安多地区早中侏罗世岩浆岩岩石地球化学和同位素年代学研究及其对构造演化的制约

Anduo area is located in the Central Tibet, the middle segment of the Bangonghu-Nujiang suture. Anduo Block is the northern part of Lhasa terrane. The relationships among the different geological bodies were determined during the 1: 250000 regional geological surveying. Petrography, petrologic geochemistry, isotopic geochemistry and geochronology of igneous rocks from the suture and granitoids from Anduo Block were analyzed systematically as a whole for the first time. Then, their tectonic setting and history are discussed.Anduo ophiolitic melange consists of metamorphic peridotites, cumulates, plagiogranites, sheeted dykes swarm, pillow lava and radiolarian cherts. The concentration of Cr and Ni in the metamorphic peridotites is very high, with Mg# about 0.94 ~ 0.97, higher 87Sr/86Sr and Pb isotopic ratios, and lower 143Nd/i44Nd ratio. LREE is enriched relative to HREE and positive Eu anomaly is very clear. The REE distribution curve is U shape. Nb and Ta anomalies from cumulate gabbro and sheeted dyke swarm are not clear, while that are slightly negative from pillow lava. Plagiogranite belongs to strong calc-alkaline series with high Si, middle Al, low Fe, Mg and low K contents. Eu anomaly (~ 1.23) from plagiogranites is slightly positive. The character of all components of ophiolite is similar to that of the MORB, while to some extent the ophiolite was influenced by crustal material. Anduo ophiolite formed in a mature back-arc basin. Additionally, intermediate acidity volcanic rocks within Anduo phiolite melange are island arc calc-alkline rocks related to ocean subduction.The early-middle Jurassic plutonic rocks are tonalite, granodiorite bearing-phenocryst, magaporphyritic hornblende monzogranite, magaporphyritic monzogranite, monzogranite bearing-phenocryst and syenogranite in turn. They belong to calc-alkaline series which developed from middle K to high K series temporally. REE distribution curves of all plutonic rocks are similar and parallel to each other. SREE and negative Eu anomaly values decrease. In the multi-element spider diagram, the curves of different plutons are similar to each other, but troughs of Nb, Sr, P and Ti from young plutons become more evident. This suggests that thereare some closely petrogenetic affinities among plutonic rocks which make up amagma plutonism cycle of the early-middle Jurassic. Magma source is mainly crustal,but abundant mafic microgranular enclaves within granitoids indicate that crastalmagma should be mixed with mantle-derived magma and the mantle-derived magmadecreased subsequently. Tonalite has features of I-type granite, magaporphyriticmonzogranite is transition type, and monzogranite bearing-phenocryst is S-typegranite. The characteristic of granitoids from Anduo Block suggest that the formingtectonic setting is active continental margin.Reliable zircon U-Pb SHRIMP ages are obtained in the study area firstly. Plagiogranite from the Anduo ophiolite of the Bangonghu-Nujiang suture is 175.1 Ma, and granitoids from Anduo Block is 172.6-185.4 Ma. Additionally, plagioclase from the plagiogranite dates a 40Ar/39Ar age of 144 Ma, while biotite and hornblend from granitoids of Anduo Block give a 163-165 Ma.Similar cooling ages of plagiogranite from the Anduo ophiolitic melange and granitoids from Anduo Block and the spatial distribution of the ophiolitic rocks between Anduo, Naqu, and Shainzha area suggest that bilateral subduction of the Bangonghu-Nujiang oceanic basin took place in the early-middle Jurassic. During this subduction, Anduo ophiolitic rocks were related to north subduction of the Bangonghu-Nujiang oceanic basin and Anduo back-arc basin spreading, while granitoids from Anduo Block were related to south subduction.

An investigation of the roles of surface aluminum and acid sites in the zeolite MCM-22

Ammonia adsorption studies reveal that the observed Lewis acidity in the zeolite MCM-22 is derived from at least two types of framework aluminum sites (Al(F)), that is, octahedral Al(F) and three-coordinate Al(F). Comparative ammonia or trimethylphosphine (TMP) adsorption experiments with MCM-22 confirm that octahedral Al species gives rise to the signal at delta(ISO) approximate to 0 in the (27)Al NMR spectrum; this is a superposition of two NMR signals from the different Al species on the water-re constructed zeolite surface. A sharp resonance assigned to framework Al reversibly transforms on ammonia adsorption to delta(ISO) (27)Al approximate to 55 from tetrahedral Al(F), while the broad peak is assigned to nonframework aluminium which results from hydrothermal treatment. This study also demonstrates the effectiveness of (27)Al magic angle spinning (MAS) and multiple quantum (MQ) MAS NMR spectroscopy as a technique for the study of zeolite reactions.

Epoxidation of propylene with dilute H2O2 over titanium silicalite containing trace aluminum

Titanium silicalite (TS-1) was successfully synthesized by using TPABr as the template and silica sol as silicon source in a 100 l stainless steel autoclave. IR, XRD, UV--vis, elemental analysis, and (2)7Al and (3)1P MAS NMR were used to characterize the synthesized products. The results show that the synthesized material has an MFI structure with high crystallinity and large crystal size and two kinds of titanium species. Trace aluminum in silica sol is also incorporated into the zeolite framework. The synthesized TS-1 exhibits high activity in the epoxidation of propylene with dilute H2O2 with high selectivity to methyl mono-ethers and low selectivity to propylene oxide (PO). The low selectivity toward PO is due to the residual acidity onto TS-1. The selectivity of PO can reach up to 90% through adjusting the pH of the reaction mixture. Extra amounts of base decrease the H2O2 utilization and the H2O2 conversion. However, in over acid-treated TS-1 in which part removal of extra-framework titanium takes place, the utilization of H2O2 is quite different: for the low Si/Ti ratio of TS-1, the H2O2 utilization increases. But the utilization of H2O2 does not change for the high Si/Ti ratio TS-1. Thermal analysis shows that the as-synthesized TS-1 exhibits high activity and thermal stability in the calcined range 540-900 degreesC.

Stable tetrahedral aluminum sites in hexagonal mesoporous aluminosilicates

A unique templating approach for the synthesis of hexagonal mesoporous aluminosilicates via self-assembly of pre-formed aluminosilcate nanoclusters with the templating micella formed by cetyltrimethylammonium bromide (CTAB) is described. The obtained materials of MAS-5 are hydrothermally stable, which is shown by X-ray diffraction (XRD) analysis. Furthermore, as characterized by NMR technique, MAS-5 has stable tetrahedral aluminum sites that is the major contributions to the acidity of aluminosilicate molecular sieve, and on non-framework aluminium species in the samples was observed.

MAS NMR studies of modified HY zeolites

The variations in structure and acidity on the internal and external surfaces of HY zeolites modified by MgO and SiO2 have been studied by MAS NMR, together with the selective adsorption of perfluorotributyl-amine. Al-27 and Si-29 MAS NMR spectra revealed that the modifications led to significant changes of the framework owing to the migration of some non-framework Si and Al into the framework in the course of the modifications. H-1 MAS NMR spectra showed that the modifications decreased the acidity of the zeolite surfaces. With an increasing of the loading of the oxides, the acidity of the surface decreased further. Both of the two kinds of Bronsted acidity of the MgO-modified HY zeolites decreased, particularly those in the supercages, while those of the SiO2-modified HY zeolites decreased less, and this result is consistent with that of NH3-TPD, from the adsorption of perfluorotributyl-amine, it was found that the acidic sites on the external surface of the HY zeolite can be completely covered by SiO2 after being modified by the chemical liquid deposition (CLD) method.

Linear solvation energy relationships regarding sorption and retention properties of hydrophobic organic compounds in soil leaching column chromatography

The capacity factors of a series of hydrophobic organic compounds (HOCs) were measured in soil leaching column chromatography (SLCC) on a soil column, and in reversed-phase liquid chromatography on a C-18 column with different volumetric fractions (phi) of methanol in methanol-water mixtures. A general equation of linear solvation energy relationships, log(XYZ) = XYZ(0) + mV(1)/100 + spi* + bbeta(m) + aalpha(m), was applied to analyze capacity factors (k'), soil organic partition coefficients (K-oc) and octanol-water partition coefficients (P). The analyses exhibited high accuracy. The chief solute factors that control log K-oc, log P, and log k' (on soil and on C-18) are the solute size (V-1/100) and hydrogen-bond basicity (beta(m)). Less important solute factors are the dipolarity/polarizability (pi*) and hydrogen-bond acidity (alpha(m)). Log k' on soil and log K-oc have similar signs in four fitting coefficients (m, s, b and a) and similar ratios (m:s:b:a), while log k' on C-18 and log P have similar signs in coefficients (m, s, b and a) and similar ratios (m:s:b:a). Consequently, log k' values on C-18 have good correlations with log P (r > 0.97), while log k' values on soil have good correlations with log K-oc (r > 0.98). Two K-oc estimation methods were developed, one through solute solvatochromic parameters, and the other through correlations with k' on soil. For HOCs, a linear relationship between logarithmic capacity factor and methanol composition in methanol-water mixtures could also be derived in SLCC. (C) 2002 Elsevier Science Ltd. All rights reserved.

Retention behavior of hydrophobic organic chemicals as a function of temperature in soil leaching column chromatography

To study the transport mechanism of hydrophobic organic chemicals (HOCs) and the energy change in soil/solvent system, a soil leaching column chromatographic (SLCC) experiment at an environmental temperature range of 20-40 degreesC was carried out, which utilized a reference soil (SP 14696) packed column and a methanol-water (1:4 by volume ratio) eluent. The transport process quickens with the increase of column temperature. The ratio of retention factors at 30 and 40 degreesC (k'(30)/k'(40)) ranged from 1.08 to 1.36. The lower enthalpy change of the solute transfer in SLCC (from eluent to soil) than in conventional reversed-phase liquid chromatography (e.g., from eluent to C-18) is consistent with the hypothesis that HOCs were dominantly and physically partitioned between solvent and soil. The results were also verified by the linear solvation energy relationships analysis. The chief factor controlling the retention was found to be the solute solvophobic partition, and the second important factor was the solute hydrogen-bond basicity, while the least important factors were the solute polarizability-dipolarity and hydrogen-bond acidity. With the increase of temperature, the contributions of the solute solvophobic partition and hydrogen-bond basicity gradually decrease, and the latter decreases faster than the former. (C) 2002 Elsevier Science Ltd. All rights reserved.

A high-resolution solid-state NMR study on nano-structured HZSM-5 zeolite

Variations in the structure and acidity properties of HZSM-5 zeolites with reduction in crystal sizes down to nanoscale (less than 100 nm) have been investigated by XRD, TEM and solid-state NMR with a system capable of in situ sample pretreatment. As evidenced by a combination of Al-27 MAS NMR, Si-29 MAS, CP/MAS NMR and H-1 MAS NMR techniques, the downsize of the zeolite crystal leads to an obvious line broadening of the Al-27, Si-29 MAS NMR spectrum, an increasing of the silanol concentration on the external surface, and a pronounced alteration of the acidity distribution between the external and internal surfaces of the zeolite. In a HZSM-5 zeolite with an average size at about 70 nm, the nonacidic hydroxyl groups (silanols) are about 14% with respect to the total amount of Si, while only 4% of such hydroxyl groups exist in the same kind of zeolite at 1000 nm crystal size. The result of H-1 MAS NMR obtained using Fluorinert(R) FC-43 (perfluorotributyl amine) as a probe molecule demonstrates that most of the silanols are located on the external surface of the zeolite. Moreover, the concentration of Bronsted acid sites on the external surface of the nano-structured zeolite appears to be distinctly higher than that of the microsized zeolite.

A novel method to synthesize amorphous silica-alumina materials with mesoporous distribution without using templates and pore-regulating agents

In this study, a novel sol-gel method is used to synthesize amorphous silica-alumina materials with a narrow mesoporous distribution and various Si/Al molar ratios without using any templates and pore-regulating agents. During the preparation procedure, only inexpensive inorganic salts were used as raw materials, instead of expensive and harmful alkoxides. The precursor sol was dried at room temperature in a vacuum box kept at 60 mmHg until it began to form the gel. The results of a nitrogen sorption experiment indicate that the synthesized materials with different Si/Al molar ratios have similar mesoporous distributions (within 2-12 nm). Moreover, it was found that the material's pore size distribution remains at a similar value during the heat treatment from room temperature to 550 degreesC. On the basis of the nitrogen sorption, TEM, and AFM characterization results, a formation mechanism of mesopores which accounts for the experimental data is also suggested. This suggested mechanism involves rearrangement of the primary particles during the drying process to form the precursors of the similarly sized mesopores. The synthesized materials were characterized by XRD, thermal analysis (TG/DTA), Al-27 and Si-29 MAS NMR spectroscopy, SEM, TEM, and AFM. The results of Al-27 and 29Si MAS NMR indicate that the distribution of silicon and aluminum in the synthesized materials is more uniform and homogeneous than that in the mixed oxides prepared via the traditional sol-gel method even at high alumina contents. The type and density of the acid sites were studied using pyridine adsorption-desorption FTIR spectroscopy. It was shown that the acidity of the synthesized materials is higher than that of the silica-alumina materials prepared by conventional methods.

Preparation of titania-based catalysts for formaldehyde photocatalytic oxidation from TiCl4 by the sol-gel method

Titania sols were prepared by acid hydrolysis of a TiCl4 precursor instead of titanium alkoxides. The effect of acid concentration on the particle size and stability of sol was investigated. Stable titania sols with mean particle size of 14 nm could be obtained when the H+/Ti molar ratio was 0.5. The titania sols were modified with Pt, SiO2, ZrO2, WO3 and MoO3 to prepare a series of modified catalysts, which were used for the photocatalytic oxidation of formaldehyde at 37 degreesC. They showed different photocatalytic activities due to the influence of the additives. Comparing with pure TiO2, the addition of silica or zirconia increased the photocatalytic activity, while the addition of Pt and MoO3 decreased the activity, and the addition Of WO3 had little effect on the activity. It is of great significance that the conversion of formaldehyde was increased up to 94% over the SiO2-TiO2 catalyst. The increased activity was partly due to higher surface area and porosity or smaller crystallite size. A comparison of our catalyst compositions with the literature in this field suggested that the difference in activity due to the addition of a second metal oxide maybe caused by the surface chemistry of the catalysts, particularly the acidity. (C) 2001 Elsevier Science B.V. All rights reserved.

Calagem e controle da acidez dos viveiros de aqüicultura.

2006

The effect of chromium on sulfur resistance of Pd/HY-Al2O3 catalysts for aromatic hydrogenation

Sulfur is a major poison to noble metal catalysts for deep aromatic hydrogenation in the petroleum refining industry. In order to study the sulfur resistance of Pd-based catalysts, a series of Pd, Cr, and PdCr catalysts supported on HY-Al2O3 were studied by NH3-TPD, pyridine-adsorption IR, TPR, IR spectra of adsorbed CO, and toluene hydrogenation in the presence of 3000 ppm sulfur as thiophene under the following conditions: 533-573 K, 4.2 MPa, and WHSV 4.0 h(-1). Cr has no influence on the acidity of the catalysts. TPR patterns and in situ IR spectra of adsorbed CO revealed a strong interaction between Cr and Pd, and the frequency shift of linear bonded CO on Pd indicates that the electron density of Pd decreases with the increase of the Cr/Pd atomic ratio. The catalytic performance of Pd, Cr, and PdCr catalysts shows that the sulfur resistance of Pd is strongly enhanced by Cr, and the activity reaches its maximum when the Cr/Pd atomic ratio equals 8. The active phase model "Pd particles decorated by Cr2O3" is postulated to explain the behavior of PdCr catalysts. (C) 2001 Academic Press.

Soja: adubacao e calagem no Brasil.

Adubacao; Gesso agricola; Correcao da acidez do solo.

Hydroisomerization of long-chain alkane over Pt/SAPO-11 catalysts synthesized from nonaqueous media

SAPO-11 molecular sieves were synthesized from nonaqueous media. The effects of Si and Al sources as well as solvents on the catalytic performance of SAPO-11 were investigated by the hydroisomerization reaction of n-dodecane. The samples were characterized by XRD, XRF, N-2-adsorption, SEM, NH3-TPD, IR-NH3 and Si-29 CP MAS NMR. The SAPO-11 samples synthesized with tetraethoxysilane as the Si source showed higher Si incorporation contents than the SAPO molecular sieves prepared with polymeric Si sources (fumed silica and Si colloidal gel). The reaction results showed that Pt/SAPO-11 catalysts synthesized from ethylene glycol and glycerol media with the monomeric Si and Al sources (tetraethoxysilane, aluminum isopropoxide) exhibited higher catalytic activities than those catalysts with the polymeric Si or Al (pseudo-boehmite) sources, due to the larger external surface area and higher acidity of the former ones. Especially, the catalyst synthesized in an ethylene glycol medium possessed the highest catalytic activity. Over this catalyst, 88% conversion of n-dodecane was achieved at a low temperature of 250 degrees C.

Efeito do reflorestamento com diferentes espécies sobre os atributos químicos em solo de cerrado.

RESUMO: O objetivo desse trabalho foi avaliar o efeito do reflorestamento com eucalipto (Eucalyptus camaldulensis), carvoeiro (Sclerolobium paniculatum) , pinus (Pinus tecunumanii) e baru (Dipteryx alata) sobre os teores de nutrientes e de carbono orgânico do solo em comparação com uma área sob vegetação de Cerrado. Foram coletadas amostras de solo nas camadas 0 cm -5 cm, 5 cm - 10 cm, 10 cm - 20 cm, 20 cm - 30 cm, 30 cm - 40 cm e 40 cm - 60 cm, em um povoamento de baru plantado em 1987, um de carvoeiro plantado em 1985, um de pinus plantado em 1984, um de eucalipto plantado em 1983 e em uma área adjacente com vegetação nativa de Cerrado. Cada amostra foi composta por dez subamostras por parcela e por profundidade, coletadas entre as linhas. Os atributos químicos analisados foram: pH em água, alumínio trocável, H + Al (acidez potencial), fósforo e potássio disponíveis, cálcio e magnésio trocáveis e carbono orgânico. Os plantios de eucalipto e de carvoeiro aumentaram significativamente os teores de carbono orgânico do solo na camada de 0 cm a 5 cm. Os teores de fósforo foram muito baixos em todas as camadas avaliadas e não foram afetados pelo reflorestamento. O plantio de pinus acarretou queda significativa no teor de potássio, de cálcio e de magnésio até a camada de 30 cm a 40 cm. A partir de 20 cm de profundidade houve redução do pH do solo sob no plantio de pinus comparado com a área de Cerrado. ABSTRACT: The objective of this paper was to evaluate the effect of reforestation with eucalyptus (Eucalyptus camaldulensis), carvoeiro (Sclerolobium paniculatum) , pinus (Pinus tecunumanii) and baru (Dipteryx alata) on soil carbon and nutrients contents in comparison to virgin area of Cerrado. Samples of soil were collected down in 0 cm - 5 cm, 5 cm - 10 cm, 10 cm - 20 cm, 20 cm - 30 cm, 30 cm - 40 cm e 40 cm - 60 cm layers in a plantation of baru planted in 1987, one of carvoeiro planted in 1985, one of pinus planted in 1984, one of eucalyptus planted in 1983 and an adjacent area of Cerrado. Every sample was composed by ten sub-samples, by plot by depth, collected between the rows. Water pH, exchangeable aluminum, exchangeable H + Al (total acidity), suitable phosphorus, suitable potassium, exchangeable calcium, exchangeable magnesium and organic carbon contents were evaluated. Eucalyptus and carvoeiro planting increased significantly soil organic carbon contents in 5 cm - 10 cm layer. The levels of phosphorus were very low in all evaluated layers and were not affected by reforestation. Pinus planting decreased significantly potassium, calcium and magnesium contents until 30 cm - 40 cm layer. There was pH reduction after 20 cm of depth in pinus planting compared with cerrado area.