分离剂甲酸溶液浓度和温度对于铝塑湿法分离的影响研究

主要针对无菌复合包装废弃物中去除了纸浆后的铝塑部分的湿法分离工艺进行研究,选用甲酸作为分离溶剂,分析其反应机理。并着重对分离过程的影响控制因素进行实验研究,就不同的分离剂浓度、不同反应温度以及不同液固比条件下铝塑分离的效果及反应速率的变化分别进行分析研究,寻找铝塑片分离各影响因素之间的关系,为工业化生产应用提供参考,以提高无菌复合包装废弃物的再生利用率。     

城市污泥热解中试系统集成一体化研究及运行效果评估

为了促进城市污泥热解工艺的工程化应用,组建了污泥热解系统、热解产物分离回收利用系统、废气净化排放系统于一体较完整的热解中试装置,在实现污泥有效处置的同时也实现了高值能源回收利用。中试工况优化,较好工况为：热解时间30-40 min,热解终温450-500℃,在此条件下,干化污泥（含水率5%）减量率为50%;热值为33.8 MJ/kg的热解油产率为17.1%左右。通过对中试运行效果的评估,得出热解油和热解气两者能量或污泥炭自身能量可供干化污泥热解本身所需能量,从而为推动污水污泥热解工艺的工程化利用提供了支持。     

模拟医疗废物在管式电阻炉上的热解特性研究

在管式电阻炉上对由聚丙烯、面巾纸、纱布、医用脱脂棉、一次性口罩、医用乳胶手套等按一定比例组成的模拟医疗废物在氮气气氛进行了热解研究。重点探讨了10 K/min,20 K/min,30 K/min和40 K/min等不同升温速率对热解产物分布、产气特性和热解过程的影响。结果表明,随着温度升高,模拟废物的热解产生气体的主要成分逐渐由CO₂和CO转变为C₃H₆、CH₄、C₂H₆、C₂H₄和C₃H₈。同时,热解处理对模拟废物的减量化效果比较明显,固体残留率仅为5.61%～7.02%。而且,加热速率对模拟医疗废物热解过程的影响较大。     

生物质废物催化热解特性及多因素优化实验

生物质废物催化热解所得生物油中富含多环芳烃(PAHs)污染物,但其分布特征及相应影响因素尚缺乏深入探讨。以Co_3O_4为催化剂,采用管式炉反应器在不同温度下热解水曲柳木屑制备生物油,并分析其化学组分和16种PAHs污染物分布特征。结果表明,生物油中以酚类化合物为主,而PAHs污染物的种类与含量均随反应温度的升高而增加,PAHs总含量从389.60μg·g~(-1)(400℃)攀升至105 435.12μg·g~(-1)(700℃)。同时,将CO_2引入热解气氛,利用Box-Benhnken曲面响应法对催化热解过程的多个工艺因素进行优化。结果显示,在热解温度为511℃、停留时间为12.7 min、热解气氛的CO_2/N_2比例为88/12时,生物油产率达到最大值,约45%。研究结果对生物质废物的高效、低污染资源化利用具有参考价值。     

污泥中抗生素热解特性及动力学分析

通过分析污泥中3种典型抗生素环丙沙星(CIP)、土霉素(OTC)和磺胺二甲嘧啶(SM2)的热解过程与失重特性,研究其热解动力学特征。结果表明:CIP、OTC、SM2主要热解温度区间分别为150~625℃、220~600℃、260~480℃;初始热解温度以及最大失重峰对应温度均为OTCSM2CIP;CIP热解具有2个失重峰,OTC与SM2热解仅有1个失重峰;且SM2热解失重峰最高,反应最剧烈;抗生素热解最终残留物均为残碳,且CIP热解残留率最低,为18.9%。抗生素热解过程可分为3阶段:第1阶段反应级数均为2级,活化能最高,频率因子最大;OTC、SM2与CIP热解平均活化能分别为50.19、72.31、81.85 k J·mol-1,说明OTC热解反应最容易进行,CIP热解则相对较难。上述结果将为污泥热解炭化工艺实现抗生素消减提供良好的理论基础。     

餐厨垃圾分选有机废物热解动力学特性分析

针对餐厨垃圾生物处理过程中产生的有机废物,为了实现餐厨垃圾的资源化利用,使用热重分析仪对其典型组分:塑料、骨头及难降解生物质,进行了单独及混合热重(TG)特性研究。结果表明:难降解生物质(BRB)、骨头等生物质类物质失重温度较低,最大失重率温度分别为325和341℃,塑料的失重温度较高,最大失重率温度在475℃;通过对混合物料的热重曲线和动力学分析,在较低温度(400℃),塑料和骨头对热解过程有一定的抑制作用,而在高温(400℃)状态下,二者在热解过程中有协同作用;含有3种组分的实际物料在166~361℃条件下热解过程符合二维相界反应(函数为2(1-α)1/2);而在361~550℃热解符合三级动力学反应(函数为(1-α)3),在整个温度阶段(166~550℃)中的实际活化能低于模拟活化能(59.6986.57 k J·mol-1),表明3种物料混合热解有协同作用。     

不干胶废弃物热重分析

为了探索不干胶类包装废弃物的热解特性,采用热重分析手段分析了不同升温速率条件下不干胶类废弃物的失重特点,并且采用Ozawa法和KAS法比较分析不同转化率条件下的表观活化能分布.热重分析结果表明,不干胶类废弃物的热解主要分为3个阶段:第1阶段(室温～ 200℃)为不干胶类废弃物的干燥阶段,第2阶段(200 ～ 590℃)为热解的主要阶段,第3阶段(590 ～800℃)为热解半焦的深度热解阶段.升温速率对热解失重率有重要影响,Ozawa法和KAS法计算结果表明,2种方法计算的热解活化能比较接近,Ozawa法得到的活化能为349.9 kJ/mol,KAS法得到的活化能为336.9kJ/mol;并且不干胶类废弃物的热解表观活化能呈现出阶段性分布.     

微波辐射对生物质热解过程的影响

自行设计加工了微波热重实验装置,研究了在微波辐射下菜籽粕热解过程特征及其产物产出规律.在此基础上,对比分析了菜籽粕微波热解与电热热解产物产出率之间的差异.结果发现,在菜籽粕微波热解过程中,半纤维素的反应区间为180 ～ 370℃,其转化率可以达到87.0％;纤维素的热解反应区间为370 ～ 550℃,其热解转化率32.8％.表明在微波作用下,纤维素的热稳定性远高于半纤维素.在菜籽粕的微波热解过程中,冷凝液的产生主要集中在100 ～400℃的温度范围内,热解得到的生物质油类主要是菜籽粕的半纤维素热解生成的.不凝气的产生主要集中在300 ～ 600℃的温度范围内,并且主要为纤维素与木质素的热解反应产生的.与电热方式相比,菜籽粕的微波热解升温速率较快,菜籽粕微波热解生物质炭的产出率较高,冷凝液产出率相对较低.     

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。     

园林废弃物与餐厨厌氧沼渣混合热解特性及动力学分析

为了探究园林废弃物和餐厨厌氧沼渣的热解特性以及2者混合热解的交互作用。采用热重分析法对餐厨厌氧沼渣、园林废弃物及其不同比例的混合样品热解特性进行了分析,并研究了混合比例和升温速率对热解过程的影响。结果表明,园林废弃物与沼渣单独热解时,园林废弃物热解反应活性高且能耗低,热解终温为400 ℃左右;沼渣热解反应活性低且能耗高,热解终温为600 ℃左右。混合热解实验中,随着园林废弃物添加比例升高,样品热解残余率不断下降,综合热解指数不断增大,园林废弃物与沼渣混合热解适宜的添加比例为50%,热解终温为600 ℃左右。采用Coats-Redfern积分法对园林废弃物、沼渣及混合样品进行动力学分析,园林废弃物和餐厨厌氧沼渣反应活化能分别为12.08和1.79 kJ·mol⁻¹,混合样品实际活化能均略高于理论值。这说明,2者混合热解过程中存在一定抑制作用,但对热解过程影响不大。本研究结果可为园林废弃物与餐厨厌氧沼渣混合热解处理提供参考。     

固体废物在固定床式热解炉内热解产气特性的实验研究

垃圾热解技术以其较低的污染排放和较高的能源回收率在固体废弃物处理领域里占有重要地位。利用小型外热型热解炉对城市垃圾、生物质及有害固体废弃物进行热解实验 ,分析发现 ,物料的挥发分、加热方式以及热解终温等对产气影响大 ,随温度的增加产气中H2 含量逐渐增多 ,C2 H4和C2 H6 的含量逐渐下降 ,气体热值有一个最大值。     

The Autothermal Pyrolysis of Waste Tires

Abstract

The growing amount of rubber waste, such as that from tires and cables, has resulted in serious environmental problems. Since rubber waste is not easily biodegradable even after a long period of landfill treatment, material and energy recovery is the preferable alternative to disposal. The potential offered by waste tire pyrolysis for solving both energy and waste treatment problems is widely recognized. Pyrolysis is one method of inducing thermal decomposition without using any oxidizing agent, or using such a limited supply of the agent that oxidization does not proceed to an appreciable extent. The latter may be described as autothermal pyrolysis and will be studied in the present work.

The main objective of this research was to study the operating parameters of autothermal pyrolysis of scrap tires in a laboratory-scale fluidized bed reactor with a 100-cm bed height (10 cm I.D.) and a 100-cm freeboard (25 cm I.D.). Scrap tires were pyrolyzed in a limited oxygen supply, so that the heat for pyrolysis of the scrap tires was provided by combustion of some portion of the scrap tires. The operating parameters evaluated included the effect on the pyrolysis oil products and their relative proportions of (1) the air factor (O.O7–O35); (2) the pyrolysis temperature (370–570 °C); and (3) the catalyst added (zeolite and calcium carbonate). The results show that: (1) the composition of the liquid hydrocarbon obtained is affected significantly by the air factor; (2) the higher operating temperature caused a higher yield of gasoline and diesel; (3) the yield of gasoline increased due to the catalyst zeolite added, and the yield of diesel increased due to the addition of the catalyst calcium carbonate; (4) the principal constituents of gasoline included dipentene and diprene.     

船舶塑料垃圾热解特性及动力学分析

利用热重分析(TGA)研究船舶塑料垃圾在不同升温速率和不同气氛下的热解特性,并得到了热解动力学参数。结果表明,船舶塑料垃圾的热解过程主要有3个阶段,比一般塑料热解复杂;随着升温速率增大,最大热解速率和最大热解速率温度等热解特性参数也增大,反应变得更剧烈;N2/CO2比为4∶1时,热解反应进行得最完全,固体残留率最少。动力学分析表明,采用3个连续一级反应模型能很好地拟合实验数据;不同的升温速率和气氛比对反应各阶段活化能均有不同程度的影响。     

Pyrolysis of wastewater sludge and composted organic fines from municipal solid waste: laboratory reactor characterisation and product distribution

Sludge from municipal wastewater treatment plants and organic fines from mechanical sorting of municipal solid waste (MSW) are two common widespread waste streams that are becoming increasingly difficult to utilise. Changing perceptions of risk in food production has limited the appeal of sludge use on agricultural land, and outlets via landfilling are diminishing rapidly. These factors have led to interest in thermal conversion technologies whose aim is to recover energy and nutrients from waste while reducing health and environmental risks associated with material re-use. Pyrolysis yields three output products: solid char, liquid oils and gas. Their relative distribution depends on process parameters which can be somewhat optimised depending on the end use of product. The potential of pyrolysis for the conversion of wastewater sludge (SS) and organic fines of MSW (OF) to a combustion gas and a carbon-rich char has been investigated. Pyrolysis of SS and OF was done using a laboratory fixed-bed reactor. Herein, the physical characterisation of the reactor is described, and results on pyrolysis yields are presented. Feedstock and chars have been characterised using standard laboratory methods, and the composition of pyrolysis gases was analysed using micro gas chromatography. Product distribution (char/liquid/gas) from the pyrolysis of sewage sludge and composted MSW fines at 700°C for 10 min were 45/26/29 and 53/14/33%, respectively. The combustible fractions of pyrolysis gases range from 36 to 54% for SS feedstock and 62 to 72% from OF. The corresponding lower heating value range of sampled gases were 11.8–19.1 and 18.2–21.0 MJ m^?3, respectively.     

预分选汽车破碎残余物热解特性及其动力学分析

我国每年产生的汽车破碎残余物 (automobile shredder residue,ASR) 数量巨大,亟需无害化处理和资源化利用。固废热解过程因产生的二次污染物少,且产品利用价值高,逐渐成为研究的热点。针对某报废汽车生产线产生的5种典型预分选ASR物料,在固定床反应器中考察了温度 (500~900 ℃) 和物料种类对ASR热解三相产物组成、热解焦微观结构及重金属分布规律的影响,通过热重 (TG) 分析ASR从常温到900 ℃热失重过程,并采用分布式活化能 (DAEM) 法计算其热解动力学。结果表明,ASR热解主要发生于200~500 ℃范围内,热解反应活化能为17.39~195.21 kJ·mol⁻¹。提高热解温度,ASR样品可产生更多热解气,且H₂、CO和CH₄等成分占比增加,焦油产生量减少,同时促进焦油二次裂解以及组分向苯环化转化。红外和拉曼光谱分析表明,热解温度升高,热解焦中主要发生-OH、-CH₃、-C=C-以及-COOH等分子基团的脱除,不同ASR热解焦I_D1/I_G值在3.77~6.57内,石墨化程度增大,热解焦中重金属分布受温度和物料种类影响显著。本研究结果可为开发ASR热解技术提供参考。     

Study of the transference rules for bromine in waste printed circuit boards during microwave-induced pyrolysis

The production of waste printed circuit boards (WPCBs) has drawn increasing global concern, especially because the high bromine (Br) content (5-15%) places obstacles in the way of simple disposal techniques. Microwave-induced pyrolysis of WPCBs provides a promising way to dispose of these hazardous and resource-filled wastes. The transference rules for Br during microwave-induced pyrolysis have been investigated experimentally. It was found that the microwave energy could be used more efficiently to accelerate the heating rate and improve the final pyrolysis temperature by adding some activated carbon (AC) as microwave absorbents. The high temperature and rapid pyrolysis process promoted the yields of gaseous products and the decomposition of brominated compounds into hydrogen bromide and then benefited the capture of Br and the debromination of byproducts. The application of a calcium carbonate (CaCO3) layer overhead led to over 95% debromination of the liquid products and over 50% capture of the total Br. It can be concluded that the presented method is suitable for the control of Br transference in the recycling of WPCBs. This method can also be extended to the disposal of the electronic scraps.     

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.     

润滑油废白土的热解处理

以润滑油废白土为原料,利用电热解法,研究了热解终温、加热速率和CaO添加量对热解产物的影响。实验结果表明:热解终温对热解产物的影响最为显著。随着热解终温的升高,不凝气产量和产油率均迅速增加。当热解终温达到600℃时,其增加的速率逐渐缓慢增大。当控制热解终温为800℃、加热速率为16℃/min、CaO添加量为0.5%时,富氢气体产量为189.2 L/kg,气体中主要成分为H2和CH4,其含量分别为27.97%和41.64%;热解残渣含油率和重金属溶出物均低于标准规定值,热解油产率为10.98%,回收率为38.94%,其主要成分为汽油、柴油和重油3部分组成,分别含19.13%、31.35%和49.52%。     

城市生活垃圾与园林废弃物的共热解特性

为实现城市生活垃圾减量化、无害化和资源化,采用热重分析天平和实验室固定床热解反应器进行城市生活垃圾（MSW）与园林废弃物共热解实验,研究了不同热解终温、松树枝和柳树枝添加比例对热解产物产率影响,并利用气质联用色谱分析仪（GC-MS）对热解油进行表征分析。实验结果表明：MSW、松树枝和柳树枝的热解过程均可以分为3个阶段,主要包括脱水、热解、炭化;MSW、松树枝和柳树枝单独热解时最大失重速率分别出现在321.48、358.23和377.83℃;MSW与松树枝共热解DTG曲线在热解反应第2阶段有2个析出峰,分别在342.32℃和471.48℃,比MSW单独热解时,失重率增加了7.29%。当城市生活垃圾与松树枝、柳树枝的添加量分别为3：1时,热解液体产物产率明显升高,热解油中醇类、羧酸类、醛类等含氧有机物的含量降低,热值增加,热解油中氧含量降低,且松树枝对共热解焦油的脱氧效果更为显著,热解油品质得到提升。