Release behaviors of arsenic (As) during pyrolysis of two Chinese coal gangues were studied in this report. The pyrolysis experiments were carried out in a temperature programmed tube furnace under N2 atmosphere with different temperature (200-1200 ºC), residence time (0-50 min), heating rate (10-50 ºC min-1) and N2 gas flow rate (100-500 cm3 min-1). The experiment results, under different pyrolysis conditions, indicate that the release ratio of As increases with increasing temperature, as well as residence time during pyrolysis of coal gangues. Besides that, higher heating rate during pyrolysis of coal gangues can stimulate the As release from coal gangue to some extent. The release ratio of As increases to a maximum and then decreases when the N2 gas flow rate is increased. The results imply that different modes of ocurrence of As exist in two coal gangues. The As release has positive relation with the volatile matter release. As is more easily released than coal gangue matrix during coal gangue pyrolysis.

Abstract Shape-selective methylation of naphthalene over SAPO-11, SAPO-5 and mordenite molecular sieves were carried out in a fixed-bed flow reactor under atmospheric pressure. Methanol and mesitylene were used as methylation and solvent agents. The experiment results showed that SAPO-11 exhibited higher stability, higher selectivity of 2,6-dimethylnaphthalene (2,6-DMN) and higher 2,6-/2,7-DMN ratio than SAPO-5 and mordenite molecular sieves. The catalytic performances for the methylation of naphthalene were mainly related to the pore structure of the catalysts. The comparison of the spent SAPO- 11 with fresh SAPO-11 suggested that structure collapse of the SAPO-11 by dealumination was occurred during the methylation of naphthalene with methanol, which may have been caused by high temperature steam from water produced in the reaction or by high temperature methanol vapor.

The dynamic release behavior of elemental Hg (Hg0) during thermal treatment of two bituminous coals was studied under N2, CO2 and air atmospheres. The results show that the profiles of Hg0 released present several peaks during thermal treatment of two bituminous coals. The Hg peak profiles for the same coal are different with the different atmosphere used. The amount of Hg0 released from the coals is about 92-94, 73-74 and 31-33% under N2, CO2 and air atmosphere, respectively. This indicates that the Hg0 is the dominant form during thermal treatment of the coals under N2 atmosphere whereas part of Hg0 is converted into the oxidized Hg during thermal treatment of the coals under CO2 and air atmosphere. The total Hg released is promoted by the volatile matter release to some extent while the Hg0 released is mainly affected by the atmospheres used.

A performance catalítica de catalisadores HZSM-5 com tratamento alcalino foi investigada em um microrreator contínuo de leito fixo. As propriedades dos catalisadores HZSM-5 de origem e modificados foram caracterizadas por difração de raio X (XRD), espectroscopia de emissão atômica com plasma indutivamente acoplado (ICP-AES), adsorção de N2 e dessorção programada por temperatura de NH3 (NH3-TPD). Os resultados mostraram que o tratamento alcalino é um método adequado para modificar o catalisador HZSM-5 para a desidratação do etanol a etileno. O catalisador HZSM-5 tratado com 0.4 mol L-1 NaOH apresentou alta atividade e boa estabilidade. As performances catalíticas melhoradas dos catalisadores com tratamento alcalino são atribuídas, principalmente, aos mesoporos criados e à diminuição de sítios ácidos fortes durante o tratamento alcalino.

The catalytic performance of alkali-treated HZSM-5 catalysts was investigated in a continuous fixed-bed microreactor. The properties of the parent and modified HZSM-5 catalysts were characterized by X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-AES), N2 adsorption and temperature programmed desorption of NH3 (NH3-TPD). The results show that the alkali treatment is a suitable method to modify the HZSM-5 catalyst for ethanol dehydration to ethylene. The HZSM-5 catalyst with 0.4 mol L-1 NaOH shows high activity and good stability. The improved catalytic performances of alkali-treated catalysts are mainly attributed to the created mesopores and the decreased number of strong acid sites during the alkali treatment.

O efeito de Zn na alquilação da cadeia lateral de tolueno com metanol sobre zeólita KX foi investigado. Descobriu-se que a adição de pouca quantidade de Zn a KX poderia aumentar significativamente a conversão de tolueno. Além disso, os resultados mostraram que a conversão de tolueno pelo catalisador ZnKX (0,8 wt. %) era quase o dobro daquela por KX. Os catalisadores foram caracterizados por difração de raios X (XRD), fisissorção de N2, dessorção programada por temperatura (TPD) de NH3, espectroscopia no infravermelho (IR) da absorção de piridina, CO2-TPD, espectroscopia fotoeletrônica de raios X (XPS) e IR da adsorção dos reagentes. Os resultados de TPD e XPS mostraram que a existência de espécies de Zn pode aumentar a força dos sítios básicos. Os resultados de IR da adsorção dos reagentes sugerem que a introdução de Zn poderia diminuir o tolueno quimissorvido e aumentar as quantidades relativas de formato unidentado. Os resultados indicaram que é possível atingir um excelente balanço entre as propriedades ácido-base do catalisador e a estequiometria de sorção de metanol-tolueno, levando à melhora da atividade catalítica.

The effect of Zn on side-chain alkylation of toluene with methanol over KX zeolite was investigated. It was found that the addition of Zn with a low content over KX could enhance toluene conversion significantly. In addition, the results showed that the conversion of toluene over ZnKX (0.8 wt. %) catalyst was almost twice as high as that over KX. The catalysts were characterized by X-ray diffraction (XRD), N2 physisorption, NH3-temperature-programmed desorption (TPD), pyridine absorption infrared (IR) spectroscopy, CO2-TPD, X-ray photoelectron spectroscopy (XPS) and IR adsorption of reactants. The TPD and XPS results showed that the existence of Zn species could increase the strength of basic sites. The IR adsorption of reactants results suggested that the introduction of Zn could decrease the chemisorbed toluene and increase the relative amounts of unidentate formate. The results indicated that an excellent balance between the acid-base properties of the catalyst and the sorption stoichiometry of methanol-toluene could be achieved, leading to the improvement of catalytic activity.

Os efeitos dos métodos de impregnação (co-impregnação e impregnação sequencial) e das condições de secagem (ar e vácuo) sobre estrutura e o comportamento catalítico de catalisadores Ni-W suportados em MCM-41 foram investigados. Os catalisadores foram caracterizados por difratometria de raios X de pó (XRD), espectroscopia de absorção no infravermelho com transformada de Fourier (FT-IR), espectroscopia de absorção no UV-Vis por refletância difusa (DRS), espectroscopia Raman, espectroscopia fotoeletrônica de raios X (XPS) e espectroscopia de absorção no infravermelho após adsorção de piridina (Py-IR). Eles foram testados para hidrodesnitrogenação (HDN) de quinolina nas temperaturas de 300-400 ºC. Os resultados de HDN mostraram que os catalisadores preparados por co-impregnação foram mais ativos do que aqueles preparados por impregnação sequencial, e que os catalisadores preparados por secagem sob vácuo foram mais ativos do que aqueles secados ao ar. A caracterização revelou que o método de co-impregnação e a secagem sob vácuo promoveram a dispersão de W, a formação de fases ativas e a formação de sítios ácidos na superfície dos catalisadores.

The effects of impregnation methods (co-impregnation and sequential impregnation) and drying conditions (air and vacuum) on the structure and catalytic behavior of MCM-41 supported Ni-W catalysts were investigated. The catalysts were characterized by powder X-ray diffraction (XRD) analysis, Fourier-transform infrared spectroscopy (FT-IR), diffuse reflectance UV-Vis absorbance spectroscopy (DRS), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and pyridine adsorbed infrared spectroscopy (Py-IR) techniques. They were tested for hydrodenitrogenation (HDN) of quinoline at temperatures of 300-400 ºC. The HDN results showed that the catalysts prepared by co-impregnation were more active than the catalysts prepared by sequential impregnation and the catalysts prepared by drying under vacuum were more active than the catalysts dried in air. Characterization revealed that the co-impregnation method and drying under vacuum promoted the dispersion of W, the formation of the active phases, and the formation of acidic sites on the catalysts.

Zeólitas SAPO-11 foram sintetizadas com sucesso utilizando três diferentes direcionadores orgânicos (dietilamina (DEA), di-n-propilamina (DPA) e di-isopropilamina (DIPA)) e um conteúdo variável de DPA (nDPA/Al2O3 = 0,8, 1,2, 1,6 e 2,0) sob condições hidrotérmicas. As amostras foram caracterizadas por difratometria de raios X de pó (XRD), microscopia eletrônica de varredura (SEM), adsorção-dessorção de N2, dessorção de amônia a temperatura programada (NH3-TPD) e ressonância magnética nuclear (NMR) de29 Si com rotação no ângulo mágico (MAS). As amostras foram também avaliadas com relação à metilação do naftaleno com metanol para obtenção de 2,6-dimetil-naftaleno (2,6-DMN). Resultados de difratometria de raios X indicaram que o efeito direcional das diferentes aminas sobre a estrutura AEL (Aluminophosphate-ELeven) decresceram segundo a ordem DPA > DEA > DIPA e o conteúdo de DPA mais adequado foi nDPA/Al2O3 = 1,2. Resultados da adsorção-dessorção de N2 mostraram que SAPO-11(DPA,1.2) exibiu a distribuição de poros mais ampla, a área superficial específica BET mais elevada e o volume de poro maior dentre todas as amostras SAPO-11. SAPO-11(DPA,1.2) exibiu também um elevado desempenho catalítico na metilação de naftaleno devido às suas elevadas cristalinidade e superfície externa e à ampla distribuição de tamanho de poro. A estrutura de poros da zeólita SAPO-11, ao invés de sua acidez, desempenhou um papel importante na obtenção de elevado desempenho catalítico na metilação de naftaleno com metanol.

SAPO-11 zeolites were successfully synthesized by using three different templates (diethylamine (DEA), di-n-propylamine (DPA) and di-isopropylamine (DIPA)) and varying DPA contents (nDPA/Al2O3 = 0.8, 1.2, 1.6 and 2.0) under hydrothermal conditions. The samples were characterized by powder X-ray diffractometry (XRD), scanning electron microscopy (SEM), N2 adsorption-desorption, temperature programmed desorption of ammonia (NH3-TPD) and29 Si magic angle spinning (MAS) nuclear magnetic resonance (NMR). The samples were also evaluated towards the methylation of naphthalene with methanol to produce 2,6-dimethylnaphthalene (2,6-DMN). XRD results indicated that the directing effect of the different templates for AEL (Aluminophosphate-ELeven) structure decreased in the order DPA > DEA > DIPA and the most suitable DPA content was nDPA/Al2O3 = 1.2. N2 adsorption-desorption results showed that SAPO-11(DPA,1.2) exhibited the broadest pore size distribution, the highest BET specific surface area and the largest pore volume among all the SAPO-11 samples. SAPO-11(DPA,1.2) exhibited high catalytic performances in the methylation of naphthalene due to its high crystallinity, high external surface and broad pore size distribution. The pore structure of SAPO-11 zeolite, rather than its acidity, played an important role in achieving high catalytic performances in the methylation of naphthalene with methanol.