Thermal valorization of footwear leather wastes in bubbling fluidized bed combustion

Transformation of hide (animal skins) into leather is a complicated process during which significant amounts of wastes are generated. Footwear is the sector that consumes the major part of leather (60%). Logically, this industry is producing the largest quantity of leather wastes. The objective of this work was to demonstrate the technical feasibility of fluidized bed technology to recover the energy from burning footwear leather wastes. Considering the characteristics of leather waste, especially the heating value (12.5-21 MJ/kg), it can be considered a fairly good fuel. Moreover, leather waste has suitable characteristics for combustion, e.g., high volatile matter (76.5%) and low ash content (5.2%). Two factors deserve special attention: N3O and NOx emissions as a consequence of its unusual high nitrogen content (14.1%) and the chromium speciation because chromium is the main element of ash (3.2%) due to its use in leather tanning. A series of experiments has been carried out in a 0.1 MWt bubbling fluidized bed pilot plant. The combustion efficiency, flue gas composition and chromium speciation were investigated. Despite having high nitrogen content, a low conversion rate of fuel-N to NOx and N2O was attained. Chromium was concentrated in the solid streams and it was consistently found as Cr(III+); no presence of Cr(VI+) was detected.     

Composites Produced from Natural Rubber and Chrome-Tanned Leather Wastes: Evaluation of their In Vitro Toxicological Effects for Application in Footwear and Textile Industries

A new composite has been developed from natural rubber and chrome-tanned leather waste for use in footwear and textile industries. The contribution of this material to environmental quality and sustained development should be highligh because chrome tanned leather wastes, a major environmental problem, can be recycled. However, the safety of this new material for human use is questionable, as it is already well reported in the literature that chromium, particularly in its hexavalent oxidation state, can be genotoxic and carcinogenic to living beings. Thus, the aim of this study was to evaluate in vitro biocompatibility of this composite material for possible use in the footwear and textile industries, through cytotoxicity, cell adhesion, and genotoxicity tests. Inductively coupled plasma optical emission spectrometry (ICP-OES) was used to measure both concentrations of total and hexavalent chromium. Based on the findings, it was concluded that the composite exhibits low levels of cytotoxicity and genotoxicity, and possesses favorable properties for initial cell adhesion. Furthermore, it was verified that the composites released low concentrations of chromium and that the predominant species released would be trivalent chromium. The results of the present study open the possibility of the incorporation of solid residues of tanned leather into chromium without necessarily the chromium contained in these residues influences the toxicity and genotoxicity of this new material.     

Transesterification reaction of the fat originated from solid waste of the leather industry

The leather industry is an industry which generates a large amount of solid and liquid wastes. Most of the solid wastes originate from the pre-tanning processes while half of it comes from the fleshing step. Raw fleshing wastes which mainly consist of protein and fat have almost no recovery option and the disposal is costly. This study outlines the possibility of using the fleshing waste as an oil source for transesterification reaction. The effect of oil/alcohol molar ratio, the amount of catalyst and temperature on ester production was individually investigated and optimum reaction conditions were determined. The fuel properties of the ester product were also studied according to the EN 14214 standard. Cold filter plugging point and oxidation stability have to be improved in order to use the ester product as an alternative fuel candidate. Besides, this product can be used as a feedstock in lubricant production or cosmetic industry.     

Recycled lightweight concrete made from footwear industry waste and CDW

In this paper two types of recycled aggregate, originated from construction and demolition waste (CDW) and ethylene vinyl acetate (EVA) waste, were used in the production of concrete. The EVA waste results from cutting off the EVA expanded sheets used to produce insoles and innersoles of shoes in the footwear industry. The goal of this study was to evaluate the influence of the use of these recycled aggregates as replacements of the natural coarse aggregate, upon density, compressive strength, tensile splitting strength and flexural behavior of recycled concrete. The experimental program was developed with three w/c ratios: 0.49, 0.63 and 0.82. Fifteen mixtures were produced with different aggregate substitution rates (0%, 50% EVA, 50% CDW, 25% CDW–25% EVA and 50% CDW–50% EVA), by volume. The results showed that it is possible to use the EVA waste and CDW to produce lightweight concrete having semi-structural properties.     

Biodegradability of leathers through anaerobic pathway

Leather processing generates huge amounts of both solid and liquid wastes. The management of solid wastes, especially tanned leather waste, is a challenging problem faced by tanners. Hence, studies on biodegradability of leather become imperative. In this present work, biodegradability of untanned, chrome tanned and vegetable tanned leather under anaerobic conditions has been addressed. Two different sources of anaerobes have been used for this purpose. The effect of detanning as a pretreatment method before subjecting the leather to biodegradation has also been studied. It has been found that vegetable tanned leather leads to more gas production than chrome tanned leather. Mixed anaerobic isolates when employed as an inoculum are able to degrade the soluble organics of vegetable tanned material and thus exhibit an increased level of gas production during the initial days, compared to the results of the treatments that received the anaerobic sludge. With chrome tanned materials, there was not much change in the volume of the gas produced from the two different sources. It has been found that detanning tends to improve the biodegradability of both types of leathers.     

Valorization of titanium metal wastes as tanning agent used in leather industry

The development of new tanning agents and new technologies in the leather sector is required to cope with the increasingly higher environmental pressure on the current tanning materials and processes such as tanning with chromium salts. In this paper, the use of titanium wastes (cuttings) resulting from the process of obtaining highly pure titanium (ingots), for the synthesis of new tanning agent and tanning bovine hides with new tanning agent, as alternative to tanning with chromium salts are investigated. For this purpose, Ti waste and Ti-based tanning agent were characterized for metal content by inductively coupled plasma mass spectrometry (ICP-MS) and chemical analysis; the tanned leather (wet white leather) was characterized by Scanning Electron Microscope/Energy Dispersive Using X-ray (Analysis). SEM/EDX analysis for metal content; Differential scanning calorimetric (DSC), Micro-Hot-Table and standard shrinkage temperature showing a hydrothermal stability (ranged from 75.3 to 77 °C) and chemical analysis showing the leather is tanned and can be processed through the subsequent mechanical operations (splitting, shaving). On the other hand, an analysis of major minor trace substances from Ti-end waste (especially vanadium content) in new tanning agent and wet white leather (not detected) and residue stream was performed and showed that leachability of vanadium is acceptable. The results obtained show that new tanning agent obtained from Ti end waste can be used for tanning bovine hides, as eco-friendly alternative for chrome tanning.     

Finished leather waste chromium acid extraction and anaerobic biodegradation of the products

Due to the amounts of chromium in the leachate resulting from leather leaching tests, chromium sulfate tanned leather wastes are very often considered hazardous wastes. To overcome this problem, one option could be recovering the chromium and, consequently, lowering its content in the leather scrap. With this objective, chromium leather scrap was leached with sulfuric acid solutions at low temperature also aiming at maximizing chromium removal with minimum attack of the leather matrix. The effects of leather scrap dimension, sulfuric acid and sodium sulfate concentration in the solutions, as well as extraction time and temperature on chromium recovery were studied, and, additionally, organic matrix degradation was evaluated. The best conditions found for chromium recovery were leather scrap conditioning using 25 mL of concentrated H₂SO₄/L solution at 293 or 313 K during 3 or 6 days. Under such conditions, 30–60 ± 5% of chromium was recovered and as low as 3–6 ± 1% of the leather total organic carbon (TOC) was dissolved. Using such treatment, the leather scrap area and volume are reduced and the residue is a more brittle material showing enhanced anaerobic biodegradability. Although good recovery results were achieved, due to the fact that the amount of chromium in eluate exceeded the threshold value this waste was still hazardous. Thus, it needs to be methodically washed in order to remove all the chromium de-linked from collagen.     

Evaluating the toxicity of food processing wastes as co-digestion substrates with dairy manure

Studies have shown that including food waste as a co-digestion substrate in the anaerobic digestion of livestock manure can increase energy production. However, the type and inclusion rate of food waste used for co-digestion need to be carefully considered in order to prevent adverse conditions in the digestion environment. This study determined the effect of increasing the concentration (2%, 5%, 15% and 30%, by volume) of four food-processing wastes (meatball, chicken, cranberry and ice cream processing wastes) on methane production. Anaerobic toxicity assay (ATA) and specific methanogenic activity (SMA) tests were conducted to determine the concentration at which each food waste became toxic to the digestion environment. Decreases in methane production were observed at concentrations above 5% for all four food waste substrates, with up to 99% decreases in methane production at 30% food processing wastes (by volume).     

Solid industrial wastes and their management in Asegra (Granada, Spain)

ASEGRA is an industrial area in Granada (Spain) with important waste management problems. In order to properly manage and control waste production in industry, one must know the quantity, type, and composition of industrial wastes, as well as the management practices of the companies involved. In our study, questionnaires were used to collect data regarding methods of waste management used in 170 of the 230 businesses in the area of study. The majority of these companies in ASEGRA are small or medium-size, and belong to the service sector, transport, and distribution. This was naturally a conditioning factor in both the type and management of the wastes generated. It was observed that paper and cardboard, plastic, wood, and metals were the most common types of waste, mainly generated from packaging (49% of the total volume), as well as material used in containers and for wrapping products. Serious problems were observed in the management of these wastes. In most cases they were disposed of by dumping, and very rarely did businesses resort to reuse, recycling or valorization. Smaller companies encountered greater difficulties when it came to effective waste management. The most frequent solution for the disposal of wastes in the area was dumping.     

Effect of organic matter and moisture on the calorific value of solid wastes: An update of the Tanner diagram

Objective of the work was to experimentally determine the effect of the organic matter and moisture contents on the calorific value of organic solid wastes. Nine substrates (i.e. newsprint, biodried municipal solid wastes, municipal solid waste derived composts, wastewater sludges, and sea weed derived compost), with organic matter contents that ranged from 12% to 91% (dry weight) were used in the experiments. All substrates were dried and ground and deionized water was artificially added in order to achieve certain target moisture contents per substrate. The higher heating value (HHV) was, then, determined experimentally for each sample using a bomb calorimeter. Best reduced models were developed to describe the higher and lower heating values as a function of organic matter, ash and moisture contents. A triangular plot was constructed and the self-sustained combustion area was determined and compared to that of the Tanner diagram. Response surfaces were drawn to visually assess the effect of organic matter and moisture contents on the calorific value of the wastes.     

Comparisons of four categories of waste recycling in China's paper industry based on physical input-output life-cycle assessment model

Waste recycling for paper production is an important component of waste management. This study constructs a physical input-output life-cycle assessment (PIO-LCA) model. The PIO-LCA model is used to investigate environmental impacts of four categories of waste recycling in China’s paper industry: crop straws, bagasse, textile wastes and scrap paper. Crop straw recycling and wood utilization for paper production have small total intensity of environmental impacts. Moreover, environmental impacts reduction of crop straw recycling and wood utilization benefits the most from technology development. Thus, using crop straws and wood (including wood wastes) for paper production should be promoted. Technology development has small effects on environmental impacts reduction of bagasse recycling, textile waste recycling and scrap paper recycling. In addition, bagasse recycling and textile waste recycling have big total intensity of environmental impacts. Thus, the development of bagasse recycling and textile waste recycling should be properly limited. Other pathways for reusing bagasse and textile wastes should be explored and evaluated. Moreover, imports of scrap paper should be encouraged to reduce large indirect impacts of scrap paper recycling on domestic environment.     

Rapid screening procedure to optimise the anaerobic codigestion of industrial biowastes and agricultural livestock wastes in Cyprus

Small-scale experimental investigations were undertaken on the anaerobic digestion (AD) and codigestion of livestock waste and industrial biowastes. A simple procedure was developed to rapidly determine the suitability of wastes for digestion. The experiment was split into two phases; initially, the seed (digested brewery waste) was replaced by the test waste over a period of 5 days. During the second phase, the test waste was incubated and monitored for methanogenesis. Dairy cattle slurry was the most efficient co-substrate which, when codigested with pig slurry in an equal ratio achieved volatile solids destruction of 32%, CH(4) production rate of 97.4 ml d(-1), maximum CH(4) content of 61.6% and total gas yield of 2229 ml after 529 h. High fat content wastes were unsuitable for AD due to low pH value and because the dominant microbial reaction was fermentation. Codigestion was investigated to overcome any inhibitions; however, dairy cattle slurry, abattoir wastewater and NaOH additions did not lead to methanogenesis. Treating these wastes by AD is feasible but without CH(4) production.     

Leachate recirculation effects on waste degradation: study on columns

The purpose of this study is to determine the impact of leachate recirculation on the degradation of municipal solid wastes (bioreactor concept). The study was carried out using columns containing approximately 50 kg of waste, in order to follow waste degradation over a limited time. Three types of waste were studied: fresh waste of standard composition, fresh waste of fermentable composition and some 8-yr-old waste extracted from a site in France. Measurement of the global parameters, such as chemical oxygen demand (COD), volatile acidity, alkalinity, leachate conductivity, methane potential of the wastes and biogas production monitoring (volume of CO2 and CH4 produced), were carried out. The quantity of oxydizable matter and biogas production was increased by the leachate recirculation, and the duration of the first degradation phases was reduced in all cases. Chloride, ammonium and organic pollution accumulation was observed according to the duration of recirculation. After 400 days of degradation, waste stabilization seemed to be reached for all of the recirculated columns (COD<300 mg/L O2, and methane potential reached).     

An alternative method for the treatment of waste produced at a dye and a metal-plating industry using natural and/or waste materials.

The aim of this study was to develop cost-effective, appropriate solidification technologies for treating hazardous industrial wastes that are currently disposed of in ways that may threaten the quality of local groundwater. One major objective was to use materials other than cement, and preferably materials that are themselves wastes, as the solidification additives, namely using wastes to treat wastes or locally available natural material. This research examines the cement-based and lime-based stabilization/solidification (S/S) techniques applied for waste generated at a metal-plating industry and a dye industry. For the lime-based S/S process the following binder mixtures were used: cement kiln dust/ lime, bentonite/lime and gypsum/lime. For the cement-based S/S process three binder mixtures were used: cement kiln dust/cement, bentonite/cement and gypsum/cement. The leachability of the wastes was evaluated using the toxicity characteristic leaching procedure. The applicability and optimum weight ratio of the binder mixtures were estimated using the unconfined compressive strength test. The optimum ratio mixtures were mixed with waste samples in different ratios and cured for 28 days in order to find the S/S products with the highest strength and lowest leachability at the same time. The results of this work showed that the cement-and lime-based S/S process, using cement kiln dust and bentonite as additives can be effectively used in order to treat industrial waste.     

Medical waste production at hospitals and associated factors

This study was conducted to evaluate the quantities of medical waste generated and the factors associated with the generation rate at medical establishments in Taiwan. Data on medical waste generation at 150 health care establishments were collected for analysis in 2003. General medical waste and infectious waste production at these establishments were examined statistically with the potential associated factors. These factors included the types of hospital and clinic, reimbursement payment by National Health Insurance, total number of beds, bed occupancy, number of infectious disease beds and outpatients per day. The average waste generation rates ranged from 2.41 to 3.26kg/bed/day for general medical wastes, and 0.19-0.88kg/bed/day for infectious wastes. The total average quantity of infectious wastes generated was the highest from medical centers, or 3.8 times higher than that from regional hospitals (267.8 vs. 70.3Tons/yr). The multivariate regression analysis was able to explain 92% of infectious wastes and 64% of general medical wastes, with the amount of insurance reimbursement and number of beds as significant prediction factors. This study suggests that large hospitals are the major source of medical waste in Taiwan. The fractions of medical waste treated as infectious at all levels of healthcare establishments are much greater than that recommended by the USCDC guidelines.     

Characterization of char derived from various types of solid wastes from the standpoint of fuel recovery and pretreatment before landfilling

Carbonization is a kind of pyrolysis process to produce char from organic materials under an inert atmosphere. In this work, chars derived from various solid wastes were characterized from the standpoint of fuel recovery and pretreatment of waste before landfilling. Sixteen kinds of municipal and industrial solid wastes such as residential combustible wastes, non-combustible wastes, bulky wastes, construction and demolition wastes, auto shredder residue, and sludges were carbonized at 500 degrees C for 1h under nitrogen atmosphere. In order to evaluate the quality of char as fuel, proximate analysis and heating value were examined. The composition of raw waste had a significant influence on the quality of produced char. The higher the ratio of woody biomass in waste, the higher heating value of char produced. Moreover, an equation to estimate heating value of char was developed by using the weight fraction of fixed carbon and volatile matter in char. De-ashing and chlorine removal were performed to improve the quality of char. The pulverization and sieving method seems to be effective for separation of incombustibles such as metal rather than ash. Most char met a 0.5 wt% chlorine criterion for utilization as fuel in a shaft blast furnace after it was subjected to repeated water-washing. Carbonization could remove a considerable amount of organic matter from raw waste. In addition, the leaching of heavy metals such as chrome, cadmium, and lead appears to be significantly suppressed by carbonization regardless of the type of raw waste. From these results, carbonization could be considered as a pretreatment method for waste before landfilling, as well as for fuel recovery.     

Thermal and enzymatic recovering of proteins from untanned leather waste

The laboratory trials of a process to treat untanned leather waste to isolate valuable protein products are presented. In this comparative study, both thermal and enzymatic treatments of leather waste were performed. The enzymatic method utilizes commercially available alkaline protease at moderate temperatures and for short periods of time. The concentration of the enzyme was 500 units per gram of leather waste which makes the method cost-effective. Amino acid composition in the hydrolysate obtained by the enzyme hydrolysis of untanned leather waste is determined. Chemical and physical properties of protein powder products from untanned leather waste were evaluated by spectrophotometric and chromatographic methods and by use of electron microscope. The results of microbiological assays confirm that these products agree to food safety standards. This relatively simple treatment of untanned leather waste may provide a practical and economical solution to the disposal of potentially dangerous waste.     

Model calibration and validation for OFMSW and sewage sludge co-digestion reactors

A mathematical model has recently been proposed by the authors to simulate the biochemical processes that prevail in a co-digestion reactor fed with sewage sludge and the organic fraction of municipal solid waste. This model is based on the Anaerobic Digestion Model no. 1 of the International Water Association, which has been extended to include the co-digestion processes, using surface-based kinetics to model the organic waste disintegration and conversion to carbohydrates, proteins and lipids. When organic waste solids are present in the reactor influent, the disintegration process is the rate-limiting step of the overall co-digestion process. The main advantage of the proposed modeling approach is that the kinetic constant of such a process does not depend on the waste particle size distribution (PSD) and rather depends only on the nature and composition of the waste particles. The model calibration aimed to assess the kinetic constant of the disintegration process can therefore be conducted using organic waste samples of any PSD, and the resulting value will be suitable for all the organic wastes of the same nature as the investigated samples, independently of their PSD. This assumption was proven in this study by biomethane potential experiments that were conducted on organic waste samples with different particle sizes. The results of these experiments were used to calibrate and validate the mathematical model, resulting in a good agreement between the simulated and observed data for any investigated particle size of the solid waste. This study confirms the strength of the proposed model and calibration procedure, which can thus be used to assess the treatment efficiency and predict the methane production of full-scale digesters.     

Environmental and economic analyses of waste disposal options for traditional markets in Indonesia

Waste from traditional markets in Indonesia is the second largest stream of municipal solid waste after household waste. It has a higher organic fraction and may have greater potential to be managed on a business scale compared to household wastes. The attributed reason is that in general the wastes generated from traditional markets are more uniform, more concentrated and less hazardous than waste from other sources. This paper presents the results of environmental and economic assessments to compare the options available for traditional market waste disposal in Indonesia. The options compared were composting in labour intensive plants, composting in a centralised plant that utilised a simple wheel loader, centralised biogas production and landfill for electricity production. The current open dumping practice was included as the baseline case. A life cycle assessment (LCA) was used for environmental analysis. All options compared have lower environmental impacts than the current practice of open dumping. The biogas production option has the lowest environmental impacts. A cost-benefit analysis, which considered greenhouse gas savings, was used for the economic assessment. It was found that composting at a centralised plant is the most economically feasible option under the present Indonesian conditions. The approach reported in this study could be applied for 'a pre-feasibility first cut comparison' that includes environmental aspects in a decision-making framework for developing countries even though European emission factors were used.     

Preparation, Characterization and Application of Leather Particulate-Polymer Composites (LPPCs)

The present study describes the preparation and characterization of leather particulate-polymer composites (LPPCs) from solid wastes (chrome shavings/buffing dusts) generated during leather manufacturing processes. Nitrile butadiene rubber (NBR), Styrene butadiene rubber (SBR) and neoprene rubber were the polymers used at different concentrations. Pretreatment of leather wastes with suitable alkaline reagents enhances the binding efficiency with polymers chosen and the high interfacial bonding prevailing reduces the chromium leaching. Mechanical properties of the resultant polymer composites showed good machinable and nailing properties. Addition of poly vinyl chloride (PVC) further enhances the above said properties. Scanning electron micrograph analyses implies complete blending of components in LPPCs. The composites exhibit good machinable and nailing properties and are easily transformed to shoe heel, shoe sole and shoe last.