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.     

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.     

A Study of the Photocatalytic Oxidation of Humic Acid on Anatase and Mixed-phase Anatase–Rutile TiO2 Nanoparticles

In this study, slurry photocatalytic oxidation process was investigated for natural organic matter removal from aqueous humic acid solutions by using different titanium dioxide (TiO₂) under UV-A irradiation. Bench scale experimental studies were conducted at different humic acid concentration at the range of 10–50 mg/L and different pH. Anatase and mixed-phase anatase–rutile TiO₂ nano particles used in the photocatalytic reactor. The results were evaluated in terms of the parameters that are specific to organic matter content such as dissolved organic carbon concentration, ultraviolet absorbance at 254 nm (UV₂₅₄), specific ultaviolet absorbance at 254 nm, and color (VIS₄₀₀). It was observed that increasing humic acid concentration decreases photocatalytic degradation efficiency. The reactivity of the mixed-phase anatase–rutile (Degussa P-25) TiO₂ was greater than individual anatase particles and the highest efficiency was observed at pH 3 for anatase TiO₂.     

Utilization of a leather industry waste

In the production of leather the main waste that remains after splitting of limed hides before tanning is the lowest layer of the skin together with the underlying fatty tissue (subcutis). It is characterized by a very high water content (up to 870 g kg⁻¹) and a balanced content of protein (40–60 g kg⁻¹ of the dry mass), fat (10–20 g kg⁻¹) of the dry mass) and carbohydrates. The object of this work was to elaborate a method to process this waste into useful products. The treatment proposed involves washing to remove the inorganic salts, separation of fat and extraction of collagen in hot water solution and additional extraction of protein from the insoluble residue after hydrolysis with alkaline proteinase. This results in the isolation of three fractions: fat—cattle tallow (4–12% of the total mass of the initial material), collagen hydrolysate—glue (5–10%) and protein concentrate for fodder (1–3% yield). Up to 95% of the protein in the initial material was extracted. Further purification of the collagen hydrolysate fraction into edible gelatin was achieved. The proposed method is applicable to every leather factory.     

Polylactic Acid (PLA) Biocomposites Filled with Waste Leather Buff (WLB)

A large amount of leather waste is generated from tanning industries and most of which are disposed of landfill or discharged into the natural water bodies without any treatment, causing environmental problems. The aim of this study is to develop eco-biocomposites using waste leather buff (WLB) as filler in Polylactic acid (PLA) matrix to reduce the environmental issues and provide sustainable solution. WLB/PLA composites were prepared by twins-screw micro extruder varying the WLB content from 2% to 30 wt%. These composite were extensively characterise by several techniques. Tensile properties of the composites showed addition of WLB resulted in improvement of tensile property of composite and reduction in percentage crystallinity of PLA matrix observed with increase in WLB content. The effect of WLB on properties of interfacial adhesion and dispersion in WLB/PLA composites were studied by SEM. Wettability of composites was tested by contact angle and water absorption studies. WLB/PLA composite showed increase in water absorption with WLB loading. These WLB/PLA composite could be used to develop low cost eco-friendly product material.     

Comprehensive modeling of HFC-23 incineration in a CDM incinerator

Considering that a significant part of used refrigerants have to be destroyed in an environmentally friendly manner together with the high global warming potential (GWP) of HFCs (hydrofluorocarbons), the development of a proper incineration method of HFCs becomes one of the viable methods in the refrigeration and air-conditioning industry. To this end, in this study, the development of a comprehensive modeling of CHF₃ (HFC-23 or R-23) incineration is made to assist in the proper design and determination of optimal operating condition of a practical HFCs incinerator, since the refrigerant of CHF₃ is one of typical HFCs. For this, numerical investigation was performed by the development of a predictive model for the thermal destruction of the CHF₃ using CH₄–air flames in an incinerator designed for CDM (clean development mechanism) project. First of all, comparison between calculation and operation data was made to evaluate the program developed in this study. Numerical calculation of CHF₃–CH₄–air flame predicts successfully the operation data of a CDM incinerator such as temperature, CHF₃ destruction rate more than 99.99 % and other species concentrations such as CO and NO at the exit of the incinerator. Further parametric study was performed also in terms of important variables such as excess air, amount of steam and incinerator size. In general, the results obtained appear physically acceptable and give a clear physical insight into the role of the important variables. Further work is strongly recommended for the development of a general turbulent reaction model for the thermal destruction of HFCs, especially for the condition of non-equilibrium turbulent reaction dominance.     

Towards a cleaner production in developing countries: a case study in a Chilean tannery.

A Chilean leather tanning industry (tannery) was studied in terms of input/output (I/O) analysis of beamhouse, tanyard and retanning processes. The physical-chemical characterization of 19 streams were investigated. Streams from the beamhouse process and some streams from the retanning process were found to have high organic contents ranging from 2.5 to 18.1 g COD L(-1). The pH ranged between 3.45 and 12.28. Sulphur was found in most of the streams whereas chromium was detected in two wastewaters from the tanyard and in seven streams from the retanning process. Pollution prevention opportunities were evaluated and an appropriate treatment strategy was proposed. The main emphasis was on determining waste reduction measures that can be easily implemented and are not particularly expensive. Measures for reduction at source were proposed to reduce water and chemicals consumption and wastewater pollution. A so-called S(index) strategy was used to evaluate proposals on segregation and specific treatment of the main chromium- and sulphur-containing wastewaters. It was suggested that some streams may be re-used, but it is necessary to apply anaerobic or aerobic treatment first, depending on their organic load. Solid wastes were also evaluated and a proposal for their reduction and disposal was made.     

Towards zero discharge of chromium-containing leather waste through improved alkali hydrolysis

The treatment of chromium-containing leather waste (CCLW), the major solid waste generated at the post-tanning operations of leather processing, has the potential to generate value-added leather chemicals. Various alkali and enzymatic hydrolysis were compared, and calcium oxide was found to be important for effective (but still incomplete) hydrolysis. Three possible reasons are given for the incomplete hydrolysis under alkaline conditions. Data for 19 amino acids are presented for four different treatment products. On the basis of the results, a novel three-step CCLW treatment process is proposed. The gelatin extracted in the first step is chemically modified to produce leather finishing agents. The collagen hydrolysates isolated in the second step are used as proteinic retanning agents by chemical modification. The remaining chrome cake is further hydrolyzed with acids in the third step, and the obtained chromium-containing protein hydrolysates could be used for the preparation of chromium-containing retanning agents for leather industry. The proposed three-step process provides a feasible zero discharge process for the treatment of CCLW.     

Leather Insole with Acupressure Effect: New Perspectives

Some wastes contain many reusable substances of high value. Solid leather waste is one such potential waste which can be converted into value added products. This study attempts to prepare leather insoles with acupressure effect from finished leather wastes and used leather wastes. Leather with acupressure effect (LAE) was fabricated using regenerated leather. LAE was characterized physico-chemically using Fourier transform infrared spectroscopy, thermo gravimetric analysis and scanning electron microscopy. Foot pressure measurements were done using LAE insoles on healthy individuals. Results proved that LAE insoles were able to increase the foot pressure of the wearer and thereby created an acupressure effect in them. Wearing of footwear with LAE insoles were beneficial compared to regular insoles. LAE possessed the required mechanical properties for insole production and it was also biodegradable in nature. The study proves that these composites could be successfully used for the production of cost-effective leather goods and therapeutic footwear. Production of useful byproducts from wastes is income generating and at the same time reduces environmental pollution and a feasible technology for waste recycling has been proved in this study.     

Long-term affected energy production of waste to energy technologies identified by use of energy system analysis

Affected energy production is often decisive for the outcome of consequential life-cycle assessments when comparing the potential environmental impact of products or services. Affected energy production is however difficult to determine. In this article the future long-term affected energy production is identified by use of energy system analysis. The focus is on different uses of waste for energy production. The Waste-to-Energy technologies analysed include co-combustion of coal and waste, anaerobic digestion and thermal gasification. The analysis is based on optimization of both investments and production of electricity, district heating and bio-fuel in a future possible energy system in 2025 in the countries of the Northern European electricity market (Denmark, Norway, Sweden, Finland and Germany). Scenarios with different CO₂ quota costs are analysed. It is demonstrated that the waste incineration continues to treat the largest amount of waste. Investments in new waste incineration capacity may, however, be superseded by investments in new Waste-to-Energy technologies, particularly those utilising sorted fractions such as organic waste and refuse derived fuel. The changed use of waste proves to always affect a combination of technologies. What is affected varies among the different Waste-to-Energy technologies and is furthermore dependent on the CO₂ quota costs and on the geographical scope. The necessity for investments in flexibility measures varies with the different technologies such as storage of heat and waste as well as expansion of district heating networks. Finally, inflexible technologies such as nuclear power plants are shown to be affected.     

Chromium Removal from Soil by Phytoremediation with Weed Plant Species in Thailand

The possibility of using phytoremediation with weed plant species in Thailand to remove chromium (Cr) from soil was investigated. Six plant species, Cynodon dactylon, Pluchea indica, Phyllanthus reticulatus, Echinochloa colonum, Vetiveria nemoralis, and Amaranthus viridis, were chosen for their abilities to accumulate total chromium (TCr) at tanning industry sites. These plant species were studied in pots at a nursery. Cynodon dactylon and Pluchea indica provided highest TCr accumulation capacities of 152.1 and 151.8 mg/kg of plant on a dry weight basis, respectively, at a pulse hexavalent Cr [Cr(VI)] input of 100 mg Cr(VI)/kg soil. Most of the Cr uptake occurred within 30 days after the input. The TCr accumulation by Pluchea indica was observed in roots, stems, and leaves at 27%, 38%, and 35% of the TCr mass uptake, respectively, whereas 51%, 49% and 0% of the TCr mass uptake accumulated in roots, stems, and leaves of Cynodon dactylon, respectively. The results on Cr accumulation and translocation in plant tissues suggest that Cr was removed mainly via phytoaccumulation and Pluchea indica is more suitable than Cynodon dactylon for the phytoremediation of Cr contaminated soil.     

Study of the evaporation process of saline waste from the tanning industry.

The second and third steps of wastewater treatment in the tanning industry generate sludges that are rich in salts, organic matter and suspended solids. Since these are formally catalogued as industrial wastes by environmental legislation, they cannot be disposed of directly but need a final treatment. One of the problems with these wastes is their high water content, which has to be reduced. In the particular case of the concentrated streams from the secondary and tertiary treatment steps, the sludges are first concentrated by evaporation, and the evaporated water is used in other parts of the plant. This study, which preceded evaporator design, analysed the evaporation process (laboratory scale) of a saline residue produced in the reverse osmosis step of the treatment of tanning wastewaters by the company Aquagest Levante, S.A. in Lorca (Murcia, Spain), to ascertain its behaviour in the evaporation process and the evolution of its physical properties. The study served to determine the exact mineralogy and ionic composition as well as the characteristics of the waste in question. This information was used in the last step of the design of the evaporation equipment.     

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.     

Conversion of calcium sulphide to calcium carbonate during the process of recovery of elemental sulphur from gypsum waste

The production of elemental sulphur and calcium carbonate (CaCO₃) from gypsum waste can be achieved by thermally reducing the waste into calcium sulphide (CaS), which is then subjected to a direct aqueous carbonation step for the generation of hydrogen sulphide (H₂S) and CaCO₃. H₂S can subsequently be converted to elemental sulphur via the commercially available chemical catalytic Claus process. This study investigated the carbonation of CaS by examining both the solution chemistry of the process and the properties of the formed carbonated product. CaS was successfully converted into CaCO₃; however, the reaction yielded low-grade carbonate products (i.e. <90 mass% as CaCO₃) which comprised a mixture of two CaCO₃ polymorphs (calcite and vaterite), as well as trace minerals originating from the starting material. These products could replace the Sappi Enstra CaCO₃ (69 mass% CaCO₃), a by-product from the paper industry which is used in many full-scale AMD neutralisation plants but is becoming insufficient. The insight gained is now also being used to develop and optimize an indirect aqueous CaS carbonation process for the production of high-grade CaCO₃ (i.e. >99 mass% as CaCO₃) or precipitated calcium carbonate (PCC).     

The development of low cost adsorbents from clay and waste materials: a review

Increased energy consumption due to industrial growth has increased the levels of carbon dioxide (CO₂) emission being released into the atmosphere. CO₂ emission is a type of greenhouse gas which is a major cause of global warming. Since the issue of CO₂ emissions has drawn much attention in recent years, the development of CO₂ capture technology has become a necessity. Although CO₂ adsorbents are still at the early development stage, it has been suggested that CO₂ adsorbents are the most effective technology in controlling CO₂ emissions. Solid adsorbents have great potential as an alternative method to conventional adsorbents in adsorbing CO₂. In this paper, low cost adsorbents including activated carbon, zeolites, mesoporous silica and clays are discussed in terms of adsorbent preparation methods and CO₂ adsorption capacity. The low cost adsorbents are mainly derived from waste materials such as fly ash, steel slag, red mud, bagasses wastes and wood wastes. Besides that, natural resources such as clays have also been applied as low cost CO₂ adsorbents. Surface modifications have also been applied to the low cost adsorbents, including metal ion exchange and amine impregnation to enhance CO₂ adsorption capacity. In the last section, the current status of CO₂ adsorbents is summarized and future trends are discussed briefly to predict the potential materials which can be applied as CO₂ adsorbents.     

The impact of pretreatment and inoculum to substrate ratio on methane potential of organic wastes from various origins

Biochemical methane potentials (BMP) of two different substrates from macroalgae (MA) and market place wastes (MPW) were investigated using anaerobic granulated sludge from food industry with different ratios of substrate to inoculum (S/X). The substrates were used as MA only, MPW only, MA–MPW mixture, pretreated MA, and pretreated MA–MPW mixture. Research involved investigation of the effects of parameters such as temperature (35, 45, and 55 °C), substrate to inoculum ratio (S/X = 0.5, 2.0, 4.0, and 6.0 as g VS_substrate/g VS_inoculum), and the type of pretreatment (by microwave, thermal, and ultrasonic) on BMP. BMP assays were performed for all substrates. The highest cumulative biogas production (and BMP) were obtained for MA only at an S/X ratio of 4.0 g VS/g VS as 357 L_biogas/kg VS (197 L CH₄/kg VS) and 33 L_biogas/kg VS (17 L CH₄/kg VS), respectively, at 35 and 55 °C. For pretreated substrates, the highest cumulative biogas production and BMP were observed as 287 L_biogas/kg VS and 146 L CH₄/kg VS using pretreated macroalgae at 35 °C. Results suggested that MA only and MA–MPW mixtures are suitable substrates for biogas production. It is also concluded that any type of pretreatment has adverse effects on biogas and methane productions.     

Selective catalytic reduction of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> using RDF char and municipal solid waste char based catalyst

Experiments were performed in order to investigate the possibility for the development of catalysts for low-temperature selective catalytic reduction (SCR) using municipal waste char and RDF byproduct. Physical and chemical activations, using water, and HCl and KOH, were employed to increase the catalytic activities. The characteristics of the activated catalysts were investigated using N₂ adsorption–desorption and FT-IR. The catalysts activated chemically using basic treatment showed higher NO _x removal efficiencies than those activated physically or chemically using acidic treatment. The de-NO _x performance of the activated catalysts was dependent on the chemical properties, such as oxygen functional groups as well as physical properties, such as specific surface area and pore volume. In order to investigate the effect of MnO _x , which has been reported to be efficient for the removal of NO _x in low-temperature SCR processes, the chemically activated catalyst was impregnated with manganese. The Mn-impregnated catalyst had the highest NO _x conversion at all of the temperatures tested in this study.     

Development and calibration of a model for biohydrogen production from organic waste

Existing models for H₂ production are capable of predicting digester failure caused by a specific disturbance. However, they are based on studies using simple sugars, while it is known that H₂ production and fermentation kinetics vary with the composition and characteristics of the substrate used. Because the behaviour of biological processes may differ significantly when the digesting material is a complex matrix, such as organic waste, the aim of this study was to develop and calibrate a mathematical model for the prediction of hydrogen production on the basis of the results obtained from a laboratory scale experimental study using source-selected organic waste. The calibration was carried out for the most important kinetic parameters in mesophilic anaerobic digestion processes and also served as a sensitivity analysis for the influence of both the specific growth rate (μ_max and the half velocity constant (k_s), both of which are strongly dependant on the substrate used. High values of μ_max led to a shorter lag-time and to an overestimate of the cumulative final H₂ production relative to the experimentally measured production. Additionally, high values of k_s associated with amino acid and sugar fermentation corresponded to a lower rate of substrate consumption and to a greater lag-time for growth of hydrogen-producing microorganisms. In this case, a lower final H₂ production was predicted than that which was experimentally observed. Because the model development and calibration provided useful information concerning the role of the kinetic constants in the analysis of a fermentative H₂ production process from organic wastes, they may also represent a good foundation for the analysis of fermentative H₂ production from organic waste for pilot and full-scale applications.     

Microbial oxygen uptake in sludge as influenced by compost physical parameters

The wide range of optimal values reported for the physical parameters of compost mixtures suggest that their interactive relationships should be investigated. The objective of this study was to examine the microbial O₂ uptake rate (OUR) in 16 sludge waste recipes, offering a range of moisture content (MC), waste/bulking agent (W/BA) ratio and BA particle size levels determined using a central composite experimental design. The 3 kg samples were maintained at a constant temperature and aeration rate for 28 days, during which a respirometer recorded O₂ uptake to provide a measure of microbial activity and biodegradability. The cumulative O₂ consumption after 14 and 28 days was found to be significantly influenced by MC, W/BA ratio, BA particle size and the interaction between MC and W/BA ratio (p < 0.05). Using multivariate regression analysis, the experimental data was used to generate a model with good predictive ability for cumulative O₂ consumption after 28 days as a function of the significant physical variables (R² = 0.84). The prediction of O₂ uptake by the model depended highly on the interaction between MC and W/BA ratio. A MC outside of the traditional 50–60% (wet basis) range still resulted in a high level of microbial O₂ uptake as long as the W/BA ratio was adjusted to maintain a suitable O₂ exchange in the sample. The evolution of OUR in the samples was also investigated, uncovering strong associations between short and long-term respirometric indices, such as peak OUR and cumulative O₂ consumption (p < 0.005). Combining peak OUR data with cumulative O₂ consumption after 14 days allowed for accurate predictions of cumulative O₂ after 28 days of aeration (R² = 0.96), implying that future studies need only run trials up to 14 days to evaluate the overall O₂ consumption or biodegradability of similar sludge mixtures.