Impact of Zn/Cr Ratio on ZnCrOx-SAPO-34 Bifunctional Catalyst for Direct Conversion of Syngas to Light Olefins

Light olefins are important building blocks for chemical industry. Direct conversion of syngas to light olefins has been investigated for decades. Meanwhile, the limit for light olefins selectivity described by Anderson-Schulz-Flory (ASF) distribution model is still a great challenge to conventional Fischer-Tropsch synthesis. The emerging strategy called oxide-zeolite concept (OX-ZEO) is a promising way to get rid of this limit. ZnCrOx was prepared by co-precipitation method and (NH4)2CO3 was used as precipitant. SAPO-34 was prepared by hydrothermal synthesis, and Tetraethylammonium hydroxide (TEAOH) was used as template, while silica sol, pseudo-boehmite, and phosphoric acid were Al, Si and P source, respectively. The bifunctional catalyst was prepared by mechanical mixing of ZnCrOx and SAPO-34. Catalytic reactions were carried out under H2/CO=2, 380 ℃, 1 MPa and 6000 mL·gcat-1·h-1 in a fixed-bed reactor with a quartz lining. Catalysts were characterized by XRD, N2 adsorption-desorption, NH3-TPD, H2-TPR, and CO-TPD. The addition of Al as structure promoter enhances CO conversion and selectivity to light olefins. Zn/Cr ratio, which decides the active component content and chemisorption property of the catalyst, influences CO conversion and selectivity to light olefins at the same time. C2-4= distribution of 86% among hydrocarbons at CO conversion of 14% was reached when Zn/Cr=1.5.

Effect of Si/Al Ratio on SSZ-13 Crystallization and Its Methanol-To-Olefins Catalytic Properties

SSZ-13 materials with different Si/Al ratio were prepared by varying the composition of aluminosilicate precursor solutions upon hydrothermal treatment at 150 °C. The Si/Al ratio of the initial system was systematically changed from 12.5 to infinity in order to study the limits of Al composition in precursor solutions for constructing CHA structure. The intermediates and final products were investigated by complementary techniques such as XRD, HRTEM, FESEM, and chemical analysis. NH3-TPD was used to study the Brønsted acidity of SSZ-13 samples with different Si/Al ratios. The effect of the Si/Al ratio on the precursor species, ultimate crystal size, morphology and yield was investigated. The results revealed that Al species determine the nucleation rate and the number of nuclei, which is tied to the morphology and yield of SSZ-13. The size of SSZ-13 increased and the yield decreased as the Si/Al ratio was improved. Varying Si/Al ratio of the initial system is a facile, commercially viable method of tailoring SSZ-13 crystal size and morphology. Furthermore, SSZ-13 materials with different Si/Al ratio were tested as catalysts for the methanol to olefins (MTO) reaction at 350 °C. SSZ-13 with the Si/Al ratio of 35 shows the best MTO catalytic performance.

The Role of Initiator in the Synthesis of Poly(Methyl Methacrylate)-Layered Silicate Nanocomposites through Bulk Polymerization

The structure-property relationship and initiator effect on bulk polymerized poly(methyl methacrylate) (PMMA)–oragnomodified layered silicate nanocomposites was investigated. In this study, we used 2, 2'-azobis (4-methoxy-2,4-dimethyl valeronitrile and benzoyl peroxide initiators for bulk polymerization. The bulk polymerized nanocomposites’ morphology was investigated by X-ray diffraction and transmission electron microscopy. The type of initiator strongly influences the physiochemical properties of the polymer nanocomposite. The thermal degradation of PMMA in the presence of nanofiller was studied. 5 wt% weight loss temperature (T5d) increased as compared to pure PMMA. The peak degradation temperature increased for the nanocomposites. Differential scanning calorimetry and dynamic mechanical analysis were performed to investigate the glass transition temperature and the nature of the constrained region as the reinforcement mechanism respectively. Furthermore, the optical properties such as UV-Vis and Total Luminous Transmission of nanocomposites are examined.

Silicon-To-Silicon Anodic Bonding via Intermediate Borosilicate Layer for Passive Flow Control Valves

Flow control valves comprise a silicon flexible membrane that deflects against a substrate, usually made of glass, containing pillars, an outlet hole, and anti-stiction features. However, there is a strong interest in using silicon instead of glass as substrate material, as it would simplify the process flow by allowing the use of well controlled anisotropic etching. Moreover, specific devices demanding a bending of the substrate would also benefit from the inherent outstanding mechanical strength of monocrystalline silicon. Unfortunately, direct Si-Si bonding is not easily achieved with highly structured wafers since residual stress may prevent the good adhesion between wafers. Using a thermoplastic polymer, such as parylene, as intermediate layer is not well adapted to this design as the wafer-to-wafer alignment is critical. An alternative anodic bonding method using an intermediate borosilicate layer has been successfully tested. This layer has been deposited onto the silicon substrate. The bonding recipe has been adapted to account for the presence of the SOI buried oxide and intermediate glass layer in order not to exceed the breakdown voltage. Flow control valves dedicated to infusion of viscous fluids at very high pressure have been made and characterized. The results are compared to previous data obtained using the standard anodic bonding method.

Cellulose Nanocrystals Suspensions as Water-Based Lubricants for Slurry Pump Gland Seals

The tribological tests were performed on a new tribometer, in order to measure the coefficient of friction of a gland seal packing material on stainless steel shafts in presence of Cellulose Nanocrystal (CNC) suspension as a sustainable, environmentally friendly, water-based lubricant. To simulate the real situation from the slurry pumps, silica sands were used as slurry particles. The surface profiles after tests were measured by interferometer microscope to characterize the surface wear. Moreover, the coefficient of friction and surface wear were measured between stainless steel shaft and chrome steel ball to investigate the tribological effects of CNC in boundary lubrication region. Alignment of nanoparticles in the CNC suspensions are the main reason for friction and wear reduction. The homogeneous concentrated suspensions showed fingerprint patterns of a chiral nematic liquid crystal. These properties made CNC a very good lubricant additive in water.

Catalytic Study of Methanol-to-Propylene Conversion over Nano-Sized HZSM-5

Methanol-to-propylene conversion was carried out in a continuous-flow fixed-bed reactor over nano-sized HZSM-5 zeolites. The HZSM-5 catalysts were synthesized with different Si/Al ratio and silicon sources, and treated with NaOH. The structural property, morphology, and acidity of catalysts were measured by XRD, N2 adsorption, FE-SEM, TEM, and NH3-TPD. The results indicate that the increment of Si/Al ratio decreased the acidity of catalysts and then improved propylene selectivity, while silicon sources had slight impact on the acidity but affected the product distribution. The desilication after alkali treatment could increase intracrystalline mesopores and enhance propylene selectivity.

Application of Stabilized Polyaniline Microparticles for Better Protective Ability of Zinc Coatings

Coatings based on polyaniline (PANI) can improve the resistance of steel against corrosion. In this work, the preparation of stable suspensions of colloidal PANI-SiO2 particles, suitable for obtaining of composite anticorrosive coating on steel, is described. Electrokinetic data as a function of pH are presented, showing that the zeta potentials of the PANI-SiO2 particles are governed primarily by the charged groups at the silica oxide surface. Electrosteric stabilization of the PANI-SiO2 particles’ suspension against aggregation is realized at pH>5.5 (EB form of PANI) by adsorption of positively charged polyelectrolyte molecules onto negatively charged PANI-SiO2 particles. The PANI-SiO2 particles are incorporated by electrodeposition into the metal matrix of zinc in order to obtain composite (hybrid) coatings. The latter are aimed to ensure sacrificial protection of steel mainly in aggressive media leading to local corrosion damages. The surface morphology of the composite zinc coatings is investigated with SEM. The influence of PANI-SiO2 particles on the cathodic and anodic processes occurring in the starting electrolyte for obtaining of the coatings is followed with cyclic voltammetry. The electrochemical and corrosion behavior is evaluated with potentiodynamic polarization curves and polarization resistance measurements. The beneficial effect of the stabilized PANI-SiO2 particles for the increased protective ability of the composites is commented and discussed.

Basicity of Jordanian Natural Clays Studied by Pyrrole-tpd and Catalytic Conversion of Methylbutynol

The main objective of this study is to investigate basic properties of different natural clays, by two methods. The first method is a gas phase conversion of methylbutynol (MBOH). The second method is the application of Pyrrole-tpd. Based on the product distribution from the first method, the acidic, basic and coordinately unsaturated sites were differentiated. It was shown that both the conversion and the selectivity for basic products did not change with reaction time. Nevertheless, a deviation from the stoichiometric ratio R of formed acetylene to acetone was observed (R=0.8…0.97). The conversion normalized to the surface area was used for establishing the activity sequence: White kaolinite > red kaolinite > bentonite > zeolite > di­ato­mite. In addition, the results were compared with synthetic amorphous alumosilicates and typical basic materials like MgO and ZnO. The basic properties were characterized using the Pyrrole-tpd.  The Pyrrole-tpd results showed the same basicity sequence as the MBOH gas phase reaction.

Studying the Behavior of Asphalt Mix and Their Properties in the Presence of Nano Materials

Due to rapid development, increase in the traffic load, higher traffic volume and seasonal variation in temperature, asphalt pavement shows distresses like rutting, fatigue and thermal cracking etc. because of this pavement fails during service life so that bitumen needs to be modified with some additive. In this study VG30 grade bitumen modify with addition of nanosilica with 1% to 5% (increment of 1%) by weight of bitumen. Hot mix asphalt (HMA) have higher mixing, laying and rolling temperatures which leads to higher consumption of fuel. To address this issue, a nano material named ZycoTherm which is chemical warm mix asphalt (WMA) additive is added to bitumen. Nanosilica modification (NSMB) results in the increase in stability compared to unmodified bitumen (UMB). WMA modified mix shows slightly higher stability than UMB and NSMB in a lower bitumen content. The Retained stability and tensile strength ratio (TSR) is more than 75% and 80% respectively for both mixes. Nanosilica with WMA has more resistant to temperature susceptibility, moisture susceptibility and short term aging than NSMB.

Treatment of Low-Grade Iron Ore Using Two Stage Wet High-Intensity Magnetic Separation Technique

This study investigates the removal of silica, alumina and phosphorus as impurities from Sanje iron ore using wet high-intensity magnetic separation (WHIMS). Sanje iron ore contains low-grade hematite ore found in Nampundwe area of Zambia from which iron is to be used as the feed in the steelmaking process. The chemical composition analysis using X-ray Florence spectrometer showed that Sanje low-grade ore contains 48.90 mass% of hematite (Fe2O3) with 34.18 mass% as an iron grade. The ore also contains silica (SiO2) and alumina (Al2O3) of 31.10 mass% and 7.65 mass% respectively. The mineralogical analysis using X-ray diffraction spectrometer showed hematite and silica as the major mineral components of the ore while magnetite and alumina exist as minor mineral components. Mineral particle distribution analysis was done using scanning electron microscope with an X-ray energy dispersion spectrometry (SEM-EDS) and images showed that the average mineral size distribution of alumina-silicate gangue particles is in order of 100 μm and exists as iron-bearing interlocked particles. Magnetic separation was done using series L model 4 Magnetic Separator. The effect of various magnetic separation parameters such as magnetic flux density, particle size, and pulp density of the feed was studied during magnetic separation experiments. The ore with average particle size of 25 µm and pulp density of 2.5% was concentrated using pulp flow of 7 L/min. The results showed that 10 T was optimal magnetic flux density which enhanced the recovery of 93.08% of iron with 53.22 mass% grade. The gangue mineral particles containing 12 mass% silica and 3.94 mass% alumna remained in the concentrate, therefore the concentrate was further treated in the second stage WHIMS using the same parameters from the first stage. The second stage process recovered 83.41% of iron with 67.07 mass% grade. Silica was reduced to 2.14 mass% and alumina to 1.30 mass%. Accordingly, phosphorus was also reduced to 0.02 mass%. Therefore, the two stage magnetic separation process was established using these results.

Photocatalytic Active Surface of LWSCC Architectural Concretes

Current trends in the building industry are oriented towards the reduction of maintenance costs and the ecological benefits of buildings or building materials. Surface treatment of building materials with photocatalytic active titanium dioxide added into concrete can offer a good solution in this context. Architectural concrete has one disadvantage – dust and fouling keep settling on its surface, diminishing its aesthetic value and increasing maintenance e costs. Concrete surface – silicate material with open porosity – fulfils the conditions of effective photocatalysis, in particular, the self-cleaning properties of surfaces. This modern material is advantageous in particular for direct finishing and architectural concrete applications. If photoactive titanium dioxide is part of the top layers of road concrete on busy roads and the facades of the buildings surrounding these roads, exhaust fumes can be degraded with the aid of sunshine; hence, environmental load will decrease. It is clear that options for removing pollutants like nitrogen oxides (NOx) must be found. Not only do these gases present a health risk, they also cause the degradation of the surfaces of concrete structures. The photocatalytic properties of titanium dioxide can in the long term contribute to the enhanced appearance of surface layers and eliminate harmful pollutants dispersed in the air, and facilitate the conversion of pollutants into less toxic forms (e.g., NOx to HNO3). This paper describes verification of the photocatalytic properties of titanium dioxide and presents the results of mechanical and physical tests on samples of architectural lightweight self-compacting concretes (LWSCC). The very essence of the use of LWSCC is their rheological ability to seep into otherwise extremely hard accessible or inaccessible construction areas, or sections thereof where concrete compacting will be a problem, or where vibration is completely excluded. They are also able to create a solid monolithic element with a large variety of shapes; the concrete will at the same meet the requirements of both chemical aggression and the influences of the surrounding environment. Due to their viscosity, LWSCCs are able to imprint the formwork elements into their structure and thus create high quality lightweight architectural concretes.

Effect of Segregation on the Reaction Rate of Sewage Sludge Pyrolysis in a Bubbling Fluidized Bed

The evolution of the pyrolysis of sewage sludge in a fixed and a fluidized bed was analyzed using a novel measuring technique. This original measuring technique consists of installing the whole reactor over a precision scale, capable of measuring the mass of the complete reactor with enough precision to detect the mass released by the sewage sludge sample during its pyrolysis. The inert conditions required for the pyrolysis process were obtained supplying the bed with a nitrogen flowrate, and the bed temperature was adjusted to either 500 ºC or 600 ºC using a group of three electric resistors. The sewage sludge sample was supplied through the top of the bed in a batch of 10 g. The measurement of the mass released by the sewage sludge sample was employed to determine the evolution of the reaction rate during the pyrolysis, the total amount of volatile matter released, and the pyrolysis time. The pyrolysis tests of sewage sludge in the fluidized bed were conducted using two different bed materials of the same size but different densities: silica sand and sepiolite particles. The higher density of silica sand particles induces a flotsam behavior for the sewage sludge particles which move close to the bed surface. In contrast, the lower density of sepiolite produces a neutrally-buoyant behavior for the sewage sludge particles, which shows a proper circulation throughout the whole bed in this case. The analysis of the evolution of the pyrolysis process in both fluidized beds show that the pyrolysis is faster when buoyancy effects are negligible, i.e. in the bed conformed by sepiolite particles. Moreover, sepiolite was found to show an absorbent capability for the volatile matter released during the pyrolysis of sewage sludge.

Comparison of Physical and Chemical Properties of Micro-Silica and Locally Produced Metakaolin and Effect on the Properties of Concrete

The properties of locally produced metakaolin (MK) as cement replacing material and the comparison of reactivity with commercially available micro-silica have been investigated. Compressive strength, splitting tensile strength, and load-deflection behaviour under bending are the properties that have been studied. The amorphous phase of MK with micro-silica was compared through X-ray diffraction (XRD) pattern. Further, interfacial transition zone of concrete with micro-silica and MK was observed through Field Emission Scanning Electron Microscopy (FESEM). Three mixes of concrete were prepared. One of the mix is without cement replacement as control mix, and the remaining two mixes are 10% cement replacement with micro-silica and MK. It has been found that MK, due to its irregular structure and amorphous phase, has high reactivity with portlandite in concrete. The compressive strength at early age is higher with MK as compared to micro-silica. MK concrete showed higher splitting tensile strength and higher load carrying capacity as compared to control and micro-silica concrete at all ages respectively.

Hydrogenation of CO2 to Methanol over Copper-Zinc Oxide-Based Catalyst

Carbon dioxide is highly thermochemical stable molecules where it is very difficult to activate the molecule and achieve higher catalytic conversion into alcohols or other hydrocarbon compounds. In this paper, series of the bimetallic Cu/ZnO-based catalyst supported by SBA-15 were systematically prepared via impregnation technique with different Cu: Zn ratio for hydrogenation of CO2 to methanol. The synthesized catalysts were characterized by transmission electron microscopy (TEM), temperature programmed desorption, reduction, oxidation and pulse chemisorption (TPDRO), and surface area determination was also performed. All catalysts were tested with respect to the hydrogenation of CO2 to methanol in microactivity fixed-bed reactor at 250oC, 2.25 MPa, and H2/CO2 ratio of 3. The results demonstrate that the catalytic structure, activity, and methanol selectivity was strongly affected by the ratio between Cu: Zn, Where higher catalytic activity of 14 % and methanol selectivity of 92 % was obtained over Cu/ZnO-SBA-15 catalyst with Cu:Zn ratio of 7:3 wt. %. Comparing with the single catalyst, the synergetic between Cu and Zn provides additional active sites to adsorb more H2 and CO2 and accelerate the CO2 conversion, resulting in higher methanol production under mild reaction conditions.

Uranium Adsorption Using a Composite Material Based on Platelet SBA-15 Supported Tin Salt Tungstomolybdophosphoric Acid

In this work, a new composite adsorbent based on a mesoporous silica SBA-15 with platelet morphology and tin salt of tungstomolybdophosphoric (TWMP) acid was synthesized and applied for uranium adsorption from aqueous solution. The sample was characterized by X-ray diffraction, Fourier transfer infra-red, and N2 adsorption-desorption analysis, and then, effect of various parameters such as concentration of metal ions and contact time on adsorption behavior was examined. The experimental result showed that the adsorption process was explained by the Langmuir isotherm model very well, and predominant reaction mechanism is physisorption. Kinetic data of adsorption suggest that the adsorption process can be described by the pseudo second-order reaction rate model.

Mineralogical and Geochemical Characteristics of Serpentinite-Derived Ni-Bearing Laterites from Fars Province, Iran: Implications for the Lateritization Process and Classification of Ni-Laterites

Nickel-bearing laterites occur as two parallel belts along Sedimentary Zagros Orogenic (SZO) and Metamorphic Sanandaj-Sirjan (MSS) petrostructural zones, Fars Province, south Iran. An undisturbed vertical profile of these laterites includes protolith, saprolite, clay, and oxide horizons from base to top. Highly serpentinized harzburgite with relicts of olivine and orthopyroxene is regarded as the source rock. The laterites are unusual in lacking a significant saprolite zone with little development of Ni-silicates. Hematite, saponite, dolomite, smectite and clinochlore increase, while calcite, olivine, lizardite and chrysotile decrease from saprolite to oxide zones. Smectite and clinochlore with minor calcite are the major minerals in clay zone. Contacts of different horizons in laterite profiles are gradual and characterized by a decrease in Mg concentration ranging from 18.1 to 9.3 wt.% in oxide and saprolite, respectively. The maximum Ni concentration is 0.34 wt.% (NiO) in the base of the oxide zone, and goethite is the major Ni-bearing phase. From saprolite to oxide horizons, Al2O3, K2O, TiO2, and CaO decrease, while SiO2, MnO, NiO, and Fe2O3 increase. Silica content reaches up to 45 wt.% in the upper part of the soil profile. There is a decrease in pH (8.44-8.17) and an increase in organic matter (0.28-0.59 wt.%) from base to top of the soils. The studied laterites are classified in the oxide clans which were derived from ophiolite ultramafic rocks under Mediterranean climate conditions.

Effect of Gamma Irradiation on Structural and Optical Properties of ZnO/Mesoporous Silica Nanocomposite

The effect of gamma ray irradiation on morphology and optical properties of ZnO/Mesoporous silica (MPS) nanocomposite was studied. The ZnO/MPS nanocomposite was irradiated with gamma rays of doses 30, 60, and 90 kGy and dose-rate of irradiation was 0.15 kGy/hour. Irradiated samples are characterized with FE-SEM, FT-IR, UV-vis, and Photoluminescence (PL) spectrometers. SEM pictures showed that morphology changed from spherical to flake like morphology. UV-vis analysis showed that the band gap increased with increase of gamma ray irradiation dose. This enhancement of the band gap is assigned to the depletion of oxygen vacancies with irradiation. The intensity of PL peak decreased gradually with increase of gamma ray irradiation dose. The decrease in PL intensity is attributed to the decrease of oxygen vacancies at the interface due to poor interface and improper passivation between ZnO/MPS.

Sustainability of Carbon Nanotube-Reinforced Concrete

Concrete, despite being one of the most produced materials in the world, still has weaknesses and drawbacks. Significant concern of the cementitious materials in structural applications is their quasi-brittle behavior, which causes the material to crack and lose its durability. One of the very recently proposed mitigations for this problem is the implementation of nanotechnology in the concrete mix by adding carbon nanotubes (CNTs) to it. CNTs can enhance the critical mechanical properties of concrete as a structural material. Thus, this paper demonstrates a state-of-the-art review of reinforcing concrete with CNTs, emphasizing on the structural performance. It also goes over the properties of CNTs alone, the present methods and costs associated with producing them, the possible special applications of concretes reinforced with CNTs, the key challenges and drawbacks that this new technology still encounters, and the most reliable practices and methodologies to produce CNT-reinforced concrete in the lab. This work has shown that the addition of CNTs to the concrete mix in percentages as low as 0.25% weight of cement could increase the flexural strength and toughness of concrete by more than 45% and 25%, respectively, and enhance other durability-related properties, given that an effective dispersion of CNTs in the cementitious mix is achieved. Since nano reinforcement for cementitious materials is a new technology, many challenges have to be tackled before it becomes practiced at the mass level.

GGE-Biplot Analysis of Nano-Titanium Dioxide and Nano-Silica Effects on Sunflower

Present investigation is performed to evaluate the effects of foliar application of salicylic acid, glycine betaine, ascorbic acid, nano-silica, and nano-titanium dioxide on sunflower. Results showed that the first two principal components were sufficient to create a two-dimensional treatment by trait biplot, and such biplot accounted percentages of 49% and 19%, respectively of the interaction between traits and treatments. The vertex treatments of polygon were ascorbic acid, glycine betaine, nano-TiO2, and control indicated that high performance in some important traits consists of number of days to seed maturity, number of seeds per head, number heads per single plant, hundred seed weight, seed length, seed yield performance, and oil content. Treatments suitable for obtaining the high seed yield were identified in the vector-view function of biplot and displayed nano-silica and nano titanium dioxide as the best treatments suitable for obtaining of high seed yield.

Optimum Design of Alkali Activated Slag Concretes for Low Chloride Ion Permeability and Water Absorption Capacity

In this research, effect of curing time (TC), curing temperature (CT), sodium concentration (SC) and silicate modules (SM) on the compressive strength, chloride ion permeability, and water absorption capacity of alkali activated slag (AAS) concretes were investigated. For maximization of compressive strength while for minimization of chloride ion permeability and water absorption capacity of AAS concretes, best possible combination of CT, CTime, SC and SM were determined. An experimental program was conducted by using the central composite design method. Alkali solution-slag ratio was kept constant at 0.53 in all mixture. The effects of the independent parameters were characterized and analyzed by using statistically significant quadratic regression models on the measured properties (dependent parameters). The proposed regression models are valid for AAS concretes with the SC from 0.1% to 7.5%, SM from 0.4 to 3.2, CT from 20 °C to 94 °C and TC from 1.2 hours to 25 hours. The results of test and analysis indicate that the most effective parameter for the compressive strength, chloride ion permeability and water absorption capacity is the sodium concentration.