Project description:The current plastic value chain is highly linear, leading to large amounts of waste plastics that harm the environment and human health. Recycling is required, and among the options, catalytic pyrolysis is particularly suited to convert polyolefin-rich plastic waste into useful chemicals such as benzene, toluene, and xylene (BTX). In this paper, we demonstrate ex situ catalytic pyrolysis of polypropylene in a continuous double-fluidized-bed reactor to produce BTX. The optimal pyrolysis temperature in the first fluidized-bed reactor was 550 °C, giving a BTX yield of 22.3 wt % (based on PP input). Lowering the nitrogen flow rate and the use of smaller catalyst particle sizes favor BTX formation. Our novel reactor concept showed good operational stability at longer times on stream (TOS, 10 h). Catalyst activity was slightly reduced during TOS, as is evident from a small decrease in BTX yields. Detailed catalyst characterization studies showed that coke formation is the main reason for catalyst deactivation. In addition, chemoselectivity was also a function of TOS and the selectivity to benzene and toluene decreased, while higher amounts of xylenes were formed.
Project description:Catalytic fast pyrolysis (CFP) of biomass is a versatile thermochemical process for producing a biogenic oil that can be further upgraded to sustainable transportation fuels, chemicals, and materials. CFP oil exhibits reduced oxygen content and improved thermal stability compared to noncatalytic fast pyrolysis oil. However, some level of reactive oxygenates remain in CFP oils, and reactions between these species can result in molecular weight growth and increased viscosity, leading to the potential for challenges during transportation, storage, and downstream processing. Previous research has provided considerable insight into the reactivity of noncatalytic fast pyrolysis oils, but CFP oils have yet to be studied in a similar fashion. Consequently, the degree of catalytic upgrading that is necessary to effectively stabilize CFP oils has yet to be established, and little is known about the mechanistic details underlying the process. The current study addresses this knowledge gap by controlling the CFP reaction conditions to systematically vary the oxygen content of the resulting oil. Accelerated thermal reactivity studies were then performed, and the CFP oils were analyzed using gas chromatography-mass spectrometry (GC-MS), Fourier transform ion cyclotron mass spectrometry (FT-ICR MS), gel permeation chromatography (GPC), and viscometry to evaluate the impact of heating on their physical and chemical properties. The results revealed that short chain carbonyls, anhydrosugars, and lignin derivatives with conjugated vinyl groups likely play a role in the thermal reactivity of CFP oils. Additionally, experiments performed across a wide variety of feedstocks revealed relatively low thermal reactivity for CFP oils with oxygen contents of <20 wt %. However, above this threshold value, the thermal reactivity grew exponentially as a function of oxygen content, resulting in large increases in viscosity and molecular weight. These results serve to deepen the mechanistic understanding of CFP oil thermal reactivity and help inform the development of quality specifications for catalytic upgrading to effectively stabilize CFP oils.
Project description:The present study is dedicated to the experimental verification of a concept for the hydrogenolysis of glycerol over in situ-generated Cu dispersed particles (Cu-DP). The Cu-DP were generated by in situ reduction of a precursor salt (Cu(OAc)2, CuSO4, CuCl2) in the presence of KOH and were active in glycerol conversion under hydrogen (T = 200-220 °C, p(H2) = 1-4 MPa), where 1,2-propylene glycol (PG) and lactic acid (LA) were detected to be the main products. The influence of the reaction conditions (temperature, hydrogen pressure, reaction time, catalyst-to-feed ratio and the KOH/Cu ratio) on the yields of the products is described. It was shown that the selectivity between the PG and LA could be tuned by changing p(H2) or by the KOH amount, i.e., higher yields of LA corresponded to lower p(H2) and higher alkalinity of the reaction media. The activity of the in situ-generated Cu-DP was found to be comparable to that of an industrial Cu-Cr2O3 catalyst. The Cu-DP catalysts were characterized by XRD, XPS, HRTEM and SEM. During the reaction, the catalyst evolved by the sintering and recrystallization of the separate Cu-DP; the crystallite sizes after 1 and 15 h reaction times amounted to 35 and 49 nm, respectively.
Project description:Microalgae are attractive feedstocks for biofuel production and are especially suitable for thermochemical conversion due to the presence of thermally labile constituents-lipids, starch and protein. However, the thermal degradation of starch and proteins produces water as well as other O- and N-compounds that are mixed-in with energy-dense lipid pyrolysis products. To produce hydrocarbon-rich products from microalgae biomass, we assessed in situ and ex situ catalytic pyrolysis of a lipid-rich Chlorella sp. in the presence of the HZSM-5 zeolite catalyst over a temperature range of 450-550°C. Results show that product yields and compositions were similar under both in situ and ex situ conditions with benzene, toluene and xylene produced as the primary aromatic products. Yields of aromatics increased with increasing temperature and the highest aromatic yield (36.4% g aromatics/g ash-free microalgae) and selectivity (87% g aromatics/g bio-oil) was obtained at 550°C. Also, at this temperature, oxygenates and nitrogenous compounds were not detected among the liquid products during ex situ catalytic pyrolysis. We also assessed the feasibility of a two-step fractional pyrolysis approach integrated with vapor phase catalytic upgrading. In these experiments, the biomass was first pyrolyzed at 320°C to degrade and volatilize starch, protein and free fatty acids. Then, the residual biomass was pyrolyzed again at 450°C to recover products from triglyceride decomposition. The volatiles from each fraction were passed through an ex situ catalyst bed. Results showed that net product yields from the 2-step process were similar to the single step ex situ catalytic pyrolysis at 450°C indicating that tailored vapor phase upgrading can be applied to allow separate recovery of products from the chemically distinct biomass components-(1) lower calorific value starch and proteins and (2) energy-dense lipids.
Project description:A novel pyrolysis char (PC), prepared by H3PO4 catalytic pyrolysis of oily sludge (OS), was presented to remove methylene blue (MB) dye from aqueous solution for the first time. The optimal preparation conditions (catalytic pyrolysis temperature of 411 °C, H3PO4 impregnation ratio of 2.44, and catalytic pyrolysis time of 59 min) were predicted by the response surface methodology. The optimal PC exhibited favorable hierarchical porous properties, which brought a large adsorption capability (322.89 mg/g). The adsorption process fitted well with the Langmuir model and pseudo-second order model. In addition, thermodynamic parameters showed that the adsorption process was endothermic (ΔH 0 > 0) and spontaneous (ΔG 0 < 0). The adsorption capability was strongly influenced by coexisting metal ions due to the competitive adsorption effect. The inhibition for MB adsorption was arranged in the following order: Al3+ > Fe3+ > Mg2+ > Ca2+ > K+ > Na+. The adsorption mechanism of MB onto the OS-derived PC includes pore filling, π-π interactions, and electrostatic interactions. The as-obtained PC adsorbent exhibited good reusability performance, which leads to great potential in practical application for wastewater treatment.
Project description:Realizing the directional conversion of volatile matter (especially tar) from catalytic pyrolysis of low-rank coal (LRC) and reducing the consumption of catalysts have been considered great challenges for the classified utilization of LRC. In order to realize this aim, in this work, combined in situ and ex situ catalytic pyrolyses (IECPs) were first applied to the conversion of low-rank coal. A small amount of in situ ZSM-5 (5 wt %) was mixed with LRC to regulate the pyrolysis reaction, and then a large amount of ex situ ZSM-5 (100 wt %) was used to control the volatiles produced by pyrolysis. The IECPs (550 °C) of LRCs were investigated in a fixed-bed reactor. For three LRCs with different coalification degrees, IECPs could obviously reduce the complexity of the tar components. When ZSM-5 dosage was 5 wt % and the reaction temperature was 550 °C, the relative content of BTX in ZT, BS, and JY tar increased from 20.23, 15.86, and 14.59% to 84.79, 77.26, and 50.11 area %, respectively. The relative contents of aliphatic hydrocarbons with a complex composition and a low price decreased from 67.84, 34.47, and 33.89 area % to 3.02, 1.81, and 7.60 area %, respectively. The catalysis mechanism was explored by TG-FTIR spectroscopy, which revealed that ZSM-5 had a great influence on the migration of aliphatic hydrocarbon intermediates in IECP, such that large amounts of aliphatic hydrocarbons of complex composition produced by IECP tended to be converted to small molecular substances (gas) or aromatic hydrocarbons (tar). It will provide a new theoretical support for the staged utilization of LRC.
Project description:In this study, soybean straw (SS) as a promising source of glycolaldehyde-rich bio-oil production and extraction was investigated. Proximate and ultimate analysis of SS was performed to examine the feasibility and suitability of SS for thermochemical conversion design. The effect of the co-catalyst (CaCl2 + ash) on glycolaldehyde concentration (%) was examined. Thermogravimetric-Fourier-transform infrared (TG-FTIR) analysis was applied to optimize the pyrolysis temperature and biomass-to-catalyst ratio for glycolaldehyde-rich bio-oil production. By TG-FTIR analysis, the highest glycolaldehyde concentration of 8.57% was obtained at 500 °C without the catalyst, while 12.76 and 13.56% were obtained with the catalyst at 500 °C for a 1:6 ratio of SS-to-CaCl2 and a 1:4 ratio of SS-to-ash, respectively. Meanwhile, the highest glycolaldehyde concentrations (%) determined by gas chromatography-mass spectrometry (GC-MS) analysis for bio-oils produced at 500 °C (without the catalyst), a 1:6 ratio of SS-to-CaCl2, and a 1:4 ratio of SS-to-ash were found to be 11.3, 17.1, and 16.8%, respectively. These outcomes were fully consistent with the TG-FTIR results. Moreover, the effect of temperature on product distribution was investigated, and the highest bio-oil yield was achieved at 500 °C as 56.1%. This research work aims to develop an environment-friendly extraction technique involving aqueous-based imitation for glycolaldehyde extraction with 23.6% yield. Meanwhile, proton nuclear magnetic resonance (1H NMR) analysis was used to confirm the purity of the extracted glycolaldehyde, which was found as 91%.
Project description:A series of ceria-based solid solution metal oxides were prepared by co-precipitation and evaluated as catalysts for glycerol cleavage, principally to methanol. The catalyst activity and selectivity to methanol were investigated with respect to the reducibility of the catalysts. Oxides comprising Ce-Pr and Ce-Zr were prepared, calcined and compared to CeO2, Pr6O11 and ZrO2. The oxygen storage capacity of the catalysts was examined with analysis of Raman spectroscopic measurements and a temperature programmed reduction, oxidation and reduction cycle. The incorporation of Pr resulted in significant defects, as evidenced by Raman spectroscopy. The materials were evaluated as catalysts for the glycerol to methanol reaction, and it was found that an increased defect density or reducibility was beneficial. The space-time yield of methanol normalized to surface area over CeO2 was found to be 0.052 mmolMeOH m-2 h-1, and over CeZrO2 and CePrO2, this was to 0.029 and 0.076 mmolMeOH m-2 h-1, respectively. The inclusion of Pr reduced the surface area; however, the carbon mole selectivity to methanol and ethylene glycol remained relatively high, suggesting a shift in the reaction pathway compared to that over ceria. This article is part of a discussion meeting issue 'Science to enable the circular economy'.
Project description:Waste lignin is a potential source of renewable fuels and other chemical precursors under catalytic pyrolysis. For this purpose, four mixed metal oxide catalytic mixtures (Cat) derived from Na2CO3, CeO2 and ZrO2 were synthesised in varying compositions and utilised in a fixed bed reactor for catalytic vapour upgrading of Etek lignin pyrolysis products at 600 °C. The catalytic mixtures were analysed and characterised using XRD analysis, whilst pyrolysis products were analysed for distribution of products using FTIR, GC-MS and EA. Substantial phenolic content (20 wt%) was obtained when using equimolar catalytic mixture A (Cat_A), however the majority of these phenols were guaiacol derivatives, suggesting the catalytic mixture employed did not favour deep demethoxylation. Despite this, addition of 40-50% ceria to NaZrO2 resulted in a remarkable reduction of coke to 4 wt%, compared to ~9 wt% of NaZrO2. CeO2 content higher than 50% favoured the increase in conversion of the holo-cellulose fraction, enriching the bio-oil in aldehydes, ketones and cyclopentanones. Of the catalytic mixtures studied, equimolar metal oxides content (Cat_A) appears to showcase the optimal characteristics for phenolics production and coking reduction.
Project description:Fast pyrolysis bio-oils possess unfavorable physicochemical properties and poor stability, in large part, owing to the presence of carboxylic acids, which hinders their use as biofuels. Catalytic esterification offers an atom- and energy-efficient route to upgrade pyrolysis bio-oils. Propyl sulfonic acid (PrSO3 H) silicas are active for carboxylic acid esterification but suffer mass-transport limitations for bulky substrates. The incorporation of macropores (200 nm) enhances the activity of mesoporous SBA-15 architectures (post-functionalized by hydrothermal saline-promoted grafting) for the esterification of linear carboxylic acids, with the magnitude of the turnover frequency (TOF) enhancement increasing with carboxylic acid chain length from 5 % (C3 ) to 110 % (C12 ). Macroporous-mesoporous PrSO3 H/SBA-15 also provides a two-fold TOF enhancement over its mesoporous analogue for the esterification of a real, thermal fast-pyrolysis bio-oil derived from woodchips. The total acid number was reduced by 57 %, as determined by GC×GC-time-of-flight mass spectrometry (GC×GC-ToFMS), which indicated ester and ether formation accompanying the loss of acid, phenolic, aldehyde, and ketone components.