The Evaluation of Mesoporous Materials as Catalyst in Fast Pyrolysis of Wheat Straw

In this study, wheat straw was chosen as a biomass sample and the fast pyrolysis of this sample was carried out with or without catalyst at different conditions in a well-swept fixed-bed reactor. Experiments were carried out in a well-swept tubular fixed-bed reactor with a heating rate of 300°C/min, between pyrolysis temperature ranges 300–800°C in the nitrogen atmosphere. The results indicated that a maximum oil yield of 31.9% was obtained at a pyrolysis temperature of 500°C in non-catalytic procedure. Siliceous and Al-MCM-41 materials were evaluated as potential catalysts in the pyrolysis experiments. Mesoporous materials have large pore dimensions with strong acid sites. These acidic sites catalyze some reactions in pyrolysis. The product yields and the quality of bio-oil were influenced with using MCM-41 materials. The bio-oil yield was reduced, whereas the gas yield increased with using a catalyst in the experiments. An increase in the fractions of pure phenol, alkyl phenols, alkenes+alkanes, carbonyls, aromatic, and cyclic compounds and a decrease in the fractions of methoxy phenols, acids+esters, furans, and alcohols were observed in the presence of Al-MCM-41 material. According to all results, the use of Al-MCM-41 materials as catalyst in the pyrolysis can be suggested to obtain both quality fuels and valuable chemicals.     

Upgrading of bio-oil from palm kernel shell by catalytic cracking in the presence of HZSM-5

Upgrading of bio-oil extracted from palm kernel shell (PKS) was performed using a lab-scale fixed-bed reactor with HZSM-5 as a catalyst. The catalytic cracking was carried out at optimized conditions: 0.3-MPa pressure, temperature of 500°C, and oil to catalyst ratio of 1:5. One of the challenges in upgrading bio-oil by catalytic cracking is deactivation of catalyst due to coke formation on catalyst surface. To overcome coke deposition, the upgrading process was carried out at 0.3-MPa pressure. Characterization of raw and upgraded bio-oil obtained through catalytic cracking was discussed in detail, indicating improvement in its physical properties. The distribution of products after cracking of bio-oil includes 58.89 wt% of organic liquid product, 15.63 wt% of aqueous fraction, 7.84 wt% of coke, and 17.64 wt% of gases. The degree of deoxygenation and calorific value of organic liquid product is 43.74% and 31.65 MJ/kg respectively. Organic liquid product obtained comprises 17.55% of hydrocarbons within the gasoline range. Hence, HZSM-5 proved its effectiveness for upgrading the bio-oil in a continuous mode.     

挥发性有机废气净化技术研究进展

本文对生物净化技术、等离子体净化技术、吸附和催化氧化技术在控制废气中挥发性有机物的研究进展及应用进行了综述。气体生物净化技术在VOCs混合物和改进设备工艺方面开展的研究工作较多,等离子体净化技术与催化技术的组合越来越受到关注。吸附和催化氧化方面则着重在吸附剂（活性炭和沸石）吸附性能的进一步研究和新型催化剂的研制。     

Preparation of jet engine range fuel from biomass pyrolysis oil through hydrogenation and its comparison with aviation kerosene

The Bio-oil was produced from the pyrolysis of agricultural wastes (Eucalyptus sawdust) and discarded soybean frying oil. The temperature of the pyrolysis system was initiated at 28°C and increased to 850°C. Atmospheric distillation of crude bio-oil was performed and a fraction at a temperature range 160–240°C (pyrolysis oil) was separated and subjected to GC-MS, ¹H-NMR, TGA and FTIR analysis to identify the different properties and compounds present in pyrolysis oil. It was noticed that there was an abundance of oxygen and nitrogen containing compounds as well as other reactive species in pyrolysis oil. To reduce the amount of these species, the pyrolysis oil was subjected to hydrogenation in the presence of NiMo as a catalyst. After hydrogenation, the atmospheric distillation of hydrogenated bio-oil was performed and another fraction at temperature range 160–240°C (hydrogenated bio-oil) was separated and analyzed by the same techniques. It was noticed that during hydrogenation, more than 60% oxygenated and other reactive species were converted into hydrocarbons. Hydrogenated bio-oil showed very similar physico-chemical properties such as distillation curve, density, viscosity, freezing point, flash point, the presence of hydrocarbons and enthalpy of combustion as aviation kerosene also known as QAV-1.     

Economic assessment of flash co-pyrolysis of short rotation coppice and biopolymer waste streams

The disposal problem associated with phytoextraction of farmland polluted with heavy metals by means of willow requires a biomass conversion technique which meets both ecological and economical needs. Combustion and gasification of willow require special and costly flue gas treatment to avoid re-emission of the metals in the atmosphere, whereas flash pyrolysis mainly results in the production of (almost) metal free bio-oil with a relatively high water content. Flash co-pyrolysis of biomass and waste of biopolymers synergistically improves the characteristics of the pyrolysis process: e.g. reduction of the water content of the bio-oil, more bio-oil and less char production and an increase of the HHV of the oil. This research paper investigates the economic consequences of the synergistic effects of flash co-pyrolysis of 1:1 w/w ratio blends of willow and different biopolymer waste streams via cost-benefit analysis and Monte Carlo simulations taking into account uncertainties. In all cases economic opportunities of flash co-pyrolysis of biomass with biopolymer waste are improved compared to flash pyrolysis of pure willow. Of all the biopolymers under investigation, polyhydroxybutyrate (PHB) is the most promising, followed by Eastar, Biopearls, potato starch, polylactic acid (PLA), corn starch and Solanyl in order of decreasing profits. Taking into account uncertainties, flash co-pyrolysis is expected to be cheaper than composting biopolymer waste streams, except for corn starch. If uncertainty increases, composting also becomes more interesting than flash co-pyrolysis for waste of Solanyl. If the investment expenditure is 15% higher in practice than estimated, the preference for flash co-pyrolysis compared to composting biopolymer waste becomes less clear. Only when the system of green current certificates is dismissed, composting clearly is a much cheaper processing technique for disposing of biopolymer waste.     

The effect of pyrolysis atmosphere on bio-oil yields and structure

A food industry waste, almond shell, was pyrolyzed under three different environment static, nitrogen, and steam to produce bio-oil and its derivatives. The oil yield obtained at pyrolysis temperature of 600°C was 24.23% in a static atmosphere, whereas it increased to 27.25% and 33.05% in nitrogen and steam atmospheres, respectively. The bio-oil obtained under steam atmosphere is very efficient due to the production of high liquid and gas yields. Moreover, co-feeding steam during the pyrolysis altered the bio-oil structure by increasing the aliphatics and reducing the asphaltenes. Moreover, steam treatment also increases H/C and heating value of bio-oils. According to the obtained results, steam pyrolysis is an alternative option for future applications in refineries.     

Recovery of biomass wastes by hydrolysis in sub-critical water

The recovery of waste substances is important not only for the prevention of environmental issues, but also for the rational utilization of natural resources. Hydrolysis reaction in sub-critical water is a promising method for the treatment of organic wastes and has been attracting worldwide attention. In this paper, sub-critical water hydrolysis was employed as a method for producing amino acids, reducing sugars, bio-oil and gas fuels from biomass wastes. The current statuses of these useful chemicals production from biomass wastes by hydrolysis in sub-critical water were reviewed. The review indicates that sub-critical water hydrolysis can be an efficient process for recovering useful chemicals from biomass wastes. This method is renewable, sustainable, efficient, and safe for the environment.     

Co-pyrolysis of paper waste and mustard press cake in a semi-batch pyrolyzer—optimization and bio-oil characterization

Under the present research study, the co-pyrolysis of paper waste and mustard press cake was conducted in a 50 mm diameter and 640 mm long semi-batch pyrolyzer in the temperature range of 673 to 1173 K in nitrogen atmosphere and synergistic relationship between the pyrolysis of two feed stocks has been observed. The paper wastes were composed of local packing paper, newspaper-based food packets of grocery, and printing paper in the ratio of 6:3:1. During co-pyrolysis, response surface methodology (RSM) technique has been employed using Design Expert Version 7.0.0 to determine the collective effects of factors, namely, A: ratio of paper waste to mustard press cake and B: pyrolysis temperature, on the yield of bio-oil, energy yield, and oxygen content of bio-oil. Optimization has been done by using RSM to identify the individual sets of values of independent parameters corresponding to maximum bio-oil yield (A: 9.0:1, B: 874.75 K), energy yield (A: 8.80:1, B: 812 K), and minimum oxygen content of bio-oil (A: 2.75:1, B: 883.06 K). Bio-oil obtained at maximum energy yield condition has been characterized using the Gas chromatography–mass spectrometry (GC-MS) and Fourier transform infrared spectroscopy (FTIR) spectroscopic analyses. The array of compounds present in the bio-oil compounds has been compared with literature data available on pyro-oil obtained from similar feed stocks.     

Recyling of plastic wastes via pyrolysis

Pyrolysis for the simultaneous generation of oils and gases can be convenient to obtain hydrocarbons and even to recover crude petrochemicals or to generate energy from waste plastics. A Gray–King apparatus has been used to pyrolyze waste polyethylene (PE), polystyrene (PS), both separately and with different compositions. Thermogravimetric analysis of waste plastics indicated the critical temperatures, which should be effective for pyrolysis. The chosen heating rate was low in order to achieve higher liquid yields. The results showed that waste PS yielded higher liquid, and waste PE yielded higher gaseous products. The dominant liquid product of PS waste was styrene whereas for waste PE, prophenylbenzene was the dominant pyrolysis product.     

Effects of reed straw, zeolite, and superphosphate amendments on ammonia and greenhouse gas emissions from stored duck manure

Stored poultry manure can be a significant source of ammonia (NH) and greenhouse gases (GHGs), including nitrous oxide (NO), methane (CH), and carbon dioxide (CO) emissions. Amendments can be used to modify physiochemical properties of manure, thus having the potential to reduce gas emissions. Here, we lab-tested the single and combined effects of addition of reed straw, zeolite, and superphosphate on gas emissions from stored duck manure. We showed that, over a period of 46 d, cumulative NH emissions were reduced by 61 to 70% with superphosphate additions, whereas cumulative NO emissions were increased by up to 23% compared with the control treatment. Reed straw addition reduced cumulative NH, NO, and CH emissions relative to the control by 12, 27, and 47%, respectively, and zeolite addition reduced cumulative NH and NO emissions by 36 and 20%, respectively. Total GHG emissions (as CO-equivalents) were reduced by up to 27% with the additions of reed straw and/or zeolite. Our results indicate that reed straw or zeolite can be recommended as amendments to reduce GHG emissions from duck manure; however, superphosphate is more effective in reducing NH emissions.     

Dry reforming of methane over oil palm shell activated carbon and ZSM-5 supported cobalt catalysts

In this study, cobalt supported oil palm shell activated carbon (Co/OPS-AC) and ZSM-5 zeolite (Co/ZSM-5) catalysts have been prepared for dry reforming of methane. Cobalt ratios of 6.0 and 14.0 wt% were deposited via wet impregnation method to the OPS-AC and ZSM-5 catalysts. The catalysts were characterized by XRD, N₂ adsorption--desorption isotherms, BET surface area, SEM, FESEM-EDX, TPR-H₂, and TPD-NH₃. The dry reforming of methane was performed using a micro reactor system under the condition of 10,000 ml/h.g-cat, 3 atm, CH₄/CO₂ ratio of 1.2:1.0 and temperature range from 923 K to 1023 K. The gaseous products were analyzed by gas chromatography (GC) with thermal conductivity detector (TCD) and further quantified to determine the conversions of CH₄ and CO₂, and the yields of CO and H₂. Experimental results revealed both catalysts exhibited lower conversions of CO₂ and CH₄ with the increase in temperature from 923 K to 1023 K. The reduced conversions may be due to the formation of carboneous substance on the catalyst known as coking. Comparatively, Co/OPS-AC gave higher conversions of CO₂ and CH₄ as well as higher yields of H₂ and CO as it has a higher surface area than Co/ZSM-5 which subsequently rendered higher activity for the reforming of methane. With the increasing cobalt loadings and reaction temperature, OPS-AC(14) catalyst exhibited improved activity and H₂/CO ratio. Based on these results, cobalt supported OPS activated carbon catalyst was suggested to be more effective for CO₂ and CH₄ conversions.     

新型L沸石在FCC汽油加氢脱硫催化剂中的应用研究

采用等体积浸渍法,制备了一系列含有相同含量活性组分(MoO3、CoO和NiO)不同USL沸石含量的加氢脱硫催化剂。通过X-射线衍射(XRD)、氮气吸附脱附、吡啶红外(Py-FTIR)和氨气程序升温脱附(NH3-TPD)等分析方法对样品进行了表征。结果表明:与Cat.0(参比剂,仅以γ-Al2O3为载体)相比,添加USL沸石催化剂所得加氢油的烯烃含量、芳烃含量和研究法辛烷值(RON)均增加;仅当催化剂载体中USL沸石加量在0~40m%之间变化时,加氢油的异构烷烃含量呈上升趋势;而当载体中USL沸石添加量在0~20m%之间变化时,催化剂的脱硫率有所升高。综合对比,当载体中USL沸石添加量约为40m%,催化剂具有最佳的综合性能指标,脱硫率达90%,RON损失仅为1.5左右。     

Allelopathic Potential of Switchgrass (Panicum virgatum L.) on Perennial Ryegrass (Lolium perenne L.) and Alfalfa (Medicago sativa L.)

This study investigated allelopathy and its chemical basis in nine switchgrass (Panicum virgatum L.) accessions. Perennial ryegrass (Lolium perenne L.) and alfalfa (Medicago sativa L.) were used as test species. Undiluted aqueous extracts (5 g plant tissue in 50 ml water) from the shoots and roots of most of the switchgrass accessions inhibited the germination and growth of the test species. However, the allelopathic effect of switchgrass declined when extracts were diluted 5- or 50-fold. Seedling growth was more sensitive than seed germination as an indicator of allelopathic effect. Allelopathic effect was related to switchgrass ecotype but not related to ploidy level. Upland accessions displayed stronger allelopathic potential than lowland accessions. The aqueous extract from one switchgrass accession was separated into phenols, organic acids, neutral chemicals, and alkaloids, and then these fractions were bioassayed to test for allelopathic potential. Alkaloids had the strongest allelopathic effect among the four chemical fractions. In summary, the results indicated that switchgrass has allelopathic potential; however, there is not enough evidence to conclude that allelopathic advantage is the main factor that has contributed to the successful establishment of switchgrass on China’s Loess Plateau.     

GC-MS法测定垃圾填埋场渗滤液中的有机污染物

采用GC-MS联用技术对深圳市两个垃圾填埋场（A和B）渗滤液中的有机污染物进行分析。垃圾场A是简易生活垃圾填埋场,垃圾场B是生活垃圾焚烧底渣填埋场。垃圾场A渗滤液中COD、TOC、NH3-N、NO3^--N等污染指标的浓度比垃圾场B渗滤液高一个数量级。两个垃圾填埋场渗滤液中分别检测出主要有机物72种和57种,其中含有大量难降解有机物,如酚类、胺类、杂环类物质。两个垃圾填埋场渗滤液中有机物组分的相对含量不同,渗滤液A中酚类物质含量最高,渗滤液B中有机物多为长链烷烃。     

Energy balances,greenhouse gas emissions and economics of biochar production from palm oil empty fruit bunches

This paper presents results from a gate-to-gate analysis of the energy balance, greenhouse gas (GHG) emissions and economic efficiency of biochar production from palm oil empty fruit bunches (EFB). The analysis is based on data obtained from EFB combustion in a slow pyrolysis plant in Selangor, Malaysia. The outputs of the slow pyrolysis plant are biochar, syngas, bio-oil and water vapor. The net energy yield of the biochar produced in the Selangor plant is 11.47 MJ kg⁻¹ EFB. The energy content of the biochar produced is higher than the energy required for producing the biochar, i.e. the energy balance of biochar production is positive. The combustion of EFB using diesel fuel has the largest energy demand of 2.31 MJ kg⁻¹ EFB in the pyrolysis process. Comparatively smaller amounts of energy are required as electricity (0.39 MJ kg⁻¹ EFB) and for transportation of biochar to the warehouse and the field (0.13 MJ kg⁻¹ EFB). The net greenhouse gas emissions of the studied biochar production account for 0.046 kg CO₂-equiv. kg⁻¹ EFB yr⁻¹ without considering fertilizer substitution effects and carbon accumulation from biochar in the soil. The studied biochar production is profitable where biochar can be sold for at least 533 US-$ t⁻¹. Potential measures for improvement are discussed, including higher productivity of biochar production, reduced energy consumption and efficient use of the byproducts from the slow pyrolysis.     

生物法处理含酚废水的研究

为了降低炼油厂污水处理场的酚负荷,对催化裂化汽提塔所排含酚废水的预处理进行了研究。进行了煤渣吸附实验,酚的生物降解动力学实验及酚在兼氧条件下的处理实验;采用４－氨基安替比林光度法测定酚浓度。实验结果表明采用煤渣填料－生物膜反应器,酚的去除率可达９０％,酚的生物降解符合一级反应动力学,酚类物质可在兼氧条件下降解     

Enzymatic oxidative transformation of chlorophenol mixtures

Chlorinated phenols are major industrial and agricultural xenobiotics that pollute soil and ground water. It has been shown that laccases catalyze the oxidative coupling of phenolic compounds. Therefore, the transformation of one or a mixture of several chlorinated phenols by a laccase from the fungus Trametes villosa was studied. Generally, if more than one phenol was added, the transformation of chlorinated phenols decreased, and if the concentration of the laccase was increased, the transformation of the phenols was enhanced. There were exceptions to these observations: for instance, the transformation of 0.1 mM 4-chlorophenol incubated with 1 mM 2,4-dichlorophenol in buffered salt solutions was not enhanced if the concentration of the laccase was increased from 2 to 20 DMP units/mL. The reason for the reduced transformation of chlorinated phenols in the presence of additional phenols is still unknown. However, in spite of some limitations, the application of laccase to decontaminate wastewater polluted with chlorinated phenols appears feasible.     

Alcohol, volatile fatty acid, phenol, and methane emissions from dairy cows and fresh manure

There are approximately 2.5 million dairy cows in California. Emission inventories list dairy cows and their manure as the major source of regional air pollutants, but data on their actual emissions remain sparse, particularly for smog-forming volatile organic compounds (VOCs) and greenhouse gases (GHGs). We report measurements of alcohols, volatile fatty acids, phenols, and methane (CH4) emitted from nonlactating (dry) and lactating dairy cows and their manure under controlled conditions. The experiment was conducted in an environmental chamber that simulates commercial concrete-floored freestall cow housing conditions. The fluxes of methanol, ethanol, and CH4 were measured from cows and/or their fresh manure. The average estimated methanol and ethanol emissions were 0.33 and 0.51 g cow(-1) h(-1) from dry cows and manure and 0.7 and 1.27 g cow(-1) h(-1) from lactating cows and manure, respectively. Both alcohols increased over time, coinciding with increasing accumulation of manure on the chamber floor. Volatile fatty acids and phenols were emitted at concentrations close to their detection limit. Average estimated CH4 emissions were predominantly associated with enteric fermentation from cows rather than manure and were 12.35 and 18.23 g cow(-1) h(-1) for dry and lactating cows, respectively. Lactating cows produced considerably more gaseous VOCs and GHGs emissions than dry cows (P < 0.001). Dairy cows and fresh manure have the potential to emit considerable amounts of alcohols and CH4 and research is needed to determine effective mitigation.     

生物滤池强化方法对水源水中乐果去除效果的试验研究

以乐果微污染水源水为研究对象,对比研究了KMnO4与O3作为预氧化剂,石英砂、沸石与活性炭作为滤料的生物滤池对饮用水水源中乐果残留物的去除效果。实验结果表明,以石英砂、沸石和活性炭作为滤料,经高锰酸钾或臭氧预氧化处理后,乐果去除率较好,特别是沸石和活性炭的去除率达到了90%以上。臭氧处理效果比高锰酸钾好,处理率提高了10%以内。从去除率、经济性和易操作性方面考虑,高锰酸钾和沸石联用更适合中国农村供水的实际情况。     

Greening of a campus restaurant at Stockholm University: sustainable development audits by means of the SDR methodology

The aim of this paper is to show how the environmental practices of a restaurant may be evaluated in a quantitative way. For this, a new methodology, sustainable development records (SDR), was used. This allows financial, environmental and social aspects of an operation to be handled in a systematic way. The results of the two sustainable development audits show that the restaurant washes more dishes per unit of chemicals used in 1994 than in 1991. However, there is a negative trend regarding the number of meals served per unit of water used and waste generated, which suggests that the restaurant in 1994 is more wasteful with these resources than in 1991. On the other hand, this might be explained by the fact that the restaurant has increased its use of primary products. The environmental ratios are increasing for both chemicals and energy, which means that more and more of the resources used are environmentally acceptable. The lowest environmental ratios are those for provisions (<2%) and transportation (<5%), which means that not more than 2% of the provisions and 5% of the transportation are environmentally acceptable in the long run. The restaurant's ratio of satisfied customers as well as its environmental image is improving, while the profitability has not changed. The results of this paper point to a general problem of environmental auditing in regard to the evaluation of perceived positive or negative developments of an individual enterprise, since there might be an opposite implication for the larger system. It is therefore crucial to look at several hierarchical levels in order to be able to assess the effects of environmental measures.