Molded micro- and mesoporous carbon/silica composite from rice husk and beet sugar

A molded carbon/silica composite with high micro- and mesoporosity, as well as a high bulk density, was fabricated by activating a disk-molded precursor made from carbonized rice husk (RH) and beet sugar (BS) at 875 °C in CO₂. The pore structure of the RH- and BS-based carbon/silica composite (RBC) was analysed in relation to the bulk density. An activation time of 2.0 h provided the largest BET specific surface area (1027 m²/g) and total pore volume (0.68 cm³/g) and a low bulk density (0.54 g/cm³). An RBC that was first activated for 1 h was immersed again in BS syrup and then activated in CO₂ for 1 h. This two-step activation process provided both a high bulk density (0.69 g/cm³) and a highly textured structure (BET specific surface area, 943 m²/g; total pore volume, 0.56 cm³/g). The immersion in BS syrup was useful for improving the texture without reducing the bulk density, in comparison to one-step activation for 1.0 h. The suspension of the RBCs was basic because of the residual inorganic compounds of potassium and calcium. However, the basicity of the suspension was alleviated by washing the RBCs with water.     

稻壳微波制备高纯白炭黑的工艺研究

采用微波反应方式,将稻壳与氢氧化钠反应获得硅酸钠溶液(水玻璃),采用沉淀法制取高品质白炭黑。以白炭黑对邻苯二甲酸二丁酯的吸收值为指标,研究了水玻璃模数、反应终点p H、反应温度对白炭黑比表面积的影响。结果表明,采用1 mol/L的H_2SO_4溶液对其滴定,当反应终点pH值为10,水玻璃模数为2.2,反应温度为95℃时,制备出的白炭黑品质最好,其对邻苯二甲酸二丁酯吸收值可达3.779 m L/g。     

稻壳微波制备高纯白炭黑的工艺研究

采用微波反应方式,将稻壳与氢氧化钠反应获得硅酸钠溶液(水玻璃),采用沉淀法制取高品质白炭黑。以白炭黑对邻苯二甲酸二丁酯的吸收值为指标,研究了水玻璃模数、反应终点p H、反应温度对白炭黑比表面积的影响。结果表明,采用1 mol/L的H_2SO_4溶液对其滴定,当反应终点pH值为10,水玻璃模数为2.2,反应温度为95℃时,制备出的白炭黑品质最好,其对邻苯二甲酸二丁酯吸收值可达3.779 m L/g。     

A facile route for the preparation of silica foams using rice husk ash

This work aims to synthesize silica foam with around 75 vol. % open porosity without using any additive or pore forming agents, in order to prevent the generation of greenhouse gases during pore formation in the silica matrix. Waste rice husk ash (RHA) derived silica is used as a silica source, which is extracted through the alkali extraction synthesis route. Several physical characterizations such as X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), differential thermal-thermogravimetric (DTA-TGA) and FTIR analysis have been done for RHA extracted silica. Silica foam specimens are fabricated through control compaction pressure and at low foaming temperature. Samples which are fired at 550°C for 30 minutes exhibit both a adequate apparent porosity (AP; ~75.82%) and significant compressive strength (~1.54 MPa). It can also be observed that the porosity and strength values are changed with the variation in compaction pressure and foaming temperature.     

Technological properties of glass-ceramic tiles obtained using rice husk ash as silica precursor

This paper reports the results of a study focused on the obtainment of glass-ceramic by using rice husk ash (RHA) as silica precursor. RHA is a by-product generated in biomass plants using rice husk as fuel for kilns or in the rice mills to generate steam for the parboiling process. Worldwide, it is annually produced about 132 Mt of rice husk, which gives rise to a production of 33 Mt/year of RHA. Glass-ceramic tiles were produced by a sinter-crystallization process using a glassy frit formulated in the MgO–Al₂O₃-SiO₂ composition system. The realized glass-ceramics were studied according to ISO rules for sintering and technological properties (water absorption, apparent density, bending strength, Young's modulus, deep abrasion, Mohs hardness). To complete the investigation crystalline phase formation and microstructural characterization of the glass-ceramic materials was carried out using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Finally, chemical durability tests on parent glass and derived glass-ceramics were performed. The results obtained showed that it is possible to use RHA to produce glass-ceramic tiles by a sinter-crystallization process, obtaining nepheline (Na₂O*Al₂O₃*SiO₂) as main crystalline phase and forsterite (2MgO*SiO₂) at 900 °C. Regarding technological features, the sintered materials showed bending strength values and Mohs hardness higher with respect to commercial glass-ceramics like NeopariesR. Other properties as water absorption (0.5%) allowed to classify these materials into the Group BIa characteristic of high sintered ceramic tiles according to European Standard rule.     

Preparation of refractory cordierite using amorphous rice husk silica for thermal insulation purposes

This study aims to investigate the effect of sintering temperatures on the phase formation and physical characteristics of refractory cordierite prepared from rice husk silica, Al₂O₃, and MgO powders. The samples were subjected to sintering temperatures of 1050–1350 °C, and development of structures was characterized using Fourier Transform Infrared (FTIR) spectroscopy, X-ray diffraction (XRD) coupled with Rietveld analysis, scanning electron microscopy (SEM) and dilatometry. The results obtained indicated the significant role of sintering temperatures on phase transformation of spinel and cristobalite into cordierite, in which at sintering temperatures of 1230–1350 °C the cordierite emerges as a dominant phase, while spinel and cristobalite are practically undetected. Formation of cordierite was followed by decrease in density, porosity, and thermal expansion coefficient, while for hardness and bending strength the opposite was true. Thermal expansion coefficient of the sintered sample at 1350 °C is 3.3×10⁻⁶/°C and the XRD analysis demonstrated that the main crystalline phase is cordierite. Based on these characteristics, the samples are considered as insulator, suggesting their potential use in refractory devices.     

稻壳制备纳米二氧化硅新工艺研究

研究以稻壳为原料,经过预处理、燃烧回收能量后获得稻壳灰,再以稻壳灰为原料,采用改良化学沉淀法,经酸化、陈化、洗涤、过滤等过程制得纳米二氧化硅。实验过程中可以回收稻壳燃烧的热能,并对废弃稻壳最大化利用。实验考察了沉淀反应体系pH、偏硅酸钠浓度、硫酸浓度、反应时间等因素对反应过程的影响,获得了较适宜的工艺条件:反应体系pH为8,偏硅酸钠浓度为0.30 mol/L,硫酸浓度为0.5 mol/L,反应时间为45 min。并对此条件下制备的产物进行多方面表征,表征结果为:所得产物为无定形二氧化硅,粒子粒径分布在50~100 nm,平均粒径D50为72 nm,比表面积为191.86 m2/g,白度为94.6%,二氧化硅纯度为98.6%。     

Chromium modified silica from rice husk as an oxidative catalyst

RH-Cr and RH-Cr500 were synthesized from rice husk by solvent extraction and gel precipitation technique. The specific surface area of RH-Cr and RH-Cr500 were found to be 0.542 and 1.20 m² g⁻¹ respectively. Energy dispersive X-ray (EDX) analysis showed that Cr(III) was homogenously incorporated in the matrix of both samples to a maximum of ca. 16% in RH-Cr500. Elemental analysis showed that RH-Cr contained ca. 15% carbon, while RH-Cr500 contained negligible amounts. FTIR analysis showed the extracted solid contained silanol (Si–OH) and siloxane (Si–O–Si) groups. Catalytic oxidation of cyclohexane with H₂O₂ using RH-Cr as the catalyst showed a 27.13% conversion to cyclohexanone and cyclohexanol with a selectivity of 57.37% and 42.63% respectively. However, RH-Cr500 showed only 14.01% conversion but with a selectivity of 64.83% of cyclohexanone and 35.17% of cyclohexanol. Epoxidation of cyclohexene using H₂O₂ with RH-Cr as the catalyst gave a conversion rate of 30.17% with a selectivity of 11.51% towards cyclohexene oxide, 63.21% 2-cyclohexen-1-one and 25.29% 2-cyclohexen-1-ol. The same reaction with RH-Cr500 as the catalyst showed 21.28% conversion with 14.65% cyclohexene oxide, 68.71% 2-cyclohexen-1-one and 16.64% 2-cyclohexen-1-ol. In the catalytic oxidation of cyclohexanol to cyclohexanone, RH-Cr showed a conversion of 12.25% while RH-Cr500 showed a conversion of 13.52%. No others products were detected in the conversion. Comparison with published catalytic systems showed that RH-Cr and RH-Cr500 to be a better catalyst even though the surface area of these catalysts were low.     

Reaction product of lime and silica from rice husk ash

Rice husk ash (about 95% silica) with known physical and chemical characteristics has been reacted with lime and water. The setting process for a lime-excess and a lime-deficient mixture has been investigated. The product of the reaction has been shown to be a calcium silicate hydrate, C-S-H(I)⁺ by a combination of thermal analysis, XRD and electron microscopy. Formation of C-S-H(I) accounts for the strength of lime-rice husk ash cement.     

Synthesis and characterization of zeolite NaY from rice husk silica

Rice husk silica (RHS) in amorphous phase with 98% purity was prepared from a waste rice husk from rice milling by leaching with hydrochloric acid and calcination. The RHS was used effectively as a silica source for the synthesis of zeolite Y in sodium form (NaY). The zeolite in pure phase was obtained from a two-step synthetic route in which the starting gels were mixed, aged for 24 h at room temperature and crystallized for 24 h at 90 °C. The diameter of single crystal particles from a scanning electron microscope was approximately 1.0 μm, whereas the average particle diameter from laser diffraction particle size analyzer was approximately 10 μm because of the agglomeration of small crystals. Longer crystallization time in this route resulted in a mixed phase containing NaY and zeolite P in sodium form (NaP). In addition, a one-step synthetic route (no aging) was studied and the product was also a mixed phase zeolite.     

3D printing of porous low-temperature in-situ mullite ceramic using waste rice husk ash-derived silica

The in-situ mullite (3Al₂O₃·2SiO₂) foams are fabricated by 3D printing (direct ink writing (DIW)) technique and utilize waste rice husk ash (RHA). The Al₂O₃-SiO₂ inks are prepared using an aqueous binder with α-alumina and two different silica sources, i.e., RHA extracted biogenic nano-silica (NS) and commercial silica (CS). The ink rheological features are first designed in terms of solid-to-liquid ratio and dispersant, and found that a higher amount of dispersant is needed for functionalization of NS-containing ink than CS (micro-sized) consisting of ink. Secondly, the DIW log-pile structures are fired at different temperatures (1200?1500 °C), and NS containing samples exhibited remarkable enhanced properties at a lower firing temperature than CS. At 1400 °C, alumina and RHA nano-silica entirely transformed into mullite and retained ～75 % porosity, ～8 MPa cold compressive strength, and thermal conductivity ～0.173 W/m·k that designate a simple and effective way to fabricate of mullite foamy structure.     

Silver modified porous silica from rice husk and its catalytic potential

Rice husk silica modified with Ag (RH-Ag) and its calcined form, RH-Ag(C) are heterogeneous catalysts prepared from rice husk. The sodium silicate was extracted from rice husk using a simple solvent extraction technique. Silver was added during the precipitation of the gel to form RH-Ag. Calcination of RH-Ag yielded RH-Ag(C). RH-Ag and RH-Ag(C) was found to have a well defined amorphous phase and a crystalline phase. TEM analysis showed that silver was encapsulated into the silica matrix. Well defined mesoporous channels were found in RH-Ag(C). The EDX analysis showed that silver was indeed incorporated in the matrix of RH-Ag but it was not homogenously distributed. The specific surface area of RH-Ag and RH-Ag(C) was found to be 447 and 419 m² g⁻¹ respectively. The cation exchange capacity (CEC) for RH-Ag was found to be 0.470 mmol g⁻¹ which was higher than that of RH-Ag(C) with 0.273 mmol g⁻¹. Both the CEC and the BET values for RH-Ag(C) was consistent with the calcination process. Catalysis of benzyl alcohol using RH-Ag and RH-Ag(C) gave two products which were identified as benzaldehyde and dibenzyl ether. Percentage conversion was higher when the reaction was conducted with pure oxygen (14.0%) than in open air (0.60%). Overall, RH-Ag(C) was found to be a better catalyst for the formation of dibenzyl ether. The optimum weight and time of reaction for the oxidation was found to be 0.3 g and 3 h respectively for both catalysts. It was found that even in an inert atmosphere, 13% of benzaldehyde was obtained with RH-Ag(C) as catalyst. Mechanisms for the formation of benzaldehyde under oxygen and inert atmosphere and the condensation mechanism assisted by the presence of the Ag on the surface of the catalyst have been suggested.     

Synthesis and characterisation of gel-derived mullite precursors from rice husk silica

The sol–gel synthesis and characterization of mullite precursor derived from rice husk silica and aluminum nitrate hydrate [(Al(NO₃)₃·9H₂O] has been investigated. The samples were characterized using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) coupled with Rietveld analysis, and scanning electron microscopy (SEM). FTIR results showed the presence of Si–O–Si, Al–O–Al, and Si–O–Al functional groups, which were associated with mullite, corundum, quartz, and cristobalite, as verified by XRD analysis. It is concluded that mullite formation started at 1150 °C, and its abundance increased rapidly with an increase in temperature from 1150 to 1350 °C, resulting in increased phase content from 30.9 to 67.7 wt%. Although mullite was formed at a low temperature, the complete reaction between corundum and silica to form mullite was not achieved. This finding demonstrated that rice husk silica is a potential alternative raw material for the production of mullite ceramic.     

高速热解条件下谷壳颗粒物理结构的演化

通过氮气等温吸附/脱附法(-196℃)、压汞法(414 MPa)、SEM等详细研究了在高速热解条件下谷壳的物理结构的演化。在热解的不同阶段,颗粒外表面特征明显不同。通过SEM测定发现,在热解中期颗粒表面孔结构明显增多,同时可以清晰地看到孔隙内表面粗糙且非规则结构。利用等温吸附/脱附法测定在高速热解过程中颗粒内微孔（micropore）演化特征,发现当热解反应率R_p等于0.8时,微孔增加速率最大。由压汞法测定得到的大孔（macropore）演化规律与微孔不太一致,在反应初期颗粒会发生强烈收缩现象,真密度增加很快,随着反应进行,颗粒的真密度基本保持恒定。     

Development of refractory ceramics from residual silica derived from rice husk ash

Rice husk has been used as a thermal energy source for electricity generation, resulting in the formation of silica from rice husk as a by-product. This research aims to develop refractory ceramic materials by replacing kaolin clay with rice husk silica at 5%, 10% and 20% volume percentages. The samples were investigated in terms of their density, apparent porosity, tensile strength in three-point bending test, compressive strength, thermal shock and mineralogical composition. The use of 20% silica resulted in an increase in the formation of cristobalite, higher packing of granular mixtures, and consequently, an improvement in the tensile strength and compression strength of the samples. However, the material that was most successful in increasing the mechanical strength without decreasing the thermal shock strength was the sample processed with 10% clay replacement by silica from rice husk.     

Electron rich porous carbon/silica matrix from rice husk and its characterization

Free electron rich porous carbon/silica matrix (ECS₈₀₀) was prepared from rice husk by carbonization at 400 °C and activation by phosphoric acid (H₃PO₄) at 800 °C. The ratio of H₃PO₄ to pre-carbonized carbon was fixed at 2.3. The surface area, pore volume, and pore size distribution of ECS₈₀₀ was measured, using nitrogen adsorption isotherms at 77 K. The unpaired electron density of ECS₈₀₀ was measured in electron spin resonance spectroscopy, using 4-hydroxy 2,2,6,6-tetramethyl piperidine-1-oxyl as the reference spin probe. ECS₈₀₀ was further characterized, using X-ray diffraction, scanning electron microscope, Fourier transform infrared spectroscope, and ²⁹Si-nuclear magnetic resonance spectroscope to study crystallization, surface morphology, functional group and different types of silicon species.     

谷壳热解过程中颗粒孔隙结构分形特性

由于颗粒相本身的复杂特性,因此研究者多是对生物质颗粒定性或就某一方面进行描述。借助分形理论可以对颗粒物理结构进行全面而精确的表征。本文利用分形BET方程,基于非线性最小二乘法,提出一种新的分形维数计算途径。该方法是根据多层吸附理论,对氮气等温吸附/脱附法测定的数据分析,直接获得表征整个吸附范围的颗粒分形维数,同时回归得到吸附过程中的吸附层数。分析表明,该方法计算得到的分形维数在数学层面上可以很好地表征颗粒内部微孔特征,同时通过对计算得到的吸附层数分析发现该计算结论也能被多层吸附理论解释,表明该方法在物理层面上也符合实际情况。利用该方法计算得到谷壳在快速热解条件下焦颗粒分形维数的变化。     

谷壳气化过程中颗粒物理化学结构的演化

对生物质气化过程的研究通常着眼于对气相组分分析,而很少对颗粒相的演化进行探讨。本文通过氮气等温吸附/脱附法(-196℃)、压汞法(414 MPa)、真密度仪(He)等详细研究了在气化条件下谷壳的物理结构的演化,同时利用元素分析和傅里叶红外对颗粒化学结构进行分析。结果表明,在气化的不同阶段,颗粒内孔的结构发生改变。BET比表面积在反应开始时增加缓慢,当反应率达到0.6以后其增加速度明显加快。由压汞法测定得到的大孔（macropore）演化规律与微孔不太一致,在反应初期大孔所占比例较高,随气化进行,这一比例快速下降,但大孔的绝对数量还是在一直增加。通过比较真密度仪和压汞法测定的结果发现,颗粒真密度与视密度变化正好相反。元素分析结果表明,在气化过程中O、H、N、S的变化规律各不相同。而红外分析也表明随反应率增加,颗粒表面上的OH、CO、CH以及Ar—H等基团快速消失。     

利用稻壳合成SiC的研究

稻壳经细粉碎、酸处理、FeCl2·6H2O浸泡、过滤、干燥、高温分解与合成、HF溶液处理,即可得到SiC含量50％～70％的合成碳化硅。     

Iron incorporated rice husk silica as a sorbent for hexavalent chromium attenuation in aqueous system

An environmentally benign metal oxide, Fe, was incorporated into silica derived from rice husk via the sol gel route and the physiognomies of both the modified (IRS) and raw rice husk derived silica (RHS) were studied via FTIR and XRD analysis and pH_PZC and surface area determinations. The stability of the Fe incorporated into the silica matrix, determined via the toxicity characteristic leaching procedure, showed that the integrity of the sorbent was intact only in basic medium but got vitiated in acidic medium. The sorption process conformed to the pseudo second order model than reversible first order and pseudo first order kinetic models and the rate of sorption of Cr(VI) onto either sorbents was determined by film diffusion. Process variables optimization showed that the amount of Cr(VI) removed per gram of sorbent reduced with increase in initial solution pH and the negative impact of the anionic interference was more in the presence of SO₃²⁻ than NO₃²⁻ and Cl⁻. The predicted Langmuir monolayer sorption capacity (mg/g) of the IRS (63.69) was higher than that of the RHS (61.35). The value of the mean free energy (kJ/mol) of sorption, obtained for IRS (267.26) and RHS (100.00), and the significant changes in the peak positions of specific functional groups on the Cr(VI) laden sorbents showed that chemisorption was the dominant mechanism of Cr(VI) uptake.