Hydrodeoxygenation of 2-methoxy phenol: Effects of catalysts and process parameters on conversion and products selectivity

The hydrodeoxygenation (HDO) of 2-methoxy phenol (MP), a lignin-derived compound, has massive prospective for valuable compounds production. The lignin derived model compounds can be used for production of green chemicals. The model compound MP conversion into cyclohexane was investigated over Ru metal loaded on various supports (ZSM-5, Y-zeolite, β-zeolite, COK-12, mordenite, ZrO₂, and TiO₂). The catalytic properties such as the acidic sites, pore size, and morphology influenced the HDO activity and selectivity of the cyclohexane. The yield of cyclohexane increases up to optimum acidity further increases the acidity of the catalyst, the product yield decreased. The experiments carried out at temperature range of 200–300 °C, and 1–25 bar hydrogen pressure in a fixed bed reactor. The parameters greatly influenced the HDO as well as the cyclohexane yield, selectivity, and MP conversion. The highest conversion (100%) and yield of cyclohexane (99.0%) observed at 250 °C under pressure of 20 bar with Ru/ZSM-5 catalyst. Further the recyclability and stability have been checked and observed that Ru/ZSM-5 is stable up to 200 h and displayed excellence activity in both HDO and cyclohexane selectivity. Weight hourly space velocity (WHSV) was investigated (0.5–1.5 h⁻¹). The suitable WHSV found for HDO of 2-methoxy phenol and cyclohexane yield was 1 h⁻¹. The reaction mechanism showed that the Ru/ZSM-5 catalyst provoked the HDO compared to the others catalyst.     

Hydrocracking of Jatropha oil to aromatic compounds over the LaNiMo/ZSM-5 catalyst

The conversion of biomass to produce high-valued chemical aromatic intermediates such as benzene (B), toluene (T), ethylbenzene (E), xylene (X), naphthalene (N) has attached booming interests. Herein, in order to obtain BTEXN aromatics on the hydrocracking of Jatropha oil, several LaNiMo/ZSM-5 catalysts (La loading from 0.5 to 15 wt%) by alkali treatment and metal impregnation methods were synthesized and investigated. Fundamentally, we found the alkali treatment engendered more mesoporosity to ZSM-5 and resulted in higher catalytic activity. It bears emphasis that further metal impregnated catalyst NiMo/ZSM-5 could improve the aromatics yield due to the increase of metal active sites and acidity sites. Besides, we noted that La loading had positive effects on coke reduction, catalytic stability and catalyst lifetime. To sum up, results confirmed the favorable 1 wt% La–NiMo/ZSM-5 had maximum 75 wt% BTEXN yield, longer catalyst lifetime for 100 h and decreased carbon deposits by 1.11%.     

Catalytic pyrolysis of biomass over Fe-modified hierarchical ZSM-5: Insights into mono-aromatics selectivity and pyrolysis behavior using Py-GC/MS and TG-FTIR

Catalytic pyrolysis has recently aroused great interest for the high potential in upgrading bio-oils as renewable energy. However, conventional catalysts often exert diffusion resistance to large intermediate oxygenates. In this study, Fe-modified hierarchical ZSM-5 prepared by alkali and Fe loading of 2, 4, 6, 8 wt% were characterized by the analysis of XRD, BET, TEM, and NH₃-TPD. Catalytic pyrolysis of poplar sawdust via Fe-modified hierarchical ZSM-5 was conducted using Py-GC/MS and TG-FTIR. The results indicated that alkali treatment and Fe loading of the catalyst introduced a hierarchical and porous structure and improved its acidity, leading to high mono-aromatics and olefins selectivity. The hierarchical ZSM-5 with 4 wt% Fe loading exhibited superior performance with high selectivity towards mono-aromatics of 15.30%. TG-FTIR analysis shows the volatiles release characteristics and FTIR spectra were consistent with pyrolysis behavior. Kinetic analysis reveals Fe-modified hierarchical ZSM-5 lowers the apparent activation energy in catalytic pyrolysis of poplar sawdust.     

Jet range hydrocarbons converted from microalgal biodiesel over mesoporous zeolite-based catalysts

In order to produce jet biofuel from lipids derived from microalgal biomass, lower-viscosity and smaller-molecular microalgal biodiesel was converted into jet range hydrocarbons over four mesoporous zeolite-based catalysts decorated with nickel. Ni/Meso-Y catalyst exhibited a high selectivity (44.5%) of jet range alkane (C₈C₁₆) from light microalgal biodiesel. The conversion pathway of light microalgal biodiesel to jet range hydrocarbons was proposed that majority of fatty acids first deoxygenated to C₁₅C₁₆ through decarbonylation and then long chain alkane cracked into short chain alkane. The other fatty acids first cracked into short chain acids and then further deoxygenated through decarbonylation to jet range alkane, in which a part of alkane converted to aromatic hydrocarbons through aromatization. Meso-Y catalyst was suitable for conversion of heavy microalgal biodiesel to jet range hydrocarbons with low selectivity (4.47%) of aromatic hydrocarbons, but the other three catalysts (Meso-HZSM-5, Meso-Hbeta and SAPO-34) gave high aromatic hydrocarbons selectivity.     

Tungstophosphoric acid incorporated hierarchical HZSM-5 catalysts for direct synthesis of dimethyl ether

HZSM-5 zeolites are active materials in dimethyl ether (DME) production with high surface acidity. In this study, hierarchical HZSM-5 catalysts were synthesized with steam-assisted crystallization (SAC) method and then in order to increase its surface acidity, TPA was loaded into the HZSM-5 catalyst having various mass ratios (5, 10, 25%) by wet impregnation method. Synthesized catalysts were characterized by N₂ physisorption (BET analysis), X-Ray diffraction and pyridine adsorbed diffuse reflectance FTIR spectroscopy techniques. Characterization analysis of tungstophosphoric acid (TPA) impregnated catalysts indicated that hierarchical HZSM-5 possesses mesoporous structures. The average pore size distribution of TPA impregnated HZSM-5 catalysts were between 17 and 20 nm. TPA impregnation promoted Brønsted acid sites of the catalyst, which favors methanol dehydration reaction. Activity tests have been performed at reaction temperatures of 200–300 °C at 50 bar reaction pressure in the presence of admixed catalysts (physically mixed commercial HifuelR-120 and HZSM-5 based catalysts with a weight ratio of 1:1). Results revealed that the increase in the amount of heteropoly acid has enhanced DME selectivity and CO conversion. Maximum DME selectivity of 57% and CO conversion of 46% were achieved in the presence of the 25TPA@HZSM-5 catalyst at the optimum reaction temperature of 275 °C. TGA analysis result of spent catalysts presented the highest amount of coke over HZSM-5. TPA incorporation decreased coke formation due to suppression of the Lewis acid site, which is responsible for the coke formation.     

Potentiality of combined catalyst for high quality bio-oil production from catalytic pyrolysis of pinewood using an analytical Py-GC/MS and fixed bed reactor

The aim of this study was to investigate the potential of combined catalyst (ZSM-5 and CaO) for high quality bio-oil production from the catalytic pyrolysis of pinewood sawdust that was performed in Py-GC/MS and fixed bed reactor at 500 °C. In Py-GC/MS, the maximum yield of aromatic hydrocarbon was 36 wt% at biomass to combined catalyst ratio of 1:4 where the mass ratio of ZSM-5 to CaO in the combined catalyst was 4:1. An increasing trend of phenolic compounds was observed with an increasing amount of CaO, whereas the highest yield of phenolic compounds (31 wt%) was recorded at biomass to combined catalyst ratio of 1:4 (ZSM-5: CaO - 4:1). Large molecule compounds could be found to crack into small molecules over CaO and then undergo further reactions over zeolites. The water content, higher heating value, and acidity of bio-oil from the fixed bed reactor were 21%, 24.27 MJkg⁻¹, and 4.1, respectively, which indicates that the quality of obtained bio-oil meets the liquid biofuel standard ASTM D7544-12 for grade G biofuel. This research will provide a significant reference to produce a high-quality bio-oil from the catalytic pyrolysis of woody biomass over the combined catalyst at different mass ratios of biomass to catalyst.     

Catalytic pyrolysis of sweet sorghum bagasse in the presence of two acid catalysts

Sweet sorghum bagasse was pyrolyzed in the presence of two catalysts, ZSM-5 (a widely known commercial zeolite) and HY-340 (a relatively unexplored acid catalyst). The vapors originating from the thermal decomposition were examined by Py-GC/MS in the biomass/catalyst mass ratios of (1:1), (1:2), (1:5) and (1:10) at 450 °C, 550 °C and 650 °C. In the tests without catalysts, the production of both olefins and aromatics increased in response to increasing reaction temperature. In the catalytic pyrolysis in the presence of ZSM-5, the formation of aromatics increased significantly and the formation of oxygenated decreased in response to increasing amounts of catalyst at all the temperatures studied. The highest concentration of aromatics was obtained in the tests at 450 °C with a bagasse/ZSM-5 ratio of (1:10). In the tests with niobic acid, the formation of furans increased with the addition of HY-340 at ratios of (1:1) and (1:2), and the formation of oxygenated decreased in response to the increase in biomass/catalyst ratio at all temperatures mentioned. Area percentages of approximately 54% of olefins were obtained in the assays at bagasse/HY-340 ratios of (1:2) and (1:5) at 650 °C.     

Hydrothermal liquefaction of macroalgae: Influence of zeolites based catalyst on products

Hydrothermal liquefaction (HTL) of Ulva prolifera macroalgae (UP) was carried out in the presence of three zeolites based catalysts (ZSM-5, Y-Zeolite and Mordenite) with the different weight percentage (10–20 wt%) at 260–300 °C for 15–45 min. A comparison between non-catalytic and catalytic behavior of ZSM-5, Y-Zeolite, and Mordenite in the conversion of Ulva prolifera showed that is affected by properties of zeolites. Maximum bio-oil yield for non-catalytic liquefaction was 16.6 wt% at 280 °C for 15 min. The bio-oil yield increased to 29.3 wt% with ZSM-5 catalyst (15.0 wt%) at 280 °C. The chemical components and functional groups present in the bio-oils are identified by GC-MS, FT-IR, ¹H-NMR, and elemental analysis techniques. Higher heating value (HHV) of bio-oil (32.2–34.8 MJ/kg) obtained when catalyst was used compared to the non-catalytic reaction (21.2 MJ/kg). The higher de-oxygenation occurred in the case of ZSM-5 catalytic liquefaction reaction compared to the other catalyst such as Y-zeolite and mordenite. The maximum percentage of the aromatic proton was observed in bio-oil of ZSM-5 (29.7%) catalyzed reaction and minimum (1.4%) was observed in the non-catalyst reaction bio-oil. The use of zeolites catalyst during the liquefaction, the oxygen content in the bio-oil reduced to 17.7%. Aqueous phase analysis exposed that presence of valuables nutrients.     

Fe/ZSM-5催化剂的酸性与孔隙特性对合成气直接制备芳烃的影响

以多级孔ZSM-5分子筛为载体,通过等体积浸渍法制备了一种双功能铁基催化剂,用于合成气直接制备芳烃。采用硅烷法合成不同硅铝比和介孔孔隙率的多级孔ZSM-5分子筛载体。催化剂的理化性质通过XRD、XRF、BET和HN₃-TPD进行表征。结果表明：具有较高酸性的分子筛有利于提高油相中芳烃的选择性,当载体的硅铝比为40时,在油相中芳烃选择性可达66.9%;通过调节硅烷剂3-氨丙基三甲氧基硅烷（3-APTMS）的加入量来控制分子筛的介孔孔隙率,可使碳氢产物中芳烃的收率大幅度提高。     

Non-catalytic and catalytic pyrolysis of Ulva prolifera macroalgae for production of quality bio-oil

Pyrolysis of Ulva prolifera macroalgae (UM), an aquatic biomass, was carried out in a fixed-bed reactor in the presence of three zeolites based catalysts (ZSM-5, Y-Zeolite and Mordenite) with the different catalyst to biomass ratio. A comparison between non-catalytic and catalytic behavior of ZSM-5, Y-Zeolite and Mordenite catalyst in the conversion of UM showed that is affected by properties of zeolites. Bio-oil yield was increased in the presence of Y-Zeolite while decreased with ZSM-5 and Mordenite catalyst. Maximum bio-oil yield for non-catalytic pyrolysis was (38.5 wt%) and with Y-Zeolite catalyst (41.3 wt%) was obtained at 400 °C respectively. All catalyst showed a higher gas yield. The higher gas yield might be attributed to that catalytic pyrolysis did the secondary cracking of pyrolytic volatiles and promoted the larger small molecules. The chemical components and functional groups present in the pyrolytic bio-oils are identified by GC–MS, FT-IR, ¹H-NMR and elemental analysis techniques. Phenol observed very less percentage in the case of non-catalytic pyrolysis bio-oil (9.9%), whereas catalytic pyrolysis bio-oil showed a higher percentage (16.1%). The higher amount of oxygen present in raw biomass reduced significantly when used catalyst due to the oxygen reacts with carbon and produce (CO and CO₂) and water.     

Insitu upgradation of biocrude vapor generated from non-edible oil cake's hydrothermal conversion over aluminated mesoporous catalysts

In this work, biocrude vapors generated from hydrothermal conversion of Pongammia pinnata cake using high pressure reactor at 400 °C and 25 kg/cm² were upgraded over three mesoporous catalyst namely SBA-15, KIT-6 and FDU-12. The catalysts were synthesized, aluminated and characterized using X-Ray Diffraction, N₂ adsorption-desorption, SEM techniques. A decrease in the surface area was observed on all three mesoporous catalyst after alumina loading with negligible effect on the pore diameter. Purely siliceous catalysts were found to give negligible effect on the yield of different product phases. Alumina supported SBA-15 (SAR 30) was observed as the suitable catalyst as compared to Al/FDU-12 (SAR 30) and Al/KIT-6 (SAR 30) for maximizing the biocrude yield with low heavy hydrocarbons (46.3 ± 2.2%), polyaromatic hydrocarbons (17.1%) and acidic compounds (9.1%) content. Therefore series of SBA-15 were synthesized by varying silicon to alumina ratio between 20 and 50 for maximizing hydrocarbons with boiling cut fractions between 195 and 317 °C corresponding to gasoline range hydrocarbons. Al/SBA-15(SAR 40) was found to give highest biocrude yield (∼34.8%) with highest selectivity towards gasoline fraction (23.7 ± 1.9%). GC/MS analysis was used to confirm the presence of aliphatic and aromatics. Highest asphaltene content was observed with Al/SBA-15 (SAR 50).     

Unique structure of fibrous ZSM-5 catalyst expedited prolonged hydrogen atom restoration for selective production of propylene from methanol

A unique mesostructured fibrous silica@ZSM-5 (HSi@ZSM-5) catalyst was synthesized via microemulsion ZSM-5 zeolite seed assisted synthesis method and successfully applied in enhanced propylene formation in methanol to olefin (MTO) process. Characterization of the catalysts were carried out by FESEM, TEM, XRD, TGA, N₂ adsorption-desorption, NH₃ and KBr probed FTIR. Catalytic performance of as-synthesized catalyst was examined using a micro-pulse reactor and compared with the commercial HZSM-5. The reaction mechanism was elucidated by in-situ methanol FTIR spectroscopy. It was found that HSi@ZSM-5 produced higher propylene selectivity (56%) and was stable for long time on stream (80 h), nearly three-fold higher than that of commercial HZSM-5. In addition, HSi@ZSM-5 displayed higher rate of methanol dehydration, surface methoxy species generation and olefin methylation, indicating that alkene catalytic cycle is the dominant reaction mechanism. The higher selectivity towards propylene was correlated to the existence of moderate acidity which impeded the formation of paraffins and polymethylbenzene intermediates. These observations are further supported by KBr probed FTIR findings which revealed negligible paraffinic carbon species on HSi@ZSM-5. Thus, the unique fibrous silica@ZSM-5 retarded coke deposition due to suppression of undesired side reactions thereby signifying intensified propylene formation, which is highly desirable in commercial MTO processes.     

Catalytic hydrotreating of pyro-oil derived from green microalgae spirulina the (Arthrospira) plantensis over NiMo catalysts impregnated over a novel hybrid support

Upgrading of pyrolysis bio-oil by a novel catalytic hydrotreating process, including hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) was found as an effective technical method for the improvement of biofuel characteristics. In this study, for the first time, the performance of a novel meso-microporous composite material, HMS-ZSM-5, as a support on the catalytic activity of NiMo-based catalysts in the bio-oil hydrotreating was evaluated. The experiments were carried out in a flow fixed-bed reactor at the temperature range of 300–360 °C, 30 bar pressure, and LHSV = 4 h-1. Also, the results were and compared with those of HMS, ZSM-5, and γ-Al2O3 supports. For all catalysts, the increase in temperature resulted in the enhancement of HDO and HDN reactions efficiency. NiMo/HMS-ZSM-5 possessed a high acid property which contributed to the removal of oxygen and nitrogen from bio-oil, with the conversion of 84.10% and 69.60%, respectively. Therefore, the novel catalyst of this study represented much superior upgrading performances compared with those of stand-alone NiMo/HMS and NiMo/ZSM-5 catalysts and also the conventional catalyst of NiMo/γ-Al2O3.     

Catalytic conversion of coal pyrolysis vapors to light aromatics over hierarchical Y-type zeolites

A series of hierarchical Y-type zeolites were prepared by a post-treatment method. All the samples were characterized using nitrogen adsorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and temperature-programmed desorption of ammonia (NH₃-TPD). The results show that hierarchical Y-type zeolites with different porosities can be obtained, and the mesopore size can be controlled by changing the treatment conditions. The acidity of catalysts was also adjusted in this process. The catalysts were evaluated with respect to catalytic conversion of coal pyrolysis vapors to light aromatics online by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Moreover, several model compounds were selected to evaluate the formation pathway of light aromatics during the upgrading of coal pyrolysis vapors over Y-type zeolite. It was found that pore-structure-modified Y-type zeolite has good catalytic performance for the upgrading of coal pyrolysis vapors. After catalytic cracking by EDY zeolites, the total amount of light aromatics such as benzene, toluene, ethyl-benzene, xylene, and naphthalene (BTEXN) in coal pyrolysis vapors increased from 5600 ng/mg (raw coal pyrolysis) to 18,800 ng/mg. The results of model compound catalytic pyrolysis show that Y-type zeolite is beneficial for the catalytic cracking of polycyclic aromatic hydrocarbons, the breaking of phenolic hydroxyl, and the decomposition of heterocyclic compounds, thus promoting the formation of BTEXN. Hierarchical catalysts with wide pore size and large mesopore volume contribute to the diffusion of bulky reactants and their contact with active sites in channels, further promoting the generation of light aromatics.     

Catalytic deoxygenation of triolein to green fuel over mesoporous TiO2 aided by in situ hydrogen production

The greenhouse gases contributed by combustion of fossil fuel has urged the need for sustainable green fuel production. Deoxygenation is the most reliable process to convert bio-oil into green fuel. In this study, the deoxygenation of triolein was investigated via mesoporous TiO₂ calcined at different temperature in the absence of external H₂. The high conversion of fuel-liked hydrocarbons showed the in situ H₂ produced from the reaction. The mesoporous TiO₂ calcined at 500 °C (M500) demonstrated the highest activity, around 76.9% conversion was achieved with 78.9% selectivity to hydrocarbon. The reaction proceed through second order kinetic with a rate constant of 0.0557 g⁻¹_trioleinh⁻¹. The major product of the reaction were diesel range saturated and unsaturated hydrocarbon (60%) further the formation of in situ H₂. It is interesting to observe that higher calcination temperature improve crystallinity and remove surface hydroxyls, meanwhile increase the acid density and medium strength acid site. The conversion of triolein increased linearly with the amount of medium strength acid sites. This result suggests that medium-strength acidity of catalyst is a critical factor in determining deoxygenation activities. In addition, the presence of mesopores allow the diffusion of triolein molecules and improve the selectivity. Hence, mesoporous TiO₂ with Lewis acidity is a fascinating catalyst and hydrogen donor in high-value green fuel.     

Catalytic pyrolysis of pinewood over ZSM-5 and CaO for aromatic hydrocarbon: Analytical Py-GC/MS study

A higher amount of oxygenates is the main constraint for higher yield and quality of aromatics in catalytic pyrolysis while a study of hydrocarbon production with a balance of reactive species lies importance in the catalytic upgrading of pyrolytic vapor. Catalytic pyrolysis of pinewood sawdust over acidic (ZSM-5) and basic (CaO) catalyst was conducted by means of Py-GC/MS to evaluate the effect of biomass to catalyst loading ratio on aromatic hydrocarbon production. Catalytic pyrolysis with four different biomass to catalyst ratios (0.25:1, 0.5:1, 1:1, and 2:1) and non-catalytic pyrolysis were conducted. It has been obtained that ZSM-5 showed better catalytic activity in terms of a high fraction of aromatic hydrocarbon. The ZSM-5 catalyst showed a potential on the aromatization as the yield of aromatic hydrocarbon was increased with a higher amount of ZSM-5 catalyst and the highest yield of aromatics (42.19 wt %) was observed for biomass to catalyst ratio of 0.25:1. On the other hand, basic CaO catalyst was not selective to aromatic hydrocarbon from pinewood sawdust but explored high deacidification reaction in pyrolytic vapor compared to ZSM-5 catalyst, whereas non-catalytic pyrolysis resulted in acidic species (13.45 wt %) and phenolics (46.5 wt %). Based on the results, ZSM-5 catalyst can only be suggested for catalytic pyrolysis of pinewood sawdust for aromatic hydrocarbon production.     

Production of aromatic compounds from catalytic fast pyrolysis of Jatropha residues using metal/HZSM-5 prepared by ion-exchange and impregnation methods

Metal based-zeolite catalysts were successfully prepared by two different methods including ion-exchange and wet impregnation. HZSM-5 synthesized by hydrothermal method at 160 °C was used as a support for loading metals including Co, Ni, Mo, Ga and Pd. The metal/HZSM-5 had surface area and pore size of 530–677 m²/g and 22.9-26.0 Å. Non- and catalytic fast pyrolysis of Jatropha residues using metal/HZSM-5 were studied using an analytical pyrolysis-GC/MS at 500 °C. Non-catalytic pyrolysis vapors contained primarily high levels acid (50.7%), N-containing compounds (20.3%), other oxygenated compounds including ketones, alcohols, esters, ethers, phenols and sugars (25.0%), while generated small amount of aromatic and aliphatic hydrocarbons of 3.0% and 1.0%. The addition of synthesized metal/HZSM-5 improved the aromatic selectivity up to 91–97% and decreased the undesirable oxygenated (0.6–4.0%) and N-containing compounds (1.8–4.6%). The aromatic selectivity produced by metal-ion exchanged catalysts was slightly higher than that produced by impregnated ones. At high catalyst content (biomass to catalyst ratio of 1:10), Mo/HZSM-5 showed the highest aromatic selectivity of 97% for ion-exchanged catalysts and Ga/HZSM-5 revealed the highest aromatics of 95% for impregnated catalysts. The formation of aromatic compounds could be beneficial to improve calorific values of bio-oils. The presence of metal/HZSM-5 from both preparation methods greatly enhanced MAHs selectivity including benzene, toluene, and xylene (BTX), while substantially reduced unfavorable PAHs such as napthalenes.     

Impact of acid-modified ZSM-5 on hydrocarbon yield of catalytic co-pyrolysis of poplar wood sawdust and high-density polyethylene by Py-GC/MS analysis

Co-pyrolysis of poplar wood sawdust and high-density polyethylene at a mass ratio of 1:1 over acid-modified ZSM-5 was studied by Py-GC/MS at catalyst to feedstock mass ratio of 1:1 to enhance hydrocarbon formation in the pyrolytic vapour. Catalysts were modified by wet impregnation using sulfuric acid (0.1 M, 0.3 M, 0.5 M and 0.7 M). Results showed that acid treatment affects the catalytic activity of ZSM-5 by changing the amount of acid sites. Co-pyrolysis with HDPE resulted in high relative content of olefin(53.32%) than pyrolysis of poplar (16.6%) and significantly reduces the amount of oxygenates except alcohol. In catalytic co-pyrolysis over acid-modified ZSM-5, the share of olefin was between 56.20% and 59.7%, whereas the lowest amount was 49.53% over P-ZSM-5. The relative content of alkane over acid-modified ZSM-5 was in the range of 23.29–25.96% and higher than that with P-ZSM-5 (21.18%). Importantly, ZSM-5 (0.5 M) was most selective one for aromatic hydrocarbon (12.72%), leading to the maximum share of hydrocarbon of 93.18% when the lowest value was 76.84% over P-ZSM-5. Furthermore, ZSM-5 (0.5 M) showed better deoxygenation among catalysts used in this study. This research could be suggested as a reference for the research of co-pyrolysis of biomass and plastic.     

Catalytic Oligomerization of ethylene over nano-sized HZSM-5

The nano-sized HZSM-5 zeolites with different Si/Al ratios were pretreated, characterized, and tested in ethylene oligomerization performed in a fixed-bed reactor under relatively mild conditions. The effects of catalyst acidity and reaction temperature on the activity, selectivity and stability were investigated, and a possible reaction route of ethylene over acidic sites of nano-sized HZSM-5 catalyst was proposed. In comparison with micro-sized HZSM-5 zeolite, nano-sized HZSM-5 zeolites exhibited higher activity and better resistance to deactivation. Under optimal conditions (T = 275–300 °C, P = 3.0 MPa, WHSV = 1.0 h⁻¹), The average ethylene conversion was 62.5% over the nano-sized HZSM-5 with an Si/Al ratio of 80, while the selectivity to C₄₊ olefins and α-olefins was 64.3% and 13.3%, respectively. Furthermore, the products of ethylene oligomerization were a complex hydrocarbon mixture due to the acid-catalyzed secondary reactions, for which the distribution of even and odd numbered carbon atoms formed a continuous volcanic shape mainly centered on C₆–C₁₀. Furthermore, these tests demonstrate that the activity and selectivity of ethylene oligomerization depend on the operating conditions and the acidity of the catalysts. These results indicate that the Brønsted acid sites may be mainly responsible for secondary reactions and deactivation of the catalyst, whereas the Lewis acid sites may be more advantageous for ethylene oligomerization.     

Comprehensive research of in situ upgrading of sawdust fast pyrolysis vapors over HZSM-5 catalyst for producing renewable light aromatics

Catalytic fast pyrolysis of sawdust was investigated over HZSM-5 zeolites (SiO₂/Al₂O₃ = 25, 50 and 80) in a drop tube quartz reactor for production of green aromatics and olefins. The effects of temperature, weight hourly space velocity (WHSV), SiO₂/Al₂O₃ ratio and atmosphere on yield and selectivity of aromatics were investigated. The results show that almost all small organic oxygen species in initial volatiles were converted into gaseous hydrocarbons and aromatics after in situ catalysis of HZSM-5. HZSM-5 whose SiO₂/Al₂O₃ is 25 exhibited the best performance with the aromatics yield of 21.8% on carbon basis at 500 °C. However, HZSM-5 can act as cracking and aromatization catalyst, but not as an agent to promote hydrogenation. The ESI-MS revealed the most abundant macromolecular compounds in initial volatiles were O₁O₂₇ species with 0–20 double bond equivalent (DBE) values and 5–40 carbon numbers, while the macromolecules were O₁O₉ species with 2–12 DBE and 10–25 carbon numbers after upgrading. Furthermore, the formation of coke on catalysts was influenced by the properties of HZSM-5 and experimental conditions.