The effect of microwave pyrolysis on product characteristics and bromine migration for a non-metallic printed circuit board.

At present, it is necessary to carry out environmentally friendly treatment of non-metallic fractions (NMFs) of waste printed circuit board (WPCB) to improve resource utilization. NMFs of WPCB are pyrolyzed by microwave heating to determine the effect of different operating conditions on the characteristics of pyrolysis products. The results show that yields for residue, oil and gas are 59.03-67.63, 7.10-28.46 and 4.86-33.88 wt%. A high temperature promotes a decrease in oil yield and an increase in non-condensable gas yield. An increase in the NaOH dose results in a more significant cracking of the oil to gas. Increasing the concentration of NaOH increases the mass fraction of the total Br in residues (from 23.62 to 86.94 %), so the addition of NaOH is beneficial to the fixation of Br. A kinetics study shows that there are two thermal decomposition regions (398-625 K and 675-925 K), and NaOH-catalyzed pyrolysis reduces the activation energy to 18.91 and 31.95 kJ mol-1, respectively. The formation of Br-containing substances in the pyrolysis oil and gas can be inhibited if the bromine fixation in pyrolysis residue increases. NaOH-catalyzed pyrolysis can reduce bromine and also reduce energy recovery efficiency. This pyrolysis process still requires further research to improve the recovery of energy and valuable materials.

Residue characteristics of sludge from a chemical industrial plant by microwave heating pyrolysis.

Sludge from biological wastewater treatment procedures was treated using microwave heating pyrolysis to reduce the environmental impact of a chemical plant. In this study, major elements, trace elements, PAHs and nitro-PAHs in raw sludge, and pyrolysis residues were investigated. The contents of major element from raw sludge were carbon 46.7 ± 5.9%, hydrogen 5.80 ± 0.58%, nitrogen 6.81 ± 0.59%, and sulfur 1.34 ± 0.27%. Trace elemental concentrations including Zn, Mn, Cr, Cd, As, and Sn were 0.410 ± 0.050, 0.338 ± 0.008, 0.063 ± 0.006, 0.019 ± 0.001, 0.004 ± 0.001, and 0.003 ± 0.002 mg/g, respectively. For various pyrolysis temperatures, Ca, Fe, Sr, Cr, and Sn contents remained at almost the same level as those in raw sludge. Results indicated that these elements did not easily volatilize. The content of 16 PAH species was about 4.78 µg/g in the raw sludge and 23-65 µg/g for pyrolysis residues associated with various temperatures. The content of ten nitro-PAHs was about 58 ng/g for the raw sludge and 141-744 ng/g for pyrolysis residues. The total nitro-PAH content was highest at 600 °C and then decreased when the temperature was over 600 °C. Total nitro-PAH content was about 247 ng/g at 800 °C.

Temperature influence on product distribution and characteristics of derived residue and oil in wet sludge pyrolysis using microwave heating.

Sludge taken from a wastewater treatment plant of the petrochemical industry was dewatered and pyrolyzed to produce liquid oil as an alternative fuel via microwave heating. Element contents of dried sludge were 45.9±3.85wt.% carbon, 7.70±1.43wt.% hydrogen, 4.30±0.77wt.% nitrogen and 3.89±0.52wt.% sulfur. Two major thermal degradation peaks of sludge were determined during the microwave pyrolysis process, one at 325-498K (most of the water was vaporized, and the weight loss was over 85wt.%) and the other at 548-898K for sludge constituent decomposition. Zn content was high in the dried raw material and residues. Other toxic elements such as Ni, Cr, Pb, As and Cd contents were 0.61-0.99, 0.18-0.46, 0.15-0.25, 0.018-0.034, and 0.006-0.017mg/g, respectively. About 14-20wt.% of oil was produced based on the dried sludge cake, and the oil major elements were C (69-72wt.%), H (5.7-6.7wt.%), N (1.9-2.2wt.%), and S (0.58-0.82wt.%). The heat values of liquid oils were 8700-9200kcal/kg at 400-800°C.

Liquid oil and residual characteristics of printed circuit board recycle by pyrolysis.

Non-metal fractions of waste printed circuit boards (PCBs) were thermally treated (200-500°C) under nitrogen atmosphere. Carbon, hydrogen, and nitrogen were determined by elemental analyzer, bromine by instrumental neutron activation analysis (INAA), phosphorus by energy dispersive X-ray spectrometer (EDX), and 29 trace elements by inductively coupled plasma atomic emission spectrometer (ICP-AES) and mass spectrometry (ICP-MS) for raw material and pyrolysis residues. Organic compositions of liquid oil were identified by GC (gas chromatography)-MS, trace element composition by ICP system, and 12 water-soluble ions by IC (ionic chromatography). Elemental content of carbon was >450 mg/g, oxygen 300 mg/g, bromine and hydrogen 60 mg/g, nitrogen 30 mg/g, and phosphorus 28 mg/g. Sulfur was trace in PCBs. Copper content was 25-28 mg/g, iron 1.3-1.7 mg/g, tin 0.8-1.0mg/g and magnesium 0.4-1.0mg/g; those were the main metals in the raw materials and pyrolytic residues. In the liquid products, carbon content was 68-73%, hydrogen was 10-14%, nitrogen was 4-5%, and sulfur was less than 0.05% at pyrolysis temperatures from 300 to 500°C. Phenol, 3-bromophenol, 2-methylphenol and 4-propan-2-ylphenol were major species in liquid products, accounting for >50% of analyzed organic species. Bromides, ammonium and phosphate were the main species in water sorption samples for PCB pyrolysis exhaust.

Element and PAH constituents in the residues and liquid oil from biosludge pyrolysis in an electrical thermal furnace.

Biosludge can be pyrolyzed to produce liquid oil as an alternative fuel. The content of five major elements, 22 trace elements and 16 PAHs was investigated in oven-dried raw material, pyrolysis residues and pyrolysis liquid products. Results indicated 39% carbon, 4.5% hydrogen, 4.2% nitrogen and 1.8% sulfur were in oven dried biosludge. Biosludge pyrolysis, carried out at temperatures from 400 to 800°C, corresponded to 34-14% weight in pyrolytic residues, 32-50% weight in liquid products and 31-40% weight in the gas phase. The carbon, hydrogen and nitrogen decreased and the sulfur content increased with an increase in the pyrolysis temperature at 400-800°C. NaP (2 rings) and AcPy (3 rings) were the major PAHs, contributing 86% of PAHs in oven-dried biosludge. After pyrolysis, the PAH content increased with the increase of pyrolysis temperature, which also results in a change in the PAH species profile. In pyrolysis liquid oil, NaP, AcPy, Flu and PA were the major species, and the content of the 16 PAHs ranged from 1.6 to 19 µg/ml at pyrolysis temperatures ranging from 400 to 800°C. Ca, Mg, Al, Fe and Zn were the dominant trace elements in the raw material and the pyrolysis residues. In addition, low toxic metal (Cd, V, Co, and Pb) content was found in the liquid oil, and its heat value was 7,800-9,500 kcal/kg, which means it can be considered as an alternative fuel.

Exhaust constituent emission factors of printed circuit board pyrolysis processes and its exhaust control.

The printed circuit board (PCB) is an important part of electrical and electronic equipment, and its disposal and the recovery of useful materials from waste PCBs (WPCBs) are key issues for waste electrical and electronic equipment. Waste PCB compositions and their pyrolysis characteristics were analyzed in this study. In addition, the volatile organic compound (VOC) exhaust was controlled by an iron-impregnated alumina oxide catalyst. Results indicated that carbon and oxygen were the dominant components (hundreds mg/g) of the raw materials, and other elements such as nitrogen, bromine, and copper were several decades mg/g. Exhaust constituents of CO, H2, CH4, CO2, and NOx, were 60-115, 0.4-4.0, 1.1-10, 30-95, and 0-0.7mg/g, corresponding to temperatures ranging from 200 to 500°C. When the pyrolysis temperature was lower than 300°C, aromatics and paraffins were the major species, contributing 90% of ozone precursor VOCs, and an increase in the pyrolysis temperature corresponded to a decrease in the fraction of aromatic emission factors. Methanol, ethylacetate, acetone, dichloromethane, tetrachloromethane and acrylonitrile were the main species of oxygenated and chlorinated VOCs. The emission factors of some brominated compounds, i.e., bromoform, bromophenol, and dibromophenol, were higher at temperatures over 400°C. When VOC exhaust was flowed through the bed of Fe-impregnated Al2O3, the emission of ozone precursor VOCs could be reduced by 70-80%.

Emission factor of exhaust gas constituents during the pyrolysis of zinc chloride immersed biosolid.

Pyrolysis enables ZnCl2 immersed biosolid to be reused, but some hazardous air pollutants are emitted during this process. Physical characteristics of biosolid adsorbents were investigated in this work. In addition, the constituents of pyrolytic exhaust were determined to evaluate the exhaust characteristics. Results indicated that the pyrolytic temperature was higher than 500 °C, the specific surface area was >900 m(2)/g, and the total pore volume was as much as 0.8 cm(3)/g at 600 °C. For non-ZnCl2 immersed biosolid pyrolytic exhaust, VOC emission factors increased from 0.677 to 3.170 mg-VOCs/g-biosolid with the pyrolytic temperature increase from 400 to 700 °C, and chlorinated VOCs and oxygenated VOCs were the dominant fraction of VOC groups. VOC emission factors increased about three to seven times, ranging from 1.813 to 21.448 mg/g for pyrolytic temperatures at 400-700 °C, corresponding to the mass ratio of ZnCl2 and biosolid ranging from 0.25-2.5.

Exhaust characteristics during the pyrolysis of ZnCl2 immersed biosludge.

Biosludge can be reused as an adsorbent after ZnCl(2) activation, pyrolysis, washing with HCl and distilled water, and drying. But the pyrolysis exhaust of ZnCl(2) immersed sludge can be hazardous to human health and the environment. The chemical composition, including carbon, nitrogen, hydrogen, sulfur and 21 trace elements, as well as the physical characteristics, including specific surface area, pore volume, pore size distribution and pore diameter of pyrolytic residue, were investigated in this work. In addition, the components of pyrolytic exhaust including 30 VOC species and 5 odorous sulfur gases were determined to evaluate the exhaust characteristics. The results indicated that the pyrolytic temperature was higher than 500°C, the specific surface area could be over 900 m(2)/g, and the total pore volume could be up to 0.8 cm(3)/g at 600°C. Exhaust concentration fractions of VOC groups were about 65-71% oxygenated VOCs, 18-21% chlorinated VOCs, 4-6% aromatic VOCs, and 6-10% acrylonitrile and cyclohexane under the specific conditions in this study.

Pyrolytic product characteristics of biosludge from the wastewater treatment plant of a petrochemical industry.

Biosludge was produced from the wastewater treatment plant of a petrochemical industry. The element compositions of pyrolytic residues, CO, CO(2), NOx, SOx, total hydrocarbons and detailed volatile organic compounds of pyrolytic gas, and C, H, N, S content and compositions in biofuel were determined in this study. Generally, 75-80% water content in sludge cakes and about 65-70% weight of water vapor and volatile compounds were volatilized during the drying process. Propene, propane, 1-butene, n-butane, isobutene, toluene and benzene were the major volatile organic compounds (VOCs) of the pyrolytic gas, and the concentrations for most of the top 20 VOC species were greater than 5 ppm. C(5)-C(9) compounds contributed 60% by weight of biofuel; 4-hydroxy-4-methyl-2-pentanone was the highest species, accounting for 28-53% of biofuel at various pyrolytic temperatures. Based on the dried residues, there was 8.5-13% weight in pyrolytic residues, 62-82% weight in liquid products (water and crude oil) and 5.8-30% weight in the gas phase after pyrolytic processing at 500-800 degrees C. Finally, 1.5-2.5 wt% liquid fuel was produced after the distillation process. The pyrolytic residues could be reused, the pyrolytic liquid product could be used as a fuel after distillation, and the pyrolytic gas could be recycled in the pyrolytic process to achieve non-toxic discharge and reduce the cost of sludge disposal.

Molecular connectivity indices for predicting bioactivities of substituted nitrobenzene and aniline compounds.

Bioconcentration and toxicity of 22 substituted nitrobenzene and aniline compounds to aquatic organisms were assessed with quantitative structure-activity relationship (QSAR). Acute toxicities of aquatic organisms, including daphnia (Daphnia pulex) and carp (Cyprinus carpio), to 22 chemicals have been determined in our previous work. In this study, the bioconcentration factors (BCFs) for carp were further investigated. By the use of multiple-regression analyses, the molecular connectivity indices (MCIs) can describe both acute toxicity and bioconcentration for the test organisms. Applicable QSAR model (0.856

Volatile organic compound constituents from an integrated iron and steel facility.

This study measured the volatile organic compound (VOC) constituents of four processes in an integrated iron and steel industry; cokemaking, sintering, hot forming, and cold forming. Toluene, 1,2,4-trimethylbenzene, isopentane, m,p-xylene, 1-butene, ethylbenzene, and benzene were the predominant VOC species in these processes. However, some of the chlorinated compounds were high (hundreds ppbv), i.e., trichloroethylene in all four processes, carbon tetrachloride in the hot forming process, chlorobenzene in the cold forming process, and bromomethane in the sintering process. In the sintering process, the emission factors of toluene, benzene, xylene, isopentane, 1,2,4-trimethylbenzene, and ethylbenzene were over 9 g/tonne-product. In the vicinity of the manufacturing plant, toluene, isopentane, 1,2,4-trimethylbenzene, xylene and ethylbenzene were high. Toluene, 1,2,4-trimethylbenzene, xylene, 1-butene and isopentane were the major ozone formation species. Aromatic compounds were the predominant VOC groups, constituting 45-70% of the VOC concentration and contributing >70% to the high ozone formation potential in the stack exhaust and workplace air. The sequence of VOC concentration and ozone formation potential was as follows: cold forming>sintering>hot forming>cokemaking. For the workplace air, cokemaking was the highest producer, which was attributed to the fugitive emissions of the coke oven and working process release.

Pyrolysis characteristics of integrated circuit boards at various particle sizes and temperatures.

A pyrolysis method was employed to recycle the metals and brominated compounds blended into printed circuit boards. This research investigated the effect of particle size and process temperature on the element composition of IC boards and pyrolytic residues, liquid products, and water-soluble ionic species in the exhaust, with the overall goal being to identify the pyrolysis conditions that will have the least impact on the environment. Integrated circuit (IC) boards were crushed into 5-40 mesh (0.71-4.4mm), and the crushed particles were pyrolyzed at temperatures ranging from 200 to 500 degrees C. The thermal decomposition kinetics were measured by a thermogravimetric (TG) analyzer. The composition of pyrolytic residues was analyzed by Energy Dispersive X-ray Spectrometer (EDS), Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). In addition, the element compositions of liquid products were analyzed by ICP-AES and ICP-MS. Pyrolytic exhaust was collected by a water-absorption system in an ice-bath cooler, and IC analysis showed that the absorbed solution comprised 11 ionic species. Based on the pyrolytic kinetic parameters of TG analysis and pyrolytic residues at various temperatures for 30 min, the effect of particle size was insignificant in this study, and temperature was the key factor for the IC board pyrolysis. Two stages of decomposition were found for IC board pyrolysis under nitrogen atmosphere. The activation energy was 38-47 kcal/mol for the first-stage reaction and 5.2-9.4 kcal/mol for the second-stage reaction. Metal content was low in the liquid by-product of the IC board pyrolysis process, which is an advantage in that the liquid product could be used as a fuel. Brominate and ammonium were the main water-soluble ionic species of the pyrolytic exhaust. A plan for their safe and effective disposal must be developed if the pyrolytic recycling process is to be applied to IC boards.

Chemical constituents in particulate emissions from an integrated iron and steel facility.

Particle emissions from four integrated iron and steel plant processes, i.e., coke making, sintering, cold forming, and hot forming, were investigated in this study. Particle compositions of 21 element species, 11 ionic species, elemental carbon (EC), organic carbon (OC) and 16 polyaromatic hydrocarbons (PAHs) were analyzed to create "fingerprints" of the particles emitted from various processes in an integrated iron and steel plant. Results indicated that element compositions (0.11-0.42 g/g), water-soluble ions (0.34-0.52 g/g), elemental carbon (0.008-0.14 g/g), organic carbon (0.02-0.06 g/g) and PAHs (0.52-6.2 mg/g) contributed to the particle mass. In general, sulfur had a higher mass contribution than the other elements, which resulted from the use of coal, flux, heavy oil, and many recycled materials in the iron and steel plant. The particle mass contribution of potassium and chlorine in the sinter plant was higher than in other processes; this may be attributed to the lower boiling point and volatility of potassium. In addition, many recycled materials were fed into the sinter plant, causing a high concentration of potassium and chlorine in the particle phase. Eight PAH compounds were analyzed in the four processes. The carcinogenic compound Benzo(a)pyrene (BaP) was detectable only in the sintering process.

Correlations between experimental and predicted equilibrium distribution coefficient of chlorobenzene and chlorophenol compounds in soil-water systems using partial solubility parameters.

Many pesticides are degraded to become chlorinated aromatic compounds in soils. Equilibrium distribution of chlorobenzene and chlorophenol compounds in soil-water systems of Yangmingshan loam, Pingcheng silty clay loam and Annei silty loam was studied with the integral distribution equilibrium equation involving the partial solubility parameters of the chemicals. If the adsorption of chemicals on soils is partitioning in soil organic matter surrounding the soil mineral particles, the absorption constant (Kd) of a chemical in soil-water system could be stated as the distribution coefficient (or partition constant, Koc) of the chemical in the two adjunct immiscible phases--water and soil organic matter. The distribution coefficient (Koc) of chemicals calculated from the integral distribution equilibrium equation agrees well with the experimental adsorption coefficient (Kd, or experimental Koc) of chemicals determined in this study, for all the three different types of soils in water according to multiple-regression analysis. Reference data of Karger or Tijssen are employed to estimate the Koc for both polar and non-polar chemicals. The integral distribution equilibrium equation can exactly describe the distribution behavior of nonionic compound of chlorobenzenes and chlorophenols in soil-water systems.

Adsorption characteristics of benzene on biosolid adsorbent and commercial activated carbons.

This study selected biosolids from a petrochemical waste-water treatment plant as the raw material. The sludge was immersed in 0.5-5 M of zinc chloride (ZnCl2) solutions and pyrolyzed at different temperatures and times. Results indicated that the 1-M ZnCl2-immersed biosolids pyrolyzed at 500 degrees C for 30 min could be reused and were optimal biosolid adsorbents for benzene adsorption. Pore volume distribution analysis indicated that the mesopore contributed more than the macropore and micropore in the biosolid adsorbent. The benzene adsorption capacity of the biosolid adsorbent was 65 and 55% of the G206 (granular-activated carbon) and BPL (coal-based activated carbon; Calgon, Carbon Corp.) activated carbons, respectively. Data from the adsorption and desorption cycles indicated that the benzene adsorption capacity of the biosolid adsorbent was insignificantly reduced compared with the first-run capacity of the adsorbent; therefore, the biosolid adsorbent could be reused as a commercial adsorbent, although its production cost is high.

Acute lethal toxicity of environmental pollutants to aquatic organisms.

The acute lethal toxicity of environment pollutants including chlorophenol, haloalkane, quinone, and substituted nitrobenzene (i.e., nitrophenol, nitrobenzene, nitrotoluene, and aniline) compounds to aquatic organisms was determined. Determination of toxicity of chemicals was performed with chlorella, daphnia, carp, and tilapia. The toxicity of chlorophenols had no relation to the number of chlorine atoms on the benzene ring, but monochlorophenol had lower activity than more chlorine-substituted compounds. The tolerance levels of daphnia and carp to haloalkanes was found to be higher than that of chlorella; toxicity to chlorella was several hundred times higher than to daphnia. The toxicity of naphthoquinone compounds to chlorella and carp was higher than that of anthraquinone. A compound with a monochloride substitution on anthraquinone ring was less toxic to carp than those substituted with amine, hydroxyl, and dichlorine groups. Nitrobenzene compounds with an additional substitution group on the p position were extremely toxic to daphnia and carp.