to reduce landfilling rates while obtaining valuable products. The usage of Ni-supported hierarchical Beta zeolite (h-Beta) for the hydroreforming of the oils coming from LDPE thermal cracking has proved to produce high selectivities to gasoline and diesel fuels (>80%). In the present work, the effect of the Ni loading on Ni/h-Beta is investigated in the hydroreforming of the oils form LDPE thermal cracking. h-Beta samples were impregnated with Ni nitrate, calcined and reduced in H2 up to 550°C to achieve different Ni contents: 1.5%, 4%, 7% and 10%. Larger and more easily reducible metal particles were obtained on Ni 7%/h-Beta and Ni 10%/h-Beta. Hydroreforming tests were carried out in autoclave reactor at 310°C, under 20 bar H2, for 45 min. Ni content progressively increased the amount of gases at the expenses of diesel fractions, while gasoline remained approximately constant about 52-54%. Maximum selectivity to automotive fuels (∼81%) was obtained with Ni 7%/h-Beta. Ni loading also enhanced olefins saturation up to Ni 7%/h-Beta. High cetane indices (71-86) and octane numbers (89-91) were obtained over all the catalysts. Regarding the different studied Ni contents, Ni 7%/h-Beta constitutes a rather promising catalyst for obtaining high quality fuels from LDPE thermal cracking oils.

Influence of the structural and textural properties of ordered mesoporous materials and hierarchical zeolitic supports on the controlled release of methylprednisolone hemisuccinate.

To alleviate the chronic inflammation, nasal obstruction, and loss of sense of smell that produces the rhinosinusitis disease, ordered mesoporous materials and hierarchical zeolites could be used for slow and sustained corticoid (methylprednisolone hemisuccinate conjugate) release. The correlations between the delivery performance of methylprednisolone hemisuccinate and the physicochemical properties of carriers' release systems, including pore mesostructure, texture and size, and surface chemistry, have been well established. Different two-dimensional (2-D) and three-dimensional (3-D) mesostructured materials (MCM-41, SBA-15, expanded SBA-15, FDU-12, and SBA-16) were employed. In addition, for the first time to the best of our knowledge, materials based on hierarchical zeolites with additional mesoporosity (h-ZSM-5 and h-BETA zeolites) were also tested. In particular, two materials (3-D cubic mesoporous silica SBA-16 and hierarchical Beta zeolite) have been probed to be potential candidates, exhibiting high drug adsorption capacities and slow drug release rates, which is the most favourable way of drug release in the particular rhinosinusitis application. Solid-state 1H-29Si HETCOR NMR analyses confirm the strong interactions of the drug with the surface of h-BETA and 3-D SBA-16 materials, via hydrogen bonding of carboxylic, ketone, and aliphatic moieties of the methylprednisolone hemisuccinate at surface silanol sites. Because of the remarkable release performance, it is expected that 3-D mesoporous silica SBA-16 and hierarchical Beta zeolite can be attractive candidates for current applications in nasal inflammation treatments. The drug release rate can be further retarded by decreasing the pH to around 4.6; at this point more attraction forces were detected as proved by zeta-potential measurements. Therefore, a slower delivery trend of methylprednisolone hemisuccinate has been observed for all the materials, which is more pronounced in the case of SBA-15 and SBA-16.

Synthesis strategies in the search for hierarchical zeolites.

Great interest has arisen in the past years in the development of hierarchical zeolites, having at least two levels of porosities. Hierarchical zeolites show an enhanced accessibility, leading to improved catalytic activity in reactions suffering from steric and/or diffusional limitations. Moreover, the secondary porosity offers an ideal space for the deposition of additional active phases and for functionalization with organic moieties. However, the secondary surface represents a discontinuity of the crystalline framework, with a low connectivity and a high concentration of silanols. Consequently, hierarchical zeolites exhibit a less "zeolitic behaviour" than conventional ones in terms of acidity, hydrophobic/hydrophilic character, confinement effects, shape-selectivity and hydrothermal stability. Nevertheless, this secondary surface is far from being amorphous, which provides hierarchical zeolites with a set of novel features. A wide variety of innovative strategies have been developed for generating a secondary porosity in zeolites. In the present review, the different synthetic routes leading to hierarchical zeolites have been classified into five categories: removal of framework atoms, surfactant-assisted procedures, hard-templating, zeolitization of preformed solids and organosilane-based methods. Significant advances have been achieved recently in several of these alternatives. These include desilication, due to its versatility, dual templating with polyquaternary ammonium surfactants and framework reorganization by treatment with surfactant-containing basic solutions. In the last two cases, the materials so prepared show both mesoscopic ordering and zeolitic lattice planes. Likewise, interesting results have been obtained with the incorporation of different types of organosilanes into the zeolite crystallization gels, taking advantage of their high affinity for silicate and aluminosilicate species. Crystallization of organofunctionalized species favours the formation of organic-inorganic composites that, upon calcination, are transformed into hierarchical zeolites. However, in spite of this impressive progress in novel strategies for the preparation of hierarchical zeolites, significant challenges are still ahead. The overall one is the development of methods that are versatile in terms of zeolite structures and compositions, capable of tuning the secondary porosity properties, and being scaled up in a cost-effective way. Recent works have demonstrated that it is possible to scale-up easily the synthesis of hierarchical zeolites by desilication. Economic aspects may become a significant bottleneck for the commercial application of hierarchical zeolites since most of the synthesis strategies so far developed imply the use of more expensive procedures and reagents compared to conventional zeolites. Nevertheless, the use of hierarchical zeolites as efficient catalysts for the production of high value-added compounds could greatly compensate these increased manufacturing costs.

The use of kidneys from living donors with renal vascular disease: expanding the donor pool.

PURPOSE: The disparity between the number of patients awaiting organ transplantation and the number of available donor organs continues to increase. We report the outcomes of transplantation using kidneys from living donors who had unilateral renovascular disease. MATERIALS AND METHODS: We identified 5 living donors who had unilateral renovascular disease, including saccular renal artery aneurysms, an arteriovenous malformation, localized atherosclerosis and fibromuscular renal artery stenosis. Each donor was normotensive and asymptomatic, and had otherwise normal renal function. RESULTS: In each case the abnormal kidney was removed, the lesion was repaired ex vivo and the kidney was successfully transplanted without complication in the donor or recipient. Each recipient had a serum creatinine of less than 2 mg./dl. and each donor remained normotensive with stable renal function at up to 3 years of followup. CONCLUSIONS: Kidneys from living donors with renovascular disease can be transplanted safely provided that careful selection, informed consent and a normal remaining kidney are ensured.

Determinants of chronic renal allograft rejection in cyclosporine-treated recipients.

We analyzed the development of chronic rejection in 511 kidney-only renal transplants in 507 patients between July 1987 and November 1994. A database was established for recipients > or = 18 years old who received cyclosporine-based immunosuppression and demonstrated graft survival for a minimum of 12 months. The 347 recipients of cadaver transplants (67.9%) and 164 recipients of live donor transplants (32.1%) were followed for 12 to 102 months (mean 51 months). Chronic rejection was diagnosed in 124 transplants (24%), with a mean time to diagnosis of 23+/-18 months (range 3-92). Risk factors were identified in a multivariate analysis using the Cox model. The impact of the timing and severity of rejection episodes was analyzed in a univariate model. The presence of chronic rejection resulted in decreased (P=0.0001) 5-year graft survival for both cadaver graft (83.7% vs. 58.2%) and live donor graft (93.2% vs. 53.1%) recipients. Significant variables for the development of chronic rejection included an acute rejection episode (P=0.0001), a black recipient (P=0.0006), donor age > or = 50 years (P=0.006), and a serum creatinine level >2.0 mg/dl by 6 months after transplantation. Severity of rejection measured by peak serum creatinine or posttreatment return to baseline was not related to chronic rejection. However, acute rejection episodes lasting for more that 5 days (P=0.03) or occurring after 6 months (P=0.001) did influence time to chronic rejection. In addition, mismatching for donor-recipient race was a significant (P=0.008) risk factor for recipients of cadaver grafts. We conclude that acute rejection is the most significant risk factor for chronic rejection, and the long-term fate of grafts may be determined as early as the first 6 months. Racial matching of donor-recipient pairs may be useful to minimize chronic rejection risk. Future advances that diminish the incidence and severity of acute rejection may have the greatest impact on long-term survival.

Transplantation into the long-term defunctionalized bladder.

PURPOSE: We evaluated the outcome of transplantation into a long-term defunctionalized bladder. MATERIALS AND METHODS: Since 1985 we performed transplantation in 5 dialysis dependent patients after excision of the ileal conduit and native kidneys. The bladder was evaluated before transplantation with cystoscopy, voiding cystography, urodynamics and demonstration of continence. Bladder rehabilitation was accomplished by cycling through a suprapubic tube or urethral catheter, and no bladder augmentation was done. All patients received antibiotic prophylaxis for several years. RESULTS: Five male recipients underwent transplantation at ages 22, 29, 30, 31 and 55 years, and they had had a defunctionalized bladder for 15, 17, 23, 25 and 26 years. All patients were alive with a functioning allograft at 6, 84, 90, 112 and 120 months after transplantation. Current serum creatinine values are 1.2, 1.6, 1.8, 2.3 and 2.5 mg./dl. Median urodynamic values before and after transplantation were bladder capacity 60 and 300 cc, respectively, peak flow rate 5 and 18 cc per second, respectively, and post-void residual 20 and 15 cc, respectively. One patient required self-catheterization. CONCLUSIONS: Renal transplantation into a long-term defunctionalized bladder can be performed safely in carefully selected patients. Bladder function and continence should be confirmed before transplantation using a program of progressive bladder rehabilitation.