Bio-oil production by fast pyrolysis of cellulose/polyethylene mixtures in the presence of metal chloride

Cellulose/polyethylene mixture (3:1 w/w) and Tetra Pak wastes with and without metal chloride (ZnCl₂, AlCl₃, CuCl₂, FeCl₃) addition were subjected to a fast pyrolysis process at 350–500 °C and heating rate 100 °C/s to evaluate the possibility of liquid product formation with a high yield. The addition of zinc, aluminum, iron and copper chlorides has influenced the range of samples decomposition as well as the chemical composition of resulting pyrolytic oils. It was found that formation of levoglucosan, the main product of cellulose thermal decomposition, and phenol and its derivatives decreased in a presence of metal chlorides. Non-catalytic fast pyrolysis of polyethylene leads to the formation of solid long chain hydrocarbons, whereas the addition of metal chlorides promotes the formation of more liquid hydrocarbons.     

氯酸钠氧化盐酸酸洗废液制备聚氯化铁

钢材在深加工过程中通常使用盐酸对其表面进行酸洗除锈,从而产生大量废液。为了实现盐酸酸洗废液的资源化处理,以氯酸钠作为氧化剂制备聚氯化铁,考察了氧化剂加入量、浓盐酸加入量、反应时间、反应温度等因素对Fe²⁺转化率的影响。实验得到的最佳工艺条件为：每处理100 mL废液需加入7.0 g氯酸钠、12 mL浓盐酸（12 mol/L）、0.3 g磷酸二氢钾,反应温度30 ℃,反应时间30 min,搅拌转速5 r/s。该条件下,Fe²⁺转化率可达98.51%,得到的聚氯化铁产品符合《水处理剂 聚氯化铁》（HG/T 4672—2014）标准。     

Methanolysis and Hydrolysis of Polycarbonate Under Moderate Conditions

Alkali-catalyzed methanolysis and hydrolysis of polycarbonate (PC) in a solvent in which PC can substantially dissolve such as N-methyl-2-pyrrolidone, 1,4-dioxane, tetrahydrofuran and so on were studied. Reaction conditions were optimized for the purpose of recycling PC in the form of bisphenol A and carbon carbonate. The results showed that both the methanolysis and hydrolysis of PC could take place under moderate conditions. Under the conditions of reaction temperature 40 °C, m(PC):m(MeOH) = 1:1, m(PC):m(NaOH) = 50:1, reaction time 35 min and using tetrahydrofuran as solvent, the methanolysis conversion of PC was almost 100% and the yield of bisphenol A was over 95%. Moreover, under the conditions of reaction temperature 100 °C, m(PC):m(H₂O) = 1:0.7, m(PC):m(NaOH) = 10:1, reaction time 8 h and using 1,4-dioxane as solvent, the hydrolysis conversion of PC was almost 100% and the yield of bisphenol A was over 94%.     

Utilization of red mud as catalyst in conversion of waste oil and waste plastics to fuel

The aim of this study was to investigate the possibilities of using a by-product (red mud) from alumina production as a catalyst for recovery of waste. The conversion of waste mineral oil (WMO) and waste mineral oil/municipal waste plastic (WMO/MWP) blends over red mud (RM), a commercial hydrocracking catalyst (silica–alumina), and a commercial hydrotreating catalyst (Ni–Mo/alumina) to fuel has been studied. The effect of the catalyst and the temperature on the product distribution (gas, liquid, and wax) and the properties of liquid products were investigated. In the case of hydrotreatment of WMO, the liquids obtained over RM at both 400° and 425°C had larger amounts of low-boiling hydrocarbons than that of thermal or catalytic treatment with hydrotreating catalyst. Gas chromatography and nuclear magnetic resonance analysis of the liquid products showed that RM had hydrogenation and cracking activity in hydrotreatment of WMO. In coprocessing of WMO with municipal waste plastics, temperature had an important effect as well as the amount of MWP in the blend and the catalyst type. The hydrocracking at 400°C produced no liquid product. In hydrocracking at 425°C, the product distribution varied with catalyst type and MWP amount. The commercial hydrocracking catalyst had more cracking ability in the conversion of WMO/MWP to liquid and gas fuel than RM. In the case of hydrocracking over RM, the largest amount of liquid having satisfactory quality was obtained only from the blend containing 20% MWP.     

Flammability Properties of Virgin and Recycled Polycarbonate (PC) and Acrylonitrile–Butadiene–Styrene (ABS) Recovered from End-of-Life Electronics

Acrylonitrile–Butadiene–Styrene (ABS), Polycarbonate (PC) and their alloys are widely used in automotive industry, computer and equipment housings. With increasing disposal of end-of-life electronic equipment, there is also an increased demand for recycling of these materials so that they do not pose environmental challenge as solid waste. One of the recycling approaches is mechanical recycling of these thermoplastics where recycled plastic is melt blended with virgin materials to obtain a high quality product. Besides obtaining desirable mechanical properties, such blends should also conform to fire safety standards. In this work, a series of blends were prepared using PC and ABS recovered from discarded computers and virgin materials using a twin-screw extruder. Their flammability properties were evaluated using burner flammability tests and Ohio State University (OSU) release rate tests. It was found that the extinguishing time, burning extent and weight loss appears to progressively decrease with the addition of both virgin or recycled PC to virgin or recycled ABS. It was also seen that the addition of the 70% of PC, virgin or recycled, to ABS virgin or recycled, appears to significantly decrease heat release and smoke evolution. The results of this study indicate that recycled polycarbonate can be used as an additive for virgin or recycled ABS, as a means of giving flame resistance to ABS in high-value applications. This result is significant when related to the result obtained by a separate study indicating that up to 25% of recycled material can be used without degradation of mechanical properties in the presence of 15% short glass fiber reinforcement.     

Treatment process for MSW combustion fly ash laboratory and pilot plant experiments

Fly ash from combustion of municipal solid waste sometimes contains large amounts of soluble salts, such as NaCl, even though the content of soluble toxic metal compounds is relatively low. Removal of the salts by washing with water has been suggested as a method to increase the stability of this type of ash. In the work presented here, a simple washing process was studied and evaluated. The process includes three steps: leaching with water, filtration and displacement washing. Basic data were obtained in laboratory experiments and used in the construction of pilot plant equipment at a full size fluidized bed boiler, where a side-stream of the cyclone ash was treated. The process was designed to minimize the water consumption while obtaining an effective removal of salts and a stable ash residue. In order to achieve this, recirculation of leaching liquor was used and the displacement washing was adjusted to become close to ideal. The results showed that an ash/water slurry with a liquid to solid ratio as low as 3 could be handled without difficulty in the mixing, pumping and filtration units. Washing of the filter cake at a liquid to solid ratio of 0.5 removed the major part of the remaining dissolved salts in the pore liquid. About 90% of the chloride content was removed from the ash, whereas the contents of Na, K, Ca, Cd, Pb and a number of other minor elements were removed by 10-30%. Before treatment, the results of ash leaching tests were sometimes too high for chloride (2003/33/EC), but the treatment reduced the amount of soluble chlorides to far below the limit values. The leachability of most metals was reduced or unaffected by the ash treatment. For Na, K and Cl, it was less than 10% of the value for the untreated ash. However, the results showed that some ash components may be mobilized by the washing. Antimony is the most important due to its toxicity.     

Removal of insoluble chloride from bottom ash for recycling

In order to recycle bottom ash and use it as raw material for cement production, the removal of insoluble chloride was investigated by testing various washing techniques. The present work is also focused on investigating the properties of insoluble chlorides and determining the conditions for dissolving these compounds in order to reduce the chlorine content to the required level, i.e., less than 0.1 wt%. Within this framework, the effect of washing with water and CO2 bubbling was investigated, because the main insoluble chloride found in bottom ash, i.e., Friedel's salt, can be dissolved by CO2. Then, in order to better understand the removal of Cl, Friedel's salt was artificially synthesized by hydration and then the effect of CO2 bubbling was investigated. If all chlorides in the ash are converted into Friedel's salt by hydration, all chlorides can then be dissolved by CO2 bubbling. In addition, the effect of pH on removing the remaining insoluble chlorides was investigated by washing the ash with sulfuric acid solution. It was found that the most effective technique to reduce the Cl content to less than 1000 ppm was washing with sulfuric acid solution, while keeping the pH value at less than 4. By using this method, Friedel's salt and other insoluble chlorides were dissolved.     

废聚碳酸酯水解法制双酚A

以1,4-二氧六环为溶剂、NaOH为催化剂,采用废聚碳酸酯(PC)常压水解法制双酚A(BPA).对反应影响因素进行了研究.实验结果表明,在反应温度为100℃、反应时间为8h、m(NaOH):m(水+溶剂)=1:33、m(溶剂):m(PC)=4:1、m(水):m(PC)=1:1的最佳反应条件下,PC水解率大于98%,BPA收率大于95%.     

Effect of Metal Compounds and Experimental Conditions on Distribution of Products from PVC Pyrolysis

Effects of heating rate, gas flow rate, and type of metal compounds on the amount of hydrogen chloride, liquid, gas, and solid pyrolyzate obtained from the pyrolysis of poly(vinyl chloride) (PVC) were investigated. The pyrolysis experiments were carried out in both a thermogravimetric analysis (TGA) instrument and a fixed-bed reactor. Products from the fixed-bed reactor were collected and analyzed by using Fourier transform infrared spectroscopy (FTIR), gas chromatography-mass spectroscopy (GC-MS), titration technique, and gravimetry. It was found that heating rate in the TGA experiments did not affect the amount of released hydrogen chloride. However, the TGA profiles significantly changed with the rate. The onset of dehydrochlorination increased with the rate. In addition, as the heating rate was increased from 10 to 20°C/min, there was no solid residue left. The amount of liquid pyrolyzate obtained from the fixed-bed reactor can be either increased or decreased with the heating rate, depending on the gas flow rate and the actual residence time in the reactor. FTIR and GC-MS analysis indicated that the liquid pyrolyzates were mainly benzene, toluene, and styrene. By comparing the efficiency of various metal compounds in trapping the HCl, it was found that Ca(OH)₂ was more efficient than Mg(OH)₂, and that CaO was more efficient than MgO. These results are discussed in light of the reaction mechanism between HCl and the metal compounds.     

高温氧化-定向转化法处理草甘膦生产含磷废料

根据草甘膦生产含磷废料的成分特点,先进行预处理及指标调节,然后采用高温氧化-定向转化法进行氧化、聚合反应,得到高品质的磷酸盐产品。实验结果表明:控制预处理后含磷废料中杂质氯化钠质量分数不超3%、p H在7~9,雾化后进入高温氧化-定向转化反应器,在750~800℃下反应50~60 min,产物中焦磷酸钠质量分数达97%以上,含磷废料的COD去除率达99%以上,杂质氯化钠分解率不超0.8%。该方法工艺条件稳定,工程化简单,可以直接得到附加值较高的焦磷酸钠、三聚磷酸钠、六偏磷酸钠等磷酸盐产品,回收产品的经济性较好,推广应用前景广阔。     

Recovery of nickel oxide from spent catalyst

This study investigates the possibility of recovering nickel from the spent catalyst (NiO/Al2O3) resulting from the steam reforming process to produce water gas (H2/H2O) in many industries. In the extraction process, nickel is recovered as sulfate using sulfuric acid as a solvent. The considered parameters affecting nickel recovery were acid concentration, temperature and time of digestion solid:liquid ratio, particle size and stirring rate. Nickel was to be directly recovered as a sulfate salt by direct crystallization method. The conversion was 99% at 50% sulfuric acid concentration, solid: liquid ratio (1:12) by weight, particle size less than 500 micron for more than 5 h and 800 rpm at 100 degrees C.     

Conventional and fast pyrolysis of automobile shredder residues (ASR)

This work aims at comparing performance and product yields in conventional pyrolysis and fast pyrolysis of automotive shredded residues. In both processes, carbon conversion to gaseous and liquid products was more than 80%. Gas production was maximised in conventional pyrolysis (about 35% by weight of the initial ASR weight), while fast pyrolysis led to an oil yield higher than 55%. Higher heating values (HHV) of both conventional pyrolysis gas and fast pyrolysis oil increased from 8.8 to 25.07 MJ/Nm3 and from 28.8 and 36.27 MJ/kg with increasing pyrolysis temperature.     

Co-processing of DVDs and CDs with vegetable cooking oil by thermal degradation

Waste DVDs and CDs were thermally degraded at 450°C by a semibatch process. In total, 40–50 wt% was converted into liquid product that consisted of phenol derivatives (∼75 wt%), bisphenol (∼10 wt%) and its derivatives, and small amounts of aromatic hydrocarbons such as benzene, toluene, ethylbenzene, dimethylbenzene, methylethylbenzene, diethylbenzene, and methylisopropyl benzene. Degradation of the polycarbonate support from DVDs and CDs was enhanced by coprocessing with vegetable cooking oil, the degradation of which gave a homologue series of hydrocarbons and organic acids with up to 25 and 18 atoms of carbon, respectively. Silver from the reflective coating on DVDs and CDs remained in the solid residue, its concentration increasing about 2.5 times compared to that of the original disks.     

Separation of polycarbonate and acrylonitrile–butadiene–styrene waste plastics by froth flotation combined with ammonia pretreatment

The objective of this research is flotation separation of polycarbonate (PC) and acrylonitrile–butadiene–styrene (ABS) waste plastics combined with ammonia pretreatment. The PC and ABS plastics show similar hydrophobicity, and ammonia treatment changes selectively floatability of PC plastic while ABS is insensitive to ammonia treatment. The contact angle measurement indicates the dropping of flotation recovery of PC is ascribed to a decline of contact angle. X-ray photoelectron spectroscopy demonstrates reactions occur on PC surface, which makes PC surface more hydrophilic. Separation of PC and ABS waste plastics was conducted based on the flotation behavior of single plastic. At different temperatures, PC and ABS mixtures were separated efficiently through froth flotation with ammonia pretreatment for different time (13 min at 23 °C, 18 min at 18 °C and 30 min at 23 °C). For both PC and ABS, the purity and recovery is more than 95.31% and 95.35%, respectively; the purity of PC and ABS is up to 99.72% and 99.23%, respectively. PC and ABS mixtures with different particle sizes were separated effectively, implying that ammonia treatment possesses superior applicability.     

A comparison study on high-temperature water–gas shift reaction over Fe/Al/Cu and Fe/Al/Ni catalysts using simulated waste-derived synthesis gas

A comparative study on Fe/Al, Fe/Al/Cu, and Fe/Al/Ni catalysts in high-temperature water–gas shift reaction (HT–WGS) using simulated waste-derived synthesis gas has been carried out. The metal oxide (Cu and Ni) and aluminum incorporated Fe catalysts were designed to get highly active HT–WGS catalysts. Despite the high CO concentration in the simulated waste-derived synthesis gas, Fe/Al/Cu catalyst exhibited the highest CO conversion (84 %) and 100 % selectivity to CO₂ at a very high gas hourly space velocity (GHSV) of 40,057 h^?1. The outstanding catalytic performance is mainly due to easier reducibility, the synergy effect of Cu and Al, and the stability of the magnetite.     

城市污泥制备水中重金属吸附剂及其吸附特性研究

本实验利用城市污水厂的脱水污泥,通过化学活化法制备活性炭.研究活化温度、活化时间、固液比和活化剂浓度等因素对制备污泥活性炭的影响,确定氯化锌法制备污泥活性炭的最佳工艺为活化温度550 ℃、活化时间30 min、固液比1∶2、氯化剂浓度45％.将制备的污泥活性炭吸附Cu2＋,Cr6＋,Cd2＋3种重金属离子模拟废水,研究pH值、吸附时间、污泥投加量、温度等因素对吸附过程的影响.实验结果表明,剩余污泥对Cu2＋,Cr6＋,Cd2＋3种重金属离子都具有良好的吸附效果,在优化条件下,3种重金属离子去除率分别达到94％,76％,81％,吸附能力大小顺序为Cu2＋＞Cd2＋＞＋Cr6＋.     

阴离子对Fenton氧化降解聚乙烯醇的影响

研究了亚铁盐中NO3-、SO42-、Cl-、Br-等阴离子对Fenton氧化降解高浓度聚乙烯醇(PVA)效果的影响。实验结果表明:酸性条件下具有氧化性的阴离子NO3-或能被氧化形成具有氧化性物质的离子Cl-、Br-对Fenton氧化降解PVA有协同促进作用,且氧化性越强越容易促使PVA大分子链断裂;含NO3-、Cl-、Br-和SO42-的Fenton氧化降解PVA,COD去除率分别为70.05%、70.60%、72.40%和87.90%。采用COD去除率相差不大、产物分子量较小的硝酸亚铁、氯化亚铁、溴化亚铁中的一种作为Fenton试剂催化降解PVA较适宜。     

Wet extraction of heavy metals and chloride from MSWI and straw combustion fly ashes

Fly ash residues from combustion often do not meet the criteria neither for reuse as construction materials nor landfilling as non-hazardous waste, mainly because of the high concentration of heavy metals and chlorides. This work aimed to technically evaluate an innovative wet treatment process for the extraction of chloride (Cl^?), cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) from fly ashes from a municipal solid waste incineration (MSWI) plant and from a straw combustion (SC) facility. Factors investigated were liquid/solid (L/S) ratio, full carbonation (CO₂ treatment), influence of pH and leaching time, using a two-level full factorial design. The most significant factor for all responses was low pH, followed by L/S ratio. Multiple linear regression models describing the variation in extraction data had R² values ranging from 58% to 98%. An optimization of the element extraction models was performed and a set of treatment conditions is suggested.     

Waste catalysts for waste polymer

Catalytic cracking of high-density polyethylene (HDPE) over fluid catalytic cracking (FCC) catalysts (1:6 ratio) was carried out using a laboratory fluidized bed reactor operating at 450 degrees C. Two fresh and two steam deactivated commercial FCC catalysts with different levels of rare earth oxide (REO) were compared as well as two used FCC catalysts (E-Cats) with different levels of metal poisoning. Also, inert microspheres (MS3) were used as a fluidizing agent to compare with thermal cracking process at BP pilot plant at Grangemouth, Scotland, which used sand as its fluidizing agent. The results of HDPE degradation in terms of yield of volatile hydrocarbon product are fresh FCC catalysts>steamed FCC catalysts approximately used FCC catalysts. The thermal cracking process using MS3 showed that at 450 degrees C, the product distribution gave 46 wt% wax, 14% hydrocarbon gases, 8% gasoline, 0.1% coke and 32% nonvolatile product. In general, the product yields from HDPE cracking showed that the level of metal contamination (nickel and vanadium) did not affect the product stream generated from polymer cracking. This study gives promising results as an alternative technique for the cracking and recycling of polymer waste.     

Catalytic degradation of PP with an Fe/activated carbon catalyst

We investigated the function of Fe and activated carbon (AC) as a catalyst by comparing Fe/AC with Fe/SiO₂ or AC, and also the effect of H₂ as a reaction gas on the product distribution in the catalytic degradation of polypropylene. Supported Fe promotes H₂ consumption to decompose solid residues, and AC support degrades heavy oil to produce light oil. As a result, using Fe/AC as a catalyst gives the maximum yield of the liquid product. For the reaction conditions, with a high reaction temperature or a long reaction time, the product distribution is more influenced by the thermal degradation than by the catalytic degradation. For the amount of Fe to load, 5wt% is the optimum condition in our reaction system. We demonstrated the mechanism of the degradation of polyolefins with hydrogen-capping catalysts.