Cleaner tanning practices for tannery pollution abatement: Role of enzymes in eco-friendly vegetable tanning

Concern about pollution related problems in the global scenario are persuading all the processing industries to adopt cleaner manufacturing practices. Thus, the leather industry is also under pressure to look for effective alternative tanning materials for chromium. Natural products like vegetable tannins are regaining importance. However, there are limitations in the use of vegetable tanning materials because of its high organic load in the effluent, which are difficult to degrade leading to high chemical oxygen demand (COD). Moreover, conventional vegetable tanning process requires partial pickling that involves the use of sodium chloride, to suppress osmotic swelling. This results in very high amount of total dissolved solid (TDS) content in wastewaters. In this investigation, an attempt has been made to design an eco-friendly vegetable tanning process combining pickle-free tanning and application of proteolytic enzymes to improve the exhaustion of vegetable tannins. Such an approach has resulted in more than 95% tannin exhaustion in the case of the experimental process, an increase of 10% compared with the conventional vegetable tanning process. The tanned leathers showed slight improvement in hydrothermal stability. Physical and tactile evaluation of experimental leathers has been better than conventionally tanned leathers. Surface colour values illustrated negligible variation in colour and shade between control and experimental leathers. The resultant leather showed opened up, split compact fibre structure that has been well coated, indicating that the enzyme assisted tanning process did not bring about any major change or destruction on the fibre structure of the leathers. The optimized system has been field tested in a commercial tannery. The results showed that the enzyme assisted tanning process is efficient in terms of improved quality of leather and also led to reduction in total solids (TS), chlorides and COD loads. The enzyme assisted tanning system presented appears to be a viable option for combating pollution arising from the conventional vegetable tanning system.     

An improved product-process for cleaner chrome tanning in leather processing

Severe restrictions imposed by the pollution control authorities on the disposal of chromium, total dissolved solids and chlorides in tannery effluents have forced the tanners to look for low-waste, high exhaust chrome tanning salts. An improved chrome syntan with more than 90% uptake of chrome has been developed. The new product serves both as tanning and retanning agent and can be applied directly to delimed pelts thus eliminating the conventional pickling stage in the leather processing. This modified process helps to reduce the chemical oxygen demand (COD), total dissolved solids (TDS) and chlorides in the spent tan liquor by 51, 81 and 99%, respectively. The product offers full, soft leathers having shrinkage temperature comparable to conventional chrome tanned skins. Since the developed product is highly reactive, it saves time and reduces the water requirement when compared to the conventional chrome tanning method. Thus the novel product/process developed not only has advantages in reducing pollution loads but also seems to be techno-economically viable.     

Reducing the environmental impact of the unhairing–liming process in the leather tanning industry

The environmental impact of the tanning industry is generally significant with outputs of wastes, i.e. high concentrations of organics, salts and heavy metals (chromium compounds), both in solid and liquid form, as a result. In order to bring the tanning industry more in line with present environmental thinking, various methods have been devised to reduce impacts.The underlying study proposes a modification of the method for unhairing–liming of hides where the unhairing–liming liquids are reused several times after being recharged by reduced quantities of chemicals. The study, therefore, aims at reducing both the economic and environmental costs of the unhairing–liming process.Experiments were carried out at lab scale with a simulation apparatus designed for the purpose. Life cycle assessment was used to evaluate the net environmental benefits of the modified method. The present value approach was used to evaluate the economic feasibility of the modified method. The quality of the produced leather was assessed by experts from the tanning sector (tanners).On the environmental level, the modified method reduced the environmental impact of the process by 24%, COD was reduced by 50% as well as sulfide which was reduced by 73% when the process water was recycled four times.The modified method requires some investment in new equipment and is a little more labor intensive as compared with the conventional method but does permit for savings in water up to 58% and chemicals up to 28% as well as wastewater treatment cost which was reduced by 58%. The modified method allowed for four times reuse of the unhairing–liming liquor without visibly affecting the quality of the final product of leather.It was concluded that both the economic and the environmental costs of the unhairing–liming process were reduced relative to the same of the conventional method.     

酸浸粉煤灰混凝法处理制革废水的研究

笔者研究了在热电厂粉煤灰中加入少量的鼓风炉铁泥和适量的助溶剂HS,在加热条件下用稀硫酸搅拌浸取2h后,制得集物理吸附和化学混凝为一体的混凝剂。这种混凝剂与聚硅酸铝铁(PSAF)絮凝剂配合处理COD为1500～2000mg/L制革废水,SS,COD,硫化物和铬的去除率分别为95%,93%,92%和88%。该法的显著特点是混凝沉降速度快,污泥体积小,处理废水费用低,此外还探讨了酸浸粉煤灰混凝剂对制革废水的混凝沉降机理。      

Evaluation of reusing alum sludge for the coagulation of industrial wastewater containing mixed anionic surfactants

A coagulation-flocculation process is typically employed to treat the industrial wastewater generated by the consumer products industry manufacturing detergents, soaps, and others. The expenditure of chemicals including coagulants and chemicals for pH adjustment is costly for treating this wastewater. The objective of this study was to evaluate the feasibility of reusing the aluminum sulfate (alum) sludge as a coagulant or as a coagulation aid so that the fresh alum dosage can be minimized or the removal e ciency can be enhanced. The experiments were conducted in a jar-test apparatus simulating the coagulation-flocculation process for simultaneous removals of organic matters, anionic surfactants, suspended solids, and turbidity. At the optimum initial pH value of 10 and the fresh alum concentration of 400 mg/L, the total suspended solids (TSS), total chemical oxygen demand (TCOD), total anionic surfactants, and turbidity removal e ciencies were 71.5%, 76.4%, 95.4%, and 98.2%, respectively. The addition of alum sludge as a coagulant alone without any fresh alum addition could significantly remove the turbidity, TCOD, and anionic surfactants. The TSS was left in the supernatants after the settling period, but would subsequently be removed by adding the fresh alum. The TSS, TCOD, and turbidity removal e ciencies were also enhanced when both the alum sludge and the fresh alum were employed. The TCOD removal e ciency over 80% has been accomplished, which has never fulfilled by using the fresh alum alone. It is concluded that the alum sludge could be reused for the treatment of industrial wastewater generated by the consumer products industry.     

蒽醌染整废水处理试验研究

本研究采用厌氧水解 好氧和单独好氧处理 2种生化方法对蒽醌染整废水进行了平行对照试验。试验结果表明 ,厌氧水解 好氧处理方法可有效地提高该废水的可生化程度 ,当进水CODCr浓度为 90 0mg L时 ,处理后出水CODCr可达 12 0～ 170mg L ,明显优于单独好氧处理的出水水质。经进一步混凝处理后 ,上述生化出水CODCr可近一步降低到10 0mg L左右     

A salt-free pickling regime for hides and skins using oxazolidine

During the last few decades new materials and technologies have being studied and applied in order to reduce the ecological impact of leather production. Severe restrictions imposed by the pollution control authorities on the disposal of chromium, total dissolved solids and chlorides in tannery effluents have forced the tanners and researchers to look for eco-benign pickling and tanning processes. In this study, we would focus on the novel process development of pickling with the presence of oxazolidine based product. Investigations indicated that oxazolidine is a potential material to replace neutral salts in pickling and, realize high chrome exhaustion in the subsequential chrome tanning.     

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.     

Cleaner beam house processes trial on cattle sofa leather

Leather processing has been an important light industry in China, which has contributed a lot to economy. The recent environmental challenges caused tremendous pressure to leather manufacture. The conventional beam house processes employ a wide range of chemicals which result in more than 60% of the total pollution in leather processing (mainly based on COD, BOD, TS, SS, NH₃–N). In this study, cleaner beam house processes were tested on cattle sofa leather to provide a clean environment. A control experiment was run parallel using conventional beam house processes. The results show that the de-hairing is complete through pelt histological microstructure, the extent of opening up of fibre bundles is very good, which is substantiated through chrome distribution analysis, scanning electron microscopic pictures of wet blue leathers and the analysis of contents of total proteins, polysaccharide and hydroxyproline in composite liquor, and the performance of the leathers is shown to be satisfied with the quality standard of sofa leather. The results from composite water analysis show that the cleaner processes enjoy in the reduction of emission water, chemical oxygen demand, total solids and ammonia-nitrogen loads by 46%, 93%, 58% and 54%, respectively, compared to the conventional processes. The total dry sludge from the clean processes is almost eliminated, and the composite cost is decreased by 10%.     

A novel integrated step-feed biofilm process for the treatment of decentralized domestic wastewater in rural areas of China

For wastewater treatment in rural areas, a novel three-stage step-feed wastewater treatment system, combined with a drop-aeration biofilm process, was tested in the laboratory to investigate its performance in removing suspended solids (SS), chemical oxygen demand (COD), NH4+-N, total nitrogen (TN), and total phosphorus (TP). The removal rates of SS, COD and NH4+-N were 90%, 80%, and 90% in efluent concentrations less than 10 mg/L, 50 mg/L and 8 mg/L, respectively. The TP removal rate was less satisfactory....     

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.     

Chemical oxygen demand reduction in coffee wastewater through chemical flocculation and advanced oxidation processes

The removal of the natural organic matter present in coffee processing wastewater through chemical coagulation-flocculation and advanced oxidation processes （AOP） had been studied. The effectiveness of the removal of natural organic matter using commercial flocculants and UV/H202, UV/O3 and UV/H2O2/O3 processes was determined under acidic conditions. For each of these processes, different operational conditions were explored to optimize the treatment efficiency of the coffee wastewater. Coffee wastewater is characterized by a high chemical oxygen demand （COD） and low total suspended solids. The outcomes of coffee wastewater treatment using coagulation-flocculation and photodegradation processes were assessed in terms of reduction of COD, color, and turbidity. It was found that a reduction in COD of 67% could be realized when the coffee wastewater was treated by chemical coagulation-flocculation with lime and coagulant T-1. When coffee wastewater was treated by coagulation-flocculation in combination with UV/H2O2, a COD reduction of 86% was achieved, although only after prolonged UV irradiation. Of the three advanced oxidation processes considered, UV/H2O2, UV/O3 and UV/H2O2/O3, we found that the treatment with UV/H2O2/O3 was the most effective, with an efficiency of color, turbidity and further COD removal of 87%, when applied to the flocculated coffee wastewater.     

First flush of storm runoff pollution from an urban catchment in China

Storm runoff pollution process was investigated in an urban catchment with an area of 1.3 km^2 in Wuhan City of China. The results indicate that the pollutant concentration peaks preceded the flow peaks in all of 8 monitored storm events. The intervals between pollution peak and flow peak were shorter in the rain events with higher intensity in the initial period than those with lower intensity. The fractions of pollution load transported by the first 30% of runoff volume （FF30） were 52.2%-72.1% for total suspended solids （TSS）, 53.0%-65.3% for chemical oxygen demand （COD）, 40.4%-50.6% for total nitrogen （TN）, and 45.8%-63.2% for total phosphorus （TP）, respectively. Runoff pollution was positively related to non-raining days before the rainfall. Intercepting the first 30% of runoff volume can remove 62.4% of TSS load, 59.4% of COD load, 46.8% of TN load, and 54.1% of TP load, respectively, according to all the storm events. It is suggested that controlling the first flush is a critical measure in reduction of urban stormwater pollution.     

混凝微滤法处理制革废水

对混凝微滤法处理制革废水进行了试验研究,通过大量试验,确定了最佳工艺条件。在最优控制的基础上,制革废水经混凝沉淀－微滤处理后,COD,BOD5,SS和色度的去除率分别为80%,87%,89%和92%左右,处理后废水可达到排放标准或回用于制革工艺。结果表明,在较低温度下,用硫酸亚铁作混凝剂仍能较好地完成混凝沉淀,验证了硫酸亚铁的低温混凝效果。因此,该工艺值得在北方寒冷地区大力推广。      

自然选育酵母菌对不同废水处理及资源化研究

从色拉油加工废水,味精废水、印染废水、钻井废水等4种特性各异的废水中筛选出酵母菌,并根据形态特征和生理生化特征对筛选到的12种酵母菌（包括2种耐氨酵母）进行了鉴定。结果表明：酵母菌处理工艺对色拉油加工废水和味精废水这两类高浓度有机废水具有较好的处理效率,如前者的TOC和后者的COD的去除率均在85%以上。但对人工合成物质含量较高的印染废水和钻井废水处理效果较差。这一结果可能与酵母菌原来所处的环境条件有关。     

Studies on the use of power ultrasound in solid–liquid myrobalan extraction process

Focus on eco-friendly processing techniques makes vegetable tanning a viable option in leather processing and establishes the subsequent need for the more efficient methods of extraction in tannin manufacture. Application of ultrasound has been tried in the extraction of tannins from myrobalan nuts in order to improve the extraction efficiency, to perform the extraction under milder process conditions and to reduce the process time. The influence of process parameters such as ultrasonic output power, time and temperature has been studied. Scale-up trials and the use of ultrasound in pulse mode have also been attempted. The results show that a three- to fivefold improvement is possible with ultrasonic output from 20 to 100 W. Extraction efficiency has been calculated from the maximum extractable materials from myrobalan nuts. Extraction efficiency is found to be 90% for ultrasound, 100 W without external heating as compared to 77% for control process at 70 °C for 4 h. Therefore, ultrasound could be employed even dispensing with provision for temperature controls. The use of ultrasound in pulse mode offered 70% extraction efficiency of continuous mode. Scale-up trials indicate that there exists an optimum ultrasonic output power depending on the amount of nuts used, to achieve better extraction efficiency. The effectiveness of ultrasonically extracted tannin solution has also been tested in the tanning process for its applicability. The degree of tanning efficacy has been assessed by shrinkage temperature measurement. The results indicate that ultrasonically extracted tannin solution is suitable for tanning process. Therefore, application of ultrasound in tannin extract manufacture is a viable option with added advantages.     

雨、污合流制城区降雨径流污染的迁移转化过程与来源研究

2003～2006年通过对武汉市汉阳城区不同尺度降雨径流、市政污水的监测,结合环境地球化学方法,研究雨、污合流制城区降雨径流污染的形成、迁移转化过程及污染来源.结果表明,雨、污合流制城区地表径流汇入排水系统,经排水系统传输,污染程度显著增加.屋面径流中TSS和COD浓度（EMC）的平均值分别为18.7 mg/L和37.0 mg/L,路面径流中TSS、COD浓度（EMC）的平均值分别为225.3 mg/L和176.5 mg/L,而在集水区出口处径流中TSS、COD浓度（EMC）的平均值分别为449.7 mg/L和359.9 mg/L;污染物的组成也发生了明显的改变,颗粒态COD增加了18%,有机污染增强.研究还发现,城市地表、雨水口、生活污水管和合流管道沉积物中P、Fe含量具有明显分异特征,可以利用沉积物中P/Fe识别集水区尺度降雨径流污染成因与来源.据此对集水区出口2次径流污染来源计算,56%±26%的悬浮物来自城市地表与雨水口,44%±26%的悬浮物源于生活污水的沉积物.生活污水中污染物对降雨径流污染的贡献是通过在合流管道中形成沉积发生的.雨、污合流管道在降雨径流污染形成过程中发挥了转化器和加重径流污染的作用.减少合流管道中沉积物的形成是削减径流污染负荷的途径之一.     

Minimization of the environmental impact of chrome tanning: a new process reusing the tanning floats

A chrome tanning process which allows the reuse of tanning floats has been developed. The most commonly used chromium salts were replaced by highly masked and basified ones. This substitution eliminates basification operation and prevents pH change and the considerable neutral salts concentration increase in the tanning float. Consequently, tanning float can be reused several times. An optimum chromium salt concentration in the tanning float between 10% and 12.5% has been determined. It has been shown that the number of times the tanning float can be reused depends on the quality of the leather grain to be manufactured. In the best case, a saving of 18 L of water per kilogram of tanned leather is calculated. This means savings of 90% of water normally used.     

A2/O流量分配处理低C/N污水性能与微生物结构

针对现有城市污水处理厂进水碳源不足的问题,通过建立多段进水改良A~2/O中试反应器处理低C/N(C/N 5)城市污水,以研究多段进水对其脱氮除磷性能和微生物种群结构变化的影响.结果表明,与传统厌氧段进水的模式相比,多段进水优化了进水碳源在厌氧段和缺氧段中的分布,从而提高了系统的反硝化脱氮和反硝化除磷性能; Q预缺∶Q厌∶Q缺=0. 1∶0. 2∶0. 3(阶段Ⅳ)为系统的最佳工况,此时出水COD、NH4+-N、TN和TP的平均浓度分别为30. 10、1. 85、9. 41和0. 71 mg·L-1,去除率分别为89. 41%、95. 30%、83. 00%和90. 09%;在120d的试验过程中,系统均未出现丝状菌膨胀现象,曝气池活性污泥沉降性能良好,好氧池活性污泥SVI随着缺氧段进水比例的增加而降低,至阶段Ⅴ达到最佳状态,此时的SVI和VSS/TSS分别为112. 09 m L·g-1和0. 84;通过对各阶段好氧区活性污泥16S rRNA基因测序数据的梳理,发现系统较好的脱氮除磷和污泥沉降性能分别与6类异养型菌属、4类反硝化菌属、5类聚磷菌属和2类菌胶团菌属的富集,3类丝状菌的淘汰密切相关.     

易腐有机垃圾单级高固体厌氧消化实验研究

在中温(35～37℃)条件下,对连续式单级高固体厌氧消化反应器处理易腐有机垃圾进行了试验研究,连续试验时间达半年以上.结果表明,系统稳定运行时,在进料TS为24.79%、VS为23.06%的情况下,单位体积反应器产气效率最高达到3.69L/(L·d),易腐有机垃圾的产气能力(以VS计)为746.33 L/kg,有机负荷(以VS计)达到4.94 kg/(m3·d),水力停留时间47 d,此时期处理效果理想;试验启动之初易发生酸化,其抑制情况严重,出现0产气,经碱性溶液调节后情况得到较好解决;反应进行至80 d后产气速率降至最高速率的一半以下,推断是氨氮浓度超过2000mg/L而产生氨氮抑制,经过投加化学药剂和调节进料C/N抑制情况得到缓解.