Thermochemical conversion of municipal solid waste into energy and hydrogen: a review

The rising global population is inducing a fast increase in the amount of municipal waste and, in turn, issues of rising cost and environmental pollution. Therefore, alternative treatments such as waste-to-energy should be developed in the context of the circular economy. Here, we review the conversion of municipal solid waste into energy using thermochemical methods such as gasification, combustion, pyrolysis and torrefaction. Energy yield depends on operating conditions and feedstock composition. For instance, torrefaction of municipal waste at 200 °C generates a heating value of 33.01 MJ/kg, while the co-pyrolysis of cereals and peanut waste yields a heating value of 31.44 MJ/kg at 540 °C. Gasification at 800 °C shows higher carbon conversion for plastics, of 94.48%, than for waste wood and grass pellets, of 70–75%. Integrating two or more thermochemical treatments is actually gaining high momentum due to higher energy yield. We also review reforming catalysts to enhance dihydrogen production, such as nickel on support materials such as CaTiO₃, SrTiO₃, BaTiO₃, Al₂O₃, TiO₃, MgO, ZrO₂. Techno-economic analysis, sensitivity analysis and life cycle assessment are discussed.

     

Stabilization of metal processing plant sludge via sequential application of phytoremediation and pyrolysis

The aim of this study is to evaluate the metal removal ability of three different plants from metal processing sludge containing Pb, Cd, and Zn. Therefore, phytoremediation and pyrolysis were sequentially applied. In the phytoremediation applications, sunflower (Helianthus annuus), corn (Zea mays), and rape (Brassica napus) seeds were sown in sludge/soil mixtures at four different levels (25/75, 50/50, 75/25, 100/0). The chelating agent, ethylenediaminetetraacetic acid, was added to the mixtures for plant uptake during phytoremediation. At the phytoremediation stage, it was noted that rape was the most effective plant for the mixture of 75/25 sludge/soil, with metal removal efficiencies ranging between 80%–90%. At the pyrolysis stage, after harvesting, contaminated plants grown in a 75/25 sludge/soil mixture were pyrolyzed at 500 °C, with a heating rate of 35 °C/min. The results show that 60%–90% of the initial metal content was held by the solid product. In addition to this, it can be concluded that pyrolysis stabilizes metals into a solid product and that this solid product can be safely landfilled as inert waste since its toxicity leaching value is lower than the limit values.     

Strengthening effects of ammonia nitrogen on the harmless biological treatment of oily sludge

To improve the efficiency of oil degradation and strengthen the harmless treatment of oily sludge, three dominant strains identified as Chryseomicrobium sp. YL2, Gordonia sp. YL3 and Acinetobacter sp. YL5 were isolated from soil near a refinery, and the effects on the bioremediation of the oily sludge from the refinery were investigated. The results showed that the efficiency of oil degradation increased by 31.5% compared with the control when the dominant strains were added to the treatment of oily sludge. Furthermore, the dominant strains could use oil as a carbon source for heterotrophic nitrification–aerobic denitrification. The addition of ammonia nitrogen resulted in a large number of remaining microbes and heightened dehydrogenase activity in the oily sludge, further accelerating oil degradation, mainly for C₁₁ to C₂₅ saturated hydrocarbons, and the oil degradation efficiency increased by 40.8%. After 120 days of bioremediation, the biotoxicity of oily sludge, which was expressed by the equivalent phenol concentration, decreased by 40.0% compared with that of the control, indicating that the addition of ammonia nitrogen enhanced the biodegradation of oil. This method can be used to strengthen the harmless treatment of oily sludge in practical engineering applications.     

Pyrolysis behaviors of oil sludge based on TG/FTIR and PY-GC/MS

Pyrolysis is an alternative technology for oil sludge treatment. Thermogravimetric Analysis-Fourier Transform Infrared Spectroscopy and Pyrolysis-Gas Chromatography/Mass Spectrometry were employed to investigate the pyrolysis process and products of oil sludge. The pyrolysis process was divided into five stages: drying and gas desorption, oil volatilization, main pyrolysis, semi-coke charring, and mineral decomposition. The main reaction temperatures ranged from 497.6 K to 753.2 K. The products were mainly composed of pairs of alkane and alkene (carbon number ranges from 1 to 27). The mechanisms consisted of random chain scission followed by end chain scission at high temperatures with volatilization occurring during the whole process. This study is useful not only for the proper design of a pyrolysis system, but also for improving the utilization of liquid oil products.     

Investigation of the sources of aliphatic hydrocarbons in the mussel Mytilus edulis from north sea oil production platforms by Capillary glc and CGCMS†

Aliphatic hydrocarbons isolated from mussels collected over a 20 month period from three North Sea Forties field oil production platforms have been examined by capillary gas chromatography and gas chromatography‐mass spectrometry.

The biological hydrocarbons consist predominantly (300–700 μh g^‐1 lipid) of C₃₁ and C₃₃ n‐alkenes with 2, 3 and 4 double bonds probably derived from a dietary intake of Emiliania huxleyi, a microscopic coccolithophorid alga. In some of the mussels C₁₈, C₂₀ and C₂₂ n‐alkanes are present in unusually high abundance compared to their odd carbon number homologues. Possible reasons for this distribution are discussed.

The concentrations of fossil fuel hydrocarbons (mainly unresolved complex mixtures) in the mussels ranged from 330 to 5,298 μg g^‐1 of lipid. No significant increase in values was detected two months after the start of discharge of treated Forties production water from the Forties D platform.

To determine the pollutant hydrocarbon sources, the sterane and terpane distributions of hydrocarbon fractions isolated from the mussels and from a number of fossil fuels, including Forties crude oil, were examined by mass fragmentography. The steranes in the mussels from the Forties C and D platforms contained higher proportions of regular 14α(H), 17α(H) components than Forties oil in which the steranes were mainly 13ß(H), 17α(H) diasteranes. In addition, the terpane distributions of the mussel fractions differed markedly from that of Forties crude oil, particularly in the relative abundance of diterpanes to triterpanes, which was higher in the mussel fractions than in the oil, and in the absence of 17α(H), 18α(H), 21ß(H)‐18, 30‐bisnorhopane, a known component of Forties crude. Furthermore, the ratio of C₂₉ to C₃₀ triterpanes was greater than unity in the mussels but much less than unity in the Forties oil. These data preclude Forties or other similar North Sea crudes as the major source of pollutant aliphatic hydrocarbons in the mussels. The relative concentrations and distributions of steranes and triterpanes suggest that the most likely source of pollutants is a Middle Eastern based oil derived either from rig activities, or from background pollution in the North Sea. The low concentration of ≥ C₂₇ steranes in the more polluted mussels (e.g. Forties B; UCM > 200 ppm dry wt.) suggests that gas oils used on the platforms may be the major source of petrogenic hydrocarbons in these samples.     

熔盐法去除污泥焚烧灰中磷的效果及热动力学分析

利用碳还原剂和氯化钙熔盐药剂在1100℃下还原污泥焚烧灰中的磷酸盐为气态磷单质并去除,采用X射线衍射分析(XRD)残渣的组成和热重质谱(TGA-MS)分析反应过程.结果表明,添加氯化钙可显著提高污泥焚烧灰除磷效率,氯化钙的最优添加量为25%质量分数,此时污泥焚烧灰除磷效率为82%.XRD结果显示,污泥焚烧灰经熔盐处理后形成了氯磷灰石(chlorapatite),珍珠云母(margarite)等物质,其中氯磷灰石的形成有利于焚烧灰中磷的还原.对TGA-MS结果进行热解动力学反应拟合,结果显示,污泥焚烧灰除磷反应在添加少量氯化钙添加时为均相反应;污泥焚烧灰除磷反应在添加较多氯化钙时为固相扩散反应.固相反应的发生有利于降低磷酸盐还原反应温度并提高去除效率.     

Co-pyrolysis of sewage sludge and biomass for stabilizing heavy metals and reducing biochar toxicity: A review

The huge amounts of sewage sludge produced by municipal wastewater treatment plants induce major environmental and economical issues, calling for advanced disposal methods. Traditional methods for sewage sludge disposal increase greenhouse gas emissions and pollution. Moreover, biochar created from sewage sludge often cannot be used directly in soil applications due to elevated levels of heavy metals and other toxic compounds, which alter soil biota and earthworms. This has limited the application of sewage sludge-derived biochar as a fertilizer. Here, we review biomass and sewage sludge co-pyrolysis with a focus on the stabilization of heavy metals and toxicity reduction of the sludge-derived biochar. We observed that co-pyrolyzing sewage sludge with biomass materials reduced heavy metal concentrations and decreased the environmental risk of sludge-derived biochar by up to 93%. Biochar produced from sewage sludge and biomass co-pyrolysis could enhance the reproduction stimulation of soil biota by 20‒98%. Heavy metals immobilization and transformation are controlled by the co-feed material mixing ratio, pyrolysis temperature, and pyrolysis atmosphere.

     

Catalytic fast pyrolysis of Kraft lignin with HZSM-5 zeolite for producing aromatic hydrocarbons

Catalytic fast pyrolysis (CFP) of Kraft lignins with HZSM-5 zeolite for producing aromatics was investigated using analytical pyrolysis methods. Two Kraft lignins were fast pyrolyzed in the absence and presence of HZSM-5 in a Curie-point pyrolyzer. Without the catalyst, fast pyrolysis of lignin predominantly produced phenols and guaiacols that were derived from the subunits of lignin. However, the presence of HZSM-5 changed the product distribution dramatically. As the SiO₂/Al₂O₃ ratio of HZSM-5 decreased from 200 to 25 and the catalyst-to-lignin ratio increased from 1 to 20, the lignin-derived oxygenates progressively decreased to trace and the aromatics increased substantially. The aromatic yield increased considerably as the pyrolysis temperature increased from 500°C to 650°C, but then decreased with yet further increase of pyrolysis temperature. Under optimal reaction conditions, the aromatic yields were 2.0 wt.% and 5.2 wt.% for the two lignins that had effective hydrogen indexes of 0.08 and 0.35.     

Co-pyrolysis of oil sludge with hydrogen-rich plastics in a vertical stirring reactor: Kinetic analysis,emissions, and products

● Collaborative treatment of plastics and OS was established to improve oil quality. ● PE addition successfully improved OS pyrolysis process by deploying H/C_eff ratio. ● Higher H/C_eff ratio promoted cracking to obtain more gas and light oil fractions. ● The degradation of PE and OS was promoted each other under their temperature range. Pyrolysis is an effective method to treat oily sludge (OS) due to its balance between oil recovery and nonhazardous disposal. However, tank bottom OS contains a high content of heavy fractions, which creates obstacles for pyrolysis due to the high activation energy. The incomplete cracking of macromolecules and secondary polymerization decreases the oil quality and causes coking during the operation process. This study introduced polyethylene (PE) into OS to deploy the H/C_eff ratio of feedstocks for pyrolysis. A strong interaction between OS and PE during copyrolysis could be observed from the TG/DTG curves. PE tightly participated in OS degradation, while OS also promoted PE degradation at high temperature. Apparent pits were generated in solid residues from copyrolysis, which was attributed to the uniform and violent gas release. In addition to HCN, other nitrogenous and sulphurous pollutants were inhibited. Accordingly, more gas products were attained after PE addition with more value-added compositions of alkanes and alkenes. Although the oil yield decreased after PE addition, the oil products from copyrolysis possessed higher heating values and higher contents of light fractions with short chains as well as paraffins. Consequently, copyrolysis of OS and PE significantly improved the pyrolysis process and resulted in high oil quality.     

Mechanistic aspects of the thermal formation of halogenated organic compounds including polychlorinated dibenzo‐p‐dioxins. Part IV†: Incorporation of inorganic chlorine into organic matter and thermochemical aromatizations

The pyrolysis and chlorination of petroleum coke in a NaCl‐KCl melt results in the production of CCl₄ and C₆Cl₆. Polychlorinated dibenzo‐p‐dioxins (PCDDs) are produced from the air oxidation and chlorination of coal using HCl or Cl₂. Smoking of tobacco containing ³⁶Cl^e provides CH₃ ³⁶Cl.

At 350°C, the rateof aromatization of 1,3‐cyclohexadiene is negligible as compared to that of 1,4‐cyclohexadiene. The aromatization of the latter diene proceeds through the molecular elimination of hydrogen; while that of 1,3‐cyclohexadiene expecially at higher pressure (10–90 Torr) and at 362–421 °C involves free radical chain mechanism.     

A steam dried municipal solid waste gasification and melting process

Considering high-moisture municipal solid waste (MSW) of China, a steam dried MSW gasification and melting process was proposed, the feasibility was tested, and the mass and energy balance was analyzed. Preliminary experiments were conducted using a fixed-bed drying apparatus, a 200 kg per day fluidized-bed gasifier, and a swirl melting furnace. Moisture percentage was reduced from 50% to 20% roughly when MSW was dried by slightly superheated steam of 150°C?C350°C within 40 min. When the temperature was less than 250°C, no incondensable gas was produced during the drying process. The gasifier ran at 550°C?C700°Cwith an air equivalence ratio (ER) of 0.2?C0.4. The temperature of the swirl melting furnace reached about 1240°C when the gasification ER was 0.3 and the total ER was 1.1. At these conditions, the fly ash concentration in the flue gas was 1.7 g·(Nm³)^?1, which meant over 95% fly ash was trapped in the furnace and discharged as slag. 85% of Ni and Cr were bound in the slag, as well as 60% of Cu. The mass and energy balance analysis indicates that the boiler heat efficiency of an industrial MSW incineration plant reaches 86.97% when MSW is dried by steam of 200°C. The boiler heat efficiency is sensitive to three important parameters, including the temperature of preheated MSW, the moisture percentage of dried MS Wand the fly ash percentage in the total ash.     

Materials,fuels, upgrading,economy, and life cycle assessment of the pyrolysis of algal and lignocellulosic biomass: a review

Climate change issues are calling for advanced methods to produce materials and fuels in a carbon–neutral and circular way. For instance, biomass pyrolysis has been intensely investigated during the last years. Here we review the pyrolysis of algal and lignocellulosic biomass with focus on pyrolysis products and mechanisms, oil upgrading, combining pyrolysis and anaerobic digestion, economy, and life cycle assessment. Products include oil, gas, and biochar. Upgrading techniques comprise hot vapor filtration, solvent addition, emulsification, esterification and transesterification, hydrotreatment, steam reforming, and the use of supercritical fluids. We examined the economic viability in terms of profitability, internal rate of return, return on investment, carbon removal service, product pricing, and net present value. We also reviewed 20 recent studies of life cycle assessment. We found that the pyrolysis method highly influenced product yield, ranging from 9.07 to 40.59% for oil, from 10.1 to 41.25% for biochar, and from 11.93 to 28.16% for syngas. Feedstock type, pyrolytic temperature, heating rate, and reaction retention time were the main factors controlling the distribution of pyrolysis products. Pyrolysis mechanisms include bond breaking, cracking, polymerization and re-polymerization, and fragmentation. Biochar from residual forestry could sequester 2.74 tons of carbon dioxide equivalent per ton biochar when applied to the soil and has thus the potential to remove 0.2–2.75 gigatons of atmospheric carbon dioxide annually. The generation of biochar and bio-oil from the pyrolysis process is estimated to be economically feasible.

     

油田含油污泥热解产物分析及性能评价

选择高含油的孤岛采油厂联合站堆放场含油污泥进行热解处理研究,采用正交实验对热解工艺进行了优化;采用ICP-MS、元素分析仪、气相色谱仪、EPS-MS对热解气体产物和残渣进行分析;热解残渣经过后续处理进行了烟气脱硫性能评价.正交实验结果表明热解最佳工艺条件为:N2保护下,热解温度600℃,热解时间4h,升温速率5℃.min-1,此时苯吸附值为47.04mg.g-1,热解残渣含油量为0.21%.最佳工艺条件下,热解油产率可达11%左右,回收率约75%,热解油的品质较好,产生的不凝气体可以作为洁净燃料气或合成气原料;热解残渣经过处理后可用于脱除烟气中的SO2,吸附脱硫能力较好,并具有进一步改进和提高的潜力.     

Urea formation from carbon dioxide and ammonia at atmospheric pressure

Urea synthesis, currently the largest use of carbon dioxide in organic synthesis, is conventionally operated at high pressure and high temperature. Here, we report for the first time that urea forms at atmosphere and ambient temperatures by negative corona discharge in gas phase. The conversion of CO₂ and yields of a solid mixture of urea and ammonium carbamate, which was identified by the ¹³C NMR spectrum, rise with reducing temperatures and increasing molar ratios of NH₃/CO₂ and discharge frequencies. The conversion of carbon dioxide was found to be 82.16?% at 20?°C and 1?atm with a molar flow ratio of n(NH₃)/n(CO₂) of 2.5. High pressure and high temperature as energy inputs are not necessary.     

Organic matter balances in anaerobic digestors

Organic carbon and COD balances in a system of 12 anaerobic units operating at organic loading levels 0.4–0.8 kg COD/m³.d and hydraulic detention times 8–20 d resulted in a mean CH₄ production of 341 ml/g COD converted and a mean CH₄ + CO₂ production 1815 ml/g OC converted. The gas retained in the liquid anaerobic effluent was mainly carbon dioxide (94–98%).     

The composition of natrophosphate (sodium fluoride phosphate hydrate)

Natrophosphate is a common trace mineral in alkaline rocks and a major salt in alkaline nuclear waste that complicates waste processing. Natrophosphate has historically been assigned the composition Na₇F(PO₄)₂·19H₂O, but this conflicts with a more recent solubility study that claimed natrophosphate is a solid solution of NaF and Na₃PO₄. It is not possible to model the solubility of natrophosphate in nuclear waste until this controversy is resolved. The present study mixed stock solutions of 0.9 M NaF and Na₃PO₄ at different ratios at 8 °C. The compositions of the liquid phase and wet natrophosphate sample were measured by ion chromatography. Plotting the tie-lines between the solid and liquid phase composition showed convergence on a single composition, indicating that natrophosphate is not a solid solution. The resulting composition is approximately the same as the composition first reported more than 140 years ago. Thus, this study resolves the long-standing controversy in the literature concerning the composition of natrophosphate.     

Ionic liquids for the inhibition of gas hydrates. A review

The formation of gas hydrates is a major issue during the operation of oil and gas pipelines, because gas hydrates cause plugging, thereby disrupting the normal oil and gas flows. A solution is to inject gas hydrate inhibitors such as ionic liquids. Contrary to classical inhibitors, ionic liquids act both as thermodynamic inhibitors and hydrate inhibitors, and as anti-agglomerates. Imidazolium-based ionic liquids have been found efficient for the inhibition of CO₂ and CH₄ hydrates. For CO₂ gas hydrates, N-ethyl-N-methylmorpholinium bromide showed an average depression temperature of 1.72 K at 10 wt% concentration. The induction time of 1-ethyl-3-methyl imidazolium bromide is 36.3 h for CO₂ hydrates at 1 wt% concentration. For CH₄ hydrates, 1-ethyl-3-methyl-imidazolium chloride showed average depression temperature of 4.80 K at 40 wt%. For mixed gas hydrates of CO₂ and CH₄, only quaternary ammonium salts have been studied. Tetramethyl ammonium hydroxide shifted the hydrate liquid vapour equilibrium to 1.56 K at 10 wt%, while tetrabutylammonium hydroxide showed an induction time of 0.74 h at 1 wt% concentration.

     

Identification and assay of microbial fatty acids during co-composting of active sewage sludge with palm waste by TMAH-thermochemolysis coupled with GC-MS

The fatty acids of two composts of active sludge with palm tree waste were investigated by thermochemolysis coupled to gas chromatography-mass spectrometry. This method (tetramethylammonium hydroxide-pyrolysis-gas chromatography-mass spectrometry) allowed the direct determination of total fatty acids (analysed as fatty acid methyl esters: FAMEs) present in the organic matter of the samples without any separation procedures. Mixture A was 1/3 sludge+2/3 palm waste and mixture B was 1/2 sludge+1/2 palm waste. The level of FAMEs rose by 8.4–33.3% and 10.8–13.4% in mixtures A and B, respectively, after 6 months of co-composting. Branched FAMEs of bacterial origin (iC15:0) rose during the thermophilic phase, in mixture A the aC17:0/aC15:0 ratio increased during the co-composting process, also in mixture B the aC16:0/C16:0 ratio rose but only during the thermophilic phase. All the FAMEs identified showed a drop at the end of co-composting except for C18:0 and C16:0. The stabilisation phase was characterised by a significant rise in the length of the aliphatic chains; the carbon preference index thus increased at the end of the composting process, indicating that the final product was proportionally richer in fatty acids of plant origin.     

Influence of light and temperature on the photosynthetic rate of marine benthic diatoms

The influence of light and temperature on photosynthetic rate as measured by C¹⁴O₂-fixation of marine benthic diatoms was investigated, using both intact sediment samples (Marshall et al., 1973) and suspensions of diatoms harvested by a lenstissue technique (Eaton and Moss, 1966). After C¹⁴-incubation, sediment samples were filtered, burned in a sample oxidizer, and their activity determined in a liquid scintillation counter. Photosynthetic rate of mixed field populations is saturated by a light intensity of approximately 10,000 lux; at still higher light intensities no photoinhibition was found. In contrast to the mixed field populations, unialgal cultures of the benthic diatom Amphiprora alata Kütz. exhibited strong photoinhibition at higher light intensities (10,000 to 60,000 lux). Within a range of 4° to 20°C, the photosynthetic rate increased about 10%/C^o. No differences in photosynthetic pattern were observed between epipelic and epipsammic species.     

Determination of polyfluoroalkyl compounds in water and suspended particulate matter in the river Elbe and North Sea, Germany

The distribution of polyfluoroalkyl compounds (PFCs) in the dissolved and particulate phase and their discharge from the river Elbe into the North Sea were studied. The PFCs quantified included C₄-C₈ perfluorinated sulfonates (PFSAs), 6:2 fluorotelomer sulfonate (6:2 FTS), C₆ and C₈ perfluorinated sulfinates (PFSiAs), C₄-C₁₂ perfluorinated carboxylic acids (PFCAs), perfluoro-3,7-dimethyl-octanoic acid (3,7m₂-PFOA), perfluorooctane sulfonamide (FOSA), and n-ethyl perfluroctane sulfonamidoethanol (EtFOSE). PFCs were mostly distributed in the dissolved phase, where perfluorooctanoic acid (PFOA) dominated with 2.9–12.5 ng/L. In the suspended particulate matter FOSA and perfluorooctane sulfonate (PFOS) showed the highest concentrations (4.0 ng/L and 2.3 ng/L, respectively). The total flux of ΣPFCs from the river Elbe was estimated to be 802 kg/year for the dissolved phase and 152 kg/year for the particulate phase. This indicates that the river Elbe acts as a source of PFCs into the North Sea. However, the concentrations of perfluorobutane sulfonate (PFBS) and perfluorobutanoic acid (PFBA) in the North Sea were higher than that in the river Elbe, thus an alternative source must exist for these compounds.