Waste polyvinylchloride derived pitch as a precursor to develop carbon fibers and activated carbon fibers

Polyvinylchloride (PVC) was successfully recycled through the solvent extraction from waste pipe with an extraction yield of ca. 86%. The extracted PVC was pyrolyzed by a two-stage process (260 and 410 degrees C) to obtain free-chlorine PVC based pitch through an effective removal of chlorine from PVC during the heat-treatment. As-prepared pitch (softening point: 220 degrees C) was spun, stabilized, carbonized into carbon fibers (CFs), and further activated into activated carbon fibers (ACFs) in a flow of CO2. As-prepared CFs show comparable mechanical properties to commercial CFs, whose maximum tensile strength and modulus are 862 MPa and 62 GPa, respectively. The resultant ACFs exhibit a high surface area of 1200 m2/g, narrow pore size distribution and a low oxygen content of 3%. The study provides an effective insight to recycle PVC from waste PVC and develop a carbon precursor for high performance carbon materials such as CFs and ACFs.     

Agricultural waste biomass converted to activated carbon as a material for gold processing

Waste biomass in the form of coconut shells was pyrolyzed and activated with steam to produce activated carbons, which were then assessed for their potential for use in the processing of gold. Activated carbons with different amounts of carbon burn-off were prepared by steam activation of carbonized coconut shells. Carbonization of the shells was performed at a pyrolysis temperature of 600?°C and the resulting chars were activated in steam at a gasification temperature of 900?°C and various durations of activation time. Textural characteristics of the derived activated carbons were determined and their effects on gold adsorption from an acidified gold chloride solution were studied. The surface area and porosity of the activated carbons increased with activation time up to 59 wt?% carbon burn-off. A further increase in the burn-off resulted in the loss of structural walls between pores and consequently, a decline in the surface area and porosity of the activated carbons. The gold adsorption capacity and rate of gold adsorption from the gold chloride solution onto the activated carbons were found to increase significantly with the total pore and micropore volumes of the activated carbons.     

Tailoring mesoporosity of poly(furfuryl alcohol)-based activated carbons and their ability to adsorb organic compounds from water

In this work it was shown that polymers can be recycled into a promising adsorbent for organic dyes and phenols waste removal. For this, a series of activated carbons (ACs) were produced from mixture of ferrocene or titanium acetylacetonate with poly(furfuryl alcohol) (PFA) by steam activation. The introduction of ferrocene as Fe precursor was found to be an efficient catalyst in mesoporosity development during carbonization and subsequent steam activation at 850 °C, whereas the polymer based only and titanium-doped ACs are typically microporous. The porous structure parameters were determined from nitrogen adsorption isotherms measured at 77 K. Scanning electron microscopy was applied to monitor the metal distribution of metal-loaded char and the surface morphology of activated carbons. The adsorption capacity was found to be dependent mainly on pore size distribution. In the case of phenol adsorption, the adsorption was defined by volume of pore with size 0.8–1.4 nm; whereas, for Congo red best fit was observed for volume of pore with size 2–5 nm.

     

Dehydrochlorination behavior of polyvinyl chloride and utilization of carbon residue: effect of plasticizer and inorganic filler

The dehydrochlorination behavior of plasticizer (DOP) and inorganic filler (CaCO₃) contained in PVC samples and the properties of the activated carbons produced from those carbon residues have been investigated. In the dehydrochlorination process, both additives contributed not only to a decrease in HCl yield but also to the prolonged evolution of HCl. Part of the Cl species were observed to be stabilized as CaCl₂ by reaction with calcium ions when CaCO₃ was added. More than 80% of chlorine removal was achieved in all samples at 533 K. The use of potassium as an activation agent led to the production of activated carbon with a specific surface area greater than 1000 m²/g at the low temperature of 1023 K and assisted also in the elimination of residual Cl species by the formation of KCl during activation. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Carbonization of johkasou sludge using batch-type equipment

The carbonization of dehydrated johkasou sludge was examined using batch-type equipment. Based on the temperature changes in the carbonization room and the gas combustion room, the carbonization process was divided into three phases: phase I, drying the sludge; phase II, thermal decomposition of the dried sludge; phase III, after phase II. The times required for phases I and II were strongly correlated with the amounts of water and solid matter, respectively, in dehydrated sludge. The reduction rate of the sludge on completion of phase I was about 90% on average, and the decomposition rate of solid matter increased with time during phase II or phase II plus phase III until it reached about 50%. TOC concentration of the eluate from the carbonized sludge was used as an index to evaluate the progress of the carbonization process, and the highest temperature in the carbonization room was recognized as an important operational factor. The specific surface area and pore volume of carbonized sludge were smaller than those of charcoals and activated carbons by 1–3 orders of magnitude and 1–2 orders of magnitude, respectively. No elution of heavy metals was observed from any of the carbonized sludges examined. The reduced amount of carbon in dehydrated johkasou sludge was estimated to be about 25% of the decomposed organic matter.     

Textural and surface chemical characteristics of activated carbons prepared from cattle manure compost

Two activated carbons (ACs) prepared from cattle manure compost (CMC) by ZnCl(2) activation were selected and out-gassed in a helium flow at various temperatures for 2h. The pore structure and surface chemical properties of the two selected ACs and their out-gassing treated ACs were characterized using N(2) adsorption-desorption, elements analysis, SEM and Boehm titration. A basic dye, methylene blue (MB), was chosen as an adsorbate to investigate the adsorption capacity for organic contaminant onto the activated carbons. It was found that the out-gassing treatment at 400 degrees C had little effect on the textural characteristics of the carbons but significantly changed the surface chemical properties such as surface functional groups concentration, pH and pH(PZC). The CMC-based activated carbons exhibited excellent performance for MB adsorption due to their high surface area, large mesopore volume and high nitrogen content. The kinetics of MB adsorption onto the activated carbons followed a pseudo-second-order equation, and the equilibrium data agreed well with the Langmuir model under the experimental conditions. The highest adsorption rate constant of k(ad) and the largest adsorption capacity of q(m) were found be 1.44x10(-4)g/mgmin and 519mg/g, respectively. The results suggested that the CMC-based activated carbons were effective adsorbents for the removal of methylene blue from aqueous solution.     

Treatment of olive mill waste water with activated carbons from agricultural by-products

A series of activated carbons prepared by a two-step steam activation of olive stone and solvent extracted olive pulp (SEOP) have been used in an attempt to investigate the total phenol removal and chemical oxygen demand (COD) decrease in olive mill waste water (OMWW). The temperature of carbonization and activation were kept constant at 850 and 800 degrees C, respectively. One of the carbons was prepared by a single-step process at 800 degrees C. Activated carbons have been characterized by adsorption of N2 at 77 K and mercury porosimetry. Their iodine values were also determined. Surface oxides of activated carbons were determined using the Boehm's method. The porosity development and the surface chemistry of carbons were correlated to increasing removal ability of organic molecules. Kinetics of adsorption was evaluated by applying the Lagegren model while adsorption isotherm data were fitted to Langmuir model. Mesoporosity seems to be the key factor for total phenol removal while micoporosity controls the adsorption of total organics as expressed by the COD decrease in OMWW. For carbons with similar structure, the adsorption of phenols or total organics might be affected by the presence of carbonyls.     

炭化核桃壳对废水中Cr（Ⅵ）的吸附

制备了炭化核桃壳,采用SEM,EDX,FTIR等方法对炭化核桃壳进行了表征,研究了炭化核桃壳对废水中Cr（Ⅵ）的吸附效果。表征结果显示,炭化后的核桃壳为片状结构,且形成了大量的微孔,微孔数量的增加使得核桃壳的比表面积明显增大。实验结果表明,炭化核桃壳吸附处理含Cr（Ⅵ）废水的最佳工艺条件为：初始废水pH 2.0、炭化核桃壳加入量16 g/L、吸附温度25 ℃、转速150 r/min、吸附时间180 min,在此最佳工艺条件下吸附处理Cr（Ⅵ）质量浓度为20 mg/L废水,Cr（Ⅵ）去除率高达98.7%,最大吸附量为8.731 mg/g。Langmuir吸附等温模型可更好地描述炭化核桃壳对Cr（Ⅵ）的吸附过程,吸附属于单分子层吸附。拟二级动力学方程能更好地描述炭化核桃壳对Cr（Ⅵ）的吸附行为,此吸附过程以化学吸附为主控步骤。     

Utilization of Porous Carbons Derived from Coconut Shell and Wood in Natural Rubber

The porous carbons derived from cellulose are renewable and environmentally friendly. Coconut shell and wood derived porous carbons were characterized with elemental analysis, ash content, X-ray diffraction, infrared absorbance, particle size, surface area, and pore volume. The results were compared with carbon black. Uniaxial deformation of natural rubber (NR) composites indicate the composites reinforced with the porous carbon from coconut shell have higher tensile moduli at the same elongation ratio than the composites reinforced with wood carbon. 40 % coconut shell composite showed a fivefold increase in tensile modulus compared to NR. Polymer–filler interactions were studied with frequency dependent shear modulus, swelling experiments and dynamic strain sweep experiments. Both linear and non-linear viscoelastic properties indicate the polymer–filler interactions are similar between coconut shell carbon and wood carbon reinforced composites. The swelling experiments, however, showed that the polymer–filler interaction is greater in the composites reinforced with coconut shell instead of wood carbon.     

Coal fly ash based carbons for SO2 removal from flue gases

Two different coal fly ashes coming from the burning of two coals of different rank have been used as a precursor for the preparation of steam activated carbons. The performance of these activated carbons in the SO₂ removal was evaluated at flue gas conditions (100 °C, 1000 ppmv SO₂, 5% O₂, 6% H₂O). Different techniques were used to determine the physical and chemical characteristics of the samples in order to explain the differences found in their behaviour. A superior SO₂ removal capacity was shown by the activated carbon obtained using the fly ash coming from a subbituminous–lignite blend. Experimental results indicated that the presence of higher amount of certain metallic oxides (Ca, Fe) in the carbon-rich fraction of this fly ash probably has promoted a deeper gasification in the activation with steam. A more suitable surface chemistry and textural properties have been obtained in this case which explains the higher efficiency shown by this sample in the SO₂ removal.     

Simultaneous treatment of PVC and oyster-shell wastes by mechanochemical means

This work presents a new process for dechlorinating poly-vinyl chloride (PVC) by the use of oyster-shell waste. The process consists of milling of PVC waste with oyster-shell waste, followed by washing the milled sample with water. The milling of PVC and oyster-shell mixture results in size reduction and rupture in bonds, leading to mechanically induced reactions between the two to form CaCl2 and hydrocarbon with C=C bonds. Washing the milled mixtures with water at room temperature allows complete removal of chlorine from the milled sample. More than 95% of chlorine in PVC was removed when 2h grinding is conducted for the mixture. The present process could offer a potential route to the handling and disposal of oyster-shell and PVC wastes.     

Adsorption of malachite green on groundnut shell waste based powdered activated carbon

In the present technologically fast changing situation related to waste management practices, it is desirable that disposal of plant waste should be done in a scientific manner by keeping in view economic and pollution considerations. This is only possible when the plant waste has the potential to be used as raw material for some useful product. In the present study, groundnut shell, an agricultural waste, was used for the preparation of an adsorbent by chemical activation using ZnCl2 under optimized conditions and its comparative characterisation was conducted with commercially available powdered activated carbon (CPAC) for its physical, chemical and adsorption properties. The groundnut shell based powdered activated carbon (GSPAC) has a higher surface area, iodine and methylene blue number compared to CPAC. Both of the carbons were used for the removal of malachite green dye from aqueous solution and the effect of various operating variables, viz. adsorbent dose (0.1-1 g l(-1)), contact time (5-120 min) and adsorbate concentrations (100-200 mg l(-1)) on the removal of dye, has been studied. The experimental results indicate that at a dose of 0.5 g l(-1) and initial concentration of 100 mg l(-1), GSPAC showed 94.5% removal of the dye in 30 min equilibrium time, while CPAC removed 96% of the dye in 15 min. The experimental isotherm data were analyzed using the linearized forms of Freundlich, Langmuir and BET equations to determine maximum adsorptive capacities. The equilibrium data fit well to the Freundlich isotherm, although the BET isotherm also showed higher correlation for both of the carbons. The results of comparative adsorption capacity of both carbons indicate that groundnut shell can be used as a low-cost alternative to commercial powdered activated carbon in aqueous solution for dye removal.     

Physical and chemical properties study of the activated carbon made from sewage sludge

Preparation of activated carbon from sewage sludge is a promising way to produce a useful adsorbent for pollutants removal as well as to dispose of sewage sludge. The objective of this study was to investigate the physical and chemical properties of the activated carbon made from sewage sludge so as to give a basic understanding of its structure. The activated carbon was prepared by activating anaerobically digested sewage sludge with 5 M ZnCl2 and thereafter pyrolyzing it at 500 degrees C for 2 h under nitrogen atmosphere. The properties investigated in the present study included its surface area and pore size distribution, its elemental composition and ash content, its surface chemistry structure and its surface physical morphology. Furthermore, its adsorption capacities for aqueous phenol and carbontetrachloride were examined. The results indicated that the activated carbon made from sewage sludge had remarkable micropore and mesopore surface areas and notable adsorption capacities for phenol and carbon-tetrachloride. In comparison with commercial activated carbons, it displayed distinctive physical and chemical properties.     

Pore structure and adsorption properties of carbonized material prepared from waste paper

We have already reported the adsorptivity and pore structure of activated carbon made from waste newspaper in order to use the waste paper for purposes other than paper-making stock. However, manufacturing the activated carbon may not necessarily be an advantageous method based on environmental concerns and the effective use of the resource because the reaction during the activating process is endothermic and the amount of carbon consumed is significant. Here, we examine the pore structure and adsorption properties of waste newspaper used as an adsorbent in the form of a carbonized material. Waste newspaper was carbonized for 2 h in the temperature range 400°–1000°C. The specific surface area of the carbonized material obtained, 418 m²/g, was highest for the sample carbonized at 800°C, which was equal to or greater than that of commercially available charcoal. Moreover, the iodine adsorption number of 581 mg/g was the highest and the rate of adsorption was the fastest for the sample carbonized at 800°C. However, the humidity control capability was highest for the material carbonized at 600°–700°C. It has been determined that it is advantageous to carbonize waste paper at 800°C in order to use the carbonized material as an adsorbent, while carbonization at 600°–700°C is more advantageous for use as a humidity control material. Received: June 23, 2000 / Accepted: January 17, 2001     

高炉渣对Cd~(2+)的吸附性能

采用包头钢铁集团炼铁厂的高炉渣为吸附剂(粒径0.154 nm)对Cd2+进行吸附,运用SEM技术对吸附剂进行了表征,研究了初始Cd2+质量浓度、吸附剂加入量、吸附时间、吸附温度和废水pH对Cd2+去除率的影响,并探讨了吸附机理。表征结果显示:高炉渣吸附剂具有疏松多孔的特点,表面十分粗糙,比表面积较大。实验结果表明:当吸附温度为室温(28℃)、废水pH为7、初始Cd2+质量浓度为10 mg/L、吸附剂加入量为8 g/L、吸附时间为60 min时,Cd2+去除率达到98.55%;高炉渣对Cd2+的吸附符合拟二级动力学方程和Langmuir等温吸附模型,且吸附反应易发生。     

Adsorption removal of pollutants by active cokes produced from sludge in the energy recycle process of wastes

This study proposes a recycling system of sludge into active cokes and the fundamental examinations for the application were carried out. In the system, active cokes were produced by carbonizing pellets of sludge in a steam stream. Pyrolysis gas yielded by carbonization can be available to a fuel for a steam generation boiler. The exhaust heat from the boiler is used sequentially for drying of sludge. The active cokes are applied to the adsorbent for dioxin removal in exhaust gas from incinerators of wastes, or for purification of gas obtained in a gasification process of wastes, particularly removal of H2S. The used adsorbent is not recycled, but incinerated in the furnace without a desorption process to decompose adsorbed dioxin or to oxidize H2S for a sequential desulfurization process of SO2. Dry pellets of sludge were carbonized in a quartz tube reactor under various atmospheres. The micro pore structure and the adsorption performance of the cokes produced without activation process were examined. The micro pore structure was influenced by the temperature, the sort of flow gas (N2, CO2 and steam) and carbonization time, and the active cokes produced under the condition of the temperature 823 K for 60 min in the steam atmosphere had a largest specific surface area in the diameter less than 5 nm. The amount of benzene adsorption as an alternative substance of dioxin into the active cokes had a similar quality to a commercial active char produced from coal if it was evaluated by adsorption per a unit specific surface area. This fundamental knowledge must be reflected to an optimum design for development of a simple continuous process to produce the active cokes by a fluidized bed type of the carbonization furnace.     

Carbon Molecular Sieving Membranes Derived from Lignin-Based Materials

Carbon molecular sieving membranes were prepared by pyrolysis of lignocresol derived from lignin by the phase-separation method. Lignocresol membranes formed by a dip process on a porous -alumina tubing were carbonized at 400–800°C under nitrogen atmosphere. The thickness of the membrane formed on the outer surface of the substrate was about 400 nm judging from SEM observation. Gas-evolving behavior of lignocresol was measured using thermogravimetry-mass spectrometry (TG-MS). The gaseous products evolved from lignocresol included a number of fragments with higher molecular weights; whereas those from phenolic resin are mainly due to phenol and methylphenol. These evolved pyrolysis fragments effectively contribute to micropore formation of carbonized lignocresol membranes. Gas permeation rates through the membrane decreased in the order of increasing kinetic molecular diameter of the penetrant gas, and the membrane behaved like a molecular sieve. The permeation properties were dependent on heating conditions, and a pyrolysis temperature of 600°C gave the best membrane performance. Gas selectivities of the membrane prepared at 600°C were 50, 8, 290, and 87 for CO₂/N₂, O₂/N₂, H₂/CH₄, and CO₂/CH₄ at 35°C, respectively.     

Removal potential of toxic 2378-substituted PCDD/F from incinerator flue gases by waste-derived activated carbons

The application of activated carbons has become a commonly used emission control protocol for the removal or adsorption of persistent organic pollutants from the flue gas streams of waste incinerators. In this study, the 2378-substituted PCDD/F removal efficiency of three types of activated carbons derived from the pyrolysis of refuse derived fuel, textile waste and scrap tyre was investigated and compared with that of a commercial carbon. Experiments were carried out in a laboratory scale fixed-bed reactor under a simulated flue gas at 275 °C with a reaction period of four days. The PCDD/F in the solid matrices and exhaust gas, were analyzed using gas chromatography coupled with a triple quadrupole mass spectrometer. In the absence of activated carbon adsorbent, there was a significant increase in the concentration of toxic PCDD/F produced in the reacted flyash, reaching up to 6.6 times higher than in the raw flyash. In addition, there was a substantial release of PCDD/F into the gas phase, which was found in the flue gas trapping system. By application of the different commercial, refuse derived fuel, textile and tyre activated carbons the total PCDD/F toxic equivalent removal efficiencies in the exhaust gas stream were 58%, 57%, 64% and 52%, respectively. In general, the removal of the PCDDs was much higher with an average of 85% compared to PCDFs at 41%. Analysis of the reacted activated carbons showed that there was some formation of PCDD/F, for instance, a total of 60.6 μg I-TEQ kg⁻¹ toxic PCDD/F was formed in the refuse derived fuel activated carbon compared to 34 μg I-TEQ kg⁻¹ in the commercial activated carbon. The activated carbons derived from the pyrolysis of waste, therefore, showed good potential as a control material for PCDD/F emissions in waste incinerator flue gases.     

Mechanochemical dechlorination of polyvinyl chloride with calcium sulfates

Polyvinyl chloride (PVC) was milled with hydrated or unhydrated calcium sulfates (CaSO₄·2H₂O or CaSO₄) in air by using a planetary mill to investigate mechanochemical dechlorination behavior. The milling process resulted in size reduction and in the breaking of bonds leading to mechanically induced solid state reaction, forming CaCl₂ and dechlorinated hydrocarbon with C=C double bonds in the product. Washing the milled mixtures with water at room temperature allowed removal of the chloride formed during milling, and more than 95% of the chlorine in PVC was removed from a mixture milled for 4 h. This process could offer a potential route for the handling and disposal of both PVC and gypsum wastes. H₂S gas was generated during milling; more H₂S was released from the unhydrated sample than from the hydrated sample.     

Sorbents for CO2 capture from high carbon fly ashes

Fly ashes with high-unburned-carbon content, referred to as fly ash carbons, are an increasing problem for the utility industry, since they cannot be marketed as a cement extender and, therefore, have to be disposed. Previous work has explored the potential development of amine-enriched fly ash carbons for CO(2) capture. However, their performance was lower than that of commercially available sorbents, probably because the samples investigated were not activated prior to impregnation and, therefore, had a very low surface area. Accordingly, the work described here focuses on the development of activated fly ash derived sorbents for CO(2) capture. The samples were steam activated at 850 degrees C, resulting in a significant increase of the surface area (1075m(2)/g). The activated samples were impregnated with different amine compounds, and the resultant samples were tested for CO(2) capture at different temperatures. The CO(2) adsorption of the parent and activated samples is typical of a physical adsorption process. The impregnation process results in a decrease of the surface areas, indicating a blocking of the porosity. The highest adsorption capacity at 30 and 70 degrees C for the amine impregnated activated carbons was probably due to a combination of physical adsorption inherent from the parent sample and chemical adsorption of the loaded amine groups. The CO(2) adsorption capacities for the activated amine impregnated samples are higher than those previously published for fly ash carbons without activation (68.6 vs. 45mg CO(2)/g sorbent).