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.     

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.     

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.     

Preparation and Characterization of PVC Matrix Composites with Biochemical Sludge

Biochemical sludge (BS), generated in the waste water treatment of paper mills, was pretreated by enzyme hydrolysis. The effect and action mechanism of the enzymatic treatment on the properties of polyvinyl chloride (PVC) matrix composites with BS were discussed. Results showed that when the filler content was 30 wt%, the tensile strength of the PVC composites filled with BS and its modified products which were pretreated by laccase, cellulase and hemicellulase can be increased by 38.64, 67.4, 63.5 and 66.3% than the PVC composite filled with calcium carbonate. When the dosage of filler was 40 wt%, the elastic modulus of PVC composites filled with BS and its above three modified products decreased by 53.3, 52.3, 50.0 and 46.3%, respectively. Meanwhile, the thermal stability of PVC composites can also be improved at the temperature of over 340 °C. It can be concluded that the enzyme pretreatment can improve the application performance of BS usage in PVC matrix composites.     

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.     

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.     

Biochemical Parameters In Soils Regenerated By The Addition Of Organic Wastes

The effect of the addition of the organic fraction from a fresh municipal solid waste on the regeneration of a degraded soil from the Mediterranean area of Spain was studied. Sufficient waste to increase the organic matter of the soils by 0.5%, 1%, 1.5% and 2% was applied to a field in plots with a 10% incline. Forty months after treatment, increases were observed in organic matter, available nitrogen, water soluble carbohydrates and compounds determined by the Folin method (polyphenols and proteins) in all the treated plots as compared to the control. Changes were the greatest in the plot whose organic matter had been increased to 1.5%. An increase in enzymatic activity was also noticed (urease, BAA hydrolysed by protease, casein hydrolysed by protease, phosphatase, β-glucosidase and dehydrogenase) in the treated soils, particularly those which received higher rates of waste. The extracellular enzymatic activity of the plots treated with higher doses also increased, indicating a regeneration of the soils from a biochemical viewpoint. A positive correlation was observed between the parameters referring to microbial biomass and the enzymatic activities determined in the soils.     

Investigation of the application of an enzyme-based biodegradability test method to a municipal solid waste biodrying process

This paper presents a study to evaluate the recently developed enzymatic hydrolysis test (EHT) through its repeated application to a waste treatment process. A single waste treatment facility, involving a biodrying process, has been monitored using three different methods to assess the biodegradable content of the organic waste fractions. These test methods were the anaerobic BMc, aerobic DR4 and the EHT, which is a method based on the enzymatic hydrolysis of the cellulosic content of waste materials. The input municipal solid waste (MSW) and the output solid recovered fuel (SRF) and organic fines streams were sampled over a period of nine months from a single mechanical biological treatment (MBT) facility. The EHT was applied to each stream following grinding to <10 mm and <2 mm, in order to investigate the effect of particle size on the release of dissolved organic carbon (DOC) from enzyme hydrolysis. The output organic fines were found to more biodegradable than the MSW input and SRF output samples in each of the test methods, significantly (p < 0.05) for the EHT and DR4 methods, on the basis of DOC released and oxygen consumed, respectively. The variation between sample replicates for the EHT was higher where sample sizes of <2 mm were analysed compared to sizes of <10 mm, and the DOC release at each phase of the EHT was observed to be higher when using particle sizes of <2 mm. Despite this, additional sample grinding from the <10 mm to a smaller particle size of <2 mm is not sufficiently beneficial to the analysis of organic waste fractions in the EHT method. Finally, it was concluded that as similar trends were observed for each test method, this trial confirms that EHT has the potential to be deployed as a practical operational biodegradability monitoring tool.     

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.     

Evaluation of buckwheat and barley tea wastes as ethanol fermentation substrates

Buckwheat tea waste (BWTW) and barley tea waste (BTW), by-products of the beverage industry, are alternative carbohydrate sources for ethanol production. In this study, optimal enzyme loading for enzymatic saccharification of BWTW and BTW was determined, and simultaneous saccharification and fermentation (SSF) was performed by Saccharomyces cerevisiae and Mucor indicus to produce ethanol. Optimal enzyme loading for enzymatic saccharification of 2?% w/v BWTW and BTW was 0.5?% (weight of enzyme/weight of tea wastes) for BWTW and 0.1?% for BTW. Ethanol production from BWTW by S. cerevisiae and M. indicus after 48?h of SSF was 49.9/100?g of BWTW and 47.9/100?g of BWTW, respectively, with 0.5?% enzyme loading. Ethanol production from BTW by S. cerevisiae and M. indicus after 48?h of SSF was 20.5/100?g of BTW and 21.6/100?g of BTW, corresponding to 62 and 66?% of the theoretical yield based on starch content, respectively, with 0.1?% of enzyme loading. Furthermore, S. cerevisiae produced 76?% of the theoretical yield based on the total glucose from starch in BWTW and BTW when a mixture of BWTW and BTW was used as a substrate, with 0.2?% enzyme loading and no additional nitrogen or mineral sources.     

氧化沟工艺在处理有机废水中的应用

以河南省某制革企业综合有机废水处理工程为实例,根据排放废水的水质水量及处理要求进行工程分析,对含铬废水的处理提出工艺流程;对综合有机废水处理工艺各构筑物的功能和设计进行了详细阐述.     

Life-cycle assessment of a waste refinery process for enzymatic treatment of municipal solid waste

Decrease of fossil fuel dependence and resource saving has become increasingly important in recent years. From this perspective, higher recycling rates for valuable materials (e.g. metals) as well as energy recovery from waste streams could play a significant role substituting for virgin material production and saving fossil resources. This is especially important with respect to residual waste (i.e. the remains after source-separation and separate collection) which in Denmark is typically incinerated. In this paper, a life-cycle assessment and energy balance of a pilot-scale waste refinery for the enzymatic treatment of municipal solid waste (MSW) is presented. The refinery produced a liquid (liquefied organic materials and paper) and a solid fraction (non-degradable materials) from the initial waste. A number of scenarios for the energy utilization of the two outputs were assessed. Co-combustion in existing power plants and utilization of the liquid fraction for biogas production were concluded to be the most favourable options with respect to their environmental impacts (particularly global warming) and energy performance. The optimization of the energy and environmental performance of the waste refinery was mainly associated with the opportunity to decrease energy and enzyme consumption.     

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.     

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.     

金属冶炼进口物料的固体废物鉴别方法

建立了金属冶炼进口物料的固体废物鉴别方法,并利用该方法对海关查扣的3种金属冶炼进口物料进行了固体废物鉴别。鉴别结果显示:物料1、2和3的自然属性分别为砷含量超标铜精矿、锰阳极泥、回转窑氧化锌,产生来源分别为有害物质超标的产品、污染控制设施产生的物质、有意识加工的目标产物;物料1和2属于我国禁止进口的固体废物,物料3不属于固体废物。本文建立的固体废物鉴别方法可行,可为金属冶炼进口物料的固体废物鉴别和监管提供参考。     

Biodegradable packing materials from hydrolysates of collagen waste proteins

Enzymatic hydrolysates of waste collagen proteins (H), from current industrial manufacture (leather, edible meat product casings, etc.) of mean molecular mass 20-30 kDa by a reaction with dialdehyde starch (DAS), produces hydrogels applicable as biodegradable (or even edible) packaging materials for food, cosmetic and pharmaceutical products. Thermo-reversibility of prepared hydrogels is given by concentrations of H and DAS in a reaction mixture. At concentrations of H 25-30% (w/w) and that of DAS 15-20% (related to weight of hydrolysate), thermo-reversible hydrogels arise, which can be processed into packaging materials by a technique similar to that of soft gelatin capsules (SGC). Exceeding the limit of 20% DAS leads to hydrogels that are thermo-reversible only in part, a further increase in DAS concentration then leads to thermo-irreversible gels whose processing into biodegradable packaging materials necessitates employment of other procedures.     

Extraction of shrimp waste pigments by enzymatic and alkaline treatment: evaluation by inhibition of lipid peroxidation

In recent years, interest has grown in the potential to utilize more natural materials in the food industry. Shrimp waste is an important natural resource with functional properties and no known side effects. The major components of shrimp waste are protein, chitin, minerals and carotenoids. In the present study, the extraction of carotenoids was performed with two methods, the use of proteolytic enzymes and extraction by alkaline and enzyme treatment, and the total amount of carotenoids present in the waste was determined. Furthermore, the effectiveness of the method was evaluated through the inhibition of lipid peroxidation. Inhibition of lipid peroxidation was effectively done with carotenoid extracted by trypsin and alkaline treatment.     

Synthesis of chromium-containing pigments from chromium recovered from leather waste

Cobalt-chromite green and chrome-tin pink pigments have been prepared from chromium extracted from leather shavings produced as a waste product of the leather-tanning industry. The alkaline agent (NaOH, CaO, MgO, NH4OH) used in the extraction process influences the nature of the final product. The effect of the NH4OH:CaO ratio on the final product in the case of cobalt-chromite green was examined. The pigments obtained were characterized by FT-IR and X-ray diffraction (XRD). Colour measurements were compared with those recorded from materials prepared from pure Cr2O3. The leaching of Cr(VI) from the materials was examined by UV spectroscopy.     

Test methods to aid in the evaluation of the diversion of biodegradable municipal waste (BMW) from landfill

This response follows on from a recent discussion by Sánchez (2009) on test methods to aid in the evaluation of the diversion of biodegradable municipal waste (BMW) from landfill. Test methods to assess the biodegradability/biodegradable content of organic waste are of great interest across Europe for different purposes, such as landfill acceptance criteria, monitoring treatment facility performance and for monitoring the diversion of biodegradable municipal waste (BMW) from landfill. Many studies have recently attempted to correlate short-term test methods with long-term anaerobic test methods. This response discusses recent findings and conclusions made by Sánchez (2009) and describes recent work undertaken at Cranfield University to develop the enzymatic hydrolysis test (EHT) method. The EHT has previously shown potential as a short-term, non-biological, biodegradability assessment tool, however there is a requirement to further develop this test method. We conclude that aerobic and anaerobic biological test methods are not the only suitable methods of assessing waste treatment process performance; and that alternative methods such as EHT are feasible and potentially suitable.