Vacuum pyrolysis of waste tires with basic additives

Granules of waste tires were pyrolyzed under vacuum (3.5-10kPa) conditions, and the effects of temperature and basic additives (Na(2)CO(3), NaOH) on the properties of pyrolysis were thoroughly investigated. It was obvious that with or without basic additives, pyrolysis oil yield increased gradually to a maximum and subsequently decreased with a temperature increase from 450 degrees C to 600 degrees C, irrespective of the addition of basic additives to the reactor. The addition of NaOH facilitated pyrolysis dramatically, as a maximal pyrolysis oil yield of about 48wt% was achieved at 550 degrees C without the addition of basic additives, while a maximal pyrolysis oil yield of about 50wt% was achieved at 480 degrees C by adding 3wt% (w/w, powder/waste tire granules) of NaOH powder. The composition analysis of pyrolytic naphtha (i.b.p. (initial boiling point) approximately 205 degrees C) distilled from pyrolysis oil showed that more dl-limonene was obtained with basic additives and the maximal content of dl-limonene in pyrolysis oil was 12.39wt%, which is a valuable and widely-used fine chemical. However, no improvement in pyrolysis was observed with Na(2)CO(3) addition. Pyrolysis gas was mainly composed of H(2), CO, CH(4), CO(2), C(2)H(4) and C(2)H(6). Pyrolytic char had a surface area comparable to commercial carbon black, but its proportion of ash (above 11.5wt%) was much higher.     

Studies of the thermal degradation of waste rubber

One kind of Chinese waste tire's sample was pyrolyzed under an inert atmosphere by using thermo-gravimetric apparatus (TGA) and differential thermal analysis (DTA). Different pyrolysis temperature ranges were determined according to the reaction transition temperature obtained by TGA and DTA. Then, at each temperature range, the pyrolysis gaseous products were analyzed by gas chromatography (GC). The influence of the temperature range on the relative yields of the major decomposition products is studied, and a mechanism for the formation of the main components was also investigated. The results indicate that pyrolysis of waste rubber follows the radical mechanism, and the major products are not seriously affected by increasing the temperature from room temperature to 420 degrees C and from 421 to 600 degrees C, but the degradation of blend rubber is different for each of the compositional elastomer.     

Tertiary recycling of PVC-containing plastic waste by copyrolysis with cattle manure

The corrosion from pyrolysis of PVC in plastic waste was reduced by copyrolysis of PVC with cattle manure. The optimization of pyrolysis conditions between PVC and cattle manure was studied via a statistical method, the Box-Behnken model. The pyrolysis reaction was operated in a tubular reactor. Heating rate, reaction temperature and the PVC:cattle manure ratio were optimized in the range of 1-5 degrees C/min, 250-450 degrees C and the ratio of 1:1-1:5, respectively. The suitable conditions which provided the highest HCl reduction efficiency were the lowest heating rate of 1 degrees C/min, the highest reaction temperature of 450 degrees C, and the PVC:cattle manure ratio of 1:5, with reliability of more than 90%. The copyrolysis of the mixture of PVC-containing plastic and cattle manure was operated at optimized conditions and the synergistic effect was studied on product yields. The presence of manure decreased the oil yield by about 17%. The distillation fractions of oil at various boiling points from both the presence and absence of manure were comparable. The BTX concentration decreased rapidly when manure was present and the chlorinated hydrocarbon was reduced by 45%. However, the octane number of the gasoline fraction was not affected by manure and was in the range of 99-100.     

Pyrolysis characteristics and kinetics of chicken litter

Chicken litter generally consists of a mixture of bedding, manure, feathers and spilled food. Flock of birds litter (flock) is a litter consisting of hardwood shavings, feed, feathers and manure; and broiler litter (broiler) is a cake of chicken litter. A kinetic investigation of the pyrolysis of chicken litter (flock and broiler) was carried out using thermogravimetric analysis (TGA) at heating rates of 5 degrees C/min, 10 degrees C/min and 20 degrees C/min. Most of the materials decomposed between 270 degrees C and 590 degrees C at each heating rate. The region of decomposition of flock and broiler was slightly lower than that of the wood chips. Wood chips (bedding material) decomposed in two stages, while flock and broiler decomposed in three stages. Apparent activation energies increased from 99 to 484 kJ/mol for the three samples when the pyrolytic conversion increased from 5% to 95%.     

Pyrolysis kinetics behavior of solid tire wastes available in Bangladesh

Pyrolysis kinetics of available bicycle/rickshaw, motorcycle and truck tire wastes in Bangladesh have been investigated thermogravimetrically in a nitrogen atmosphere at heating rates of 10 and 60 degrees C/min over a temperature range of 30-800 degrees C. The three tire wastes exhibited similar behaviors in that, when heating rate was increased, the initial reaction temperature decreased but the reaction range and reaction rate increased. The percentage of total weight loss was higher for truck tire waste and lower for bicycle/rickshaw tire waste. The pyrolysis of truck tire waste was found to be easier than that of bicycle/rickshaw and motorcycle tire wastes while it was comparatively more difficult for motorcycle tire waste. The overall rate equation for the three tire wastes has been modeled satisfactorily by one simplified equation from which the kinetic parameters of unreacted materials based on the Arrhenius form can be determined. The predicted rate equation compares fairly well with the measured TG and DTG data. DTA curves for all of the samples show that the degradation reactions are three main exotherms and one endotherm.     

Pyrolysis of latex gloves in the presence of Y-zeolite

In this study we have investigated the possibility of processing waste rubber gloves using pyrolysis. Y-zeolite catalyst was employed to upgrade the pyrolysis products to give higher yields of valuable aromatic compounds such as toluene and xylenes. The composition of the pyrolysis products was determined using gas chromatography with linked mass spectrometry (GC-MS), gas chromatograph equipped with a flame ionization detector (GC-FID), gas chromatograph fitted with dual thermal conductivity detectors (GC-TCD), and Fourier Transform Infra-Red Spectrometry (FT-IR). It was found that when rubber gloves were pyrolysed in the absence of a catalyst, the pyrolysis oil consisted mainly of limonene and oligomers of polyisoprene. When Y-zeolite was added to the reaction system, the yields of toluene, xylene, methylbenzenes, ethylbenzenes, and naphthalenes increased dramatically. The Y-zeolite also catalysed the decomposition of limonene, which was absent from the catalytic pyrolysis products. The presence of the Y-zeolite catalyst also increased the yield of hydrocarbon gases. The tests were carried out at both 380 degrees C and 480 degrees C and it was found that the higher reaction temperature led to increased yields of all the major compounds, both in the presence and absence of the Y-zeolite catalyst.     

Pyrolysis kinetics of waste PVC pipe.

The pyrolysis kinetics of waste PVC pipe was investigated with a thermal gravimetric analysis system at heating rates of 5, 10, and 30 degrees C/min in a nitrogen atmosphere. Freeman-Carroll method was employed to evaluate kinetic parameters. Two dominant peaks were observed on derivative gravimetric curves, hypothetically suggesting a two-stage apparent reaction model. The first-stage reaction was likely to be represented by stoichiometric reaction to yield volatiles (mainly HCl) and intermediates. The second-stage reaction might be described by thermal degradation of intermediates competitively into gas, liquid, and solid by-products. Quasi-isothermal operations were introduced to verify the reaction types of the first and second reaction. The generation reaction of intermediates achieved at lower temperatures was carried out independently with their decomposition reaction at higher temperatures. The effects of additives on the pyrolysis kinetics of waste PVC pipe seem to be significant, especially on the first-stage reaction. The first-stage reaction was retarded. A merged peak at low temperatures was observed on the derivative thermogravimetry (DTG) curve instead of two peaks usually observed for that of pure PVC resin. The first peak on the DTG curve of pure PVC resin may shift more, resulting in the complete overlap of two peaks. The quantity of evolved HCl was likely to decrease because of interaction of metal components of stabilizers with either HCl or active chlorine atom or both. The final residual fraction increased as a result of pyrolysis of organic forms of additives to yield extra char. On the other hand, the second-stage reaction kinetics demonstrates a similar pattern to that of pure PVC resin, implying that the effects of additives may be less significant in comparison with that at the first-stage reaction.     

Deactivation and regeneration of ZSM-5 zeolite in catalytic pyrolysis of plastic wastes

In this work, a study of the regeneration and reuse of ZSM-5 zeolite in the pyrolysis of a plastic mixture has been carried out in a semi-batch reactor at 440 °C. The results have been compared with those obtained with fresh-catalyst and in non-catalytic experiments with the same conditions. The use of fresh catalyst produces a significant change in both the pyrolysis yields and the properties of the liquids and gases obtained. Gases more rich in C3-C4 and H₂ are produced, as well as lower quantities of aromatic liquids if compared with those obtained in thermal decomposition. The authors have proved that after one pyrolysis experiment the zeolite loses quite a lot of its activity, which is reflected in both the yields and the products quality; however, this deactivation was found to be reversible since after regeneration heating at 550 °C in oxygen atmosphere, this catalyst recovered its initial activity, generating similar products and in equivalent proportions as those obtained with fresh catalyst.     

Pyrolysis characteristics of bean dregs and in situ visualization of pyrolysis transformation

Biomass is an important renewable and sustainable source of energy. Waste products from biomass are considered as attractive feedstocks for the production of fuel. This work deals with the pyrolysis of bean dregs, a biomass waste from soybean processing industry. A technique has been developed to study bean dregs pyrolysis by in situ visualization of bean dregs transformation in a quartz capillary under a microscope using a charge-coupled device (CCD) camera monitoring system. The technique enables us to observe directly the processes and temperatures of bean dregs transformation during pyrolysis. In situ visualization of reaction revealed that how oily liquids are generated and expulsed concurrently from bean dregs during pyrolysis. Pyrolysis characteristics were investigated under a highly purified N₂ atmosphere using a thermogravimetric analyzer from room temperature to 800 °C at different heating rates of 10, 30 and 50 °C/min. The results showed that three stages appeared in this thermal degradation process. The initial decomposition temperature and the peak shifted towards higher temperature with an increase in heating rate. Kinetic parameters in terms of apparent activation energy and pre-exponential factor were determined.     

Oil adsorbent produced by the carbonization of rice husks

In this study, rice husks considered to be agricultural waste are converted into an adsorbent intended for use in the disposal of oil spills. The raw and refined (defiberized) husks of Japanese Akita Komachi rice were pyrolyzed in a vacuum (500 Pa) at 300-800 degrees C. The amount of A-heavy and B-heavy oils adsorbed on the carbonized rice husk were then evaluated. Oil adsorption is dependent on the type of oil. Rice husks refined and then pyrolyzed at 600-700 degrees C (1.0 g) adsorbed >6.0 g of B-heavy oil and <1.5 g of water, which indicates their usefulness as an adsorbent for oil spill cleanup in Japan. The refining process contributes to an improvement in the oil adsorption capacity, while the carbonization time (at 600 degrees C) has only a minor influence. The residual fluid components in the carbonized rice husks, rather than their porosity, are closely related to oil adsorption capacity.     

Experimental and kinetic modeling of oxygen-enriched air combustion of municipal solid waste

The characteristics of oxygen-enriched air combustion of raw municipal solid waste (MSW) were studied by thermogravimetric analysis. Experiments on oxidative pyrolysis of MSW were carried out under different atmospheres (N(2), N(2):O(2)=7:3, N(2):O(2)=5:5, N(2):O(2)=4:6, and N(2):O(2)=2:8) at 30 degrees C/min. Two distinct peaks of weight loss were obtained according to the derivative thermogravimetric curves; one of them is centered on 305 degrees C with about 40% weight loss, and the second is centered on 420 degrees C with about 20% weight loss. Effects of oxygen concentration on the decomposition process and char combustion were analyzed, and then the process of oxygen-enriched air combustion of MSW was divided into four steps. Kinetic parameters were observed by direct non-linear regressions. According to the obtained data, the apparent activation energy and reaction order decreases along with the combustion process, while that of char combustion increases as oxygen concentration increases.     

用废旧电路板热解油制备酚醛树脂

在碳酸钙存在下,采用热解技术将废旧电路板中的树脂转化为富含酚的热解油,然后直接加入甲醛溶液反应制备热解油型酚醛树脂,实现了废旧电路板中树脂的再生,酚醛树脂的性能结构类似于氨催化的酚醛树脂。实验结果表明：在n（甲醛）：n（热解油）为1．8～2．1的条件下,无需外加催化剂,在60,80,90℃下分别反应30min制备的热解油型酚醛树脂的性能最佳,且可满足GB／T14732—93《木材工业胶黏剂用脲醛、酚醛、三氧氰胺甲醛树脂》中层压材料用酚醛树脂产品的相关标准。     

Characteristics of gas and residues produced from electric arc pyrolysis of waste lubricating oil

An attempted has been made to recover high-calorific fuel gas and useful carbonaceous residue by the electric arc pyrolysis of waste lubricating oil. The characteristics of gas and residues produced from electric arc pyrolysis of waste lubricating oil were investigated in this study. The produced gas was mainly composed of hydrogen (35–40%), acetylene (13–20%), ethylene (3–4%) and other hydrocarbons, whereas the concentration of CO was very low. Calorific values of gas ranged from 11,000 to 13,000 kcal kg^?1 and the concentrations of toxic gases, such as NO_x, HCl and HF, were below the regulatory emissions limit. Gas chromatography–mass spectrometry (GC/MS) analysis of liquid-phase residues showed that high molecular-weight hydrocarbons in waste lubricating oil were pyrolyzed into low molecular-weight hydrocarbons and hydrogen. Dehydrogenation was found to be the main pyrolysis mechanism due to the high reaction temperature induced by electric arc. The average particle size of soot as carbonaceous residue was about 10 μm. The carbon content and heavy metals in soot were above 60% and below 0.01 ppm, respectively. The utilization of soot as industrial material resources such as carbon black seems to be feasible after refining and grinding.     

Dechlorination and decomposition of Aroclor 1242 in real waste transformer oil using a nucleophilic material with a modified domestic microwave oven

This research was done to assess the dechlorination and decomposition of polychlorinated biphenyls (PCBs) in real waste transformer oil through a modified domestic microwave oven (MDMW). The influence of microwave power (200–1000 W), reaction time (30–600 s), polyethylene glycol (PEG) (1.5–7.5 g), iron powder (0.3–1.5 g), NaOH (0.3–1.5 g), and H₂O (0.4–2 ml) were investigated on the decomposition efficiency of PCBs existing in real waste transformer oil with MDMW. Obtained data indicate that PEG and NaOH have the greatest influence on decomposition of PCBs; while, iron did not influence, and H₂O decreased, the decomposition efficiency of PCBs. Experimental data also indicated that with the optimum amount of variables through a central composites design method (PEG = 5.34 g, NaOH = 1.17 g, Fe = 0.6 g, H₂O = 0.8 ml and microwave power 800 W), 78 % of PCBs was degraded at a reaction time of about 6 min. In addition, the PCBs decomposition without using water increased up to 100 % in the reactor with the MDMW at 6 min. Accordingly, results showed that MDMW was a very efficient factor for PCBs decomposition from waste transformer oil. Also, using microwave irradiation, availability and inexpensive materials (PEG, NaOH), and iron suggest this method as a fast, effective, and cheap method for PCB decomposition of waste oils.     

废印制线路板真空热解产物分析

在自行设计的间歇式固定床真空热解装置中热解废印制线路板(PCB),对热解产物进行了分析.在热解温度为550 ℃、热解压力为20 kPa、恒温时间为60 min的条件下,得到的热解产物质量分数为:热解渣70%;热解油3%～4%;不可冷凝热解气26%～27%.经气相色谱-质谱联用(GC-MS)分析,热解油经常压蒸馏后得到的低沸点液态油中含有29种化合物,主要有苯酚、对异丙基酚、3-乙基酚、4-甲酚及2-溴苯酚,还含有少量含溴化合物和含氯化合物.热解油经简单的蒸馏就可达到回收酚类化合物的目的.热解渣经风选可实现铜与黏附有碳黑的玻璃纤维的分离,其中铜质量分数约30%,黏附有碳黑的玻璃纤维质量分数约70%.     

Reaction Kinetic Model For Optimal Pyrolysis Of Plastic Waste Mixtures

Reaction kinetics at various temperatures for pyrolysis of mixtures of plastic waste [polyethylene(PE) and polystyrene(PS)] are modelled in terms of five types of pyrolysis reaction. The model development is based on the assumption that as plastic wastes are heated in a non-reactive environment they are decomposed homogeneously to various products of gas, oil and char by a first-order rate, irreversible reaction and isothermal condition. Among the five models, the type II model in which the activated polymer exists as an intermediate product is the most accurate in predicting the pyrolysis products of pure PE or pure PS. Also, for mixtures of plastics both type II and IV models can be used to explain the composition of pyrolysis products. Furthermore, from the analysis of variance (ANOVA), the mixing ratio and temperature are shown to be the parameters that have the greatest effect on the pyrolysis reaction of polymer waste mixture. The pyrolysis reaction time for the maximum oil production from PE-PS mixtures is shorter than for PE alone and approaches that of PS alone. Oil production increases with increase of PS content. The optimal temperature for maximum oil production is 600°C for the pyrolysis of 2:8, 5:5 and 1:0 mixtures (w/w) of PE and PS. Oil production for PS alone is constant when the pyrolysis is above 600°C.     

Thermogravimetric analysis and kinetic study on pyrolysis of representative medical waste composition

To obtain detailed information on the pyrolysis characteristics, a thermogravimetric study on the pyrolysis of 14 typical medical waste compositions was carried out in thermogravimetric analysis (TGA) equipment using dynamic techniques in a stream of N(2). An index representing pyrolysis reactivity of waste was presented. Kinetic parameters were obtained by Coats-Redfern method and used to model the TG curve. The results showed that: (a) Plastic, protein, cellulosic material, synthetic fibre, and rubber entered pyrolysis process in succession. (b) There was one decomposition stage in the pyrolysis of one-off medical glove, operating glove, cellulosic waste, absorbable catgut suture and adhesive plaster, while other components had two obvious weight loss stages. (c) The obtained apparent activation energy for second stage pyrolysis was comparably higher than that for first stage. (d) Each stage was controlled by only one kinetic mechanism, in which kinetic parameters were constant. (e) The degradation kinetics of medical waste may be affected by special physical and chemical treatment in the product manufacturing process. (f) Among 13 waste samples, the pyrolysis index of cellulosic matter was the highest, which indicated cellulosic matter had strong pyrolysis reactivity. (g) With increasing heating rate, TG curve and DTG peak shifted to high temperatures and main reaction interval of the sample became longer.     

Quality improvement of pyrolysis oil from waste rubber by adding sawdust

This work was aimed at improving the pyrolysis oil quality of waste rubber by adding larch sawdust. Using a 1 kg/h stainless pyrolysis reactor, the contents of sawdust in rubber were gradually increased from 0%, 50%, 100% and 200% (wt%) during the pyrolysis process. Using a thermo-gravimetric (TG) analyzer coupled with Fourier transform infrared (FTIR) analysis of evolving products (TG–FTIR), the weight loss characteristics of the heat under different mixtures of sawdust/rubber were observed. Using the pyrolysis–gas chromatography (GC)–mass spectrometry (Py–GC/MS), the vapors from the pyrolysis processes were collected and the compositions of the vapors were examined. During the pyrolysis process, the recovery of the pyrolysis gas and its composition were measured in-situ at a reaction temperature of 450 °C and a retaining time of 1.2 s. The results indicated that the efficiency of pyrolysis was increased and the residual carbon was reduced as the percentage of sawdust increased. The adding of sawdust significantly improved the pyrolysis oil quality by reducing the polycyclic aromatic hydrocarbons (PAHs) and nitrogen and sulfur compounds contents, resulting in an improvement in the combustion efficiency of the pyrolysis oil.     

超声波协同催化氧化法脱除废旧轮胎热裂解油中的硫

采用超声波氧化与催化氧化脱硫技术相结合,脱除废旧轮胎热裂解油中的硫,对脱硫工艺进行了研究.最佳操作条件为:超声波声强0.25 W/cm~2,超声时间10 min,V(H_2O_2)∶V(油)=0.04,V(CH_3COOH)∶V(H_2O_2)＝0.5,V(FeSO_4·7H_2O) ∶ V(H_2O_2)＝0.15.在上述最佳操作条件下,进行4次脱硫,可使热裂解油中硫质量分数降至0.21%,脱硫率达到72%.     

Pyrolysis characteristics of organic components of municipal solid waste at high heating rates

The pyrolysis characteristics of six representative organic components of municipal solid waste (MSW) and their mixtures were studied in a specially designed thermogravimetric analysis apparatus with a maximum recorded heating rate of 864.8 degrees Cmin(-1). The pyrolysis behavior of individual components was described by the Avrami-Erofeev equation. The influence of final temperature on individual components was studied, and it was concluded that final temperature was a factor in reaction speed and intensity, but that it played only a limited role in determining the reaction mechanism. The interactions between different components were evaluated, and it was concluded that the interaction between homogeneous materials was minimal, whereas the interaction between polyethylene and biomass was significant.