Stabilization of heavy metals in solid waste and sludge pyrolysis by intercalation-exfoliation modified vermiculite.

Increasing amounts of solid waste and sludge have created many environmental management problems. Pyrolysis can effectively reduce the volume of solid waste and sludge, but there is still the problem of heavy metal contamination, which limits the application of pyrolysis in environmental management. The intercalated-exfoliated modified vermiculite (IEMV) by intercalators of sodium dodecylbenzene sulfonate, hexadecyltrimethylammonium bromide and octadecyltrimethylammonium bromide were used to control the release of Cd, Cr, Cu, Zn and Pb during pyrolysis process of sludge or solid waste. The retention of heavy metals in sludge was generally better than that in solid waste. The IEMV by octadecyltrimethylammonium bromide as the intercalator calcined 800 °C (STAB-800) was the best additive for heavy metal retention, and the retention of Cr, Cu and Zn was significantly better than that of Pb and Cd. Cr, Cu, Zn and Pb were at low risk, while Cd had considerable risk under certain circumstances. New models were proposed to comprehensively evaluate the results of the risk and forms of heavy metals, and the increasing temperature was beneficial in reducing the hazards of heavy metals by the addition of STAB-800. The reaction mechanism of heavy metals with vermiculite was revealed by simulation of reaction sites, Fukui Function and Frontier Molecular Orbital. Thermal activation-intercalated-exfoliated modified vermiculite (T-IEMV) is more reactive and had more active sites for heavy metals. Mg atoms and outermost O atoms are the main atoms for T-IEMV to react with heavy metals. The Cr, Cu and Zn have better adsorption capacity by T-IEMV than Pb and Cd. This study provides a new insight into managing solid waste and sludge and controlling heavy metal environmental pollution.

Effective stabilization of heavy metals in solid waste and sludge pyrolysis using intercalated-exfoliated modified vermiculite: Experiment and simulation study.

Pyrolysis is effective in reducing the volume of solid waste and sludge, and produces less pollutants than incineration and landfill, but the process still suffers from heavy metal pollution. Four types of intercalated-exfoliated modified vermiculite (UIV, DIV, TIV and 3IV) were prepared using urea, dimethylsulfoxide, tributyl phosphate and 3-aminopropyltriethoxysilane as intercalators for the control of Cd, Cr, Cu, Pb and Zn in municipal sewage sludge (MSL), paper mill sludge (PML), municipal domestic waste (MWA) and aged refuse (AFE). The larger the interlayer spacing of the vermiculite, the more favorable the retention of heavy metals. 3IV was the most effective additive, with an average retention of more than 75 % of all heavy metals at 450 ℃ for the four raw materials. Cr, Cu, Pb and Zn were all at low potential ecological risk (Pr), while Cd was moderate or considerable Pr, and the addition of 3IV reduced the Pr. Distribution of intercalators between vermiculite interlayers was haphazard, and interlayer spacing results were close to those of the experiment (except for tributyl phosphate). The reactive electrons mainly flowed from the Highest Occupied Molecular Orbital (HOMO) of vermiculite flakes to the Lower Unoccupied Molecular Orbital (LUMO) of heavy metal chlorides. In contrast, the reactive electrons mostly flowed from the HOMO of heavy metal oxides to the LUMO of vermiculite flakes. Heavy metal oxides were more readily adsorbed on vermiculite flakes than heavy metal chlorides, and the adsorption capacity of Cr and Zn was stronger than that of Cd, Pb and Cu.

Density functional theory study on the formation mechanism of CaClOH in municipal solid waste incineration fly ash.

Municipal solid waste incineration (MSWI) fly ash is defined as a kind of hazardous waste because of its high levels of multiple pollutants. The main component of MSWI fly ash is CaClOH, and the characteristics have not achieved consensus. And density functional theory (DFT) was used to calculate the formation process of CaClOH in this study, which mainly included HCl adsorption on CaO (0 0 1) surface and Ca(OH)2 (0 0 1) surface and the surface reaction process. The reaction mechanism was investigated. The results showed that the maximum adsorption energies of HCl on CaO and Ca(OH)2 surfaces reached - 195.17 kJ/mol and - 83.48 kJ/mol, respectively, representing strong chemisorption. The chemisorption process was shown as the adsorption of H atom on O site, and the adsorption capacity was reflected in the adsorption range of O site. The significant electron density overlap between O site and H atom meant that a new chemical bond formed, which made the adsorption structure stable. The adsorption energy of multi-HCl adsorption on the crystal surfaces was not proportional to the number of HCl molecule, indicating that the adsorption processes were influenced by each other. After surface reaction, the H-Cl bond was broken completely, and the structure of CaO and Ca(OH)2 changed to new structures. According to transition state (TS) search, the formation of CaClOH had a higher priority, easier than that of CaCl2, explaining the presence of CaClOH in fly ash. The study provides helpful information for the solidification treatment of fly ash.

Influence of silica-aluminum materials on heavy metals release during paper sludge pyrolysis: Experimental and theoretical studies.

It is of great significance to reduce the secondary risk of heavy metals during the pyrolysis of paper sludge. This study used kaolin and alumina-silica-based xerogels to control heavy metals released during sludge pyrolysis. Pyrolyzing a mixture of sludge and 7% kaolin at 400 °C achieved high retention rates for Cu (95.85%), Zn (95.97%), Pb (97.15%), Cd (84.23%), and Cr (84.05%) when the pyrolysis tail gas was treated with 9 g of xerogel. The addition of kaolin facilitated the transformation of Cu, Zn, Pb, and Cr from the unstable fraction to the stable fraction in pyrolysis biochar, reducing their leachability. The xerogels also played a crucial role in adsorbing and stabilizing the heavy metals. The results of thermodynamic equilibrium calculations showed that Pb(g), PbS(g), PbCl2(g), PbCl(g), Zn(g), ZnCl2(g), and Cd(g) were the main gaseous products of Zn, Pb, and Cd during paper sludge pyrolysis. The Pb atoms in PbCl2 and PbS, and the Zn atoms in ZnCl2 bond with the oxygen atoms on the kaolin surface by covalent bonds, while the Cl atoms in PbCl and the Pb atoms of elemental lead form ionic bonds with H and O atoms on the kaolinite surface, respectively. These experimental and simulation results offer new ideas for controlling heavy metals during sludge pyrolysis.

Experimental, Grand canonical Monte Carlo, and Density Functional Theory studies for comparing halloysite and kaolinite on heavy metals fate during pyrolysis of solid waste.

In this study, we utilized low-cost halloysite (Hal) for the first time to enhance the solid-phase enrichment and stability of heavy metals (HMs) during solid waste pyrolysis through experimental and theoretical methods, and compared with kaolinite (Kao). Experimental results demonstrated that Hal was superior to Kao in improving the solid-phase enrichment of HMs. Specifically, the solid-phase enrichment of Cd increased by 32.6 % (500 °C) and 25.94 % (600 °C), while that of Pb and Zn increased by 17.37 %/16.83 % and 19.82 %/22.37 % (700/800 °C), respectively. Adding Hal reduced the proportion of HMs in the unstable fraction (F1 + F2), consequently lowering the environmental risk of biochar and the extractable state of HMs. Through Grand canonical Monte Carlo and Density Functional Theory (DFT) simulations, we analyzed the adsorption amounts, adsorption sites, and adsorption mechanisms of Cd/Pb compound on Hal/Kao surfaces, revealing that the primary factor influencing the adsorption performance of Hal and Kao was the difference in specific surface area. The adsorption amounts of HMs by Hal were significantly higher than Kao and decreased with increasing temperature, while the difference in adsorption performance caused by structural bending was negligible. The DFT results indicated that Cd and Pb monomers were stabilized by establishing covalent bonds with OH or reactive O atoms on the Al-(001) surface, whereas the covalent bonds with ionic bonding properties formed between Cl atoms and unsaturated Al atoms played a crucial role in stabilizing HM chlorides. Furthermore, the adsorption energy of Hal on HMs increased with the removal rate of OH. Our study highlights the potential of Hal in stabilizing HMs during pyrolysis without requiring any modifications, thereby avoiding the generation of modified waste solutions and unnecessary cost loss.

Co-pyrolysis of sewage sludge as additive with phytoremediation residue on the fate of heavy metals and the carbon sequestration potential of derived biochar.

Considering the characteristics of municipal sewage sludge (MS) and Sedum alfreddi L. (SA, a hyperaccumulator plant), we attempted to use MS to enhance the enrichment and stability of heavy metals (HMs) in pyrolysis residue during SA pyrolysis. The effects of pyrolysis temperature (400-800 °C) and co-pyrolysis on migration behavior, chemical speciation, long-term leaching toxicity of HMs, and the environmental risk and carbon sequestration potential of biochar were systematically investigated. Besides, thermodynamic equilibrium simulations were performed to study the transformation of HM compounds during pyrolysis. When the pyrolysis temperature increased from 400 °C to 800 °C, the unstable fractions (F1+F2) of Cd, Pb, Cu, and Cr in MS1SA3 800 had decreased to less than 6% and Zn to 20.4%, and long-term leachability of HMs decreased continuously. Meanwhile, biochar's ecological risk was reduced to a low level, while its carbon sequestration potential improved with little released HMs. Compared with SA pyrolysis alone, adding MS increased the relative residue content of Cd and Zn in biochar, whereas no apparent effect on Pb, Cu, and Cr, and the proportion of stable fractions (F3+F4) increased. Co-pyrolysis enhanced the carbon sequestration potential of biochar, attributed to the inherent minerals of MS. Equilibrium calculations showed that the influence of MS on the fate of HMs during SA pyrolysis is mainly attributed to its high sulfur content, while Si and Al preferentially combine with alkali metal (K)/alkaline earth metal (Ca) and then interact with Zn. The findings in this paper suggest that co-pyrolysis of MS as an additive with hyperaccumulator plants is a feasible proposal, and the co-pyrolysis biochar obtained at suitable temperatures has the potential for safe application.

Thermodynamic evaluation on chemical looping conversion of Cd- and Zn-contained phytoremediation plant with different CaO pathways.

With the development of phytoremediation for soil contamination, disposal of phytoremediation plant becomes a serious problem. Thermochemical conversion of phytoremediation plant can greatly reduce the volume and mass, meanwhile the clean and reusable utilization is realized. As one of the thermochemical conversion technologies, chemical looping (CL) offers a carbon negative way for clean utilization of biomass. In this technology, CaO has binary roles of heavy metal solidification and CO2 sorption for gasification enhancement. To assess the CaO pathway in CL of phytoremediation plant, two different CL processes are constructed and comparatively studied based on thermodynamic evaluation. The effects of different operating parameters on the products of gasifier (GR) and reduction reactor (RR) are compared and discussed. Results demonstrated that the CaO addition in GR is beneficial to the production of pure combustible gases. Increasing RR temperature can promote the chemical looping reactions in RR. Under lower temperature, CaO in RR can consume more CO2 leading to CO2 free environment. When it is higher than 850 °C, there is no effect of CaO in RR. Increasing the amount of OC in system can enhance the conversion of combustible gases. When αOC is higher than 0.3, the OC is reduced to a mixed state of Fe3O4 and FeO. When the CaO circulates only between GR and calciner, pure CO2 can be captured at the outlet of calciner. Existence of CaO is beneficial to retain Cd and Zn in solid phases. When the gasification temperature increases from 500 °C to 800 °C, the Cd(g) increases while Cd decreases in both CL1 and CL2. For a long lifetime of OC, CaO is suggested to circulates between GR and calciner.

Experimental and numerical investigations of desulfurization wastewater evaporation in a lab-scale flue gas duct: evaporation and HCl release characteristics.

The evaporation of desulfurization wastewater using flue gas has been considered as a promising technique. However, the release of HCl during the evaporation hinders the application of this technique. Herein, we investigated the evaporation in a laboratory-scale flue duct through experimental and numerical methods. The influences of operating parameters on characteristics of evaporation and HCl release were experimentally explored. The results show that when inlet gas temperature increases from 200°C to 350°C, gaseous HCl concentration significantly increases from 5.02 ppm to 70.96 ppm and HCl release ratio accordingly increases from 1.57% to 17.32%. However, when the wastewater only contains CaCl2, the HCl release is effectively inhibited. Subsequently, the established CFD model was validated with the experiments. It was found that relative deviations between predicted and experimental outlet gas temperatures mostly locate within the range of -10%∼0%. The negative deviations are attributed to the neglect of the crust formation. Numerical studies also reveal that droplet evaporation temperature is close to the wet-bulb temperature of the inlet gas ranging from 321.47 K to 337.85 K. Moreover, thermodynamic analysis shows that when the wastewater contains equimolar MgCl2 and CaCl2, MgCl2·6H2O first crystalizes at about d/d0 = 0.3. However, when the wastewater only contains CaCl2, CaCl2·2H2O begins to crystallize at about d/d0 = 0.25. Before crystallization, the equilibrium partial pressure of HCl is close to 0 Pa, indicating the HCl is mainly released at the particle drying stage. Further analysis suggests HCl should be mainly released from the decomposition of MgCl2·6H2O into MgOHCl.

Facile use of coal combustion fly ash (CCFA) as Ni-Re bimetallic catalyst support for high-performance CO2 methanation.

The industrial waste coal combustion fly ash (CCFA) was used as a cheap catalyst support and by facile co-impregnation method, the active component Ni and promoter Re was loaded to form a bimetallic catalyst for high-performance CO2 methanation. The physico-chemical properties of the prepared catalyst were further measured by a series of characterizations such as X-ray fluorescence (XRF), N2 isothermal adsorption-desorption, X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR) et al. The effect of reaction temperature and gas hourly space velocity (GHSV) on the catalytic performance was carefully investigated on a continuous fixed-bed reactor. The results showed that in comparison with the non-promoted monometallic Ni/CCFA catalyst, the bimetallic Ni-Re/CCFA catalyst displayed a superior activity, which could achieve 99.55% of CO2 conversion and 70.27% of CH4 selectivity under the condition of 400 °C, 2000 h-1, 1 atm and H2:CO2:N2 = 4:1:0.5, possibly owing to the higher Ni dispersion and more active sites in Ni-Re/CCFA. Besides, the addition of Re promoter was beneficial to enhance the catalyst anti-sintering and anti-coking abilities as reflected by the smaller Ni particle size growth and less carbon deposition amount in Ni-Re/CCFA. The in-situ diffuse reflection infrared Fourier transform spectrum (in-situ DRIFTS) was finally carried out to determine the CO2 adsorption state and its methanation intermediates, from which a loop mechanism of CO2 methanation process was proposed and depicted.

COx co-methanation over coal combustion fly ash supported Ni-Re bimetallic catalyst: Transformation from hazardous to high value-added products.

The hazardous industrial waste, coal combustion fly ash (CCFA), was creatively applied as Ni-Re bimetallic catalyst support. The expected catalyst was facilely prepared by co-impregnation method and further tested for COx co-methanation in a continuous fixed-bed reactor. The physico-chemical properties of the catalyst were examined by a series of techniques including XRF, ICP, XRD, N2 isothermal adsorption, H2-TPR, SEM and TEM. The results showed that compared to non-promoted monometallic Ni catalyst, the addition of Re promoter forming Ni-Re bimetallic catalyst was able to facilitate NiO reduction and increase Ni dispersion as well as inhibit carbon deposition and Ni sintering during reaction. The performance tests revealed that Ni15Re1.0 presented superior COx co-methanation activity over Ni15Re0, Ni15Re0.5 and Ni15Re1.5 due to its better anti-coking and anti-sintering ability. Based on in-situ DRIFTS analysis, a possible cycle reaction mechanism of COx co-methanation was reasonably proposed in the end. The reaction pathway for CO and CO2 methanation differed from each other, where CO was linearly adsorbed on Ni metals followed by stepwise hydrogenation while CO2 was first immobilized by the surface hydroxyl group and then gradually reacted with H2 to form CH4.

Synthesis, Characterization, and High-Temperature HCl Capture Capacity of Different Proportions of Potassium Fluoride-Doped CaMgAl Layered Double Hydroxides.

In this work, potassium fluoride-doped Ca-Mg-Al layered double hydroxides (CaMgAl-LDHs) were synthesized by a coprecipitation method, after which they were further used as strong adsorbents for HCl gas adsorption in a quartz reactor at high temperature. The physiochemical properties of the as-prepared KF/CaMgAl-LDHs and CaMgAl-LDHs were investigated by X-ray diffraction, thermogravimetric, scanning electron microscopy, energy-dispersive system, and Brunauer-Emmett-Teller. The HCl adsorption test showed that 25 wt % KF loading of the KF/CaMgAl-LDOs was the optimal adsorbent for HCl removal. The highest adsorption capacity of the KF/CaMgAl-LDH adsorbent was achieved with 0.2968 g at 600 °C, 500 ppm HCl concentration, and 0.5 g adsorbent. Furthermore, the microstructure of the adsorbents after the reaction revealed that the adsorbents were encapsulated by dense chloride. The adsorption process was mainly dominated by chemical adsorption, strong acid-base properties, specific surface area, and mesopore number.

A novel two-stage biomass gasification concept: Design and operation of a 1.5 MWth demonstration plant.

To gasify the biofuel of low ash melting temperature and overcome the high content of tar in bio-gas, a novel two-stage gasification concept is proposed. This concept enables the tar-free bio-gas generated in the gasification process under thermal cracking. On that basis, a demonstration project is introduced. Rice husk acts as the feedstock for its accessibility on-site in the commissioning period. System reliability has been confirmed for the stable operation of more than 60 days. Tests have been performed under some typical operating conditions. As the results suggest, the bio-gas of 6.7 MJ/Nm3 LHV is generated with cold gas efficiency and carbon conversion of 67.5% and 87% respectively. Elementary economic evaluation of this concept is also made in accordance with the commissioning results. As a result, the annual net profit of 40.92 K USD is yielded without a subsidized price for biomass materials.

Characterization of ash melting behaviour at high temperatures under conditions simulating combustible solid waste gasification.

To achieve high-temperature gasification-melting of combustible solid waste, ash melting behaviour under conditions simulating high-temperature gasification were studied. Raw ash (RA) and gasified ash (GA) were prepared respectively by waste ashing and fluidized bed gasification. Results of microstructure and composition of the two-ash indicated that GA showed a more porous structure and higher content of alkali and alkali earth metals among metallic elements. Higher temperature promoted GA melting and could reach a complete flowing state at about 1250°C. The order of melting rate of GA under different atmospheres was reducing condition > inert condition > oxidizing condition, which might be related to different existing forms of iron during melting and different flux content with atmosphere. Compared to RA, GA showed lower melting activity at the same condition due to the existence of an unconverted carbon and hollow structure. The melting temperature for sufficient melting and separation of GA should be at least 1250°C in this work.

Study on adsorption properties and mechanism of Pb2+ with different carbon based adsorbents.

Different activated carbon materials are prepared from a series of solid wastes (sawdust, acrylic fabric, tire powder and rice husk) by combination of the KOH activation method and steam activation method. The influences of several parameters such as pH, contact time, adsorbent dosage and temperature on adsorption performance of Pb2+ with those different carbon adsorbents are investigated. The results demonstrate that Crice husk performance well in the adsorption process. In the following, the Crice husk is used to explain the adsorption mechanism of Pb2+ by SEM-EDS, FT-IR and XPS. The results illustrate that the surface oxygen-containing functional groups such as carboxyl, lactone group, phenolic hydroxyl and other alkaline metal ions like Na+ and K+ have significant effect on the adsorption process. A reasonable mechanism of Pb2+ adsorption is proposed that the ion exchange play key roles in the adsorption process. In addition, the effects of Cu2+, Zn2+ on the Pb2+ adsorption capacity with the four carbon adsorbents are also studied and the results demonstrate that other heavy metals play positive effects on the adsorption of Pb2+.

Catalytic pyrolysis of black-liquor lignin by co-feeding with different plastics in a fluidized bed reactor.

Catalytic co-pyrolysis of black-liquor lignin and waste plastics (polyethylene, PE; polypropylene PP; polystyrene, PS) was conducted in a fluidized bed. The effects of temperature, plastic to lignin ratio, catalyst and plastic types on product distributions were studied. Both aromatic and olefin yields increased with increasing PE proportion. Petrochemical yield of co-pyrolysis of PE and lignin was LOSA-1 > spent FCC > Gamma-Al2O3 > sand. The petrochemical yield with LOSA-1 is 43.9% which is more than two times of that without catalyst. The feedstock for co-pyrolysis with lignin is polystyrene > polyethylene > polypropylene. Catalytic co-pyrolysis of black-liquor lignin with PS produced the maximum aromatic yield (55.3%), while co-pyrolysis with PE produced the maximum olefin yield (13%).

Effects of temperature and composite alumina on pyrolysis of sewage sludge.

An interactive dual-circulating fluidized bed system has been proposed in which the pyrolysis of sewage sludge (SS) and incineration of biomass proceed simultaneously, and alumina is used as the bed material and heat carrier. The alumina coated with biomass ash would mix with sewage sludge in the pyrolysis reactor of this device. It is important to know the influence of composite alumina (CA) on the pyrolysis progress. Sewage sludge was pyrolyzed in a fixed bed reactor from 400 to 600°C using CA as catalyst. The effects of temperature and CA additive ratio on the products were investigated. The product yields and component distribution of non-condensable gas were more sensitive to the change of temperature, and the maximum liquid yield of 48.44 wt.% and maximum Useable Energy of Liquid of 3871 kJ/kg sludge were observed at 500°C with 1/5 CA/SS (mass ratio). The gas chromatography-mass spectrometry results showed that the increase of temperature enhanced devolatilization of organic matter and promoted cyclization and aromatization of aliphatics. The presence of CA could strengthen secondary cracking and interaction among primary products from different organic compounds, such as acid-amine condensation, and reduce the content of oxygenated compounds. When the CA additive amount exceeded a certain proportion, the aromatization was clearly strengthened. The effects of CA on decomposition of fatty acids and formation of aromatics were similar to that of temperature. This means that the reaction temperature could be lowered by introducing CA, which has a positive effect on reducing energy consumption.

Characterization of top phase oil obtained from co-pyrolysis of sewage sludge and poplar sawdust.

To research the impact of adding sawdust on top phase oil, a sewage sludge and poplar sawdust co-pyrolysis experiment was performed in a fixed bed. Gas chromatography (GC)/mass spectrometry (MS) was used to analyze the component distribution of top phase oil. Higher heating value, viscosity, water content, and pH of the top phase oil product were determined. The highest top phase oil yield (5.13 wt%) was obtained from the mixture containing 15% poplar sawdust, while the highest oil yield (16.51 wt%) was obtained from 20% poplar sawdust. Top phase oil collected from the 15% mixture also has the largest amount of aliphatics and the highest higher heating value (28.6 MJ/kg). Possible reaction pathways were proposed to explain the increase in the types of phenols present in the top phase oil as the proportion of poplar sawdust used in the mixture increased. It can be concluded that synergetic reactions occurred during co-pyrolysis of sewage sludge and poplar sawdust. The results indicate that the high ash content of the sewage sludge may be responsible for the characteristic change in the top phase oil obtained from the mixtures containing different proportions of sewage sludge and poplar sawdust. Consequently, co-pyrolysis of the mixture containing 15 % poplar sawdust can increase the yield and the higher heating value of top phase oil.

Catalytic conversion of biomass pyrolysis-derived compounds with chemical liquid deposition (CLD) modified ZSM-5.

Chemical liquid deposition (CLD) with KH550, TEOS and methyl silicone oil as the modifiers was used to modify ZSM-5 and deposit its external acid sites. The characteristics of modified catalysts were tested by catalytic conversion of biomass pyrolysis-derived compounds. The effects of different modifying conditions (deposited amount, temperature, and time) on the product yields and selectivities were investigated. The results show KH550 modified ZSM-5 (deposited amount of 4%, temperature of 20°C and time of 6h) produced the maximum yields of aromatics (24.5%) and olefins (16.5%), which are much higher than that obtained with original ZSM-5 catalyst (18.8% aromatics and 9.8% olefins). The coke yield decreased from 44.1% with original ZSM-5 to 26.7% with KH550 modified ZSM-5. The selectivities of low-molecule-weight hydrocarbons (ethylene and benzene) decreased, while that of higher molecule-weight hydrocarbons (propylene, butylene, toluene, and naphthalene) increased comparing with original ZSM-5.

Biomass catalytic pyrolysis to produce olefins and aromatics with a physically mixed catalyst.

Zeolite catalysts with micropores present good catalytic characteristics in biomass catalytic pyrolysis process. However, large-molecule oxygenates produced from pyrolysis cannot enter their pores and would form coke on their surfaces, which decreases hydrocarbon yield and deactivates catalyst rapidly. This paper proposed adding some mesoporous and macroporous catalysts (Gamma-Al2O3, CaO and MCM-41) in the microporous catalyst (LOSA-1) for biomass catalytic pyrolysis. The added catalysts were used to crack the large-molecule oxygenates into small-molecule oxygenates, while LOSA-1 was used to convert these small-molecule oxygenates into olefins and aromatics. The results show that all the additives in LOSA-1 enhanced hydrocarbon yield obviously. The maximum aromatic+olefin yield of 25.3% obtained with 10% Gamma-Al2O3/90% LOSA-1, which was boosted by 39.8% compared to that obtained with pure LOSA-1. Besides, all the additives in LOSA-1 improved the selectivities of low-carbon components in olefins and aromatics significantly.

Catalytic fast pyrolysis of straw biomass in an internally interconnected fluidized bed to produce aromatics and olefins: effect of different catalysts.

A novel reactor, named internally interconnected fluidized bed (IIFB), was specially designed for catalytic fast pyrolysis (CFP) of straw biomass. Catalytic characteristics of four types of catalysts (ZSM-5, LOSA-1, Gamma-Al2O3 and spent FCC catalysts) for producing aromatics and olefins were investigated in this reactor. The results show that IIFB reactor can realize CFP process. The maximum carbon yields of aromatics (12.8%) and C2-C4 olefins (10.5%) were obtained with ZSM-5. ZSM-5 shows the highest selectivity of naphthalene (12.1%), whereas spent FCC catalyst presents the highest selectivity of benzene (45.5%). The selectivity of ethylene and propylene are equal in the present of ZSM-5 and LOSA-1. Gamma-Al2O3 and spent FCC catalysts show a higher selectivity of ethylene than that of propylene. This paper provides a new reactor for CFP process and some suggestions for choosing catalyst.