高速粉碎机作用下的电路板真空热解渣破碎特性

首先利用高速粉碎机对大颗粒废弃电路板真空热解渣进行破碎处理,然后采用筛分和颗粒计数法研究破碎产物的破碎规律与解离特性。结果表明,大颗粒废弃电路板真空热解渣在破碎过程中存在着显著的选择性破碎,金属铜主要分布在较粗粒级产物中,玻璃纤维和炭黑则主要分布在较细粒级产物中,并且铜能在较大粒级上实现充分解离;98.64%的铜分布在粒级为0.45~4.0 mm的破碎产物中,而92.05%的玻璃纤维和炭黑分布在粒级为-0.45 mm的破碎产物中;当粒级为-2.0 mm时,铜的解离度达到100%。     

废轮胎热解炭黑及其改性后的特性研究

对废轮胎热解炭黑(简称热解炭黑)采用硝酸酸洗及酸洗后加入硬脂酸2种改性方法,制备出热解炭黑、酸洗炭黑及硬脂酸改性酸洗炭黑3种炭黑。运用SEM、XPS等分析手段进行了表征。研究表明,硝酸酸洗后热解炭黑的灰分从20.5%降到了4.0%,BET表面积从54.92 m2/g增大到69.62 m2/g,DBP吸收值从123 mL/100g提高到170 mL/100 g。加入硬脂酸后BET表面积和DBP吸收值略有下降。XPS结果显示:热解炭黑表面覆盖有碳质沉积物,表面官能团极性较低;酸洗炭黑表面C—C,C—H含量降低,C—OR、C—OEt和COOR、COOH官能团含量增加;硬脂酸改性后表面含碳官能团基本没有变化,但其表面双键氧的含量高于热解炭黑和酸洗炭黑。     

废旧电路板与碳酸钙共热解脱卤的研究

采用热重分析仪和石英管式炉热解反应器，分别对以酚醛树脂为基板的废旧电路板和混合碳酸钙后的废旧电路板进行热解实验研究，着重考察了添加碳酸钙后的酚醛树脂基板废旧电路板热解特性及添加量不同对卤素脱除效果的影响。实验结果表明，碳酸钙的加入对废旧电路板的降解行为和热解油的基本组成没有明显的影响，但热解油的各组分含量有所差异；随着热解温度的提高或者CaCO₃含量的增多，卤素可以更多地由有机卤向无机卤转变并束缚在固体残渣中，由此得到较好的脱卤效果。当60%PR-WPCBs与40%CaCO₃共热解，热解油中的溴化物也减少了7.6% 。在600℃等量CaCO₃与PR-WPCBs共热解时生成75.6%无机卤，其中70.62%束缚于固体残渣中，可见达到较好的脱卤效果。     

废弃中药渣催化热解制取生物油的研究

利用热重分析仪(TGA)对植物类中药渣的热解特性进行了研究,用Coats-Redfern积分法计算了其热解动力学参数,得出中药渣热解反应符合一级反应动力学方程,其活化能较低,为36.0kJ/mol。考察了热解温度对气体、液体、固体产物的影响,在723K时,液体产物生物油产率最高,为39%。以介孔分子筛SBA-15以及分别负载Al、Sn、Ni、Cu和Mg的SBA-15作为催化剂,研究催化热解对气体、液体、固体产率及生物油组分的影响。研究表明,Al-SBA-15的催化效果较好,液体产率最高,为36%;采用元素分析仪和热值测定仪,得到用Al-SBA-15作为催化剂时生物油的氧质量分数最低,低位热值最高。用GC/MS对生物油组分的分析结果表明,添加Al-SBA-15后,热解产物中脂肪族和芳香族化合物增加,而含氧化合物减少。     

悬浮电解法回收废旧电子印刷线路板中的铜

以废旧电子印刷线路板中的金属铜为处理对象,采用悬浮电解法制取纯铜粉。选择了4个影响铜粉的纯度、脱落率和电流效率的因素,每个因素3个水平进行正交实验。实验结果表明,硫酸铜的浓度、氯离子的浓度和电流密度对铜粉的纯度、脱落率和电流效率有较大的影响。通过对正交实验结果的分析得出最优的电解条件,在此电解条件下可得到铜粉的纯度99.8%、脱落率99.6%和电流效率99.7%。     

基于复合球团的以生物质焦油为还原剂的铬渣无害化处理

结合目前铬渣解毒现状,提出生物质焦油热解还原铬渣的新技术,利用生物质气化副产物焦油作为解毒剂,进而提高铬渣解毒和资源化水平,降低能耗。将生物质焦油和铬渣混合制成球团通过热解实现Cr(VI)向Cr(III)的形态转化,对影响焦油热解还原铬渣的主要因素:温度、铬渣粒径、球团尺寸、铬渣与焦油当量比等进行探讨。结果表明:还原铬渣的质量随温度升高而提高,温度超过400℃后无明显变化,减小铬渣粒径与球团尺寸可明显提高还原质量。当热解温度为400℃,还原时间10 min,铬渣与焦油当量比2.29,铬渣粒径0.074 mm,球团粒径2.5 mm时,可得到Cr(VI)还原率98.65%的还原铬产品。     

铬渣的热解无害化处理

采用热解工艺无害化处理铬渣,探讨了稻秆在铬渣无害化处理中的作用.研究了热解温度、稻秆与铬渣质量比、铬渣粒径及保温时间对铬渣热解无害化处理的影响,并分析了热解前后热解产物中铬元素形态的变化.结果表明,热解工艺能有效地将铬渣中Cr(Ⅵ)还原,稻秆热解过程中产生的气相挥发分对Cr(Ⅵ)的还原起核心作用.较为适宜的热解条件:热解温度为400 ℃,稻秆与铬渣质量比为0.10,铬渣粒径<2 000 μm,保温时间为10 min.在该热解条件处理下,热解产物中的Cr(Ⅵ)质量浓度为121 mg/kg,低于热解前铬渣中的Cr(Ⅵ)(3 400 mg/kg).热解后,可交换态及碳酸盐结合态铬含量降低,大部分铬转化成了稳定的有机结合态和残渣态,极大地降低了铬渣的危害.第一作者:张大磊,男,1982生,博士研究生,研究方向为固体废弃物热处理.     

生物质废弃物快速热解制取富氢气体的实验研究

采用管式炉对红松锯屑快速热解制取富氢气体进行了实验研究,分析了反应器温度、物料粒径和催化剂对热解产物组成的影响.结果表明高温能加快生物质快速热解进程,减少炭和焦油生成量,利于富氢气体的生成,800℃时气态产物比例可达56.9 wt.%,气态产物中H2体积分数由4.3%(500℃下)上升至17.2%,H2 CO体积分数达68.3%.小粒径能增大热解气态产物的比例,但对气态产物组成的影响很小,这可能与红松锯屑本身质地疏松有关.以与生物质直接混合方式添加的煅烧白云石能使热解产物中H2含量增加,但造成产气过程变缓,炭生成量增多,富氢气体总产量未能得到提高.     

微波辐照热解废印刷电路板产物的分析研究

为了减少电子废弃物对环境的危害,实现其资源化回收利用,研究了微波辐照热解废印刷电路板的效果,并采用红外光谱、气相色谱质谱和X荧光光谱等方法对热解产物的组成及性质进行了分析.结果显示:微波热解得到的气体、液体、固体的产率分别为7%～33%、26%～45%、31%～51%,其中气体主要由CO、CO2、H2及有机烃类组成,可燃性气体占70%(体积分数)左右,可作为燃料气加以利用;液体分为水相及油相,经常压蒸馏后得到的120～250 ℃馏分主要为单酚化合物,苯酚高达50%(质量分数)左右,甲基苯酚和邻甲基苯酚为25%(质量分数)以上,是良好的化工原料;固体中除炭外,还含有许多金属如铅、锡和铜等,可以回收利用.说明微波热解技术处理电子废弃物可实现资源化回收利用.     

鸟粪石循环利用处理高氨氮废水的热解行为

为了循环利用鸟粪石处理高氨氮废水,探讨了鸟粪石煅烧与加碱热解的脱氮率,利用电镜扫描(SEM)和X射线衍射(XRD)对2种热解产物进行了分析。鸟粪石煅烧条件为:温度100～225℃,时间1～5 h;加碱热解条件为:温度60～95℃,时间0.5～4 h,加碱量OH-∶NH4+摩尔比值0.4～1.5。结果表明,虽然XRD分析显示2种热解产物都已失去鸟粪石的特征峰,但是鸟粪石加碱热解效果更好,最佳热解条件为:加碱量OH-∶NH4+摩尔比值1,温度90℃,时间2 h,鸟粪石脱氮率95%以上;加碱热解产物表面为多孔状,完全失去了晶体结构;煅烧热解鸟粪石脱氮率仅为80%左右,热解产物晶体结构破坏不完全。鸟粪石在最佳条件下热解循环处理高氨氮废水,可循环使用6次,氨氮去除率80%以上,出水磷浓度小于8 mg/L。     

Pyrolysis kinetics and residue characteristics of petrochemical industrial sludge

This study investigated the pyrolysis characteristics of sludge from wastewater treatment plants in the petrochemical industry and focused on the pyrolysis kinetics, elemental composition of residue, and volatile organic compounds (VOCs) of exhaust gas. As pyrolysis temperature increased to 773 K, the increasing rate of crude oil production tended to a stable condition. The result indicated that the optimal temperature of crude oil and water mixed production was 773 K. When pyrolysis temperature increased from 673 to 973 K, carbon, oxygen, nitrogen, and hydrogen concentrations of residue decreased and the sulfur concentration of residue increased. The concentrations of benzene, toluene,ethylbenzene, and styrene increased by the increasing pyrolysis temperature. We found that the reaction order of sludge pyrolysis was 2.5 and the activation energy of the reaction was 11.06 kJ/mol. We believe that our pyrolysis system is transitional between devolatilization and combustion.     

两段式热解厨余垃圾实验研究

通过厨余垃圾的工业分析，发现其挥发分比例较高，适合热解利用；采用热重分析方法分析了不同条件下厨余垃圾的热解特性，提出了厨余垃圾两段式热解转化利用的思路，得出了厨余垃圾热解的合适工艺条件。在自行设计建造的一段回转炉、二段焦化罐中对厨余垃圾热解，并分析了产物的组成和性质。     

Characteristics of leachate from pyrolysis residue of sewage sludge

The pyrolysis residue (SP) of sewage sludge (SS) produced at 500 degrees C was subjected to batch and column leaching tests to investigate the release of its organic and inorganic constituents and metals. For comparison, incineration ash (SI) obtained from a SS incinerator was also tested. Pyrolysis and incineration reduced organic matter of SS from 0.78 kg kg(-1)-dry SS to 0.16 and 0.01 kg kg(-1)-dry SS, respectively. Heavy metals remained in SP without being volatilized, although Cd and Pb were transferred into the off-gas during incineration. In the batch leaching test with the leaching liquid-to-solid mass ratio (L/S)=10, the pH of the SS, SP, and SI filtrates was 6.3, 7.9, and 11.0, respectively. The total organic carbon concentrations were in the order SS (877 l mg l(-1))>SP (99 mg l(-1))>SI (26 mg l(-1)). The SP and SI filtrates met the landfill standard for the Cd and Pb concentrations (<0.3 mg l(-1)). In the column tests, although the SP contained more organic matter than that of SI, its carbon discharge into the leachate under aerobic conditions was similar to that of SI under anaerobic conditions. The leaching of heavy metals, such as Cd, Cr, Pb, and Zn, was also suppressed in SP during the active decomposition of organic matter. We demonstrated that pyrolysis reduces the potential release of pollutants from sewage sludge in landfill, making it a promising method of treating sewage sludge before landfilling.     

Pyrolysis Kinetics and Residue Characteristics of Petrochemical Industrial Sludge

ABSTRACT

This study investigated the pyrolysis characteristics of sludge from wastewater treatment plants in the petrochemical industry and focused on the pyrolysis kinetics, elemental composition of residue, and volatile organic compounds (VOCs) of exhaust gas. As pyrolysis temperature increased to 773 K, the increasing rate of crude oil production tended to a stable condition. The result indicated that the optimal temperature of crude oil and water mixed production was 773 K. When pyrolysis temperature increased from 673 to 973 K, carbon, oxygen, nitrogen, and hydrogen concentrations of residue decreased and the sulfur concentration of residue increased. The concentrations of benzene, toluene, ethylbenzene, and styrene increased by the increasing pyrolysis temperature. We found that the reaction order of sludge pyrolysis was 2.5 and the activation energy of the reaction was 11.06 kJ/mol. We believe that our pyrolysis system is transitional between devolatilization and combustion.     

Remote sensing-based estimates of annual and seasonal emissions from crop residue burning in the contiguous United States

Crop residue burning is an extensive agricultural practice in the contiguous United States (CONUS). This analysis presents the results of a remote sensing-based study of crop residue burning emissions in the CONUS for the time period 2003-2007 for the atmospheric species of carbon dioxide (CO2), methane (CH4), carbon monoxide (CO), nitrogen dioxide (NO2, sulfur dioxide (SO2), PM2.5 (particulate matter [PM] < or = 2.5 microm in aerodynamic diameter), and PM10 (PM < or = 10 microm in aerodynamic diameter). Cropland burned area and associated crop types were derived from Moderate Resolution Imaging Spectroradiometer (MODIS) products. Emission factors, fuel load, and combustion completeness estimates were derived from the scientific literature, governmental reports, and expert knowledge. Emissions were calculated using the bottom-up approach in which emissions are the product of burned area, fuel load, and combustion completeness for each specific crop type. On average, annual crop residue burning in the CONUS emitted 6.1 Tg of CO2, 8.9 Gg of CH4, 232.4 Gg of CO, 10.6 Gg of NO2, 4.4 Gg of SO2, 20.9 Gg of PM2.5, and 28.5 Gg of PM10. These emissions remained fairly consistent, with an average interannual variability of crop residue burning emissions of +/- 10%. The states with the highest emissions were Arkansas, California, Florida, Idaho, Texas, and Washington. Most emissions were clustered in the southeastern United States, the Great Plains, and the Pacific Northwest. Air quality and carbon emissions were concentrated in the spring, summer, and fall, with an exception because of winter harvesting of sugarcane in Florida, Louisiana, and Texas. Sugarcane, wheat, and rice residues accounted for approximately 70% of all crop residue burning and associated emissions. Estimates of CO and CH4 from agricultural waste burning by the U.S. Environmental Protection Agency were 73 and 78% higher than the CO and CH4 emission estimates from this analysis, respectively. This analysis also showed that crop residue burning emissions are a minor source of CH4 emissions (< 1%) compared with the CH4 emissions from other agricultural sources, specifically enteric fermentation, manure management, and rice cultivation.     

Characterization of carbonaceous combustion residues. I. Morphological,elemental and spectroscopic features

Scanning electron microscopy, surface area determination, elemental analysis, organic matter extraction and solid-state cross polarization/magic angle spinning and Bloch decay/magic angle spinning 13C nuclear magnetic resonance (NMR) spectroscopy were used to investigate distinctive features among carbonaceous combustion residues. Black carbon (BC) samples included diesel soot, urban dust, carbon black, chimney soot, vegetation fire residues, wood and straw charcoals. Particles varied from small spheres (<50 nm) in fossil BC (>100 m(2)/g), to large layered structures in plant-derived BC (generally <8 m(2)/g). Chimney soot also included large (>1 micrometer) liquid-like structures, while spherules >100 nm were unique to urban dust. The ratios of amorphous to soot carbon (SC) (isolated by thermal degradation) were not necessarily correlated with the degree of aromaticity estimated from H/C ratios. In particular, values of SC in diesel soot were clearly overestimated. Solvent-extractable organic matter (SEOM) was <2% for charcoals and carbon black, but >13% for urban dust, chimney and diesel soot. SEOM is thought to clog pores or to form large waxy globules, hence reducing surface areas. The ratio of polar/nonpolar SEOM was generally <7 for fossil BC, but >30 for plant-derived BC. NMR analysis revealed essentially one chemical shift in the aromatic C region of charcoals, while diesel soot also showed important aliphatic contributions. Aliphatic and oxygenated C predominated over aryl C in urban dust and chimney soot. These morphological and chemical characteristics of the BC samples are discussed in terms of their environmental implications.     

Correlation of polychlorinated naphthalenes with polychlorinated dibenzofurans formed from waste incineration

Isomer composition of polychlorinated naphthalenes (PCNs) was measured for municipal waste incinerator fly ash samples and for emission samples produced from soot and copper-deposit experiments conducted at the United States Environmental Protection Agency (US-EPA). Two types of PCN isomer patterns were identified. One pattern contained specific PCN isomers in which chlorine atoms are substituted as if the peri(alpha-) position were dechlorinated from the higher chlorinated PCNs one by one. In another pattern, the isomers had a tendency for the chlorine atoms to assume successive positions on the naphthalene ring, which may be caused by specifically oriented chlorination. Some of these isomers increased, together with several polychlorinated dibenzofuran (PCDF) and a few polychlorinated dibenzo-p-dioxin (PCDD) isomers. The ratios between some specific PCN, PCDF, and PCDD isomers measured for the fly ash samples agree with those obtained from the soot and copper-deposit experiments. The observations suggest that these isomers were formed possibly from de novo synthesis utilizing the carbon structure contained in soot under the catalytic effect of a copper compound. Typical isomers for PCNs and PCDFs produced from incineration emissions were identified.     

A morphological investigation of soot produced by the detonation of munitions

The morphology of three different detonation soot samples along with other common soot materials such as carbon black, diesel soot and chimney soot was studied by elemental and proximate analysis, X-ray diffraction and electron microscopy. The goal of this study was to better define the morphology of the detonation soot in order to better assess the interactions of this type of soot with explosive residues. The detonation soot samples were obtained by the detonation of artillery 155mm projectiles filled with either pure TNT (2,4,6-trinitrotoluene) or composition B, a military explosive based on a mixture of TNT and RDX (trimethylentrinitramine). The carbon content of the soot samples varied considerably depending on the feedstock composition. Detonation soot contains less carbon and more nitrogen than the other carbonaceous samples studied, due to the molecular structure of the energetic materials detonated such as TNT and RDX. The ash concentration was higher for detonation soot samples due to the high metal content coming from the projectiles shell and to the soil contamination which occurred during the detonation. By X-ray diffraction, diamond and graphite were found to be the major crystalline carbon forms in the detonation soot. Two electron microscopy techniques were used in this study to visualise the primary particles and to try to explain the formation mechanism of detonation soot samples.     

Effects of residue incorporation and plant growth on soil labile organic carbon and microbial function and community composition under two soil moisture levels

This study investigates the effects of residue incorporation coupled with plant growth and soil moisture level on wheat biomasses, soil nutrients, labile organic carbon (LOC), microbial metabolic profiles, and community composition. Four management practices were used in a 180-day pot experiment: (1) control (CON), (2) maize (Zea mays L.) residue incorporation without plants (MR), (3) wheat (Triticum aestivum L.) plants without maize residue (WP), and (4) maize residue incorporation with wheat plants (MRWPs). Each management practice included soil moisture at both 40 and 80% of field capacity. At wheat harvest, soil nutrient contents in the WP and MRWP treatments were significantly lower than in the CON and MR treatments. In comparison with the CON treatment, MR, WP, and MRWP treatments resulted in 35, 23, and 67% increases in dissolved organic carbon content; 17, 12, and 34% increases in hot-water extractable organic carbon content; and 78, 50, and 150% increases in microbial biomass carbon content. Furthermore, microbial utilizations of carboxylic acids and polymer carbon sources in the MR, WP, and MRWP treatments were 261 and 88%, 239 and 105%, and 300 and 126% higher than in the CON treatment. The MR and CON treatments had similar phospholipid fatty acid (PLFA) content but the WP and MRWP treatments had significantly increased gram-negative content and changes to community composition compared with the CON and MR treatments. The wheat biomass, LOC, and PLFA contents significantly increased with greater soil moisture. Overall, these results suggest an additive effect of residue incorporation and plant growth on LOC contents, primarily due to the changes in microbial utilization of carbon sources and community composition.     

Fate of bromine in pyrolysis of printed circuit board wastes

Behavior of Br in pyrolysis of the printed circuit board waste with valuable copper and oil recycling has been studied in the present work. Experimentally, pyrolysis of the printed circuit board waste generated approximately 40.6% of oils, 24.9% of noncondensible gases and 34.5% of solid residues that enriched in copper (90-95%). The cuts of the oils produced from pyrolysis of the printed circuit board waste into weighted boiling fraction were primarily light naphtha and heavy gas oil. Approximately 72.3% of total Br in the printed circuit board waste were found in product gas mainly as HBr and bromobenzene. However, by extended X-ray absorption fine structural (EXAFS) spectroscopy, Cu-O and Cu-(O)-Cu species with bond distance of 1.87 and 2.95 A, respectively, were observed in the solid residues. Essentially, no Cu-Br species was found.