Thermal cracking of oils from waste plastics

Thermal cracking of decomposed waste plastic oil produces a good yield of olefins. The solvent extraction of such waste plastic oil seems to be efficient for increasing gas yields and recycling monomers. To assess the potential of monomer recovery from municipal waste plastics, the oils were cracked using a laboratory-scale quartz-tube reactor. The waste plastic oils were provided by two commercial plants of the Sapporo Plastic Recycle Co. and the Dohoh Recycle Center Co. in Japan. A model waste plastic oil made in a laboratory was also examined. Yields of ethene, propene, and other products were measured at different temperatures. Two-step pyrolysis reduces coking compared with the direct thermal degradation of plastics. The raffinates from waste plastic oils extracted by sulfolane were also cracked. The primary products were almost the same as those from nontreated oils. The maximum total gas yield was 78wt%–85wt% at 750°C, an increase of about 20wt% compared with that of nonextracted oil. Solvent extraction removes stable aromatic hydrocarbons such as styrene, which is more coked than cracked.     

Multi-step approach for comparing the local air pollution contributions of conventional and innovative MSW thermo-chemical treatments

In the sector of municipal solid waste management the debate on the performances of conventional and novel thermo-chemical technologies is still relevant. When a plant must be constructed, decision makers often select a technology prior to analyzing the local environmental impact of the available options, as this type of study is generally developed when the design of the plant has been carried out. Additionally, in the literature there is a lack of comparative analyses of the contributions to local air pollution from different technologies. The present study offers a multi-step approach, based on pollutant emission factors and atmospheric dilution coefficients, for a local comparative analysis. With this approach it is possible to check if some assumptions related to the advantages of the novel thermochemical technologies, in terms of local direct impact on air quality, can be applied to municipal solid waste treatment. The selected processes concern combustion, gasification and pyrolysis, alone or in combination. The pollutants considered are both carcinogenic and non-carcinogenic. A case study is presented concerning the location of a plant in an alpine region and its contribution to the local air pollution. Results show that differences among technologies are less than expected. Performances of each technology are discussed in details.     

Tracing the sources of refractory dissolved organic matter in a large artificial lake using multiple analytical tools

Structural and chemical characteristics of refractory dissolved organic matter (RDOM) from seven different sources (algae, leaf litter, reed, compost, field soil, paddy water, treated sewage) were examined using multiple analytical tools, and they were compared with those of RDOM in a large artificial lake (Lake Paldang, Korea). Treated sewage, paddy water, and field soil were distinguished from the other sources investigated by their relatively low specific UV absorbance (SUVA) values and more pronounced fulvic-like versus humic-like fluorescence of the RDOM samples. Microbial derived RDOM from algae and treated sewage showed relatively low apparent molecular weight and a higher fraction of hydrophilic bases relative to the total hydrophilic fraction. For the biopolymer types, the presence of polyhydroxy aromatics with the high abundance of proteins was observed only for vascular plant-based RDOM (i.e., leaf litter and reed). Molecular weight values exhibited positive correlations with the SUVA and the hydrophobic content among the different RDOM, suggesting that hydrophobic and condensed aromatic structures may be the main components of high molecular weight RDOM. Principal component analysis revealed that approximately 77% of the variance in the RDOM characteristics might be explained by the source difference (i.e., terrestrial and microbial derived) and a tendency of further microbial transformation. Combined results demonstrated that the properties of the lake RDOM were largely affected by the upstream sources of field soil, paddy water, and treated sewage, which are characterized by low molecular weight UV-absorbing and non-aromatic structures with relatively high resistance to further degradation.     

The use of anthracene as a model compound in a comparative study of hydrous pyrolysis methods for industrial waste remediation

Polycyclic aromatic hydrocarbons are very stable compounds and tend to bioaccumulate in the environment due to their high degree of conjugation and aromaticity. Hydrous pyrolysis is explored as a technique for the treatment of industrial water containing PAH, using anthracene as a model compound. The reactivity of anthracene under a range of temperatures and durations are studied in this paper. Aliquots of 1.0-10.0 mg of anthracene in a range of 1.0-5.0 mL of H₂O are subjected to hydrous pyrolysis under varied conditions of temperature, reagents and duration. The conditions include oxidising systems comprising distilled water, hydrogen peroxide and Nafion-SiO₂ solid catalyst in water; and reducing systems of formic acid and formic acid/Nafion-SiO₂/Pd-C catalysts to assess a range of redox reaction conditions. Oxygen in air played a role in some of the reaction conditions. Pyrolysed products were identified and quantified by the use of Gas Chromatography-Mass Spectrometry (GC-MS). The major products were anthrone, anthraquinone, xanthone from oxidation; and multiple hydro-anthracene derivatives from reductive hydogenation. The nature of reaction conditions influenced the extent of anthracene degradation. The products formed are more reactive (less stable) as compared to anthracene the starting material and will therefore be less persistent in the environment.     

Experimental and CFD-DEM study of the dispersion and combustion of wheat starch and carbon-black particles during the standard 20L sphere test

The 20L sphere is one of the standard devices used for dust explosivity characterization. One concern about the effectiveness and reliability of this test is related to the particle size variation due to particles' agglomeration and de-agglomeration. These phenomena are related to the turbulent regime of the dust cloud during the dispersion. This variable must be considered since it determines the uncertainty level of the ignitability and severity parameters of dust combustion. In this context, this study describes the influence of the cloud turbulence on the dust segregation and fragmentation through a study combining both, experimental and computational approaches. The behavior of the gas-solid mixture evidenced with the standard rebound nozzle was compared with that observed with six new nozzle geometries. Thereafter, the time-variation of the Particle Size Distribution (PSD) within the 20L sphere was analyzed for two different powders: carbon-black and wheat starch. On the one hand, the turbulence levels and PSD variations were characterized by Particle Image Velocimetry (PIV) tests and granulometric analyses, respectively. On the other hand, a computational approach described the dispersion process with CFD-DEM simulations developed in STAR-CCM + v11.04.010. The simulation results established that the homogeneity assumption is not satisfied with the nozzles studied. Nonetheless, the particles segregation levels can be reduced using nozzles that generate a better dust distribution in the gas-solid injections. Subsequently, an additional first-approach CFD model was established to study the behavior of the combustion step for a starch/air mixture. This model considers the gas-phase reactions of the combustible gases that are produced from the devolatilization of wheat starch ($CO,C{H}_4,C_2{H}_4,C_2{H}_6,C_2{H}_2,$ and $H_2$) and allowed to establish the approximate fraction of the particle mass that devolatilizes, as well as to confirm that the modeling of the pyrolysis stage is essential for the correct prediction of the maximum rate of pressure rise.     

固体废弃物轮胎的热解技术

综述了国内外对废轮胎的处理状况，并详细地讨论了废轮胎热解技术的发展、分类以及典型工艺流程。热解技术主要包括油化技术、气化技术和炭化技术三种，并可制得衍生油、燃料气、碳黑等产品。分析了废轮胎热解工艺存在的问题，指出了如何开发环境友好的集成工艺是废轮胎热解工艺的发展方向。     

Two-step fast microwave-assisted pyrolysis of biomass for bio-oil production using microwave absorbent and HZSM-5 catalyst

A novel technology of two-step fast microwave-assisted pyrolysis(f MAP) of corn stover for bio-oil production was investigated in the presence of microwave absorbent(Si C) and HZSM-5catalyst. Effects of f MAP temperature and catalyst-to-biomass ratio on bio-oil yield and chemical components were examined. The results showed that this technology, employing microwave, microwave absorbent and HZSM-5 catalyst, was effective and promising for biomass fast pyrolysis. The f MAP temperature of 500°C was considered the optimum condition for maximum yield and best quality of bio-oil. Besides, the bio-oil yield decreased linearly and the chemical components in bio-oil were improved sequentially with the increase of catalyst-to-biomass ratio from 1:100 to 1:20. The elemental compositions of bio-char were also determined. Additionally, compared to one-step f MAP process, two-step f MAP could promote the bio-oil quality with a smaller catalyst-to-biomass ratio.     

Catalytic fast pyrolysis of walnut shell for alkylphenols production with nitrogen-doped activated carbon catalyst

• N-doped activated carbon was prepared for catalytic pyrolysis of walnut shell. • Alkylphenols were selectively produced from catalytic pyrolysis process. • The alkylphenols yield increased by 8.5 times under the optimal conditions. • Formation mechanism of alkylphenols was proposed. Alkylphenols are a group of valuable phenolic compounds that can be derived from lignocellulosic biomass. In this study, three activated carbons (ACs) were prepared for catalytic fast pyrolysis (CFP) of walnut shell to produce alkylphenols, including nitrogen-doped walnut shell-derived activated carbon (N/WSAC), nitrogen-doped rice husk-derived activated carbon (N/RHAC) and walnut shell-derived activated carbon (WSAC). Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments were carried out to reveal the influences of AC type, pyrolytic temperature, and AC-to-walnut shell (AC-to-WS) ratio on the product distributions. Results showed that with nitrogen doping, the N/WSAC possessed stronger capability than WSAC toward the alkylphenols production, and moreover, the N/WSAC also exhibited better effects than N/RHAC to prepare alkylphenols. Under the catalysis of N/WSAC, yields of alkylphenols were significantly increased, especially phenol, cresol and 4-ethylphenol. As the increase of pyrolytic temperature, the alkylphenols yield first increased and then decreased, while high selectivity could be obtained at low pyrolytic temperatures. Such a trend was also observed as the AC-to-WS ratio continuously increased. The alkylphenols production achieved a maximal yield of 44.19 mg/g with the corresponding selectivity of 34.7% at the pyrolytic temperature of 400°C and AC-to-WS ratio of 3, compared with those of only 4.67 mg/g and 6.1% without catalyst. In addition, the possible formation mechanism of alkylphenols was also proposed with the catalysis of N/WSAC.     

有机固体废弃物的热解处理研究

通过对锯末、稻壳、纸屑、橱芥、塑料和橡胶6种具有代表性的有机固体废弃物原料的热解实验,测量了它们三相产物收率,并分析了它们固体、液体和气体三相产物的组成.特别对液体产物,针对它们的特殊性分别采用了层析、模拟蒸馏和全烃气相色谱分析,详细探讨了热解焦油的具体组分,得到了热解法处理有机固体废弃物的一些有意义的数据.     

Preparation and characterization of boron-doped corn straw biochar: Fe (Ⅱ) removal equilibrium and kinetics

Nowadays, iron ions as a ubiquitous heavy metal pollutant are gradually concerned and the convenient and quick removal of excessive iron ions in groundwater has become a major challenge for the safety of drinking water. In this study, boron-doped biochar (B-BC) was successfully prepared at various preparation conditions with the addition of boric acid. The as-prepared material has a more developed pore structure and a larger specific surface area (up to 897.97 m²/g). A series of characterization results shows that boric acid effectively activates biochar, and boron atoms are successfully doped on biochar. Compared with the ratio of raw materials, the pyrolysis temperature has a greater influence on the amount of boron doping. Based on Langmuir model, the maximum adsorption capacity of 800B-BC_1:2 at 25 °C, 40 °C, 55 °C are 50.02 mg/g, 95.09 mg/g, 132.78 mg/g, respectively. Pseudo-second-order kinetic model can better describe the adsorption process, the adsorption process is mainly chemical adsorption. Chemical complexation, ions exchange, and co-precipitation may be the main mechanisms for Fe²⁺ removal.