Reclamation treatment of the chrome leather scrap

A novel method to extract protein and Cr(III) from the chrome leather scrap discarded by leather industry is described.Chrome leather scarp was hydrolyzed under basic condition to remove chromium compound and extract protein. The extracted protein was mixed with substrate and used as feed protein after being dried and ground. The basic residue was treated with sulfuric acid to obtain chrome(III) sulfate which can be used as tanning agent again after adjusting pH with base. The acidic residue was processed and used as flower fertilizer. The safety of the protein powder produced has been by toxicology and nutriology test. This reclamation method has been industrialized.     

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.     

铬革渣资源化处理研究Ⅶ.蛋白质的水解及其测定

铬革渣在碱性介质中脱鞣提取蛋白质的过程中,当反应体系的ｐＨ＝１３,反应压力为１．４ｋｇ／ｃｍ＾２,１１ｈ后出现蛋白质水解产物氨基酸,随反应时间的延长,水解度随之增大。这种水解,随体系的ｐＨ值升高而加快。实验表明,用改进的甲醛滴定法可测定铬革渣在碱性介质中蛋白质的水解度。     

铬革渣资源化处理研究(Ⅲ)--饲料蛋白粉的动物喂养试验

由铬革渣提取蛋白质加工成的饲料蛋白粉,作为动物性蛋白质添加剂加入饲料,小白鼠喂养6周后增重率超过对照组,共喂7批,二代,剖检各器官未见异常。0.5kg的小鸡喂养27d后,1kg的中鸡喂养17d后增重率超过对照组,产蛋前期的产蛋率比对照组高40％,剖检各器官未见异常,肌肉、肝脏和蛋中未发现铬(ppm级)。     

用铬革渣制备L-脯氨酸等六种氨基酸

铬革渣经碱性处理提取蛋白质,用6mol HCl水解,活性炭脱色,调节pH,由732~#阳离子交换树脂初步分离,得到的脯氨酸组分再由717#阴离子交换树脂分离,所得L-脯氨酸洗脱液减压蒸发浓缩,用无水乙醇结晶,得色谱纯L-脯氨酸。在732~#阳离子交换树脂上最后流出的是精氨酸,经处理得色谱纯L-精氨酸盐酸盐。在717~#阴离子交换树脂上分离可分别获得L-谷氨酸、L-天门冬氨酸、L-丙氨酸和甘氨酸。     

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.     

铬革渣资源化处理研究Ⅸ──胶原蛋白分子量及分子量分布

以含０．０２％叠氮钠的蒸馏水为流动相,宽分布Ｔ１０和Ｔ７０葡聚糖为标样,用水相凝胶色谱法（ＷＰＧＣ）测定了从铬革渣中按不同条件提取的胶原蛋白的分子量及分子量分布。在实验中设定的反应时间和介质的ｐＨ值范围内胶原蛋白的数均分子量（Ｍｎ）均低于４０００,分子量分布较宽（ｄ＝Ｍｗ／Ｍｎ＝３．１９－８．３５）。     

Ecological utilization of leather tannery waste with circular economy model

Circular economy (CE) focuses on resource-productivity and eco-efficiency improvement in a comprehensive way, especially on the industrial structure optimization of new technology development and application, equipment renewal and management renovation. The leather industry on the one side boosts the local economic development, on the other side however leads to the tremendous environment pollution and biological chains destruction. The CE model has been implemented as a new way of raw materials, water and energy consumption reduction in the leather industry. Reduce, Reuse, Recycle and Recover of the tannery effluents have been discussed in detail according to the different operation processes. The successful treatment approaches with analysis in the aspects such as wastewater, solid waste, sulfide, Chemical Oxygen Demand (COD), ammonium salt, chloride and chrome of the leather tannery with CE model provide guidance for the sustainable development of leather industry in the future.     

典型铬渣污染场地的污染状况与综合整治对策

对比了国内外污染场地的管理现状.通过方法学筛选国内2处化工厂的铬渣堆存场地作为典型铬渣污染场地,并对土壤和地下水进行采样分析.结果表明,这2处铬渣污染场地均存在土壤和地下水污染,特别是在铬渣堆积区域的土壤中w(总Cr)超过当地土壤背景值的数倍～数十倍,地下水中w(Cr6+)超过Ⅴ类地下水质量标准达1 000倍.Cr6+极易迁移扩散,污染面积大,其中1号铬渣污染场地污染土壤总量约19.5×104 m3,2号场地污染土壤深度约达4 m.通过分析2处典型铬渣污染场地污染特性,提出了全国铬渣污染场地综合整治对策的技术路线和规划.      

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.     

A chemo-enzymatic pathway leads towards zero discharge tanning

Leather processing has been an important industrial activity, which has gained significant economic relevance in India. The recent practices of leather manufacture cause difficulties with regard to environmental challenges. The conventional method for making the skins ready for tanning and the tanning by itself employs a wide variety of chemicals which result in an increase in chemical oxygen demand (COD), total dissolved solids (TDS), chlorides, sulfates and chromium in the tannery effluent. In this study, an integrated chemo-enzymatic methodology has been explored which would minimize or to some extent eradicate the unsafe chemicals involved in the process to provide a clean environment. The sequence involves an enzymatic dehairing, NaOH based fibre opening and a pickle-less chrome tanning. The modified process results in decrease in COD and TS (total solids) loads by 67 and 78%, respectively, as compared with control process. The process explored appears to be economically viable.     

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%.     

3MRA风险模型在铬渣整治项目制定过程中的应用

选用美国环境保护署现行废物风险评价模型(3MRA)对某铬渣整治项目进行环境风险评价.模拟了治理前后区域内环境风险情况.分析了污染物暴露途径及危害对象.通过模型对该项目预定处置方法可行性进行了验证.模拟结果显示,在95%受保护对象、95%置信水平条件下,铬渣堆存区域存在显著的环境风险,周边居民致癌风险在10-4数量级,水域生态风险危害商数>1.而在对铬渣进行解毒填埋处置后,环境风险将有效降低,验证了此项目处置方法的可行性.     

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.     

Power ultrasound in fatliquor preparation based on vegetable oil for leather application

In recent years, power ultrasound has taken a significant place in chemical and physical activities of the process industries as an effective and non-polluting method of activation. Oil in water emulsions known as fatliquors are used for the lubrication of tanned leather fibres to get softness and also to improve the strength properties. In the present study, ultrasound has been used as a tool for the preparation of fatliquor emulsion for application in leather fatliquoring process. An emulsion is a fine dispersion of one liquid in another liquid. Sulphation is one of the common methods followed to prepare fatliquor emulsion where sulphuric acid is used. In the conventional process, emulsifying agent is also added to increase the stability of oil in water emulsions. The emulsifying agents generally used are chemicals or metal soaps. The potential use of ultrasound in the preparation of stable oil in water emulsions dispensing with sulphation process and with the minimum use of emulsifying agent has been studied and reported in this paper. This process enjoys the benefit of less pollution load in the form of chemical entities. The studies included the effect of process parameters such as ultrasonic output power and amount of oil used. Fatliquor emulsion prepared using ultrasound has been applied in leather fatliquoring process and the strength properties of the leathers were assessed. Emulsion particle size, which is another important parameter for diffusion through leather, has been measured using Laser Diffraction Technique. The stability of the ultrasonically prepared fatliquor emulsion has been found to be good. The results indicate that ultrasound could be effectively utilized in the preparation of non-ionic fatliquor emulsion eliminating sulphuric acid and impart required properties in leather.     

表面强化层受力失效的一种判别方法

为了找到在实际应用中评价表面强化层的力学性能的量化计算依据 ,通过B Cr RE共渗技术处理后的 45钢试样的力学性能试验 ,测得了表面破损时所对应的压力 ,并利用文中提出的模型 ,得出了渗层破损时 ,基体处于屈服阶段的结论 ,并求出了渗层的抗压极限。并可利用将表面强化层与基体联合起来考虑的处理方法 ,分析其他表面强化层的不同受力状态。     

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.     

高精度磁测在圈定铬渣堆积范围中的试验研究

界定铬渣堆积范围对于场地环境的维护和管理具有现实意义。工业生产过程中燃烧产生尾渣的磁化率是土层的几十倍,为高精度磁测在铬渣污染场地中的调查提供了前提条件和物理基础。文章采用高精度磁测对青海海北某一铬渣堆积场地进行调查,根据异常曲线的特征和定性拟合解释剖面,判定为铬渣填埋体为三度体,可近视看成为球体,球体的直径为5.8 ...     

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.     

高浓度含铬废水的综合利用

探讨了高浓度含铬褪铜废液的处理方法 ,根据该废液铬含量高 ,具有回收利用价值的特点 ,提出了一条综合利用含铬废液的工艺路线。将含铬废液在合适的条件下把Cr(Ⅲ )氧化为Cr(Ⅵ ) ,加合适的沉淀剂除杂质后 ,加入铅盐溶液 ,生成铬黄