Thermal decomposition of expanded polystyrene in a pebble bed reactor to get higher liquid fraction yield at low temperatures

Expanded polystyrene is one of the polymers produced in large quantities due to its versatile application in different fields. This polymer is one of the most intractable components in municipal solid waste. Disposal of polymeric material by pyrolysis or catalytic cracking yields valuable hydrocarbon fuels or monomers. Literature reports different types of reactors and arrangements that have uniform temperatures during pyrolysis and catalytic cracking. The present study focuses on reducing the temperature to maximize the quantity of styrene monomer in the liquid product. A bench scale reactor has been developed to recover the styrene monomer and other valuable chemicals. Experiments were carried under partial oxidation and vacuum conditions in the temperature range of 300-500 degrees C. In the pyrolysis optimization studies, the best atmospheric condition was determined to be vacuum, the pyrolysis temperature should be 500 degrees C, yield of liquid product obtained was 91.7% and yield of styrene obtained was 85.5%. In the characterization studies, distillation and IR spectroscopy experiments were carried out. The remaining of the liquid product comprises of benzene, ethyl benzene, and styrene dimers and trimers.     

Investigation of hydrocyclones for the separation of shredded fridge plastics

The recycling of fridges produces a mixed plastic product of limited value. In order to maximise its value, the separation of the individual polymers that include high impact polystyrene (HIPS), acrylonitrile butadiene styrene (ABS), polyvinyl chloride (PVC) and polyethylene (PE) must take place. The effectiveness of a hydrocyclone system for the separation of these plastics, using both water and calcium chloride solutions, has been investigated. In addition a qualitative procedure for the determination of the HIPS content of a mixed ABS/HIPS product, by selective dissolution in R-limonene, has been developed. It was found that the effective density of separation depended on the particle size and aspect ratio. As the particle size and aspect ratio decreased, the separation became more efficient and the offset between separation density and hydrocyclone medium density decreased. This suggests that, for efficient density separation, closely sized, fine plastic fractions are required. Using these criteria, it was found that the removal of high density plastic such as PVC was readily achieved using a hydrocyclone. A partial separation of HIPS from ABS was found to be possible, taking advantage of a small density difference, using a hydrocyclone medium density of 1035kgm(-3).     

Analysis of Products Generated from the Thermal and Catalytic Degradation of Pure and Waste Polyolefins using Py-GC/MS

The possibility of transforming waste plastics into valuable hydrocarbons via catalytic cracking and reforming is attracting increasing interest. Pyrolysis coupled with Gas Chromatographic separation and Mass Spectrometry detection (Py-GC/MS) has been used in this work to study the product selectivity of various catalysts in the conversion of pure and residual polyethylene samples into hydrocarbon products. Five acid solids of comparable aluminium contents but different textural and acid properties were tested as catalysts, including three zeolites (standard ZSM-5, nanocrystalline n-ZSM-5 and Beta) and two mesostructured solids (Al-MCM-41 and Al-SBA-15). Thermal cracking of the pure and residual polymers generated a similar range of products to each other, with a high proportion of linear paraffins and olefins of varying lengths. The presence of zeolitic materials resulted in complete elimination of heavy linear products, an increase in the light hydrocarbon fraction and a marked selectivity towards the formation of single-ring aromatic species, particularly benzene, toluene and xylene. Aromatic formation was particularly notable with the small crystal size n-ZSM-5 (aromatic selectivity up to 53.9%) and less marked in the case of standard ZSM-5 (up to 36.4%) and Beta zeolite (up to 35.0%). Mesostructured catalysts like Al-MCM-41 and Al-SBA-15 favoured the production of light C₂–C₅ hydrocarbons (up to 57.9%) while the formation of aromatic products was significantly lower than with zeolitic materials. The paper examines the extent and the causes for this product selectivity and discusses its connection with the acid and textural properties of each catalyst. It was also observed that, under the experimental conditions employed, the products generated were not significantly affected by the nature and origin of the polymers employed.     

Effects of heating rate and temperature on product distribution of poly-lactic acid and poly-3-hydroxybutyrate-co-3-hydroxyhexanoate

In this study, poly-lactic acid (PLA) and poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (PHBH) were pyrolyzed at various temperatures (300, 350, 400, 500, 600, and 700 °C) and heating rates (5, 10, 20, 30, and 40 °C min⁻¹) using a pyrolysis–gas chromatograph/mass spectrometer (Py–GC/MS). The results revealed that the main pyrolysis products of PLA were acetaldehyde, lactide (including meso-lactide and d-, l-lactide), and oligomers. Crotonic acid and its oligomers accounted for most of the PHBH pyrolyzates. The pyrolysis temperature significantly correlated with the product distribution, but the heating rate had a small effect on the product distribution. Lactide and crotonic acid were two kinds of high-value chemicals, and their highest yields were obtained at 400 and 600 °C with 29.7 and 72.6 area %, respectively. Secondary reactions could not be neglected at 700 °C, and acetaldehyde and crotonic acid decreased to 65.0 and 69.6 area %, respectively. These results imply that pyrolyzate selectivity can be controlled by temperature management during pyrolysis.

     

Construction, Characterization and Biological Activity of Chiral and Thermally Stable Nanostructured Poly(Ester-Imide)s as Tyrosine-Containing Pseudo-Poly(Amino Acid)s

In this paper we studied the synthesis of biodegradable optically active poly(ester-imide)s containing different amino acid residues in the main chain. These pseudo-poly(amino acid)s were synthesized by polycondensation of N,N′-(pyromellitoyl)-bis-l-tyrosine dimethyl ester as a diphenolic monomer and two chiral trimellitic anhydride-derived diacid monomers containing s-valine and l-methionine. The direct polycondensation reaction of these diacids with aromatic diol was carried out in a system of tosyl chloride (TsCl), pyridine (Py) and N,N′-dimethylformamide (DMF) as a condensing agent. The structures and morphology of these polymers were studied by FT-IR, ¹H-NMR, powder X-ray diffraction, field emission scanning electron microscopy (FE-SEM), specific rotation, elemental and thermogravimetric analysis (TGA) techniques. TGA profiles indicate that the resulting PEIs have a good thermal stability. Morphology probes showed these polymers were noncrystalline and nanostructured polymers. The monomers and prepared polymers were buried under the soil to study the sensitivity of the monomers and the obtained polymers to microbial degradation. The high microbial population and prominent dehydrogenase activity in the soil containing polymers showed that the synthesized polymers are biologically active and microbiologically biodegradable. Wheat seedling growth in the soil buried with synthetic polymers not only confirmed non-toxicity of polymers but also showed possibility of phyto-remediation in polymer-contaminated soils.     

Pyrolysis of municipal plastic wastes II: Influence of raw material composition under catalytic conditions

In this work, the results obtained in catalytic pyrolysis of three plastic waste streams which are the rejects of an industrial packing wastes sorting plant are presented. The samples have been pyrolysed in a 3.5 dm(3) reactor under semi-batch conditions at 440 °C for 30 min in nitrogen atmosphere. Commercial ZSM-5 zeolite has been used as catalyst in liquid phase contact. In every case, high HHV gases and liquids which can be useful as fuels or source of chemicals are obtained. A solid fraction composed of the inorganic material contained in the raw materials and some char formed in the pyrolysis process is also obtained. The zeolite has shown to be very effective to produce liquids with great aromatics content and C3-C4 fraction rich gases, even though the raw material was mainly composed of polyolefins. The characteristics of the pyrolysis products as well as the effect of the catalyst vary depending on the composition of the raw material. When paper rich samples are pyrolysed, ZSM-5 zeolite increases water production and reduces CO and CO(2) generation. If stepwise pyrolysis is applied to such sample, the aqueous liquid phase can be separated from the organic liquid fraction in a first low temperature step.     

Novel Bioactive Chiral Poly(amide–imide)s Containing Different Amino Acids Linkages: Studies on Synthesis, Characterization and Biodegradability

In this paper chiral bioactive poly(amide–imide)s (PAI)s were synthesized from four different diacids containing chiral amino acids with 4,4′-methylene bis(3-chloro 2,6-diethylaniline) as a diamine via direct polycondensation reaction in a system of tetra-n-butylammonium bromide and triphenyl phosphite as a condensing agent. The structures of these polymers were confirmed by FT-IR, ¹H-NMR, specific rotation, elemental and thermogravimetric analysis (TGA) techniques. TGA showed that the 10 % weight loss temperature in a nitrogen atmosphere was more than 378 °C, which indicates that the resulting PAIs have a good thermal stability. The biodegradability of the monomers and prepared polymers was investigated in culture media and soil burial test for assessment of the susceptibility of these compounds to microbial degradation. The results showed that the synthesized monomers and theirs derived polymers are biologically active and nontoxic to microbial growth.     

Tar and soot generation behaviors from ABS,PC and PE pyrolysis

In this study we performed a non-isothermal thermogravimetric analysis on three thermoplastics—ABS, PC and PE. The Coats and Redfern method (Nature 201:68–69, 1964) was then used to approximate the kinetic parameters of each material. In addition, we performed a series of pyrolysis experiments in a batch reactor, for each plastic. The experiments were performed over the temperature range of 600–1000 °C at a constant residence time. The liquid and solid products of the pyrolysis, were collected, separated and weighted. Those products were categorized as soot, tar and char (PC only), and their relative weight to initial sample weight (DAF) was plotted against the temperature. The tar measured was exclusively medium to high molecular weight (>80 g/mol). Results revealed that relative tar and soot production, for all three materials, first increases and then decreases with temperature increase. The maximum achieved tar yields for ABS, PC and PE were at 700, 650 and 800 °C, respectively; and the maximum soot yields were at 1000, 1000, 950 °C, respectively.     

Pyrolysis characteristics of the mixture of printed circuit board scraps and coal powder

Thermogravimetric (TG) analysis and infrared spectroscopy were used to analyze the pyrolysis characteristics of printed circuit board scraps (PCBs), coal powder and their mixtures under nitrogen atmosphere. The experimental results show that there is a large difference between waste PCBs and coal powder in pyrolysis processing. The pyrolysis properties of the mixing samples are the result of interaction of the PCBs and coal powder, which is influenced by the content of mixture. The degree of pyrolysis and pyrolysis properties of the mixture are much better than that of the single component. The TG and the differential thermogravimetric (DTG) curves of the PCBs mixed with coal powder move towards the high-temperature zone with increasing amount of coal powder and subsequently the DTG peak also becomes wider. The Coats–Redfern integral method was used to determine the kinetic parameters of pyrolysis reaction mechanism with the different proportion of mixture. The gas of pyrolysis mainly composes of CO₂, CO, H₂O and some hydrocarbon. The bromide characteristic absorption peak has been detected obviously in the pyrolysis gas of PCBs. On the contrary, the absorption peak of the bromide is not obvious in pyrolysis gas of the PCBs samples adding 40% coal powder.     

废塑料的回收利用

介绍了国外废塑料再生利用、热分散回收低分子化合物和焚烧回收热能的技术与方法。     

Extraction of polybrominated diphenyl ethers contained in waste high impact polystyrene by supercritical carbon dioxide

A new recycling process for the supercritical CO₂ (sc-CO₂) extraction of polybrominated diphenyl ethers from waste high impact polystyrene (HIPS) was developed in this paper. HIPS was first dissolved in d-limonene. The remaining decabromo diphenyl ether (decaBDE) particles in solution were then removed by centrifugation, and the PBDEs in the centrifugate solution were further extracted by sc-CO₂. The influence of temperature and pressure, the volume ratio of sc-CO₂ to plastic solution, and the concentration of decaBDE in the solution on the separating efficiency were investigated. The decaBDE particles in 20 % of the HIPS solution can be removed by centrifugation at a speed of 10,000 r/min at 30 °C. The suitable sc-CO₂ fluid conditions were 65 °C and 20 MPa, and the optimum volume ratio of the sc-CO₂ to the HIPS solution was 2:1. More than 97 % of the PBDEs were successfully removed, and the concentration of PBDE residues in the recycled HIPS was reduced to lower than 0.1 % (dry) by this recycling process.     

Structural Differences Between Lignin Model Polymers Synthesized from Various Monomers

In a plant cell wall, lignin is synthesized from several monomeric precursors, combined in various ratios. The variation in monomer type and quantity enables multifunctional role of lignin in plants. Thus, it is important to know how different combinations of lignin monomers impact variability of bond types and local structural changes in the polymer. Lignin model polymers are a good model system for studies of relation between variations of the starting monomers and structural variations within the polymer. We synthesized lignin model polymers from three monomers, CF??based on coniferyl alcohol and ferulic acid in monomer proportions 5:1 and 10:1 (w/w), CP??based on coniferyl alcohol and p-coumaric acid in proportion 10:1 (w/w) and CA??based on pure coniferyl alcohol. We studied structural modifications in the obtained polymers, by combining fluorescence microscopy and spectroscopy, FT-IR and Raman spectroscopy, in parallel with determination of polymers?? molecular mass distribution. The differences in the low M _w region of the distribution curves of the 10:1 polymers in comparison with the CA polymer may be connected with the increased content of C=C bonds and decreased content of condensed structures, as observed in FT-IR spectra and indicated by the analysis of fluorescence spectra. The 5:1 CF polymer contains a different type of structure in comparison with the 10:1 CF polymers, reflected in its simpler M _w distribution, higher homogeneity of the fluorescence emitting structures and in the appearance of a new high-wavelength emission component. We propose that this component may originate from ??-conjugated chains, which are longer in this polymer. The results are a contribution to the understanding of the involvement of structural variations of lignin polymers in the cell wall structural plasticity.     

Effect of some environmentally degradable materials on the pyrolysis of plastics II: influence of cellulose and lignin on the pyrolysis of complex mixtures

Pyrolysis of polymer mixtures with a composition similar to that of municipal plastic waste containing polyvinyl chloride (PVC) and of municipal plastic waste free of PVC was performed in the presence of components of biomass, namely lignin, cellulose, or both. The pyrolysis products were characterized by standard methods utilized in the petrochemical industry, i.e., paraffins-isoparaffinsolefins-naphthenes-aromatics analysis, proton nuclear magnetic resonance and infrared spectroscopy, and gas chromatography-mass spectrometry. Up to 3 wt% lignin, cellulose, or both in mixed polymers changed the material balance of pyrolysis by decreasing the amount of waxy products. The presence of both PVC and biomass components significantly changed the material balance by decreasing the waxy product yield and increasing the gas and coke yield. The composition of all pyrolysis products was also modified with the addition of PVC, components of biomass, or both.     

Effect of Poly(l-Lactide) and Poly(Butylene Succinate) on the Growth of Red Pepper and Tomato

Seeds of red pepper and tomato were sowed and cultivated in a soil blended with powdery poly(l-lactide) (PLLA), and poly(butylene succinate) (PBS). PBS depressed the growth of the two plants significantly even at a concentration as low as 5%, whereas PLLA up to 35% affected negligibly or even boosted the growth of the two plants. pH and number of microbial cells in the soil after 80 days of cultivation were almost the same independently whether the soil was blended with the two polymers or not. In contrast, the molecular weight of PBS decreased much faster than that of PLLA. Because succinic acid and 1,4-butane diol, from which PBS was synthesized, exhibited toxicity to both plant and animal cells to retard the germination rate of young radish seeds and to deform the morphology of HeLa cells significantly [1], the monomers and the oligomers produced from the PBS degradation should have a detrimental influence on the growth of the two plants.     

Investigation on thermal dechlorination and catalytic pyrolysis in a continuous process for liquid fuel recovery from mixed plastic wastes

A continuous system (feeding rate >1 kg/h) consisting of thermal dechlorination pre-treatment and catalytic pyrolysis with Fe-restructured clay (Fe-RC) catalyst was developed for feedstock recycling of PVC-containing mixed plastic waste. The vented screw conveyor which was specially designed for continuous dechlorination was able to achieve dechlorination efficiency of over 90 % with a feedstock retention time longer than 35.5 min. The chlorine content of the pyrolytic oil obtained after dechlorination was in the range of 6.08–39.50 ppm, which meet the specification for reclamation pyrolytic oil in Japan. Fe-RC was found to significantly improve the yield of pyrolytic oil (achieved to 83.73 wt%) at the optimized pyrolysis temperature of 450 °C and catalyst dosage of 60 g. With the optimized parameters, Fe-RC showed high selectivity for the C₉–C₁₂ and C₁₃–C₁₉ oil fraction, which are the major constituents of kerosene and diesel fuel, demonstrating that this catalyst can be applied in the pyrolysis of mixed plastic wastes for the production of kerosene and diesel fuel. Overall, the continuous process exhibited high stability and consistently high-oil yield upon reaching steady state, indicating its potential up-scaling application in the industry.     

WEEE recycling: Pyrolysis of fire retardant model polymers

Pyrolysis treatments of model polymers were made with the aim of studying the recycling of wastes from electronic, electric equipment containing brominated flame retardants. Pyrolysis of flame retarded high impact polystyrene and epoxy resins were made both in flow and closed systems. Products of pyrolysis were analysed with FT-IR spectroscopy and GC-MS and the evolution of bromine was followed with a bromine ion specific electrode. The effect of alkali on pyrolysis was also studied demonstrating, as far epoxy resin is concerned, to be effective on decreasing bromine content in oil and volatile products leading to the recovery of bromine from the residue by washing. The alkali treatment was shown to be less effective in styrenic polymers containing brominated flame retardants.     

Pyrolysis of polyolefins for increasing the yield of monomers' recovery

Pyrolysis of plastic waste is an alternative way of plastic recovery and could be a potential solution for the increasing stream of solid waste. The objective of this work was to increase the yield the gaseous olefins (monomers) as feedstock for polymerization process and to test the applicability of a commercial Ziegler-Natta (Z-N): TiCl(4)/MgCl(2) for cracking a mixture of polyolefins consisted of 46%wt. of low density polyethylene (LDPE), 30%wt. of high density polyethylene (HDPE) and 24%wt. of polypropylene (PP). Two sets of experiments have been carried out at 500 and 650°C via catalytic pyrolysis (1% of Z-N catalyst) and at 650 and 730°C via only-thermal pyrolysis. These experiments have been conducted in a lab-scale, fluidized quartz-bed reactor of a capacity of 1-3kg/h at Hamburg University. The results revealed a strong influence of temperature and presence of catalyst on the product distribution. The ratios of gas/liquid/solid mass fractions via thermal pyrolysis were: 36.9/48.4/15.7%wt. and 42.4/44.7/13.9%wt. at 650 and 730°C while via catalytic pyrolysis were: 6.5/89.0/4.5%wt. and 54.3/41.9/3.8%wt. at 500 and 650°C, respectively. At 650°C the monomer generation increased by 55% up to 23.6%wt. of total pyrolysis products distribution while the catalyst was added. Obtained yields of olefins were compared with the naphtha steam cracking process and other potentially attractive processes for feedstock generation. The concept of closed cycle material flow for polyolefins has been discussed, showing the potential benefits of feedstock recycling in a plastic waste management.     

Renewable hydrocarbons through biomass hydropyrolysis process: challenges and opportunities

Considering the current issues of carbon control and the desire to become less dependent on imported oil, the utilization of renewable hydrocarbons for the reduction of CO₂ emission and production of liquid synthetic fuels/chemicals has been proposed by researchers worldwide. Efforts to make chemicals/fuels from renewable resources have escalated over the past few years. Biomass-based renewable hydrocarbons are considered to be one of the sources with the highest potential to contribute to the energy needs of modern society for both developed and developing economies worldwide. Fast pyrolysis is becoming an important thermal route to convert biomass to liquid fuels; however, the raw bio-oils obtained have a number of negative properties such as high acidity, high water content, and variable viscosity over time. To overcome this problem and produce bio-oil of good quality, process of ‘hyropyrolysis’ has been developed. The scope for using pyrolysis under hydrogen pressure and also by process of hydropyrolysis followed by in situ hydroconversion of vapors to give oils with much lower oxygen contents has been reviewed.     

Poly(hydroxyalkanoate) Biosynthesis from Crude Alaskan Pollock (Theragra chalcogramma) Oil

Six strains of Pseudomonas were tested for their abilities to synthesize poly(hydroxyalkanoate) (PHA) polymers from crude Pollock oil, a large volume byproduct of the Alaskan fishing industry. All six strains were found to produce PHA polymers from hydrolyzed Pollock oil with productivities (P; the percent of the cell mass that is polymer) ranging from 6 to 53% of the cell dry weight (CDW). Two strains, P. oleovorans NRRL B-778 (P = 27%) and P. oleovorans NRRL B-14682 (P = 6%), synthesized poly(3-hydroxybutyrate) (PHB) with number average molecular weights (M_n) of 206,000 g/mol and 195,000 g/mol, respectively. Four strains, P. oleovorans NRRL B-14683 (P = 52%), P. resinovorans NRRL B-2649 (P = 53%), P. corrugata 388 (P = 43%), and P. putida KT2442 (P = 39%), synthesized medium-chain-length PHA (mcl-PHA) polymers with M_n values ranging from 84,000 g/mol to 153,000 g/mol. All mcl-PHA polymers were primarily composed of 3-hydroxyoctanoic acid (C_8:0) and 3-hydroxydecanoic acid (C_10:0) amounting to at least 75% of the total monomers present. Unsaturated monomers were also present in the mcl-PHA polymers at concentrations between 13% and 16%, providing loci for polymer derivatization and/or crosslinking. Mention of trade names or commercial products in this article is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture.     

TG-DSC and FTIR study on pyrolysis of irradiation cross-linked polyethylene

Irradiation cross-linked polyethylene (PEX) and irradiation cross-linked polyethylene with carbon black filler (CB-PEX) are two types of scraps, generated in electric cable production. Their pyrolysis is studied in this work using instrumental TG\DSC\FTIR techniques and kinetic analysis. The experiments are performed at a constant heating rate of 10 °C/min in nitrogen flow at atmospheric pressure. It is found that the main pyrolysis stage is in the temperature range of 395–503 °C for PEX, and in range of 408–515 °C for CB-PEX. In the main pyrolysis stage, CB-PEX requires more external heat than PEX does. Olefins are the major products of pyrolysis for both materials, but they are quite different in their composition and molecular weight distribution. PEX can be converted almost quantitatively into volatile compounds. CB-PEX has a stronger coking tendency, as well as a larger residue composed of carbon black.