Ultrasound-accelerated enzymatic hydrolysis of solid leather waste

The leather industry is a heavy pollution industry and looking for clean technology. The utilization of enzyme and ultrasound in the industry are potential eco-friendly technologies.Enzymes can degrade the untanned solid leather waste. According to our investigation, ultrasound (40 kHz, 0.64 W/cm²) has little effect on the activity of one alkaline protease from Bacillus licheniformis. It is the first time to use ultrasound to accelerate the enzymatic hydrolysis of the untanned solid leather waste. With the application of ultrasound, the value of k_A for the enzymatic hydrolysis of the untanned solid leather waste increases 18% and K_M is almost unchanged, compared with that obtained without ultrasound. Ultrasound improves the ultimate conversion ratio from 57.6% to 84.1%. The reason is that ultrasound can facilitate the protease through the pores of skin and impair the integrity of collagen. Amino acid analysis indicated that ultrasound can promote the breakdown of helical regions of collagen which are difficult to attack by proteases.In view of environment protection, the use of enzyme and ultrasound in combination is a promising clean technology for the disposal of the untanned solid leather waste.     

Material flows in the life cycle of leather

This paper presents a study on the resource and environmental profile of leather for communicating to the consumers about the environmental burdens of leather products. The results indicate that significant environmental impacts were caused during the tanning and finishing of leather as well as the electricity production and transportation required in the life cycle. The use of fossil fuels in the production of energy has greater impact with increased emissions leading to about 15190 kg CO₂ equivalent of global warming and about 73 kg SO₂ equivalent of acidification while producing 100 m² of leather for shoe uppers. Further resource use of 174 kg of coal, 6.5 kg of fuel oil, 17.4 m³ of water and 348 kg of chemicals of which about 204 kg are hazardous are consumed, and wastewater of about 17 m³, BOD of 55 kg, COD of about 146 kg, TDS of 732 kg and solid waste of about 1445 kg are generated during the life cycle for the production of 100 m² of leather. The total solid waste generated is 1317 kg, out of which about 80% is biodegradable contributed by slaughtering, tanning and finishing stage, 14% is non-biodegradable contributed by tanning, finishing and electricity production stages and 6% is hazardous mainly from tanning and finishing stage of leather.     

Using supercritical carbon dioxide as solvent to replace water in polyethylene terephthalate (PET) fabric dyeing procedures

Dyeing fabrics in supercritical carbon dioxide (SCD) instead of water can save energy, reduce water use and prevent pollution. The special pilot plant was designed to test dyeing procedures in supercritical carbon dioxide and the analyses of the results indicate major benefits as compared to water based procedures. The dyeing of polyethylene terephthalate (PET) fabric in supercritical carbon dioxide using special pilot plant was investigated. Disperse dye, C.I. (color index) Disperse Blue 79, was used in this study. After dyeing, rinsing in supercritical carbon dioxide, which removes the excess dyes, was also discussed. At the same dyeing conditions, K/S (color yield) of dyed fabric significantly increased with increasing the dye concentration from 1% o.w.f. (on weight of fabric) to 5% o.w.f. Dyeing temperature and pressure had a strong influence on the color yield. When the temperature rose above 110 °C, the increase in color yield was obvious. At 20 MPa, 120–130 °C, dyeing reached equilibrium after 60 min. The excess dye of the dyed PET fabric was small. The suitable condition in supercritical carbon dioxide for removal of excess dye from the dyed fabric was 70 °C, 20 MPa. The PET fabric dyed in supercritical carbon dioxide had good fastness and physical properties.     

Recovery and reuse of chromium from chrome tanning waste water aiming towards zero discharge of pollution

The leather industry faces very challenging task because of the regulations enforced by the various pollution control bodies to maintain the discharged norms of the chemical in the treated water. The pollution due to the use of chromium and other chemicals in the leather industry is critically analyzed for the harmful effects. Many studies have been undertaken to optimize the amount of chemicals used in leather processing. The pollution due to chromium is one of the major constraints in the leather processing operation. Chrome recovery and reuse methods have become the compulsory recovery methods in the leather industry to recover and reuse the chromium present in the effluent. Several precipitation methods are emerging but still they are not feasible. In this paper, an attempt has been made to recover the chromium present in spent tan liquor using neutralized wattle extract. The wattle extract at different pH conditions (pH 7, 8, and 9) was used for recovery of chromium. The neutralized wattle extract was made to react with chromium in the spent liquor and allowed to settle for a period of 6 h. Major amount of chromium settles at the bottom leaving minimal amount in the supernatant. The chrome was recovered and reused for tanning the pelt. The wattle extract that was left in the tanning bath was reused for post-tanning process as a retanning agent. Therefore, complete utilization of the chromium and wattle extract has been achieved in this work. It has also been noticed that increased level of chrome exhaustion of 85% and 87% (precipitate and supernatant) in experimental leather could be obtained in comparison with the exhaustion of 74% in control sample. The physical strength and color properties of the experimental leather were comparable to the control leather. The overall results show that the recovered chromium can be well used for tanning purpose to obtain the leather of comparable properties.     

Approach towards zero discharge tanning: role of concentration on the development of eco-friendly liming–reliming processes

Beam house processes¹ in leather processing are known for their uncleanness. More than 60% of the total pollution is emerging from the liming–reliming processes. The use of lime and sodium sulphide is purely empirical without quantification. Lime has a potential to drive swelling in a gradual manner due to its low solubility; however, the use of lime is currently creating a lot of environmental concern. Huge amounts of lime sludge and total solids formation are the main drawbacks of lime. Sulphide plays a detrimental role in effluent treatment plants. This is mainly due to the application of lime, sulphide, water and other chemicals without any rationalization. An approach has been made to apply the beam-house chemicals with optimal requirement. This is based on the fact that swelling requires only 20 to 40% water (based on raw skin weight before soaking) for conventional opening up. This would, in principle, make possible the use of only one tenth of the chemicals conventionally used in liming–reliming processes maintaining the same concentration gradient. The process employs 40% water, 0.35% sodium sulphide and 1% lime for liming and 40% water and 1% lime for reliming, with conventional process time in a drum. Commercial post-reliming processes and operations were adopted. A control experiment was run parallel using conventional liming–reliming processes. It has been found that the dehairing is complete and the extent of opening up of fibre bundles is comparable to that of the control. This has been substantiated through scanning electron microscopic, stratigraphic chrome distribution analysis and softness measurements. Performance of the leathers is shown to be on par with conventionally opened up leathers through physical and hand evaluation. Especially, softness of the leathers is numerically proven to be comparable with that of control. The process also enjoys reduction in chemical oxygen demand and total solids load on environment by 85 and 12%, respectively compared to the conventional process. The total dry sludge from the liming–reliming processes is brought down from 152 to 6 kg for processing 1 ton of raw skins, which has been demonstrated for the first time.     

Screening of leather auxiliaries for their role in toxic hexavalent chromium formation in leather—posing potential health hazards to the users

With increasing concern about the potential health hazards of toxic chemicals in consumer articles such as leather products, many countries importing these articles have introduced stringent stipulation for the permissible levels of such chemicals in these articles. Hexavalent chromium is one such toxic metal ion included in the list of regulated substances. The problem is unique to leather industry as it uses only trivalent chromium based salts in the tanning process but faces the problem of presence of Cr(VI) in the end product. Efforts are being made to understand the reasons for the presence of hexavalent chromium in leather and to devise strategies for eliminating the same in processing. This paper describes our attempt to investigate the role of potential post-tanning (wet finishing) and finishing auxiliaries used in leather processing in the conversion of Cr(III) to Cr(VI) in the chrome-tanned leather. The auxiliaries were also screened for the presence of oxidizing functionality and the amount estimated as persulfate. The study reveals that the auxiliaries suspected of having a role in Cr(VI) formation do have considerable quantities of residual oxidizing functionality capable of converting Cr(III) to Cr(VI). The study with persulfate as the model oxidizing agent confirms the role of oxidizing agents in the formation of quantities of Cr(VI) well above the permissible limit of 3 mg/kg in leather matrix, which basically provides a reducing environment.     

Process modification in the scouring process of textile industry

The effects of scouring parameters on the scouring efficiency, including the weight ratio of de-sizing agent and fabric (5–80 g/g fabric), temperature of de-sizing agent tank (60–90 °C) and dipping time (2–8 s), were investigated. The results demonstrated that weight loss of sizing agent was significantly observed only in the de-sizing agent tank particularly in the first de-sizing tank and was found to a small extent in water tank. The optimum condition in the scouring machine was found at a de-sizing agent to fabric ratio of 20 g/g fabric, with a temperature of the first de-sizing agent tank of 80 °C, a temperature of the second de-sizing agent tank of 90 °C, and dipping time of fabric of 7 s. According to these conditions, more than 89% of the sizing agent was eliminated and only 3.52 mg/g fabric of sizing agent remained in the scoured fabric which was in an acceptable range for feeding to the down stream process known as dyeing process. Application of our results to actual textile plant has shown that there is a cost reduction due to improved utilization of rinse water, chemicals and energy in the process and consequent decreases in the generation of wastewater. Furthermore, the production capacity was increased from 30 m/min to 34.4 m/min.     

Nanosecond pulsed laser micromachining of PMMA-based microfluidic channels

This paper reports an investigation into the effects of nanosecond laser processing parameters on the geometry of microchannels fabricated from polymethylmethacrylate (PMMA). The Nd:YAG solid-state pulsed laser has a wavelength of 1064 nm and a measured maximum power of 4.15 W. The laser processing parameters are varied in a scanning speed range of 400–800 pulses/mm, a pulse frequency range of 5–11 Hz, a Q-switch delay time range of 170–180 μs. Main effects plots and microchannel images are utilized to identify the effects of the process parameters for improving material removal rate and surface quality simultaneously for laser micromachining of microchannels in PMMA polymer. It is observed that channel width and depth decreased linearly with increasing Q-switch delay time (hence average power) and increased non-linearly with higher scanning rates and not much affected by the increase in pulse frequency.     

Natural dyeing of wool and hair with indigo carmine (C.I. Natural Blue 2), a renewable resource based blue dye

Indigo carmine can be used as a source of blue dye for wool and hair dyeing. The option to use indigo carmine in combination with other natural dyes in a one-bath procedure as a hybrid dyeing concept is of interest both for natural dyeing and for coloration of hair. The present study shows that indigo carmine dyeing on wool exhibits the substantial sorption in the range of pH 4–5 and temperature between 40 and 60 °C. Experiments with human hair samples indicate that the experiments on wool can serve as a model that can be applied for hair dyeing. Comparisons of the energy, water and chemical consumption between two-bath dyeing with indigo and natural dyes separately and a one-bath dyeing using indigo carmine together with other natural dyes demonstrates the advantages of the one-bath hybrid dyeing concept.     

Reuse of printing and dyeing wastewater in processess assessed by pilot-scale test using combined biological process and sub-filter technology

In this work, a pilot-scale (300 m³/d) wastewater reclamation system was tested for printing and dyeing wastewater treatment from a textile factory. The wastewater was first hydrolyzed under anoxic condition, and then was treated under aerobic condition. Biologically treated wastewater was filtered by sub-filter technology (Patent: CN1308024A). The results showed that the average concentration of CODcr, color and turbidity in the effluent were less than 50 mg/L, 10 times and 2 NTU, respectively. The average CODcr, color and turbidity removal efficiencies were 91%, 92.5% and 90.9%, respectively. The treated effluent quality satisfied the requirement of water quality for printing and dyeing process. The most attracting part of the work was its extremely low color, low turbidity, low concentration of Fe and Mn, which was always demanded in textile sectors for an improved finish and better quality dyeing.     

The study of ultrasound-assisted oxidative desulfurization process applied to the utilization of pyrolysis oil from waste tires

In recent years, the increasing world population and rapid industrial development has increased the consumption of fossil fuel-derived oils. In response to the resulting exhaustion of fossil fuel energy, many countries around the world are investigating methods of waste energy recovery and reuse, including oil recovery from the pyrolysis process of waste tires. This study investigates the efficiency of an ultrasound-assisted oxidative desulfurization (UAOD) process in sulfur reduction from diesel oil and the pyrolysis oil from waste tires treatment. The results indicate that the oxidation efficiency increases as the doses of transition metal catalyst are increased. Longer sonication time also enhances the oxidation process, apparently through the biphasic transfer of oxidants, which results in a high yield of organic sulfur oxidation products. The best desulfurization efficiency was 99.7% (2.67 ppm sulfur remaining) and 89% (800 ppm sulfur remaining) for diesel and pyrolysis oils, respectively, via a process executed by two UAOD units connected in series and combined with solid adsorption using 30 g of Al₂O₃ in 6 cm columns. These batch experiment results demonstrate clean waste energy recovery and utilization, while fulfilling the requirements of Taiwan EPA environmental regulations (sulfur concentrations less than 5000 ppm).     

A promising clean process for production of diosgenin from Dioscorea zingiberensis C. H. Wright

This study proposes a new approach for diosgenin production from Dioscorea zingiberensis C. H. Wright tubers with respect to resources utilization and clean production. This process consisted of two successive parts, i.e., recovery of starch from raw material, and microbial hydrolysis of the residue to produce diosgenin by Trichoderma reesei. In the first step, about 75.4% of hemicellulose and 98.0% of starch were removed from the tubers. In the second step, about 90.2% of diosgenin was released from saponins by T. reesei at 30 °C, at an aeration of 0.80 vvm and agitation rate of 300 rpm in a 5.0 L bioreactor. Significant reduction of pollutant production was detected by replacing the traditional approach with the proposed new method. About 99.2% of reducing sugar, 99.4% of chemical oxygen demand, 99.2% of total organic carbon, 100% of SO₄^2?, and 100% of acid was reduced in the new processing wastewater.     

The precautionary principle and environmental persistence: prioritizing the decision-making process

There is continuing activity among regulatory bodies to assess and prioritize chemicals used in commerce based on their potential to be persistent, bioaccumulative, and toxic (PBT). Reliable data needed to perform a PBT hazard or risk assessment, however, may not always be readily available. Consequently concern may arise regarding the potential for false positives and false negatives to be wrongly classified. In order to more effectively classify substances, adequate time is needed to acquire the necessary data to support the overall PBT assessment. Of particular interest is the question of whether or not restrictions on the use and manufacture of a substance can be delayed to allow time to conduct the necessary field and laboratory studies of a particular substance? To address this question it is demonstrated that chemical partitioning property and environmental persistence information can be effectively combined to provide guidance for regulatory priority setting. Specifically, it is argued that substances that have media specific half-life values that exceed the regulatory threshold value for persistence under the EU chemicals REACH program, for example, are more likely to have a ‘legacy’ associated with their use when the log K_OA > 8, and when they are emitted to air or soil. Thus, precautionary actions limiting the use and manufacture of the substance may be warranted. Whereas substances emitted to air with log K_OA < 6 and log K_AW > ?2 are less likely to have a ‘legacy’ associated with their use. Thus precautionary actions in the absence of data may not be warranted.     

Integrated environmental assessment of biodiesel production from soybean in Brazil

This paper presents the results of an environmental impact assessment of biodiesel production from soybean in Brazil. In order to achieve this objective, environmental impact indicators provided by Emergy Accounting (EA), Embodied Energy Analysis (EEA) and Material Flow Accounting (MFA) were used. The results showed that for one liter of biodiesel 8.8 kg of topsoil are lost in erosion, besides the cost of 0.2 kg of fertilizers, about 5.2 m² of crop area, 7.33 kg of abiotic materials, 9.0 tons of water and 0.66 kg of air and about 0.86 kg of CO₂ were released. About 0.27 kg of crude oil equivalent is required as inputs to produce one liter of biodiesel, which means an energy return of 2.48 J of biodiesel per Joule of fossil fuel invested. The transformity of biodiesel (3.90E + 05 seJ J^?1) is higher than those calculated for fossil fuels as other biofuels, indicating a higher demand for direct and indirect environmental support. Similarly, the biodiesel emergy yield ratio (1.62) indicates that a very low net emergy is delivered to consumers, compared to alternatives. Obtained results show that when crop production and industrial conversion to fuel are supported by fossil fuels in the form of chemicals, goods, and process energy, the fraction of fuel that can actually be considered renewable is very low (around 31%).     

Toward chemical-free reclamation of biologically pretreated greywater: solar photocatalytic oxidation with powdered activated carbon

Heterogeneous photocatalytic oxidation is a water reclamation technology which avoids chemical consumption and can be powered by solar radiation. Because this generally sustainable process is of limited efficiency for the treatment of biologically pretreated greywater, it was combined with activated carbon adsorption. The effluent of a constructed wetland for treatment of separately collected greywater was subjected to photocatalytic oxidation using the photocatalyst titanium dioxide (TiO₂) “P25” in both the absence and the presence of powdered activated carbon (PAC). Photocatalytic oxidation alone with UV fluences of about 10 Wh L^?1 was not capable of reducing total organic carbon (TOC) from an initial concentration of 5.5 mg L^?1 safely below 2 mg L^?1 as a prerequisite for high-quality water reuse purposes. However, when PAC was added, TOC concentrations subsequent to photocatalytic oxidation were less than 2 mg L^?1 even after reusing the TiO₂/PAC mixture 10 times. PAC addition is estimated to reduce the insolation area necessary to achieve this target by solar photocatalytic oxidation of biologically treated greywater by a factor 7. This combination process represents an innovative chemical-free technology within wastewater reuse schemes.     

Assessing the recycling potential of glass fibre reinforced plastic waste in concrete and cement composites

At present glass fibre reinforced plastic (GRP) waste recycling worldwide is very limited due to its intrinsic thermoset properties, lack of characterisation data and non availability of viable recycling and recovery routes. In the present study, efforts were made to recycle GRP waste powder and fibre in concrete and cement composites and assess its quality to comply with the British standards for use in construction applications. Results revealed that the mean compressive strength of concrete composites using 5%–50% GRP waste powder under water curing varied from 37 N/mm² to 19 N/mm². Increase in the concentration of GRP waste decreased the compressive strength. However, increase in curing duration (14–180 days) resulted in improving the compressive strength of concrete with 5% GRP application to 45.75 N/mm². Moreover, the density of concrete with 50% GRP waste was reduced by about 12% as compared to the control sample. The bending strength in terms of modules of rupture (MOR) of 12 mm thickness cement composites developed using 5% GRP waste fibre attained 16.5 N/mm². The findings of this work pave the way for further GRP waste recycling in precast construction products for use in various applications.     

Effectiveness of buffer strips in removing pollutants in runoff from a cultivated field in North-East Italy

Buffer strips are an efficient and economical way to reduce agricultural nonpoint source pollution. Local researches are necessary to gain information on buffer performance, with particular emphasis on narrow buffers. The effect of a 6 m buffer strip (BS) in reducing runoff, suspended solids and nutrients from a field growing maize, winter wheat and soybean was assessed in a field experiment conducted in North-East Italy during 1998–2001. The BS was composed of two rows of regularly alternating trees (Platanus hybrida Brot.) and shrubs (Viburnum opulus L.), with grass (Festuca arundinacea L.) in the inter-rows.The BS reduced total runoff by 78% compared to no-BS, in which cumulative runoff depth was 231 mm over 4 years. With no-BS runoff appeared to be influenced mostly by total rainfall, while with BS maximum rainfall intensity was more important. The filtering effect of the BS reduced total suspended solids (TSS), particularly after the second year, when the median yearly concentrations ranged from 0.28 to 0.99 mg L⁻¹ and were smaller than 0.14 mg L⁻¹, with no-BS and with BS respectively. The combination of lower concentrations and runoff volumes significantly reduced TSS losses from 6.9 to 0.4 t ha⁻¹ over the entire period.A tendency to increased concentrations of all forms of N (total, nitrate and ammonium) while passing through the BS was observed, but total N losses were reduced from 17.3 to 4.5 kg ha⁻¹ in terms of mass balance. On the contrary, P concentrations were unmodified (soluble P), or lowered (total P) by the BS, reducing total losses by about 80%. The effect on total P, composed mainly of sediment-bound forms, was related to particulate settling when passing through the BS.A numerical index (Eutrophic Load Index), integrating water quality and runoff volumes, was created to evaluate the eutrophication risk of runoff with or without the BS. It showed that the BS effect was mostly due to a reduction of runoff volumes rather than improving the overall water quality.     

On wear resistance of tool steel

Maintaining a reasonably low cutting tool wear when producing forming tools is a general challenge in the development of new forming tool materials. The tool life of a hot forming tool steel (H13) has been significantly improved by reducing its Si-content from 1.0 to 0.06 wt.%. However, this modified H13 (MH13) also displays a reduced cutting tool life due to higher cutting forces and a stronger tendency to form built up layers (BUE) on the cutting edge. This paper explains why.Gleeble tests of MH13 revealed a significantly higher flow stress in the 820–900 °C temperature interval in MH13 compared to H13. Thermo-Calc simulations showed that when reducing the Si-content from 1.0 to 0.06 wt.% the initial temperature for ferrite-to-austenite transformation (A1) was reduced from 900 °C to 820 °C. Knowing that austenite has totally different mechanical and thermal properties than ferrite, the difference in A1 between the two steels explains the higher cutting forces and higher tendency for BUE-formation. The conclusion is that the difference in machinability between H13 and MH13 is primarily related to their difference in A1.An attempt was also made to find a new tool material composition that can combine the wear resistance of MH13 and the good machinability of H13. Thermo-Calc simulations were performed with slightly modified alloying content without changing its properties as a good forming tool material, with the aim to increase A1. For instance, reducing the Mn content from 0.5 to 0.05 wt.% proved to increase A1 from 820 to 850 °C.     

Metal-cored arc welding process for joining of modified 9Cr-1Mo (P91) steel

In the present work, metal-cored arc welding process was used for joining of modified 9Cr-1Mo (P91) steel. Metal-cored arc welding process is characterized by high productivity, slag-free process, defect-free weldments that can be produced with ease, and good weldability. Toughness is essential in welds of P91 steel during hydro-testing of vessels. There is a minimum required toughness of 47 J for welds that has to be met as per the EN1557:1997 specification. In the present study, welds were completed using two kinds of shielding gases, each composition being 80% Argon + 20% CO₂, and pure argon respectively. Microstructural characterization and toughness evaluation of welds were done in the as – weld, PWHT at 760 °C – 2 h and PWHT at 760 °C – 5 h conditions. The pure argon shielded welds (‘A2’ and ‘B2’) have higher toughness than 80% argon + 20% CO₂ shielded welds (‘A1’ and ‘B1’). Pure argon shielded welds show less microinclusion content with low volume fraction of δ-ferrite (<2%) phase. Themo-calc windows (TCW) was used for the prediction of equilibrium critical transformation points for the composition of the welds studied. With increase in post-weld heat treatment (PWHT) duration from 2 h to 5 h, there was increase in toughness of welds above 47 J. Using metal-cored arc welding process, it was possible to achieve the required toughness of more than 47 J after PWHT at 760 °C – 2 h in P91 steel welds.     

Application of CGP-cross route process for microstructure refinement and mechanical properties improvement in steel sheets

A modified method of severe plastic deformation (SPD) entitled constrained groove pressing-cross route (CGP-CR) was introduced for imposing a high magnitude of equivalent strain of about 2.32 per pass on the sheet form samples. The major benefit of this improved route compared to previous common route was the more homogeneity of strain in the rolling (RD) and transverse (TD) directions of sheets. In this study, low carbon steel samples were used for examination of evolutions in microstructure and mechanical properties during SPD via CGP-CR process. Mechanical properties improvement were measured by tensile and macro hardness tests. The results indicate that CGP-CR process can effectively improve tensile strength; and also, yield stress and hardness of as-received low carbon steel samples were improved up to about 100% after two deformation passes. Also, high magnitude of inhomogeneity can be observed in hardness distribution through first pass of the process which diminishes in the subsequent passes. Microstructural evolutions during process were monitored by optical microscopy observations and X-ray diffraction analysis. The results demonstrate that initial ferritic microstructure with grain size of about 30 μm was refined to a 225 nm cell structure after two passes of CGP-CR process.