Catalytic Pyrolysis of Sewage Sludge for Upgrading Bio-Oil Quality Using Sludge-Based Activated Char as an Alternative to HZSM5

Due to the concerns about the depletion of fossil fuel sources and the deteriorating environment, the attempt to investigate the production of renewable energy will play a crucial role as a potential to alleviate the dependency on mineral fuels. One particular area of interest is generation of bio-oil through sewage sludge (SS) pyrolysis. SS can be a potential candidate in contrast to other types of biomasses due to its availability and low cost. However, the presence of high molecular weight hydrocarbons and oxygenated compounds in the SS bio-oil hinders some of its fuel applications. In this context, catalytic pyrolysis is another attainable route to upgrade bio-oil quality. Among different catalysts (i.e., zeolites) studied for SS pyrolysis, activated chars (AC) are eco-friendly alternatives. The beneficial features of AC derived from SS comprise the comparatively large surface area, porosity, enriched surface functional groups and presence of a high amount of metal species that can improve the catalytic activity. Hence, a sludge-based AC catalyst was fabricated in a single-step pyrolysis reaction with NaOH as the activation agent and was compared with HZSM5 zeolite in this study. The thermal decomposition and kinetics were invested via thermogravimetric analysis (TGA) for guidance and control of pyrolysis and catalytic pyrolysis and the design of the pyrolysis setup. The results indicated that the pyrolysis and catalytic pyrolysis contain four obvious stages and the main decomposition reaction occurred in the range of 200-600 °C. Coats-Redfern method was applied in the 2nd and 3rd devolatilization stages to estimate the reaction order and activation energy (E) from the mass loss data. The average activation energy (Em) values for the reaction orders n = 1, 2 and 3 were in the range of 6.67-20.37 kJ/mol for SS; 1.51-6.87 kJ/mol for HZSM5; and 2.29-9.17 kJ/mol for AC, respectively. According to the results, AC and HZSM5 both were able to improve the reaction rate of SS pyrolysis by abridging the Em value. Moreover, to generate and examine the effect of the catalysts on the quality of bio-oil, a fixed-bed pyrolysis system was designed and implemented. The composition analysis of the produced bio-oil was carried out via gas chromatography/mass spectrometry (GC/MS). The selected SS to catalyst ratios were 1:1, 2:1 and 4:1. The optimum ratio in terms of cracking the long-chain hydrocarbons and removing oxygen-containing compounds was 1:1 for both catalysts. The upgraded bio-oils with HZSM5 and AC were in the total range of C4-C17 with around 72% in the range of C4-C9. The bio-oil from pyrolysis of SS contained 49.27% oxygenated compounds while the presence of HZSM5 and AC dropped to 7.3% and 13.02%, respectively. Meanwhile, generation of value-added chemicals such as light aromatic compounds were significantly improved in the catalytic process. Furthermore, the fabricated AC catalyst was characterized by BET, SEM-EDX, FT-IR and TGA techniques. Overall, this research demonstrated that AC is an efficient catalyst in the pyrolysis of SS and can be used as a cost-competitive catalyst in contrast to HZSM5.

The Effect of Zeolite on Sandy-Silt Soil Mechanical Properties

It is well known that cemented sand is one of the best approaches for soil stabilization. In some cases, a blend of sand, cement and other pozzolan materials such as zeolite, nano-particles and fiber can be widely (commercially) available and be effectively used in soil stabilization, especially in road construction. In this research, we investigate the effects of CaO which is based on the geotechnical characteristics of zeolite composition with sandy silt soil. Zeolites have low amount of CaO in their structures, that is, varying from 3% to 10%, and by removing the cement paste, we want to investigate the effect of zeolite pozzolan without any activator on soil samples strength. In this research, experiments are concentrated on various weight percentages of zeolite in the soil to examine the effect of the zeolite on drainage shear strength and California Bearing Ratio (CBR) both with and without curing. The study also investigates their liquid limit and plastic limit behavior and makes a comparative result by using Feng's and Wroth-Wood's methods in fall cone (cone penetrometer) device; in the final the SEM images have been presented. The results show that by increasing the percentage of zeolite in without-curing samples, the fine zeolite particles increase some soil's strength, but in the curing-state we can see a relatively higher strength toward without-curing state, since the zeolites have no plastic behavior, the pozzolanic property of zeolites plays a much higher role than cementing properties. Indeed, it is better to combine zeolite particle with activator material such as cement or lime to gain better results.

Influence of Nanozeolite Particles on Improvement of Clayey Soil

The problem of soil stabilization has been one of the important issues in geotechnical engineering. Nowadays, nanomaterials have revolutionized many industries. In this research, improvement of the Kerman fine-grained soil by nanozeolite and nanobentonite additives separately has been investigated using Atterberg Limits and unconfined compression test. In unconfined compression test, the samples were prepared with 3, 5 and 7% nano additives, with 1, 7 and 28 days curing time with strain control method. Finally, the effect of different percentages of nanozeolite and nanobentonite on the geotechnical behavior and characteristics of Kerman fine-grained soil was investigated. The results showed that with increasing the amount of nanozeolite and also nanobentonite to fine-grained soil, the soil exhibits more compression strength. So that by adding 7% nanozeolite and nanobentonite with 1 day curing, the unconfined compression strength is 1.18 and 2.1 times higher than the unstabilized soil. In addition, the failure strain decreases in samples containing nanozeolite, whereas it increases in the presence of nanobentonite. Increasing the percentage of nanozeolite and nanobentonite also increased the elasticity modulus of soil.

Effect of Leachate Presence on Shear Strength Parameters of Bentonite-Amended Zeolite Soil

Over recent years, due to increased population and increased waste production, groundwater protection has become more important, therefore, designing engineered barrier systems such as landfill liners to prevent the entry of leachate into groundwater should be done with greater accuracy. These measures generally involve the application of low permeability soils such as clays. Bentonite is a natural clay with low permeability which makes it a suitable soil for using in liners. Also zeolite with high cation exchange capacity can help to reduce of hazardous materials risk. Bentonite expands when wet, absorbing as much as several times its dry mass in water. This property may effect on some structural properties of soil such as shear strength. In present study, shear strength parameters are determined by both leachates polluted and not polluted bentonite-amended zeolite soil with mixing rates (B/Z) of 5%-10% and 20% with unconfined compression test to obtain the differences. It is shown that leachate presence causes reduction in resistance in general.

The Optimum Operating Conditions for the Synthesis of Zeolite from Waste Incineration Fly Ash by Alkali Fusion and Hydrothermal Methods

The fly ash of waste incineration processes is usually hazardous and the disposal or reuse of waste incineration fly ash is difficult. In this study, the waste incineration fly ash was converted to useful zeolites by the alkali fusion and hydrothermal synthesis method. The influence of different operating conditions (the ratio of Si/Al, the ratio of hydrolysis liquid to solid, and hydrothermal time) was investigated to seek the optimum operating conditions for the synthesis of zeolite from waste incineration fly ash. The results showed that concentrations of heavy metals in the leachate of Toxicity Characteristic Leaching Procedure (TCLP) were all lower than the regulatory limits except lead. The optimum operating conditions for the synthesis of zeolite from waste incineration fly ash by the alkali fusion and hydrothermal synthesis method were Si/Al=40, NaOH/ash=1.5, alkali fusion at 400 oC for 40 min, hydrolysis with Liquid to Solid ratio (L/S)= 200 at 105 oC for 24 h, and hydrothermal synthesis at 105 oC for 24 h. The specific surface area of fly ash could be significantly increased from 8.59 m2/g to 651.51 m2/g (synthesized zeolite). The influence of different operating conditions on the synthesis of zeolite from waste incineration fly ash followed the sequence of Si/Al ratio > hydrothermal time > hydrolysis L/S ratio. The synthesized zeolites can be reused as good adsorbents to control the air or wastewater pollutants. The purpose of fly ash detoxification, reduction and waste recycling/reuse is achieved successfully.

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.

Liquid Fuel Production via Catalytic Pyrolysis of Waste Oil

Pyrolysis of waste oil is an effective process to produce high quality liquid fuels. In this work, pyrolysis experiments of waste oil over Y zeolite were carried out in a semi-batch reactor under a flow of nitrogen at atmospheric pressure and at different reaction temperatures (350-450 oC). The products were gas, liquid fuel, and residue. Only liquid fuel was further characterized for its composition and properties by using gas chromatography, thermogravimetric analyzer, and bomb calorimeter. Experimental results indicated that the pyrolysis reaction temperature significantly affected both yield and composition distribution of pyrolysis oil. An increase in reaction temperature resulted in increased fuel yield, especially gasoline fraction. To obtain high amount of fuel, the optimal reaction temperature should be higher than 350 oC. A presence of Y zeolite in the system enhanced the cracking activity. In addition, the pyrolysis oil yield is proportional to the catalyst quantity.

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.

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.

Resistance to Chloride Penetration of High Strength Self-Compacting Concretes: Pumice and Zeolite Effect

This paper aims to contribute to the characterization and the understanding of fresh state, compressive strength and chloride penetration tendency of high strength self-compacting concretes (HSSCCs) where Portland cement type II is partially substituted by 10% and 15% of natural pumice and zeolite. First, five concrete mixtures with a control mixture without any pozzolan are prepared and tested in both fresh and hardened states. Then, resistance to chloride penetration for all formulation is investigated in non-steady state and steady state by measurement of chloride penetration and diffusion coefficient. In non-steady state, the correlation between initial current and chloride penetration with diffusion coefficient is studied. Moreover, the relationship between diffusion coefficient in non-steady state and electrical resistivity is determined. The concentration of free chloride ions is also measured in steady state. Finally, chloride penetration for all formulation is studied in immersion and tidal condition. The result shows that, the resistance to chloride penetration for HSSCC in immersion and tidal condition increases by incorporating pumice and zeolite. However, concrete with zeolite displays a better resistance. This paper shows that the HSSCC with 15% pumice and 10% zeolite is suitable in fresh, hardened, and durability characteristics.

Microstructure, Compressive Strength and Transport Properties of High Strength Self-Compacting Concretes Containing Natural Pumice and Zeolite

Due to the difficult placement and vibration between reinforcements of reinforced concrete and the defects that it may cause, the use of self-compacting concrete (SCC) is becoming more widespread. Ordinary Portland Cement (OPC) is the most widely used binder in the construction industry. However, the manufacture of this cement results in a significant amount of CO2 being released, which is detrimental to the environment. Thus, an alternative to reduce the cost of SCC is the use of more economical and environmental mineral additives in partial or total substitution of Portland cement. Our study is in this context and aims to develop SCCs both economic and ecological. Two natural pozzolans such as pumice and zeolite are chosen in this research. This research tries to answer questions including the microstructure of the two types of natural pozzolan and their influence on the mechanical properties as well as on the transport property of SCC. Based on the findings of this study, the studied zeolite is a clinoptilolite that presents higher pozzolan activity compared to pumice. However, the use of zeolite decreases the compressive strength of SCC composites. On the contrary, the compressive strength in SCC containing of pumice increases at both early and long term ages with a remarkable increase at long term. A correlation is obtained between the compressive strength with permeable pore and capillary absorption. Also, the results concerning compressive strength and transport property are well justified by evaporable and non-evaporable water content measurement. This paper shows that the substitution of Portland cement by 15% of pumice or 10% of zeolite in HSSCC is suitable in all aspects. 

Comparison of Adsorbents for Ammonia Removal from Mining Wastewater

Ammonia in mining wastewater is a significant problem, and treatment can be especially difficult in cold climates where biological treatment is not feasible. An adsorption process is one of the alternative processes that can be used to reduce ammonia concentrations to acceptable limits, and therefore a LEWATIT resin strongly acidic H+ form ion exchange resin and a Bowie Chabazite Na form AZLB-Na zeolite were tested to assess their effectiveness. For these adsorption tests, two packed bed columns (a mini-column constructed from a 32-cm long x 1-cm diameter piece of glass tubing, and a 60-cm long x 2.5-cm diameter Ace Glass chromatography column) were used containing varying quantities of the adsorbents. A mining wastewater with ammonia concentrations of 22.7 mg/L was fed through the columns at controlled flowrates. In the experimental work, maximum capacities of the LEWATIT ion exchange resin were 0.438, 0.448, and 1.472 mg/g for 3, 6, and 9 g respectively in a mini column and 1.739 mg/g for 141.5 g in a larger Ace column while the capacities for the AZLB-Na zeolite were 0.424, and 0.784 mg/g for 3, and 6 g respectively in the mini column and 1.1636 mg/g for 38.5 g in the Ace column. In the theoretical work, Thomas, Adams-Bohart, and Yoon-Nelson models were constructed to describe a breakthrough curve of the adsorption process and find the constants of the above-mentioned models. In the regeneration tests, 5% hydrochloric acid, HCl (v/v) and 10% sodium hydroxide, NaOH (w/v) were used to regenerate the LEWATIT resin and AZLB-Na zeolite with 44 and 63.8% recovery, respectively. In conclusion, continuous flow adsorption using a LEWATIT ion exchange resin and an AZLB-Na zeolite is efficient when using a co-flow technique for removal of the ammonia from wastewater. Thomas, Adams-Bohart, and Yoon-Nelson models satisfactorily fit the data with R2 closer to 1 in all cases.

Surface Temperature of Asphalt Pavements with Colored Cement-Based Grouting Materials Containing Ceramic Waste Powder and Zeolite

The heat island phenomenon and extremely hot summer climate are becoming environmental problems in Japan. Cool pavements reduce the surface temperature compared to conventional asphalt pavements in the hot summer climate and improve the thermal environment in the urban area. The authors have studied cement–based grouting materials poured into voids in porous asphalt pavements to reduce the road surface temperature. For the cement–based grouting material, cement, ceramic waste powder, and natural zeolite were used. This cement–based grouting material developed reduced the road surface temperature by 20 °C or more in the hot summer season. Considering the urban landscape, this study investigates the effect of surface temperature reduction of colored cement–based grouting materials containing pigments poured into voids in porous asphalt pavements by measuring the surface temperature of asphalt pavements outdoors. The yellow color performed the same as the original cement–based grouting material containing no pigment and was thermally better performance than the other color. However, all the tested cement–based grouting materials performed well for reducing the surface temperature and for creating the urban landscape.

Transesterification of Waste Cooking Oil for Biodiesel Production Using Modified Clinoptilolite Zeolite as a Heterogeneous Catalyst

Reduction of fossil fuels sources, increasing of pollution gases emission, and global warming effects increase the demand of renewable fuels. One of the main candidates of alternative fuels is biodiesel. Biodiesel limits greenhouse gas effects due to the closed CO2 cycle. Biodiesel has more biodegradability, lower combustion emissions such as CO, SOx, HC, PM and lower toxicity than petro diesel. However, biodiesel has high production cost due to high price of plant oils as raw material. So, the utilization of waste cooking oils (WCOs) as feedstock, due to their low price and disposal problems reduce biodiesel production cost. In this study, production of biodiesel by transesterification of methanol and WCO using modified sodic potassic (SP) clinoptilolite zeolite and sodic potassic calcic (SPC) clinoptilolite zeolite as heterogeneous catalysts have been investigated. These natural clinoptilolite zeolites were modified by KOH solution to increase the site activity. The optimum biodiesel yields for SP clinoptilolite and SPC clinoptilolite were 95.8% and 94.8%, respectively. Produced biodiesel were analyzed and compared with petro diesel and ASTM limits. The properties of produced biodiesel confirm well with ASTM limits. The density, kinematic viscosity, cetane index, flash point, cloud point, and pour point of produced biodiesel were all higher than petro diesel but its acid value was lower than petro diesel. Finally, the reusability and regeneration of catalysts were investigated. The results indicated that the spent zeolites cannot be reused directly for the transesterification, but they can be regenerated easily and can obtain high activity.

Effect on Surface Temperature Reduction of Asphalt Pavements with Cement–Based Materials Containing Ceramic Waste Powder

The heat island phenomenon becomes one of the environmental problems. As countermeasures in the field of road engineering, cool pavements such as water retaining pavements and solar radiation reflective pavements have been developed to reduce the surface temperature of asphalt pavements in the hot summer climate in Japan. The authors have studied on the water retaining pavements with cement–based grouting materials. The cement–based grouting materials consist of cement, ceramic waste powder, and natural zeolite. The ceramic waste powder is collected through the recycling process of electric porcelain insulators. In this study, mixing ratio between the ceramic waste powder and the natural zeolite and a type of cement for the cement–based grouting materials is investigated to measure the surface temperature of asphalt pavements in the outdoor. All of the developed cement–based grouting materials were confirmed to effectively reduce the surface temperature of the asphalt pavements. Especially, the cement–based grouting material using the ultra–rapid hardening cement with the mixing ratio of 0.7:0.3 between the ceramic waste powder and the natural zeolite reduced mostly the surface temperature by 20 °C and more.

Petro-Mineralogical Studies of Phosphorite Deposit of Sallopat Block of Banswara District, Rajasthan, India

The Paleoproterozoic phosphorite deposit of Sallopat block of Banswara district of Rajasthan belongs to kalinjara formation of lunavada group of Aravalli Super Group. The phosphorites are found to occur as massive, brecciated, laminated and stromatolitic associated with calcareous quartzite, interbedded dolomite and multi coloured chert. The phosphorites are showing alternate brown and grey coloured concentric rims which are composed of phosphate, calcite and quartz minerals. Petro-mineralogical studies of phosphorite samples using petrological microscope, XRD, FEG- SEM and EDX reveal that apatite-(CaF) and apatite-(CaOH) are phosphate minerals which are intermixed with minor amount of carbonate materials. Sporadic findings of the uniform tiny granules of partially anisotropic apatite-(CaF) along with dolomite, calcite, quartz, muscovite, zeolite and other gangue minerals have been observed with the replacement of phosphate material by quartz and carbonate. The presence of microbial filaments of organic matter and alternate concentric rims of stromatolitic structure may suggest that the deposition of the phosphate took place in shallow marine oxidizing environmental conditions leading to the formation of phosphorite layers as primary biogenic precipitates by bacterial or algal activities. Different forms and texture of phosphate minerals may be due to environmental vicissitudes at the time of deposition followed by some replacement processes and biogenic activities.

Effectiveness of Natural Zeolite in Mitigating Alkali Silica Reaction Expansions

This paper investigates the effectiveness of two natural zeolites in reducing expansion of concrete due to alkali-silica reaction. These natural zeolites have different reactive silica content. Three aggregates; two natural sands and one crushed stone aggregate were used while preparing mortar bars in accordance with accelerated mortar bar test method, ASTM C1260. Performances of natural zeolites are compared by examining the expansions due to alkali silica reaction. Natural zeolites added to the mixtures at 10% and 20% replacement levels by weight of cement. Natural zeolite with high reactive silica content had better performance on reducing expansions due to ASR. In this research, using high reactive zeolite at 20% replacement levels was effective in mitigating expansions.

Phenols and Manganese Removal from Landfill Leachate and Municipal Wastewater Using the Constructed Wetland

Constructed Wetland (CW) is a reasonable method to treat wastewater. Current study was carried out to co-treat landfill leachate and domestic wastewater using a CW system. Typha domingensis was transplanted to CW, which encloses two substrate layers of adsorbents named ZELIAC and zeolite. Response surface methodology and central composite design were employed to evaluate experimental data. Contact time (h) and leachate-towastewater mixing ratio (%; v/v) were selected as independent factors. Phenols and manganese removal were selected as dependent responses. At optimum contact time (48.7 h) and leachate-towastewater mixing ratio (20.0%), removal efficiencies of phenols and manganese removal efficiencies were 90.5%, and 89.4%, respectively.

Preparation of Protective Coating Film on Metal Alloy

A novel chromium-free protective coating films based on a zeolite coating was growing onto a FeCrAlloy metal using in – situ hydrothermal method. The zeolite film was obtained using in-situ crystallization process that is capable of coating large surfaces with complex shape and in confined spaces has been developed. The zeolite coating offers an advantage of a high mechanical stability and thermal stability. The physicochemical properties were investigated using X-ray diffraction (XRD), Electron Microscopy (SEM), Energy Dispersive X–ray Analysis (EDX) and Thermogravimetric Analysis (TGA). The transition from oxide-on-alloy wires to hydrothermally synthesised uniformly zeolite coated surfaces was followed using SEM and XRD. In addition, the robustness of the prepared coating was confirmed by subjecting these to thermal cycling (ambient to 550oC).

Butene Catalytic Cracking to Propylene over Iron and Phosphorus Modified HZSM-5

HZSM-5 zeolites modified by iron and phosphorus were applied in catalytic cracking of butene. N2 adsorption and NH3-TPD were employed to measure the structure and acidity of catalysts. The results indicate that increasing phosphorus loading decreased surface area, pore volume and strong acidity of catalysts. The addition of phosphorus significantly decreased butene conversion and promoted propylene selectivity. The catalytic performance of catalyst was strongly dependent on the reaction conditions. Appropriate reaction conditions could suppress side reactions and enhance propylene selectivity.