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，C2H4和C2H6的含量逐渐下降，气体热值有一个最大值。     

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.     

催化剂掺混对污泥快速热解产气的影响

将干污泥(DS)与3种催化体系(CaO、焦炭、CaO-焦炭)掺混,经机械化学预处理后制得热解混合样品,考察催化剂掺混对DS快速热解产气的影响。研究表明,CaO可以提高DS热解综合产气效果,促进热解气相产物中的CH4和CO2向H2和CO转化,当CaO和DS质量比为1.00∶1.00时,热解气相产物中H2、CO体积分数之和、气体产率、产气低位热值及H2产量均达到最大值,分别为77.04%、0.412 m3/kg、62.75kJ/kg和6.88 mol/kg;焦炭可以改善DS热解气相产物品质,当焦炭和DS质量比为1.00∶1.00时,热解气相产物中H2体积分数和氢占比(H2与CO的体积比)最优,分别为38.90%和1.23;CaO-焦炭体系可以明显提高DS热解液相产物质量分数,当CaO、焦炭和DS质量比为0.50∶0.50∶1.00时,热解液相产物的质量分数达到最大值50.17%。研究结果为剩余污泥的资源化利用提供数据支持。     

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。     

利用旋转炉热解城市污泥的产物特性

采用旋转管式加热炉实验台在惰性条件下对城市污泥进行了热解实验,系统研究了不同热解温度对气态产物和固态产物成分的影响。结果表明:污泥经热解后的产物在600℃时,比表面积最大值为158.02 m2/g,孔容最高为109.58 mm3/g。随着热解温度的升高,气态产物和液态产物的产率增加,而固态产物则减少。在热解温度450~750℃,热解产物中的固态产物产率由53.65%降至31.69%;气体产率从11.23%升至24.74%,其中H_2、CO、CO_2、CH_4、C_2H_4、C_2H_6和C_2H_2占总气体的75%以上,H_2含量随着热解温度的升高而升高。热解气中小分子碳氢化合物含量较高,600℃时热解气体中含氢气体主要包括:H_2、CH_4、C_2H_4、C_3H_8、正丁烷(C_4H_(10))及C_2H_6等,其中H_2和CH_4含量分别为27.98%和23.63%。CH4、C3H8、C_4H_(10)等气体的含量随着热解温度的升高呈现先增后减趋势,且在600℃达到最大值,C_2H_2、C_2H_6在450℃时其浓度最高。随着热解温度的升高,N、C和H3种元素在热解固态产物中的质量分数呈明显下降的趋势。     

镍基催化剂对污泥微波热解制生物气效能的影响

为实现污水污泥减量化、无害化及资源化的目标,在微波热解污水污泥基础上,进行了镍基催化剂对制取生物气效能影响的研究。采用元素分析对污泥元素进行检测,气/质联用分析(GC-MS)和气相色谱(GC)对热解生物气的组成和含量进行测定。实验结果表明,镍基催化剂的添加对微波热解污水污泥制取生物气有较大促进作用。5%添加量与800℃热解终温条件下具有最佳催化效果:生物气中H2、CO产量最大,H2产量由29 g/kg增加到35.8 g/kg,提升23.4%,CO产量由302.7 g/kg增加到383.3 g/kg,提升26.6%;同时催化剂还能提高热能利用效率,降低热解终温,即5%添加量在700℃热解终温时可达到空白800℃时的产气效果;镍基催化剂主要在500~600℃时发挥催化作用,加快了H2和CO的释放。微波热解污泥制取的生物气具有产量大、富含H2与CO等优点,可推动污水污泥的资源化进程。     

污泥连续式微波热解制备生物气

采用升温迅速的微波能作为热源,利用自主设计微波设备对含水率为82%(m/m)的湿污泥进行高温热解实验。采用单因素实验法,探究热解终温、停留时间、活性炭添加量对污泥热解生物气组分和含量的影响规律,确定连续式运行的最佳工况条件:热解终温900℃,停留时间50 min,活性炭添加比例为30%,热解功率1 600 W;在此基础上进行连续12h微波高温热解实验,共热解污泥56 kg,产生生物气32.26 kg,热解油10.98 kg,固体残渣12.66 kg,产气转化率高达57.8%,生物气组分H_2+CO含量高达67%,热解产物具有良好的工业利用价值。污泥热解生物气中H2S浓度超标10倍以上,而NH_3浓度未超标,硫化氢的去除技术研究值得关注。     

脱水淋滤-UBF工艺处理餐厨垃圾中试研究

以常州市餐厨垃圾为研究对象,采用脱水淋滤-UBF工艺,通过现场实验研究该工艺处理餐厨垃圾过程中厌氧工艺参数(SCOD、p H值和VFA)的变化及产气效能。结果表明:脱水淋滤厌氧反应阶段餐厨垃圾减量率在84%以上,SCOD和VFA浓度先升高后降低,最高达到120 000 mg·L~(-1)和900 mmol·L~(-1)以上;UBF反应阶段p H逐渐上升,运行稳定后维持在7.0~7.5;SCOD逐渐降低,出水在8 000 mg·L~(-1)以下,去除率90%以上;VFA逐步降低,出水降低至100 mmol·L~(-1)。UBF运行稳定后,每吨餐厨垃圾产气量达到83 m3以上,产气效率较为理想。可见脱水淋滤-UBF工艺处理餐厨垃圾是可行的,具有较好经济效益和社会效益。     

2种烟煤掺混干化污泥中温热解制气

以2种不同产地烟煤和某污水处理厂污水污泥作为研究对象,在实验室预处理,将两者按不同比例掺混后使用管式电阻炉进行中温热解实验,探讨了烟煤与干化污泥掺混热解产气特性。实验结果表明:烟煤掺混干化污泥热解,不改变两者热解产H_2、CO和CH_4的规律。在相同热解温度下,烟煤的掺混比例越高,产生H_2体积百分含量越大。对于CH_4,掺混物料产气峰值热解温度由800℃降低至700℃。混合物料中污泥掺混比例增加会增加CO含量。通过热重实验,随着物料中配入干化污泥质量比重增加,热解反应所需活化能减小。     

炼焦煤尾煤催化热解制取富氢燃料气

以炼焦煤原煤、尾煤为研究对象，采用微量热重、常量固定床实验装置对其在热解过程中的质量变化和气相产物进行了对比分析。考察了温度、6种催化剂（CaO、MgO、Fe、Ni、NaOH、A1）及其添加比例对炼焦煤尾煤热解制取富氢燃料气的影响。结果表明，尾煤中富集的无机矿物质对热解制取富氢燃料气有促进作用，单位尾煤热解H2产率要比原煤高出1．93％。温度是影响尾煤热解产气的重要参数，热解终温的上升有利于H2产量的提高，随终温800℃升高到950℃H，产量增长了32．59mL／g。在催化热解实验中，除Al和MgO对尾煤热解有抑制作用外，CaO、Fe、Ni及NaOH均对尾煤热解产H2有促进作用，以CaO和Fe效果最为明显。并且不同添加比例的CaO和Fe对热解制取富氢燃料有一定的影响。     

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%。     

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。     

Formation characteristics of aerosol particles from pulverized coal pyrolysis in high-temperature environments

The formation characteristics of aerosol particles from pulverized coal pyrolysis in high temperatures are studied experimentally. By conducting a drop-tube furnace, fuel pyrolysis processes in industrial furnaces are simulated in which three different reaction temperatures of 1000, 1200, and 1400 degrees C are considered. Experimental observations indicate that when the reaction temperature is 1000 degrees C, submicron particles are produced, whereas the particle size is dominated by nanoscale for the temperature of 1400 degrees C. Thermogravimetric analysis of the aerosol particles stemming from the pyrolysis temperature of 1000 degrees C reveals that the thermal behavior of the aerosol is characterized by a three-stage reaction with increasing heating temperature: (1) a volatile-reaction stage, (2) a weak-reaction stage, and (3) a soot-reaction stage. However, with the pyrolysis temperature of 1400 degrees C, the volatile- and weak-reaction stages almost merge together and evolve into a chemical-frozen stage. The submicron particles (i.e., 1000 degrees C) are mainly composed of volatiles, tar, and soot, with the main component of the nanoscale particles (i.e., 1400 degrees C) being soot. The polycyclic aromatic hydrocarbons (PAHs) contained in the aerosols are also analyzed. It is found that the PAH content in generated aerosols decreases dramatically as the pyrolysis temperature increases.     

Optimising the preparation of activated carbon from digested sewage sludge and coconut husk.

Preparation of activated carbon from sewage sludge is a promising way to dispose of sewage sludge as well as to produce a low-cost adsorbent for pollutant removal. This research work aimed to optimise the condition for activated carbon preparation from anaerobically digested sewage sludge with the additive coconut husk. The sewage sludge sample was mixed with the additive coconut husk. The preparation condition variables investigated involved the concentration of the ZnCl2 solutions, heating temperature, dwell time and heating rate in pyrolysis and the mixing ratio of coconut husk to sewage sludge. Surface area, pore size distribution, aqueous phenol adsorption capacity and the production yield of the final products were determined and compared. Experimental results revealed that low concentrations of ZnCl2 solution tended to improve the microporosity of the final product. Heating temperature had a considerable impact on the surface area, pore size distribution and phenol adsorption capacity of the final products, whereas dwell time and heating rate performed comparatively insignificantly. The effect of increasing the mixing ratio of coconut husk to sewage sludge was principally to increase the microporosity of the final products. The activated carbon with the highest BET surface area was produced with the activation of 5 M ZnCl2 solution and, thereafter, pyrolysis at a heating temperature of 500 degrees C for 2 h with a heating rate of 10 degrees C/min. The mixing ratio of 1:4 in terms of coconut husk to sewage sludge based on their dried weights was found to be most cost effective.     

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.     

不同升温速率下城市污水污泥热解特性及动力学研究

利用差热-热重分析法和Coats-Redfern积分法,对杭州某污水处理厂污泥在不同升温速率下的热解特性及反应动力学特征进行研究。实验结果表明,热解温度从室温升至900℃时,污泥热解过程可分为4个失重阶段;升温速率对污泥热解转化率、挥发分析出温度以及最大失重率等热解特性参数都有显著影响。升温速率越高污泥最大失重率越大;而较低的升温速率延迟了污泥热解反应时间,导致污泥失重量相对较大。根据Coats-Redfern积分法计算结果,污泥在氮气氛围下的热解反应为二级反应模式。提高升温速率可显著增加污泥热解的表观活化能和频率因子。     

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.     

铝塑包装废物热解过程能量平衡分析

热解是实现铝塑包装废物中有机物和金属铝分离的有效方法。利用外热式固定床反应系统对其进行热解实验,研究热解时物质与能量流向的变化趋势。结果表明:(1)铝塑包装废物最佳热解温度为723～773 K;(2)热解产生的可回收能量远大于反应所需能量,可以实现热解系统的自供热;(3)铝塑包装废物热解的净能源回收效率为62%～63%。     

城郊乡村生活垃圾衍生燃料热解特性研究

将城郊乡村生活垃圾加工成粒径6.0 mm左右的垃圾衍生燃料(RDF),采用热重(TG)分析和红外光谱等研究其热解特性.结果表明:(1)在RDF挥发分阶段和生物质挥发分阶段,助燃添加剂处于活泼分解阶段,加入了30％(质量分数)秸秆、玉米芯等生物质作助燃添加剂后的RDF(以下简写为混合RDF)分子碎片正发生内部氢重排,总体挥发分产物较多,并且有明显的二次裂解,失重提高到4.85 mg,失重率约提高12％.在RDF与生物质重叠的碳固定阶段,助燃添加剂失重率有一定提高,热重微分(DTG)峰值速率增加,为RDF碳固定阶段的进一步热解提供了良好的支持.(2)快加热产气速率均大于慢加热.(3)热解终温越高,越有利气体析出.(4)RDF的热解固体产率随着热解终温的升高而降低,在850℃时为31.9％;热解气体产率随着热解终温升高而迅速升高,在850℃时可达49.8％.(5)根据红外光谱图,城郊乡村生活垃圾加工成的RDF中所含的氯元素基本上以HCl形式释放.(6)一级动力学反应可以准确地描述物料热解过程.     

Bio-syngas production with low concentrations of CO2 and CH4 from microwave-induced pyrolysis of wet and dried sewage sludge

This paper assesses the feasibility of producing syngas from sewage sludge via two pyrolysis processes: microwave-induced pyrolysis (MWP) and conventional pyrolysis (CP). The changes in the composition of the produced gas as a function of the pyrolysis treatment and the initial moisture content of the sludge were evaluated. It was found that MWP produced a gas with a higher concentration of syngas than CP, reaching values of up to 94vol%. Moreover, this gas showed a CO2 and CH4 concentration around 50% and 70%, respectively, lower than that obtained in the gas from CP. With respect to the effect of moisture on gas composition, this was more pronounced in CP than in MWP. Thus, the presence of moisture increases the concentration of H2 and CO2 and decreases that of CO, especially when CP was used. In order to elucidate the behaviour of CO2 during the pyrolysis, the CO2 gasification kinetics of the char obtained from the pyrolysis were investigated. It was established that in microwave heating the gasification reaction is much more favoured than in conventional heating. Therefore, the low concentration of CO2 and the high concentration of CO in the microwave pyrolysis gas could be due to the self-gasification of the residue by the CO2 produced during the devolatilization of the sewage sludge in the pyrolysis process.